A Hsitory of Platinum

A History of Platinum Allied Metals
D O N A L D M c D O N A L D & LESLIE B. H U N T
and its
A History of Platinum and its Allied Metals
A History of Platinum
and its
Allied Metals
Donald M cDonald
and
Leslie B. H unt
jM m
JOHNSON MATTHEY H atton Garden, London, EC 1
F I R S T P U B L I S H E D I N G R E A T B R I T A I N IN 1982 C O P Y R IG H T JO H N S O N M A T T H E Y
ISBN 0 905118 83 9
D istributed by E U R O PA P U B L IC A T IO N S L IM IT E D 18 Bedford Square, London W C IB 3JN, England by arrangem ent with JO H N S O N MATTHEY
This book has been typeset in Photon Bodoni and Baskerville and printed an d bound in England by STA PLES P R I N T E R S ST ALBANS L IM IT E D at T he Priory Press, Hertfordshire
A History of Platinum and its Allied Metals, by Donald McDonald and Leslie B. Hunt
Foreword
BY T H E R T . H O N . L O R D R O B E N S O F W O L D I N G H A M C h airm an of J o h n so n M a tth ey
S ince m a n first discovered fire a n d invented th e w heel th e re h a s b ee n a c o n tin uou s effort t h ro u g h the c e n tu ries to p u s h back th e fro n tiers of k n o w led g e a n d this still goes o n w ith m a rk e d success. F r o m th e very b e g in n in g s of m o d e rn ind u stry th e in h e re n t ch a ra c te ris tic s of p l a t i n u m - its hig h m e ltin g p o in t c o m b in e d w ith its exceptional resistan c e to c o rro sio n - o p e n e d u p fields for its ap p lica tio n a n d gave it, in fact, a u n iq u e p lace in th e h isto ry of re s e a rc h a n d invention. T h e researches of F a ra d a y , Davy, a n d of those w h o followed th e m in developing o u r know ledg e of electricity show h ow g re atly they relied u p o n p la tin u m to provide a m e a n s of ca rry in g, m a k in g a n d b re a k in g a c u r re n t, while the d evelopm ent of th e electric teleg rap h , of th e in c a n d e s c e n t la m p a n d l a te r of the th erm io n ic valve all involved the use of p la tin u m , as d id th e early in ternal co m b u s tio n engines, first for ig niter tu b es a n d la te r for m a g n e to co ntacts. S o m e of these p io neering a p p lica tio n s have b e e n s u p e r se d e d b y o th e r m ateria ls, but fu rth e r a n d b r o a d e r d e m a n d s have arise n a n d b e c o m e w idely established. T o d a y very large a m o u n ts of p l a t i n u m a re em ployed, for exam ple, as a c a ta ly st in the p r o d u c tio n of nitric acid a n d th e n c e in the m a n u f a c t u r e of h u g e q u a n titie s of fertilisers to increase the grow ing of food for a n ever-increasing a n d h u n g ry w orld po pulation , w hile the refo rm in g of c r u d e p e tro le u m w ith a p la tin u m catalyst yields not only o u r high o c ta n e petrol b u t also a ra n g e of c h e m ic a l in te r m ediates re q u ire d for th e p r o d u c tio n of plastics, s y n th etic fibres, dyestuffs a n d p h a rm a ceu tica ls. T h e m a n u f a c tu r e of optical glass a n d of fibre-glass w o u ld not be possible w ith o u t th e use of p la tin u m , w hile th e in vention of the fuel cell e n a b l ing space to be c o n q u e re d a n d m a n s j o u r n e y to th e m o o n to b e ac co m p lish e d a n d now being u sed to g e n e ra te electricity also d e p e n d s u p o n the m etal. The usefulness of p l a t i n u m s five allied m etals - p a lla d iu m , rh o d iu m , iridium, r u t h e n i u m a n d o s m iu m - w as la te r in d e v e lo p m e n t t h a n w ith p la tin u m itself, b u t over th e p a s t fifty years or so th ey too have fo u n d g row ing ap p lic a tio n s in chem ical, electrical a n d electronic engineering. In all these a n d in m a n y o th e r d ev e lo p m e n ts th e p l a t i n u m m etals have play ed a very special p a r t in th e lives of m a n k in d , a n d in this book the au th o rs, w hose co m b in e d len g th of service w ith J o h n s o n M a t t h e y exceeds n inety years, have traced their history from th e d a y th e q u alitie s of p l a t i n u m w e re first discovered in 1750. It is a w ork of historical im p o rta n c e a n d will u n d o u b te d ly en co urag e the scientific a n d technical re searc h ers to seek p a s tu re s new w ith this
1982 Johnson Matthey
re m a rk a b le noble m etal w h ic h h a s im p rov ed the q u a lity of life in m a n y diverse ways. O n e of th e latest a c h ie v em en ts has b e e n th e use of a co m p lex p l a t i n u m c o m p o u n d to p ro d u c e a d ru g k n o w n a s C i s p l a ti n w h ich , u sed e ith e r as a single agent or m o re usually in c o m b in a tio n th e r a p y , is active a g a in st several ty pes of h u m a n tu m o u rs. S ince this discovery f u r t h e r re s e a rc h is leading to a ra n g e of a n t i t u m o u r drugs for w h ich m a n y c a n c e r sufferers will b e grateful. B u t the en d of th e p r o d u c t lin e by th e use of p l a t i n u m h a s not yet b ee n re ached. R e s e a rc h goes o n ceaselessly a n d new benefits to m a n will flow from the efforts of the scientists w h o a lre a d y see so m u c h yet to c o n q u e r in the d evelopm ent of p la tin u m usage. Yes, p la tin u m is a noble m e t a l a n d a n o ble task h as b e e n ac c o m p lis h e d by th e a u th o rs w h o have b e e n a s s o c ia te d w ith it for m o st of th e ir w o rk in g lives a n d have seen so m u c h th a t is g ood for m a n k i n d em e rg e from its use. M o s t un fo rtu n a te ly M r D o n a l d M c D o n a l d , w h o first co m p ile d a history of p l a t i n u m in 1960, died at th e a g e of 92 w hile th is book, m u c h e n la rg e d a n d b r o u g h t u p -to -d a te by D r Leslie H u n t , w as in th e press.
Preface
O f all the che m ic al elem ents p l a t i n u m h a s a t t r a c t e d th e active in tere st of m o re d istin g u ish ed scientists t h a n a n y o th e r since it w a s first b r o u g h t to their a tte n tio n in 1750. Its hig h m eltin g p o in t a n d th e g re a t difficulties en c o u n te re d in re n d e rin g its inv alu able p ro p e rtie s available for p ra c tic a l use fru stra te d m a n y able m e n over a long p erio d of y ears a n d th e story of th e ir strug gles is one of p erseveran ce a n d ingenuity. O n l y after th e discovery in 1803 a n d 1804 th a t native p l a t i n u m d id not consist of j u s t o n e e lem e n t b u t c o n ta in e d at least four o th ers - p a lla d iu m , rh o d iu m , irid iu m a n d o s m iu m - a n d their identification a n d s e p a ra tio n w as it possible to o b ta in p l a t i n u m in a s ta te of relatively high purity. T h e n the w ell-kn ow n w ork of W illia m H y d e W o lla s to n in devising a p o w d e r m etallurgy process to b rin g it into m a lle a b le form, p u b lis h e d only after his d e a th in 1828, led to its first c o m m e rc ia l ap plica tion s. F ro m th e n o n w a rd s th e refining a n d fa b ric a tio n of p la tin u m , as well as the stu d y of its ch e m is try a n d m etallu rg y , w ere ta k e n up m o re w idely a n d a n u m b e r of in d u strial con c ern s c o m m e n c e d o p e ra tio n s in E n g la n d , F r a n c e a n d G e rm a n y , this leading o n to th e search for fu rth e r sources of m in era l. T h i s slow b u t c o n tinuous d eve lop m e nt over som e tw o h u n d r e d y ea rs w a s th e sub ject of A H isto ry of P la tin u m from th e E arlie st T im e s to th e 1880s w ritte n b y m y senior colleague D o n a ld M c D o n a l d a n d p u b lis h e d by J o h n s o n M a t t h e y in 1960. T h is was b a s e d not only u p o n his long ex p erience in w o rk in g w ith p l a t i n u m b u t also on a g reat deal of p a in sta k in g re searc h in th e early scientific l ite r a tu r e in five languages as well as in th e c o m p a n y s archives. D u r i n g t h e in terv enin g tw en ty two years a c o n s id e ra b le a m o u n t of re searc h h a s b e e n c a rrie d o u t by h isto rian s of science o n th e lives a n d w ork of a n u m b e r of th e m e n a ss o c ia te d with p latin u m , a n d w ith th e en th u s ia s tic a g r e e m e n t of M r . M c D o n a l d , w h o sadly died while this bo ok w as in th e press, I have u n d e r ta k e n the p r e p a r a t i o n of a com pletely revised a n d e n la rg e d v olum e to re co rd in g re a te r detail th e history of th e p la tin u m g ro u p of m etals. Also, th e scale of p r o d u c tio n a n d use of these m etals has in cre ased alm o st five-fold since 1960 so th a t they now play a n even m o re im p o rta n t p a r t in m a n y p h a se s of in d u s try a n d in daily life a n d th e period covered h a s therefo re b e e n ex te n d e d by som e seventy-five y ea rs o r so to include the m a jo r discoveries of new sources of s u p p ly as well as th e ir m o re recent applications. T h e p re sen t volum e re ta in s th e gene ral s t r u c t u r e of D o n a ld M c D o n a l d s book b u t includ es c o n sid erab ly m o re b io g ra p h ic a l m a te r ia l on tho se w h o feature in the story, w ith m a n y of th e ir p o rtra its, w hile I have a t t e m p t e d to b rin g out bo th their p e rs o n a l m o tiv a tio n in ta k in g up th e w ork a n d th e ir influence one
u p o n another. In this I have also trie d to follow th e p re c e p t laid d o w n by Dr. J o h n s o n in a n o th e r context. I n i n tr o d u c in g his Life of A d d i s o n h e w rote:
N ot to nam e the school or the m asters of m en illustrious for literature is a kind of historical fraud by w hich honest fa m e is injuriously d im inished.
M y th a n k s a re d u e to a g re a t m a n y p e o p le for m a k in g this book possible. First, to my fo rm e r colleagues on t h e B o a rd of J o h n s o n M a t t h e y for s p o n so rin g its p u b lic a tio n a n d th e n to D r. W . A . S m e a to n , a to w er of s tre n g th a n d advice to m e o n th e history of science over t h e p a st tw e n ty y ea rs a n d m ore. T o P rofessor M e lv y n U ss e lm a n of th e U n iv e rs ity of W e s te r n O n t a r io , a n d to D r. J o h n C h a ld e c o tt, form erly of th e S c ie n c e M u s e u m , I ow e a g re a t d e b t for th e ir c o n tin u in g researches on th e life a n d w o r k of W o llasto n , as I do to th e late D r. A. E. W a le s for sim ilar re searc h es on S m i t h s o n T e n n a n t , to D r. P e te r C o llins for his stu d y of D b e re in e r a n d to P ro fe ss o r G e o rg e K a u f f m a n for his re s e a rc h e s on R u s s ia n scientists. T o M r. M a x W o o d a n d A i r C o m m o d o r e F. J . P. W o o d I am m ost grateful for in fo rm a tio n o n t h e i r an c e s to r C h a rle s W o o d w h o first b r o u g h t sp ec im e n s of p l a t i n u m to E n g la n d , w hile to D r. J . R . F is h e r of th e U n iv ersity of Liverpool I owe g u id a n c e on th e e a r l y h isto ry of p l a t i n u m m in in g in th e S p a n is h colonies of S o u th A m erica. T o M . R o g e t C h r i s t o p h e I a m in d e b te d for his re s e a rc h on the early history of p l a t i n u m fa b ric a tio n in F r a n c e a n d to Dr. H e r m a n n R e n n e r for p rov id ing full details of th e early h isto ry of DEGUSSA. T o D r. P e ta B u c h a n a n I a m i n d e b t e d for p a in s ta k in g re se a rc h o n a n u m b e r of genealogical p ro b le m s a n d to M r s . V. E. H a r d i n g , u n til re cen tly lib ra ria n of J o h n s o n M a tth e y , for p ro c u rin g c o p ie s of p u b lic a tio n s difficult of access. I have also h a d the benefit of access to t h e archives o f j o h n s o n M a t t h e y , in c lu d in g the long co rre s p o n d e n c e of G e o rg e M a t t h e y , a n d th e ir early B o a rd m in u te s. F o r facilitating m y ow n re s e a rc h e s I have p le a s u r e in ac k n o w led g in g the helpfulness of th e lib ra ria n s a n d t h e i r staffs of T h e B ritish L ib ra ry , T h e R o y al Society, the R o y al Society of C h e m is tr y , T h e R o y a l I n s titu tio n , T h e Science M u s e u m , T h e U niversity of C a m b r i d g e , T h e U n iv e rs ity of E d i n b u r g h , T h e In s titu tio n of M in in g a n d M e t a l l u r g y , the G eo log ical Society, T h e V ic to ria a n d A lb e rt M u s e u m , G u y s H o s p ita l, T h e W e llc o m e In s titu te , T h e S o ciety of F rien d s, the B ib lio tq ue N a tio n a le , T h e A c a d m ie R o y a l des Sciences, T h e B undesarchiv, T h e W r t t e m b u r g i s c h e L a n d e s b ib lio th e k , th e Pflzische L and e sb ib lio th ek , T h e B a y e ris c h e n S ta a ts b ib lio th e k a n d th e R o y a l S w ed ish A c a d e m y of Sciences. F o r answ erin g m y m a n y q u e s tio n s on specific p o in ts o r a b o u t individual scientists or for providin g v a lu a b le in fo rm a tio n I a m also m o s t grateful to Dr. R o b e rt A nderson, Dr. R o b e r t B u d , Dr. B ria n Bowers, D r. J ill A u s t i n a n d M r. P eter M a n n , all of the Science M u s e u m , to Dr. W a rw ic k B ray of th e I n s titu te of Archaeology, U niversity of L o n d o n , to M rs . S h irley B u ry of th e V icto ria a n d A lb e rt M u s e u m , M r. H e n r y W o lla s to n , Pro fessor M a u r i c e C ro sla n d , Professor C yril S tanley S m ith, M r. P eter E m b r e y of th e N a t u r a l H is to ry M u s e u m , Dr. L in d sey H u g h e s of th e U niv ersity of R e a d in g , M rs . U n a des F o n ta in e s , M r. R o b e r t C op elan d , D r. Ia n F raser, M i s s A n n Petrie, M rs. C l a r e Le C o rb e ille r of Vili
the M e tr o p o lita n M u s e u m of A rt, N e w York, M r. J a m e s V. C ra w fo rd , P re s id e n t of U .O .P ., M . O liver S oulet of Paris, M r. K. W. M a x w e ll of R u s te n b u r g P la tin u m M ines, P rofessor A r n e F r e d g a of th e S w edish A c a d e m y of Sciences, M r. Niels G r a m a n d Dr. F ro d e G a lsb ^ l of C o p e n h a g e n , H e r r U . K u n z of DEGUSSA, M . J e a n P ie rre S a v a r d of Paris, D r. C h r i s t o p h R a u b of S c h w b is c h G m n d , D r. F. W . J . M c C o s h , M r. R o b e rt B arker, D r. J a n e t C u tle r, M r. Paul W eindling, M r. P. A. L ovett a n d M r . S. T . P a y n e of In c o E u ro p e , M r . G r a h a m D y e r of the R o y a l M in t, M r. V in ce n t N e w m a n , M iss B a r b a r a P y ra h , H e r r W illy F uchs of F ra n k fu rt, Professor G i a n M a r i a G ro s -P ie tro a n d Dr. D o n n a d O ld e n ic o of T u r i n , D r. H a n s P re s c h e r of D re s d e n , M a d a m e T a m a r a P r e a u d of th e M a n u f a c t u r e n a tio n a le de Sves, D r. J . G . B ru ijn a n d D r. E. Bock of the N e th e rla n d s a n d P rofessor F ra n c is ic o A r a g o n d e la C r u z of M a d r id . Lastly it is a p le a su re to ackn ow ledge the g en e ro u s h elp received fro m my colleagues o n Platinum Metals Review, m y sec retary M rs . J u l i e A d a m s w ho nobly struggled w ith the ty pin g of th e m a n u s c r ip t a n d its n u m e r o u s revisions an d additions, M r . I. E. C o t ti n g t o n for re a d in g th e proofs, su g gesting m a n y im p ro v e m ents a n d p r e p a r in g th e n a m e index, M rs. S u s a n A s h to n for m u c h lib ra ry work involving w restling w ith i n n u m e r a b le in correct references in th e li te r a t u r e and for p re p a rin g the subject index, M is s P avla K n o p o v a for s e a rc h in g for p a t e n t s a n d for tra n s la tio n from R u ss ia n . F in a lly m y th a n k s also go to M r. H . D. S m ith, M a n a g in g D ir e c to r of S ta p le s P rin te rs St. A lb a n s L im ite d , for his lively personal in tere st in th e ty p o g rap h y , d esign a n d p ro d u c ti o n of th e book. H a tt o n G a r d e n L on d o n J u n e 1982
LESLIE B H U N T
IX
Contents
Chapter 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 T h e B eginning of the Story T h e Platinum of N e w G ranada Early Scientific E nquiries into th e Properties and N a tu re of P la tin u m Early A ttem p ts to M elt and W ork P latinu m T h e A rsenic P rocess and its U se by th e F rench G o ld sm ith s T h e P latinum A ge in S p ain T h e W id en in g of Interest in P latinu m and its Properties T h e P rofessional S cien tists of L on d on and their S o cieties T h e Partnership of S m ith son T en n a n t and W illiam H y d e W o lla sto n T h e P latinum Industry in France after the R ev o lu tio n Progress in E n glan d after W ollaston T h e D iscovery and Early H istory of C atalysis T h e F ou n d ation of the R u ssia n P latinum Industry T h e P latinu m M etals in Early N in eteen th C en tu ry C hem istry T h e M eltin g of P latinu m and the N ew M eta llu rg y of D ev ille and D eb ra y G eorge M a tth ey and the B u ild in g of the British P latin u m In du stry T h e D evelop m en t of th e P latinum Industry in C o n tin en ta l E u rop e T h e P latinu m M etals in the P eriodic S ystem Platinum in the M easu rem ent o f H igh T em p era tu res Platinum E xtraction and F abrication on the A m erica n C o n tin en ts T h e G row th of Industrial C atalysis w ith the P la tin u m M eta ls Production of the P latinu m M etals in Soviet R u ssia T h e D iscovery of the W o rld s G reatest P latinu m R esou rces T h e Story C on tin u es . . . N am e In dex Subject Index 435 443 Page 1 13 29 55 75 93 109 133 147 179 195 219 235 253 271 289 317 333 351 365 385 403 411 422
Ju liu s Caesar S ealiger 1484-1558

T h e first kn ow n lite rary r e f e r e n c e to p la tin u m is to be fou nd in the E xo terica ru m E xe rc ita lio n u m com piled by Sealiger and pu b lis h ed in P a ris in 1557. T his was larg e ly a polem ical work criticising the g reat work of a n o th e r Italian s c h o l a r , H ie r o n im o C a r d a n , who had de fine d a metal as a substa nc e th at c a n b e m elted a n d which h a r d e n s on cooling"
1
T h e B eginning of the Story
A s u b s t a n c e w h i c h it has n ot h i t h e r t o b e e n possible to m e l t
b y f i r e o r b y a n y o f t he
JU L IU S C A E SA R SC A L IG E R
S p a n i s h arts.
U ntil the pre sen t c e n tu r y the only form in w h ic h n a tu ra lly o c c u rrin g p l a t i n u m was available to c o m m e rc e was th a t of th e w a te r-b o rn e g ra in s fo u n d in alluvial gravels, u su ally in co n ju n c tio n w ith gold. T h e s e g ra in s w e re m etallic a n d co n tained ro u g h ly 50 to 80 p e r cent of p la tin u m , th e r e m a i n d e r c o n sistin g of the o th e r m em b e rs of th e p l a t i n u m g ro u p , r u t h e n i u m , r h o d iu m , p a lla d iu m , o s m iu m a n d irid ium in v arying a m o u n ts , to g e th e r w ith a c e r t a i n a m o u n t of iron, c o p p e r a n d oth er b a s e m etals. I n b o th cases s am p les w e re c o n t a m i n a t e d w ith heavy black m in era l s a n d s su c h as c h r o m ite a n d m a g n e tite , from w h ic h it was difficult to effect co m p lete sep a ra tio n . T h e r e w ere also som e s p a n g les of gold a n d in the early sp ecim ens alw ays som e globules of m e rc u ry . T h i s w a s th e m a te r ia l w hich confron ted the first c ra fts m e n a n d scientists w ho c a m e into c o n ta c t w ith it a n d it p re sen ted th e m w ith m a n y difficulties. But it so o n b e c a m e evident th a t t h e p re sence of th e m e rc u ry was d u e to th e a t t e m p t s m a d e at th e p lace of orig in to remove th e gold b y m e a n s of a m a lg a m a tio n . T h e earliest a t t e m p t s to w o rk the m etal were confined to th e selection of single g ra in s a n d these w ere t h e n h a m m ered o u t or so ld ere d together. All the early a t t e m p t s to m elt th e m a te r ia l in bulk failed, a n d m u c h p a tie n t re searc h over m a n y y ea rs a t th e h a n d s of a succes sion of b rillia n t scientists w a s necessary before a re a s o n a b ly m a lle a b le m e ta l was produced.
T he Egyptian Find
It is very do u b tfu l w h e th e r p l a t i n u m was re co gnised as a s e p a r a t e b o d y in the early civilisations. O ccasio n ally trac es of it have b e e n fou n d a m o n g artifacts from an c ie n t E gypt, th e best kn o w n ex a m p le b ein g a sm all strip of native p la tin u m set on th e surface of a box a m o n g m a n y hiero g ly p h ic inscriptions, m a d e of gold on on e side a n d of silver o n th e o ther. T h is h a d o rig inally com e from T h e b e s a n d is d a te d to th e seventh c e n tu ry BC In 1900 it w a s s u b m itte d by the K eeper of E g y p tia n A n tiqu ities in th e Louvre for e x a m in a tio n b y th e F ren c h scientist M a rc e lin Berthelot, w ho fou nd th a t one of th e c h a r a c te r s o n th e side 1
having hieroglyphics in silver differed c o n s id erab ly from th e others. H is careful series of tests sh ow ed th a t it w a s alm o st insoluble in a q u a regia a very sin g u la r resistance to a t t a c k as h e d esc rib ed it in th e c o u rse of a p a p e r to th e A c ad em ie des Sciences (1), s u r p a s s in g t h a t of gold o r of p u r e p l a t i n u m . H e co nsid ered th a t it m u st be a c o m p l e x alloy c o n ta in in g several of th e m etals of th e p l a t i n u m group. B erthelot also f o u n d no evidence th a t th e E g y p tia n c r a fts m a n h a d noticed a n y d istinction b e t w e e n this p a r ti c u la r piece of m e ta l a n d th e silver he h a d used for th e o th e r c h a r a c te r s . It h a d b ee n h a m m e r e d o u t in the sam e way, a n d its o cc u rre n ce a m o n g t h e o th e r w a s p r o b a b ly q u i t e fo rtu ito u s - it h a d sim ply been m ista k en for silver. Since B e rth e lo ts tim e m a n y e x a m p le s of p l a t i n u m m e ta l inclusions in gold artifacts from ancient tim es have b e e n re corded , a n d it h as b e e n e s ta b lis h e d th a t they o ccur q u ite co m m o n ly in allu v ial gold, m ost often as co m p lex o sm iu m irid iu m - ru th e n iu m -p la tin u m alloy s or c o m p o u n d s . T h e i r p re s e n c e a n d co m p o s i tio n have b ee n well reviewed by J . M . O g d e n (2).
T h e Classical Wniters
Several a tte m p ts have b ee n m a d e over t h e years to sh o w t h a t references to p l a t i n u m c a n be fo un d in an c ie n t G re e k a n d R o m a n lite rary works. T h e earliest of these was a dissertatio n by a n I t a l i a n scholar, D o n A ngelo M a r i a Cortinovis, w ith th e title D ella P la tin a C o n o s c iu ta degli A n tic h i w ritte n in 1778 a n d p u b lis h e d in 1790 (3). In this he s o u g h t to prove t h a t th e n a m e e l e c t r u m , th e n a t u r a l alloy of gold a n d silver m u c h u sed in a n tiq u ity , also referred to p la tin u m . In 1845 Professor J . S. C. S c h w e ig g e r (1779 1857) of H alle, th e invento r of th e g alvan om eter, w rote a long p a p e r after his re tire m e n t O n P la tin u m , O ld a n d N e w (4) in w h ich he m a i n t a i n e d t h a t th e su g g estio n of C ortinovis could not b e su p p o rted , b u t t h a t P lin y s d e s c r ip tio n of p l u m b u m a l b u m , w h ite lead, of th e sam e w eigh t as gold, in th e N a t u r a l H i s t o r y Book X X X I V , c h a p te r 47, g ene rally ac c e p te d as referring to tin, s h o u ld b e in te r p r e te d as p l a tin u m . H e w e n t o n fu rth e r to suggest at som e le n g th t h a t a reference in th e G u id e to Greece w ritte n by th e traveller a n d g e o g r a p h e r P a u s a n iu s in th e sec o n d c e n tu r y AD to a kin d of elec tru m found as a n a t u r a l p r o d u c t in th e s a n d s of t h e E rid a m o s (the R iv er P o) w h ich is extrem ely r a r e a n d v a l u a b l e m u s t necessarily b e c o n s tru e d as m e a n in g p la tin u m . S ch w e ig g e r also d re w u p o n H o m e r , w h o d esc rib ed th e costly a r m o u r of A g a m e m n o n in t h e Iliad (Book X I) b e in g m a d e of stripes, twelve of shining gold a n d t w e n t y of t i n . H e co n sid e re d t h e l a tte r as a poor s a fe g u a rd a g a in st the th ru s t of a s p e a r a n d th a t th ey c o u ld well have been p la tin u m . Five years la te r a F re n c h c h e m i s t n a m e d Paravey, in a letter to th e A c ad em ie des Sciences (5), a g a in a rg u e d for P l i n y s p l u m b u m a l b u m , fo u n d in th e gold m in es of L u s ita n ia a n d Calicia i n Spain, b eing p la tin u m . Follow ing u p this t h e m e m a n y years afte rw a rd s a S p a n i s h physicist, P ina de R u b ie s (6) a g a in 2
ad v a n ced the view th a t p l a t i n u m w as in fact th e p l u m b u m a l b u m o f Pliny a n d th a t it h a d b e e n discovered in S p a in before th e first c e n tu r y AD. A m ore recent su ggestion t h a t P lin y s a d a m a s , d e s c rib e d in his Book X X X V I I , C h a p t e r 15, was in fact p l a t i n u m h as b e e n m a d e b y O g d e n (2) a n d has a little m o re feasibility. T h e q u o ta tio n re a d s in t r a n s l a t i o n : Adamas was the name given to the knot of gold found very occasionally in mines in association with gold. . . . The hardness of adamas is indescribable, and so too that property whereby it conquers fire. (7) But th e last w o rd on this r a th e r d u b io u s a r g u m e n t a b o u t th e k n o w led g e of p la tin u m in a n tiq u ity is p r o b a b ly t h a t of Professor J . F. H e a ly w ho w rites in the c h a p te r on native m etals in his re cen t s tu d y of th e s u b j e c t : The second group, platinum, iridium and osmium, plays no part in Greek or Roman mining or metallurgy. (8)
Early European Literature

It is significant t h a t th e re is no reference w h a te v er in th e n u m e ro u s books on m etallurgy, assaying a n d ch e m is try w ritte n by k n o w le d g a b le a n d ex perien ced observers th a t b e g a n to a p p e a r in E u ro p e in th e six teen th c e n tu ry w h e n the invention of p rin tin g h a d m a d e these possible. T h e well k n o w n w orks of Biringuccio, Agricola, Ercker, G la u b e r, K unckel, a n d L ibavius, for exam p le, show no trac e of a n y th in g t h a t m ig h t b e identified as p la tin u m . T h e only possible reference is c o n ta in e d in the v o lum inou s works of a B o h e m ia n priest a n d historian, B ohuslav B alb in u s (1621 1688), w h o referred briefly in his M iscellanea H is to ric a R e g n i B o h e m ia , p u b lis h e d in P r a g u e in 1679 (9), to Aurum album (argentum esse jurares, nisi pondus et quaedam tam en fulvedo per metallum fusa aliud svaderent) album aurum, inquam, in montibus effosum, vidi non semel. ( White gold (which one would swear to be silver except that its weight and a certain yellowish tinge pervading the metal persuaded otherwise), white gold, I say, which is dug out of the mountains, I have seen more th an once. ) T h is p assa g e was referred to by M ich ae l B e rn h a rd V alentin i (1657 1729), a ph ysician a n d scientist of G iessen in G e rm a n y , w h o w as elected to the R oyal Society in 1717. In his H is to ria L ite ra ria A c a d e m ie N a t u r a e C u r i o s o r u m pu blished in 1708 h e c o n sid erab ly am plified th e brief s ta te m e n t m a d e by B a lb in u s : Who would have believed that white gold deprived of all its colour had been discovered, but the authority for this is the most honourable in reputation the Jesuit Father Balbinus who states that one would swear it was silver if it was not for the familiar properties found in gold such as its weight, ductility, resistance to fire and to nitric acid and its solubility in aqua regia. (10) A letter a b o u t a sp ec im e n of w hite gold from th e A rc h D u k e F e r d i n a n d of Bohemia, w ritte n in 1560 to th e M a s t e r of th e M i n t in P rag ue, is q u o te d by C o u n t K a s p a r M a r ia S te rn b erg (1 76 1-183 8) in his tw o -v o lu m e w ork o n the 3
EXERCIT ATIO
LXXXVIII.
Qua: adMetalla.
E t a i l v m , inquis,eft quod Iiquefcere poteft : & cu redir,durum m aner.O blitocibi magni lllius uicari; metailorumhicc exciderunt. Aurum merallorum rex eft : Ar gentum uiuum ty rannus.Quod ex tua definitione metallum non erit. Eft autem tyrannus, quia cactera omnia abfiimir. Plinius in uiceimo nono ira icribit: A uroliqueicenriii Gallina? carnes admiiceantur,abillis rapi.Itaqueauri uenenum eie.Qud C i uerum eft : fanficpricintius atque commodius adipiicemur aurum e(culcntum, qum ex tua inani indicanone, aurum potabile . Prsercrea (cito,in Funduribus,quitraiiVus eft inter Mexicum,&: D anem ,fodinasefleorichalci:qudnuiloigm ,nullis Hiipanicis artibushatenus liqueicere poruit. Adhacc non omnibus metallis uerbum,liqueicere,uidemus conuenire.
T h e passage from Scaligers' c o m m e n t a r y de alin g with the n a t u r e of m etals a n d re b u ttin g C a r d a n s assertion, concluding th at t h e r e a re m in es in South A m e r ic a lhat con ta in a substance t h a t it has not hith erto been possible to m e l t by fire or by a n y of the Spanish a r ts
h isto ry of m in in g in Bohem ia, p u b l i s h e d in th e last y ears of his life (11). H e suggests th a t th e re m a rk s of B a lb in u s m ig h t have referred to this specim en, b u t says t h a t gold was never foun d in t h e m o u n ta in s of B ohem ia.
Rum ours from the New W o r ld

W h ile therefore very little c a n r e a lly b e s a id of p l a t i n u m in th e O l d W o rld it seem s th a t ru m o u rs from the N e w b e g a n to re a c h E u ro p e d u rin g the sixteenth ce n tu ry . T h e earliest k n o w n re fe re n c e h aving som e solid fo u n d a tio n occurs in th e w ritings of J u liu s C a e s a r S c a lig e r o r D ella Scala, a well k n o w n Ita lia n s ch o la r a n d poet. In 1551 the I t a l i a n m a t h e m a t i c i a n a n d p h ilo s o p h e r H ie ro n im o C a r d a n h a d p u b lish ed his gre at w o rk D e S u b tilitate R e r u m , co m b in in g the s o u n d e s t physical know ledge of h i s tim e w ith som e a d v a n c e d sp eculation . His c o n te m p o r a ry Scaliger th e n h a d t h e h ig hest scientific a n d lite rary r e p u ta tio n of a n y m a n in E u ro p e a n d h a d w r i t t e n a n u m b e r of c o m m e n ta rie s , in c lu d in g one o n C a r d a n s work. This, his E x e r c i t a t io n e s o n th e D e S u b tilita te , was p u b lis h e d in Paris in 1557 a n d s h o w s b o t h a n encyclopedic k now led ge a n d a vigorous polem ical style (12). 4
It is in C h a p t e r 88 th a t th e historic reference to p l a t i n u m is to be found. C a r d a n h a d defined a m etal as a su b s ta n c e th a t c a n be m e lte d a n d w hich h a rd e n s o n co o lin g , a n d S caliger was at p ain s to fault h im as far as he could, first by reference to m e rc u ry a n d th e n by citing th e u n m e lta b le m etal u n d o u b te d ly p la tin u m - of w h ic h he h a d h e a r d from S o u th A m eric a. T h e p assa g e is illu stra te d here a n d th e essential p a rts, th e first a n d last sentences, re a d in tran slation :
M etal you say is som ething that can be m elted but w h en it co o ls rem ains hard. . . . M oreover, I know that in H onduras, a district b etw een M ex ico and D arien, there are m ines con taining a su b stan ce w hich it has not hitherto b een p ossib le to melt by fire or by any of the S pan ish arts. T h u s w e see that the w ord m elt can n ot be applied to all m eta ls.
T h is q u o ta tio n c a n re a s o n a b ly be h eld to a p p ly to p l a tin u m , a lth o u g h the m etal has never b e e n found o cc u rrin g n a tu ra lly in th e are a s m e n tio n e d by Scaliger. It is, however, q u ite likely t h a t p l a t i n u m objects w ere tra n s p o r te d a b o u t S p an ish A m eric a a n d m ig h t well have b e e n e n c o u n te re d in th e h a n d s of people living in the c o u n try b e tw e e n M exico a n d th e I s t h m u s of D arien. O n the oth er h an d , th e re was at th e tim e of S c a lig e rs w ritin g a g re a t deal of u n c e rta in ty in E u ro p e a b o u t the g eo g ra p h y of these regions. T h e next e x a m p le of this sort of reference from S ou th A m e r ic a occurs in a c h a p te r o n gold a n d silver in H is to ria N a tu r a l y M o ra l D e Las I n d i a s p u b lish ed in Seville in 1590 b y th e J e s u it priest J o s de A c o sta (15 39 1600), one of a n u m b e r of S p an ish m issio naries sent to th e colonies in 1571. T h i s re ad s in a c o n te m p o ra ry tr a n s la tio n :
Y ea there is another kinde w hich the Indians call papas de plata and so m etim es they find pieces very fine and pure, like to sm all round rootes, the w hich is rare in silver but usual in g o ld .
T h e r e is a ta n ta lis in g reference to this in R o b e rt B oy les T h e Sceptical C h y m is t p u b lis h e d in L o n d o n in 1661. After q u o tin g A c o s t a s p a r a g r a p h he ad ds :

I m yself have seen a lum p of O ar not long since d igged up, in w h ose stony part there grew, alm ost like trees, divers parcels thou gh not of gold , yet of (w hat perhaps M ineralists will m ore w onder at) another m etal w hich seem ed to b e very pure or unm ixt w ith any heterogeneous su bstan ces, and were som e o f th em as b ig as my finger, if not bigger. But upon observations of this kind, thou gh p erhaps I could, yet I m ust not at present dw ell any lo n g er . (16)
A fu rth e r a n d eq ua lly v ague m e n tio n is m a d e b y A lonso B a rb a , a S p an ish priest who, like Acosta, sp en t m a n y years in th e S p a n ish C olonies. H e lived in the fam ous silver m in ing district of Potosi a n d w ro te his A rte de los M e t a l e s , p u b lished in M a d r id in 1640, from long o b s erv atio n a n d experience. H e refers to :
C hum pi, called thus on account of its grey colour is a stone o f the nature o f Emery w ith som e Iron. It shines rather darkly; and the treatm ent thereof is difficult, because
Specim ens of platin u m alloy jew ellery fou nd in the E sm eralda* region of E cuado r an d now in the N a tio n a l M u seum in C o p en h ag en . T h ese d a te from several centuries before the S p a n is h conqu est of Sou th A m erica
it offers resistance to heat. It is found with Black Sulphide and Ruby-Silver in Potosi, Chocaya and other places. (15) The alchemist Johann Joachim Becher (1635 1682) in his Physica Subterranea published in Frankfurt in 1669 referred to the adulteration of gold with smiridis hispanica, and this was later commented upon by William Lewis in his translation of T he Chemical Works of Caspar Neumann published in London in 1759. In the course of considerable additions to the original work Lewis wrote in a footnote about Platina: These properties, together with the place where it is found, and the prohibition said to be laid upon its exploitation by the King of Spain, afford sufficient grounds to presume that the Smiris Hispanica of the alchemists, employed for augmenting gold, was no other than this Platina or some mineral containing it; more especially as Becher expressly declares that this augmentation was really an abuse; that the Gold so augmented was pale and brittle; and that though it stood all the established tests of perfect Gold, yet it would not bear amalgamation with quicksilver, the Mercury retaining the Gold, and throwing out the Smiris in form of a reddish powder. Platina mixed with Gold is thrown out in the same manner; though it is not easy by this method to obtain a perfect separation. (16) This smiris may well have been a mixture of crude platinum and magnetic sand, but by the time that Lewis made these observations more was becoming
6
kn o w n of th e o cc u rre n ce of a s o m e w h a t u n u s u a l m etal in th e S p a n is h colonies. Long before this, however, th e native In d ia n s of th e n o rth -w e s te rn p a r t of South A m eric a h a d intere ste d them selves in th e new m in e ra l a n d ta k e n a d v a n ta g e of its properties.
The P re-C olu m b ian Indians of E cu ad o r and C olom bia

T h is re m a rk a b le case of th e successful e x p lo ita tio n of p l a t i n u m in a n isolated a re a in th e N e w W o rld of th e A m eric as m a n y h u n d r e d s of y ea rs before th eir discovery c a m e to light in th e n in e te e n th c e n tu r y after E c u a d o r h a d g a in e d its in d ep en d e n ce from S p an ish colonial rule. F ollow ing som e y ea rs of in tern a l dissension a m o re ab le a n d energetic p re sid e n t, G a b rie l M o re n o , c a m e to p o w e r in 1865 a n d sou ght the help of a n u m b e r of J e s u it scientists a n d te a c h e rs to aid in th e d evelop m ent of his country. A m o n g th e m w a s T h e o d o r Wolf, (1 8 4 1 -1 9 2 4 ) a G e r m a n geologist eng a g ed to re p o rt o n th e m in e ra l resou rces of the c o u n try w ho r e m a in e d to b ec o m e Professor of G eology at Q u ito . W h ile e x p lo rin g the coastal region in n o rth -w e s te rn E c u a d o r, in th e d e p a r t m e n t of E s m e r a ld a s a n d at a place called L ag arto, W olf u n e a r t h e d a n u m b e r of sm all w o rk e d trin k e ts of gold a n d of p l a t i n u m th a t h a d a p p a r e n t l y b ee n w a sh e d o u t of native b u ria l m o u n d s b y tidal fluctuations. A m o n g th ese w as a tiny ingot of p l a t i n u m w h ich he analy sed; it co n ta in e d 84.95 p e r cent p l a tin u m , 4.64 p e r ce n t p a lla d iu m , rh o d iu m a n d iridiu m , 6.94 p e r cent of iron a n d a little over o ne p er ce n t of copper. O t h e r specim ens w ere of g old alloys c o n ta in in g only m o d e st a m o u n t s of platin um . Wolf, w hose findings w ere p u b lis h e d in 1879 in th e last of a th ree -v o lu m e w ork describing his jo u rn e y s (17), realised t h a t th e te rrito ry of E c u a d o r h a d b e e n in the possession of th e In cas for only h a lf a c e n tu r y before th e arrival of the S p a n iard s a n d he c o n c lu d e d :
A race that knew how to produce the alloys that I have ju st en u m erated can certainly not be called uncultured and in m etallu rgy at least it w as not inferior to the Incas as long as w e can assum e that the old Lagarto Indians carried out this industry for them selves and did not acquire these objects by trade. T h e presence of the platinum , pure and alloyed w ith gold, is a strong argum ent in support of the first supposition, that is to say o f a native in d u stry .
An e x p e d itio n to the province of E s m e ra ld a s in E c u a d o r in 1907, led by Professor M a r s h a ll Saville of N ew York, ex p lo red a n u m b e r of large b u rial m o u n d s on the sm all islan d of La T o lita at th e m o u t h of th e S an tiag o River. H e re they ex cavated a large q u a n tity of very sm all pieces of jew ellery , rings, pen d a n ts, m in u te m asks of filigree work, nose, e a r a n d lip o r n a m e n t s a n d so on, som e of these b eing m a d e in p l a t i n u m or of p l a t i n u m a n d gold c o m b in e d together. Professor Saville re p o rte d t h a t :
T h e use of p latinu m is a u niq ue feature o f the section of South A m erica ex ten d ing from this province northw ard into the region o f th e C hoco River. . . . In this particular phase of ancient art the E sm eraldas p eop le seem to stand a lo n e . (18)
Paul Bergsê
18 7 2 - 1 9 6 3 \ f t e r r e tire m e n t from d irec ting his secondary tin sm e lte r in C o p e n h a g e n Dr P a ul Bergsê e m b a r k e d on a study of the m an y small p latin u m objects from E c u a d o r that had been found d u rin g (aiming for a ll u \ ia l gold, l i e not only c arried out analyses of these o r n a m e n ts but by c areful e x a m i n a t io n of pieces of metal in various stages successfully established th e ir m etho d of working as a n ingenious process of sinterin g in the p r e sence of a liquid phase . Bergsê was also an a c t i \ e lec ture r a n d b r o a d c a s te r on scientific s u b jects and in 1959 was p r e se n te d with the Oersted G old Medal of the Society for N a tural Sciences by the King of D en m ark
F u r t h e r exam ples of th e n a t i v e s skill in fa b ric a tin g b o th g old a n d p l a t i n u m w ere foun d o n the edge of a n artificial m o u n d o n th e island of L a T o l i ta in 1912 a n d w ere the subject of a later r e p o r t by W illia m C u rtis F a ra b e e (1865-1925), the d istingu ished an th ro p o lo g ist of the U niv ersity of P en nsy lv ania M u s e u m w h e re the collection is preserved. (19) H e wrote, after describ ing t h e e n o r m o u s n u m b e r of o r n a m e n ts of a n im m e n se variety of forms a n d d e s ig n s fou nd there:
T h e native Indian workers o f E sm erald as w ere m etallu rgists of m arked ability; they were the only people w ho m anu factu red p latinu m jew ellery. In our collection will be seen objects o f pure p la tin u m , objects w ith a p latinu m background set w ith tiny balls of gold used to form a b ord er, and objects w ith one sid e p latin u m and the other g o ld .
An Early Use of Powder M etallurgy

S im ila r objects fou n d on th e c o a s t of E s m e ra ld a s , m ostly at L a T o lita w ere actively studied by Dr. Paul Bergsjzre, the fo u n d e r of a sec o n d ary tin sm elter in C o p e n h a g e n , after he h a d re tire d from th e contro l of his works in th e early 1930s. Bergs 0fe not only c a rrie d o u t a n u m b e r of analyses of m a n y sm all objects, finding p la tin u m con ten ts ra n g in g fro m 26 to 72 p e r cent w ith sm all a m o u n ts of irid iu m a n d the o th er p la tin u m m e ta ls , som e gold a n d a little silver, b u t gave a great deal of atte n tio n to the likely m e t h o d of th eir m a n u fa c tu re . 8
Som e of the tiny fragm en ts of platin um which g a \e BergsfJe the clue to the m ethod em ployed by the native Indians. They were first coated with gold dust and then heated by m eans of a b lo w p ip e on pieces of charcoal: the m olten gold then served to sin te r them so that they could be forged
IM iolograpli l\ rourle*i\ of llie D a n is h N atio n al M u - r u m . ( 'iMwihagrn
The clue to his discovery he found in a number of very small grains of platinum that were mixed with gold dust. These, illustrated here, consisted of flat pieces weighing from 1 to 2 0 grams and were clearly in a half-finished stage of working. Bergspe came to the conclusion that the native Indians had used a quite sophisticated technique of powder metallurgy - sintering in the presence of a liquid phase - a technique which he admits greatly astonished him. He wrote a preliminary account of his findings in 1935 in a letter to Nature (20), and later published a monograph in Copenhagen giving full details and many illustrations (21). His collection of specimens, including the part-finished grains, is now in the Danish National Museum. He described this technique as he envisaged it: The small grains of platinum were mixed with a little gold dust and small por tions placed upon a piece of wood charcoal; when the gold runs it will coat the grains of platinum with gold . . . the grains are simply soldered together. If the piece is now further heated by means of the blowpipe, ... a portion of the fused gold permeates the platinum and simultaneously a little of the latter is dissolved in the molten gold. This mixture of gold and platinum can now withstand a light blow of the hammer, especially when hot. By alternately forging and heating it is possible gradually to build up a homogeneous mixture." Some of the pieces of jewellery examined by Bergsoe showed evidence of platinum cladding over gold, either on one side or on both. Again, he considered that a small piece of the sintered platinum alloy would have been placed on top of a bead of gold, heated and then hammered out together with occasional annealings. Useful reviews of this work on the Pre-Columbian metallurgy of platinum were published by Rivet and one of his colleagues in the 1940s. (22) More recent studies have confirmed Bergscres concepts and the high degree of craftsmanship of the natives of this small area in South America in the working of crude platinum. In a paper by D. A. Scott and W. Bray recently published (23) the authors report on the use of modern metallographic and analytical techniques to examine specimens from both the National Museum of
9
T w o p l a tin u m nose o r n a m ents m ad e by the In d ia n s of C olom bia. T h a t 011 the left is in a native iron platin u m alloy with sm all platin u m inclusions visible on the surfac e: on the right is a nose ring m a d e in a n a tu ra l c o p p e r la tin u m alloy with p sm a ll in c Iu s io n s of osm irid ium
Ph o to g rap h l\ co urtesy o f I he M useo d e l O r o . Bogota
D e n m a rk a n d the M u seo del O r o in Bogota, C olo m bia. F ro m th e la tte r source tw o nose rings, illu stra te d here, w e re s h o w n to consist of native iro n -p la tin u m alloy (left) a n d of a n a tu r a l c o p p e r - i r o n - p la ti n u m alloy w ith sm all inclusions of o sm irid ium . P h o to m icro g rap h s o f sections of som e of Bergsjares specim ens, b o th startin g m ate ria ls a n d fin ish ed objects, clearly sh o w e d th e p re s e n c e of sin terin g a n d the disp ersio n of p l a t i n u m partic le s in a g old m a trix . U n fo rtu n ately few of the p l a t i n u m finds fro m E c u a d o r or n eig h b o u rin g C o lo m b ia have a n estab lished a rc h a e o lo g ic a l context, m ost of th e m h aving been u n e a r t h e d by tre a s u re h u n te rs a n d to m b ro b b e rs. T h e r e is also evidence t h a t a few objects of p la tin u m w ere e x p o r te d from th e m a n u f a c t u r i n g reg io n a n d m a d e th e ir w ay either s o u th w a r d s along th e coast or in la n d to th e A n d e a n hig h lan d s. T h e i r d atin g is therefore difficult to establish, b u t th e site a t La T o lita from w h ich m ost of the p l a t i n u m items i n m u s e u m s have co m e has b e e n th e subject of ra d io -c a rb o n d e te rm in a tio n s r a n g in g from the first to th e fo u rth c e n tu ries A D w hile it h a d p ro b a b ly been a b a n d o n e d early in th e n in th c e n tu r y at latest a lth o u g h jew ellery co n tin u e d to b e m a d e in this a r e a u p to th e tim e of the c o n qu est, p re s u m a b ly in clud ing o b je c ts of p l a t i n u m (23). But it w as m a n y h u n d r e d s of years before th e S p a n i s h settlers in S o u th A m e ric a re-discovered the source of p la tin u m a n d even l o n g e r before E u r o p e a n scientists succeeded in re n d e rin g it m alleable a n d useful.
10
References for C h a p t e r 1
1 M . Berthelot, C.ompt. rend., 1901, 132, 7 2 9 -7 3 4 ; Ann. Chim., 1901, 23, 5 32 2 J. M. O gd en , J . H ist. M et. Soc., 1977, 11, (2 ), 53-71 3 A. M . C ortinovis, O p u sco li S celti sulle S cien za e su lle A rte, 1790, T o m X III, (4), 21 7 -2 4 2 4 J. S. C. Schw eigger, J . Prakt. C h e n , 1845, 3 4. 385^120 5 C. de Paravey, Compt. rend., 1850, 31, 179 6 P. de R ubies, An. Soc. Espaola Fsica y Qumica, 1915, 4 2 0 433 7 8 9 10 11 12 13 Pliny, N atural H istory, Book X X X V I I , C hap. X V , 5 5 -6 0 ; Loeb ed ition , 2 0 7 -2 0 9 J. F. H ealy, M in in g and M etallurgy in the Greek and R o m a n W orld, L ondon, 1978, 35 Bohuslav B albinus, M iscellan ea H istrica R egn i B ohem iae, Prague, 1679, Book I, Chap. X IV , 40 M . B. V alen tini, H istoria Literarca S .R .I. A ca d em ia e N a tu ra e C uriosorum , G iessen, 1708, 12 G raf K. Sternberg, U m risse einer G e sch ich te der B h m isch em Bergwerke, Prague, 1837, V ol. I, Part 2, 38-41 J. C. Scaliger, Exotericarum exercitation u m ber q uin tu s d ecim u s de S ub tilitate ad H ieronym um C ardanum , Paris, 1557, 1 3 4 -1 3 5 J. de A costa, H istoria N atural y M oral D e Las Indias, Seville, 1590, Book 4, C hap. 4, 201; T h e N aturall and M orall H istorie of the East and W est In dies, T rans. E. G rim ston, L ondon 1604, 212 Robert Boyle, T h e Sceptical C hym ist, L ondon, 1661, 371 373; Everym an edition, London, 1964, 198 A lonso Barba, El Arte de los M etales, M adrid, 1640, C hap. X III, 12 W . Lewis, T h e C hem ical W orks of C aspar N eu m a n n , L ondon, 1759, 43 T . W olf, V iajes C ientficos por la R ep b lica del E cuador, V ol III, M em oria Sobre la G eografa y G eologia de la Provincia de E sm eraldas, econ una C arta Geogrfica, G u ayaqu il, 1879 M . H. Saville, V erhan dlun gen X V I Internat A m erikan isten K ongres, V ienna, 1908, 2, 3 31-345 W . C. Farabee, Museum Journal, Univ. Pennsylvania, 1921, 12, 4 3 52 P. Bergsê, Nature, 1936, 137, (1), 29 P. Bergs0e, T h e M etallu rgy and T ech n o lo g y of G old and P latin u m am ong the Pre-C olum bian In d ia n s, Ingenioervidensk. Skr. (A 4 4 ), C op en h agen , 1937 P. Rivet, Revista Inst. Etnologico Nacional, 1943 1, 3 9 4, 45; P. Rivet and H. A rsandaux, Trav. et. M em . Inst. d E th nologie, 1946, 39, 113 115 D. A. Scott and W. Bray, Platinum M etals Rev., 1980, 24, (4), 147-157
14 15 16 17
18 19 20 21 22 23
11
Don A n to n io d e Ulloa 1716-1795

T h e Spanish naval officer, a s t r o n o m e r a n d m a th e m a tic ia n who was a m e m b e r of a F re n c h e x p e d itio n to E c u a d o r in th e years 1736 to 1743. T h e journal of his voyage, pu b lis h ed in 1718 in M adrid and soon transla ted into o ther langu a ges, c onta ined a r e fe r e n c e to the new m etal platin um whic h quickly a r o u s e d the interest of scientists in E u rope
2
T h e P latinum of N ew G ran ada
This p l a t i n a is a S t o n e o f s uch R e s i s t a n c e t hat it is not easily b r o k e n by a b l o w u p o n an Anv il. It is not s u b d u e d b y Cal ci nat ion, a n d it is verydi ffi cul t to e xt ract the M e t a l it co n ta i ns e v e n with much Labour and Expence."
A N T O N I O I)K I LI.O.A
F rom the p re c e d in g c h a p te r there seems to be no d o u b t th a t the p l a t i n u m th at b e g a n to re ach E u ro p e from th e S p a n is h colonies in S o u th A m eric a in the m iddle years of th e eig h te e n th ce n tu ry w as th e first to b e recovered in an y q u a n tity a n d th e first to a ttra c t th e curiosity of scientists. T h e source was in the w estern p a r t of w h a t is now the R e p u b lic of C o lo m b ia, b u t before e m b a r k in g u p o n a stu d y of its history it is necessary for th e r e a d e r to have a little b a c k g ro u n d know ledge of the political c irc u m sta n c e s of th e time. Following u p o n the discovery of the A m ericas by C o lu m b u s , th e S p a n ia rd s in t h e early years of the sixteenth ce n tu ry o v erran in a c o m p arativ ely sho rt tim e a vast are a of bo th no rth ern a n d so u th e rn co n tin en ts, while a t th e sa m e tim e th e P o rtu g u e s e were colonising in Brazil. After som e bickering th e possessions of the tw o co un trie s were defined by a line d r a w n by th e Borgia Pope A le x a n d e r VI in 1494, ru n n i n g n orth a n d sou th m o re or less along the forty-seventh degree of lo n g itu d e from the m o u th of the A m a z o n to s o u th e rn Brazil. T h e S p a n ia rd s p ro c e e d e d to develop their possessions to the west of this line a n d to ex clu de all o th e r p eop les from settlem ent in th e m or t r a d e w ith th em . It is i m p o r t a n t to u n d e r s t a n d this overall p ro h ib itio n of t r a d e a n d ex po rt b ec a u s e la te r o n in o u r story we shall find some au tho rities saying th a t th e m in in g a n d exp ort of p l a t i n u m was fo rb id d e n by definite G o v e rn m e n t a c tio n a n d o th e r a u th o ritie s of a p p a r e n t l y eq u a l s ta n d in g denying th a t an y special regu la tio n s to this e n d w ere issued. T h e s e tw o points of view are recon cilab le if in fact th e p ro h ib itio n was real w ith re g a rd to e x p o rt to n o n -S p a n is h destin atio n s b u t w as m erely on e aspect of a g e n e ral co m m e rc ia l exclusiveness. T h e S p an ish territories n o rth of the Is th m u s of P a n a m a c o n s titu te d th e vice royalty of N ew Spain, a n d those in a n d to the so u th of th e Is th m u s th e vice royalty of Peru, th e c a p ita l of th e form er b ein g M exico a n d of the latter L im a. In 13
\ m a p dating from a b out 1730 showing t h e territory of New G r a n a d a in the n o rth - w e s te r n part of the Spanish colonies of South A m e r ic a . P la ti n u m from the Choco district n e a r th e Pacific coast was smuggled from the port of C a r ta g e n a , m ainly to British controlled J a m a i c a
1718, for strategic reasons arising o u t of a tta c k s by o th e r co u n trie s in th e C a r i b b ea n , a viceroyalty of N ew G r a n a d a was ca rv ed o u t of th a t of P eru, h avin g its seat at the an c ie n t I n d ia n city of S a n t a F de Bogot, now th e ca p ita l of the R e p u b lic of C o lo m b ia u n d e r th e la s t p a r t of this n a m e alone. T h i s vice-royalty w as su p p re sse d in 1722 b u t was revived in 1740. It in clu d ed th e I s t h m u s a n d the n o rth -w est of S ou th A m erica, a n d in it w e re all th e a r e a s c o n c e rn e d w ith the o cc u rre n c e of p la tin u m . T h e E m p i r e was a d m in is te re d at h o m e in S p a in by a C o u n cil of th e Indies, o p e r a tin g t h r o u g h a S ecretary of State. T h i s b ody a c q u ir e d volum inous archives still i n existence at Seville a n d a m o n g t h e m m a n y references to p la tin u m c a n be found. A p a rt from various sm all a n d s tric tly local occu rren ces, th e m a i n d ep osits of the m etal are in th e sou th ce n tral p a r t of the C h o c region, a long n a r r o w strip of c o u n try betw e en th e m a in C o rd ille ra of th e A n d e s a n d th e Pacific. Q u i t e early 14
in th eir explorations of th e coastal areas the S p a n ia rd s le a rn t th a t th e re w as gold in the Choco, b u t th e in la n d reg io n w as m ost difficult of access a n d subject to high te m p e r a tu re s a n d ex trem ely heavy rainfall in a s e ttin g of d en se ju n g le , sw am ps a n d m e a n d e rin g rivers as well as b eing o cc u p ie d b y hostile natives. By th e 1560s several sm all expeditions into the b a s in s of th e Rivers A tra to a n d San J u a n , w h ere the rich est p la tin u m finds w ere even tually m a d e , h a d also re p o rte d deposits of gold, a n d no d o u b t t h e r u m o u rs re a c h in g J u l i u s C a e s a r Scaliger, m e n tio n ed in the previous c h a p te r, ow ed th e ir o rig in to th ese forays. It was not, however, un til a b o u t 1690 th a t th e C h o co was really settled an d pacified, nearly tw o ce n tu ries after th e b e g in n in g of th e c o n q u e s t, a n d alm ost im m ed iately o rg a n ise d e x p lo ita tio n of the m in era l re so u rces b eg a n . O v e r the next tw en ty years S p a n is h im m ig ra tio n in creased m a rk e d ly , as did th e i m p o r t a tion of slaves from W est Africa to w ork th e alluvial deposits. (1) T hese sources of gold th e g re at objective of th e c o n q u is ta d o re s were am o n g the richest th e n k n o w n in th e w o rld a n d w ere eagerly w orked , b u t the n uisance c a u s e d by th e p re se n c e of p l a t i n u m m u s t quickly have beco m e a p p a re n t. It c o n c e n tra te d w ith th e gold in w a sh in g in the form of w h ite grains like small shot a c c o m p a n ie d by heavy black m ag n etic s a n d s a n d it d e m a n d e d a good deal of l a b o u r to rem ove it, e ith e r by e x te n d e d a m a l g a m a ti o n a n e x p e n sive a n d u n p o p u l a r m e th o d as th e m iners fo u n d m e rc u ry difficult to o b t a i n and not too effective - o r by careful a n d lab orio us sortin g b y h a n d . It o c c u rre d in the placer deposits in varying a m o u n ts , a n d th e g re a te r th e p ro p o r ti o n of p la tin u m to gold the less in c lin a tio n th e re w as to w o rk th e dep o sit a n d in som e cases it w ould be a b a n d o n e d for this reason. T h e S p a n ia rd s called this w h ite m etal P latin a, a d e ro g a to ry d im in u tiv e of p lata, th eir w o rd for silver, a n d it b e c a m e k n o w n as P la tin a del Pinto, a small river near P o p a y a n in N e w G r a n a d a no lo ng er k n o w n by t h a t n am e. It w as also know n as oro b i a n c o , w h ite gold, o r j u a n b i a n c o . T h e local archives c o n ta in the first reference to p l a t i n a in 1707, by w h ich tim e it h a d b ee n u sed to a d u lte ra te the gold a n d a decree h a d b e e n issued fo rb id d in g this p ra c tic e (1). D espite this restriction, a n d o th e r re g u la tio n s im p o sin g co nfiscation a n d fines on a ny one c a u g h t so doing, a d u l t e r a t io n c o n tin u e d for m a n y years, b u t p la tin u m itself was re g a rd e d as w orthless right up to th e 1780s, a n d was d is c a r d e d a n d either th ro w n back into th e rivers or sc a tte re d o n th e g ro u n d . It w as th o u g h t by som e th a t this an n o y in g m etal was a kind of u n rip e gold th a t h a d not b e e n long en ou gh in th e g ro u n d to m a t u r e a n d to t u r n yellow. However, it seems th a t at least som e p l a t i n u m w as p u t to g o o d use, m ost p ro b a b ly by the m e th o d originally devised by th e nativ e In d ia n s t h a t was described in C h a p t e r 1. It is likely th a t the In c as w h o o v e rra n w h a t is now C olo m b ia well before th e S p a n is h c o n q u e s t a d o p te d these te c h n iq u e s to m ake o rn a m e n ts of various kinds a n d th a t a few articles w ere sim ilarly fa b ricated by S pan ish craftsm en. A ccording to the chem ist J u a n Fag es y Virgili som e m e m o ra n d a left by the M a r q u e s de los Castillejos c o n ta in a reference to a gift m a d e in a b o u t 1730 to D o n J o rg e de Villalonga, th e Viceroy of N e w G r a n a d a , of 15
T h e almost inaccessible region of the C h o c o in New G r a n a d a in which deposits of p latinu m were discovered b\ the Spanish C o n q u i s t a d o r e s late in the se v e n te en th c e n tu ry . T his shows the confluence of the Rivers San J u a n a n d Condoto w h e re the p la tin u m o c cu rre d to the richest extent am ong the alluvial gold.
a rapier guard and a set o f buckles in p latinum , althou gh it is asserted that it had not sufficient coh eren ce and w as a b rittle m etal, althou gh heavier than gold, with w hich it w as m ixed as a dross in the m ines o f the province of C itaro in the district of C h o c ."
(2)
Som e fu rther evidence of this is to be fo u n d in one of th e letters to th e Royal Society w ritte n in 1750 by Dr. W illia m B row nrigg th a t will be d ea lt w ith m o re fully in C h a p t e r 3. H e re he m e n tio n s :
T h e Spaniards have a W ay of m eltin g it dow n, either alone, or by m eans of som e Flux, and cast it into Sw ord-hilts. B u ck les, Snuff-boxes, and other U te n s ils . (3)
Antonio de U llo a s Voyage of D iscovery

T h e first p erson to m a k e E u ro p e f a m ilia r w ith the n a m e p l a t i n a , however, was a y o u n g S p an ish naval officer n a m e d A n ton io de Ulloa, a n d this c a m e a b o u t in a m ost indirect m a n n e r. In the 1730s o n e of th e q uestio n s b eing d iscussed a m o n g a s tro n o m e rs w as w h e th e r the e a rth w a s an o b la te sphero id , as N e w to n h a d p r e 16
dieted, or a pro late sp h ero id ; th a t is to say w h e th e r it w as flattened or s h a rp e n e d at the poles. T o resolve this it w as necessary to m e a s u r e th e len g th of a d eg ree of longitude at the e q u a to r a n d a g a in a t s o m ew h e re as n e a r as possible to one of the poles. T h e A cad em ie des Sciences in Paris took the m a t t e r in h a n d a n d a r ra n g e d for one exp ed itio n to go to L a p la n d , in th e far n o rth of S w eden, led by the fam ous m a th e m a tic ia n iM aupertuis, while o n its b e h a lf Louis X V so u g h t the p erm ission of his un cle King Philip V of S p a in for a n o t h e r m ission to visit Q uito. T h e exclusion of foreigners from th e S p an ish colonies h a d b e e n m u c h relaxed u n d e r the B o u rb o n Kings of Spain, a n d p e rm issio n w as given w ith th e proviso th at two S p a n is h scientifically tra in e d naval officers s h o u ld b e in clu d ed in the party. T h e ex peditio n, led by th e F re n c h g e o g ra p h e rs C h a rle s M a r ie de la C o n d a m in e (1701 1774) a n d Pierre B ouguer (1698 1758), w as th erefore to be ac c o m p a n ie d by D o n J o r g e J u a n a n d D o n A ntonio de Ulloa, th e n respectively only tw enty-on e a n d n ineteen years old, a n d b o th p ro m o te d to th e ra n k of frigate lieutenants. T h e y left S p a in in M a y 1735 a n d a w a ite d th e ir F re n c h colleagues in C arta g e n a , the c o m p lete p a r ty arriving at Q u ito in M a y of th e following year. After m aking th eir m a n y o b servatio ns u n d e r gre at difficulties Ulloa h a d am p le tim e to explore th e territory before the p a r ty set ou t o n th e ir r e tu r n jo u rn ey , sailing r o u n d C a p e H orn. N o rth of the Azores th e ir ship was c a p tu r e d by an English p rivateer b u t m a n a g e d to escape, only to b e seized by a British naval vessel w h e n they r e a c h e d L o u isb o u rg in Nova Scotia in A u g u st 1745. U lloa and his com p an io n s w ere im p riso n e d a n d conveyed to L o n d o n , w h e re all his p ap ers were confiscated by the A d m iralty . However, he w a s b e frien d ed by M a r ti n Folkes, th e n P resident of the R oy al Society, a n d by W illia m W a tso n , w h o was later to play a m a jo r p a r t in th e discovery of p la tin u m . U lloa was elected a Fellow of the R oyal Society in 1746, h a d his p a p e rs re sto re d to him , a n d in the
L ii.P 7 .
to 6
R elac i n
d i V iag i
T h e passage in the book by Don A n to n io <le I lloa desc ribing the o c cu rre nce of platinum am o ng the alluvial gold workings in the district ol t.hoco
Caf. X . regularmente mientras los unos eftan lavando fe emplead los otros en cortar Material ; y afsi no tienen lugar de pa rar los bitairroi. La Lcji de elle Oro es por lo regular de i a . Quilates alguno pafl de ella, y llega halla 1 3 ; y por el contrario baxa tambin , aunque no es comn que fea menos de 1 1 . Quilate. En el Partido del Choce , haviendo muchas Minas de Lrtadtro , como las que C acaban de e explicar, fe encuentran umbien algunas, donde por eftar disfrazado, y envuelto el Oro con otros Cuerpos Metlicos, Jugos , y Piedras, necefsita para fu beneficio del auxilia a e f / ^ i i f y tal vez fe hallan Minerales-; donde la Tlatmt <Piedra de tanta refitencia, que no es fcil romperla , ni dcfmenuzarla con la fuerza del golpe fobre el Yunque de Acero) es caufa de que fe abandonen i porque ni la calci nacin la vence, ni hay arbitrio ^>ara extraer el Metal, que encierra, fino a expenfas de mucho trabajo, y corto. Taro-
17
sa m e year was allow ed to r e t u r n to Spain. H e re he c o m p iled a n a c c o u n t of the expedition, p u b lish e d in S p a n i s h in 1748 (4) a n d soon tra n s l a t e d into several o th e r languages. A d o ze n copies w e re sent to m e m b e r s of th e R oyal Society in L o n do n, a n d u n d o u b te d ly c o p ie s were sent to scientists in o th e r E u ro p e a n countries. It was in this book th a t a re fe re n c e w as m a d e to p l a t i n u m a n d a tra n s la tio n of th e relevant passage, given a t t h e h ea d of this c h a p te r, w as r e a d to th e Royal Society by W a ts o n in 1750. A m o r e m o d e r n version r e a d s :
In the district of C hoco are m a n y m ines of lavadero or w a sh gold, like those we have just described. T here are a lso som e w here m ercury m ust be used, the gold being enveloped in other m etallic b o d ie s, stones and b itu m en s. Several of the m ines have b een ab and oned on account of th e platina, a su b stan ce of su ch resistance, that, w hen struck on a anvil of steel, it is not e a s y to be separated; nor is it calcin ab le; so that the m etai enclosed w ithin this o b d u ra te body co u ld only be extracted w ith infinite labour and ch arge.
T h e jo in t lead er of the e x p e d itio n , Pierre B ouguer, also m a d e a b rie f m e n tio n of p la tin u m in his ow n accoun t, L a F igure de la T e r r e p u b lis h e d in Paris in 1749. After describing th e s e p a r a t i o n of th e gold from th e sa n d y m a te ria l by the use of c e rta in p la n t ex tracts he w r o t e :
Som etim es also they have recou rse to a q uite different exp ed ien t: they m ake use of m ercury, and are often obliged to do so in th e C h o co w here the m eta l is m ixed w ith platina, a kind of pyrites peculiar to the reg io n . (5)
Th e Irish Naturalist William Bowles

It has often b ee n s tated th a t U l l o a b ro u g h t h o m e to M a d r i d a s am p le of p la tin u m , b u t th e re is no real e v id en c e for this. H ow ever, his bo ok a n d his later travels were to have a c o n s id e r a b le effect u p o n th e ea rly scientific w ork on p la tin u m . After h e r e tu r n e d to M a d r i d Ulloa, n o w p r o m o t e d to L ie u te n a n tG e n e ra l in th e S p an ish Fleet, w a s c o m m issio n e d by th e n ew K ing of Spain, F e r d i n a n d VI, to u n d e r ta k e a n ex tensive j o u r n e y th r o u g h o u t E u r o p e to stu dy scientific progress a n d in the c o u r s e of the y ears 1750 to 1752 h e visited F rance, H o lla n d , D e n m a r k a n d Sweden. It w as on his r e t u r n th r o u g h P aris th a t h e m et a n Irish n atu ra list, W illiam B ow les (1705 1780) a n d p ro p o s e d to h im th a t he en te r th e service of the S p an ish G o v e rn m e n t. Bowles h a d left his native co u n try in 1740, s p en d in g th e intervening y e a rs in in vestigating th e m in e ra l a n d veget able resources of France, a n d U llo a realised th e p o te n tia l value of his experience in s u p e r in te n d in g the m ines of S p a i n . Bowles a c c e p te d th e offer a n d s p en t the re m a i n d e r of his life in his newly a d o p t e d c o u n try . In 1753, early in his w ork in S p a in , h e received from th e M in iste r for th e Indies in M a d r id a small b ag of p l a t i n u m to g e th e r w ith a n ote re a d in g :
In the Bishopric of Popayan, Suffragan o f Lim a, there are several gold m ines am ong w hich there is one called C h o c o . In a part of the m ou n tain s w h ich con tain s it there is a large quantity of a sort o f sa n d w hich the p eop le o f th e cou n try call platina and w hite g o ld .
18
T h e openin g page of the dissertatio n on p latinu m by the Irish n a tura list ^ illiam Bowles, re cru ite d by Don Antonio de I lloa to su p e r in te n d the Spanish mines. Before describing the e x perim ents he c arried out in 1753 he gives a warning against the f r a u d u le n t use of platinu m a n d of ""letting it loose in c o m m erce. L ater he was m ore enthusiastic a b o u t the poten tial value a n d applications of p latin u m . T h e book was d edicated to King C arlo s III
DISERTACION
SOBRE LA P L A T I N A Y LOS
AXT1CUOS VOLCANES DE ESPAA.
E n r 75 3 el M !nisterio me hizo entregar una porcton suficiente de Platina con orden de hacer mis experien cias , y decir mi parecer acerca del uso bueno malo q u e poda tener. 1 saquillo de Platina vena acompa ado de la nota siguiente. E n e l Obispado de Popay in , sufragneo de Lim a, hai muchas minas de O re, y entre ellas na que se llam a C h o c - E n una pordon de a montana en que est hai gran cantidad de una especie de arena que los del pais llam an Platina, y O r o blanco. En mi vida haba oido hablar de tal a r e n a , y c o menzando i examinarla hall que era una materia m ui pesada , y q u e tena mezclados varios granos de oro de color de hollin. Separados e'stos quedaban los g r a nos de la Platina como municin menuda perdigo nes de p lo m o , y con mas propiedad se pareca en el color i aquel semimetal que los Alemanes llaman Speis,e\ qual es un rgulo de C obalto que se halla m u chas veces enclavado en el Safre . El peso de la Pla tina me sorprehend i, por que efSivamente es mas pesada que el oro de veinte quilates. Puse algunos granos sobre un y u n q u e , y batindolos con un marV 2 ti(i) Quando se trate del Cobalto de Aragn se ver lo que c% Sufre.
T h e M in iste r asked Bowles to advise h im o n th e use - g o o d or b a d - to w hich this could b e put, a n d after m a k in g a n u m b e r of e x p e rim e n ts o n this q u ite new m ineral, in cluding d e te r m in in g its high density, its in so lub ility in sim p le acids a n d its miscibility w ith gold, he r e p o r t e d :
Platina is a m etallic san d that is sui generis w hich ca n be very pern icious in the world b ecau se it m ixes easily w ith gold and becau se, alth ou gh by ch em istry it is easy to find the m eans of recognising the fraud and of separatin g th e tw o m etals, sin ce this m eans w ou ld be availab le only in the hands o f a few p eop le and as cu p id ity is a general m alady, tem p tation seductive, the m eans of d eceiving easy and in every b o d y s reach, there can only be great danger in letting p latina loose in com m erce. (6)
Counterfeiting and Smuggling

T h e g overnm ent p a id a t te n tio n to this re p o rt a n d c o n firm e d th e p r o h ib itio n on th e export of p l a t i n u m from N e w G r a n a d a to E u ro p e , b u t it w as too la te eith er to prevent its f r a u d u le n t use o r to h a lt th e vigorous s m u g g lin g t r a d e th a t w e n t on 19
The w a rn ing given by W illia m Howies against the f r a u d u l e n t use of p la tin u m was not w ithout significance. F r o m as early as 1763 dishon e st e m plo yees of the mints in Bogota and P o p a y a n began lo forge the gold coinage by using p latin um a n d then gilding the pieces. T h is sp e c im en of a forged 8 -escudo coin d a te d 1778. shows the bust of C a r lo s III
P h o to g rap h b\ ro u rle s) of H e r r W illy F u c h s
from C a rte g e n a to J a m a ic a , chiefly w ith British m e r c h a n t s there. O n e exa m ple of this was given in a letter f r o m the d is tin g u is h e d L o n d o n m inera logist E m a n u e l M en d e s da C osta, re a d t o th e R o y al Society in D e c e m b e r 1750:
In January 1742-3 there w ere brought from J a m a ica in a M a n of W ar, several Bars (as th ou gh t) of G old, co n sig n ed from different M erchan ts o f that Island to their different C orrespondents here, as Bars of G old. T h ese Bars had the sam e specific G ravity, or rather m ore than G old, an d were eq u ally like that M etal in C olour, G rain, etc. A Piece of one o f these cou n terfeit Bars w as sent to th e M int to be tested , and it w as found to be tw enty one C arats th ree G rains w orse than S ta n d a r d . (7)
In o th er w ord s these bars c o n t a i n e d so m e th in g like 10 p e r ce n t only of gold, th e b a la n c e p re s u m a b ly being p l a t i n u m . A sim ilar case was re p o rte d b y W illia m Brownrigg, of w h o m m u c h m o re will be said in the next c h a p te r, in one o f his letters to th e R o y al Society in 1750:
I am told that one Mr. O rd, form erly a Factor to the South Sea C om p any, took in paym ent from som e Spaniards G o ld to th e value of 500 1 Sterling w hich bein g m ix d w ith P latina w as so brittle th a t he cou ld not d ispose of it, n either co u ld he get it refined in London, so that it w as q u ite useless to him. (3)
A n o th e r form of fra u d u le n t p ra c t i c e involved the use of p l a t i n u m in the forgery of coinage. Specim ens of co lo n ia l escud os a n d of th e fa m o u s do u b lo o n s have b e e n found, m a d e of p l a t i n u m a n d t h e n gilded to give t h e tru e a p p e a r a n c e of gold, b e a rin g dates from 1763 o n w a r d s , w hile the p ra c tic e w as also followed in S p ain b eginn in g in the late 1770s. (8) T h e s e cou nterfeits w ere m a d e by 20
dishonest em ployees of t h e m ints a t P o p a y a n a n d S a n ta F d e Bogota a n d later of course in M a d r id a n d Seville, using th e g en u in e dies em p lo y e d for th e gold coinage.
L eb lo n d s M em oir
T h e best d e s c rip tio n of w h e re th e p l a t i n u m w as fo u n d a n d h o w it w a s recovered was not given until som e years la te r w h e n a p a p e r w as re a d to th e A c a d m ie des Sciences in Paris. T h is w as in J u n e 1785, a n d w h e n the m e m o ir w as p r i n t e d a few m o n th s la te r in R o z i e r s Observations sur la Physique (9) t h e a u t h o r was given only as M L. a n d for very m a n y y ea rs his a n o n y m ity w as m a in ta in e d . In 1969, however, Dr. W. A. S m e a to n successfully identified h im as M o n s ie u r J e a n B aptiste L e b lo n d (1 7 4 7 -1 8 1 5 ) w h o h a d sp en t s o m e y e a rs in S o u th A m e ric a a n d w ho h a d b r o u g h t h o m e to P aris no less t h a n 200 p o u n d s of p la tin u m , alm ost ce rtain ly illegally (10), w h ic h he th e n a t t e m p t e d to sell in E n g la n d th ro u g h th e good offices of Sir J o s e p h Banks, th e P resid en t of th e R o y al Society. L eb lo n d records in his p a p e r th a t th e only n e ig h b o u rh o o d w h e re th e r e was any co nsiderable o cc u rre n c e of p l a t i n u m was in th e tw o provinces of N o vita and C ita ra in th e district of th e Choc. T h e gold a n d p l a t i n u m o c c u rre d m ixed to g eth er in alluvial deposits of w h ic h th e g ra in s of b o th w ere a p p r o x im a te ly the sam e size. T h e p ro p o r tio n of th e tw o varied in different localities a n d acco rd in g to L eblond it m igh t b e one, two, three, four o r even m o re o u n ce s p e r p o u n d of gold. T h e g re a te r the p ro p o r tio n of p l a t i n u m to gold th e less in c lin a tio n th ere was to work th e deposit a n d it m ig h t even be a b a n d o n e d , since th e m o re th ere was of p l a t i n u m th e less th e a m o u n t of gold o b ta in e d from t h e s a m e a m o u n t of lab o u r a n d costs. T h e gold a n d p l a t i n u m were recovered to g e th e r by w a sh in g
M M O I R E
S U R LA P L A T I N E O U O R B L A N C ;
Lu VAcadmie R oyale des Sciences en Juin 1 7 8 $ ; F ar M L.

L e point do fe dveloppe l'Amrique m ridionale, la C ordillre, eft le thtre la fois grand <c rerrible, o l' il furpris voie avec 5 adm iration ces abmes profonds que creufent les cor reos qui fe prci pitent des monragnes ; ces normes rochers qui menacenr ruine, fe dtachent & entranent dans leur chute pouvantable, les arbres, les p lan tes, les terres & les minraux ; enfin, ces monrs fuperbes dont la blancheur blouit & la haureur tonne, la plupart couronns datfreux v o lcan s, dont l'explofion fubite c rerrible bouleverfe O menace le c m onde d u n e dtftrultion prochaine; la terre trem ble; des cendres, des rochers calcins font lancs dans les airs ; d immenfes amas de neige (o n t fondus, un dluge en eil form : les hommes & les animaux que furprend ce dfartre, fuyent faifis d'horreur, leurs habitations font d truites & les campagnes dvalue* par ces imptueux courans-deau , d o n t la violence entrane tout ; ces dbris emports par les correns, forment
\ detailed a cc ou nt of where the platinu m was found in the Choc a n d how it was recovered was read to the Xcadmie des Sciences in 1785 In one M.I.. who p r e ferred to re m a in a nonym ous. Mis identity has only recently been established as Je a n Baptiste L eblond
21
T h e conclusion of th e letter from J e a n Baptiste I.eblond. d a te d July 30. 1780. to Sir Jo s e p h B ank s, shortly to beco m e P re sid en t of (he Royal Society. In this he seeks to dispose of 200 pound s of p latin u m he had bro ugh t lo P a ris, an d asks B ank s " to accept his m em oir on the n a tu ral history of p latin u m that I read last year a t th e A c a d m i e d e s Sciences
Trustees
Photograph b\ courtesy of the of the B ritish M u se u m
and were then separated grain by grain with a knife blade or other similar means on a very smooth board, the last stages being achieved by the assistance of amalgamation with mercury. All the Choc gold output, Leblond states, went to the two Mints at Santa F de Bogot and Popayan, and here a second very careful separation was effected of any platinum still remaining present: The Kings Officers keep this and when they have a certain quantity of it they go, accompanied by witnesses, to throw it into the Bogot River two leagues from Santa F or into the Cauca which is one league from Popayan; this was a prudent expedient thought out by the Government, which in addition forbids its export in order to prevent fraud arising from melting it with gold; it appears that today it is sent to Spain. Formerly an alloy was made of it with different metals like copper, antimony, etc., but such work has ceased because of the labour, always expensive in America, which considerably increases the value without real improvement in the utility. Leblond believed that the platinum had an origin in the mountains, since he says: The larger size the gold and platinum have, the more they seem to be nearer to the place of their origin; on the contrary, the smaller they are the further they appear to be from it; the aspect of the country confirms this for large grains of platinum or gold are rarely found in the plains at some distance from the mountains.
22
Jean Baptiste Boussingault 1 8 0 2 -1 8 8 7

Following the fo rm atio n of the Republic of Colombia from the fo rm e r Spanish colony of New G r a n a d a , a small team of scientists was re cru ite d to investigate the economic p otential of the country. Boussingault. a F r e n c h m an who had trained in m ining and metallurgy a n d was later to becom e a pioneer in a g ric u ltura l chem istry, was one of this group a nd was responsible for locating the reef which was the so urce of the a lln\ ial p la tin u m deposits in the Choco district
T h e Source of the Alluvial Platinum

T h e m ineralised source was not, in fact, discovered u ntil forty years after L eb lo n d re a d his m em o ir. It w as lo cated by J e a n B ap tiste B o u ssin g a u lt, a F ren ch m etallu rg ist a n d m in in g e n g in ee r re c ru ite d b y A le x a n d e r von H u m b o l d t in 1822 at th e re q u e s t of S im n Bolivar as one of a te a m of scientists called u p o n to investigate th e m in era l a n d a g ric u ltu ra l p o te n tia l of th e new ly in d e p e n d e n t R epu b lic of C o lom b ia. H e was first of all a p p o in te d a p rofesso r at th e Escuela N a cio n ia l de M in e ro s in B ogot, b u t as w ith th e o th e r m e m b e r s of th e g ro u p he was given assign m ents th a t took him to v ario u s p a r ts of th e c o u n try as inspecto r of mines, p rospector, assa y er a n d surveyor (11). O n one of these m issions in 1826 he asc e n d e d a 9000 feet high p la te a u to th e village of S a n t a R o sa de Osos n ea r M ede llin in th e province of A n tio q u ia w h e re gold m in in g w as active. T h e r e he found r o u n d e d grain s of p la tin u m , m ixed w ith oxides or iron, in th e syenite veins th a t w ere being m in e d for gold. T h e s e gra in s w e re entirely sim ilar in form a n d a p p e a ra n c e to those e x tra c te d in th e valleys of th e C ho c. B o u ssin gault re p o rte d his discovery of th e origin of th e p l a t i n u m in a letter to his friend a n d p a t r o n H u m b o ld t, w ho p u b lis h e d it im m e d ia te ly in th e Armales de Chimie el de Physique. (12) Persistent sta te m e n ts will be fo und in th e lite ra tu re o n p l a t i n u m t h a t the S pan ish G o v e rn m e n t p ro h ib ite d its m in in g a n d recovery, b u t L e b lo n d denies this categorically:
T h ose w ho believe that the S pan ish M inister has cau sed the p la tin a m ines to be shut up have certainly been m isinform ed, sin ce there are no su ch m ines for p latinu m
23
alone. All he has done is to p ro h ib it its in trod u ction into Europe, b eca u se of the inconvenience w hich m ight have resu lted from its b ein g alloyed w ith gold, w hich w as not easy to recognise at that tim e; a w ise p recau tion w h ich has assu redly forestalled a large num ber of frauds in the gold trade.
H e goes on to ind icate th a t t h e q u e s tio n c a rrie d its o w n c u re in th a t it was not profitable at th a t tim e to collect th e p la tin u m , th e only uses sug g ested for it ro u n d ab o u t 1740 being as sm all shot or in sm all b ag s for clock weights. It was th r o w n aw ay a n y w h ere a n d ev e ry w h ere, a n d th e sto ry of th e rivers no d o u b t arose solely from the pra ctice of t h e tw o M in ts d e sc rib e d above. C a s u a l th ro w in g a w ay led to curious scenes years a f te r w a r d s w h e n p l a t i n u m h a d b ec o m e a v alu ab le co m m o dity , a n d th ere is a s to ry of h o w th e m in in g village of Q u i b d o was w recked com pletely in a n e n t h u s ia s tic s e a rc h for d is c a r d e d m etal a m o n g its fo u n d a tio n s (13).
Samples of Platinum sent to E u ro p e

Sm all sam ples h a d re ach e d L o n d o n , Paris a n d S to c k h o lm d u r in g the 1740s, as will be seen in th e next c h a p t e r , a n d r u m o u r s b e g a n to re a c h th e S pan ish au th o rities of th e intense scientific in te re st b e in g a r o u s e d by this newly discovered m etal. In 1759 th e V ice ro y of N e w G r a n a d a w as o rd e re d to collect a large q u a n tity of p la tin u m from th e d u m p s a r o u n d th e m in ts at P o p o y a n a n d Bogot a n d to sen d it to S p a in (14), a n d from this s h ip m e n t, over th e next th irty years or so, q u ite s u b s ta n tia l a m o u n t s w e re willingly fo rw a rd e d o n re q u e s t a n d w ith o u t ch a rg e to ch em ists a n d scientific in stitu tio n s t h r o u g h o u t E u ro p e , often in ex c h ang e for m ineralo gical s p e c im e n s for th e R oy al C a b in e t of N a tu r a l H is to ry established in M a d rid . T h e s e sam ples w ere sent a m o n g others, to M a c q u e r , th e C o m te de Milly, the C o m te de Buffon, G u y to n de M o r v e a u a n d J e a n D a rc e t in F ra n c e a n d to W illia m Lewis in E n g lan d , all o f w hose w o rk o n p l a t i n u m will be reviewed in C h a p te r s 3 a n d 4, b u t as in tere st in cre ased a n d p ra c tic a l ap p lic a tio n s b e g a n to a p p e a r the d e m a n d grew for b o t h le g itim a te sup plies a n d th r o u g h th e extensive sm u ggling o peratio n s from C a r t a g e n a to J a m a i c a . A F ren c h p a r ty led by th e c e le b r a t e d n a tu ra lis t J o s e p h D o m b e y (1742-1794) arrived in 1777, nom inally w ith b o t a n i c a l objectives, b u t before they left o n th eir voyage the g reat s ta te s m a n A n n e R o b e r t J a c q u e s T u r g o t, a t th a t tim e C o m p tro lle r-G e n e ra l to Louis X V I , in s tru c te d D o m b e y
to spare no pains to procure for m e n of scien ce su ch a q u an tity of p latina as m ight be useful in their researches. (15)
D o m b ey was successful in th is p a r t of his m ission, for he w as ab le to w rite to C o n d o rc e t at th e A cad m ie des S ciences: I have put on board the v e sse l Bueno C onsefo w h ich leaves C allao on the 3rd April for C adiz, seven cases for th e K in g s C abinet o f N atu ral H istory. M . le C om te de Buffon, to w hom I have ad d ressed all of them , w ill sen d to you 11 livres of p latina w hich I earmark for the R oyal A c a d e m y of S cien ces so that it ca n m ake som e ex p eri m en ts on a m etal w hich has b e c o m e the object of the cu riosity of savants. I send a like 24
Don Jos C eleslino Mutis 1 7 3 2 -1 8 0 8

G oing to New G r a n a d a in 1760 as physician to the Viceroy. Mutis m a d e a n u m b e r of scientific j o u rn ey s to study the flora a n d the m ine ral de posits of the area. A fte r his d e a th his re cords were brought back to M adrid a n d provide a va lu a ble so urce of i n f o r m a tion on the early explo itation of platin um
am ount of it to M . T urgot and an oth er eleven livres to M . le C om te de Buffon to be placed in th e K in g s C abinet. H ow ever, if the 33 livres are required for a large-scale experim ent, I have no doubt ab out the zeal that an im ates th ese tw o great m e n . (16)
T h e S p a n ia rd s also sent out th e ir o w n scientists to stu d y th e n a t u r a l histo ry of their colonies. O f these the first a n d m ost fam ous was D o n J o s C elestino M u tis (1732-1808) w h o originally w e n t out as p h y s ic ia n to th e Viceroy Pedro M essia de la C e r d i a in a b o u t 1760 b u t late r m a d e m a n y scientific j o u r n e y s to stu d y bo th th e flora a n d th e m in e ra l deposits. M u t i s in c lu d e d in his long and intensive investigations th e history a n d possible ap p lic a tio n s of p l a t i n u m a n d in a m a n u s c rip t letter in 1774 he referred to tw o p o rtra it m ed a llio n s of King C h arles III t h a t h a d b ee n m a d e b y F rancisco Benito, a S p a n i a r d e m p lo y e d as an engraver at the m in t in B ogot (17). M o r e will b e h e a r d of b o th M u t i s an d B enito later in this w ork w h e n discussing th e p l a t i n u m in d u s try in Spain. In 1777, in a n a t t e m p t to re d u c e or h a lt the vigorous s m u g g lin g t r a d e in b o th gold a n d p la tin u m , the S p a n is h au th o ritie s o rd e re d the erectio n of a refinery at N ovita in th e C hoc, stip u la tin g t h a t only gold cast into b a rs w o u ld b e allow ed 25
to b e expo rte d once the p la n t w a s in o p e r a tio n (18). T h i s m ove w as strongly re s e n te d a n d resisted by th e m i n e o w n e rs w h e n th e refinery o p e n e d in 1782, p a rtic u la rly on ac co u n t of the h i g h c h a rg e s m a d e for m eltin g losses a n d for d i s p l a t in a r , th e rem oval of th e p l a t i n u m from th e gold sent in. T h e y also c o m p la in e d of the inefficiency of t h e o p eratio n . In fact th e illegal traffic in b oth m etals was s tim u la te d r a th e r t h a n cu rtailed .
Platinum after Independence from Spain

In 1810 a revolu tion ary m o v e m e n t b e g a n in the colonies ag a in s t th e co n tin u in g S p a n ish d o m in atio n , a n d a p e r i o d of in s u rre c tio n c o n tin u e d for m a n y years, c u lm in a tin g in th e founding of t h e R e p u b lic of G r a n C o lo m b ia by S im n Bolvar in 1820 b u t w ith the obvious ill effects o n th e e c o n o m y a n d p a rtic u la rly o n th e m in e ra l industry. A scathing c o m m e n ta r y o n t h e a d m i n i s tr a t i o n of th e new re p u b lic in re la tio n to its m ineral w e alth was m a d e b y a n E ng lish naval officer, C a p t a i n C h arles S tu a r t C o ch ra n e, w h o so ugh t t w o y e a r s leave from th e A d m ira lty to visit C o lo m b ia in th e years 1823 a n d 1824. A fter d esc rib in g th e m e th o d s of s e p a r a t ing p la tin u m from gold, a n d s a y in g th a t t h e m in es c o n s id e re d w o rth w o rk in g for p l a t i n u m give tw o p o u n d s of p l a t i n u m to six of g o l d , h e goes on:
T h e governm ent are now en d eavo u rin g to b u y up all th e p latin a an d having it sent to Bogota' in order, as report says, to m ak e a coin age of it. But as British m erchants here offer eight or ten d ollars a p oun d for it, about five sixth s are ob tain ed by them and sm uggled to J a m a ica . It is great im p o licy that th e C ongress does not entirely do aw ay w ith the old S p a n ish system of m onop oly; if they w o u ld put on a m oderate d uty and allow the ex p o rta tio n o f gold and p latin a, they w o u ld secure a h and som e revenue from it; but a s they entirely prohibit the exp ortation of these m etals, the w hole is sm uggled to J a m a ic a an d at a m oderate rate. T h e co n seq u en ce is that scarcely a p oun d of gold dust rem ain s in C o lom b ia and hardly a sh illin g is draw n from the m ines of C hoc tow ards t h e exigen cies of the state. W h at b lin d policy. (19)
O n several occasions, b e g in n in g in 1821, the new g o v e rn m e n t n u r t u r e d ideas of a p la tin u m coinage, a n d in 1825 a L o n d o n m e r c h a n t i n g house, T h o m s o n B o n a r a n d C o m p a n y , was asked t o a r r a n g e for s p e c im e n coins to b e struck by th e R o y al M i n t in L o n d o n (20). T h i s u n u s u a l re q u e s t w as ag re e d to a n d a few coins w ere m ade, b u t n oth in g m o r e w as h e a r d of th e m atter. T h e r e is one o th e r story to relate c o n c e rn in g p l a t i n u m in th e new ly i n d e p e n d e n t republic. In 1825 th e C o n g re s s voted to erect a n e q u e s tr ia n statu e, to b e cast in p la tin u m , of th eir n a t i o n a l hero Bolivar, this to be erected in the c e n tre of Bogot. B oussingault, w h o h a d j u s t discovered th e p la n tin ife ro u s reef, w as a p p o in te d to s u p e r in te n d its castin g a n d installation. T h e e m b a r ra s s e d scientist in form ed th e M in iste r of F in a n c e th a t h e c o u ld no t possibly u n d e r ta k e this w ork as th e necessary q u a n t i t y of p l a t i n u m w as so g re at t h a t all th e m ines in C o lo m b ia co uld not p ro d u c e it i n the co urse of a ce n tu ry , a n d th a t since p l a t i n u m was infusible b y th e u s u a l processes it w o u ld not in a n y case be possible to cast su ch a statue. B o u s s in g a u lt re co rd s th a t th e M in iste r said to h im 26
th a t while all this w as correct, it sh ow ed th a t C o ngress w a s ig n o ra n t, w h ic h w o uld be inexcusable, a n d th a t he s h o u ld m erely w rite to th e effect t h a t he w ould sp are no effort to assure th e success of this i m p o r ta n t w ork; in this w ay n o b ody w o u ld be offended a n d th e e n te rp ris e w o u ld soo n b e forgotten. T h i s duly h a p p e n e d , a n d B o ussin g a u lt received only tw o k ilogram s of p l a t i n u m w h ic h he used to m ak e several pieces of la b o ra to ry a p p a r a tu s . (11) In the m e a n tim e th e p l a t i n u m placers w ere b eing w o rk e d only in a n in te r m itte n t m a n n e r b y ca su al prospe cto rs. L a b o u r w as scarce as th e n ew re g im e h a d e m a n c ip a te d th e negro slaves, w hile th e m o re accessible deposits w e re b e c o m in g exh au sted . But b y this tim e o th e r sources of p l a t i n u m w e re b e c o m in g available to E u ro p e a n refiners from R u s sia a n d it w as not u n til very m u c h la te r th a t C olo m b ia a g a in b e c a m e a m a jo r factor.
R e fe r e n c e s fo r C h a p te r 2 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 R. C. W est, C olonial P lace M inin g in C olom bia, B aton R ouge, 1952, 6 3 -6 4 J. Fages y V irgili, Los Q u im icos de V ergara, D iscursos leidos a n te la R eal A cadem ia de C iencias exactas, fsicas y n aturales, 27 J u n io 1909, 41 W. Brownrigg, Phil. Trans., 1 7 4 9 /5 0 , 46, 587 J. Juan and A. de U lloa, R elacin histrica del viaje a la A m erica M erid ion al hecho de order de S. M ag, M adrid, 1748, 2, Book 6, C hap. 10, 606 P. Bouguer, La Figure de la Terre, Paris, 1749, lxii W. Bow les, D isertacin sobre la p latina, In trodu ccin a la H istoria N atu ral y de La G eografia fisica de Espaa, M adrid, 1775, 1 5 5 -1 6 7 E. M. da C osta, Phil. Trans., 1 7 4 9 /5 0 , 46, 589 W . Fuchs, P latinm iinzen und M ed aillen , W alldorf, H essen, 1975, 2 6 -2 7 ; 3 8 -3 9 M. L. (J. B. L eblond), Obsns. Physique(Rozier), 1785, 27, 3 6 2 -3 7 3 W . A. Sm eaton, Platinum M etals Rev., 1969, 1 3 ,1 1 1 -1 1 3 F. W. J. M cC osh , Platinum M etals Rev., 1977, 2 1, 97 99 J. B. Boussingault, Ann. Chim., 1826, 32, 2 0 4 -2 1 2 E n ciclop ed ia U niversal Ilustrada E u rop eo-A m erican a, B arcelona, 1907, 45, 559 A rchivo G eneral de Indias, Santa F, 835 A. M . R ochon, Phil. M ag., 1 7 9 8 /9 , 2, 21 A. Lacroix, Figures des Savants, Paris, 1938, 3, 131 A. F. G redilla, Biografia de J os C elestino M utis, M adrid, 1911, 1 5 7 -1 6 3 W . F. Sharp, Slavery on the S pan ish Frontier, N orm an , O k lah om a, 1976, 54 60 C. S. C ochrane, Jou rn al of a R esid en ce and T ravels in C olom b ia, L ondon, 1825, 2, 4 2 1 -4 2 2 Public R ecord O ffice, M in t 1 /2 4
27
C harles W o o d
1702-1774
Horn in W o lv erh am p to n , t h e sixth so n of the fam o us W illiam W ood, ironm aster an d the p ro d u c e r of the c o p p e r coinage kn o w n as W o o d s H alfp ence. C h arles spent s o m e tim e in J a m a ic a a fte r the failure of a sch em e pro m o te d In his f a t h e r for sm elling iron with coal in the n o r th west of Kngland. In 1741 he re tu rn e d to E nglan d for a tim e, bringing with him the firs! sam p les of n ative p la tin u m to reach E u ro p e an d to be sub m itted to scientific e x a m in a tio n
1 h n to g r a p h f r o m a p o r tr a it in the possession of the Tamil) b\ courtesy o f X ir- C om m o do re K. J . I*. ^ ood
3
Early Scientific Enquiries into the Properties and N ature of P la tin u m
Up on t he w h o l e this S e m i - m e t a l s e e m s a verys ingul ar B o d y t ha t m e r i t s an e x a c t e r I n q u i r y i nt o made. its
Nature
than
hath
hitherto
been
W IL L IA M B R O W N R IG G
T h e first p l a t i n u m to be su b je c te d to scientific investigation b y E u r o p e a n scientists ca m e to E n g lan d , b r o u g h t h o m e in 1741 by C h a rle s W o o d from J a m a ic a . E arlier sam p les h a d re a c h e d E u ro p e in o n e w ay o r a n o th e r, p artic u la rly th r o u g h Spain, b u t b e y o n d b e in g re g a rd e d as a c u rio u s su b s ta n c e w ith s o m ew h a t r e m a rk a b le p ro perties, no p u b lis h e d w ork w a s d o n e u p o n them . T h u s C harles W o o d m u st be given p rio rity since his sam p les led to full scientific ex am in ation, identification a n d p u b licatio n . W h e n this book was first p u b lis h e d very little w as k n o w n a b o u t W o o d , b u t as a result of th e exhaustive genealogical re searc h es of his g re a t- g r e a t- g r a n d s o n M r. M . H . W o o d som e details of his life a n d activities b e c a m e av a ila b le to th e original a u t h o r in 1965 a n d form ed th e s u b ject of a p u b lis h e d p a p e r (1). C h a rle s was b o r n at W o lv e rh a m p to n , th e sixth son of th e fam o us W illia m W o od (1671-1730), a n iro n m a s te r a n d a m a n of g re a t e n te rp ris e a m o n g w hose u n d e rta k in g s w as the m ak in g of c o p p e r c o in ag e for b o t h I r e la n d a n d the A m e ric a n C olonies - a w ork th a t b r o u g h t u p o n h im a vitriolic a tta c k b y D e a n Swift. In 1729 W illiam W ood, w h o enjoyed th e p a t r o n a g e of th e P rim e M in iste r R o b ert W alpole, to g e th e r w ith tw o of his sons, F ra n c is a n d C h arles, p ro m o te d a co m p a n y fin anced by p ublic s u b s c rip tio n to e s tab lish a n iron w ork s at Frisington n ear W h ite h a v e n in C u m b e r l a n d a n d th e re to p ro d u c e m a lle a b le iron by sm elting w ith coal. W illiam died in th e following y e a r a n d b y 1733 th e e n te rp ris e h a d collapsed, leaving th e tw o sons b a n k r u p t. A r u in e d a n d d is a p p o in te d m an , C harles W o o d w ent off to C a ro lin a for a tim e, re tu r n e d to C u m b e r l a n d w h e re he m arrie d in 1735, a n d th e n settled in J a m a i c a w h e re th e first ch ild of the m a r r ia g e was b o rn in 1739. H e re he seems to have e n g a g e d in m etal m in in g of so m e kind, a n d he ce rtain ly p ra ctise d as a n assayer. H e h as b e e n desc rib ed b y a n u m b e r of 29
^ illiam Brownrigg
1711-1800
\ native of C u m b e r la n d . B row nrigg co m b in ed a distingu ished scientific c areer with a m odest an d retiring natu re. After taking his M.I). in L eyd en he settled dow n to practice m ed icin e in W h ite h a v en a n d was elected a Fellow of the Koval Society in 1742. H e beca m e friendly with C harles VI ood. who passed to him the specim ens of p la tin u m , bu t although B row nrigg later carried out one or two e x p e rim e n ts on th em he passed them on to the Royal Society for fu rth e r e x am in a tio n
F r o m a p o r tr a it p a in te d fo rm e rly in the B oard hite h a x e n H o s p ita l in a b o u t 1790 R o o m o f the
writers as the Assay Master to the Jam aican Government at this time, but the post was not in fact created until 1747. More recently, however, research by Mr. Robert Barker in Jamaica (2) has established that Wood again spent some time there and that he was appointed the first Assay Master in that year, several pieces of Jamaican silverware made during the period 1747 to 1749 showing his assayers mark, C.W. During his first period there some samples of native platinum had reached Wood from Cartagena, no doubt from a smuggler, and on his return to England in 1741 he passed them on to William Brownrigg, a doctor practising in Whitehaven who had published the results of a number of researches on subjects ranging from the gases found in mineral waters and the problem of fire dam p in coal mines to the purification of common salt, his papers being presented to the Royal Society by his friends in London. Nothing was apparently done with these specimens until Woods final return to England on giving up his appoint ment in 1749, when he set up with others an iron forge at Low Mill, near Whitehaven. Renewing his friendship with Brownrigg, whose brothers-in-law were among the investors in the Low Mill enterprise, Wood now persuaded him
30
to e x a m in e th e sam p les of p l a t i n u m a n d to u n d e r ta k e a few e x p e rim e n ts u p o n them . I n th e m e a n tim e , p re s u m a b ly in his la b o ra to ry in K ingston , J a m a i c a , W o o d h a d c a rried ou t som e ex a m in a tio n s of his own, finding t h a t th e m e ta l was p re sen t in sm all w h ite shot-like g ra in s a m o n g a black m a g n e tic s a n d a n d t h a t it c ould b e m elted only after m ixing w ith m o re fusible m e ta ls s u c h as cop per, silver a n d tin. H e s u b m itte d the native m e ta l to c u p e lla tio n w ith lead a n d found no alte ra tio n in eith er its b e h a v io u r or its w eight, w hile it also w ith s to o d a tw elve-hour digestion w ith nitric acid. T h e specim ens th a t W o o d b r o u g h t h o m e w ith h im w ere well ch o s e n to show th e essential facts a b o u t th e metal. T h e y c on sisted of:
XII. Several Papers concerning a new SemiMetal, called Platina; communicated to the Royal Society by M rt Wm. Watfon F. R. S.
E x tr a c t o f a L e tte r fro m W illiam Brownrigg M . T>. F. R . S. to W m . W atlbn f . R . S. D e a r S ir, ff'bitfhavm, Die. 5 , 1 7 5 0 . Rt*d Dec. 13 Y T A K E the Freedom to in dofe to you *75an Account o f a Semi-metal call'd T lo tin a d i Pinto-, which, fo far as I know , hath not been taken notice o f by any Writer on Mine rals. Mr. H ill, w ho is one o f the moft modern, makes no mention o f it. Prcfuming therefore that the Subjeft is new , I requcft the Favour o f you to fay this Account before the R o ya l Society, to be by them read and publilhed, if they, think it defcrving thofe Honours. I fhould fooner have publiihcd this Account, but waited, in hopes o f finding Leifure to make further Experiments on this Body with fulphureous and other Cements 5 alfo with Mercury, and fcvcral corrofive M enjirua. But thefe Experi m ents 1 fhall now defer, until I learn how the above u receiv'd. T he Experiments whicn I have related were fcvcral o f them made by a Friend, whofc Exattneis in performing them, and V cncity in relating them, I can rely on : However, for greater Cer tainty, I (hall m yfelf repeat them I am, dear Sir, Tour moft obedient S erva n t,
T h e covering letter from Dr. William Brownrigg, read to the Royal Society by William W atson on Decem ber 13, 1750. W ith this he enclosed a n u m b e r of sam ple s of n a tiv e platinum "first presented to me a b o u t nine years ago a n d an acco unt of the prelim inary e x p erim e n ts c arried out by Charles W ood a n d himself. In his second letter Brownrigg described W ood as a skilful and inquisitive m etallurgist who is not a m bitious to a p p e a r in p r i n t"
W. Brownrigg.
31
illiani Vi atson
1715-1787 T h e English phy sician and scientist well known for his re sea rc h es on electrical p h e n o m e n a . Elected to the Royal Society in 1741. W a tso n was a most active Fellow as well as a f o u n d e r m e m b e r of the Royal Society C lub, and enjoyed a wide circle of f r ie n d s am ong c o n te m p o ra ry scientists. It was to him that Brownrigg passed the sa m ple s of p la tin u m , with a n a c c o m p a n y in g letter on his p r e lim in a r y findings, for p r e se ntatio n to the Royal Society. In the last year of his life he received a kn ighthoo d for his services to science
1 2
3
4
Platinum grains m ixed w ith b la ck sand (m a g n etite) N ative platinu m grains separated from the sand Platinum that had b een fused (after a llo y in g ) A piece of such fused m etal fash ion ed into part of the pom m el of a sw ord
B ro w nrigg ca rried out a few p r e lim in a ry ex p e rim e n ts o n th e native p l a tin u m , including unsuccessful a t t e m p t s to b rin g a b o u t either its fusion o r its cu p e lla tio n w ith lead, a n d th e n d e c id e d to p ass th e sp ecim ens o n to th e R oyal Society to g eth er w ith a n ac c o u n t of W o o d s e x p e rim e n ts a n d of his o w n views on th e m a te ria l a n d its occurrence. H i s friend W illia m W a ts o n , a d istin g u ish ed p hysicist a n d a m e m b e r of th e R o y a l Society, w as asked to m a k e th e p r e s e n t a tion a n d this he did on D e c e m b e r 13th, 1750, a d d in g som e c o m m e n ts of his ow n to B ro w n rig g s c o n trib u tio n (2). In th e first letter B row nrig g d e s c rib e d h o w he h a d com e into possession of the sam p les of p la tin u m a n d w ent on:
It is found in con sid erable q u a n titie s in the S p a n ish W est In dies (in w hat part I cou ld not learn) and is there know n b y the n am e of P latina di Pinto. T h e S pan iard s p rob ably call it P latina from the resem b la n ce in colour that it bears to silver. It is bright and shining, and of a uniform texture; it takes a fine polish , and is not subject to tarnish or ru st.
32
After describing his few e x p e rim en ts h e co n c lu d e d :

It appears that no know n body ap proach es nearer to the nature of gold, in its m ost essential properties of fixedness and solidity, than the sem i-m etal here treated of; and that it also bears a great resem b lance to gold in other p a rticu la rs.
W o o d s first wife h a d d ied a n d in F e b r u a r y 1756 he m a r r ie d B ro w n rig g s w id ow ed sister J e m i m a a n d th e n in 1765 m oved from C u m b e r l a n d to S o uth W ales w h e re he bu ilt a n iron works a t C a rf a rfa n e a r M e r t h y r Tydfil. T h i s grew in im p o rta n c e to bec o m e th e largest of its tim e in W a le s a n d here W o o d spen t his last years a n d died in 1774. Before leaving C h arles W oo d, however, th e re m u s t be re p o rte d a cu rio u s isolated in ciden t th a t has co m e to light from a n en tirely u n e x p e c te d source, nam ely T h e M e m o irs of C asano va. T h e reference is to a visit p a i d b y C a s a n o v a in 1757 in Paris to a w e a lth y w o m an , th e M a r q u is e d Urf, w h o w a s in tere ste d in alchem y a n d the occult a n d h a d ex p ressed a w ish to m eet him . In th e co u rs e of th e visit she took h im to h e r alch e m ic al la b o ra to ry a n d sh ow ed h im a vessel c o n taining so m e p la tin e del Pinto w h ich she w as a b o u t to convert into gold . . .
C tait M . V ood en personne qui lui en avait fait prsent l an n e 1 7 4 2 .
H e w as s ho w n th e p l a t i n u m resisting th e a c tio n of su lp h u ric , n itric a n d h ydrochloric acids sepa rately b u t yielding to a q u a regia. She was m e ltin g it by m ean s of a b u rn in g -m irro r , saying t h a t alo n e it c o u ld not be m elted o therw ise, w h ich sh o w ed it to be s u p e rio r to gold. She also sh o w ed h im h ow it w as p r e c ip itated by s a l-a m m o n iac , w h ic h h a s never b e e n ab le to p re c ip ita te g o l d . No fu rther e x p la n a tio n of these s ta te m e n ts h a s so far e m e rg e d b u t it m u s t b e b o rn e in m in d th a t C asan o v a did not ac tu a lly w rite his m e m o irs un til 1792 a n d by th a t tim e m ost of th e facts a b o u t p l a t i n u m w ere k n o w n a n d h a d b e e n widely p ublished. (4)
William W atso n s Contributions

After re ad in g B ro w n rig g s letter to th e R o y al Society, giving all th e d etails of W o o d s ex pe rim en ts, W a ts o n re ad a fu rth e r c o m m u n i c a t i o n of his ow n, q u o tin g as m e n tio n e d in th e p recedin g c h a p te r, th e i m p o r t a n t p as s a g e from U l l o a s jo u rn a l. T h e P resid ential C h a ir w as still o cc upie d by M a r t i n Folkes, who together w ith W a ts o n h a d b efriend ed U lloa d u r in g his co n fin e m en t in L o n d o n in 1746. T h e n in th e following F e b r u a r y he was asked to re a d to th e R oyal Society a fu rth e r letter from B row nrigg (3) in w h ic h th e w rite r disclosed for the first tim e th e n a m e of C h arles W o o d a n d w ent o n to d esc rib e his e x p e rim e n t to show th a t p l a t i n u m did not resist th e a c tio n of lead in c u p e lla tio n as he h a d p r e viously th o u g h t. As one of his b io g ra p h e rs has w ritte n (5), w hile B ro w n r ig g s a c tu a l c o n t r i b u tion to o u r know ledge of th e p ro p e rtie s of p l a t i n u m w as n o t p e r h a p s of m a jo r im p ortance, he n o ne the less p la y e d a vital role in th a t th e p u b lic a tio n of his 33
Shortly a fte r re ad in g Brovvnriggs letters an d a p a p e r of his ow n to the Koval Societv W atson w rote two letters to his frien d P ro fesso r Bose in W ittenberg giving ail accoun t of these earlv investigations on p latin u m . Bose im m e d ia te ly p u b lis h e d th e m in G e rm a n , w ith the h ead ing "A Newly Discovered Metal in South A m eric a , a n d they served to arouse considerable interest a m o ng chem ists throughout Europe. T his shows the o p ening page of W atson's first letter of J a n u a rv 1751
findings brought them to the notice of scientists throughout England and con tinental Europe. Possibly his most significant comment was that quoted at the head of this chapter. William Watson played a large part in this dissemination of knowledge. In January 1751 he wrote an informative letter to his friend Georg Matthias Bose (1710-1761), Professor of Natural Philosophy at the University of Wittenberg, with whom he had been in constant correspondence on the new subject of static electricity. Bose immediately published the letter in German in the first number of a journal on popular science, Physikalische Belustigungen, just established by Christopher Mylius in Berlin (6 ). A second letter from Watson followed in May of the same year in which Watson apologised for the delay in answering Boses letter of acknowledgement of February 20th, this being occasioned by the death of the Prince of Wales (Frederick, elder son of George II, a most popular prince, had died of pneumonia on M arch 31st at the early age of forty-four) and in which he gave more details on platinum and referred to Ulloas published work. He also mentioned that it takes a high polish and suggested its use for the mirrors of telescopes. These two letters aroused considerable interest among chemists throughout Europe as many comments to this effect confirm in the literature. One example, written many years later by the great French chemist Antoine Francoise de Fourcroy, is typical: These first attempts, which announced very extraordinary properties, made a great commotion in Europe, at a time when the discovery of a metal as singular as this appeared to be was a phenomenon entirely unexpected. Then the great chemists of Europe set to work on platinum and its distinctive properties. (7)
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Scheffers Researches in Sweden

In the m id d le years of the eig h te e n th c e n tu r y th e re w as a very active in tere st in th e sciences in Sw eden. A c o u n try rich in m in era ls, it p r o d u c e d a n u m b e r of d is t inguished ch e m ists a n d m etallu rgists, a n x io u s to s tu d y th ese dep o sits a n d to identify th e m etallic elem ents th ey co n tain e d . B eginning w ith G e o rg B r a n d t the list includes J o h a n n G ottsch alk W alleriu s, H e n rik T h e o p h il Scheffer, Axel Fred rik C ro n ste d t, T o r b e r n O lo f B erg m an , K a rl W ilh e lm Scheele a n d J o h a n n G ottlieb G a h n , all extrem ely well k n o w n for th e ir c o n trib u tio n s to early m etallu rgical science. In 1733 B ra n d t discovered cob a lt a n d c a rrie d o u t a system atic inv estigation of arsenic a n d its c o m p o u n d s ; in 1751 C ro n s te d t discovered nickel in a m in e ra l from a cob a lt m ine, while Scheffer, in th e s a m e year, m a d e a m a jo r c o n tr ib u tio n to o u r early kno w led g e of p la tin u m . H. T . Scheffer s tu d ie d at th e U niversity of U p p s a la , w h e re he le a rn t m a th e m a tic s from A n d e rs Celsius, b u t as th e re was t h e n no co urse ava ila ble in chem istry he e n te r e d th e M in in g College, w h e re his fa th e r w as secretary, at the age of tw en ty -o n e a n d b e c a m e o n e of B r a n d t s m ost en th u s ia stic pupils. H e also established a p riv ate la b o ra to ry for a n a ly tica l work. F o r te n y ears from 1739 he was m a n a g in g a m in e a n d a m etal works p ro d u c in g c o p p e r a n d a little go ld b u t the en terp rise d id not succeed a n d in 1749 he re tu r n e d to S to c k h o lm to w o rk in the M in in g College a n d also as a n assay er a t th e M in t, w hile in a d d itio n h e gave lectures in che m istry . H e was elected a m e m b e r of th e R o y a l Sw edish A c a d e m y of Sciences in 1746 a n d p u b lis h e d a n u m b e r of p a p e rs in th e ir tr a n s a c tio n s . By far th e m ost im p o r t a n t of these, however, was his c o n tr ib u tio n to th e discovery of p la tin u m in 1751. It has b e e n m e n tio n e d in C h a p t e r 2 th a t D on A n to n io de U lloa, after his a d v en tures a n d his r e tu r n to M a d r id , h a d b e e n co m m iss io n e d by King F e rd in a n d VI to u n d e r ta k e a m ission t h r o u g h o u t E u ro p e to s tu d y scientific d evelopm ents a n d in th e a u t u m n of 1751 h e was for so m e weeks in Stockholm . H ere he w as w e lc o m e d by th e S w edish scientists a n d , at a m e e tin g of the A cadem y on O c to b e r 12th, he was p ro p o s e d for m e m b e r s h ip by th e secretary, Pehr W ilhelm W a rg e n tin , also a n a s tr o n o m e r a n d m a t h e m a t i c i a n w ho w o u ld have kn ow n of U l l o a s work, a n d he was du ly elected. W h e th e r o r not he m et Scheffer a n d d iscu ssed p l a t i n u m w ith him is not known, b u t it is m ost likely th a t, in seeking ou t those w h o c o u ld advise h i m o n science a n d in d u s try a m o n g th e sm all n u m b e r of scientists in Stockholm , su ch a m eeting took place. H ow ever th a t m a y b e Scheffer, u n d o u b te d ly p r o m p t e d b y U lloa or b y the letters from W a ts o n to Bose or possibly bo th , very soon p ro d u c e d a p a p e r for the A cadem y, s u b m itte d on N o v e m b e r 19th a n d re ad o n th e 28th, w ith t h e title T h e W h ite G old or S eventh M etal, ca lle d in S p a in P la tin a del p i n t o , Little Silver of Pinto, Its N a tu r e D e s c rib e d (9). In this he reco rd s t h a t in J u n e 1750 he received a sa n d y sp e c im e n co n ta in in g flat t r i a n g u l a r scales, w h ite as silv er th a t were not a t t r a c t e d by a m ag n et, th a t th e s a m p le h a d b e e n o b t a i n e d from 35
< e t h v ita G n llc t, e lle r jjttn d e M e ta lle n . D kaUadtiSp.it/ic-H , Platina del P in to , *Pintos jm S t i f t e r , b e jk r if v i t t i l fin n a tu r
Af
HENR. T H E O . SCHEFFER.
0
A
dien.
r i 7 f o i J u n i M."nad, fick j a g a f H e r r AiTcsf o r R i DF.NsKoi.Den m o rk f a n d , h vilken H e r r Affefforcn hade futt i S p a n i e n , m ed den u n d e r ra tte lfe , at d e n vore ifr a n V a l l - I n
Denna fand be ltod i a f m o r k a f m - k o m . 2 . a f jarn-targade Jarnm alm s k o r n , hvilk a d rog os a f M a g n e te n . 3. a f fa g ed ign a g u llk o rn . 4 . a f flata fcalena T r i a n g l a r , h vita fora S ilf v e r , h v i l k a M a g n e te n aldeles icke drog. D e (Ta trekantifja M e ta ll-fm u lo r fy ntes va ra J e r n , hvilk et a f n ' g o t tilialle hade b i if v i t h v i tt utan u p p j m en d e t bciy nneriigafte v a r , at d et ickc drogs a f M a g n e t e n , fall n d e t v a r fa fm id i g t , fom niigot jurn kan vara (a at d e t, d e n n a > M e t a l l , otorikylt ullgges at vara o f m i d i g : i den iu n -
T h e op e n in g of H e n r ik T h eo p h il S r h e f f e r 's p a p e r re ad to the Royal Swedish A c ad e m y of Sciences on N o v e m b er 28th . 1751. T h e title reads: " T h e W hite Gold or Seventh Metal called in Sp ain 'P l a t i n a del Pinto". Little Silver of Pinto, its N ature Described ". T h is re cord s that ill J u n e 1750 he had received a sam ple of native p latin u m from the P re sid e n t of t h e A c ade m y . I lric R u d e n sk o ld . A fte r rem oving the sandy c o n te n t the sam p le w eighed only forty grains, but Seh e ffe r was none the less a b le to m a k e a th oro ugh e x a m in a tio n of the new metal
S p a in a n d th a t h e u n d e r s to o d it c a m e fr o m t h e W e s t I n d ie s . H e h a d b e e n g iv e n th e m e ta l b y U lr ic R u d e n s k o ld , t h e n P r e s id e n t o f th e S w e d is h A c a d e m y o f S c ie n c e s , w h o h a d s p e n t th e y e a r s fro m 1 7 4 0 to 1 7 4 4 in t h e S w e d is h e m b a s s y in M a d r id a n d m u st h a v e b e e n a c q u a in t e d w it h m a n y p e o p le in in flu e n tia l p o s i t io n s in S p a in . A fter r e m o v in g t h e s a n d y c o n t e n t h e w a s left w it h o n ly fo rty g r a in s o f a m e t a llic n a tu r e ; th e s e h e fo u n d c o u ld b e m e lt e d r e a d ily w it h c o p p e r , th a t t h e y w e r e n o t a tta c k e d b y s u lp h u r ic o r n itr ic a c id b u t d is s o lv e d in a q u a r e g ia , w h ile w it h th e a d d it io n o f a sm a ll a m o u n t o f a r s e n ic t h e m a te r ia l m e lt e d e a s ily . (H is c h o ic e o f a r s e n ic m u s t su r e ly h a v e o c c u r r e d to h im fro m t h e w o rk o f h is m a ste r , G e o r g B r a n d t, o n th is e l e m e n t ) . H is c o n c lu s io n s w e r e : 1 T hat this is a m etal hard b u t m alleable, but of the h ardness of m a llea b le iron. 2 T hat it is a precious m etal o f d urability like g o ld and silver. 3 T hat it is not any of the s ix old m etals; sin ce first it is w h o lly and entirely a precious m etal, con taining n o th in g of cop p er, tin, lead, or iron b eca u se it allow s n oth ing to be taken from it. It is not silver, nor is it gold; but it is a seventh m etal am on g those w hich are know n up to now in all la n d s. F in a lly h e r e c o m m e n d e d t h a t : T h is m etal is the m ost su ita b le of all to m ake telesco p e m irrors b eca u se it resists as w ell as gold the vapours of the air, it is very heavy, very den se, colourless and m uch heavier than ordinary gold, w h ich is rendered u n su ita b le for this particular use by lacking these tw o latter p rop erties. T here rem ains only to be found the m anner of giving w hite gold unity and a p rop er state an d a m ixture that ca n aid to m elt it and to m ake it capable of receiving a p o lish .
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T h is was th e first a c c u ra te e x a m in a tio n of p l a tin u m , c a rrie d o u t o n an ex trem ely sm all q u a n tity , b u t im m e d ia te ly afte rw a rd s, a n d also d a te d N o v e m ber 28th, 1751, Scheffer r e a d a sh o rt p a p e r to th e A c a d e m y A n A d d e n d u m on th e Sam e M e t a l (10) in w h ich he refers to a n o t h e r s a m p le of m a te ria l t h a t he h a d received from B ran d t, w ho h a d also h a d it from R u d e n s k o ld . In this s u p p le m e n ta r y c o m m u n ic a tio n h e re p o rte d th a t the m etal, unlike gold, w as no t p r e c ip itated from s o lu tio n in a q u a regia by ferrous su lp h a te , b u t th a t it w as p r e c ip ita te d by alkalies a n d b y a m m o n ia in th e form of a red p o w d e r. T h is last observation, as will be seen, was a very i m p o r t a n t o n e th a t led o n to m u c h useful research.
William Lewis of London

Before W illiam W a t s o n s c o m m u n ic a tio n s w ere p u b lis h e d b y th e R o y al Society a n d therefore well before Scheffer h a d s ta rte d his work, a L o n d o n p h y s ic ia n a n d lectu rer h a d b e g u n a m a jo r series of e x p e rim e n ts w ith p la tin u m . T h is w as Dr. W illiam Lewis (1 708 -1 781 ) of K in g s to n -u p o n -T h a m e s , b u t as he d id not p u b lish his findings un til 1754 Scheffer m u s t b e a c c o rd e d p rio rity as th e first follower of W a ts o n in th e p u b lic a tio n field.
LXXXVI. Exprimentai Examination of a -bite metallic Subftanct [aid to be found in the Gold Mines o f the Spanifh WeftIndies, and there Inown by the Appella tions o f Platina, Platina di Pinto, Juan Blanca. B y William Lew is, AC B. F. R . S.
P A P E R L
Read M ay 30 , 154.
Experiment I. H E fnbftance brought into England tmder the name ofplatina appears a mixture of dilftmilar particles. The moft conspicuous, and by far the largeft part o f the mixt, are, white, fhining grains, o f feemingly fmooth furfaces, irregular figures, generally planes with the edges rounded off. Upon examining thefe with a microfcope, the furface appear'd in fome parts irregular -, the prominencies fmooth, bright, and ihimng ; the cavities dark-colour'd and roughiih. A few of them were at trailed, tho weakly, by a mag netic bar. T h e grains above deicrib'd are the true platina. The heterogeneous matters intermingled among them, in the feveral parcels, were, i. A
B efo re S e h e ffe r's re se a rc h e s were kn ow n to him W illiam Lewis had e m b a r k e d on a long series of resea rc hes on p la tin u m . Vi thin five weeks from late May lo early July in 1754 he read fo ur p a p e r s to th e Royal Society, with a f u r t h e r two in 1757. T h is is the o penin g page of his first p a p e r fro m the P h ilo so p h ic a l T ransactions
37
Lewis w as a skilled e x p e r i m e n t e r as well as a prolific a u t h o r a n d editor, a n d in his tim e he was th e u n d i s p u t e d a u th o rity o n any subject o n w h ic h he wrote. H e h ad, in fact, a co n s id e ra b le influence o n the c h e m ic al tech n o lo g y of the In d u s tria l Revolution. Lewis s tu d i e d m edicine first at C h ris t C h u r c h , O xford, a n d later at E m m a n u e l College, C a m b rid g e . H e t h e n settled in L o n d o n a n d soon b e c a m e esta b lis h e d as a p u b l i c le c tu re r o n c h e m istry a n d o n th e im p ro v e m e n t of p h a r m a c y a n d th e m a n u f a c t u r i n g arts. In 1745 he w as elected a Fellow of th e R oyal Society a n d tw o y e a rs la te r h e m oved to K in g s to n w h e re he eq u ip p e d a large lab o ra to ry . A n excellent a c co u n t of th e life a n d w ork of W illia m Lewis, until th en a lm o s t a fo rg otten m an, w as pro v id ed by th e late F . W . G ib b s in 1952 (12). Lewis was a c q u a in te d w ith B row n rigg , a n d he w as p e r m i t t e d to select a sm all sam ple from th e sp ecim ens t h a t h a d b ee n p re s e n te d to th e R o y al Society. O n these he m a d e a few p r e lim in a r y observ atio n s b u t it w as not u n til early in 1754 th a t he o b ta in e d a sufficient q u a n t i t y for his extensive re searc h . T h is he sec u red from G e n eral R i c h a r d W a ll (1694 1778), a n Irish R o m a n C ath o lic w ho, un ab le to h old an y p ublic office b e c a u s e of his faith, h a d served th e S p an ish King F e rd in a n d VI in a n u m b e r o f posts, inclu d in g o ne in th e S o u th A m e ric a n colonies. In 1747 he was a p p o i n t e d S p a n is h a m b a s s a d o r to L o n d o n a n d was elected to th e Royal Society in 1753, clearly b ec o m in g k n o w n to Lewis a t th a t time. T h r o u g h W a ll s influence, L ew is w as sent o ne h u n d r e d o u n ce s of p la tin u m from Spain, w ith a fu rth e r q u a n t i t y a y ea r or tw o later. T h e results of L e w iss long a n d ex ha ustive series of e x p e rim e n ts w ere re a d to t h e Royal Society in 1754 in four long p a p e rs over th e c o u rse of only five weeks (13). H e w e nt a b o u t his w ork a n d re p o rte d his findings in a m a n n e r so logical, c lear a n d alm ost m o d e rn in c h a r a c t e r t h a t his p a p e rs p re s e n t th e first a u t h o r i tative a n d co m p re h en siv e a c c o u n t of the p ro p e rtie s of p la tin u m . In the first p a p e r Lewis s u m m e d u p his c o n c lu s io n s : That the pure platina is a white metallic substance, in some small degree malle able; that it is nearly as ponderous as gold, equally fixd and permanent in the fire, equally indestructible by nitre, unaffected by sulphur. T h a t it is not to be brought into fusion by the greatest degree of fire procurable in the ordinary furnaces, whether exposd to its action in close vessels, or in contact with the fuel; by itself, or with the addition of inflammable, saline, vitreous or earthy fluxes. T h e second p a p e r re corded t h e effects of acids u p o n p l a t i n u m freed from its c o n ta m in a tin g d ust, m e rc u ry a n d gold. Its inso lub ility in su lp h u ric, hyd rochlo ric a n d nitric acids w a s noted, a n d of co urse its so lubility in a q u a regia, b u t his m ost im p o rta n t discov ery w as th a t : The spirits of sal-ammoniac add ed to solutions of platina (in aqu a regia) diluted with distilled water, precipitated a fine red sparkling powder; which, exsicated and exposd to the fire in an iron ladle became blackish; without at all fulminating, which calces of gold, prepard in the same manner, do violently. P ap ers III a n d IV described a lo n g series of ex p e rim e n ts in th e m eltin g of p l a t i n u m alloyed w ith p ra c tically every o th e r m etal th e n k n o w n a n d som e of 38
th eir alloys, b u t cu riou sly h e d id not th e n try th e effect of arsenic. T h e idea was th a t th e best h o p e of b rin g in g p la tin u m into a m a lle a b le form t h a t co u ld be fa b ric a te d was b y alloying it w ith a n o t h e r m etal, b u t little p ro g ress re s u lte d from these e x p e rim en ts except his finding th a t if a n alloy of lead a n d p l a t i n u m was th o ro u g h ly oxidised at a hig h t e m p e r a t u r e it yielded a spon gy m ass t h a t could be forged. After the p u b lic a tio n of P apers I to IV Lewis o b ta in e d a copy of Scheffers c o m m u n ic a tio n to th e S w edish A c a d e m y in w h ic h h e foun d
a rem arkable exp erim en t seem ing to show that p la tin a and arsenic have som e d isposition to unite.
an d he at once set a b o u t re p e a tin g it in several different w ays w ith o u t great success. H e co n c lu d e d th a t :

It appears upon the w hole, that p latina does m elt w ith arsenic, but less perfectly than w ith other m etals; and that it w ould b e very difficult, if not im possible, to bring it, on this foun dation to sufficient fusion for b ein g poured into a m o u ld . (14)
O n m elting p l a t i n u m to g e th e r w ith a n eq u a l p a r t of gold Lewis o b ta in e d a b rittle alloy a lth o u g h it c o u ld be w ork ed after a n n e a lin g , a n d this finding d re w a letter from B row nrigg to W a ts o n , re a d to th e R o y al Society in th e following Decem ber, in w hich he w rote:
Dr. Lewis w ill find that Platina being m ixt w ith G old destroys th e d u ctility of that m etal. H ow G old is affected w ith a very sm all p rop ortion o f P latina I know not, but m y acq u ain tan ce M r. C harles W ood (w ho w as A ssay M aster in J a m a ica ) a very curious m an th o he m ight be m istaken in som e thin gs, sh ow ed m e ab out a drachm w eight of a su b stan ce w h ich he said w as P latina and G old m ixed by him in equal quantities. T h is m ixture w as extrem ely b rittle. (15)
Lewis was lavish in his use of p l a t i n u m in his e x p e rim e n ts , for in m o st of th e m he took a t least one o u nce a n d som etim e s even th re e or four ou nces as starting m aterials. O n e o th e r aspect of his w ork, p o in te d o u t by Professor Cyril Stanley S m ith (16) is t h a t he m a d e o ne of th e earliest o b servation s of the m ic ro s tru c tu re of a n alloy as a n a id to in te rp re tin g its c o n s titu tio n w h e n he noted th e com plex s tr u c tu r e of in com pletely m elted alloys of p l a t i n u m a n d gold: Some appeared to have suffered no alteration; others exhibited an infinite number of minute globular protruberances, as if they had just begun to m elt. For this o u ts ta n d in g w ork Lewis was a w a r d e d th e C o pley M e d a l by the Royal Society in 1754, b u t he c o n tin u e d his e x p e rim e n ts, p r o m p t e d by B row nrigg s letter, o n th e alloying of p l a t i n u m w ith gold, in a n a t t e m p t to ascertain :
w hether there is reason to credit the report o f great frauds having b een com m itted by m ixing them together; how far su ch abuses are p racticable; and w hat is o f m ore im portance, the m ean s by w hich they are d isco v era b le.
So Papers V a n d VI, r e a d to the R oyal Society in M a r c h 1757, (17) d ealt largely w ith the m e th o d s of assaying a n d s e p a ra tio n of th e m etals. 39
In 1763 W illiam Lewis pu blished his elassir " C o m m e rc iu in PhilosophicoT e e h n ie u m " . d e d ica te d to G eorge III to w hom he h a d g i\e n private tuition w hen he was P rin c e of W ales. T his included a long section ru n n in g to 170 pages that form ed the first a u th o rita tive an d c o m p re h e n siv e work on the history an d the p ro p e rties of platinum . T his work was m u c h consulted f >r the next th re e -q u a rte rs of a c en tu ry , and e \ e n as late as 1880 J o h n Percy, P ro fessor of M etallurgy at the Royal School of M ines in L ond on, re ferred to it as 'a vo lum e rarely a p p re ciated as it ought to be . . . it c ontains m uch infor m atio n of scientific interest and of practical \ alue
There was yet more to come from William Lewis. Beginning in 1763, he published a massive volume in parts, the Commercium Philosophico Technicum A long section was devoted to the chemistry and applications of gold, and, follow ing another part dealing with colours and pigments, there appeared a 170 page section on The History of Platinum (14). Lewis wrote in introducing this: Nothing now is so much wanted, as a regular history of what has already been done, or a connected view of the experiments that have been made upon it. and this he set out to provide. It included of course his own work as well as that of the leading chemists of Sweden, Germany and France whose work had to a large extent stemmed from his own.
W illiam Bowles and his Researches in Spain It was mentioned in the last chapter that in 1753 the Irish naturalist William Bowles examined a sample of native platinum from South America at the request of the Spanish Minister of the I ndies and that he issued a warning on the dangers of admitting this new metal into commerce. His report on his experi ments describes how, after separating the gold and the blackish sand:
40
The grains of platina then resembled lead shot, still more the semi-metal which the Germans called speiss, which is a regulus of cobalt often included in saffre. The weight of the platina surprised me because it exceeds that of 20 carat of gold. I put several pieces of it on an anvil and hit them with the hammer. I saw they extended their diameter five or six times, remaining white as if they were silver. This deter mined me to send them to a gold beater to determine the extent of their malleability, but when tested between the beaters skins they broke up at once. In remarking that the sand was only malleable to a certain extent I wished to try to melt it in a furnace which a very clever Swiss used for the separation of gold by the dry way. The fire was so violent that it melted a part of the crucible and the grains of platina united themselves in a group without any loss of colour or sign of true fusion, after two hours of the most lively fire. Seeing the grains joined together, I thought that the platina might contain some portions of true sand and that this would be vitrified by the phlogiston of the metal. To convince myself, I washed a little of the platina and put it in another crucible glazed with common melted salt. After three hours nothing had melted but the grains were not so strongly united as the first time, several even remaining separate. H e th e n found t h a t th e p la tin a w as not a tta c k e d by su lp h u ric a n d nitric acid b u t there was som e atta c k (p ro b a b ly o n th e s a n d s ) by h y d ro c h lo ric acid. T h e p la tin a w as dissolved after I th re w o n th e acids a stro n g dose of sala m m o n i a c . H e n o ted th a t th e g ra in s of p la tin a w h ic h h a d b e e n u n ite d b y h e a t broke up u n d e r a very light h a m m e r blow. H e e x a m in e d th e a c tio n of s u lp h u r, lead a n d cu p e lla tio n ; he n o te d t h a t th e solubility in gold w as lim ited a n d th a t the alloy w ith lead could be m elted a n d co u ld be p a r t e d in n itric acid, leaving an infusible black pow d er. (18) No fu rth e r re s e a rc h w ork on p l a t i n u m took p lace in S p a in for a q u a r t e r of a ce n tury a n d a n a c c o u n t of this will be fou nd in C h a p t e r 6.
M arggrafs W ork at the Berlin A cadem y of Sciences

Soon after his accession to th e t h ro n e of P russia in 1740 F red e rick th e G reat, am o n g m a n y o th e r activities, revived the declin ing R oy al P ru ss ia n A c a d e m y of Sciences th a t h a d bee n fo u n d e d in 1700 b y his g r a n d f a t h e r F rederick I, o n the p e rsu asio n of Leibniz, to e m u la te th e R oyal Society of L o n d o n a n d th e F re n c h A c ad em y of Sciences. T o this e n d he invited to B erlin b o th L e o n h a r d Euler, the Swiss m a th e m a tic ia n , a n d la te r Pierre Louis M a u p e r t u is from th e F re n c h A c adem y of Sciences. E u le r was sent a s a m p le of p l a t i n u m from L o n d o n in a b o u t 1754, a n d this he passed o n to his lead in g assistant, A n d re a s S ig is m u n d M arggraf, w ho h a d stu d ie d m edicine at H a lle a n d t h e n m e ta llu rg y at F reiberg, a n d w ho was given c h a rg e of th e chem ical la b o ra to ry in th e Berlin A c a d e m y in 1753. M a r g g ra f c a rrie d out a long series of e x p e rim e n ts re p o rte d to th e A c ad em y in 1757 (a lth o u g h not p u b lish e d until 1759) w ritte n in F ren c h , th e official langu age insisted u p o n by F rederick, while th e y w e re later p u b lis h e d in G e r m a n in a collection of his p a p e rs (19). 41
M a r g g r a f a p p lied m u c h th e s a m e p ro c e d u re s as th e o th e r investigators w h ose work has a lre a d y b e e n re c o rd e d . H e a g a in observed th a t a t a very high te m p e r a t u r e p la tin u m grains s in te re d to g e th e r s o m e w h a t b u t th a t th ey h a d not b e e n m elted a n d w ere easily b r o k e n up u n d e r th e h a m m e r . H e also n o ted the trac es of m e rc u ry a m o n g th e n a tiv e p l a t i n u m a n d c o n c lu d e d t h a t it w as a re sid ue from a n a m a l g a m a ti o n process. H e fou nd th a t h y d ro c h lo ric acid dissolved som e iron from th e m i n e r a l a n d t h a t a q u a regia also dissolved the p l a t i n u m itself. F ro m this s o lu tio n p re c ip ita te s w ere form ed b y co p p e r, iron, tin, lead, m erc u ry , zinc a n d a n tim o n y , a n d w ith r e g a rd to th a t fo rm ed b y zinc M a r g g r a f re m a rk s t h a t to all a p p e a r a n c e s th e p l a t i n u m h a d b e e n p r e c i p i ta te d u p o n it. T h e r e was no p r e c ip ita te by solutions of m in e ra l fixed alkali (so da); w hile salt of t a r t a r (p o tassiu m c a r b o n a t e ) gave a yellow p re c ip ita te . H e cupelled som e of this last w ith lead a n d o b t a i n e d a ro u g h , greyish a n d very b rittle b u t t o n w hich was exactly like t h a t o b t a i n e d w h e n o rd in a r y p l a t i n a w as cupelled w ith l e a d . H e re p e a te d th e e x p e r i m e n t using s a l-a m m o n ia c as th e p r e c ip ita n t a n d o b ta in e d a precisely s im ilar result. T h e sa m e th in g h a p p e n e d w h e n he e v a p o ra te d his p la tin u m s o lu tio n in a q u a regia to dryness, ig n ite d th e residue a n d cupelled it w ith lead. H e n o t e d th a t in all these cases th e cu p e lle d b u t t o n alw ays co n tain e d som e lead. N e x t he alloyed a sim ilar b u t t o n w ith so m e p u re gold a n d a n excess of silver a n d p a r t e d th e alloy in n itric acid. H e fo u n d th a t in th e course of this o p e r a tio n th e p l a t i n u m d is a p p e a re d , th e final in solub le re sidu e b ein g only th e right w eight of fine gold. H e next d e m o n s t r a t e d th e p re sen ce of iro n in native p la tin u m b y o b t a i n i n g from its s o lu tio n a p re c ip ita te of P ru ssian
A ndreas S igism un d Marggraf I 709-1782

A native of Berlin, M a rg g raf was a p p r e n tic e d to his fa th e r , the Court A poth ecary , a n d then stu d ied m edicine at H a lle a n d m etallu rgy at Freiberg. Afte r his r e tu r n to Berlin he was elected to the A c ad e m y in 1738. He was singled out as the best ch em ist and in 1759 he was pu t in c h a rg e of the chem ical lab o ra to ry in the A cadem y, succeedin g E ule r as Director in 1766. He was the first to discover that the pre c ip ita te o b ta in e d from a p latin um solution by m e a n s of a m m o n i u m c h lo rid e re v e rte d to m etal on heating
42
T h e beginning of the p a p e r read to the Koval Academy of Sciences in Berlin in 1757 u n d e r the title " E x p e r i m e n t s C o n cerning the New Kind of M ineral Body known u n d e r the nam e of P la tin a del Pinto**. T h e official language of the Academy was F re n c h on th e insistence of King F re d e ric k the G re at
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< M W > < K < H H 0 O < > 0 0 O < -< H W > < K O O iO < >
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1 1 y dj quelques annes que lon eft parvenu en A ngleterre la conooiliance de corps minral mtallique, auquel on a donn le PU tina Je! Pinto. Les Auteurs Anglois qui en p arlent, difnt qu'on le trouve dans les M ines clO r des Indes O ccidentales Espagnoles. (V oyez les Tranfaffm m , Vol. 48 . p. 6 3 8 - ) Suivanr dautres rlarions, ce minral doit fe trouver en form e de ible d.ins les rivires de la Province de Q ia tn, & cela en trs grande quantit. O n ne (uroit donc dire avec aucune certitu d e, fi c cil une matire relle m ent-minrale, ou une iimple raclure que leau entrane de quelque veine e n ti re , & port avec elle dans ion cours ; ou mme fi ce ne pourroit point tre un p u r rcrm ent m tallique, d o les F.fpagnols, i qui appartiennent les mines de ces contres, auroienr tir de manire ou d autre ce mtal parfait. U n de nos dignes Confrres O fibre M. le Profefleur ZtVVr, dans une L ettre q u il lui a crite, q u il tient de la bouche d un Eipagnol qui a t dans cette Province, de qui en i apport de la Phitina, quo n la trouve rpandue fur la cam pagne, prs du fleuve qui traverie les m ontagnes du Prou auprs de Quito. Dans les commencemens il toit fort difficile de fc p ro curer quelque chantillon de cetto matiere ; les Efpagnols n en vouloicnt point com m uniquer, caufe que pouvant tre aiiement mle avec (*) Mr. Brrtrnd de Genert
Blue on a d d in g alkali th a t h a d previously b e e n calcin ed w ith b l o o d ( blutlauge, co ntain ing p o ta s s iu m ferrocyanide). T h e re su lts of all these ex p e rim e n ts entitle him to be called th e first m a n to s e p a ra te m etallic p l a t i n u m from its m in era l. T o say, as som e of th e textboo ks do, th a t he was th e first to p r e p a r e p u r e p l a t i n u m is of course incorrect, even by th e s t a n d a r d s of p u r ity t h e n c u s to m a ry , since the m etal c o n ta in e d all th e o th e r p l a t i n u m m etals, as well as o th e r im purities.
Researches in France
F ran c e lagged b e h in d th e o th e r E u r o p e a n c o u n trie s in a p p ly in g scientific m ethod s to th e stu d y of p la tin u m . In M a y 1751 a brief reference was m a d e to th e first le tter to Bose from W a ts o n (w ith his n a m e m is-spelt) in th e Journal Oeconomiqueu n d e r th e h e a d in g :
METAL NOUVELLEMENT DECOUVERTE
E xtrait d u ne lettre ecrite de L ondres par M . G u illa u m e W a b so n a M . * * * * d atee du 25 Jan vier 1751 (20).
T h is seems to have aro u s e d no interest w hatsoever, w hile a fu r th e r m e n tio n in the sam e j o u r n a l in 1755, referring to th e fr a u d u le n t use of p l a t i n u m in the a d u lte ra tio n of gold a n d to Scheffers work, d re w very little m o re a tte n tio n (21). 43
But in J a n u a r y 1758 th ere a p p e a r e d a long letter to th e edito rs of th e Journal des Savans, the first scientific p e r io d ic a l t h a t b e g a n p u b lic a tio n in 1665, o n A N e w M e ta l called P l a t i n a , from M . D e la la n d e de 1 A c a d m ie R o y a l D es S cie n c e s . T h e w rite r was J o s e p h J e r o m e le F ra n o is de L a l a n d e (1 7 3 2 -1 8 0 7 ) w h o was later to bec o m e th e l e a d i n g a s tro n o m e r in his c o u n try b u t w h o w as also a prolific w riter on m a n y scientific subjects. His letter o pen s b y referring to the re searches c a rrie d out o n p l a t i n u m in E n g la n d a n d G e rm a n y , a n d goes o n to ju stify his a p p e a ra n c e in p rin t :
Because nothing has been p u b lish ed in our la n gu age on the subject, except a very sm all extract in the Journal Oeconomique, I offer for your cu riosity a sum m ary of th ese experim ents and the co m p a riso n w h ich results b etw een p la tin u m and the m etals already k n ow n .
L aland e, a t th e age of only n in e te e n , h a d b ee n sent to B erlin in 1751 to m a k e observations on th e p a ra lla x of t h e m o o n a n d here, d u rin g his stay of n ea rly tw o years, he im pressed b o th F re d e ric k th e G r e a t a n d E u ler a n d w a s elected to the A cad em y. H e w o uld have d o u b tle s s m et M a r g g r a f d u rin g this visit, b u t his letter refers only briefly to the l a t t e r s w ork o n p la tin u m while it gives a lengthy a c c o u n t of th e p ro fo u n d r e s e a r c h e s of W illia m Lewis. L a t e r in 1758 th ere w as p u b l i s h e d in P a ris a sm all book u n d e r th e title L a P latine, l O r Blanc, ou le H u i t i m e M e t a l , consisting of a sh o rt preface by th e a u th o r, the two letters from W i l l ia m W a ts o n to Professor Bose, a n ac c o u n t of the ex p e rim en ts of C h arles W ood a n d the c o m m e n ts of B row n rig g u p o n th em , Scheffers p ap e rs to th e R o yal A c a d e m y of Sw eden, L e w is p a p e r s of 1754, a n d a so m e w h a t alchem ical letter c o m m e n t i n g o n all these from a n a n o n y m o u s Ita lia n living in Venice (23). In fact, t h e book c o n ta in e d a very g o o d s u m m a r y of th e work ca rried out on p la tin u m in o t h e r c o u n trie s u p to a n d in c lu d in g 1755. It was p r i n t e d a n o n y m o u sly b u t th e a u t h o r s n a m e w as given as M . M o rin , a m a n zealous in the process of science a n d a s a v a n t h im s e lf , by M a c q u e r , to w h o m th e m a n u s c r ip t h a d been s u b m i t t e d for ap p ro v a l in O c to b e r 1757, in his D ictio n n aire d e C him ie, p u b l i s h e d in 1766. H ow ever, th e tr u e id en tity of this m a n re m a in s s o m ew h a t in d o u b t. T h e book has often b e e n a t t r i b u t e d to C la u d e M o rin , a law yer in Dijon, b u t he w as no scientist a n d it is m u c h m o re likely to have been the w ork of J e a n M o r i n (1 7 05-176 4), C a n o n a n d Professor of Philoso p h y at C h artre s, w h o was a c o r r e s p o n d i n g m e m b e r of th e A c a d m ie des Sciences from 1736 o n w a rd s a n d w h o w ro te tw o or th re e o th e r scientific works, m a in ly on the subject of electricity. T h i s book w as given a long a n d qu ite e n th u s ia s tic review in th e J u n e issue of th e Journal des Savans, a n d th e effects of th ese p u b lic a tio n s o n t h e scientists of Paris was now im m e d ia te, p a r ti c u la r l y u p o n M a c q u e r himself. H is colleague A n to in e B aum h a d o b ta in e d at t h e e n d of th e s u m m e r of 1757 a b o u t a p o u n d of p l a t i n u m p re s e n te d b y J o s A r c a d io O rte g a , th e secretary of th e A c a d e m y of M edicine, M a d r id , a n d to g e th e r t h e y set o u t to re p e a t som e of th e e x p e rim en ts c a rrie d out by th e ir predecessors, e s ta b lis h in g to th e ir satisfac tio n t h a t this new 44
T h e title page of the small book published anonym ously in P a ris in 1758 and including F renc h translatio ns of all the c o n trib utio ns so far m a d e on platinu m , with reflections on the n a tu re a n d on the essence of this singular su b s ta n c e". T h e a u th o r was given as M orin b\ M a c q u er. who had been req u ired to approve the m anu script p rio r to p ublic a tion , and was most p ro ba bly J e a n Morin, a priest a nd scientist of C h a r tre s who was a co rresponding m em ber of the Academ ic des Sciences. T h is little book. to gether with the paper published by L alan d e a few m onths earlier, at last p ro m p te d the scientists of Paris to ta k e an interest in p latin um
L A PLATINE, LO R B L A N C ,
ou LE HUITIEME M E TA L ;
R E C U E I L E xpriences faites dans le s A cadm ies R o y a les de L on dres, de S u ed e, &c. fur une n o u v e lle Subftance m tallique tire des M ines du P r o u , qui a le poids S i la fixit de lOr. Ouvrage intrejfant pour Us Amateurs de l'H iftoire naturelle, de la Phyjque & de la Chymie, Ncceflaire aux Orfvres & Affineurs, pour ntre point tromps fur des Alliages qui rftent aux preuves de l'Or.
Iftile dans Us A r ts , qui peuvent employer cette Sul/lance fabriquer des Miroirs qui ne Je lernijptnt point l'A ir , (/ iu r au Cuivre f a facilit contracter U Vcri-dc-gris.
P A R I S ,
f L E B R E T O N , Imprimeur ordinaire \ du R O I , rue de la Harpe. J D U R A N D , rue du Foin. ; ' P I o S O T1, ..>: de Conty. o r S c r\ t quai j . r L A M B E R T , rue de la Comdie Franoile. V M. D C C . L V I I I . Avec Approbation & PtrmiJJion du R o i
body was in d eed a new elem ent. ( M a r g g r a f s p a p e r h a d not yet a p p e a re d in p rin t at this tim e). T h e ir p a p e r w as re a d to th e A c a d m ie in N o v e m b e r 1758 and pu b lish ed in th e M em o irs for t h a t y ea r a lth o u g h these w e re not p r in te d until 1763 (24). T h e p a p e r opens w ith a n exp ressio n of
a kind of tem erity in p ub lish in g at present a work carried out in a very short space of tim e and in w hich one has only repeated a part of th e researches of M . L e w is,
b u t also m ak es the i m p o r t a n t po in t realised by th e scientists of th e tim e :

As it is im possible to exam in e the essen tial properties of a m etal, that is to say
45
Pierre Joseph Ylacquer 1 7 1 8 -1 7 8 4

A lthough beginning his c a r e e r as a physician M a r q u e r was especially in terested in chem istry and in 1745 he was elected to the Acadm ie des Sciences. He began to publish p a p ers from then on a n d in 1757. in c o lla b o ra tion with A ntoine B a u m . started courses on chem istry in th e ir laborato ry. In the following year they u nd e rto o k a study of p latinu m but a lth oug h they were unsuccessful in a tt e m p t s to bring a b o u t its fusion they satisfied themse lves that it was a distinct metal. M a c q u er later b e ca m e Irofessor of Chemistry at the J a r d i n du Koi a nd the leading Fre n c h a uth ority on the subject
those from w hich one can ju d g e th e u sefulness that on e m ight ex p ect from it, su ch as its d uctility and hardness, w ithout m eltin g it alone to o b ta in a n ingot o f a certain size, w e have first thou ght it necessary t o ascertain w h eth er there is an y h ope of m elting this m etal.
At this tim e M a c q u e r, a p a r t f r o m his le ctu rin g on c h e m is try , h a d j u s t been a p p o in te d a s sistan t to J e a n H ellot, th e scientific d ire c to r of th e p o rc e la in factory at Sevres, a n d after a n abortive a t t e m p t , lasting fifteen h o urs, to m elt p la tin u m in a w o o d fire, he exposed a small q u a n t i t y in a crucible in th e p o rc e la in furnace, th e greatest degree of fire k n o w n . After five d ay s a n d n ig h ts no c h a n g e was discernible in the p la tin u m , b u t t h e crucible h a d collapsed. After several m o re u n successfu l a tte m p ts M a c q u e r a n d B a u m e d ecided to d e te r m in e w h e th e r p la tin u m was e s s e n tially infusible o r not by ex po sing it to the h e a t from a large concave b u r n i n g m irro r, a device t h e n t h o u g h t to be m ore pow erful t h a n any k ind of fire. W i t h this m irro r, m a d e of m e rc u ry -c o a te d glass a n d 22 inches in d iam eter, they q u ic k ly m elted iro n a n d several m in era l su b stances. T h e n , on O c to b e r 16th, 1758, th e s u n b ein g perfectly c le a r a n d th e air very c l e a n , they p lace d at th e focal le n g th of th e m i r r o r a sm all piece of p l a t i n u m th a t h a d a lre ad y b ee n t h r o u g h th e p o rc e la in fu rn a c e a n d t h a t w as suf ficiently a g g lo m e ra te d to b e held i n a p a ir of pincers. T h e y w e re at least p artia lly 46
successful this time, in t h a t glistening r o u n d e d p artic le s of a silvery-w hite m etal b e g a n to a p p e a r at a few points in th e sm all m ass of m a te ria l. S e p a r a tin g the largest of th ese from th e u n m e lte d re sidue w ith th e ir fingers, th ey fo u n d t h e m to be readily m alleab le a n d w ere ab le to h a m m e r t h e m to foil w ith o u t a n y signs of cracking. But M a c q u e r s hopes of p ro d u c in g even a sm all ingot of p l a t i n u m w ith which to d e te rm in e its p ro p e rtie s w ere not fulfilled. T h e y c o n firm e d th e solubility of p l a t i n u m in a q u a regia a n d its p r e c ip ita tio n b y sal-a m m o n iac , a n d a t t e m p t e d to m elt th e p re c ip ita te u n d e r a flux a n d found t h a t the result, w h ich at first sight looked like fusion, w as really n o th in g m ore t h a n a n a g g lu tin a tio n of the particles, th e p r o d u c t b ein g q u ite brittle. In the course of p re c ip ita tio n s of th e p l a t i n u m w ith vegetable fixed alkali ( p o ta s h ) a n d volatile alkali ( a m m o n ia ) they fo u n d th a t the co lo u r of th e p re c ip ita te s varied from one occasion to a n o th e r, from b rig h t red t h ro u g h all sh ad e s of o r a n g e to p u re yellow. M a c q u e r th o u g h t t h a t this d e p e n d e d on th e s tre n g th of th e solu tion, while B a u m e a t t r i b u t e d it to th e excess o r o th erw ise of p re c ip ita n t. Lewis h a d c o m m e n te d on these conclusions b u t he did not p u r s u e th e m a tte r, a n d the an sw e r c a m e only w ith th e discovery of irid iu m n early h a lf a c e n tu r y later. A full
A ntoin e Bau m e 1728-1804

A m a s te r a p o th e c a r y . B a u m e o p e n ed a p h a r m a c y in P a ris in 1753 and m a n u f a c t u r e d d ru g s on a c on sidera ble scale. In 1757 he c o -o p e ra te d with M a c q u e r in c o n du cting courses in both chem istry a n d p h a r m a c y w hich con tinue d for sixteen years. Baume e q u ip p in g the lab oratory a n d p r e p a r in g the e x p erim e n ts, l i e first suggested that p la tin u m c ould be con solidated by he ating a n d forging
47
account of all this work will also b e found in M a c q u e r s Dictionnaire de Chimie (25) but a very im portant de d u c tio n from it did not see the light of day until Baum published his three volum e textbook Chym ie Exprim entale et Raisone in 1773 (26). Here he says of p latin u m : It combines in its admirable properties a quality still more precious which is lacking in gold, hardness. This approaches very nearly that of iron. So many excellent properties united in a single metal make it desirable that it should be introduced into commerce. There is every reason to believe that it will be possible to derive very great benefits from its use in an infinity of utensils, which made out of this metal will not be susceptible to attack by any kind of rust. For example, I have noticed that it submits to forging and welding like iron, without the introduction of any other metal. I have taken two pieces of platinum which have been cupelled in a Svres furnace; I have raised them to a white heat in a good forge: having placed them one on the other, and struck them with a sharp hammer blow, they have welded together just as well and solidly as two pieces of iron would have done. This property of platinum of being malleable when hot and being capable of welding in that state, leads one to hope for the greatest advantages by treating it in this way when one cannot reach finality by fusion. The case of platinum would then be the same as that of iron, with which all kinds of work can be done without our being obliged to melt it. It will be sufficient to melt this new metal a single time, either alone, or by means of lead or bismuth, and subsequently to destroy these metals in the manner we have described above. This observation of B a u m s a n d the conclusion th at he drew from it were responsible for the start of the fabrication of p latinum for comm ercial uses and underlie the industry that g rad u a lly grew up during the next h u n d red years. T he right of priority in this discovery w a s accorded to Baum by his contem poraries w ithout any hesitation and a typical example of the credit will be found in Professor Joseph Blacks L e c tu re on Platina, or P la tin u m delivered to his students in the University of E d in b u rg h during the 1780s. (27) This method of compacting platinum and uniting the parts of it by percussion, when strongly heated, was first suggested by Mr. Baum; and it must be employed in every case in which this metal is refined. We cannot unite the parts of it by fusion with any heat that furnaces can give.
T h e I r o n -G o ld T h e o r y Although M acquer a n d Baum, as well as their predecessors Brownrigg, Scheffer a n d Lewis, were fully satisfied th a t p latinum was an individual metal, a contrary view suddenly becam e apparent i n France. In J u ly 1773, at the invitation of de M orveau, the great naturalist G e o rg e le Clerc, C o m te de Buffon, m ad e a visit to the Dijon Acadmie des Sciences, founded in 1740, to read a m em oir on p latin u m taken from his first su pplem ent volume to the Histoire Naturelle in which he included the findings of b o th de Milly and de M orveau to their great gratification (28).In the course of th is he m aintained : It is improper that chemists have regarded it as a new metal, perfect, individual and different from all the others . . . it is not believable that one may include in the
48
The Com te de B uffon
1 7 0 7 - 1 78H T h e fam ous naturalist G eorge Louis le Clere. Com te de B u ffon . a u th o r of the forty-four volum e "H isto ire N aturelle and S u p e rin te n d a n t of the J a r d in du Roi from 1739 as well as trea su re r of the A cadm ie des Sciences. claim ed in 1773 that platinum was not an individual m etal but merely a n a tu ral alloy of iron an d gold. Ilis great re p u tatio n persu a d e d the Com te de Mill y an d G u y to n de M orveau to sup port this vie but only lor a short lime
class of metals a substance that is neither ductile nor fusible ... It is not at all a new metal but a mixture, an alloy of iron and gold formed by nature. He went on to quote the work of the Comte de Milly, who had extracted some iron from native platinum and who also maintained that it was a natural alloy of iron and gold. Buffon further asserted that those who sold platinum were guilty of roguery. Now' Buffon, the Intendant of the Jardin du Roi, was most highly regarded for his researches in many subjects and for his massive Histoire Naturelle that eventually ran to forty-four volumes, and his views naturally carried a great deal of weight, although he was apt to indulge in rather hasty generalisations. During his visit to Dijon he presented a small quantity of native platinum to Guyton de Morveau and urged him to continue experiments and to seek a method of melting it, pointing out that a magnet would separate it into two parts, one con taining iron and the other gold. Guyton confirmed these observations and at first supported Buffons view. In the following July there appeared a letter from Professor Blondeau of the Naval Academy at Brest, (29) questioning both Buffons conclusions and de Millys reason for supporting them. Both Guyton and Milly began to have reservations, and the iron-gold theory was finally disposed of by Bergman in 1777.
49
T o r b e r n O lo f B e r g m a n
1735-1784 P rofessor of C hem istry in (he I Diver sity o f I p p s a l a f r o m 17 67 u n t i l h is d e a t h . B e r g m a n d e v e l o p e d m e t h o d s of q u a n tita tiv e analysis a n d w rote a t r e a t i s e o n c h e m i c a l a f fi n i t i e s . In 1777 h e p r e s e n t e d a p a p e r o n p l a t i n u m lo th e Sw edish A cadem y of Sciences, b e g i n n i n g by sa y i n g t h a t " w e still lack p r e c i s e i n f o r m a t i o n a b o u t m a n y of its l o n g e s t k n o w n p r o p e r t i e s " , b u t he d i s p o s e d o n c e a n d f o r all of B u f f o n 's view that platinum w a s not an indiv d u a l m e t a l
F ro m a p o r tr a it p a in te d by L o re n s P a s o h ih e \ o u n g e r in 1 7 7 8 in th e p o s s e s s io n o f ih e I im e rsitN o f I p p s a la
T h e W ork o f B ergm an T h e work of T o rbern Olof B e rgm an (1735-1784) took place considerably later th a n the work already recorded in this chapter, but is related to this earlier work in th at it provides a summ ing u p a n d clarification of w hat went before. As we travel on in the study of the history of platin u m it will be found th a t on several occasions, after a certain a m o u n t of sporadic work has been carried out, there has come along a major scientific m ind which has taken up the scattered results an d co-ordinated an d completed th em : Bergm an was the first of these; he was followed in the eighteen-thirties b y Berzelius, curiously enough an o th er Swede, in the eighteen-fifties by the F r e n c h m e n Deville a n d Debray; so Bergman, although he did not publish until late r definitely belongs to this chapter. In 1777 he presented a p a p e r to the Swedish Academy. This was subse quently printed in Latin in 1779 i n B e rgm ans collected O p u s c u la , in French in 1780, and in English in 1784 (30). Bergm an ha d obtained a quantity of platinum through his friend C la u d e Alstrom er the botanist, who ha d spent some time in Spain on the suggestion o f Linnaeus and who was the son of the founder of the Swedish Academy of Sciences. T h e re had been some doubt am ong the ealier investigators as to w hether mineral fixed alkali (soda) p recipitated p latin u m from its solution in a q u a regia or not. Bergman showed that while potash a n d am m onia, even in small quantities, gave a precipitate w ith the acid solution, soda gave it only when present in large quantities th ro u g h neutralisation of all the free acid present or by direct addition. He noted that lime also precipitated platin u m from its solu tion but did not realise that this reaction requires the influence of daylight and
50
takes place only very slowly, if at all, in the dark. He examined the precipitate produced by sal-ammoniac in a platinum solution and thought it to be a triple salt containing the constituents of sal-ammoniac as well as platinum, an observation which is quite correct. He noted that the crystalline precipitates obtained by adding to the acid solution small quantities of potassium or ammonium carbonates were red if the solution was strong and yellow if it was very dilute, an observation that remained unexplained for twenty-five years until iridium had been discovered. He also experimented on the melting of platinum and found that the sal-ammoniac precipitate appeared to be more easily melted than the native metal.
Platinum a Distinct Metal The concluding part of Bergmans paper dealt with the question of whether platinum was in fact a distinct metal. Here he declared against Buffons ideas and demolished his argument once and for all by both experiment and deduc tion: Since platina surpasses all metals except gold in weight, and is always found to be contaminated by iron, some scientists have believed that it could not be freed from this, that platina is nothing but a mixture of gold and iron. However, Dr. Lewis has, for several reasons, rejected this opinion. By melting together gold and iron, in whatever proportion, no such alloy is obtained which in specific gravity or other properties resembles platina in the least. Furthermore the amount of iron in the natural platina can be so reduced that it becomes hardly detectable. We do not know of any native metals that are found entirely pure. . . . When we add to this the fact that the last traces of a foreign contaminant are infinitely difficult to remove, because they are the smallest part making up the whole mass, so it is not strange if iron adheres to platina in this most obstinate manner, and rather that the difficulty in melting of platina has up to now put a special obstacle to their separation. In a final paragraph Bergman expressed his view that it was a great pity that more platinum was not available in Europe so that it could be melted in some quantity, and that in the supplies of metal that do arrive there are many impurities that must be sought for with great attention to separate them all. Bergmans work on classification and nomenclature is well known. He con tinued to make use of many of the old alchemical symbols and added new ones, including one for platinum, as illustrated here, combining the old symbols for
B ergm an co n tin u ed In use alchem ical sym bols for the ele m e n ts an d he d o i s e d one for the new m etal p la tin u m , based up on a c om bin atio n of those for gold an d silver. He also p ro posed the n a m e platin u m instead of the word platin a used up to that tim e
51
gold an d silver. He also proposed the use of the na m e p la tin u m instead of the older p la tin a in line with a n u m b e r of other metals for which he had adopted the Latin ending urn .
C o n c lu s io n From among the results of all this adm irable work conducted in five countries, most of it in quite a short p eriod of years, several facts emerged that were to prove of great im portance in paving the way tow ards the ultim ate fabrication of p latinum into sheet a n d wire. T h e s e were : ( 1 ) T h a t platinum , as M a c q u e r put it, was a particular metal as fixed, indestructible and una lte ra b le as gold and silver, different from all other known metals. (2) Lewis discovery of the p recipitation of p latin u m from solution by salammoniac, which effected its separation from iron a n d gold. (3) Scheffers observation that th e addition of a small am o u n t of arsenic to a m uch larger quantity of p la tin u m brought about the complete fusion of the latter at a comparatively low tem perature. (4) T he discovery by M a rg g ra f th a t the precipitate obtained from a p latinum solution by means of a m m o n iu m chloride w hen heated reverted to metal. Also th at the metal was th ro w n out of solution by metallic zinc. (5) T h e observation by several people, but more especially studied by M acquer and Baum, that the grains of native p latin u m a n d the sponge produced by the ignition of the a m m o n iu m chloride precipitate, agglutinated or sintered to g ether w hen exposed to the highest possible tem perature. (6) T he discovery, first by M a c q u e r a n d Baum and afterwards by Bergman, that platinum could be su b m itte d to at least partial fusion an d was then non-magnetic and malleable. (7) T he suggestion by Baum th a t p latinum might be consolidated by heat and percussion. As will be seen from later chapters, all the essentials necessary for the advances towards fabrication were present in these seven points.
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References for C hapter 3

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 D. M c D o n a ld , Platinum M e ta ls Rev., 1965, 9, 20 25 M r . R o b e r t B a rk e r, p r iv a te c o m m u n ic a ti o n , A u g u s t 1981 W . W a ts o n , Phil. Trans., 1749-50, 46, 584596 ( T h e p a g i n a t i o n of th e se c o n t r i b u tions is g re a tly in erro r) L. B. H u n t, Platinum M e ta ls Rev., 1962, 6, 2 8 -3 0 J . R u ssell-W o o d . Platinum M eta ls Rev., 1961, 5. 6 6 - 6 9 ; A n n . Science, 1950, 7, 199-202 W . W a ts o n . T w o letters to Bose, Physikalische Belustigungen, 1751, (1), 107108; (4), 2 8 5 -2 87 A. F. F o u rc ro y , S y s t m e des C o n n a is s a n c e s C h i m iq u e s , P aris, 1800, 6, 4 0 2 - 4 0 3 L. B. H u n t, P latinum M e ta ls Rev., 1980, 24, 3 1 - 3 9 H . T . Scheffer, K ungl. V etensk.A kad. H andl., 1752, 13, 2 6 9 - 2 7 5 H. T . Scheffer, ibid., 1752, 13, 2 7 6 -2 7 8 A. F. C r o n s te d t, A m innelse-tal fver Framledne Directeuren Och K ongl, Vetensk. Acad. Ledamot, Valborne H err H en n e Theoph. Scheffer, S to c k h o lm , 1760 F. W. G ibbs, A n n . Science, 1952, 8. 122 151; P latinum M e ta ls Rev., 1963, 7, 6 6 - 6 9 W. Lewis, Phil. Trans., 1755, 48, 6 3 8 -6 8 9 W . Lewis, C o m m e r c i u m P h ilo s o p h ic o -T e c h n ic u m , L o n d o n , 1763 W. Brow nrigg, L e tte r to W . W a ts o n , R o y a l S ociety A rchives 1754, II, 547 C. S. S m ith , in P o w d e r M e ta llu rg y , ed. J. Wolff, C lev e lan d , 1942, 66 W. Lewis, P h il Trans., 1757, 50, 148-166 W . Bowles, D is e rta c i n so b re la p la tin a , I n tr o d u c c i n a la H i s t o r i a N a t u r a l y d e la G eografa fsica d e E s p a a , M a d r i d , 1775, 155167 A. S. M a rg g r a f , N ouvelle M e m . Acad. Roy. Sei., Berlin, 1757, 3 1 - 6 0 ; C h e m is c h e Schrifter, Berlin, 1768, 1, 1 42 J . Oeconomique, 1751, M a y , 9 3 -9 4 J . Oeconomique, 1755, J u ly , 148-149 D ela la n d e, J . des Savans, 1758, J a n u a r y , 46 59 M o rin , La P latin e, l O r Blanc o u le H u iti m e M e ta l, Paris, 1758 P. J. M a c q u e r , M e m . Acad. Roy. Sei. P ans, 1758, 119-133 P. J. M a c q u e r , D ic tio n n a ire de C h im ie , Paris, 1766, 2, 2 4 8 -2 6 3 A. B aum e, C h y m ie E x p r im e n ta le et R a iso n n e , P aris, 1773, 3, 193 J . Black, P l a t i n u m o r P la tin a , L e c tu r e s o n th e E l e m e n t s o f C h e m is t r y , ed. J . R obison, P h ila d e lp h ia , 1806, 3, 3 8 8 -3 9 5 G. L. Buffon. Obsns. Physique ( R ozier), 1774, 3, 3 2 4 - 3 2 8 ; H isto ire N a tu r e lle , Paris, 1774, S uppl. L 3 0 1 -339 L. Blondeau, O bsns. Physique (R o zier), M I A . 4, 154 T . O. B e rg m an , K ungl. Vetensk. A ka d . H andl., 1777, 3 8, 3 1 7 - 3 2 8 ; Opuse. Phys. C h em , 1779, 2, 166-183 (in L a t in ) ; Obs. sur la I^hysique, 1780, XV. 38 45; P hysical a n d C h e m ic a l Essays, trans. E d m u n d C u llen , L o n d o n , 1784, 166-183
53
Louis B e rn a rd G u v lo n de M orveau 1737-1816
Horn in Dijon, (hen (he c a p i(a l of th e P ro v in ce of B u rg u n d y . G u y to n firs( entered the legal pro fessio n and then be ca m e a m e m b e r of (lie Dijon p a rlia m e n t, a dding to his n a m e de M o rv e au from a family estate. H e later tu rn e d to c h em istry a n d is chiefly re m e m b e re d for his collaboration with L avo isier in m odernisin g chem ical n o m e n c la tu re but his work on platin u m , c o n tin u e d over m an y years, was of m ajor im portance in establishing its p ro p e rties an d m ethod s fo r its fabrication
4
Early Attempts to Melt and Work Platinum
A n d w e r e th e p r o p e r t i e s o f p l a t in u m m o r e f u l l y in v e s tig a te d m e t h o d s f o r w o r k in g it e a s ily into u ten sils m ig h t b e d is c o v e r e d , a n d th en it m ig h t j u s t l y b e c o n s id e r e d as o n e o f th e m o st u s efu l o f the m e ta llic su bsta n ce s.
JO SE PH BLACK
After the experiments of a n u m ber of scientists described in the last ch a p te r to establish the striking properties of p latinum their thoughts began to turn towards making use of them, but before this could be done it was necessary for the granular native metal to be converted into malleable sheet. T he great difficulty in the way of achieving this was the presence of the iron an d copper which were intimately alloyed with the p latin u m in the grains of the native metal. M ost of the early workers m ade some a tte m p t to melt these grains and found that under ordinary conditions they did nothing more th an agglutinate more or less loosely together, a full fusion being prevented by the for m ation of surface films of iron an d copper oxide at the high tem perature at which the attem pts were conducted. It was necessary to remove the iron before advantage could be taken of the power of self-welding at high tem peratures that the metal seemed to possess, and this was the task before the workers of the seventeen seventies. As we have seen, Baume was the first to dem onstrate th at p latinum could be welded when forged at a high tem perature, after the removal of the iron and copper, which he brought about by cupelling the native metal with lead or bism uth at a very high tem perature (1). Following Wood, Brownrigg, Lewis and others, he confirmed their observations that this process was never complete under the conditions usual at that time, the p latinum rem aining as a solid mass retaining a certain am ount of the added base metal. T h e quantity of the latter left depends on the tem perature available, an d if the applied heat is very strong and long continued, the am ount can be reduced to nothing. This no doubt explains the differing results obtained by the earlier experimenters. Lewis for instance failed to drive off all his lead because his furnace was not hot enough,
55
but in spite of this he was the first to notice that the p roduct could be forged. M acquer a n d Baum carried o u t the cupellation in a furnace at the Svres porcelain works where a very high tem perature was available, with a result that the lead or bism uth that they a d d e d was entirely removed a n d the p latinum left behind was found to have lost a sixteenth of its weight a n d to have become reasonably malleable (2). It was shown chemically to be free from base metals and it was this metal that B a u m was able to weld by forging. T here is no evidence that he went on to a p p ly the discovery to practical uses an d this is not surprising. T h e product was a half-fused lump, full of cavities. Guyton de Morveau (1737-1816), who h a d had the honour of collaborating with Buffon - a m an already fam ous an d thirty years his senior - in the p re p a ra tion of the la tte rs Histoire N aturelle des M in r a u x an d h a d been urged by him to find a m ethod of m elting some p latin u m that he provided, examined B a u m s process a n d found that th e mass could be broken up into pow der and that it still contained iron; it w a s weakly m agnetic a n d actually yielded iron w hen fused with nitre an d heated w ith sulphuric acid (3). So B aum s process, valuable though it was in its indication of welding power, led no further an d the th o u g h ts of the scientists tu rn e d to the iron-free metal produced by calcining the precipitate obtained by adding a m m o n iu m or potassium chloride to the solution of native platin u m in a q u a regia, to see w hether this could be welded m o re satisfactorily. Before we tu rn to further a tte m p ts at the melting of p latin u m we m ust therefore consider these early exam ples of pow der metallurgy.
T h e In tr o d u ctio n o f P o w d e r M e t a llu r g y b y d e l Isle A part from the rudim entary exam ples of the use of pow der m etallurgy by the natives of Colombia, described in C h a p te r 1, the first to achieve success in this direction on any scale was Nicholas A nne de 1Isle (1723-1780). (T he nam e is used in several spellings such as Delisle a n d de Lisle). Little is know n of him or of his interest in scientific m atters except th at he was interested in mineralogy and that he formed a n im portant collection of minerals. In the first edition of this book he was referred to, following several earlier authorities, as the distinguished crystallographer a n d m ineralogist J e a n Baptiste Louis de R om de l Isle, but later this identification was queried by Dr. W. A. Sm eaton in a review of G uyton de M orveaus work on platin u m (4) a n d further investigation by the original a uthor confirmed this a n d show ed that the m a n of the sam e na m e to w hom the credit is due was the one already m entioned. (5) (This confusion arose of course from the regrettable French ha b it of not giving initials to the authors of papers.) This de l lsle served with the R o y a l M usketeers from 1739 to 1743 a n d was then transferred to the supply service of the French armies, serving in Germany, Flanders, Italy, M inorca an d Corsica until 1769. He was th en brought back to the D partem ent de la G uerre in Paris and, with the rank of prem ier co m m is, took charge of supplies for the troops in Corsica, retiring in 1776.
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It was in the August of 1775 th at Lavoisier announced to the Acadmie des Sciences that
M. Delisle, p r e m i e r c o m m is d u b u r e a u d e la g u erre, avait tr o u v u n m o y e n trs sim p le de fon dre le pla tin e , il a r p t ses e x p e rien c es avec b e a u c o u p de succs e t q u il a o b te n u u n m ta l b la n c , tr e s - d u r , et u n p e u m a l l e a b l e (6)
De l Isle was fully conscious of the need to remove the sands a n d the alloyed iron from the platinum before working it and he set about achieving this by dissolving in a q u a regia a n d precipitating with sal-am m oniac. M ore details of his procedure were given by the mineralogist a n d assayer B althasar Georges Sage (1740-1824), the founder of the Ecole des M ines, in his Elm ents de M inralogie published in Paris 1777 :
S a l- a m m o n ia c dissolved in th e cold in d istilled w a t e r is p o u r e d in to a s o lu tio n of p l a tin u m m a d e by a q u a regia; th e re is a r e d d is h p r e c i p i t a t e c o m p o s e d of p l a t i n u m a n d s a l-a m m o n ia c ; . . . this p r e c ip ita te of p la t i n u m , e x p o s e d to a violent fire, m elts a n d p ro d u c e s a b u t t o n of m a lle a b le p l a t i n u m of a w h itis h -g r e y c o lo u r r e s e m b lin g t h a t of silver, a n d w h ic h does not a lte r in th e air. (7)
De llsle discussed his procedure freely am ong his contem poraries, to w hom he distributed a n um ber of his small discs of u ndoubtedly malleable platinum , but there is no evidence that he fabricated any articles from his p roduct or worked on any scale but a laboratory one. There is however, one other reference to this work that should be quoted, curiously from the other de 1Isle, who was the a u th o r of a four-volume treatise on crystallography published in Paris in 1783, after the death of Nicholas Anne de l lsle. In a footnote (8) he wrote:
M. de Buffon h a s su g g e ste d t h a t p la tin a m a y b e o n ly a fe rru g in o u s s u b s t a n c e m o r e d en s e a n d of h ig h e r specific gravity t h a n o r d in a r y iron, in ti m a t e ly c o m b in e d w ith a la rg e q u a n t i t y of gold. But w h a t d em o lish e s this th e o ry is t h e fact t h a t I possess a b u t t o n of p la tin a m e lte d b y t h e la te M . d e l lsle a n d several l a m in a e of this s a m e p la tin a f latten e d u n d e r th e h a m m e r , w h ic h h a v e not th e slig h test a c tio n o n t h e m a g netic needle; w h ic h proves t h a t all th e ir o n w h ic h o c c u rs in te r p o s e d in p la tin a w h e n it is in grain s c a n b e s e p a r a te d from it b y m e a n s of s a l - a m m o n i a c as e m p lo y e d b y M . de l l s l e . . . .
O th e r scientists, including Guyton de Morveau, the Count von Sickingen and the Comte de Milly, as recorded below, carried his work further a n d con solidated his findings, but clearly it is to this rath e r mysterious M. de 1Isle that the honour belongs of being the first to devise a process th at still forms the basis of m odern platinum refining.
T h e R esearch es o f G u y to n d e M o r v e a u Before com m unicating de l lsle s work to the Acadmie des Sciences, Lavoisier wrote to G uyton de M orveau in Dijon not only describing the new m ethod but reporting that he had himself repeated the experiment. H e had treated the
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S U R t' HI ST. N A T U R E L L E E T L E S
ARTS.
i < h
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BU FFO N ,
Sur U fujtciliti , lu maniabilit , le magntifme , la cnfitc , la cryjlallifation de la platine , & fo n alliage avec l'acier.
T h e o p e n i n g o f t h e long l e t t e r f r o m G u y t o n d e M o r \ e a u to t h e C o m t e d e B u f f o n in 1775 r e p o r t in g h is e x p e r i m e n t s o n t h e properties of platinum , its fusibility. m alleability. mag netism and d en sity . The p ractical ap p licatio n s of c h em istry alw ays interested G u y t o n a n d in t h e l e t t e r he concluded: " I f p l a t i n u m o n e day b e c o m e m o r e c o m m o n , as o n e w o u ld h o p e a n d d e s i r e . I d o not d o u b t t h a t t h e A r t s will d e r iv e so m e fru its fro m these re se a rc h e s ; a b o v e all th e \ will o w e a n o b l i g a t i o n to M. D elis le f o r it is h e w h o e s t a b l i s h e d by his m e t h o d t h a t it is s u s c e p t i b l e o f b e i n g w o r k e d by t h e h a m m e r , by t h e file a n d by c u t t i n g to o l s
, tour ce que vous m iniez prend une nouvelle face, 6c produit un nouvel intrt. Votre Mmoire fur la Platine a veill les Phyficiens Sc les Chymiftes : ils ont port leurs recherches fur cette matire il finguiire , li digne detre obferve , 8c vous avez fans doute oui parler du procd qui a t dcouvert depuis peu par M . Delifle pour la fondre : ce que jen ai appris , & ouil a bien voulu me confirmer lui - m m e, m a engag profiter de quelques momens de loifir pour rpter fes expriences , 8c reprendre celles que javois nglig de pourfuivre depuis plus d un an ; jai recom menc traiter ce minral dont t grce i votre gnront , il me reftoit encore une aflez grande q u antit; 6c je m e perfuade que vous verrez avec plaifir le rcit exalk de tous les phnomnes curieux & intrefans que m'a prfent ce nouveau travail , quoiquil ne foirpas encore pollible de tous les concilier. La premire nouvelle de la dcouverte de M . Deliile m avoit t donne par M. Lavoifier, 8c ce favant mav o it crit qu'il en avoit fait lpreuve avec fuccs ; quayant diiTous la platine dans leau rgale , l'ayant enfuite prcipite par une diftolution trs-concentre de Tel ammoniac , ce prcipit trait avec m on fiux rducVif , lui avoit donn au bout dune neure, un beau bouton fufceptible de fe p o lir, de fe lim er, mais non pas m allable; (le flux dont parle ainl M. Lavoificr , cft celui que jai publi , comme devant rem placer minemment le procd fccret de M . Bouchu pour leflai des mines de fer). M. Delifle mavoit marqu poftrieurcment , quil n'avoit employ aucun fondant , quil avoit Amplement traire fa platine dans un double creufet de h elle au feu d'une forge anime >ar le vent de deux Courtiers , 8c quil avoit eu un bouton rrcs-bien i , brillant , qui setoit laiffe piler 8c lim e r, & de plus , fuffifamment mallable i les deux petites plaques q u il avoit joint fa let* crc en fourntllbient la preuve la plus complette.
precipitate with a flux and h a d obtained a beautiful b u tto n of p latin u m that could be filed and polished b u t w a s not malleable. A little later de 1Isle himself wrote to G uyton to say that:
H e h a d not e m p lo y e d a n y flux, t h a t he h a d sim p ly t r e a t e d his p l a t i n u m in a d o u b le H e ss ia n cru c ib le in th e fire of a forge a n i m a t e d b y th e w in d of tw o blow ers, a n d th a t he o b ta in e d a very c o m p a c t a n d b rillia n t b u t t o n w h ic h c o u ld b e flattene d a n d filed, a n d m o reover w as r e a s o n a b l y m a lle a b le ; th e tw o little p la te s w h ic h he en closed w ith his letter fu rn ish a m o s t c o m p le t e p r o o f of t h i s . (9)
These two letters prom pted G u y to n de M orveau to set about reproducing the m ethod as it clearly represented a great improvement on the Baum e cupellation procedure. He first investigated the difference that Lavoiser ha d found by the use of a flux in the heat tre a tm e n t stage an d found th at reducing fluxes (glass, borax and charcoal) never yielded a malleable metal, but th at with them there was frequently real fusion into beads (no doubt due to the reduction of
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small am ounts of phosphorus, silicon, etc., from the fluxes an d charcoal ash which lowered the melting point of the p latinum a n d at the same tim e destroyed its malleability). But w hen the sal-am m oniac precipitate was sufficiently heated in a crucible entirely by itself, as originally recom m ended by de 1Isle, a better result was obtained. T h e volume of the m aterial was considerably reduced and the red precipitate changed into a piece of grey metal looking rath e r like badly m elted silver, rough a n d g ranular in structure. He reported his results to Buffon in a long letter published in Observations sur la Physique for July 1775 (9), reporting am ong other findings that: there was no trace of the salts with which the platinum was combined in the pre cipitate; the crucible was clean, and instead of the least adherence, the metallic matter appeared only to have taken the shape of the vessel; 1judged by this first ins pection that the platinum had simply been regenerated but that it had not undergone complete fusion, no doubt because the fire had not been lively enough or continued long enough: but what was my surprise when having put this material on the anvil, I saw it flatten almost as easily as silver, and the file and the knife make an impression on it in the same way; moreover, the magnet has no longer any influence on the pieces which I detached from it, any more than on those which M. de 1Isle had sent me. A determ ination of the specific gravity of the m aterial showed that before forging it was only 10.045 whereas in the fully ham m e re d state it ha d become 20.170. It was evident therefore th a t the product of the heat tre a tm e n t was not fully consolidated and required the subsequent forging to complete the process. M a cquer was under no illusion as to w hat had really h a p pened in de l lsle s process and in his Dictionary of Chem istry (10) he makes this statem ent: It is M. de 1I lie (sic) who has made this discovery and I have verified it. The experi ment consists in exposing to a good ordinary forge or furnace fire platina precipitated by sal-ammoniac from its solution in aqua regia. This precipitate appears to melt just as easily as an ordinary metal, into a metallic mass quite compact and dense, but it completely lacks malleability, when it has only been exposed to a moderate heat, and only assumes it, although always imperfectly, when subsequently subjected to a much greater degree of heat. Particles of platina being infinitely divided in the precipitate, it is not surprising that the heat penetrates such very small molecules much more effectively than the ordinary grains of platina which in comparison are of enormous size; and their softening occurring in proportion, they should show the extraordinary effect on their agglutination in the proportion of their points of contact; moreover, these points being infinitely more numerous than can be those of much greater molecules, solid masses result which have all the appearance of quite dense metal, melted and solidified by cooling, but they are really nothing but the result of a simple agglutination among an infinite number of infinitely small particles and not that of a perfect fusion as with other metals. This looks like the first scientific contribution to the study of powder metallurgy. In the course of his research de M orveau not only tried the effect on the precipitate of straight reducing fluxes b u t also of a flux containing arsenic on native platinum. H e reported to Buffon (9):
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I p u t into a cru c ib le a m i x t u r e of 1 g ros (72 g r a in s ) of c r u d e p l a t i n u m , 2 gros of p o w d e r e d n e u tra l arse n ica l salt, 1 g ro s of c h a r c o a l d u s t a n d 2 gros of th e d u s t of b o n e c h a r c o a l b u r n e d in closed vessels, th e w h o le co vered w ith 2 gros of p o w d e r e d w hite glass.
He subjected this to the greatest heat th a t could be got from a special blast furnace designed by M acquer, a n d found, un d e r a clear green slag, three well shaped white metallic buttons, weighing in all 74 grains. These buttons were brittle but not appreciably magnetic, so that the iron h a d been removed but evidently the metallic earth contained in the neutral arsenical salt has been revivified in contact with the carbonaceous m atte r and alloyed with the p la tin u m . This observation ha d im portant results, to be described in the next chapter. Guyton also pointed out that the m ore m alleable the metal the less it was a ttrac ted by the magnet, but he w a s still unable to agree with the m ajority of his contem poraries that the m agnetism of some samples was due to impurities.
T h e W ork o f C o u n t K arl v o n S ick in g en At m uch the same time that de 1Isle was perfecting his pow der metallurgy process in Paris, another worker was busily engaged in a ttem pts to produce m alleable platinum by the a q u a regia m ethod. This was the G raf Karl von Sickingen who held the post of A m b a s s a d o r of the G e r m a n Princedom of the Palatinate at the court of Louis X V . His long series of experiments, no less than ninety-seven are recorded, carried out in his private laboratory sometimes with the help of distinguished friends including the statesm an T u rg o t a n d the Duc de la Rochefoucauld d Enville, both active p atrons of the sciences, suffered many interruptions because of his diplom atic duties a n d although begun in 1772 they were not reported to the A cadm ie des Sciences until 1778. H is two extremely lengthy memoirs were not, however, published by the A cadm ie and although m any of Sickingens contem poraries were aw are of his work it was not until 1782 th at Professor Georg Suckow of Heidelberg, anxious th a t Sickingens valuable work should be presented in his native G erm an, m ade a translation available under the title Versuche ber d ie P la tin a ( 11). A t the same tim e Lorenz Crell, the well known editor and publisher, included both a sum m ary of the work and a review of Suckows translation in his Neueste Entdeckungen in der Chemie (12). F urther publication of Sickingens work was m ade by J a n Ingen-housz, of whom m ore will be said later, in both G e r m a n an d French (13). For a full study of these findings reference should b e m ade to these original sources, as num erous m isinterpretations a n d errors have crept into later text-book summaries. This is not altogether surprising, as th e C o u n ts description of his work is highly involved a n d detailed and only his essential findings can be sum m arised here. He was fully conscious of the need to remove the sand from the native m ineral by dissolving in a q u a regia, and also of the need to get rid of the alloyed iron that went into solution. H e effected th is by adding a solution of blutlauge, of which
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T h e C o u n t K a r l H e in r ic h von S ie k in g e n 1737-1791
T h e last d e s c e n d a n t o f a long l i n e o f n o b l e m e n , a n d t h e so n o f a n a l c h e m i s t , the C ount von Sickingen c a rrie d out a lo n g s e ri e s o f e x p e r i m e n t s on p l a t i n u m in his l a b o r a t o r y in P a r i s w h i l e s e r v i n g as A m b a s s a d o r of t h e P a l a t i n a t e to th e f r e n c h c o u r t . S e v e r a l of his d i s t i n g u i s h e d f r i e n d s as siste d h i m f r o m ti m e to ti m e , i n c l u d i n g t h e s t a t e s m a n T u r g o t , t h e D u c d e la R o c h e f o u c a u l d d 'E n v i l l e . a n d E tie n n e \lig n o t de M ontigny, the P resident of th e A cad m ie des S ciences and a collaborator also of L a v o i s i e r 's . A l t h o u g h his p r o c e d u r e w a s d if fic u lt a n d e x p e n s i v e h e w a s t h e first to p r o d u c e p l a t i n u m in t h e f o r m o f w ir e a n d sh e e t
F ro m a p ortrait hy Jo h a n n G e r h a r d Ihu-k. by courtesy of the k urp falzisch e s M use u m . H e id e lb e rp
the active constituent was potassium ferrocyanide. T his first precipitated the iron as Prussian blue but afterwards began to precipitate the p latinum also as potassium chloroplatinate. He filtered at this stage a n d then precipitated m ost of the rest of his platinum from solution by a considerable addition of oil of tartar (deliquesced potassium tartra te or, in the original G erm an, zerfiossenes Weinsteinsalz. ) T h u s von Sickingen used potassium salts as his prcipitants rather than am m onium chloride. From this metal he w as able to produce platinum in the form of sheet, an d according to one of his contem poraries, the author a n d traveller Georg Forster, he possessed a piece of platin u m sheet more th an one foot square that looked like silver a n d was quite p liable (14). T he red precipitate of potassium chloroplatinate so obtained was filtered off, placed in a crucible a n d subjected to a white heat until all the potassium chloride and other fumes h a d disappeared. T h e re was left behind
a kin d of m etallic flake of a silver-w hite c o lo u r w h ic h w h e n h e a t e d to a w h ite h e a t welds u n d e r th e h a m m e r a n d c a n b e forged. I n th is s ta te th e p l a t i n u m is perfectly ductile a n d lends itself to a lm o st all th e o p e r a tio n s of t h e a rts a n d does n o t se em to act noticeably o n th e m a g n e tic n e e d le .
Von Sickingen found it necessary for the best results to forge a n d alternately heat the metal to the highest possible tem perature, a n d the forging took place on
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S ick in g en s two long m m oires on platin u m read to the A cadm ie des Sciences in 1778 w ere never p rin ted , but fo u r years later P ro fessor G eorg A do lp h Suckow of the University of H eidelb erg , feeling that this im p o rtan t w ork sho uld be m a d e available in Sickingen's own language, pu blished a G e rm a n tran slatio n of w hich this is the title page. L orenz Crell also published m uch of the work in his Neueste Entdeckungen in der Chemie, and in intro ducin g the a u th o r he wrote: so fa r in this nation we have but rarely had an ex am p le of a m an of noble birth , great fortun e a n d high office who could find in chem ical re sea rch es as d e lig h tfu l an e n te rta in m e n t as in the usual brilliant pastim es of the great w o rld
a well-polished piece of steel. O n one occasion the temperatures were so high that the inside of his furnace melted down. His early work was on four ounces of native platinum which he had been given by the Baron Holbach, but Lavoisier was so interested in the results that he presented him with a further eight ounces. Working with this larger amount he found it profitable to calcine his precipitate to metal before putting it into the crucible for the heat treatment. This enabled him to produce a little ingot which he was able to draw into wire through all the holes of a drawing machine, whose least hole had the diameter of 19/140ths of a ligne (0.0125 inch). This was undoubtedly the first occasion on which platinum had successfully been drawn into wire.
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T h e resis tan c e of th e p l a t i n a to this t r e a t m e n t d id n o t se em to b e a n y g r e a te r t h a n t h a t of gold, w h ic h b e c a m e like gold m o r e b r ittle u n d e r th e d r a w i n g a n d h a d to be a n n e a l e d m o re often th e s m a lle r a n d m o r e fragile th e w ire b e c a m e . It is well k n o w n t h a t all m etals, w i t h very few exceptions, b e h a v e in this w ay . . . . O n e p ie ce of p l a t i n a w ire b ro k e for th e first tim e in d ie 54 w h o se d i a m e t e r w a s h a lf a lig n e ( 0 .0 4 0 inch).
But it was noticed th at the fracture ha d occurred at a place where the b a r had not been completely welded. Discussing this, von Sickingen points out how necessary it is in the case of iron that the pieces being welded m ust hold the heat as long as they are being forged. W ith p latinum the pieces h andled were so small that this was impossible a n d hence the dangers of imperfect welding were con siderable. In spite of this von Sickingen carried on with the draw ing of wires down to about 1/ 16th of a ligne (0.0055 inch) and found that this wire could be rolled thin without any tendency to break. Later he worked on eight pounds of native platina a n d with this large am ount he found it necessary to boil his calcined p latinum with distilled water to remove residues of chloride before welding. From one six ounce lot he obtained a n ingot weighing over 3{ ounces which was completely without cracks. It is interesting that after dissolving these considerable quantities of platinum he collected together the insoluble m atter an d atte m p te d to melt it under borax. He obtained a rough unm elted mass but was prevented by a journey from examining this, otherwise he m ight have anticipated the discovery of iridium by thirty years. Unwittingly, however, von Sickingen was the first m an to produce platinum comparatively free from iridium. By the addition of potassium ferrocyanide, a strong reducing agent, to his original p latin u m solu tion, he brought about the reduction of the iridic salts present to the iridous state and so prevented their precipitation by the potassium salts. Hence his platinum contained less iridium th a n that of any of his predecessors an d this accounts for the fact that he was able to draw it down to such fine dimensions, a feat not repeated by his successors for m any years. He remained, however, modestly uncertain of the im portance of his work. In a letter to Crell in 1782 he w r o te :
As p l a t i n u m b y itself is infusible a n d not d uctile, b u t b e c o m e s so w h e n tr e a te d w ith acids, is a s tr a n g e p h e n o m e n o n as you r e m a rk . I d o not p u r s u e th is p o in t in my work b e c a u s e I a m no friend of h y p o th e s e s a n d find no g r o u n d for th e m h e r e . (15)
Nicolas C hristiern d e T h y , C om te d e M illy

Another Paris aristocratic figure who becam e deeply interested in p latinum at this time was the Com te de Milly. He had served in the arm y as colonel com m andant of the dragoons but after the battle of M in d e n in 1759 resigned his commission and entered the service of the D uke of W rttem berg, returning to Paris at the conclusion of the Seven Y ears W a r in 1763. H ere he took up the study of chemistry, equipping a laboratory at Chaillot, a n d like m any of his con temporaries becam e involved with the newly created porcelain industry as well
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N ic o la s C h r i s t i e r n d e T h y , C o m te de \1 illy 1728-1784
A f te r a d i s t i n g u i s h e d c a r e e r in t h e F r e n c h a r m y a n d t h e n in t h e se r v i c e of the D u k e of W r tte m b e r g , the C om te d e Mill) r e t u r n e d to P a r i s in 17 63 a n d took u p t h e s t u d y of c h e m i s t r y , b e c o m ing e s p e c ia lly i n t e r e s t e d in p l a t i n u m . F o r a t i m e h e s u p p o r t e d B u f f o n 's view t h a t t h i s w as a n allo y of ir o n a n d g old , b u t t h e n c a r r i e d o u t his ow n i n v e s t i g a tio n s in c o n t i n u a t i o n o f t h e w o r k o f d e I 'l s l e a n d C o u n t S i c k i n g e n o n t h e a m m o n i u m c h l o r i d e p r e c i p i t a t e . H is w o r k w as no t p u b l i s h e d in F r a n c e , b u t in 17 78 h e c o m m u n i c a t e d his r e s u l t s to t h e s c i e n t is t s o f S p a i n , w ith i m p o r t a n t c o n s e q u e n c e s in t h a t c o u n t r y
as with platinum, a supply of w h ic h he h a d obtained from the Spanish Govern ment. For a time, as we have seen, h e supported Buffon in his view th at this con sisted merely of an alloy of iron a n d gold, b u t the work of de 1Isle convinced him that this theory was untenable, a n d he th e n set about some investigations of his own in c ontinuation of that work as well as th at of the Count von Sickingen with a view to simplifying the la tte rs procedure. As with de 1 Isles a n d S ickingens m emoires to the Acadmie des Sciences, no account of M illys paper was printed, but it is possible to establish the approxim ate date as sometime before 1778 from other sources. In a paper on the assaying of p latinum -gold alloys read to the Acadmie in N ovem ber 1778 (16) M athieu Tillet (1714-1791), the Royal Com m issioner for Assays and Refining at the Paris M in t, m entioned that : I h a d r e a d this m e m o ire to t h e A c a d e m y w h e n M . le C o m te d e M illy gave m e a piece of ductile p l a tin u m w h ic h he h a d o b ta in e d b y his e x p e r im e n t s o n th is m e ta l a n d w h ic h he h a d use d successfully for v a r i o u s a rticle s of je w e lle ry . In another reference in the sam e pa p e r Tillet says that
P la tin u m , w h e th e r forged or in its n a t u r a l state, m a y b e r e n d e r e d d u c tile by th e processes w h ic h M . le C o m te de S ic k in g e n h a s m a d e k n o w n , a n d by th o s e w h ic h M . le C o m t e de M illy is to p u blish.
T his last reference to publication b y Milly was the cause of a somew hat acid note by Sickingen in the preface to his Versuche iiber die P la tin a . After
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writing that some of his contem poraries who were aware of his work did not hesitate to claim a share in the discovery he continued: The Count de Milly, following an early discovery of the two excellent refiners, Lewis and Baume, that sal-ammoniac precipitates platinum out of its solution, made use of this information and adapted it to the method given in this present work, obtaining after calcination a workable and ductile platinum. He immediately sent a description of the process to the Spanish Academy of Sciences. There has not yet been sufficient experience to enable one to say whether this method of freeing platinum from its iron is as good as the one here described, the author doubts it but only experience can decide. No record has been found of a com m unication from Milly to any Spanish academy of the time, but no doubt he felt un d e r a c ertain obligation to report his results at an early stage to the country th a t had given him his raw material. At all events his action prom pted the chemists of Spain to undertake some highly successful work, to be described in C h a p te r 6. Fortunately we have virtually a first-hand account of M illys procedure given by a rather curious individual who acted as a n effective correspondent a n d gobetween among the scientists of his time throughout Europe. This was Joao Jacin to de M agelhaens (1722 1790), m ore generally known as M agellan, a Portuguese who h a d devoted himself to science after an early career as a monk a nd who was friendly, among others, with Priestley, Lavoisier, W atson, Ingenhousz and Banks. Am ong his m any activities in 1788 he edited, with most lengthy additions of his own, a n English translation of A. F. C ro n s te d ts Essay towards a System of M ineralogy an d in the course of this he gives the following a c c o u n t: Platina may be reduced otherwise to a metallic state. The method by which the late Count de Milly employed in Paris, and which he was so obliging as to do in my presence and at my request, is as follows: First he separated all the sand and other heterogeneous particles, by blowing them out whilst the grains of platinum were letting down from one paper to another paper. He put the metal in a matrass (flask) with twenty times its weight of aqua regia on a strong heat; the next morning he decanted it from a sediment composed of some whitish particles, of a metallic appearance, mixed with blackish matter, which he told me was a molybdenic substance. He then mixed with it an equal quantity of distilled water; precipitated the platinum by a solution of ammoniacal salt, and he filtered the liquor through blotting paper; this and the residue being dried in a plate over the fire was put on a Hessian crucible which he guarded within another large crucible. This was covered with a test and put on a blast furnace until it was red hot, even to a white heat, during half an hour; he then opened the crucible where I saw the metallic substance, like a filamentous mass; this he pressed down with an iron rod whose end was formed into a flat button; he covered it again, and continued to fire for ten or twelve minutes; the crucible being taken out, the solid mass was collected at the bottom; this could be forged and beaten on the anvil with a hammer into any form, like iron. (17) The work of the three experimenters so far dealt with represents considerable progress in the application of powder m etallurgy to platin u m since it dem ons
65
trated that under the best conditions the sal-am m oniac or potassium chloride precipitate of platinum could be consolidated at high tem p e ra tu re a n d forged to a fully malleable metal. Both de 1Isle a n d de Milly preferred to use a m m onium chloride as the precipitant r a th e r th a n potassium salts in spite of its higher cost because of the greater ease with w hich the precipitate could be calcined to metal. Von Sickingen and de Milly b o th diluted their p latinum solution before pre cipitation a n d reduced the possibility of base m etal impurities being entrained. Von Sickingen in his later experim ents found it helpful to calcine his precipitate separately an d then to wash it thoroughly with water to remove the last trace of undecomposed chlorides before p utting it into the crucible for the heat tre a t ment. As our story unfolds, it will be found th at all these devices later becam e parts of the sta n d a rd practice for refining platinum . But no one followed von Sickingen in adding a reducing agent to his original solution a n d so preventing the precipitation of iridium with th e platinum . T h e others all worked on red pre cipitates, an d it is the a m m o n iu m chloriridate th a t gives this colour to the yellow am m onium chloroplatinate. T h is was not known until T e n n a n t discovered iridium in 1804, an d wires of th e fineness achieved by von Sickingen were not draw n again for a generation. In fact no one repeated his work; his process was too complex and difficult and it is not surprising to find Lavoisier in 1790 dismissing it as trs pnible, b u t he h a d effectively d e m onstrated w hat the possibilities of the new metal really were. De Milly simplified the process by going back to de 1Isles sal-ammoniac, but lost the advantage of the removal of the iridium. He m ade a new addition to the procedure by assisting the sintering of the metal pow der by pressing it down with an iron tam per, another device th at becam e part of s ta n d a rd practice. In this way, by consolidating the work of his two precursors a n d adding an improvement or two of his own, d e Milly was able to work on a larger scale and to produce good metal in qu a n tity sufficient for the m aking of jewellery. Also, as already mentioned, he paved the way for a p latinum industry in Spain, but we now have to turn to the num erous a ttem pts to bring about the successful melting of platinum.
T h e Great B u r n in g Glasses
After the partially successful a tte m p ts of M a cq u e r and Baum in 1758 to bring a bout the fusion of native p la tin u m by m eans of a concave b u rning m irror nothing more of significance took place in this direction until 1772, when a new phase of activity commenced u n d e r the auspices of the A cadm ie Royale des Sciences. Some indecisive experiments, again u n d e r the direction of M acquer, who was by now the Professor of C h e m istry at the J a r d i n du Roi and highly regarded as the senior chemist of his time, and w ith the help of the apothecary Louis C laude C adet (1731-1799) and A n toine L a urent Lavoisier (1743-1794) then
66
A f t e r u n s u c c e s s f u l e x p e r i m e n t s w ith tw o o l d e r b u r n i n g g las ses t h is e n o r m o u s p i e c e of e q u i p m e n t w as b u i l t f o r t h e A c a d e m i c K o y a le d e s S c i e n c e s a t t h e e x p e n s e o f L a v o i s i e r s f r i e n d J e a n C h a r l e s P h i l i b e r t T r u d a i n e d e M o n t i g n y . I n s t a l l e d o u t s i d e t h e L o u v r e in 1 7 7 4 . it w a s u se d by a d i s t i n g u i s h e d c o m m i t t e e o f s c i e n t is t s led by M a c q u e r a n d i n c l u d i n g L a v o i s i e r b u t fa ile d to a c h i e v e t h e m e l t i n g o f p l a t i n u m
only a ju n io r m em ber of the establishment, had been carried out on the results of heating diam onds in both the presence an d the absence of air. T o conduct further trials it was then decided to ask perm ission from the Acadmie to m ake use of a great burning glass that had been kept there as a curiosity for over fifty years. T h e pioneer of the burning glass ha d been a rich G e rm a n noblem an, Count Ehrenfried W alther von T schirnhaus (1651-1708), a chemist a n d a m athem atician, who ha d devoted some of his great wealth to building a glass works on his estate. Tschirnhaus was a frequent visitor to Paris a n d had been elected a m em ber of the Acadmie des Sciences in 1682, an d one of his burning glasses was bought in 1702 by Philippe Duke of O rleans (the nephew of Louis X IV a n d on the la tte rs death regent for the young Louis XV). T his was for the use of his protg, the chemist Guillaum e H om berg (1652-1715) for w hom he had equipped a splendid laboratory in the Palais Royal. It was later consigned as a m useum piece into the care of the Acadmie. In July 1772 Cadet, with the support of the physicist M a th u rin Jacques Brisson (1723 1806), asked for the use of the great lens. Permission was at once granted by the Acadmie, who asked M a cq u e r a n d Lavoisier to join a com m ittee
67
to take part in the proposed experim ents. T h e a p p a ra tu s was retrieved and, together with another T sc h irn h a u s lens owned by the Com te de la T o u r d Auvergne, was set up in the J a r d i n de l infante, a terrace beside the Louvre, where the Acadmie occupied room s allocated to them by Louis X IV in 1699, and the investigation b egan in m id-A ugust. All m anner of substances w ere exposed to this m ethod of heating, and then on August 14th a small piece of native p latinum was exposed to the heat of the T o u r d Auvergne lens. Lavoisier described the result :
T h e sky b eing b u t little f a v o u r a b le b e c a u s e of m a n y light clouds, th e p l a t i n u m ex posed for 24 m in u te s d id not m e l t b u t softened a n d a g g l o m e r a t e d m o r e t h a n it h a d d o n e in ea rlier e x p e r im e n ts a n d w a s still a t t r a c t e d b y a m a g n e t . (18)
O n the 29th of the same m onth a further trial again resulted only in a gglom era tion, while on September 5th, as Lavoisier describes it:
a sm all m ass of p la tin u m , s t r o n g ly a g g l u tin a te d , t h a t h a d a l r e a d y b e e n exp o sed tw ice in th e fire, exp o sed for 22 m i n u t e s in s tr o n g s u n lig h t, h a r d ly c h a n g e d .
An account of these experim ents was read to the Acadmie by M a cq u e r on November 14th and was im m ediately published in the new jo u rn a l founded by the Abb Rozier, Observations sur la Physique. (19) Some further experiments w ere carried out in the late su m m e r of 1773, but the two Tschirnhaus lenses were not proving altogether satisfactory. T hey both contained bubbles, striations a n d other defects a n d the com m ittee felt that a better effect would be obtained w ith a n a p p a ra tu s consisting of two large pieces of glass with a curvative forming p a rt of a sphere, joined at their circumferences an d then filled with alcohol. T h is suggestion was taken up by J e a n Charles Philibert T ru d a in e de M ontigny (1733 1777), a n older friend of Lavoisier and the Intendant General of Finances. At his expense such a piece of a p p a ra tu s was constructed by the engineer de Bernires, the very large pieces of glass being m ade in a newly built furnace in the Paris works of Saint Gobain, who donated the glass to the Acadmie. This enomous piece of equipm ent, illustrated here, was installed in the J a rd in de l infante and was re a d y for operation at the beginning of O ctober 1744. T he great lens was four feet in diam eter, against the three feet of the Tschirnhaus lenses, and was m o u n te d on a carriage to enable the movement of the sun to be followed. T h e focal length was ten feet, at which point the light was so strong as to harm the eyes of th e observer, a n d a smaller lens was arranged to concentrate the s u n s rays still further. Iron was readily melted by this means, but once again no success was ob tain e d with native platinum . A report of the experiments by T r u d a in e de M ontigny, M acquer, Cadet, Lavoisier and Brisson was read to the A cadm ie on Novem ber 12th, 1774 by Brisson and printed in the M m oires of the Acadmie for th at year, although these were not published until 1778 (20). It contains the following p a ra g ra p h :
H a v in g e x p o s ed to th e fire s o m e g ra in s of p l a t i n u m in a c a r b o n cav ity it a p p e a r e d to c o n g r e g a te a n d to be r e d u c e d i n v o lu m e a n d to b e a b o u t to m elt. A little la te r it
68
b u b b le d a n d f u m e d a n d all th e g r a in s u n ite d in to a single m a ss, b u t w ith o u t fo rm in g a sphe ric al b u t t o n as w ith th e o th e r m e tals. A fter this k in d of se m i-fu sio n th e p l a tin u m w as no long er a t t r a c t e d b y a m a g n e t as it h a d b e e n befo re b e in g e x p o s ed to the a c tio n of th e sun.
T hus platinum had still not been melted, at least partially on account of its adm ixture in its native form with iron a nd sand an d the consequent form ation of a refractory iron oxide. But the Count von Sickingen, who had been invited to take p a rt in these experiments, achieved success with his precipitated platinum . T h e report con tinued :
T h e B a ro n Sickingen, M in i s te r of th e E le c to r P ala tin e , w h o c u ltiv a tes th e sciences w ith as m u c h success as sagacity, su b je c te d to th e s a m e h e a t a p o r tio n of p l a tin u m t h a t he h a d s tr ip p e d of its iro n b y a p a r t i c u l a r p ro c e ss a n d t h a t w a s not a t tr a c t e d b y a m a g n e t; this p l a t i n u m w as r e d u c e d in volum e, gave off s m o k e a n d th e n u n ite d into a single m a ss w h ic h c o u ld b e flatten e d u n d e r a h a m m e r .
L a v o isie r M elts P la tin u m W ith O x y g e n

Now it was just at this time that Joseph Priestley had discovered oxygen or dephlogisticated a ir as he called it - and as is well known, on a visit to Paris in the O ctober of 1774 he acquainted Lavoisier with his findings during the course
A n to in e L a u r e n t L a v o is ie r
1 743-1794 R e a l is i n g t h e s i g n i f i c a n c e o f P r i e s t l e y 's d i s c o v e ry o f o x y g e n . L a v o i s i e r c o n f i rm e d a n d e x t e n d e d t h e st u d y of the c o n stitu en t of air that su p p o rte d a n d t o o k p a r t in c a l c i n a t i o n a n d c o m b u s t io n . T h i s he firs t c a l l e d vital a i r " , the p u r e s t p a r t o f t h e a i r . In 1 7 8 2. w ith a m a s s i v e p i e c e o f a p p a r a t u s h e h ad d e s i g n e d to y i e l d a c o n t i n u o u s s t r e a m o f o x y g e n , h e w as t h e firs t to s u c c e e d in b r i n g i n g a b o u t t h e t r u e m e l t i n g of p l a t i n u m , a l t h o u g h o n ly o n a very s m a l l s c ale
69
T h e a p p a r a t u s d e s i g n e d by L a v o i s i e r a n d b u ilt by his i n s t r u m e n t m a k e r P i e r r e M g n i to b u r n c o n t i n u o u s s t r e a m s o f o x y g e n a n d h y d r o g e n . B e f o r e t h is h a d b e e n c o m p l e t e d h e u s e d it in A p r il 17 8 2 to d i r e c t b u r n i n g ox y g en o n to a s m a ll q u a n t i t y o f p l a t i n u m h e l d in a p i e c e o f c h a r c o a l . T h r e e m o n th s later he re p eated the e x p e r im e n t at a m e e tin g o f the A c a d m ie R o y a le des S c ie n c e s b e f o r e a d i s t i n g u i s h e d a u d i e n c e i n c l u d i n g t h e G r a n d D u k e P a u l o f R u s s i a a n d B e n j a m i n F r a n k l i n , t h e n in his s e v e n t y - s e v e n t h y e a r . T h e d r a w i n g , as w ith all t h o s e i l l u s t r a t i n g his p a p e r s , w as p r e p a r e d by M a d a m e L a v o i s i e r
of a dinner party given by him, a n announcem ent that occasioned considerable surprise. No thought of using th is new kind of air for the melting of refractory metals seems to have occurred t o Priestley, b u t his friend a n d neighbour the famous astronomer and geologist the Reverend J o h n Michell (1724-1794), on learning of the discovery observed th at possibly platina might be melted by m eans of i t , a comm ent th a t Priestley included in his Experim ents and Observations on Different Kinds o f A ir , published in 1775 (21). This publication, as w ith m a n y others, was forwarded by M agellan to Lavoisier, who was now directing his thoughts m ore a n d more to the role of the air, or some part of it, in com bining with metals during calcination. A few years later, also well known to chemists everywhere, he announced that he w ould give the nam e oxygen to this most salubrious an d purest p a rt of the a i r . In the m eantim e Franz Karl A c hard in Berlin had m ade use of Priestleys dephlogisticated a ir to yield higher tem peratures th a n had hitherto been possible, directing a stream of oxygen on to a piece of carbon. This he reported to the Royal Academy in Berlin in 1779, although the m moires were not published until two years later (22), but it clearly gave Lavoisier the impetus to conduct some further experiments. H e ha d already designed a caisse p n e u m a tiq u e or gasometer to p ro d u c e a blast of oxygen or hydrogen, or both together, a n d in April 1782 he em ployed the first of these gasometers in a rather spectacular experiment to direct th e stream of oxygen into a hollowed-out piece of charcoal in which he had plac e d a small quantity of platinum . T h e a p paratus is illustrated here; its construction and use were described in a long paper to the
70
Acadmie, Sur un M oyen d a u gm enter considrablem ent l action d u Feu et de la Chaleur, dans les O prations c h im iq u e s , read in 1782 (23). T his includes a reference to this air that M. Priestley has discovered nearly at the sam e time as myself a n d describes the melting of p latinum held in a small piece of charcoal in the stream of oxygen:
T h e p l a t i n u m h a d m e lte d c o m p le te ly , a n d th e sm all p a rtic le s w e r e u n ite d in a perfectly r o u n d g lobule ; th e m e ltin g w as c o m p le t e a n d ea sy w h e t h e r I e m p lo y e d o r d in a r y p l a t i n u m t h a t on e finds c o m m e r c ia lly o r w h e t h e r th e m ole cules a t t r a c t e d by a m a g n e t h a d previously b e e n rem oved.
This experiment, which was reported to a meeting of the Acadmie des Sciences on April 10, caused something of a sensation in scientific circles in Paris, and w hen a special meeting of the Acadmie was arranged three m onths later for the entertainm ent of the G ra n d Duke Paul of Russia a n d his G rand Duchess the a p paratus was transported there at considerable trouble and expense. T h e G ra n d Duke, the son of C atherine the G reat, and the future T s a r Paul I, was travelling incognito as the Com te du N ord although his true identity was well known, and on J u n e 6, 1782 he was able to witness this historic melting of platinum before going on to a party given for him at Versailles by Louis XVI and Marie Antoinette.
B en jam in Franklin w rites to P riestley

Another famous observer of the scene, and one of an entirely different character, was Benjamin Franklin, who had been resident in Paris since 1776 as the representative of the revolutionary U nited States Government. H e had been elected a Foreign M em ber of the Acadmie in 1772 and had developed a close friendship with Lavoisier, whose experiments he had frequently been invited to watch at the Arsenal. He was also, of course, a close friend of Priestley, w hom he had first met in London in 1765 and with w hom he m aintained a steady correspondence over the years. O n the day following the platinum melting dem onstration Franklin con cluded a letter to Priestley:
Y este rd a y th e C o u n t d u N o r d w as at the A c a d e m y of Sciences, w h e n s u n d r y E x p e rim e n ts w ere e x h ib ite d for his e n t e r t a i n m e n t : a m o n g th e m , o n e b y M . Lavoisier to show t h a t th e stro n g est fire w e yet kno w is m a d e in a C h a r c o a l b lo w n u p o n w ith d e p h lo g istic a te d air. I n a H e a t so p r o d u c e d , he m e lte d P la ti n a p r e s e n tly th e fire being m u c h m o r e p ow erful t h a n t h a t of th e stro n g e s t b u r n in g m irro r. (24)
Two weeks later Franklin wrote a very similar letter to an o th e r of his scientific friends, J a n Ingen-housz, then in Vienna, who was already m aking his own contribution to the investigation of platin u m and its properties. Lavoisier carried out further experiments in the following year an d in a paper to the Acadmie reported th at :
N a tiv e p l a tin u m ex p o sed to a c u r r e n t o f 'v i t a l a i r m e lts in 15 o r 20 m in u t e s if th e q u a n t ity does not exceed 5 to 6 grain s; th e fu sion is q u ite c o m p le te , a n d th e m e ta l
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T h e concluding p a ra g ra p h of a letter fr o m B enjam in F ra n k lin , w ritten to P riestley on J u n e 7, 1782. the day following Lavoisier's s p e c ta c u la r d em o n stratio n of th e m elting of p la tin u m . A sim ilar letter was w ritten two weeks l a t e r to a n o th e r of F ra n k lin 's frien ds. J a n Ingen -hou sz
P h o to g r a p h In courtesy o f the L ib ra ry o f C ongress. W a s h in g to n
forms round globules, but if the quantity is a gros (72 grains) or thereabouts the fusion is very difficult (25). He also exposed in the same way a piece of platinum that had been forged by the Comte de Milly and concluded that the forged metal was a little more fusible than native platinum. So platinum had at last submitted to fusion, if only in minute quantity, and the news was carried swiftly to Priestley. Lavoisier, with his ingenious piece of equipment, using the dephlogisticated air discovered by Priestley seven years earlier, and perhaps owing something to the suggestion made by the English parson and scientist John Michell, had achieved success where others had failed for so long. But it was to be a very long time before platinum was able to be melted on a larger or a commercial scale.
R eferences for C hapter 4

1 2 3 4 5 6 7 8 9 10 11 12 13 14 A. Baum e, C h y m ie E x p r im e n ta le et R a iso n n e , Paris, 1773, 3, 189 194 P. J. M a c q u e r , M em . Acad. Roy. Sei. P ans., 1758, 132 G. B o u c h a r d , G u y t o n M o r v e a u , C h i m i s t e et C o n v e n tio n e l, P aris, 1938, 8 9 - 9 2 W . A. S m e a to n , Platinum M eta ls Rev.. 1966, 10, 24 28 D. M c D o n a ld , Platinum M e ta ls Rev., 1967, I L 106 108 A. L. Lavoisier, O eu v res, Paris, 1868, 4, 237 B. C. Sage, E le m ens de M in ra lo g ie , Paris, 1777, 2, 361 J. B. L. R. Delisle, C r y s ta llo g r a p h ie , 2nd E d n ., P aris, 1783, 1, 487 490 L. B. G u y to n de M o rv e a u , Obsns. Physique ( R ozier), 1775, 6, 193 203 P. J. M a c q u e r , D ic tio n n a ire d e C h im ie , 2 n d edn., Paris, 1778, 4, 197 K. H . von Sickingen, V e r su c h e b e r die P latin a, tra n s. G. A. S uckow , M a n n h e i m , 1782 L. Crell, Neueste Entdeckungen in der Chemie, 1781, (3), 2 7 1 -2 7 2 ; 1782, (5), 2 6 8 -2 7 0 ; (6), 197-206 J. In g en -h o u sz, N ouvelle E x p e rie n c e s et O b s e r v a tio n s , Paris, 1 785-1789, 1, 446; 2, 506-517 L e tte r from G eorg F o rste r in V ie n n a to S. T . S m m e r in g , A u g u s t 14, 1784; H, H e ttn e r , G eo rg F o r s t e r s Briefwechsel m it S. T . S m m e r in g , B r a u n s c h w e ig , 1877, 111 K. H. von S ickingen, Neueste Entdeckungen in der Chemie, 1782, (6), 141 147 M . T illet, M em . Acad. Roy. Sei. Paris., 1779, 373-377 ; 3 8 5 -4 3 7 ; 5 4 5 -5 4 9 A, F. C r o n ste d t, A n E ssay to w a r d s a S y ste m of M in e ra lo g y , t r a n s . G. von E n g e stro m , 2 n d e d n ., ed ite d J . H . M a g e lla n , L o n d o n , 1788, 2, 574 A. L. Lavoisier, M a n u s c r ip t, A rch ives of A ca d . R oy. Sei., P aris; Lavoisier, O eu v res, 1865, 2, 6 1 2-616 P. J . M a c q u e r , Obsns. Physique ( R osier), 1772, D e c e m b e r, 93 106 T r u d a i n e de M o n tig n y , M a c q u e r , C a d e t, Lavoisier, a n d Brisson, M e m . Acad. Roy. Sei. Pans, 1774, 88, 6 2 -7 2 J. Priestley, E x p e r im e n ts a n d O b s e r v a t io n s o n D ifferent K in d s of Air, 1775, 2,
100-101
15 16 17 18 19 20 21 22 23 24 25
F. K. A c h a rd , N ouveaux M e m . Acad. Roy. Berlin., 1781, 2 0 -2 6 A. L. Lavoisier, M e m . Acad. Roy. Sei. Pans, 1782, 4 5 7 ^ 7 6 L e tte r in L ib r a r y of C o n g ress, L ist 1048 A. L. Lavoisier, M em . Acad. Roy. Sei. Pans, 1783, 6 0 5 -6 0 6
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F ra n z K a rl A chard
1753-1821 T h e son of a pastor. A c h a r d studied c hem istry u n d e r M argg raf in the Berlin Royal Academ y of S ciences, becom ing his friend a n d eventually his successor as Director o f the Physical Class an d the Chem ical L aboratory in 1782. As a y o u n g m an of only 26 he succeed ed , w here his predecessors had failed, in m elting p la tin u m with the aid of arsenic, describing his results in o n e of th re e m m oires read to the Berlin \c a d e m y . In 1788 he p u b lish e d a little-know n book. " R e c h e rc h e s sur les P ro prits des \lliages M ta lliq u e " , the first c o m pilation of d a ta on alloy systems
P h o lo p r a p h l> co urte s) o f ih e ^ el Ironie I ru-lees \
5
The Arsenic Process and its Use by the French Goldsmiths
J3uf th e se c h e m ic a l p r o c e s s e s , w h ic h h a v e as
y e t b ee n p r a c t i s e d u p o n s m a ll q u a n titie s o f p l a t i n a , d o not p r o v e so m u c h w ith r e s p e c t to th e p o s s i b il i t y o f w o r k in g p la tin a in a larg e w a y a n d o f e m p lo y in g it u s e fu lly in the arts, as th e tw o p ie c e s w h ic h I n ow
show
to
the
A c a d m i e m a d e b y M. J a n e tty.
A N T O IN E L A U R E N T L A V O IS IE R
T h e discovery by H. T. Scheffer in 1751 th at by the addition of a small quantity of arsenic to platinum a n d then heating to redness it melts in the twinkling of an eye exercised a great fascination on those seeking a m ethod of rendering it workable. T hey had, however, great difficulty in confirming this effect. Lewis was unable to produce a melt fluid enough to pour into a m ould; M a rg g ra f could not achieve com bination at all, and neither could M a c q u e r a n d Baum. As we have seen, G uyton de M orveau was successful in 1775, b u t there was still no understanding of what was happening. T h e process was successfully used and explained in 1779, w hen Franz Karl Achard, M a rg g ra fs successor, read a p a p e r to the Royal A cadem y of Sciences in Berlin although this was not published until two years later (1). A ch ard heated in a luted crucible to as high a tem perature as he could get a m ixture of 120 grains of native platinum with a similar weight of powdered white arsenic and 180 grains of potash. O n cooling a n d breaking open, he found that the platinum had melted into a well-rounded b u tto n weighing 120 grains, which was very hard and brittle. T o see if the arsenic had com bined with the p latinum or had merely acted as a flux he heated a portion of the b u tto n in a muffle, a n d observed that as soon as it had reached a dull red heat it began to give off white arsenical fumes. Taking it out for inspection he was very surprised to find that it had softened to the consistency of tin amalgam. O n raising the tem perature of the muffle the metal melted, b u t after an h o u rs treatm ent it ha d become solid again and no longer gave off white fumes. Its weight h a d decreased from 77 grains to
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64, an d under the ham m er it a p p e a re d to be fully m alleable a n d as ductile as gold; moreover it could be filed easily. It could not be melted at the highest tem perature that he could attain, b u t this further treatm ent did not produce any more loss in weight, so that he p re s u m e d that all the arsenic h a d been removed. From these results A chard concluded th at p latinum does com bine with arsenic, becoming readily fusible and very brittle, and th at the two can be separated by heating. H e noted that during the initial fusion with arsenic a n d potash, the weight of the button was the same as that o f the original p latinum in spite of the fact that a quite considerable quantity of arsenic h a d been taken up. H e explains this as due not to any loss of platinum b u t rath e r to the separation a n d destruction of the heterogeneous and chiefly ferruginous p arts which it c o n ta in e d , as was confirmed by the brown colour o f the slag which covered the melted material. A c h a rd then went on to com m ent o n the experience of his predecessors, conclud ing th at the failure of most of t h e m to achieve fusion was due to the fact that un d e r the conditions of their w ork the arsenic volatilised and was lost before it could act upon the platinum. H e contended th at the alkali (potash) he added prevented this and enabled fusion to take place, a n d further he found by num erous experiments that, to en su re no arsenic escaped, three parts of potash h a d to be added for every two p a r t s of the former. H e m a d e no reference to the work of de M orveau, the results of which can be explained in a similar way.
T h e First P la tin u m C r u c ib le s A c h a r d s p a p e r - actually three consecutive memoirs dealt with arsenic and its com bination with a large n u m b e r of metals an d com pounds, but apparently the effects he obtained with p la tin u m interested him m ore th an most. H e con tinued his work on this an d in 1784, in the very first n u m b er of Lorenz C re lls Chemische Annalen , he published a n o th e r p a p e r under the title Easy M ethods for M aking Vessels from P la tin u m (2). By then he had satisfied himself that the procedure outlined above could b e repeated as often as desired, an d he went on to suggest that this property of arsenic of making platinum fusible and then being afterwards completely rem ovable by heat, m ad e it possible for us to make from it all kinds of small vessels a n d especially small fusion crucibles which can be useful in certain operations . H e then described a small former he had m ade out of clay in which such a vessel could b e m ade by filling up the space between the inner a n d outer parts of the form er with pow dered arsenical p la tin a , and heating the whole to a high tem perature.
T h e a rse n ica l p la tin a melts, a n d w h e n th e arse n ic h as volatilised a g a in solidifies a n d takes th e s h a p e of th e space. A fter cooling th e fo rm e r is b r o k e n o p e n a n d th e crucible, w h ic h h as b e e n m a d e f r o m the p la tin a , is h a m m e r e d a little o n a m a n d re l, a n d is th e n r e a d y .
A chard says: I have s ucceeded very w e l l . . . in making a fusion crucible from

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\ c h a r d s 1779 papers dealt with the m elting of a wide range of metals with arsenie. hut he was particularly interested in the effect obtained with p latin um a n d in 1784 published his *'Kas\ M ethods for m aking Vessels of Platinum *' in the first n u m b e r of Crell s ( .hpniische in n a lrn
T h e small di agram in his pape r shows his met hod of making a crucible by pushing po wd er ed arsenical platinum into a clay mould and heating to a high te m pe rat ure
platina and therefore it is to be presumed that he did manufacture at least one such vessel. If that is so, then this was the first platinum crucible ever made. The call for these crucibles came from those who were attempting to make analyses of minerals on the basis of the methods recommended by Bergman and involving fusion of the material with alkalis. For this purpose platinum offered itself as ideal and so found its first niche in laboratories. It seems unlikely, however, that Achard made many crucibles. After the volatilisation of the arsenic the shape must have been in a very fragile form and, if surviving the breaking up of the mould around it, required the most delicate handling in the earlier stages of con solidation and during the hammering that had to be applied both inside and out. Little more was heard in fact, of Achards crucibles but in 1785 Guyton de Morveau took up the process, finding that the flux of white arsenic and potash caused excessive swelling. This he remedied by adding common salt and powdered charcoal and he was able to show three crucibles to the Dijon Academy (3). One of these was rather spongy but the larger of the other two was sound, of equal wall thickness throughout, shining and free from blisters. This he found much more useful for the analysis of minerals than the iron crucibles recommended by Bergman although it was still attacked by metals and by nitre.
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In a p a p e r read to the Dijon A cadem y in 1785 Guy ton de M orveau described \ r h a rd 's p ro c e d u re for m ak ing a platin u m crucible but considered he had im p roved on this m ethod by elim inating the swelling caused by the arsenical flux. By a d d in g com m o n salt an d charcoal to the m ix tu re he was able to m a k e th re e crucibles larger than A chards
The K in gs Goldsmith Janety The seed that Achard had sown fell upon fertile ground in an unexpected quarter and for the first time interest in platinum became evident among crafts men as well as among scientists. In the time of great French prosperity under Louis XIV and Louis XV there had grown up in Paris and elsewhere a very able and well-organised craft of goldsmiths and jewellers and it was among these that the interest appeared. As will be seen, one or two others entered upon this development, but by far the most outstanding was Marc Etienne J anety (1739 1820), Royal Goldsmith to Louis XVI. The name of this man is spelled variously in the literature, some examples being Janetty, Janetti, Geanty, Jeanety, Jeanetty and Gianetti, the last probably giving a clue to his origin. In this story the spelling Janety will be used
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throughout because that was the one used in the register of his adm ission to the craft as a M aste r Goldsmith of Paris on J u ly 26th, 1777 (4), as well as in the signed letter to Sir Josep h Banks to be m entioned later. Before that he had been an apprentice to Vincent Brant, a m em b e r of an old-established goldsmithing family, and w hen the latter retired in 1778 J a n e ty took over his business in the R u e de l Arbre Sec. H e continued his work on plate and jewellery, but according to B ertrand Pelletier (1761 1797) he h a d already turned his attention to platinum in 1786, a date fully confirmed by the one sur viving piece of his, the sugar bowl illustrated here (5). By 1788 Pelletier was able to say of him, in the course of a p a per read to the Acadm ie des Sciences, th at he
h a s b u s ie d him self for m o r e t h a n tw o years o n w o rk in p l a t i n u m a n d h a s su c ce ed ed in m a k in g it in large a m o u n t s very p u r e a n d very m a lle ab le . H e h a s m a d e c ru c ib le s of it, snuff-boxes, etc., w h ic h several ind iv id u als hav e p o sse sse d for a long tim e. H e m akes use of arsenic to m e lt it; b u t he has special m e t h o d s of r e m o v in g it afte rw a rd s. It is th e fruit of a w ork not o nly a s s id u o u s a n d tr o u b le s o m e b u t also very d a n g e r o u s , since he h a s several tim es b e e n seen in a n a t m o s p h e r e full of a r se n ic fum es.
This arsenic process as applied by J a n e ty and one or two others to be mentioned later was not merely a subterfuge for getting the p latin u m melted but was a real refining process for the removal of the iron a n d copper, producing a more or less pure platinum in a form suitable for hot forging. T h e difficulties were many a n d will be more easily understood if we examine the scientific limits within which it had to be carried out. T h e eutectic, that is the alloy of the arsenic-platinum series th at melts at the lowest tem perature, contains 13 per cent of arsenic a n d melts at 597C. This fact governs the melting, or at any rate the softening, of any m ixture of the two metals.
No p o r t r a i t se e m s to ex ist o f J a n e t y . t h e R o y al G o l d s m i t h to L ouis X V I . l i e is k n o w n to h a v e b e e n a p p r e n t i c e d to V i n c e n t B r a n t w h o lived a n d w o r k e d in t h e R u e d e I*A r b r e Sec. n e a r t h e L o u v r e , a n d to h a \ e s u c c e e d e d h i m in 1778. A y e a r e a r l i e r h e w as a d m i t t e d as a M a s t e r in the P a r i s G u i l d o f G o l d s m i t h s a n d i n s c r i b e d h is m a r k , a c r o w n e d f l e u r- d e - l y s w ith tw o g r a i n s a n d t h e in it i a l s M. E. J. o n a m a r c w eig h t. By 1786 h e h a d m a s t e r e d t h e a r s e n i c p r o c e s s o f m a k i n g p l a t i n u m m a l l e a b l e a n d of p r o d u c i n g b o t h a r t i c l e s of j e w e l l e r y a n d pieces o f c h e m i c a l a p p a r a t u s . T h e p l a t i n u m c o f f e e po t h e m a d e in t h e s a m e \ e a r w as s h o w n to a m e e t i n g of t h e A c a d m i e d e s S c i e n c e s in 17 90 b \ L a v o isie r , w h o e x p l a i n e d t h a t s o m e p a r t s h a d b een s h a p e d by h a m m e r i n g t h e m e t a l co ld w h i l e o t h e r p a r t s h a d b e e n s o l d e r e d . T h i s was last se en in a n e x h i b i t i o n h eld in P a r i s in 1 9 3 3 . o n l o a n f r o m a p r i v a t e c o l l e c t i o n , b u t un fo rtu n ately d is a p p e a re d d u r in g th e second world w ar
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T he o nly s u rv iv in g piece m ad e in p la tin u m by J a n e ty , now in the M e tro p o lita n M u s e u m o f A rt in New ^ o rk. this b e a u tifu lly designed a n d s k ilfu lly m a d e sugar bow l is seven inches in length an d is fitted w ith a d a rk b lu e glass lin e r ag ainst w h ic h the w h ite b rillia n c e o f the p la t in u m is p a rtic u la rly effective. It is signed an d d ate d a lo n g the rim o f the base:
P L A T IN A JA N E T Y F E C IT IT86 ( h o lo g ra p h b \ c o u rte s y o f M rs. (Jar* l.p C .o rb e ille r a n d lli r M e tr o p o lita n M u s e u m o f \ r I
It was therefore necessary to avoid melting since the removal of the arsenic was much easier if the surface of the material remained large and it was desir able that the temperature at which this process was conducted should not approach 600C. Now arsenic oxidises fairly freely at quite a low temperature and the arsenious oxide produced volatilises appreciably at 300C and freely above 450C. The object of the refiner therefore was to obtain a rapid oxidation and volatilisation of the arsenic without melting the alloy, although later, as we shall see, he tried to keep it in a reduced state in the last stages of its removal. Janetys interest in the working of platinum must have received a great stimulus by the arrival at his house in 1786 of Pierre Franois Chabaneau who, as we shall learn in the next chapter, also began in 1786 to produce malleable platinum in some quantity in Spain. He was escorted by his patron, the Spanish Ambassador to France, the Count Pablo Abarca Aranda, and brought w ith him
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ingots of malleable platinum weighing 44 marcs, an d together they carried out experiments in producing coffee pots, plates, w atch chains, m u s ta rd pots, tea pots and dress-coat b u tto n s (6). T his work cannot have failed to teach J a n e ty much about the properties of the metal in quantity, to encourage him to push forward his own difficult task and to work on a m uch larger scale. His work soon began to a ttract a great deal of attention on the p a rt of the chemists of the capital and his products cam e into considerable dem and. In 1787, in a letter to Lorenz Crell from Paris, de M orveau (7) reports that platinum is now being fabricated very well here. . . M. Janett already makes excellent work from this metal and he will soon be able to make from it anything he wishes. I had advised him to quench the red hot platinum quickly in molten saltpetre in order to secure even greater purification. He assured me afterwards that by this procedure he had made malleable a piece of platinum that was brittle under the hammer; but at the same time it must not be left too long in the saltpetre because the latter begins to attack it. There is no lack of platinum so we shall soon be able to make vessels and other apparatus. T h e last sentence is of interest, confirming that a supply of the m etal was now being smuggled out of South America. In 1790 another of C re lls correspondents, Professor A n to n von R u p re c h t of Chemnitz, writes on a visit to Paris: Without any doubt you will have known for a long time that some excellent chemical artists have found out how to work platinum like other metals, but it will scarcely have been believed how this work has multiplied. I can now assure you that from Janety one can get immediately at a very reasonable price snuff-boxes, watchchains, spoons, toothpicks, little blowpipes and anything of that kind that one wants and orders, made from pure platinum in the neatest and most tasteful manner. (8)
T h e Effects o f th e F rench R e v o lu tio n All was not going smoothly, however, with J a n e t y s work. T h e beginning of the French Revolution in Ju ly 1789 found him with a considerable stock of m alle able platinum for which he could not foresee a market, an d in D ecem ber of that year he wrote to Sir Josep h Banks, President of the Royal Society, appealing for his help. This letter, which was located in the British M u s e u m by D r W. A. Smeaton (9) reads in translation: Sir, Without having the honour of being known to you, I nevertheless take the liberty of writing. By the most persistent labour I have succeeded in making platinum malle able. This discovery, from which at any other time I would have greatly benefited, is of no advantage to me here, because of circumstances that are known to all Europe. Knowing the interests, Sir, that you take in the arts and sciences, I think 1 may permit myself to offer you a quantity of very malleable platinum in bars. If you are able to accept my proposition, I shall also divulge my process to you. I am not suf ficiently vain to believe that if you wish to turn your attention to the subject you would need my small amount of knowledge, but much patience is required, and this would delay the full utilisation of the substance.
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T h e o u tb re a k of the French Revolution in J u l \ 1789 seriousK affected Jan ety 's business, leaving him with a q u a n tity of m a lle a b le platin um on his ha n d s, and on D e ce m b er 13th he wrote to Sir Jo se p h B ank s. P re sident of the Royal Society, hoping to enlist his help in disposing of it. T h is is the second page of the letter in the course of w hich Jan ety o ffers to divulge the secret of his process if B anks can find a m ark et for the platin um
P h o to g r a p h by courtesy o f the T rustees o f the H ritish M u se um
Mr Ingenouse, who must now be in London, does me the honour of being friendly towards me. As he will doubtless have the honour of seeing you, he will be able to tell you whether you can have confidence in me. Here I sell an ounce of platinum for 30 livres tournois [about 26 shillings], but to dispose of a fairly large quantity I would make a reduction. I ask you to excuse the liberty that I take. . . . Janety Master Goldsmith, at the corner of the Rue de lArbre Sec and the Rue Bailleul. Paris, 13Xbre [December] 1789. Banks was unable to dispose of any substantial quantity of this platinum. His pencil notes on the letter show that six ounces were bought by Henry Cavendish and three ounces each by Alexander Dalrymple, the hydrographer to the Admiralty, and by Alexander Aubert, an amateur astronomer who had a well-equipped observatory. Janetys work on platinum suffered a further interruption. Early in the Revolution there was a great shortage of copper for both coinage and cannon and the large quantities of high-tin bronze contained in the bells of the many disused churches attracted the attention of the authorities. The chemist Fourcroy was called up to devise a process to separate the two metals, and in this he had the assistance of Janety who developed a satisfactory method of refining, yielding ductile copper from which several thousand cannon were made ( 1 0 ).
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J a n e ty need not have worried unduly about his stock of platin u m because as we shall see the Acadmie took m ore th a n 400 ounces in 1791. M eanw hile, in 1790 he was honoured by Lavoisier himself introducing to the A cadm ie des Sciences two pieces of his work, one of which was a coffee-pot (11). After outlin ing the various means available at the time for purifying platinum , Lavoisier pointed out that not only h a d they hitherto been employed on b u t very small quantities of material, but had often led to no m ore th a n imperfect results.
J fo
A n n a l e s
Enfin, jai fait voir que le platine, lorfquil eft allie un mtal volati! ou calcin able, elt fiifcepiible dune efpce daffinage analogue celui que reoit le fer dai.s les forges. Mais ces diffrens procds chim iques, qui nont encore t em ploys que fur d e petites quantits de platine , & dont plufieurs m m e nont conduit qu des rfultats im parfaits, ne prouvent pas autant fur la poiibilit de traiter le nlatine en grand & d e lem ployer utilement dans les arts, que les deux pices que je mets dans ce moment fous les yeux d e lacadm ie; elles ont t fabriques par M . Ja n etty , avec du platine quil a trait lui-m m e par un pro cd qui lui eil particulier, en forte que le mrite de ce travail lui appartient en entier. C eil galement lui qui avoit excut en pla tine , fous la direction de M. C h a b a n o , un fuperbe ncefluire deilin pour le roi dE fpagne. Ces pices, & principalement le vafe qui eil fous les yeux de lacadm ie, prouvent quon peut fabriquer avec le platine des ullenfiles d e toute efpce ; ce vafe contient en effet d es parties planes froid, telles que le fon d , & des parties fondes. Il neft rien quon ne puifTe exccutcr fivec la runion de ces deux m oyens,
l u his p a p e r O b s e r v a t i o n s o n P l a t i n u m " , p r e s e n t e d to th e X c a d m ie d e s S c i e n c e s in 17 90. L a v o isie r s u m m a r i s e d tin* s e v e ra l m e t h o d s so f a r proposed for b rin g in g p l a t i n u m in to a w o r k a b l e f o r m a n d w e n t o n to r e f e r to J a n e t v ' s w ork in t h e p a s s a g e q u o t e d at t h e h e a d of this ch ap ter, lie concluded: "It d ep en d s therefore e n tir e ly on t h e S p a n i s h g o v e r n m e n t , w h i c h h a s in its p o ssessio n t h e o n ly m i n e s of p l a t i n a t h a t a r e k n o w n , w h e t h e r we sha ll be p e r m i t t e d to enjoy th e ad v an tag es which m ight b e d e r i \ e d to society f r o m t h e use o f a m e t a l w h i c h is so u n a l t e r a b l e , a n d w h i c h , for m an y p u r p o s e s , in \ a r i o u s a r t s , is p r e f e r a b l e e v e n to gold i t s e l f "
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Greater possibilities of large-scale work were indicated by the two specimens which he now presented to the meeting: they have been fabricated by M. Janety from platinum which he has himself treated by a process of his own devising so that the whole of the credit for this work belongs to him. . . . These specimens and especially the vessel which is before the eyes of the Acadmie prove that utensils of every kind can be made in platinum; in fact this vessel contains cold-worked parts, such as the bottom and soldered parts. By using together these two means there is no limit to what can be made. Further evidence of Janety making apparatus in platinum for use by the chemists of the time is given in the diary of the Scottish geologist and chemist Sir James Hall, revealed by Dr J. A. Chaldecott (12). During a second visit to Lavoisier in 1791 - he had first made his acquaintance five years earlier Hall met Armand Seguin (1765-1835), Lavoisiers young assistant, and on July 5 records : Went with M. Seguin to Jannetti rue de larbre sec. He works in Platina. I bespoke a little spoon for the blow pipe & cup with some wire of that metal. M. S told me that as it is thus prepared the metal does not stand the action of pure caustic alkali when urged by a great heat, for by this means it becomes porous and lets the alkali through by acting as it is supposed upon the arsenic which has not been thoroughly driven off. Yet in this state it will answer many purposes.
Appreciation by the A cadm ie des Sciences By now Janetys work had become so well known that the Acadmie des Sciences appointed Claude Louis Berthollet and Bertrand Pelletier as Com missioners to investigate his process and to determine if it was deserving of
In 1791 I he well kn ow n Scottish geologist a n d chem ist Sir J a m e s Hall, d u rin g a visit to Paris, a ccom panied L avoisiers assistant A rm a n d Seguin to Jan et\* s w orkshop to o rd e r several items of platin u m a p p a ra tu s. This entry from his diary for July 5th records the occasion
P h o to g r a p h b> courtes\ o f D r. J . \. ( h a lde co tt a n d th<* N a tio n a l l.ibrar\ o f S cotland
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public support. T h e ir report was published in 1792 (13) and gives a m ost generous account of J a n e t y s struggles and eventual success: M. Jeanety regarded it as an important aim for the goldsmiths trade of the capital to seek means for working this metal; animated by a desire to be useful to his country he neglected his former occupations, the work in objects of gold and silver; he no longer busied himself with anything but researches on the means of working platinum. None of the scientists failed to recognise the obstinacy and courage with which this artist carried on his work; the sacrifices that he has made, the dangers he has undertaken and the success he has finally obtained are known to the whole of Europe. They went on to record that the Acadmie h a d tu rn e d to J a n e ty to o b tain a b ar of platinum no less th a n 14 feet long, a ball weighing 18 m arks (144 ounces), two bars 19 feet long each weighing 22 marks (176 ounces), a b a r 19 inches long and a pendulum bob weighing 12 m arks (96 ounces) a n d th at he h a d m ade con siderable num bers of crucibles, snuff-boxes and watch-chains as well as a set of buttons and a watch-chain of the most rare b eauty for the K in g . Finally the Commissioners concluded: You will readily agree that to have introduced into commerce a metal so precious and with such important uses is to have earned the right to a national reward. Earlier in their report Berthollet an d Pelletier gave an account of J a n e t y s procedure - ju s t as M. J e an e ty has subm itted it to the C om m issioners . In essence he first cleansed the native platinum by washing to remove as m u c h as possible of the sand from it. H e then mixed 24 ounces of it with 48 ounces of white arsenic powder (arsenious acid) and 16 ounces of refined potassium car bonate. This m ixture he melted in a crucible with careful stirring w ith a platinum rod; after cooling a n d breaking up, a well-formed b u tto n was disclosed which was still magnetic. W h a t had happened was th at the m ixture melted with an evolution of carbon dioxide while p a rt of the iron an d copper present in the native platinum was oxidised an d passed into the slag. T his cam e about at the expense of some of the arsenious acid with a production of free arsenic. A second reaction taking place at the same time was based on the affinity of arsenic acid for potassium an d resulted in another portion of arsenious acid decomposing into arsenic acid (becoming potassium arsenate) a n d m ore free arsenic. T h e free arsenic produced by both these reactions alloyed with the platin u m and brought about its fusion. J a n e ty realised the im portance of removing all th e iron before attempting to work the metal a n d therefore he pow dered his b u tto n and treated it in the sam e way a second time and, if necessary, a third. H aving obtained a non-magnetic alloy he melted it with a little m ore arsenic a n d potash in such a m anner as to obtain flat circular cakes of uniform thickness and about 3j inches in diameter, weighing about 27 ounces. H e then placed these cakes in a shallow muffle leaning m ore or less vertically against the wall, and carefully heated them in such a way th at they were equally heated all round until the arsenic began to volatilise. T h e tem perature was very carefully m aintained for six hours, the posi tions of the cakes being changed from time to time to ensure even heating; the
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greatest care h a d to be taken t h a t the tem p e ra tu re did not rise sufficiently to cause sagging or melting. T h e cakes were next quenched in c om m on oil, replaced in the muffle an d h e a te d for an o th e r six hours at a tem p eratu re suf ficient to drive off all the oil a n d smoke. In this p a rt of the process the residual arsenic rem ained in the metallic state an d was driven off in vapour. W hen this had ceased the tem perature was raised as m uch as possible. J a n e t y s account concludes: If the preliminaries that I have indicated have been well followed the operation lasts only eight days. Then I clean my buttons in nitric acid and boil them in distilled water until they do not contain any more acid. I then place several of them one upon the other; I apply to them the greatest possible degree of heat and I strike them with a pestle, taking care at the first heating to bring them to redness in a crucible in order that no foreign matter shall be introduced into my buttons which are only spongy masses before this first compression. Afterwards I heat them harder and I form from them a square which I strike on every face for a more or less considerable time accord ing to their volume. It is highly doubtful that J a n e t y actually received any rew ard for his prodigious efforts in the troubled times of the F rench Revolution. H e continued his work in the R u e de lA rbre Sec, but after the execution of Louis X V I in J a n u a r y 1793 he decided that th e office of Royal G oldsm ith h a d become rather incompatible with the revolutionary atm osphere an d he retired to Marseilles where he set up again as a m an u fa ctu rer of clock components. His stay here was not long, but his retu rn on a su m m o n s from the governm ent an d his subsequent im portant work on p latinum will have to aw ait a later chapter.
Jacq u es D a u m y an d th e A b b R o ch o n O n e other goldsmith who took u p the arsenic process in Paris was Jacq u e s D aum y, practising at 58 R ue de la Verrierie. A dm itted a M a ste r in February 1783, he first becam e well known as a m aker of d o u b l , gold clad on silver or copper, but soon interested him self in p latinum although not on the sam e scale as Janety. A n account of his pro ce d u re is given by Dr. J a n Ingen-housz in the second volume of his book pu b lish ed in Paris in 1789 (14). Describing him as Sieur Domi, Ingen-housz writes t h a t he melts the native metal two or three times in succession with three or four tim es its weight of arsenic (presum ably as oxide or salt), adding a few ounces of salt of tartar: The button which he obtains is very brittle; he reduces it to powder and exposes it, spread out to a moderate heat like that of a bakers oven (a cupellation furnace is very suitable) for the eight hours or until the powder no longer loses weight; he then subjects the powder, placed in a Hessian crucible, to a strong heat for several hours, while pressing the powder, now red hot and amenable, into a coherent mass which can then be forged with a hammer, after having been struck two or three times by a pestle. The success of this operation demands especially the avoidance of heating the powder or button high enough to melt it and being careful not to forge it without making sure that all the arsenic has gone. When the arsenic has all evaporated from
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Alexis Marie Rochon

1741- 1817
A stronom er to the F re n c h Naval A cadem y at Brest, the A bb R ochon m ad e e x tensile voyages a n d o b serv a tions. His interest in m irrors for refiecting telescopes led him to the study of p latinum and its m ethods of fa b ric a tion. He was also the first to melt optical glass in large platin um crucibles
the platinum no heat can produce a true fusion, one can then only agglutinate it forging it at red or white heat; it does, however, answer to the hammer in the cold and it is very ductile. Daumy was called upon to employ this process by Alexis Marie Rochon who, as a young man became a priest but who managed to obtain a sinecure post of Abb that yielded him an income sufficient for him to pursue his enthusiasm for travel and astronomy. On one of his voyages he stayed for a time in Corunna during 1770 and here he was given an ingot, weighing some eight ounces, of platinum alloyed with copper and zinc that had come from South America. This gave him the idea of making large mirrors for reflecting telescopes from a metal whose polish will be bright and unchangeable. At first Daumy prepared the platinum for him and then it was alloyed with tin, copper and arsenic and cast into a mould. The final polishing was carried out by an engineer named Carrochez. In a memoir read to the Acadmie des Sciences (15) on the occasion of his admission to membership in 1780 - but not published until 1798 on account of his long periods of travel - Rochon stated that he had constructed a telescope with platinum that magnifies the diameter of objects five hundred times with a degree of clearness and distinctness requisite for the nicest observations. The
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large speculum of platinum weighs 14 pounds and is 8 inches in diameter and its focus is 6 feet. Experience with this p r o d u c tio n of m irrors deepened R o c h o n s interest in p latinum a n d he began to experim ent with m ethods of purifying it in quantity. O n e was as follows: 1 pound of native p latin u m is mixed with 10 pounds of arsenic and 4 pounds of flux (sandifer), th e n melted until perfectly fluid an d cast into a mould. Platinum in this state is exceedingly fragile and brittle; were it exposed to a red heat, the operation would absolutely miscarry. The arsenic, by disengaging itself too rapidly, would reduce it to scales which would no longer have any adhesion. It may readily be conceived that this accident must have occurred to me more than once. I have however been able to avoid it by enclosing pieces of platinum, which I have melted, in a box of plate iron, filled with sand and powdered charcoal. I then exposed them for more than a month to a fire graduated from the heat of boiling water to that which fuses silver. Platinum in this state no longer resembles a metal: it might rather be taken for a metallic calx. The particles which compose it are very close but they have only a very feeble adhesion, like that of an earthen vessel dried in the shade. It is then that the platinum must be exposed to the most violent fire; and when the metal has undergone that operation, it resumes its natural state, is sonorous, malleable, and the strongest heat gives it always new degrees of improvement. In the course of experiments m a d e in the famous glass works of Saint G obain R ochon claims to have m ade in th is way a crucible of platinum , capable of con taining 30 pounds of flint glass, to which he gave m ore strength by covering it on the outside with a case of cast iro n an inch thick. If this is true, it supports his claim to have been the first w ho treated p latin u m in a large m ass in a m an n e r truly useful to the a rts . But he generously acknowledges the assistance rendered by the metallic talents o f D a u m y j u n io r . His experiments he says do not permit me to doubt of the utility of crucibles made of platina in bringing flint glass to perfection. T his last comm ent, com pletely correct, was m ade well before the time when this procedure becam e adopted in industry and foreshadowed some early work of F a ra d a y s to be described later. T h e A bb R ochon had been allowed by the C o u n t von Sickingen to observe his m ethod of producing m alleable platinum , an d from this he benefited by giving up the use of arsenic. H e goes on in his p a p e r to relate that: A little time after I had read this memoir the learned Dr. I ngen-housz begged me to unite into a mass for him about two ounces of platina which he had carefully purified by means of the nitro-muriatic acid. I was obliged to enclose in a very thin foil of platinum all the fragments of this metal, which were too scattered and too minute to be subjected separately to the action of the fire and of the stamper; but, when this united, I gave them the highest degree of heat possible to be produced by charcoal excited by a pair of bellows, and I soon obtained by striking them with the stamper a ductile and malleable mass. After the success of this experiment, I employed myself in purifying in the fire, and in a crucible, platinum in grains, by means of nitre and
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sandifer (glass-makers flux), which must be afterwards washed in the nitric acid; and by striking at a white heat these grains contained in laminae of platinum, I procured at a small expense considerable masses of malleable platinum. This process will render unnecessary hereafter the use of the oxide of arsenic, unless the worker wishes to obtain by casting, large crucibles or muffles of platinum. An additional detail of this process was given by G u y to n de M orveau in his letter to Crell in 1789: The Abb Rochon uses a hammer of 250 pounds falling from a height of 4 j. By alternate heating and forging (always by a single hammer blow each time) he produces cylinders which weigh nearly a pound and are suitable to pass the wire drawing plant. (7) (No measure is given for the h a m m e r drop; perhaps feet were understood.) T h e translation of R o c h o n s p a p e r into G e rm a n - and only in this version includes the statem ent I communicated this new method to Janety and he promised me to use it. It seems likely, however, that J a n e ty still adhered to his arsenic process for many years.
P e l le t i e r s P h o s p h o r u s Process
A process with some similarity to the arsenic process was proposed at a meeting of the Acadmie des Sciences in 1788 by B ertrand Pelletier (1761-1797) who had studied the arsenates and phosphates of a n u m b e r of metals. T h is consisted in treating p latinum with phosphoric glass and carb o n (5), which led to a reduction of phosphorus and the com bination of the latter with the p la tin u m to produce a melting similar to th at obtained with arsenic. T h e phosphorus was subsequently oxidised to a slag at a high tem p e ra tu re and the p roduct forged. Pelletier mentions that J a n e ty had tried this m ethod and by m eans of it had m ade for him a pair of balance pans which he had presented to the Acadmie. Pelletier claimed th at the procedure was less dangerous to health b u t adm itted that it was difficult an d that it took a long time to get rid of the last traces of phosphorus. H e adds that several others are using the arsenic method, which is inexpensive but dangerous for the workman.
C o n clu sion Credit must undoubtedly be given to the arsenic process, and principally to J a n e ty s practice of it, for leading to the first real exploitation of p latinum in the production both of articles of jewellery a n d of crucibles and other apparatus. Moreover, it perm itted for the first time the real properties of the metal to be appreciated not only by scientists but by the wider public, because it now became available in some quantity. Ineren-housz sums them up very well in his book (14).
The value of this new metal is not measured solely by its scarcity but, since it has been possible to render it perfectly malleable, it is possible to begin to recognise the
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eminent qualities that it possesses. Its indestructibility by fire, its brilliance unalter able by the causes which tarnish even the purest silver, and its ductility, which does not appear to be less than that of gold and silver, have already placed it among the precious metals. Its specific gravity, surpassing considerably that of gold, has caused the latter metal to pass from the first to the second place among the metals with regard to this quality, which was the most certain indication of its purity, the test of Archimedes. But platinum possesses a quality or rather a perfection which is lacking in gold and silver, that is its hardness. Gold and silver when perfectly pure, cannot be put to several uses because of their flexibility and softness. It is necessary to debase them or alloy them with non-noble metals like copper, to make from them articles of jewellery, cooking utensils or plate. . . . A vessel made of pure platinum has sufficient hardness to need no alloy whatever. T h e arsenic process is of course essentially a m eans for removing the base metals from the native p latin u m and getting it into a form suitable for forging under heat. In suitable hands it proved more m anageable th a n the working of the sal-ammoniac precipitate, b u t eventually as we shall see the latter caught up a nd the arsenic process disappeared. But this was not until it had supplied a growing d e m and for crucibles a n d other a p p a ra tu s from the chemists of Europe for the best p art of a generation. Finally, the appearance of t h e translation of R o c h o n s p a p e r in the second volume of the Philosophical M a g a zin e , published in 1798, served to alert several English scientists to the special properties of p latinum and to the desirability of developing a n improved and econom ical m eans of rendering it workable, with im portant results that will be c o m e app a re n t in later chapters.
III. Ohfcrvations on Platina, a n d ils U tilityin ib iA rti, toge ther with fame Remarks on the Advantages "which refieCling have over achromatic Telefcopes. B y A l e x is R o ch o n , Director o f the M arine Oifervatorjt at J 3refi. From the Journal dc Phyfique, 1798.
p L A T I N A is metal exceedingly refra&ory, unchange able, very compact, and capable o f receiving a fine polilb. This Angular metal has never yet been found but in the gold mines o f Choco. The Spaniards gave it the name of ju a n iianca, that it to fay white gold, and platitto- d e l Pinto, which figni6es little filvemf Pinto. It is brought to us from Choco, under the form of triangular grains the angles of which are rounded. Thefe grains are irregular, du&ile, and fufceptible of being attracted by the loadltonc. It is never pure, and always contains a black fhining fand, over which an artifi cial magnet has great power. This (and is interfperfed with gold grains and fragments of fmall coloured cryftals. The fpcotfic gravity of platina is to that of gold as 22 to 19 J * . Like that precious metal, it refifts the ation o f fimplt acids,
M i hare feen fome plitin a w here th e riiffcreocc w as ftilj greater. E d i t .
C2
and
T h e m e m o i r r e a d to t h e A c a d m i e d e s S c i e n c e s by t h e A b b R o c h o n w as r e p r o d u c e d in E n g li s h in T i l l o c h ' s Philosophical Magazine in 1 7 9 8 a n d u n d o u b t e d l y a r o u s e d t h e i n t e r e s t of R ic h a rd K n ig h t. T illoch h im self and other E n g lis h s c i e n t is t s in the p r o p e r t i e s o f p l a t i n u m a n d in t h e n e e d to d e v i s e a p r o c e s s f o r r e n d e r i n g it m alle a b le a n d th e r e f o r e useful. T his show s the o p e n in g page of the p a p e r
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1 2 3 4 5 6 F. K. A c h a rd , N ouveaux M em . Acad. Roy. Set. Berlin, 1781, 12, 107 109 F. K. A c h a rd , Chem. A nn. ( Crell), 1784, I, 2 5 L. B. G u y t o n d e M o r v e a u , N ouv. M em . Acad. Dijon, 1785, (i), 1 0 6-112 H . N o cq , L e P o in o n de P aris, 1927, 2, 353 B. Pelletier, Obsns. Physique ( R osier), 1789, 3 4, 193-197
V. R e stre p o , E l P l a t i n o , E s tu d io so b re las M i n a s d e O r o y P la ta d e C o lo m b ia , Bogota, 1884, 208 212 7 L. B. G u y t o n d e M o r v e a u , Chem. Ann. ( Crell), 1787, ii, 2 4 3 -2 4 5 8 M . von R u p r e c h t, Chem. A nn. ( Crell), 1790, ii, 53 54 9 W. A. S m e a to n , Platinum M eta ls Rev., 1968, 12, 64 66 10 A. F. F o u rc ro y , A nn. Chim., 1791, 9, 3 0 5 -3 5 2 11 A. L. Lavoisier, A nn. Chim., 1790, 5 , 137-141 12 J. A. C h a ld e c o tt, A nn. Set., 1968, 24, 2 1 -5 2 ; N a t i o n a l L ib r a r y of S c o tla n d M S 6332, ff 4 9 -5 0 13 C. L. B e rtho lle t a n d B. Pelletier, A nn. Chim., 1792, 14, 2 0 - 3 3 14 J . I n g en -h o u sz, N ouvelles E x p rie n c e s et O b s e r v a t io n s s u r D iv ers O b j e t s de Physique, Paris, 1789, 2, 505 517 15 A. M . R o c h o n , J . Physique, 1797-98, 4, 3 -1 5 ; Phil. M a g ., 1798, 2, 19-27, 170-177; Ann. Physik (G ilbert), 1800, 4, 2 8 2 -2 8 9 ( T h e r e a r e sig nificant differences in th e th ree versions)
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P ierre F ra n o is C h abaneau 1 7 5 4 -1 8 4 2
B o r n a t N o n t r o n in t h e D o r d o g n e a n d s e l f e d u c a t e d in P a r i s , at t h e age o f only t w e n t y - t h r e e he l e f t F r a n c e to b e c o m e P r o f e s s o r o f P h y s i c s in t h e S e m i n a r i o P a t r i o t i c o a t V e r g a r a in t h e n o r t h o f S p a i n . In 1 7 8 6 . a f t e r m e e t i n g w ith m a i n d i f f i c u l t i e s a n d w i t h t h e c o - o p e r a t i o n o f F a u s t o d e F l h u y a r . h e s u c c e e d e d in p r o d u c i n g m a l l e a b l e p l a t i n u m o n a l a r g e r s c ale th an had e \ e r before been a c h ie v e d
6
The Platinum Age in Spain
/
h o p e th at E u r o p e w i ll soon b e c o m e a w a r e o f
th e v a lu a b le p r o p e r t i e s o f this n e w n o b le m e ta l w h o se w o rth is b e y o n d alt im a g in a tio n a n d then that S p a in , th e sole p o s s e s s o r o f this treasu re, w i ll rea p u s e fu l b en efits th a t o n ly tim e w i ll reveal.
P IE R R E FR A N C O IS C H A B A N E A l
As we have recorded in C h a p te r 2, for m any years p latin u m was regarded as worthless a n d as a troublesom e im purity in the gold from the Spanish colony of New G ranada. N one the less the first researches on this newly discovered metal, collected together in M o r in s book published in Paris in 1758, brought about some change of attitude am ong the authorities in M adrid. In the following year, for example, J u a n W endlingon (1715-1790), Professor of both M a th e m atic s and Geography there a n d also the royal cosm ographer for the Indies, instructed the Viceroy of New G ra n a d a to collect a substantial quantity of p latin u m from the heaps of discarded metal lying a round the m ints in Bogot an d P o p ayan a n d to despatch it to M a d rid (1). Again in 1765 the Royal Council of Com m erce requested the Secretary of State for the Indies, J u lia n de Arriaga, to acquire further quantities and by the following J a n u a r y the Viceroy, Pedro Messia de la Cerdia, had replied that metal had already been shipped to Spain from the Choc region an d that it was abundant in that area (1). A new era had opened in Spain in 1759 w hen Carlos III succeeded his halfbrother Ferdinand VI on the throne. T h e new ruler was interested in prom oting agriculture an d industry as well as the sciences, an d throughout his thirty-year reign there developed a m uch m ore enlightened and energetic atm osphere, in p art under the influence of the French philosophers of the time. A m ong the K ings initiatives were the establishment in 1771 of a C a binet of N a tu ra l History in Madrid, based upon a large collection of mineralogical specimens formed and presented to the G overnm ent by D on Pedro F raneo Davila, and the a p p o in t ment of the Irishm an W illiam Bowles to be its director. Am ong this collection were several specimens of platinum , and Bowles now gave m ore attention to its
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properties an d possible uses th a n he had in earlier years w hen he w arned against the dangers of its fraudulent potential. In a long footnote to his dissertation on platinum he now concluded: Finally I emphasise that platina can be available for an infinite number of uses and for making a multitude of utensils that would not be subject to rust or corrosion since this metal, with various alloys, can be worked and further submits to forging and welding like iron. See especially what M. Baume has to say about that. (2)
T h e Royal M o n o p o ly in P la t in u m
T h e n in 1774 D on Jos Celestino M u tis wrote hom e from Bogot describing the two portrait medallions of C a rlo s III m entioned in C h a p te r 2, one m ade in p latinum a n d the other in a c o p p e r-p la tin u m alloy, that had been m ade by D on Francisco Benito in the mint a n d forwarded to the King. T h e s e were passed on to D on Miguel M usquiz, the F in a n c e M inister, an d thence to the Council of C om m erce who proposed that B enito should be granted a n aw a rd and that details of his procedure should b e obtained. T h e Viceroy in N ew G ra n a d a, D on M a n u e l de Guirior, seems to h a v e advised Benito, however, to keep his process to himself, a n d there is in fact n o reference to it whatever in the voluminous archives of the Indies. T h e consequence of this was t h e issue of an edict th at platin u m should be worked exclusively for His M a je s ty as was the case with gold , a n d this was followed in 1778 by instructions th a t all p latin u m m ust be handed over to the K in g s representatives but w ith o u t payment. Not unnaturally very little metal was brought in on these terms (3). T h e event th at was to have a m a jo r influence in changing this state of affairs and of bringing about the so-called Platinum A g e in S pain had taken place some years earlier. This was th e foundation in 1764, w ith the approval and encouragem ent of King Carlos I I I and his chief minister C o u n t Grimaldi, of a society for the promotion of science, industry and commerce. Form ed in the three Basque provinces of Viscaya, Guipzcoa a n d Alava by the nobility of the region, and based in the small to w n of V ergara near S an Sebastian, this was known as the Real Sociedad E conom ica V ascongada de los Amigos del Pais (the Royal Basque Economic Society o f Friends of the C ountry) a n d was in fact the forerunner of a num ber of similar organisations in the other provinces of Spain. T h e principal founder of this body, a n d its director, was Francisco Javier de M unibe, the Count of Peaflorida (1723-1785), who had been educated partly in France. His elder son, Don R a m o n M a ria de M u n ib e (1751-1774), com pleted his studies with the society in 1768, and, in line with their policy of secur ing the most up-to-date know ledge from other countries, he was sent at the societys expense on a three-year tour of France, G erm any, Sweden, H olland an d Italy in the care of the scientist Eugenio Izquierdo, the eventual successor to W illiam Bowles. T hey visited m in e s and iron works, attended lectures, learnt assaying from Cronstedt, and s e n t back regular reports to the society, some of
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these being printed as anonymous contributions from A Travelling M ember in their journal, Extrados de las Juntas Generates de la Real Soaedad. One of these, published in 1775, after the young M unibes unfortunate death at the age of only twenty-three, contained a long account of the work of William Lewis on platinum and a review of the state of knowledge about it at that time. This awakened the interest of the society and supplies of the native metal were obtained from the government through the Marques de los Castillejos (4).
The Seminario at Vergara The society had the intention to establish a school of university standard to make available to its members the best teaching of the time, but this naturally required several years to design and build. Their Real Seminario Patriotico finally opened its doors in the autumn of 1777, and Count Penaflorida had some time earlier sought for suitable professors. O n the recommendation of Izquierdo, who with the young Munibe had met them in Paris, the choice fell upon two very young Frenchmen, Pierre Franois Chabaneau (17541842) to teach physics
Fausto dt> Flhuyar 1755-1833

A pp ointed P ro fesso r of M ineralogy in the S e m in a rio a t V ergara a fte r a long lour of E u ro p e a n centres of m in ing and m etallurgy. E lh u y a r took part in the research on platin u m with C h ab an e au but left to beco m e d irec to r of m in es in Mexico before the work was bro ugh t to a successful conclusion
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and the better known Joseph Louis Proust (1754 1826) for the chair of chemistry, with very handsom e salaries provided by King Carlos III. Proust was to play little part during his stay i n V ergara and in 1781 he returned to France, although a later period he spent in Spain did have an influence. C h a b a n e au (usually spelt Chavaneau in S panish), on the other hand, becam e the leading figure in developing the platinum industry in his adopted country but not until several years after his app o in tm e n t, being occupied first in such tasks as the analysis of the m ineral waters of t h e nearby spa at Cestona. In 1781 the Seminario dec id e d to establish a chair of mineralogy and to appoint as professor a young S p a n iard , Don F austo de E lh u y a r de Zubice (1755-1833), who was apparently assisted on the metallurgical side by his elder b ro th er Don j u n Jos (17541804). T h e y came of a good Basque family, had been educated in Paris and ha d been travelling in Europe, j u s t as had D on R a m o n de M unibe, spending so m e time at the School of M ines in Freiberg in p rep aration for their work at the Sem inario. T h e King had also arranged for the elder brother to go to New G r a n a d a to supervise m ining an d metallurgical operations there, and to this end he had spent some time under Bergm an in Uppsala. T h e ir first research in V e rgara was on tungstic acid, resulting in their being the first to isolate metallic tungsten, a discovery they announced in the Extractos of the society in 1783 and w h ic h brought them considerable attention from chemists throughout Europe. T h e year before this Fausto d e E lhuyar ha d added to his duties the chair of chemistry vacated by Proust a n d at some time after this he began work on platinum , together with his colleague C h a b a n e au , draw ing u p o n the supplies of native metal that had been o b ta in e d from the M a rq u e s de Castillejos. T hey met with many difficulties and a grea t deal of frustration, b u t by M a rc h 1786 they were able to announce the successful p roduction of m alleable platin u m to a m eeting of the council of the society. Sadly Peaflorida, the societys m ain progenitor, was no longer alive to h e a r the news. N ot only was their p ro ce d u re kept a closely guarded secret b u t the p art which each of them played in this work is most difficult to establish, depending upon whether one relies upon S p a n ish or F rench sources, each of course accord ing greater praise to their own com patriot.
C h a b a n e a u s M a lle a b le P la t in u m Before the work was completed, E lh u y a r ha d left the Sem inario in Septem ber 1785 in order to visit H ungary to study the improved a m alg am atio n process for gold devised by Baron von Born before going to M exico as director of mining. T h is led to C h a b a n e a u taking over the chair of chemistry in addition to that of physics and to his carrying on the work alone. Before D o n F austo left for Mexico, however, he paid a brief visit to Vergara in the spring of 1786, finding that considerable advances had b e e n made, and fortunately he recorded w hat he
96
T h e S e m i n a r i o , a sc h o o l o f u n i v e r s i t y s t a n d a r d e s t a b l i s h e d by t h e S o c i e d a d V a s c o n g a d a a t V e r g a r a n e a r S a n S e b a s t i a n in 1777. T h e firs t tw o p r o f e s s o r s a p p o i n t e d w e r e b o t h f ro m F r a n c e , P i e r r e F r a n c o i s C h a b a n e a u to t h e c h a i r of p h y s i c s a n d J o s e p h L o u is P r o u s t to t h a t o f c h e m i s t r y . P r o u s t r e m a i n e d o n l \ tw o y e a r s a n d w a s s u c c e e d e d b v F a u s t o d e E l h u y a r w h o , t o g e t h e r w ith C h a b a n e a u . b e g a n w o r k o n p l a t i n u m . In 1 7 8 5 F l h u v a r w as s e n t to M e x ico a n d C h a b a n e a u c a r r i e d o n a l o n e , s u c c e s s f u l l y p r o d u c i n g m a l l e a b l e p l a t i n u m in t h e f o l lo w in g y ear.

( 'h o lo g r a p h by c o u rte s y o f P r o fe s s o r F r a n c is c o A ra g o n He la C ru z
found in two letters to his brother who was by now settled in Bogot. Even more fortunately, Don J u a n Jos m ad e copies of these letters for the interest they aroused a n d in case they prove useful to New G r a n a d a in the f u tu re , an d these copies went into the files of his chief, Jos Celestino M utis. Twenty-five years later, when the liberation revolution broke out in Colombia, these files were rescued, brought to Spain and lodged in the Botanical G a rdens in M a d rid as the M utis Collection. W orking on them in 1911 in connection with the com pilation of his biography of M utis, Professor A. F. Gredilla, the Director of the Botanical Gardens, cam e upon the two copies of D on F a u s to s letters a n d he published their contents in his book (3). T h e ir value is unique since, as soon as it was known that an im portant discovery had been m ade about m aking p latinum malleable, the M inister issued the strictest orders to C h a b a n e a u that on no
97
account was he to publish his m ethods. C h a b a n e a u told the M inister that he had already informed Don F a u sto about the process a n d the latter then received similar orders. These were duly tra n s m itte d to D o n J u a n Jo s and presum ably the original letters were destroyed. T h e letters revealed th at C h a b a n e a u had successfully used a powder m etallurgy process based u p o n those of Sickingen and Milly. T h e first begins: Vergara, March 17th, 1786. In my former letter I told you that I was going to Hungary on behalf of the Minister for the Indies, in order to learn about the new method of amalgamation. . . . As you must already know, when I went away to Madrid, Chabaneau took charge of the work on platinum to complete the research that I had promised to the Minister and he has now made some very important dis coveries. The method is similar to that of von Sickingen in so far as the reduction of the precipitates and salts is concerned but in other respects it is much better. Sickingen used Prussian alkali to precipitate the aqua regia solution which is the very worst means for freeing the platinum from iron and one might almost say that it is the surest means of obtaining a mixture of the two. Chabaneau has employed the method of the Count de Mylli [.ne] which consists in precipitating the said solution by salammoniac, by which no iron is deposited. By this means he has obtained large pre cipitates and from them some very fine pieces of platinum. D on Fausto goes on to say th at C h a b a n e a u also discovered a more economical m ethod of dissolving the native p latin u m , namely, by attacking it by means of nitric acid an d com m on salt. T h e r e follows some rath e r confused m a tte r from which one gathers that they som etim es precipitated by m eans of other alkalis, a n d it is known that later on C h a b a n e a u used p o tash instead of sal-am m oniac as another measure of economy. But however the p latin u m was separated, there is no doubt about what happened afterw ards. The whole precipitate is placed in a crucible on an enclosed hre, when the con tents diminish in size and lose their aqua regia. When crushed with an iron pestle it soon loses it brownish-grey colour, which changes to a beautiful silver-white, and with pressure gains consistency and becomes concentrated. When the precipitate has sintered, it is removed from the crucible, hammered very lightly to unite the particles and then annealed and hammered alternately until it is really firm. This mass is then exposed to more intense heating in a crucible in order to evaporate the salt occluded in its interior and is then annealed and hammered again. Finally it is exposed to the fierce heat of a forge for half an hour, when it is removed from the crucible, heated on an iron forge, forged and drawn into bars, commencing by striking very lightly in order to unite all the particles not previously affected. This is the method used by us in an operation completed today, when in a single operation we have obtained a piece weighing 13 ounces which we are going to send to the Minister in the form of a bar. Just as we have been able to correct in the course of this operation defects previously noted, so we have observed defects in this procedure which will be obviated on future occasions. It has been noticed during the last heating up and drawing of the bar that a glassy crust forms on the surface of the metal and which seems to sweat through from the interior, and we believe that this is caused by residual unreduced salts. If at the outset care is not taken to destroy those unreduced salts, the mass will crack and quickly break up into small pieces. This defect has been remedied in part by an additional treatment which consists in putting the hot casting in water. If these last
98
traces of salts are completely removed, this metal is more easily drawn into bars than silver, and one might even say that anything can be done with it! During the first operations, that is before beginning to compress the mass in the crucible, it should be well stirred with an iron bar in order to facilitate the evaporation of the salt and thus avoid inconvenience later when forging. I shall keep you advised of any further progress we may make, but it would be as well if you started to carry out experiments yourself in order to be fully prepared to install appropriate plant there, for although there is every possibility that a more economical method will be discovered, this one of course would serve very well. We estimate that the expenses would be less than 4 pesetas (8 reales or 1 Spanish dollar) per pound and we believe that the metal will find a ready market at a much higher price than that of silver. . . . I am enclosing, wrapped in paper, a small piece of platinum and although it is not the best possible sample, it will allow you to form an idea of the colour of the metal and how well it can be polished. T h e second letter, addressed from Paris on M a y 19th 1786, again refers to the need for secrecy: Chavaneau sent to the Minister for the Indies some bars of platinum produced by the method I wrote to you about in my recent letter, and he has asked him not on any account to make known his discovery before receiving instructions. He has also sent Chavaneau more native platinum with which to continue his investigations. In his reply Chavaneau had to inform the Minister that he had confided details of his new process to me, and as a consequence I later received orders not to make known to any one the secret in which I shared. My reply, as that of Chavaneau, has been to the effect that I had already written to you about the discovery, since as you are already in the country where large quantities of the mineral can be obtained, you are therefore well placed to carry out useful work on it. In this im portant correspondence it is obvious that, although D o n F austo gives most of the credit for the discovery to C h a b a n e au , there is very definite indication of his own participation in the work. It is also interesting th a t in D on F a u sto s first letter there is confirmation of the C ount von Sickingens statem ent that de M illy sent particulars of his process to Spain. T h e discovery of the way to m ake platin u m malleable m arks the end of C h a b a n e a u s stay at Vergara. T h e King, wishing to have him in M adrid, created for him a special C h a ir there of M ineralogy, Physics a n d C hem istry in the School of the N atu ral History M useum , where Bowles h a d been until his death in 1780. H e also installed him in one of the royal palaces with a n annual salary of 2,200 Spanish dollars, in addition to a life pension of 2,800 dollars a year provided he rem ained in Spain, and a medal specially struck for him in platinum. H e was also m ade Director of a Chem ical L aboratory m aintained by the T reasury an d situated first in the Calle de H orteleza an d later moved to a part of a glass warehouse in the Calle del T u rc o in M adrid. T his was devoted to the refining and fabricating of p latin u m a n d was m an a g e d by one of C h a b a n e a u s old assistants, D on J o a q u im C abezas (4). Before all this took place, however, C h a b a n e a u had been taken off to Paris in 1786 by his patron the C ount of A ra n d a who, after a period as prim e minister,
99
T h e firs t o b j e c t m a d e in S p a i n from C h a b a n e a u 's m alleable p la tin u m w as this ch alice, m a d e by his silversm ith Francisco A l o n s o , a n d p r e s e n t e d b y C a rl o s III to P o p e P i u s VI in 1789. It is t h i r t y c e n t i m e t r e s in h e i g h t a n d w e i g h s a l m o s t tw o k i l o g r a m m e s . T h e in sc rip tio n on the plinth reads:
C A R I.OS III H 1 S P A N ET IN I) REX P R I V I I T I A S H AS P L A T IN A E A FR C H A V EN EA l D U C T IU S R E D D I T A E P I O VI P. O .M .D .I) . + C h a rle s I I I, K in g of Sp ain a n d th e In d ie s , gives as a gift t h e first f r u i t of p l a t i n u m m a d e m alleab le by F ran cisco C havaneau to Pius VI. S u p r e m e P o n t i f f of all the W orld ( Pon tific i O m n iu m M a x im o D o n o D e d i t ) ]
In sid e th e c u p a n o t h e r inscription reads:

H IS P A N E l.A B O R A V IT ANN R . J . M D C C LX X X V III * FRA N CISCU S ALONSO [F rancisco A lonso th e S p a n i a r d fa s h io n e d ( t h i s ) in th e y e a r A.D. 1788.]
T h e c h a l i c e is still o n p u b l i c vi ew in t h e T r e a s u r y o f St. P e t e r s in Rome
h a d been appointed Spanish A m b a s sa d o r to France in 1773. T his was in order to visit the Royal G oldsm ith to Louis X V I, M a rc Etienne J a n ety , who, as described in C h a p te r 5, had successfully m anufactured m any articles in p latinum by m eans of the arsenic process. Vicente R estrepo (3) quotes a letter from Ja n e ty recording this visit: The King of Spain sent one of his chemists to Paris in 1786 with 44 marcs (about 350 ounces) of very malleable platinum bar. His Embassador the Conde Aranda honoured me by accompanying him to my home for the purpose of carrying out certain experiments together. We made these experiments: we made coffee pots, plates, watch-chains, mustard pots, tea pots and dress coat buttons in my home, so many in soldered form with half a n ounce of platinum in one marc of pure silver. D u ring the visit Ja n e ty tried h a r d to elicit C h a b a n e a u s procedure from him but failed to do so. None the less a c o m m e n t by G u y to n de M orveau in 1787 records:
100
Many sorts of useful vessels are now being made in Paris by the method of M. Chabaneau for the King of Spain in which this metal is so pure that its specific gravity is 24. (5) O n his return to Spain C h a b a n e a u trained his own silversmith, D o n Francisco Alonzo, in the working of p latinum to m ake jewellery a n d instrum ents and provided him with a room in the laboratory in the Calle de Turco. T h e first object made here was a large chalice for King Carlos III, who, as recorded on the plinth, presented it in 1789 to Pope Pius VI. T h e chalice rem ained am ong the private possessions of the Popes until some time in the last century w hen Pius IX presented it to the Vatican. It is still on public view in the T re a s u ry of St. P e te rs. C h a b a n e a u s secret was well kept for more th a n a century. I n 1795 he read a paper on platinum to the Royal M edical A cadem y in M a d rid to which he had recently been elected and this was published as a pam phlet a n d later, in 1797, in
RESUMEN
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In 1795 C h a b a n e a u a t last p r e s e n t e d a p a p e r on t h e p r o p e r t i e s a n d p o t e n t i a l a p p l i c a t i o n s of p l a t i n u m bu t w i t h o u t giving t h e least d e t a i l s o f his p r o c e d u r e in r e n d e r i n g it m a l l e a b l e . T h i s sh ow s the title p a g e o f his e i g h t p a g e p a m p h l e t . p r e s e r v e d in t h e B i b l i o t h e q u e N a t i o n a l e in P a r i s . It d i d not a p p e a r in t h e M e m o r i a s d e la R e a l A c a d e m i a M e d i c a d e M a d r i d u n t i l t h e first issue of t h e j o u r n a l w as p u b l i s h e d in 1797.
D E OR D T K Sl P ER im .
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101
the first issue of the A ca d e m y s proceedings (6). In this com m unication he stated that he was still unable to describe his m ethod of obtaining m alleable platinum because a royal com m and issued in 1787 had forbidden him so to do. H e gave only an account of the principal properties of the metal already of course well known - and drew attention to its potential uses. Its infusibility he thought might make it a suitable substance for m easuring high tem peratures, while its resistance to corrosion should lead to its use in navigational a n d astronomical instruments. Platinum crucibles he considered might be used, as well as for analysis, for the m anufacture of optical glass needed for the best telescope lenses, an d he also suggested th at vessels could be m ade of copper clad with a thin sheet of platinum. H e had, in fact, already found that p latin u m an d copper could be united so intimately that the com posite m aterial could be ham m e re d into any shape without the two metals separating. C h a b a n e au rem ained in c h a rg e of the p latinum work until 1799 when, largely on account of poor health, he left Spain, forfeiting his pension, and retired to his native N o ntron in t h e Perigord were he lived quietly until his death in 1842 at the age of 88. His work rem ained largely unknow n to the scientific world, but in 1857 a local resident, Jules Delanoue, who had known him only in his declining years, published a 16-page p a m phlet w ith the title Notice sur C habaneau, Chim iste P e rig o u rd in . This was reprinted in 1862 an d both edi tions are in the Bibliothque N a tio n a l in Paris, b u t a p a rt from securing a brief m ention in the article on p latin u m by H e n ri D ebray in W u r t z s D ictionnaire de C him ie in 1876, where he spells th e nam e C h a b a n o n (7), a n d an o th er in 1906 in M o is s a n s T rait de Chim ie M in ra le (8) no attention was pa id to it until a copy of this rare pam phlet cam e into t h e hands of Louis Q uennessen, the head of the Paris firm of platinum refiners. Q u e n n e s s e n h a d earlier provided the notes for Moissan, an d in 1914 he published a sum m ary of the pa m p h le t in Paris and also brought it to the notice of Professor J . Lewis Howe, the A m erican bibliographer of platinum. Professor H ow e then achieved wider publication by c ontributing an extensive sum m ary to Popular Science M onthly from which it was reproduced in The Chemical N ew s o i London (9, 10). Unfortunately, this rather over-eulogistic little work contains a n u m b er of obvious errors of both fact and chronology, as well as attributing all the credit for the production of malleable p la tin u m to C h a b a n e a u with no m ention at all of Fausto de Elhuyar. O n e episode th a t has the ring of truth, however, relates that the C ount of A randa, making one of his frequent visits to the laboratory Found Chabaneau in a frenzy engaged in throwing out of the doors and windows his dishes, flasks, and ores as well as all the solutions of platinum which he had pre pared with so much trouble and difficulty, saying 'Away with it all! I ll smash the whole business; you shall never again get me to touch the damned metal; and in fact he broke up all the apparatus of the laboratory. Nevertheless, the work did g o on a n d D elanoue records that only three m onths later C h a b a n e a u showed A r a n d a a large cube of p latinum measuring 10 cm along the sides, and weighing about 750 ounces Troy.
102
T h e Spaniards paid little attention to the work for even longer a n d it was not until well into the present century that com m ents b egan to appear. T h e first was in an address on T h e Chemists of V e rg a ra delivered to the Spanish Academy of Sciences i n j u n e 1909 by the prom inent chemist, D o n j u n Fages y Virgili (4). T h e second arose from the discovery in 1911 by Professor A. F. G redilla of a full account of the research in copies of two letters from D on F austo to his brother already described. T h e n in 1933, the c elebration of the centenary of the death of Don Fausto de E lhuyar brought forth two other papers, the first by A. de Galvez-Caero y Alzla in the B o le tn d el In s titu to G eologico y M in e r o de E s p a a (11), and the other a section of a Sym posium in the A n a le s S o cie d a d E sp a o la de F sic a y Q u m ica mostly contributed by the same a u th o r (12). Both dealt with D on F a u sto s career and, as in all of these S panish papers, there is a tendency to decry the ability and contribution m ade by C h a b a n e a u and to hold up Don Fausto as the m ajor factor in the platinum work, although Fages (4) adm its not only the certainty of Chavaneaus discovery but also that it was he who gave it practical application, and converted it into a practical fact useful to the progress of the sciences and arts, and certainly lucrative for himself.
T h e S econ d R oyal M o n o p o ly T h e success C h a b a n e au h a d achieved in producing m alleable p latin u m in some quantity immediately prom pted the Spanish governm ent to order the Viceroy of New G ra n a d a - now Antonio C aballero y G ongora - to collect all the p latinum he could obtain while keeping its new value a secret. A bout 150 pounds of native metal were shipped to Spain, this time the miners being p a id two or three reales a pound. F u rth e r shipments necessitated the price being raised to four reales a pound, and the authorities in M a d rid recom m ended the im portation of many more negro slaves to work the deposits and approved a scheme for the im p o rta tion of tools for sale to the workers in the hope of increasing output. In 1788 it was decreed that platinum was to be sold only to the crown and penalties were established for anyone detected in hoarding the metal. By the end of th a t year more than three thousand pounds of platinum had been despatched from the Choc to C arta g e n a for shipm ent to Spain, but great quantities were still smuggled out of the Choc to be sold to other purchasers prep a re d to pay m uch more (13). J o sep h Louis Proust T h e brief period of P ro u s ts holding the chair of chemistry in V ergara has already been mentioned. H e returned to France in 1781, but five years later, on the recom m endation of Lavoisier to C ount A ra n d a and on the invitation of Carlos III, he again cam e to Spain, first of all lecturing and carrying out research in M a d rid and then in 1788 moving to the Artillery School at Segovia as professor of chemistry. His laboratory there was equipped, at the expense of the
103
Joseph Louis Proust 17541826

Horn in Angers the son of an a p o th ec a ry , P ro ust spent three years at \ erg a ra. re turned to F ra n c e an d then in 1786. at the in\ itation of the K ing of S pain an d on L avoisier's re c o m m e n d a tion. cam e again to Spain and in 1799 succeed ed C h a b a n e a u in c harge of a labo ratory in M adrid e q u ip p e d with an i m m e n s e a m o u n t of p l a t i n u m a p p a ra tu s . H ere P ro u st continu ed and e x te n d e d the work o n platin um fabric ation until in 1808 his laboratory was destroyed by a mob du rin g the siege of M adrid by N apoleon's forces
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new King Carlos IV, with great luxury and an extraordinary amount of platinum apparatus, and he remained there until Chabaneaus departure from Spain in 1799 when he took over the latters laboratory in Madrid. Here one of his first activities according to Fages y Virgili was to improve still further his equipment and he asked through his director for forty pounds of pure platinum and twenty-five pounds of the native metal in grains. This was granted, the metal being provided by Don Joaquin Cabezas, but on condition that he con tinued his experiments on platinum. He had already carried out a long series of researches on native platinum while at Segovia, using relatively large quantities in his experiments, mainly concerned with the dissolution of platinum in aqua regia. The insoluble residue he described as nothing less than graphite or plumbago, failing to grasp that it contained other metals of the platinum group. These results he published in the very first issue of the Anales de Historia Natural in 1799 under the title Experi mentos hechos en la Platina and his paper was reproduced in translation in both French and English (14). Proust promised at the end of this communica tion to present a further contribution on platinum but this was never forth
104
coming, apart from a short letter to V auquelin written from M a d r id in 1803 that was of no great significance ( 15). A part from the chalice presented by Carlos III to Pope Pius VI a n d the use of so m uch platinum ap p a ra tu s in P ro u sts laboratory there is little evidence of serious applications of the metal in this period in Spain. T h e re is a brief reference in the Archives of the Indies to the need for platinum to m ake a table service for the King and to use the metal in the royal chapel, while later a set of standard weights was m ade in a new workshop set up by Carlos IV to establish the art of making scientific instrum ents in Spain. As in Colombia, the counterfeiting of gold coins with p latinum flourished am ong dishonest workers in the mints, first using solid platinum with a thin gilding an d later a copper core with a thin layer of platinum , also followed by gilding. T h e production of these spurious pieces continued for m any years. But the Napoleonic wars were now causing m ajor disturbances; in the first F rench invasion of 1794 the Sem inario at Vergara h a d been burnt a n d the Sociedad V ascongada had been broken up. T h e reign of science in Spain was coming to an end.
T h e P la tin u m R oom in the R oyal P alace

There, was however, one last flam boyant fling to the Platinum Age. For many years there had been a royal palace at Aranjuez, some fifty kilometres south of M adrid. This h a d been enlarged or embellished by successive m onarchs and in 1802 Carlos IV decided to build the so-called L a b o u r e r s C ottage in the grounds, in imitation of the Petit T r ia n o n devised by Louis X V at Versailles. N apoleons famous architects, Charles Percier and Pierre Franois Fontaine, who had designed a num ber of elegant buildings in Paris, were called u p o n by the King to design the interior and to provide the richest possible decoration. T h e architects record with some distaste the display of ornate embellishment contrary to the simplicity of the nam e of the bu ild in g , consisting of mirrors and medallions not only in bronze and gold but also in platinum (16). T he second invasion of Spain by N apoleons forces in 1808 brought about the abdication of Carlos IV. T h e presence of a F rench garrison in M a d rid stirred the Spaniards to revolt a n d on the famous 2nd of M a y the crowds rioted and am ong other acts destroyed the laboratory in which Proust worked, leaving him destitute so that he was forced to sell his collection of minerals in order to live and then to make his escape back to France.
C o n c lu sio n T h e rise and fall of the Spanish platinum industry were historically im portant because the metal produced seems to have been the best in quality m ade avail able up to that time. Also the quantities involved were m uch greater th a n had been the case in earlier work, as is exemplified by the 750 ounce ingot shown to Aranda. But nevertheless the whole affair was merely a n episode in the history of
105
\ contem porary e n g r a \in g o f th e P l a t i n u m R o o m a t A r a n j u e z . D e s i g n e d by t h e l e a d i n g French arch itects P ercier a n d F o n t a i n e f o r C a r l o s IV a n d his Q u e e n M a r i a L u is a , the e x trem e!) o rn a te d e c o ra tio n of t h e o t h e r w i s e s i m p l e L a b o u r e r ' s Cottage** in the g ro u n d s of the royal palace inclu d ed m ed allions and p la q u e s m a d e of p la tin u m and engraved with m ythological su bjects and I t a l i a n l a n d s c a p e s . T h e ro o m m ay still b e s e e n by v i s i t o r s to the p alace
platinum. M ost of the researches, and all the technique that resulted from them, were shrouded in secrecy and know ledge of them disappeared with the scatter ing by the Napoleonic W ars of those who employed them. T h e y had no effect whatever on later practice, w hich had far out-distanced them by the time they had again been brought to light. C h a b a n e a u s great hopes, q u o te d at the head of this chapter, were not to be fulfilled. T h e episode, however, had one result of lasting importance, since it brought native platinum to p u b lic notice and caused it to be sought after and to acquire a value. T h e metal b e c a m e at once a n article of trade, an d w hen the Spaniards tried to monopolise it the brisk smuggling prospered a n d took supplies to other countries. T h i s continued on an increasing scale until the
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d eparture of the Spaniards from New G ra n a d a, w hen the Republic of Colom bia took over the Choco. Despite the researches of C h a baneau, E lh u y a r and Proust, and the output from Colom bia running to some 500 kilograms a year as esti m ated by H u m b o ld t during his visit in 1819 1820, very little use was m ad e of platinum during this period, and w hen peace returned after the disturbances of the Napoleonic wars the new governm ent of the restored King, Ferdinand VII, found a great accum ulation of unrefined metal on their hands. Some p a rt of this, as will be seen in C h a p te r 10, served as a basis for the further development of the platinum industry in France.
R e fe re n c es for C h a p t e r 6 1 2 3 Archivo G eneral de Indias, Seville, S a n ta F, 835 W illiam Bowles, D isertacin sobre la platina, Introduccin a la H isto ria N a tu ra l y a La Geografa fisica de Espaa, M ad rid , 1775, 155 167 A. F. Gredilla, Biografa de Jo s Celestino Mutis, M ad rid , 1911, 157-158; V. Restrepo, Estudio sobre las M in a s de O r o y Plata de C olom bia, Bogot, 1884, 208-214 J. Fages y Virgili, Los Q um icos de V ergara, in D iscurso del limo, M a d rid , 1909, 41-43; 57-61 L. B. G uy to n de Morveau, Chem. Ann. (Crell), 1787, (i), 333 P. F. C h a b a n e a u , R esu m en de las Propiedades del Platino y sus Aplicaciones a las A rtes , Im p re n ta Real, M a d rid , 1795; reprinted in Memorias de la Real Academia Mdica de M adrid, 1797, I, 183-188; W. A. Smeaton, Platinum M etals Rev. , 1978, 22, 61-67 A. W urtz, D ictionnaire de Chim ie p ure et applique, Paris, 1876, 2, 1034 H. Moissan, T ra it de Chim ie M inrale, Paris, 1906, 5, 661 L. Quennessen, Rev. Sci., 1914, 52, 553-557 J. L. Howe, Pop. Sci. Mon., 1914, (Jan), 64 Chem. News, 1914, 109, 229 70: 231 A. de G alvez-Caero y Alzla, Bol. Inst Geol. y M in . Esp., 1933, 53, 377 629; A puntes Biografeos de D. F austo de Elhu yar An. Soc. Esp. Fis. Quim., 1933, 31, 115-143; El P rim er C e n te n a rio de D. F a usto de Elhuyar Archivo H istrica Nacional de Colom bia, Bogot, 1786-1788 J. L. Proust, An. Hist. Nat., 1799, 1, 51-84; Ann. Chim., 1801, 38. 146-173; 225-247; Phil. Mag., 1801-2, 11, 44-55; 118-128 J. L. Proust, Ann. Chim., 1804, 49, 177-180 C. Percier an d P. F. Fontaines, Residences des Souverains, Paris, 1833, 235 236
4 5 6
7 8 9 10 11 12 13 14 15 16
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J a n Ingen-housz 1 7 3 0 -1 7 9 9
H o r n in B r e d a in i h e N e t h e r l a n d s . I n g e n - h o u s z s t u d i e d m e d i c i n e a n d c a m e to E n g l a n d to p r a c t i s e i n 1765. T h r e e y e a r s l a t e r , h a v i n g p l a y e d a n i m p o r t a n t p a r t in t h e e a r l y d a y s of i n o c u l a t i o n a g a i n s t s m a l l p o x , h e w as a p p o i n t e d c o u r t p h y s i c i a n t o t h e E m p r e s s M a r i a T h e r e s a in V i e n n a . H e r e he c a r r ie d out e x p e r im e n ts o n p la tin u m a n d later, trav ellin g b e t w e e n t h e r e a n d P a r i s a n d L o n d o n , h e e n c o u r a g e d o t h e r s c i e n t is t s to i n t e r e s t t h e m s e l v e s in t h e s u b j e c t . In his l a t e r y e a r s in E n g l a n d he h a b i t u a l l v d i s p l a y e d a set o f t h r e e p l a t i n u m w a i s t c o a t b u t t o n s m a d e for h i m bv M a t t h e w B o u l t o n
7
The W idening of Interest in Platinum and its Properties
T h e V alu e o f this n e w m e ta l is n o t m e a s u r e d s o lely b y its sca rc ity, b u t sin ce it has b een p o s s i b le to r e n d e r it p e r f e c t l y m a l le a b le it is p o s s i b le to begin to r e c o g n ise the e m in e n t
J A N I N G E N - H O I SZ
q u a litie s that it p o s se s s e s."
T h e last few chapters have recounted the intensive an d progressive work of a small group of men, leading gradually up to the achievements of the seventeeneighties in France and Spain. W e now come to a rather less progressive period, disturbed by revolution and war, but one in which the interest in platinum nevertheless spread more widely throughout E urope with the gaining of experience of its properties and uses. There were several factors to account for this. O n e was the intense interest being taken in experimenting with m agnetism and static electricity and especially in the effects of passing the electric fire through wires of various metals. A nother was the considerable increase during the last two decades of the eighteenth century in the n um ber of scientific jou rn a ls th at began publication, these not only giving a more speedy account of researches th a n the older tra n sa c tions of the academies but also encouraging m uch correspondence from country to country, as well as reproducing papers from one to another, while a third was an increase in the travelling of scientists from one capital city to a n o th e r and their discussions and occasionally evenjoint experimentation. O n e other interesting example indicative of the increased interest in platinum is contained in a m em oire written by A. F. Fourcroy in 1785 immediately after his election to the Acadmie des Sciences. T h e great French navigator J. F. de L a Prouse was about to em bark on his voyage ro und the world and the Acadmie had been asked for advice on the work to be undertaken. Fourcroy included in his suggestions the rem ark th at new sources of platinum would be especially valuable (1). U nfortunately L a Prouse and his crew were later all lost in the South Pacific and nothing was ever heard of any search he might have m ade for platinum.
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T h e Influence o f Jan I n g e n -h o u s z T h e most fascinating figure of this phase of activity was J a n Ingen-housz, a D u tc h m a n by birth but an inveterate traveller and a pioneer in the field of plant physiology. As a very young m a n he was encouraged by Sir J o h n Pringle, then the chief medical officer of the British Army, w ho had met the family during his service in the Low countries in t h e W a r of the A ustria n Succession. Ingen-housz took his M .D . at Louvain and t h e n studied physics at Leyden under M usschenbroek, the inventor of the L e y d e n jar. After a brief period at the University of E dinburgh he settled as a physician in his native Breda until 1765 when, on the advice of Pringle, now the leading figure in L ondon medical circles, he came over to establish his own practice th e re (2). H ere he met Priestley a n d Benjamin Franklin and worked with W illiam W a ts o n at the Foundling Hospital in the early days of inoculation against smallpox. W a ts o n s interest in both electricity and platinum may well have p r o m p te d Ingen-housz to pursue these m atters further, but in 1768 he was chosen by Pringle, and with the approval of George III, to go to Vienna to inoculate th e children of the Em press M a ria T heresa. T his led to an appointm ent as court physician with a handsom e salary which he used in p a rt to set up a laboratory a n d to cultivate his taste for experim entation in physics and chemistry. In V ie n n a he entertained a n u m ber of distinguished visitors, including M a ria T h e r e s a s son the E m peror J o s e p h II, as well as visiting scientists. H e was elected a Fellow of t h e Royal Society in 1769 a n d in one of his early papers, dated November 1775 (3) he described several experiments on p latinum a n d its magnetic properties, following this with a n account of his melting the metal in a narrow glass tube into which he directed five or six electrical explo sions from three very large j a r s . H e concluded:
By this experiment it sho u ld seem as if platina (which hitherto could never be m elted by com m on fire by itself, b u t only in the focus of a very strong b u rn in g glass such as was a little while ago m a d e at Paris) were equally fusible if not more so th a n iron, by electrical fire.
T h u s Ingen-housz was the first to melt p latin u m by m eans other th a n a burning glass. Between 1775 and 1782 h e sent no fewer th a n nine papers to the Royal Society, although most of these concerned the respiration of plants, and he becam e a respected m em ber of t h e scientific com m unities of Vienna, Paris and London. T h e greater p art of the years 1777 to 1779 he spent in London, where he delivered the Bakerian lecture to the Royal Society, dealing with electrical p henom ena an d supporting F r a n k lin s O n e -flu id theory (4). H e rem ained in V ienna from 1780 until 1788, continuing the work on plant respiration that m ade him famous but also experim enting on platinum . D uring the visit to V ienna by the C ount von Sickingen in 1784 Ingen-housz was shown the C o u n t s m ethod of rendering platinum m alleable and they collaborated in a further experiment with the electric discharge, using a piece of wire provided by
110
T h e title p a g e o f t h e first v o l u m e of r e s e a r c h e s p u b l i s h e d by I n g e n - h o u s z in F r is in 1 7 8 5 a n d d e d i c a t e d to his a friend B e n ja m in F ran k lin. T his i n c l u d e d a d e t a i l e d a c c o u n t o f t h e w ork o n p l a t i n u m c a r r i e d o u t b> t h e C o u n t \ o n S ick in g e n a n d by t h e A b b e R o c h o n . w ith b o t h of w h o m h e h a d c o l l a b o r a t e d , f o llo w e d by a d e s c r i p t i o n o f his o w n e x p e r i m e n t a l w o r k o n t h e m e l t i n g of a p l a t i n u m w ir e by m e a n s of a n e l e c t r i c d i s c h a r g e f r o m a Ley d e n j a r w h ile t h e w ir e w as s u r r o u n d e d by o xy g en . H is su g g e stio n s for the c l a d d i n g b a s e m e t a l s with p l a t i n u m a r e also gi\ e n
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Sickingen. In a letter to his friend J a c o b van B reda of Delft he described their experiment, and also included it in his m ajor publication (5, 6).
A wire of platin um of the thickness of a large knitting needle was su rro u n d e d by a steel wire of which the point was very sharp; we raised the steel wire to incandescence by m eans of a Leyden jar inside a flask of good quality dephlogisticated air. T h e steel wire bu rn e d a n d to all ap p e a ra n ce s co m m u n ica te d the flame to the platinum . . . which was found to be in perfect fusion an d h a d lost neither its colour nor its malleability. T h is experim ent dem o nstrates th a t p la tin u m is a true metal endowed with all the qualities tha t m ake the o ther metals useful in the arts and trades; that it can be melted; th at the melting destroys none of its valuable properties, an d in consequence it only rem ains for us to take adv antag e of it, to see it in com m erce an d to find a less expensive m etho d for melting it.
His work on platinum continued when he received a gift of six pounds of the native metal from the M arquis de Santa C ruz an d at the same tim e obtained
111
information about the work of C h a b a n e a u in Spain. Going to Paris in J u ly 1778 to study Lavoisiers new chem istry he wrote th a t he found the chemists there were not taking very m uch interest in research on platinum .
1 did w hat I could to a w a k e n the interest of some of the best chemists of my ac q u ain tan ce a n d encouraged th e m to take up afresh their work on this metal tha t they had almost abandoned. I succeeded in draw ing them out of their inactivities: am ong others M. Pelletier, w ho se talents a n d learning are well known, having resum ed his researches, soon succeeded in taking a large step fo rw a rd.
During this visit to Paris (w hich was b ro u g h t to an a b ru p t end by the storm ing of the Bastille on July 14 1789) he m ad e contact, as we have seen in C h a p te r 5, with Ja n ety and with the A b b R o c h o n while he also collaborated with Pelletier in preparing malleable p la tin u m from the sal-amm oniac precipitate:
O n e should ra m it a n d p re ss it into a red-hot-crucible a n d th e n strike it with a blow of a pestle, or one forges it with a h a m m e r while hot a n d I have m ade from it several objects, among others a m e d a l w hich was very successful.
Ingen-houszs own account o f his work on platin u m is b o u n d up with reports of a num ber of other of his m an y researches in a book w ritten for publication in F rench in 1781 (6). However, a G e rm a n translation of it by his friend Niklas K arl M olitor appeared first in V ienna in one volume in 1782, an d then in a second edition of two volumes also in V ienna two years later, both u n d e r the title of Vermischte Schriften (7). O n l y in 1785 did the first volume in F rench m ake its appearance in Paris, with the second delayed until 1789, all with the title of Nouvelles Expriences et O bservations. T h e first service that Ingen-housz rendered was to give a detailed account of von Sickingens simplified m e th o d of refining platinum . H e th en describes R o c h o n s work on his m irrors a n d discloses the fact th a t he possesses two of them worked by Carrochez. N e x t he reports the use of R o c h o n s p latinum by two prom inent clockmakers, R o b e r t R o b in a n d Louis Berthoud, who used the metal for pendulum s and movements. T h e n he describes D a u m y s procedure, mentioning his m anufacture of do u b l metal, tu rn s for a m om ent to J a n e ty and from him to Pelletier. Finally com es a sum m ary of the properties of platinum , at the end of which he points out th a t in its hardness it possesses a property in which it transcends both gold a n d silver, these two metals having to be hardened by means of base metals like c o p p e r to m ake them useful for jewellery or plate, while a vessel m ade of pure p la tin u m has sufficient hardness to need no alloy whatever. Ingen-housz adds to this th e statem ent th a t it was he who suggested to D au m y the cladding of copper w ith a thin foil of platinum in the same way as he doubles this metal in his w orkshop w ith a foil of silver or gold to m ake it into ornam ents and p late . T h e a tte m p t was successful a n d Ingen-housz points out the possibilities open to copper doubled or covered with this indestructible p re cious metal, unalterable and u n ta rn ish a b le by exposure to air or by contact with substances which spoil the brilliance of the purest silver a n d blacken it (6).
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T h u s Ingen-houszs direct addition to the knowledge of p latin u m was by no means negligible, but his principal contribution was probably m ade by his journeying from one capital to another an d by his discussions in the best academic circles. H e emphasised w hat he had to say by having a set of three waistcoat buttons m ade in platinum a n d displaying these to his friends. T hese were m ade by M atthew Boulton, whose works in B irm ingham he visited during his later period in England, an d w hen he also attended a meeting of the famous L unar Society, and they are referred to in a letter to Boulton d ated M a rc h 9, 1792 that survives in the collection of Boulton m anuscripts:
I would have acknowledged long ago the receipt of the p la tin a b u tto n s you was so good as to m ake for me out of the piece I left u n d e r your hands, if 1 h a d not desired to know before the ju d g e m e n t of some of my friends abou t them. T h e y all adm ire them very much. Several questions were m a d e ab ou t the price of them. F o r my p a r t I am much delighted w ith them a n d am not a little astonished, th a t they could fall out so well a n d the p latina w ithout mixture of other metals is susceptible of such high polish: which however I think it would not have acquired in less able hands. Receive my gratefull acknowledgement for the civility I received from you at B irm in gh am an d nominaly for the trouble you p u t yourself at in m a nufactu ring these triple beautifull an d everlasting buttons, for which I am ready to p a y the expenses if you let me know the am ou nt of them, tho you was so kind as to receive it w hen I h a d the pleasure of being at your h o u s. (8)
Ingen-housz spent the last few years of his life in England, which he loved, as the guest of the Earl of Shelburne at Bowood an d was perm itted to m ake use of the laboratory created there for Josep h Priestley in 1773. T h e r e is no doubt that he was a prim e factor in the widening of interest in p latin u m th at was soon to bring about im portant advances.
V an M a r u m s Giant G enerator Another friend a n d c o u n try m an of Ingen-housz, M a rtin u s van M a ru m , (17501837) carried out a rem arkable series of experiments on the effects on a n um ber of metals subjected to the electrical discharge. H e had an enorm ous electrostatic generator, built by the London instrum ent m aker J o h n C u th b e rtso n and installed in the Teyler F ou n d a tio n building in H aarlem . T h is consisted of two glass plates over five feet in diameter, which ha d to be turned by two workm en standing on a specially constructed table; in m o d ern term s it was capable of discharging half a million volts. After investigating the oxidation of a n u m b er of metals and alloys van M a ru m recorded:
Finally, in April 1790 I a tte m p ted the calcination of Platinu m , which I had specially m ade for the purpose by M . Je a n e ty in Paris a n d w hich I h a d received shortly beforehand. T h e wire was d raw n to a thickness of 1/75 inch; a n d when I now examined its fusibility by the electric discharge, it seemed to m e th a t it was almost the same as tha t of silver. T h e electric discharge also reduces p la tin u m as readily as silver to a fine grey pow der . . . this c a n be considered as a n oxide so long as it has not been dem onstrated by decisive experim ents th a t the effect of the discharge on this m etal is a totally different o n e (9). 113
W illia m P a r k e r s B u rn in g L e n s
Before these applications of th e electric fire , however, there are several attem pts to record on the m elting of p latin u m by the m uch-used m ethods of both the burning glass and the furnace. In 1782 W illiam Parker, the L ondon in strum ent m aker who had generously supplied Priestley with his burning glasses, constructed at his own expense, running to some 700, a three-foot diam eter solid lens that he hoped to sell to the Royal Society. In a letter to Sir Jo sep h Banks, the President, Parker requested him to a ttend trials of this lens, but although a num ber of scientists a tte n d e d Banks was not am ong them. Parker wrote to Banks a g a in two weeks later giving a few details of his melting of a n um ber of metals (10).
Yesterday and today m yself w ith several G e n tle m e n have m a d e Some E xp eri ments with my Lenses of which I give you as follows a n d I shall Esteem it a Singular favour if you will favour me with y o u r Presence on a fine D ay w ith any G entlem en you please to m ake w hat Experim en ts you think pro per a n d am Sir Your M o st H u m b le Servant W m P ark er Fleet Street 16 J u 1 1782 y j oz cast iron 15 seconds 10 G rain s F in e G old 13 seconds 10 G rain s P la tin a 30 seconds
Among those present was th e ubiquitous M agellan, who recorded th at M r. P a rk ers burning lens in L o n d o n perfectly melted platina in less th a n two m in u tes (11). A more conservative account was given later, however, by P a rk e rs son Samuel, writing i n T h e C y c lo p a ed ia published by A b ra h a m Rees in 1819. H is account reads ( 12):
Platina: T h e experiments evince th a t the specimens were in different states of approach to a complete metallic form, several of th em th rew off sparks, w hich in most cases were m etallic.
(T h is account m isp rints th e t i m e for the m elting of p l a t i n u m as only 3 se conds)
T h e A ctivities o f L o r e n z C r e ll Yet another attem pt to m ake use of the high tem p e ra tu re of a porcelain furnace was m ade in 1784 w hen Lorenz Crell, w ho was to have m u ch greater influence through his publications, paid a visit to the Fiirstenberg factory th at had been established by the Duke of Brunswick in 1747. T o g e th er w ith its director, J o h a n n Ernst Kohl, Crell experim ented with some p latinum foil a n d wire he had been given by the C ount von Sickingen as well as with some native platinum , but found that none of his samples m elted (13). H e concluded, however, that each new investigation taught something. Crell had studied in Strasbourg, Paris, L ondon a n d E d in b u rg h a n d had been greatly influenced by both C u lle n and Black. In 1774 he becam e a professor in
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his native city of H e lm stadt and three years later decided to found a n d edit a periodical on chemistry. At first issued quarterly, this becam e the m onthly Chemische Annalen in 1784 and created a m edium in which G e r m a n an d other chemists could exchange their findings. Even before this Crell was a tireless correspondent with scientists in other countries, am ong others with Jo sep h Black at Edinburgh, an d one interesting exchange of letters, preserved in the University of E dinburgh Library, concerned the process devised by the C ount von Sickingen. In April 1782 Crell informed Black that Sickingen h a d melted twenty pounds of p latinum an d obtained a metal that was almost m ore ductile th an gold itself . In the following Septem ber Black included in his reply
T h e C ou nt of Sickingens success in melting Platina in such q u an tity as 20 lib is very remarkable, have you learnt his m etho d? B ergm an has some curious observations upon the means for giving it fusibility.
O n O ctober 24th Crell replied to Black, and an extract from this letter is reproduced over page. It m ust be rem em bered that Crell adhered to the old nomenclature and was a confirmed phlogistonist, hence the archaic nature of his comments. Black was clearly interesting himself in the properties of platinum and its fabrication, but it was not until some years later that he obtained two pounds of native platinum from one of his former students, Ignacio Ruiz de Luzuriaga, now practising medicine in M a d rid and later to become physician to the King of Spain. O n e consquence of this interest by Black was the influence it
L orenz F lorenz F rie d ric h von Crell 1745-1816

A n a t i v e o f H e l m s t a d t in t h e D u c h y of B ru n sw ic k , C rell stu d ie d m e d ic in e and c h e m i s t r y in S t r a s b o u r g , P a r i s . L o n d o n a n d E d i n b u r g h , r e t u r n i n g to H e l m s t a d t as a p r o f e s s o r in t h e u n i v e r s i t y t h e r e . A lthough he c a r r ie d out a se ries of u n s u c c e s s f u l a t t e m p t s to m e l t p l a t i n u m in t h e p o r c e l a i n f u r n a c e at E u r s t e n b e r g his greater co n trib u tio n w as the f o u n d a t i o n o f his ('.hemisehe A nnalen, t h e first j o u r n a l to b e d e v o t e d to c h e m i s t r y , a n d his enthusiastic* e d i t i n g and t i re le s s correspondence w ith sc i e n t if i c w o r k e r s t h r o u g h o u t E u r o p e . H e w as e l e c t e d a F ello w o f t h e K ov al S ociety in 17 88
115
\ n extract from a letter from L o re n z Crell to P ro fesso r Jo se p h Black of E d in b u rg h , dated O ctob er 24th 1782. in answ er to the le tte r en q u irin g a b o u t the Sickingen process. In m odern term s this reads: T h e C ount of Sickingen has p u b lis h e d his m ethod : it seem s to m e very ingenious: he dissolxes the p latin u m in aq u a re g ia , precipitates the iron by P ru ssian Blue: evap o ra te s the clear fluid, calcines it in a crucible, a n d puts the m etal red hot on the anvil, w here w hen very well beaten with the h a m m e r, it u n ite s into one m ass a n d is to be e x te n d e d in fine wires, as gold, an d similarly into leaxes.
had on another of his students, Smithson Tennant, who as we shall see later in Chapter 9 made a visit to Crell in 1784 and discussed Sickingens method with him.
Thomas Willis of Wapping Another long but unsuccessful series of experiments was carried out by a manufacturing chemist and druggist named Thomas Willis, operating in Wapping on the Thames just below the Tower of London. His attempts to melt platinum with a variety of fluxes, with charcoal and, following Pelletier, with phosphorus, were at least partly satisfactory, but in no case was his product capable of being forged. Willis also tried to melt the sal-ammoniac precipitate, but his manipulative skill was not of the highest order and he lost the precipitate in his fire. He had the assistance in this work of the younger Thomas Henry, then only twenty-one, who had been sent to London by his father, the leading figure in the Manchester Literary and Philosophical Society, and it was pre sumably for this reason that Willis submitted his paper to that body. His apologetic introduction is reproduced here, but he did not carry out the promise to pursue his objective. The paper received wide publicity, however, in translation into French and Germ an periodicals (14). Lavoisiers Larger Scale Attempts A further cause of greater activity directed towards the melting of platinum was the report of the Acadmie des Sciences, prepared with the encouragement of Guyton de Morveau, to the French National Assembly in 1790 recommending the adoption of the metric system and the preparation of standards made in
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T h e i n t r o d u c to r y l e t t e r f r o m T h o m a s Wi l l i s . the I.o n d o 1 1 chemical m an u factu rer. acco m p an y in g the a c c o u n t of his m a n y unsuccessful a t t e m p t s to m elt p l a t i n u m a n d to yield a m a l l e a b l e p r o d u c t . T h e p a p e r was p r e s e n t e d to t h e M a n c h e s t e r L i t e r a r y a n d P h i l o s o p h i c a l S o ciety , f o u n d e d in 1 78 5. largely b e c a u s e t h e y o u n g so n of Thomas H e n r y , o n e o f its vicep r e s i d e n t s . h a d a s siste d W i 11is in th e w o r k . D e s p ite t h e lack o f su c cess r e p o r t e d in th e p a p e r it w as widely r e p r o d u c e d in F r e n c h a n d G e r m a n journals
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W illis,
Cbemift, at the Hermitage,

Thomas H enry,
I " 89.
London. Communicated by M r.
F . R . S. &c.
READ
AUGUST
IJ,
T O
M *.
T H O M A S
H E N R Y .
JULY 18, 1 78 9 .
LONOON,
S I R,
H E R E W I T H inclofe you a few experiments on platina, and beg the favour o f you to lay them before your truly com m endable fociety. I fhould have been happy could 1 have fucceeded jn rendering this extraordinary metal malleable, as it would have been o f the greateft con fequence in conftru&ing optical inftruments, on account o f its not being affe&ed by the air. I do not defpair o f fucceeding, as my intention is to purfue this objeft ftill further, and I lhall with pleafure com m unicate my future proceffes to the public through your m od excellent inftitution. I am , S f r . Y our moft obedient, & c. T H O M A S W IL L IS .
platinum. T h e only platinum available in Paris at this time was J a n e t y s m ade by the-arsenic process, an d this was on a relatively small scale. Lavoisier was well aware that any m ethod for melting platinum on a larger scale would prove difficult and expensive, yet in 1789 he was proposing to construct a very simple furnace for this purpose, of very refractory e a r th , an d to pass oxygen through this from several of his gasometers to produce a heat greatly more intense than any hitherto know n (15). Lavoisier was m uch occupied with other m atters, and the work of designing a n d building the furnace was delegated to his assistants A rm and Seguin and J e a n Meusnier. T h e diaries of Sir J a m e s Hall studied by Dr. J. A. C haldecott an d already referred to in C h a p te r 5, (16) show that in 1791 such a furnace was u n d e r con struction, the objective being the melting of some 50 kilogramm es of platinum
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III 1791 L avoisier an d his Iwo a s s i s t a n t s S egii i n and M eusnier began to design a fu rn ac e, to be fed with oxygen, in w hich to melt fifty kilo gram m es of platin u m and sought the advice of Josiah W edgw ood on the most su it a b le refractory to w ithstand the very high te m p e ra tu re s involved. W edgw ood felt u n a b le to help a n d passed on th e e n q u i r y to J o s e p h Priestley . T h is is the relevant passage fro m W edgw ood's letter to Priestley of S e p te m b e r 2nd 1791
for the preparation of the standards of length and weight for the Commission of Weights and Measures. T he search for a suitable refractory was however a major problem, and Lavoisier and Seguin called upon Josiah Wedgwood for advice. Wedgwood felt unable to recommend a clay of the most infusible nature and in turn appealed to Priestley for his views (17). T h e latter also felt unable to advise except to say that he considered magnesia to be the most likely substance to withstand such intense heats (18). That these efforts of Lavoisier and his two colleagues did not meet with success is evident from the fact that the Commission turned to Janety for their needs of platinum, as will be shown in Chapter 10.
The Properties of Eighteenth Century Platinum The early workers in platinum checked the purity of their product by determin ing its specific gravity and considered that the higher it was, the purer the metal must be. The method was rather rough, since at first the amounts of platinum available were very small and the accuracy of the balances of the time not high. Nevertheless, the check had its value and increased in exactitude as the quality of the apparatus available improved. From time to time, however, the figures quoted were too high, being greater than what is now generally accepted as the correct value for the pure metal (21.45). Von Sickingen, the first man to prepare
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malleable metallic p latinum in more th a n m inute quantities, found its gravity to be 21.061. T h e n cam e C habaneau, claiming th at his forged metal was so pure that it had a gravity of 24, but de M orveau could not m ake a sam ple of it yield a figure higher th a n 20.833 (19). At the sam e time he exam ined a piece of hardworked wire bought in Paris and probably m ade by J a n e ty a n d found its gravity to be 20.847. Ingen-housz, working before 1789, obtained a figure of 22.285 for a piece from a C h a b a n e a u bar, whereas two medals m ade by himself and J a n e ty showed 20.108 for the former and 21.0 for the latter (6). Incidentally, Ingenhousz says th at Ja nety, like C hab a n e au , claimed a gravity of 24 for his best metal, but it is interesting that in 1813, by which time the accuracy of balances had improved considerably, a sample of his metal showed a gravity of 20.01, against 21.04 given by some of the undoubtedly pu rer products of Wollaston. (20). T h e only other physical property of platinum that cam e into account in the eighteenth century was its tensile strength, and the m easurem ent of this becam e a practical possibility w hen von Sickingen produced a metal pure enough to be draw n into fine wire. For his own m easurem ents he designed a n ingenious testing m achine illustrated here a n d used a wire of diam eter 0.025 inch, o b ta in ing a figure which, w hen translated into m odern terms, represents a breaking strain of 24.9 tons per square inch. T h e test was repeated in 1795-1796 by Guyton de M orveau on platinum which probably cam e from J a n ety , an d he obtained a result equivalent to 25.2 tons per square inch. De M o rv e a u s specimen was in cold-worked condition, and so no doubt was von Sickingens. It is interesting to com pare these figures with those given by a m odern product,
W h en the C o u n t von Sick i n g e n s u c c e e d e d in p r o d u c i n g p l a t i n u m in t h e f o r m o f w ire it b e c a m e p o s s i b l e to d e t e r m i n e its t e n s i l e s t r e n g t h . T h i s shows the m a c h in e designed a n d b u i l t by S i c k i n g e n . o ne of th e very earliest m e c h a n i c a l t e s ti n g d e v i c e s to b e i n t r o d u c e d in to p h y s i c a l m etallurgy
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a n d to find th at the comm ercial platin u m of today (99 per cent p latin u m ) can yield a figure of up to 22.3 tons per square inch in the cold-worked state. It is therefore evident that in p u rity the eighteenth-century metal was but little inferior to the commercial metal of today. It should be realised, however, that with the exception of von Sickingen and to some extent of C habaneau, all the workers in p latin u m up to this point had a per cent or two or possibly even more of iridium in their metal. W h e n native platinum is dissolved in a q u a regia a considerable proportion of the iridium also goes into solution as iridic chloride, which m ay later be reduced to iridous chloride. W h e n am m onium chloride solution is added, if all the iridium is there as iridic chloride, most of it is prec ip ita te d as a m m o n iu m chloriridate with the am m onium chloroplatinate a n d the latter is thereby coloured red. It will be rem em bered how m any of the early workers described their precipitates as red or reddish. If, however, the iridium is all present in the solution as iridous chloride, the sal-ammoniac will not precipitate any of it, since am m onium chloriridite is soluble, an d the p la tin u m precipitate will be a pure yellow in colour. Thus, in practice there will be all sorts of gradations betw een these two extremes according to the way i n which the dissolving of the native metal has been effected. T h e re are other factors, too, th a t enter into the m atter. T h e platinum tends to be precipitated first, since the solubility of the chloroplatinate is a little less th a n that of the chloriridate; dilution of the solution tends to hold back precipitation of the chloriridate for the same reason; the presence of excess hydrochloric acid is said to delay precipitation of the iridium salt; a n d of course if the aqua regia used in the original attack on the native m etal is dilute less iridium is dissolved. All these things were unsuspected by the workers before the discovery of iridium an d three o t h e r metals of the group by S m ithson T e n n a n t an d W ollaston in the early years of the nineteenth century (to be recounted in C h a p te r 9) an d this was responsible for m ore th a n a few of their differences and difficulties with what they su p p o sed to be one distinct metal.
A c h a r d s S tu d y o f P la tin u m A llo y s So far only the properties of relatively p u re p latinum ha d been studied, but in 1788 there appeared a rem arkable book from the hands of F ra n z Karl A c hard in Berlin. He will be rem em bered a s the discoverer of the arsenic process for p re paring malleable platinum described in C h a p te r 5, but he now published the results of a laborious an d com prehensive pro g ra m m e on the alloys of eleven metals, including platinum , with ea ch other (21). In this he pointed out that the properties of alloys are quite different from, those of the pure metals and are unpredictable. All the alloys w e re in the as-cast condition and on these he carried out tests for density, hardness, resistance to im pact a n d to the file and then on the effects of exposure to air, to hydrogen sulphide and to acids on polished surfaces. H e attem pted to alloy p la tin u m in the proportions of 1:2 an d 2:1 with cobalt, copper, iron, lead, tin, zinc, bism uth, antim ony an d arsenic, and finally
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T h e lilie page of the ra re and a lm o s t f o r g o t te n b o o k pu blished in Berlin by F ranz K arl A chard in 1788. A m ong no less th an 894 sam ples of the binary alloys of eleven m etals A c h ard reco rded his r e s u lt s w ith a ll o y s of platin um with most other base m etals available at the time, but un fo rtu n a te ly few ol these were sound enough to w ithstand his tests for h a r d n e s s , d u ctility a n d resistance to impact
RECHERCHES
SUR LES
A L L I A G E S
MTALLIQUES.
PA R Directeur de la OalTe de Phy fique dam l'Acadmie Royale de* Sciences Je Belles .Lettres dePrufTe, Membre de 1*Acadmie Royale Sc Impriale dis curieux de la (nuira, de* Acadmies Royales de Turin, de Soede, d'Orlans, de O ijun, de Milan, des Acadmies K klonle. de Bavire Sc Mat-nce, Membre de la Socit HoUanduife de Hadcm, de la Socivtc Pliyfiquc de L)aiuic, de h Socit littraire de Halle, de la Socit plryfiq.ie de Berlin, de U Socit Royale de Francfort fu l'Oder, de la Socit Oeconomique k Patriotique de Silfie Sc de plufieuza autres Acadmies, te Socit littraires.
PROPRITS DES
c h a r d
IMRIM CHEZ GCOBOE JACQUES DECEfcR le FlLS, IMPRIMEURS PRIVS OU Roi.
B E R L I N
17 88.
produced a ternary alloy of equal parts of copper, iron and platinum which he found to give considerable hardness as measured by the diameter of the flat small impression made on a small sphere falling repeatedly from successively greater heights. Not all of the binary alloys were of course sufficiently sound to withstand his series of mechanical tests, while his specific gravity figures he admitted were so low as to indicate considerable porosity. These results were published in a book Recherches sur les Proprits des Alliages Mtalliques, written in the French language insisted upon by Frederick the Great, but unfortunately it was virtually ignored by metallurgists everywhere, while Achard himself turned to the development of the beet sugar industry in Germany. This rare work was brought to light only in recent years by Professor Cyril Stanley Smith (22) to whom the present writer is indebted for his attention having being drawn to it.
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C oun t M u s s in - P u s h k in s M e t h o d
Interest in platinum was now spreading not only in those countries where scientists had already been w orking with it but also into other parts of Europe. T h e first initiative in Russia w as taken by another aristocrat, the C ount Apollos M ussin-Pushkin, a m e m b e r of the R ussian court and the founder of the M ining College in St. Petersburg. His work began in 1797 a n d continued until his death in 1805, the principal contribution being a m ethod of refining platinum and rendering it m alleable by the use of mercury. H e precipitated an aqua regia solution of p latinum with sal-am m oniac as usual, washed the precipitate w ith a little cold water, dried it, calcined it to sponge and washed the latter tw o or three times with boiling water. After that he boiled it with dilute hydrochloric acid to remove residual iron, ignited it and then mixed it into a paste in a m o rta r with mercury. W h a t he produced was not a true am algam since the two m etals did not form one, but it was a thick paste that could be moulded and handled. T h is so-called a m algam was then com pressed
in tubes of wood, by the p re ssu re of a n iron screw u p o n a cylinder of wood, a d apted to the bore of the tube. T his forces out the s u p e r-a b u n d a n t m ercury from the am algam a n d renders it solid. A fte r two or three hours I b u r n u p o n the coals, or in a
C o u n t A p o llo s M u s s i n - P u s h k i n 1760-1805
An o f ficial of t h e I m p e r i a l C o u r t s u r r o u n d i n g C a t h e r i n e t h e G r e a t in St P e t e r s b u r g a n d t h e f o u n d e r of t h e M ining College th e r e , M u s s in - P u s h k in devised a m e th o d of com pressing platin u m sponge w ith m ercury, f o l lo w e d by h e a t i n g a n d f o rg in g . H e trav e l l e d w id ely in E u r o p e o n b e h a l f of the m in in g au th o ritie s, m eeting m anv o t h e r s c i e n t is t s , a n d w a s e l e c t e d an H o n o ra ry M e m b e r of the R ussian A c a d e m y o f S c i e n c e s in 1 79 6 a n d a F ellow o f t h e R o y a l S o ciety in 1 7 99 . H e a ls o r e - o r g a n i s e d t h e C o lle g e of M in e s i n to t h e m o r e a c t i v e M i n i n g C a d e t C o r p s in 1804. I n 1 8 0 2 . a f t e r t h e a n n e x a t i o n of G e o r g i a b y R u s s i a , h e w a s s e n t t h e r e to s t u d y t h e m i n e r a l r e s o u r c e s a n d c o n t i n u e d his w o r k on p l a t i n u m in a l a b o r a t o r y in Tiflis
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crucible lined with charcoal, the sheath in which the amalgam is contained and urge the fire to a white heat; after which I take out the platina in a very solid state fit to be forged. (23) M ussin-Pushkin published his first pa p e r on his p latinum a m a lg a m in the
Annales de Chemie in 1797 (24). T w o years later, in a letter to Je re m ia s Benjamin
Richter, the assayer and chemist to the Berlin porcelain factory w ho had introduced the concept of stoichiometry in 1792, he asked for an opinion on the am algam and R ichter passed the letter to Lorenz Crell for publication in his Chemische Annalen. In a footnote Richter, whose ideas had been sorely neglected, wrote: This scientists prevailing curiosity (I will not say enthusiasm) for a new area of mans knowledge demands that I should publicly express my warmest thanks to him. (25) Several other papers followed, written from widely different parts of Russia, concluding with a letter summ arising his process written to the English chemist and Fellow of the Royal Society Charles H atchett, which was published in 1804 in the Journal o f N ational Philosophy Chemistry and the Arts founded by J o h n Nicholson in 1797. I n this he added: The whole of the operation seems to be governed by the pressure of the atmos phere and the laws of cohesive attraction: for the air is driven out from between the molecules of the platina, which by their solution in mercury are most probably in the primitive and consequently uniform figure. It is very visible and at the same time a very amusing phenomenon to observe how the platinum contracts every way into itself as if pressed by some external force. (26) T h e only new contribution of M ussin-Pushkin was his m eth o d of getting his platinum into forgeable form, but the care he took to remove the last traces of iron from his sponge should be noted, in that he w ashed the original precipitate with cold water, then washed the ignited sponge an d in addition boiled it in dilute hydrochloric acid. This is the only p art of his process th a t found its way into later practice.
T h e M archese C o sim o Ridolfi No work of significance ha d yet been undertaken on platin u m in Italy. In 1784 the Chevalier Nicolis de Robilante, the Inspector G eneral of M ines, had pre sented a paper on the subject to the Acadmie Royale des Sciences de T u r in (27) but this recorded work carried out m uch earlier on p latinum received from Spain through the Piedmontese am bassador there and contained nothing that Lewis had not discovered by 1755 although he refers to the work of T il let in 1779. M uch later some work was undertaken by a distinguished Italian whose early years were devoted to science but who then turned to politics. In 1815 the Marchese Cosimo Ridolfi, the son of a rich and noble family who ha d installed a laboratory in their palace in Florence, contributed a long p a per O n the Purifi123
T h e M a rc h e se C o sim o Ridolf 17941865

\ f t e r s t u d y i n g p h y s i c s , c h e m i s tr y a n d b o t a n y in t h e M u s e u m of N a t i o n a l H i sto r v in F l o r e n c e a n d w r i t in g a t e x t b oo k o n b otanx f o r t h e b e n e f i t of a g r i c u l t u r a l i s t s Kidolfi es ta l)lish e d a l a b o r a t o r y in t h e fa m ily p a l a c e in 1813. H e r e h e c a r r i e d o u t a lo ng se rie s of e x p e r i m e n t s o n p l a t i n u m , h o p i n g to d e x e l o p a s i m p l e r p r o c e s s t h a t w o u ld l e a d to a n i n c r e a s e in its a p p l i c a t i o n s , l i e l a t e r b e c a m e D i r e c t o r o f t h e M in t in F l o r e n c e a n d f o r a b r i e f p e r i o d in 1848 he w as p r i m e m i n i s t e r to t h e G r a n d D uke of Tuscanv
cation, Fusion and Economic U se s of P la tin u m to the Giornale di Scienza ed Arte. After reviewing the procedures a d o p te d by J a n e ty , Pelletier and L eithner and then the m ercury am algam m e th o d of M ussin-Pushkin, Ridolfi proposed a simpler m ethod that would m ak e its use more possible in the m an u fa ctu res . H e h a d observed that no-one h a d succeeded in com bining p la tin u m with sulphur and so conceived the idea that by converting all the other metals found in native platinum it should be easy to purify. After removing as m uch of the sand an d iron as possible from t h e crude p latinum and washing in hydrochloric acid Ridolfi melted his metal w ith lead a n d then granulated it by pouring into cold water. It was then pulverised, mixed with its own weight of sulphur, put into a white-hot clay crucible a n d heated for ten minutes. After cooling the metallic button, freed from iron a n d copper, was fused again with enough lead to remove the sulphur, the resulting lead-platinum alloy being heated and forged with a hot h am m er until all the lead was squeezed out. Ridolfi claimed that his platinum was malleable and ductile with a density of 22.63 and that he successfully produced wire as well as foil th at could be employed for the clad ding of copper and brass, but his process never becam e anything more th a n a laboratory curiosity. His p aper received brief sum m aries in T illo c h s Philosophical M agazine a n d rather later in T h o m s o n s Annals o f Philosophy (28).
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The applications of platinum in the late eighteenth century were but few. Janety produced ornamental items and one or two pieces of tableware but a growing demand for crucibles made itself felt very soon and he had to turn his attention to these. Similarly Chabaneau had confined himself to decorative objects and a few platinum medals had been struck. There was, however, one other application and the first in the long history of the uses of platinum in manufacturing industry that began to develop before the close of the century. Contemporary with the early scientific studies of platinum were those on porcelain and its decoration. In the winter of 1788-89 a paper O n the Use of Platina in the Decoration of Porcelain was read to the Berlin Academy by Martin Heinrich Klaproth (29), the most distinguished German chemist and the leading analyst and mineralogist of his time. Beginning as a poor apothecary, he had later studied under Marggraf and in 1780 had married his wealthy niece, so being able to buy himself a laboratory, and from here there poured out analyses of hundreds of minerals as well as many papers to the Academy. His activities did not end here, however, and for some years he was retained as a con sultant to the Royal Berlin Porcelain Factory. Klaproth had not been among the numerous chemists who had worked on platinum, but he was obviously thoroughly familiar with the progress that had
P la tin u m in the D e c o r a tio n o f P o rcela in
M artin H einrich K la p ro th 1743-1817
T h e greatest G e rm a n chem ist of his time. K laproth also took an active interest in technology and served for som e years as a consultant to the Berlin Porcelain Factory. In 1788 he p r e sented a paper to the Berlin Academ y of Sciences describing his experim ents 011 the use of platin u m for the d e co ra tion of porcelain an d displaying a n u m b e r of specim ens, so initiating the first application of platin u m in m an ufacturing industry
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so far been made. After a s u m m a ry of w h at was then known and a reference to the work of my worthy colleague M . A c h a r d K la p ro th wrote
How far platina may be e m p lo y ed in porcelain pa inting has never yet, as far as I know, been examined: I therefore th o u g h t it of considerable im p ortance to m ake some experim ents on this subject, w h ic h did not deceive m y expectation; b u t on the co n trary, convinced m e that this object, in the h a n d s of a n ingenious artist, m ay be bro ught to perfection.
K laproth exhibited to the m eeting a n u m b e r of samples of porcelain m ade in the Berlin factory and o r n a m e n te d with platinum . H e described his simple and easy process as follows:
I dissolve crude platina in a q u a regia, a n d precipitate it by a s a tu ra te d solution of sal am m oniac in water. T h e r e d crystalline precipitate thence prod uced is dried, and being reduced to a very fine pow der is slowly b ro u g h t to a red heat in a glass retort. As the volatile neutral sa lt, com bined w ith the p la tin a in this precipitate, becomes sublimated, the metallic p art rem ains b ehind in the form of a gray soft powder. T h is pow der is then sub jected to the same process as gold; th a t is to say, it is mixed with a small qu a ntity of t h e same flux as th a t used for gold, a n d being ground with oil of spike is applied with a brush to the porcelain; after which it is b u rn t-in u n d e r the muffle of a n e nam ellers furnace, a n d th e n polished with a b urnish in g tool. T h e colour of platina b u rn t in t o porcelain in this m a n n e r is a silver white, inclin ing a little to a steel gray. If the p la tin a b e mixed in different proportions with gold, different shades of colour m ay be o b ta in e d ; the gradations of w hich m ay be num bered from the white colour of u n m ix e d platina to th e yellow colour of gold. Platina is capable of receiving a co nsid e ra b le a dd itio n of gold before the tran sition from the white colour to yellow is p e r c e p tib le .
T h e bound collection of papers, including K la p ro th s, read before the Berlin Academy in 1788-89 appeared in 1793, an d was certainly a rath e r exclusive publication and little attention was p a id to this interesting and attractive development until his paper was rep roduced in 1802 in the Allgemeine Journal der Chemie, founded by Alexander N icholas von Scherer in Leipzig in 1798, and immediately afterwards in E n g lish in the Philosophical M agazine an d again in an abridged version in N icholson J o u rn a l (30). s By 1791, however, J e a n D A rcet, Professor of C hem istry at the Collge de France and M a c q u e r s successor as technical director of the famous Svres porcelain factory, had introduced p latinum decoration there. H e had interested himself in platinum some twenty-five years earlier and had tried unsuccessfully to melt it in the porcelain fu rn a c e at the factory established by the C om te de L auraguais in Alenon (31). Platinum decoration was also introduced into the V ienna porcelain factory by their colour chemist Joseph L e ith n e r in about 1804 although a n account of his work did not appear until s o m e years later (32). H e mixed p latinum in the form of very fine powder with oil of turpentine a n d applied the paste in several layers, each coating being dried before the next was added, a n d then fired the porcelain at about 800C. In a curious variation of this procedure Leithner similarly built-up successive layers of p latin u m on to p a per so that, after
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Platinum decoration on p o r c e l a i n c a m e in to u se in t h e S e v r e s f acto ry only t h r e e y e a r s a f t e r K l a p r o t h r e a d his p a p e r in B e rl i n a n d b e f o r e it \*as p u b l i s h e d . T h i s is o n e of a set o f S e v r e s h a r d p a s t e p o r c e l a i n p l a t e s d a t e d 1792 on w h i c h t h e d e c o r a t i o n h as b e e n c a r r i e d o u t in g o ld a n d p l a t i n u m . All t h e f a c e s a n d m any o f t h e a r c h i t e c t u r a l d e t a i l s a r e in p l a t i n u m o n a b l a c k g r o u n d . T h e gift of L ew is E in s t e i n in 1 9 6 2 . th is is now in th e M etropolitan M u s e u m of A r t in New Y o rk
heating, a thin sheet of the metal rem ained that could be worked into any desired shape, It was used for a tim e to repair cracks and holes in crucibles but was not of course of significant importance.
English Lustre Ware T h e wider publicity given to K la p ro th s work by the English translations led to the British pottery m anufacturers taking advantage of p latin u m as a decorative medium. T h e date of its introduction into the Staffordshire potteries in E ngland has, however, been the subject of great debate and of m any claims th at cannot be upheld. H a d Jo sia h W edgwood still been alive and active w hen K la p ro th s paper appeared in English the story might well have been different; he was of course a Fellow of the Royal Society and a keen reader of the scientific journals, but he had retired by 1790 an d he died in 1795. M a n y writers on ceramics have m aintained that the silver lustre w a re as it was called was produced by the W edgwood factory in the 1790s or early 1800s, but in fact it was not until 1806 that any real evidence can be presented for their use of platinum , a n d then they were following the practice of a rival pottery. It is to one J o h n Hancock, employed by H enry Daniel as a n enameller in the Spode factory, th at credit must be given for a process that m ad e metallic decora tion with platinum a commercially successful technique. H ancock had been
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apprenticed to the D erby P orcelain Factory u n d e r W illiam D uesbury where he acquired his knowledge of the p r e p a r a tio n of colours. H e was taken on by Daniel in 1805 under a curious a rra n g e m e n t by which undecorated w are was passed on to Daniel, working inside t h e Spode factory as a n independent decorator. Hancock must have read, or h a d his atte n tio n draw n to, one of the English translations of K la p ro th s p a p e r, for by the closing m onths of 1805 he had successfully developed metallic lustre decoration. T he details of this sequence of events have been established by L e o n a rd W h ite r in his study of the Spode family an d factory (33). U n d e r the a rra n g e m e n t ju s t m entioned Daniel had to pay Spode a rental for the equipm ent used in the p rep a ra tio n of colours, and he had no intention of revealing H a n c o c k s invention to his employer. W h ite r continues:
T his presented him with th e p rob lem of how to enter in the record the grinding of platinum , the very m ention o f which w ould tell too much. N o such secrecy was necessary for pale go ld (which D a n ie l m a d e in the prop ortion of half a n ounce of p r e p a re d gold to 12 gram m es of p r e p a r e d silver) a n d in his colour book he noted N ovem ber 11th 1805 half p o u n d p latin a entered b y the na m e pail gold in Mr. S. book.
T h e earliest surviving pieces of Spode ware with lustre decoration show the rath e r dull leaden variety a n d is likely th a t several years of experim entation and failure by Hancock and by o thers were necessary to bring the process to full success. T h e secret could not be kept however H ancock is said to have sold the recipe for a small sum of money to anyone who w anted it (34) an d very soon Wedgwood, among others, was em ploying platinum decoration. By Decem ber 1806 J o h n W edgwood had sent j u g s decorated all over with p latin u m a n d gold respectively to their friend J o h n Leslie, the Professor of M a th e m atic s in E d in burgh University, who had once b e e n employed as tu to r for his children by the first Josiah. Leslie, afterwards Sir J o h n , a n d the great authority on heat radiation, sent a characteristic reply to J o s ia h I I :
26 Deer. 1806 I have to thank your b ro th er J o h n for th e hand so m e present of the Ju gs. T h e y are very m uch admired. I wish you c o u ld inform me how the metallic coating is applied. W hile the C o m m o n J u g cools d o w n in 60 m inutes the platina one required 80 an d the gold one 70 to come to the same point. T h e p latina coating is therefore m u ch thicker. I would strongly recom m end it for coffee p o ts . (35)
Unquestionably silver lu stre , an essentially English development, becam e commercially successful and was exploited throughout Staffordshire and also by the potteries in Leeds, Swansea, Newcastle, S u n d e rla n d and elsewhere. W hen applied all over the ware it was seen as a cheap substitute for the silver and Sheffield plate tea pots, cream ju g s, sugar basins and so on, a n d for m any years, until the introduction of electroplating in the 1840s, there was a great pro d u c tion of such articles in rigid im ita tio n of the shapes of the silverware. T h e all-over usage then declined, but the use of p latinum decoration in a m ore artistic form ha d arisen in which either a p a tt e r n or its background was p ainted on to white
128
T h e p u b l i c a t i o n of K l a p r o t h ' s p a p e r in E n g li s h t r a n s l a t i o n s in 1 8 0 4 q u i c k l y a r o u s e d t h e i n t e r e s t of t h e E n g lis h p o r c e l a i n a n d p o t t e r y m a n u f a c t u r e r s o f S t a f f o r d s h i r e a n d by t h e e n d o f t h e fo llo w in g y e a r a m e t a l l i c l u s t r e d e c o r a t i o n h a d b e e n s u c c e s s f u l l y d e v e l o p e d in t h e S p o d e f a c t o ry . T h i s t e a - s e t is d e c o r a t e d w ith d e e p b a n d s o f p l a t i n u m a n d w ith g o ld b o r d e r s . It is p r e s e r v e d in t h e S p o d e M u s e u m in S t o k e - o n - T r e n t
D u r i n g t h e early y e a r s of t h e n i n e t e e n t h c e n t u r y t h e soc a lle d s i l v e r l u s t r e w as u se d e x te n s iv e ly o n e a r t h e n w a r e by B r i t i s h p o t t e r s . A p p l i e d all over the w are, the platinum coating was inten d ed to s i m u l a t e the a p p e a r a n c e of silv er. A little later a m ore artistic form arose com bining enam el c o l o u r s w ith t h e p l a t i n u m . T h i s ty p ic a l s i l v e r r e s i s t " ju g . now in the V i c t o r i a a n d A l b e r t M u s e u m in L o n d o n , is d e c o r a t e d in u n d e r g l a z e b l u e com bined w ith platinum . S p e c i m e n s o f th is k i n d a r e no w collectors* pieces a n d v erv r a r e
129
ware with a n aqueous solution of a viscous substance such as gum or honey before the platinum was applied. After drying, the resist was dissolved off in water, leaving the decorative p la tin u m effect on firing. A fuller account of the developm ent of p latin u m decoration on porcelain and later on earthenw are has been given elsewhere by the present w riter (36).
C o n c lu s io n T his chapter has recorded a p e rio d of consolidation rath e r th a n of great progress in the history of platinum alth o u g h a few scientists spread over several countries introduced m inor variations in its treatm ent. But ju s t as there h a d been a great upsurge of scientific activity in S p a in a generation earlier so as the eighteenth century drew to a close a nother i m p o r ta n t p hase opened in London. In addition, platinum was now available th e re in growing quantities. T o g e th er these factors led to the im portant work to be described in the next two chapters.
R e f e r e n c e s fo r C h a p t e r 7 1 W. A. Smeaton, Fourcroy, L o n d o n , 1962, 28-29 2 J . Wiesner, J a n Ingen-housz, V ienn a, 1905; P. Smit, Janus, 1980,67, 125-139 3 J. Ingen-housz, Phil. Trans. Roy. Soc., 1776, 6 6 , 257-267 4 J. Ingen-housz, Phil. Trans. Roy. Soc., 1778, 6 8 , (ii), 1027-1055 5 J. Ingen-housz, letter to Ja c o b v a n Breda of Delft, April 17, 1784. I a m indebted to Dr. J. G. de Bruijn of H a a rle m for this reference. 6 J. Ingen-housz, Nouvelles E xpriences et O bservation s su r divers O b jets de Physi que, Paris, 1785-1789, 1, 446; 2, 505-517 7 J . Ingen-housz, V erm ischte Schriften, trans. N. K. M olitor, 1st edition (1 vol.), 1782; 2nd edition (2 vols.), 1784, b o th publish ed in V ienna 8 Letter from Ingen-housz to M a t t h e w Boulton, Boulton MSS., L ib ra ry of B irm ingham Assay Office 9 E. Lefebre a n d J . G. de Bruijn, M a r tin u s van M a r u m , Life a n d W ork, Leyden, 1974, 5, 209 10 W. Parker, Letter to Sir J o s e p h Banks, British M u s e u m Add. MS. 33,977, ff 159-160 11 J. H. M agellan, in A. F. C ro n ste d t, A n Essay towards a System of Mineralogy, trans. G. von Engestron, 2nd. e d n ., 1788, 2, 573 12 A. Rees, T h e Cyclopaedia, L o n d o n , 1819, 5, Article on B urn in g Glass, not paginated 13 L. Crell, Chem. Ann., 1784, (i), 32 8-334 14 T. Willis, M em . L it. Phil. Soc. Manchester, 1789, 3, 467-480; Obsns. Physique. 1789, 35, 217-225; Chem. Ann. (Crell), 1790, (iii), 242-247; Ann. Chim., 1791, 9, 219 15 A. L. Lavoisier, T ra it E l m e n ta ire de Chim ie, Paris, 1789, 2, 552-558 130
16 J. A. C haldecott, Notes and Records Roy. Soc., 1967, 22. 155172; Ann. Science, 1968, 24, 21-52 17 Keele University L ibrarv W edgw ood MS., 4091 J . A. C haldecott, Platinum 5; Metals Rev., 1970, 14, 24-28 18 Royal Society Misc. MSS., V. L etter 30; J. A. C haldecott, Reference 17 19 L. B. G u y to n de Morveau, Ann. C.him., 1798. 25, 1 20 20 A. F. Gehlen, J . Chem. Physik ( Schweigger), 1813, 7, 309-316 21 F. K. A chard, Recherches sur les Proprits des Alliages M talliques, Berlin, 1788 22 C. S. Smith, F our O u ts ta n d in g R esearches in M etallurgical History, Philadelphia, A.S.T.M ., 1963, 11-17 23 A. M ussin-Pushkin, A llg .J . Chem., 1804, 3, 450-455. 24 25 26 27 28 29 30 31 32 33 34 35 36 A. Mussin-Pushkin, Ann. Chim., 1797, 24, 205-215 A. M ussin-Pushkin, Chem. Ann. ( Crell), 1799, ii, 3-9 A. M ussin-Pushkin, J . N at. Phil. Chem. & Arts ( Nicholson), 1804, 9, 65 67 N. d iR o b ila n te , M em . Acad. Roy. Sei. Turin, 1784 2. 123-147 85, C. Ridolfi, Giomale Sei. ed Arte, 1816, 1, 24 35; 125-139; Phil. M ag., 1816, 48, 72-73; Ann. Phil., 1819, 13, 70-71 M. H. Klaproth, S a m m lu n g der deutschen A b h a n d lu n g e n Knig. Akad. der Wissenschaft zu Berlin i n j a h r e n 1788 u. 1789, Berlin, 1793, 12-15 M. H. Klaproth, A llg .J . Chemie (Scherer), 1802, 9, 413-422; Phil. M ag., 1803 17, 4. 135-138; J . N at. Phil. Chem & Arts ( Nicholson), 1804, 7, 286-287 Obsns. Physique, 1771/2, In tro I, 108 A. N. Gehlen, J . Chem. Physik (Schweigger), 1813, 7, 309-316; Ann. Phil. ( Thomson), 1815, 5, 20-21 Leonard W hiter, Spode; A H istory of the Family, Factory a n d W ares from 1733 to 1833, London, 1970, 43 Simeon Shaw, H istory of the Staffordshire Potteries, H anley, 1829, 227 W edgwood Archives, E tru ria 1,315 L. B. H u n t , Platinum M etals Rev., 1978, 22. 138148; The Connoisseur, 1979, 200. (M arch), 185-189
131
William Allen 1770-1843

T h e centre of a r e m a r k a b le group of scientists w ho not only e a rn e d a living by their professional activities b u t fo rm e d an extensive netw o rk of societies for ex p e rim e n t a n d discussion, A llen was p ro d u c in g sm all articles of platin u m by 1805 a n d enco u ra g in g one of his young assistants, T h o m a s Cock, to develop a process for its refining an d fabrication
F ro m a p o rtra it by H . P . Briggs in the possession o f the P h a r m a c e u t ir a l S ociety
8
The Professional Scientists of London and their Societies
P la tin u m is a m o st v a lu a b le m e ta l; as it is not o x id is a b le nor fu sib le under com m on circ u m s ta n c e s , a n d o n ly w ith d i ffic u lty c o m b in a b le w ith s u lp h u r a n d n ot a c t e d u p o n b y c o m m o n acids, it is a d m i r a b l y a d a p t e d f o r the uses o f th e p h ilo s o p h ic a l c h e m i s t . "
H U M P H R Y DAVY
T h e thirty year period from 1790 until 1820 was a vital and productive ph a se in the development of both pure an d applied science. Lavoisiers chemical revolu tion had cleared the minds of chemists, his definition of an element had opened the way to the discovery of m any more, an d m ethods of analysis, if still rath e r simple, had become established. T h e chemical industry b e g a n to expand while the scientific study of mineralogy was aiding in the development of m ining and metallurgy. At the same time there existed a body of scientists, particularly in London, who were interesting themselves in technology a n d who were able to secure an income for themselves from their professional work by lecturing, by editing and publishing, by the m anufacture of chemicals or by the m aking of scientific instruments. T hese m en tended to associate into groups or small societies for joint experim entation and discussion. T h e y were particularly interested in the metals recently discovered including titanium , m olybdenum , tungsten and niobium, a n d although it would be a considerable overstatem ent to say that they were particularly concerned with p latinum they none the less took an active interest in its properties an d its fabrication and from their activities stemmed several im portant advances.
T h e L ead in g R ole o f W illia m A lle n O n e of the first to engage in lecturing was Bryan Higgins (1741 1818) at his School of Practical C hem istry in Greek Street, Soho, started in 1774, and from which developed the Society for Philosophical Experim ents and Conversations,
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A l l e n 's l a b o r a t o r y a t P l o u g h C o u r t i n th e e a r l y n i n e t e e n t h c e n t u r y . A s u c c e s s f u l p h a r m a c e u t i c a l b u s i n e s s w as c a r r i e d o n h e r e a n d a sc h o o l o f y o u n g r e s e a r c h a s s i s t a n t s w a s b u i l t u p. M e e t i n g s o f b o t h t h e A s k e s i a n S o c i e t y a n d t h e B r i t i s h M i n e r a l o g i c a l S o c ie ty w e r e a ls o h e l d h e r e f r o m 1 7 9 6 u n t i l 1 8 0 7 w h e n t h e m e m b e r s t o o k p a r t in t h e f o u n d i n g o f b o t h t h e G e o l o g i c a l S ociety a n d t h e L o n d o n I n s t i t u t i o n
founded in 1794. A nother very active organisation was the Physical Society of G u y s Hospital, recognised as a n im portant meeting place for scientists from its foundation in 1771 until the m id d le of the nineteenth century. In 1792 the young W illiam Allen, the son of a Q u a k e r silk m an u fa ctu rer who disliked his fathers business, e n tered the famous Plough C o u rt Pharm acy, established in 1715 in L o m b a rd Street in the C ity of L o n d o n by J o s e p h G urney Bevan, a leading m em ber of t h e Q uakers. H e began at once to attend the lectures given by Bryan Higgins and to devote his spare time to studying the new system of chem istry a n d in 1794 he also becam e a m em b e r of the Physical Society at G u y s Hospital. In th a t year Bevan retired, being succeeded by Sam uel M ildred who took Allen into p a rtn e rsh ip but retired in 1797, leaving the business in A llens charge (1). N ext door to the p h arm acy there worked a prin te r nam ed J a m e s Phillips who had two sons William (1775-1828) and R ic h a rd (1778-1851). T h e elder was establishing himself as a m ineralogist, while the younger R ic h a rd becam e apprenticed to Allen at Plough C ourt. I n the sam e neighbourhood there lived W illiam H asledine Pepys, the s o n of a cutler a n d m aker of surgical instruments, a n d it was these very young m en who took the initiative in forming the Askesian
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Society in M a rc h 1796, the n am e being taken from the Greek w ord for exercise or training. T hey appointed a n older man, Sam uel Woods, a woollen d ra p e r also of L o m b a rd Street, as president an d were soon jo in e d am ong others by A lexander Tilloch, the founder in 1798 of The Philosphical M agazine, a n d later by two distinguished surgeons, Astley C ooper (1768 1841) an d W illiam B abington (1756-1833). T h e latter, a n older m a n th a n most of the m em bers of the Askesian Society a n d resident apothecary at G u y s Hospital, h a d tried to melt p latinum in 1797, writing in his lecture notes preserved there: The most violent fires are insufficient to melt it though its parts may be made to cohere together into a solid button by the strong heat of a wind furnace. (2) M eetings were held fortnightly at Plough C o u rt an d a collection of a p p a ra tu s was assembled. In D ecem ber 1798 Allen wrote in his diary: I am making great progress in chemical experiments - fused platina with oxygen on charcoal. (3) At a meeting held in the Askesian Societys room on April 2nd 1799 attended by Allen, Pepys, Tilloch, R ic h a rd Knight, the son of a L o n d o n ironm onger who becam e a n instrum ent maker, a n d W illiam Lowry, the engraver a n d geologist, it was resolved that those present do form themselves into a Society under the Denomination of the British Mineralogical Society. (4) T h e n um ber of m em bers was not to exceed twenty a n d was to be confined to those able a n d willing to undertake the chemical analysis of m ineral substances. It was felt th at the absence in England of any school or college of scientific minerology such as the cole des M ines established in France in 1783 could be remedied by the collective activities of the m em bers in applying science to mining a n d metallurgy. Before the end of the year the founders were jo in e d by W illiam Phillips, Charles R ochem ont Aikin an d his b ro th er A rth u r, the latter becoming president of the society. O th e r m em bers included Dr. Babington, R ichard Phillips an d R o bert Bingley, the Assay M a ste r a t the Royal M int, while William H enry of M anchester, C harles H a tc h e tt a n d R ic h a rd K irw a n were among those elected corresponding m embers. Bingley ha d already conducted a series of experiments on p latin u m and particularly on its separation from gold in the course of norm al assaying. T hese he described in a long letter to Charles H a tc h e tt (5) in which he wrote: That it is a source of great satisfaction to be able compleatly to separate two metals which have so many properties in common, and by such means as are not in the least destructive to gold. M eetings were held fortnightly at Plough Court, reports being read on the analyses of minerals, and on J a n u a r y 9th 1800 a p a p e r was read by R ic h a rd K night (1768-1844) entitled A New and Expeditious Process for R endering Platina M a lleab le (6). T h e author, who displayed to the meeting a specimen of his malleable metal, opened his rem arks in these words:
135
THE
PH ILO SO PH ICA L MAGAZINE.
TEBRVART
1800.
I.
A ttr.u nnd rxptJitLnu Proctft fo r rendtr'mg PlaJm* mal treble. By Mr. R i c h a r d K n i s h t , Mtmbrr t f tbr Bntijb Miiuralogital Socttj. CommtuvcaUd by A t Author.
At a m eetin g of the B ritish M i n e r a l o g i c a l S o c ie ty o n J a n u a r y 9 t h 1 8 0 0 . R i c h a r d K n i g h t , t h e so n o f a n i r o n m o n g e r ill t h e City o f L o n d o n a n d a c o m p eten t analyst an d in stru m en t m a k e r , r e a d a p a p e r d e s c r i b i n g his m ethod of p roducing m alleab le p l a t i n u m . H i s p r i n c i p a l a d v a n c e lay in a m o r e fo rc e fu l c o m p re ss io n of the s p o n g e w h i l e h o t. T h e r e is no e v i d e n c e t h a t K n i g h t m a d e m o r e t h a n tw o or t h r e e p i e c e s o f a p p a r a t u s f r o m his p l a t i n u m , b u t it is l ik e ly t h a t h i s p a p e r served to a r o u s e t h e i n t e r e s t of W ollasto n a n d T e n n a n t whose m ajor c o n t r i b u t i o n is d e s c r i b e d in t h e n e x t chapter
H E many peculiar advantages w hich platina in a m al leable (late poffelTes over every other metal for the fabric!tion of a variety of inllrum ents and utenfils particularly ufeful for the purpofes of chem iftry, together w ith the extreme difficulty of procuring it, being hitherto o n ly to be obtained from Paris, o f a very indifferent quality, and at a price, equal to that of gold, firft induced me to turn m y attention to th* fubjeft. After having repeated a variety o f experim ent^ 'from the different writer on th it fubftance, without effeft, I at length completed a procefs, the fucoefs of w hich baa fu lly anfwered m y expeQations. By the procefs w hich I follow 1 am able to reduce any quantity i f crude platina to a perfectly malleable (late, entirely free from im purity, and capable of being wrought into any form whatever. A s thik is a circum ilance of con&derable im portance to (he chem ical w orld, and the advantages w hich may re fu lt from it to fo* ciety in general are perhaps incalculable, I would confid# m yfel{deferving of cenfure, could I allow an y motive whatever to induce me to withhold it from the public. By fending it for publication in work of fuch exttnfiv* circuJatiso as the V o l . VI. B Wiil*.
The many peculiar advantages which platina in a malleable state possesses over every other metal for the fabrication of a variety of instruments and utensils particularly useful for the purposes of chemistry, together with the extreme difficulty of procuring it, being hitherto only obtained from Paris, of a very indifferent quality, and at a price equal to that of gold, first induced me to turn my attention to the subject. After having repeated a variety of experiments, from the different writers on this substance, without effect, I at length completed a process, the success of which has fully answered my expectations. By the process, which I follow I am able to reduce any quantity of crude platina to a perfectly malleable state, entirely free from impurity, and capable of being wrought into any form whatever.
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H e dissolves the native platina in a q u a regia, allows the insoluble to settle, decants the clear liquor, precipitates with the sal-ammoniac, again allows settle ment, decants an d washes the precipitate with cold distilled w ater until it is free from acid. T h e last water is then poured off and the precipitate evaporated to dryness . H e goes on to say: So far my process is in a great measure similar to that which some others have also followed; but my method of managing the subsequent, and which are indeed the principal manipulations, will be found to possess many advantages over any that has yet been made public. The best process hitherto followed has been to give the pre cipitate a white heat in a crucible, which in some measure agglutinates the particles; and then to throw the mass into a red-hot mortar or any similar implement, and endeavour to unite them by using a pestle or stamper. But the mass is so spongy that it is hardly possible to get a single stroke applied to it before the welding heat is gone; and though by peculiar dexterity and address some have in this way succeeded, it has been found to require such innumerable beatings and hammerings, that most of those who have attempted it have either failed entirely or given it up as being too laborious and expensive. I have succeeded in obviating all these difficulties by adopting the following simple, easy and expeditious method. In this the dry precipitate is tam ped tight into a strong, hollow inverted cone of crucible earth with a conical stopper of the same m aterial m ad e to fit the opening. T h e whole is slowly raised to a white heat with a cover resting lightly on top. T h e n the conical stopper is m ade red hot and is gradually pressed down by means of tongs until the platina becomes m ore solid. It is then repeatedly struck with the stopper, as hard as the nature of the materials will admit, till it appears to receive no farther impression. T h e cone is then removed from the furnace, the platina knocked out in a metallic b u tto n which is worked as desired. T his process avoids any contact between the platinum and red-hot iron, with which it readily becomes con tam inated, having a great affinity for it at high tem peratures. K night claims that platinum prepared by this m ethod is of a higher purity th a n hitherto, having a specific gravity of 22.26. W h a t R ic h a rd Knight did was essentially to reduce the process to its simplest possible form. Perhaps, in the light of a fuller knowledge, he is unduly uncom plim entary to the achievements of his forerunners, b u t there is no reason why his own product could not have been a good one. T h e principal advance brought in by him was, as he himself suggests, the stronger hot com pression of the sponge, so far applied only lightly by hand. T h e re is no evidence th at K night himself ever m ade great practical use of his process or m an u fa ctu red m ore than two or three articles from it. T h e publication of this p a per in The Philosophical M agazine probably stimulated greater interest in p latinum am ong the group comprising these two societies, and a few years later, sometime in the winter of 1804-1805, Alexander Tilloch himself contributed a p a per to the Askesians, O n a N ew Process of Rendering Platina M a lleable (7). In this he reviewed earlier procedures and
137
then proposed his own. In this the native metal is to be dissolved and pre cipitated with sal-ammoniac in the usual manner. The precipitate is calcined to metallic sponge and the latter is wrapped up in a piece of platinum foil and the whole spread out by means of a flatting mill. The foil and its contents are then exposed repeatedly to a sufficient temperature and hammered between each exposure until the whole is brought to a compact state. This it will be seen is merely a modification of a method earlier proposed and practised by Rochon.
The Work of Thomas Cock Whether or not Tillochs paper gave a further stimulus to Allen, he evidently and immediately took up the production of articles of platinum, the first mention of his refining and fabricating being in January 1805. In this work he was assisted by one of his young men, Thomas Cock (1787-1842) the son of a wealthy merchant who had prospered in the textile trade with Germany. His father had died when he was four years of age and his mother when he was fourteen. His elder brother was married and his guardian was his sisters husband, the rising young surgeon Astley Cooper, afterwards a very famous figure in his profession. Both Astley Cooper and William Allen were by now fellow lecturers on their respective subjects of anatomy and chemistry at the medical school of G uys Hospital, and Cooper was a frequent visitor at Plough
T w o pages fro m the cost sheets of the Plough C ourt P h a rm a c y , now Allen and H a n b u rv s , for J a n u a r y 1805 in W illiam A llen's h a n d w riting show the expenses in c u rre d in refining som e 5 6 ounces of c ru d e platin um . T h e first sheet is he ad ed with the n a m e of T h o m a s Cock, th en a young m a n of only eigh teen who later m arrie d th e sister of P ercival N orton J o h n s o n s wife and a fte r w a rd s devoted m u c h of his tim e to the platin um refining side of Joh n so n 's business in H a tto n G a rd e n
138
Court and for a time a member of the Askesian Society. There seems little doubt that, his young ward having shown some tendency to be interested in chemistry and metallurgy, Cooper arranged with Allen for him to become one of the young men at Plough Court. This is confirmed by the mention of his name as such in A llens diary in the autum n of 1804, when he accompanied him on an extensive visit to the mines of Cornwall (8), and in the December he was proposed as a member of the British Mineralogical Society by W . H. Pepys and seconded by Allen. The entries in Allens cost-book, reproduced here, headed with the name T. Cock, show that 56 ounces of crude platinum, costing 4s. 6d. an ounce, were refined by the usual precipitation method, while an entry dated February 13th 1805 is as follows:
rf
1 9 4 0 4
5 33.9/16 Deduct Cuttings
Small Platina 5 I l f at 4/6
18/-
30 4 2 1 1 27 12 2 6 29 18
Making etc. 4 Crucibles
Wrought crucibles 30/3 oz. oz. L H. Crucible 5 1/8, 1/16, 1/32 at 30/Henry ,, 4 J, 1/5, 1/16, 1/32 R. Phillips 5 1/8,1/32 Davy 4 f
.y 7 16 7 9 7 14 6 15
6 0 8 0 2
29 15
(The initials L. H. represent A llens one-time partner Luke Howard, Henry is W illiam Henry of Manchester, Richard Phillips has already been mentioned, and Davy was of course A llens friend H um phry Davy) Platinum tubes were also being made by rolling up sheet and soldering with gold, as is shown by a further item in the cost books in October 1805:
s d
Platina T ubes
Borax & Mur: Acid Charcoal Gold Attendance
1 1 11 6
3 6 3 0
10 0
139
O n the facing page is the following entry, initialled T. C. Adding to platina tube 1 Borax & Muriatic Acid G oldS _^{5 Charcoal" } B Attendance 1 Day Credit bits T. C. 1/16 at 13 2
s d
1
j d
6
5 9 4 0 1 17 0
6 1
1 6 8
16
Thomas Cock continued to work at Plough Court on platinum and other subjects until his marriage in 1809 to a Miss Anna M aria Smith whose sister Elizabeth later married Percival Nortonjohnson. In 1807 there was published in A Dictionary of Chemistry and Mineralogy by A. and C. R. Aikin (9) an account of the latest method for rendering platinum malleable, and one that has been attended by compleat success. This was invented by Mr. T. Cock, through whose liberality we are enabled to communicate it to our readers. The platina being dissolved in nitro-muriatic acid, the liquor is to be filtered through clean white sand, in order to separate the black powder which floats among it. The clear solution being then decomposed by sal-ammoniac the yellow precipitate is to be collected, moderately well washed in warm water and dried. It is then to be distributed into saucers which are placed in a small oven constructed for the purpose, where they are exposed for a short time to a low red heat in order to bring the platina to the metallic state, and to drive off by sublimation the greater part of the muriated ammonia. When withdrawn it is a spungy mass of a grey colour. About half an ounce of the platina in this state is to be put into a strong iron mould about 2\ inches long by If wide and is to be compressed as forcibly as possible by striking with a mallet upon a wooden pestle cut so as accurately to fit the mould; another f ounce is then added and treated in the same manner, and so on till 6 ounces have been forced into the mould; a loose iron cover just capable of sliding down the mould is then laid upon the platina, and by means of a strong screw press, almost every particle of air is forced out from among the platina. This is a part of the process that requires especial care, for if any material quantity of air is left in the mass, the bar into which it is formed is very apt in the subsequent operations to scale and be full of flaws. The pressure being duly made, the mould is to be taken to pieces, and the platina will be found in the form of a dense compact parallelopiped. It is now to be placed in a charcoal forge fire and heated to the most intense white heat in order compleatly to drive off the remaining ammoniacal muriat; this being done it is to be quickly placed on a clear bright anvil and gently hammered in every direction by a clean hammer. This is to be repeated several times, at the end of which the mass will be perfectly compact, and fit to be laminated or wrought in any other manner that the artist chuses. It is to be observed that while the platina is heating it must lie loose in the fire, for if it were held by the tongs they would infallibly become welded to the platina, and thus greatly damage it. By the time that the platina is thus drawn down to a compact bar it will be covered by
140
A rth u r Aikin
1 7 7 3 -1 8 5 4
T r a i n e d by his f a t h e r s f r i e n d J o s e p h P r i e s t l e y , A i k i n m o v e d to L o n d o n in 17 96 a n d t h e r e e s t a b l i s h e d a c o n s i d e r a b l e r e p u t a t i o n a s a geo lo g ist, c h e m i s t a n d l e c t u r e r . In 1 8 0 7 . t o g e t h e r w ith his b ro th e r C harles R o c h e m o n t A ikin. he com piled A D ictionary of C h e m is try a n d M i n e r a l o g y " in w h i c h h e i n c l u d e d as a n o r i g in a l c o n t r i b u t i o n a full a c c o u n t of T h o m a s C o c k 's p r o c e s s fo r pro d u cin g m a lle a b le p la tin u m that has been a tte n d e d w ith c o m p l e a t su c c e s s " . A i k i n w as a close f r i e n d of Pereival N orton J o h n s o n fro m their e a r l y y e a r s in S t o k e N e w i n g t o n . In his l a t e r life h e w a s a f o u n d e r m e m b e r of the C h e m i c a l S o ciety a n d P r e s i d e n t f ro in 1845 to 1817
a somewhat reddish semi-vitreous crust proceeding chiefly from particles of the ashes melted down upon it and extended over its surface by the hammer. To remove this, the bar being made red hot is to be sprinkled over with pulverised glass of borax, and then kept for a few minutes at a white heat; when moderately cool it is to be plunged into dilute muriatic acid by which the borax and other vitreous matter will be dissolved, leaving the platina with a perfectly clean white surface. C ocks contributions to the advanced technique were: Complete removal of all material insoluble in aqua regia The calcination of the ammonia chloroplatinate precipitate takes place rapidly and at a low temperature High pressure is brought to bear on the cold sponge by means of a screw press before heating and forging Forging takes place at the most intense white heat The surfaces of anvil and hammer must be clean and bright. C om m ent on the im portance of such factors as these will be m ad e in the next chapter, but it seems that Cock m ade no a tte m p t to purify his solution from iron and base metals before precipitating it, nor did he a p p e a r to be aw are of the
141
presence in his native metal of iridium , osmium, palladium an d rhodium , all of which as will again be seen in t h e next chapter, ha d been discovered and their existence reported two or three ye a rs before the publication of his procedure.
T h e N etw o r k o f S ocieties a n d In stitu tion s

T h e skills an d the opportunities o f the L o n d o n scientists were further displayed in a num ber of other societies a n d institutions, these having m any m em bers in com m on and the whole c onstituting a complex network of personal associations. In 1807 the mem bers of the British M ineralogical Society agreed to merge with the Askesian Society as a dvantageous to each in their design of prom oting Philosophical R e se a rc h , but a lth o u g h meetings continued to be held for a time at Dr. B abingtons house, both very soon decided to d isband themselves, largely because of the foundation of t h e L ondon Institution to which most of their m em bers were subscribers and a lso as the new body offered the advantages of a school of mineralogy. Later in th e sam e year the Geological Society was formed, the founder m em bers including Allen, Pepys, Babington, H u m p h r y Davy, A rth u r Aikin, R ic h a rd Phillips a n d R ic h a rd K night (10). Earlier, in 1797, the Royal In stitu tio n h a d been founded by Benjamin T h o m p so n C ount Rumford, an d D avy ha d been appointed lecturer in chemistry in 1801. Allen, Pepys and R i c h a r d Phillips at once becam e associated with the new institution and with Davy him self a n d by 1803 Allen ha d been invited by
W illiam H asled in e P ep ys 1 7 7 5 -1 8 5 6
T h e so n o f a L o n d o n c u d e r a n d s u r g ical i n s t r u m e n t m a k e r , P e p y s w a s o n e of th e early m e m b e r s of the A skesian So ciety a n d , w ith A l l e n . K n i g h t a n d T illo ch , a f o u n d e r of th e B ritish .M in e ralog ical S o ciety in 1799. H e to o k c o n s i d e r a b l e i n t e r e s t in p l a t i n u m a n d t h e a t t e m p t s to b r i n g a b o u t its f u s i o n b y t h e e l e c t r i c d i s c h a r g e . H e w as a s k i l f u l a n d i n g e n i o u s d e s i g n e r of sc ie n tif ic i n s t r u m e n t s a n d a p p a r a t u s a n d h e also s u p e r v i s e d t h e c o n s t r u c t i o n o f t h e g r e a t b a t t e r y of 2000 plates for th e Royal Institution
142
A f t e r (he iso l a t i o n o f t h e a l k a l i m e t a l s by H u m p h r y D a v y by h o l d i n g h e a t e d p o t a s h a n d s o d a in a p l a t i n u m s p o o n a n d c o n t a c t i n g t h e m w ith a p l a t i n u m w i r e c o n n e c t e d to a p o w e r f u l b a t t e r y s e v e r a l d e s i g n s of a p p a r a t u s w e r e p r o p o s e d fo r t h e r e p e t i t i o n a n d d e m o n s t r a t i o n of t h e s e classic e x p e r i m e n t s . T h e m o s t s i m p l e a n d su c c e s s f u l a p p a r a t u s , d e s i g n e d by W . H . P e p y s a n d m a d e by R i c h a r d K n i g h t , w as fitted w ith a p latinum w i r e h a v i n g tw o p l a t i n u m discs a t t a c h e d to c o n t a i n t h e al k a l i
Davy to give the lectures he h a d been delivering jointly with B abington at G u y s Hospital to the audiences at the Royal Institution. W h e n reporting his famous discovery of potassium and sodium in 1807 Davy described how he held pieces of caustic potash and caustic soda on an insulated disc of p latinum and brought them into contact with a platinum wire con nected to the negative side of his large b a tte ry , and acknow ledges the assistance of both Allen and Pepys. T hese two went on to repeat a n d to dem onstrate the classic experiments before the members of the Askesian Society and the British M ineralogical Society, employing the piece of platinum ap p a ra tu s shown here, designed by Pepys an d constructed by Richard Knight (11). Another experiment on platin u m was carried out in A ugust 1808 by Allen, Pepys and Davy at the hom e of J . G. C hildren (1777-1852) with a great b a tte ry the latter h a d constructed. A piece of platin u m wire eighteen inches in length an d l /3 0 t h of a n inch in diam eter was completely fused in about twenty seconds, while a three-feet length of the sam e wire was heated to a bright red, visible by strong daylight ( 12).
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Earlier W. H. Pepys had also built a very large battery and in February 1803, together with a number of his scientific friends, he ignited or melted a number of metals including platinum wire 1 / 16th of an inch in diameter which became red hot, white, and fused into globules at the contact (13). Pepys extended his fathers cutlery business into the manufacture of scientific instru ments, but in 1805 he also began to produce cutlery in platinum. Among his products were a pair of fruit knives which he presented to King George III and Queen Charlotte through the good offices of Sir Joseph Banks (14). Another informal group was the London Philosophical Society, initiated by Samuel Varley, an instrument and watch maker, in which Pepys and Tilloch were active together with John Francillon (17441818), a medical man and also a gemmologist and entomologist, who had sometimes assisted Pepys in his experiments. At a meeting of this society in the autumn of 1798 Francillon had proposed the construction of a furnace in which a stream of oxygen could be directed into a crucible containing eight ounces of platinum surrounded by charcoal so that:
In 1805 P e p y s m a d e a pair of fruit knives in platinum w hich he asked Sir Joseph B ank s, the P re sid en t of the Royal Society, to presen t on his b e h a lf to K ing G eorge III a n d Q u e en C harlotte. This is the letter from B ank s telling Pepys that the knives were re ceived by their M ajesties in the most gracious m a n n e r
P h o to g r a p h by courtesy of the R o y a l In s titu tio n
144
means might be devised to fuse large quantities of crude platina and at the same time to obtain the metal pure and malleable, an object so desirable that the Society resolved at least to make the attempt. (15) W hen this experim ent was carried out at a further meeting a b u tto n of platinum was found at the bottom of the crucible b u t it broke u n d e r the ha m m e r and the m em bers concluded that: though platina may be reduced and brought to a state of purity by oxydating the iron by means of a stream of oxygen gas, it will require a considerable degree of address to be able to apply this on a scale of any considerable extent. T here were several other interlocking societies formed during this period, including the London Chem ical Society proposed by Frederick A ccum in 1806 and the Chem ical Club, founded in 1807 and lasting until 1826, in w hich all the scientists already m entioned were am ong the m em bers an d where guests included D a lto n and Berzelius. But by now the Royal Society was absorbing the interests of the former m em bers of the Askesian Society a n d other groups; Allen, Pepys and C hildren were elected in 1807-8 with others to follow in later years. A nd the rather diffuse activities of all these m en on the problem s of platinum were followed by m uch m ore concentrated and successful efforts at the h a n d s of two of their distinguished friends and earlier fellows of the R oyal Society whose work is now to be detailed.
R eferences for C h a p te r 8
1 E. C. Cripps, Plough Court, London, 1927; D. Chapman-Houston and E. C. Cripps, Through a City Archway, London, 1954 2 W. Babington, Lectures on Chemistry, MS in Library of G uys Hospital 3 Anon, Life of William Allen, London, 1846, 1, 42 4 Minutes of the British Mineralogical Society, British Museum (Natural History); P. J. Weindling, forthcoming in I. Inkster and J. B. Morrell (eds.), Metropolis and Province, British Science 1780-1850 5 Letter from Robert Bingley to Charles Hatchett, Read to Royal Society, May 1, 1800, Royal Society MSS. 6 R. Knight, Phil. Mag., 1800, 6, 1-3 7 A. Tilloch. Phil. Mag., 1805, 2 1, 175 8 Ref. 3, 1, 74 9 A. and C. R. Aikin, A Dictionary of Chemistry and Mineralogy, London, 1807, 2, 233 10 I. Inkster, Ann. Science, 1977, 34, 1-32 11 W. H. Pepys, Phil. Mag., 1808, 31, 241 12 J. G. Children, Phil. Trans., 1809, 32-38 13 Anon, Phil. Mag., 1803, 15, 94 96 14 P. J. Weindling, Platinum Metals Rev., 1982, 26, 34 37 15 Anon, Phil. Mag., 1800, 8, 21-29; 262-266
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W illiam Hyde Wollaston 1 7 6 6 -1 8 2 8

T h e outstand in g figure in t h e history of p la tin u m , W ollaston was the first to refine the native m e ta l on a c o m m ercial scale a n d to develop its uses in industry, while in t h e course of his analytical work on the m in eral he also discovered p a lla d iu m a n d rh o d iu m . D u rin g a brilliant scientific c are er he m ad e o t h e r fu n d a m e n ta l discoveries in a n u m b e r of d iffe ren t bra n c h e s of science
F ro m a p o r t r a it by J o h n J a c k s o n , by courtesy o f the R o y a l S ociety
9
The Partnership of Smithson T en n an t and W illiam H yde W ollaston
A q u a n t i t y o f p l a t in a w a s p u r c h a s e d b y m e a f e w ye a r s sin c e w ith the d esig n o f r e n d e r in g it m a l le a b le f o r th e d i f f e r e n t p u r p o s e s to w h ic h it is a d a p t e d .
T h at
object
has
now
been
a tta in e d .
WILLIAM HYDE W OLLASTON
U p to the end of the eighteenth century the attem pts to p ro duce malleable platinum h a d advanced mainly in the hands of practical m en aim ing at its p r e paration and fabrication rath e r th a n at the solution of scientific problems. T hese were now to be attacked with a m arked degree of success by two rem arkable but very different m en who first becam e friends during their student days at C a m bridge and who formed a working partnership in 1800 designed not only for scientific purposes but also for financial reasons. T h e y were of the sam e g enera tion and m uch the same background as the professional scientists of L ondon whose work was described in C h a p te r 8, an d to w hom they were well known, but with the exception of H u m p h r y Davy they were of greater stature a n d m ad e a greater advance in the development of platinum metallurgy than their predecessors. T heir com bined achievements over a relatively short span of years included the successful production for the first time of m alleable p latin u m on a truly com mercial scale as well as the discovery of no less th a n four new elements contained in native platinum , a factor th at was of m aterial help in the purification and treatm ent of platinum itself. T h e ju n io r partner, who was in fact to carry most of the b u rd e n after the first few years, W illiam H yde W ollaston, kept meticulous records of his experiments and of his expenditure and later of his sales of platin u m b u t these rem ained undiscovered for m any years. A collection of his note-books and other m anuscripts relating to his life and work, including brief drafts for an unw ritten biography by his friend H e n ry W a rb u rto n , were eventually found in 1949 by the late L. F. Gilbert in the D e p a rtm en t of M ineralogy and Petrology in the University of C a m bridge an d formed the subject of a p a p e r of his in 1952 (1). In
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W ollastons p a rtn e r in the long investigatio ns of native p la tin u m . S m ithson T e n n a n t, be ca m e interested in the m etal while still a s tu d e n t at C a m bridge. T h is ex tra c t fro m his d iary for O ctober 4th 1784, when he was only 2 2 . describes his visit to L orenz Crell at H e lm sta d t and records the details of the Count von S ic k in g e n s m eth o d of re n d e rin g p la tin u m m alleab le
more recent years these note-books and papers, now in the care of the Library of Cambridge University, have been studied in more detail by Dr. M. C. Usselman (2), and by Dr. J. A. Chaldecott (3). Other note-books compiled by Tennant and in the same keeping have enabled Dr. A. E. Wales to publish valuable information on his part in the joint enterprise (4). This chapter therefore owes much to their respective publications, while the original author of this book also contributed a study of Tennant (5). Taking the older man first, Smithson Tennant (1761-1815) was born at Selby in Yorkshire, the son of a clergyman. In 1781 it was proposed that he should study under Joseph Priestley, now settled in Birmingham, but this did not materialise and instead he entered the University of Edinburgh to study chemistry under Joseph Black with whom he developed a close relationship and from whom he may very well have acquired his early interest in platinum. He moved to Cambridge in October 1782, first at Christs College and later at Emmanuel, and in 1785 while still an undergraduate he was elected a Fellow of the Royal Society. During the summer vacation of 1784 he made a journey through Denmark and Sweden, visiting mines and chemical plants and meeting Scheele and Gahn, and on his return journey visited Lorenz Crell at Helmstadt. The extract from his diary reproduced above shows that he was already interest ing himself in the problem of producing malleable platinum. In the following year he paid a visit to Paris to meet Lavoisier and then to Dijon where he was the guest of Guyton de Morveau, both of these men of course having been active only a few years earlier in working with platinum. (An amusing side light on these visits is to be found in a letter from Guyton de Morveau to Crells Chemische Annalen in 1786 ( 6 ). The writer refers to one of my chemical friends the Englishman Herr Tennant, to which Crell adds in a footnote: I also have the pleasure of counting Herr Tennant among my chemical acquaintances ). In his la'ter period at Cambridge Tennant became friendly with his younger fellow student in medicine, Wollaston, who was at Gonville and Caius from 1782
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until 1789 a n d who was particularly interested in the older m a n s accounts of his visits to the leading chemists in Europe. W ollaston took up medical practice after leaving C am bridge, first in H u n t ingdon an d then in Bury St. E dm unds, b u t in 1797 he moved to a practice in London where his friends considered he would have greater scope for the high ability he had already shown as a physician. T e n n a n t h a d already settled there four years earlier, also after a brief spell as a physician, work for w hich he found himself tem peram entally unsuited. In this same year he presented a short p a p e r to the Royal Society O n the Action of N itre on G old and P la tin a (7), quoting the earlier work of Lewis an d M a rg g ra f on the native metal before describing his own results on the corrosive attack on his more or less p u re platinum . In 1799, Wollaston, by now devoting most of his time to scientific researches, p urchased small am ounts of p latinum and began to study the most efficient means of its dissolution in varying formulations of a q u a regia. By the end of the following year, undoubtedly stim ulated by the similar leanings and knowledge of his friend Sm ithson T e n n a n t and probably after m u ch discussion of the problem, the two m en entered into an informal and unpublicised p a rtnership directed towards various chemically-based commercial endeavours, one of which was the production an d m arketing of malleable platinum , and W ollaston abandoned his medical practice. O n C hristm as Eve 1800 they invested 795 in the p urchase of the very large qu a n tity of 5959 ounces of alluvial p latinum from one H utchinson of w hom nothing is known b u t who was almost certainly a L ondon agent connected with the J a m a ic a n end of the smuggling trade from Cartagena. In the following F e b ru ary they bought a further 800 ounces from R ic h a rd Knight who ha d a pparently not p u t his process to com m ercial use. T h e underlying reasons for their undertaking this jo in t enterprise, one that was to lead to long years of chemical research and frustration before success was achieved, goes back to their time at C a m b rid g e b u t a sense of urgency was given them by the prospects opened up by the two publications referred to earlier, the A bb R o c h o n s paper th at app e are d in English translation in the first volume of The Philosophical M agazine in 1798 and R ic h a rd K n ig h ts p a p e r read to the British Mineralogical Society in J a n u a r y 1800 a n d also published in The Philoso phical M agazine in the following m onth. An interesting an d possible link is that just opposite R ichard K n ig h ts establishm ent in Foster Lane was the C h u rc h of St. Vedast in which his parents had been m arried in 1766 an d where the Rector from 1779 until 1815 was in fact W ollastons father, the Reverend Francis Wollaston, F.R.S. In any case it was becoming very clear th at if a process that was technically sound could yield malleable p latinum in q u a n tity and at a reasonable price a handsom e financial retu rn might well be expected. T e n n a n t was a wealthy m a n by inheritance. It has often been said that W ollaston needed to earn a living from his researches b u t Dr. U sselm an in the course of a detailed review of one episode of W o llastons career has revealed that in 1799 his elder brother George had m ad e him a present of securities valued at some 8000 (8), making it possible for him at the age of 34 to a b a n d o n the
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medical practice he disliked a n d to devote the rem ainder of his career to the scientific pursuits he so m uch preferred. W ollaston had a great a d m ira tio n for T e n n a n t, who as we have seen had m ade personal contacts with several of the F re n c h an d G e rm a n workers on platinum and who may thus have influenced the choice of project, while his brilliant if rather erratic m ind w o u ld have been of great value in the early years of the partnership.
T h e D is c o v e r y o f Irid iu m a n d O s m iu m Before we can consider W o lla s to n s principal work, the laborious investigation of the means of producing m alleable p latin u m in q u a n tity an d its success after five years of frustrating experiments, we have to tu rn to the parallel investiga tions carried out by him and by T e n n a n t that showed the presence, unsuspected by the earlier workers, of four other elements in native platinum . It will be rem em bered that when crude p la tin u m was dissolved in a q u a regia there was always a black insoluble residue left. Sickingen had tried to melt it under borax but was prevented by his diplom atic duties from investigating it further. Proust noted that it formed some two to three per cent of the original mineral b u t con sidered that it was nothing else th a n graphite or p lu m b a g o . Early in their joint researches it was decided t h a t while W ollaston should p ursue the study of the a q u a regia solution of p la tin u m T e n n a n t should concentrate on the insoluble residue. His curiosity was a ro u s e d and by the su m m e r of 1803 he h a d begun to investigate this insoluble m atter, fortunately m entioning this at the time to Sir Jo sep h Banks, President of the R oyal Society, writing th at it did not, as was generally believed, consist of p lu m b a g o , but contained some unknow n metallic ingredients . In this way h e established his priority because almost simultaneously work on the sam e problem had b e gun in France. It had been observed by m a n y of the earlier workers th a t the precipitate formed by sal-ammoniac in the solution of native p latinum in a q u a regia differed from time to time in colour, be in g sometimes a pale yellow, sometimes showing various orange tints and som etim es a red that might even be a very dark one. T h e first to investigate this w a s the F rench mining engineer, H. V. ColletDescotils (1773-1815), who read a paper to the Institut N ational on Septem ber 26, 1803, published in the Annales de Chimie and reproduced in N icholsons Journal in the following year (9). H e reported th at the black insoluble powder is gradually attacked by aqua regia, especially in the presence of extra nitric acid, and he was able to trace a connection betw een this and the colour of the p re cipitate produced by sal-am m oniac in the liquor. T h e m ore completely the black powder was dissolved the redder w as the precipitate. Next he found that if a red precipitate was calcined and th e sponge treated with a q u a regia, there always rem ained a certain am ount of insoluble black powder, an d the solution gave with sal-ammoniac a precipitate a little less red th a n before. Finally, he noticed that the presence of reducing a gents in the p latin u m solution resulted in the
150
formation of yellow precipitate only, a n d th a t the red colours were obtained only after the solution had been oxidised. H e concluded that these properties appear to me not to belong to any one of the known metals and force me to regard as a new substance a metal which colours red the salts of platinum. At the same time as Collet-Descotils was carrying on this work a parallel research was taking place at the hands of Antoine Francoise de Fourcroy (1755-1809) with, as his p a rtn e r a n d assistant, Nicholas Louis V auquelin (1763-1829) of w hom more will be said in the next chapter, a n d the first p a rt of their paper was read to the Institut immediately after Descotils (10). T h e y set out to find what influence the foreign bodies th at accom pany platin u m in its ore, might have on the working of this metal on a large scale . T h e y identified and removed all the minerals and base metals and th en cam e u p o n P ro u s ts insoluble black powder. As acids h a d so little effect on it, they tried alkalies and found that it was attacked, eventually completely, by m olten caustic potash. T h e melt yielded a green solution with w ater and a green flocculent residue. C hrom ic acid was suspected in the former, and the solids after dissolving in acid were tested in various ways, the results leading the investigators to the theory that there was present the same substance th at causes the diversity of colours assumed by the precipitates of p latinum formed by sal-am m oniac. T h e y believed that this was a new metal b u t wished to isolate it in a metallic state before being convinced. Next they found that if a solution of native p latinum was precipitated in two stages with sal-ammoniac, the first was a pale yellow or orange in colour, while the second was dark red. T h e y confirmed Collet-Descotils discovery th at the latter, if calcined and treated with a q u a regia, always left some insoluble black powder. In this they recognised a perfect resem blance to the m etal they had discovered in the insoluble m a tte r left behind w hen native platin u m is attacked by aqua regia. All this metal was not removed by a q u a regia from the platinum coming from the red salt because the new solution also yielded a precipitate that was reddish though less so th a n before, b u t if these operations were repeated several times with the same platinum then eventually the strange metal was removed entirely. T hey also found this metal in the p latinum purified by J a n e ty in almost as great a quantity as in native platinum . At the end of their pa p e r they proposed to go on with their experiments to obtain a larger qu a n tity of the new metal, to examine its properties further an d to seek better m ethods for the purification of platinum. T hey were not, however, left alone in the field. T e n n a n t continued his work during the winter of 1803 a n d carefully studied the papers of Collet-Descotils 4 and of Fourcroy and Vauquelin. (T he great advantage he h a d on the French chemists lay in the large am ount of residue he could work with, a by-product of W ollastons researches on the purification of platinum .) H e soon realised, however, th at whereas they suspected the presence of only one new metal in the black powder, there were in fact two. For breaking up the m aterial he used a
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X V I.
On two Metah, found in the black Powder remaining after the Solution of Platina. By S m ithson T ennant, Esq. F. R . S.
Read June s i , 1804.

p o n making some experiments, last sum m er, on the black powder which remains after the solution of platina, I observed that it did not, as was generally believed, consist chiefly of plumbago, but contained some unknown m etallic ingredients. Intending to repeat my experiments with m ore attention during the winter, I mentioned the result of them to S ir J o s e p h B a n k s , together with my intention of com m unicating to the Royal Society, my examination of this substance, as soon as it should appear in any degree satisfactory. T w o m em oirs were after wards published in France, on the same subject; one o f them by M. D e s c o t i l s , and the other by Messrs. V a u q u e l i n and F ourcroy. M . D e s c o t i l s chiefly directs h is attention to the effects produced by this substance on the solutions of platina. H e remarks, that a small portion of it is alw ay s taken up by nitro-muriatic acid, during its action on platina ; and, principally from the observations he is thence enabled to make, he infers, that it contains a new metal, which, am ong other properties, has that of giving a deep red colour to the precipitates of platina. M. V a u q u e l i n attempted a more direct analysis o f the sub stance, and obtained from it the same metal a s that discovered by M. D e s c o t i l s . But neither of these chem ists have observed,
E a r l y in t h e i r j o i n t i n v e s ti g a t i o n s it w as ag reed that T e n n a n t should exam in e the black inso lu b le p o w d e r re m a in in g a f t e r t h e d i s s o l u t i o n of p l a t i n u m in a q u a regia w hile ^ ollaston should c o n c e n tr a te on th e so lu b le p o rtio n . B egin n i n g w o r k in t h e s u m m e r o f 18 03 T e n n a n t i d e n t i f i e d tw o new e l e m e n t s w hich he n a m e d irid iu m from the s t r i k i n g variety o f c o l o u r s w h i c h it g ives w h i l e d i s s o l v i n g in m a r i n e a c i d " a n d o s i m i u m . f r o m t h e p u n g e n t sm e ll o f its v o l a t i l e o x i d e . T h i s s h o w s t h e o p e n i n g of h is p a p e r r e a d to t h e R o y a l S ociety in 1 8 0 4
m ethod similar to that employed by Vauquelin, namely, the alternate action of caustic alkali an d of acid. T h e second metal he found in the alkaline solution which had been suspected by V a u q u e lin to contain chrom ium . T e n n a n t was unable to confirm this latter conclusion, but further exam ination showed that the solution contained a volatile oxide which could be separated by acidification an d distillation. This was a colourless body, condensing first to an oily liquid and then solidifying into a sem i-tran sp a re n t mass. In all stages it ha d a strong an d very characteristic smell. It w a s this th a t caused him to confer on the metal the nam e of O s m iu m , from a Greek w ord m eaning smell. W ith regard to the other metal, T e n n a n t s work confirmed a n d extended the observations of Fourcroy an d V auquelin on the subject, an d this one he nam e d Iridium from the striking variety of colours w h ic h it gives while dissolving in m arine a cid . T e n n a n t read his paper, a m asterpiece of clarity a n d conciseness, to the Royal Society on J u n e 21st, 1804 (11) and was aw arded the Copley M edal for that year. It is a tribute to him th at t h e F rench workers accepted the priority of his discovery without question in 1806 in a pa p e r on the new metals discovered in crude platinum (12).
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O ne of W ollastons nole-books open at the page eontaining the first record of pallad iu m as C . A note on the facing blotting p a p e r reads: T h e u p p e r p art of opposite page was w ritten July 1802. I believe the C m ea n t C eresium a n a m e which I once thought of giving to P a lla d iu m
P h o to g r a p h by courtesy o f the S y n d ics o f C a m b r id g e I niversity
Another worker had also noticed the varying colours of the sal-ammoniac precipitate. Luigi Brugnatelli, professor of chemistry in the University of Pavia and a colleague of Volta, wrote to his friend Baptiste Van Mons of Brussels, the editor of a chemical journal there, to say that he had seen the French papers and that he had obtained several years before the substance that gave colour to solutions of platinum, enclosing a specimen of the red precipitate (13).
The Discovery of Palladium Early in his work on the solution of platinum in aqua regia Wollaston suspected that something was present after the precipitation with sal-ammoniac that was neither platinum itself nor Tennants iridium. The first reference to this is in one of his note-books, dated July 1802, in which the properties of an alloy of lead with C are described. O n the facing page he later wrote:
1 53
The upper part of the opposite page was written July 1802. I believe the C meant Ceresium, a name which I once thought of giving to Palladium". Palladium is first mentioned by that name in August. The planet Ceres had been discovered by the Germ an astronomer Heinrich Olbers in January 1802; he discovered another minor planet which he named Pallas at the end of March in the same year and this doubtless caused Wollaston to change his mind. Wollaston proposed to do some further work on the solution and did not therefore publish his results, but in order to establish his priority he resorted to a most unorthodox procedure that was to involve him in an unpleasant and embarrassing controversy. Towards the end of April in 1803, some nine months after the note-books record the discovery of palladium, and by which time he had been able to isolate a reasonable quantity of metal, members of Londons scientific community received in their post a small hand-bill describing the properties of a new noble metal known as Palladium or New Silver. The leaflet, illustrated here in its actual size, announced that this new metal was to be obtained only from the shop of Mr. Forster of Gerrard Street in Londons Soho in samples at five shillings, half a guinea or one guinea each. This shop has
In April 1803 a n u m b er of .small lea fle ts w ere d i s tr i b u te d a n o n y m o u s ly a m o ng scientists in L ondon annou ncing the discovery of a new noble m etal called P a llad iu m or New Silver. T his described the m ajor p ro perties of the new m etal, w hich was to be obtained only from the shop of Jacob F o r s te r. a well k n ow n collector of m inerals, in L o n d o n s Soho. T his unusual p ro ce d u re aroused great con troversy and caused consider a b l e e m b a r r a s s m e n t to ^ ollaston. T h e leaflet is reproduc ed here in its actual size
P h o to g r a p h b\ courtesy of the Synd ics of C a m b r id g e I rmersit\
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been identified by Professor Clifford Frondel of H a rv a rd as belonging to Ja co b Forster (1739 1806), a well known collector an d dealer in m inerals after whom the m agnesium silicate mineral Forsterite was later nam ed (14). H e travelled widely an d spent several years in R ussia where in 1802 th e C o u n t M ussinPushkin purchased from him a large collection of specimens for the M ining Cadet Corps for 50,000 roubles. M ussin-P ushkin also relates th at he acquired his own supplies of native p latinum from Forster who, strangely enough, was a relative of Georg Forster whose letter describing the C o u n t von Sickingens large piece of platinum sheet was m entioned earlier. In his absence in St. Petersburg it was M rs. Forster w ho conducted the business in L ondon and she duly received a q u a n tity of palladium foil a m o u n t ing to 420 grains together with a copy of the leaflet, the source being quite unknown to her. J o h n Nicholson, the founder and editor of the Journal fo r N atural Philosophy, Chemistry and the Arts, also received a copy an d in an editorial com m ent wrote: Mrs. Foster (sic) it appears is only the vendor and totally unacquainted with the person who brought the metallic substance and the printed paper to her house .. . I received a small piece by the post (15).
T h e C o n tr o v e r s y w ith C h e n e v ix Apart from attracting general attention in scientific circles this unusual means of announcing the discovery of a new element aroused the intense interest of a quite distinguished young Irish chemist, R ic h a rd Chenevix (17741830), a great nephew of the famous Bishop of W aterford of the sam e name, who had already established a reputation as a n analyst and ha d been elected to the Royal Society in 1801. H e immediately visited the shop in G e rra rd Street and purchased for fifteen guineas the whole 332 grains of palladium th at had not yet been sold, suspecting that this curious procedure was nothing but a fraudulent imposition. After a fortnights hectic experim entation Chevenix read a long paper to the Royal Society on the two evenings of M a y 12th a n d 19th describing his investigations (16). H e agreed that the substance possessed all the properties claimed for it on the hand-bill, but m aintained that it was merely a n alloy of platinum a n d m ercury in the proportions of two to one. H e a dm itted th a t he had been unable to confirm this by analysis but m aintained that he had successfully synthesised palladium, although he rem ained puzzled by the great discrepancy in the specific gravities expected for alloys of platinum an d m ercury which should have been much higher th a n the value of 11.3 to 11.8 claim ed for palladium in the handbill. H e was not deterred even by a n experim ent he recorded, carried out by H u m p h ry Davy in his presence, in which a slip of palladium was ignited by the strong galvanic batteries of the Royal Institution and b urned with a very vivid light an d a white smoke but no m ercury was separated by this op e ra tio n .
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XII. Enquiries concerning the Nature o f a m etallic Substance lately sold in London, as a nezv M etal , under the Title of Palladium . By Richard Chenevix, Esq. F . H. S. and M. R . I. A. Read Ma y
12, 1803.
O n the 29th of April I learned, by a printed notice* sent to Mr. K n o x , that a substance, which was announced as a new metal, was to be sold at Mr. F o r s t e r ' s , in Gerrard-street. T h e mode adopted to make known a discovery of so much import ance, without the name of any creditable* person except the vender, appeared to me unusual in science, and was not calcu lated to inspire confidence. It was therefore with a view to detect what I conceived to be an imposition, that I procured a specimen, and undertook some experiments to learn its properties and nature.
I he nature of the anonymous a n n o u n c e m e n t o f t h e d is c o v e r y o f p a lla d iu m a r o u s e d the suspicions of R ic h a rd C henevix who im m ediately p u r c h a s e d t h e b u l k of t h e m e t a l a n d p r o c e e d e d to c a r r y o u t a r a p i d s e ri e s o f e x p e r i m e n t s . A f t e r o nly tw o w e e k s h e s u b m i t t e d a p a p e r to t h e R o y a l Societv in w h i c h h e m a i n t a i n e d t h a t it w as no t a new m etal as shameful l v a n n o u n c e d b u t m e r e l y a n allo y o f p l a t i n u m a n d m e r c u r y . H e p e r s i s t e d in th is view u n til W o l l a s t o n d i s c lo s e d t h a t he w a s t h e d i s c o v e r e r in 1 80 5
T h is paper, of which the introduction is illustrated here, caused something of a sensation and it was quickly rep ro d u c e d in the F rench and G e rm a n journals (17). O n M ay 4th Chenevix w rote to V auquelin in Paris, his letter beginning: The scientific world here talks of nothing but palladium: everyone received a few days ago a printed note like the one I enclose. I am sending you a little piece together with the notice so that you can see for yourself what it is (18). V auquelin duly checked the properties claimed in the hand-bill and found them to be correct, but he was q u ite unable to find either p latinum or m ercury in the specimen and tentatively suggested th a t it might in fact be a new element. A note by the editors of the Annales de Chimie ap p en d ed to his report concluded that all this m ust give rise to d o u b t . Shortly after reading his p a p e r Chenevix left for Paris to meet Berthollet and then spent over a year in G e rm a n y , visiting chemists in M a n n h eim , Cassel, Leipzig, Erfurt and Freiberg a m o n g other places. H e re the controversey was entered into by several scientists. T h e two well known Berlin analysts V alentin Rose and A. F. Gehlen carried o u t num erous careful experiments in a n attem pt to reproduce the p latinum -m ercury alloy of Chenevix, obtaining specific gravities of 14 to 15 but failing to produce palladium (19). J. B. R ichter similarly followed the procedures described by Chenevix for the prep a ra tio n of artificial p a lla d iu m but again without success (20). K laproth, in a letter from Berlin to Vauquelin in J a n u a r y 1804, also wrote th at he had been quite unable to repeat this synthesis (21), but p e rhaps the most critical com m ent was th at m ade by Professor Trom m sdorff of E rfu rt after Chenevix had left him for a long stay in Freiberg. I have repeated in vain part of the research followed by Chenevix to prepare the so-called palladium: heaven knows how it comes about (22).
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o f \a tu r a l Philosophy. Chemistry and the Arts
In December 180 3 W ollaston, still anony m ously, wrote to Nicholson's Journal offering a re w ard of 20 to anyone who could m ak e t w e n ty g r a i n s of re al pallad iu m be fo re "any three gentlemen c h y mists'" appointed by Nicholson. The rew ard was, of course, never claim ed
Then early in 1804 there appeared in Nicholsons Journal a second curious anonymous notice, reproduced here in full (23), offering a reward of 20, deposited with Mrs. Forster, to anyone who could make only 2 0 grains of real palladium before any three gentlemen chymists you please to name, yourself one if you like. Nicholson chose Charles Hatchett and Edward Howard, both distinguished chemists and Fellows of the Royal Society, to join him as assessors but there is no evidence that any claim to the reward was ever put forward.
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The writer of this notice was of course Wollaston, who had repeatedly tried to convince Chenevix of his error, but further controversy, embarrassing Sir Joseph Banks and involving a second paper from Chenevix admitting that only four out of a thousand experiments had been successful (24), (and fully related in Usselmans survey of the whole sequence of events ( 8 )) was yet to come.
The Discovery of Rhodium On June 24th 1804, only three days after the reading of Smithson Tennants paper on iridium and osmium, Wollaston read a paper to the Royal Society, O n a new Metal, found in crude Platina, describing his discovery of: another metal, hitherto unknown, which may not improperly be distinguished by the name of Rhodium, from the rose-colour of a dilute solution of the salts containing it (25). He went on to refer to the results of various experiments: which have convinced me that the metallic substance which was last year offered for sale by the name of Palladium is contained (though in very small proportion) in the ore of platina ... if we consider the difficulty of producing even an imperfect imitation of palladium the failure of all attempts to resolve it into any known metals ... as well as the number and distinctness of its characteristic properties I think we must class it with those bodies which we have most reason to consider as simple metals. Wollaston still did not disclose that he was the mysterious advertiser, but in the following February he wrote again to Nicholsons Journal announcing himself as the discoverer of palladium and offering an explanation of his unusual behaviour. After referring to his project to produce malleable platinum he wrote:
T his extract from W ollastons notebook of Ju n e 14th 1804 describes the discovery an d the nam ing of rho dium from the rose-red colour of its salts. On this occasion the discovery was im m ediately ann o u n c ed in a p a p e r read to the Royal Society on J u n e 24th
P h o to g rap h b\ courles> of the S yndics o f C a m b r id g e I i m entity
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The object had now been attained and during the solution of it various unforeseen appearances occurred; some of which led me to the discovery of palladium; but there were other circumstances which could not be accounted for by the existence of that metal alone. On this, and other accounts, I endeavoured to reserve to myself a deliberate examination of those difficulties which the subsequent discovery of a second new metal, that I have called rhodium, has since enabled me to explain, without being anticipated even by those foreign chemists, whose attention has been particularly directed to this pursuit (26). Finally, in a lengthy paper read to the Royal Society o n j u l y 4th 1805, O n the Discovery of Palladium ; with O bservations on other Substances found with P la tin a (27), W ollaston put a n end to the mystery. T h is disclosure cam e of course as a complete surprise to Chenevix after his long arg u m e n t against the existence of this new element, b u t he appears to have accepted defeat gracefully, contrary to the ju d g m e n ts of earlier writers who have described his reputation in ruins , a n d he was a guest of W ollastons at the Royal Society C lub more th a n once in later years. H e afterwards turned to the writing of novels and plays. W ollastons motives in the anonym ous announcem ent of his discovery of palladium have been the subject of m any speculations, b u t there seems to be no need to look further th an his own statem ent in his letter to N icholson in February 1805. T h e m ain object of his work was to discover the best way of producing malleable platinum, b u t in the course of his labours he came across evidence of the presence of first one unknow n metal and th en another. Anxious to pursue these to a conclusion, conscious th a t Descotils, Fourcroy and Vauquelin were close on his heels, it does not seem u n n a tu ra l th a t he should wish to shelve one enquiry without losing his right of priority in another. Also, as Usselm an has pointed out (8), a m ajor factor in his delay was that not until 1805 did he finally succeed in preparing really malleable platin u m after five years of intensive an d often frustrating research. T h e entry of the rath e r pugnacious Chenevix into the affair clearly upset his plans.
T h e P ro d u ctio n o f M a lle a b le P la tin u m W e can now return to the m ain achievement of W ollaston, the painstaking development of a process for the production of malleable p latin u m on a con siderable scale and the prom otion of its industrial uses. T e n n a n t s part in this work was the lesser of the two although he gave m uch practical assistance in the early years. His financial participation ceased in 1809. T h e large purchase of native metal in D ecem ber 1800 has been referred to already. In February 1801 W ollaston set about his purification in earnest, working in a laboratory at the rear of his house in Buckingham Street off Fitzroy Square, dissolving his material in 16 or 20 ounce lots followed by precipitation with salammoniac, heating a n d forging. T hese early trials were beset by difficulties and m any of his ingots cracked or split on ham m ering, a problem that was m uch reduced after the meticulous chemical analysis of his crude
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platinum allowed the removal of t h e previously unknow n metals palladium and rhodium. Further, by cleverly adjusting the proportions of hydrochloric and nitric acids in his aqua regia, a n d later by using m ore dilute mixtures, he succeeded in achieving the most econom ical m eans of dissolution. Next he turned his attention to the technique of pow der m etallurgy and by a n u m b er of detailed im provem ents on the m ethods of K night a n d Cock he was eventually successful, after more t h a n three years of unrem itting effort, assisted by his faithful m anservant J o h n Dowse, in obtaining a saleable product. T h e whole process, subjected to m odifications an d improvements over the years, was kept a closely guarded secret a n d not until long after the work had ceased and W ollaston knew in 1828 that he w a s suffering from a fatal illness did he consent to publish any account of his process. T h e n he gave a full description dictated from his bed to his friend H enry W a r b u r to n and read as the Bakerian Lecture to the Royal Society on Novem ber 2 0 th of th at year, a m onth before his death (28). Before discussing the details o f his procedure, therefore, we should consider both his sources of supply and t h e n the m arketing of his products.
T h e R ole o f J o h n J o h n s o n T h e am ount of native platinum p u rc h a s e d by Wollaston, until 1815 jointly with T e n n a n t, totalled the rem arkable figure of 47,000 ounces. I n a recent closer study of the m anuscripts at C a m b rid g e a n d of W o lla sto n s account at C o u tts bank Usselm an (29) has confirm ed and extended the findings of Gilbert (1) and the views expressed in the first edition of this book th at by far the m ajor portion of this, over 38,000 ounces, was supplied by J o h n J o h n s o n during the years 1808 to 1819. T his m a n s father, also J o h n Jo h n so n , had established himself in M a id e n Lane in the City of L o n d o n in 1777 as a n assayer after a short career as a goldsmith. T h e son, born in 1765, was apprenticed to him in 1779 and took over the business on his fathers d e a th in 1786, developing the assaying of ores a n d metals still further and also engaging in the buying and selling of bullion (30). He was in fact the only com m ercial assayer in London, the others being employed by the Royal M int a n d the W orshipful C o m p a n y of Goldsmiths. For nearly twenty years J o h n s o n both lived a n d worked in M a id e n Lane, now a pa rt of G resham Street, and then in 1805, his business flourishing, he moved to a country house in Stoke N ew ington, the centre of a n u m b er of scientists, m any of them of the Q u a k e r persuasion. H e r e he becam e friendly w ith both the Aikin an d the Cock families among others, a n d he h a d already m ade contact with W ollaston for whom he had c a rrie d out assays. A confirm ation of their associa tion is contained in a letter fro m J o h n s o n to his son Charles, serving with W ellingtons arm y in Spain and d a te d April 22nd, 1814. In this he refers to my friend Dr. W ollaston (31). J o h n s o n had come across p la tin u m as a n adulterant in gold in his assay work a n d this may well have p ro m p te d him to take a n interest in the metal and to enter into its im portation and sale, acting as an agent for m erchants in Ja m a ica .
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T h e first recorded sales to W ollaston occur in D ecem ber 1806 and J a n u a r y 1807, followed by a quantity of 1000 ounces at 2s lOd per ounce in O c to b e r 1808 a n d a further 1750 ounces at 2s 9d later in the same month. A charge of 3s 6d was m ade for each delivery by hired horsem an. T ransactions of this kind, ranging from only 72 ounces up to 5,100 ounces at a time, continued over th e next eleven years. W ollaston was apparently p repared to purchase all the native platinum that J o h n s o n could obtain an d held a running account with him for this purpose, the dealings yielding handsom e profits to both men. J o h n s o n retired tem porarily at the beginning of 1817, leaving the business in the hands of his son Percival, the founder later in th at year of the firm th at becam e Johnson, M a tth e y an d Co., but he returned in 1818 and continued to be active until his d eath in 1831. A nother indication of the J o h n s o n s early interest in the p latin u m m etals is disclosed in a pa p e r subm itted to The Philosophical M agazine in 1812 by Percival, then only 19, on the assaying of platinum -gold alloys to which a postscript initialled by both father and son reads: It may also be worthy the notice of your readers that we find palladium to be such a general alloy of Brazil gold as often to alter the colour thereof. We have particularly observed it in the Brazil coin many of which were rejected at first sight, suspecting them to be counterfeits. We found it a short time since in a Brazil bar to the amount of 20 per cent, altering the colour to nearly that of palladium (32). In the later years of W ollastons work other sources of supply were som e times draw n upon, including some 2000 ounces from a rath e r extraordinary character J u s tu s Erich Bollmann (1769 1821), a G e rm a n physician a n d chemist and something of an adventurer who ha d em igrated to Am erica an d then divided his time betw een Philadelphia an d L o n d o n with occasional visits to Colombia an d Ja m a ica . A n account of his colourful career and his connections with W ollaston has recently been given by Dr. J. A. C haldecott (33). O n e of his last purchases was of 600 ounces in April 1819 from H o d g s o n , w ho was most probably J o h n H odgson of Bucklersbury, a South A m erican m erchant, a n d last of all a further 400 ounces from J o h n J o h n s o n in August of the sam e year. From his total intake of 47,000 ounces of crude p latin u m W ollaston produced an d m arketed a little over 38,000 ounces of refined a n d malleable metal at an average price of 16 shillings per ounce. H is very large purchases clearly am ounted almost to a m onopoly and would have m a d e it difficult if not impossible for any potential c om petitor in E n gland to have secured supplies. But by 1820 platinum becam e most difficult to obtain from the now independent Colombia a n d his activities drew to a close, leaving orders unfulfilled.
T h e M arketing o f W o lla s t o n s P la tin u m By early in 1805 W ollaston ha d the production process u n d e r control and was at last in a position to offer his platin u m for sale. Evidently he did not wish to involve himself in num erous small comm ercial transactions and he therefore came to an arrangem ent with one W illiam C a ry (1759-1825), a L ondon scientific instrum ent m aker with premises in the Strand. C a ry ha d become well
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By 1805, a fte r long an d frustrating researches, o lla sto n w as a b le to produce marketable p la tin u m in q u antity. A m ong his first p ro d u c ts were crucibles a n d lids, m a rk e te d th ro u g h W illiam C ary, a well kn ow n L o n d o n in stru m en t m ak er. T his shows o n e of his early c rucibles th at was re ta in ed by the W ollaston fam ily until it was given to the Science M u seum in 1932. It is a b o u t 2 inches in height an d weighs 1.59 oz troy, a great deal lighter th an the crucibles m a d e at a b o u t the sam e tim e by W illiam Allen a n d T h o m a s Cock
known to the family some ten years earlier when he had made a transit circle to the complete satisfaction of Wollastons father, the Rev. Francis, while Wollaston himself had purchased a number of instruments from him. These and other details of their association have recently been fully recounted by Dr. J. A. Chaldecott (34). In February and March 1805 Wollastons notebooks record the supply of a number of crucibles and of bars and rods for wire drawing to a total weight of 258 ounces. Little or no publicity seems to have been given to the arrangement although on M arch 22 a letter from Sir Joseph Banks to Richard Chenevix includes the statement that: Wollaston has now opened a Manufactory of Platina Crucibles, etc, which are sold in his name to such as chuse to bespeak them, by Carey, the Mathematical instrument maker (35). The first published reference to a Wollaston crucible came in May 1806 in the course of a paper on the analysis of a new mineral found in Cornwall by Professor John Kidd of Oxford, a former student and a friend of Astley Cooper. In this investigation he reported using a small crucible of platina prepared by Dr. Wollaston (36). Altogether the note-books show that approximately 1700 ounces of platinum were made into crucibles and lids - a development that greatly assisted the analysts of the time in their discipline, by now brought to a reasonable degree of accuracy. One indicative comment came from the great Berzelius, the leading chemist and analyst, in a letter to his friend and patron Baron Hisinger in October 1815: I have just received from England a delicious platinum evaporating dish holding more than | stop. It is a jewel (37).
(T he old Swedish unit of capacity, a stop, w a s equivalent to 654 millilitres).
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T h e o t h e r e a r l y a p p l i c a t i o n f o r W o l l a s t o n s p l a t i n u m w a s f o r t h e t o u c h - h o l e s of flin t-lo ck p isto ls a n d s p o r t i n g g u n s , r e p l a c i n g gold a n d h a v i n g t h e a d v a n t a g e s of g r e a t e r h a r d n e s s a n d h i g h e r m e l t i n g p o i n t . T h i s d o u b l e b a r r e l l e d s p o r t i n g g u n . m a d e in a b o u t 1 8 1 0 w ith p l a t i n u m f a c e d t o u c h - h o l c a n d d e c o r a t i o n , is now in t h e A r m o u r y o f t h e T o w e r of L o n d o n . L a r g e q u a n t i t i e s o f p l a t i n u m w e r e a ls o u s e d as c o u n t e r p o i s e w e i g h t s o n g r a v i t a t i n g s to p s , a n i n v e n t i o n p a t e n t e d by J o s e p h M a n t o n in 1 8 1 2 to p r e v e n t t h e a c c i d en tal disc h arg e of cocked guns
N um erous other items of chemical apparatus, including balance pans and blow-pipes, were produced by W ollaston an d sold through C a ry over the period 1806 to 1822, b u t a m uch greater quantity was in the form of bars or ingots, the total am ounting to over 28,000 ounces. But by far the largest sales were m ad e to the L ondon gunm akers for the touch-holes an d pans of flintlock pistols an d sporting guns. T his type of firing mechanism, well-established by the end of the seventeenth century, utilised a piece of flint held in the jaw s of a pivoted dogshead or cock. W h e n the trigger was pressed the cock swung forward and the flint struck sharply against the steel fixed on the cover that protected the prim ing charge, the sparks caused by the impact igniting the charge. T h e explosion resulted in considerable corrosion and erosion of the metal touch-hole which thus becam e slowly enlarged and led to a loss of power w hen the gun was fired. T o avoid this deterioration it had become the practice to line the touch-hole of the best quality guns with gold, b u t the advent of malleable platinum now offered the additional advantages of a higher
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T his label from the case holding guns m ad e by the greatest L ond on gun m ak er Jo se p h Vlanton a n d dating from 1805 includes the words In v en to r of P latin a T ouch H oles
melting point, a greater hardness and a lower cost. At this time London was the centre of fine gun-making, and among the leaders were the brothers John and Joseph Manton, both of whom introduced platinum touch-holes in the early years of the century, to be followed by almost all other English gunmakers, of whom there were at least two hundred. A full account of this phase of the history of platinum and its uses has recently been given by I. E. Cottington (38) who supports the view of Dr. Usselman (2) that no less than 27,000 ounces of Wollastons platinum could have been absorbed in this way - the largest single application for his malleable metal. By the end of the period in question percus sion ignition had replaced the flintlock but while this type of mechanism still required small amounts of platinum the Wollaston era was over and the supply had greatly diminished.
The Sulphuric Acid Boilers While the greater proportion of his platinum was sold through Cary, Wollaston retained to himself a major product in which he took a personal initiative and in which the quantity of platinum was by far the greatest for each individual sale. In the manufacture of sulphuric acid the lead chamber process, introduced by John Roebuck and Samuel G arbett in 1746, yielded a relatively weak acid that needed concentration, a procedure that was carried out in glass retorts bedded in sand inside iron pots with considerable risk of breakage. By Wollastons time the manufacture of sulphuric acid had increased very greatly and the cost had of course decreased. As early as December 1805 Wollaston had constructed his first boiler in platinum for a small acid manufacturer named Philip Sandman of
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T he application of p latin u m that most interested W ollaston lay in its great a dvantage as boilers for the c o n c en tra tion of sulphu ric acid, replacing the fragile glass vessels previously relied upon. T his outlet he retain ed to him self, designing the vessels, specify ing their m a n n e r of construction by m etal w orkers a n d interesting him self in their p e rfo rm a n c e in service. T h e first platin um boiler ever m ad e was supplied in 1805 to a sm all sulphu ric acid m a k e r n a m ed P hilip S a n d m a n of S ou th w ark on the south b a n k of the T h a m e s and W ollastons sketch is shown here together with the weight of p latin u m involved, 406 ounces, an d the cost. 282 9s 0 d. A fter S a n d m a n s death in 1815 this boiler was bought by the fam ous Glasgow chem ical firm of C harles T e n n a n t who fou nd it so satisfactory that they very soon pu rch ased four m ore
Southwark. This weighed some 406 ounces and held 30 gallons, the price being 282. Wollastons relevant note-book entry is illustrated here. There is some evidence that Smithson Tennant played some part in the design and construc tion of this boiler, but it was fabricated by a Sheffield silversmith, Charles Sylvester, for a little over 50. An interesting comment on this first boiler is given by Samuel Parkes (1761-1825), himself an acid manufacturer, in his Chemical Catechism of 1807: The important uses to which this precious metal may be applied can be easily conceived when it is considered that it unites the indestructibility of gold to a degree of hardness almost equal to that of iron; that it resists the action of the most violent fire and also of the most concentrated acids. Aware of these properties, a chemist in the neighbourhood of London has been induced to spend several hundred pounds in the fabrication of a single utensil for rectifying sulphuric acid (39). Four years passed before Wollaston succeeded in persuading a second sul phuric acid maker to purchase a platinum boiler. The firm of Richard Farmer and Son had been established at Kennington Common in 1778, and in 1809 the son Thomas ordered a larger boiler together with a siphon. For the fabrication work Wollaston now turned to a young cousin of John Johnsons named George Miles (1783-1837) who had been brought up in the Johnson family after the
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death of his parents and who had established himself as a silversmith in Clerkenwell in 1804. Wollastons notes for the costs incurred in making this boiler are shown here, but it seems that Miles was either inexperienced or had underestimated the work involved as in a letter to Thomas Farmer dated February 14th 1810 Wollaston wrote: When I last parted from you I was in hopes that the additional charges for finishing the vessel might not require an appendix to the imperfect account which I gave you; but when I came afterwards to converse with Miles upon the subject, I found that the former sum of 14 10. 0 was not such as to satisfy him for his time and labour and actual expenditure and that he now demands an addition amounting in the whole to 19 saying at the same time that, if he could have foreseen the trouble, he would not have undertaken it for less than 30. Now, tho I have no doubt that a little more sense would have saved a great deal of labour, we employed him such as he is and I am inclined to think he ought to be paid (40).
W o llastons second boiler was o rd ere d in 1809 by T h o m a s F a r m e r of R ich ard F a r m e r an d Son of K e n n in g to n C o m m o n, L ond on. T his is believed to have be en fa b rica te d by G eorge Miles, a silxersm ith in C lerken w ell who was a young cousin a n d pro tege of Jo h n Jo h n so n . T h e cost sheet shows that it was m a d e by gold solderin g from sheets that had been flattened by h a m m e rin g betw een sheets of copper. W ollaston also designed a p la tin u m syphon for this an d later boilers to m ak e co n tinuous o p era tio n possible
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Clearly W ollaston was not impressed with Miles, and w hen he secured a further order for a boiler from P epper and Smith, sulphuric acid m akers of O ld Ford, east of London, he turned to his friend J o h n J o h n s o n for assistance. Jo h n so n had no facilities and no space for such fabrication in his assaying business and it seems likely that, after purchasing the 413 ounces of p latinum required, he supervised his young cousin M iles an d ensured th at this time a more satisfactory procedure was carried out according to W o lla sto n s specifica tion. Miles was not particularly successful in his vocation an d in 1810, perhaps not surprisingly, he abandoned it and becam e an assayer with the W orshipful Com pany of Goldsmiths. T h irte en more boilers are shown to have been m ade in the note-books, and for ten of these W ollaston turned to a L o n d o n coppersm ith nam ed J o h n K epp of Chandos Street, Covent G arden. (This business later becam e R ic h a rd and E dw ard Kepp, who described themselves as Braziers and C o p p e r a n d Platina Sm iths until 1854 w hen the nam e changed to B enham a n d F ro u d late R and E K e p p , and the fabrication of p latinum was still being carried out by them long after W ollastons death). In 1811 Sam uel Parkes, whose chemical works in Shoreditch included the m anufacture of sulphuric acid, bought a W ollaston boiler holding exactly thirty gallons. A n indication of the great care an d interest that W ollaston took in the design a n d the perform ance of his boilers is given in a letter from him to Parkes in J a n u a r y 1812:
As it is now m ore th a n twelve m onths th a t you have been in possession of your large vessel it m ay reasonably be supposed th a t you have full trial of its m erits and I hope you will not think it u n reaso n ab le in m e to req u est a few lines u p o n th a t subject as it w ould gratify m e to h ear th a t it has fully answ ered your expectations . . . . if you w ould take th e trouble of adding any fu rth er inform ation on po in ts of econom y w hich I presum e you have carefully estim ated (saving of tim e, saving of fuel, saving of breakage, saving of lab o u r) you w ould confer an ad d itio n al favour on Sir, your m ost obedient h u m b le servant W m . H. W o lla sto n (41).
Parkes reply is not recorded, but in one of W o llastons note-books u n d e r the date J a n u a r y 17th 1812 there is a brief entry: S. Parkes, P la tin u m retort answers well while in the second edition of P a rk es Chem ical Essays published in 1823 after W ollaston had ceased to produce m alleable platin u m on account of the shortage of native metal he wrote:
I had one of these vessels a n d found it to be easily m an ag ed a n d very econom ical . . . It w ould now, however, be very difficult to p ro cu re such a vessel in consequence of the g reat scarcity b o th of cru d e and m alleable p la tin u m (42).
T h e great Glasgow chemical firm of C harles T e n n a n t bought W o lla sto n s first boiler from S a n d m a n on his death in 1815 an d its efficiency p rom pted the purchase of two more in the following year, and one each in 1817 and 1818. A note in W ollastons han d in F e b ruary 1816 records th at T e n n a n ts:
boil off 3 tim es p er day an d tu r n out 50 bottles of 150 lb p er week. T h e y reckon to save the p rim e cost in 2 years, oil of vitriol being now at 3js. to 3-jS . per lb. (43).
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O th e r p latinum boilers were supplied t o j o h n Smith, the surviving p a rtn e r of P epper and Smith, t o j . W. N o rris of Halifax, to J o h n M c K e n n y of D u b lin and to Gregg and Boyd of Belfast, with three m ore to Farm er. A report that a p latinum boiler and siphon w ere supplied to the Newcastle acid m anufacturer D oubleday and Easterby, rep o rted by G ilbert an d others, has been shown to be in error by W. A. C am pbell (44) w ho identifies the purchaser as the neighbour ing works of H. L. Pattison, the inventor of the lead desilverisation process. Altogether over 7,000 ounces of W o llastons p latinum were accounted for in this application. It will be seen from the note-book entry about F a r m e r s boiler that the vessels were fabricated by gold soldering separate sheets of platinum that had been flattened by h a m m e rin g betw een sheets of copper. W h e n the activity ceased in about 1819 W o lla sto n still h a d seven orders in han d that rem ained unfulfilled including fu rth e r requests from C harles T e n n a n ts, Farm er, M cK enny and one from D o u b le d a y an d Easterby. T h e sulphuric acid boiler remained, however, a sta n d a rd p ro d u c t for m ore th an a century, m ade for a period in France and later in E ngland.
O th er A p p lica tio n s o f W o l l a s t o n s P la t in u m M etals A p a rt from laboratory a p p a ra tu s and the touch holes of guns already con sidered, W ollaston introduced several other uses of platinum , while he also endeavoured, although without great success, to find applications for his palladium and rhodium. O n e of his earliest ideas for taking advantage of the properties of platinum , a n d one that was to be taken up m o re actively by others later on, was in the con struction of a bi-metallic therm om eter. As Dr. C haldecott has revealed (45) in 1807 there are references in his note-books to two p latina th erm o m e te rs and to Platina Therm om eter, for M . T e n n a n t . A pparently the bi-metallic ele ments, platinum soldered to c o p p e r an d rolled down, were m ad e by Charles Sylvester of Sheffield, while the finished therm om eters were constructed by the instrum ent m aker Charles M a la c rid a of H igh H o lb o rn in London. T h e note-books also record m o d est sales of platin u m through C a ry to several L ondon goldsmiths and of some 3000 ounces to a B irm ingham goldsm ith and silversmith T h o m a s Parsons an d also one to a dental surgeon, while Sylvester is known to have m ade a n u m ber of knives, one of which, an ivory handled paper knife, rem ained in the W o lla sto n family until its recent presentation to the Science M useum . It is inscribed:
T h is b lade form ed a p a rt o f one of the first m asses of p la tin u m w hich was w orked by W. H . W ollaston, M .D ., an d w as by him given to his b ro th e r F. J . H. W ollaston, w ho gave it to his son F . H. W ollaston, by w hom it w as p u t into its present form.
Another m inor application, a n d again one th a t rem ains in practice to this day, was the production of extrem ely fine wires, still known as W ollaston Wires, for the eye-pieces of astronomical instrum ents. T h is arose from his great interest
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in astronomy and was more of a philanthropic th a n a comm ercial exercise, the intention being to improve the accuracy of telescopic m easurem ents. T o produce wires as fine as 1/10,000 of an inch or less in diam eter was of course beyond the limits possible with normal wire drawing. By casting m olten silver in a cylindrical m ould in which he h a d placed centrally a p latinum wire draw n to 1/100 of an inch diameter, drawing the solidified rod to as fine a diam eter as possible and then dissolving away the silver in nitric acid he was able to produce platinum wires ranging from 1/10,000 down to 1/30,000 of an inch diameter. T h e process was described in a pa p e r on A M e th o d of D raw ing Extrem ely Fine W ires read to the Royal Society in 1813 (46), while U sselm an a n d two of his colleagues have recently described the progress of his experim ental work in some detail (47). W ollaston was less successful in finding outlets for his palladium and rhodium. In a recent survey of his enterprise in this direction U sselm an (48) has m ade the point that these two metals becam e available well before science and technology could put them to use. F rom the 47,000 ounces of cru d e platinum refined by W ollaston betw een 1800 and 1821 he isolated about 300 ounces of palladium and some 250 ounces of rhodium . T h e former was offered for sale at an exceptionally high price and appeared to have no properties th at would make it uniquely suitable for any specific application. T h e most familiar application was in the form of gold-palladium alloys for the graduations of astronom ical in struments, developed in collaboration with the well known instrum ent m aker E dw ard Troughton. T h e best known example is the great m ural q u a d ra n t erected at Greenwich in 1812, while th e F re n c h instrum ent m aker J e a n Nicholas Fortin used a similar alloy for the m ural circle in the Paris Observatory. As early as J u ly 20th 1805 R ic h a rd Knight purchased one ounce of palladium for twelve guineas a n d prom ptly wrote to Nicholson who included in the August issue of his Journal the following notice:
By a letter from M essrs K n ig h t of F o ster L an e I am inform ed th a t the new m etal, palladium , m ay be p u rch ased at th e ir w areh o u se (49).
O th e r small sales of palladium are recorded to R obert Bingley at the Royal M int and to Frederick Accum at the Royal Institution, while a few examples are known of its use as analytical weights, a n idea that W ollaston p u t forward for especially accurate work. O n e historic set of palladium weights, discovered after many years in the University of St. Andrews, is believed to have been m ad e by him for J o h n D alton a n d later passed to their m utual friend Professor T h o m a s T hom son (50). Eventually W ollaston presented a considerable q u a n tity of palladium to the Royal Society. If the possibilities for the sale of palladium were poor, those for rhodium were even more depressing. It could neither be melted nor m ade malleable, and the only outlet that W ollaston found was as an alloy with tin in the proportions of 4 : 1 for pen points which he supplied to the instrum ent and balance m aker T hom as Charles R obinson who had earlier purchased platin u m pa n s and
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weights for his balances. A rh o d iu m -tin tipped pen given by W ollaston to this friend Sir E d w ard Codrington in 1822 survived in the family a n d is now in the Science M useum.
W o lla s to n s Process R e v e a le d Not until he knew he was close to death in the last weeks of 1828 did W ollaston consent to disclose the details of his process for the refining of platinum . H e then dictated from his bed to his friend H e n ry W a rb u r to n a p a p e r for the Royal Society (28) setting out in full detail the results of his final procedures arrived at after careful and continued experim entation. T h is was read as the Bakerian Lecture on N ovem ber 20th and w a s printed early in the following year, a m onth or so after he died. In the opening p a ra g ra p h s he doubted w hether sufficient care had been taken in the past to avoid dissolving the iridium in the solution. H e sought to do this by properly diluting the a q u a regia solvent a n d he recom m ended that to every m easure of the strongest m uriatic acid employed, there be added a n equal m easure of w ater; and moreover, that the nitric acid used be w hat is called single aquafortis . T h e n he applied heat slowly in a gradually increasing m an n e r so that the digestion continued for three to four days, always in the presence of a n excess of native metal. All these are m easures taken to reta rd solution of iridium. T h e n h e decanted the solution a n d allowed it to settle for a considerable time. After decanting again he a dded specified quantities of a strong solution of sal-ammoniac. T h e precipitate was filtered a n d very carefully washed until free from impurities. It was then compressed a n d heated very cautiously in a black-leaded pot w ith so low a heat as j u s t to expel the whole of the sal-ammoniac, and to occasion the particles of p latina to cohere as little as possible; for on this depends t h e ultim ate ductility of the product. T h e grey spongy product, if properly prep a re d , w ould be lightly coherent an d it was then ru b b ed between the hands of t h e operator into a pow der so fine as to pass through a fine lawn sieve. T h e coarser parts were then g round in a wooden bowl with a wooden pestle b u t on no account with any h a rd e r material, capable of burnishing the particles of platina; since every degree of burnishing will prevent the particles from cohering in the further stages of the process. In the later stages of the grinding, w a te r was added to wash the metal and also to elutriate the finer particles. W ashing, shaking an d decanting were repeated until a uniform m ed or pulp was obtain e d ready for the next process. F o r this a brass barrel was required 6f inches long, tapered slightly inside and plugged at its larger end with a steel stopper t h a t entered the barrel to a depth of a q u a rte r of an inch. T h e inside was well creased a n d the slurry introduced u n d e r w ater to prevent the inclusion of any air. T h e two ends of the cylinder were carefully closed and a high pressure a pplied with a specially designed toggle press in which the applied power was m ultiplied three h u n d red times or more. T h is produced a h a rd cake of platin u m firm enough to be handled without dan g er of breaking. It was heated slowly to redness on a charcoal fire to drive off
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T h e p o w e r f u l h o r i z o n t a l p r e s s d e s i g n e d a n d u s e d by W o l l a s t o n to c o m p r e s s his w et p l a t i n u m s p o n g e . It is p r e s e r v e d in t h e W h i p p l e M u s e u m o f t h e H i s t o r y of S c i e n c e a t C a m b r i d g e b u t u n f o r t u n a t e l y t h e c y l i n d e r a n d p i s t o n h a v e b e e n lost. T h e v er y h i g h p r e s s u r e d e v e l o p e d y i e l d e d a c a k e o f p l a t i n u m s t r o n g e n o u g h to b e h a n d l e d d u r i n g t h e h e a t i n g a n d f o rg i n g o p e r a t i o n
the moisture an d to give it more cohesion. T h e cake was th en placed standing upright on one of its ends on a layer of clean q uartz sand on a n e a rthen stand. It was next covered up by a refractory pot, care being taken th a t this did not touch the cake. T h e whole was placed in a wind furnace a n d the m axim um possible heat applied for about twenty minutes.
T h e cake is now to be rem oved from the furnace, a n d being placed u p rig h t on an anvil, is to be struck, w hile hot, on the top, w ith a heavy h am m er, so as at one heating effectually to close the m etal. If in this process of forging, the cylinder should becom e bent, it should on no acco u n t be ham m ered on th e side, by w hich tre a tm e n t it w ould be cracked irrem ediably; b u t m u st be straig h te n ed by blow s u p o n the extrem ities, dexterously directed, so as to reduce to a straig h t line th e p a rts w hich project . . . . T h e ingot m ay be reduced, by the processes of h eating a n d forging, like th a t of any o th e r m etal, to any form th a t m ay be re q u ire d .
Directions were given for cleaning off any scale an d there were details of the mechanical properties of the p latinum so produced. W ollaston claimed th a t his product ha d a specific gravity of 21.25 to 21.5; the tensile strength (presum ably
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W ollaston began his a ttem p ts to p ro d u c e m alleab le p latin u m in 1801. w orking in a labo ratory b ehind his house a n d assisted only by his m an servant J o h n Dowse. T his record of his n u m e ro u s a ttem p ts in that year shows that his so-called casts"' suffered m any m echanical failures du rin g the forging op eration. T his was of course before iridium , o sm ium , p allad iu m and rh o d iu m had be en discovered and isolated fro m the p latin u m
P h o to g r a p h b> courtesy o f the S> ndies o f C a m b r id g e I niversity
in the hard-drawn state) he found to vary between 27 and 36 tons per square inch. It is interesting to examine this process in the light of present-day knowledge of the techniques of platinum refining and of powder metallurgy, and to see how in several essential points Wollaston anticipated their details. In the first place, he used diluted aqua regia in dissolving, together with slow heating in the pre sence of an excess of native platinum. This procedure tended to diminish solu tion of iridium and so largely obviated the necessity of separating it from the platinum later. Further, the precipitation of ammonium chloroplatinate from a diluted solution gives coarse crystals of precipitate, which on slow calcination at the lowest possible temperature yield a product with a more skeletal structure and of greater surface activity.
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O n e hundred years after W o llastons lecture an experienced worker in the field, J. S. Streicher, Chief M etallurgist of the Am erican P la tin u m W orks (51) added his appreciation of his success, emphasising the following points: (1) Reduction of the sponge to powder without applying any more pressure than necessary, avoiding particularly any contact with metal, leads to a minimum of cold work on the metallic particles. Any agglomoration by burnishing is particularly harmful. Attention to this preserves the surface activity of the particles at a maximum. (2) Reducing the sponge powder to a uniform size by sieving and elutriation, and then treating with quantities of water, assures the removal of nearly all traces of salts. (3) Forming the cake from the sponge under water avoids the inclusion of any gas. (4) Very slow drying of the wet cake, followed by a steady heating up to about 800 to 1,000C, promotes the maximum cohesion during the next operation. (5) Forging the cake at the highest possible temperature completes the process and produces the highly malleable metal for which Wollaston became famous. T h e suggestion that insufficient care had been taken in removing iridium has given rise to a widespread impression that the presence of traces of iridium was responsible for irregularities in the products of earlier workers. This, as recently pointed out by Dr. J. C. C h a sto n (52) is simply not true, a n d W'ollaston m ust have known it to be untrue, since it is not conceivable that he, so closely associated with Sm ithson T e n n a n t, the discoverer of iridium, had not observed its action as an alloying element with platinum . M ixtures of platinum and iridium powders can be consolidated and worked as readily as pure platinum, and for m any years pow der m etallurgy was the preferred m eans of preparing alloys containing from 5 to 30 per cent iridium. C h a sto n suggests that this rather impish attem pt to cloud the issue of the secret of perfection in powder metallurgy is in line with W o llastons known liking for a little mystifica tion. W ollastons p a per does little, in fact, to explain how he avoided the splits, breaks, and snapped samples recorded in his notebooks for 1801. T here can be no doubt, however, that he produced the best p latinum so far m ade and that it was m any years, perhaps as long as a century, before its equal was seen again. Unfortunately some years after his death a suggestion began to be m ade that his success was not due entirely to his own efforts but th at he owed certain of the fundam ental principles to another. T his story found its way into a num ber of text-books and encyclopedia and is sometimes still quoted, so th at the facts should be set out here. T h o m a s Cock, whose work at Plough C o u rt has been described in the preceding chapter, is alleged to have claimed that the continued pressure of the platinum sponge was proposed by him to W ollaston during a visit he m ade to W illiam A llens laboratory there. N ow we have seen how the welding of spongy platinum under hot forging gradually developed in the hands of one worker after another, each adding a little to the technique. De Milly pressed the hot metal with a n iron rod; J a n e ty struck his heated cakes with a pestle; Elhuyar and C h a b a n e a u c ru sh e d the hot sponge with an iron pestle;
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R ochon w rapped up the sponge in a piece of foil and then struck it while hot with a s ta m p e r , a n d R ic h a rd K nig ht tam ped down his precipitate in a clay cone as it was gradually heated u p to a white heat. C o c k s m ethod was to com press his sponge cold, and no longer by a mere tam ping action but under con siderable mechanical pressure i n a screw press. Gilbert found a note in the W ollaston M SS at C am bridge, u n d a te d b u t he believed almost certainly written in November 1800, in which W o lla sto n asks himself w hether the metal should be extremely compressed before h a m m e rin g (1). T h is shows th a t the idea was in his m ind when Cock was still a school-boy, and G ilbert also records his purchase, together with S m ith so n T e n n a n t, of two presses as early as 1801. No doubt the power of the press increased as time went on, until the pattern described in the Bakerian L e c tu re was attained. A t the sam e time, it gradually becomes apparent that W o lla sto n was applying the cold compression to his pow der in the wet state. T h e first m ention of m u d in the notebooks was found by Gilbert occurring with reference to A ugust 1802 (1). F ro m these d ata the reader can ju dge for himself how much, if anything, W ollaston learned from Cock. And however th at may be, we m ust rem em ber how small a part in W ollastons whole process was p layed by this cold c om pression and how great a p a rt in its success was due to t h e other details. It is obviously utterly wrong to suggest that the success was du e to Cock and th a t he was the real discoverer of the process. Cock, by the early p u b lic a tio n of the account of his work played his p a rt in the progress of the technique, b u t it is obvious th a t W ollaston was in a m uch further advanced state of know ledge and experience t h a n he at the time of W ollastons visit to Plough C o u rt, and th at he could have learnt little or nothing from what he saw there.
C o n c lu sio n T h e advantages that accrued from W o llastons work a n d th at of his p a rtn e r in the earlier years, Sm ithson T e n n a n t, stem m ed first of all from their analytical work with its identification of p allad iu m , rhodium , iridium, an d osmium. For the first time the real com position of native platin u m was almost completely disclosed, enabling the five elem ents obtained from it to be refined. T h is paved the way for a sta n d a rd product a n d thus simplified the subsequent processes of m anufacture, although it req u ired m any years of work by others before the lessons were fully absorbed into th e routine of comm ercial refining an d fabrica t i o n - possibly a m easure of the e xtent to which he was a pioneer. A letter from Berzelius to th e ir friend A lexandre M a rc e t gives b u t one indica tion of the esteem in which he w a s held in the scientific comm unity. Fie h ad met W ollaston during a visit to L o n d o n in 1812, a n d in writing to Berthollet in Paris said among other comments: But what I value most of all is the personal acquaintance of the admirable Wollaston . . . I am sure that among the chemists who are at present in the prime of life there is none that can be compared with Wollaston in mental depth and accuracy
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as well as in resourcefulness and all this is combined in him with gentle manners and true modesty (53). Early in 1829 Berzelius wrote to his former student E ilh a rd t Mitscherlich, but now professor of chemistry in Berlin: Wollastons death grieves me. His specifications for making platina malleable were circulated at the same time as the news of his death . His achievements were celebrated in 1953 - the 150th anniversary of the discovery of palladium - with a m ajor exhibition in L on d o n organised by the Institution of M etallurgists with the support of Baker Platinum , J o h n s o n M atthey, the M o n d Nickel C o m pany and the Sheffield Sm elting C om pany, at which a great m any of his products and other m em orabilia were gathered together (54). His p a rtn e r T e n n a n t, a m an of fitful genius, played less a n d less p art in the platinum work after the early years, b u t was undoubtedly a prim e mover in the initiation of the whole research. In 1813 he was appointed Professor of Chem istry at C a m bridge and early in J u ly of the sam e year he would have gained some satisfaction from attending a two-day meeting at the house of J o h n George C h ild re n (1777 1852) at T o n b rid g e in K ent where he m aintained a private laboratory equipped among other things with a n enorm ous battery. O n J u n e 20th T e n n a n t wrote to Berzelius about his thoughts for his first session of lectures a n d a bout his choice of a galvanic m a c h in e , continuing: On the 2nd of next month I am going to Mr. Childrens house to see a machine of which the plates are 16 square feet. The object is only to produce a very high temperature and I shall try its effect on iridium, which a flame even intensified with oxygen will not even touch (55). Thirty-eight scientists, including Davy, W ollaston, T e n n a n t, H a tc h e tt and Allen, dined together on th at evening, spent the night there, a n d in the m orning succeeded in melting a small piece of iridium the m odern value of its melting point is 2443C - by passing a high current through it from the battery (56). Sadly T e n n a n t gave only one course of lectures at C am bridge. T aking advantage of the restoration of peace after N a p o le o n s abdication in 1814 he again spent some m onths touring in F ra n ce b u t on a riding excursion on his return to Boulogne in F ebruary 1815 he met with a fatal accident. His tragic death at the age of only 53 was a great misfortune for C a m b rid g e a nd for science in general. W ollastons adm iration for T e n n a n t was profound and he once expressed his despair of ever becoming his equal as a chemist, b u t while W ollaston was persevering and self controlled T e n n a n t exhibited a lassitude an d indecisiveness. N one the less his influence on W ollaston was considerable a n d has not always been recognised.
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Re f erences for Chapter 9
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35
L. F. Gilbert, Notes & Records Roy. Soc., 1952, 9, 311 332 M. C. Usselman, Platinum M etals Rev., 1978, 22, 100-106 J. A. Chaldecott, Platinum M etals Rev., 1979. 23, 112-123 A. E. Wales, Nature , 1961, 19 2 , 1224 1226; The Life and Work of Smithson Tennant, forthcoming D. McDonald, Notes & Records R o \. Soc., 1962, 17, 77 Platinum M etals Rev., 1961, 94; 5. 146-148 L. B. Guyton de Morveau, C'hem. Ann ( Crell), 1786, (i), 156-157 Smithson Tennant, Phil. Trans., 1797, 219-221 M. C. Usselman, Ann. Science, 1978, 35, 551-579 H. V. Collet-Descotils, Ann. Chim ., 1803, 48, 153-176; J . N at. Phil. Chem. Arts ( Nicholson ), 1804, 8, 118-125 A. F. Fourcroy and N. L. Vauquelin, Abridged in Ann. Chim., 1803, 48, 177-183; in full in Ann. Chim.. 1804, 49, 188-218 Smithson Tennant, Phil. Trans., 1804, 94, 411-418 A. F. Fourcroy and N. L. Vauquelin, Ann. M us. H ist. Naturelle, 1806, 7, 401-409 L. Brugnatelli. J . Chim. de Van M ons, 1803. 4, 357-358 C. Frondel, M ineral. M ag., 1972, 38, 545 550 J. Nicholson, J .N a t . Phil. Chem. Arts, (Nicholson), 1803, 5, 136 R. Chenevix, Phil. Trans , 1803, 9 3 , 290-320 R. Chenevix, Ann. Chim., 1803, 47, 151-202; J . des M ines, 1803, 14, 372-408; J .d e Phys., 1803, 57, 127-139, 217-218; Neues A llg .J . Chem., 1803, 1, 174-212 N. L. Vauquelin, Ann. Chim., 1803, 46, 333-337 V. RoseandA. F. Gehlen, Neues A llg .J . Chem., 1803, 1, 529-547 J. B. Richter, Neues Allg. J . Chem., 1803, 1, 547-554 M. H. Klaproth, Ann. Chim., 1804, 49, 255 256 J. B. Trommsdorff, Neues Allg. J . Chem., 1804, 2, 238-239 J . Nat. Phil. Chem. Arts ( Nicholson) , 1804, 7, 75 R. Chenevix, Phil. Trans, 1805, 9 5 , 104 130 W. H. Wollaston, Phil. Trans, 1804, 94, 419-430 W. H. Wollaston, J . N at. Phil. Chem. Arts (Nicholson), 1805, 10, 204 205 W. H. Wollaston, Phil. Trans, 1805, 95, 316-330 W. H. Wollaston, Phil. Trans, 1829, 119, 1-8 M. C. Usselman, Ann. Science, 1980, 37, 253-268 D. McDonald, Thejohnsons of Maiden Lane, London, 1964 Letter from Johnson to his son Charles dated April 22nd 1814 in the possession of the Johnson family P N. Johnson, Phil. M ag., 1812, 40, 3-4 J. A. Chaldecott, Platinum M etals Rev., 1981, 25, 163-172 J. A. Chaldecott, Platinum M etals Rev., 1979, 23, 112-123 British Museum (Natural History), Sir Joseph Banks Correspondence, Dawson Turner Collection, 15, 338-340
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36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56
J . K idd, J . N at. Phil. Chem. Arts (Nicholson), 1806, 14, 134140 H. G. S derbaum , Jac-B erzeliu s Brev, U ppsala, 1921, 4, (i), 45 I. E. C ottin g to n , Platinum M etals Rev., 1981, 25, 74 81 S. Parkes, C hem ical C atechism , 2nd edn., L ondon, 1807, 368-369 L etter from W ollasto n to F a rm e r now in the L ib rary of the Science M useum , London, M S 3d-14 L etter form erly in th e New ell H isto ry of C hem istry C ollection, U niversity of Boston, quoted by P. T . H inde, J . C'.hem. Ed., 1966, 43. 673 676 S. Parkes, C hem ical Essays, 2nd edn., London, 1823, 535 W ollaston M SS,. N otebook H , 4 W. A. C am pbell, T h e C hem ical In d u stry , L ondon, 1971, 20 J . A. C h ald eco tt, Ann. Science, 1971, 27, 409 411; Platinum M etals Rev., 1972, 16, 57-58 W . H. W ollaston, Phil. Trans. Roy. Soc., 1813, 103, 114-118 L. L. C oatsw o rth , B. I. K ro n b erg and M . C. U sselm an, Hist. Technol., 1981, 6, 91-111 B. I. K ronberg, L. L. C o atsw o rth an d M . C. U sslem an, Am bix, 1981. 28, 20-32 J . Nat. Phil. Chem. Arts (Nicholson), 1805, 11, 304 J. S. Fonda, Hexagon, 1924, 15, 81 82 J . S. S treicher, in Pow der M etallu rg y , ed. J . Wolff, C leveland, 1942, 16 J. C. C h asto n , Platinum Metals Rev., 1980, 24, 70-79 H. C. S derbaum , Jac-B erzeliu s Bref, U psalla, 1912-1914, 1 ,4 0 -4 2 P latinum M etals E xhibition, T h e In stitu tio n of M etallu rg ists, L ondon, 1953 U npub lish ed letter in archives of th e Sw edish A cadem y of Sciences, by courtesy of Dr. A. E. W ales. Anon, Life of W illiam A llen w ith Selections from his C o rrespondence, L ondon, 1846, 1, 67
N icolas Louis V a u q u e lin
1 7 6 3 -1 8 2 9
An assistant to Fourcrov a n d later his c o llab o ra to r, V a u q u e lin was a first-class ex p e rim e n ta l c h e m ist an d analyst a n d the disco verer ol b eryllium an d ch ro m iu m . A fte r a long series of research es on the co n stituents of native p la tin u m he be ca m e associated with two com m ercial enterprises engaged in its refin in g and fa brication
10
The Platinum Industry in France after the R evolution
T oday p la tin u m has ob ta in e d a d u c tility which se em e d to have been refu sed to it by nature, it has e n te re d into the d o m a in o f the useful arts, and France has the advan tage o f supplying the outside w orld.
JE A N P IE R R E JO S E P H D A R C ET
By 1795 the worst excesses of the F rench Revolution were over, an d a new phase of both pure and applied chemistry becomes apparent. T h e arrest of Lavoisier and his execution in 1794 ha d robbed F ra n ce of her greatest chem ist while others associated with the work on p latin u m ha d by now passed on. G u y to n de M orveau - now plain C itizen G u y to n was still active, however, a n d continued to be so throughout the Napoleonic era, while Berthollet led the new generation of chemists which included Fourcroy and a little later his protg a n d successor Vauquelin, both of w hom were to be involved in different ways with the c o n tin u ing work on p latinum and its associated metals. T h e acceptance an d the propagation of Lavoisiers new system of chemistry by these men, the patronage of science by N apoleon B o n aparte and the develop ment of industrial chemistry under the economic pressures of the R epublican and Napoleonic W a rs combined to bring about a period of great scientific activity in France, a n d in this context some further im p o rtan t progress was m ade on the understanding a n d the fabrication of platinum .
T h e N ew M etric Standards O n e of Lavoisiers last preoccupations was with the new m etric system of weights and m easures and his proposal for a n oxygen-blast furnace in which to melt large quantities of platinum for the sta n d a rd metres a n d kilogrammes. Fourcroy was also associated with the C om m ission of W eights an d M easures, and in O ctober 1793 he presented a report to the government on the progress of its work and the expenses involved, details of which he would have obtained in great part from Lavoisier. In this he concluded:
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T h e sta n d a rd kilogram m e w eig h t, k n o w n as the K ilo g ra m m e des A rchives, m a d e in p l a t i n u m by M a r c E t i e n n e J a n e t y in 1 7 9 8 . T h e l a b e l o n t h e c a s e r e a d s , u s i n g t h e F r e n c h R e v o l u t i o n a r y C a l e n d a r , K i l o g r a m m e C o n f o r m la loi d u 18 G e r m i n a l A n 3, p r s e n t l e 4 M e s s i d o r A n 7
The Commission, occupying itself with the choice of metal most suitable for the standards has come to the conclusion that the original standards to be kept in the pre mises of the National Convention should be made in a metal that is well known to be the most durable and the least alterable by time and weather and they propose to use platinum which, in this regard is greatly superior to all other known metals and which eminently possesses all the properties that could be desired for the production of invariable standards. (1) W ithout Lavoisier and his furnace the Com m ission now turned to M arc Etienne J a n e ty who, as recorded in C h a p te r 5, ha d felt it p ru d e n t to leave Paris in 1794, and sum m oned him to re tu rn from his works in Marseilles. H e arrived back in Septem ber 1795, taking new prem ises in w hat h a d formerly been the A bbaye de Saint G erm ain des Prs but had been used as a saltpetre factory during the revolution, a location t h a t was to be of im portance to him later (2). T h e Com m ission of W eights an d M easures gave him 200 m arcs (just under 50 kilogrammes) of native platin u m , fixing the price of fabrication at 15 francs an ounce with an allowance of 25 per cent for scrap. J a n e ty began the work in Novem ber 1795, still using his arsenic m ethod, a n d over the next three years he produced four metres and four k ilogram m e weights, these being finally adjusted by the well known instrum ent m a k e r Nicholas F ortin and the engineer Etienne
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Lenoir. O n e of each sta n d a rd was solemnly deposited in the Archives of the Republic in J u n e 1799, these still being known as the M e tre et K ilogram m e des Archives . T h e others are also still in existence in Paris. T h e kilogram m e is illustrated here; the m etre is a flat strip 25.3 millimetres in width a n d 4 millimetres thick, the length being defined by the distance from end to end, but these now show signs of wear. A final report on all this work was presented in O ctober 1801 by the physicist M a th u r in Ja c q u e s Brisson, the m athem atician A ndrieu M a rie Legendre and Guyton, Sur le Travail du Platine p o u r les Etalons des Poids et M esures p a r le Citoyen J a n n e t i (3). In this they quote J a n e t y s statem ent that he had ha d to m ake thirty kilogram m e weights in order to obtain four good ones a n d report that they h a d paid him 2620 francs in cash and a further 1260 francs after he had finished repairing one of the weights that had been dam aged by Fortin during its calibration. After these labours J a n e ty returned to his norm al business as a jew eller and metal worker, achieving yet more renow n for his fabrication of p latinum as we shall see later in this chapter.
T h e C am p o F orm io M ed al T h e foundation in 1795 of the Institut N ational des Sciences et des A rts provided a meeting place for scientists as well as for historians and literary men, the First
T h e C a m p o F o r m i o m e d a l d e s i g n e d by B e n j a m i n D u v i v i e r a n d s t r u c k in p l a t i n u m in 17 98 to c o m m e m o r a t e B o n a p a r t e ' s v icto ry in his I t a l i a n c a m p a i g n . H e is sh o w n r e t u r n i n g f r o m t h e w a r w ith a n olive b r a n c h h e l d h i g h in h is r i g h t h a n d , his h o r s e led by B e ll o n a a n d P r u d e n c e w h i l e V i c t o r y r a i s e s a l a u r e l w r e a t h o v e r his h e a d c a r r y i n g a s t a t u e o f t h e A p o l l o B e l v e d e r e
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Class being allocated to the scientists a n d replacing the A cadm ie des Sciences that had been suppressed in 1793. It was to this body that the young G eneral B onaparte was elected in 1797 on his retu rn from the successful Italian cam paign th at was concluded b y the treaty signed in C a m p o Formio, a village near Udine. T o com m em orate th is victory a large platinum m edal was struck to the design of Benjamin Duvivier, the former medallist to Louis X V I, and p re sented to the Institut who in t u r n presented it to B o n aparte in O c to b e r 1799 after his return from Egypt. T h e medal, illustrated here, shows him returning in trium ph from the cam paign in Italy. It is 57 millimetres in diam eter and weighs 173 grams. T h e platinum has ta k e n the design to perfection, but there is a fine crack to be seen on the reverse.
T h e Later W ork o f G u yto n d e M o rv e a u T h e earlier work of G uyton de M o rv e a u on p latinum a n d his contribution to a study of its physical properties h a v e been described in C h a p te r 7. I n 1791 he left Dijon for Paris on his election to t h e N ational Assembly a n d rem ained a m em ber of the Convention which succeeded it a year later, while as a m em ber of the C om m ittee of Public Safety he w a s active in the establishm ent in 1794 of the cole Polytechnique, the first college of technology in the world, where he becam e one of the professors o f chemistry (4). In 1799 he was appointed A dm inistrator of the M ints, of which there were nine altogether, and here, possibly inspired by the part p la y e d by Isaac N ew ton w hen M a s te r of the Royal M in t from 1696 until his death i n 1727 he interested himself in the activities of counterfeiters and personally investigated the possibility of p latin u m being used
T h e P latin u m P y ro m e te r o f G uyton d e M orveau

T h e first of m a n y a p p l i c a t i o n s of p l a t i n u m in t h e m e a s u r e m e n t o f h ig h t e m p e r a t u r e s , t h i s p y r o m e t e r was d e s i g n e d by G u y t o n d e M o r v e a u in 1 803. A p l a t i n u m r o d 4 5 m i l l i m e t r e s lo n g s u p p o r t e d in a g r o o v e f o r m e d in r e f r a c t o r y clay h a d its f r e e e n d in c o n t a c t w ith t h e s h o r t a r m o f a b e n t l ev er, t h e l o n g e r a r m s e r v i n g a s a p o i n t e r m o v i n g o v e r a g r a d u a t e d s c ale, a l l m a d e in p l a t i n u m . T h e t h e r m a l e x p a n s i o n o f t h e ro d t h u s gave an indication of te m p e ra tu re . In la te r years G u y t o n m o d i f i e d a n d i m p r o v e d t h e d e s i g n o f his p y rom eter
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to adulterate gold. In a p a p e r in 1803 he described a series of experiments with gold alloys to determ ine the effect of additions of platinum on b o th their colour and their specific gravity, also m aking the point th a t the use of a thin coating of gold on a platinum coin could readily be detected by treating the piece with a drop of a q u a regia which w ould expose the grey colour of platin u m (5). He concluded: As fast as the counterfeiters try to perfect their pernicious art one finds the means to discredit their products. Guyton was also interested in the m easurem ent of high tem peratures in fur naces and kilns and in the same year, 1803, he presented to the First Class of the Institut a pyrom eter he had invented based upon the expansion of a platinum rod (6). T h is instrum ent has been more fully described by Dr. J . A. C haldecott (7) and a sketch of its design is reproduced here from a G e r m a n account of the pyrometer (8), no illustration being given in the original paper. A further study of G u y to n s in 1809 concerned the tensile strength of a num ber of metals including platinum (9). H e determ ined the weight that a wire of each metal 2 millimetres in diam eter would support before fracture, iron not breaking until a load of 250 kilogrammes was reached, copper 137 a n d platinum 125 kilogrammes. A com m ent that would have done him credit a h undred years later concluded his paper: The force of cohesion is not appreciably diminished while the ductility of a metal permits its parts to slide over each other without breaking.
T h e C h e m istry o f the P la tin u m M etals Reference was m ade in C h a p te r 9 in connection with S m ithson T e n n a n t s discovery of iridium and osmium to the work carried out almost simultaneously in France by Descotils and jointly by Fourcroy and V auquelin on the con stituents of native platinum . Descotils had investigated the cause of the varying colours of the precipitate formed by the addition of sal-am m oniac to its solution in aqua regia and ha d concluded that a new substance was present b u t he neither isolated it nor gave it a nam e (10). Fourcroy and V auquelin had been asked by the Institut to investigate the purification of p latin u m an d the m ethod put forward by M ussin-Pushkin, as well as the argum ents of Chenevix about the composition of palladium , and they also concluded th at a new an d unknown metal was present (11). They had in fact observed some of the properties of iridium but again they did not propose a nam e for it, while they also noticed a volatile substance obtained from the insoluble residue that affected the eyes and throat and which they thought to be an oxide of the m etal already described. Smithson T e n n a n t s paper of 1804 clearly identified an d nam ed both iridium and osmium, the metal with the volatile oxide, an announcem ent th a t prom pted further work by the F rench chemists. W hen this news reached V auquelin i n j u n e 1805 he was about to leave for a
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H ip p o ly te V ictor Collet-Dcscotils
1773-1815
A stu d e n t of Y a u q u elin in his early years. Descotils was invited to a c c o m p a n y B erthollet an d Monge in the scientific party acc o m p a n y in g N a p o leon B o n a p a rte in his expedition to Egypt. On his re tu rn he was a p p o in ted to the Ecole des M ines w here he spent the rest of his career. H e was the first to investigate the cause of the varying colours of the salts of the p latin u m m etals a n d he also devised an eco nom ical process of refining
P h o to g r a p h by courtesy o f the ferole des M in e s a n d of P ro fe ssor M a u r ic e C rosland .
visit to Marseilles to meet Fourcroy and from there he wrote to his colleague Bergman at the Musum d Histoire Naturelle, asking him to work on various problems and continuing: I also beg you to continue the experiments on platinum and to endeavour to discover whether it contains two new metals or only one. It is absolutely essential to clear up this question and to admit our error if we have made one. ( 1 2 ) Fourcroy and Vauquelin duly continued their work, and in a paper read to the Institut in March 1806 they reviewed the properties of all four newly discovered elements, iridium, osmium, palladium and rhodium, acknowledging the more precise work of T ennant (13) although their own experimental work was accurate and detailed. In a later brief note they also acknowledged the part played by Descotils in the early stages of these discoveries (14). Descotils had been a member of the group of scientists led by Berthollet who accompanied Bonaparte to Egypt in 1798 and on his return he was appointed to direct the laboratory of the Ecole des Mines. His continuing friendship with Berthollet resulted in an invitation to become a member of the Socit dArcueil founded by the latter and Laplace in 1807, a semi-formal organisation of eminent scientists who met and carried out research in Berthollets country house outside Paris and whose work has been the subject of a full study by
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A ntoine F ran o is de F ourcroy 1755-1809

P rofessor of C hem istry fo r over t w e n ty - fiv e y e a r s at t h e J a r d i n d u Hoi. re-nam ed th e M usum d 'H i s t o i r e N aturelle a f te r the F re n c h R evolution, F o u rc ro y held several o th e r a c a d e m ic p osts d u r i n g his d i s t i n g u i s h e d c a r e e r . M u c h o f his r e s e a r c h w a s c a r r i e d o u t in c o l l a b o r a t i o n w ith Y a u q u e l i n w h o w as a p p o i n t e d to t h e M u s u m in 1804. T o gether they in v estig ated the insoluble re s id u e fro m native p la tin u m b u t w e r e less su c c e s s f u l t h a n t h e E n g lish m an Sm ithson Tennant in i d e n t i f y i n g i r i d i u m a n d o s m i u m . In th is p o r t r a i t by t h e f a m o u s F r e n c h p a i n t e r I ) a \ i d h e is p o i n t i n g to a v o l u m e o f his classic w o r k . S y s t m e d e s C o n n a i s s a n c e C h i m i q u e s , p u b l i s h e d in 1800. W h e n F o u r c r o y d i e d t h e titles of his p r i n c i p a l w orks w ere en g rav ed on a platin u m p l a q u e h e l d by a p l a t i n u m c h a i n p l a c e d r o u n d his n e c k b e f o r e his b u r i a l
Professor M aurice Crosland (15). In the first year of its existence Descotils read a paper, O n the Purification of Platinum (16) in which he proposed both an economy in the am ount of a q u a regia to be used and a m eans of reducing the am ount of iridium precipitated with the platinum . Instead of dissolving the native metal directly in the acids he proposed to alloy it with zinc and then to remove this with sulphuric acid, leaving a soft residue of the p latinum metals that could be treated effectively by half the quantity of a q u a regia needed for the direct attack. H e also noticed that it was advantageous to pour the nitric acid on to the metal first, gradually adding the hydrochloric acid until this produced no further effect. T o separate the iridium more effectively after filtering all the insoluble black powder, he evaporated the solution to perfect dryness . T h e addition of a little water left the gold a n d some of the palladium insoluble. T h e rest of the palladium was precipitated with mercuric cyanide as proposed by W ollaston and the iron and base metals by c arbonate of soda. T h e filtrate from all this was m ade alkaline with more soda and then on leaving it exposed for some time to the air, the iridium would be separated in the form of a green se d im e n t, a
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T h e lectu re th e a tr e a n d ch em ical l a b o r a to r y of th e M u s u m d 'H is to ire N a tu r e lle , f o rm e rly the J a r d i n du Roi, w h e re F o u rc ro y a n d V a u q u e l i n c a r r ie d o u t the m a jo r ity of th e ir joint re sea rch es. A f t e r F o u r c r o y s d e a t h in 1 80 9 V a u q u e l i n c o n t i n u e d to p u b l i s h h is w o r k o n t h e r e f i n i n g of irid iu m , o sm iu m , p a lla d iu m a n d r h o d i u m a n d on th e ir p r o p e rtie s
process that could be expedited by w arm ing to 50C. After filtering, the platinum was precipitated with sal-am m oniac as usual, washed repeatedly with small quantities of water and red u c e d to metal, Descotils claiming the p ro d u c tion of platinum in its greatest k n o w n state of p u r ity . Some time after F ourcroys d e a th in 1809 V auquelin, still working in the M u su m d Histoire Naturelle, r e a d two further papers to the Institut, the first in 1813 on palladium and rhodium (17) an d the second early in 1814 on iridium and osmium (18). In the first of these he paid a graceful tribute to the discoverer of the two metals: Although M. Wollaston operated on only 1000 grains of native platinum and had at the most 6 or 7 grains (half a gram) of each of the new metals at his disposal, he yet recognised their principal properties, which does infinite honour to his sagacity, for the thing appears at first to be incredible. For my part, although I employed about 60 marcs (15 Kilograms) of crude platinum I found many difficulties in separating exactly the palladium and rhodium from the platinum and the other metals that are present in this mineral and in obtaining them perfectly pure. In the second paper, devoted a t great length to the separation of iridium and osmium and to their properties, he again acknowledged T e n n a n t s discovery of these new elements which we h a d taken, M . Fourcroy and I, for two modifica tions of one unique species . U n fortunately he a ttrib u ted the blue colour of a solution he obtained in this work to iridium, so missing the discovery of the sixth platinum metal, ruthenium , which w as not identified until 1844.
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A nother associate of V a u q u e lin s and a cousin of Fourcroy, A n d r Laugier (1770-1832) also interested himself in osm ium an d read a p a p e r to the Institut in 1813 on a new m ethod of separating it from native platin u m in greater quantities th a n before and at lower cost (19).
T h e P r o d u c tio n s o f J a n e ty Father a n d Son

After completing his arduous work on the sta ndard metres and kilogrammes, M arc Etienne J a n e ty turned again to the m anufacture of p latinum jew ellery and further extended his efforts in the making of chemical apparatus. A t a n exhibi tion in Paris in 1802 he displayed examples of these for which he was aw arded a silver medal. His new house and factory were in the R u e Colombier, now the R ue Jacob, between the Seine and the Boulevard Saint G erm ain, and here in 1800 Fourcroy and V auquelin had acquired an adjacent factory for the m anufacture of fine chemicals, sharing with J a n e ty a well a n d a p u m p in a com m on courtyard (20). T his proximity m ust have interested the two professors while equally they m ust have encouraged J a n e ty in his platin u m work. T h e re is in fact one reference to his being assisted by the advice of the great chemist V auquelin (21 ). In 1801 a new organisation was established in Paris, the Socit d Encouragem ent pour l ind u strie Nationale, modelled on the British Society for the Encouragem ent of Arts, M a n u fa c tu re rs and C o m m erce founded in 1754 and now known as the R oyal Society of Arts. A com m ittee for applied chemistry was appointed and included Fourcroy, G u y to n de M orveau, V a u q u e lin and Descotils with Berthollet as chairm an, and several reports of this com m ittee over the next fifteen years or more provide a great deal of information on J a n e t y s activities an d those of his son Franois J o s e p h M a rc J a n e ty who joined him in the business and later succeeded him. In 1810 a report to the Society b y j . P. J . d Arcet reads: M. Janety to whom we owe the best process up to now for working platinum and making it malleable has presented to the Society since its last public meeting various articles made from this metal which appear to merit your full attention; you have charged the Committee on Applied Chemistry to examine these articles and it is in their name that I now report to you. M. Janety has presented to you: ( 1) Ten platinum medals of the same diameter but of different types. (2) A bucket shaped vessel 189 millimetres in diameter and 135 millimetres deep that has been planished and hammered until it weighs only 160 grammes. (3) A retort with neck capable of holding 1 litre and weighing only 800 grammes. You know with what perseverance M. Janety pre has struggled for more than thirtythree years against the obstacles opposing the reduction of native platinum into malleable platinum. It is only by long labours and by the loss of his health, of his fortune, of his profession, that he has succeeded in conquering them, and the happy results that he has presented to you are without any doubt the fruit of the greatest and most willing sacrifice that has been made in the advancement of an a rt (22).
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T w o years later d Arcet re p o rte d again in the na m e of the committee, this time referring to M. J a n e ty fils, pupil and successor to his fa th e r , who retired at about this time. T h e objects prese n ted to the Society by the son on this occa sion were two still larger vessels holding respectively 22 an d 16 litres and designed to line cast iron boilers for the concentration of sulphuric acid, together with a saucepan and a travelling knife with several blades. T h e younger J a n e ty also announced that for more t h a n a year he h a d ceased to use arsenic in the preparation of his p latinum an d h a d turned to pow der m etallurgy (23). Yet again, at a general m eeting of the Society in 1814 it is recorded that J a n e ty ju n io r presented several objects in p latinum including cutlery, watchchains, crucibles and capsules, o n e of the latter over 300 millimetres in diam eter of exquisite workm anship the m o re surprising as everyone knows the extreme difficulty of rendering p latinum m a lle a b le (24). T h e progress and the p raise continued. In 1818 the two Ja n e ty s were aw arded a silver medal by the Socit d Encouragem ent, the citation going on: We ought to remember that M. Janety the first opened this career in which France has preceded and surpassed the other nations; that he has sacrificed to this work thirty-three years of his life, his fortune, his health; that his son has been able to value and improve this patrimony of persevering research; that in 1812 vessels and articles of jewellery, presented by him, excited a sort of surprise, and we have regarded it as a duty to mark in a solemn manner this new branch of industry (25). A Great Exhibition was held in Paris in the following year, 1819, and yet another silver medal was a w a r d e d to J a n e ty ju n io r and a new p a rtn e r of his, L eonard Chatenay, by the ju ry chaired by Berthollet for p latinum vessels and jewellery and for some sta n d a rd rules in platin u m m ade for the Royal Society of L ondon and the Academy of Sciences of St. Petersburg (26). J a n e ty senior died in 1820, th e business continued for a few years, and then in 1823 Ja n e ty ju n io r died and B r a n t took over the business from the widow as the Ancienne M aison J a n e t y . A s late as 1828 it has been shown by Dr. W. H. Brock that Liebig was still bu y in g p latinum a p p a ra tu s from J a n e ty (27) but, by 1830 he had turned to C uoq a n d Couturier. T h e activities of the Janetys, extending over more th an forty years, none the less constitute a n im portant section of this history and they m a d e a very great contribution in their chosen field.
T h e A c h ie v e m e n ts o f J ea n R o b e rt Brant T h e j a n e t y s were not without a com petitor. Shortly after the fall ofN a p o le o n in 1815 and the restoration of F e r d in a n d VII to the Spanish throne the government in M a d rid decided to dispose of a large quantity of platin u m that had accum ulated in their hands since the days of C h a b a n e a u and Proust and for which they now had neither a n application nor a m ethod of treatm ent. This cam e to the knowledge of Pierre A u g u stin e C uoq (1778 1851) a lawyer in Lyons who travelled widely in business and turned to m erchanting and exporting.
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Taking into partnership one Couturier, a metal m erchant, he purchased a round 1000 kilogrammes of Spanish p latinum and established the firm of C uoq C outurier et Cie in Paris. N either h a d any knowledge of chem istry and they turned for advice to one of the assayers at the Paris M int, J e a n R o b e rt Brant (1775-1850). A native of N orm andy, Brant had seen service in the mints in Rouen, Toulouse and L a Rochelle before being appointed to Paris in Septem ber 1814, and he also had no expertise in the refining of platinum . H e had, however, come to know Vauquelin, also a native of N orm andy, an d after securing his advice and spending some time in his laboratory Brant agreed to u ndertake the refining of this very large quantity of metal. At this time W ollastons m ethod ha d not been published, an d it is likely that Brant relied upon the processes of T h o m a s Cock and R ic h a rd Knight. I n any case he achieved quite rem arkable results very quickly, making large ingots, and by February 1817 C uoq an d C outurier were able to present to the Socit d Encouragem ent a boiler m ade from a single sheet of platin u m refined by Brant, weighing 15 kilogrammes and holding no less th a n 162 litres (28). Several other boilers had been m ade at the same time for the concentration of sulphuric acid. Even before this Brant had m ade a boiler from four sheets of platinum , m ade from ingots weighing 5 kilogrammes each, which were first riveted together and then soldered with gold. This was provided to the chemical works at Les T erm es outside Paris where the younger C h a p ta l was in p a rtnership with J. P. J. d'Arcet for experimental work in the concentration of sulphuric acid, but Brant was not satisfied with this m ethod of fabrication and so increased the size of his ingots to produce sheets as m uch as four feet square. H e also succeeded in the autogenous soldering of platinum and displayed to the Society a tube six feet in length of which the edges were perfectly united w ithout the use of solder . T h e same report refers to the great reduction in time in the c oncentration of sulphuric acid to as little as a q u a rte r of th at needed w hen using glass vessels as well as to the elimination of the risk of breakage. T hese boilers were adopted in the French sulphuric acid industry, and a little later Brant supplied siphons in platinum to perm it continuous operation. A detailed description of one of his platinum siphons and of the economics effected in its use was given by the sulphuric acid m an u fa ctu rer Auseline Payen, the partner of Cartier, in whose works at Pontoise this equipm ent was installed (29). This was fitted with water cooling and reduced the time required for dcantation of a large boiler from half an hour to six minutes. At the Exhibition of 1819 C uoq and C o u tu rie r showed laboratory a p p a ra tu s in platinum, a n u m ber of medals, and platin u m leaf reduced to the same degree of thinness as gold leaf, as well as another large sulphuric acid boiler of 200 litres capacity. For these they were aw arded a silver medal while Brant received a similar m edal for having purified p latinum on a large scale, having rendered it malleable and at a price m uch less t h a n form erly (26). In 1819 also Brant pa rte d com pany with his colleagues and set up for
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himself at 64 R u e M o n tm a rtre w hile C u o q and C o u tu rie r continued to operate in the R ue de Richelieu near the P a lais Royal, later moving to the R u e Lulli where they rem ained until well into th e 1830s, w hen the parties cam e together again in joining with a firm named D esm outis whose sundry successors are still in opera tion. T h e further progress of this com pany will be described in a later chapter. T h e refining process em ployed by Breant was described in full detail, not by him but by J e a n Pierre Baruel (1780-1838), of the Ecole de M edicine in an English translation at the req u e st of a chemical gentlem an from this country who wished to know the actual m eth o d now practised at Paris for p reparing the great masses of platinum of w h ic h C outuriere forms his beautiful alem bics (30). J u s t as i n j a n e t y s procedure, the native metal was first w ashed in a stream of water to remove all sand. Any m erc u ry present was then driven off by heating. Next there was a short tre a tm e n t with weak a q u a regia to remove gold and copper, with usually a little p latinum . T h e undissolved m aterial was washed with water and am m onia and b oiled in a retort with strong a q u a regia, a process that was repeated five times. T h e insoluble black p o w d e r was filtered off and the filtrate evaporated down, a distillate containing osm ium being collected. T h e concentrated platinum solution was diluted with water, precipitated with salamm oniac solution and the prec ip ita te filtered an d calcined. T h e resulting metal sponge was treated with dilute a q u a regia which dissolved the p latinum but left most of the iridium. After filtering off the latter, the solution was again treated with sal-ammoniac a n d the prec ip ita te filtered and calcined. H ere, therefore, for the first time in a published com m ercial process, an a tte m p t was m ad e not only to diminish the solution of the iridium b u t also to remove th a t w hich ha d gone forward into the first precipitate by redissolving in dilute a q u a regia the sponge yielded by the latter. C o n sequently a m uch m ore uniform an d m ore malleable metal was obtained. T o consolidate it th e sponge was charged into a crucible, heated and, as it contracted a n d sintered together u n d e r compression, more was added even to the am ount of 20 o r 30 p o u n d s . W h e n this h a d been attained, the crucible was covered and h e a te d up to whiteness, an d the p latinum was then transferred quickly to a steel m o u ld in which it was com pressed several times in a strong coining screw press. T h is process was continued five or six times in the m ould under a fly press a n d by then the metal was sufficiently consolidated to be transferred to an open charcoal fire an d alternately h e a te d and forged about thirty times. T h e ingot was then ready for rolling out in to the sheet which was subsequently fashioned by the ham m er into the beautiful alembics of C o u tu rie re . Baruel also gives detailed directions for the recovery from the various insolubles an d m other liquors of palladium, rhodium, irid iu m an d osmium in a m ore or less pure form. O f the chemical p a rt of the process, the English tra n sla to r rem arks that it is fundam entally the same as th at published by M. V auquelin in 1813 in the 88th volume of the Annales de Chimie (17). T h e process as described by B a ru e l ha d several new features. T h e dissolution
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in aqua regia and the subsequent boiling-down were carried out in retorts or similar distillation apparatus, so that a distillate could be collected and a con siderable part of the osmium which was volatilised as its tetroxide could be recovered. Next, as has already been pointed out, the F rench in order to obtain platinum reasonably free from iridium, were not content, like W ollaston, with minimising the am ount taken into solution by using dilute a q u a regia, b u t set about separating it physically from the first p latin u m sponge by treatm ent of the latter with weak a q u a regia. T h e ir recovery of palladium w as based on V auquelins procedure of precipitating an am m o n ia proto-sub-m uriate of p a lladium (dichloro-diam m ino-palladium ) a n d not on W o lla s to n s equally effective use of mercuric cyanide. T hey also took steps to isolate a n d collect the rhodium and osmium. In all previous commercial work, m ost of these metals had either rem ained in the final product or had been wasted in m other liquor or fumes. T o some extent these rem arks apply even to the work of W ollaston, b u t as regards the working qualities of the p latin u m produced there seems to have been little to choose betw een the English and F rench metal. T h e tra n sla to r of B a ru e ls paper remarks that they seem to be at present equally pure, m alleable and ductile, and the price is nearly the sa m e . T h e French technique of fabrication shows considerable advance on the British in th at the production of bigger and bigger, but still sound, ingots enabled larger and larger sheets to be prepared. This in turn m eant less and less recourse to soldering an d therefore sounder vessels. Not only did this represent a true advance, but the introduction by Brant of forge-welding m ade possible for the first time an autogenous platinum joint.
T he A pp eal o f P a lla d iu m In the course of his refining of the 1000 kilogrammes of S panish platinum mineral Brant was able to extract an d purify some 900 gram m es of palladium, an achievement of which he seems to have been especially proud. H is superior at the Paris M int, Aim Puym aurin, who was deputy-director to his father, the Baron Puym aurin, succeeding him in 1830, encouraged B rant in this connec tion and in J u ly 1823 contributed a p a per on palladium to the Bibliothque Universelle (31). In this he refers to the rarity of this metal being so great th a t it was unlikely that so favourable a n opportunity of obtaining it would occur again. He then details the properties of palladium as determ ined by Brant and concludes:
Should this unoxidisable m etal becom e sufficiently com m on to add to our industrial m aterials it m ight well be used successfully for m edals and for chem ical ap p a ra tu s; its ductility and its lustre m ight well m ake it a su b stitu te for silver in articles of jew ellery, w hile it could be used for m ilitary b ra id as its lu stre is never ta rn ish e d .
A m onth earlier Brant, accom panied by the Baron P u y m a u rin , had been
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From B r e a n f s sm all slock of p a llad iu m he m ad e two cups, a large one presen ted to K ing C h arles \ on his accession in 1824 and a sm aller replica show n here for him self. T his he kept on his desk at the P aris Mint as a sou ven ir of his success in extracting an d refining pallad iu m
received in audience by Louis XVIII to whom he presented a medal struck in palladium (32). This carried the bust of the King on one side, and on the other the inscription:
1823. Sous le rgne d e LOI IS-LE-DES1R P ro te cteu r d e s lettres, des sciences et des arts. Po u r la p r e m i r e fois, le p a llad iu m purifi P a r M. B rant A servi la fabrication des m dailles. M daille e n p a llad iu m pr sen t e au Roi. P ar M. B rant.
Another medal struck from Brants palladium commemorated the opening of the Museum of the Dpartement des Monnaies et Mdailles by King Louis Philippe and Queen Amlie in 1833. Earlier, from his small stock of palladium, Brant had made two cups, a larger one, 44 centimetres in diameter, that he presented to King Charles X on his succeeding his brother Louis XVIII in 1824 which is still preserved in the Trianon at Versailles, and a smaller one for himself. In both cases only the bowl is in palladium, the base being made of silver. The smaller cup, shown here, Brant kept on his desk at the M int where he became director in 1846, until his death six years later, as a constant reminder of his work in the refining of the platinum metals and the fabrication of large ingots of platinum sound enough to be rolled into large sheets and to yield better vessels for the French chemical industry.
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References for Chapter 10
1 P rocs-V erbaux
2
3 4 5 6
7
8
9
10
11
12
13 14 15 16 17 18 19 20
21 22
du C om it D In stru c tio n P u b liq u e de la C onvention N ationale, Ed. J . G uillaum e. Paris, 1894, 2, 638-646 G. K ersaint, Rev. H ist. Pharm., 1959, 4 7, 25-30 M . J. Brisson, A. M . L egendre a n d L. B. G u y to n de M orveau, q u o ted in C. J . E. Wolf, Ann. Chim., 1882, 25, 66 W. A. Sm eaton, Platinum M etals Rev., 1966, 10, 24 28 L. B G u y to n de M orveau, Ann. Chim., 1803, 47, 300-302 L. B. G u y to n de M orveau, Ann. Chim., 1803, 46. 276 278 J . A. C h ald eco tt, Ann. Science, 1972. 28, 347 368 L. B. G u y to n de M orveau, Francos. Ann. allg. Naturgesch. Phys. Chem., 1803, 3, 28 31 L B. G u y to n de M orveau, Ann. Chim., 1809, 71, 189-199 H. V. C ollet-D escotils, Ann. Chim., 1803, 4 8, 153-176 A. F. Fourcroy an d N. L. V auquelin, Ann. Chim., 1803, 48, 177 183; ibid, 49, 188 224; 1804, 50, 5-26 L etter from V au q u elin to B ergm an, J u n e 18, 1805, B ib lio th q u e N atio n ale Archives, q u o ted by G. K ersain t, Bull. Soc. Chim., 1958, 1603 A. F. Fourcroy a n d N . L. V auquelin, Ann. M us. Hist. N at., 1806, 7, 401-409 A. F. Fourcroy an d N. L. V auquelin, Ann. M us. H ist. N at., 1806, 8, 248 M . C rosland, T h e Society of A rcueil, London, 1967 H. V. C ollet-D escotils, M m . Phys. Chim. Soc. d'Arcueil, 1807, 1, 370-378; Ann. Chim., 1807, 64, 334 335; Phil. M ag., 1811, 37, 65-69 N. L. V auquelin, Ann. Chim., 1813, 88, 167-198 N. L. V auq u elin , Ann. Chim., 1814, 89, 150-181; 225-250 A. Laugier, Ann. Chim., 1814, 89, 191-198 G. K ersaint, Rev. Hist. Pharm., 1959, 47, 25-30 H. Vever, H isto ire de la B ijouterie F ranaise au X IX e Sicle, Paris, 1906, 119-120 J . P. J . d A rcet, Bull. Soc. Enc. Ind. N at., 1810, 9, 54 57 J . P .J . d A rcet, ibid, 1812, 11, 207-208 Anon, ibid, 1814, 13, 75 Anon, ibid, 1818, 17, 388-389 E xposition de 1819, R a p p o rt du J u r y C e n tra le sur les P ro d u its de lin d u strie Franaise, 170 W. H. Brock, Platinum M etals Rev., 1973, 17, 102-104 J . F. L. M rim e, Bull. Soc. Enc. Ind. N at., 1817, 16, 33-36 A. Payen, Bull. Soc. Enc. Ind. N at., 1827, 26, 20-22 J. P. Baruel, Quart. J . Sci. U t. Arts, 1822, 12, 246-292; Phil. M ag., 1822, 59, 171-179 A. P uym aurin, Bibliothque Universalle, 1823, 23, 235; Bull. Soc. Enc. Ind. N at., 1823, 22, 163-164 Le M o n iteu r U niversel, 1823, J u n e 22, 76
23 24 25 26 27 28 29 30 31 32
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Percival Norton Johnson 1 7 9 2 -1 8 6 6

A pp ren ticed to his fa th e r, the assayer J o h n Jo h n s o n , in 1807 Percival set u p for him self as an a s s a y e r an d gold re fin er in 1817, taking u p the refining of platin u m a n d its allied m etals a fte r W ollaston ha d a b a n d o n e d this work. T h is p o rtra it by G. J. R o b e rts o n in the possession of J o h n so n Vlatthey show s him re ad in g an assay re p o rt d a te d 1830 an d w earing a chain m ad e f r o m platin u m he had refined. H e was elected a Fellow of the Royal Society in 1846
11
Progress in England after W ollaston
This beautiful, m agnificent a n d valu able m etal is v e r y re m a rk a b le in m a n y p o in ts besides its know n special uses.
M ICHAEL FARADAY
W hen W ollaston found that he could no longer obtain supplies of native platinum and so ceased to offer his products to industry in 1820 only Percival Norton J o h n s o n rem ained as a refiner and fabricator, although for some years on a smaller scale. T his dom inant position he m aintained for m an y years although for a time the F rench were im portant competitors. At the age of twenty-five J o h n s o n had separated from his fath e rs long established practice as an assayer in the City of L o n d o n a n d on J a n u a r y 1st 1817, with a capital of 150, ha d set up for himself as Assayer an d Practical M ineralogist , initially in the City a n d then in 1822 in H a tto n G a rd e n (1). O n the very first day of his independence he m arried Elizabeth Lydia Smith, one of whose older sisters had earlier m arried T h o m a s Cock (1787-1842), a wealthy young m a n who until then had been an assistant in the famous laboratory of Willima Allen at Plough C o u rt an d who ha d developed a process for producing malleable platinum as related in C h a p te r 8. Cock carried on his chemical work in a laboratory in his house after leaving Plough C o u rt on his m arriage and when J o h n s o n em barked on the refining of platinum it was C o c k s process that he employed and it was Cock himself who supervised operations, spending m uch of his time in the H a tto n G a rd e n laboratories for the rest of his life. Johnson, as we have already seen, was keenly interested in p latin u m an d he m aintained the contacts with W ollaston th at his father ha d enjoyed. At first, however, he becam e more heavily involved in palladium with which he a n d his father had become acquainted in Brazilian gold as early as 1812. In th e course of his gold assaying work he achieved a n accuracy m u ch greater th a n anything known before and this brought him into conflict with the bullion dealers who had been accustom ed to wider margins and therefore easier profits. H is results were challenged, an d his imm ediate response was to offer to buy any gold on the basis of his own assays. W ith a substantial injection of capital provided by one of his wifes brothers, Lieutenant W. R. B. Smith, R .N ., a gold refinery was built behind the H a tto n G a rd e n house an d from the first this was called upon to treat
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considerable amounts of the palladium-bearing Brazilian gold as Johnson was the only refiner in London capable of handling it. His process remained undisclosed for many years, but in 1846, when he was a candidate for election to the Royal Society, he at last gave full details of his procedure in a letter to the then President, the Marquis of Northampton (2). This begins: My Lord, I am requested to lay before the Society the process I discovered and have adopted since 1817 for the extraction of Palladium which exists in combination with the Gold of the Gongo Soco Mine in the Brazils and also of the Candonga Mine in the same country, with some observations as to the nature of the rock and gangue of the formation in which it is found and the applications of the metal for useful purposes. The letter goes on to describe the process of melting the gold with excess of silver, parting with nitric acid, precipitating the silver with sodium chloride and
T h e concluding p art of the letter from Percival Norton J o h n s o n to the Presid ent of the Royal Society describing the process for the extraction of pallad iu m fro m Brazilian gold that he had been em p loying since 1817, and the properties of this m etal a n d som e of its allovs
P h otograp h b> cou rtesy o f the R o val Societv
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T h e b u i l d i n g in H a t t o n G a r d e n , no w d e m o l i s h e d , to w h i c h P e r c i v a l N o r t o n J o h n s o n m o v e d in 1 8 22 . As his b u s i n e s s d e v e l o p e d a d d i t i o n a l h o u s e s o n e i t h e r sid e o f t h e o r i g in a l l o c a t i o n a t No 7 9 w e r e t a k e n o v e r a n d a r e f i n e r y w a s set u p b e h i n d t h e offices a n d l a b o r a t o r i e s
then throwing down the palladium with zinc, redissolving in nitric acid. T h e palladium, am ounting to some 4 per cent of this native gold, was finally pre cipitated with am m onium chloride, followed by heating to reduce it to a metallic sponge. As with platinum , this was compressed in an iron box, carefully forged and then either draw n into wire or rolled to sheet. T h e final p a ra g ra p h of J o h n s o n s letter, reproduced here, described his suggestions for the uses of palladium as a protective coating for silver, as a n alloy with silver for dental purposes and in a ternary alloy with copper a n d silver for the construction of instruments.
A P a lla d iu m C h ain for K in g G eorge IV As W ollaston had found, J o h n s o n met with considerable difficulty in dispos ing of the considerable am ounts of palladium he was accum ulating a n d he sought to prom ote its applications. O n e of his early ideas was to present a massive ceremonial chain in palladium to King G eorge IV, the offer being m ade through Sir Astley Cooper, surgeon to the K ing an d of course a relative of
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In J u n e 1826 J o h n s o n sought to p u b l i c i s e t h e m e r i t s of p a l l a d i u m b y p r e s e n t i n g th is m a s s i v e c e r e m o n i a l c h a i n to K i n g G e o r g e IV. T h e o f f e r w a s m a d e t h r o u g h S i r A stley C ooper, the distinguished s u r g e o n w h o h a d m a r r i e d th e s i s t e r o f T h o m a s C o c k in 1798 a n d w ho had exercised h is i n f l u e n c e in a n u m b e r of d i r e c t i o n s , firs t by s e c u r i n g a n a p p o i n t m e n t fo r C o c k at P l o u g h C o u r t a n d l a t e r by tak in g an in terest in J o h n s o n s activities. The g r e a t p a l l a d i u m c h a i n is still p r e s e r v e d in W i n d s o r C a s t l e
P h o to g r a p h by p e rm is s io n o f H e r M a je sty th e Q u e e n
J o h n s o n s by marriage. T his c h a in is still preserved at W indsor Castle and is illustrated here by the kind cooperation of the Surveyor of the Q u e e n s W orks of Art, M r. Geoffrey de Bellaigue. T h e letter from Sir Astley Cooper to Sir W illiam Knighton, the K in g s physician w ho had been appointed K eeper of the Privy Purse, is also in the archives at W in d s o r C astle and was recently located there by M rs. Shirley Bury of the Victoria a n d A lbert M u s e u m (3). T h e am ounts of Brazilian gold extracted began to increase substantially when a new mining company started operations in 1826 but because of the difficulties in refining their unsaleable stocks built up in their L o n d o n warehouse. This situation came to J o h n s o n s knowledge in 1832 a n d he at once set about treating the gold bars by the process j u s t described and over the next twenty years he refined over a qua rte r of a m illion ounces of Brazilian gold, recovering large quantities of palladium . By the N o v e m b e r of 1835 he ha d in fact extracted 2600 ounces, and he continued his p ro m otional cam paign, advocating the use of
198
T h e letter from Sir Astley C o o p e r to S ir W illiam K nighton who was K e ep e r of the Privy Purse to G eorge IV. It reads: "M r. J o h n so n who is a great M etallurgist has a C hain of P a llad iu m which is the only one which has been ever m ad e, and w hich he w ishes to present to ou r beloved M onarch. F rom his taste and talent I believe his Majesty w ould be pleased to accept it"
P h otograp h b\ perm ission of H e r M ajeslv the Queen
palladium for the pans and beams of chemical balances, for rust-free surgical instruments, for lighthouse reflectors and as a substitute for steel in many small applications. In a letter to one of the first issues of The M ining Journal in 1835, addressed from Assay Office and Metal Works, 79 Hatton G arden, he wrote: Palladium has not until within the last few years been an object of attention from its great scarcity, the ore of platinum being the only source from which this metal was derived and in which Dr. Wollaston first discovered it in 1803. I noticed the existence of palladium in the Brazilian gold in the year 1812 but until my engaging with the Imperial Brazilian Mining Company its extraction to any extent in a state of purity had not been effected . . . The properties of this metal render it intrinsically valuable in the arts, having most of the characters of platina, which it also resembles in colour, is perfectly malleable, and being only 11} specific gravity, has an advantage over platina in its introduction. (4) In September 1836 another letter appeared in The M ining Journal (5), point ing out an error in the previous weeks issue where it had been stated that palladium had so far only been obtained from crude platinum and had never found any applications. The writer went on to emphasise that this metal had been extensively procured from Brazilian gold and is being used for many valu able purposes. His letter continued:
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Mr. Percival Johnson of 79, Hatton-garden, lately delivered a lecture on metallurgy, at Hampstead, and thus describes the metal: Its resisting the atmosphere and most of the weak acids, render it useful for dental purposes, for the graduated scales for mathematical instruments, and as an alloy for the tips of pencil-cases, in lieu of steel; having the same elasticity, without being liable to corrosion. Its oxide gives a hair-brown in enamel painting. It may be added, that this metal is capable of a very high polish, and might be most beneficially used for reflectors to lighthouses, and for surgical instruments, particularly for foreign use in climates where the atmospheric damp is so prejudicial to steel. It is partially used for vaccine points, and here its superiority over steel must be obvious, since it has not unfrequently happened that patients have been vaccinated in distant counties from the metropolis with a rusty lancet, and the inflammation caused by the rust has been mistaken for the disease; and hence, in some cases, the occurrence of small-pox after supposed vaccination. It is also particularly useful for fine experiment balances: the Americans are so convinced of this fact, that several assay balances are now being m ade for the United States Mint, in Philadelphia, of this metal. I have also seen two in use in England. If you think this notice worthy a place in your valuable publication, I shall feel obliged by its insertion, and beg to subscribe myself your obedient servant,
W . M . POUSSETT.
Chapter-house, St. Paul Aug. 29, 1836. s,
P.S I am able to state, from my own knowledge, that several hundred ounces have been used for these purposes. W. M. P. T h e writer of this letter, W illia m Poussett, had m arried yet another of Mrs. J o h n s o n s sisters a n d in 1823 h a d been taken into the office at H a t to n G a rd e n by J o h n s o n as clerk and salesman! T h e address he gave was that of their father-inlaw, T h o m a s Smith, who held t h e post of Receiver-General to the D ean and C h a p te r of St. P a u ls. Some years earlier J o h n s o n h a d m ade a lengthy visit to G e rm a n y and had spent several weeks at the M in in g Academ y at Freiberg, establishing a friend ship with the professor of chem istry a n d m etallurgy there, W ilhelm August L a m padius (1772-1842). In 1836 he sent over to L a m p a d iu s samples of the Brazilian ore, of the double salt of palladium as precipitated an d of the metal produced by its reduction on heating. T hese were all closely exam ined and formed the subject of a paper in th e following year (6) which the a uthor hoped would: come opportunely as a contribution to the chemical history of palladium with grate ful recognition of the appreciation which Mr. Johnson has won through this new method of treatment of palladium-gold . A further promotional exercise occurred in 1845 w h e n J o h n s o n presented to the Geological Society, of which h e had been a m em b e r since 1824, a quantity of palladium sufficient to provide th e ir W ollaston m edals for some years to come. T h e process devised by T h o m a s Cock ha d taken no account of the other metals of the platinum group discovered by W ollaston and T e n n a n t between
200
O n e of t h e ^ o l l a s t o n M e d a l s a w a r d e d a n n u a l l y by t h e G e o l o g i c a l S ociety fo r o utstanding research. F or som e years th is w a s s t r u c k in p a l l a d i u m f r o m a q u a n t i t y p r e s e n t e d to t h e S o ciety bv P e r c i v a l N o r t o n J o h n s o n w ho h a d b e e n a m e m b e r sin c e 1 82 4
1803 a n d 1805, but Johnson, with C o c k s cooperation, was successfully extract ing and refining these very shortly after establishing his business. O n e of the early researches carried out by M ichael F a ra d a y at the Royal Institution, in collaboration with a m uch older m an, J a m e s S todart (1760-1823), a well known maker of cutlery a n d surgical instruments, was on the effects of additions to steel of platinum , palladium , iridium, osmium a n d rhodium , as well as of silver and gold. T h e object of the investigation, which continued for some five years from its beginning in 1819, was to ascertain w hether any such alloy steels would yield better cutting edges or would prove less susceptible to corrosion. A first account was presented to the Royal Institution in 1820 (7), with a longer p a p e r to the Royal Society two years later (8). A lthough this research was too far ahead of the time w hen alloy steels would be understood a n d put into service, some con siderable success was achieved, particularly with the platin u m a n d rhodium additions. A platinum -steel specimen, for example, after lying exposed for many m onths h a d not a spot on its surface while in a letter to his friend Professor G a s p a rd de la Rive in Geneva, F a ra d a y wrote: Perhaps the best alloy we have yet made is that with Rhodium. Dr. Wollaston furnished us with the metal so that you will have no doubts of its purity and identity. One and a half per cent of it was added to steel and the button worked. It was very malleable but much harder than common steel and made excellent instruments. Razors made from the alloy cut admirably . N o appreciable results followed from these laborious experiments of F a rad a y and Stodart, reviewed in detail by Sir R obert H adfield in 1931 (10), b u t at least
201
\1 ichael Faraday
17> 1-1867
A l m o s t a n e x a c t c o n t e m p o r a r y of J o h n s o n . Fa r a d a v d r e w his s u p p l i e s o f p l a t i n u m a n d its a s s o c i a t e d m e t a l s from him for the resea rch e s he carrie d out at the Royal Institution on electrochem istry, on the m agnetic p ro p e rtie s of m etals a n d c o m p o u n d s a n d o n t h e m e l t i n g o f o p t i c a l g lass in p latin u m . He w as am ong th o se s p o n s o r i n g J o h n s o n f o r e l e c t i o n to the R o y a l Society
one steel an d cutlery m an u fa ctu rer was sufficiently interested to p ursue the m atter. T his was a Sheffield firm, G reen Pickslay a n d Co., who wrote to F a ra d a y in April 1824 to the effect that they were proposing to m ake experi ments in the large w a y . L ater in the sam e year they wrote again: Green, Pickslay & Co., have great pleasure in informing M. Ferrady that they have made a number of experiments with the alloys recommended by him and find the steel greatly improved by them; they send a specimen alloyed with silver, iridium and rhodium which they consider the best they have produced, these alloys with some valuable practical hints have been furnished by Mr. Johnson, No. 79 Hatton Garden; the report of the forgers is that the steel works better under the hammer than any they have before used, and likewise hardens in a much superior manner. Green Pickslay & Co. beg Mr. Ferradys acceptance of a pair of rasors made from this steel. They will have great pleasure in sending other specimens of cutlery etc., as they continue their experiments (11). T h u s by 1824 at latest J o h n s o n was able to produce and supply the other m etals associated with platinum . A later testimony to this a n d to his growing reputation concerns the developm ent of iridium for the tipping of the early gold nibs. Following W ollastons use of a rhodium -tin alloy for this purpose, an English engineer, J o h n Isaac H a w k in s (1775-1865), found th at iridium gave a better performance and this he o btained for a time from Johnson. But by 1835
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H aw kins h a d selected all the suitable particles of iridium suitable for his purpose from J o h n s o n s stock. H e th en records: I therefore went to the British Association for the Advancement of Science which met at Dublin on the 10th of August, 1835, to inquire of the great Chemists of the time, expected to be there assembled, where I could be supplied with the precious material. On asking Dr. Dalton of Manchester, Dr. Thomas of Glasgow, Dr. Daubeny of Oxford, and many other eminent Chemists present at the meeting where I could procure the substance each, without communicating with any of the others, answered that I could obtain it of Mr. Johnson, Hatton Garden, London (12).
M eltin g O ptical Glass in P la tin u m After S to d a rts death in 1823 F a ra d a y discontinued his investigations on steels and in the following year he was commissioned by the Royal Society to undertake a quite different study on the improvement of glass for optical purposes. A distinguished com m ittee including the President, H u m p h r y Davy, Wollaston, W a rb u rto n , H a tc h ett, B rande and D olland was appointed to discuss the subject with the m em bers of the Board of L ongitude in an endeavour to improve the quality of telescopes while the leading glass m akers Apsley Pellat and Ja m e s Green of the Falcon Glass W orks in Southw ark were requested to build a suitable furnace. Little progress was m ade for some time, an d th en in 1827 a furnace was built at the Royal Institution so th at F a ra d a y could be freed from travelling to the works. M elting in the traditional clay crucibles still produced many defects in the glass, a n d then in April 1828 F a ra d a y tu rn e d to the use of platinum an d recorded his first comm ent: Find that in small quantities in platina foil a clear glass may be made contain ing as much as 70 litharge to 10 of silica (13).
H e pursued this new m ethod for a further six m onths, encountering m any difficulties caused by the reduction of the lead and its attack on the platinum and from the iron plate on w hich stood the platinum vessel. But by substituting a p latinum foil beneath the latter, b y j a n u a r y 1829 he could record: The platinum vessel has stood well but a very little glass had crept over on to the foil beneath but there was no appreciable loss (14). T h e results of this long an d tedious research were reported to the Royal Society in the Bakerian Lecture in N ovem ber and D ecem ber 1829 O n the M anufacture of Glass for O ptical P urposes , a long p a p e r requiring three even ings for its presentation (15). In the course of this F a ra d a y recom m ended that the glass be melted first in crucibles of pure porcelain a n d then poured from a platinum ladle into a platinum dish. T h e rough glass so obtained was then to be re-melted in a platinum tray about 10 inches square that m ust have come from a good ingot that had been rolled very gradually and carefully . T h e m uch improved samples of glass were prepared for use by the optician George Dolland and sent for exam ination to the astronom er Sir J o h n Herschel. A report by the C om m ittee for the Im provem ent in O ptical Glass in 1831 stated:
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S o m e of t h e p i e c e s of o p t i c a l glass m a d e by F a r a d a y . H e first p r o p o s e d t h e m e l t i n g o f glas s for t e l e s c o p e s i n p l a t i n u m e q u i p m e n t d u r i n g a lon g i n v e s t i g a t i o n c a r r i e d o u t f o r t h e R o y a l S o ciety in c o o p e r a t i o n w ith t h e B o a r d of L o n g i t u d e b u t it w as v e r y m a n y y e a r s b e f o r e t h is b e c a m e s t a n d a r d p r a c t i c e in t h e glass i n d u s t r y

Bv c o u rte s y o f ih e K oval I n s titu tio n
The telescope made with M r. Faradays glass has been examined by Captain Kater and Mr. Pond. It bears as great a power as can reasonably be expected, and is very achromatic. The Committee therefore recommend that Mr. Faraday be requested to make a perfect piece of glass of the largest size that his present apparatus will admit, and also to teach some person to manufacture the glass for general sale. F a ra d a y begged to decline any fu rth e r involvement in this work but once again he was well ahead of his time a n d it was very m any years before the melting of optical glass in platinum becam e s ta n d a r d practice.
W illia m J o h n Cock j o in s J o h n s o n
J o h n s o n developed a n um ber of interests in the th en boom ing lead, copper, silver an d tin mines of Devon and C ornw all, first as assayer a n d th en as the owner of several mines, this side of his activities involving him in long and frequent absences from London. Feeling t h e need for assistance, in 1826 he engaged an assayer nam ed George Stokes w h o m he took into partnership in 1832, but this ended with the death of Stokes o n ly three years later. H e then turned for advice
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W illiam John Cock 1813-1892

T he son of Thom as Cock. Johnson s brother-in-law who had devised a m etho d of p ro du cing m alleab le platinum v%hile working with William Allen at Plough Court in 1805. ^ . J. Cock was a partner of Johnson s in the development of the platinum business from 1837 until 1845 when he retired on account of his poor health. Both he and his uncle were founder m em bers of the Chemical Society and he con tributed a paper to them on the refining and alloying of palladium in 1843
to his old friend, brother-in-law and collaborator Thomas Cock, who proposed the name of his second son William John, now approaching 21. He had been articled to a solicitor in 1828 but like his father had a bent for the physical sciences and on receiving an offer from Johnson abandoned this profession and entered the business, becoming a partner in 1837, the firm then changing its name tojohnson and Cock. The younger Cock quickly acquired a knowledge of chemistry and metallurgy and began to increase the size of the equipment and thus of the platinum ingots from a mere six ounces to about sixty, introducing a sectional mould and replacing an old screw press with an hydraulic one. There is however, no evidence of any attempt to profit by the work of Wollaston and to apply hjs methods for maintaining the surface energy of the metal in the most active possible state. In particular, the platinum sponge was always pressed dry as recommended in Cocks original specification, and never wet as prescribed in Wollastons elutriation process. There can be little doubt that the metal was not so good as Wollastons and suffered from blisters and porosity, but it was apparently good enough to satisfy the demands of the period.
205
As time went on the ingots and the sheets produced from them gradually increased further in size. Following Wollastons example, Johnson and Cock entered the business of making sulphuric acid boilers, and in the course of a series of lectures on mineralogy and metals given to the City of London Literary Institute in 1843 Johnson stated that he had made such a vessel holding 63 gallons at a cost of 750 (16). T h e fabrication of this vessel was most probably the work of the Kepp firm who had made most of Wollastons boilers and with whom Johnson had close business relations. Another application for Johnsons platinum, following the French precedent, was for standard weights. In 1829 the German scientist Christian Heinrich Schumacher (1780-1850), Professor of Astronomy at Copenhagen, who had carried out experimental work on legal units of weight for the Danish govern ment, ordered a copy in platinum of the Imperial Standard Troy Pound that had been made in brass in 1758 from Thomas Charles Robinson, the famous maker of balances, for comparison with the Danish weight. This copy he considered must not be made of a metal liable to oxydation, but of platina. A platina pound was therefore ordered of M r. Robinson. To carry out the comparison he sent over to London one of his assistants, Captain Nehus, who also took the opportunity to calibrate this new weight against another platinum troy pound that had been made some years earlier by William Cary at the request of the Royal Society (17).
After the destruction of the Imperial S tand ard Weights in the fire that destroyed the Houses of Parliam ent in 1834 it was decided to have new standards m ade in platinum. The new stan d ard pound, together with four copies and a n um ber of smaller weights, were m ade in 1844 by Henry Barrow from a hundred ounces of platinum provided by Johnson and Cock. T he standard pound shown here was formerly held by the Exchequer but is now in the care of the National Physical Laboratory.
206
T o c e l e b r a t e t h e c o r o n a t i o n o f Q u e e n V i c t o r i a in 1 83 8 a n u m b e r o f m e d a l s w e r e s t r u c k by t h e R o y a l M i n t in p l a t i n u m in a d d i t i o n to t h o s e m a d e in s i l v e r a n d b r o n z e . D e s i g n e d by t h e r o y a l m e d a l l i s t B e n e d e t t o P i s t r u c c i , t h e s e s h o w e d t h e c r o w n e d h e a d o f V i c t o r i a , w ith o n t h e r e v e r s e t h e Q u e e n h o l d i n g h e r s c e p t r e a n d o r b w ith t h r e e h e l m e t e d f ig u re s r e p r e s e n t i n g E n g l a n d . S c o t l a n d a n d I r e l a n d p r e s e n t i n g h e r w ith a cr o w n .
T h e n in 1834 a disastrous fire b u rn t down the Houses of P arliam ent and among many other valuable objects the Imperial S ta n d a rd W eights were either totally lost or rendered useless. In 1838 a Com m ission was appointed to supervise the restoration of the standards a n d three years later m ade their report recommending that the avoirdupois pound of 7000 grains be adopted instead of the old troy pound of 5760 grains and that the new standard, together with four copies of it, should be m ade in platinum . T hese together with a n u m b e r of smaller auxiliary weights, were duly m ade in 1844 by H e n ry Barrow (1801-1870) who had taken over R o b in s o n s business on his death in 1841, some 101 ounces of platinum being provided by J o h n s o n and Cock. T h e calibration of these standards, in which Professor Schum acher gave some assistance, was described in great detail by Professor W. H. M iller of C a m b rid g e in a p a p e r to the Royal Society (18) a n d the stan dards were solemnly legalised by Act of Parliament, the principal weight being deposited in the Office of the E xchequer at W estminster, one copy going to the Royal O bservatory at Greenwich, one to the Royal Society and one to the Royal M int, while the fourth was im m ured in a wall of the rebuilt Houses of Parliament. T h e possible use of p latinum for medals was also not entirely overlooked in this country. O n the occasion of Q ueen V ictorias coronation in 1838 a n um ber of platinum medals were struck to the design of Benedetto Pistrucci, the Royal Medallist, in addition to the m any silver and bronze medals (19).
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Both J p h n s o n and Cock b e c a m e founder m em bers of the Chem ical Society in 1841 and the latter contributed a paper on the extraction of palladium to the first volume of their proceedings, also presenting the Society with a specimen of this metal (20). J o h n s o n was the Societys first H o n o ra ry A uditor and served on its Council from 1842 to 1844, later presenting a qu a n tity of palladium to provide the Societys first ten F a r a d a y M edals. As already mentioned, J o h n s o n was elected a Fellow of the R o y a l Society in 1846, his sponsors including M ichael Faraday, W. H. Pepys a n d Charles W heatstone. In the previous year he h ad been closely in touch with F a r a d a y - with w hom he was almost exactly con tem porary - when he was studying the m agnetic properties of a wide range of metals and other substances an d discovering the phenom enon of diamagnetism. F a r a d a y s paper to the Royal Society on this subject (21) includes the two following paragraphs: Platinum - I have, as yet, found no wrought specimens of this metal free from magnetism, not even those prepared by Dr. Wollaston himself and left with the Royal Society. Specimens of the purest platinum obtained from Mr. Johnson were also found to be slightly magnetic. Palladium - All the palladium in the possession of the Royal Society prepared by Dr. Wollaston amounting to ten ingots and rolled plates, is magnetic. Specimens of the metal from Mr. Johnson, considered as pure were also slightly magnetic. F a r a d a y s diary for the p e rio d also m entions his obtaining from J o h n s o n specimens of rhodium, iridium a n d osm ium as well as various com pounds of these metals for the same investigation (22).
T h e B eg in n in g s o f E le c tr o c h e m is tr y F a r a d a y s famous series of q u a n tita tiv e researches on electrochemical decomposition, beginning in 1832 and following up D a v y s earlier studies, put the new subject of electrochemistry firmly upon its foundations. W ith the advice of the Reverend W illiam W hew ell of T rin ity College C a m b rid g e he also proposed the terms we still use today, anode and cathode, electrolysis and electrolyte. M ost of his brilliant experim ental work was carried out with platinum plates as electrodes in the ingenious a p p a ra tu s he designed, as he appreciated the great a d v a n ta g e of the opportunity afforded am ongst the metals of selecting a substance for the pole which shall not be acted upon by the elements to be evolved . T h e enormous batteries devised by Pepys, W ollaston an d others now began to give place to simple prim ary cells as a source of current, although the earlier designs were found to be subject to deterioration on standing a n d to polarisation caused by bubbles of gas accum ulating on the surfaces of the electrodes. Not until 1836 was this problem solved when Professor J. F. Daniell (1790-1845) of K in g s College, London, a great friend and adm irer of F araday, devised his selfdepolarising cell or constant b a t t e r y (23). T h is was followed in 1839 by the cell proposed by W. R. Grove, th e outstanding feature of this being the use of a
208
^ illiam R o b e r t G ro v e
181 1-18%
B o r n in S w a n s e a , a n d e d u c a t e d at B r a s e n o s e C o lle g e O x f o r d a n d c a lle d to the B a r in 1 8 3 5 . G r o v e s p e n t s e v e r a l years at ho m e o n r e s e a r c h e s in e l e c t r o c h e m i s t r y , d e v i s in g a p r i m a r y cell u s i n g a p l a t i n u m e l e c t r o d e a n d also i n v e n t i n g t h e n o w f a m i l i a r f u e l cell. In l a t e r y e a r s h e h a d a d i s t i n g u i s h e d legal c a r e e r , b e c o m i n g a Q .C. in 1 8 5 3 , a j u d g e in 1871 a n d b e i n g k n i g h t e d a y e a r la t e r
platinum electrode immersed in strong nitric acid contained in a porous pot which separated it from the zinc element imm ersed in weak sulphuric acid (24). T h e idea of the porous diaphragm was due to Antoine C esar Becquerel (1788-1878), professor of physics at the M u su m d H istoire Naturelle, a n d the two collaborated in the design of batteries. At the meeting of the British Associa tion for the A dvancem ent of Science in B irm ingham in S eptem ber 1839 Grove read a paper O n a small Voltaic Battery of Extraordinary E n e rg y , describing a battery of his construction th at had been presented to the A cadm ie des Sciences by Becquerel in the previous April (25). This consisted of seven liqueur glasses containing the bowls of com m on tobacco pipes, the m etals of zinc and p latin u m th at produced a current equal to the most powerful batteries of the old type. A diagram of this construction is given over page. By assem bling a num ber of such units in a wooden box Grove was able to provide a most useful source of constant and continuous current, and the first such ba tte ry is still pre served in the Science M u seu m in L ondon (Inventory 1876 82). T h e y were used successfully for m any years, particularly in the early days of telegraphy in the U nited States and also for the first Atlantic cable. Grove was also responsible for the origin of the fuel cell, generally regarded as a mid-twentieth century development. In a postscript dated J a n u a r y 1839 to a letter to The Philosophical M agazine about his battery he described an
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G r o v e s O ri g in a l P r i m a r y Cell
T h e p r i m a r y b a t t e r y d e v i s e d by W . R. G r o v e in 1839 c o n s i s t e d of a n u m b e r o f s m a l l ce lls c o n t a i n e d in g la s s v e s s e ls , t h e e l e c t r o l y t e s b e i n g s e p a r a t e d b y m e a n s o f t h e b r o k e n - o f f b o w l s of clay t o b a c c o p i p e s . T h e p o s i t i v e p o l e w a s of zin c a n d t h e n e g a t i v e p o l e o f p l a t i n u m . T h e s e he d e m o n s t r a t e d to b o t h t h e B r i t i s h A s s o c i a t i o n for the A d v a n c e m e n t of Science a n d the A c a d e m ie d e s S c i e n c e s in P a r i s . L a t e r h e e m p l o y e d a m o r e so p h isticated design a n d the b a tte r ie s w ere used fo r m a n y y e a r s , p a r t i c u l a r l y in t e l e g r a p h y
experiment (26) on an im p o rta n t illustration of the com bination of gases by p la tin u m in which a galvanom eter was perm anently deflected w hen connected with two strips of p latinum covered by tubes containing oxygen an d hydrogen. By 1840 he ha d been elected F.R .S., a n d ha d been a ppointed Professor of E xperim ental Philosophy at the L ondon Institution in Finsbury Circus and it was from there th at he addressed a further letter, dated O ctober 29, 1842, to The Philosophical M agazine, O n a G aseous Voltaic B a tte ry (27). T his paper, as well as a similar private letter to F a ra d a y , describes the first practical fuel cell, employ ing platinum foil coated with spongy platin u m produced by electrolysis of the chloride. A series of fifty pairs, c o nstructed as shown here in G roves original diagram, with dilute sulphuric acid as the electrolyte, was found to whirl ro u n d the needle of a galvanom eter, to give a painful shock to five persons joining hands, to give a b rilliant spark between charcoal points, and to decompose hydrochloric acid, p o tassiu m iodide an d acidulated water.
E lectrop la tin g w ith P la t in u m an d P a lla d iu m T h e introduction of the electrodeposition of gold and silver in the early 1840s, mainly by the Elkingtons of B irm in g h am and their associate J o h n W right, naturally prom pted attem pts to electroplate with p latinum and palladium . It was at first assum ed that p latin u m , having so m any similar properties to those of gold, would be equally a m e n a b le to electrodeposition, b u t unfortunately
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T h e First Fuel Cell
In 1842 'A. R. Grove devised the first fuel cell, employing platinum foil coated with spongy platinum as the electrodes and sulphuric acid as the electrolyte. This is his letter to Faraday written a week before he wrote of his invention to the editor of The Philosophical Magazine. His diagram shows the construction, ox denoting the tube supplying oxygen, hy that supplying hydrogen, and the hatched lines the platinised platinum electrodes
By courtesy of the Royal Institution
its insolubility as an anode and the complex chemistry of its salts presented severe technical problems. These were nevertheless tackled with enthusiasm by a number of scientists in England, France and Germany and attempts to develop a reliable process continued throughout most of the nineteenth century until satisfactory standards of quality were achieved. But it was one of DanielPs old students in the chemistry department at Kings College who tackled the problems most successfully. This was Alfred Smee whose grandfather and father had both been employed by the Bank of England, the father becoming Chief Accountant in 1831. At that time the Chief Accountant lived with his family in an official residence in the Bank, the necessary security confining them at home in the evening hours. O n leaving college young Alfred therefore set up a laboratory in a room leading out of the
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A lfre d S m e e 1818-1877
B o r n in C a m b e r w e l l , e d u c a t e d a t St. P a u l ' s S c h o o l a n d K i n g 's C o llege. L o n d o n , a n d t h e n t r a i n e d as a s u r g e o n a t St. B a r t h o l o m e w ' s H o s p i t a l , S m e e c a r r i e d o u t all his r e s e a r c h e s in e l e c t r o p l a t i n g in a r o o m set a s i d e for h i m in t h e B a n k of E n g l a n d w h e r e his f a t h e r lived as C h i e f A c c o u n t a n t . H e w as e l e c t e d a F ellow o f t h e R o v a l Society in 1 8 4 1 . t h e y e a r a f t e r h e p u b lish ed his E le m e n ts of E le c tro m e ta llu r g y , or the A rt of W o r k i n g in M e t a l s b y t h e G a l v a n i c F l u i d a t t h e e a r l y age o f 22. T h e d i s t i n g u i s h e d s u r g e o n Sir A s tle y C o o p e r i n t e r e s t e d h i m s e l f in t h e c a r e e r o f t h e y o u n g A l f r e d S m e e . a n d it w a s u p o n his e m p h a s i s i n g to t h e t h e n G o v e r n o r of t h e B a n k o f E n g l a n d t h a t y ou d o n 't k n o w w h a t a t r e a s u r e y o u h a v e got in t h a t y o u n g m a n t h a t S m e e w a s g iv e n a n a p p o i n t m e n t t h e r e a s s u r g e o n . S ir A s tle y w as r e l a t e d by m a r r i a g e to b o t h T h o m a s Cock a n d P erciv al N orton Johnson and S m e e 's in terest in p l a t i n u m a n d p a l l a d i u m w as n o d o u b t e n c o u r a g e d a n d s u p p o r t e d by th e m
family drawing room and next to the ledger office and here, working alone with elementary equipment, some lent by Daniell, he carried out a rem arkable series of experiments in electrochemistry. His first self-imposed task w a s to devise a battery m ore suitable for work in electrodeposition, and on F e b r u a r y 28th, 1840 he was able to read a p a p e r to the Royal Society, O n the Galvanic Properties of the M etallic E lem entary Bodies with a description of a new C h e m ico-M echanical B a tte ry (29). Sm ees battery relied upon his observation th at an electrode having a roughened surface caused the h ydrogen formed during the reaction to disperse, preventing the build-up of a film of bubbles. His cathodes were either of silver etched with acid or of platinum a b ra d e d with sandpaper, b o th being placed in a cell containing nitro-m uriate of p l a tin u m as the electrolyte. T his produced a thin layer of platinum in the fo rm of a black powder, yielding a n electrode simply and cheaply and one unaffected by the strength of acid in any cell. Banks of cells could be employed varying from the size of a tu m b ler to a 10 to 12 gallon vessel . Its success lay, however, in its simplicity, a n d it aroused great interest in the art of depositing o n e metal u p o n another.
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By the end of 1840 Smee, still only 22 years old, had compiled and published a remarkable text book, Elements of Electrometallurgy, a term he himself coined. In this he described his processes for both platinum and palladium plating, writing that: Hitherto the reduction of these metals, in any other state than that of theblack powder, has been always considered impossible. He claimed that processes for platinating and palladiating rested upon the authority of his book and went on: Platinating metals by the galvanic current is a new feature in science. The process is similar in all respects of gilding but is more difficult. The solution of the nitro-muriate of platinum must be very weak, and the battery must be charged with dilute acid. The object to be coated must be very smooth, and thoroughly cleansed by potash, before the process is commenced. Having proceeded thus far, and the solution of platinum being ready, a very fine platinum wire, in connection with the silver of the battery, must be placed so as to dip into the solution, but must not be immersed beyond a very short distance. The object to be platinated is now ready for connection with the zinc of the battery, after which is effected, it is to be dipped in the solution. Immediately, oxygen gas will be given off from the platinum wire, in connection with the silver. From the copper or other metal to be platinated, no gas will be evolved, provided too much electricity be not generated. In a few minutes the object will be coated with platinum. It is needless to say that it has a beautiful appearance. It would
A sketch of Alfred Sm ees laboratory made by his brother-in-law William Hutchinson and autographed by the sole occupant. Using app aratu s lent by Professor Daniell and batteries of his own design employing platinised silver cathodes, he carried out here a long series of investigations on the electrodeposition of metals without assistance of any kind. T he laboratory lay between the family drawing room and the ledger room of the Bank of England, and the occasional dropping of a ledger by a clerk would be suf ficient to ruin one of Sm ees experi ments by breaking the contact with his battery
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S ir A stley P a s t o n C o o p e r
1 7 6 8 -1 8 4 1 T h e d i s t i n g u i s h e d s u r g e o n to K i n g G e o r g e IV a n d P r e s i d e n t o f t h e R oy al C o l l e g e o f S u r g e o n s , e l e c t e d a F ello w o f t h e R o y a l S o ciety in 1 8 02 . A l t h o u g h h e took n o a c t i v e p a r t in t h e r e s e a r c h e s o n p l a t i n u m h is i n f l u e n c e w a s m o r e t h a n o n c e o f g r e a t v a l u e . In 1 8 0 0 h e s e c u r e d t h e e m p l o y m e n t of his y o u n g b r o t h e r - i n - l a w . T h o m a s C o c k in his friend W illiam A l l e n s l a b o r a t o r y : l a t e r h e w a s i n s t r u m e n t a l in t h e p re se n ta tio n of Jo h n s o n 's p a lla d iu m c h a i n to G e o r g e I V . w h i l e in the last y e a r o f h is l ife it w as h e w h o p e r s u a d e d th e G o v e r n o r of the B ank o f F n g l a n d to a p p o i n t A l f r e d S m e e to a p o s i t i o n in w h i c h h e c o u l d p u r s u e h is e l e c t r o c h e m i c a l w o r k
be of great value as a coating for telescopes, microscopes, quadrants, and a hundred other articles which must be exposed to the action of the weather. (30) For palladium plating S m e e used a similar electrolyte, nitro-m uriate of palladium with a p alladium a node: This metal is whiter than platinum, but not so bright as silver. It might be used in the same cases, and with the same advantages as platinum; and we have, besides, twice the bulk of metal in the same weight. Sm ees reputation as a n electrochem ist was rapidly established. H e was elected a fellow of the Royal Society i n j u n e 1841, while earlier in the sam e year a special post, somewhat honorary in its duties, was created for him in the Bank of England. This appointm ent w as m ad e largely u p o n the recom m endation of Sir Astley Cooper, the distinguished surgeon, and brother-in-law of T h o m a s Cock, who was a friend of Sir J o h n R a e Reid, the Governor, an d who ha d sometimes visited Sm ees laboratory to see his experiments. H e considered th at the Bank should tu rn S m e e s scientific genius to good ac co u n t , a n d accordingly the young m an was appointed S u rg e o n to the Bank of E n g la n d on J a n u a r y 1st, 1841. Astley C o o p e rs relationship with Percival N o rto n J o h n s o n leaves little doubt that S m e e s interest in p la tin u m a n d palladium plating would have been encouraged by him, an d that h e supplied the necessary metals an d salts. T h a t they were well known to each o t h e r is established by Sm ees acting as a steward at a dinner given in 1844 by the Society for T eaching the Blind, a n organisation just established on the initiative o f J o h n s o n a nd his wife.
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Sm ees electrolyte could not have been very successful, an d it was only one of a num ber put forward during the course of the next twenty years or so. His remark that p latinum plating was similar to gilding b u t m ore difficult proved to be well founded. O n e worker who realised that because of the insolubility of the anode the solution m ust be periodically supplied with additions of a suitable com pound was H e n ry B eaum ont Leeson (1803 1872), a lecturer in chem istry at St. T h o m a s s Hospital in London, who filed a massive p a te n t in 1842 (31) cover ing the electrodeposition of a whole range of metals and including the concept of agitating either the article to be plated or the plating solution in order to obtain smooth deposits at high current densities. H e realised the cause of S m e e s difficulties with the plating of platinum an d palladium an d pointed out that: The solution must be supplied with a fresh portion of the metal by adding to or placing within such solution or electrolytic fluid a further supply of some suitable salt to be dissolved or taken up from time to time as the fluid becomes exhausted. In 1846 a further p atent was filed by one George Howell of L ondon a n d this contained the first reference to a solution that becam e known as the stabilised platinum electrolyte, m ad e by dissolving p latinum chloride in caustic soda and adding oxalic, citric, tartaric or acetic acid followed by caustic potash (32). Lastly, so far as the period at present under discussion is concerned, cam e T hom as H etherington H e n ry (1816-1859) who was for m any years from 1837 employed as chemist in the brewery of T r u m a n H a n b u r y and Buxton in Spitalfields, London, later setting up as a consulting analytical chemist in L incolns Inn. H e was another founder m em ber of the Chem ical Society an d was elected F.R.S. in 1846. T h e re is no record of the process he employed b u t p re served among the J o h n Percy collection of specimens at the Royal School of M ines is a thin sheet of copper plated on both sides with palladium and accompanied by a note in Professor P ercys ha n d stating that he was given it by the late T. H. Henry. T h e beam s of two O ertling balances shown at the G re a t Exhibition of 1851 were also plated by Henry, one with p latin u m a n d the other with palladium (33). All these investigations, together with similar researches carried out in France and G erm any an d the later and more successful developments in the field have recently been described in detail by Dr. Peta B u c h a n a n (34).
C on clu sio n T h u s the three decades from the time w hen W ollaston ha d to a b a n d o n his production of malleable p latinum until about 1850 were dom inated on the one hand by the scientific genius of M ichael F araday, later supported by several of his disciples, and on the other by the metallurgical skill a n d enterprise of Percival N orton Johnson. In 1845, however, the younger C o c k s health was giving him great trouble and he retired from his partnership, the firm again becoming P. N. J o h n s o n and C om pany. H e was succeeded in the platin u m work by a young m an nam e d George M a tth e y who h a d entered the business as an
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T o c e l e b r a t e t h e p r o d u c t i o n o f a p a r t i c u l a r l y l a r g e in g ot o f p l a t i n u m in 1850 P e r c i v a l N o r t o n J o h n s o n h a d t h e lid o f a s n u f f - b o x m a d e f r o m p a r t o f t h e r o l le d sh e e t . T h e b o d y o f t h e b o x is in s i l v e r b e a r i n g t h e B i r m i n g h a m h a l l m a r k f o r t h a t y e a r , w h i l e t h e lid c a r r i e s a r e l i e f s h o w i n g t h e R o m a n C o n s u l L u c i u s J u n i u s B r u t u s c o n d e m n i n g h i s so ns to d e a t h f o r c o n s p i r a c y . I t h a s now b e e n p a s s e d to t h e V i c t o r i a a n d A l b e r t M u s e u m
apprentice in 1838 at the age of thirteen. H is extraordinarily long career and his great achievements in building up the p latin u m industry in England will be related in a later chapter, but o n e last reference to J o h n s o n should be included here. By 1850 the size of p la tin u m ingots had increased considerably and had exceeded the capabilities of the L o n d o n m etal workers to roll them. In that year, to celebrate the production of his largest ingot so far, J o h n s o n took it to Birm ingham, in com pany with his brother-in-law Sm ith (who ha d now taken his m o th e rs m aiden nam e of Sellon) to have it rolled. F rom a piece of the resulting sheet he had m ade the lid of a snuff-box showing in relief the R o m a n Consul Lucius Ju n iu s Brutus con d e m n in g his two sons to death. T h e snuff box, the body of which is m ade in silver, is now preserved in the Victoria and Albert M useum in London.
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1 D. M cD onald, Percival N o rto n Jo h n so n , L ondon, 1951

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23 24 25 26 27 28 29 30 31 32 33 34
L etter from P. N. J o h n s o n d ated M a rc h 11th, 1846, A rchives of th e R oyal Society; abridged in Phil. M ag., 1846, 29, 130 L etter from Sir A stley C o o p er to S ir W illiam K nighton, J u n e 25th, 1826, R oyal Archives, W in d so r C astle, R A /2 6 2 9 6 P. N. Jo h n so n , M ining J ., 1835, 1, 83 W . M. Poussett, M ining J ., 1836, 3, 75 W. A. L am p ad iu s an d P. N. Jo h n so n , J . Prakt. Chem., 1837, 11, 309-315 J . S to d art an d M . F arad ay , Quarterly J . Science, 1820, 9, 319-329 J . S to d art an d M . F arad ay . Phil. Trans. Roy. Soc., 1822, 1 12, 253-270 L etter from F a ra d a y to de la Rive, J u n e 26, 1820, qu o ted in L. P earce W illiam s, T h e Selected C o rresp o n d en ce of M ichael F arad ay , C am b rid g e, 1971, 1, 117 120 Sir R o b ert H adfield, F a ra d a y an d his M etallu rg ical R esearches, L ondon, 1931 L etter from G re e n Pickslay & C o., to F arad ay , A rchives of th e R oyal In stitu tio n J . Foley, H istory of th e Inv en tio n a n d M aking of F o ley s D iam o n d P ointed G old Pens, N ew York, 1875, 58 60 M. F arad ay , G lass F u rn a c e N otebook, Roy. Soc. M SS, O c to b e r 8, 1828, 234 ibid, J a n u a ry 16, 1829, 287 M. F arad ay , Phil. Trans. Roy. Soc., 1830, 120. 1-58 P. N. Jo h n so n , M ining J ., 1843, 13, 182 C. H. S chum acher, Phil. Trans. Roy. Soc., 1836, 126, 457-495 W.' H. M iller, Phil. Trans. Roy. Soc., 1856, 146, 753-945; Phil. M ag., 1856, 12, 540-552 Public R ecord Office, M in t 4/48, 49 W .J . Cock, Proc. Chem. Soc., 1843, 1, 161-164 M. F araday, Phil. Trans. Roy. Soc., 1846, 136, 41-62 M . F arad ay , R oyal In stitu tio n A rchives, D ecem ber 12-19, 1845 J . F. D aniell, Phil. Trans. Roy. Soc., 1836. 107-124 W. R. Grove, Phil. M ag., 1839, 14, 388-390 W. R. Grove, B ritish Assocn. R ep o rt, 1839, 36-38 W. R. Grove, Phil. M ag., 1839, 14, 129-130 W. R. Grove, Phil. M ag., 1842, 21, 417 420 E. M. Sm ee (M rs. O d lin g ), M em oirs of Alfred Sm ee, L ondon, 1878 A .S m ee, Phil. Mag., 1840, 16, 315-321 A. Smee, E lem ents of E lectrom etallurgy, London, 1840, 94 H. B. Leeson, B ritish P aten t 9374, 1842 G. Howell. B ritish P aten t 11,065, 1846 R eport of th e ju rie s , E x h ib itio n of 1851, 258 F. D. B uchanan. Platinum M etals Rev., 1981, 25, 32-41
Johann ^ olfg a n g D o b erein er
Born the son of a co a ch m an in B avaria, D obereiner first practised as an apothecary and then, to his great surprise, was invited to become Professor of Chemistry at J e n a w here he also acted as chemical adviser to Goethe. His discovery of the pow er of finely divided platinum to promote the oxidation of alcohol and to synthesise water from hydrogen and oxygen caused a great sensation in the chemical world and founded the study of catalysis
From a portrait in the possession of G oethe-N ationalm useum der Nationale Forschung* und (edenkslatlen. VI eim ar
1780-1849
12
The D iscoverv and Early History of Catalysis
j j
j
/ have trie d to p ro d u c e these p h e n o m e n a with various m etals hut I have su cceeded only with
platinum and palladium .
H U M PH R Y DAVY
T h e point had now been reached w hen the more im portant physical properties of platinum and some of its associated metals had become reasonably well understood an d had formed the basis of several applications. O n e m ajor property, and one that was later to m ake a most significant contribution to chemical industry, was, however, yet to be discovered. As is so often the case, this discovery cam e incidentally from a quite different investigation. A disastrous explosion in a coal mine in the N o rth of E n gland in 1812, shortly followed by a n um ber of similar explosions, pro m p te d an appeal for advice to H u m p h ry Davy at the Royal Institution and resulted in his wellknown researches on flame and his invention of the m in e rs safety lamp. In a paper read to the Royal Society on J a n u a r y 23rd 1817 Davy described his experiments on the increase in the limits of combustibility of m ixtures of coal gas and air with increasing tem perature: For this purpose, I introduced a small wire-gauze safe-lamp with some fine wire of platinum fixed above the flame, into a combustible mixture containing the maximum of coal gas, and when the inflammation had taken place in the wire-gauze cylinder, I threw in more coal gas, expecting that the heat acquired by the mixed gas in passing through the wire-gauze would prevent the excess from extinguishing the flame. The flame continued for two or three seconds after the coal gas was introduced; and when it was extinguished, that part of the wire of platinum which had been hottest remained ignited, and continued so for many minutes. It was immediately obvious that this was the result which I had hoped to attain by other methods, and that the oxygen and coal gas in contact with the wire combined without flame, and yet produced heat enough to preserve the wire ignited, and to keep up their own combustion. I proved the truth of this conclusion by making a similar mixture, heating a fine wire of platinum and introducing it into the mixture. It immediately became ignited nearly to whiteness, as if it had been itself in actual com bustion, and continued glowing for a long while, and when it was extinguished, the inflammability of the mixture was found entirely destroyed.
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T he opening page of the m anuscript of Sir H um phry Davy's p aper read to the Koval Society on January 23rd. 1817. Some new experim ents and observations on the combination of gaseous mixtures, with an account of a method for keeping a continued light in mixtures of inflam m able gases and air without flame". T he p aper goes on: **I had intended to expose fine platinum wires to oxygen and olefiant gas and to oxygen and hydrogen during their slow com bination under different circum stances. when I was accidentally led to the discovery of a new and curious series of p h e n o m en a.* * D avy had d isc o v e red h ete ro g e n eo u s c a ta ly tic o x id a tio n but u n fo rtu n a te ly he did not appreciate the significance of his fi n<lings
By rourtes* of the Koval Institution
Thus Davy discovered the phenomenon of heterogeneous catalytic oxidation and although he obtained the same results with ether and alcohol, obtaining an acidic product that Faraday and later Daniell identified as a mixture of acetaldehyde and acetic acid, he did not carry further the study of this profoundly important effect. His mind was fully occupied with problems of combustion, he was by now fully satisfied with the safety-lamp and he tended to regard the phenomenon he had discovered, as he wrote to one of his colliery manager friends, as more like magic than anything I have seen . . . it depends upon a perfectly new principle in combustion ( 2 ).
I have tried to produce these phenomena with various metals; but I have succeeded only with platinum and palladium; with copper, silver, iron, gold and zinc, the effect is not produced. (1)
The Researches of Edmund D avy Despite this Davys paper aroused great interest; it was translated into German and French and it also encouraged his cousin Edmund Davy to take up the matter. Edmund, seven years younger than Humphry, had been engaged as the
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A younger cousin of H um phry Davy. Edm und first assisted the latter at the Royal Institution and then held the chair of chemistrv at the Royal Cork Institution. Here he prepared finely divided platinum and found that it would oxidise alcohol vapour at room tem perature, sufficient heat being generated to raise the metal to a white heat. Again. E dm und Davy failed to grasp the significance of his discovery, but it led immediately to the much m o re e ffe c tiv e re s e a r c h e s of Dobereiner
From a portrait in the possession of ihe Ko\al Dublin Society
Edmund Davy 1785-1857
latters assistant in 1804 and then in 1831 had secured an appointment as Professor of Chemistry at the Royal Cork Institution. While still at the Royal Institution in London he had made several studies in the chemistry of platinum and published long papers in The Philosophical M agazine (3). In 1817 he carried these researches further and presented a paper to the Royal Society on a new fulminating compound of platinum (4). He stood much in the shadow of Humphry, and when in 1820 he published a paper describing the preparation of finely divided platinum by reducing a solution of platinum sulphate with alcohol and its great activity at room temperature in the oxidation of a further quantity of alcohol, he merely wrote:
In this case the acid first noticed by Sir H. Davy (in his beautiful experiment of the ignited platinum wire, and since more fully examined by Mr. D aniell) is produced . . . This mode of igniting a metal seems to be quite a new fact in the history of chemistry, but the means of keeping it in a state of ignition is only another illustration of the facts previously pointed out by Sir H. Davy, in his late valuable researches. (5)
Johann Wolfgang Dobereiner Edmund Davys paper was reproduced in German in Schweiggers Journal fiir Chemie in the spring of the following year and attracted the attention of Johann
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W o lfg a n g D b e re in e r w ho w as t o o p en u p a m u c h m o re vigorous study of th e p h e n o m e n o n a n d to c a u se q u ite a s e n s a tio n a m o n g his scientific c o n tem p o raries. D b e re in e r, b o r n the son of a c o a c h m a n in 1780, first served a n ap p re n tic e s h ip to a n a p o th e c a ry a n d th e n s p e n t five y ea rs as a n a p o t h e c a r y s ass is ta n t in K a r l s r u h e a n d S tra s b u rg , a t t e n d i n g lectures o n c h e m is try a n d m in era lo g y in his free time. O p e n in g his o w n p h a r m a c e u t i c a l m a n u f a c t u r i n g business, he b e g a n to c o n trib u te p ap e rs to G e h l e n s Neues Allgemeine Journal f r Chemie b u t his b u siness failed a n d he was left im p o v e ris h e d . In 1810, to his g re at surprise, D b e r e i n e r w as a p p o in te d to th e Professorship of C h e m is tr y in the U niversity of J e n a , t h e c h a ir c r e a te d by C a r l A u g u st, D u k e of S a x e -W e im a r-E is e n a c h in 1789 a n d now left v a c a n t by th e d e a th of its first ho lder, J o h a n n G ttling. T h e a p p o i n t m e n t was m a d e b y th e D u ke, a n e n lig h te n e d p a t r o n of th e arts a n d sciences, to g e th e r w ith his M in is te r of S ta te G o e th e on th e re c o m m e n d a tio n o f G e h le n , a n d D b e r e in e r r e m a in e d for th e rest of his life m o st grateful for this o p p o r t u n i t y , refusing several offers of ch a irs in o t h e r universities. A n e x t r a o r d i n a r y frien dsh ip grew b e tw e e n D b e re in e r, the G r a n d D u k e (as he b e c a m e in 1815 ) a n d G o e th e , b o th in te re ste d in chem istry. By th e A u g u s t of 1821 he h a d n o t only re p e a te d E d m u n d D a v y s e x p e rim en ts b u t h a d fully a p p re c ia te d th e ir significance, righ tly re g a rd in g th e im p o rta n t discovery as th e activity of th e p l a t i n u m r a t h e r th a n , as h a d b o t h th e Davys, as t h e a c tio n u p o n it of the alcohol. H e believed a t th e tim e th a t E d m u n d D a v y s p r o d u c t was a sub-ox ide of p l a t i n u m a n d h e wrote: The platinum sub-oxide moreover, does not undergo any change during this transformation of the alcohol a n d can immediately be used again to acidify fresh, perhaps limitless, quantities of alcohol . . . a circumstance that permits its use for the large scale preparation of acetic acid. (7) I n J u l y 1823 he t u r n e d his a t t e n t i o n to th e m e ta l itself, a n d p r e p a r e d p l a t i n u m in p o w d e r form by h e a t i n g a m m o n i u m c h lo ro p la tin a te . T h i s he found w o u ld ignite a m ix tu re of h y d r o g e n a n d e ith e r air o r ox y g en even at room t e m p e r a t u r e or below: There now followed in a few moments that strange reaction; the volume of the gases diminished and after ten minutes all the oxygen in the admitted air had con densed with the hydrogen to water. (8) H e also gave som e th o u g h t to th e m o st s u ita b le form to a d o p t for the p l a t i n u m p o w d e r a n d m a d e use o f sm all m o u ld e d pellets of p o t t e r s clay im p re g n a t e d w ith p l a t i n u m - the first e x a m p l e of a s u p p o r te d catalyst. D b e re in e r was quick to m a k e his findings kno w n. T w o d ay s after this e x p e rim e n t - w h ich he re p e a te d a t least th irty tim es t h a t d a y a n d alw ays w ith t h e sa m e re s u lt he w rote to G o e th e : Permit me, your Excellency, to give you news of a discovery that seems to be important in the highest degree from the points of view of both physics and electrochemistry. (9) H e also w ro te similarly to L o r e n z O k e n , th e ed ito r of a scientific j o u r n a l Isis,
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D b e r e i n e r b e g a n his c a r e e r as P r o f e s s o r o f C h e m i s t r y in r o o m s in t h e p a l a c e of h i s p a tro n . D uke C arl A ugust of S a x e -W e im a r-E ise n a c h . but th e se soon p ro v e d i n a d e q u a te a n d in 1816 a l a r g e h o u s e w a s a c q u i r e d , s h o w n o n t h e r ig h t o f th is i l l u s t r a t i o n , f o r u se as b o th a l a b o r a t o r y a n d a h o m e . L a t e r , in 1 8 33 . a new l a b o r a t o r y , v isib le b e h i n d t h e t r e e s , w as b u ilt fo r h i m to p l a n s d r a w n u p by t h e D u k e 's M i n i s t e r o f S t a t e , G o e t h e
p u b lish ed in J e n a , a n d sent d e tailed ac c o u n ts to his f r i e n d j . S. C. S c h w e ig g e r in B a y re u th a n d to L. W. G ilb e rt in L eipzig w ho b o th p u b lis h e d his letters in their respective j o u r n a l s (10), w hile he quickly p r o d u c e d a sm all book, U b e r neu E n td e c k te hchst M e r k w rd ig e E ig e n sc h a fte n des P la t in s , p u b lis h e d in J e n a , also in 1823. O n A u g u st 3rd D b e re in e r m a d e a n even m o re striking ex p e rim e n t by m erely directing a s tre a m of h y d ro g e n a t th e p l a t i n u m p o w d e r so th a t it was m ixed w ith air before re a c h in g its target. T h e p l a t i n u m im m e d ia te ly b e c a m e w hite hot a n d ignited the h y d rog en . T h is, re p o rte d a t o nce to th e editors alre ad y m entioned, a n d p u b lis h e d by th e m as a p p e n d ic e s to his first a n n o u n c e m e n t (10), c a u sed even m o re excitem ent. A n u n n a m e d friend in P a ris w ro te to D b e re in e r to say th a t his news h a d a ro u s e d a g re a t se n s a tio n h ere an d excited th e liveliest in te re s t , w hile his p a tro n , th e G r a n d D u k e C a rl A u g u s t w rote to him: I am delighted that your splendid discovery excites the attention of foreign countries. I return to you the letter from Paris and thank you for the published paper. (11) A t the second a n n u a l m eeting, h eld in H a lle in S e p te m b e r, of the Gesellschaft d e u ts c h e r N a tu r fo rs c h e r u n d rtze, D b e re in e r p re s e n te d a p a p e r an d, to th e s u rp rise a n d delight of th e m e m b e rs, gave a p ra ctical d e m o n s tra tio n . A m on g his m o re significant c o m m e n ts was: Most likely a new natural principle is operative here that will become apparent through further investigation (12). 223
All incidental result of D o b e rein e rs discoveries was his invention of the first lighter. Phis employed hydrogen, generated from zinc and sulphuric acid, passing over finely divided platin um which then glowed sufficiently to ignite the gas. \ num ber of d ifferent types produced in G erm any and in Kngland became very popular and m any thousands of them were in use over a long period of time. Dobereiner refused to file a patent for his lighter with the comment I love science m ore than money**. These are but three of the many designs that were produced
By courtesy of the Science Museum
The reaction in France was also swift. O n Sunday August 24th a brief notice of Dobereiners work was published in a daily newspaper, th e Journal des Debats, including the comment that
This also quickly attracted attention, while Professor Karl Kastner of the University of Erlangen wrote to his former student Liebig, then studying under Gay-Lussac in Paris, to give an account of Dobereiners work. Liebig immediately passed on the news to the Acadmie des Sciences through Louis Jacques Thenard, Professor of Chemistry at the cole Polytechnique, who had earlier been interesting himself in reactions such as the decomposition of
224
This beautiful discovery is going to open up a new field of research in physics and chemistry. (13)
L ouis J a c q u e s T h n a r d
1 7 7 7 1 8 5 7 B o r n in the v illag e o f La L o u p t i e r e , now k n o w n in his h o n o u r a s La L o u p tiere-T h en a rd . n ear \o g e n t- s u r S c i n e . T h e n a r d c a m e to P a r i s at t h e a g e o f s e v e n t e e n d u r i n g t h e R e ig n of T error to study pharm acy. His k e e n n e s s b r o u g h t h im to t h e n o t i c e of Y a u q u e l i n a n d F o u r c r o y . b o t h of w h o m a d v a n c e d his c a r e e r . I n 1 80 4 h e r e p l a c e d . V a u q u e l i n in t h e c h a i r of c h e m i s t r y a t t h e C o lleg e d e F r a n c e w h ile in 18 10 h e w a s a p p o i n t e d P r o f e s s o r at t h e cole P o l y t e c h n i q u e and succeeded Fourcroy in the A c a d m i e d e s S c ien ces . I m m e d i a t e l y t h e n ew s o f D o b e r e i n e r ' s d isc o v ery r e a c h e d P a r i s h e a n d his c o l l e a g u e D u lo n g b e g a n to i n v e s ti g a t e t h e e f f e c t s of p latin u m , p allad iu m , rh o d iu m and o t h e r m e t a l s o n t h e c o m b u s t i o n of h y d r o g e n a n d ox yg en
B \ c o u rte s y o f th e W e llc o m e I n s titu te o f th e H isto ry o f M e d ic in e
a m m o n ia over h e a te d m etals. T h e n a r d w as m o s t excited by this d ev e lo p m e n t and, to g ether w ith his y o u n g e r c o lla b o r a to r P ie rre L ou is D u lo n g , he im m ediately b e g a n a n investig ation into th e n ew p h e n o m e n o n b y s tu d y in g the effects of h e a te d solid m etals o n in fla m m a b le m ix tu re s of gases. T h e y o b ta in e d sam ples of p a lla d iu m a n d rh o d iu m from W o llasto n , a n d they d e m o n s t r a t e d th a t platin u m , p alla d iu m , rh o d iu m , cobalt, nickel, gold a n d silver re q u ir e d in c re a s ingly high te m p e ra tu re s , in t h a t order, to b rin g a b o u t th e c o m b i n a t i o n of h y d ro g e n a n d oxygen. As p ro m p tly as S e p te m b e r 15th th ey r e a d a first re p o rt to the A c ad m ie a n d t h ro u g h th e influence of th eir friend G a y -L u s s a c , th e editor, this was sq ueezed into th e S e p te m b e r issue (in sm all ty p e ) of th e Annales de Chimie (14) before D b e r e i n e r s p a p e r h a d a p p e a r e d in F r e n c h tr a n s l a t i o n in the sam e jo u rn a l. S hortly a fte rw a rd s T h e n a r d a n d D u lo n g p r o d u c e d p a lla d iu m , r h o d i u m a n d iridiu m in p o w d e r form a n d fou n d th a t th ey w e re effective at ro o m te m p e r a tu re , this result being re p o rte d to th e A c a d m ie only a week after th e ir o rigin al p a p e r was re ad (15). D u rin g th e w in ter of 1823 fu rth e r re searc h w as c a rrie d o u t b y A d o lf Pleischl the Professor of C h e m is tr y in th e U niv ersity of P rag u e , w h o w as an x io u s to discover w h y it was th a t th e ex p e rim e n ts so m etim e s failed. H e c o n c lu d e d q u ite rightly th a t th e im p o rta n t factors w ere th e degree of fineness a n d t h e poro sity of
225
A d o lp h M a rtin P leisch l
1787-1867
A n a t i v e of B o h e m i a a n d P r o f e s s o r of C h e m i s t r y at t h e U n i v e r s i t y o f P r a g u e f r o m 1815 u n t i l 1 83 3 w h e n h e m o v e d to V i e n n a , P le ise h l q u i c k l y f o llo w e d u p D o b c r e i n e r s w o r k a n d in N o v e m b e r 18 23 he e s t a b l i s h e d t h a t t h e a c tiv ity of th e p la tin u m p o w d e r d e p e n d e d up o n its fin en ess. H e f o u n d t h a t p l a t i n u m p o w d e r that h ad previously been e ffe c tiv e fa i l e d if p r e s s e d h a r d t o g e t h e r , w h i l e a n e s p e c ia lly fine p o w d e r w o r k e d e x t r e m e l y well at a lo w er t e m p e r a t u r e t h a n usu a l
By c o u rte s y o f th e ^ e llc o m e I n s titu te o f th e H isto ry o f M e d ic in e
his p la tin u m pow der, a f in d in g th a t d re w a n a p p re c ia tiv e letter from D o berein er, p u b lis h e d as a n a p p e n d i x to the p a p e r. A few weeks later he estab lish ed th a t p a lla d iu m also b e h a v e s in a s im ilar w a y to p l a t i n u m b u t w ith low er activity, a n d he a d d e d th a t u n fo r tu n a te ly he h a d no iridium , r h o d i u m or o s m iu m available to him a lt h o u g h he felt th a t th ey m ig h t well exh ib it the sam e p r o p e rty (17). In his well kn ow n a n n u a l r e p o r t s o n th e pro g ress of c h e m is try B erzelius gave th e highest p ra is e of w h ich he w a s c a p a b l e to D o b e re in e r for t h e y e a r 1823: From any point of view the m ost important and, if I may use the expression, the most brilliant discovery of last y ear is, without doubt, that fine platinum powder has the ability to unite oxygen and hydrogen even at low tem peratures. (18) O n e b y -p ro d u ct of D o b e r e i n e r s w ork was t h e inv en tio n of th e ligh ter th a t still b e a rs his nam e, th e D o b e r e i n e r F eu erzeu g . In this hy d ro g e n , g e n e ra te d from zinc a n d s ulph uric acid, p a s s e d th r o u g h a nozzle over a sm all a m o u n t of finely divided p la tin u m held on t h i n p l a t i n u m wires a n d b e c a m e ignited, the flam e th e n b eing passed to a c a n d le . M a n y t h o u s a n d s of th e s e lighters w ere p r o d u c e d in G e r m a n y a n d in E n g l a n d b u t D o b e re in e r refused to accep t an y financial re w a rd for his invention. 226
F o r a m o re d etailed ac c o u n t of D b e r e i n e r s life a n d w o rk a m o s t v a lu a b le source is to b e fou nd in a n u n p u b lis h e d thesis by D r. P e te r C o llin s a n d in a sh o rter version of this p u b lis h e d in 1976 (19) u p o n w h ic h th e p re s e n t w rite r has d ra w n heavily a n d gratefully in th e foregoing section.
Further In vestig ation s in Great Britain

O n the d ay following th e r e a d in g of D u lo n g a n d T h e n a r d s first p a p e r to the A c adm ie des Sciences the F r e n c h physicist J . N. P. H a c h e t t e (1 7 6 9 -1 8 3 4 ) w rote one of his m a n y letters to M ic h a e l F a r a d a y (20). T h e c o n c lu d in g p a r a g r a p h read s in tran s la tio n : I saw demonstrated yesterday the beautiful experiment of Dobereiner, a Germ an scientist (of Stuttgart, I think). You are no doubt familiar with it. It consists in direct ing a current of hydrogen on to platinum powder obtained from the solution of this metal in aqua regia by precipitation with the ammonium salt. T h e hydrogen gas inflames, by simple contact. In your hands this fact will not be the last of its k ind . F a r a d a y w as of cou rse highly in tere ste d in this piece of news, a n d by S e p t e m b er 27th he h a d p r e p a r e d p l a t i n u m in p o w d e r form by h e a tin g a m m o n i u m c h lo ro p la tin a te a n d h a d re p e a te d D b e r e i n e r s e x p e rim e n t to his e n tire satisfac tion (21). H e at once w ro te a s h o rt n ote for th e O c t o b e r issue of th e Quarterly Journal of Science, edited from th e R o y a l In s titu tio n by P ro fessor W illia m B ran de, D a v y s successor. In this h e w rote:
C o n c e r n e d a t t h e lack o f d e t a i l in D o b c r e i n e r ' s a c c o u n t o f his e x p e r i m e n t o n t h e c o m b i n a t i o n of ox y g en a n d h y d r o g e n . W i l l i a m H e r a p a t h . a n a n a l y t i c a l c h e m i s t w h o l a t e r b e c a m e P r o f e s s o r o f C h e m i s t r y a n d T o x ic o lo g y a t t h e B r isto l S c h o o l o f M e d i c i n e , r e p e a t e d t h e e x p e r i m e n t s in O c t o b e r 1 8 2 3 . u s i n g t h e a p p a r a t u s s h o w n h e r e , a n d r e a d a p a p e r to t h e n e w l v - f o r m e d B ristol P h i l o s o p h i c a l S o c ie ty o f I n q u i r e r s v e r y so o n a f t e r t h e p u b l i c a t i o n o f F a r a d a y ' s b r i e f n o t e . H y d r o g e n a n d o x y g e n w e r e s u p p l i e d f r o m t h e tw o b l a d d e r s a n d p a s s e d o v e r t h e s p o n g y p l a t i n u m in t h e vessel P h e l d in a c a p s u l e
227
A most extraordinary experiment has been m ade by M. Dobereiner. It was com municated to me by M. Hachette; and having verified it I think every chemist will be glad to hear its nature (22). L a te r in the sam e y ea r F a r a d a y p r e p a r e d a review of th e w ork so far ca rried out, O n the A c tion of P la tin a o n M ix tu r e s of O x y g e n , H y d r o g e n a n d o th e r G a s e s (23). In this, after d e s c rib in g D o b e r e i n e r s ex p e rim e n ts , he reviewed D u lo n g a n d T h e n a r d s p a p e rs m o s t favo urab ly a n d w e n t o n to m e n tio n a p a p e r by W illiam H e r a p a t h of Bristol w h o h a d re p e a te d D o b e r e i n e r s e x p e rim e n ts in O c to b e r 1823 a n d co nfirm ed t h a t the p l a t i n u m u n d e r w e n t no che m ic al c h a n g e a n d th a t o th e r m etals did not give th e sa m e effect (24), a n d to o ne A le x a n d e r G a rd e n , a ch em ist of O x fo rd S tre e t, L o n d o n , w h o h a d s h ow n th a t the black re sidue left w h e n c ru d e p l a t i n u m is dissolved in a q u a regia w a s also active in the s a m e way (25). However, F a r a d a y t u r n e d to o th e r m a tte rs a n d did not r e tu r n to this subject for a fu rth e r ten y e a rs , as will a p p e a r late r in th is c h a p te r. I n 1825 H u m p h r y D av y m a d e his only reference to th e p h e n o m e n o n since his original discovery, a n d in a r a t h e r o b s c u re place. In 1818 he h a d p u b lish e d a book O n th e Safety L a m p . . . w i t h S o m e R e se a rc h e s o n F l a m e , b u t in 1825 he w as m oved to p u b lish a second e d i t i o n b e c a u s e his experience, as he w ro te in the preface having shewn that the precautions which it was intended to describe either are not known or are not attended to, I have thought it might assist the cause of humanity to advertise the book a second tim e (26). T h i s edition co n tain e d several a p p e n d ic e s , a n d in A p p e n d ix No. 2 he re tu r n e d to th e subject a n d to th e later w ork o f D o b e re in e r w ith finely divided p l a t i n u m such as E d m u n d D a v y h a d used, a n d o f D u lo n g a n d T h e n a r d , w h o h a d s h o w n th a t various metals in a finely divided state have the same property of hastening or producing combinations at a lower temperature than those at which they usually occur. D a v y continued: It is probable that the rationale of all these processes is of the same kind. Whenever any chemical operation is produced by an increase of temperature, whatever occasions an accum ulation of heat, must tend to give greater facility to the process; a very thick wire of platinum does not act upon a mixture of oxygen and hydrogen, at a heat below redness; but if beat into thin laminae, it occasions its com bustion at the heat of boiling mercury, and, when in the form of the thinnest foil, at usual temperatures. I cooled the spongy platinum to 3 of Fahr., and still it inflamed hydrogen nearly of the same temperature, issuing from a tube cooled by salt and ice. It may be supposed that the spongy platinum absorbs hydrogen, or that it con tains oxygen; but neither of these hypotheses will apply to the fact that I first observed, of the ignition of fine wires in different mixtures of inflammable gases and air, at temperatures so far below ignition. Im m e d ia te ly after the p u b l i c a t i o n of this sec o n d e d itio n D a v y b e c a m e ill a n d e x h au sted, a n d after four years of w a n d e r i n g in E u r o p e h e d ied in G e n e v a a t the early age of 50 o n M a y 29, 1829.
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In the meantime William Henry (1775-1836), the Manchester chemist and manufacturer, had carried out an investigation on the use of Dobereiners reac tion in the analyses of gases, using the latters pellets of china clay and platinum sponge (27) while Edward Turner (1796-1857), later to become the first professor of chemistry at University College, London, but then an extra-mural lecturer in Edinburgh, read a paper to the Royal Society of that city on the applications of Dobereiners discovery to eudiometry (28). Again he made use of small pellets of pipe-clay mixed with spongy platinum, dried and then fired in a spirit lamp. He found that the action of platinum affords a neat and expeditious method of ascertaining the purity of hydrogen or oxygen, but could not agree with Henry that platinum could be helpful in gas analysis.
The Contact Process for Sulphuric Acid As early as 1831 the industrial possibilities offered by heterogeneous catalytic oxidation were grasped by a young man engaged, with his father and the latters partner, in the manufacture of vinegar in Bristol, an enterprise started in 1824
P H I L L I P S ' S P E C IF IC A T IO N . TO A LL TO WHOM THESE PRE8ENT8 S H A L L COME, I, Peikokine P hillips , Junior, o f Bristol, Vinegar Maker, send greeting. W HEREAS H is present most E xcellen t Majesty K in g W illiam the Fourth, b y H is Letters Patent under the G reat Seal o f (irea t Britain, bearing date 5 at W estm inster, the Tw enty-first day o f March, in the first year of His reign, did, for Himself, H is heirs and successors, give and grant unto me, the said Perigrine Phillips, His especial licence, sole privilege and authority, that 1 the said Peregrine Phillips, my exors, adniors, and assigns, or such , others aa 1 the said Peregrine Phillips, m y exors, admors, or assigns, should , 10 at any time agree with, and no others, from time to time and at all times during the term o f yeare therein mentioned, should and law fully might make, use, exercise, and vend, within Eugland, Wales, and the Town o f Berw ickupon-Tweed, my Invention o f C u t a i i Ixrzovxaxvrs ur M a m in cm Sultxttxic Acu coxhovlt CALI.TO 0 u or Virxioi; in which said Letters Patent 15 is contained a proviso that I, the said Peregrine Phillips, shall cause a parti cular description o f the nature o f m y said Invention, and in w hat manner the same is to be performed, to be inrolled in H is said M ajestys H igh Conrt oi Chancery within six calendar months next and immediately after the date o f the said in part recited Letters Patent, as in and by the same, 20 reference being thereon to had, w ill more fully and at large appear. NOW KNOW Y E , that in compliance with the said proviso, I, the said Peregrine Phillips, junior, do hereby declare that the nature o f my said im provements are herein set forth and explained; but for the better understanding
The patent specification filed by the m y ste rio u s P e r e g rin e Phillips in 1831 for the m anufacture of sulphuric acid by passing sulphur dioxide and air through a platinum tube con taining finely divided platinum. Apart from the fact that he was the son of a vinegar m anufacturer in Bristol nothing is known of him or of how he acquired his knowledge of chemistry. A year after the patent was granted the vinegar business closed and Peregrine Phillips, although still a young man. was never heard of again
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a n d tra d in g as Phillips, T h o r n e a n d Co. F a t h e r a n d son w e re b o th n a m e d P eregrine Phillips, a n d the y o u n g e r one w ith d re w from the p a r tn e r s h i p in 1831. U n fo rtu n a te ly n oth in g is k n o w n a b o u t this y o u n g m a n d esp ite a m eticu lou s research c a rrie d out in the local records in 1926 by S ir E rn e s t Cook, a d ist ing uished c h e m ist w h o b e c a m e L o r d M a y o r of Bristol, except th a t his fa th e r h a d b e e n a tailor from 1803 until t h e e s ta b lis h m e n t of the v ineg ar firm a n d th a t only a y e a r after th e s o n s w ith d r a w a l the bu sin ess w as a b a n d o n e d a n d th e p rem ises sold at auction. (29) N o n e the less P ere g rin e j u n i o r m ust have a c q u ir e d a n a d e q u a t e k n ow ledg e of ch e m istry to bec o m e one of t h e relatively few m en to devise a n entirely new ch em ical process, in his case th e m a n u f a c t u r e of s u lp h u ric acid. H is p a t e n t No. 6096 covers C e r t a i n I m p r o v e m e n t s in M a n u f a c t u r i n g S u lp h u r ic A c id c o m m o n ly called O il of Vitriol. T h e specification states: The first improvement then, namely, the instantaneous union of sulphurous acid with the oxygen of the atmosphere, I effect by drawing them in proper proportions by the action of an air pump or other mechanical means th ro an ignited tube or tubes of platina, porcelain, or any other m aterial not acted on when heated by the sulphurous acid gas. In the said tube or tubes I place fine platina wire or platina in any finelydivided state, and I heat them to a strong yellow heat, and by preference in the chamber of a reverberatory furnace; and I do affirm that sulphurous acid gas being made to pass with a sufficient supply of atmospheric air through tubes as described, properly heated and managed, will be instantly converted into sulphuric acid gas, which will be rapidly absorbed as soon as it comes into contact with water. In the following y ea r P ro fe ss o r G u s ta v M a g n u s of th e U n iv ersity of Berlin p u b lis h e d a brief review of P h i l l i p s p ro p o s e d process, co n firm in g his findings b u t dra w in g a tte n tio n to th e fact t h a t th e p l a t i n u m p o w d e r w as effective only at high te m p e r a tu re s (30). It was, how ever, to be a n o t h e r seventy y ea rs before the process was a d o p te d in in d u s try after s o m e fu r th e r re s e a rc h in to th e co n dition s re q u ire d for c o m m ercial success; d etails of this a r e set o u t in C h a p t e r 21.
F a ra d a y s Return to the S u b ject

T e n years after his review of th e w o rk of D o b e re in e r a n d T h e n a r d , F a r a d a y h a d o ccasion to take up a g a in th e c u r io u s p h e n o m e n o n he h a d th e n discussed. In the m id d le of his classic r e s e a rc h e s on elec tro ch e m istry , believing th a t h e h ad established th e co n s ta n t c h e m ic a l a c tio n of a given q u a n t i t y of electricity a n d busily co nstructin g his new v o lta m e te r, he was m ystified b y th e p e c u lia r re a c tio n of th e p la tin u m electrodes o n th e gases p r o d u c e d in electrolysis: I was occasionally surprised at observing a deficiency of the gases resulting from the decomposition of water and a t last an actual disappearance of portions which had been evolved, collected and m easured. H is im m e d ia te re a c tio n w a s th a t this arose from a co m p letely new p h e n o m e n o n th a t re q u ire d t h o r o u g h investigation, a n d in the long p a p e r he read to th e R oyal Society i n j a n u a r y 1834 (31) he wrote:
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These experiments reduced the phenomenon to the consequence of a power possessed by the platina, after it had been the positive pole of a voltaic pile, of causing the combination of oxygen and hydrogen at common, or even at low, temperatures. This effect is, as far as I am aware, altogether new. H e went o n to em p h a sis e th a t this p ro p e rty of in d u c in g c o m b i n a t i o n w as the sam e as th a t discovered b y D b e re in e r to belong in so e m in e n t a d eg ree to spongy p l a t i n a , a n d t h e n t u r n e d to th e d iscu ssion of a th e o ry a d v a n c e d som e years earlier by a p h y s ic ia n in F lo ren ce, A m b ro g io F u sin ie ri (1 7 7 3 -1 8 5 3 ). I n his p a p e r (32) F usinieri c o n te n d e d th a t d u rin g th e re actio n s first observed by H u m p h r y D avy co nc rete l a m i n a e of th e c o m b u s tib le s u b s ta n c e c o u ld b e seen on the p la tin u m surface, these th e n d is a p p e a rin g by b u rn in g . H e p ro p o s e d the con cep t of native c a lo ric (calorico nativo) as a n ex p la n a tio n . F a r a d a y h a d learn t I ta lia n d u rin g his E u r o p e a n to u r w ith S ir H u m p h r y a n d L ad y D avy in th e years 1813 to 1815, b u t h e was p u zz le d b y th e r a t h e r arch aic lan g u ag e in w hich F u s in ie ris p a p e r w as w ritte n a n d confessed th a t h e could not form a distinct idea of the p o w e r to w h ic h he refers th e p h e n o m e n a . ( F a r a d a y s difficulties in this co n n e c tio n have b e e n d iscussed m o re recently by Professor A. J. B. R o b e rts o n a n d tw o of his colleagues (33)). T h e th eory th e n ad v a n c e d by F a r a d a y involved th e s im u lta n e o u s a d s o r p tio n of b o th re a c ta n ts on th e p l a t i n u m surface, th e only essential c o n d itio n b ein g a perfectly clean a n d m etallic surface: T he effect is evidently produced by most, if not all bodies, weakly perhaps by many of them, but rising to a high degree in platina . . . T h e platina is not considered as causing the combination of any particles with itself, but only associating them closely around it. A lth o u g h a ce n tu ry a n d a half late r this p h e n o m e n o n re m a in s s o m e th in g of a m ystery to chem ists, F a r a d a y was in deed close to th e t r u t h of th e m a tte r.
T h e E n terp rise o f F rdric K u h lm a n n

Im p o r t a n t investigations into th e p ro d u c ti o n of b o th nitric a n d s u lp h u ric acids by passing th e a p p r o p r ia te gases over h e a te d p l a t i n u m w e re c a rrie d out in F ra n c e by a n energetic a n d en te rp ris in g chem ist a n d m a n u fa c tu re r , F rd ric K u h l m a n n (1803-1881). C o m b in in g th e Professorship of In d u s tria l C h e m is tr y at the U niversity of Lille w ith in d u s tria l p rojects after stu d y in g u n d e r V a u q u e lin , he h a d stu d ied the w ork of H u m p h r y a n d E d m u n d Davy, D b e re in e r a n d T h e n a r d . H e w as also greatly in tere ste d in th e p a r t p la y e d b y n itro g e n p r o d u c ts in agriculture, a n d in fact in later y ea rs c a rrie d o u t investigations o n the use of a m m o n iu m salts as fertilisers on his o w n estate. W i t h this as his b a c k g ro u n d , K u h l m a n n w ent to w ork vigorously o n the nitric acid p rob lem , a n d fou nd th a t by p assing a m ix tu r e of a m m o n i a a n d air over p la tin u m sponge h e a te d to a b o u t 3 00C in a glass t u b e he o b t a i n e d nitric acid. H e filed a p a t e n t a p p lic a tio n for this inv en tio n in D e c e m b e r 1838. (34) A t this tim e s a ltp etre w as readily a n d ch e a p ly available, a n d th e n ew process
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c o u ld not offer any co m m e rc ia l a d v a n ta g e , b u t in th e c o u rse of a p a p e r given to th e A c ad m ie in the sa m e year, K u h l m a n n m a d e these p ro p h e tic re m a rk s : If in fact the transformation of ammonia to nitric acid in the presence of platinum and air is not economical, the time may come when this process will con stitute a profitable industry, and it may be said with assurance that the facts pre sented here should serve to allay completely any fears felt by the government on the difficulty of obtaining saltpetre in sufficient quantities in the event of w ar. (35) O n the sam e d ay as his p a t e n t for a m m o n i a o x id a tio n w as g ra n te d K u h l m a n n secured a second p a t e n t for th e m a n u f a c t u r e of s u lp h u ric acid by the ox id atio n of s u lp h u r dioxide over finely divided p l a t i n u m s u p p o r te d on glass or o th e r m aterial not atta c k e d b y the acid (36). H e w as p r o b a b ly a w a re of P eregrin e P h illip s p a t e n t of 1831, filed o nly in E n g la n d , b u t u nlik e Phillips he w as able to p u t his idea into p r a c t i c e in th e c h e m ic al firm t h a t he founded, E ta b liss e m e n ts K u h l m a n n at L o o s, a lth o u g h it w as a g a in very m a n y years before it b e c a m e a full scale c o m m e r c ia l process.
B erz eliu s C oins th e T erm C ata ly sis

It m a y have b e e n noticed th a t t h r o u g h o u t this c h a p te r, o th e r t h a n in its h eadin g, th e w o rd c a ta ly sis has h a r d ly b e e n used. It w a s not in fact ever em p lo y ed by th ose whose researches have b e e n described, b u t w as co in ed b y J . J . Berzelius only in 1836. In his a n n u a l r e p o r t to th e S w e d is h A c a d e m y of Sciences for the previous y ea r he reviewed som e o f th e re su lts of these w o rkers a n d realising th a t th e re m u st b e a c o m m o n ca use fo r this effect, he coined a n a m e for it, w riting: This is a new power to produce chemical activity belonging to both inorganic and organic nature, which is surely more widespread than we have hitherto believed and the nature of which is still concealed from us. W hen I call it a new power, I do not mean to imply that it is a capacity independent of the electrochemical properties of the substance. O n the contrary, I am unable to suppose that this is anything other than a kind of special manifestation of these, but as long as we are unable to discover their mutual relationship, it will simplify our researches to regard it as a separate power for the time being. It will also make it easier for us to refer to it if it possesses a name of its own. I shall therefore, using a derivation well-known in chemistry, call it the catalytic p o w e r of the substances, and decomposition by means of this power catalysis , just as we use the word analysis to denote the separation of the component parts of bodies by means of ordinary chemical forces. Catalytic power actually means that substances are able to aw aken affinities which are asleep at this temperature by their mere presence and not by their own affinity (37). T h u s we owe to Berzelius, to his p e r c e p tio n a n d his gift for enric h in g ch e m is try w ith a p p r o p r ia te te rm in o lo g y , a te rm th a t has c o m e to signify a p h e n o m e n o n of vital a n d fa r-re a c h in g i m p o r t a n c e in m o d e r n ch e m ic a l in d u s try a n d one associated p re -e m in e n tly w ith th e p l a t i n u m m etals.
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References for C hapter 12 85 1 H. Davy, Phil. Trans. Roy. Soc., 1817, 107, 77
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3 4 5
6 8
9
10
11
12
13
14 15 16 17 18 19
20 21
22
23
24 25 26
27 28 29 30
31
32 33 34 35 36
Letter from Davy to John Buddie, British M useum Add. MSS 33963 f 114 E. Davy, Phil. Mag., 1812, 40, 209-220; 263-278; 350-365 E. Davy, Phil. Trans. Roy. Soc., 1817, 107, 136-157 E. Davy, Phil. Trans. Roy. Soc., 1820, 110, 108125 E. Davy, J .fiir Chem. ( Schweigger), 1821, 31, 340-356 J. W. Dobereiner, Ann. Phys. ( Gilbert), 1822, 72, 193-198 J. W. Dobereiner, J .fiir Chem. (Schweigger), 1823, 38, 321-326 J. Schiff, Briefwechsel zwischen Goethe und Johann Wolfgang Dobereiner, Weimar, 1914, letter 94, July 29, 1823 J .fiir Chem. (Schweigger), 1823, 38, 321-326; Ann. Phys. (Gilbert), 1823, 74, 269 273 O. Schade, Briefe des Grosherzogs Carl August und Goethe an Dobereiner, Weimar, 1856, letter 21, August 9, 1823 J. W. Dobereiner, J .fur Chem. (Schweigger), 1823, 39, 3-4 J . des Debats, 1823, August 24, 4 P. L. Dulong and L. J. Thenard, Ann. Chim., 1823, 23, 440-443 P. L. Dulong and L. J. Thenard, Ann. Chim., 1823, 24, 380-387 A. Pleischl, J .fiir Chem. ( Schweigger), 1823, 39, 142 159 A. Pleischl, J . fur Chem. (Schweigger), 1823, 39, 201-205; 351-356 J. J. Berzelius, Jahres-Bericht, 1825, 4, 60-61 P. Collins, The Development of Heterogeneous Catalysis, 1817-1823, Thesis sub mitted in ju n e 1974, University of Oxford: Ambix, 1976, 2 3 ,9 6 -1 1 5 Letter from J. N. P. Hachette to Faraday, September 16, 1823, I.E.E. Archives M. Faraday, Royal Institution Laboratory Notebook No. 8, 81 M. Faraday, Quart. J . Science, 1823, 16, 179 M. Faraday, Quart. J . Science, 1823, 16, 375 377 W. Herapath, Phil. M ag, 1823, 62. 286-289 A. Garden, Ann. Phil., 1823, 22, 466 467 H. Davy, O n the Safety Lamp for Preventing Explosives in Mines, Houses Lighted by Gas, Spirit Warehouses, or Magazines in Ships etc., with Some Researches on Flame, 1825, Appendix 2, pp 148-151 W. Henry, Phil. Trans. Roy. Soc., 1824, 114, 266-289 E. Turner, Edin. Phil. J ., 1824, 11, 99-113; 311-318 Sir Ernest Cook, Nature, 1926, 117,419-421 H. G. Magnus, Ann. Phys., ( Poggendorff), 1832, 24, 610-612 M. Faraday, Phil. Trans. Roy. Soc., 1834, 124, 55-122 A. Fusinieri, Giornah di Fisica, 1824, 7, 371-376 M. Farinelli, A. L. B. Gale and A. J. B. Robertson, Ann.Sci., 1974,31. 19-20 F. Kuhlmann, French Patent 11331 F. Kuhlmann, Compte Rendus, 1838, 7, 1107 1110 F. Kuhlmann, French Patent 11332 J.J. Berzelius, Jahres-Bericht, 1836, 15. 243; Ann. Chim., 1836, 6 1, 146 151 233
P e te r G r i g o r i e v i c h S o b o le v s k y
T he son of a surgeon. Sobolevsky served in the army until 1804 when he took up an ad m in istrative and technical career. In 1826 he was appointed D irector of the large new chemical laboratory just erected for the M ining C adet Corps in St. Petersburg and here he devised a successful process for the extraction and refining of Russian p latin um . His bust in the library of the Mining Institute com m em orates this achievem ent
1781-1841
13
The Foundation of the Russian Platinum Industry
Anxious to find a sure m arket f o r the new precious m etal whose production p r o m is e d to he rich and considerable, the Finance M inister Count K a n k rin p la n n e d to e m p lo y it as coinage.
E R N ST K H R IS T IA N O V IC H FR IT SM A N
S om e years before its a c tu a l or official discovery ru m o u r s h a d b e e n c irc u latin g th a t p la tin u m w as to b e fou n d in R u ssia . In 1806, for exam ple, V a u q u e l in wrote:
A rumour has spread for some years that platinum has been discovered in Siberia but this has not yet been confirmed (1).
A gain, G u y t o n de M o rv e a u , w ritin g o n p l a t i n u m in 1810, m e n tio n e d th at:

it has also been let drop, without denial, and no doubt prematurely, that this metal exists in Siberia (2).
It was not until 1819, however, th a t sm all pieces of a heavy w h ite m etal found in the gold fields o n the e a s te rn slopes of th e U r a ls s o u th of E k a t e r i n b u r g (now Sverdlovsk) w ere b r o u g h t to th e a tte n tio n of a n y o n e in a u th o rity . T h e R u s s ia n e s tab lish m en t w as m u c h m o re fa v ourably p la c e d t h a n th e S p a n is h au tho rities in C o lu m b ia h a d b e e n to deal w ith su ch a discovery. S ince a b o u t 1745 gold m in in g h a d b e e n c a rrie d o n in this area, a n d th e re w as a m in in g lab o ra to ry in E k a te r in b u r g to w h ic h s am p les of th e new w h ite m e ta l w e re sent for exam in atio n. I n 1822 th e D ire c to r of th e la b o ra to ry , Ig n a ty e v itc h V arv insky (1797-1832) b e g a n a stu d y of these sam p les a n d finding th a t th ey c o n ta in e d p la tin u m sent a fu rth e r sp ecim en to St. P e te rs b u r g for e x a m in a tio n in the chem ical la b o ra to ry of th e M in in g C a d e t C o rp s t h a t h a d b e e n esta b lis h e d by C o u n t M u s s in -P u s h k in in 1804. T h e analysis w as c a rrie d o u t b y Vasily Vasilyevitch L y u b a rs k y (17951852), w ho sh ow ed it to be o s m irid iu m , identical w ith th a t fo und in C o lo m b ia. By 1824 L y u b a r s k y was ab le to c o m p le te a q u an tita tiv e analysis show ing: irid iu m 60 p e r cent, o s m iu m 30 p e r cent, p la tin u m 2 p e r cent, gold 0.7 p e r c e n t a n d iron 5 p e r cent.
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In A u g u st of the sam e y e a r th e first native p l a t i n u m w as fou nd in gold p lace rs to th e n o rth of E k a t e r i n b u r g a n d f u r th e r sim ilar discoveries quickly followed in the n e ig h b o u rh o o d o f G o r o b l a g o d a t w h e re th e re w a s a n iro n works m a n a g e d b y Nikolai R o d io n o v ic h M a m y s h e v , a m a n w h o not only lo cate d these d eposits b u t w ho was to p lay a n i m p o r t a n t p a r t in th e early refining of R u s s ia n p latin u m . In the y ea r 1825 eleven p o o d s, or 180 k ilogram s, of native p l a t i n u m h a d been collected a n d sent to St. P e te rs b u r g , w h e re it was a n a ly s e d a n d re p o rte d to c o n ta in 87 p e r cent of p la tin u m w i t h gold, silver a n d th e o th e r p l a t i n u m m etals. T h e earliest analyses of th e R u s s i a n dep o sits m a d e in W e s te r n E u r o p e w ere r e p o rte d by A n d r L a u g ie r ( 1 7 7 0 - 1 8 3 2 ) F o u r c r o y s cou sin a n d his successor at th e M u s u m d H isto ire N a tu r e lle . T h e s e w e re c a rrie d o ut o n tw o q u ite small a n d different sam p les th a t t h e fam ous G e r m a n n a tu ra lis t a n d traveller e x tra o rd in a ry A le x a n d e r von H u m b o l d t h a d m a n a g e d to secure after tw o years of fruitless a t t e m p t s (3). L a u g i e r sho w ed t h a t o n e s a m p le from th e gold b e a rin g s a n d s gave 67 p e r cent of p l a t i n u m , w hile th e o ther, from E k a te rin b u rg , show ed rou ghly 25 p e r cent of o s m irid iu m , only 20 p e r ce n t of p la tin u m , 50 p e r cent iron w ith small a m o u n ts of copper, a n d rh o d iu m , b u t no p a llad iu m . In J u n e 1825 even rich e r d e p o sits ru n n in g a t a b o u t 83 per c e n t of p la tin u m , b e g a n to be located to th e n o rth -w e s t of E k a t e rin b u rg , in th e d istrict of N i z h n y T a g il o n la n d belonging to th e a n c ie n t a n d n oble fam ily of th e D e m id o v s w ho ow n e d profitable gold, silver a n d c o p p e r m in es in the area. W h ile little d ev elo p m e n t work was taking p lace i n th e G o r o b la g o d a t field, th e D e m id o v s w ere highly energetic a t N i z h n y - T a g il a n d th e ir o u t p u t in cre ased ra p id ly , th e h ea d of th e family, C o u n t N ikolai N ik itic h D e m id o v (17741828) sen d in g four y oun g m e n to be tra in e d at th e M in in g A c a d e m y in F re ib e rg ac c o rd in g to a letter from P rofessor A u g u s t B reith au p t, t h e P rofessor of M in e ra lo g y th e r e (4), w h o h a d a lre a d y m a d e a stu d y of th e R u s s i a n deposits (5).
P la tin u m D ecla red a State M o n o p o l y

T h e im p o rta n c e of th e discoveries of 1824 a n d 1825 w as no t lost u p o n the Im p e ria l R u s s ia n G o v e rn m e n t w h o at once d e c la re d p l a t i n u m to b e a S ta te M o n o p o ly , in w hich no dealing s c o u ld ta k e p la c e except u n d e r licence. W h ile p riv a te individuals were allow ed to c o n d u c t t h e m in in g o peration s, all refining w as to take p lace u n d e r th e c a r e of th e St. P e te rs b u r g M i n t a n d no ex po rt of native m etal was allowed. A tax o f 10 p e r ce nt w a s levied on p riv ate o u tp u t, b u t t h e owners w ere allowed to d is p o s e of it, s u b ject to licence a n d p rio rity of S ta te d e m a n d . T h e a d m in is tr a tio n o f this o rd e r c a m e u n d e r th e D e p a r t m e n t of M in in g a n d Salt In d u stry . F r o m th e b e g in n in g , however, th e cond itio n s of S ta te M o n o p o ly exercised in a r e m o t e p a r t of th e c o u n try w ere very favourable to th e existence of flourishing s m u g g lin g activities a n d these d uly m a d e their a p p e a ra n c e , grow ing to such a n e x t e n t as to vitiate all t h e p u b lish e d statistics for th e R u s s ia n o u tp u t of p la tin u m e v e n long after th e S ta te M o n o p o ly h a d ceased. 236
Early R efining Processes

It is to M a m y s h e v th a t credit m u s t b e given for th e initial a t t e m p t s at refining a n d fabrication. T h e s e took place in th e U ra ls u n d e r his en erg etic lead e rsh ip . In 1825 th e re h a p p e n e d to be in his works, for th e m o m e n t w ith o u t e m p lo y m e n t, a m ining eng in ee r n a m e d A le x a n d e r N ikolaevich A rkhipov, w h o h a d a lre a d y show n a n interest in p la tin u m by w o rkin g out m e th o d s for s e p a r a tin g it from gold a n d d e m o n s tra tin g t h a t th e native m in era l excelled th a t of A m e r ic a n origin in purity, co n ta in in g u p to 75 p e r cent of p l a t i n u m . M a m y s h e v there fore t u rn e d to him w ith th e re q u est to e x a m in e the refining of th e m etal a n d its fabrication. H e gave him tw o assistants, o n e a fellow m in in g en g in e e r n a m e d G. A. J o s s a a n d th e o th e r a works m e c h a n ic , V. Sysoev, a n d th e w ork b e g a n in the lab o ra to ry of th e K ushvinsk y works at G o r o b la g o d a t. T h e process u sed w as th a t of J a n e ty , b y w h ich p la tin u m w as re n d e re d m a lle a b le by m e a n s of arsen ic; even in th a t re m o te n eig h b o u rh o o d k n o w led g e of this process existed a n d was em ployed w ith a q u ite co n s id e ra b le d egree of success. F ollo w in g M a m y s h e v s suggestions, they b e g a n b y m a k in g a p l a t i n u m ring, followed by a teasp o o n , a n d then Sysoev m a d e a n in k -s ta n d from all th re e m etals p r o d u c e d in th e G o ro b la g o d a t area, cast iron, gold a n d p la tin u m . T h e n c a m e a little ch a in , som e p rim in g -p a n s for pistols a n d finally a n a lta r shrin e o r ta b e r n a c le of c o n s id e ra b le size. N ext A rkhipov m a d e u p alloys of c o p p e r a n d p l a t i n u m (20:80 a n d 33:67) for w h ich he claim ed v alu ab le p ro p e rtie s in colour, m a lleab ility a n d ta rn is h resistance, a n d ne also e x p e rim e n te d in th e d e c o ra tio n of glass a n d p o rc e la in by m eans of th e new m etal. L ast of all, also in 1825, M a m y s h e v su g gested th a t it should be a p p lied to coinage (6). T h a t all this w ork s h o u ld have b e e n so successfully c o n d u c te d in a works la b o ra to ry in a d is ta n t p a r t of th e U ra ls, w h e n tra n s p o rt was slow or non-existent, is a n e n o rm o u s trib u te to the en e rgy a n d know ledge of M a m y s h e v a n d his assistants. Several of the articles they m a d e a re still preserved in the M in in g I n s titu te a t L en in g ra d .
T h e W ork o f S o b o le v sk y
W h ile this w ork w as takin g p lace in th e field, o th e r re se arc h es w e re b eing actively p u rs u e d in St. P etersb u rg . T h e s e w e n t o n in the c o m b in e d l a b o ra to ry of the M in in g C a d e t C o rp s a n d th e D e p a r t m e n t of M i n i n g a n d S alt In d u s try , to w hich th e G o v e rn m e n t h a d released 20 p o u n d s of G o r o b la g o d a t p l a t i n u m for ex p erim en tal p u rp o se s in 1826. T h e w ork w as p u t u n d e r a very ab le a n d highly qualified chem ist, P eter G rigo riev ich Sobolevsky (1781 1841), th e o u ts ta n d in g figure in this p erio d of th e history of p l a t i n u m in R u ssia , w h o h a d as his chief assistant the very c a p a b le ch em ist L y ub arsky . S obolevskys first ac tio n on tak in g up th e w ork was to se n d to th e U ra ls for Sysoev, in o rd e r th a t h e m ig h t r e p e a t th e w ork of A rk h ip o v a n d d e te r m in e w h e th e r th e arsenic process w as satisfactory for larger-scale work. H e soon decided th a t it w as not, since it took several d ays to p r e p a r e a single p o u n d of p latin u m , it w as d an g e ro u s to th e w orkers a n d it co uld be a p p lie d only to very
237
In S obolev s k y s p r o c e s s , d e v i s e d b e f o r e W o l l a s t o n h a d p u b l i s h e d his m e t h o d , t h e p l a t i n u m p o w d e r w a s p a c k e d i n t o t h e m o u l d a , c o v e r e d w ith t h e ste el c y l i n d e r b a n d p u t u n d e r t h e sc rew p r e s s c. T h e r e s u l t i n g disc s w e r e t h e n b r o u g h t to a w h i t e h e a t w h i l e still in t h e m o u l d a n d a g a i n c o m p r e s s e d . T h e y w e r e t h e n s u f f ic ie n tly c o m p a c t t o be f o r g e d a n d r o l le d i n t o s h e e t
sm all pieces. So he a n d L y u b a r s k y set to w o rk to find a new process, first e x a m i n ing all the w ork th a t h a d b ee n c a r r i e d ou t in W e s te r n E u r o p e as far as it was re cord ed in accessible literature. By 1827 Sobolevsky was a b le to re a d a p a p e r to th e A n n u a l M e e tin g of the Scientific C o m m itte e of the M i n i n g C o r p s a n d the D e p a r t m e n t of M in i n g a n d S alt Indu stries. H e prefaced his a c c o u n t of th e ir process w ith a very co m p lete s u m m a ry of th e results of e a rlier w orkers, a n d there fore it is possible to see how som e m odifications a n d im p ro v e m e n ts w ere in tro d u c e d in th e R u s s ia n work. T h e native m etal w as c h a rg e d i n t o a re to rt c o n n e c te d w ith a co u p le of receivers c o n ta in in g w ater, a n d boiled w i t h four tim es its w e igh t of a q u a regia. After boiling do w n to a thick con sistency, th e liq u o r was p o u r e d off from th e black insoluble residue a n d e v a p o r a te d to dryness, w hile a fresh p o rtio n of ore was t re a te d in th e retort. T h e e v a p o r a te d m a te ria l w a s ta k e n u p in ho t w ater, filtered a n d tre a te d w ith a cold s a t u r a te d so lu tio n of sal-a m m o n ia c . T h e p r e p a r a tio n of m a lle a b le m e ta l from th e ca lc in ed c h lo ro p la tin a te followed u p o n a n observ ation m a d e b y Sobolevsky w h e n try in g to m elt the p la tin u m spon ge in a c a rb o n -lin e d crucible. H e noticed th e a g g lo m e r a tio n of the
238
m etal and, a p p ly in g co m p re s s io n in a screw press, o b ta in e d a fragile m etallic cake. T h is h e h e a te d to a w hite h e a t a n d a g a in a p p lie d c o m p re s s io n to give a satisfactory m a lle a b le metal. H is large-scale w o rk in g involved p re ssin g the spongy m etal w hile cold: We pack cold refined platinum in the form of sponge very tightly in a thick iron circular mould of a chosen size (this mould can equally be in any other form; the round appeared to us to be the more convenient); we press it with the strong compres sion of a screw-press, and having extracted it from the mould, we have a dense round tablet with a metallic sheen. In this state the platinum disc has as yet no malleability and the cohesion of the particles among themselves does not resist a strong blow; it fractures and crumbles up. To convert such discs into malleable platinum, it is only necessary to heat them to a white heat and at this temperature to subject them to the pressure of the same press. From a single compression the disc of platinum entirely alters its appearance; its granular structure becomes dense and it becomes completely malleable. T he size of the tablets does not make any difference in this affair; large and small discs at a single compression become equally malleable and ductile. After this pressing the discs are forged into strips or rods of any desired form. Sobolevsky a n d his R u s s ia n followers claim t h a t he evolved this process himself, b u t th e first p a r t of the p a p e r of 1827 in w h ic h he describes it show s th a t he was well a c q u a in te d w ith th e w ork of m ost of t h e m e n w h o h a d w o rked on p la tin u m in W e s te rn E u ro p e d o w n to th a t time. H e m e n tio n s th e w ork of B aru e l b u t not th a t of C ock; he knew a b o u t B r e a n t s w ork b u t not th e n a t u r e of his process; in 1827 W o l l a s t o n s w ork h a d not yet b e e n p u b lish ed . T h e screw press is rem in iscent of Cock, b u t th e sim plicity of S obo lev sky s process does him credit. In ju s tific a tio n of his claim , he h im self p o in ts ou t th ese differences: in the final form of his process th e spo nge is first p ressed cold, th e first cake is h e a te d to whiteness s e p a ra te from th e m o u ld a n d it is p ressed only once afte rw a rd s, w ith such h a m m e r in g as is necessary for fabrication. I n all th ese re sp ects his p r o c e d u re differs from C o c k s, as Sobolevsky him self says in a footnote to his p ap e r. T h e p l a t i n u m was now available in pieces of a n y desire d size, th e re was practically no loss in refining, a n d it gave re lia b le results. Sobolevsky first d e m o n s tra te d his process in J a n u a r y 1827 after p ro d u c in g 20 p o u n d s of refined metal, a n d o n th e following M a r c h 21st he m a d e it fully p u b lic to a n a s se m b ly of the Scientific C o m m itte e of the M in in g C o rp s a n d D e p a r t m e n t of M i n i n g a n d Salt In d u stry , a full a c co u n t b eing p u b lis h e d in th e R u s s ia n M ining Journal for 1827 (7). W h e n re a d in g the p a p e r he d isp lay ed a n u m b e r of objects m a d e of platin u m , inclu d in g som e m edals, wires, dishes, crucibles a n d several ingots, one of w hich w eighed 6 pounds. Platinum prepared by us was used for the stamping of medals and counters; not a small part of it was also used by goldsmiths who showed that articles could be made out of it, and these showed that this platinum was not inferior in this respect to that prepared by the French. O n e series of m ed als was struck in p l a t i n u m to c o m m e m o r a te th e c o ro n a tio n of th e T s a r N ich o las I in 1826. A sp ec im e n has survived in the po ssession of J o h n s o n M a t t h e y a n d is illu stra te d over page.
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T o c o m m e m o r a t e t h e c o r o n a t i o n o f t h e T s a r N i c h o l a s I in 1826 m e d a l s w e r e s t r u c k in p l a t i n u m f r o m t h e r e c e n t l y d i s c o v e r e d d e p o s i t s in t h e I r a ls. T h e o b v e r s e sh o w s t h e h e a d of t h e e m p e r o r w i t h t h e i n s c r i p t i o n :
I li s M a je s ty N ic h o la s I. E m p e r o r a n d A b s o lu te K ille r o f A ll R u s s ia .
T h e rev e r s e r e a d s :
A P le d g e o f H a p p in e s s f o r O n e a n d A ll. C ro w n e d in M oscow 1 8 2 6 .
T h e m e d a l s w e r e 5 c e n t i m e t r e s in d i a m e t e r a n d w e i g h e d 131 p r a m s
W h ile th e w ork of Sobolevsky a n d L y u b a r s k y w as going on, th e energetic M in is te r of F in a n c e a n d ex-officio h ea d of th e M in i n g D e p a r t m e n t , C o u n t E gor F ran tsev ich K a n k rin w as s e n d in g ou t sa m p le s of native p l a t i n u m to foreign ch em ists a n d scientific societies, asking th e m to ex p e rim e n t w ith it a n d re p o rt th e ir results to h im to g e th e r w i t h su g gestions for its ap p lica tio n . H e sent a p o u n d to th e R oyal Society in L o n d o n a n d h a lf- a -p o u n d to W o lla s to n ; a p o u n d each to the I n s titu t a n d the S o cit d E n c o u r a g e m e n t in F ra n c e ; h a lf-a -p o u n d to Berzelius in S w ed en a n d four p o u n d s to O s a n n in D o rp a t. T h e e n q u iry also foun d its way, p e r h a p s via th e R o y a l Society, to P. N. J o h n s o n in L o n d o n , a n d G e o rg e M a tth e y records in a l e t t e r d a t e d J u n e 9th, 1851, of w h ic h the c op y is still preserved b y j o h n s o n M a t t h e y , th at: M r Johnson twenty-four years ago supplied the Russian Government at the request of Chevalier Benkhausen (the Russian Consul in London) with every infor mation respecting the method of preparing platina, the intrinsic value, uses, and adaptation to coinage as a currency or circulating medium. But the m ost sp e c ta c u la r re s u lts c a m e from B erzelius in th e form of the p u b lic a tio n of his classic w ork o n th e c h e m ic a l p ro p e rtie s of th e m etals of the p la tin u m gro u p a n d the m e th o d s to b e u sed for th e analysis of s u b s ta n c e s c o n ta in in g th em a n d th eir s e p a r a t i o n one from a n o th e r ; these i m p o r t a n t researches will be discussed in th e next c h a p te r .
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C o u n t E g o r F r a n ts e v i c h K a n k r i n
I775-1845 As M i n i s t e r of F i n a n c e to T s a r N i c h o l a s I K a n k r i n w a s also h e a d of t h e D e p a r t m e n t of M i n i n g a n d h e it was w h o c o n c e i v e d t h e i d e a o f e m p l o y ing p l a t i n u m as c o i n a g e d e s p i t e w a r n ings f r o m A l e x a n d e r v o n H u m b o l d t
T h e In tr o d u ctio n o f P la tin u m C o in a g e
T h e grow ing o u tp u t from the m ines, co u p le d w ith th e success o fS o b o lev sk y a n d L y u b a r s k y s w ork o n refining a n d fabricatio n, u rg e d C o u n t K a n k r i n to still m ore energetic e x p lo ra tio n of th e fields in w h ic h th e new m etal m ig h t be exploited as a m e a n s of stre n g th e n in g the n a tio n a l e c o n o m y a n d b rin g in g som e m u c h needed m o n ey into th e T r e a s u ry . U n fo r tu n a te ly th e re w as not in R u s sia the sam e scope as h a d b e e n ava ila b le in W e s te r n E u ro p e . T h e r e w as n ot so m u c h scientific w o rk going on a n d there fore th e re w ere fewer la b o ra to rie s to be eq uip p ed ; th e re w as no che m ic al in d u stry to sp ea k of, a n d as for je w e lle ry the flam b o y a n t tastes of th e w e a lth y R u s sia n s w e re not a t t r a c t e d by th e dull w hite colour of th e new m etal. It w as n ecessary th erefore th a t new a n d previously u n trie d uses sh ould be sought, if th e G o v e rn m e n t a n d the c o u n try w e re to profit by th e new discovery, so K a n k r i n t u r n e d back to M a m y s h e v s su ggestion of 1824 th a t p la tin u m sh o u ld b ec o m e a coin ag e m etal. A cco rd in g ly sp ec im e n coins w ere m a d e by th e M i n t a n d in A u g u s t 1827 th e E m p e r o r a p p r o v e d th e design, b u t expressed th e w ish th a t th e o p in io n of c o m p e te n t p eo p le sh o u ld be s o u g h t . T h erefo re K a n k r i n w ro te to A le x a n d e r von H u m b o l d t , w h o w as t h e n travelling in C o lo m b ia inspecting th e p la tin u m m ines, ask ing his advice a n d se n d in g som e sam p le coins. A fter th ree m o n th s sp en t in collecting in fo rm atio n , von H u m b o l d t replied from B erlin expressing c o n s id e ra b le m isgivings a b o u t the p ro p o sa l. T h e
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Many h u n d r e d s of th o u s a n d s r o u b l e s in \ a l u e w e r e s t r u c k i n a n d c o n t i n u i n g u n til K a n k r i n ' s 10 .55 g r a m s , t h e six r o u b l e 2 0 . 7
of p l a t i n u m n c o i n s of t h r e e , six a n d t w e l v e t h e M i n t al St. P e t e r s b u r g , b e g i n n i n g in 18 28 d e a t h in 1 8 4 5. T h e t h r e e r o u b l e p i e c e w e i g h e d g ra m s a n d the tw elve r o u b le 41.4 grains
chief g ro u n d s for this w ere t h a t p l a t i n u m was available in S o u th A m eric a, and t h a t it w o uld therefore b e difficult to c o n tro l th e p ric e sufficiently to prevent d e p re c ia tio n a n d counterfeiting o f th e p ro p o s e d cu rren c y . K a n k r i n s e n th u s ia s m w as not d a m p e d , however, a n d h e replied m a in ta in in g his a r g u m e n t s a n d asking for fu rth e r co nsideratio n. B ut h e w as too im p a tie n t to w ait for th e answ e r, a n d o n M a r c h 8th, 1828, he o rd e re d t h e p r e p a r a ti o n of dies for a 3 -rou ble coin. O n April 24th issue of th e coins w a s au th o ris e d , a n d he w ro te to von H u m b o l d t sen din g him a specim en. M e a n w h i l e the w ork p ro c e e d e d on 6 -ro u b le a n d 12ro u b le coins a n d in d ue co urse issue to th e p u b lic b eg a n , a large q u a n t i t y of p la tin u m having b ee n p u r c h a s e d from C o u n t D em idov. B ut in his an xiety to avoid the troub les p re d ic ted by H u m b o l d t he seem s to have p itc h e d too high the value a t w hich th e p la tin u m was c o in ed , as will be seen a little later. T h e exciting news from R u s s i a p r o m p t e d several visits from overseas by geologists a n d others. In 1829, at t h e invita tio n of N ich o las I, a n d a t his expense, A le x a n d e r von H u m b o l d t u n d e r to o k a n e ig h t-m o n th long to u r of S ib eria a c c o m p a n ie d by G u s ta v R ose (1 7 9 8 1873), Professor of M in e ra lo g y in Berlin, a n d his colleague C h r is tia n G o t t f r i e d E h r e n b e r g (17951876). T h e i r jo u rn e y w as too hu rrie d they covered o v e r 9,000 miles for a n y intensive s tu d y of th e
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p la tin u m deposits, a lth o u g h H u m b o l d t p o in te d out h ow r e m a rk a b le it w as th a t p la tin u m was fou nd in a b u n d a n c e only o n th e w e ste rn E u r o p e a n slopes of the U ra ls while the rich gold p lace rs w e re o n th e A siatic side. S o m e tim e after th eir re tu r n R o se c o n trib u te d a p a p e r on th e geology of th e p l a t i n u m dep o sits (8). T h e n in 1831 a n A m e r ic a n m ineralogist, J a m e s D ickson, w ho h a d had experience of th e p l a t i n u m w orkings in S o u th A m eric a, p a id a visit to R u ssia. C o u n t N ikolai D em id ov h a d died th re e years earlier a n d h a d b e e n s u cc eed e d by his son A n aloti (1 8 1 2 -1 8 7 0 ) w ho w as a w ay travelling in Italy b u t D ick so n was given every assistance by his agent a n d relative Danilov. H e w a s a s to n is h e d at the collection he w a s s h o w n of large a n d b ea u tifu l sp ecim ens of native p la tin u m , som e w eighing seven or eight p o u n d s, a n d m o st of th e m d e stin ed as p re s e n ts for the cro w n ed hea d s of E uro pe. H e w e n t o n in his re po rt: T he Demidovs, Davidovs and many other Russian families are acquiring princely revenues . . . more especially since all the platina is now coined at the Imperial Mint and established as part of the current coin of the realm. T hough many hundred pounds weight of platina are coined monthly they disappear rapidly from circulation . . . I consider their price much above the London price of malleable platinum, which is at present about twenty-five shillings per ounce: considering that the crude platina is the product of the country, the Russian price for malleable platina, which is about twenty-eight shillings, is too extravagant (9). A ra th e r different p o in t of view w as ex pressed a little la te r by a n E ng lish visitor, W illia m M a r s h a ll (1799 1844), also a geologist a n d th e V ice -P resid en t an d H o n o ra ry C u r a t o r of M in e ra lo g y to th e Y o rk s h ire P hilo so p h ica l Society, to w hich he m a d e a full re p o rt o n his re tu rn , p re s e n tin g th e m w ith a large sp ecim en of native p la tin u m (10). M a r s h a ll w as at so m e p a in s to criticise W o l l a s t o n s p ro c ed u re for th e p ro d u c tio n of m a lle a b le p l a t i n u m by c o m p a r is o n w ith the m u ch sim pler m e th o d a d o p te d by Sobolevsky w h ic h he re g a rd e d as p ro d u c in g the m etal in a sufficiently p u r e s ta te for p ra c tic a l purposes. At th e m eetin g of th e G esellschaft d e u ts c h e r N a tu r fo rs c h e held in S tu t t g a r t in S e p te m b e r 1834 Sobolevsky p re s e n te d a p a p e r giving details of th e discovery of p la tin u m in th e U rals, of his refining p ro c e d u re , a n d now c o m p a r in g it w ith the W o lla s to n process m a d e k n o w n in 1828, co nclu din g: From all this it can be seen on what a great scale platinum is being worked in Russia today and to what degree of simplicity this process has been brought which formerly gave so much trouble to metallurgists (11). In fact Sobolevsky h a d greatly in creased th e sp ee d of his o p e ra tio n s from their painfully slow beginnings. A t first only 3 p o o d s (1,575 o unces tro y) could be refined in a week, yielding only 1,050 ou nces of p u r e p la t i n u m ; this gave 2,000 coin b lan k s a n d 440 ounces of scrap b u t by 1834 the refinery w as ab le to cope w ith one p o o d (525 troy o u n ces) of native p l a t i n u m p e r d a y a n d th e coiners h a d increased th e ir ca p a c ity accordingly. I n incre asing th e sp eed of refining, however, Sobolevsky h a d by no m e a n s im p ro v ed his process. In s te a d of evaporatin g his a q u a regia to dryness, tak ing u p w ith w ater, a n d th e n p r e c i p i ta t ing incom pletely w ith s a l-a m m o n ia c he h a d now a b a n d o n e d th e e v a p o ra tio n to
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dryness in seeking to save t im e a n d w as a d d in g s a l-a m m o n ia c direc tly to the original a q u a regia solution, re ly in g o n a n excess of a q u a regia to r e ta r d p r e c ip itatio n of th e iridium , a n d o n long w a sh in g of th e p re c ip ita te w ith w a te r to rem ove such ch lo ro irid a te as n e v e rth eless a p p e a re d . T h e ev a p o ra tio n to dryn ess t e n d e d to d e c o m p o s e th e irid iu m ch lo rid e into the soluble iridous form, a n d t h e in co m p lete p re c ip ita tio n t e n d e d to leave any u n d e c o m p o s e d iridic salt in so lu tio n . In th e new process th e p re s e n c e of excess a q u a regia k ept th e iridium sa lt oxidised a n d therefo re easily p re c ip ita te d , the acidity of th e solution did n o t h i n g to p re v e n t th is p re c ip ita tio n , a n d th e excessive w ash in g rem oved c o n sid erab le q u a n t i t ie s of p l a t i n u m in large volu m es of w ashw a te r which h a d to b e a v a p o r a t e d for its recovery. T h e p ro c e d u re w as b a d an d after S obolevskys d e a th in 1841 it gave p la c e to a n im p ro v ed process.
D o b e r e in e r s R efining P rocess
A close c o n n e ctio n b etw e en t h e R u s s ia n a u th o ritie s a n d J o h a n n W olfgang D o b e re in e r a n d his work on p l a t i n u m in J e n a , d e sc rib ed in th e last c h a p te r, developed th ro u g h M a r i a P av lov na, a d a u g h t e r of T s a r P au l I a n d a sister of his successors N icholas I a n d A l e x a n d e r I. I n 1804 she h a d m a r r ie d C a r l F ried rich , th e son a n d h eir of D u k e C a rl A u g u s t of W e i m a r a n d of c o u rse h a d settled there.
The Grand Duchess Maria Pavlovna

I 7 8 6 - 185 *)
A d a u g h te r of T s a r P au l I w ho had w it n e s s e d L a v o i s i e r 's m e l t i n g o f p l a t i n u m in P a r i s in 1782 a n d a s is te r of his s u c c e s s o rs N ic h o la s I a n d A l e x a n d e r I. the (ra nd Duchess m arried C a rl F riedrich, the son and heir of D o b e r e i n e r s p a t r o n . D u k e C a rl A u g u s t o f W e i m a r . As well as b e i n g i n t e r e s t e d in c h e m i s t r y sh e was in clo se t o u c h w ith h e r b r o t h e r s M inister of F in a n c e . C o u n t k a n k r i n . a n d w as a b l e to s e c u r e a m p l e s u p p l i e s o f n a t i v e p l a t i n u m for D o b e r e i n e r s r e s e a r c h e s . L a t e r sh e w as i n s t r u m e n t a l in s e c u r i n g h is se rv i c e s to im prove the m e t h o d s of r e f i n i n g Russian platinum
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S he took a g re a t in terest in ch e m is try a n d in D o b e r e i n e r s activities a n d occasionally help ed to s u p p o rt him financially. S h e w a s also in close to u c h w ith her b r o t h e r s M in is te r of F in a n ce, C o u n t K a n k r i n w h o w as also H e a d of th e M in in g D e p a r t m e n t in St. P ete rs b u rg . N e ith e r K a n k r i n n o r Sobolevsky was satisfied w ith th e p l a t i n u m refining processes in use a n d th e G r a n d D u c h e s s d re w their a tte n tio n to th e possibility th a t D o b e r e i n e r s skill a n d e x p e rien ce m ig h t be of value. K a n k r i n a t once a d o p te d h e r suggestion, b u t D o b e r e i n e r w as u nw illing to leave J e n a . In s te a d his son F ra n z travelled to R u s s ia a n d a c c o m m o d a t io n was a r ra n g e d for him in O s a n n s la b o ra to ry in th e U n iv ersity of D o r p a t (n o w k n o w n as T a r tu ) , a n d a D r. F ried rich W eiss of th e U n iv ersity C h e m ic a l D e p a r t m e n t was assigned to assist him , w ith D o b e re in e r h im self a c tin g as c o n su ltan t. U n lim ite d supplies of native p l a t i n u m w ere of c o u rs e ava ila b le to th em , as well as access to th e refining o p e ra tio n s in St. P ete rs b u rg . I n th e ir a p p r o a c h to the p ro b lem th ey p ro p o s e d to free th e solution in a q u a reg ia from iron a n d c o p p e r by th e a d d itio n of alkalies, a p r o c e d u re t h a t h a d b e e n trie d by C h a b a n e a u in S p a in in the 1790s w ith o u t success. I n th e m e a n t i m e th e E n g lish a s t r o n o m e r a n d chem ist S ir J o h n F. W. H e rsc h e l (17921871) h a d m a d e a r e m a r k a b l e discovery a b o u t p l a t i n u m in th e course of so m e w ork h e w as do in g o n th e influence of light on chem ical action, w ork w hich h a s p la c e d his n a m e a m o n g th e list of the inventors of p h o to g ra p h y . I n a p a p e r re a d to th e B ritish A sso cia tio n at its O x fo rd m eetin g in 1832 (12) he sh o w e d t h a t if a so lu tio n of th e m e ta l in a q u a regia is n e u tra lis e d w ith lime, a n d after filtering s o m e m o re lim e is ad d e d , nothing h a p p e n s as long as th e m ix tu r e is k ep t in th e d a r k b u t t h a t if it is exposed to su n lig h t th ere is quickly form ed a copio us w h ite p re cip ita te . T h is h a p p e n e d less ra p id ly in clo udy day lig h t a n d d id not ta k e p lace a t all in red or even yellow light. H e rs c h e l found th e p re c ip ita te to b e a c o m b i n a t i o n of the oxide of p l a t i n u m w ith lim e in w h ic h th e o x ide seem s to p e rfo rm th e p a r t of an acid. F u r t h e r e x p lo ra tio n w as c a rrie d out in D o r p a t b y W e iss a n d th e y o u n g e r D o b e re in e r (13). T h e y sho w ed t h a t from solutions of native p l a tin u m , th e lime a p p e a re d to p re c ip ita te at once th e iridiu m , rh o d iu m , co p p e r, iron, lead, titan ium , etc., p re s e n t in th e solution, as oxides c o n ta in in g no calcium , w hile the p la tin u m r e m a in e d dissolved as long as th e liq u id w a s not w a r m e d o r e x posed to light. In th e la tte r case th e w hite p re c ip ita te d e s c rib e d b y H e rs c h e l w as form ed; in th e former, if th e m ix tu r e is b o iled for so m e tim e th e p l a t i n u m is co nverted into a form in w h ic h it is not p re c ip ita te d b y a m m o n i u m chloride. T h e p a lla d iu m b e h a v e d in a n in te rm e d ia te a n d u n c e r t a i n m a n n e r , slowly yielding even in th e d a rk a w h ite p r e c ip ita te c o n ta in in g lime. T h is, however, d id not prev ent a n a t t e m p t to a p p ly th e new k n o w le d g e to the large-scale refining of p l a t i n u m from th e U r a ls a t St. P e te rs b u rg , a n d in 1841 a new process b a s e d u p o n it w as in tro d u c e d a n d refining o p e r a tio n s w ere tran sferre d to th e St. P e te rs b u rg M in t. I n th e new tr e a tm e n t, d e sc rib ed in som e detail in a p a p e r b y a C olonel K o v a n ko in th e Russian M ining Journal in 1843 (14), the a q u a regia so lu tio n h a d m ilk of lim e a d d e d to it un til it r e m a in e d only 245
slightly acid. T h e p re c ip ita te w a s filtered, th e solution e v a p o ra te d to dryness, a n d the re sid ue calcined at a b rig h t re d h e a t u ntil no fu r th e r ev olution of chlo rine took place. T h is d e c o m p o s e d th e c a lc iu m c h lo ro p la tin a te into calcium chloride a n d m etallic p la tin u m . T h e form er w as leac h ed o ut w ith w a te r a n d the p la tin u m pressed a n d forged. T h i s l a tte r p a r t of th e process h a d also been altered, a n d not for the better. T h e p ressin g of th e cold spo nge w as c a rrie d o u t as before, b u t the s u b s e q u e n t h e a ti n g w as effected by placin g a pile of th e pressed discs in a fu rn ace w h e re the firing of p o rc e la in w as going o n at t h e sa m e time, so that their heating continues for a day and a half. Given the conditions of first-class refining of the platinum and, especially, good washing, a very malleable and service able platinum is produced by this firing . But the results w ere not very successful a n d th e re a s o n for this w as w ith o u t d o u b t the erratic b e h a v io u r of t h e vario us m etals of th e p l a t i n u m g ro u p u n d e r refinery conditions. N o t only w a s th e finished m e ta l of p o o r q u ality , b u t piles of residues b e g a n to a c c u m u la te w h i c h w e re even larg e r a n d m o re co m p lex th a n those p ro d u c e d by the earlier processes. Before, however, passing o n from th e w ork of th e D o b e re in e rs it will p ro b a b ly be a p p r o p ria te to d e s c rib e in m o d e r n te rm s w h a t th e fu n d a m e n ta l occurrences w ere in the course o f th e ir process. T h e a d d itio n of lim e to th e solu tion of p la tin u m in a q u a regia i n th e d a r k d id not p e r m it a n y a p p r e c ia b le p r e cip itatio n of th e m etal, b u t u n d e r the influence of actinic light a process of hydrolysis set in, leading to p r e c i p i ta ti o n of th e p l a t i n u m in t h e form of succes sive m em b ers of a series o f h y d ro x y -c h lo ro p la tin a te s , c u lm in a tin g in h e x a h y d ro x y p latin ate, all of ca lc iu m . T h is re su lted in th e s o lu tio n b ein g ro b b e d of som e or all of its p la tin u m a c c o r d i n g to the intensity of th e light a n d of the len g th of the exposure. T h e process was too long a n d clum sy, a n d it w as finally a b a n d o n e d , b u t not before D o b e re in e r senior h a d p u b l i s h e d a m o n o g ra p h , Z u r C h e m i e d e s P la t in s , d e d ica ted to C o u n t K a n k r i n th a t w a s r e m a rk a b ly c o m p re h e n s iv e for its time.
T h e C essation o f C o in in g
T h e issue of the ro u b le coins w e n t on satisfactorily u n d e r K a n k r i n s w atchful g u id a n c e a n d u n d e r the s t im u lu s of this d e m a n d th e o u t p u t of th e m ines in creased ra p id ly to som e 6 0,0 00 o un ces in 1830, re a c h in g a re c o rd of a b o u t 120,000 ounces in 1843 b u t th e n d ec lining rapid ly. T h i s w as occ asio n ed by a serious fall in the d e m a n d for p l a t i n u m o u tsid e R u ssia , c a u s in g a fall in price in the w estern m ark e ts a n d a d ro p i n p r o d u c tio n in C o lo m b ia . In 1843 th e o u tp u t th e re was only 1,600 ounces a n d i n d u e co u rse th e p rice fell to a level low er th a n the ex ch ang e value of th e R u s s i a n p l a t i n u m coins. K a n k rin , a l a r m e d a t the p ro sp e ct of extensive co u n terfeitin g , p u t a severe lim ita tio n o n th e a m o u n ts co ined an d s tre n g th e n e d his c u s t o m s re g u la tio n s at th e frontiers. B u t shortly after 1844 he retired from office a n d his successor V ro n c e n k o w a s a tim id m a n w ith n one of his strength, e x p e rie n c e a n d convictions. U n d e r h im s o m e th in g like
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pan ic su pervened, a n d in 1846 he o rd e re d th e c e s satio n of co ining a n d th e w ith d ra w al of the w hole p la tin u m cu rrency. So von H u m b o l d t s w orst fears of 1827 w ere fully realised a n d th e p u blic re tu r n e d to th e T r e a s u r y 3,263,292 ro ubles, or a b o u t th re e -q u a r te rs of th e a m o u n t th a t h a d b e e n issued, th e r e m a i n d e r being either h o a r d e d or sm u ggled a b r o a d . T h e coins h a d b e e n in issue for eighteen years a n d th e total n u m b e r of th e m was: 3-roubles, 1,373,691; 6-roubles, 14,847; a n d 12-roubles 3,474; w ith a total face value of 4,251,843 roubles. T h e y w eighed 0.333, 0.666 a n d 1.332 ounces tro y e a c h respectively. T h e to tal a m o u n t of p la tin u m used was 485,505 ou nces troy (15).
Karl K laus an d the D is c o v e r y o f R u th e n iu m

Before con c lu d in g this survey of th e R u s s ia n p l a t i n u m in d u s try in its early years th ere has to be re co rd e d th e discovery of th e sixth a n d last m e m b e r of the p la tin u m g ro u p of m etals. It will be re m e m b e re d th a t very soon after its discovery C o u n t K a n k r i n sent sam ples of native p la tin u m to a n u m b e r of scientists. A m o n g these w a s G o ttfried W ilhelm O s a n n (1 79 7-1 866 ) w ho h a d b ee n one of D o b e r e i n e r s s tu d e n ts i n j e n a a n d was now Professor of Physics a n d C h e m is tr y in D o r p a t , b ec o m in g Professor at W u r z b u r g in 1828. By m ean s of b lo w p ip e tests h e c a m e to th e c o n clusion th a t he h a d found indicatio ns of th e p re sence of th re e new m etals to be called p luran, r u t h e n a n d polin (16). H e sent sa m p le s of his p r e p a r a ti o n s to Berzelius j u s t at th e tim e w h e n th e latter h a d a tt a i n e d a g re at deal of confidence in his know ledge of th e b e h a v io u r of the p l a t i n u m m etals. B erzelius re p o rte d th a t he could not recognise in p l u r a n a n y th in g a lre a d y k n o w n to him , a n d t h a t it m ight be th e oxide of a new m etal since it h a d som e p e c u lia r pro p e rtie s. It w a s a heavy w hite pow d er, volatile, w ith o u t o d o u r, a n d giving a solution c o lo u re d grey by su lp h u re tte d h y drogen. T h e p o lin a n d r u t h e n w e re sim ply a m ix tu r e of silica, titania, zirconia a n d oxides of iridiu m . M oreover, O s a n n s an a ly se s of native p la tin u m a n d th e residues did not c o m p a r e in a c c u ra c y w ith those of the S w edish chem ist. E v en tually he p u b lis h e d a notice revoking th e discovery of an y new m etal (17). N evertheless this p a in s ta k in g w o rk of O s a n n s sho w ed th a t there was still a g re a t deal a b o u t th e p l a t i n u m m e ta ls re m a in in g u n ex p lain e d , a n d th a t m u c h h a d still to b e done. S om e years late r this w as ta k e n up by K a rl K a rlo v ic h K laus, o r C a rl E rn s t C lau s in the G e r m a n version of his nam e, a p h a r m a c i s t from D o r p a t w ho was ap p o in te d to a new c h a ir of che m istry in th e U niversity of K a z a n in 1838. H e w orked chiefly on an aly tica l m eth o d s, b u t his m a i n efforts w e re d irec ted to processes to be used on w ork on a n in d u s tria l scale a n d especially to th e w orking up of th e m a n y difficult residues p ro d u c e d in su ch o p eratio n s. In 1844 in th e course of the work he discovered a n d con firm ed th e sixth m e m b e r of the pla tin u m g ro u p m etals, a n d n a m e d it r u t h e n i u m in h o n o u r of his a d o p te d co u n try a n d to p e r p e tu a te th e m e m o ry of O s a n n . In 1840 he h a d t u r n e d his a tte n tio n to th e resid ues w h ich w ere b eing
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K arl K a rlo v ic h K lau s I796-1864 H o r n in D o r p a t . no w T a r t u in E s t o n i a , M a u s first p r a c t i s e d as a p h a r m a c i s t t h e r e , b e c o m i n g a n a s s i s t a n t in th e c h e m ic a l d e p a r t m e n t of the university. In 1 83 6 h e w a s a p p o i n t e d P r o f e s s o r of C h e m i s t r y in t h e I n i v e r s i t y o f K a z a n a n d a few y e a r s l a t e r b e g a n w o r k on llu* i n s o l u b l e r e s i d u e s f r o m t h e r e fi n i n g of p la tin u m . B e sides d iscovering the si x th m e m b e r o f t h e g r o u p , r u t h e n i u m , h e c a r r i e d o u t e x t e n s i v e r e s e a r c h e s 011 irid iu m and rhodium and finally assem b led the results of m ore than t w e n ty years of research in a m o n o g r a p h t h a t w a s no t p u b l i s h e d until so m e y e a rs a f te r his d e a th
p ro d u c e d by Sobolevsky in th e St. P e te rs b u rg p l a t i n u m refinery in o rd e r to see if they th rew a n y light on th e p r o b l e m of O s a n n s n ew m etals. H e h a d been interested for som e tim e in t h e c o m p o s itio n of native p l a t i n u m , a n d these residues seem ed to p resent a c o n c e n t r a t e d o p p o rtu n ity . H e asked Sobolevsky for, a n d o b ta in e d , 2 p o u n d s of th e m a n d p ro c eed e d to stu d y these, first by re p eatin g c a refu lly th e w ork of his p re d e c e s so r O s a n n , a n d th e n lau n c h in g o u t for himself. I n a d d itio n to th e four o th e r p l a t i n u m m etals, he w as surp rise d to find a c o n t e n t of 10 p er ce n t of p l a t i n u m itself, a n d this richness of th e residues, ly in g uselessly in c o n s id e ra b le q u a n titie s in the la b o ra to ry of the M in t a t St. P e te rs b u r g , a p p e a r e d to m e to be so i m p o r ta n t th a t I re p o rte d to th e m in in g a u th o r itie s a n d in 1842 set off for th e c a p i t a l , w h e re he saw K an k rin . T h e la tte r fully a p p r o v e d of his d esire to e x a m in e a la rg e r q u a n tity of th e m ateria l a n d he r e t u r n e d to K a z a n w ith half a pood. T h is, however, t u r n e d out to be m u c h p o o re r i n p l a t i n u m t h a n th e first a n d th e h op e of my m e th o d for th e profitable e x t r a c t i o n of th is m etal from t h e m d is a p p e a re d ; there re m a in e d only investigations of in te re s t to s c ien c e . It was in th e course of tw o y e a r s of a r d u o u s w o rk t h a t he discovered th e new m etal. T h is he d id b y tak in g a p o r t i o n of th e insoluble o s m irid iu m re sidue a n d fusing it w ith p o ta s h a n d n itre i n a silver crucible. A fter k ee p in g th e m ix tu re m o lte n for a n h o u r a n d a half a t b rig h t re d n ess he p o u r e d o u t t h e co n te n ts into a n iron capsule. H e th e n d issolved the cak e in w a te r to yield a n o ra n g e-c o lo u red solution a n d tre a te d this w ith n itr ic acid, p ro d u c in g a b la c k p re c ip ita te co n sist
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ing of th e oxides of o s m iu m a n d r u th e n iu m . H e distilled this w ith a q u a regia a n d c o n d e n sed the o sm iu m tetroxide. T h e re sid u e consisted m a in ly of th e tw o chlorides of ru th e n iu m a n d o n a d d in g a m m o n i u m chloride, a m m o n i u m c h lo ro r u th e n a te was pre cip ita te d . T h is w h e n calcin ed yielded r u t h e n i u m sp on ge to the q u a n tity of 6 gram s. K lau s r e ta in e d th e n a m e r u t h e n i u m b o th for patrio tic reasons, since r u t h e n i u m is a latinised n a m e for R u ss ia , a n d also in h o n o u r of the earlier work of O s a n n , w hose r u t h e n did c o n t a i n a sm all q u a n tity of the new m etal a lth o u g h m o st of it h a d b ee n lost in th e h y d ro c h lo ric acid solutions which O s a n n did not exam ine. K laus sent a sam p le of his p o ta s s iu m c h lo r o r u th e n a te to B erzelius w h o at first believed it to be a salt of irid ium , b u t after som e fu r th e r e x a m i n a ti o n he w ith d rew this verdict a n d expressed th e o p in io n th a t th e salt c o n ta in e d a m etal w hich was u n k n o w n to him. K laus pu b lish ed his w ork as it was being d o n e in a series of sh o rt articles in the B ulletin of the R u s s ia n A c a d e m y of Sciences a n d a c o n s o lid a tio n of the whole a p p e a r e d in 1844 in the Scientific R eco rd s of th e U n iv ersity of K a z a n . It r a n to 188 pages a n d was r e p rin te d as a booklet in 1845 u n d e r th e title C h e m ic a l E x a m in a tio n of the R esidu es from U r a l ia n P la t in u m O r e a n d of th e M e ta l R u t h e n i u m . T h is a p p e a rs to have b ee n a p riv ate p u b lic a tio n a n d d id not re ach the o u tsid e world. A s u m m a ry , u n d e r th e h e a d in g of D iscovery of a new M e t a l , a p p e a re d in Poggendorffs Annalen for 1845 a n d was re p r o d u c e d in The Philisophical M agazine (18) a n d a g a in by Berzelius in his Jahresbericht for 1841 (19), bu t the first full ac coun t of the whole w ork given to W e s te r n E u ro p e seem s to b e th at in L ie b ig s Annalen for 1847 as B eitrge z u r C h e m ie d e r P la t in m e t a ll e (20). T h is last also was p u b lish ed as a p a m p h l e t in G e r m a n a n d u n d e r th e above title, at D o rp a t in 1854 (21). After this K lau s co n tin u e d to take a close interest in th e refining o p eratio n s going on at St. P etersb u rg a n d in th e p ro p e rtie s of p la tin u m . At o ne tim e he gave p a r tic u la r a tte n tio n to m e th o d s for keeping th e c h lo ro p la tin a te so lu tio n free from iridium and, m o re im p o rta n tly , free from silica, a m a t t e r w h ic h h ad bedevilled m a n y workers in clu din g W o llasto n :
This silica remains in the platinum sponge and is capable later during the heating of the platinum of uniting intimately with the platinum, indeed of alloying with it, and therefore making it brittle and unsuitable for use.
K laus co n tin u e d to ca rry ou t re searc h o n the p l a t i n u m m e ta ls w hile at K a z a n a n d com piled the results of n ea rly tw e n ty years of re se a rc h o n ru th e n iu m , o sm iu m a n d rh o d iu m in a sm all book p u b lis h e d th e re in 1859 to c o m m e m o r a te th e fiftieth an niv ersary of his university. M ea n w h ile , in 1852 K lau s h a d r e tu r n e d to the U niversity of his b irth p lace , D o rp a t, w here he h a d served as a n ass is ta n t b e tw e en 1831 a n d 1837, to o cc u p y a new ly-founded C h a ir of P h a r m a c y a n d th e re he form ed a d esire to p u b lish a m o n o g ra p h on the p la tin u m m etals a n d th eir alloys, in c o rp o r a tin g th e resu lts of his tw en ty y e a rs research in this field, as well as th e h istory of th e m etals, references to th e work of o th e r scientists a n d a d e s c rip tio n of th e ir tech n ic al a n d
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in d ustrial app licatio ns. T o h e lp him to this en d, th e R u s s ia n G o v e rn m e n t sent him to F ra n c e a n d G e rm a n y t o visit th e la b o ra to rie s a n d refineries in w hich p la tin u m was being h a n d le d a n d to stu d y th e history of the m e ta ls in the libraries of B erlin a n d Paris. H e left D o r p a t in M a y 1863 a n d his j o u r n e y w as som eth in g of a triu m p h a l p ro g ress. I n B erlin he m e t H e in r ic h a n d G u s ta v Rose, Poggendorff, M a g n u s a n d o th e rs , a n d th e P ru s s ia n A c a d e m y of Sciences m a d e h im a C o rre s p o n d in g M e m b e r . M e n s c h u t k i n in a p a p e r on K lau s (22) goes o n to say:
Before him doors opened to which entrance was strongly forbidden to strangers, and he succeeded in making a thorough acquaintance with the organisation of the business in platinum in the works of Heraeus at Hanau, Desmoutis Quennessen in Paris, Chapuis & Co in Paris, M atthey in London .
E arly in 1864 he r e tu r n e d t o D o r p a t a n d set a b o u t the co llatio n of his m ateria l, b u t a n im p o rta n t m e e t i n g of th e P h a rm a c e u tic a l Society called him to St. P etersb urg, a n d on his w a y h o m e he took a chill, b e c a m e ill a n d d ied on M a r c h 12th. T h e m a n u s c r ip t o f th e first th re e c h a p te r s of his book w as found a m o n g his p ap e rs a n d p r e p a r e d for p u b lic a tio n in 1865 b y his colleagues, the A cad em ician s F ritzsche a n d J a k o b i , b u t c irc u m s ta n c e s a n d t h e n th e d e a th of the tw o sponsors intervened a n d n o t h i n g w as achieved. F o rtu n a te ly , however, the script was rescued from o bliv ion eig h tee n y ears la te r by K l a u s s fo rm e r pupil a n d his successor in th e C h a i r at K a z a n , A le x a n d e r M ik h a ilo v ic h Butlerov (18281886) a n d this tim e p u b l i c a t i o n took p la c e a t th e h a n d s of th e R u s s ia n A c a d e m y of Sciences u n d e r the title F r a g m e n t e in er M o n o g r a p h ic des P latins u n d d er P la tin m e ta lle a n d as a to k e n of respect to K l a u s s m em o ry . T h e little book is of th e g reatest value to t h e h isto ria n of p la tin u m .
C o n c lu sio n
W ith the cessation of th e d e m a n d for co in ag e th e re e n d e d w h a t th e R u s s ia n w riters call T h e F irst P e r i o d o f th e R u s s ia n p l a t i n u m in d u stry . T h e r e w as no o th e r a p p lica tio n available to s u p p o r t th e m ark e t, a n d price a n d o u t p u t fell t o such a n extent th a t over th e n e x t eight years, 1845 to 1852, th e w hole of the U ra ls p ro d u c e d only 113 poods (6 0,00 0 ounces). A fter th a t, however, a revival took place, s tim u la te d b y th e ac tiv ity in th e W e s t by the firm s of J o h n s o n a n d M a t t h e y in L o n d o n a n d of D e s m o u t i s Q u e n n e s s e n in Paris, a n d later on by th e scientific a n d technical w ork of D eville a n d D e b r a y to w h ic h reference will be m a d e in C h a p t e r 15. But to s u m u p the very i m p o r t a n t resu lts of this early w ork: first, it effectively e x p lo red a n d o p e n e d up th e i m p o r t a n t new source of native p l a t i n u m t h a t was d estin ed to sup p ly p ra ctically t h e w h o le w o r l d s needs of w h a t g ra d u a lly b e c a m e a vital raw m a teria l from the eigh tee n -six ties un til at least 1917. A fter th at, its i m p o rta n c e declined as o th e r s o u rc e s w ere fou nd a n d exploited, b u t even th e n it was ab le to sup p ly all R u s s ia n n e e d s a n d still to m a k e o ccasional a p p e a ra n c e s in th e w estern m arkets. Secondly, it w a s th e m e a n s b y w h ic h w ere m a d e the first
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intensive e x a m in a tio n of th e che m ic al a n d physical p ro p e rtie s of th e whole g ro u p of six p l a t i n u m m etals. T h e o th e r g re a t fe atu re of th e c h a p t e r is the lifetim es w o rk of K laus. T h e result, as we have seen, w as th e discovery of the sixth p la tin u m m etal, r u th e n iu m , a n d a satisfying e lu c id a tio n of its p ro p e rtie s as well as those of irid ium , o s m iu m a n d rh o d iu m . A lot w as left for th e future, b u t the fou n d a tio n s w e re well a n d tru ly laid.
R eferences for C hapter 13 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 N. L. Vauquelin, Ann. C him ., 1806, 60, 317 322 L . B. Guyton de Morveau, Ann. C h im ., 1810, 73, 334 335 A . Laugier, Ann. C him ., 1825, 29, 289 295; P hil. M a g ., 1825, 66, 285 288 E din. N e w P h i l . J , 1828-29, 6, 197-198 A . Breithaupt, Ann. Phys. ( Poggendorff), 1826, 8 , 500 505 E. K. Fritsman, Ann. In st. P latine ( I m in g r a d ) , 1927, 5, 23-74 P. G. Sobolevsky, M in in g J . (R u s sia ), 1827, 2, 84: reproduced in A nn. Inst. R a tin e ( L eningrad), 1927, 5 , 206 219 G. Rose, Ann. Phys. ( Poggendorff), 1834, 3 1, 673 676 J. Dickson, M o n th ly A m . J . Geology (F eatherstonehaugh), 1831, Sept., 118 124 W. Marshall, Phil. Mag., 1832, 11, 321-323; J. Tech. Chem., 1832, 14, 319-322 P. G. Sobolevsky, Ann. Phys. (P oggen dorff), 1834, 33, 99 109; Ann. Chem . (L ie b ig ), 1835, 13, 42-52 .J. F. W. Herschel, P hil. M a g ., 1832, 1, 58-60 F. Weiss and F. Dbereiner, Ann. Chem . ( L ie b ig ), 1835, 14, 15 21 Kovanko, M in in g J . (R u s sia n ), 1843, 447; reproduced in Ann. In st. P latine, 1927, 5. 219-225 E. K. Fritsman, Ann. Inst. P latine, 1927, 5, 23 74 G. W. Osann, Ann. Phys. (P oggen dorff), 1827, 11, 311-322; 1828, 14, 329 357 G. W. Osann, Ann. Phys. ( Poggendorff), 1829, 15. 158 C. Claus, Ann. Phys. (P oggen dorff), 1845, 64, 192-197; P h il. M a g ., 1845, 27, 230-231 J.J. Berzelius, J a h res-B eric h t, 1847, 26, 181-184 C. Claus, Ann. Chem . ( L ie b ig ), 1847, 63, 337 360 C. Claus, N eue Beitrge zur Chemie der Platinmetalle, Dorpat, 1863. This is based on Clauss papers in J . p ra k t. Chem., 1860, 79, 28 59; 1860, 80, 282 317; 1861, 85, 129-161; 1863, 9 0 , 65 105 B. N. Menschutkin, Ann. Inst. R a tin e, 1928, 6, 1-10
22
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J o n s Jacob B erze liu s
After studying at the U niversity of U ppsala Berzelius was appointed assistant professor of b otan y and chemistry in the University of Stockholm, becoming professor in 1807 and later, in 1818. secretary of the Koval Swedish Academ y of Sciences. His enorm ous output of work included a brilliant investigation of the platinum metals, their sep ara tion. methods of analysis a n d their atomic weights
From a portrait b> J o h a n ^ a \ . b> rourte*\ of the Koval Swedish Acaderm of Science*
1779-1848
14
The Platinum Metals in Early Nineteenth Century Chemistry
Only one who h im se lf has w o r k e d with the c h em istry o f the p latin u m m etals can fu lly understan d a n d evaluate the difficulties Berzelius had to overcom e. H e not on ly d e te r m in ed the atom ic weights o f pla tin u m , p a lla d iu m , rhodium , iridium an d osm ium but also investigated a large nu m ber o f the most im portant c om pou nds o f these metals.
H E N R IK G U S T A V S O D E R B A U M
T h e first q u a r te r of th e n in e te e n th c e n tu r y saw th e t r a n s f o r m a tio n of c h e m istry into a n exact science. F ollow ing th e g re a t c o n trib u tio n s of Lavoisier, his ap p reciatio n of the role of oxygen, his use of th e b a la n c e a n d his in tro d u c tio n of th e new n o m en cla tu re, a second m a jo r ad v a n ce w a s m a d e w ith th e es ta b lis h m e n t of the q u a n tita tiv e basis of che m ic al c o m b in a tio n . It is p o ssib le h ere only to su m m arise very briefly th e d e v e lo p m e n t of this n u m e ric a l a p p r o a c h a n d to set th e scene for th e g re a t c h a n g e b r o u g h t a b o u t in in o rg an ic c h e m is try a n d its im p a c t on th e stu d y of th e p l a t i n u m m etals. T h is b e g a n w ith th e r a th e r o b s c u re a n d s o m e w h a t n eglected w ritin gs of J e r e m ia s B en jam in R ic h te r (1762 1807), th e o rig in a to r of the term s to ich io m e try a n d of th e co n c ep t of eq uiv ale n t w eights of base s a n d acids. R ic h te r stu d ied u n d e r th e g re a t G e r m a n p h ilo s o p h e r I m m a n u e l K a n t at K nigsberg a n d his cho ice of sub ject for his d o c to ra l thesis, T h e U s e of M a th e m a tic s in C h e m i s t r y , w a s m ost p ro b a b ly in sp ired b y K a n t. H is book, p u b lish ed in 1792, w as p re fac ed w ith a q u o t a t i o n in G re ek from th e A p o c ry p h a : Thou hast ordered all things in measure and number and weight. (1) In 1799 J o s e p h Louis P ro ust, w h o se w o rk o n p l a t i n u m in th e R o y a l L a b o r a to ry in M a d r i d h as b e e n d esc rib ed in C h a p t e r 6, p u t fo rw a rd his L a w of C o n s ta n t C o m p o sitio n , a c o n c ep t th a t h e later s u m m a r is e d in th e p h ra se:
253
J o h n D a lto n
1766-1844
T h e c o n c e p t of a t o m i c w e i g h t i n t r o d u c e d by D a l t o n t o g e t h e r w ith his law s of c o n s t a n t a n d m u l t i p l e p r o p o r t i o n s in chem ical c o m b in a tio n gave a great i m p e t u s to i n o r g a n i c a n d a n a l y t i c a l c h e m i s t r y a n d p r o m p t e d B e r z e l i u s to e m b a r k o n his s y s t e m a t i c i n v e s ti g a t i o n s
A compound is a substance to which Nature assigns fixed proportions; it is in a word a being which she never creates even in the hands of man, except with the aid of a balance. (2) T h is b ro u g h t P rou st into a lo n g co ntrov ersy w ith C l a u d e L o uis B erthollet (1748 -1 822 ), w h o m a in ta in e d t h a t fixed p ro p o rtio n s w e re ex c eptio nal r a th e r t h a n a general rule, b u t the a to m ic th eo ry p r o p o u n d e d by J o h n D a lto n , in c o rp o ra tin g his d o ctrin e th a t t h e elem ents w e re c o m p o se d of a to m s of c o n s ta n t w e ig ht a n d th a t c o m p o u n d s w e r e form ed by th e ir u n io n in sim p le n um erical pro p o rtio n s, p u t a n e n d to this a r g u m e n t . O n O c t o b e r 21st, 1803 D a lt o n re a d a p a p e r to th e M a n c h e s te r L i t e r a r y and P hiloso ph ical Society - p u b lis h e d only late r in 1805 - in w h ich he c o n c lu d e d : An enquiry into the relative weights of the ultimate particles of bodies is a subject, as far as I know, entirely new: I have lately been prosecuting this enquiry with remarkable success. (3) D a lto n b e g a n his d e t e r m in a ti o n of a to m ic w eigh ts w ith th e gases, b u t by 1804 he h a d t u rn e d to the m e t a l s a n d th e c a lc u la tio n of th e ir a to m ic w eights from the p u b lis h e d analyses o f o th e r w orkers, selecting th e values w hich d isag re ed least with the often in c o n s is te n t analyses of th e ir oxides a n d a d d in g new results as fu rth e r lite ratu re a p p e a r e d . H is views o n p latin u m , a b o u t w hose ato m ic w e igh t he re m a in e d u n certain , m a y b e seen in the r e p r o d u c t i o n here of a p a ss a g e from A N e w S ystem of C h e m ic a l P h ilo s o p h y p u b l i s h e d b e tw e e n 1808 a n d 1810. D a lto n also in tro d u c e d his a r b itra ry m a r k s o r sym bols to re p re s e n t th e elem ents.
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Dalton began publishing his New System of Chemical Philosophy' in 1808. the second part following two years later. This extract from Part II shows his thoughts on platinum at that time. He also devised a n um b er of symbols for the elements, three of them illustrated here
The weight of the ultimate particle of pla ting cannot be ascertained from the data we have at present: from its combination with oxygen, it should seem to be about 100; but, judging from its great specific gravity, one would be inclined to think it must be more. Indeed the proportion of oxygen in the oxides of platina cannot be considered as ascertained. Platina is chiefly used for chemical pur poses ; in consequence of its infusibility, and the difficulty of oxidizing it, crucibles and other utensils are made of it, in preference to every other metal. Platina wires are extremely useful in electric and galvanic researches, for like reasons.
At first Daltons views made very little impression, but in 1807 Thomas Thomson, Professor of Chemistry in the University of Edinburgh and the founder of the Annals of Philosophy, published the third edition of his book, A System of Chemistry, and included in this an account of the atomic theory based upon a conversation he had had with Dalton in Manchester in 1804. A year after this Thomson read a paper to the Royal Society in which he confirmed the law of multiple proportions by the analysis of some neutral compounds (4). Immediately following this a paper from W. H. Wollaston not only gave further support to Dalton but disclosed that he had himself been turning his mind in the same direction:
I thought it not unlikely that this law might obtain generally . . . and it was my design to have pursued the subject with the hope of discovering the cause, to which so singular a relation might be ascribed. But since the publication of Mr. D altons theory of chemical com bustion the enquiry which I had designed appears to be superfluous as all the facts that I had observed are but particular instances of the more general observations of Mr. Dalton that in all cases the simple elem ents of bodies are disposed to unite atom to atom singly or if either is in excess, it exceeds by a ratio to be expressed by some simple m ultiple of the number of its atoms. (5)
The Massive Researches of Berzelius It was this paper of Wollastons, reproduced in Nicholsons Journal in November 1808, that first gave Berzelius any indication of Daltons theory as the Napoleonic blockage had prevented his receiving earlier publications from England. He was in the course of preparing a text book of chemistry in Swedish and had been impressed by his reading of Richters work on stoichiometry when Wollastons paper reached him and he realised at once the enormous
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significance of D a l t o n s g en e ra lis a tio n . Im m e d ia te ly B erzerlius set him self the task of d e term in in g the definite a n d sim p le p ro p o r tio n s in w h ic h th e c o n s ti tu e n t p arts of inorganic s u b s t a n c e s are u n ite d w ith ea ch o t h e r , p ro p o sin g to estab lish the atom ic weights of a ll the elem ents th e n k n o w n a n d to this en d to im pro ve the infant tech n iq u e s of q u a n t i t a t i v e analysis. By 1814 he was able to p u b l i s h in T h o m s o n s Annals of Philosophy (tra n sla ted m u c h later into G e rm a n ) a te n ta tiv e ta b le of ato m ic w eights, b a s e d on oxygen ta k e n as 100, including those for r h o d i u m , p l a t i n u m a n d p a lla d iu m , w ith all the evidence on w hich he h a d b ase d h i s calcu latio ns, while a t th e s a m e time, b e c o m ing w earied w ith the need to re fer re p e a te d ly to th e e lem e n ts by th e ir full nam es, he p ro p o se d the use of o u r now fa m ilia r sy m b ols b a s e d u p o n th e initial letter of th eir L atin nam es (or u p o n this follow ed b y a secon d letter from th e b o d y of the n a m e ) to replace th e r a th e r c u m b e r s o m e circ u la r sy m bo ls devised by D alto n. T h u s we a c q u ired the sym bol P t for p la tin u m , w hile his first suggestion for p a lla d iu m PI, was later revised to Pa to avoid confu sion w ith p l a t i n u m a n d finally to Pd. Sim ilarly he p r o p o s e d I for irid iu m la te r revised to Ir, a n d R, c h a n g e d to Rh, for rh o d iu m . (6) I n 1818 a fuller version of t h e atom ic w eig hts of a lm o s t all th e elem e n ts a p p e a re d b u t still excluding ir i d i u m a n d o sm iu m (7). T h e s e w e re a g a in all b ase d u p o n th e atom ic weight of o x y g e n tak en as 100 a n d w e re re a s o n a b ly close to m o d e r n values except th a t s ev e ral w ere in error, b ein g twice th eir real value b ec a u s e of his a s s u m p tio n th a t m o s t oxides h a d a sim p le form u la, consisting of one a to m of m etal a n d tw o of o xy g en , a n e r ro r t h a t he la te r corrected. T h i s a m az in g achievem ent w a s s u rp a ss e d so m e te n years late r in so far as one of his favourite p ursuits, th e c h e m i s t r y of th e p l a t i n u m m etals, w as c o n c e r ned. R eferen ce was m a d e on p a g e 240 to C o u n t K a n k r i n s en d in g to Berzelius tw o sm all sam ples of native p l a t i n u m from th e U ra ls to g e th e r w ith a perso n al note asking him to an alyse th e m a n d to b e good e n o u g h to re p o r t his results. H e h a d a lre ad y noticed th a t th e e a r l y results o b ta in e d in the R u s s ia n m in in g la b o ra to ry a n d in Paris by L a u g i e r sho w ed m a rk e d differences a n d he realised t h a t th ere w as a g re at deal still t o be esta b lis h e d a b o u t th e m e a n s of s e p a ra tin g the five m etals of th e p la tin u m g r o u p so far know n. Berzelius th ere fo re e m b a r k e d u p o n a th o rou gh ex a m in a tio n of th e s e specim ens. H e b e g a n w ith r h o d i u m a n d quickly fou nd th a t his earlier w o r k (6) c a rrie d o u t on a s a m p le p re s e n te d to him by W ollasto n, co n ta in e d errors i n his c a lc u la tio n of its a to m ic w eight. T h i s he pro c e e d e d to correct, a n d h e t h e n went o n to d e t e r m in e th e a to m ic w eights of palla d iu m , iridium , p la tin u m a n d o sm iu m . F r o m all this w ork he p u t to g e th e r a r a th e r c o m p licated schem e for th e s e p a ra tio n of th e c o n s titu e n ts of native p l a t i n u m on a n an aly tical scale a n d so for th e first tim e pro v id ed m e a n s for a re aso n ab ly a c c u ra te analysis for t h i s m a te r ia l a n d th e p r o d u c ts o b ta in e d from it (7). H e found th a t th e N izh n y T a g i l m in e ra l c o u ld be div ided into m a g n e tic and n o n -m a g n e tic portions a n d he a n a ly s e d th e s e sep a rately . O n th e o th e r h a n d , the m in era l from G o ro b la g o d a t w a s com pletely n o n -m a g n e tic , b u t from a n o th e r p o in t of view was n o tew o rth y i n being alm o st co m p letely free from iridiu m
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(a p art from o sm irid iu m ). F or th e sake of c o m p a r is o n he c o n d u c te d a t the sa m e tim e analyses of som e native p l a t i n u m from C o lo m b ia. H is results a r e given in his p a p e r as follows:
Platinum Iridium Rhodium Palladium Iron Copper Osmiridium Insoluble Nizhny Tagil Non-Magnetic Magnetic 78.91 73.58 4.97 2.35 0.86 1.15 0.28 0.30 11.01 12.98 0.70 5.20 1.96 2.30 Goroblagodat 86.50
Colombia 81.30 1.46 3.46 1.06 5.31 0.74 1.03 (Os)
1.15 1.10 8.32 0.45 1.40
T h is m assive a n d m a sterly a c c o u n t of th e ch e m is try of th e e n tire g ro u p of p la tin u m m etals th e n k n o w n to exist, inclu d in g a stu d y of th eir salts a n d d o u b le salts, was p re s e n te d to the R o y al S w edish A c a d e m y of Sciences, in 1828 a n d re p ro d u c e d in G e r m a n in P o gg en d o rffs Annalen in th e s a m e y e a r a n d in F ren c h a y ear later (8). Klaus, in his m o n o g r a p h referred to in th e last c h a p te r, w rote th a t this trea tise b e c a m e a governing factor for all th e s u b s e q u e n t w o rk o n this su b je c t . A fu rth e r ten years p asse d before Berzelius c a m e to express his a to m ic weights on th e basis of h y d ro g e n as unity. H is revised ta b le of 1838 (9) includes these values, alongside w h ich have b e e n set th e a c cep ted figures today.
0 = 100 Platinum Rhodium Palladium 1215.026 750.680 714.618 H=1 194.753 120.305 114.526 Modern Value 195.09 102.9055 106.4
A nd so Berzelius, a m o n g his m a n y o th e r activities, p u t th e analysis of the p la tin u m g ro u p of m etals o n a s o u n d a n d p r o p e r basis a n d e s ta b lis h e d m o st of their atom ic weights.
T h e C o n tr ib u tio n s o f F ried rich W o h le r

A n u m b e r of G e r m a n stu d e n ts s p e n t p e rio d s of tim e w ith B erzelius in S to c k h o lm before tak in g up im p o rta n t c a ree rs in ch e m is try in th eir o w n co u n try . O n e of the first of these was F rie d ric h W o h le r, w h o m a d e th e j o u r n e y in 1823 o n th e advice of his te a c h e r at H eid e lb e rg , L eo p o ld G m elin , sp e n d in g a y e a r u n d e r g o in g a rigorous tra in in g in ch em ical an alysis a n d form ing a life-long frie n d sh ip with Berzelius. Before leaving H e id e lb e rg , however, W o h le r in c o lla b o r a tio n w ith G m e lin h a d p u b lis h e d a p a p e r o n th e discovery of th e d o u b le p o ta s s iu m cyanides of b o th p la tin u m a n d p alla d iu m . (10) T h e discovery of new elem e n ts w as a p r o m i n e n t fe atu re of inorganic c h em istry d u rin g this period, a n d after O e r s t e d s discovery of a lu m in iu m W ohler, on his r e tu r n to Berlin, set him self th e task of its iso latio n b y h e a tin g its
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F r ie d r ic h W o h l e r
O ne of ill* firsi G erm an students to benefit from a period under Berzelius. \\ oilier becam e his life long friend and the translator of his works into (erman. ^ bile Professor of Chemistry at Cassel he investigated the separation of the platinum metals and devised a method of separating iridium and osmium that was used commercially. F or many years afterw ards he was Professor of Chemistry at Gottingen, the I diversity founded by King George II of England, and his interest in the platinum metals continued
1800-1882
chloride with potassium but found that the reaction was so violent that his glass apparatus was immediately shattered. He therefore turned to the use of a platinum crucible with a cover, held on by a piece of platinum wire. He succeeded in obtaining molten aluminium in 1827 recording that: A year later he successfully undertook the preparation of metallic beryllium (then known as glucinium) by exactly the same procedure. ( 1 1 ) Some years later, when Professor of Chemistry at Cassel, and following up an earlier observation by Berzelius, Wohler investigated the separation of the platinum metals and devised a method for the refining of iridium and osmium by heating the insoluble residues with sodium chloride in a stream of chlorine. This converted the two metals to soluble chlorides that could then be separated in solution (12). This process w'as used by platinum refiners for many years, while Wohlers interest in the subject also remained alive for a long period. The great American historian of chemistry, Dr. Edgar Fahs Smith (1854-1928), who had spent two years in the 1870s under Wohler, now Professor of Chemistry at Gott ingen University, once reminisced towards the end of his life about this formative
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At the moment of reduction the crucible becam e intensely red hot, both within and without, but the metal of the crucible was not sensibly acted upon.
period a n d recalled th a t o ne of W o h l e r s favourite q u e stio n s to a c a n d i d a t e for the Ph.D . degree w as: Will you tell me how you would separate the platinum metals from each other. (13) A t least tw o of W o h l e r s s tu d e n ts w e re to p lay lead in g p a r ts in th e d ev elo p m ent of th e p l a t i n u m in d u s try in G e r m a n y , as will b e seen later.
P la tin u m in the D e v e lo p m e n t o f A n a ly tica l C h e m istr y

T h e general ac ce p ta n c e of th e a to m ic th eo ry a n d of the co n c e p t of definite n um erical p ro p o rtio n s in chem ical c o m p o s itio n gave a g re a t im p e tu s to analytical chem istry. In th e tim e of th e ea rlier an aly sts, B e r g m a n a n d V a u q u e lin for exam ple, the c o m p o sitio n of very few m in e ra ls w as k n o w n w ith a n y deg ree of certainty. K la p r o th was p r o b a b ly th e first to d e te r m in e th e re a s o n a b ly exact c o n stitu tio n of a g re a t n u m b e r of m in era ls, b u t it w as Berzelius w ho laid th e foun dation s of m o d e r n g rav im etric analysis, im p ro v in g its a c c u ra c y a n d devising a n u m b e r of p ro c e d u re s th a t are still in u se today. A n im p o r t a n t p a r t in this progress w as b r o u g h t a b o u t by th e in tro d u c tio n of crucibles m a d e in p l a t i n u m to replace th e clay crucibles form erly u sed for ignitions a n d fusions. E a r ly in his ca ree r he lodged w ith th e w e a lth y iron m a s te r a n d m inero log ist W ilh e lm H isin g er (1 7 6 6 -1 8 5 2 ) a n d in 1808 Berzelius co uld re co rd th at: Only one single platinum crucible was to be found in Sweden. It was owned by Hisinger, who was kind enough to put it at my disposal, but it was too heavy for the balance. (14) T w o years later, however, h e w as re p o rtin g th e use of a p l a t i n u m crucible as a m a t t e r of ro u tin e (15), w hile m u c h later on, in a p a p e r d ea lin g w ith analy tica l pro ced ures a n d a p p a ra tu s , he w rote: Since platinum crucibles have been available they have become quite indispensable in chemical research and so much has become possible that was for merly impracticable. (16) T h e develop m ent of m in in g a n d of th e eng in ee rin g in d u s try in th e n in e te e n th c e n tu ry n ec essitated even g re a te r a tte n tio n b ein g p a i d to m e th o d s of analy sis a n d this s ta te m e n t from Berzelius was la te r ec hoed b y J u s t u s von Liebig (1803-1873). W ritin g from his fa m o u s re se a rc h a n d teac h in g l a b o ra to ry in G iessen in 1844 he co m m e n te d : Without the use of platinum the composition of most of the mineral species would still be unknown. (17)
T h e C o -o r d in a tio n C o m p o u n d s o f P la tin u m
E arly in the n in e te e n th ce n tu ry th e stu d y of th e c o m p o u n d s of p l a t i n u m b e g a n to interest a n u m b e r of chemists. T h e existence of a m m o n i u m c h lo ro p la tin a te was of course well k n o w n as the source of th e p u r e m etal o n heatin g, a n d o th e r sim ilar triple salts w ere soon recognised. O n e of th e first to u n d e r ta k e a n
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investigation of a w ide ra n g e o f c o m p o u n d s w as E d m u n d Davy, th e y ou ng c o u sin of H u m p h r y Davy, w h o se initial discoveries in th e field of cataly sis w ere d escribed in the previous c h a p te r. I n 1812, w hile still a n a s s is ta n t to his c o u sin at th e R o yal In s titu tio n in L o n d o n , he p u b lis h e d a long p a p e r in The Philosophical M agazine (18), O n Som e C o m b in a ti o n s of P l a t i n a , in w h ich he re p o rte d his findings on its reactio ns w ith s u lp h u r, p h o s p h o ru s , oxygen, c h lo rin e a n d a m m o n ia, con c lu d in g his p a p e r w i t h a r a t h e r p r o p h e tic c o m m e n t: Platina appears to be characterised no less by its valuable properties than by its disposition to form peculiar triple compounds; and there can be little doubt that a more extensive acquaintance w iih the combinations of this metal will add con siderably to the number of such substances. It would be an interesting inquiry, whether the same laws which seem to govern the formation of binary compounds extend likewise to those of ternary compounds. For an investigation of this kind no metal seems so well adapted as platina. In the following y ea r V a u q u e l i n re p o r te d th e discovery of a c o m p o u n d of p a lla d iu m w ith a m m o n ia a n d ch lo rin e , a salt of a very a g re e a b le rose c o l o u r t h a t w e now know as [ P d ( N H 3) 4] [ P d C l J or as V a u q u e l i n s salt. (19) T w o chlorides of p la tin u m w e r e k n o w n at a n early stage, p la tin ic chloride, P t C l 4 w hich was investigated b y Berzelius w h o em p lo y ed its d o u b le salt w ith , p o ta s siu m chlorid e in his first d e t e r m i n a t i o n of th e ato m ic w e igh t of p la tin u m , a n d p latin o u s chloride, P t C l 2. I t w a s w hile w orking w ith this l a tte r c o m p o u n d d u r in g his stay w ith Berzelius in 1827 t h a t H e in r ic h G u stav M a g n u s discovered th e co rresp o n d in g p la tin u m salt, [ P t ( N H , ) J [ P t C l J . (20) T h e co n stitu tio n a n d s t r u c t u r e of these first c o - o rd in a tio n c o m p o u n d s r e m a in e d u n k n o w n for m a n y y e a r s a n d th ey w e re cu s to m a rily n a m e d after th eir discoverers. T his, his new c o m p o u n d - th e first p l a t i n u m a m m i n e to b e p r e p a r e d - was k n o w n then, a n d still is., as M a g n u s G r e e n S alt; it h a s b e e n th e subject of a gre at deal of stu d y ever since a n d h a s p la y e d a n i m p o r t a n t p a r t in the developm en t of c o - o rd in a tio n ch e m is try b e c a u s e of th e g re a t stab ility of this a n d o th er p la tin u m c o m p o u n d s . A review of this p io n eerin g w o rk b y M a g n u s a n d its significance w as c o n t r i b u t e d to Platinum M etals Review a few y ea rs ago by Professor G e o rg e K au ffm an . (21) T e n years later a tw e n ty -o n e year old s tu d e n t from A lsace n a m e d J a m e s G ros, working in L ie b ig s la b o r a t o r y in G iessen, p r e p a r e d several ch lo rin a te d derivatives of M a g n u s salt w h i c h h e d e s c rib e d in L ie b ig s Annalen in a p a p e r O n a N ew C lass of P l a t i n u m S a l t s (22), w hile in 1840 J u l e s Reiset (1818 1896), w orking in th e p r iv a te la b o ra to ry of Professor P elo u ze in Paris, p re p a re d th e base P t ( N H 3) 4( O H ) 2, of w h ic h he re g a rd e d th e salts of b o th M a g n u s a n d G ros as c o m p o u n d s . (23) T h e subject w as ta k e n u p by a n Ir is h chem ist, R o b e r t J o h n K a n e (1809 1890) a fte rw a rd s S ir R o b e r t th e P rofessor of N a t u r a l P h ilo so p h y to the R oyal D u b lin Society. In 1836 K a n e h a d also s p en t som e tim e in L ie b ig s la b o ra to ry a n d in a c o n tr ib u tio n to The Philosophical M agazine in 1841 he a rg u e d th a t R e is e ts salt was not at all c o n s titu te d as th e la tte r h a d d e sc rib ed it (24).
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Heinrich Gustav Magnus 1802-1870

A fter t a k i n g his d o c t o r a l d e g r e e in t h e I n i v e r sity o f B e r l i n in 1827 M a g n u s , a d v i s e d by M i t s c h e r l i c h a n d W o h l e r , w en t to S t o c k h o l m fo r f u r t h e r stu d y u n d e r B e rz e l i u s . It w a s h e r e t h a t he d i s c o v e r e d t h e first c o m p l e x c o m p o u n d of p l a t i n u m a n d a m m o n i a , k n o w n a l w a y s as Ma gn us* G r e e n S a l t , a n d the f o re r u n n e r of a great n u m b e r of co o rd in a tio n co m p o u n d s . H e was later a p p o i n t e d P r o f e s s o r of T e c h n o l o g y a n d P h y s i c s in t h e I niv ersity of B e rl i n
R eiset p u rs u e d th e m a tte r, a n d late r o b ta in e d a second series of c o m p o u n d s c o n tainin g only h alf th e a m o u n t of a m m o n i a as in th e first series from w h ic h th e socalled R e is e ts S eco n d C h lo rid e w as p r e p a r e d (25). S im ultaneo usly, a n d qu ite in d e p e n d e n tly , a n Ita lia n , M ich ele P eyrone (1814-1883), a g a in in L ie b ig s la b o ra to ry , p r e p a r e d a yellow c h lo rid e h av in g the sam e c o m p o sitio n as this second ch lo rid e of R e i s e t s b u t differing en tirely in its pro perties (26), a finding th a t w as tre a te d w ith incredibility b y m a n y chem ists until the co n cep t of isom erism , a n o t h e r te rm co in ed b y Berzelius, w as a c cep ted for inorganic c o m p o u n d s. P ey ro n e h a d stu d ie d m e d ic in e at th e U n iversity of T u rin , b u t at th e age of twenty-five a b a n d o n e d th is profession to ta k e up chem istry, s tu d y in g first u n d e r D u m a s in P aris a n d th e n going to G iessen. H is p a p e r was a b s tra c te d by Reiset in th e j o u r n a l he h a d j u s t fo u n d e d , Annuaire de Chimie, b u t the e d ito r c la im e d th e discovery as his o w n (27). P ey ro ne re s p o n d e d sm artly to the effect th a t his o w n discovery h a d b e e n m a d e m o re t h a n ten m o n th s before its p u b lic a tio n a n d th a t tw o of R e i s e t s friends a n d co lleagues h a d b e e n observers of his w ork in G iessen d u rin g 1843. (28) In the succeeding volu m e of his new j o u r n a l R e is e t r e m a in e d u n im p ressed . H e duly a b s tra c te d P e y ro n e s seco nd p a p e r, b u t a d d e d : T he study of these isomers is of great interest, but the conditions surrounding these phenomena must be subjected to a rigorous definition which M. Peyrone has not always managed to obtain. (29)
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P eyrone was not, however, d ese rv in g of these stric tu re s o n his ability. H e was in fact the first to identify t h e tr u e fo r m u la tio n of M a g n u s G r e e n Salt as [ P t ( N H s) J [ P t C l J . P ey ron e late r re tu r n e d to I t a l y as a Professor, first in G e n o a a n d th e n in the U niversity of T u r in , taking a le a d in g p a r t in a g ric u ltu ra l ch e m istry . H e c o n tin u e d to w ork o n isom ers of M a g n u s Salt, re p o rtin g his re s u lts to th e R oyal A c ad em y of Science of T u r i n in 1847, his p a p e r b ein g p u b lis h e d by L ieb ig with w h o m he m a in ta in e d a life-long c o r r e s p o n d e n c e (30). P e y ro n e h a s som e claim to d istin ction in th a t his first c o m p o u n d , still k n o w n as P e y r o n e s ch lo rid e b u t now identified as m - d i c h l o r o d i a m m i n e - p l a t i n u m (II), h as b e e n fo u n d in re c e n t years to b e a m ost effective m e a n s of t r e a t i n g a n u m b e r of types of cancer. F u r t h e r investigations w e re c a rrie d ou t b y a R u s s ia n ch e m ist n a m e d Rajewski, w orking u n d e r P e lo u z e a t th e C ollege de F r a n c e in P a ris a n d k n o w n th e re as R aew sky, w ho re a c te d M a g n u s salt w ith n itric acid a n d o b ta in e d yet a n o th e r series of c o m p o u n d s differing from th o se p r e p a r e d by G ro s (31). M u c h d iscussion a b o u t th e c o n s titu tio n of th e s e c o m p o u n d s w as n o w going o n and th e d e b a te w as en tered b y th e t w o fa m o u s b u t u n f o r tu n a te c o lla b o ra to rs C h a rle s G e r h a r d t a n d A u g u s te L a u re n t. I n tw o p a p e rs p u b lis h e d in t h e j o u r n a l th ey h a d them selves estab lish ed (32) a n d i n a fu r th e r re p o rt to th e A c a d m ie des Sciences by G e r h a r d t alone (33) they a s c r ib e d fo rm u la e in the m a n n e r of th e tim e to all these p re p a ra tio n s a n d gave a p l a u s i b l e e x p la n a tio n of th e ir stru c tu re s a n d of the re latio nsh ip of one series to a n o th e r . A few years later interest w a s still increasing, not only in p l a t i n u m b u t in its allied m etals, a n d by 1854 K a rl K l a u s c o u ld o p e n a p a p e r w ith th e s e co m m e n ts: The discovery of Gros Salt led the way to a series of curious compounds of platinum which so attracted the attention of chemists that very shortly thereafter Reiset, Peyrone, Raewsky, Laurent and G erhardt occupied themselves with the subject and considerably increased their number. J u st recently Skoblikoff [in St. Petersburg] and Hugo Miiller [in Gttingen] have made known two new such com pounds of iridium and palladium a n d I can now add two others based upon rhodium and a second of iridium, to join them, while at the same time I am in the course of pre paring similar compounds of osmium and ruthenium. (34) O n e of the rh o d iu m c o m p le x e s m e n tio n e d , c h l o r o p e n t a m m i n e rh o d iu m chloride, was inevitably k n o w n f r o m th e n o n w a rd s as K l a u s Salt. M u c h later a m a jo r stu d y of th e s e a m m o n ia c a l p l a t i n u m c o m p o u n d s was u n d e r ta k e n by th e S w edish c h e m is t P e r T e o d o r Cleve (1840 1905) w ork in g in th e la b o ra to ry of th e A c a d e m y o f Sciences in S to c k h o lm after a sh o rt p e rio d of stu d y u n d e r Professor W u r tz i n Paris. H e first e x a m in e d th e c o m p o u n d s o b ta in e d by G ros, R eiset a n d R a e w s k y , p u b lis h in g his fin din gs o nly in Swedish, a n d th e n discovered a n entirely n ew series of salts c o n ta in in g tw o a to m s of p l a t i n u m by th e a c tio n of a m m o n i a o n th e iodine derivatives of G r o s base, while he also found th a t tetra v alen t p l a t i n u m yielded a series of a m m o n i u m c o m p o u n d s . T h is w ork occu p ie d h im for six years, a n d he finally a ss e m b le d all his results in a m e m o ir in E ng lish d e ta ilin g th e system atic a r r a n g e m e n t of th e m a n y c o m p o u n d s t h e n k n o w n (35). 262
A lfre d W e r n e r 1866-1919
F o r m an> y e a r s t h e s t r u c t u r e o f t h e m a n ) c o m p l e x c o m p o u n d s of p l a t i n u m a n d o th er m etals re m a in e d u n certain . In 18 93 W erner, ju st appointed P r o f e s s o r o f C h e m i s t r y at Z r i c h , a f t e r c a r r y i n g o u t r e s e a r c h o n t h e m etal* a m m o n i a c o m p o u n d s , p u t f o r w a r d his c o -o rd in a tio n theory a n d e x p la in e d the sp a tia l a rra n g em en ts of th e c o m p o n e n t s o f th e s e c o m p l e x e s . In 19 13 h e was a w a r d e d t h e N o b e l P r i z e in C h e m i s t r y f o r t h is a c h i e v e m e n t
G re a t difficulty w as still ex perienced in th e assigning of s tru c tu re s to th e ever growing n u m b e r of co m p lex c o m p o u n d s of this type, b u t in 1893 th e well k n o w n c o -o rd in a tio n theo ry p u t fo rw a rd by A lfred W e rn e r , P rofessor of C h e m is tr y at Z u ric h at th e age of only twenty-six, not only y ielded a satisfacto ry e x p la n a tio n b u t also e n a b le d new c o m p o u n d s w ith p re d ic ta b le p ro p e rtie s to be synthesised (36). H e followed w ith a p a p e r jo in tly w ith his friend a n d c o lla b o r a to r A r t u r o M io la ti (1869-1 956 ), a n Ita lia n w h o h a d b ee n a fellow s tu d e n t of W e r n e r s at th e T e c h n ic a l H ig h School in Z u rich . T o g e t h e r they m e a s u r e d t h e m o le c u la r conductivities of m a n y co m p lex c o m p o u n d s inclu d in g th o se of p la tin u m , finding th a t th e n u m b e r of ions always agreed w ith th e c o - o rd in a tio n theo ry (37). In 1966, the c e n te n a ry of W e r n e r s b irth, a review of his w ork o n th e s tr u c tu r e of p la tin u m com plexes w as c o n trib u te d to Platinum M etals Review , by Dr. W . A. S m eato n, w hile a m o re d e tailed ac c o u n t h as b e e n given by P rofessor G e o rg e B. K a u ffm a n of W e r n e r s controversy w ith yet a n o t h e r D a n e, Professor S o p h u s M a d s j 0 r g e n s e n (1 8 3 7 -1 9 1 4 ) of the U niv ersity of C o p e n h a g e n , w h o h a d also p re p a re d a n u m b e r of co -o rd in a tio n c o m p o u n d s of p l a t i n u m a n d rh o d iu m . (39)
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T h e First O r g a n o m e ta llic C o m p o u n d s
T h e stu d y of orga n o m e tallic c o m p o u n d s of the p l a t i n u m m etals h a s b ec o m e intensive only d u rin g th e last tw o o r th ree decades, w hile th e ir gre at usefulness in h o m ogeneo us catalysis h as b e e n recognised a n d is now b ein g a d o p te d in the c h e m ic al in dustry. T h e origin of t h i s m a j o r d ev e lo p m e n t goes b a c k very m a n y years, however, a n d once a g a in to S c a n d in a v ia . T h e first p l a t i n u m c o m p o u n d of this ty pe - in fact th e first s u c h c o m p o u n d of an y tra n s itio n m etal - was a p l a t i n u m ethy lene com plex p r e p a r e d in 1830 b y W illia m C h r i s t o p h e r Zeise in C o p e n h a g e n a n d kno w n inevitably from t h e n o n w a rd s as Z e is e s Salt. T h e son of a n ap o th ec ary , Zeise b e c a m e a l e c tu r e a s sistan t to H a n s C h r i s t ia n O e r s t e d a n d th e n in 1822 w as a p p o in te d P ro fe sso r of C h e m is tr y in th e U n iversity of C o p e n h a g e n after sp en ding som e t im e u n d e r Professor S tr o m e y e r at G o ttin g en . I n th a t year he discovered the x a n t h a t e s a n d in 1825 h e p r e p a r e d a c o m p o u n d of p la tin u m , c a rb o n a n d oxygen w h i c h he fo u n d w o u ld ignite alcohol j u s t as w o u ld E d m u n d D a v y s p r e p a r a ti o n m e n t i o n e d e a rlier in C h a p t e r 12 (40). F ollow ing th is line of researc h five years l a t e r he inv estigated th e re a c tio n b e tw e e n alcohol a n d p latin o u s ch loride a n d p r e p a r e d the p o ta s s iu m salt K [ P t C l 3( C 2H 4)] in the form of b eau tifu l yellow c r y s t a l s . T h is basic discovery was a c tu a lly first r e p o rte d in L a t i n to the R o y al D a n i s h A c a d e m y of Sciences in N o v e m b e r 1830 a n d w as re p ro d u c e d in th e follow ing y e a r in m o s t of th e G e r m a n ch em ical
W illia m C h r i s t o p h e r Zeise
I 789-1847 B e g i n n i n g his c a r e e r as a p h a r m a c i s t , Z eise b e c a m e a n a s s i s t a n t to O e r s t e d in the University of C o p e n h a g e n and t h e n , a f t e r a p e r i o d w ith S t r o m e y e r in G o t t i n g e n , r e t u r n e d t h e r e as P r o f e s s o r o f C h e m i s t r y . H e p r e p a r e d t h e first org an o m etallic c o m p o u n d s of p la tin u m in 1830. so l a y in g t h e f o u n d a t i o n s of t h e m u c h l a t e r i n v e s ti g a t i o n s o f t h e g r e a t n u m b e r o f s u c h c o m p o u n d s o f all the platinum m etals and their u s e f u l n e s s in h o m o g e n e o u s c a t a l y s i s
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jo u rn a ls (41). Zeise gave full details of his analysis of th e new c o m p o u n d , b u t he u n fo rtu n a te ly b e c a m e th e recipient of som e h a r s h criticism from J u s t u s von Liebig, a lre ad y in deep controversy w ith D u m a s a b o u t th e c o n s titu tio n of alcohol a n d ether, w ho cla im e d t h a t Z e ise s analysis w as in e r ro r (42). O b j e c t ing strongly to L ie b ig s u n p l e a s a n t co m m e n ts , Zeise re p e a t e d his analyses, c o m pletely verifying th e c o m p o s itio n of th e new salt (43), b u t Liebig, re p ro d u c in g th e p a p e r in his o w n Annalen , followed it im m e d ia te ly w ith a n o t h e r long polem ical c o n trib u tio n O n th e E t h e r T h e o r y w ith S pecial R e fe re n c e to th e P r e ceding C o m m u n ic a tio n of Z e is e (44). T h e co rrectness of Z e is e s re su lts was established, a n d he w e n t o n to p r e p a r e fu rth e r o rg a n o m e ta llic c o m p o u n d s of p la tin u m w ith aceton e (45), as well as som e a m m o n i u m a n d p o ta s s iu m ethyl p la tin u m com plexes t h a t he d escribed in a text book in D a n is h th a t h e p u b lis h e d d u rin g the last y e a r of his life. (46) T h is w ork was followed up by C h a rle s A d o lp h e W u r tz (1817 1884), a n o th e r s tu d e n t of L ie b ig s, w h o discovered m e th y la m in e a n d e th y la m in e in 1849 ju s t after he h a d succeeded D u m a s as lectu rer in o rg a n ic c h e m is try at th e cole de M d e cin e in Paris. In th e course of this investigation he p r e p a r e d golden-yellow crystalline com plexes of p la tin o u s ch lo rid e w ith b o th th ese new c o m p o u n d s . (47) T h e th irty -y ea r old controversy b e tw e e n Zeise a n d L ieb ig w a s revived in L o n d o n by tw o assistants of A u g u s t W ilh e lm H o f m a n n (1818 1892), yet a n o th e r Liebig s tu d e n t w h o h a d b ee n p e r s u a d e d by th e P rin ce C o n s o rt to accep t the post of Professor of C h e m is tr y in th e newly fo u n d e d R o y a l C o lleg e of C h e m is try in 1845. T h e s e w ere J o h a n n P eter G riess (1 8 2 9 -1 8 8 8 ) w ho h ad stu d ied first at J e n a a n d t h e n u n d e r K o lb e at M a r b u r g a n d w h o h a d been invited to L o n d o n in 1858 b y H o fm a n n , a n d C a rl A l e x a n d e r M a r ti u s (1838 1920) w hose in a u g u ra l d iss e rta tio n a t G o ttin g e n before co m in g to L o n d o n h a d b e e n on th e cy a n ides of th e p l a t i n u m m etals. T h e y first confirm e d Z e is e s fo rm ula a n d d e m o n s tra te d th a t eth y len e w as lib e ra te d w h e n his c o m p o u n d was d ecom posed, going o n to p r e p a r e a n a lo g o u s salts c o n ta in in g s o m e of the new organ ic m olecules discovered by H o f m a n n such as d ip h e n y l am ine, ethylene d ia m m in e a n d aniline (48). G riess is b e tte r k n o w n for his discovery of the diazo c o m p o u n d s a n d for his later long c a re e r as c h e m ist to A lls o p p s b rew ery in B u rto n -o n -T r e n t, la te r b e c o m in g a Fellow of th e R o yal Society a n d one of th e fo und ers of th e In s titu te of C h e m is try , w hile M a r ti u s w as the discoverer of n a p h th a le n e dyes a n d th e fo u n d e r of th e A G F A c o n c e rn in Berlin. T h e stu d y of these o rg a n o m e tallic c o m p o u n d s of p l a t i n u m w as also ta k e n up by K arl B irn b a u m (1839 1887), P rofessor of C h e m is tr y in th e K a r ls r u h e Polytechnic, w h o in 1867 u n d e rto o k th e ir synthesis b y a different route, sta rtin g w ith ethylene itself. H e succeed ed in o b ta in in g not only th e o riginal Z eise salt b u t its hom o log us w ith p ro p y le n e a n d am ylen e. (49) No fu rth e r w ork seems to have bee n c a rried o ut on these co m p lex e s for a very long time, in fact not until 1907 w h e n W. J. Pope (later Sir W illia m J a c k s o n Pope) a n d his colleague Stanley J o h n P eac h y at th e U n iversity of M a n c h e s t e r
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a n n o u n c e d to a m eeting of th e C h e m i c a l Society t h a t all th e six p la tin u m m etals h a d b ee n found to react w ith m a g n e s i u m m ethy l iodide. T w o y ears later they described in detail th e p r e p a r a t i o n of a n u m b e r of alkyl c o m p o u n d s of p la tin u m (50). T h e c h a ir m a n of the e a r l i e r m eeting, S ir H e n r y R oscoe, c o n g r a tu la te d these tw o a u th o rs on having opened out an entirely new branch of investigation which might indeed be said to be a wonderful find. T h e r e is now, of course, a v a s t lite ra tu re on th e o rg a n o -m e ta llic c o m p o u n d s of all six p la tin u m m etals, on t h e i r c o n s titu tio n a n d o n th e ir a c tu a l a n d p oten tial a p p lica tio n s in chem ical ind ustry.
T h e A b s o r p tio n o f H y d r o g e n by P a lla d iu m
O n e fu rth e r n in etee n th c e n tu r y discovery th a t h as b e c o m e of co n s id e ra b le indu strial im p o rta n c e was th e a b ility of p a lla d iu m , far in excess of t h a t of any o th e r m etal, to a b s o r b h y d rog en . T h is s te m m e d from th e re s earc h es of T h o m a s G r a h a m (1805 1869) w ho s u c c e e d e d A n d r e w U r e as L e c t u r e r in ch e m is try at A n d e r s o n s College in G lasgow a n d t h e n in 1837 followed E d w a r d T u r n e r as Professor of C h e m is tr y at U n iv e rs ity College, L o n d o n . I n a p a p e r re ad to the R o y a l Society of E d i n b u r g h in 1831 (51), G r a h a m su cceed e d in es ta b lis h in g th e re lation ship b e tw e en the ra te of diffusion of a gas a n d its d ensity - th e well k n o w n G r a h a m s L a w - a n d for t h e re m a in d e r of his life he c o n tin u e d to interest him self in p ro b lem s of diffusion. In 1854 he resigned from U n iv e rs ity C ollege o n his a p p o i n t m e n t as M a s t e r of the R o y a l M i n t in succession to S ir J o h n H e rs c h e l a n d his energies w e re for som e years entirely devoted to t h e duties of his office, in c lu d in g th e supervision of th e m a jo r c h a n g e from c o p p e r to b ro n z e coinage. L a t e r he w as ab le to c o n tin u e his w ork on diffusion, a n d in 1866 h e p re s e n te d a p a p e r to th e R o y al Society, O n th e A d s o rp tio n a n d D ialy tic S e p a r a t i o n of G a s e s b y C olloid S e p t a (52). H e h a d first stu d ie d th e b e h a v io u r of h y d ro g e n exposed to re d -h o t p la tin u m a n d h a d found th a t n o t only w as it a b s o r b e d b u t th a t it cou ld be re ta in e d for a n indefinite time, a n d th a t no o th e r gases sh o w ed th e s a m e effect. T u r n i n g from p la tin u m to p a l l a d i u m , G r a h a m fou nd th a t it c o u ld a b s o rb five o r six h u n d r e d times its ow n v o lu m e of h y d ro g e n a n d t h a t w h e n exposed to coal gas only the h y d ro g e n p e n e t r a t e d th e m etal. N o such effect cou ld be o b ta in e d w ith irid iu m a n d o s m iu m . A y ea r later he show ed t h a t h y d ro g e n c o u ld be o c c lu d e d by p a lla d iu m electrolytically w h e n im m e rsed i n dilute s u lp h u ric acid a n d in c o n ta c t w ith a piece of zinc (53). H is last m a j o r co n trib u tio n , p u b lis h e d only a few m o n th s before his dea th , was on the r e la t io n of h y d ro g e n to p a l l a d i u m (54). I n this he c o n sid ered th a t they form ed a n a llo y or c o m p o u n d a n d t h a t h y d ro g e n w as th e v a p o u r of a highly volatile m e t a l w h ic h he n a m e d H y d ro g e n iu m . H e also s tu d ie d the occlusion of h y d r o g e n by alloys of p a l l a d i u m c o n ta in in g v arying p ercen tag e s of silver m a d e for h i m by G e o rg e M a t t h e y , a n d fo u n d t h e m to give th e sa m e effect p rov ided th a t th e a llo y in g e le m e n t did not exceed 50 p e r cent.
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In 1869, only shortly before his death. G raham had a n um b er of m edallions m ade at the Mint in what he conceived to be an alloy of palladium and ikhydrogenium ,\ the nam e he coined for the form in which hydrogen existed when absorbed. These he distributed to his many friends to dem onstrate the nature of this unusual com bination of a gas and a metal
In all this work Graham had the co-operation of his personal assistant, a young graduate from the Royal School of Mines named W. C. Roberts. On Grahams death Roberts was appointed Chemist to the Mint and became famous later as the metallurgist Sir William Chandler Roberts-Austin whose work with platinum will be referred to later. Exercising his influence at the Mint, Graham had a number of small medal lions struck in his palladium-hydrogenium alloy and distributed these to his many friends. In presenting one to the then Chancellor of the Exchequer, Robert Lowe, he wrote rather quaintly: Some of the curious effects of this unusual phenomenon, particularly the dimensional changes that occur when palladium is alternatively heated and cooled in hydrogen, were investigated in 1893 by Copius Hoitsema in the University of Leyden, working under Professor Bakhuis Roozeboom who had done much to interpret alloy systems in terms of Willard Gibbs Phase Rule. He concluded that two distinct hydrogen-palladium phases were formed, changing as hydrogen is occluded or released (55). (Curiously Hoitsema also left the chemical profession to become Master of the Mint in Utrecht in 1909). This study was but the first of literally hundreds of investigations that have been carried out over the past century and are still continuing. But it was Graham who laid the foundations, and the modern outcome of his work is to be seen in the design arrd operation of equipment to generate high purity hydrogen from a
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The little medallion is com posed of about 9 parts of palladium (a rare m etal) and 1 part of hydrogenium by bulk If the latter took the form of gas, it would measure 8 or 9 cubic inches, or 3 port wine glasses full, to be very plain.
variety of in take gases th a t are n o w relied u p o n by m a n y ty p es of in d u strial users. H y d ro g e n generators, b u ilt b y J o h n s o n M a t t h e y , in c o rp o r a tin g diffusion tu b e s in a silver-p alladiu m alloy, a r e now in service in ap p lic a tio n s as diverse as t h e h y d ro g e n a tio n of edible oils, the m a n u f a c t u r e of s e m i-co n d u c to rs, the a n n e a lin g of stainless steel a n d th e cooling of p o w e r s ta tio n a lte rn a to rs. (56)
R eferen ces for C hapter 14 1 J. B. Richter, Anfangsgrnde der Stchyometrie oder Messkunst chymische Elemente, Breslau and Hirschberg, 1792 2 J. L. Proust, J . de Phys., 1806, 63, 367-369 3 J. Dalton, Mem. Manchester Lit. and l^hil. Soc., 1805, 1, 271-287 4 T. Thomson, Phil. Trans., 1808, 9 8 . 63-95 5 W. H. Wollaston, Phil. Trans., 1808, 98, 96-102, J . Nat. Phil., (Nicholson), 1808, 21, 164-169 6 J. J. Berzelius, Ann. Phil. (Thomson), 1814, 3, 252 257; 353-364; J. (. em. h ( Schweigger), 1817/18, 21, 307-341; 22, 51-77; 317-343 7 J .J . Berzelius, Essai sur la Thorie des Proportions Chimiques, Paris, 1819 8 J. J. Berzelius, Kongl. Vetensk. Akad. Handl., 1828, 16, 25-116; Ann. Phys. ( Poggendorfj), 1828, 13, 435-188; 527-565; Ann. Chim., 1829. 40, 51-82; 138-165; 257-285; 337-350 9 J. J. Berzelius, Ann. Chim., 1838, 28.426^127 10 L. Gmelin and F . Wohler, J . ('hem. ( Schweigger), 1822, 36. 230-231 11 F. Wohler, Ann. Phys. (Poggendorfj), 1827, 1 1, 146 161 12 F. Wohler, Ann. Chim., 1828, 39. 77-84 13 E. F. Smith, J . Chem. Ed., 1928. 5, 1554-1557 14 J .J . Berzelius, Autobiographical Notes, trs. O. Larsell, Baltimore, 1934, 63 15 J. J. Berzelius, Afhandl. Fysik. Kemie Mineralogen, Stockholm, 1810; Ann. Phys. (Gilbert), 181 1, 37, 249-339 ' 16 J. J. Berzelius, J. tech. Chem., 1832, 13, 358 17 J. Liebig, quoted by H. F. Keller, J . Franklin Inst., 1912, 174, 541 18 E. Davy, Phil. Mag., 1812, 40, 209-220; 263-278; 350-365 19 N. L. Vauquelin, Ann. Chim., 1813, 88, 167 186 20 H. G. Magnus, Ann. Phys. ( Poggendorfj), 1828, 14, 239-242 21 G. B. Kauffman, Platinum Metals Rev., 1976. 20, 21-24 22 J. Gros, Ann. Chem. ( Liebig), 1838. 27, 241 256 23 J. Reiset, Comptes Rendus, 1840, 10, 870 872 24 R. J. Kane, Phil. Mag., 1841, 18, 293-296 25 J. Reiset, Ann. Chim., 1844, 1 1, 41 7-43 3 26 M. Peyrone, Ann. Chem. (Liebig), 1844, 51, 1 Ann. ('.him., 1844, 12. 193 29; 211 27 J. Reiset, Annuaire de Chim., 1845, 1, 166 28 M. Peyrone, Ann. Chem. ( Liebig), 1845, 55, 205 213 268
29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56
J. Reiset. Annuaire de Chim., 1846, 224 225

M. Peyrone, Ann Chem. ( Liebig), 1847. 61. 178-181 M. Raewsky, Comples rendus, 1846, 23. 353 354; 1847, 24. 1151-1154; 25, 794-797 A. Laurent and C. Gerhardt, Compt. rend. Trav. Chim., 1849, 5. 1 13 115; 1850, 6, 273-304 C. Gerhardt, Comptes rendus, 1850, 31, 241-244 C, Claus, J . prakt. Chem., 1854, 63, 99-108 P. T. Cleve, On Ammoniacal Platinum Bases, Stockholm, 1872 A. Werner, .anorg. Chem.. 1893, 3. 267-330 A. Werner and A. Miolati, Phys. Chem., 1893, 12, 35 55 W. A. Smeaton, Platinum Metals Rev.. 1966, 10, 140-144 G. B. Kauffman, Chymia, 1960, 6, 180-224 W. C. Zeise, Oversegt Kongl. Dansk. Videnskab Forhandl., 1825-6, 13; Ann. Phys. ( Poggendorff), 1827, 9, 632 W. C. Zeise, Ann. Phys. {Poggendorff), 1831, 21, 497-541; J . Chem.. ( Schweigger), 1831, 62, 393-441; 63, 121-135 J. Liebig, Ann. Chem. (Liebig), 1834, 9, 1-39 W. C. Zeise, Ann. Chim., 1836, 63, 411-431; Ann. Chem. ( Liebig), 1837, 23, 1-11 J. Liebig, Ann. Chem. (Liebig), 1837, 23, 12-42 W. C. Zeise, Ann. Phys. Poggendorff, 1838, 45, 332 336: 1839, 47, 478 480; Phil. Mag., 1839, 14, 84-87 W. C. Zeise, Haandbog de Organiske Staffers almindelige Chemie. Copenhagen. 1847 C. A. Wurtz, Ann. Chim., 1850, 30, 443-507 J. P. Griess and C. A. Martius, Ann. Chem. (Ijebig), 1861, 120. 324 327; Comptes rendus, 1861, 5 3 ,9 2 2 -9 2 5 K. Birnbaum, Ann. Chem. ( hebig), 1868, 145, 67-77 W. J. Pope and S. J. Peachev, Proc. Chem. Soc., 1907, 23, 86; J. Chem. Soc.. 1909, 95, 571-576 T. Graham, Phil. Mag., 1833, 2, 175-190; 269-276; 351-358 T. Graham, Phil. Trans., 1866, 156, 399-439 T. Graham, Proc. Roy. Soc., 1867/8, 16, 422-427 T. Graham, Proc. Roy. Soc., 1868/9, 17, 212-220; 500-516 C. Hoitsema, phys. chem., 1895, 17, 1-42 D. A. Stiles and P. H. Wells, Platinum Metals Rev., 1972, 16, 124-128; M. J. Cole, Platinum Metals Rev., 1981, 25, 12-13
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1781-1858 Born in Philadelphia the son of a brew er who had em igrated from England. H are studied chem istry u nd er Jam es W oodhouse and carried out research on the p roduction of high tem peratu res in his free time. By means of his oxy-hvdrogen blowpipe he becam e the first scientist to succeed in melting platinum in substantial quantity
From a p o rtra it in the possession of (he University of Pennsylvania
R o b e rt H a re
15
The Melting of Platinum and the New Metallurgy of Deville and Dehrav
/ t is therefore necessary to h ave a m e th o d o f treatm ent m ore expeditious a nd m ore p ractical than that now adopted. It is f o r this reason that w e are proposing an entirely new m etallurgy f o r platinum .
H E N R I S A IN T E -C E A IR E D E M I .I E AND JU LES H E N R I DEBRAY
All th e p la tin u m so far d e sc rib ed as having b e e n w o rk ed into useful articles h a d been p r e p a r e d from th e p o w d e r form by hot forging, a n d all a t t e m p t s at its m elting h a d su cceeded only o n a m o st m in u te scale. T h e tim e was a p p r o a c h in g , however, w h e n m elted p la tin u m w as to b e c o m e av ailable to in d u stry . T h e first effective p ro c e d u re w as devised by R o b e r t H a r e , the y o u n g so n of a b re w e r of th e sam e n a m e in P h ila d e lp h ia w h o h a d e m ig ra te d from E n g l a n d in 1773 a n d w ho later b e c a m e S p e a k e r of the S ta te S e n a te of P en nsylv ania. W h ile a t t e n d i n g the lectures o n c h e m istry given b y J a m e s W o o d h o u s e at th e U n iv e rs ity of P en nsylv ania a n d also helping his fa th e r in th e b re w e ry bu sin ess th e y o u n g e r R o b e rt H a r e u n d e rto o k re searc h in his s p a re tim e in t h e cellar of t h e h o u se in which he lodged o n th e c o rn e r of D ock S tre e t a n d W a l n u t S tre e t (1). H e was deeply interested in th e possibility of o b ta in in g very hig h t e m p e r a t u r e s by m e a n s of a n o x y -h ydrog en blo w -p ip e a n d h e w as also a w a re of L a v o is ie rs m e ltin g of a very small a m o u n t of p la tin u m b y th e use of oxygen alone, d es c rib e d in C h a p t e r 4. H e felt t h a t L avoisiers a p p a r a t u s w as b o th too un w ield y a n d too expensive, while he re a so n ed th a t a n even h ig h e r t e m p e r a t u r e w o u ld b e o b ta in e d b y the co m b u s tio n of h y d ro g e n a n d oxygen together. H e th ere fo re d e s ig n ed a n d built the a p p a r a t u s illustrated on th e following page, b a s e d u p o n a b a r re l from the brew ery a n d not n o ticea b ly less u nw ield y or less c o m p lic a te d t h a n L av o isiers e q u i p m e n t ! By su p p ly in g a la m p or a c a n d le w ith a c o n tin u o u s s tre a m of oxygen a n d hy d ro g e n k ep t in sto rag e vessels a n d expelled by h y d ro s ta tic p re s su re th ro u g h a c o m m o n orifice, H a r e w as able to m elt a n u m b e r of su b stan ce s, am ong th e m p latin u m , th a t h a d h ith e rto b e e n r e g a rd e d as e x tre m ely refractory. H e h a d in fact achieved the highest t e m p e r a t u r e as yet a ttain ed .
271
T he ap p aratu s designed and built by Robert H are in 1801 for the melting of platinum and other refractor) sub stances. Based upon a barrel from his father's brew ery, it co m p rised two sep ara te storage vessels for hydrogen and oxygen, the gases being driven through a common orifice into the flame of a lamp, shown at the top left, m ounted on an adjustable table
Hare had become a member of the Chemical Society of Philadelphia, founded in 1792, of which James Woodhouse was President, and in December 1801 he demonstrated his apparatus before the society. His long and detailed account of the equipment and his experiments was immediately published in pamphlet form by the society and was reproduced in England in The Philosophical M agazine and in France in the Annales de Chimie (2). Among his fellow boarders in the house was Benjamin Silliman (1779-1864) who had been invited to accept the chair of chemistry at Yale but having no knowledge of the subject had been sent to study at the University of Pennsylvania. He and Hare co-operated in improving the apparatus and in obtaining a higher purity oxygen by heating potassium chlorate in stone retorts. Silliman later recorded in his autobiography: The retorts were purchased by me at a dollar each and as they were usually broken in the experiment the research was rather costly, but my friend furnished experience and as 1 was daily acquiring it 1 was rewarded both for labour and expense by the brilliant results of our experiments. (3) During the winter of 1802-1803 Hare had an opportunity of demonstrating
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his blo w -pipe to the discoverer of oxygen, J o s e p h Priestley, now a p p r o a c h in g seventy, w ho it will be r e m e m b e r e d h a d b e e n in form ed by B e n ja m in F ran k lin tw en ty years earlier of L av oisiers ex p e rim en t. P riestley ac k n o w led g ed th a t H a r e s ex p e rim en ts were q u ite o rig in a l . (4) F o r a n u m b e r of years H a r e w as o cc u p ie d in th e b re w ery business, a n d th e n in 1818 he b e c a m e for a sh o rt tim e P rofessor of N a tu r a l P h ilo so p h y at the College of W illia m a n d M a r y in W illia m s b u rg b u t w as so on a p p o i n t e d to the post he h a d long earn estly desired, Professor of C h e m is tr y in th e M e d ic a l School of the U niversity of P ennsylv ania. H e re he took up th e s tu d y of electricity, co llabo rating w ith J o s e p h H e n r y a n d c o rre s p o n d in g w ith M ic h a e l F a ra d a y . Sillim an, on th e o th e r h a n d , a n n u a lly d e m o n s tr a te d th e fusion of p l a t i n u m a n d of o th e r su b stan ce s by m e a n s of H a r e s b lo w -p ip e to his s tu d e n ts at Yale.
T h e C o n tr o v ersy w ith Professor C larke

A lth o u g h H a r e did not p u r s u e his b lo w -p ip e re search es any f u r th e r for a n u m b e r of years he was aro u s e d to g re a t in d ig n a tio n in 1819 by w h a t a p p e a re d to him a n a p p r o p r ia tio n of his invention. A letter from a M r . H. I. B rooke of K eppel S treet in L o n d o n to T h o m s o n s Annals of Philosophy in 1816 d e s c rib e d the design of a new form of blo w -p ip e w h ic h th e w rite r h a d as k e d th e in s tr u m e n t m a k e r J o h n N e w m a n to co n s tru c t (5). T h is c a m e to th e notice of E d w a r d D a n ie l
E d w a rd D an iel C la rk e I 769- I 8 2 2 P r o f e s s o r o f M i n e ra l o g y al C a m b r i d g e an d a frien d of W ollaston. S m ithson T e n n a n t an d H u m p h ry Davy, C larke e x p e r i m e n t e d w ith a n i m p r o v e d f o r m o f blow p i p e f r o m 1 81 6 u n t i l his d e a t h , su c cess fu lly m e l t i n g sm a ll q u a n t i t i e s of p l a t i n u m . A f t e r d e s c r i b i n g h is r e s u lts in s e v e ra l p a p e r s , in 18 19 he p u b l i s h e d a sm a ll book t h a t p r o v o k e d R o b e r t H a r e to an i n d i g n a n t r e s p o n s e
2 73
C larke, Professor of M i n e r a lo g y at C a m b r i d g e , w h o h a d b e e n in th e h a b it of su b m ittin g his m in era l s p e c im e n s to th e o rd in a r y blow -pipe. C l a r k e p e r s u a d e d N e w m a n to modify his a p p a r a t u s to so m e e x ten t a n d th e n p ro c e e d e d to c a rry ou t a n u m b e r of ex pe rim ents w i t h it, usin g h y d ro g e n a n d ox ygen in th e carefully co ntrolled p ro p o rtio n s of tw o t o one. H e m e lte d a r a n g e of su b s ta n c e s , in clu din g p la tin u m a n d p alla d iu m , a n d b e g a n to p u b lis h a series of p a p e rs , first in the R o y a l I n s titu tio n s Quarterly Journal o f Science a n d th e n in th e Annals of Philosophy (6). In the first of these p a p e rs h e wrote: Platinum was not only fused the instant it was brought into contact with the flame of the ignited gas, but the melted metal ran down into drops. W o llasto n th e n w ro te to h i m su gg esting t h a t he trie d to m elt o re of i r i d i u m a n d this he claim ed to have d o n e successfully as well as m eltin g a sm all q u a n t i t y of irid iu m -o sm iu m re sidu e t h a t h a d b elo n g ed to S m ith s o n T e n n a n t . A fter m a n y fu rth e r experim ents, a n d after suffering a d a n g e ro u s explosion of his a p p a ra tu s , C la rk e devised a w o o d e n screen to p ro te c t him self o r his m a n -s e rv a n t, a n d ag a in he m elted p la tin u m b u t only i n sm all q u a n titie s . T h e n in 1819 he p u b lis h e d a sm all book (7) describing th e w h o le ra n g e of his work, the in tro d u c tio n in c lu d ing th e sentence: The American Chemists lay claim to it as their invention in consequence of
I n s t e a d o f u sin g tw o s e p a r a t e c o n t a i n e r s f o r his o x y g e n a n d hydrogen C lark e em ployed o n ly o n e . w ith t h e c o n s e q u e n t d a n g e r o f e x p l o s io n . A f t e r one su c h experience he d e v i s e d a w o o d e n s c r e e n to p r o t e c t h i m s e l f o r his m a n servant w h ile m eltin g platinum and other su b s t a n c e s w ith h is blow pip e.
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experiments made in 1802 by Mr. Robert Hare, junior, Professor of Natural Philoso phy in Philadelphia. O n receiving a copy of th e book H a r e im m e d ia te ly re a c te d angrily, a d d r e s s ing a long letter to his friend S illim an w ho h a d j u s t recently fo u n d e d t h e American Journal of Science and Arts , q u o tin g som e lines of Virgil w ritte n o n h e a rin g th a t the R o m a n d r a m a tis t B athyllus h a d cla im e d som e of his ow n verses (8). T h e o pening p a g e of this d ia trib e is r e p ro d u c e d here. O n e of his m o re intere sting co m m en ts was: He (Clarke) would evidently wish the reader to adopt the false impression that the facility with which platinum may be fused is owing to the great improvements made fourteen or fifteen years after I had devised and used them. Will Britons tolerate such conduct in their professors?
H a rt's Blowpipe*
C H E M IS T R Y , PH Y SIC S AND T H E A R T S .
281
A jit. X I I I . Strictures on a publication , entitled Clark's
Gas Blow pipe ; by R o b e r t H a r k , J\l. D . Professor of Chemistry in the mcdical department o f the University o f Pennsylvania , and the real inventor o f the compound or hydro-oxygen fdourpipe, in that safe and cjficicnt fo rm which the fusion o f tkr most refractory earthst and the u o/atUization and combustion o f P latinum teas fir s t accom plished.
(los ego vrrsiculos fed , tulit alter honores, S ir vos non vobis niWtiiciiiis ;ves, Sic vos non vubis V *llra frrti * ves, Sic vos non votws nHili<-atic apes, Sic vos non vobis fen is aratra Coves. VI ROIL.
by
T h e o p ening page of H a r e 's letter to t h e A m erican Journal o f Science in w h i c h h e a t t a c k e d C l a r k e f o r w h a t he c o n s i d e r e d to b e t h e a p p r o p r i a t i o n of his in v e n t i o n . T h e L a t in l in e s f r o m Virgil r e a d in t r a n s l a t i o n :

I in d e e d h av e m a d e th e se v erses a n o th e r h as re c eiv ed th e h o n o u r. So y o u r b ird s m a k e n ests, not yo u rselv es. So y our sh ee p b e a r fleeces, not yo u rselv es. So y o u r bees m a k e h o n e y , n o t y ourselves. So y our oxen do not b e a r th e p lo u g h y ourselves. but fo r fo r fo r fo r
D r . C i .a r k h as p u b lish ed a book o n the G as B low pipe, in w hich he professes a sincere de sire to re n d e r ev ery one his due.** T h a t it w ould be ditiicult for th e co n d u ct o f an y a u th o r to b e m ore d iscordant w ith these professions, I p ledge m y self to prove in the follow ing pages, to any re a d e r w hose love o f ju s tic e m ay gain for th e m an attentive perusal. In the y e a r 1802, in a m em oir repu b lish ed in th e 14th V ol. o f T illo c h s P h ilo so p h ic a l M agazine, L o n d o n , and in d ie 4 5 th V ol. o f the A nualc* de C liim ie , 1 had given the rationale o f the heat p ro d u c e d by th e com bustion o f the a erifo n n e le m en ts o f w ater, and hud dev ised a in o d e o f ig niting them free from the d an g er o f exp lo sio n . I had also stated in th e sam e m e m o ir that the lig h t and h e a t o f the flam e thus p ro d u c e d w ere so intense, that the e y e s could sca rc e ly sustain the o n e , n o r the m ost refracto ry substances resist the o th e r, and had likew ise m en tio n ed ih e fusion o f th e pure e a rth s and volatilization o f th e pe rfe c t m etals as am ong the re su lts o f the invention. * S u b s e q u e n tly in the first p art o f th e 0 th V ol. o f A m erican P h ilo so p h ic a l T ra n s a c tio n s, an a c c o u n t o f th e fusion of s tro n tite s , an d th e volatilization o f P la tiu u iu , w as published by m e.
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T h e letter also c o n ta in e d a series of d ra w in g s of t h e variou s form s of th e c o m p o u n d blow -pipe as devised by H a r e over th e years. C la rk e d ied in 1822 a n d th e re is no evidence th a t he ever r e s p o n d e d to or ac k n o w led g ed this r a t h e r h a rs h piece of criticism, or th a t h e p u r s u e d his w ork o n th e m eltin g of p l a t i n u m any further. O n his p art, H a r e ag a in took u p th e s u b ject after a long interval. I n 1836 he m a d e a visit to E n g la n d a n d a t t e n d e d th e m eetin g of th e B ritish A sso cia tio n for the A d v a n cem en t of Science, h e l d t h a t y e a r in Bristol, m e e tin g th e leading scientists of th e tim e in clu din g t h e seventy y e a r old J o h n D a lto n , th e n a ViceP resid en t of the C h e m is try S ectio n , a n d c o n trib u tin g several sh o rt p a p e r s on im pro vem en ts in chem ical a p p a r a t u s . In A u g u s t 1837 he w ro te to D a lto n to re p o rt his m elting of a m o re s u b s t a n t i a l q u a n t i t y of p la tin u m : I beg leave through you to communicate to the British Association for the Advancement of Sciences that by an improvement in the method of constructing and supplying the hydro-oxygen blow-pipe, originally invented by me in the year 1801, I have succeeded in fusing into a malleable mass more than three fourths of a pound of platina. In all I fused more th a n two pounds fourteen ounces into four masses, averaging of course nearly the weight above mentioned. I see no difficulty in succeed ing with much larger weights. T h is letter was duly re a d t o th e B ritish A sso cia tio n by D a l t o n d u rin g its m eetin g in Liverpool a m o n t h la te r (9), b u t H a r e w as still no t satisfied. In S e p te m b e r 1838 he ex hib ited to th e C h e m ic a l Society of P h ila d e lp h ia a n even larg er sp ecim en of p la tin u m , w r itin g to S illim an: I have by improvements in my process for fusing platina succeeded in reducing twenty-five ounces of that metal to a state so liquid that, the containing cavity not being sufficiently capacious, abou t two ounces overflowed it, leaving a mass of twentythree ounces. I repeat that I see no difficulty in extending the power of my apparatus to the fusion of much larger masses. (10) After a fu rth e r interval of s o m e eight y ea rs H a r e , to w a rd s th e e n d of his oc c u p a tio n of th e c h a ir of c h e m is try , a n n o u n c e d the m e ltin g of b o t h irid iu m a n d rh o d iu m , specim ens of w h ic h he h a d o b ta in e d from J o h n s o n a n d Cock. (11) H a r e took no c o m m ercial a d v a n ta g e of his lo n g series of investigations, b u t his w ork did lead to tw o fu rth e r d ev e lo p m e n ts in q u ite different directions. First, his o xy-h y d ro g en b low -pip e w a s a d a p t e d to good effect b y th e S c o ts m a n T h o m a s D r u m m o n d ( 1 7 9 7 - 1 8 4 0 ) w h o served in his e a rlier y ea rs in th e B ritish O r d n a n c e Survey w h e re he d evised a so u rc e of inten se w h ite light by d irecting th e flame o n to a block of lim e. T h i s w as d esig n ed as a n im p ro v e m e n t to navigational safety, a n d his in v e n tio n b e g a n to be in stalled in ligh tho uses in 1829, later being a d o p te d for t h e th e a t r e from w h e re t h e ex p ressio n in th e lim e lig h t originated. W o rk in g w ith this m e a n s o f illu m in a tio n in P aris, M a r c A n to in e G a u d i n (18041880), a fo rm e r stu d e n t o f b o th D u m a s a n d A m p r e w h o w as em p lo y ed by t h e B u rea u of L ong itu de, p r e s e n t e d a p a p e r to th e A c a d m ie des Sciences in 1838 in w hich he described his m e t h o d of p re p a r i n g a cry sta llin e form of lime
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from w h ich he m a d e crucibles (12). I n these h e w as a b le to m elt a n alloy of 10 p e r ce n t iridiu m a n d 90 p e r cent p la tin u m , a lm o s t c e rtain ly th e first o cc a s io n on w hich a synthetic alloy of p l a t i n u m h a d b e e n p ro d u c e d . H e c o m m e n t e d o n the lustre, th e m alleab ility a n d th e ex tre m e re s is ta n c e to c o rro sio n of his alloy. T h e second a n d m o re significant o u tc o m e of H a r e s w o rk was d u e to his a ssistant in th e U n iversity of P en nsy lvania. T h i s w as J o a q u i m Bishop (1806-1886) w h o after w ork ing in th e je w e lle ry t r a d e a n d th e n in a b ra s s foun dry b e c a m e H a r e s in s tru m e n t m a k e r in 1832 a n d took p a r t in t h e ex p e ri m ents o n p la tin u m . Leaving H a r e in 1839, he set u p in b u sin ess for h im self a n d so fo un ded th e p l a t i n u m works t h a t b o re his n a m e for very m a n y y e a rs a n d th a t will be dealt w ith m o re fully in a la te r c h a p te r.
T h e W ork o f D e v ille a n d D eb ra y
H a r e noticed t h a t if he m a in ta in e d his m o lte n p l a t i n u m in a n oxidising a tm o s p h e re it g ra d u a lly freed itself from a n y b ase m e ta ls p re s e n t by o x id ation, a n d it was this ob serv atio n th a t led to th e nex t m a jo r step fo rw a rd in th e history of p la tin u m , this tak in g p lace in P aris in th e eighteen-fifties at th e h a n d s of Deville a n d D e b ra y a n d co n s titu tin g a revolu tio n in th e p l a t i n u m in dustry. H e n ri S a in te -C la ire Deville w as b o r n in St. T h o m a s , o n e of th e V irg in Islands, the son of a p ro s p e ro u s ship o w n e r w h o h a d e m ig ra te d from F ra n c e . H e was sent to Paris to b e ed u c a te d , stu d y in g m ed icin e b u t also a t t e n d i n g the lectures of T h e n a r d a t th e S o rb o n n e. In 1839 he set up a sm all p riv ate la b o ra to ry in w hich he b e g a n to m a k e original investigations o n o rg a n ic s u b s ta n c e s in c lu d ing essential oils. O n th e r e c o m m e n d a tio n of T h e n a r d h e was a p p o in te d Professor of C h e m is tr y at B esan o n in 1845 a t th e age of only tw enty-six. W h e n B a la rd was a p p o in te d Professor of C h e m is tr y in th e C o llege d e F r a n c e in 1851 Deville succeeded h im at th e cole N o r m a le w h e re h e r e m a in e d for th e rest of his life, converting a m ost i n a d e q u a te la b o ra to ry for th e tra in in g of te a c h e rs into one of th e o u ts ta n d in g centres of re s e a rc h in E u ro p e . H e r e he fou n d J u l e s H e n r i D e b ray , a native of A m ie n s w ho h a d b ee n a s tu d e n t th e r e since 1847 a n d w h o m he a p p o in te d as his assistan t in 1855, th e association d eveloping in to a g re at friendship a n d a m ost fruitful c o lla b o r a tio n w ith D e b r a y ev e n tually su cceeding him as professor. T h e ten years following D evilles a p p o i n t m e n t w e re c h a ra c te ris e d by q u ite exceptional activity a n d ac h ie v em en t in th e field of h ig h t e m p e r a t u r e reactions. F irst he su cceeded in p ro d u c in g a l u m i n iu m by th e re d u c tio n of its ch lo rid e w ith p o tassium , later w ith sodium , a n d his results b ein g b r o u g h t to th e a t t e n t i o n of N a p o le o n III b y D u m a s , he was given a g o v e rn m e n t g r a n t to estab lish a pilot p la n t at Javel. T h is was followed by th e erectio n of a larg e r w o rks a t N a n te rre , Deville a n d his colleagues D e b r a y a n d P aul M o r i n su b s c rib in g ca p ita l to form the Socit de P A lu m in iu m de N a n te rre . W ith p ro d u c tio n established, Deville r e tu r n e d to his l a b o ra to ry a n d a g a in gave his m in d to th e need for b e tte r m e th o d s of p r o d u c in g h ig h te m p e r a tu re s . In 277
H e n r i S a in te - C la ir e I)ev il le
1818-1881
P r o f e s s o r o f C h e m i s t r y a l the E c o le N orm ale in Paris. D e v i l l e f o l lo w e d u p his r e searches on ihe p roduction o f a l u m i n i u m by s t u d y i n g the m etallurgy of the p latin u m m e t a l s . In 1857 h e a n d J u l e s D e b r a y d e v i s e d t h e lim eb lo ck f u r n a c e fired by a m i x t u r e o f o x y g e n a n d co al g as w h i c h fo r t h e first t i m e m a d e it p o s s i b l e to r e f i n e a n d m e l t p l a t i n u m a n d al l o y s o n a l arg e sc a le . T h e i r m e t h o d r e m a i n e d in u se u n t i l t h e d e v e lo p m e n t of th e in d u ctio n f u r n a c e in t h e 1920s
1856 he h a d p u b lish ed a long s t u d y of th e use of coal gas a n d oxygen in blo w pipes a n d th e ir a p p lic a tio n to b o t h m eltin g a n d w e ld in g in w h ic h he referred to th e earlier w ork of G a u d in (13). At first Deville a n d D e b ra y used th e e q u i p m e n t to p ro d u c e m an g a n e s e , c h r o m i u m , nickel a n d c o b a lt in a s tate of purity , using crucibles m a d e of lime or m a g n e s ia . T h e y th e n t u r n e d to th e p l a t i n u m m e ta ls a n d for four y ea rs p u r s u e d th eir research es w ith gre at activity. A lr e a d y in the 1856 p a p e r Deville h a d m a d e the p o in t th a t his m elted p la tin u m h a d p ro p e rtie s q u ite different from th o se of the p o w d e r m e tallu rg y p ro d u c t. H e h a d enjoyed t h e co -o p e ra tio n of a P a r is ia n go ld s m ith a n d m a n u f a c t u r e r of d o u b l or rolled gold, A u g u s te F ra n o is S avard, a n d he co m m en ted : Cast and refined platinum is a metal as soft as copper, as confirmed by the Paris Mint; it is whiter than ordinary platinum and does not have the porosity that has so far proved to be an obstacle in the manufacture of an impermeable doubl of platinum.
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S avard, w hose firm, fo und ed in 1829, still exists in th e R u e S a in t Gilles, h a d p u t his furnaces a n d rolling mills at D evilles d isposal a n d h a d m a d e a very th in piece of p la tin u m - c la d c o p p e r t h a t co m p letely resisted th e a c tio n of n itric acid. Deville a n d D e b r a y s final d esign of a fu rn a c e for th e m eltin g of p la tin u m , illu strated here, c o m p ris e d tw o cy lind rical blocks of lime b o u n d t o g e th e r w ith steel strip. A hollow w as form ed in the low er block to c o n t a i n t h e m etal, a p o u rin g c h a n n e l b eing p ro v id ed to t h e edge. T h e u p p e r block w as also hollow ed out to form a roof w hich was p ie rc e d to receive th e coal g as a n d oxygen. T h e whole unit could be tilted for p o u rin g th e m o lte n p l a tin u m . By this m e a n s p la tin u m was not only m e lte d in q u a n t i t y for th e first tim e b u t c o u ld also be refined to som e extent b y exp o su re to a n oxidising a tm o s p h e re , w hile th e lime served to a b so rb a n y slag form ed b y th e o x id a tio n of b a s e m e ta l im purities. Following this, Deville a n d D e b r a y w e n t o n to devise a process for refining native p la tin u m . T h e i r p re lim in a ry results w e re desc rib ed to th e A c a d m ie des Sciences in 1857 (14) a n d in th e s a m e y e a r b o t h F r e n c h a n d B ritish p a t e n t s were filed, not in D evilles n a m e b u t in t h a t of D e b ra y , a n d a ssig n ed for s o m e re aso n to th e Socit d e l A l u m i n u m de N a n t e r r e (15). T h e B ritish rig hts w e re a t once
Ju le s H e n ri D e b ray 1 827-1888 A n a t i v e o f A m i e n s . D e b r a y s t u d i e d at the Ecole N o r m a le a n d th e n b e c a m e first an assistant and later a c o l l a b o r a t o r o f D e v i l l e s, e v e n t u a l l y s u c c e e d i n g h i m a s P r o f e s s o r t h e r e in 1881. T h e i r a s s o c i a t i o n w a s e x t r e m e l y clo s e, a n d t h e i r j o i n t w o r k o n t h e m e l t i n g o f p l a t i n u m a n d its alloy s ex tended over m anv years
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F ran ois A ugu ste Savard 1 8 0 3 -1 8 7 5

T h e f o u n d e r o f a f i rm p r o d u c i n g r o lle d go ld in P a r i s in 1 8 2 9 , S a v a r d t u r n e d to the production of platin um -clad c o p p e r , b r a s s a n d s i l v e r in 1854. D u rin g th e re se a rc h e s of Deville a n d D e b r a y h e p u t a t t h e i r d i s p o s a l b o t h his f u r n a c e s a n d his r o l l i n g m i l l s so t h a t th ey c o u l d i n v e s t i g a t e t h e p h y s i c a l p r o p e r t i e s o f t h e i r allo y s. H e also p r o d u c e d e x t r e m e l y t h i n c o a t i n g s of p la tin u m on c o p p e r fro m th e ir m elted m etal th at disp lay e d com p lete freedom from porosity. H is c o m p a n y c o n tin u es in o p e r a t i o n to t h is d a y
P h o to g r a p h by c o u rte s y of VI. J e a n P i e r r e S a v a rd
acquired by George M a tth e y w hose long career in the p latin u m industry will be described in the next chapter, w hile the F rench p atent was shortly afterwards acquired by D esmoutis a nd C h apuis. T h e response from Russia w a s even more positive. J u s t at this time the government in St. Petersburg w a s considering restarting the m inting of a platinum coinage, an d in J u n e 1859 their representative, A cadem ician Boris Semenovich Yacobi (K nown in W e s te rn E u ro p e as M oritz H e r m a n n Jacobi), Industrial Adviser to the M in istry of Finance, visited Paris to study the techni ques of Deville and Debray. His visit coincided with the publication of a long p a per by them, O n Platinum a n d the M etals th a t A ccom pany It (16), in which they detailed not only the properties of each of th e six p latin u m m etals but gave a complete scheme for their analysis and finally proposed a simple a n d economical process for yielding a ductile a n d industrially useful iridium -rhodium -platinum alloy directly from the Russian m ineral. T h e process included the prelim inary alloying of the native platinum w ith lead to separate osm iridium an d earthy m atter, the lead alloy then being cupelled to leave the p latin u m rich material ready for melting.
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T h e opening page D evi lie and num erous papers m etallurgy of the m etals. T h is on e.
o f o n e of De b r a y 's on the p latinum from the
DE LA
MTALLURGIE DU PLATINE
HT M U
Annates de C him ie et de P hysique in 1 8 6 1 . d e s c r i b e s

t h e i r w o r k o n t h e r e f i n i n g of n a t i v e p l a t i n u m o n b e h a l f of the Russian go v ern m en t
P ab
MTAUX QUI L ACCOMPAGNENT,

MM. H . SAINTE-CLAIRE DEVILLE e t H . DEBHAY.
Nous avons expos, dans le L VIe volume de ces Annotes, un projet de mtallurgie nouvelle du platine fonde sur lemploi des moyens de la voie sche : notre travail tait liai et publi, lorsque le Gouvernem ent russe, par linter mdiaire de M. Jaco b i, conseiller d tat et membre de lAcadmie des Sciences de Saint-Ptersbourg, nous pro posa d tudier, sur une chelle relativem ent assez grande, touie la partie pratique de la question que le manque de matriaux nous avait obligs de ngliger momentanment. Nous avons accept cette mission avec empressement, en nous imposant nous-mmes la condition de diriger nos travaux de telle m anire quils pussent tre adapts le plus compltement possible aux besoins du Gouvernem ent russe. La Monnaie de Russie reoit en effet chaque anne des quantits de minerai de platine de l'O ural assez variables, q u elle traite elle-mme par un procd qui sera bientt
Deville a n d D ebray dem onstrated their process to Jacobi, w ho was so impressed that he asked his M inister of Finance to sponsor further research on melting and on the working up of the residues that had a ccum ulated in great quantity in the refinery in St. Petersburg. An agreem ent was quickly concluded by which the R ussian government financed the setting up of furnaces a n d of an oxygen plant in the cole Norm ale and Deville and D ebray were enabled to carry out their experiments on m uch larger quantities of material. O n February 23rd they received from St. Petersburg some 56 kilograms of m ineral from the Demidov workings at Nizhny Tagil, demonetised coinage an d refinery residues. O n J u n e 15th after three and a half m onths of incessant work day and n ig h t, they delivered to Jacobi 42 kilograms of ingots, rolled sheet and cast objects, together with an ingot of iridium weighing ju s t over a kilogram. T h e ir loss of platinum am ounted to only 120 grams. T his rem arkable piece of work was described in detail in a further long paper (17), of which the opening page is reproduced here, with full particulars of the am ounts of lead, oxygen and reagents consumed.
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A n o r i g i n a l d r a w i n g of ih e lim e-block f u rn a c e devised bv D e v ille a n d D e b r a y for ib e m elting of p la tin u m . T h e Iw o c y l i n d e r s A a n d B w e r e h o l l o w e d o u t a n d p i e r c e d at K to a d m i t t h e o x y g e n - c o a l gas b u rn e rs . T h e m olten p la tin u m was p o u r e d thro u g h t h e c h a n n e l o n t h e r ig h t by tiltin g t h e f u r n a c e bv m e a n s o f t h e l e v e r C. T h i s t y p e of f u r n a c e r e m a i n e d in u se in th e ind u stry for m anv years u n t i l t h e d e v e l o p m e n t o f the induction fu rn ac e
Jacobi also enjoyed the use of the melting furnaces a n d rolling mills of Savard as well as of the facilities of the Paris M in t through the co-operation of its Director, Professor Pelouze, a n d in the D ecem ber of 1859 he was able to send to the M inister of F inance thirty-eight m edals struck in several alloys of platinum containing 5, 10 and 20 per c e n t of iridium. T hese were first shown to the Acadmie des Sciences by Pelouze, together with an ingot of iridium weighing 267 grams which Jacobi p resented to the A cadm ie (18). Unfortunately, despite J a c o b i s recom m endation in a p a m p h le t published in 1860 (19), the Russian government abandoned all th o u g h ts of a new p latinum coinage. Despite this disappointm ent, Deville and D ebray continued their intense work, elaborating their m ethods of preparing p latin u m a n d the other metals of the group in commercial q u antities and in a high state of purity. In 1860 they laid before the Acadmie two ingots of p latinum weighing together 25 kilograms (20) while two years later they rep o rted to them on the industrial progress so far m ad e with their melting process (21). In this they referred to the casting of an ingot of platinum weighing 100 kilograms by George M atthey, the mass becoming so liquid that it filled exactly with m etal every p a rt of the m ould and reproduced all its imperfections w ith unexpected precision . In a footnote to one of their earlier papers (16) they h a d already recorded in referring to their two licensees that Today these procedures are functioning and are being perfected every day in the hands of the clever craftsmen to whom they have been confided.
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B o ris S e m e n o v ic h J a c o b i
1 8 0 1 -1 8 7 4
B o r n in P o t s d a m in G e r m a n y a n d k n o w n in his e a r l y y e a r s a s M o r i t z H e r m a n n v o n J a c o b i , h e left to m a k e his c a r e e r i n R u s s i a a n d w as a p p o i n t e d Pro fesso r at th e U niversity of D o rp a t in 1834. l a t e r m o v i n g to St. P e t e r s b u r g to t a k e c h a r g e o f t h e P h y s i c s l a b o r a t o r y o f t h e A c a d e m y o f S cien ces . I n 1 8 5 9 , by t h e n s e r v i n g also as I n d u s t r i a l A d v i s e r to t h e R u s s i a n M i n is try of F i n a n c e , h e v isited P a r i s a n d s p o n s o r e d f u r t h e r i n v e s ti g a t i o n s by D e v ille a n d D e b r a y b u t f a i l e d to p e r s u a d e his g o v e r n m e n t to r e - i n t r o d u c e a p l a t i n u m c o in a g e
T h e N e w Standard M etres Jacobi was again destined to play a p art in the work of Deville and Debray. In 1867 a G reat International Exhibition was held in Paris, he was am ong the visit ing scientists and he took the opportunity to jo in in discussions on sta ndard weights an d m easures in which the F rench were deeply interested because of their long sustained efforts to spread the use of the metric system. W ith J a c o b i s support a comm ittee of delegates from a large n u m b e r of countries was formed and strongly recom m ended the universal adoption of metric weights and measures, this resulting in the setting up of the International M etric C o m m is sion in 1869 for the construction and verification with the best appliances of modern science of new international standards of the metre and the kilogram.
T he Franco-Prussian W a r delayed things, but in 1872 the first full meeting took place with twenty-nine countries represented, leading to the Convention du M etre signed in Paris in 1875. T his finally achieved the support of all the
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In 187 3 t h e P r e s i d e n t o f F r a n c e , L o u i s A d o l p h e T h i e r s , t o g e t h e r w ith a n u m b e r o f his m i n i s t e r s , p a i d a visit to D e v ille 's l a b o r a t o r y in t h e E c o l e N o r m a l e to w i t n e s s t h e m e l t i n g o f ten k i l o g r a m s o f i r i d i u m l a t i n u m f o r t h e p r o d u c t i o n o f t h e n ew s t a n d a r d m e t r e . p D eville is s t a n d i n g in f r o n t o f t h e d o o r l o o k in g t h o u g h t f u l : D e b r a y is a t t h e o p p o s i t e e n d o f t h e f u r n a c e , w h i l e t h e i r a s s i s t a n t C l e m e n t is ti l t in g t h e l i m e - b l o c k to p o u r t h e a lloy . T h e P r e s i d e n t is h o l d i n g a p r o t e c t i v e g lass in f r o n t of h is e y e s
im portant countries and the establishm ent of the still existing International Bureau of W eights an d M easures with its hea d q u arte rs in Paris (22). A n examination of the original s ta n d a rd metre, the M tre des Archives, m ade by J a n e ty in 1796 and described earlier in C h a p te r 10, showed th at the ends were no longer plane, but t h e Convention decided that they would not go back to the original definition of the m etre as one ten-m illionth of a q u a rte r of the w orlds m eridian, as there w a s no agreem ent as to its exact value. T h e y p re ferred to use the M tre des Archives in the state in which it is fo und but to convert its length from a n e n d s ta n d a r d to a m arked line standard. T h e next question to be decided was the most suitable m aterial from which the new sta ndard and its copies sh o u ld be m ade, an d in 1862 Deville and D ebray p ut forward a suggestion that a n alloy of p latinum with 10 per cent of iridium offered the best possibilities. It h a s to recom m end it high density, high melting point, great resistance to h u m id ity and air, a fine grain, perfect polish, great hardness and full malleability. Deville a n d D e bray claimed to have put in ten years of study, assisted by m a n y other people, before they arrived at the possibility of preparing this m ate ria l in a satisfactory form an d were satisfied
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that it was better th an anything else available. O n e of their greatest troubles had been encountered in the p rep aration of large ingots of this alloy, completely free from blisters an d cavities. T h e only m ethod available in those days of detecting their presence was the undertaking of very careful density determinations. Deville himself carried out large num bers of these, working long hours into the night and exhausting his strength in the service of the posterity th at he dream ed of but could not hope to see (23). In one way an d another the a ttem pts to produce a sufficiency of homogeneous m etal occupied several years at the hands of Deville himself an d his assistants, the Norw egian O. J. Broch, the Belgian J. S. Stas, an d George M atthey (24). T im e after tim e the m etal failed and, even after attaining the necessary qualities at its original preparation, was found to have taken up iron during the subsequent m echanical fabrication. A detailed account of these m atters and of the m a jo r role played by George M atthey will be given in the next chapter. During this work a n immense n um ber of analyses of the p latin u m metals and mixtures thereof ha d to be undertaken, an d the conscientiousness of Deville and his collaborators was such th at continual advances were m ad e in the accuracy of the determinations. T h e final m ethods were set out by Deville and Stas in 1877-1878 an d these rem ained the last word on the subject for a generation or more afterwards (25). All these labours connected with the m etre filled up the last years of Devilles life, but he had the satisfaction of seeing them completed before he died in 1881.
C on clu sio n T h e im portant invention of the lime furnace by Deville and D e bray enabled platinum to be melted commercially on a large scale for the first time and remained the sole m eans of effecting this until the coming of the induction furnace a great m any years later. But it m ust not be thought th a t this a t once solved all the problems of the fabricator of platinum . It provided him with a means of preparing alloys b u t it was not the answer to all the questions raised in handling pure platinum . H e re problem s of purity gradually grew to be of param ount im portance and it becam e evident th a t not only were th e gases of the blowpipe capable of introducing impurities (and not only gaseous ones) into the melt, but th a t at the high tem perature involved the refractory was capable of yielding them too. T h e former could introduce oxygen, iron dust, and carbon and sulphur products from the coal-gas; the latter calcium and silicon from the reduction of the oxides of these elements in the lime. So the forging of sponge continued for a long time, a n d was still used by refiners for m any years. In addition to the introduction of melting, Devilles work covered the com mercial analysis, the refining, the alloying an d the fabrication of all the six members of the p latinum group metals. Over twenty-five years of careful experi mental work in these fields by such a n experienced scientist p u t a t the disposal of the platinum industry a rationalised technique that formed the basis for the
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F o r sixty y e a r s , u n t i l t h e d e v e l o p m e n t of t h e Ajax* N o rth ru p h ig h-freq uen cy in d u c t i o n f u r n a c e in 1 9 18 . th e m e l t i n g o f p l a t i n u m a n d its allo y s w as c a r r i e d o u t o n an i n d u s t r i a l s c a l e in t h e l im e b lo c k f u r n a c e i n t r o d u c e d by D e v ille a n d D e b r a y , w ith a n o x y -h y d ro g e n flam e a n d the ti l t in g o f t h e f u r n a c e to p o u r t h e m o l t e n m e t a l in to an in go t m o u l d
operations of all the firms w orking in it for at least the next thirty or forty years. In the hands of Deville, science and practice were brought together an d an im portant industry m ade possible. In July 1981 to com m em orate the centenary of Devilles death, an apprecia tion of his life an d work was com piled by Dr. J. C. C h a sto n (26) who concluded his contribution with these w o r d s : The platinum industry has, since then, expanded to an extent far beyond any thing he could have foreseen, but among those who laid its foundations there are few who deserve commemoration more than the modest, hard-working research worker and teacher, platinum chemist and technologist, Henri Sainte-Claire Deville. T h e successful adoption of Deville a n d D e b ra y s m ethod of melting p latinum by leading refiners in England, F ra n c e a n d G e rm a n y will be described in the following two chapters.
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R eferences for C hapter 15
1 E. F. Smith. The Life of Robert Hare, Philadelphia, 1917 2 R. Hare, Memoir on the Supply and Application of the Blow-Pipe, Chemical Society of Philadelphia, 1802; Phil. M ag., 1802, 14, 238-245; 298-308; Ann. C.him., 1803, 45, 113-138 3 N. Reingold, Science in Nineteenth Century America, London, 1966, 7 9 4 E. F. Smith, loc. cit., 8 5 H I. Brooke, Ann. Phil., 1816, 7, 367 6 E. D. Clarke, Quart. J . Sci., 1817, 2, 104 125; Ann. Phil., 1817, 9, 89-96 7 E. D. Clarke, The Gas Blow-pipe, or Art of Fusion by Burning the Gaseous Constituents of Water, London, 1819 8 R. Hare, A m .J . Sci., 1820, 2, 281-302 9 R. Hare, A m .J . Sci., 1838, 33, 195-196 10 R. Hare, A m .J . Sci., 1839, 35, 328-329; Phil. M ag, 1839, 15, 487-488 11 R. Hare, Am. J . Sci., 1846, 2, 365 369 12 M. A. Gaudin, Comptes rendus, 1838, 6, 861-863 13 H. Sainte-Claire Deville, Ann. Chim., 1856, 46, 182-203 14 H. Sainte-Claire Deville and H. J. Debray, Comptes rendus, 1857, 44, 1101-1104 15 French patent 18532, British patent 1947, of 1857 16 H. Sainte-Claire Deville and H. J. Debray, Ann. C.him., 1859, 56 , 385-496. This was also published as a pamphlet 17 H. Sainte-Claire Deville and H. J. Debray, Ann. Chim., 1861, 61, 5-146 18 T .J. Pelouze, Comptes rendus, 1859, 49, 896 897 19 B. S. Jacobi, About Platinum and its Use in Coinage, Imperial Academy of Science, St. Petersburg, 1860 (in Russian) 20 H. Sainte-Claire Deville and H. J. Debray, Comptes rendus, 1860, 50, 1038-1039 21 H. Sainte-Claire Deville and H. J. Debray, Comptes rendus, 1862, 54, 1139 1144; Chem. News, 1862, 6, 150-151 22 A. Perard and C. Volet, Les Mtres prototype du Bureau International, Paris, 1945; B. Swindells, Platinum Metals Rev., 1975, 19, 110 113 23 H. Sainte-Claire Deville and H. J. Debray, Comptes rendus, 1875, 8 1, 839 24 O. J. Broch, H. Sainte-Claire Deville and J. S. Stas, Ann. Chim., 1881, 22, 120-144 25 H. Sainte-Claire Deville and J. S. Stas, De lAnalyse du Platine iridi, Paris, Gauthier-Villars, 1878; Procs-Verbaux de Comit International des Poids et Mesures, 1877 26 J. C. Chaston, Platinum Metals Rev., 1981,25, 121-128
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G eorge Matthey
1825-1913
Joining P. N. Johnson as a n apprentice at the age of thirteen, he retired as C hairm an of Johnson M atthey and Co. Lim ited when he was eightyfour. During this extraordinarily long career he developed the refining and fabrication of p latin u m from a laboratory scale to a successful industrial operation upon w hich his successors have been able to build. He was elected a Fellow of th e Royal Society in 1879
From a p o rtra it in the possession of Jo hn son M atthey
16
George Matthey and the Growth of the British Platinum Industry
M an y a ph ysicist a n d m an y a chem ist has gained distinction as the result o f researches upon the p r o p e rtie s o f platinum , iridium and other m etals which such m etallurgists as Mr. M a tth e y have e n a b led them to obtain in the desired form and condition; and too often have they forgotten that the glory and honour should b y right be shared with those w h o have labou red to p ro d u c e the specim en s upon which they have operated.
T H E T IM E S , 1913
T h e early history of the L ondon firm of J o h n s o n M a tth e y a n d Co. has already been outlined in C h a p te r 1 1. W hile always interested an d active in the treatm ent and applications of p latin u m from its foundation in 1817, it did not begin to assume international im portance in this field until after 1851. In the preceding years Jo h n so n had developed a n u m b er of interests in the then boom ing lead, copper, silver and tin mines in Devon an d Cornwall, a n d in 1838, with plans for the expansion of his then very modest business in m ind he concluded an agree ment with his great friend J o h n M atthey, a wealthy stockbroker and foreign exchange dealer whose father Sim on had left his hom e town of L e Locle in Switzerland in about 1790 to settle in London. By the terms of the agreement, in return for an injection of new capital, two of J o h n M a tt h e y s sons were to be apprenticed to Johnson. George, the third son, at once entered the business at the age of only thirteen to work in the assay laboratory, to be followed by his youngest brother E d w a rd in 1850. At the time of G eorges entry, and until 1845, the firm was k now n as J o h n s o n and Cock, and besides benefiting from J o h n s o n s own excellent training the young M atthey was fortunate in having W. J. Cock as his m entor in the very early days of p latinum refining and fabrication. But in 1845 C o c k s health failed
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and he retired from the partnership, leaving George Matthey, still only twenty years old, in charge of the work. He set about his new task with great determination, and there now began that remarkable period of persistent scientific endeavour combined with an acute business sense (Cock, although a great chemist, was no business man) in which George Matthey transformed a laboratory activity into an industrial enterprise and made platinum available for use throughout the world. The work was hard, and the hours were long from 7 in the morning until well after 6 in the evening, for six days a week. Cock had been given but a short time in which to begin re-organising platinum production, and George Matthey had to put in hand the preparation of larger, sounder and more malleable ingots as well as introducing more effective separation of the other platinum metals and their refining. By December of that year he was supplying Michael Faraday - for his studies on magnetism with wire and foil in both platinum and palladium, with rhodium, iridium and osmium in metallic form and with a number of com pounds of all the five metals then known. In 1849 the Prince Consort, then President of the Royal Society of Arts, put forward a suggestion to hold a Great Exhibition to further the application of science to industry, but his proposal met with great opposition from many quarters. Johnson, like many other industrialists, was unwilling to support the exhibition, but young George M atthey realised the opportunity it presented and finally persuaded his employer to take part to the extent of a small glass case
containing p latinum crucibles, capsules and a large basin, together with specimens of palladium a n d some of its alloys and specimens of iridium and rhodium. A prize m edal was a w arded for this exhibit, but any p rid e or pleasure that M atthey ha d taken in this success was very swiftly dissipated w hen he walked along to see the exhibit m ounted by his F rench competitor, Q uennessen of Paris. T h e re he found a large p latinum still, holding thirty gallons, m a d e in one piece without seam or solder , for the concentration of sulphuric acid as well as a complete ap p a ra tu s in p latinum for the distillation of hydrofluoric acid.
Russian P la tin u m S u p p lie s a n d a P a rtn er sh ip T his at once stiffened his resolve to become pre-em inent in the platinum business, and he now also had a m uch more assured supply of raw material. H itherto the only source of native platinum was the C hoc area of Colombia, and much of the m eagre flow from there was smuggled out. T h e new source, discovered on the eastern slopes of the Ural m ountains in Russia, was subjected to an Im perial monopoly by the T s a r s governm ent which insisted th at all refining should be u n dertaken by the M in t at St Petersburg. However, in 1850 George M a tthey was successful in coming to a n a rrangem ent with one of the mine owners, C ount A natole Demidov, whereby he becam e the sole refiner and selling agent, platinum to be delivered in parcels of 1000 ounces at a time. This achievement, finalised in the O c tober of 1851, p ro m p te d P. N. J o h n s o n to take the young m a n into partnership, the nam e of the firm then being changed from P. N. Jo h n so n & Co. to J o h n s o n and M atthey. T h e reafter Jo h n so n , now aged 59, began to relinquish control of the business leaving M a tth e y in m ore o r less full charge. U n d e r his creative guidance and determ ination a n d his keen eye for new applications p latinum refining an d fabrication developed, as we shall see in this chapter, into a flourishing business. T h e C o m m ercia l M e ltin g o f P la tin u m At this time the only m eans of producing p latinum in m alleable form was by the powder metallurgy m ethod of pressing the sponge in a m ould and hot forging, introduced by T h o m a s Cock and Wollaston. W hile a n u m b er of scientists had succeeded in melting small samples, the resulting metal was nearly always brittle because of contam ination by carbon or refractory materials. But a m ajor development sprang from George M a tth e y s visit to the Paris E xhibition in 1855. H ere he becam e friendly with Paul Francois M orin, one of Devilles collaborators in the work on alum inium at the cole N o rm ale an d now works director of the Socit de l Alum inium, and as a consequence of this meeting a letter arrived from Jules Debray in August 1857 offering the British rights in the melting process described in the last chapter. M a tth e y imm ediately recog nised the potential value of this development and at once replied expressing his interest and a wish to see the process in operation, his letter ending:
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You may not be aware that I am the only refiner and worker to any extent in Platina in this country; it will be therefore for your consideration which is most advantageous, to allow any one indiscriminately to participate in the patent, or to confine your negotiations entirely to me. Before the end of Septem ber G eorge M atthey was in Paris, bringing with him a qu a n tity of platinum and residues for trial melting in the Deville and Debray furnace. T h e results were highly satisfactory, and the negotiations were finalised with M . M orin w hen a cheque for 500 was handed over for the assignm ent of the British patent (No. 1947). T h e process was at once put in han d in H a tto n G arden, but there were m any difficulties, and it was several y e a rs before satisfactory operation was achieved. O xygen was not then available comm ercially, an d had to be prep a re d on the spot from m anganese dioxide, w h ile the pressure of the L o n d o n coal gas was extremely low. W. J. Cock had returned to H a t to n G arden, no longer as a partner, but in his own words to help o u t , an d he proved an invaluable assistant to his younger colleague in getting the process going, although his health began to fail once again a n d he finally left in Septem ber, 1861. A few entries in C ocks diary earlier in t h a t year indicate some of the difficulties. Wednesday, 6 Feb. Read Devilles last letter to Matthey. Prepared and set iron retort in furnace room and charged it with 98 lbs ox manganese. Friday, 8 Feb. A little rain. Set retort again and lit fire. When some oxygen had come over the retort melted. Had old wrought iron retort re-fitted. Monday, 11 Feb. A little snow. Charged wrought iron retort and set it ready in furnace for lighting tomorrow morning. Tuesday, 12 Feb. Fine. Oxygen fire kept going all day, but ox came over very slowly. Wednesday, 13 Feb. A little rain. Tried fusion of platinum with G.M. . . . Dr. Faraday was present. O n e week later F a raday delivered his famous Lecture on P la tin u m one of his last appearances at the R o y a l Institution in which he described the new melting process and referred to Messrs Johnson and M atthey, to whose great kindness I am indebted for th ese ingots and for the valuable assistance I have received in the illustrations . In M a rc h George M atthey h a d to appeal to Deville. P a rt of his letter reads: For nearly two years I have been working in this manner and am afraid you will be disappointed with me. I can only assure you that my numerous disappointments have rather increased than diminished my efforts to succeed, and if you will yet suspend your judgement of me and grant me a little assistance I do hope to realise some great and profitable results . Devilles response was to invite M a tth e y to Paris, b u t he found himself unable to leave H a tto n G ard en and C o c k went instead. In addition, Deville sent over his garon de laboratoire , one J u le s , who established that the m ajor trouble lay in the impurities in the oxygen.
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Jo h n S c u d a m o r e Sellon
1836-1918 A n e p h e w o f J o h n s o n ' s w i f e . S ello n j o i n e d t h e firm as a n a p p r e n t i c e a t t h e ag e o f fifteen a n d b e c a m e a p a r t n e r in 1860. H is c o m m e r c i a l a b i l i t i e s w e r e of i n x a l u a b l e s u p p o r t to G e o r g e M a t t h e y d u rin g the b u ilding u p of the p la tin u m b u s i n e s s , a n d in 1 8 7 2 . a f t e r m a n y f r u s t r a t i o n s , h e w as s u c c e s s f u l in s e c u r ing t h e very l a r g e s t o c k s o f R u s s i a n p l a t i n u m for r e f i n i n g a n d f a b r i c a t i o n
By the end of M ay success ha d been achieved. Progress continued, the size of melt increased, and in M a rc h of 1862 Deville cam e to L ondon a n d together M atthey and he cast a huge ingot, measuring twelve inches by eight by six, and weighing 3215 ounces or 100 kilograms. It was placed on display at the Second International Exhibition of Industries in L ondon that year together with numerous other forms of platinum , including tubes joined by fusion welding with a blow-pipe flame, an d a specimen of melted iridium.
T w o N ew Partners During these tedious struggles with the new melting process the structure of Johnson and M a tth e y underw ent a m ajor change. J o h n s o n finally retired and two further partners joined George M atthey. His young brother E dw ard had been apprenticed in 1850 at the age of fourteen, and in 1855 had been persuaded by George, conscious of the need for a more professional chemical and metallurgical knowledge in the business, and with a great deal m ore foresight than most of his contem porary industrialists, to em bark on a course of study at the Royal School of M ines (then known as the G overnm ent School of M ines, in J e rm y n Street). H ere E dw ard had the benefit of instruction by H o fm an n in chemistry a n d by the great J o h n Percy in metallurgy, and in 1860 he was m ad e a
29 3
\ younger brother of George, whom he followed as an apprentice in 1850. E d w a rd stu d ie d chem istry an d metallurgy at the Royal School of Mines and was taken into partnership in 1860. T he three partners then rem ained in control of the business for o \e r fifty years. He is show n here in the uniform of the London Rifle Brigade from which he retired as Colonel in 1901
Edward Matthey 1836-1918
junior partner together with a nephew of Mrs. Johnson, John Scudamore Sellon, the firm now becoming Johnson Matthey and Co. Sellon had his strongest gifts on the commercial side, where his personal character and his keen insight amounting frequently to vision were of the utmost value to the firm. He had had no scientific training, but yet had a flair for scientific matters that ensured great intimacy of co-operation with George Matthey in the utmost speed of development of new technical enterprises. And it was he who in 1872 arranged a most favourable deal with the Russian State Bank whereby Johnson and M atthey took over the entire remaining stock of platinum amounting to well over 300,000 ounces. Sellon, whose father Captain William Smith, mentioned in connection with his brother-in-law Percival Norton Johnson in Chapter 9, had adopted his mothers maiden name in 1847, also brought with him the goodwill of some influential relations including the famous surgeon Sir Benjamin Brodie and his son, also named Benjamin who, after studying under Liebig, became Professor of Chemistry at Oxford in 1855 and President of the Chemical Society from 1859 to 1861. Edward Matthey was of entirely different character; he brought to the partnership an element of solidity and strength that was a necessary comple ment to the activities of his two brilliant colleagues. He provided a steadying
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influence, a willingness to serve his colleagues at home, and a m o rd a n t wit which m aintained in them both a very necessary sense of proportion. T his left G eorge M atthey with more time and energy to devote to the refining an d fabrication of his beloved platinum and to seeking applications for it in the growing industries of the time. T h e strength of the com bination is shown by the fact th at it remained in control, of the firm for full fifty years and in th at time built up a great business that has played a leading p art in the world of p latin u m ever since.
T h e Search for A p p lic a tio n s In his correspondence for the years 1865 and 1866, copies of which are still p re served, there are to be found letters advocating the electroplating of p latin u m on brass and gun metal, the supplying of platinum sheet for Grove cells, seeking business for platinum foil for the contacts on the new electric telegraph systems, as well as stimulating agents he had appointed in E u ro p e an countries and in the U nited States to greater efforts in the sale of p latinum laboratory a p p a ra tu s and chemical equipment. In 1867 an International Exhibition was to be held in Paris, a n d George M atthey a n d his colleagues determ ined to show w h a t a British firm could achieve. T h e exhibit comprised over 15,000 ounces of platinum , including two huge boilers. T his exhibit created something of a sensation in showing platinum m anufactures on a scale never so far imagined. It was aw arded a gold medal for perfection and improvement in the working of p la tin u m an d George M a tth e y was created a Chevalier in the Lgion d H onneur. T h e prestige of J o h n s o n and M atthey in their field was established beyond doubt. T h e Standard M etres a n d K ilo g r a m s George M atthey was entitled to take great pride a n d pleasure in this achieve ment, just fifty years after the foundation of the firm by Johnson, but it was during the course of this exhibition that another significant m atter was first set in train, as m entioned in the last chapter, the production of new sta n d a rd metres and kilograms in iridium -platinum . T h e proposal m ade by Deville and Debray that this alloy should be used ha d been accepted, but now cam e the problem of melting, casting an d fabricating the very large am ounts of alloy required a n d of obtaining sufficient quantities of the two metals in a high enough state of purity. It was also decided that in order to ensure uniformity of all the standards likely to be required they should be m ade from one ingot weighing no less th a n 250 kilograms. T he largest casting th at had ever been m ade so far was the 1 0 0 kilogram ingot cast by George M atthey in H atton G a rden in 1862 in the pre sence of Sainte-Claire Deville, and it was only natural that the latter should now tu rn to M atthey for advice and co-operation. He first provided the two metals, both originating from R ussian mineral, an d early in 1874 they were alloyed and cast into three ingots weighing 80, 85 and 90 kilograms. T h e se were cut
2 95
G e o r g e V latth ey p l a y e d a n i m p o r t a n t p a r t in t h e p r o d u c t i o n o f s t a n d a r d m e t r e s a n d k i l o g r a m s in hig h p u r i t y i r i d i u m - p l a t i n u m f o r t h e I n t e r n a t i o n a l M e t r i c C o m m i s s i o n . In 1874 t h r e e l a r g e c a s t i n g s , w e i g h i n g 8 0 . 8 5 a n d 9 5 k i l o g r a m s , w e r e c u t i n t o p i e c e s a n d r e m e l t e d to e n s u r e h o m o g e n e i t y i n t o a s i n g l e c a s t i n g m e a s u r i n g 14 2 by 18 bv 8 c e n tim e tre s a n d w eighing 236 k ilo g ra m s . T h is o p e r a tio n , c a r rie d out at th e C o n s e r v a to ire d e s A rts et M t ie r s in P a r i s , w a s c o n d u c t e d by G e o r g e M a t t h e y a n d H e n r i T r e s c a . P r o f e s s o r of M e c h a n i c s a t t h e C o n s e r v a t o i r e a n d S e c r e t a r y o f t h e F r e n c h s e c t i o n o f t h e I n t e r n a t i o n a l M e t r i c C o m m i s s i o n . B o t h D e v i l l e a n d D e b r a y w e r e p r e s e n t as t e c h n i c a l a d v i s e r s . T h i s e n g r a v i n g , f r o m t h e F r e n c h m a g a z i n e I / I l l u s t r a t i o n o f M ay 1 6 t h . 1 8 7 4. s h o w s t h e m e l t i n g o p e r a t i o n in p r o g r e s s
into small pieces and on M ay 13th, at the Conservatoire des Arts et M tiers in Paris, they were remelted and c a s t into a single ingot u n d e r the direction of the secretary of the French section o f the International Com m ission H enri Tresca, his son Gustav an d George M a tth e y , with Deville and D ebray in technical control. After cleaning the ingot weighed 236 kilograms and m easured 142 x 8 x 8 centimetres. It was exhibited to the Acadmie des Sciences by the Director of the Conservatoire w h o was also Vice-President of the French section of the International Commission, General Jules M orin ( 1 ) an d was then forged into a square bar 4.5 metres in length, cut into small pieces and again forged and cold draw n to yield the X -cross-section designed by T resca with the idea of giving it m axim um rigidity. It had originally been in te n d e d to make 65 metre standards, but there had been some cracking of the forged bars an d the operation of converting them to
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the open X-shape by cold drawing had given rise to a considerable amount of scrap. As a result it was possible to obtain only 27 sound metres, weighing about 90 kilograms, from the working of the great block. The Committee supervising the operations met in October 1874 and expressed itself as satisfied with this result, but unfortunately at this moment Deville found that the density of the metal was barely 21.1, whereas it should have been at least 21.385. Analyses showed that iron and ruthenium were present in appreciable quantities, in spite of the fact that Deville had himself purified the metal which George Matthey had provided. By way of explanation he suggested that the iron had probably entered the metal during the forging and drawing, and also that there had been a leak in the melting crucible. As for the ruthenium, delays in getting the mineral from Russia had not left him enough time to purify it as much as he would have liked.
Lively discussion and much research followed and Deville suggested that the whole of the metal should be remelted and subjected to a longer heating than before in order to get rid of the iron and ruthenium; this he had been led by his experiments to believe to be a possibility. Tresca and the other members of the French section were alarmed by the risks of another large melting and professed to be satisfied with what had been achieved, subject only to a remelting of the scrap. They took the view that the amount of impurity indicated did not interfere at all with the properties required in the metres and they deciced that the work should proceed. (2)
In April 1875 there came into existence the Comit International des Poids et Mesures, a body of much the same complexion as the former supervising committee with two extra members. This body at once took an interest in the
question and did not see eye to eye with the French section. Argument continued for some time and eventually a Commission consisting of Broch, Deville and Stas, which had been appointed to analyse and determine the density of the alloy, reported that it did not satisfy the requirements laid down in 1872 by the Commission Internationale, in that it contained:
Platinum Rhodium Ruthenium Iron 87.7 per cent 0.4 1.4 0.8 Iridium Palladium Copper 9.4 per cent 0.1 0.2
In consequence of this, on September 19th, 1877, the new committee decided to reject the metres that had been made from the alloy of the French section and to call for new ones satisfying the specification of 1872. These decisions were no doubt supported by the discovery of the cracks and fissures in the metres. The committee immediately addressed itself to the question of obtaining the new metal, acting through the same committee of Broch, Deville and Stas. They at once sought and obtained the collaboration of George Matthey and also of M. Brunner, instrument-maker of Paris. On the advice of the former it was decided provisionally to abandon the X-form and to make at first only bars of rectangular section. He believed that it was impossible to achieve the X-form by drawing without introducing iron into the metal and he thought it at least doubtful whether planing would not incur the same danger. The committee therefore decided on September 15th, 1877, to have two metres made of rectangular cross section and the order for them was sent by Stas to Matthey in January 1878. The latter immediately made a casting of 17.5 kilograms and the two metres were made out of that, together with some weights ordered by the Norwegian Government. The metres were planed, drawing being applied only to obtain the final shape. They contained only 0.23 per cent of foreign metals as compared with 2.9 per cent in those of 1874, while the density was 21.52 against 21.08, so that it was demonstrated that metres could be successfully made from pure platinum and iridium in small separate melts. This was sufficient to encourage the committee to attempt to make a metre with the X-shape from pure metals in the same way, and this was duly produced by Matthey in October 1879. In the same year he also made three iridium-platinum cylinders for kilogram standards. In 1878 George Matthey achieved another striking success in making a standard 4 metres long for the Association Godsique Internationale. This also was prepared in the rectangular form by rolling, with drawing applied only in the last stages. The metal had a density of 21.516 and contained only 0.33 per cent of metals other than platinum and iridium. This he described in some detail in a letter to the Association published by the Acadmie des Sciences, his communication being followed by comments on its density by Deville, and by further observations from Henri Tresca and finally by commendation and
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thanks from Professor J. B. Dum as, the Secretary of the Acadmie (3). In giving his account of this work, later on George M a tthey m entions that in 1876 he had been asked to produce a sta ndard metre in tu b u la r form a n d had done so by using his autogenous welding process. After that he had m ade others, of both round and square section an d exhibited samples at the Paris Exhibition of 1878. (4) W ith George M a tth e y s production of these various metres the era of experi ments was past, since in the course of it he had proved that metres m ade of pure iridium -platinum could be produced industrially and with the X-form. T he Governments of the interested countries were asked what they w anted and whether they would take it in the old or new alloy, and practically all asked for the latter. T h e French section, which was still officially charged with the provi sion of them, were not anxious to repeat their experiences and turned to Johnson, M atthey & Co for the work. An arrangem ent m ade betw een the com pany and the French Government on August 23rd, 1882 provided for the production of 30 Standards at 1.20 metres each in the X-form as well as 40 kilograms. M a tthey had proved that the single casting was not necessary for the achievement of identity, but he nevertheless offered to cast 250 to 300 kilograms if it were demanded. H e was left free to employ whatever m ethods he thought best. All the metals had to be analysed and passed by D ebray as representa tive of the French section and by Stas as representative of the Com it In te r national. O f the thirty m etres No. 6 eventually becam e the sta n d a rd metre, because its length at 0C was found to be precisely equal to th at of the provisional standard less 0.006 m m, and therefore it was of exactly the same length as the M tre des Archives. At the same time one of M a tth e y s kilograms was designated the International Prototype Kilogram and still rem ains as the ultimate world standard. T he production of standard metres and kilograms went on for over twenty years, the last orders from the French Government being delivered in 1887. One result of this substantial usage of irid iu m -p la tin u m was undoubtedly a greater understanding of refining and melting problems and a distinct improvement in purity, both of great value in the later applications of the p latinum metals, while the long association with the French scientists, particularly Deville an d Debray, brought M a tthey their close friendship and from tim e to time their invaluable advice.
I m p r o v e m e n ts in P la tin u m R efin in g George M atthey was disturbed by the presence of impurities in the p latin u m he had sent to Paris in 1874 for the preparation of the sta n d a rd metres and he promptly gave his mind to improving his m ethod of refining, turning to alloying platinum with lead which not only increases the solubility of rhodium in acidic solvents but renders the iridium almost completely insoluble in them. In 1879 he gave a full account of his revised process in the course of a paper
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to the Royal Society to which his election had already been proposed by a dist inguished list of supporters including Dum as, W urtz, Sorby and RobertsAusten. His account, T h e P re p a ra tio n in a State of Purity of the G roup of M etals known as the P latinum Series, and Notes upon the M a nufacture of Iridio-Platinum (5) described th e process of producing high purity p latinum as an operation of extreme d e lic ac y . After melting with six times its weight of lead of known purity and g ra n u la tin g the alloy it was attacked slowly in dilute nitric acid. This dissolved most o f the lead, taking with it a portion of the copper, iron, palladium and rhodium present. After separation of the insoluble part the bulk of the lead was removed from this solution by crystallisation as lead nitrate, the other metals being recovered by well-known m e th o d s . T h e black metallic residue obtained from the nitric acid attack consisted of iridium crystals and lead compounds of platinum a n d rhodium with only small proportions of the other metals originally present. It was next digested in weak a q u a regia, which completely dissolved the p la tin u m together with some rhodium and all the lead. T h e solution after filtering and evaporation was treated with enough sulphuric acid to remove the lead as s u lp h a te an d then the p latinum was precipitated as usual with an excess of a m m o n iu m chloride. T h e whole was then heated to about 80C and allowed to s ta n d for some days. T his consolidated the pre cipitate so that most of the rem aining rhodium stayed in the surface liquor to which it gave a rose tint. T h e precipitate was then filtered a n d repeatedly washed, first with a saturated solution of a m m onium chloride and then with dilute hydrochloric acid. In spite of this, rhodium was still liable to be retained, and to remove it the precipitate was dried, mixed with bisulphate of potash with a little am m onium b isu lp h a te and subjected to a gradual heat slowly brought up to a dull red. This tre a tm e n t converted the rhodium into a soluble state and it could be dissolved completely by boiling with water, leaving the platinum in a state of absolute purity of the density 21.46 . T here is a state m ent about this purity in a letter written o n j u n e 12th, 1879, by George M atthey to Deville, in which he says th a t he has 31 7 kilograms of platinum sponge in stock containing as sole im p u rity six parts per 1 0 , 0 0 0 of rhodium and some insignificant traces of iron. He also has 4 3 j kilograms of sponge containing seven or eight ten-thousandths of rh o d iu m and 31 kilograms containing fifteen tenthousandths of it which we propose to refine fu rth e r . (6 ) T h e iridium removed from t h e p latinum by m eans of a q u a regia still con tained rhodium, ruthenium, iro n and possibly some osmium. H e alloyed it afresh with ten times its weight of lead, attacked the alloy in nitric acid and a q u a regia in succession as before and then fused the product with potassium bisulphate, which almost entirely removed the rhodium . H e then melted the insoluble residue with ten times its weight of dry caustic potash and three times its weight of nitre in a gold crucible, the process being prolonged for a consider able time to convert the ru th e n iu m completely into potassium ruthenate. After solidification the cake was leached with w ater a n d the ru thenium distilled from the mixture as tetroxide, to be collected in hydrochloric acid. T h e fusion and
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distillation treatm ents were repeated until no further ruthenium was extracted and the residual iridium oxide was ignited to metal (after further cleaning in turn with bisulphate, chlorine w ater and hydrofluoric acid) a n d if perfectly pure should possess a density of 22.39. George M a tth e y rem arks at the end of his paper T h e highest density I have yet attained is 22.38 . This paper to the Royal Society was prom ptly reproduced in the G e r m a n and R ussian scientific periodicals, and in J u n e of the same year he was duly elected a Fellow of the Royal Society, being described as: Distinguished as a Metallurgist, having special knowledge of the metals of the Platinum Group. The development of the Platinum Industry was mainly due to his efforts.
T h e D esign o f S u lp h u r ic Acid B oilers O n e of the most im portant products - at least as far as the consum ption of platinum was concerned was the boiler for the concentration of sulphuric acid. Reference has been m ade to the boiler exhibited by the F rench firm of Q uennessen at the 1851 Exhibition an d to George M a tt h e y s determ ination to compete. T h e m eans he adopted to achieve success in the field can now be detailed. In C h a p te r 9 the activities of W ollaston in producing the first vessels of this kind were described, and in C h a p te r 10 the work of J e a n B reant that followed. T h e object was to concentrate the acid produced in the c h a m b e r process at 77 and 78 per cent strength up to oil of vitriol at 95 to 98 per cent, or even higher. Originally this operation was conducted in comparatively small glass vessels but their fragile nature and the continual breakages caused frequent losses and accidents. T h e early platinum boilers were operated on a b a tc h principle, the acid being boiled down to the correct strength a n d then siphoned off before another charge could be treated. T h is intermittent process subjected the boilers to great wear and tear and led to the opening of the m any joints in vessels fabricated from the gold-soldered small sheets at that time available. By the time that George M a tth e y began to produce these pieces of e q u ip ment the size of his platinum ingots had reached 500 ounces and the rolling of these into sheets had to be contracted out to a firm in Birm ingham . M a tth e y realised that if progress was to be made, and if platinum was to replace glass, he had to offer continuous operation an d an a p p a ra tu s economical in metal, in time and in fuel consumption. T o this end he retained the services of one of the very earliest chemical engineers, W illiam Petrie of C h a rlto n in Kent, the father of the famous archaeologist Sir Flinders Petrie. After taking a course in chemistry under Professor Daniell at K in g s College in London, Petrie had spent some time in Frankfurt studying electricity and on his retu rn to L ondon he took up this latter subject professionally, becoming associated with W illiam E dw ards Staite (1809-1854), one of the pioneers of electric lighting. T hey were unable to secure adequate financial support, however, and Petrie turned to electro301
F r o m 18 55 u n t i l w ell in to t h e t w e n t i e t h c e n t u r y o n e o f t h e m a j o r u se s o f p l a t i n u m w a s f o r t h e c o n s t r u c t i o n o f b o i l e r s to c o n c e n t r a t e t h e w e a k s u l p h u r i c a c i d p r o d u c e d in t h e l e a d c h a m b e r p r o c e ss . G e o r g e M a t t h e y w as p r i m a r i l y r e s p o n s i b l e f o r t h e g r o w t h o f th is a c tiv ity a n d s e v e ra l h u n d r e d b o i l e r s w e r e s u p p l i e d to a c i d m a n u f a c t u r e r s t h r o u g h o u t t h e w o rld . E a c h q u o t a t i o n w as a c c o m p a n i e d by a l a r g e c o l o u r e d d r a w i n g s u c h as th is, m u c h r e d u c e d in r e p r o d u c t i o n h e r e , s h o w i n g a d e s i g n o f 1 8 6 7 c a p a b l e of t r e a t i n g five t o n s o f acid per day
chemistry and chemical engineering. H e becam e associated w ith the sulphuric acid m anufacturing firm T h o m a s F a r m e r of K ennington which it will be rem e m bered was one of W ollastons first custom ers for a platin u m boiler in 1809. H ere he introduced improvements in th e operation of the plant and in 1854 began to collaborate with George M atthey. T h e first result of their joint endeavours was shown at the Paris Exhibition of 1855, the boiler having a m uch larger bottom surface for exposure to the heat with the result that it operated w ith a m uch less depth of acid. H e a t transfer was also improved by heating by m e a n s of direct radiation from the surface of a clear fire, as distinguished from h eating by drau g h t through flues in p a rt out of sight of the fire . Furtherm ore, th e boiler was arranged for continuous operation by direct feed and w ithdrawal b y siphon. Its capacity was 40 gallons and its o u tp u t 34 cwt. of strong acid per day. After 1860 an entirely new factor was introduced into the construction of the boilers by George M a tth e y s invention of the fusion welding of p latin u m by an
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W illiam Petrie
1821-1908 E d u c a t e d u n d e r D a n i e l i at K i n g s C o llege a n d t h e n in F r a n k f u r t . P e t r i e first e n g a g e d him self h e a \il\ but u n s u c c e s s f u l l y in t h e e a r l y y e a r s of e l e c t r i c lig h tin g a n d t h e n t u r n e d to in d u strial ch e m is try a n d the technology of su lp h u ric acid m a n u f a c tu re . For s o m e tw e n t y y e a r s , b e g i n n i n g in 1 8 54 , h e c o l l a b o r a t e d w ith G e o r g e M a t t h e y in t h e d es ig n o f p l a t i n u m b o i l e r s , a p p l y ing s o u n d p r i n c i p l e s of c h e m i c a l e n g i n e e r i n g a n d h e l p i n g to e s t a b l is h a l e a d e r s h i p in th is field t h a t c o n t i n u e d until the early y ears of the tw entieth centur\
oxy-hydrogen blow-pipe which m ade possible fully autogenous and therefore m uch stronger joints as well as reducing the cost of the boilers. By now energetic developments were taking place in chemical engineering. In a letter to one of his A m erican agents in 1859 George M a tth e y wrote th at he had come to the conclusion that in designing these vessels the most attention should be paid to the area of the botto m and the sides rath e r th an to the volume : the gallons of liquid per hour which the vessel will rectify or distil depends on the number of square feet of heat-absorbing surface of the vessel, while the bulk of liquid contained at one time is quite unimportant if the system of continuous running in and out at the same time be adopted. (6) Further improvements were m ade in boiler design by W illiam Petrie, covered in a patent filed in 1862 (7). This was for a vessel constructed in iridiumplatinum in which the concentrated acid left the boiler by a tube passing through the side from a separate com partm ent in the centre, it then being cooled by arranging for it to pre-heat the cold feed of incoming acid. This vessel, shown at the London Exhibition of 1862, would yield two tons of concentrated acid per day. A nother refinement devised by Petrie was the introduction of a gauge or indicator to show the degree of concentration of the acid. T his comprised a bi303
The in diratin g p yrom eter d e s i g n e d by W i l l i a m P e t r i e to d e t e r m i n e t h e b o i l i n g p o in t and thence the ro n ren tratio n of t h e s u l p h u r i c a c i d . T h e e le m e n t consisted of a bi m e t a l l i c h e lix o f i r i d i u m plalinurn a n d platin u m -g o ld . T h e in stru m e n t has now been p l a c e d in t h e k e e p i n g o f the Science M u seu m
metallic helix of a platinum -gold alloy lam inated to a n iridium -platinum alloy of different co-efficient of e xpansion a ttached to a pointer th a t would indicate the boiling point of the acid and th u s its degree of concentration. T h e capacity of the boilers w a s also increased, and in 1865 a quotation was m ade for one able to treat 5 tons per day, while a further improvement was the upw ard instead of the dow nw ard slope of the swan-neck to the condenser so that any splashes were returned to t h e vessel. T h e n in 1867 a boiler was shown at the Paris Exhibition able to handle 8 tons per day and was sold to a sulphuric acid m anufacturer in R ouen under th e noses of the French competition. T h e next development was d u e to M a n n in g Prentice (1846-1898) who had studied chemistry at University College, London, before joining his family firm of Prentice Brothers in S tow m arket in Suffolk, m anufacturers of gun cotton and of sulphuric and nitric acids. In 1875 Prentice conceived the idea that by making the bottoms of the retorts c o rru g a te d he would both stiffen the vessel and increase the heating surface. H is patent (8) was acquired by George M atthey, a n d the principle was also ap p lie d to the open platin u m used pans ahead of the boilers for the preliminary con c en tra tio n of the weak c h am ber acid. Almost immediately afterw ards there came the third m ajor development in design. This was brought a b o u t by Gustav Delplace (1845-1913), born in N a m u r in Belgium the son of a p lu m b e r who, after following his fath e rs trade, progressed into the construction of lead cham bers for sulphuric acid a n d then established a chemical plant m a n u fa ctu rin g business in Frankfurt (9). Delplace proposed the use of a very flat vessel and a thin layer of acid, resulting in con siderable economy in the weight of p latin u m used and still greater evaporating power. Again M atthey secured th e right to use this idea, while he also incor porated Prentices corrugated b o tto m in a new series of boilers. A n installation of this type, illustrated here, w a s shown at the Paris Universal Exhibition in
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A Johnson Matthey sulphuric acid boiler of 1876 incorporating both the corrugated bottom and the open pans of M anning Prentice an d the square shallow form proposed by Gustav Delplace, this design providing increased strength an d economy in operation with high purity of acid. I ntil the contact process for the m an u factu re of sulphuric acid came into full use some hundreds of boilers of this type were supplied to acid m akers throughout the industrialised countries of the world
1878. Among the visitors to this exhibition was Professor Benjamin Silliman from the United States who recorded in his review of the exhibits:
Now, by very simple modification in the form and mode of using the platinum boilers, their cost is greatly reduced and the daily product of concentrated acid at the same time very much increased. The new boilers, first introduced by Messrs Johnson M atthey and Co., are rectangular in shape, with corrugated bottoms which offer extended surface with additional strength and evaporating power so that the econom y of the new form of boiler is shown to be about fifty per cent each in the first weight of platinum and in the consumption of fuel, with an important saving in the cost of attendance and labour. (10)
For an output of four to six tons of acid per day the still measured three feet by one foot six inches and usually two were worked in series to provide a degree of concentration higher than any before obtained commercially in platinum apparatus worked continuously. From this time onwards there was little change in the general design of boilers other than increases in size; in 1893 one was shown at the Chicago Exhibition capable of concentrating ten tons per day. They remained a prominent feature of Johnson Mattheys work for the rest of the century and into the early years of the next until the contact process using a platinum catalyst came into full use. The last order received for platinum boilers was from the well known makers of sulphuric acid Spencer Chapman and Messel of Silvertown in East London in August 1914. This was for two boilers for the concentration of their chamber acid, each with a capacity of ten tons a day of 99.4 per cent acid, weighing 2396 ounces together. The last recorded case of a boiler being taken out of service was as late as 1926 when the last two vessels from an original set of twenty-six built in 1895 were returned as scrap by the African Explosives plant at Modderfontein. (11)
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T he success of these boilers, an d their adoption in great num bers throughout the industrial world, were u n d o u b ted ly due to the application of sound chemical engineering principles by G eorge M a tth e y and his three collaborators in a period when such concepts were only ju st beginning to be appreciated.
T h e G ro w in g Uses o f P la tin u m
T h e sulphuric acid boiler was not of course the only product to come from Johnson M atthey. Apart from an increasing output of p latinum crucibles, dishes, spoons, foil and wire to m eet the d e m ands of the rapidly growing num ber of laboratories, there now began to emerge several industrial developments that called for platinum in one form or an o th e r the electric telegraph, the incandescent electric lamp, the first m otor cars, an d even photography. T he invention of the electric telegraph the forerunner of course of the tele phone, the radio and all m o d ern telecom m unication systems - has been described m any times, together with the disputes and litigation between the early workers W heatstone, Cooke, Henry, M orse and others. Its success depended upon the concept of a relay by which an electric c urrent could be actuated at a great distance. T h e first such device, proposed by Professor Joseph H enry at Princeton in 1833, utilised a U -shaped piece of wire that could be caused to dip into a cup of m ercury by exciting an electromagnet, but by 1837 a m ore reliable relay or electrical renew er as he called it - has been developed by Edw ard Davy, a chemist of Fleet Street in L ondon and distantly related to Sir H u m p h ry and his family. C o n c e rn ed at the advances m ade by Cooke and W heatstone, Davy filed a p a te n t for his invention (12), the first such device to employ metallic m ake-and-break contacts, an d his sketch of the m echanism is reproduced here. He had d e m o n stra ted his telegraph system in R e g e n ts Park and held an exhibition in a hall in London, but just as his success seemed to be assured the breakdow n of his m arriage p rom pted him to leave England for
O n e o f t h e m a j o r u se s of p l a t i n u m a n d its a llo y s , fo r m a k e - a n d - b r e a k c o n t a c t s in s e n sitiv e e l e c t r i c a l d ev ices , b e g a n w ith t h e d e s i g n o f t h e first e l e c t r o m a g n e t i c r elay fo r the electric teleg rap h by E d w a r d I)a>y. T h i s is his d iagram taken from th e p a t e n t h e filed in 18158
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F o l l o w i n g u p o n E d w a r d D a v y 's r e l a y , o r e l e c t r i c r e n e w e r a s h e c a l l e d it. S a m u e l M o r s e e m p l o y e d a s i m i l a r d e v i c e in his e l e c t r i c t e l e g r a p h in 1840. T h i s sh o w s o n e o f his e a r l y d e s i g n s , w ith t h e p l a t i n u m c o n t a c t p o i n t s i n d i c a t e d a t K
Australia where he spent the rem ainder of his life, leaving the field entirely open to his rivals. His idea was shortly taken up by Samuel M orse in Am erica in 1838 and became a n essential feature of telegraphy (13). O n e of M o rs e s early relays with platinum contact points is illustrated here. It was the prototype of the m any mil lions of more sophisticated relays that have incorporated p latin u m or platinum alloy contacts to ensure their reliability.
T h e Electric Light As early as 1845 the use of a coil of platinum wire sealed into a glass con tainer to form an incandescent electric lamp had been proposed by W. R. Grove (14), while W. E. Staite had devised a lamp containing an arch of iridiumplatinum wire in 1848 (15), but m any years were to pass before a reliable means of illumination could be produced. Joseph Wilson Swan (1828-1914) who had attended a lecture in his native Sunderland by Staite that first set him upon the road to success had, however, to await the invention of the vacuum p u m p by H erm ann Sprengel in 1865 before this could be achieved with a lam p having a carbon filament supported on platinum wires and with thinner p latinum lead-in wires fused through the wall of the glass. This he was able to exhibit to the Newcastle-upon-Tyne Chem ical Society in 1878, a n d the Sw an Electric Lam p Com pany was formed in 1881.
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T he first practical incandescent lamp m ade by Joseph W ilson Swan in 1878. His carbon filament was held between two platinum supports that served also as lead-in wires. T hom as Edison, after experim enting with platinum and iridium filaments, also turned to carbon held in platinum supports and for m any years all electric lamps em ployed platinum lead-in wires sealed through the glass envelope
Photography by courtesy of the Science M useum
In the meantime Thomas Edison (1847-1931) in America had been carrying out similar experiments but using platinum, iridium-platinum alloys and even iridium filaments; a letter from him dated January 9th, 1879, still exists in the Johnson Matthey archives in which he enquired the price of sticks of iridium 1/64 inch in diameter and 1 inch long and also the price of ingots. Hearing of Swans success, however, Edison abandoned these and turned to carbon, their two English enterprises then being merged into the Edison and Swan United Electric Light Company Limited. For many years thereafter the supply of platinum leading-in wires, based upon the fact that the co-efficient of expansion of platinum is very close to that of glass, continued to be a feature of Johnson M attheys business until cheaper substitutes were eventually found. In 1897 Carl Auer von Welsbach (18581929) of Vienna, after inventing his gas mantle, developed a process for preparing osmium in the form of filaments for an incandescent lamp but the lamps were expensive and the filaments very fragile and production ceased after a few years.
The T herm ionic Valve The development of the incandescent lamp, important enough in itself, led to another most significant discovery, the emission of electrons from a hot metal electrode in a vacuum. This was first observed by Johann Wilhelm Hittorf
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(1824 1914), Professor of Chem istry and Physics at the University of M nster, who found in 1884 th at w hen an electrode of p latinum or iridium was heated inside an evcacuated glass envelope the conductivity of the gaseous space rose rapidly with increasing tem perature (16). Independently two other G e rm a n scientists, Ju liu s Elster (18541920) and H ans Geitel (1855 1923), both of the W lfenbuttel G ym nasium , showed that electrified particles were given off by a p latinum wire in a n exhausted glass bulb (17). During his work on the incandescent lam p E dison h a d already noticed in 1883 th at a p latinum spiral heated in a vacuum gave rise to a deposit of the metal on the inner surface of his glass bulb, and also th at a carbon filament produced the same result except where the glass was screened by the positive limb of the filament, a phenom enon that becam e know n as the Edison Effect (18). This was further investigated b y j . A. (later Sir A m brose) Fleming, the first Professor of Electrical Engineering at University College, London. Since 1882 he ha d also been scientific adviser to the Edison Electric Light C om pany (which m erged with S w a n s com pany a year later) an d was thus fully acquainted with the problem s in the early days of electric lighting, a n d he dem onstrated that a plate or a wire zigzag of platinum , placed before the nega tive leg of the carbon filament would almost stop the effect occurring (19). T h e n in 1899 Fleming took up another consulting post, this time to M a rc o n is Wireless Telegraph Com pany, a n d in seeking a m eans of converting the feeble oscillations produced in the receiving aerial into a unidirectional current his thoughts turned back to these earlier experiments. By 1904 he had invented the first thermionic valve, using either a p latin u m or an alum inium cylinder surrounding the filament (20), a device that was im m ediately adopted by M arconi and that led to all the revolutionary developments in electronics. T h e c arbon filament was replaced by tungsten in 1908, but an o th er type that came into use was the oxide-coated filament due to A rth u r R u d o lp h W ehnelt (1871 1944), Professor of Physics at Erlangen. T h is consisted of a n iridiumplatinum alloy wire having a coating of b a riu m or strontium oxide, this giving greater emission on heating (21). Some years later H e n ry J o s e p h R o u n d of the M arconi C o m pany patented a platinum cathode in tu b u la r form, coated with calcium oxide (22).
Early A u t o m o b ile Ign ition T h e birth of the internal com bustion engine operating on light oil or petrol, chiefly associated with Gottlieb D aim ler (1834 1900), brought with it yet another application for platinum . Earlier gas engines had employed a small tube of iron or nickel closed at its outer end, screwed into the top of the cylinder and externally heated by a flame. In 1878 Sir Dugald Clerk produced the first twostroke engine a n d filed a patent for the use of a small qu a n tity or bundle of platinum which is sufficiently heated to ignite the m ixture of air an d g a s (23). This was later modified to consist of a small cage or box of platin u m with a
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In the early internal combustion engines ignition of the m ixture was achieved by a small platinum tube inserted into the head of the cylinder and heated by a Bunsen burner. This shows an early D aim ler engine of 1898 with the platinum tube m arked E at the upper left of the d raw in g , w ith its b u rn e r, m arked 19. Below are two typical forms of platinum igni tion tubes from an early Johnson Matthey catalogue
number of ribs, also of platinum, running across it, housed in a cavity at the side of the cylinder (24). When in 1884 Daimler produced his small high speed engine (25) he incorporated a small platinum tube at the top of each cylinder heated externally by Bunsen burners! Incredible as this may now seem, the device was used in automobiles from 1885 until replaced many years later by the sparking plug and the magneto, and Johnson Matthey and their competitors in Europe produced great numbers of these platinum tubes. The progression of the original low voltage magnetos of about 1895 to the high voltage design of around 1902 is primarily associated with the names of the well-known British engineer Frederick Richard Simms (1865 1944) and of Robert Bosch (1861-1942) of Stuttgart. While the former type relied upon copper and silver, the high tension magneto first employed platinum contacts but when further improvements in design raised the voltage to 45,000 this was found to be too soft to withstand the conditions. As a result Simms appealed to Johnson Matthey to supply him with a much harder material, a 25 per cent iridiumplatinum alloy, for his contacts, this continuing in use for a number of years until its replacement by tungsten. (26)
Platinum in Photography During the early years of the evolution of photography there was consider able concern about the fading of prints and a great deal of effort went into the
310
search for a m eans of securing perm anence. T h e problem was tackled by William Willis am ong others who set out to find a metal th a t would w ithstand any conditions and produce prints that would out-last those based u p o n silver. After some years of experim entation in his laboratory at Bromley in K ent he invented and patented a process in which the p a p e r was sensitised with a mixture of ferric oxalate and potassium chloroplatinate. O n exposure to light the oxalate was reduced to the ferrous state an d this in tu rn reduced th e platin u m salt to metal (27). By this m eans p e rm anent prints of excellent quality were produced with the most delicate shades of half-tones, while the procedure was relatively simple to m anipulate. By 1879 Willis had formed the Platinotype Com pany which licensed photographers for only five shillings and supplied the sensitised paper. For m any years until the outbreak of the first W orld War, when platinum supplies were com m andeered by the government, this process was used for the highest class of p ortraiture and for docum entary photography and the supply of potassium chloroplatinate by Johnson M a tth e y to Willis reached ten thousand ounces a year. Platinotype pa p e r is no longer available commercially, but in recent years the process has been revived by creative enthusiasts who appreciate the quite rem arkable results that it can offer.
Vi i l l i a m Vi i 11 is
1 8 4 1 -1 9 2 3
O n e of t h e p i o n e e r s o f p h o t o g r a p h y , W il l i s first w o r k e d in e n g i n e e r i n g a n d b a n k i n g b e f o r e l e a v i n g to w o r k with h is f a t h e r , t h e w e l l - k n o w n l a n d s c a p e e n g ra v e r w ho orig in a te d the aniline process for copying en g in e e rin g d r a w in gs. o n a new p h o t o g r a p h i c silv er p r o c e s s . H e w a s d i s s a t i s f i e d b \ t h e lack of p e r m a n e n c e of the silver process, a n d w o r k e d f o r m a n y y e a r s to d e v e l o p a m ore satisfactory p ho tographic p r in tin g p rocess using p la tin u m . He obtained several patents for his P latinotype process and received a w a r d s from the Koval P h o to g ra p h ic S ociety a n d the I n te rn a tio n a l In v e n t i o n s E x h i b i t i o n . H is m a n y i n t e r e s t s i n c l u d e d t h e s p e e t o g r a p h i c a n a l y s i s of m inerals and m etals, undertaking m u c h o r i g in a l w o r k o n t h e m , b u t w h i c h he n e v e r p u b l i s h e d
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The First Artificial Fibres Another application of platinum that originated in this period - and one that continues and increases - was in the production of the first man-made fibre, artificial silk, or as it became known later, viscose rayon. The initial invention was due to Charles Frederick Cross, Edmund John Bevan and Clayton Beadle, consulting chemists in London, who first produced cellulose xanthate from wood pulp in 1892 (28). Their patent was acquired by the old-established silk weaving firm of Courtaulds who, after some years of further development, began the manufacture of yarn in Coventry in 1904. The heart of the process was a spinn ing jet, a top-hat shaped device having a great number of very small and accurately drilled holes through which the highly alkaline viscose solution is extruded into fibres in the sulphuric acid coagulating bath. To withstand these aggressive conditions, and to avoid attrition of the holes that govern the size and quality of the fibre, platinum became the obvious choice for the spinneret material and although several alloys of platinum with either rhodium or gold have since replaced the pure metal the application remains the same and many thousands of such spinnerets are in use at any one time in a modern viscose rayon plant. For some time Johnson Matthey provided only the platinum in sheet form but later took up the manufacture of the spinnerets. The develop ment of the presses has been described in more detail by J. W. S. Hearle and A. Johnson (29).
This laboratory dem onstra tion of the formation of a multifilament viscose rayon yarn shows the pum ping of th e a l k a l i n e c e ll u l o s e xanthate solution through the h o le s in a s p i n n e r e t im m ersed in the acidic coagulating solution. Only platinum or its alloys can withstand these highly corro sive conditions. Beginning in 1904. the m anufacture of rayon now requires many thousands of such spinnerets in any one viscose rayon plant
B\ courtesy of C ourtaulds Lim ited
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T h e M eltin g an d W o rk in g o f I rid iu m T h e melting of platinum and its alloys in the lime-block furnace had been successfully established, but iridium melting at 2443C, still presented difficulties. In 1882 work on this problem was undertaken by H enry A ndrew Kent who had come over from J o h n H a rriso n of Clerkenwell, the firm employed for platinum fabrication work until the death of the owner in 1874. Kent, encouraged by Sir William Crookes (1832-1919) the p rom inent Victorian scientist and the founder of The Chemical N ew s, eventually succeeded in melting pure iridium in some quantity and in forging and rolling it to sheet, a n d at Crookes request m ad e a n um ber of crucibles. L ater Crookes read a p a p e r to the Royal Society (of which he becam e President in 1913), O n the Lise of Iridium Crucibles in Chem ical O p e ra tio n s beginning:
1 should like to draw th e a tte n tio n of chem ists to th e great advantages of using crucibles of p u re iridium instead of p la tin u m in laboratory work. T h ro u g h the kindness of M essrs. Jo h n so n an d M a tth e y I have had a n o p p o rtu n ity of ex p e rim e n t ing w ith crucibles of w rought iridium , and have used one for several m o n th s in the usual o p erations of qu an titativ e analysis in my la b o ra to ry (30).
He reported that his iridium crucible resisted the fusion of m any fluxes, including caustic soda, and were unattacked by m olten lead, zinc, nickel, iron and gold. Crookes was well in advance of his time in advocating the use of iridium for this purpose; in the last twenty years they have been used extensively for the growing of single crystals from oxide melts for use in electronics.
On* of t h e i r i d i u m c r u c i b l e s m a d e by J o h n s o n M a t lh e y f or S ir \& illiam C r o o k e s still survives in the c o m p a n y 's p o ss e s sio n . T h e y were mac le b\ II enr y \n d r e w K en t, an assistant to J o h n S e llo n . w h o p l a y e d a p r o m i n e n t p a r t in t h e ea rl\ period of p la tin u m f a b r i c a t i o n f r o m 1875 to 1893
313
C o n c lu sio n
G eorge M atthey finally retired in 1909 after a career spanning no less th an seventy years. From a laboratory scale operation he had transform ed the refining and fabrication of p la tin u m into a n im p o rtan t b ran c h of industry. T h e earliest recorded figures show th e sales of platin u m by J o h n s o n M a tth e y as some 15,000 ounces in 1860, increasing to 75,000 ounces by 1880. H e died in 1913 at the age of 87, an d a leading article in The Tim es included the observation:
T h e d eath of M r. G eorge M a tth e y , F .R .S ., serves to rem ind us of the p a rt w hich th e rare an d precious m etals h av e played in the general advance of p ractical science w ithin the last half -c e n tu ry .
and continued with the sentence q u o ted at the head of this chapter. H e had been succeeded as c h a ir m a n of the com pany by J o h n Sellon, a m an who had shared his resolve to m ake J o h n s o n M a tth e y pre-em inent in the platinum industry, until his o w n death in 1918, the year in which E dw ard M a tth e y also died. O n e tribute to the work of these three p a rtners for so m any years was m ade by Sir William R oberts-A usten in the course of a lecture on the rare r metals given to the Royal Institution in 1895. Referring to a range of exhibits of the platinum metals on view to the audience, he said:
W e are in debted for this m ag n ificent display to m y friends M essrs G eorge and E d w ard M a tth e y a n d to M r. S ellon, all m em bers of a g reat firm of m etallurgists. Y ou should specially look at th e sp le n d id m ass of p alladium , ex tracted from native gold, at the m elted an d rolled iridium , a n d at the m asses of osm ium and rhodium . N o o ther n atio n in the w orld could show s u c h specim ens as these an d we are justly p ro u d of th e m (31).
T h e succession was co n tin u e d by G e o rg e s son Percy St. Claire M a tth e y (1862 1928), nam ed after his f a th e r s friend and collaborator Sainte-Claire Deville and educated for a time a t the cole N orm ale, and then on his death by E d w a r d s son H ay W hitw orth Pierre M a tth e y (1876 1957) w ho h a d worked closely with his cousin Percy on p la tin u m a n d who served as c h a irm a n until the close of his life. O n the foundations that G e orge M a tth e y had laid so painstakingly his successors were able to build a n d expand to an even greater extent. T h e y were not, however, without active com petitors in continental E urope as the following c hapter will show.
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R eferen ces for C h ap ter 16
1 A .J. M orin, Comptes rendus, 1874, 78, 15021506

2
3 4 5
6
7
8
10
1 1
12
13 14 15 16 17 18 19
20
21 22
23 24 25 26 27 28 29 30 31
A. P erard an d C. Volet, Less M tres Prototypes du B ureau In te rn a tio n al, Paris, 1945, 7-25 G. M atthey, Comptes rendus, 1876, 83, 1090-1091; H. S ainte-C laire Deville, ibid., 1091 1093; H. T resca, ibid., 1093 1096; J. B. D um as, ibid., 1096-1097 G. M atthey, Chem. News, 1879, 39, 175-177 G. M atth ey , Proc. Roy. Soc., 1879, 28, 463 471 Letters of G eorge M atth ey in the possession of Jo h n so n M atth ey an d Co. L im ited W. Petrie, British P atent 1528 of 1862 M. Prentice, British Patent 4391 of 1875 A. Nemes, Chem. 'eitung, 1913, 37, 237 B. Sillim an, Eng. and M in. J ., 1878, A ugust 31, 147-148 M. S. Salom on, A.E. and C I. R ep o rter, 1926, F eb ruary E. Davy, British Patent 7719 of 1838 S. F. B. M orse, U.S. Patent 1647 of 1840 W. R. Grove, Phil. Mag., 1845, 27, 442^145 W. E. Staite, British Patent 12,212 of 1848 A. W. H ittorf, Ann. Phys. (Wiedemann), 1883, 20, 705 755; 21, 90-139 J. E lster a n d H. G eitel, Ann. Phys. (Wiedemann), 1887,31, 109-126 T . A. Edison, Engineering, 1884, D ecem ber 12, 553 J . A. Flem ing, Phil. Mag., 1885, 20, 141-144 J. A. Flem ing, Proc. Roy. Soc., 1905, 74, 466 487 A. R. W ehnelt, Ber. Phys. Med. SozErlangen, 1903, 150-158 H. J. R ound, B ritish P aten t 6476 of 1915 D. Clerk, British P atent 3045 of 1878 D. Clerk an d G. A. Burls, T he G as, Petrol an d O il Engine, London, 1913, Vol II, 271-272 G. D aim ler, British Patent 4315 of 1885 F. R. Sim m s, personal com m unication, Ju ly 1942 W. W illis, British Patents 2011 of 1873, 2800 of 1878, 1117 of 1880 and 1681 of 1887 C. F. C ross, E. J . Bevan an d C. Beadle, B ritish P aten t 8700 of 1892 J . W. S. H earle an d A. Jo h n so n , Platinum Metals Rev., 1961, 5, 2-8 W. Crookes, Proc. Roy. Soc., 1908, 80A, 535 536 W. C. R oberts-A usten, Proc. Roy. Inst., 1895, 14, 497 520
315
W i l h e l m C a rl H e r a e u s
I827-1904 T h e d e s c e n d a n t of a l o n g line o f a p o t h e c a r i e s . H e r a e u s s t u d i e d c h e m i s tr y u n d e r P r o f e s s o r ^ h l e r at G t t i n g e n a n d in 1851 e s t a b l i s h e d his r e f i n e r y . P l a t i n s c h m e l z e W .C . H e r a e u s . in H a n a u . r e m a i n i n g in c o n t r o l u n t i l his r e t i r e m e n t i n 1889
17
The Development of the Platinum Industry in Continental Europe
/ have been refining and w orking platinum now f o r sixteen years , always b y the m eth od that the renow ned I)r. W ollaston brought to such perfection.
PIE R R E A i d S T I N E C l O Q . 1833
T h e establishment of an effective platinum industry in France originated with the acquisition, shortly after the fall of N apoleon a n d the restoration of the Spanish monarchy, of the accum ulated stock of native platinum for which, without C h a b a n e au and Proust, the S paniards had no outlet, by one Pierre Augustine Cuoq (1778 1851). Born in the village of Tence south of St. Etienne, Cuoq served in the French Revolutionary Arm y on the Rhine a n d then in N apoleons Italian campaign. After the peace of C a m p o Formio he returned to civilian life in local adm inistration and then in 1801 as a lawyer in Lyons where he met his future p a rtn e r Couturier with whom he joined forces in a m erchanting business in 1807. Cuoq travelled widely in the course of his comm ercial activities, visiting Germany, the Near East, Italy and above all Spain where he spent several periods of time. It was on one of these last visits th at he negotiated the p urchase of about 1000 kilograms of the native platinum that had earlier been im ported from New G ra n a d a by the Spanish authorities an d for which they now h a d neither a method of refining or any forseeable use. There is some evidence that Cuoq was acquainted with Vauquelin, at the time associated with the M int in Paris, and that he provided him with a n u m b er of samples of this native metal. It is also clear th at the firm of Cuoq and Couturier moved to Paris; both m en are listed as m em bers of the Socit d Encouragem ent in 1817, described as m erchants with the same address in the Rue de M enard. T heir arrangem ent for the refining of this imm ense q u a n tity of platinum with J e a n Robert Brant (1775-1850), also a n assayer at the M int and well known to and advised by Vauquelin, has been described in C h a p te r 10. It led to the production of large ingots and of the first sulphuric acid boilers to be m ade in France and in only a short period of time to the foundation of the
317
leading m anufacturers of p la tin u m anyw here in the world, an d in France to a position of dom inance that they a n d their successors held for almost a century. Brant was not only successful in his refining treatm ent, he also evolved a technique of forge welding to avoid his earlier procedure of soldering with gold, a n d by the F ebruary of 1817 he a n d C uoq and C outurier were able to show the Socit d Encouragem ent a sulphuric acid boiler holding 162 litres, both parties receiving the com m endation of t h e society for their achievements as well as for having reduced the price of p la tin u m (1). T his association was not to last long, however. In 1819 Brant established his own small works an d rolling mill in the R ue de M o n tm a rtre, continuing to m anufacture boilers, with a larg e r refinery in the Place du Com m erce in the suburb of Grenelle in premises next to those of a M. H. D esm outis who shortly entered into partnership with B rant. C u o q and C outurier continued to operate in the Rue du Richelieu, later m oving to the R ue Lulli. In 1820 W ollaston m ade an entry in one of his notebooks giving the price of p latin u m from Cuveq, Couturier an d C o and m entioning a vessel they had m ade holding 300 litres an d weighing 776 ounces (2). In 1833 a letter from C uoq a n d C outurier in the J o u rn a l fu r techmsche chemie (3) rebutted an allegation that their p latin u m contained arsenic a n d included the phrase quoted at the head of th is chapter. T his statem ent cannot have been altogether true, as W ollastons process was not of course m a d e public until 1829, and no doubt in their earlier years they were basing their fabrication m ethods on those of T hom as Cock and R ic h a r d Knight. In 1837 Brant no longer appears, being no doubt m ore fully occupied at the M int, where he eventually b e c a m e D irector in 1846, and he was succeeded by one M ontrelay while Cuoq h a d set up his own m erchanting business in Marseilles in the previous year a n d h a d also become a D eputy for his native D e partm en t de la H a u te Loire. I n 1845 the firm becam e known as Desmoutis, M o rin and Chapuis, successors to Brant, M ontrelay, C uoq an d Couturier, con tinuing in this style until 1854. T heir subsequent history is som ew hat com plicated an d difficult to piece together, the firm undergoing several changes of nam e and partners. N othing is known of M orin; there were tw o brothers Prosper and A n d r Chapuis, the second one also a fabricator of p latin u m who continued in business until the 1860s, exhibiting a n um ber of p la tin u m items a t the London Exhibition of 1862.
T h e T w o Q uennessens In about 1856 the D esm outis com pany was joined by Franois Adrien Q uennessen (1813-1889) who w a s to rem ain a most effective p a rtn e r and later, followed by his son, to control t h e business for very m any years. Q uennessen had earlier been fabricating p la tin u m on his own account in the R ue de Bouloi an d it will be rem em bered from C h a p te r 16 that it was he w ho greatly surprised George M a tthey with his display of chemical plant at the 1851 Exhibition. T h e report of the J u r y on that occasion reads: (4)
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Quennessen (France. No. 1683). This exhibitor stands first in the exhibition of chemical apparatus having exhibited a platina alembic for sulphuric acid containing 250 pints, made in one piece without seam or solder, also long platina tubes made without seam, besides crucibles capsules etc. all of which are executed with the greatest care and appear to be of the most finished and exquisite workmanship. Among the articles exhibited by M. Quennessen is an apparatus for the distillation of hydrofluoric acid of a very complete and perfect kind. A Council Medal is awarded to M. Quennessen. In the same year Q uennessen had obtained a F rench p a te n t for the fabrica tion of a platinum siphon by autogenous welding, (5) m u ch less expensive than those m ade by soldering, for the decantation of sulphuric acid or other acids. His medal from the London Exhibition was followed on his retu rn hom e by the aw ard of the Cross of the Legion of H o n o u r and he was clearly established as a leading fabricator of platinum . In 1855 he exhibited a p latin u m boiler at the Paris Exhibition un d e r the nam e of Adr. Q uennessen et Cie (6), b u t about this time he joined the Desmoutis com pany as a n employee, the firm later becoming Desmoutis, C hapuis a n d Q uennessen, still in the R ue M ontm artre. In Deville a n d D e b r a y s earlier papers on the melting of platin u m in 1857 they expressed their gratitude to Desmoutis a n d C hapuis and separately to Quennessen for their generous provision of platinum , while in 1859 they record the licencing of their patents to Desmoutis, C hapuis an d Q uennessen as one entity. In 1862 under this last nam e they exhibited at the L ondon International Exhibition a magnificent case of platinum , melted, ham m e re d a n d w rought and in chemical c o m bination (7). In the 1870s the nam e was changed again to Desmoutis Q uennessen a n d Le Brun, and under this last nam e they were producing sulphuric acid boilers incorporating some of the improvements in design already introduced by George M atthey and his team of chemical engineers, exhibiting them in Paris in 1878 and 1889. T h e F rench com pany was active in the production of platin u m for all the developing applications, the ignition tubes for the early automobiles, lead-in wires for incandescent lamps and platinum com pounds for p hotography, as well of course as meeting the normal dem ands for laboratory ap p a ra tu s, while they were also producing palladium in various forms an d rhodium , iridium, osmium and ruthenium for use by researchers. While the French com pany was in competition with J o h n s o n M a tth e y to only a limited extent, particularly in the sulphuric acid boiler field, the two were in direct and fairly fierce competition in their needs for native platinum . A part from an occasional shipm ent of mineral from Colombia, the only source was Russia, where it will be rem em bered coining had ceased in 1846 an d the rem a in ing stocks of p latinum ha d been transferred to the State Bank. W h e n George M atthey m ade his agreement in 1851 with Count Demidov there was a proviso that a similar arrangem ent should be m ade with a French refiner, and both Joh n so n and M atthey went out of their way to draw this to the a ttention of Desmoutis, M orin an d Chapuis with the suggestion that they should m ake application. After some hesitation they decided so to do, a n d cam e to a similar
319
T he French com pany, first established by Brant in the Rue M ontm artre in 1819. u nderw ent many changes of p artnership o \e r the years, eventually being headed by \d rie n Quennessen. After the latter V death his son Louis, who had carried out research on the platinum metals at the Ecole Normale, joined the firm which then adopted the st\ le show n here
arrangement with Demidov which lasted satisfactorily until the outbreak of the Crimean War in 1854. When peace returned in 1856 business with Russia remained extremely difficult to conduct from England, and Count Demidov con cluded a series of two-year contracts to supply the Paris company. It was not until 1872, as recorded in the last chapter, that John Sellon was able to close a most favourable deal with the Russian State Bank by which Johnson Matthey took over the whole of the remaining stocks of platinum in all forms including coin and residues. Adrien Quennessen had been seeking a similar arrangement, but failed to achieve it and his firm was now faced with a great problem of supply. Coming to London to negotiate, he was offered and accepted half the great quantity of metal that had been purchased, this leading to a lasting friend ship between the two houses, who now had adequate supplies at their disposal. Adrien Quennessen had a son Louis who studied chemistry under Professor Emile Leidi (1855-1904) at the cole Normale, staying on to do post-graduate research, and in this he was most fortunate as he became part of an almost apostolic succession in the chemistry and metallurgy of the platinum metals. Quennessen senior was in and out of Devilles laboratory during the develop ment of the melting process for platinum and its alloys and was well known to him and to Debray. One of Devilles students, Alphonse Joly (1845-1897) remained to become director of the chemical laboratory at the cole Normale, responsible to Debray after Devilles death, and contributed a number of research papers to the Acadmie des Sciences over the next few years. The first of these, jointly with Debray, was on ruthenium and its compounds in 1888, while his own papers also dealt with the same subject and with the atomic weight of ruthenium, with compounds of iridium and the atomic weight of the metal and with osmium compounds (8). Leidi, after obtaining his doctorate with a thesis on the chemical compounds of rhodium in 1889 (9), began to collaborate with Joly in a series of researches, first on the separation of the platinum metals, on the atomic weight of palladium and then on the complex compounds of the platinum metals (10). After Jolys death at the age of only fifty-two Leidi continued his studies on the chemistry of the platinum metals and their separation (11) being joined in his researches by the young
320
Q uennessen in 1901, three papers on extraction m etallurgy an d analytical methods resulting from their collaboration (12). U nfortunately Leidi also died at an early age, but Louis Q uennessen persued the sam e line of investigation on his own, submitting several papers to the Socit C him ique de Paris on the absorption of hydrogen by palladium , on the separation of iridium from platinum and on the com pounds of iridium (13). He was thus well equipped to join the family business, which had again changed its name, the elder Q uennessen having died in the 1880s, to Desm outis Lemaire, the latter representing the widowed d a u g h te r of Adrien Q uennessen. In 1907 the firm was re-organised as Q uennessen, de Belmont, L egendre et Cie, Successeurs de Desmoutis et C ie . T h e de Belmont n am e was th at of the son-in-law of Desmoutis, a m an of wealth but no technical knowledge, while Legendre was the com pany secretary, and M a d a m e Lem aire rem ained a substantial shareholder.
T h e C o m p to ir L y o n - A le m a n d Unfortunately the outbreak of w ar in 1914 came as a very severe blow to the company. T h e refining and working of p latinum was their only activity and Russia their only supplier of raw material. Small quantities were secured for a time, but the R ussian revolution p u t an end to this and in 1917 they went into voluntary liquidation. Louis Q u e n n e ssen s last contribution to the literature was a long paper sum m arising the history of the p latinum metals, their occurrence, mineralogy and m ethods of analysis, published in the same year (14). In 1919 the shares of Q uennessen, de Belmont an d Legendre, b u t not those of M a d am e Lemaire, were taken over by the C o m ptoir Lyon-Alem and. T his had been established in Paris in 1800 by J o s e p h A lem and who was joined by his daughter who, m arried to one Lyon, succeeded her father in 1813, continuing in the business together with her three sons until 1826, the firm th en becoming C om ptoir Veuve Lyon-Alemand until 1880 w hen it was incorporated un d e r its present name. In 1925, on the death of M a d a m e Lemaire, her holding in the Quennessen com pany was also acquired, and in the sam e year the C om ptoir Lyon-Alemand also acquired another bullion an d platin u m company, M a rre t Bonnin Lebel et Guieu, founded in 1810, becoming the sole F rench refiner of the platinum metals. Located in the R u e de M o ntm orency in Paris, they continue in operation as one of the leading p latinum com panies of the world. T h e H o u se o f H eraeu s T h e year 1851 was a rem arkable one in the history of platinum . Not only did George M atthey enter into his partnership with Johnson, only to be stirred into greater activity by the exhibition m ounted by his French com petitor Q uennessen at the G reat Exhibition in London, but a new entrant appeared in the industry, this time in G erm any, in the person of W ilhelm Carl Heraeus.
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Since 1660 his ancestor Isaac H eraeus had been established as a pharm acist in H anau, trading under the sign of the W hite U nicorn in the N e u stad te r M arkt an d serving the Court of the C o u n t of H anau. T h e young W ilhelm Carl was first trained as a pharm acist and was then sent by his father to study chem istry u nder Professor Friedrich W ohler at G ottingen. O n his retu rn to take charge of the family business he found that his m ind was not sufficiently occupied by the pharm aceutical practice and he tu rn e d first to chemical preparation, building himself a laboratory, and then to the refining of the precious m etal scraps and residues from the num erous old established goldsmiths and silversmiths of the town, returning to them the p u re metals including small am ounts of platinum . His interest in this metal p r o m p te d him to establish the W. C. H eraeus Platinum Refinery in 1851 w h e n only twenty-four years of age, an d six years later he becam e aware of the new melting techniques proposed by Deville through the latters friend a n d his old teacher Wohler. In th at year there appeared a modest advertisem ent on the last page of Poggendorffs Annalen ;
W . C . I l e r a e u s in H a n a u O w n e rs of a R efinery fo r P l a t i n u m , P a lla d iu m , C o ld a n d S ilv er; d eliv e rs w o r k e d p l a t i n u m 2 0 p e r e e n l c h e a p e r t h a n h a s h i t h e r t o b e e n t h e p r a c t i c e in G e rm a n y , n a m e ly a t 4 66* G u ld e n p e r K ilo g r a m , w ith a d is c o u n t o f 3 p e r cent on th e o r d e r o f a w hole k i lo g r a m a n d 5 p e r ce n t o n 3 k ilo g ra m s . F a b r ic a tio n is c h a r g e d f o r a t c h e a p r a t e s ( 1 5 ) .
For his refining process H e ra e u s dissolved native p latin u m in a q u a regia in a closed vessel under pressure, this m eth o d effecting a more r apid an d more nearly complete dissolution. T h e solution was then evaporated to dryness an d the residue heated to 125C, reducing the chlorides of p alladium a n d iridium to a lower valency an d ensuring that th ey were not p recipitated when treating the re dissolved material with a m m o n iu m chloride. T h e precipitate was pressed, broken into pieces and then m elte d in the lime furnance (16). As early as 1862 Deville a nd D e b ra y reported: A new process for casting platinum is now used, invented by M. Heraeus, a manufacturer at Hanau who by the advice of his illustrious master M. Wohler, has adopted for several years the processes we published on the treatment of platinum which in the hands of a clever manufacturer and an enlightened chemist have undergone already, as we anticipated, simiplification and improvement. M. Heraeus runs the platinum into moulds of iron, which we have given up, but he obviates all the inconvenience arising from the fusibility of iron by placing at the bottom of the mould a sheet of platinum 1 millimetre thick which withstands the first contact of the molten metal (17). T h e platinum ingots, weighing about 2 kilograms each, were forged by a local smith on his anvil, the rolling of sheet then being carried out in his laboratory by H eraeus and his w orkpeople, a work of great h a rd s h ip , while the making of crucibles and o th e r pieces of a p p a ra tu s was turned over to coppersm iths and goldsmiths in th e tow n (18). As early as 1857 H eraeus m ade his first export sale of 30 kilograms of rods, sheet a n d wire to a firm in New York,
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T h e old a p o th e c a ry , At the S ign o f t h e W h i t e U n i c o r n , in w h i c h t h e H e r a e u s f a m i ly h a d c o n d u c te d th e ir business sin ce the se v en teen th c e n t u r y , b e c a m e t h e first home of th e p latin u m r e f i n e r y in 1 8 5 1. L a t e r m o r e m odern p rem ises w ere e r e c t e d in l l a n a u
while his total sales for 1859 am ounted to 59 kilograms, growing to 400 kilograms by 1879 a nd to over 1000 ten years later. Heraeus was not satisfied with the purity of his platin u m an d he investigated methods of making a m uch pu rer product an d of preparing the o ther m etals of the platinum group separately a n d in quantity. In this work he appears to have run along similar lines to those adopted by Deville an d D ebray a n d by George M atthey, described in the last two chapters, but his progress was rather slow and it was not until 1891 that he was able to report success, but unfortunately he did not provide any analyses to com pare with those of Deville a nd M atthey. This work was carried out with the co-operation of the Physikalisch-Technischen Reichsanstalt recently founded at C ha rlo tte n b u rg by W erner Siemens and directed by H e r m a n n Helmholtz (19). In the course of this investigation he also studied the alloys of platinum with iridium and rhodium a n d he succeeded in drawing into wire metal containing as m uch as 40 and even 50 per cent of the alloying elements.
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O ne im portant product introduced by the H eraeus com pany in about 1900 was the platinum w ound electric furnace that enabled extremely high tem peratures to be achieved in the laboratory. This shows one of the earliest designs intended for melting point determ inations, and it was soon followed by horizontal tubular forms capable of attaining a tem peratu re of 1500C
Competition from Heraeus became important soon after he began his operations and joined the British and French companies in the manufacture of platinum boilers for the concentration of sulphuric acid, believing however, that better results could be obtained by lining the platinum with gold. This he achieved by pouring molten gold on to the surface of platinum blocks heated to a temperature above the melting point of gold and rolling into sheet (20). Wilhelm Carl Heraeus had two sons, Wilhelm (1860-1948) and Heinrich (1861 1910) who took over the business on their fathers retirement from active work in 1889 and continued to build on the foundations he had laid. Both had qualified as pharmacists; Wilhelm had also studied chemistry and Heinrich metallurgy, and they had both already absorbed the techniques of refining and working platinum in their fathers business. In 1890 they were joined by Dr. Richard Kiich (1860-1915), a physicist who was to make important scientific contributions to the company, including the production of high purity platinum. For a very long period the platinum work had been carried out in the old apothecary building, illustrated on page 323, in which Isaac Heraeus had estab lished himself in 1660, but naturally this had rapidly become much too small and in the years 1891 to 1896 a new plant was built on the outskirts of Hanau. Here they were able to expand the mechanical production of platinum and its alloys and to meet the new demands arising from the early telegraph, the electric light and the ignition of Daimlers early motor car engines. A little later, by 1901, they had pioneered the design and construction of platinum resistance elements in electric furnaces for laboratory use at temperatures up to 1500C (21). A detailed account of this development has recently been given by Dr. R. C. Mackenzie in Platinum M etals Review (22).
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In 1919 the business was incorporated as a limited com pany w ith the two brothers, together with R ichard K ch and W ilhelm s brother-in-law Charles Engelhard, their A m erican agent, as directors. In 1951 the H eraeus com pany celebrated its centenary with the publication of a small book (18) and a larger technical work containing contributions by a num ber of their research scientists an d opening with a com m em orative p a p e r by Professor W alther Gerlach, Rector of the University of M unich. T h e com pany continues to be am ong the leading refiners an d fabricators of p latinum with members of the original family still represented am ong its directors.
T h e R oessler F a m ily B u sin ess A nother great G e rm a n concern, established some years later th a n H e ra eu s but also with antecedents going back to m u ch earlier times, originated with Friedrich E rnst Roessler, w arden of the m int then being re-opened by the city of F rankfurt-am -M ain in conjunction with the setting up of a state-operated refinery. H e ha d been appointed to this post in 1841 after consultations with his father, Jo h a n n H ector Roessler (1779-1863) who directed the G r a n d D ucal M int in D a rm sta d t to which the free Im perial City of Frankfurt had been constrained to place their orders for coinage as their own m int h a d become obsolete. T h e younger Roessler had studied the natural sciences and engineering in M unich and had benefited from the experiences of his brother-in-law Franz Xavier H andl, the chief refiner of the Royal Bavarian M int. H e ha d also worked in the D a rm stadt m int and had spent some time at those in Vienna and Paris. He was therefore well qualified for his new appointm ent, a n d only two years later the City Council decided to lease to him the plant a n d buildings of their gold and silver refinery, these to be operated for his personal account while he continued to be responsible to them for the m inting of coin. T h e m inutes record ing this unusual division of responsibility describe Roessler as a m an whose reputation and credit leave nothing to be desired , going on to describe the refining business as
such activities are always operated with more enthusiasm for the account of private persons rather than by nationalised undertakings. T h e refining business soon increased to such a n extent th at Roessler h a d to find a new site in order to expand and he erected a chemical plant on a plot of land he h a d bought for this purpose - a plot still identifiable in the heart of the com panys present headquarters in Frankfurt. T h e new refinery handled increasing quantities of demonetised coin as well as crude silver containing gold from the lead mines on the Rhine. Recovery of the small am o u n t of p latinum contained in the gold and silver coins began during the 1850s a n d some years later several kilograms were recovered from the slag produced in smelting the gold with nitre although some of the platin u m metals were lost w hen the gold
325
F rie d ric h E rnst R oessler

1813-1883
M a s t e r o f t h e m i n t t h e n o p e r a t e d by th e F r e e C ity o f F r a n k f u r t , R o e ssle r w a s i n v i t e d bv t h e C ity C o u n c i l in 18 43 to t a k e o v e r f o r his o w n a c c o u n t the a s s o c i a t e d r e f i n e r y w h i l e c o n t i n u i n g to r e m a i n r e s p o n s i b l e f o r t h e co in ag e. T h e refinery p ro sp e re d a n d l ater becam e the n u cleus from w h ic h d eveloped the D eutsche G old-und Silber Scheideanstalt, founded in 1 87 3 a n d now k n o w n as DEOt SSA
was dissolved in aqua regia a n d reprecipitated with ferrous sulphate. In ad d i tion, platinum was being recovered from discarded laboratory apparatus. T h e successful cam paign of 1866 designed by Bismarck to bring about the unification of G erm any under the H ohenzollern dynasty b rought about a change in Roesslers affairs. F ra n k fu rt lost its status as a free city, the mint passed under the control of the P russian authorities, a n d for a time it seemed th at the refinery would cease to operate, but in view of its im portance to the economic well-being of F rankfurt it was finally reprieved but its control ha d to be separated from that of the m int. Roessler accordingly p urchased the refinery a n d immediately transferred it to his two elder sons, retaining his post in charge of the mint until his retirement a t the age of sixty in 1873. Six years later the mint was finally closed down. T h e refinery was now re-established under the nam e of Friedrich Roessler Sohne, the two sons being J o h a n n H ector Roessler (1842 1915) and H einrich (1845-1924). Hector, a g raduate of the M ining A cadem y of Freiberg, ha d been m anaging a small chemical w orks since 1863, while H einrich had also spent some time at Freiberg and h a d then studied chemistry u n d e r W ohler at Gottingen, obtaining his d o c to ra te in 1866 with a dissertation on the double cyanides of platinum and palladium . A n u m b er of technical improvements were m ade, the volume of business increased, a n d by 1873 it was decided to form the business into a limited company, to be known as the D eutsche G old-und SilberScheideanstalt vormals Roessler.
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An advance in the recovery of the platin u m metals stem m ed from a sugges tion put forward by Professor M ax Pettenkofer (1818-1901) of the University of M unich who had earlier served in the m int there a n d who ha d become a friend of Friedrich Roessler. By substituting ferrous chloride for ferrous sulphate the platinum metals were separated more readily and in greater am o u n t from the gold refining operations. An account of the whole complex process was given by Ludwig Opificius (1849-1910) w ho had started as a boy u n d e r Friedrich Roessler in 1865, becoming refinery m anager ten years later (23). By the end of the 1880s some twenty kilograms of p latin u m and approxim ately one kilogram of palladium were being obtained each year. T h e adoption of the Wohlwill electrolytic process for gold refining in 1896 m arked another step forward in the recovery of the platin u m metals. T hese collected in the anode slimes, which were then enriched and the individual metals separated and refined to a state of high purity. M eanw hile atte n tio n had been given to the fabrication of p latinum an d its growing uses in industry a n d in research. O n e outlet in which H einrich Roessler took an interest was the p re paration of solutions containing the p latinum metals for use in the decoration of pottery and glass alongside the older gold preparations, an d in 1885 he described his formulations in a p a p e r to the ceramics jo u rn a l Sprechsaal (24). In 1901 the two brothers H einrich and H ector w ithdrew from the b o a rd of management, although the former rem ained on the supervisory b o a rd until his death in 1924, but the Roessler family continued to be represented for m any years by a son and a nephew.
H e in ric h R o e ssle r 18 4 5 - 1 9 2 4 T h e second son of F rie d ric h , H e in rich R o e s s l e r first s t u d i e d m e t a l l u r g y a t t h e F re ib e rg M ining A cad e m y a n d then c h e m i s t r y u n d e r W o h l e r at G o t t i n g e n . Vi ith his e l d e r b r o t h e r H e c t o r h e to ok o v e r t h e r e f i n e r y in 1 8 6 7 . b o t h r e m a i n in g a c t i v e as d i r e c t o r s o f t h e l i m i t e d c o m p a n y f o r m e d in 1 8 7 3 u n t i l 1901
327
In 1928 it seemed to the th en directors that the rather long an d complicated nam e under which they operated could well be simplified, an d it was then that the present nam e of DEGUSSA w a s coined. T h e further progress of this inter national enterprise formed the subject of several publications on the occasion of their centenary in 1973 (25).
T h e S iebert P la tin u m R efin ery A nother establishment that s ta rte d as a service to the H a n a u jewellery industry b e g a n to undertake p latinum refining in 1881. This developm ent was initiated by Wilhelm Siebert (1862-1927), the son of a cigar-box m anufacturer, Georg Siebert (1835-1909) who had b e g u n to treat the local g o ldsm iths scrap in 1864. W ilhelm ha d become familiar w ith the m ethods of assaying during a period spent with a com pany in Pforzheim, Dr. R ichter an d Co., a n d on his return hom e he began to experiment in th e processing of platinum , first from the gold s m iths residues and then from a share of the R ussian coinage and other m aterial that ha d been acquired b y J o h n s o n M atthey. T h e new refinery was successful, a n d prospered further after 1884 when W ilhelm Siebert visited Russia a n d secured the promise of deliveries of platinum concentrates from the Urals on a long term basis. H e recorded later t h a t : We set about the refining of native platinum and the production of platinum in the highest possible purity and in maximum quantity. This gave us a great deal of work and anxiety with many set backs to be overcome (26). In 1889 W ilhelm s younger b ro th e r J e a n Siebert (1870-1925) joined the business an d succeeded in expa n d in g the m arket for platin u m products, includ ing of course lead-in wires for electric lamps, contacts for the telegraph an d tele phone industry an d ignition tu b es both at hom e an d abroad. T h e fabrication of sulphuric acid boilers was also u n d e rta k e n and a paper describing an improved design of a cascade ap p a ra tu s w as published in 1893 (27). Contacts between the Siebert com pany an d the D eutsche G o ld-und SilberScheideanstalt had been close since the beginning of the form ers operations, a n d in 1906 the latter becam e a shareholder. This enabled the Sieberts to expand, while it provided the Roesslers with greater access to the m arket for fabricated platinum . In 1921 this share was increased to 50 per cent and the firm was incorporated as a limited com pany, G. Siebert G .m .b.H ., H a n a u , which was wholly acquired by DEGUSSA in 1930. A year later, to com m em orate their fiftieth anniversary, the com pany published a valuable Festschrift containing m any scientific contributions b o th from their own staff arid from distinguished academics such as O stw ald an d T a m m a n (26). T h e H a n a u plant becam e the h e a d q u arte rs of D eg u ssa s metallurgical work, with a n extensive range of pro d u cts fabricated from p la tin u m a n d its allied metals. T hen in 1975 an entirely new refinery was built at Wolfgang near H a n a u a nd the pyrometallurgical an d chem ical work was transferred there, together
328
^ ilh elm S ie b e rt 1862-1927 P r a c t i s i n g first as a n a s s a y e r in P f o r z h e i m . S i e b e r t b e g a n to w o r k in p l a t i n u m in 1881 a n d a f t e r a visit to R u s s i a in 1884 to s e c u r e s u p p l i e s of native metal from t h e I r a ls he developed the refining a n d fa b ric a tin g a c tiv itie s most s u c c e s s fu l l y . T h e firm of (. S i e b e r t was l a t e r a b s o r b e d by l)Ef; I ss \
with a m odern research departm ent, providing the largest facility of its kind in continental Europe.
D e v e lo p m e n ts in the L o w C o u n tries For many years the other E uropean countries were supplied with their needs of platinum by the established sources already described, b u t later on two other enterprises entered the industry in H olland a n d Belgium respectively, both stemming originally from gold a n d silver refining. In 1827 H a n s Halbes Drijfhout set up a small gold refinery in the village of Balk in Friesland, to be followed by his son W illem who moved to A m sterdam in 1886, the business then becoming H. Drijfhout and Zoon an d including rolling and wire drawing facilities. Later he began to u ndertake th e refining and working of platinum on a relatively small scale, but in 1927 the com pany was absorbed by the C om ptoir Lyon-A lem and of Paris and continues as their sub sidiary in Am sterdam .
329
Brussels was also a centre of the jewellery industry in the nineteenth century, a n d in 1864 Antoine Pauwels foresaw the need for a service of recovery of their scrap gold, silver and p latinum a n d established such a business in 1864, supply ing the jewellers with refined metals. Antoine died in 1906 and his sons Ferdinand and Franois succeeded him, developing and expanding the business, now known as Pauwels Freres, a n d including the m anufacture of platinum and its alloys and com pounds in all the forms required by industry. In 1961 the company becam e p a rt of the J o h n s o n M a tth e y organisation.
A n In tern atio n al R esearch In stitu te

In 1921 a joint initiative by th re e interested groups, the city of Schwbisch G m nd, the state of W rtte m b e rg and the industrial com panies engaged in the refining and fabrication of the noble metals in G erm any, led to the foundation of a research organisation uniquely associated with these metals a n d the only one of its kind in the world, the F orschungsinstitut fr Edelmetalle. T h e city of Schwbisch G m n d , some 50 kilometres east of Stuttgart, was chosen as the hom e of the In stitu te prim arily because it was one of the three G e rm a n locations of the noble m etals industry, the others being H a n a u and Pforzheim, and secondly because there already existed in the town a training school for craftsmen, the Staatliche H here Fachschule fr die Edelmetallindustrie, which could house the newly formed institute and in which m em bers of its staff could take p a r t in teaching. T h e first three directors of t h e Institute in its early years were Dr. R udolf Vogel from the University of G ttingen, th en Dr. H a n s M oser, the director of the State M int at Stuttgart, and later D r. J. A. A. Leroux. In 1928 a young m etallurgist who ha d ju s t obtained his Ph.D at the University of M nster joined the Institu te as a research associate; six years later he was appointed its Director a n d his association with the Institute continues to this day. This was of course Dr. Ernst R aub, who has a n exceptionally wide international reputation in his field. U nder Dr. R a u b s direction the great contributions to the physical metallurgy of platinum and the o th e r noble metals began, an d the first of a long series of investigations of the e q u ilib riu m diagram s of platin u m alloys was published in 1935. Since that tim e a great m any papers have emerged from the Institute both on alloy systems a n d on the electrodeposition of the platinum metals. T he Institute continues to carry out both basic research supported by government departm ents an d specialised contract research funded by national an d international companies, su c h as investigations on the development of new electrical contact materials a n d th e ir performance in service. Collaboration with industry has been most successful, and there are m any products now com mercially successful in which the Institute has played a decisive role in their development. Its unique cha ra c te r has also led to the establishm ent of valuable connections with both industry a n d the universities throughout the world.
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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27
J. F. L. Mrime, Bull. Soc. Enc. Ind. Nat., 1817, 16, 33-36 W. H. Wollaston, MSS 7736, Cambridge University Library Cuoq Couturier et Cie., J . Tech. Chem., 1833, 16, 376-377 Reports of the Juries, Exhibition of 1851, London, 1852, 296 A. Quennessen, French patent 5530 of 1851 Exposition des Produits de lindustrie de toute les Nations 1855, Catalogue Officiel, French Empire, Class 16, IIL item 4934 W. W. Smyth, Reports of the Juries, International Exhibition, London 1862, Class II, Section A, 34 A. Joly, Comptes rendus, 1888, 106, 328-333; 1888, 107, 994-997; 1890, 111, 969-972 E. Leidi, Ann. Chim., 1889, 17, 257 313 A. Joly and E. Leidi, Comptes rendus, 1891, 112, 793 796; 1259-1261; 1893, 116, 146-148; 1894, 118.468-471; 1885, 120, 1341-1343; 1898, 127, 103-106 E. Leidi, Comptes rendus, 1899, 129, 214-215; 1899, 129, 1249-1251; Bull.Soc. Chim., 1900, 23, 898-899 E. Leidi and L. Quennessen, Bull. Soc. C.him., 1901, 25, 840 842; 1902, 27. 179 183; 1903, 2 9, 801-807 L. Quennessen, Bull. Soc. Chim., 1905, 33, 191 193; 875 879; 1308 1310; 1906, 35, 619-621 L. Quennessen, L Industrie Chimique, 1917, 4, 752-754; 774-775; 5, 6-7 Ann. Phys. ( Poggendorff), 1857, 101, 644 J. Philipp, Poly J . ( Dingier), 1876, 2 2 0 , 95-96 H. Sainte-Claire Deville and H. Debray, Comptes rendus, 1862, 54, 1139-1141 O. Heraeus and F. Kch, Hundert Jahre Heraeus, Hanau, 1951 Instrument Kunde, 1891, 11,262 264 W. C. Heraeus, W. C. Heraeus, angewand. Chem., 1892, 300 301 H. Danneel, Elektrochem, 1902, 8, 822-824; E. Haagn, ibid, 509-512; R. C. Mackenzie, Anal. FVoc. Chem. Soc., 1980, 17, 79 81 R. C. Mackenzie, Platinum Metals Rev., 1982, 26, in the press L. Opificius, Poly. J . (Dingier), 1877, 2 24, 414-417 H. Roessler, Sprechsaal, 1885, 385; P oly.J . ( Dingier), 1885, 258, 275 Aller Anfang ist Schwer, Bilder zur Hundertjahringen Geschichte der Degussa, Frankfurt, 1973; Edelmetall und Chemie, Frankfurt, 1973 H. Houben, Festschrift zum Fnfzigjhrigen Bestehen der Platinschmelze G. Siebert, Hanau, 1931 G. Siebert, angewand. Chem., 1893, 346 347
331
D m itri I v a n o v i c h M e n d ele ev 1 8 3 4 -1 9 0 7
B o r n in T o b o l s k in S i b e r i a . M e n d e l e e v c a m e lo St. P e t e r s b u r g in 1 8 5 0 to s t u d y a t t h e t e a c h e r t r a i n i n g i n s t i t u t e o f t h e U n i v e r s i t y . In 1 8 5 9 h e t r a v e l l e d to P a r i s to w o r k w i t h R e g n a u l t a n d t h e n to H e i d e l b e r g u n d e r k i r c h h o f f a n d he a t t e n d e d t h e K a r l s r u h e C o n f e r e n c e in 1 86 0. I n 1 86 6 he w a s a p p o i n t e d P r o f e s s o r o f C h e m i s t r y a t St. P e t e r s b u r g a n d t h e n in 18 6 9 d e s c r i b e d his first P e r i o d i c T a b l e to t h e n e w ly f o r m e d R u s s i a n C h e m i c a l Society
F r o m a p o r tr a it b \ I. A. R e p in
18
The Platinum Metals in the Periodic System

The six know n platiniferous m etals , f r o m a certain point o f view , m a y be rightly con sidered as fo rm in g a separate and w ell-defin ed group .
K \ K I . k \ K I . < ) \ 1( 11 M . M S . I 8 6 0
The gradual increase in the num ber of elements being discovered a n d isolated during the early p a rt of the nineteenth century led to a n u m b er of attem pts at their classification. As early as 1816 the great physicist A ndr M arie Ampre (1775 1836), Professor of M athem atics an d M echanics at the cole Polytechni que but at this stage of his career very interested in chemistry an d in the whole concept of classification, put forward a scheme of ordering the elements that would bring out the most num erous and essential analogies and be to chemistry what the natural m ethods are to botany and zoology (1). All the ele ments then known were classified into five groups, one of these being called the Chrysides , derived from the Greek word for gold, and including palladium , platinum, gold, iridium and rhodium . O sm ium , however, he grouped with titanium. Some of the similarities between the p latinum metals were thus recog nised at this early date, but A m p re s m ethod contained no num erical concept.
D o b e r e in e r s T riads T h a t such a quantitative component was necessary was first recognised by J. W. Dbereiner who noticed in 1817 that the molecular weights for calcium oxide, strontium oxide and barium oxide formed a regular series or triad with th a t of strontium being the arithm etic m ean of the other two. Twelve years later he published his paper on the Classification of the Elements in Poggendorffs Annalen der Physik und Chemie, curiously immediately following a n abridged translation of W ollastons p a p e r on the production of m alleable platin u m given to the Royal Society in 1828 (2). Expressing first his great interest in the atomic weights of Berzelius, Dbereiner again showed that w hen the elements were arranged in groups of three resembling each other chemically the atomic weight
333
of the middle one was the m ea n of the other two. After discussing the halogens, the alkaline earths and the g ro u p of sulphur, selenium a n d tellurium am ong others, he tu rn e d to the sim ilarities between iron, nickel a n d cobalt and then to the p latinum metals: The interesting series of analogous metals that occur in native Platina, namely Platinum, Palladium, Rhodium, Iridium, Osmium and Pluran, fall according to their specific and atomic weights into two groups. To the first belong Platinum, Iridium and Osmium, to the other Palladium, Rhodium and Pluran, which last corresponds with osmium, as rhodium does with iridium and palladium with platinum . His Pluran, to which he referred in a footnote ( T h e existence of Pluran is however somewhat doubtful ) w a s one of the supposed elements discovered by O s a n n in 1827 in native p la tin u m from the Urals an d given th at n am e from the two initial letters of Platinum a n d Urals. O nly in 1844 was the true sixth m em ber of the group, ru th e n iu m , discovered by Klaus, as recorded earlier in C h a p te r 12. Very little was heard of D o b e re in e rs triads. Not until 1853 in fact did any serious notice a ppear to have b e e n taken of them, but in th at year J o h n Hall Gladstone (1827-1902), a former student of T h o m a s G r a h a m and Liebig, then a lecturer in chemistry at St. T h o m a s H ospital in L ondon an d later Fullerian Professor of Chemistry at the R o y a l Institution, published a p a p e r in The Philoso ph ical M agazine, O n the R elations between the Atomic W eights of Analogous Elements. In the course of this he c o m m e n te d : Who has failed to remark that the platinum group has double the atomic weights of the palladium group (3). Four years later Ernst Lenssen, one of the young assistants in Professor Fresenius analytical laboratory in W iesbaden, also speculated on the triads, grouping the elements by their chem ical a n d physical characteristics and even by the colour of their oxides (4) included one consisting of palladium , ruthenium an d rhodium (in that order) a n d another com prising osmium , platin u m and iridium, again incorrectly a rr a n g e d by their then atom ic weights, or rather the equivalents, that he employed.
T h e S ch em es o f O d lin g an d N e w l a n d s A more comprehensive scheme for the classification of the elements was also published in 1857 by William O d lin g , at that time Professor of Chem istry at G u y s Hospital in London. In this he arranged forty-nine elements into thirteen groups of which the last contained the p latinum m etals a n d gold. H e wrote: The propriety of associating gold with the platinum group is very questionable. Palladium appears to present a relation of parity with rhodium and ruthenium, platinum with iridium and possibly with osmium, though indeed many osmic reac tions are altogether special (5).
D uring their work on the p la tin u m metals described in C h a p te r 15, Deville
334
W illiam O dling 1829-1921

T h e so n o f a L o n d o n d o c t o r . O d l i n g entered G u v 's H o sp ita l to st u d y m edicine a n d ch em istry , becom ing a d e m o n s t r a t o r in t h e l a t t e r s u b j e c t in 1850. A f t e r a p e r i o d o f st u d y u n d e r G e r h a r d t in P a r i s h e w a s a p p o i n t e d a lecturer and then Professor of P r a c t i c a l C h e m i s t r y in 1856. T h e first o f his s e v e ra l p a p e r s o n t h e c la s sif ic a tion o f t h e e l e m e n t s a p p e a r e d a y e a r l ater. In 1859 h e w as e l e c t e d a Fellow o f th e R o y a l S o ciety a n d in t h e f o l lo w ing y e a r h e a t t e n d e d t h e K a r l s r u h e C o n g r e s s. In 1868 he succeeded F a r a d a y as F u l l e r i a n P r o f e s s o r of C h e m i s t r y at t h e R o y a l I n s t i t u t i o n , m oving to O xford as W aynflete P r o f e s s o r o f C h e m i s t r y in 1872. In t h a t y e a r h e m a r r i e d t h e d a u g h t e r of A l f r e d S m e e , t h e s u r g e o n to t h e B a n k of F n g lan d . whose w ork on the e l e c t r o p l a t i n g of t h e p l a t i n u m m e t a l s h a s b e e n d e s c r i b e d in C h a p t e r 1 1
and D ebray also emphasised the resemblances betw een these elements. I n 1859 they wrote: The family of the platinum metals has a particular character, completely apart from the more or less natural families formed by the other metals. It is true that they are not entirely analogous on every point, but they have their own character, a common appearance that separates them, while from the point of view of a rational classification one should separate them from the diverse families of elements (6). Odling returned to this subject later, revising an d extending his classification in 1861 and again in 1864, but in the interval Karl Klaus presented a p a p e r on the platinum metals to the Academy of Science in St. Petersburg in which he also recognised them as a distinct group of elements (7): These metals may be arranged in two superimposed series, the superior horizontal which I designate the principal series because the metals which constitute it predominate in the various platinum ores. This series is characterised equally by an elevated atomic weight and by almost the same specific gravity . . . The second horizontal series contains the remainder of the platiniferous metals, which also possess almost identical atomic and specific weights, but have in this respect but half the quantities of the principal series.
335
J o h n A le x a n d e r R e in a N e w la n d s
1837-1898 H o r n in L o n d o n of a S c o t t i s h f a t h e r and an Italia n m o th e r. N ew lands jo in ed G a r ib a ld i's rev o lu tio n a ry m o v e m e n t in I 8 6 0 , r e t u r n i n g in 18 63 to study u n d e r H o f m a n n at th e Royal C o lle g e o f C h e m i s t r y , l a t e r b e c o m i n g a t e a c h e r o f c h e m i s t r y a n d t h e n in 1868 c h i e f c h e m i s t to a s u g a r r e f i n e r y . His n u m e r o u s p a p e r s on t h e c la s sif ic a tio n o f t h e e l e m e n t s w e r e r e c e i v e d with s c e p t i c i s m , b u t h i s " L a w of O ctaves'* w a s a n i m p o r t a n t if d e f e c t i v e f o r e r u n n e r o f M e n d e l e e v *s P e r i o d i c S y s t e m
Klaus went on to show that th e metals vertically above one another in his table resembled each other, the pairs ru th e n iu m an d osmium, rhodium and iridium, and palladium and p la tin u m having identical reactions in the formation of their compounds.
K l a u s s H o r iz o n ta l S e rie s
Principal Series Secondary Series
Osmium Ruthenium
Iridium Rhodium
Platinum Palladium
It will be seen that Klaus h a d his metals in the correct order as established m uch later on. In his famous Lecture on P latinum , given to the Royal Institution in February 1861, Faraday clearly accepted these conclusions and quoted Klaus almost verbatim (8). O d lin g s revised and enlarged scheme of 1861 included fifty-seven elements arranged in seventeen groups, the last two being very similar to those of Klaus (9),
336
and then in 1863 the first of a long series of papers by J. A. R. N ew lands appeared in Chemical N ew s, followed by several more in the next three years (10). In his final table of the elements, arranged numerically in the order of their atomic weights, he pointed out that the numbers of analogous elements generally differ either by seven or by some mul tiple of seven; in other words members of the same group stand to each other in the same relation as the extremities of one or more octaves in music . . . This relationship I propose to provisionally term the Law of Octaves. Newlands was uncertain how to deal with the p latinum metals a n d he achieved his arithm etical symm etry only by assigning one n u m b er to each of the pairs rhodium a n d ruthenium in the earlier series a n d to p latinum and iridium in the later, while he placed osmium alongside tellurium in another group. He also predicted that another element should exist betw een iridium a n d rhodium and another between palladium and platinum . U nfortunately for N ew lands the Chemical Society declined to publish his paper, Odling, later the President, explaining that they m ade it a rule not to publish papers of a purely theoretical n a tu re . Newlands continued to interest himself in arranging the elements so as to emphasise the family relationships, assigning consecutive atomic or o r d in a l numbers to them and leaving blanks for elements as yet to be discovered, a n d in a small book he produced in 1884 he claimed with some justification to have been the first to publish a list of the elements in the order of their atom ic weights and to have described the periodic law (11). M eanwhile in 1864 Odling, probably unaw are of N e w la n d s later publica tion, contributed a p a per O n the Proportional N um bers of the E le m e n ts to the Quarterly Jou rn al o f Science in which he listed sixty-one elements in increasing order of atomic weight (12). In this he gave rhodium , ru thenium an d palladium in that order an d then platinum , iridium and osmium.
T h e K a r lsru h e C ongress T he accuracy of the atomic weights so far determ ined was in grave doubt and the subject of much controversy. Some values were only one half of their now established figures while some were twice as great. Friedrich W ohler had com plained that the confusion can be tolerated no longer . From this state of chaos order was restored by the well-known p a p e r from Stanislao Cannizzaro, (1826-1910), Professor of Chem istry at Genoa, given at the K arlsruhe Congress in 1860 (13). This famous gathering of more th a n 120 chemists, the first inter national scientific conference, was proposed by August Kekule a n d some of his colleagues to secure more precise definitions of the concepts of atom s and molecules a n d to bring uniformity into the values of atomic weights. William Odling, one of the very few who ha d already read C a n n iz z a ro s p a p e r was among the signatories calling this meeting and he was present for the discussion.
337
Earlier he had studied chem istry in Paris u n d e r G e rhardt, h a d translated L a u re n ts M ethode de C him ie into English in 1855, and supported their unitary theory, the atomic weight to b e taken as the smallest quantity of a n element present in the molecular weight of any of their compounds. But it was C a n nizzaro, whose paper, a rep rin t of a n earlier contribution given in 1858, was distributed by his colleague A ngelo Pavesi, Professor of Chem istry at Pavia, after the close of the meeting that settled the whole problem of atomic weights based upon the earlier proposals of G e r h a rd t a n d Laurent. H alf a century of confusion was cleared up and it was now possible to ascribe the correct atom ic weights to all the known elements.
L othar M e y e r and M e n d e l e e v Among those attending the K a rlsru h e Congress was Julius L othar Meyer, at that time Professor of C h e m istry at Breslau, a n d he recorded later how on reading C annizzaros p a per d u rin g his retu rn jo u rn e y the scales fell from my eyes, doubt vanished, an d was replaced by a feeling of peaceful c e rtain ty . W hen preparing a text-book M e y e r was thus able to take account of the numerical relationships betw een the elements and in his Die M odernen
J u li u s L o th a r M ey er 1 8 3 0 -1 8 9 5
A n a t i v e o f t h e s m a ll t o w n o f V a r e l n e a r O l d e n b u r g in n o r t h G e r m a n y , M e v e r w as f a r f r o m r o b u s t as a c h ild a n d w as giv en a n o u t - d o o r e d u c a t i o n u n d e r t h e h e a d g a r d e n e r to t h e D u k e o f O l d e n b u r g . H e b e g a n his h i g h e r e d u c a tio n a t Z r i c h a n d t h e n t r a n s f e r r e d to W r z b u r g . A f t e r g r a d u a t i o n he w e n t to H e i d e l b e r g to s t u d y u n d e r B u n s e n a n d K i r c h h o f f a n d in 18 64 p u b l i s h e d his b o o k on t h e m o d e r n t h e o r i e s of c h e m i s t r y , this c o n t a i n i n g a t a b l e of m o st o f t h e e l e m e n t s a r r a n g e d in o r d e r o f t h e i r a t o m i c w eigh ts . H e b e c a m e P rofessor of C hem istry in the T e c h n i s c h e H o c h s c h u l e at K a r l s r u h e in 1869 a n d in 1876 a c c e p t e d a s i m i l a r c h a i r in t h e I n i v e r sity o f T ii b i n g e n . In 1 88 2 h e a n d M e n d e l e e v w e r e join tly a w a r d e d t h e Davy M e d a l by t h e R o yal S o c i e t y f o r t h e i r d e v e l o p m e n t of t h e p e r i o d i c system
338
T heorien der Chemie, written in 1862 but not published until 1864, he included a table of most of them (14). Here he placed correctly the three lighter m em bers of the platinum group, ruthenium , rh o d iu m and palladium , b u t wrongly gave the heavier three in the order platinum , iridium an d osmium, an error th a t he was later to rectify. In the m eantime, however, the most clear and comprehensive tre a tm e n t of the elements and their classification was devised, as every chemist knows, by the outstanding genius D m itri Ivanovich Mendeleev, the great R ussian scientist whose nam e has ever since been firmly associated with the Periodic Table. Mendeleev had studied at St. Petersburg an d he ha d been m ore th a n fortunate in his teachers. T h e senior of these, Professor Nikolai Nikolaevich Zinin (1812-1880) had travelled widely in western Europe, spending a year with Liebig at Giessen an d returning to the University of K az a n where in 1841 he had been a close colleague of Klaus before being called to St. Petersburg in 1847. He accepted the new concepts of G erhardt and Laurent, the first to do so in Russia, a nd he attended the K arlsruhe Congress in 1860. M endeleevs other mentor, who became closely attached to his brilliant student and gave him private lessons during a period of illness, was Professor Aleksyei Andreivich Voskressenskii (1809-1880) who ha d also spent some time w ith Liebig a n d who was affectionately known to his students as the grandfather of Russian chem istry . He was also a disciple of G e rh a rd t and Laurent. Mendeleev, after graduating, visited Paris to study u n d e r Victor R egnault and then spent a period in Heidelberg where he opened a private laboratory. It was from there that he travelled to K arlsruhe and his appreciation of those discussions is shown in a letter he wrote to Voskressenskii th at was published in the St. Petersburg Gazette. This began: The chemical congress just ended in Karlsruhe produced such a remarkable effect on the history of our science that I consider it a duty, even in a few words, to describe all the sittings of the congress and the results that it reached. After giving a brief account of these discussions he c o n c lu d e d : Cannizzaro spoke heatedly, showing that all should use the same new atomic weights. There was no vote on the question, but the great majority took the side of Cannizzaro. Mendeleev had devoted long years to the accum ulation of evidence for his developing ideas on the classification of the elements, carrying out hun d red s of experiments, reading widely in the literature an d corresponding with chemists throughout Europe to collect appropriate data. All this information, on their physical an d chemical properties, on the nature of their com binations a n d o n the isomorphism of their compounds, was then inscribed on to small white cards which he arranged until he was satisfied with their sequence. Early in 1869 he distributed privately a pam phlet entitled A n Experim ental System of the Ele ments based on their Atomic W eights and Chem ical Analogies , and then in the
339
following M arch, at a meeting o f the R ussian Chem ical Society which he had done so m uch to organise in the previous year, a n d with Zinin presiding, a paper from Mendeleev was read by his friend a n d colleague Professor Nikolai M enschutkin because the author had been taken ill. This was published in the first volume of the Societys tra nsactions (15), an d was briefly referred to in the G e rm a n periodicals, giving their readers some indication of M endeleevs ideas. It was not, however, a complete periodic table as we know it b u t rath e r a p re liminary study in which he m erely a rranged the elements in six colum ns and, as he later emphasised, he was u n a w a re of the publications of M eyer and Newlands a n d only of O d lin g s first com m unication of 1857 an d Lenssens even earlier work. As with his predecessors, M endeleev had difficulties with the p latinum group of metals on account of their close similarity and the very small differences in their atomic weights as th en determ ined. In this first system he arranged them: R h 104.4 Pt 197.4 Ru 104.4 Ir 198 O s 199 Pd 106.6 In a second paper read to a meeting of R u ssian scientists in M oscow in August 1869, O n the Atomic V olum e of Simple Bodies , (16), he produced a clearer table, a prototype of his final version, in which he showed the eighth group in the same order as before but he now assum ed the presence of an empty period between the ru thenium a n d the osm ium groups. T h e n in 1870 L othar M eyer contributed a p a p e r to Liebigs Annalen, T h e N a tu re of the Chemical E lem ents as a F u n c tio n of their Atomic W e ig h ts , (17) in which he arranged the p la tin u m metals in their correct order but with some uncertainty: Ru 103.5 O s 198.6? R h 104.1 Ir 196.7 Pd 106.2 Pt 196.7 He commented: To obtain this arrangement, some few of the elements whose atomic weights have been found to be nearly equal, and which have probably not been very carefully determined, must be rearranged somewhat, Os before Ir and Pt, and these before Au. Whether this reversal of the series corresponds to the properly determined atomic weights must be shown by later researches . Partly arising from this p a p e r of M e y e r s, Mendeleev published a further account of his system a year later, and this was translated in full in the Annalen (18). R unning to almost a h u n d r e d pages in the G e rm a n version, this gave a m uch clearer and more com prehensive description of his periodic system - the first time he actually used the p h r a s e - a n d dealt at length not only with the properties of the elements but also with their com pounds. M ore courageous than
340
I> jn n a I. H =1 Tat>a*teeaie u e MCHru. L i= 7 N i= 2 3 K =39 (Ouz=63) R b=85 M 6-1 (**-=106) C*=133
rp jn n 11.
r |iju n a HI-
rpjnn
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r |i j o n t V.
Tpinn* VI.
r p jn n a VII.
r p ja n * V III. n rfja I,
1
B *= 9,4 =*4 C a=40 Z n= 6ft S r z 87 LU11 Ba137 B11 A l= 2 7 ,3 -= 4 4 - =_68 (?Y t= 8 8 ?) la =113 - =137 Zrrz90 Sn=118 C -I38? Ti=5>? -= 7 2 V=S1 A c = 75 N b -9 4 Sb=132 C=12 H = l. P=31 C r=32 Se=78 Mu6 T e * _ l 28? 0=1 8=31 F=19 C 1=36,4 M n=M Br=8<) -= lttl J 127
F e 5,
5* |
i f f i l l 5 j l i l l
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-
i 3
Co=69, N i= 5 , C u = 6 3
R n = 1 0 4 ,R u = 1 0 4 , P d = H 4 ,A f= l0 8
111
::: ill - 9 -"

hi
-
(A n = J 9 7 j
-
T=182
r
W - 184 L =240 r -
0 = lt* 9 ? ,Ir= 1 9 8 ? , 1*1=197, Aii = 1 9 7
H|T=*Jf. -
T l= 2 0 4
P b = * l7 T h r r 132
Bi=2U8
HW>
c o jh h m
B ucuiai
OBIICb.
K *0
RO* a j m KO
R*0* (RH*?)
RH) a j a HO* RH
O '
i
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Bucioee ao*opoxnoe coejaaeine.
RH*
RH*
T h e r e v i s e d a n d c o m p r e h e n s i v e P e r i o d i c T a b l e p u b l i s h e d by M e n d e l e e v in t h e J o u r n a l of t h e R u s s i a n C h e m i c a l S o ciety in 1871. T h e p l a t i n u m m e t a l s w e r e n o w p l a c e d in t h e i r c o r r e c t o r d e r in G r o u p V I I I , a l t h o u g h this a ls o i n c l u d e d c o p p e r , s i l v e r a n d gold. A s p a c e was left fo r a s yet u n d i s c o v e r e d m e m b e r s o f t h e p l a t i n u m g r o u p b e t w e e n t h e l i g h t e r a n d t h e h e a v i e r t r i a d s a n d t h e a t o m i c w e i g h t s w e r e g iv e n o nly in r o u n d fig u res b e c a u s e of M e n d e l e e v 's u n c e r t a i n t y a b o u t t h e i r a c c u r a c y
Lothar Meyer, he ascribed different atom ic weights to a n u m b e r of elements, based solely upon their chemical analogies, calling for new determ inations to be made. In the case of the three heavier platinum metals he wrote: Three elements stand in the system in succession between W = 184 and Hg = 200. Their atomic weights are actually smaller than W, but the succession does not correspond to expectations, for in considering that Os, Ru, Fe are similar, but that Ru and Fe have smaller atomic weights than Pd and Ni, it is to be expected that the atomic weight of Os is smaller than that of Pt, and that Ir, standing between Pt and Os, has a middle value of atomic weight. Moreover, the inaccuracy of the atomic weight determinations of the Pt metals is readily understood, not simply because their separation from one another is difficult but also because their compounds that have been used for atomic weight determinations are not of great stability. M endeleevs table of 1871 is reproduced here from the original R ussian version. It will be seen th at in addition to iron, cobalt an d nickel an d to the platinum metals he had included copper, silver and gold in G roup V III but had left alternative positions for them in G roup I, an d that, unaw are of most of the rare earth elements, he ha d again left gaps for an extra series betw een the two
341
K a r l F r i e d r i c h O tto S e u b e r t 185 1-1 921

T h e son of a P ro fes so r at the K a r ls r u h e T e c h n i s c h e H o c h s c h u l e , S e u b e r t first stu d ied p h a rm a c y th e re a n d then t u r n e d to c h e m i s t r y , s e r v i n g f o r s e v e r a l y e a r s as a s s i s t a n t to L o t h a r M e y e r a n d a c c o m p a n y i n g h i m to B r e s l a u a n d t h e n to T b i n g e n o v e r a p e r i o d o f t w e n t y y e a r s a n d s u c c e e d i n g h i m as P r o f e s s o r . H i s d o c t o r a l t h e s is w as on t h e a t o m i c w e i g h t o f i r i d i u m a n d he w e n t 011 to r e - d e t e r m i n e t h e a t o m i c w e i g h t s o f all t h e o t h e r p l a t i n u m m e t a l s , c o n f i r m i n g t h e o r d e r in w h i c h M endeleev had placed them
platinum metal triads. This h a d the inevitable result of pro m p tin g the re exam ination of native platinum for the a p parently missing elements and led to a n um ber of discoveries th at will be referred to a little later. Also, as is well known, he successfully predicted from a knowledge of their adjacent elements all the essential properties of as yet undiscovered elements, later to be identified as germ anium , scandium, gallium, r h e n iu m and technetium. In this table Mendeleev se p a ra te d th e elements into their m ain and sub groups, while he also confined his atomic weights to round num bers as he could not be sure of their accuracy. H is predictions about the correct order for the platinum metals were fully confirm ed a few years later by Karl Seubert (1851-1921), a student and later a colleague of L othar M e y e r s at Tiibingen. Seubert also distrusted some o f the old values a n d set about their re determination, arriving at the following arrangem ent a n d so confirming M endeleevs views (19): Ru 101.4 R h 102.7 Pd 106.35 Os 190.3 Ir 192.5 Pt 194.3
342
S om e S p u rio u s P la tin u m M etals Several supposedly new elements of the platin u m group were claim ed before the publication of M endeleevs Periodic Table, but the gaps he left, as already mentioned, led to further claims for the isolation of further m em bers of the group. In 1877 Sergius K ern of the Obouchoff Steel W orks in St. Petersburg wrote to Chemical N ew s that he h a d perceived the presence of a new metal of the platinum group which has been called by me davyum in honour of the great English chemist Sir H u m p h ry D a v y (20). This claim was investigated in 1898 by Professor J. W. Mallet, a n Irish chemist who ha d settled in Am erica to become Professor of Chem istry at the University of Virginia, an d who thought this m ight indeed be a m em ber of the missing triad of p latinum metals. W hile he was able to confirm K e r n s experimental observations, he quickly showed that the new m etal was merely a mixture of iridium and rhodium with a little iron, and hence that we have not yet reason to believe in the existence of a third group of platinum metals (21).
A further discovery was claimed by a French chemist, A ntony G u y a rd in 1879: Some years ago, about 1809, I discovered in some commercially fabricated platinum from Russian mineral a new member of the platinum group to which I give the name of Ouralium to commemorate its origin (22). T h e atomic weight was given as 187.25, its specific gravity as 20.25 a n d its ductility was said to be greater th a n that of platinum , but the experim ental work was of a very low order and ouralium was again almost certainly a m ixture of platinum with some iridium an d rhodium . T h e se two fallacious discoveries, together with several others, were reviewed in m ore detail by Dr. W. P. Griffith in 1968 (23).
T h e M o d e r n P e r io d ic T a b le Mendeleev continued for the rem ainder of his life to take a n active interest in his Periodic Law and used it as a base in his famous text-book, T h e Principles of Chemistry, first published in Russia in 1869 and in m any later editions, with an English translation in 1891 a n d G e rm a n an d French versions a few years later. His chapter on the platinum metals opens with a statem ent of the naturalness of the tra nsition from zirconium, niobium an d m olybdenum to silver, cadm ium and iridium through ruthenium , rhodium and palladium , and similarly from tantalum and tungsten through osmium, iridium a n d p latin u m to gold and mercury. This is followed by an account of the chemistry of the platinum metals that would have been creditable to an a u th o r m any years later, as for th at m atte r would the whole of the book. But it was not until the discovery of the electron by Sir J . J. T h o m s o n in 1879 and then M oseleys work on the X -ray spectra of the elements th at led to the concept of atomic n um ber ju s t before his death in 1915 in the E uropean W ar that a sound theoretical basis could be established for the periodic system.
343
The Platinum Metals and their Neighbours in the Periodic Table

Group VIA First long period Second long period T h ird long period C r 24 M o 42 G roup VIIA M n 25 T c 43 R e 75 G roup VIII F e 26 C o 27 N i 28 R u 44 R h 45 P d 46 G roup IB Cll 29 A g47 Au 79
w7 4
0S6 Ir 77 Pt7 7 8
T h e part of the m odern ta b le in which the platin u m metals occur is reproduced above with their a to m ic num bers, this including of course rhenium discovered in 1925 and p redicted by Mendeleev as dri-m anganese, and technetium, his eka-manganese, discovered only in 1937 in the b o m b a rd m e n t of m olybdenum by deuterons in a cyclotron. J u s t as Mendeleev emphasised, the greatest similarities are found in the vertical groups; there is a strong resemblance between ru thenium a n d osmium, betw een rhodium an d iridium, a n d between palladium and p latin u m . At the same tim e there are obvious analogies in the horizontal series, betw een for example palladium an d silver and betw een platinum and gold, w hile ru th e n iu m a n d osm ium m ore closely resemble technetium a n d rh enium , or in certain respects m olybdenum and tungsten, th a n they do iron. R h o d iu m an d iridium are m ore closely allied to cobalt than to any other m etal, while p latinum and p a lladium have close analogies with nickel. In the two p latinum metal tria d s the hardness a n d m echanical strength decrease from left to right a n d a r e greater in the second triad th a n in the first. R u th e n iu m and osmium, both close-packed hexagonal in crystal structure are brittle although they can be fabricated with difficulty at high tem peratures, while palladium and platinum faced-centred cubic metals, are soft and readily workable in the cold. A review of these similarities in properties and of the relevant chemical properties of t h e group was contributed some years ago by the w riters colleague A. R. Powell (24).
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R efe re n c es fo r C h a p t e r 18 1
2
3 4 5
6
7
8
9
10
11 12
13 14 15 16 17 18 19
20
21
22
23 24
A. M. Ampre, Ann. C h im , 1816, 1, 295-308; 2, 5-32 J. W. Dobereiner, Ann. Phys. ( Poggendorff), 1829, 15, 301-307 J. H. Gladstone, Phil. M ag., 1853, 5, 313 320 E. Lenssen, Ann. Chem. ( Liebig), 1857, 103, 121-131; 104. 177-184 W. Odling, Phil. M ag., 1857, 13, 422-^39; 480-497 H. Sainte-Claire Deville and H. Debray, Ann. Chim., 1859, 56, 385-389 C. Claus, J . prakt. Chem., 1860, 79, 28-59; 80, 282-317; Chem. News, 1861, 3, 194-195; 257-258 M. Faraday, A Lecture on Platinum, bound with The Chemical History of a Candle, London, 1861, 173-204; Chem. News, 1861, 3, 136-141 W. Odling, A Manual of Chemistry, Part 1, London, 1861, 3 J. A. R. Newlands, Chem. News, 1863, 7, 70-72; 1864, 10, 59-60; 94-95; 1865, 12. 83 J. A. R. Newlands, On the Discovery of the Periodic Law, London, 1884 W. Odling, Q_.J. Sci., 1864, 1, 642-648 S. Cannizzaro, Il Nuovo Cimento, 1858, 7, 321 366; English translation in Alembic Reprint 18; for an account of the Karlsruhe Congress see C. de Milt, J . Chem. Ed., 1951, 28, 421 425 J. L. Meyer, Die modernen Theorien der Chemie, Breslau, 1864 D. I. Mendeleev, ^ [hur. Russ. Khim. Obshch., 1869, 1, 60-77 D. I. Mendeleev, Proc. 2nd Meeting Scientists, 23 Aug, 1869, 62-71 J. L. Meyer, Ann. Chem. ( Liebig), 1870, Supp. VII, 354 364 D. I Mendeleev, %hur. Russ. Khim. Obshch., 1871, 3, 25 Ann. Chem. ( Liebig), 1871, 56; Supp. VIII, 133-229 K. Seubert, Ann. Chem. ( Liebtg), 1891, 26 1, 272-279 S. Kern, Chem. News, 1877, 36, 4; 114-115; 164 J . W. Mailet, Am . C hem .J., 1898, 20, 776 A. Guyard, M oniteur Scientifique, 1879, 9, 795-797 W. P. Griffith, Chemistry in Britain, 1968, 4, 430^134 A. R. Powell, Platinum M etals Rev., 1960, 4, 144-149
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1850-1936 Born in Paris. I,e Chatelier spent some tim e u n d er Sainte-Claire Deville at the Ecole Normale b ut his education was interrupted by the F ranco/Prussian W ar. I.ater he studied at the Ecole des Mines and becam e a mining engineer but in 1877 he retu rn ed there to teach chemistry, being appointed Professor ten years later. He was the first to employ a platinum against rhodium -platinum alloy therm ocouple, so initiating a reliable means of determ ining high tem peratu res
H e n r i L o u is L e C h a te lie r
19
Platinum in the Measurement of High Temperatures

Much attention has lately been dr awn to an alloy o f p ur e platinum with 10 p e r cent of rhodium which has become important from the excellent service it has rende red in the determination o f high temperatures."
K l ) \ * A R I M A T T I I K . I HM2
Very soon after the unique properties of p latinum its very high melting point and its resistance to attack - were recognised its possibilities for the m easure ment of high tem peratures were also grasped an d led to a n im p o rta n t use of the metal in m any branches of industry. At first reliance was placed u p o n its
PYB.OMETRE D E PLATINE.
citoyen G uyton a prsent , la sance de l'institut du 2 6 floral dernier , un instru ment excut pour mesurer les degrs de Ta plus haute chaleur de nos fourneaux. Il consiste en une verge ou lame de pla tine pose de cham p dans une rainure pra tique dans un tourteau dargile rfracta ire. Cette lame sappuie lune de ses extrm i ts sur le m assif qui termine la rainure ; lautre extrm it porte sur un levier cou d , dont la grande branche forme aigu ille, sur tin arc de cercle gradu. D e sorte que le deplacement de cette aiguille marque lallon gement que la lame de mtal prend par la chaleur. 347
Le
T h e o p e n i n g o f t h e p a p e r by G u y t o n d e M o r v e a u in t h e Annales do C him ie of 1803. T h i s d e s c r i b e d a p y r o m e t e r he had invented, based u p o n the e x p a n sio n o f a p l a t i n u m r o d . to m e a s u r e t e m p e r a t u r e s in f u r n a c e s a n d p o t t e r y k iln s
T h e b i-m e ta llic th e r m o m e te r devised in 1 8 1 7 by t h e P a r i s i a n w a t c h m a k e r A b r a h a m L o u is B r e g u e t a n d his son A n t o i n e wh o h a d b e c o m e his p a r t n e r in 1 807. T h i s c o m p r i s e d a s p i r a l e l e m e n t of platinum and silver soldered t o g e t h e r w ith go ld. T h e o r i g i n a l i n s t r u m e n t is p r e s e r v e d in t h e C o n s e r v a t o i r e d e s A rts et M e t i e r s in P a r i s
coefficient of expansion, as in t h e very early pyrom eter devised by G uyton de M orveau in 1803 and described o n page 182. This relied merely upon the e x p a n sion of a platinum rod that o p e ra ted a lever moving over a g rad u a ted scale, but the idea of using a bi-metallic device in which p latinum was bonded to a metal of m uch lower coefficient of e xpansion was also adopted at a n early stage. W. H. W ollaston apparently m ade use o f this principle in 1807, w hen his note-books contain a reference to Platina T h e r m o m e te r for M r. T e n n a n t , one of two that he h a d caused to be m ade by C h a rle s M alacrida, a L ondon instrum ent maker. T hese were constructed from p la tin u m bonded to copper by Charles Sylvester of Sheffield and formed the subject o f a paper by Dr. J. A. C haldecott (1). A few years later the famous Parisian w atchm aker A b ra h a m Louis Breguet (1747-1823), together with his so n Antoine, invented a bi-metallic therm om eter in which the helical element was com posed of strips of p latinum a n d silver (2), while in 1821 Professor J. F. Daniell of K in g s College, London, reverting to a single rod of platinum , introduced a pyrom eter in which the te m p e ra tu re was determ ined by the difference in e xpansion betw een it a n d an earthenw are tube (3). N one of these instrum ents was capable of m easuring really high tem peratures, nor were they of g re a t accuracy. A discovery was about to be made, however, that was to lead to one of the two reliable an d accurate m ethods of tem perature m easurem ent th at a re still in extensive use in both m an u fa ctu r ing industry an d scientific research.
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T h e D is c o v e r y o f T h e r m o e le c tr ic ity Shortly after the discovery by A m pre th at a current flowing in a wire lying parallel with a magnetic needle h a d the power to deflect it, T h o m a s J o h a n n Seebeck (1770 1831) found that w hen two different metals were joined in a closed circuit and the two junctions were kept at different tem peratures an electric current would flow. Seebeck was a native of Reval in Estonia but left there at an early age to study medicine in Berlin and then moved to J e n a where he was associated with Goethe, his p a tro n Karl August the D uke of W eim ar, Dbereiner and others of their circle. In 1818 he returned to Berlin, taking a post in the Academy there, and it was here that he began a long series of experiments on the magnetic character of the electric current. In August 1821 he announced his discovery of th erm o m a g n e tism as he called it to the Academy, describing the deflection of the magnetic needle arising from the difference in tem perature of the metallic junctions, the variation of the effect with different m etals an d the increasing effect w ith rising tem peratures (4). His discovery caused a great deal of interest among E u ropean scientists and his experiments were quickly repeated by many, including M ichael Faraday. It did not occur to Seebeck to make use of his findings for the m easurem ent of tem perature, although very curiously he did employ them to check the purity of native platinum , finding that long exposure to a high tem perature caused an alteration in the thermom agnetic action because of the oxidation of base metal impurities (5). T h e first suggestion to make use of Seebecks discovery as a m eans of measuring tem perature came from Antoine C esar Becquerel (1788-1878) in a paper read to the Acadmie Royal des Sciences in Paris on M a rc h 13th, 1826 (6). His investigations included observations of the needle deflection obtained with a num ber of combinations of metal wires w hen one ju n ctio n was heated in a spirit lamp, and he deduced that, for certain of these combinations, the intensity of current developed was proportional to the rise in tem perature. T h e most suit able combination, he decided, was a circuit consisting of p latin u m and palladium wires, an d with this com bination he obtained a straight line relationship betw een tem p eratu re and electromotive force up to 300C and by extrapolation he was able to determ ine tem peratures roughly up to 1350C. Becquerel further showed that the characteristics were independent of the diam eter of the wire, and also th at an im pure p latinum wire would give rise to a current if coupled with a pure platinum wire; he pointed out, in fact, the necessity for cleaning the p latinum in nitric acid to avoid spurious effects due to contamination. In 1836 Professor C. S. M. Pouillet (1790-1868), of Paris, also before the Acadmie Royal des Sciences, put forward his m agnetic p y ro m e te r and detailed its construction (7). This instrum ent, almost incredible by to d ay s standards, comprised a platinum wire sealed into the breech of a gun, the wire passing up the barrel but prevented from touching the sides by a filling of m ag nesia or asbestos. T h e breech of the gun was then to be inserted into the hot zone.
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In the course of his long a n d classic researches on heat H enri Regnault (1810-1878) m ade use of P ouillets iron-platinum couple, b u t he found such irregularities that he em phatically condem ned the whole idea of the th erm o electric m ethod (8). R e g n a u lts u n h a p p y experiences were due partly to his use of iron as one element, a n d a lso to his failure to employ a high-resistance galvanometer. Later, in 1862, E d m o n d Becquerel (1820-1891) took up the study of his fathers p latinum -palladium therm ocouple and used it as a n interm ediary with an air therm om eter in determ ining the melting points of a n u m b er of sub stances (9). As a result of his researches he succeeded to some extent in rehabilitating the reputation of t h e thermocouple, an d he derived an expression that was m uch too complex for the relationship betw een tem p e ra tu re and electromotive force. T h e problem of devising an a c c u ra te relationship betw een these factors was further studied by Professor P e te r Tait (1831 1901) of E d in b u rg h University (10). After a series of experiments with a n u m b e r of combinations in a n attem pt to construct thermoelectric d ia g r a m s he concluded th at the electromotive force was in general a parabolic function of the absolute tem perature. H e also reported that a very small a m o u n t of impurity, or even of p e rm a n en t strain, is capable of considerably altering th e line of a metal in the diagram . Professor T a it used platinum-iridium alloys containing respectively 5, 10 and 15 per cent of the latter metal- These were prepared for me from pure metals by Messrs. Johnson and Matthey. This was the first use of irid iu m -p la tin u m alloys coupled with pure platinum , but T a i t s research did n o t lead to any serious application of this type of thermocouple.
T h e W ork o f H e n r i Le C h a t e lie r It is to H enri Louis Le Chatelier t h a t we owe the successful practical use of the p latinum therm ocouple which for m a n y years was in fact known by his name. Among his m any activities Le C h a te lier was engaged in the study of silicates and cements and needed a reliable m e th o d of m easuring high tem peratures. In 1886 he reported to the Acadmie d e s Sciences a n investigation on the use of thermocouples for this purpose in which he ha d tried to verify the parabolic relationships found by Professor T a i t betw een the electromotive force an d the tem perature of the hot junction, t h e cold ju n c tio n being at 0C. Using various metals and alloys against platinum , which he calibrated at the known melting points of lead, zinc, aluminium, silver, gold, copper a n d palladium , he obtained results that agreed with his calculations to w ithin 20C (11). H e also cam e to the conclusion that of the various com binations he ha d used, p latin u m against 10 per cent rhodium -platinum gave th e most consistent results. M a n y years later, in the preface to a book published in 1912 in collaboration with G. K. Burgess he recalled this w ork:
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In 1885, when I attacked the problem of the measurement of high temperatures, it is fair to say there existed nothing definite available on this important question; we possessed only qualitative observations for temperatures above 500C. Engaged at that time in industrial studies relative to the manufacture of cement, I sought a method which above all would be rapid and simple, and decided on the use of thermo electric couples, intending to determine the order of magnitude of the sources of error noticed by Regnault. The readings of even a crude galvanometer might be very useful in technical work, provided the limitations of its accuracy were appreciated. I soon recognised that the errors attributed to this method could easily be eliminated by discarding in the construction of the couples certain metals, such as iron, nickel, and palladium, which give the rise to singular anomalies. Among the different metals and alloys studied, pure platinum and the alloy of platinum and rhodium which are still used today, gave the most satisfactory results. (12) Le Chatelier devoted considerable time and effort to the development of the thermocouple pyrometer, and arranged for the instrum ent to be m anufactured by Carpentier, the successor of the famous Ruhmkorff, at 20 R u e Delambre, Paris. T h e reputation of these instrum ents spread both rapidly an d widely and they were adopted in a n um ber of industries a n d laboratories. I n 1890, for example, the great Am erican m etallurgist Professor H enry M a rio n Howe, w ro te : Thanks to the labors of M. Le Chatelier, we have at last a pyrometer capable of measuring easily, accurately and rapidly extremely high temperatures, indeed, those approaching the melting point of platinum. And this is not an apparatus which each must construct for himself; it is for sale ready made. Indeed, it is so far simplified that it has actually entered into practical use for the control of high temperatures in steel works, glass works and gas works. (13) T h e development of the Le Chatelier therm ocouple analysis of steels practicable a n d this was immediately Floris O sm ond (1849 1912) of the Le Creusot works metallographic studies on carbon steels were carried laboratory. also m ade the therm al taken advantage of by (14). In fact his later out in Le C h a te liers
T h e C o n tr ib u tio n o f R o b e rts-A u sten Engineers were becoming increasingly concerned at the lack of u n d e rsta n d in g of the properties of steels and other m aterials and the Institution of M echanical Engineers therefore established its Alloys R esearch Com m ittee. T h e ir choice of an investigator was W. C. Roberts-A usten who com bined the posts of Chemist to the Royal M in t and Professor of M etallurgy at the Royal School of Mines. In his first report (15) in 1890 to the Institution, Professor (later Sir William) Roberts-Austen wrote: In the present investigation it is necessary to measure much higher temperatures; and fortunately an accurate method is at hand. Early in 1889 I had occasion to employ the pyrometer devised by M. H. Le Chatelier, and was satisfied as to its being extremely trustworthy and convenient up to temperatures over 1000C. or
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1800Fahr. The instrument in fact enabled me to confirm the fundamental observa tions of M. Osmond respecting the critical points of iron and steel, and to demons trate the results in a lecture delivered before the members of the British Association in September 1889. Since 1875 R oberts-Austen h a d interested himself in the problem s of liquida tion or segregation of the constituents of alloys, an d h a d been most painstaking in his m easurem ent of tem p e ra tu re s using the laborious calorimetric m ethods then available. H e therefore w elcom ed most readily the new type of instrum ent and proceeded to a d a p t it for th e production of autographic records of the cooling an d solidification of m o lten metals and alloys. His a p p a ra tu s is illustrated on the facing page.
P r o b le m s o f H o m o g e n e it y Some doubt still remained, however, concerning the absolute reliability of the rhodium -platinum alloy, and R o b e rts-A u sten referred to this: It is asserted that even long wires of the platinum-rhodium alloy are homogeneous, and therefore do not give rise to subsidiary currents which would disturb the effect of the main current produced by heating the junction; but very careful experiments to determine whether this is the case have yet to be made.
Sir W illiam C handler R oberts-A uslen 18 4 3 - 1902

B o r n W i l l i a m C h a n d l e r R o b e r t s , he a d d e d t h e n a m e of a n u n c l e A u s te n in 1 885. A f te r s t u d y i n g a t t h e R oy a l S ch o o l of M in e s he w as a p p o i n t e d c h e m i s t to th e R o y a l M i n t in 18 70 a n d l a t e r P r o f e s s o r of M e t a l lu r g y a t t h e R o y a l School of M in e s. T h e first i n v e s t i g a t o r to t h e A llo ys R e s e a r c h C o m m ittee of the Institution of M e ch an ical E ngine ers. R o b e rts -A u s te n w a s q u i c k to a p p r e c i a t e t h e u s e f u l n e s s of Le C h a te lie r's th erm o co u p le p y r o m e t e r in p h y s i c a l m e t a l l u r g y a n d a d a p t e d it to p r o d u c e a u t o g r a p h i c r e c o r d s o f t h e c o o l i n g a n d s o lid if ic a tio n o f m o l t e n m e t a l s a n d alloy s
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This uncertainty aroused the interest of Edward Matthey, who carried out a lengthy investigation on the liquidation of alloys of the platinum metals and reported his results in a paper to the Royal Society (16). On the rhodiumplatinum alloys he had the following comment to make:
Much attention has lately been drawn to an alloy of pure platinum, with 10 per cent of rhodium, which has becom e important from the excellent service it has rendered in the determination of high temperatures. The alloy of platinum with 10 per cent of rhodium is used with pure platinum as a thermocouple, and it is, therefore, interesting to be able to set at rest any doubt which might arise as to this alloy being uniform in com position when melted and drawn into wire.
Matthey prepared a melt of one and a half kilograms of 10 per cent rhodiumplatinum, which he cast into a sphere of two inches diameter. The sphere was then sectioned, and samples were taken for analysis from a number of lotations between the surface and the centre. The maximum difference between the centre
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an d the outside was found to be 0.06 per cent of platinum a n d 0.04 per cent of rhodium. H e concluded: This result proves that the alloy is not subject to liquation, and fully justifies the high opinion that H. Le Chatelier and Roberts-Austen have formed as to its suitability for thermometric measurements. At m uch the same time, 1892, E d w a rd M a tth e y was concerning himself with the extraction a n d refining of b ism u th an d he contributed a series of papers on this subject to the Royal Society. A n extract from one of these papers (17), dealing with the tem perature at w hich arsenic c a n be oxidised off from bism uth, reads at follows: The work of Roberts-Austen has shown that a thermo-junction is practically the only form of pyrometer that can be used for delicate thermal investigations of this kind, but the question arose which particular thermo-junction should be adopted. Was it well to use the platinum-iridium one as advocated by Barus, or the platinumrhodium one suggested by H. Le Chatelier? My previous work on the alloys of platinum and rhodium, lately published in the Philosophical Transactions, settled the question in favour of the rhodium-platinum thermo-junction, for I was satisfied that the alloy of platinum with 10 per cent of rhodium is as homogeneous as any known alloy could well be, and is therefore admirably adapted for use as a thermo-junction, pure platinum being the opposing metal. Clearly the platinum th erm ocouple could not be used to m easure tem peratures higher th a n the m elting point of the metal, and in the course of a lecture to the Royal Institution i n 1892 R oberts-A usten referred to this: Metals with higher fusion points than platinum are, however, available; thus iridium will only just melt in the flame produced by the combustion of pure and dry hydrogen and oxygen. By the kindness of Mr. Edward Matthey a thin rod of iridium has been prepared with much labour, and it can be used as a thermo-junction with a similar rod of iridium alloyed with 10 per cent of platinum. The junction may be readily welded in the electric arc, and by this means a temperature may be registered which careful laboratory experiments show to be close to 2000C (18). T h e further development of p la tin u m metal therm ocouples a n d of their useful ness in industry will be reviewed later in this ch a p te r as in the m eantim e an alternative m ethod of te m p e ra tu re m easurem ent was being developed although not for such an elevated range of tem peratures.
T h e First P la tin u m R esista n c e T h e r m o m e t e r

T h e first suggestion for making use of the effect of tem perature on the resistance of a metal for the determ ination of that tem perature was due to Carl W ilhelm Siemens. H e arrived penniless in E n g la n d in 1843, ju st before his tw entieth b irth day, and after studying physics, chem istry and m athem atics at Gottingen, and very soon established himself in the rapidly growing electric telegraph an d sub m arine cable industry (19). D u rin g the a u tu m n of 1860 the Siemens C om pany was charged by the British governm ent to superintend the m aking and laying of
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S ir W i l l i a m S i e m e n s
1823-1883 B o rn C arl V i l h e l m S iem ens n ear H a n o v e r , h e c a m e to E n g l a n d w h e n not y et t w e n t y a n d q u i c k l y m a d e a r e p u t a tion in t h e e arly d a y s o f t h e e le c t r i c a l i n d u s t r y . In 1 8 6 0 h e d e v i s e d t h e first resistance t h e r m o m e te r, using c o p p e r w i r e , to c h e c k t h e t e m p e r a t u r e o f coils o f s u b m a r i n e c a b l e s , a s t e p t h a t sa v e d a n e x p e n s i v e c a b l e f r o m d e s t r u c t i o n by spontaneous o v erheating. T en years later he intro d u ced a platinum resistan ce th e rm o m e te r for th e m e a s u r e m e n t o f h ig h t e m p e r a t u r e s . H e w as t h e first P r e s i d e n t of t h e S o c i e t y of T e le g ra p h E n g in e ers, later re -n a m e d the In stitution of E lectrical E ngine ers, a n d s h o r t l y b e f o r e his d e a t h was k n i g h t e d by Q u e e n V i c t o r i a
R e p r o d u c e d by c o u rte s y o f th e B B C l lu l to n P ic tu r e L ib ra ry
a cable between Rangoon and Singapore but the ship was delayed by storms and Siemens becam e concerned th at the spontaneous generation of heat in the coils of cable lying in the hold could lead to its deterioration. H e therefore devised a n instrum ent based on the fact th a t the resistivity of a copper wire increases in a simple ratio with increasing tem perature. In describing this new instrument in a letter to Professor J o h n T y ndall at the Royal Institution he concluded: By substituting an open coil of platinum for the insulated copper coil this instru ment would be found useful as a pyrometer (20). In 1862 Siemens, now naturalised as Charles W illiam Siemens, was elected a Fellow of the Royal Society, a m ark of the eminence he ha d achieved as a scientist, a n d although he continued to be actively engaged in the cable industry for the next few years he was eventually able to devote m u ch of his energy to research. In 1871 he was invited to give the Bakerian Lecture to the Royal Society and chose for his subject O n the Increase of Electrical Resistance in C onductors with Rise of T e m p e ra tu re and its A pplication to the M e asu re of O r d in a r y and Furnace T e m p e r a tu r e s . This was unfortunately published only in a b stract (21) but the m anuscript is preserved in the archives of the Royal Society. In his opening p a ra g ra p h Siemens em phasised th at researches on the effect
355
of tem perature on resistance h a d been limited to the range of tem peratures betw een the freezing and the boiling points of w ater an d that platinum , the most suitable metal for extending the range, ha d been left out of consideration. In carrying out his own investigations he h a d used platinum wire of 0.021 inch diameter prepared by Johnson and Matthey by the old welding process, which gives a much more conductive and therefore purer wire than the more recent process by fusion in a De Ville furnace. H e continued by referring to the great utility of his first resistance th erm o m eter in saving cables from destru c tio n and then described his new instru m ent in which the platinum wire was w ound in helical grooves on a cylinder of pipe clay contained in an iron tu b e for measuring with great accuracy the temperature at distant or inaccessible places including the interior of furnaces where metallurgical or other smelting operations are carried on. Siemens also gave a lecture, O n M easuring T e m p e r a tu r e by Electricity , to the Royal Institution in M a r c h 1872, in which he described his instrum ent as the result of occasional experimental research, spread over several years, and it aims at the accomplishment of a double purpose, that of measuring high temperatures, and of measuring with accuracy the temperatures of inaccessible or distant places (22) while earlier he had presented a p a per to the Iron a n d Steel Institute at its m eeting in M e rth y r Tydfil in S e p tem b e r 1870, in which he proposed the use of the new pyrometer for m easuring the tem p e ra tu re in annealing ovens a n d of the hot blast supplied to blast furnaces and em phasised th a t he was not seeking for any commercial reward, through the Patent Office or otherw ise (23).
The fi r s t re sista n c e t h e r m o m e t e r s , i n v e n t e d bv S ir W i l l i a m S i e m e n s in 1 8 7 1 . c onsisted of a coil of p l a t i n u m w ir e w o u n d o n a n i n s u l a t i n g fire clay c o r e a n d c o n t a i n e d in a n ir o n t u b e . T h e r e m a i n i n g p o r t i o n of th is i n s t r u m e n t , w h i c h w a s in u se in t h e R o y a l A r s e n a l a t W oolw ich in 1 8 90 . w as e x a m i n e d by C a l l e n d a r w h o f o u n d t h a t t h e p l a t i n u m w ir e had suffered a m arked c h a n g e in r e s i s t i \ i t y . m a in ly due to c o n t a m i n a t i o n by silica in t h e r e f r a c t o r y body
P h o to g ra p h by c o u rte s y o f th e S c ie n c e M u seu m
356
H u g h L o n g b o u r n e C a lle n d a r
1 8 6 3 -1 9 3 0
T a k i n g a first clas s d e g r e e in classics and m athem atics and w ith no know ledge of physics, C a lle n d a r e n t e r e d t h e C a v e n d i s h L a b o r a t o r y in 1885. W i t h i n o n ly e i g h t m o n t h s h e had developed a p la tin u m resistance t h e r m o m e t e r t h a t p r o v e d to be a c c u r a t e a n d r e l i a b l e . A t his s u g g e s t i o n t h e first t e m p e r a t u r e s c ale w as e s t a b l i s h e d w ith the p la tin u m re sistan ce t h e r m o m e te r u se d to d e f i n e a m a j o r p o r t i o n o f t h e r a n g e . In l a t e r y e a r s he w as p r o f e s s o r of ph y sic s at I n i v e r s i t y C o lle g e , L o n d o n , a n d t h e n at t h e R o y a l C o lle g e o f S cien ce
Siemens lecture to the Royal Society naturally a ttracted the attention of the Council of the British Association, who prom ptly recom m ended at their meeting in E dinburgh in 1871 that a comm ittee be formed, with power to ad d to its number, for the purpose of testing the new pyrom eter of Mr. Siem ens . Unfortunately the committee, whose work was carried out by Professor George Carey Foster (1835-1919) in the Physics D e p a rtm en t at University College, London, produced a most unfavourable report on the reliability of the instru ment (24), although one mem ber, Professor A. W. W illiam son - the only chemist on the com m ittee - considered th at the observed deterioration of the platinum wire could have resulted from contam ination by the reduction of silica from the fine-clay cylinder on which the coil was wound, a com m ent th at was only too correct.
C a lle n d a r s R e h a b ilita tio n o f th e R esistance T h e r m o m e t e r Siemens resistance therm om eter thus rem ained in disfavour for a n um ber of years, sadly until after his death in 1883. Its rehabilitation was due to the foresight an d the experimental skill of two rem arkable m en in the University of Cambridge. In 1884 J. J. T hom son was appointed, at the age of only 27, Professor of Physics and Director of the Cavendish L aboratory in succession to Lord Rayleigh, holding these posts, as is well known, with great distinction until
357
his retirement in 1919. In the autum n of 1885 he received into his laboratory a new research student, H. L. Callendar, who had taken his degree in classics and mathematics, had never carried out any practical work in physics and had read scientific works only as a hobby. After a few weeks in the laboratory Thomson realised that Callendar had considerable gifts as a skilful experimenter and set about finding him a suitable research project that would give full play to his strong points and yet minimise his lack of experience. He decided that the most suitable work would be the accurate measurement of the resistance of platinum, its variation with temperature, and thus its use for the measurement of temperature. Many years later he wrote:
Siemens had actually constructed a thermometer on this principle, but this was found to have grave defects w hich m ade accurate determ inations of temperature impossible. The simplicity and convenience of using a piece of wire as a thermometer was so great that it seemed to m e very desirable to make experiments to see if the failure of Siem ens instruments w as inherent to the use of platinum as a measure of temperature, and not to a defect in the design of the instrument. Callendar took up this problem with great enthusiasm and showed that, if precuations are taken to keep the wire free from strain and contam ination from vapours, it makes a thoroughly reliable and very convenient thermometer. This discovery, which put thermometry on an entirely new basis, increasing not only its accuracy at ordinary temperatures, but also extending this accuracy to tem peratures far higher and far lower than those at which hitherto any measurements at all had been possible, was made with less than eight m onths work (25).
By taking care to avoid strain or contamination of the platinum wire Callendar established that its resistance was always the same at a given temperature at least this was the case with the specimens used in these experiments, obtained from the well-known firm of Johnson Matthey & Co. His work was carried out in most difficult conditions, on a window-sill in a passage between two rooms in the Cavendish Laboratory, but by sealing his platinum coil, wound on a piece of mica, inside the glass bulb of the air thermometer he was using as a standard he completely overcame the earlier troubles and developed a reliable formula relating change in resistance to temperature. In June 1886 he read a long paper to the Royal Society on his
358
E rn est H o w a r d G riffith s
1 8 5 1 -1 9 3 2
I n k n o w n to C a l l e n d a r . G r i f f i t h s w as a ls o d e v e l o p i n g a p l a t i n u m r e s i s t a n c e t h e r m o m e t e r at S i d n e y S u ss e x C o lle g e . C a m b r i d g e , p r i m a r i l y to assist H e y c o c k a n d N eville in t h e i r e a r l y r e s e a r c h e s on alloy s y s te m s. In 18 8 9 he and C a lle n d a r co m b in ed forces and e s t a b l i s h e d fixed p o i n t s f o r t h e c a l i b r a tio n of t h e i n s t r u m e n t . In 1901 G r i f f i t h s w as a p p o i n t e d P r i n c i p a l of t h e I n iv e r sity C o lle g e o f S o u t h Vt a les
findings (26), a contribution that earned him a Fellowship of T rin ity College, and in the following year he filed his first patent on the resistance therm om eter (27). U nknow n to Callendar however, there was another research about to start along similar lines, also in Cam bridge. In 1888 those two founding fathers of physical metallurgy C. T. Heycock an d F. H. Neville, studying the depression of the freezing points of metals by alloying additions and confined in their work to very low melting point solvents by the limitations of m ercury therm om eters, appealed for help to E. H. Griffiths, one of Nevilles colleagues at Sidney Sussex College. Working in a crude wooden laboratory th a t ha d been built against the outside wall of the college grounds, Griffiths constructed a n u m b er of platinum resistance therm om eters for Heycock a n d Neville a n d collaborated with th em in calibrating these at a n um ber of fixed points, including those of ice, steam, the boiling points of several organic compounds, an d finally at the boiling point of sulphur, so making it possible to determ ine with accuracy the melting points of many metals and alloys.
359
In 1889 Griffiths became a w a re of C a lle n d a rs work a n d the two joined forces and succeeded in determining te m p e ra tu re s up to 1100C (28). T h e accuracy an d reliability of the device were now established, and C allendar a n d Griffiths approached Horace Darwin, the h e a d of the C a m b rid g e In stru m e n t Com pany, who readily agreed to its m anufacture, together with the necessary indicating equipm ent. These were quickly in tro d u c ed into iron a n d steel m aking a n d into other industries where they have proved their usefulness over the years for both industrial tem perature m ea su rem e n t and control and precise laboratory work (29). O ne early example was t h e use of the th erm o m e te r to determ ine steam tem peratures, this having an im p o rta n t effect on the design of steam turbines. Over the past three q u arters of a century designs have improved to meet industrial needs, more m an u fa ctu rers have engaged in its production, new techniques have been introduced, including the replacem ent of the coil of wire by thick films, and smaller a n d more robust therm om eters have been m ade available. Production of p la tin u m resistance therm om eters for industrial use now runs to several millions a y e a r (30), while the accuracy of the tem peratureresistance characteristics is e n s u re d by the continuing availability of the special high purity platinum upon which th e functioning of the instrum ent is based.
M e a s u r in g th e T e m p e r a tu r e o f L iq u id Steel
T o retu rn now to the platinum therm o co u p le a n d its later applications, we find it in use in a wide variety of industries including glass m anufacture, refractory making, the iron foundry and the nuclear energy industry, but almost certainly the most significant success it achieved was in the steel industry. In the course of a discussion o n m odern m ethods of m easuring tem perature held by the Institution of M echanical Engineers in 1913, opening with a com prehensive paper by R. S. W h ip p le of the C a m b rid g e Scientific Instrum ent C om pany, Sir Robert Hadfield a p p e ale d for further work to be done in deter mining the tem perature of m olten m etals: There was no doubt that the casting temperatures to which molten steel was heated were of greater importance than commonly imagined (31). Four years later a m ajor discussion on pyrom eters an d pyrom etry was organised by the Faraday Society and in a p a per by Dr. W. H. Hatfield of the Brown Firth Research L aboratories he stated th at he h a d used a similar instru ment to determine the te m p e ra tu re of molten steel w hen poured into the ladle b u t added: Although the temperature at which steels are cast must have an influence upon their ultimate physical properties, no ready and really reliable method for measuring such temperatures from the works standpoint is available (32). It was not until twenty years later, however, th a t such a ready and reliable m e th o d was forthcoming. In 1937, after considerable co-operation with the steel industry, Dr. F. H. Schofield and his colleague A. G race of the National
360
T h e m e a s u r e m e n t o f t h e t e m p e r a t u r e o f m o l t e n ste e l was fo r m a n y y e a r s a m u c h s o u g h t a f t e r m e a n s o f c o n t r o l l i n g (|u ality in t h e o p e n h e a r t h o r o t h e r t y p e s o f f u r n a c e s . T h e p r o b l e m was e v e n t u a l l y so lv e d by S c h o f ie ld a n d G r a c e a! t h e N a t i o n a l P h y s i c a l L a b o r a t o r y w h o d e v i s e d a q u i c k - i m m e r s i o n m e t h o d e m p l o y i n g a p l a t i n u m:rho< l itun p l a t i n u i n t h e r m o c o u p l e led t h r o u g h a ste el t u b e m o u n t e d o n a trolley
Physical Laboratory put forward their quick-imm ersion m ethod in w hich a platinum : rhodium -platinum thermocouple, sheathed in twin fine-clay insulators an d led through a steel tube bent at a right angle at the hot ju n ctio n and m ounted on a trolley, could be employed to determ ine the te m p e ra tu re of molten steel in open hearth and electric arc furnaces and in Bessemer converters by dipping into the molten steel for about twenty seconds (33). T h is technique was rapidly adopted in the steel industry throughout the w orld a n d h a d a m arked effect in improving quality. T h e difficulties th at ha d to be surm ounted were graphically described by two leading metallurgists, W. C. Heselw ood and D. M anterfield of the United Steel Companies, who also played their p art in the development of this procedure:
Some tw enty inches of m olten steel at a tem p e ratu re of a b o u t 1,620C , covered by p erh ap s five inches of m olten slag a t 1660C and c o n tain ed in th e h earth of a furnace typically fifty by fifteen by ten feet w ith refractory w alls an d roof at tem p eratu res up to 1650C, a n d th ro u g h w hich ro a r at sixty m iles an h o u r flam e and gases at 1800C; those are typical conditions w ith in an open h e a rth steel m aking furnace a n d it is not surprising th a t the p ractical problem of m easu rin g accu rately the liquid steel tem p eratu res rem ain ed unsolved for m any y e a rs (34). 361
T hese problems were of co u rse solved, and in later years improvements and simplifications have been introduced into the quick-im m ersion m ethod which continues to serve as a most valuable m eans of controlling the quality of steel. At the present time more th a n a h u n d r e d million readings a year are taken in the steel industry throughout the w orld, resulting in the p roduction of more tons per hour th an was formerly possible a n d longer furnace campaigns.
T h e In tern ation al T e m p e r a tu r e Scale T h e accuracy an d reliability of t h e enorm ous n u m b e r of tem p e ra tu re m easure ments m ade every day in m an u fa c tu rin g industry with either the platinum resistance therm om eter or w ith p latinum therm ocouples depend upon the acceptance of a recognised prac tic a l scale of te m p e ra tu re a n d its precise defini tion. Such a scale was first p roposed by C a llendar in a p a per to the British Association in 1899 (35) an d in 1903 the m atte r was placed in the care of the newly formed National Physical L a b o ra to ry at T eddington. After a great deal of study and discussions with th e A m erican Bureau of Standards, the Physikalische Technische R eic h an stalt a n d the Bureau Internationale des Poids et Mesures, the work was in te rru p ted by the first w a r b u t it was again taken up and the first International P ractical Scale of T e m p e ra tu re was agreed upon in 1927. Several revisions have since taken place, b u t it is now firmly based upon the use of the p latinum resistance therm om eter from 259.34C, the triple point of equilibrium between the solid, liquid an d vapour phases of hydrogen, and 630.74C, the freezing point of antim ony, a n d from th a t point on to the freezing point of gold at 1063C by t h e platinum : 10 per cent rhodium -platinum therm ocouple (36).
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1 J . A. C haldecott, Ann. Sei., 1971, 27, 409-411; Platinum M etals Rev., 1972, 16, 57-58 315. 2 A. L. B. and A. Breguet, Ann. Chim., 1817, 5, 312 J. F. D aniell, Quart. J . Set., 1821, 11, 309-320 3
6
7
8
9
10
11
12
13 14 15 16 17 18 19 20
21
22 23 24 25 26 27 28 29 30 31
T . J . Seebeck, A b h an d lu rg en d er physikalische K lasse der K niglichen A kadem ie der W issenschafter zu Berlin, 1822-23, 265-373 T. J. Seebeck, J . tech. kon. Chem., 1828, 2, 102-104 A. C. Becquerel, Ann. Chim., 1827, 31, 371-392 C. S. M . Pouillet, Comptes rendus, 1836, 3, 782 790 H. V. R egnault, R elations des E xperiences, Paris, 1847, 1, 246 E. Becquerel, Comptes rendus, 1862, 55, 826 P. G. T a it, Trans. Roy. Soc. Ediru, 1872 27, 125-140 73, H. L. Le C hatelier, Comptes rendus, 1886, 102, 819-822 G. K. Burgess an d H. Le C hatelier, T h e M ea su rem e n t of H igh T e m p era tu res, London, 1912, vi H. M. Howe, Eng. and M in . J ., 1890, 50, 426 F. O sm ond, M eth o d e G enerale p o u r lA nalyse M ic ro g rap h iq u e des Aciers au C arbone, Paris, 1895 W. C. R oberts-A usten, 1st R eport, Alloys R esearch C om m ittee, Inst. Mech. Eng., 1891 E. M atth ey , Phil. Trans. Roy. Soc., 1892, 183, 629 645 E. M atth ey , Proc. Roy. Soc., 1893, 52, 467-472 W. C. R oberts-A usten, Proc. Roy. Inst., 1892, 13, 502-518 L. B. H u n t, Platinum M etals Rev., 1980, 24, 104-112 C. W. Siem ens, Phil. M ag., 1861, 2 1, 73 C. W. Siem ens, Proc. Roy. Soc., 1871, 19, 443 445 C. W. Siem ens, Proc. Roy. Inst., 1872, 6, 438-448 C. W. Siem ens, J . Iron Steel Inst., 1871, 1, (i), 50-55 B ritish A ssociation R ep o rt, 1874, 242 J . J . T hom son, R ecollections a n d R eflections, C am bridge, 1936, 132 H. L. C allen d ar, Phil. Trans. Roy. Soc., 1887, 178, 161-233 H. L. C allen d ar, B ritish Patent 14,509 of 1887 H. L. C a lle n d a r an d E. H . Griffiths, Phil. Trans. Roy. Soc., 1891, 182, 119-157 R. Price, Platinum M etals Rev., 1959, 3, 78-82 J . S. Jo h n sto n , in T e m p e ra tu re M easu rem en t 1979, ed B. F. Billing a n d T . J. Q uinn, In stitu te of Physics, L ondon, 1975, 80 Sir R obert H adfield, Proc. Inst. Mech. Eng., 1913, (3 766-768 4), W. H. H atfield, Trans. Faraday Soc., 1917-18, 13,289 294 F. H. Schofield, Iro n Steel Inst., Special R eport No. 16, 1937, 223-238 W. C. H eselw ood and D. M anterfield, Platinum M etals Rev., 1957, 1, 110-118 H L. C allen d ar, Phil. M ag., 1899, 48, 519; B ritish A ssociation R eport, 1899, 242-243 C. R. B arber, Platinum M etals Rev., 1969, 13, 65 67; T . J. Q u in n an d T . R . D. C handler, ibid., 1972, 16, 2 -9 363
J o a q t i i m B ish o p
1806-1886
F o r s o m e y e a r s a s s i s t a n t a n d i n s t r u m e n t m a k e r to P r o f e s s o r R o b e r t H a r e at t h e I n i \ e r s i t y o f P e n n s y l v a n i a . B i s h o p set u p in b u s i n e s s in P h i l a d e l p h i a in 18 12 a n d p u t H a r e s c o m p o u n d b l o w p i p e to c o m m e r c i a l u se in th e m e l t i n g of p l a t i n u m . H is a c t i v i t i e s in t h e m a n u f a c t u r e o f p l a t i n u m e q u i p m e n t e x p a n d e d a n d h is c o m p a n y l a t e r b e c a m e p a r t of t h e . J o h n s o n M a t th e y g r o u p
20
Platinum Extraction and Fabrication on the American Continents
The applications o f platinum have steadily increased, and never so rapidly as in the last two decades. For m any purposes no substitute for platinum has been found. "
P R O F E S S O R J A M E S L E W I S II O W K. I 9 0 0
T h e platinum industry, in so far as refining and m anufacturing are concerned, took far longer to establish itself in the Americas th a n in E urope although, as related earlier, the original supplies of the native metal cam e from there, the principal source being New G ra n a d a, later securing its independence as the Republic of Colombia late in 1819. Shortly afterwards the new government decided to prohibit the export of p latinum and to build up stocks with the idea of a platinum coinage in mind. In the following year, however, the Colom bian Vice-President Francisco Antonio Zea (1766-1822) arrived in E urope with two objectives, to contract a loan of up to 5 million sterling and to seek the recogni tion by E uropean powers of the newly established republic. In L o n d o n Zea met Ju stu s Erich Bollmann, by then a m anufacturing chemist whose activities in the fabrication of platinum in the U nited States will be described a little later, who was instrumental in securing a n advance of 20,000 towards a projected loan of 2 million that Zea eventually contracted in 1822. O n e half of this advance was contributed by Bollmann himself, and as a guarantee Zea, apparently unaw are of the intention to m int a coinage, signed a n agreem ent with him whereby 40,000 pounds of platinum (an impossibly large am ount) supposedly held in the Colom bian M in t in Santa F de Bogot, would be released for sale in London, no doubt for use by Bollmann himself and by Wollaston, whose supplies had virtually ceased by this time. Z e a s authority to contract a loan was revoked in August 1821 by the C o lo m bian governing council although news of this did not reach L ondon until the O ctober of the following year by which time Bollmann, who had visited Colombia in connection with the proposed shipm ent of platinum , had died in Ja m a ic a on his way home, while Zea himself died only a m o n th later. T h e government declined to honour the agreem ent m ade betw een these two
365
\ f t e r two c e n t u r i e s o f h a n d o p e r a t i o n by n a t i v e s in t h e C h o c o d i s t r i c t o f C o l o m b i a , m e c h a n i c a l e q u i p m e n t w as b r o u g h t i n by t h e C o m p a n i a M i n e r a C h o c o P a c i f i c o in 19 15. T h i s is o n e o f s e v e ra l d r e d g e s in o p e r a t i o n in t h e m a i n p l a t i n u m - b e a r i n g a r e a
m en for the supply of platinum , n o doubt because of their intention to m int a platinum coinage, authorised in S e p te m b e r 1821 but never put in hand. T hese events, recently uncovered by Dr. J . A. C haldecott and to be described by him in m ore detail in a forthcoming p a p e r in Platinum M e ta ls Review, were undoubtedly responsible for the statem ent b y the unknow n translator in his footnote to B aruels p a per in The Philosophical M a g a zin e of 1822 referred to on page 190: This valuable memoir derives particular interest from the large importation of the above ore, daily expected from South America, in consequence of the negotiation between M. Zea and some London merchants. (1). T his consignment never of course arrived, b u t its supposed existence has often been referred to, even by Sir E d w a rd T horpe, who wrote quite erroneously in his Essays in Historical C h e m is try : Whole cargoes of the native metal are said to have lain unpurchased for years in London as it could not be turned to account. (2) T h e possibility of minting a p la tin u m coinage in C olom bia arose again in 1829, p rom pted by the R ussian m oves in this direction, a n d H u m b o ld t was c on sulted by Sim on Bolivar, b u t w ith the resignation of the L iberator in 1830, and his death very soon afterwards, n othing m ore was heard of the idea.
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Later P r o d u c tio n in South A m erica

Production of platinum in Colom bia rem ained at a low level for m any years, confined to the activities of native workers. In 1879, however, a small refining and assaying establishm ent was set up in M edellin by the G utirrez family. A younger m em ber was sent over to J o h n s o n M a tth e y in L ondon to gain experience a nd the Fundicin Gutirrez is still active at the present time. In 1911 the Anglo-Colom bian Development C o m p a n y was formed jointly by Consolidated Gold Fields an d J o h n s o n M a tth e y to work the p latinum deposits of the Choc an d dredging operations were begun, output beginning to increase by 1914. L ater this com pany was taken over by the South A m erican Gold and Platinum C om pany, formed in the U nited States with a subsidiary o p e ra t ing company, C o m p a a M in e ra Choc Pacifico. T h is organisation pu t a second dredge into service in 1920, a third in 1923 and a fourth in 1932 (3). Production of platinum thus increased considerably, reaching 30,000 ounces a year by 1920 but now representing a smaller p a rt of world production.
T h e Fabrication o f P la tin u m in the U n ite d States Although as was said at the beginning of this c hapter Am erica was late in enter ing the platinum industry, there was one quite rem arkable exception. In 1796 there arrived in New York the G e rm a n physician and adventurer J u s tu s Erich Bollmann already m entioned in his later dealings with Zea. H e had been imprisoned after two attem pts to release Lafayette from his confinement by the Austrians and then expelled from the country. For his efforts on behalf of Lafayette he was given a w arm welcome by George W a sh in g to n and he established a m erchanting business in Philadelphia. T h is proved to be unsuccessful, however, a n d he decided to take up practical chemistry, devoting his efforts to the production of malleable platinum and the development of its industrial uses. No details of B ollm anns process have survived, but he could well have been aware of the publications of R ic h a rd Knight in 1880 and of T h o m a s Cock in 1807 referred to in C h a p te r 8. Cock had not attem pted to remove the other platinum metals, although their discovery had been reported by W ollaston and T e n n a n t between 1802 a n d 1804, but as a m em ber of the A m erican Philoso phical Society since 1800 Bollm ann could have learnt something from a paper read there in 1809, although not published until 1818, by J o s e p h C loud of the Philadelphia M in t (4). T h is described the separation of palladium a n d rhodium from native platinum , a n d possibly he adopted this procedure. T h e first announcem ent of his success cam e in a note from Professor T h o m a s C ooper of Dickinson College in Pennsylvania, the editor of the Em porium o f A rts and Sciences, in 1813(5). This p rom pted a letter from Bollmann, p art of which is reproduced here, in which he claimed to be the first to render p latinum m alleable in America by means of a process which adm its being executed on a large scale , going on to say that he had m ade sheets of thirteen inches square and th at he
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Justus E ric h R o llm a n n 1769-1821
G e r m a n p h y s ic ia n . a d v e n t u r e r , m erchant, economist, au th o r and m anufacturing chemist. liollmann arrived in Neu York from Kngland in 1796. after acquiring a knowledge of chemistry in Paris. H e lived for most of th e e n s u in g tw e n ty y e a rs in P hiladelphia where he becam e a m em ber of the Am erican Philosophical Society. He was the first to prepare m alleable platinum on a commercial scale in the United States, and was responsible for providing the first platinum boiler used in Am erica for concentrating the weak sulphuric acid produced by the lead cham ber process
had in preparation platinum vessels that would hold from twenty to thirty gallons (6). In a letter to the Governor of Pennsylvania, Simon Snyder, in 1814 (recently discovered by Dr. J. A. Chaldecott, to whom the present writer is indebted for these details) in the State Archives of Pennsylvania (7) Bollmann wrote:
There has been a Boiler m ade here, of rolled Platina, for the C ondensation of Oil of Vitriol, which holds 25 gallons and is the largest vessel of Platina, probably, in existence.
Pari of Bollm anns letter of 16 Ju n e 1813 to Professor T hom as Cooper wherein he gives some inform ation about his own production and use of m alleable platinum . He also expressed the hope that his process would become beneficial to the arts, and to society. Cooper published the letter in August 1813 in his Em porium of Arts and Sciences"
A s th e article stands it gives the impression, that I only do what M r. C lo u d did before, but better. T h e fact however is, that M r. C lou d , w hose m erits I w ell know and fully acknowledge does not se e m to have intended m ore than to produce a cabinet piece of the g rea te st possible purity and specific gravity, and he has done so : bu t I have first rendered platina malleable in this country,by means o f a process, which admits being executed on a large scale, and w h ich , I hope, will become beneficial to the arts, and to soci ety. P ie c e s have been made o f the w eight o f tw o pounds, and up wards. Sheets have been rolled o f thirteen inchcs square, and vessels o f platina are now m aking, and it preparation, which will hold fro m twenty to thirty gallons.
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Dr. Chaldecott considers that this still was m ad e for J o h n H a rris o n of Philadelphia, the first successful large-scale m an u fa ctu rer of sulphuric acid in the U nited States, who introduced the lead cham ber process there a ro u n d 1793. T h e still weighed 700 ounces, held 25 gallons, and was in service for some fifteen years (7). Bollmann tried repeatedly to prom ote further applications for platinum , in glass manufacture, in the decoration of porcelain, for coins and m edals an d for standard weights a n d measures, but none of these cam e to anything. O n a visit to E ngland in 1814 he met Wollaston, from w hom he would have learnt of the latte rs success several years earlier in the production of m alleable p la tin u m and the making of large sulphuric acid boilers (7). In 1816 he left N o rth Am erica for England, never to return.
T h e E n terprise o f J o a q u im B ish o p After B ollm anns departure there appears to have been no refining or fabrication of platinum in the U nited States for some twenty-five years an d the d e m and for laboratory ap p a ra tu s and other uses was met by the E u ro p e a n producers, each having its agents in N ew York and Philadelphia. T h e n in 1842 a n establishment came into existence th a t was to continue firmly until the present day. This was set up by J o a q u im Bishop, the son of English parents who lived in O p o rto in P ortugal where he was born. T h e F rench wars disturbed the family, a n d in 1810 they emigrated to America, settling first in Baltimore and then in Philadelphia. In 1826 J o a q u im becam e a n apprentice to a m anufacturing jeweller but left him to become a finisher in a brass foundry. His experience in metal working was com bined with some scientific reading in his spare time a n d in 1832 he secured the position of assistant and instrum ent m aker to Professor H a re in the University of Pennsylvania. H e re he took p a rt in building the a p p a ra tu s for the later series of H a r e s experiments in the melting of the platinum metals (described in C h a p te r 15) b u t he left the university in 1839 to become a M achinist a n d Philosophical In stru m e n t M a k e r . In 1842 he was urged by his friends most probably also by H a r e to take up the refining and fabrication of platinum , using the famous blow-pipe. Already in 1845 he was aw arded a silver medal by the Franklin In stitute for skill and ingenuity in the m anufacture of platinum scientific in stru m e n ts . In 1858 he moved from Philadelphia to R adnor, an d th en again in 1865 to Sugartow n where he bought a 43 acre estate and built a new hom e and work shop. T here he set up a melting shop with equipm ent for the production of hydrogen and oxygen, a forge an d rolling mills and a draw bench. T h e platinum was melted in 20-ounce ingots and he m anaged to secure an d to treat native platinum from Russia as well as purchasing sheet from the agents of the European refiners. T h e staff nu m b ere d only two or three, with Bishop himself as skilled w orkm an a n d salesman. T h e quality of both his m etal and his workm anship were highly spoken of by contem porary users (8) an d from the beginning his several steps were crowned with rem arkable success . (9)
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T h e .second p l a t i n u m w o r k s e s t a b l i s h e d in 1 8 6 5 b y J o a q u i m B i s h o p at S u g a r t o w n . C h e s t e r C o u n t y . P e n n s y l v a n i a , w ith t h e f o u n d e r o n t h e le f t a n d his sm a ll s ta ff. T h e p l a n t i n c l u d e d a m e l t i n g s h o p w ith m e a n s fo r p r o d u c i n g h y d r o g e n a n d o x y g e n , a f o r g e , o n e l a r g e a n d t w o s m a ll r o l li n g m ills, a w i r e draw ing bench and a chem ical la b o ra to ry
In 1876 he was aw arded a b ro n z e m edal for an exhibit of p latinum at the Philadelphia Centennial Exhibition, an d he continued to be active in his business until two years before his death in 1886. His assistant a n d later partn e r E dw in Cox carried on the business until 1889, when B ishops g randson and heir J. B. M atlack came of age. In 1903 the refinery and workshops were destroyed by fire, but the business continued, a new works being built at Malvern, and then in 1909 the firm was incorporated as J . Bishop and Co. Platinum Works. In this form it continued to expand, producing all the types of p latinum a p paratus needed and also taking up the m a n u fa c tu re of spinnerets for the Am erican works established by C ourtaulds in 1909 to m anufacture artificial silk. T h e n in 1927 J o h n s o n M a tth e y purchased a shareholding in the com pany, acquiring full control in 1933. Later the nam e w a s changed to M a tth e y Bishop Inc., and more recently to J o h n s o n M a tthey Inc. N ew and m uch greater facilities have of course been built in recent years to m ee t the ever increasing d e m and for the platinum metals, including a refining a n d chemical complex, a catalyst m anufacturing plant and a new centre for m etallurgical an d fabricating operations.
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C harles E n gelh a rd Bishop was not without com petition in the platin u m business. In 1875 Daniel W. Baker with his sons Charles an d C yrus set up in Newark, New Jersey, first as a m anufacturing jeweller but later taking up the fabrication of platin u m a n d by 1892 they ha d issued a catalogue of laboratory a p p a ra tu s (10). L a ter another small com petitor emerged, the Charles F. Croselm ire C om pany, also in Newark. In the m eantim e there had arrived in New York in 1891 Charles E ngelhard, the brother-in-law of Dr. W ilhelm Heraeus, to serve as the representative of the H a n a u company. This was a n event of great significance in the platinum industry an d its future development in the U nited States. A m a n of great energy and vision, he em barked after some years in Am erica on a policy of acquisition and expansion. In 1901 he acquired the Croselm ire C om pany, a small m anufacturer of platinum wire a n d sheet and on this basis formed the Am erican Platinum Works, taking over the Baker firm in 1904. W h e n the extraction of platinum from Colombia, m entioned earlier in this chapter, yielded im portant quantities of metal during the first W orld W ar, a large refinery was erected by Baker an d from then onw ards the com pany played a leading p a rt in the A m erican industry an d established branches in m any parts
C h a rles E n g elh ard 1867-1950 A native of lla n a u an d brother-in -law o f Dr. W i l h e l m H e r a e u s , E n g e l h a r d w a s s e n i lo N ew Y o r k in 1891 a s a g e n t f o r t h e H e r a e u s c o m p a n y . A m a n of considerable e n e r g y , h e b e g a n to a cquire several sm all com panies e n g a g e d in t h e w o r k i n g of p l a t i n u m an d b ecam e P resid en t of B ak er and C o m p a n y , now k n o w n as E n g e l h a r d I n d u s t r i e s . A f t e r t h e firs t w o rld w a r he s e c u re d th e su p p lie s of p la tin u m m etals produced by th e Mond N ick el C o m p a n y a n d r o s e to a p r o m i n e n t p o s i tio n in t h e p l a t i n u m i n d u s t r y
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of the world. T h e founder, C h a rle s Engelhard, died in 1951 a n d was succeeded by his son Charles W. E n g e lh a rd (1917-1971) who in 1955 changed the style a n d title of his enterprise to E n g e lh a rd Industries.
Scientific W ork on P la tin u m in the U n ite d States From the earliest years of independence, and the high times of Benjamin Franklin, Philadelphia had been the cradle of scientific activity. T h e work of R o bert H are and his co-operation with B enjam in Silliman has been reviewed in C h a p te r 15, together with its c o n tin u a tio n in France by Deville and Debray. A nother early piece of research w a s carried out by J o s e p h C lo u d (1770-1845), the chemist and refiner of the P h ila d e lp h ia M in t from 1797 until 1836. In 1807 he received some small gold b a rs from Brazil th at were only of a pale yellow colour and found that they co n ta in ed a metal that would resist the cupel and was soluble in the nitric and nitro-m uriatic acids . In a p a p e r to the Am erican Philosophical Society he began: Notwithstanding the numerous experiments that have been made by several eminent chemists, on a metallic substance, discovered by Dr. Wollaston, in combina tion with crude platinum and by him called palladium, there still remains much doubt with respect to the existence of such a simple substance (11).
Cloud went on to prepare a specim en of this m etal, finding th a t its properties did indeed agree with those described a few years earlier by W ollaston and con firming that palladium had been isolated from a n entirely new source. C lo u d s further paper on the separation of palladium and rhodium from native p latinum has already been m entioned in c onnection with B o llm anns procedure (4). But the leading research chem ist in the U nited States for m any years was W olcott Gibbs, a native of N ew York who after g rad uating from Colum bia College spent some time as a ssistant to H a r e and th en visited E u ro p e to study in tu rn under Heinrich Rose, Liebig and D um as. O n his re tu r n he was appointed Professor of Chem istry at the new ly established Free A cadem y which later becam e the City College of N ew York a n d then the City University there (12). H e re he rem ained for fourteen years a n d in collaboration w ith Frederick Augustus G enth, formerly an a ssistant to Bunsen at M a rb u rg , carried out a long series of researches on the p la tin u m metals and their co-ordination com pounds (13). Largely as a result of this work he was called to H a r v a rd in 1863 as Professor of N atu ral Sciences, a post he retained until his retirem ent in 1887. G ibbs introduced into A m e ric an science the G e rm a n system of research as a m eans of chemical instruction (12), and one of his im portant achievements was the initiation of electrogravimetric analysis, employing a p latin u m crucible as the cathode connected to a B u n se n cell, the anode being a length of platinum wire immersed in the solution (14). In this way he m ad e determ inations of copper and nickel and pioneered a m ethod of analysis th at gave excellent service for very m any years. Gibbs also devoted his efforts to research on the separation of the platinum
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metals from each other a n d to their m ethods of analysis. F o r m a n y years he edited the American Jou rn al o f Science established by Silliman, a n d he was one of the founders of the A cadem y of Sciences. Yet another P hiladelphian to interest himself in the p la tin u m m etals was Dr. William H enry W ahl (1848-1909). After studying at H eidelberg he was appointed secretary and editor to the Franklin Institute in 1871, a position he continued to hold until his death. H e was especially concerned with electrodeposition, and in 1883 published a book on the subject (15) in which he dealt with both platinum a n d p alladium plating a n d their electrolytes. In a later paper, O n the Electrodeposition of P la tin u m , read to the F ra n k lin In stitute in 1890 (16) he reviewed the whole problem of p latinum plating, saying that while each of the earlier baths w ould yield satisfactory results for a time the peculiar difficulties met with in the practice of platinum plating render it impossible to maintain the chemical integrity of those electrolytes and in consequence thereof they soon become inefficient or inoperative by reason of contamination with the secondary products formed therein. W ahl therefore experimented with anodes consisting of porous carbon im pregnated with platinum to provide a m eans of dissolution in acidic
W olcott G ibbs 1822-1908

B o r n in N ew Y o r k . G i b b s first a t t e n d e d C o l u m b i a C o l l e g e a n d t h e n s e r v e d as a n a s s i s t a n t to R o b e r t H a r e a t th e U niversity of P e n n s y lv a n ia , la te r being a p p o i n t e d P r o f e s s o r o f C h e m i s t r y at w h a t is now t h e C ity U n i v e r s i t y o f New Y ork. H e re h e in tro d u c e d th e G e r m a n s y s t e m o f r e s e a r c h a s a m e a n s of i n s t r u c t i o n in c h e m i s t r y w h i l e h e c a r r i e d o u t s o m e of t h e e a r l i e s t r e s e a r c h e s in t h e U n i t e d S t a t e s o n t h e c h e m i s t r y of t h e p l a t i n u m m e t a l s . L a t e r h e w as ap p o in ted P rofessor of N atural S ciences at H a r v a r d
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electrolytes, but his deposits w e re black an d non-adherent. H e then turned to alkaline baths containing oxalic acid an d he was the first to employ an electrolyte free from chloride a n d to use platinic h y d r a te to m ain ta in the metal content of his bath, so avoiding the build-up of undesirable compounds. A major contribution, a lth o u g h of a ra th e r different kind, to the history and the chemistry of the platinum m eta ls b e g a n to be m ade in the late nineteenth century by J a m e s Lewis Howe, Professor of C hem istry at W a sh in g to n a n d Lee University in Lexington, Virginia. His chemical researches were largely devoted to the com pounds of ruthenium , a metal that he felt was the most interesting of the group and of which the least was known, including the confirmation and extension of the earlier work of J o ly in France (17). But his most im p o rtan t con tribution was his Bibliography of the M etals of T h e Platinum G r o u p , first published by the Sm ithsonian In stitu tio n in 1897 an d followed by a n u m b er of further and more up-to-date editions. T h is was a most p ainstaking achievement, containing well over two th o u s a n d entries from some thirteen h u n d red authors,
SM ITHSONIAN MISCELLANEOUS COLLECTIONS
I084
BIBLIOGRAPHY OF THE METALS OF
THE PLATINUM GROUP

P L A T IN U M . P A L L A D IU M . IR ID IU M , R H O D IU M . OSM IUM , R U T H E N IU M
1 7 4 8 - I 89
P r o f e s s o r J a m e s L ew is H o w e ( 1 8 5 9 1 9 5 5 ) , w as b o r n a t N e w b u r v p o r t in \1 a s s a c h u s e t t s a n d s t u d i e d u n d e r W o h l e r a t G t t i n g e n f r o m 1 8 8 0 to 1 882. In 1 8 9 4 h e w a s a p p o i n t e d P ro f e s s o r of C he m istry at W a shington and L ee U n i v e r s i t y a t L e x i n g t o n , V i r g i n i a , r e m a i n i n g t h e r e fo r al m o s t fifty y e a r s. H e b e c a m e t h e l e a d i n g au th o rity on ruthenium and its c o m p o u n d s b u t his m o st \ a l u a b l e a n d b e s t - k n o w n w o r k w a s his ' B i b l i o g r a p h ) o f t h e M e t a l s of t h e P l a t i n u m G r o u p , first p u b l i s h e d in 1897 w ith a n u m b e r of s u b s e q u e n t ed i t i o n s
JA S . L E W IS H O W E
C IT Y O F W A SH IN G TO N P U B L IS H E D B Y T H E SM ITH SO N IA N IN S T IT U T IO N
897
374
T h o m a s A lva E d iso n 18 4 7 1931

The great American inventor, born of poor p a r e n t s a n d s e l f - t a u g h t in c h e m i s t r y a n d p h y s i c s , was a c t i v e l y i n t e r e s t e d in t h e p r o p e r t i e s a n d u s e f u l n e s s of p l a t i n u m . H e p u r i f i e d th e m etal from d isc ard ed G rove ce lls a n d r e d u c e d it to w ires of o n l y 0 .0 0 1 i n c h d i a m e t e r f o r u s e in his e a r l y a t t e m p t s to d e v e l o p t h e i n c a n d e s c e n t l a m p , w h i l e h is o b s e r v a t i o n th a t a p la tin u m spiral heated in a v a c u u m g a v e a d e p o s i t of m e t a l o n t h e i n s i d e o f th e glass b u l b l e d , in t h e h a n d s of S ir A m b r o s e F l e m i n g , to the d e v e l o p m e n t of t h e t h e r m ionic \ al\ e
extracted from a hu n d red scientific journals. H ow e began by consulting the m onograph compiled by Karl Klaus (page 250) which contained a fairly com plete bibliography of the p latinum metals up to 1861 b u t which included a num ber of errors th at he had to rectify. His bibliography and his position as the leading A m erican authority on the chemistry of the platin u m metals led to his appointm ent in 1917 as ch a irm a n of a com m ittee on platin u m of the N ational Research Council.
T h o m a s E d is o n s W ork w ith P la tin u m T h e inventive genius of T h o m a s Alva Edison has already been referred to in con nection with the incandescent electric lamp, b u t this was of course only one of his m any achievements. His interest in platin u m began as early as 1863 when, aged only sixteen, he was a night telegraph operator on the railway at Stratford Ju n ction in O ntario. Finding that several old Grove batteries had been discarded, he obtained permission to remove the p latinum electrodes and added them to his quite large stock of chemicals in the laboratory he had built in the cellar of his p a r e n t s house and where he spent most of the daylight hours. Later some of this platinum was almost certainly used, after being draw n to fine wire, in his initial experiments on the electric light. In 1879 he presented a paper, O n the Phenom ena of H e a tin g M etals in Vacuo by M eans of an Electric C urrent, to the meeting of the American Associa tion for the A dvancem ent of Science, held that year in S aratoga Springs, New York (18). This included an account of the behaviour of iridium -platinum alloy
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wires which, w hen brought to incandescence, gave rise to a deposit of platinum on the inner surface of the glass b ulb. In studying further this E d is o n effect (page 309) in 1884 he m ade lamp bulbs containing a thin plate o f platinum placed betw een the limbs of the filament and found th at if this p l a t e was connected to the positive end a current would flow across the vacuum b u t that no c urrent would flow if it were co n nected to the negative limb (19). Edison m ight therefore have discovered the grid, devised m uch later by his fellow A m erican Lee de Forest (1873-1961) in 1907 (20) b u t unfortunately he w a s too far ahead of his time a n d the only use he could foresee was for an in d ic a to r to record variations in the potential of his lighting circuits.
A N e w Source o f P la tin u m i n C anada In 1888 a group of gold miners w orking a small property in the S udbury district of O n ta rio cam e upon a rich copper-nickel ore, a sam ple of which was sent to Francis Lewis Sperry, a chemist a t the C a n a d ia n C o p p e r Com pany. In m aking a fire assay for gold Sperry o btained a small white metallic bead which he passed along to his old professor H o r a c e Lemuel Wells who, w ith his colleague Professor Samuel Penfield e xam ined this further a n d identified the m ineral as an arsenide of platinum to which th e y gave the na m e Sperrylite. F u rth e r samples were sent to Frank W igglesw orth Clarke, the chief chemist to the U.S. Geological Survey (an experienced operator with the platin u m metals and the great worker on atomic weights) w h o reported th at
this is the first au th en tic in stan ce of the o ccurrence of p latin u m in tru e m etalliferous vein m aterial, a n d it has therefore re m a rk a b le in te re st .
C larkes analysis of the m ineral showed only 0.025 ounce of p latinum per ton, on which he comm ented:
W h eth er it could be p ro fitab ly ex tracted is an open question.
T h e copper-nickel deposit w a s worked w ith m any difficulties by the C a n a d ia n C opper Com pany, together with the O rford C o p p e r C om pany, separating the copper from th e nickel but w ithout recovering any of the p latin u m metals. In 1902 these two enterprises were m erged into the In te r national Nickel C om pany and m o re attention began to be p a id to improved m ethods of producing nickel and to the recovery of the platin u m metals, b u t for m any years only a fraction of th ese was successfully extracted, the rem ainder going into the copper a nd nickel. T h e first process for their recovery on a comm ercial scale stem m ed from the activities of Ludwig M ond, a m a n of great energy a n d vision who after some years experience in chemical m a n u fa c tu re in G e rm a n y h a d settled at W idnes in E ngland in 1867 and established himself in the chemical industry in partnership with J o h n Brunner. O n e of the m a n y problem s he faced later in his career con cerned the corrosion of nickel valves an d the accum ulation upon them of a
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L udw ig Mond
1839-1909
B o r n in C a s s e l in t h e G r a n d D u c h y of H e s s e . M o n d s t u d i e d c h e m i s tr y u n d e r k o l b e at M a r b u r g a n d t h e n w ith B u n s e n at H e i d e l b e r g . A f t e r s o m e y e a r s e x p e r i e n c e in t h e c h e m i c a l i n d u s t r y in G e r m a n y a n d H o l l a n d he c a m e to E n g l a n d in 1867 a n d b e g a n to b u i l d u p his c h e m i c a l e n t e r p r i s e s in p a r t n e r s h i p w i t h B r u n n e r . D e s p i t e his m any business problem s he devoted s o m e t i m e to r e s e a r c h a n d in 18 8 9 d e v i s e d a r u d i m e n t a r y fuel cell w ith p l a t i n u m e l e c t r o d e s , w h ile a y e a r l a t e r he d i s c o v e r e d t h e r e a c t i o n b e t w e e n c a r b o n m o n o x i d e a n d nickel t h a t led to t h e c a r b o n y l p r o c e s s fo r its r e fin in g . T o make this process com m ercially s u c c e ss fu l required a source of m i n e r a l , a n d M o n d s a c q u i s i t i o n o f a c o p p e r - n i c k e l o r e b o d y in C a n a d a led to t h e f o r m a t i o n of t h e M o n d N ickel C o m p a n y a n d t h e n to t h e e x t r a c t i o n of t h e sm a ll p r o p o r t i o n of t h e p l a t i n u m m e t a l s f ro m t h e r e s i d u e s o f t h e c a r b o r n I p ro cess
deposit of carbon, and this he set out to investigate in a laboratory he h ad set up in the stables of his private house in London, taking on a young A ustrian chemist, Carl Langer who had studied under Victor M eyer at Z u ric h a n d then served as a research chemist at the Badische Anilin u n d S oda Fabrik at Ludwigshaven. In 1889 M o n d and Langer, together with a young G e rm a n chemist Friedrich Q uinke and M o n d s elder son Robert, discovered the form a tion of a gaseous com pound of nickel and ca rb o n monoxide w hen this gas was reacted with finely divided metallic nickel. T his discovery was at once reported to the Chemical Society (23) b u t to M o n d it suggested th at here was a possible method of refining nickel, an d he decided to build a large scale pilot plant for this purpose in the works of Flenry W iggin in Birm ingham , C arl Langer undertaking its design and construction. After some three years of experim entation Langer developed a reliable process and applied it to treat the copper-nickel sulphide m atte th a t Wiggins were receiving from C anada, producing pure nickel a n d leaving a residue from which the p latinum metals could be recovered. If M o n d was to enter the nickel business on a large scale he now needed supplies of suitable mineral, and having m ade this decision he engaged a G e rm a n mining engineer, Dr. B ernard M ohr, to investigate possible sources,
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T o provide a so u rce of m in eral for h i s carb o n y l process of refining nickel L udw ig M ond a c q u i r e d a p r o p e r t y in t h e S u d b u r y d i s t r i c t o f O n t a r i o , o p e n e d a m i n e a n d e r e c t e d a s m e lt e r . T h i s s h o w s t h e p r o p e r t y , n a m e d t h e V i c t o r i a M i n e , s h o r t l y a f t e r it c o m m e n c e d o p e r a t i o n s in 1900. T o d a y t h e s c e n e is very d i f f e r e n t , wi t h a g r e a t c o m p l e x o f m i n e s a n d m etallurgical plan ts from w hich the p l a t i n u m m e ta ls a r e ev entually re co v ered
including those in C anada, and in 1899 M o n d p urchased two properties in the S udbury area that he re-nam ed the Victoria M in e a n d where he erected a smelter to produce a matte. A y e a r later a nickel refinery was built at C lydach in South Wales, with Langer in charge, and this p la n t received the copper-nickel m atte from C anada, producing p u r e nickel and copper sulphate. T o link these two operations together the M o n d Nickel C o m p a n y was founded in 1901 with Carl Langer as managing director. T h e presence of the platinum metals in the ore was confirmed, the refinery residues containing them began to accumulate, and considerable thought was given to the prospect of their recovery. Ludw ig M o n d had earlier interested himself in platinum and its properties, a n d one of the first inventions coming from his private laboratory s te m m e d from the original fuel cell devised by W. R. Grove in 1839 (described on page 211). M o n d felt th at his p roducer gas, rich in hydrogen, m ight be used to p ro d u c e electricity. H e and L a nger therefore set about designing a gas b a tte ry , u sing strips of p la tin u m im m ersed in dilute sul phuric acid, then changing to p o ro u s d iaphragm s covered with fine p latinum foil an d coated with a thin film of p la tin u m black. T h e investigation was reported in a pa p e r to the Royal Society in 1889 (24), but unfortunately the life of this ru d i m en ta ry fuel cell proved to be to o short, and although he prom ised further studies the pressure upon M o n d in his industrial empire prevented this. His interest in platinum continued, however, an d in collaboration with Sir W illiam R a m say of University College he p u rsu e d a research on the occlusion of oxygen and hydrogen by platinum and pa lla d iu m (25).
378
C arl L anger
1 8 5 9 -1 9 3 5
Horn in M oravia, now part of Czechoslovakia. L anger was b ro u g h t u p in B u d a p e s t a n d t h e n s t u d i e d c h e m i s tr y u n d e r \ ictor M e y e r at Z r i c h , o b t a i n i n g his d o c t o r a t e t h e r e in 1882. H e t h e n j o i n e d t h e B a d i s c h e A n ilin u n d S o d a F a b r i k as a r e s e a r c h chem ist, but L udw ig M ond invited him to L o n d o n to b e c o m e h is p e r s o n a l a s s i s t a n t. A f t e r t h e i r d isc o v ery o f t h e c a r b o n y l p r o c e s s f o r r e fi n i n g n i c k e l L a n g e r d e s i g n e d a n d bu ilt t h e r e f i n e r y at C l y d a e h in S o u t h V a le s a n d a ls o i in v e s ti g a t e d p o s s ib le o r e b o d i e s in Canada. L ater he supervised the d e v e l o p m e n t of a p r o c e ss f o r t h e e xtraction a n d refining of the p la tin u m m etals from the nickel residues
T h u s the intention to recover the platinum m etals was well in front of L udw igs mind, and in 1902 samples of the residues were sent in to Jo h n so n M atthey for analysis. T his presented a n um ber of difficulties because of their unusual an d varying nature, but regular deliveries began a little later a n d the refining and preparation of pure p latinum a n d palladium were und e rta k en on a contract basis by J o h n s o n M atthey. H e re again m u ch difficulty was encountered, the residues containing only about 7 per cent of total platinum metals, but a process was duly worked out. T his continued until 1919, by which time some 33,000 ounces of platinum and 53,000 of p a lladium had been produced, and then the M o n d Nickel C o m p a n y decided to undertake their own refining by a process th at h a d been developed at C lydach by a young Swiss chemist, Dr. Christian Heberlein. A small-scale plant was set up in Southwark, across London Bridge, with H eberlein as chief chemist and M a jo r C u thbert Jo h n so n (1882-1962), whose father had been associated with Ludw ig M o n d s early work in the alkali industry, as manager. By 1924 the process had been improved, expansion becam e necessary, a n d a new refinery was erected at Acton to the west of London. Jo h n s o n was joined by R alph Atkinson and later by Alan Raper, both former students of m etallurgy under Professor Heycock at C am bridge. T h e complex series of smelting op e ra tions, electrolysis, dissolution of the p latinum a n d palladium in a q u a regia and
379
T h e first p r o c e s s i n g p l a n t f o r t h e s e p a r a t i o n a n d p u r i f i c a t i o n o f t h e p l a t i n u m m e t a l s in t h e A c t o n r e f i n e r y o f t h e M o n d N i c k e l C o m p a n y . O r i g i n a l l y b u i l t in 1 9 2 4 . m a j o r e x t e n sions w ere m a d e in 19 30 in o r d e r to t reat the in creasin g q u a n t i t i e s of p l a t i n u m -c o n t a in i n g r e s i d u e s f r o m b o t h t h e n i c k e l c a r b o n y l p r o c e s s a n d t h e e l e c t r o l y t i c o p e r a t i o n s in C a n a d a
then the separation of the insoluble metals rhodium , ru th e n iu m an d iridium, was described in a paper by C a r l Langer and C u th b e rt J o h n s o n given to the Em pire M ining an d M etallurgical Congress held in T o ro n to in 1927 (26). T h e n in 1929 the M o n d Nickel C om pany, now led by L u d w ig s son Alfred, created Lord M elchett in 1928, m erg e d w ith the International Nickel Com pany, the prim ary reason for this b e in g the developm ent of a new copper-nickel deposit, nam ed after its discovery the Frood mine, which was owned partly by each company. T h e mineral was richer in nickel th a n the other C a n a d ia n ores, this m eaning of course a higher c o n te n t of the p latin u m metals. Until now only a small proportion of these elem ents had been recovered by International Nickel, m ainly from an electrolytic c o p p e r refining process th at left them in the anode residues, but following the u n io n with M o n d all platin u m metal refining was consolidated at Acton and the c o m p a n y becam e the w o rld s largest producer, a position it continued to hold u n til the growth of the South African platinum mines that will be described in C h a p t e r 23. Production rose to 300,000 ounces of total platinum metals a year a n d the m arketing was entrusted to Charles Engelhard and his organisation, this again giving him dom inance of the situa tion for a time. In 1937 a m ore up-to-date a n d detailed account of refining operations at
380
Acton, and of the complex chemical engineering problem s involved, was given by J o h n s o n an d Atkinson (27).
P la tin u m M in in g in Alaska In 1933 an entirely new source of platin u m m ade its a p p e ara n ce in a quite unexpected q uarter, at Goodnews Bay on the Bering Sea coast of Alaska. Alluvial platinum had been discovered there in 1926 by a n Eskimo n am ed W a lter Smith while panning for gold. H a n d m ining began in the following year in the shallow gravels and continued until 1933, yielding some 3000 ounces of p la tin u m that was purchased by J o h n s o n M a tth e y for refining. T h e n in 1934 a dragline excavator a n d ancillary equipm ent were installed and the G oodnew s Bay M ining C om pany was incorporated. T o expand production a Y u b a dieselelectric dredge was bought and output rose to 37,000 ounces in 1938 in the short mining season from M a y to November. In th at year J o h n s o n M a tth e y con tracted to take the output on a long term basis, refining taking place in L ondon until a new refinery was built at the M alvern plan t of J. Bishop and Co. in
T h e on ly p r i m a r y s o u r c e o f t h e p l a t i n u m m e t a l s in t h e U n i t e d S t a t e s lies o n t h e wes t c o a s t o f A l a s k a w h e r e t h e G o o d n e w s B a y M i n i n g C o m p a n y b e g a n d r e d g i n g o p e r a t i o n s in 193 5. B e fo r e t h e s e c a n b e g i n e a c h s e a s o n , la s ti n g f r o m M a y to N o v e m b e r , s o m e t e n t h o u s a n d tons of ice h a v e to b e r e m o v e d f r o m t h e w o r k i n g a r e a a n d t h e d r e d g e c a n t h e n r e a c h t h e p l a t i n u m - b e a r i n g g r a v e l s l y in g fifty f e e t below w a t e r level
381
W h e n o p e r a t i o n s b e g a n a t G o o d n e w s B a y t h e o n l y h a b i t a t i o n w a s a sm a ll t r a d i n g po st in a log c a b i n . W h e n a p o s t office a n d a g e n e r a l s t o r e w e r e e s t a b l i s h e d t h e r e a y e a r l a t e r a n o fficial n a m e h a d to b e a d o p t e d f o r t h e s e t t l e m e n t a n d P l a t i n u m " w a s c h o s e n
Pennsylvania in 1939. A detailed account of the development of the Goodnews Bay property, the only prim ary source of p latin u m in the U nited States, and also a n im portant source of iridium, was given by their Vice-President, Charles J o h n s to n in 1962 (28).
R e fe re n c e s fo r C h a p te r 20 1 E. Baruel, Phil. Mag., 1822, 59, 171-179 2 Sir E d w ard T h o rp e, Essays in H isto rical C hem istry, L ondon, 1911, 577 3 P. H. O Neill, M in. E n g , 1956, M a y , 496-500 4 J. C loud, Trans. Am. Phil. Soc., 1818, 1, 161 165 5 T . C ooper, Emporium Arts and Sciences, 1813, 1, 181 6 J. E. B ollm ann, ibid., 1, 344 346 7 J. A. C haldecott, Platinum M etals Rev., 1981, 25, 163 172 8 E. C hild, T h e T ools of the C h em ist, New York, 1940, 150 9 E. F. Sm ith, T h e Life of R o b ert H a re . P hiladelphia, 1917, 5 382
10 11
12
13 14 15 16 17 18 19 20
21
22
23 24 25 26 27 28
A non, Chem. News, 1894, 70, 234 J. C loud, Trans. Amer. Phil. Soc., 1809, 6, 407-411 G. K auffm an, Platinum M etals Rev., 1972, 16. 101-104 W. G ibbs, A m e r.J . Sei., 1861, 3 t 63-71; 1862, 34, 341-356; 1864, 37, 57-61; Chem. News , 1861, 3, 130-131, 148-149; 1863, 7, 61-63, 73-76, 97-98; 1864, 9, 121-122 W . G ibbs, anal. Chem., 1864, 3, 334 335 W. H. W ahl, G alvanoplastie M a n ip u latio n s, P hiladelphia, 1883, 354 364 W. H. W ahl, J . Frankin Inst., 1890, 30. 62-75 G. K auffm an, J . Chem. Ed., 1968, 45, 804 811; Platinum M etals Rev., 1972, 16. 140-144 T . A. Edison, Proc. Amer. Assoc. Adv. Sci., 1880, 173-177 T . A. Edison, U.S. P aten t 307,031 of 1884 L. de Forest, U.S. P aten t 841,387 of 1907 H. L. W ells an d S. L. Penfield, Am . J . Sei., 1889, 37, 67-73 F. W. C lark e an d C. C atlett, A m .J . Sei., 1889, 37, 372-374 L. M ond, C. L anger an d F. Q uinke, J . Chem. Soc., 1890, 57, 749-753 L. M o nd an d C. Langer, Proc. Roy. Soc., 1889, 46, 296 304 L. M ond, W. R am say an d J . Shields, Proc. Roy. Soc., 1895, 58, 242 243; 1897, 62, 50-53 C. L anger an d C. Jo h n so n , Trans. Inst. Canad. M in . M et. Soc., 1927, 30, 903-909 C. Jo h n so n an d R. H. A tkinson, Trans. Inst. Chem. Eng., 1937, 15, 131 149 C. Johnston, Platinum M etals Rev., 1962, 6, 68-74; South Ajr. M in . Eng. J ., 1962, June 15, 1297-1302
383
F r ie d r ic h W ilh e lm O stw ald 1853-1932 Born in Riga, and for some years Professor of Chem istry there. Ostwald accepted a similar chair in Leipzig in 1887 and established a leading school of physical chemistry. His m ajor achievem ents were in research in catalysis and the developm ent of the am m onia oxidation process for the m anufacture of nitric acid and thence of fertilisers. For this he was aw arded the Nobel Prize for Chemistry in 1909
21
The Growth of Industrial Catalysis with the Platinum Metals
/ / one considers that the deceleration o f reac
tion by catalytic means occurs without expenditure o f energy or material, and is in this sense gratis, it is evident that the systematic use o f catalysts m ay lead to the most far-reaching advances in technology.
W I L H E L M OSTW \ L I ) . 1901
T h e discovery of the great activity of p latinum and palladium in the catalysis of chemical reactions and the early researches of the two Davys, Dbereiner, Faraday and others were reviewed in C h a p te r 12, together with the famous patent of Peregrine Phillips of Bristol in 1831 and the early practical applica tions of Frdric K u h lm a n n in the production of sulphuric a n d nitric acids in his chemical works in France in 1838. For almost forty years no progress was m ade in the further application of catalysis in industry. T h e phenom enon was but little understood, while the chemical engineering techniques required to handle gases at high tem peratures had not been developed. But as the dyestuffs industry grew the need for more concentrated sulphuric acid increased and two independent steps were taken in 1875. T h e n Dr. R udolph Messel (1848 1920), who had come to L ondon five years earlier after studying chemistry in Zrich, Heidelberg and T b in g e n to jo in William Stevens Squire (1835-1906), later to found the firm of Spencer C h a p m a n and Messel, devised a process of producing oleum by passing the vapour of ordinary sulphuric acid over platinised pum ice at a red heat. T h e patent was filed in S q u ire s nam e only (1), and the process was put into o p e ra tion, an account being given to the Chem ical Society (2). Almost simultaneously a paper was published by Clemens W inkier (1838-1902), Professor of C hem istry at the Freiberg School of M ines, in which he proposed the use of platinised asbestos in what was virtually Peregrine Phillips m ethod of employing sulphur dioxide and oxygen in stoichiometric proportions (3). W inkler did not p a te n t his process, but used it in a chemical works in Freiberg of which he was a director.
385
R u d olf T h eop h il J o sef K n ielsch 1 8 5 4 -1 9 0 6

\ n a t i v e of O p p e l n in w h a t is now Poland, knietsrh first becam e a m e c h a n i c a n d t h e n s t u d i e d c h e m i s tr y in B e rl i n . In 1884 he j o i n e d (he B a d isch e \ n i l i n und Soda F ab rik a n d c a r r i e d o u t a long a n d s u c c e s s fu l i n v e s ti g a t i o n o n t h e p r o d u c t i o n o f s u l p h u r i c a c i d by (h e o x i d a t i o n o f s u l p h u r d i o x i d e o v e r a p l a t i n u m c a t a l y s t . H is stu d y of varying conditions of t e m p e r a t u r e , t h e r a t e of flow o f t h e r e a c t a n t s a n d t h e p o i s o n i n g of th e c a t a l y s t by a r s e n i c a l f u m e s m a d e p o s s i b l e t h e l a r g e sc a l e p r o d u c t i o n of a c i d by t h e c o n t a c t p r o c e s s w h i c h t h e n b e g a n to s u p e r s e d e t h e l e a d c h a m b e r m ethod
P h o t o g r a p h In rourt*s\ of Ita riische Anilin ii ih I S o d a Kahr ik
However, his m ethod pointed th e way for others until the researches of R udolf Knietsch at the Badische A nilin u n d Soda Fabrik. In a lecture given to the D eutschen Chem ischen Gesellschaft in 1901 (4) he reported a n extensive series of investigations on the behaviour of platin u m catalysts in varying conditions of tem perature and showed clearly that the concept of using a stochiometric m ixture of gases was fallacious. T h e contact process thus began to replace the lead cham ber process (and so t h e days of the p latinum boiler was also n u m bered) first in G erm any and th en in England and the U nited States. Very large quantities of platinum were c o nsum ed over a long period but during W o rld W a r I the supply in G erm any was interrupted an d as a substitute vanadium pentoxide was used and began to be adopted in about 1926 by A m erican acid m anufacturers and later in E ngland.
T h e M anu factu re o f N itric A c id W hile the use of a platinum catalyst for the p roduction of sulphuric acid becam e one of the few applications of p la tin u m to fall away, a very different state of
386
affairs has characterised the production of nitric acid and here p latin u m is still in use in large quantities. During the latter years of the nineteenth century discussion began to arise among m en of science who were interested in the b roader issues of their subject on what later becam e known as T h e N itrogen P ro b le m . Typical of the exposi tions which now an d then reached even the public press was the Presidential Address given by Sir W illiam Crookes to the British Association for the Advancement of Science at its Bristol meeting in Septem ber 1898 (5). Crookes was concerned to show that at the prevailing rate of increase of p opulation the w orlds supplies of wheat would soon prove insufficient, and that the land would not continue to produce the sam e yield year after year unless adequate quantities of nitrogenous m an u re were ploughed back. H e appealed to the chemist to help remove the fear of famine by establishing a m eans of fixing atm ospheric nitrogen, since the only available source Chile saltpetre might be exhausted in a comparatively short period of years. T his problem, of obtaining from the unlim ited supplies of uncom bined nitrogen in the atm osphere those com pounds principally am m onia an d nitric acid - required for agricultural needs, was soon intensified by the realisation in a num ber of E u ro p e an countries th at a precisely similar need for assured supplies of nitric acid existed in the m anufacture of explosives, and that in the event of w ar the Chile nitrates m ight well prove to be inaccessible. This is not to say that such thoughts inspired governm ental action in any p a rt of Europe; they were, in fact, confined to but a handful of scientists who could forersee their countries long-term needs. O n e such m a n was Professor Wilhelm Pfeffer, (1845-1920), the famous botanist of the University of Bonn who in 1901 expressed his concern about the need for supplies of fixed nitrogen to his friend in the University of Leipzig, Professor W ilhelm O stw ald. A t this time O stw ald had occupied the C h a ir of C hem istry at Leipzig for some fourteen years and had built up a school of physical chemistry, devoting m uch of his energy to investigating the effects of catalysts on chemical reactions. His response to Pfeffers representations was immediate; it was obviously his duty as a chemist to play his part in m aking his country independent of Chile saltpetre, and in obtaining nitric acid from other sources. T w o possible lines of investigation presented themselves. E ither free nitrogen an d oxygen from the air could be combined, or am m onia, th en readily available from the gas industry, could be oxidised to give nitric acid. As it seemed m ore simple to re-combine nitrogen which was already fixed th a n to fix free nitrogen, O stwald decided to give his attention to the oxidation of amm onia. T h e reaction was known, a n d O stw a ld would have been well aware of the earlier work of K uhlm ann. It was clear to him that the theoretical basis of the a m m onia oxidation reaction would have to be elucidated before it could be developed on a large scale, and experiments were begun by Dr. E b e rh ard Brauer, at th at time O s tw a ld s private assistant. T h e first experiments were m ade using a clean glass tube only a few milimetres in diam eter containing
387
T h e h i s t o r i c a p p a r a t u s w ith w h i c h O s t w a l d a n d B r a u e r first s t u d i e d t h e oxidation of a m m o n ia o \ e r a p la tin u m c a t a l y s t to p r o d u c e n i t r i c a c i d in t h e I n i v e r s i t y o f L e i p z i g in 1901. T h e investigation sh o w ed that the c o n v e r sion was p r a c t i c a b l e a n d r e l a t i v e l y s i m p l e b u t m a n y p r o b l e m s h a d to b e solved b e fo re a c o m m e rc ia l process could be d e \ eloped
platinised asbestos. A m m onia a n d air were passed over the catalyst in known quantities and with known velocities, and it was at once clear th at the conversion to nitric acid was practicable a n d relatively simple to carry out, although some difficulties lay in the absorption of the reaction products. T h e historic a p p a ra tu s used at this stage is shown above. T h e first experiments using platinised asbestos gave only small yields and a platinum -lined tube proved little better. A new reaction tube was therefore made, consisting of a glass tube 2 m m in diam eter in which was coiled a strip of p latinum about 20 cm long. T h e w hole tu b e was heated to redness, a n d the first experiment gave a converison of m o re th a n 50 per cent, while increasing the gas velocity gave a converison of 85 p e r cent. Investigations were then ca rrie d out on the effects of variations in the am m onia: air ratio, in the time of contact an d in the tem p e ra tu re of the catalyst. T h u s were laid the foundations o f a technical process for producing nitric acid from ammonia, but the tra n sla tio n from idea to practice presented m any problem s before the project was b r o u g h t to fruition. O stw ald filed patents for his procedure in 1902 (6) although his G e rm a n pa te n t was disallowed on account of K u h lm a n n s earlier disclosures. A small factory was m ade available to O stw a ld an d Brauer, and here a pilot
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By 19 0 4 a p ilo t s c a l e a m m o n i a o x i d a tio n p l a n t c o m p r i s i n g t h r e e r e a c t o r s h a d b e e n b u i l t in a s m a ll p o w d e r factory p u t a t O s t w a l d s d i s p o s a l by t h e D i r e c t o r of t h e G e r m a n E x p lo s iv e s C o m b in e. P o ro u s p la tin u m sheets w ere u se d as th e c a t a l y s t s , a y ield o f 75 p e r c e n t o f n itric a c i d w as o b t a i n e d , a n d it w as d e c i d e d to e r e c t a l a r g e r p l a n t to p r o d u c e 3 0 0 k i l o g r a m s of a c i d a d a y
plant was developed. By 1904 the three converters illustrated above h a d been built and operated, and it was decided to erect a larger-scale plant at the Gewerkschaft des Steinkohlenbirgwerks Lothringen at G erthe, near Bochum, to produce 300 kg per day of nitric acid. This plant was brought into operation in M a y 1906 and fully proved the feasibility of the process. A larger-scale plant was then designed and built, and by the end of 1908 was producing some three tons of 53 per cent nitric acid per day. T h e catalyst used at this time consisted of a roll of corrugated p la tin u m strip about 2 cm wide a n d weighing about 50 g, heated initially by a hydrogen flame. T h e life of the catalyst was no more th a n a m o n th or six weeks. T h e disadvantages of the process included the relatively large a m o u n t of platinum required per unit of acid produced, and the uncertainty of tem p e ra tu re control of the catalyst, but improvements were not long wanting.
T h e P la tin u m G au ze Catalyst Professor Karl Kaiser, of the T echnische Hochschule, C harlottenburg, attacked the problem, and filed patents in 1909 covering the pre-heating of the air to 300
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or 400C and the use of a layer, usually four in num ber, of platin u m gauzes. H e was the first to employ p latin u m in the form of gauze, and it is a tribute to his experimental skill that the precise form of gauze he settled on - wire 0.06 millimetre diam eter woven to 1050 mesh per square centim etre - is still very largely employed. By 1912 K a is e r had a pilot plan t in operation at Spandau, Berlin, but while this was inspected repeatedly by British, F rench and A m erican industrialists, he failed to interest them in his process, although a plant was erected at Kharkov in Russia. F urther work was carried o u t by N ikodem C a ro a n d A lbert Frank at the Bayerische Stickstoffwerke. Several patents were filed during 1914, the process being based upon a single p la tin u m gauze which was electrically heated. Progress was slow for a time, a n d num erous experimental plants failed, but the outbreak of w ar gave a m uch g re a te r urge to the project and by 1916 the picture h a d changed radically. T h e F r a n k an d C aro converter ha d by then been engineered by the Berlin-Anhaltische M a sc h in e n b au A.G. (B A M A G ), who had constructed m ore th an thirty plan ts, first for the supply of nitric oxide to lead cham ber sulphuric acid plants a n d later for nitric acid production. T h e single platinum gauze was subsequently replaced by multiple gauzes, a n d the electrical heating was discontinued. T h is type of plant supplied all the nitric acid required for explosives in G e r m a n y during the later years of the war. T h e converter had a diam eter of 20 inches, the catalyst consisting of a layer of three p latinum gauzes woven from 0.006 inch diam eter wire of 80 m esh to the linear inch, operating at about 700C. A m uch greater catalyst life w a s obtained in this design of plant, extending to six m onths provided that conditions were uniform and th at the gases were free from impurities that might have a poisoning effect.
T h e Synthesis o f A m m o n ia Shortly after O s tw a ld s developm ent of the am m onia oxidation process the raw material began to become more readily available. T h e same considerations on the great im portance of the fixation of nitrogen p ro m p te d Fritz H a b e r (1868-1934), then an assistant professor at the K arlsruhe Technische Hochschule, to investigate the catalytic form ation of am m o n ia from its elements, nitrogen and hydrogen. This rea c tio n h a d already been studied in 1881 by George Stillingfleet Johnson, a d e m o n stra to r in chemistry at K in g s College, London, who obtained am m onia in small q u a n tity by passing the two gases over heated platinum sponge (9), a n d O stw a ld had given some consideration to the process in 1904, but H a b e r established th a t a successful process depended upon the reaction being carried out u n d e r high pressure an d at a high tem perature. T h e investigation was taken over in 1909 by the Badische Anilin und Soda Fabrik who assigned Carl Bosch (1874-1940) to carry the project further. H a b e r h a d employed osmium as his c a ta ly st (10) b u t the comm ercial success of the process required a metal that w a s both less expensive an d available in greater
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quantity, and after some twenty thousand experiments by Alwin M ittasc h (1869-1953), the head ofcatalyst research at BASF, a so lu tio n w a s finally arrived at with a mixture of iron and its oxides. Both H a b e r and Bosch were aw arded Nobel Prizes for Chemistry, the latter com m enting on the initial experim ents at high pressures in the course of his address:
T h e two co n tact tubes, m ad e by M an n esm a n n , h a d an o p eratin g life of eighty hours, th en they bu rst. If we h ad filled them w ith osm ium in stead of th e new catalyst the entire w orld stock of this precious m etal, w hich we had by now bought, w ould have disappeared. (11)
T h e P r o d u c tio n o f N itric A cid in A m erica

At the beginning of the 1914 w ar the U nited States possessed no source of nitric acid other th a n Chile saltpetre, and it becam e distressingly evident th at the nation was dependent upon a foreign country in this respect, while the pro d u c tion of nitric acid from this starting-point required large quantities of sulphuric acid already in short supply. C yanam ide had been m anufactured at N ia g a ra Falls since 1909, and in 1916 the first A m erican plant for the oxidation of am m onia produced from cyanam ide was established by the A m erican C y a n a m id C o m p a n y at W arners, New Jersey. T h e catalyst employed was a single platinum gauze, electrically heated. I n the meantime, the ordnance departm ent had decided to take action, an d Dr. C. L. Parsons, of the Bureau of Mines, was asked to investigate E u ro p e a n m ethods for nitrogen fixation. As a result the A m erican C ya n a m id C o m p a n y was requested, in 1917, to form a subsidiary company, A ir N itrates C orporation, to act as agent for the United States Governm ent for the construction a n d operation of a plant at Muscle Shoals, Alabam a, to produce 110,000 tons a year of am m onium nitrate. This plant comprised some seven hu n d red catalyst units each containing a single rectangular p latinum gauze woven from 0.003 inch diam eter wire, 80 mesh, and heated electrically to 750C. T h e total weight of p latin u m was a little over 300 oz, an d the loading ratio about 1 kg per daily ton of am m onia.
D e v e lo p m e n ts in A m m o n ia O x id a tio n in Great Britain T here had been little or no commercial interest in nitrogen fixation in G reat Britain before the outbreak of w ar in 1914, and th ro ughout the w a r period the supply of nitrogen products for m unitions depended almost entirely on shipments of C hilean nitrate. T here were, however, a n um ber of attem pts to m ake nitric acid by the o xida tion of ammonia, either from gas-liquor or cyanam ide. A n O stw a ld plant was set up at D agenham Dock by the N itrogen Products C o m p a n y in 1916 1917, but never achieved successful operation. T h e G as Light a n d Coke C o m pany developed a plant at Beckton using a p a d of three or four flat p la tin u m gauzes as catalyst, and attained an output of a ton of nitric acid per day. A systematic investigation was undertaken, at the instigation of the Nitrogen
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S ir Eric R ideal
I890-1974 E d u c a te d at T rin ity College. C a m b r i d g e . a n d t h e n a t t h e U n i v e r s i t y of B o n n . B i d e a l s e r v e d in t h e B o y a l E n g i n e e r s in W o r l d W a r I b u t w as i n v a l i d e d o u t in 1 9 1 6 a n d t h e n j o i n e d th e M u n itio n s Invention B oard t o g e t h e r w i t h J . B. P a r t i n g t o n , J. A. M a rk e r , H . C. G r e e n w o o d , E. B. M a x t e d a n d o t h e r s wi t h t h e o b j e c t of e stab lish in g the a m m o n ia o xidation p r o c e s s i n E n g l a n d . E a r l i e r , w h i l e on l e a v e f r o m F r a n c e , h e h a d s t u d i e d th is r e a c t i o n in t h e I n s t i t u t e of C h e m i s t r y in L o n d o n . T h e p r o j e c t , c a r r i e d ou t at U n i v e r s i t y C o l l e g e , L o n d o n , led to t h e c o n s tru ctio n o f a successful co n v e rte r b u t o n a v e r y s m a l l sc ale. H i s d i s t inguished career included much i m p o r t a n t r e s e a r c h in c a ta ly s is
Products Com m ittee, by J. R. P a rtin g to n , E. K. (later Sir Eric) Rideal and others and was carried out in the laboratory of the M unitions Inventions D e partm ent (13). A n effective design of converter was evolved, employing either an electrically heated pa d with two gauzes or a thicker p a d th at was selfsustaining in tem perature w h e n reaction had been established. Somewhat similar converters were con stru c te d by B runner M o n d & C o m p a n y and by the U nited Alkali Com pany, both of w h o m tu rn e d to J o h n s o n M a tth e y for advice on the production of the catalyst gauzes. Although it cam e too late to b e of service in the war, the decision taken in 1917 to erect a synthetic a m m o n ia p lan t using the H aber-B osch process led directly to the building of the B illingham plant by Synthetic A m m onia and N itrates Ltd. (now Imperial C h em ical Industries Ltd.). T h e am m o n ia plant first cam e into operation in D e c e m b e r 1923 and the nitric acid plant - tne first successful large-scale plant in th is country during 1927. A n account of the early years of this development h a s been given by A. W. H olm es (14). Although the process rem ains unchanged in principle a n d even in some details such as the mesh sizes of t h e gauze pads - the size an d complexity of the plant units has been trem endously increased.
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T he platinum gauze catalyst, s u p p l i e d by J o h n s o n M a tth e y . used in the researches carried out for the Munitions Invention D epart ment in 1916. Measuring only six inches by four inches, it comprised two gauzes m o un ted in an alum inium fram e with silver leads for the heating current
After the war the work of the Munitions Invention D epartm ent was taken over by B runner Mond and Com pany (later to become part of Im perial Chemical Industries) and this atm ospheric pressure am m onia oxidation plant was installed at Billingham in 1927. T he platinum gauzes were twenty inches in diam eter, by contrast with those now employed running up to five metres in diam eter
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From the 50 grams of c o rru g a te d foil in a n O stw a ld unit, the weight of platinum in a single converter has steadily increased until it m ay now reach from 20 to 30 kilograms, while the diam eter of the rh o d iu m -p latin u m gauzes, introduced in 1928 by E. F D u P o n t as a n improvement on the p u re platinum formerly used ( 15), can be as grea t as five metres.
T h e M anu factu re o f H y d r o g e n C y a n id e
A nother process, developed so m e years later by Leonid Andrussow, like O stw a ld a native of Riga, at the I.G . F a rbenindustrie plan t in M a n n h eim , also makes use of woven gauzes of rh o d iu m -p la tin u m alloy to convert methane, am m onia and air to hydrogen cyanide (16). T h is is required in enormous quantities for the m an u fa ctu re of acrylic resins such as polymethyl methacrylate, known in B ritain as Perspex, in A m erica as Lucite an d in G e rm a n y as Plexiglas, and adiponitrile, an interm ediate in the production of Nylon (17). O p erating tem p e ra tu re s in th e process are appreciably higher than in am m onia oxidation plants, ran g in g up to 1200C, so th at the m echanical strength of rhodium -platinum at high tem peratures and its resistance to oxida tion play an im portant role in a d d itio n to its catalytic activity.
C atalysis in th e O rganic C h e m ic a l In d u stry T h e wider adoption of catalytic reactions with the p latin u m metals in the m anufacture of organic chemicals, eventually to achieve im m ense significance in the pharm aceutical, dyestuffs, plastics a n d synthetic fibre industries, occurred m uch later th a n was the case w ith inorganic products. A great deal of the basic research had been carried out by t h e beginning of the twentieth century and even before, but the transition into com m ercial applications was slow in development. As early as 1874 Professor P ro s p e r de W ilde of the University of Brussels discovered that acetylene could b e hydrogenated to ethylene an d then to ethane over a platinum catalyst (18) w hile in 1894 Professor Paul S a batier and his assistant the A bb J e a n Baptiste Senderens (1856-1936) at the University of T oulouse published the first of th e ir very num erous papers on catalysis (19). Sabatier had been intrigued by L u d w ig M o n d s discovery in 1890 of the reaction betw een nickel and carbon m onoxide (page 377) a n d in 1902 he an d Senderens reduced carbon monoxide to m e th a n e over a nickel catalyst (20). By 1911 Sabatier had reported at length o n the m an y hydrogenation a n d dehydrogena tion reactions that could be c a rrie d out in the laboratory and he becam e the leading authority on catalysis of his tim e although he m ad e no attem pt to introduce any industrial processes. F in e ly D iv id e d P la tin u m a n d P a lla d iu m M u c h of the early work involved th e use of very finely divided metals, generally in a colloidal state. Carl Ludwig P a a l (1860-1935) Professor of C hem istry in the University of Erlangen and later in Leipzig, m ade a long series of studies on the
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P aul S a b a tier 18 5 4 -1 9 4 1
B o r n a t C a r c a s s o n n e , a f t e r s t u d y i n g at t h e E c o l e N o r m a l e in P a r i s S a b a t i e r b e c a m e a n as sistant to M a rce li n Be rth elo t a t t h e C o l l e g e d e F r a n c e . In 1 8 8 2 he m o v e d to T o u l o u s e , b e i n g a p p o i n t e d P r o f e s s o r o f C h e m i s t r y in 1 8 8 4 a n d r e m a in in g th e r e for th e r e m a i n d e r of h is l ife d e s p i t e a n o f f e r o f a c h a i r at the S o r b o n n e in s u c c e s s i o n to M o i s s a n . H e w a s a p i o n e e r in t h e field o f c a t a l y s i s a n d w a s a w a r d e d t h e N o b e l P r i z e in c h e m i s t r y f o r this w o r k in 1 91 2. H is m any p a p e rs on th e subject w ere s u m m a r i s e d . t o g e t h e r w ith t h e w o r k of o t h e r s , in h is b o o k . L a C a t a l y s e en C h i m i e O r g a n i q u e " \ p u b l i s h e d in 1913
preparation of colloidal platinum and palladium and of their effectiveness on catalytic reactions (21) while A ladar Skita (1876 1953), Professor of C hem istry at Karlsruhe, pursued similar investigations on the hydrogenation of aldehydes and ketones with colloidal platinum and palladium (22) a n d the two collaborated in 1909 in filing a p atent for causing these reactions (23). But the use of colloidal preparations was not a practical proposition outside the laboratory because of the difficulty of separating them from the reaction products and attention turned to the so-called blacks , a finely divided form of the metal containing a n uncertain am ount of oxygen. Platinum black had been discovered by Dobereiner in 1833 (page 222), although the product described by Zeise in 1827 (page 264) was possibly of the same nature, b u t a reliable m ethod for its preparation was first devised by O sc a r Loew (18441941), a plant physiologist in M unich, in 1890 (24). His m ethod was improved by R ichard W illstatter (1872-1942) in 1912 while he was for a period D irector of the K aiser W ilhelm Institute after a long series of investigations on the hydrogenation of aromatics (25). Professor Gustave Vavon of the University of N ancy also carried out a massive research on the hydrogenation of aldehydes an d ketones in the presence of platinum black, describing these in his doctoral thesis to the
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Roger Adams 1889-1971

\ graduate of Harvard. Adams spent some time studying under Professor Richard ^ illsttter at the Kaiser ^ ilhclrn Institute in Berlin and in 1916 he was appointed Professor of Chemistry at the I niversity of Illinois where, apart from intervals of govern ment service during two world wars, he remained until his retirement. Under V illsttter he had been engaged in the i preparation of platinum black for use as a catalyst and on his return from the first war in 1919 he successfully developed a procedure for its produc tion in a state of high activity and reliability. This useful catalyst still bears his name and is widely used, particularly in the pharmaceutical industry
University of Paris in 1914 (26), while V ladim ir Ipatieff (1867 1952) in St. Petersburg, another prolific w o rk er in catalysis, after a series of investigations with nickel, studied a num ber of catalytic reductions with palladium black in 1912(27). At about this time Nicolai D m itrievich Zelinsky (1861-1953) also began his long series of researches, converting cyclohexane into benzene with both platinum and palladium blacks as catalysts and continuing these investigations for m any years (28). During this early period, however, the platin u m blacks often showed a low or a varying activity and it was not until 1919, w hen the problem was tackled by Professor Roger A dam s who h a d spent some time u n d e r W illstatter at the Kaiser Wilhelm Institute, that a p r o d u c t of uniform activity was obtained con sistently. Searching for an active catalyst for organic reductions, A dam s and his students developed a successful p ro c e d u re for w hat is still known as A d a m s Platinum Oxide Catalyst (29). A n account of their work with com m ents by Professor A dam s himself may b e found in Platinum M e ta ls R eview (30). This
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catalyst was at first prepared by individual workers in their laboratories, but before long it cam e into use in the pharm aceutical industry and the dem and increased. Scaling up was u n dertaken by platin u m refiners in the U nited States, while in E ngland J o h n s o n M a tth e y c ollaborated with M a y a n d B aker to develop a process for its p rep aration in relatively large batches for use in a variety of liquid phase hydrogenation reactions (31).
S u p p o rte d P la tin u m a n d P a lla d iu m Catalysts T hese early forms of finely divided p latinum and palladium catalysts were, however, largely superseded by supported catalysts, m ore especially of palladium in the first place, to m ake more effective use of the metal a n d to enable a wider range of reaction conditions to be met. Am ong a great m any materials used as supports, including alum ina, asbestos and silica gel, the m ost generally useful has been activated charcoal, and palladium -on-charcoal catalysts have played an im portant p a rt in low pressure liquid phase hydrogenation reactions in the pharm aceutical industry to produce vitamins, cortisone and dihydrostreptom ycin among other products. T h e ir usefulness, an d also th a t of platinum -on-charcoal in one establishment, M erck of N ew Jersey, has been described by W. H. Jo nes (32). T h e G row th o f C o m m e r c ia l Processes Slowly processes based upon catalysis began to come into industrial use for the production in large quantities of chemicals that were otherwise difficult or impossible to produce, although not at first with p latinum metals catalysts. T h e first m ajor liquid phase processes were for the conversion of anim al and veget able oils into edible fats, generally with finely divided nickel catalysts. In gas phase reactions the first recorded processes, as m entioned earlier, was devised by Sabatier and Sanderens in 1902 for the production of m eth a n e from carbon monoxide an d hydrogen, also over a nickel catalyst (20) while, following up this work in 1923, a m ajor step forward was m ade by F ra n z Fischer (1877-1935) an d H a n s T ropsch (1889-1935) at the Kaiser W ilhelm Institut fur Kohlenforschung at MCilheim in the R uhr, in developing their well known syn thesis of liquid hydrocarbons by the gasification of coal and by reacting the hydrogen an d carb o n monoxide produced in the presence of a catalyst, first of cobalt and later of iron (33). But the great stimulus to the use of the p latinum metals as catalysts came when petroleum began to replace coal tar as the m ajor source of organic chemicals, and with the realisation that the p latinum metals, although more expensive initially, often displayed greater activity and m ade it possible to carry out commercially im portant reactions at appreciably lower tem peratures and pressures th a n those necessary with base metal catalysts. G re a te r product selectivity could be achieved, while the platinum metals could readily be recovered a n d recycled, making their use m uch m ore commercially attractive.
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T h e P r o d u c tio n o f H igh O c ta n e F u els a n d A ro m a tic C h e m ica ls

As long ago as 1894 Francis Clifford Phillips (1850-1920), Professor of Chem istry at W estern U niversity in Allegheny, Pennsylvania - another researcher well in advance of industrial exploitation - studied the n a tu re and constituents of the natural gas a n d petroleum found in his native state and carried out a long series of investigations on the oxidation of hydrocarbons over finely divided platinum , pa lla d iu m , iridium, rhodium and osm ium supported on asbestos (34). Before W orld W a r II the catalytic reforming of petroleum to increase the octane rating of petrol was in troduced in Britain, the U nited States and G erm any, using a m olybdenum o n alum ina catalyst, but this was found to be uneconomical and was superseded by a process developed by Universal Oil Products and known as P la tfo rm in g (35). T his was devised from the great expertise on catalysis built up in t h e later thirties u n d e r the leadership of Ipatieff a n d T r o p s c h , both of whom had b y then jo in e d U .O .P., and by one of Ipatieffs first students at Northw estern University, V ladim ir Haensel. T h e process involved the reforming of c ru d e n a p h th a s to arom atic hydrocarbons, particularly benzene, toluene a n d the xylenes, over a p latinum on alum ina
V l a d i m i r Ha e ns e l
Born in Germany. Haensel received his early training in Moscow and then under the leading catalytic expert Professor Vladimir Ipatieff at North western University in Elvaston, Illinois. He joined Universal Oil Products in 1937. working with Ipatieff who divided his time between teaching and directing research there for many years. His major con tribution was the development of a platinum on alumina catalyst that made it possible to produce not only high octane petrol but also a range of aromatic hydrocarbons from crude petroleum. The process, known as Platforming. has been adopted on a world wide basis. In 1964 he was a p p oin ted V ice-P resid en t and Director of Research at U.O.P., while in 1974 he was awarded the National Medal of Science by the U.S. Govern ment for his outstanding research in the catalytic reforming of hydrocar bons which has greath enhanced the econom ic value of our petroleum natural resources".
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One of the early Platforming units commissioned by British Petroleum for the produc tion of both high-octane petrol and a range of aromatic chemicals. The process, licensed from Universal Oil Products, employs a platinum-on-alumina catalyst and great numbers of plants of this type were erected in all parts of the world
catalyst, and apart from yielding the high octane petrol needed for m odern automobile engines opened the way to the trem endous growth in the production of synthetic fibres, plastics, synthetic rubbers, insecticides an d m any other chemical products. Catalyst requirem ents were m et by Universal O il Products for m any users, but in 1953 catalyst m anufacturing facilities were set up in the U nited Kingdom by Universal-M atthey Products, a subsidiary com pany of Universal Oil Products an d Jo h n so n M atthey, in order to meet the growing d e m a n d from E u ropean licensees of the Platforming process, while a few years later a similar plant was established in Cologne. T h e initiative taken by Universal Oil Products was quickly followed by others in the petroleum industry in developing broadly similar reforming processes employing platinum catalysts (36). In fact the response was enormous, and by the mid-1950s plants were being built in m any countries of the world (37). Platinum reforming becam e one of the most versatile procedures available
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to the oil industry - as well as a m a jo r user of p la tin u m - and has continued to provide a wide range of interm ediates for the chemical industries. T h e benzene produced has many uses, including the m anufacture of styrene an d polystyrene, of cyclohexane for the production of Nylon (first discovered by W. H. Carothers whose doctoral thesis under Professor Roger A d am s dealt with the catalytic hydrogenation of aldehydes with p latin u m black (29)), as well as of phenol for phenolic resins, dichlorobenzene for dystuffs an d maleic an h y d rid e for polyester resins. T h e toluene produced finds extensive use as a solvent for nitrocellulose lacquers, while ortho-xylene yields phthalic anhydride for plasticisers, dyes and pigments and para-xylene is u sed to produce terephthalic acid for polyester fibres. T h u s the m any types of synthetic m aterials th at provide our fuel, our clothing and the m any other items m ade from plastics depend for their production upon large-scale industrial processes in w hich the vital p a rt is played by platinum .
R e f e r e n c e s for C h a p te r 2 1
1 2 3 4
W. S. Squire, British Patent 3278 of 1875 R. Messel and W. S. Squire, Chemical News, 1876, 33, 177 C. Winkler, Poly. J .( Dingier), 1875, 218, 128-139 R. Knietsche. Ber. Deutsh. Chem. Gesellschaft. 1901, 34, 4069-4115; J . Soc. Chem. Ind., 1902, 21, 172-173
5 Sir William Crookes, British Association Report, 1898,3-38 6 W. Ostwald, British Patents 698 an d 8300 of 1902; Chem. 'eitung, 1903, 27, 457-458 7 K. Kaiser, German Patent 271,517; British Patent 20,325 of 1910; U.S. Patent 987,375 of 1911 8 A. Frank and N. Caro, German Patents 286991, 304269, 303822 9 G. S. Johnson, J . Chem. Soc., 1881, 39, 128 133 10 F. Haber, Elektrochem, 1910, 16, 244-246; Badische Anilin und Soda Fabrik, German Patent 223408 of 1910 11 E. Frber, Nobel Prize Winners in Chemistry, New York, 1953, 126 12 E .J. Pranke, Chem. and M et. Eng., 1918, 19, 395 396 13 Ministry of Munitions, Munitions Invention Dept., H.M.S.O. London, 1919; J. R. Partington and L. H. Parker, The Nitrogen Industry, London, 1923 14 A. W. Holmes, Platinum M etals Rev., 1959, 3, 2-8 15 E. I. Du Pont de Nemours, British Patent 306382 of 1928 16 L. Andrussow, German patent 549055 of 1932; angewand. Chem., 1935, 48, 593-595 17 J. M. Pirie, Platinum Metals Rev., 1958, 2, 7-1 1 18 P. de Wilde, Berichte, 1874, 7, 352-357
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21 22
23 24 25 26 27 28 29 30 31 32 33 34 35 36 37
P. Sabatier and J. B. Senderens, Comptes rendus, 1897, 124, 616 618; 1358-1361 P. Sabatier and J. B. Senderens, Comptes rendus, 1902, 134, 514 516; 689-691 C. L. Paal, Berichte, 1907, 40, 2201-2200; 1908, 41, 805-817; 2273-2282 A. Skita, Z- ongewand. Chem, 1913, 26. (i), 601-602 A. Skita and C. Paal, German Patent 230724 of 1909 O. Loew, Berichte, 1890, 23, 289-290 R. Willsttter and D. Hatt, Berichte, 1912, 45, 14641481 G. Vavon, Ann. Chim , 1914, 1, 144 200 V. N. Ipatieff, Berichte, 1912, 45, 3218 3226 N. D. Zelinsky, J . Russian Phys. Chem. Soc., 1912, 44, 274 275 V. Voorhees and R. Adams, J . Amer. Chem. Soc., 1922, 44, 1397 1405; W. H. Carothers and R. Adams, J . Amer. Chem. Soc., 1923, 45, 1071-1086 L. B. Hunt, Platinum M etals Rev., 1962, 6, 150-152 D. H. O. John, Chem. and Ind., 1944,43, 256 W. H. Jones, Platinum M etals Rev., 1958, 2, 86 89 F. Fischer and H. Tropsch, Brennstoff Chem, 1923, 4, 276-285; 1924, 5, 201-208 F. C. Phillips, Am. C hem .J. 1894, 16, 163-187; 255-277; 340-365; 406-429 V. Haensel, U.S. Patent 2,479,109 of 1949 S. W. Curry, Platinum M etals Rev., 1957, 1, 38-43; H. Connor, Platinum M etals Rev., 1961, 5, 9-12 B. M. Glover, Platinum M etals Rev., 1962, 6, 86-91
401
N ikolai S e m eno v ich R u rn a k o v

18 6 0 - 19 4 1 O n e o f the p r in c ip a l fo u n d e r s of the m o d e rn p la tin u m industry in the I .S .S .R .. K u r n a k o v was first a s tu d e nt an d th e n in 1893 P rofessor of In o rg a n ic C he m istry in the M in in g In s titu te in St. P e te rsb u rg . H is w ork o n the com plex c o m p o u n d s o f the p la tin u m m etals m a te ria lly assisted re fin in g m e tho d s an d on the d e a th o f C h u g a e v in 1922 he was a p p o in te d D irecto r o f the P la tin u m In s titu te
P h o t o g r a p h b ' ro u rte s > o f ih e lal* A c a d e m ic ia n I. I. ( h e r n \ a e \ a m i P r o fe s s o r ( i e o r p e K a u f f m a n
22
Production of the Platinum Metals in Soviet Russia
Entering again the w o r ld platin u m m a rk e t after the R evolution o f 1017, our country not only had to re-establish the fo r m e r ou tpu t o f platin u m but also to re-organise its extraction on the basis o f m odern technology.
O. E. Z V Y A G I N T S E V , 1 9 2 7
For m any years before the outbreak of the first world w ar the p latinum industry in Russia was dom inated by the E u ro p e a n refiners. T h e two large producers, C ount Demidov and C o u n t Schuvalov, were supplying them with large quantities of native metal from the Urals, while a small refinery a n d workshop had been set up in 1875 in St. Petersburg jointly by J o h n s o n M a tth e y and Desmoutis Q uennessen to meet the very limited R u ssian needs for platinum laboratory apparatus. T his control of the industry by foreigners was m uch resented by both the intelligentsia an d the politicians, and in 1910 a conference was arranged by the M inistry of T r a d e and Industry, presided over by Professor Kurnakov, to consider the question of the refining of p latinum in Russia. Recom m endations were made, but no action was taken, a n d then in 1913 the M inistry imposed a duty of 30 per cent on exported p latinum and a year later, on the outbreak of war, prohibited its export altogether. In the sam e year the setting up of a refinery was authorised and this was built at E k a terin b u rg (now Sverdlosk), the centre of the U ral m ining industry. T h e Q ue n n e ssen com pany was to take on the financing, H eraeus to provide a suitable engineer, and Joh n so n M a tthey to design the buildings an d plant, to provide the m ethods of refining and to prepare and ship the equipm ent. T h e first local collaborator was the largely uncom m itted mining concern, the Nikolai-Pavdinsky M ining Com pany, which was to find the site and to build the refinery. M a n y delays occurred, however, and it was not until after the o utbreak of w a r in A ugust 1914 that building began. O perations began on a small scale in 1915 with N. N. Baraboshkin, a former student of K urn a k o v s at the M ining Institute of St. Petersburg, as manager, and by the end of 1917, when all R u ssian mineral
403
One of the American built dredges in operation in 1923 to extract native platinum from the alluvial deposits in the river b eds of the Urals. The operating season extended only from May until the end of N o vem ber. During the next five years several larger dredges were installed, the crude platinum b eing transferred to a refinery built at Sverdlosk
resources were nationalised, o u tp u t had increased to some 30,000 ounces a year. T h e refinery was then taken over by the new governm ent under the term s of a state monopoly for the production, refining an d m arketing of platinum . T h e general disorder during the first years of the revolution greatly reduced p ro d u c tion, however, which fell to only a r o u n d 6,000 ounces in 1922 ( 1).
A R esearch Institute for the P l a t in u m M etals D uring the w ar the shortage of platin u m for the contact process for the m anufacture of sulphuric acid h a d caused great concern - the large Tenteleev organisation in St. Petersburg h a d been producing acid by this process since 1900 - and in 1915 a commission w as set up for the study of all R u ssian natural resources, with a section devoted to p latinum u n d e r Kurnakov. A n appeal was m ade to Lev Aleksandrovich C hugaev, Professor of Chem istry at the University of St. Petersburg, an d as well as urging the creation of a state monopoly he proposed the establishment of a research institute for investigations on all the platinum metals, their m ethods of refining and analysis, their alloys an d their co-ordination compounds. After t h e revolution this scheme came to fruition and in 1918 Chugaev was appointed director of the newly formed In stitute for the Study of Platinum and other N o b le M etals (2). T h is organisation at once set out to provide the refinery with im proved m ethods, as well as conducting m any
404
Lev A le k s a n d r o v ic h C h u g a e v 18 7 3 -1 9 2 2
Born in Moscow where he studied at the University, in 1908 Chugaev be c am e P rofessor of Inorganic Chemistry in the I niversity of St. Petersburg. succeeding Mendeleev, and remained there until his early death at only forty-nine. Apart from his researches on platinum complexes he proposed the establishment of an institute for comprehensiv e research on the platinum metals, a project that came to fruition in 1918 when he was appointed the first Director of the Platinum Institute of the Academy of Sciences in Petrograd. now Leningrad
researches on the chemistry of the platinum metals, particularly on their co ordination compounds. T h e ir results were published in a jo u r n a i established in 1920, the Izvestia of the P latinum Institute, the first a n d for three decades the only jo u rn a l devoted exclusively to the p latinum metals (3). U nfortunately Chugaev died in 1922 at the early age of 49 and he was then succeeded by Kurnakov who continued to stim ulate the refinery m anagem ent at Sverdlovsk a n d to contribute to the study of the co-ordination com pounds of the p latin u m metals. In 1934 the P latinum Institute, the Institute of Physicochemical Analysis and the G eneral C hem istry L a boratory of the A cadem y of Sciences were combined into the Institute of General Chem istry in Moscow, with Kurnakov as Director. O n his death in 1941 this was re-nam ed the N.S. Kurnakov Institute in his honour. A n appreciation of his life and work has been compiled by Professor Kauffm an and will be published shortly (4). C h ugaevs proposal for a nationalised industry had, however, already been adopted w ith the form ation late in 1921 of a commercial trust, T h e State Association of Platinum M iners of the Urals, abbreviated to U r a lp la tin . T h e new organisation found th at nearly all the old dredges used to excavate the
405
IP y a Ilich C h e rn y a e v 1893-1966
A f o r m e r s t u d e n t o f C h u g a e v s, in 19 18 C h e rn y a e v jo in e d the In stitu te for the S t u d y o f P l a t i n u m o f t h e A c a d e m y of S c i e n c e s in P e t r o g r a d a n d r e m a i n e d th e r e u n tii h is d e a t h , s u c c e e d i n g K u r n a k o v as D i r e c t o r in 1 94 1 . T h e r e he c a r r ie d out im p o rta n t w o rk on the refining of the p la tin u m m etals a n d t h e i r p r e p a r a t i o n in a s t a t e o f hig h p u r i t y . H e w a s a ls o c o - e d i t o r of t h e Izvestia o f t h e P l a t i n u m I n s t i t u t e f r o m 1 9 4 7 u n t i l 19 55 w h e n it c e a s e d p u b l i c a tion
alluvial platinum from the river beds ha d ceased to operate for lack of spare parts, and new Am erican dredges were purchased, beginning in 1925 an d con tinuing for several years. T hey c o u ld operate only from M a y to D ecem ber as they were forced to stop working when the accum ulations of ice becam e too great (5). In 1921 a representative of J o h n s o n M atthey, M r. A. B. Coussm aker, then the c o m p a n y s mining engineer who h a d considerable experience in the p latinum fields in the Urals, secured an interview with M a x im Litvinov with a view to obtaining supplies of native metal for refining. Litvinov, later the Soviet A m bassador in London and t h e n Foreign M inister in Moscow, emphasised, however, that his government w a s well aw are of the extent to which the world was dependent upon R ussian supplies of platin u m a n d th at they firmly intended to do the refining themselves. Refining a n d separation of th e platin u m m etals progressed in the E k a terin burg plant under the guidance of B a ra b o sh k in an d with the close co-operation of
406
T o p u b l i s h t h e r e s u l t s o f r e s e a r c h in t h e newly f o u n d e d I n s t i t u t e for t h e S t u d y of P l a t i n u m a n d o t h e r N o b l e M e t a l s Chugae\ founded a journal, the fzvestia. first p u b l i s h e d in 1920. T h i s i n c l u d e d a m a s s i v e s e r i e s of p a p e r s by C h u g a o h i m s e l f a n d by his c o l l e a g u e s o n t h e c h e m i s t r y a n d m e t a l l u r g y of all th e p l a t i n u m m e t a l s . T h i s s h o w s t h e c o v e r of t h e v o l u m e f o r 1 93 6. w ith t h e title g iv e n in F r e n c h , a n d t h e n e d i t e d by N. S. k u r n a k o v a n d O. E. Z v y a g i n ts e v . The journal ceased p u b l i c a t i o n in 1955
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Kurnakov a n d his staff in improving the processes; high purity platinum , palladium, iridium and rhodium were successfully produced, and a state factory in Moscow carried out the fabrication work. By 1924 negotiations with the Russians yielded an agreem ent for J o h n s o n M atthey to take the whole of their output of refined metal for the following year, estimated at 70,000 ounces. T his was shared with the other E u ro p e an p latinum companies, and further quantities were m ade available on the sam e basis in 1926 and 1927, but then a m arketing com pany was set up in Berlin by the R ussian government for the direct disposal of their metal.
T h e D is c o v e r y o f P la tin u m in Sib eria Extraction of the alluvial p latinum in the U rals continued, an d a detailed survey of the mineral resources there was undertaken by a leading Swiss geologist, Professor Louis D uparc, with a R ussian assistant, M arguerite Tikanovitch (6), but it was realised that a search m ust be m ad e for the prim ary
407
A fter t h e d i s c o v e r y o f a l a r g e n i c k e l - c o p p e r o r e b o d y i n n o r t h - w e s t e r n S i b e r i a t h e e x t r a c tio n of t h e p l a t i n u m m e t a l s f r o m t h i s s o u r c e b e g a n to i n c r e a s e . In t h e e a r l y p e r i o d b e f o r e W o r l d W a r II t h e m i n e r a l w a s s h i p p e d to M u r m a n s k a n d t h e n to a r e f i n e r y a t M onchegorsk w h ere the nickel w a s refin ed electrolytically. the p la tin u m m etals a c c u m u l a t i n g in t h e a n o d e r e s i d u e s a n d t h e n b e i n g s e p a r a t e d a n d r e f i n e d i n d i \ du ally
rock from which these w a te r-b o rn e deposits em anated. In 1919 while prospect ing for coal, R ussian geologists discovered a large nickel and copper ore body in the far north-west of Siberia a n d in 1924, after some samples ha d been sent to Leningrad, this was found to c o n ta in the platin u m metals. Some years passed before any further action was ta k e n and then in 1935 the N o rilsk M ining and M etallurgical C om bine was established to exploit this large body of mineral. First of all a railway had to be b u ilt to link the future mining operations with the port of D udinka on the River Yenisei, open only for four m onths of the year. By 1938 the railway h a d been c om pleted despite the most h arsh Arctic conditions, and extraction operations co u ld begin. Initially the ore was shipped from D u dinka to M u rm ansk and th e n to M onchegorsk where a nickel refinery had been opened in 1938, but in 1940 N orilsk had its own smelter a n d refinery and becam e a vital source of nickel a n d copper during the second world war. T h e ore is first treated along similar lines to those in use at Sudbury, smelted to a m atte and the final refining of copper a n d nickel carried out by electrolytic methods. From these two last operations the anode residues containing the platinum metals are flown to a refinery b u ilt at Krasnoyarsk, the capital city of the region nearly a thousand miles to the s o u th on the T ran s-S ib e rian Railway. H ere the individual p latinum metals are s e p a ra te d and refined. By far the m ajor p a rt of the R ussian output of platinum m e ta ls now comes from this source.
408
In m o r e r e c e n t y e a r s a l a r g e s m e l t i n g c o m p l e x h a s b e e n b u i l t a t N o ril sk to r e f i n e b o th n ickel a n d c o p p e r . T h e final a n o d e r e s i d u e s a r e t h e n t r e a t e d a t a p l a t i n u m r e f i n e r y a t K r a s n o y a r s k , n early a t h o u s a n d m i l e s to t h e s o u t h
T h e ore-body at N o rilsk is, unlike the rich p latin u m m ineral from the Urals, m uch richer in palladium th a n in platinum , while the fact th at these metals emerge only as by-products from the extraction of nickel an d copper m eans that production is governed by the d e m and for these two base metals. O u t p u t figures for Russian p latinum are most difficult to establish, but pro d u ctio n has increased m any times since the opening of the N o rilsk operations in 1940 and for a time constituted the greater proportion of world supplies until it was sur passed by the increasing output from the South African mines, to be reviewed in the next chapter.
R e fe re n c es fo r C h a p t e r 22
1 2 3 4 5 6
E. K. Fritsman, Ann. Inst. Platine, 1927, 5, 23 74 G. B. Kauffman, Platinum M etals Rev , 1973, 17, 144 148 G. B. Kauffman, Platinum M etals Rev., 1974, 18, 142 148 G. B. Kauffman, Platinum M etals Rev., forthcoming J. B. Bubb, Eng. and M in. J ., 1928, 126, 284-286 L. Duparc and M. N. Tikanovitch, Le Platine et les Gites platiniferes de lOural et du Monde, Geneva, 1920
409
Arthur B lakeney Coussmaker 1885-1974

A fter gaining valuable experience in the platinum m ining area of the Urals prior to the 19141918 war C oussm aker was appointed a Director of Johnson Matthey and d eterm in ed to seek a m ajor new source of native platinum to expand th eir refining and fabricating activities. T he discovery of the Merensky Heef in 1924 m ade it possible for him to achieve this objective
From a p ortrait b> I)a \id Jaeg er in the possession of Joh nso n M atth e\
23
The Discovery of the W o rld s Greatest Platinum Resources
This alluvial platin u m must com e from s o m e w h ere in the surrounding basic rocks, a n d if only w e can find it in p a y a b le quantities in the m ain source, the m other reef, then w e w o u ld have d iscovered som ething f a r bigger an d f a r m ore im portant than the Russian and Am erican d e p o s its
H A N S M E R E N S K Y . 1 92 4
T h e cessation of supplies of crude platin u m from R ussia faced J o h n s o n M atthey with a serious problem and a challenge. T h is was taken up by A. B. Coussmaker, the c o m p a n y s mining engineer who h a d been appointed a director in 1925 a n d who now resolved to search tirelessly for new sources of platinum and to restore the pre-em inent position in the industry that had been built up by George M a tth e y an d J o h n Sellon. Before the first world w a r he had m ad e a series of prospecting missions in C anada, A ustralia an d N ew Z ealand without success, but an entirely new era was now about to open. Rum ours of p latinum being found in South Africa had begun to circulate in 1923 and ha d alerted a n um ber of prospectors. T h e n in J u n e 1924 a small bottle of greyish-white concentrates arrived by post in the J o h a n n e s b u rg office of the consulting geologist Dr. H a n s Merensky. T h is had been sent by H.C. D u n n e whose brother-in-law A ndries L om baard, a farm er with some experience of panning for gold, had found w hat he thought was evidence of p latinum in one of the streams on his farm at M aandagshoek to the north of L ydenburg in the Transvaal. Analysis quickly confirmed the presence of platinum , as well as of rhodium an d iridium, a n d M erensky imm ediately went to investigate. T ogether with L o m b a ard an d two of his wifes cousins, Schalk and W illem Schoem an, he examined a large stretch of country a round the stream a n d within a few weeks, with great geological insight and deductive reasoning, h a d located the basic mineral in a reef running parallel to the m o u n ta in range in a northerly direction and again in a southerly direction, extending in all some sixty miles. M e re n sk y s
411
first thought was to christen it T h e L o m b a a rd R e e f , but his colleagues over ruled him and it was nam ed T h e M erensky R eef . Finance was provided by a sm all syndicate, soon to become Lydenburg P latinum Limited, but this c o m p a n y was later taken over by a m ore substantial concern controlled by C o n solidated Gold Fields w ho began m ining operations. H a n s M erensky explored still fu rth e r a n d traced the reef at Potgietersrust to the north-west, and then m uch fu rth e r afield at R ustenburg, some sixty miles west of Pretoria, the indications in the latter area pointing to richer deposits. T his caused the emphasis to move away from L ydenburg an d Potgietersrust to R ustenburg an d so to the most re g u la r a n d most valuable p a rt of the platinum bearing reef. T h e Merensky Reef forms a layer in the Bushveld Igneous Complex, an irregular oval or saucer-shaped a r e a of some 15,000 square miles in the Central Transvaal. T h e reef varies in d e p th , from outcrops at the surface dow n to about 3,000 feet, but averages only th re e feet in thickness. A detailed account of its mineralogy was given in 1929 b y Dr. Percy A. W agner, for m any years the m ining geologist to the South A frican government, who not only dedicated his book on the platinum deposits a n d mines of South Africa to M erensky but wrote in his preface: The story of the opening up of these deposits - which transcend in magnitude and importance anything that had hitherto been dreamt of in the way of platinum
The beginning of the great discovery of the platinum metals in the Transvaal. Dr. Hans Merensky, standing on the left, is explain in g the features of the deposit to a party of \ isitors. including the then Prime M inister of South Africa. General Hertzog. in 1925
412
The seene 011 the same part of the Merensky Reef thirty years later, the su rface plant of Rustenburg Platinum Mines giving some indication of the great activity underground. The shallower parts of the mine, which now stretches for over thirty miles, are worked from inclined haulages, while the deeper areas are opened up from vertical shafts ranging in depth from 50 0 to 3.000 feet
occurrences has often been told, but the writer feels that sufficient credit has never been given to Dr. Hans Merensky for the part that he played in this epic of mineral exploration (1). T h e geological features of the Bushveld Igneous Com plex and its resources of platinum were later reviewed by C.A. Cousins (2). T h e discovery of the M erensky Reef was quickly followed by a boom in platinum mining and a great m any small companies were floated, generally by those whose experience had been confined to the m ining of gold with its unlimited m arket and fixed price and who gave little or no thought to the means of extraction from the complex minerals. In J u n e 1925 A.B. Coussm aker, keenly interested in this new source of platinum, went out to South Africa and with E.C. Deering from the Research D epartm ent as analyst, m ade contact with the owners of the several properties, sampling the mineral from outcrops throughout the reef a n d bringing to the survey his outstanding knowledge of platinum from its geology to its marketing. H e was fully aware of the serious problem of devising m ethods for the extraction of the platinum metals an d on his retu rn to L ondon in A ugust he assigned the task to the Research D epartm ent, headed by A.R. Powell, who was assisted
413
Hans Merensky
1 8 7 1 -1 9 5 2
The son of a German medical mis sionary to the Transvaal. Merensky returned to study geology at the Technical High School in Breslau and then at the University of Berlin. Going back to South Africa in 1904 he set up as a consulting geologist and mining engineer but he was interned for five years during the 19141918 war. The following years were difficult ones, but in 1924, hearing of the discovery of alluvial platinum in the Transvaal, he immediately prospected for the basic rock and quickly discovered the exten sive reef that was named after him, so initiating the development of a great platinum industry
a little later by Deering, now back from South Africa w ith considerable knowledge of the deposits. T h e m inerals w ere of a type not previously worked in quantity, and the platinum metals were associated with the sulphides of nickel, copper a n d iron, but intensive w ork over the next two years yielded a successful a nd economical process for tre a tin g the flotation concentrates by smelting in blast furnaces to a nickel-copper m a tte a n d treating this to obtain a residue carrying the p latinum metals that could th en be refined by the norm al m ethods employed for alluvial platinum. A p a te n t covering this process was filed on M a y 1, 1928 (3). In the m eantim e large samples of concentrates had been sent by the m ining companies to K ru p p Grusonwerk in G erm any, to various A m erican refiners, to the R a n d M ines laboratory in J o h a n n e s b u rg and to the Chem ical and M etallurgical C orporation in E n g la n d , a c o m pany associated with Consolidated Gold Fields having a hydro-m etallurgical plant treating lead an d zinc ores at R u n c o rn in Cheshire. N othing was heard of any m e th o d s of tre a tm e n t tried in America. A process devised by K rupps, smelting to a m a t te a n d then leaching with sulphuric acid, gave an extraction of 78 per c e n t of the p latinum metals, the R a n d M ines
414
developed a chlorination process th at gave good results on a small scale b u t later proved to be im practicable on larger scale trials (4), while the Chem ical and M etallurgical C orporation also relied upon dissolution in hydrochloric acid and chlorine followed by precipitation of the platin u m m etals with zinc (5), b u t by early 1930 they ha d decided to a b a n d o n the project (6). T h e only workable process rem ained that devised by Powell and Deering, and Johnson M a tth e y secured the appointm ent of refiners of the whole of the output of the only two remaining mining companies, all of the smaller concerns having failed or abandoned their operations. Those still active were m ore substantial concerns, W aterval Platinum, controlled by Consolidated Gold Fields, and Eerstegeluk Platinum, owned by Potgietersrust Platinum a n d controlled by Jo h a n n esb u rg Consolidated Investment T ru st, both operating adjacent p ro p erties on a small scale at R u ste n b u rg with small gravity concentration and flotation plants. In 1928 C oussm aker again set out for South Africa and visited these two companies. F rom this and his earlier survey he cam e to the firm con clusion that this section of the reef was the most promising a n d could well become an im portant source of platinum . H e discussed the position fully with the two companies a n d stressed the great advantages to be derived from their
Alan R ichard Powell

18 9 4 1 9 7 5 Joining Johnson Matthey in 1918 to establish a research department, Powell remained to manage a growing activity for thirty-six years. In 1926 he initiated work on a process for the extraction of the platinum metals from the newly discovered and complex source of mineral in South Africa and with his c o lle a g u e s su cc e ssfu lly developed a method of treatment that led to Johnson Matthey becoming the sole refiners to Rustenburg Platinum Mines. His many contributions in the refining, purification and analysis of the platinum metals were recognised in 1953 by his election as a Fellow of the Royal Society
415
E rn est C harles D eering

Educated at K ings College, London, and joining Johnson Matthey in 1918. Deering was sent out to South Africa in 1925 to set up a laboratory in Johan nesburg for the analyses of samples from the many platinum properties that were being established. Returning to London a year later he joined Powell in the Research Department in developing the process for extracting the platinum metals, and also the nickel and copper, from Rustenburg mineral and then put the process into production in a smelting works he designed and built at Rrimsdown on the outskirts of London. He remained in charge of this plant until his appoint ment as a director in 1949, becoming Chairman in 1964 until his retirement in 1966
amalgam ation. This rather difficult proposition was m ade a little easier as both Consolidated Gold Fields and J o h a n n e s b u r g Consolidated Investm ent T ru st h a d been substantial shareholders in J o h n s o n M a th e y since 1918 when, on J o h n Sellons death, his holdings had b e e n offered to them in equal proportions, while for m any years, until the building of the R a n d Refinery in 1922, the gold from both com panies mines had been refined by J o h n s o n M atthey. Negotiations went ahead for some time, with the co-operation of Lord B rabourne (1863-1933) a dire c to r of both C onsolidated Gold Fields and J o h n s o n Matthey, Dr. Ja m e s G u n s o n L aw n (1868 1952), a director a n d the consulting engineer to J o h a n n e s b u r g Consolidated, and J o h n A lexander Agnew (1872 1939), the distinguished m in in g engineer who was then the c h a irm a n of W aterval Platinum and also a d irector of C onsolidated Gold Fields. Initially co operation was confined to joint investigation of the problem s of extraction by the consulting metallurgists, an d w hen the T h ird Em pire M ining a n d M etallurgical Congress met in J o h a n n esb u rg in April 1930 a p a p e r on T h e M etallurgy of T ra n sv a a l Platinum O r e s was p resented by F. W artenw eiler of J o h a n n e s b u rg Consolidated and A. King of C onsolidated Gold Fields. T his recorded their early work on flotation but they em p h a sise d that the extraction of platin u m to
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Operations at Rustenburg Platinum Mines include the haulage of the mineral by trains of 15-ton trucks to the main hoisting shafts. To produce one ounce of platinum ten tons of ore have to be brought to the surface, crushed, milled and treated by dotation and smelting processes before refining can begin
m arketable form presented most difficult metallurgical problem s a n d needed a vast am ount of research a n d experimental w o rk (7). Finally in 1931 the m erger was achieved with the form ation of R u stenburg Platinum Mines, the shares being held as to 52.5 per cent by Potgietersrust Platinum and 47.5 per cent by the W aterval Platinum M ining C om pany, with J o h n so n M atthey continuing to be responsible for the refining a n d m arketing of all the platinum metals produced. C oussm aker was on the way to seeing his great resolve come to fruition. Unfortunately the G re a t Depression was now causing growing problem s in finding a market for the increasing output from R u ste n b u rg a n d operations there were reluctantly discontinued in April 1932 while serious thought was given by the parent companies to their complete w ithdraw al from the m ining of platinum in South Africa. C o ussm akers faith in the future a n d in the development of new industrial uses, as well as in the great potential of R u ste n b u rg as a producer, rem ained unshaken and again he urged the desirability of keeping the mines open on a m aintenance basis, prep a re d to resum e operations w hen a sufficiently attractive market seemed assured (8). T his policy was accepted, an d by August 1933 a courageous decision was m ade to re-open the R u s te n b u rg mine.
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After the development of a proress f o r the extraction o f the platinum metals from the Rustenburg Platinum Mines this sm eltin g plant was built by Johnson Matthev at Brimsdown near London, ffere the m a tte produced from the flotation concentrates was smelted to vield crude nickel and copper which were then refined electrolytically, leaving the platinum metals in the a n o d e residues to be separated and refined in the wet process refinery
F or the first time platinum an d its allied metals were being m ined as prim ary products, with nickel and copper a s by-products, by contrast w ith the mines in C a n a d a and Siberia, essentially sources of nickel and copper with the p latinum metals as by-products. This difference was to become of great im portance in enabling R ustenburg to respond m ore quickly and effectively to increasing de m a n d and to become the w o rld s largest p ro d u ce r of platinum . M eanw hile progress was being m ade in the extraction and refining of the p latinum metals, but as the depth o f the mine increased it was found th at the ore was gradually changing from a w e a th ere d an d oxidised form to a n unaltered sul phide and that the Powell-Deering process needed to be modified accordingly. In 1929 a smelting plant had been designed and built by Deering at Brimsdown to the north of London, capable o f expansion to meet increasing dem and, and here further experimental work h a d to be carried out. M a n y of the operations were novel a n d new problems a n d difficulties were frequently encountered but successfully overcome. T h e early years following the re-opening of the m ine in 1933 were not without their difficulties. Production g rad u a lly increased, b u t d e m a n d was small and in the year 1938 the through-put of p la tin u m in the J o h n s o n M a tth e y refineries
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In ihe earlier years the flotation concentrates were smelted to a matte in a series o f blast furnaces, but later submerged arc electric furnaces were installed at Kustenburg to cope with increasing demand. Each has six four-feet diameter consu m able electrodes in line
am ounted to only 25,000 ounces. D uring the w ar this reached 40,000 ounces a year, but thereafter continual expansion began in order to meet the steadily increasing dem and, this stem ming largely from the ado p tio n of the m elting of optical glass in p latinum equipm ent, from the increasing ou tp u t of fibre glass and from the extensive use of p latinum therm ocouples in the steel industry. As the scale of operations increased it was found desirable to carry out certain of the earlier operations in South Africa a n d a smelting p lan t was erected at R ustenburg to deal with the flotation concentrates an d to yield a m a tte suitable for treatm ent at Brimsdown. Later, to cope with the increasing o u tp u t from the mines, arrangem ents were m ade to duplicate the p rim ary stage of the Brimsdown process and a com pany known as M a tte Smelters was formed in South Africa as a joint subsidiary of R u ste n b u rg and J o h n s o n M atthey. In 1948 the U nion P latinum M ining C om pany, also operating on the M erensky Reef some 60 miles further north, was acquired by R u s te n b u rg and its property now constitutes the U nion Section of R u ste n b u rg P latinum Mines. Tw o years later the quantities of m atte being received at the J o h n s o n M a tth e y refinery at Brimsdown had increased to the extent th at a completely new plant was added there. A detailed account of the complex a n d lengthy cycle of
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The final section of the Johnson M atth ey platinum refinery, the largest o f its kind in the world. This plant, built in 1956. repla ced an older and smaller refinery and handled the precipitation, re-dissolving and re-precipitation of platinum and palladium, while the insoluble metals rhodium, ruthenium, iridium, and osmium were treated in another part of the refinery
operations required to effect the c o m p le te recovery of all six m etals in a state of high purity was given by two of D e e rin g s colleagues, A.F.S. G ouldsm ith and B. W ilson (9). A nnual production had now reached 70,000 ounces, b u t then d e m a n d from the petroleum industry for the reform ing of crude n a p h th a s to both high octane petrol and a range of aromatics, described on page 398, began to take effect and by 1955 the annual production of p la tin u m had risen to 200,000 ounces. A more extensive expansion program m e a t the mine was then set in tra in together with a m ajor expansion of the Jo h n so n M a tt h e y refineries, and ou tp u t was increased to 850,000 ounces, reaching a m illion ounces a year by 1973. O u t p u t of the other five p latinum metals increased of c o u rse in the sam e proportion. T o anticipate this history a little, annual o u tp u t of p latin u m from R u ste n b u rg has now risen to approxim ately o n e -a n d -a -q u a rte r million ounces, with more th a n 40,000 workers employed. T h i s achievement has been b ro ught about by a series of capital expenditure p ro g ra m m e s aim ed at m atching supply with dem and, by bringing new m ining areas into operation, by the m echanisation of
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mining m ethods and by the development of improved m ethods of extraction. R u stenburg Platinum M ines is now the largest und e rg ro u n d m ining operation in the world, extending over thirty-three miles in length, a n d constituting the w o rld s largest source of p latin u m a n d its allied metals. A further development in 1972 was the form ation of M a tth e y R u stenburg Refiners, jointly owned by R u s te n b u rg Platinum M ines and J o h n s o n M atthey, which now undertakes the whole of the extraction and refining operations in three plants. T h a t at R u ste n b u rg treats the m a tte and separates the base metals from the platinum metals and also refines the nickel and copper, leaving con centrates containing a round 50 per cent of total p latinum metals. T h e two plants at R oyston in E ngland and at Wadeville near J o h a n n e s b u rg then separate and refine the individual metals to the high degree of purity required for their many applications by means of a num ber of selective precipitation techniques from solutions of the mixed metals. D u rin g the past few years, however, research by J o h n s o n M a tth e y and development work by M a tth e y R u s te n b u rg Refiners have shown that improved recoveries m ay be obtained by a solvent extraction process and a new refinery is being built at R oyston to operate this process. T h e new technique reduces both the n u m b er of refining stages and the time required, improves the yield and enables increased a u tom ation to be utilised in the refinery (10). T h u s together R u ste n b u rg P la tin u m M ines and J o h n s o n M a tth e y ensure to industry throughout the world adequate and continuing supplies of the platinum metals. T h e know n reserves in the M erensky Reef ru n to over 300 million ounces of p latinum alone, while below this is another reef containing as m uch platinum again.
R e f e re n c e s fo r C h a p t e r 23
1 P.A. Wagner, Platinum Deposits and Mines of South Africa, London, 1929; reprinted Cape Town, 1973 2 C.A. Cousins, Platinum M etals Rev., 1959, 3, 94 99 3 A.R. Powell and E.C. Deering, British Patent 316,063 of 1928 4 R.A. Cooper and F.W. Watson, J . Chem. M et. M in . Soe. South Africa, 1929, 29, 220-230 5 S.C. Smith, British Patent 289,220 of 1928 6 Chem. Trade J . , 1930, 86, 357 and 405 7 F. Wartenweiler and A. King, Proc. Third Empire M in . and M et. Congress, 1930, Part III, 331-356 8 A.B. Coussmaker, Personal communication, 1960 9 A.F.S. Gouldsmith and B. Wilson, Platinum M etals Rev., 1963, 7, 136-143 10 M.J. Cleare, P. Charlesworth and D.J. Bryson, J . Chem. Tech. Biotechnol., 1979, 29, 210-214; P. Charlesworth, Platinum Metals Rev., 1981, 25, 106-112
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24
The Story Continues . . .
W ollaston was a man o f great imagination, but I do u b t if e v e n he could have fo re se e n the im m en se im p o rta n c e o f the p la tin u m m etals in m odern in d u s tr y
H .R .H . T H E D U K E OF E D I N B U R G H , 1953
T h e story of p latinum and its allied metals, their discovery, mining, extrac tion, chemistry, fabrication and uses, has now been carried along to a ro u n d the nineteen-fifties an d to a stage w h e n the literature on the subject has grown to enormous proportions and is readily available to those interested. But the con tinuing technological progress in w hich these metals find an increasing n u m ber of im portant applications requires a brief final chapter. T h e last thirty years have in fact seen more new developm ents in the uses of these metals th an occurred during the whole of th e ir earlier history an d there is every indication that research now being carried o u t will lead to further new industrial applica tions. It was in fact to ensure t h a t information was readily available on the researches being carried out on t h e properties of p latin u m a n d its allied metals and on their further potential applications that J o h n s o n M atthey, supported by R ustenburg P latinum Mines, undertook in 1957 the publication of the quarterly jo u rn a l Platinum M eta ls Review. In this way a link is provided betw een researchers and the many industrial scientists and technologists who have the responsibility of finding practical solutions to th e m aterial problem s of m odern technology. Part of the increasing volume of production has certainly been absorbed by the growth of applications that w ere established some time ago. T h e se include electrical contacts for an en o rm o u s range of relays, sensitive switches and m easuring instruments in which a low a n d stable contact resistance m ust be maintained, and either the c a rrying of a current without overheating or the closing of the circuit after a long p eriod of idleness - or both - are vital to their operation and reliability. F or so m e applications platin u m has been used for m any years, but alloys containing iridium, ru th e n iu m or nickel are m ore often selected for their greater hardness. Palladium is used extensively in telephone relays, but again alloys of p a lla d iu m with either silver or copper are m ore fre quently employed in m any other types of relay and control equipm ent.
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Great numbers of relays manufactured over the past fifty years and more have been fitted with platinum or palladium contacts to ensure their reliability. These, made by Bell Telephone Labora tories, have palladium con tacts and have an expectation of life of at least two hundred million operations
Another well-established application that has grow n considerably is in the m easurem ent of high tem peratures. T h e p latinum resistance therm om eter has found m any more uses while the addition to the wire-wound form of devices based upon thick film technology has still further extended their range of useful ness from industrial control to domestic appliances, medical applications and food processing. T h e p latin u m :rhodium -platinum thermocouple, still very m uch in demand, is obviously not capable of m easuring tem peratures approaching the melting point of platinum , and to meet the need for higher determ inations other combinations have been developed such as 20 per cent rhodium -platinum : 40 per cent rhodium -platinum for use up to almost 1900C, and iridium: 40 per cent iridium -rhodium for m easuring tem peratures up to 2000C. Again, the world-wide increase in the need for nitrate fertilisers to enhance our food supplies, particularly in the developing countries, has led to an enormous increase in the use of rhodium -platinum catalyst gauzes for the oxidation of am m onia to nitric acid. At the present time some 60 million tons of acid are produced a nnually throughout the world by this process. T h e glass m anufacturing industry, which began to use p latin u m melting equipm ent in 1934 for the production of lamp bulbs, has also greatly increased its dem and for p latinum in the melting of improved optical glasses for spectacles, cam era lenses and television tubes, while the m an ufacture of fibre glass for insulation and for a growing range of fibre-reinforced products is requiring increasing quantities of rhodium -platinum alloys for the bushings through which the glass is extruded at very high tem peratures. A further development from this, of more recent origin, is the concept of fibre optics , glass fibres to replace coper wires in telecom m unication systems, their production depending upon the use of special high purity platinum equipm ent.
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For fifty years or more optical glass has been melted in platinum crucibles in order to avoid contamination although more recently con tinuous melting in platinum equipment has been adopted
T h e electrodeposition of platin u m , first developed by Alfred Sm ee working in the Bank of E ngland in 1840 (page 211), developed relatively slowly, an d though platinum plating found a n u m b er of applications it was eventually replaced by the advent of rhodium plating. D escribed first by Professor C olin Fink of C olum bia University in 1933, t h e electrodeposition of rhodium offered con siderably greater hardness, h igher reflectivity an d greater resistance to wear combined with reasonable ease of deposition. D u ring W orld W a r II it played an important part as a sliding c o n ta c t surface in the radio-frequency equipm ent then being developed so intensively. M o re recently the electrodeposition of palladium has established itself as a replacem ent for the m ore expensive gold deposits used in electronic equipm ent, while ru thenium plating is also receiving more consideration in the same field. Platinum plating has returned, however, in a new form in recent years by the replacement of aqueous electrolytes by a b a th of m olten cyanides. By this process m uch thicker deposits of p la tin u m having greater ductility and freedom from porosity are now being a pplied to some of the refractory metals such as m olybdenum and tungsten for use at high tem peratures. O n e such example is the use of platinum clad m oly b d e n u m wire in quartz-halogen lamps.
G r o w in g U ses b ased u p o n O l d D is c o v e r ie s But in recent years there h a s developed a n increasing d e m a n d for the platinum metals for applications th a t did not formerly exist a n d were probably quite unforeseen thirty years ago, a lth ough in a few cases the scientific seeds had
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An economical method of preventing the corrosion of ships hulls and steel structures exposed to marine conditions is provided by cathodic protection systems in which a platinum-clad anode is con nected to the steel and a small direct current is passed, ensuring freedom from attac k. The nuclearpowered United States submarine Seawolf** was one of the first vessels to be fitted with a platinum cathodic protection system in 1956 and since then many ocean-going vessels and a number of off-sh ore oil rigs have been similarly protected
been sown very m any years before. O n e such example is the technique of cathodic protection of steel structures and sea-going vessels. As long ago as 1824 Sir H u m p h ry Davy was consulted by the British Adm iralty who were concerned about the rapid decay of the copper sheeting of His Majestys ships of war and the uncertainty of the time of its duration. Davy proposed the attachm ent of a small piece of zinc to nullify electrochemical action on the copper sheathing, while he also investigated an impressed current system, but reliable batteries had not then been developed. It was not until 1956 that the U nited States Navy seriously began to experiment with platinum -clad titanium anodes for the protection of their ships and submarines. A great deal of development work had to be undertaken by those concerned in the design and construction of cathodic protection systems, and in more recent years niobium has replaced titanium as the substrate metal, but today this invaluable m eans of avoiding corrosion is an established technique on m an y types of ships a n d steel structures, including off-shore oil rigs themselves u n d rea m t of thirty years ago. M u c h has been heard of the fuel cell as a source of pow er com bining high
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The high catalytic activity of platinum, together with its great resistance to oxidation, account for one of its major uses, in the form of woven rhodium-platinum alloy gauzes, in the oxidation of ammonia to nitric acid, a reaction taking place at around 850 C . This shows a new pack of gauzes being installed
Among the most severe con ditions in which platinum is employed are those in the manufacture of fibre glass. Molten glass at temperatures up to 1400 C flows rapidly through a great number of p r e cise ly d im en sio n ed orifices in a r hodium platinum alloy trough or bushing, these orifices having to retain their exact size and alignment o \ e r a long period of use
The fuel cell, in which electricity is generated by the reaction between either hydrogen or a hydrocar bon with oxygen at electrodes coated with a catalyst, has been the subject of extensive development in recent years. Working in collaboration with United Technologies Corporation in the United States. Johnson Matthey developed platinum-based catalysts for this purpose and large 4.5 megawatt units are now being installed in both New York and Tokyo. This shows a 1 megawatt pilot plant that has been operating for some years, the six fuel cell stacks in the foreground containing the platinum catalyst
A complex platinum compound, cis-diamminedichloroplatinum II. first discovered as a potential means of treating some types of cancer by Professor Barnett Rosenberg, has received the approval of the government authorities of the United Kingdom and the United States for use in chemotherapy. It is now being manufactured by Johnson Matthey Incorporated in the United States in equipment specially designed for clinical conditions
therm al efficiency with very low risk of environm ental pollution. After m any difficulties and extensive research projects, commercial m egaw att generating systems are now in the course of installation in the U n ited States and J a p a n , these relying upon a coating of p la tin u m dispersed on carbon applied to the electrodes to activate the electrochemical reaction that converts hydrogen, or a hydrocarbon, and oxygen into electrical energy. T h e origin of the fuel cell goes back, however, as far as 1842, w h e n the L ondon scientist, W . R. Grove, published a paper on A G aseous Voltaic B a tte ry in which he described the first practical fuel cell c o n stru c te d from p latin u m foil coated with spongy platinum and with dilute sulphuric acid as the electrolyte (see page 210). T h e great advances in m icroelectronics have also relied to some extent upon the platinum metals in the form o f a range of metallising preparations based upon platinum and palladium , or th e ir alloys with gold or silver, to provide thick conductive films on ceramic substrates, while ru th e n iu m is used similarly for resistors. These compositions consist of the powdered m etal or alloy mixed with finely ground particles of glass and suspended in a n organic m edium for applica tion by screen printing on to selected areas and firing. T h e y owe their original concept to the famous G e rm a n chem ist, M a rtin K la p ro th who, working with the Berlin Porcelain works in 1788, first succeeded in decorating porcelain with such a preparation as described on pa g e s 125 to 127. N aturally, rath e r m ore scientific m ethods are employed nowadays in their com pounding a n d application. A n im portant application of p a lla d iu m that also ha d its origins over a century ago is in the supply to in d u stry of p u re hydrogen. T h e selective diffusion of hydrogen through a p a lla d iu m m em b ran e was discovered by T h o m a s G ra h a m in 1866, as described on p a g e 266, but unfortunately it was later found that serious dimensional changes occurred when p a lladium is alternately heated and cooled in hydrogen. T h e discovery in the 1950s that an alloy of palladium with silver - in a narrow range of proportions - not only gave a higher rate of
\ range of metallising prep arations including platinum and platinum-gold, platinumsil\er. palladium-gold and palladium-silver alloys is employed for the production of thick film conductors in multi-layer hybrid circuits such as this, fabricated by K.R. V Technology Ltd
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transfer b u t rem ained dimensionally stable, m ade it possible to m anufacture diffusion units for the production of high purity hydrogen for a n u m b e r of industrial purposes, while in m ore recent years generators have been m ade avail able for yielding hydrogen by the cracking of a m ethanol-steam m ixture followed by separation of the high purity hydrogen from the carbon m onoxide through silver-palladium alloy m em branes.
M od ern Industrial A p p lica tio n s Still further uses of the platinum metals stem from m uch more recent research and development. O n e such m ajor application of platinum lies in the field of pollution control or abatement. From the m anufacture of nitric acid and the elim ination of noxious tail gases with a platinum catalyst to m an y of the m ore everyday industrial processes such as plastics m anufacture, printing, wire enamelling, paint drying and m any others, p latinum catalytic com bustion systems can now eliminate m any of the toxic gaseous waste products th at were formerly a cause of unpleasantness, irritation, or even disease. A more extensive use in recent years is in the control of autom obile exhaust gases. Platinum metal catalysts systems have been successfully developed to eliminate from the atm osphere the three principal forms of noxious emissions from petrol engines, carbon monoxide, nitrogen oxides and hydrocarbons, while similar catalysts for the control of both gaseous and particulate emissions from diesel-engined vehicles are in the course of development. Again in the field of autom obile engineering, research being u n d e rta k en by Ricardo Consulting Engineers jointly with J o h n s o n M a tth e y shows promise in the development of a n engine with a p latin u m catalyst instead of spark ignition, this both reducing dangerous emissions a n d giving m ore economical running. Improvements in the performance of gas turbine blades have also been the subject of a num ber of joint studies leading to the development of a platinum alum inide diffusion coating to increase their corrosion resistance an d durability at high operating tem peratures in aircraft engines. F u rth e r research by J o h n s o n M atthey has shown that small additions of p latinum group metals as alloying elements in new nickel-based superalloys can appreciably enhance their resistance to oxidation an d corrosion while retaining their original mechanical properties. In an entirely different field, the use of a complex com pound known as cisdichlorodiam m ineplatinum (II) in cancer therapy has resulted from outstanding research and development following the discovery by Professor Barnett R o se n berg in 1967 of this m ethod of treatm ent. T h is original com pound, know n com mercially as Cisplatin or Neoplatin, is now well established, but further research is leading to an improved range of a nti-tum our drugs that are now undergoing clinical trials.
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During the last few years effective and d u ra b le platinum catalyst systems have been introduced by several platinum manufacturing companies to meet the regulations covering the emission of exhaust gases from automobiles and well over 50 m illio n cars have now been fitted with these devices. Further research by Johnson Matthey has yielded a lead-tolerant catalyst system that has shown its durability for 5 0,0 0 0 kilometres road usage. Here a Morris Marina is undergoing laboratory tests in which the exhaust emissions are being measured
The production of hydrogen for a number of industrial processes is now well established by a process based upon the catalytic cracking of a methanol-steam mixture and then the separation of high purity hydrogen by d iffu sio n through silverpalladium alloy membranes. This typical installation, m a n u fa c tu r e d by Johnson Matthey, comprises the generator and the diffusion unit inside the red cylinder, with the control panels on the left
Some of the important economic advantages obtainable by the use of platinum group metal homogeneous catalysts are well illustrated by the process developed jointly by Union Carbide, Davy McKee and Johnson Matthev for the hydroformylation of propylene to butyraldehyde, required among other uses in the production of flexible polyvinyl chloride. This plant, one of a number already working, is operated by Chemische Werke Hills in West Germany and has a designed capacity of 250.000 tons a year, employing a complex rhodium compound as the catalyst
One modern application of iridium is as a crucible material for the growth of the large and perfect single crystals of semi-conductor materials required for lasers and other electronic devices. Here a single crystal is being pulled from an iridium crucible at approximately 1600C
H e te r o g e n e o u s and H o m o g e n e o u s C atalysis T h e great advances m ade in th e em ploym ent of the platin u m metals in heterogeneous catalysis have been described in C h a p te r 21. T h e m any types of chemical products now p ro d u ce d by the reforming of crude petroleum, economically an d in bulk, by such catalytic reactions include high-octane petrol a nd a range of com pounds such a s benzene, toluene and the xylenes, all the latter serving as vital interm ediates for th e m anufacture of synthetic fibres, plastics, dyestuffs and other p ro d u cts required in m odern ways of life. But alongside these reactions an essentially different form of catalysis has been developing more recently. T h e chemistry of the organom etallic com p o u n d s of all six p latin u m metals has been the subject of investigations by very m any academ ic workers during the past ten years or so, the principal industrial consequence being the increasing use of homogeneous catalysis in w hich the catalyst is soluble in the reactant. This has advantages in terms of high activity per unit weight of metal, high selectivity and long life of the catalyst, with obvious savings in operational costs, while in some cases this is the only possible route to the desired product. H igher yields and operation at lower pressures and tem peratures are also m ad e possible by com parison with heterogeneous catalytic reactions. Processes recently introduced include the conversion of ethylene to vinyl acetate, of propylene to acetone, and of m ethanol to acetic acid, all employing palladium com pounds as catalysts, while one other large scale process is the hydroform ylation reaction first discovered by Professor Sir Geoffrey W ilkinson at Im perial College and then developed jointly by U nion C a rbide, J o h n s o n M a tth e y a n d D avy M c K e e which converts propylene into aldehydes such as n-butyraldehyde using a soluble rhodium co-ordination com pound. In this last process an ou tp u t of some two million tons of the product, an im p o rta n t interm ediate in the m anufacture of polyvinyl chloride, involves the use of less th a n one ton of rhodium . M etallu rgical D e v e lo p m e n ts T h e metallurgy of the p la tin u m metals and their alloys has, of course, also developed, with studies of their constitutional diagram s and the provision of new or improved alloys. For example, a series of platin u m alloys having a wide range of resistivities com bined with low te m p e ra tu re coefficients of resistance has been m ade available for use in precision potentiom eters and transducers in industrial control equipm ent, while a c o b a lt-p la tin u m alloy provides an exceptionally powerful perm anent m agnet th at c a n be used in complex shapes or small sizes that would be im practicable with t h e conventional p e rm a n en t m agnet m aterials. But the most outstanding achievem ent during recent years has been the successful production of dispersion strengthened p latinum and certain of its alloys. These materials contain a uniform distribution of extremely fine refractory precipitate dispersed th ro u g h o u t the mass, and the mechanically worked material develops a highly fibrous recrystallation structure on annealing
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and is unusually stable. In this condition it is m any times m ore resistant to creep failure at elevated tem peratures and thus when un d e r stress at 1400C disper sion strengthened pure p latin u m c an endure for at least twice as long as a n alloy of platinum with 40 per cent rhodium , previously regarded as the strongest commercially available high-tem perature alloy. Such m aterials can be used with advantage for the construction of equipm ent required to operate in air at very high tem peratures; for example, dispersion strengthened rhodium -platinum and platinum have both found widespread use in the p roduction of optical and fibre glass where their high strength and resistance to con ta m in a tio n have resulted in considerable process improvements. T h u s the story of platinum an d its allied metals continues, w ith new applica tions continually developing based u p o n their rem arkably useful combinations of properties. From their past history it is evident th at still further uses will be found in the course of time a n d that they will continue to m ake significant contributions to the m aterial needs of our increasingly complex and rapidly changing world.
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Name Index
Page numbers in bold type indicate portraits
A c c u m , F. 145, 169 A c h a r d , F. K. 7 0 ,7 4 ,7 5 ,7 8 ,1 2 0 , 121, 126 A c o sta , J . de 5 A d a m s , R. 3 9 6 , 397 A g n e w , J . A. 416 Aikin, A. 1 3 5 ,1 4 0 ,1 4 1 ,1 4 2 Aikin, C. R. 1 3 5 , 1 4 0 ,1 4 1 A lem and, J. 321 A l e x a n d e r I, T s a r 244 Allen, W . 132, 1 3 3-13 5. 138, 139, 142-143, 145, 162, 173, 175, 195, 205 A lonso, F. 100, 101 A ls tro m e r, C. 50 Alzola, A. d e G . - C . y 1 0 1 ,1 0 3 A m p r e , A. M . 276, 333, 349 A n d r u s s o w , L. 394 A r a n d a , C o u n t P. A. 81, 100, 102, 103 D A rc et, J . 126 D A r c e t , J . P . J . 179,187-189 A rk h ip o v , A. N . 237 A r r i a g a , J . d e 92 A tk in so n , R . 379, 381 A u g u s t, C ., D u k e of S a x e - W e i m a r E is e n a c h 222, 223, 244, 349 A uv e rgne, C o m t e d e la T o u r d 68 Bergs(4e, P. 8, 9, 10 B e r th e l o t, M . 1, 2 B e r th o lle t, C . L. 85, 156, 174, 179, 184, 187, 188, 254 B e rth o u d , L. 112 B e rze lius, J . J . 50, 145, 162, 174, 175, 226, 232, 240, 247, 249, 2 5 2 , 25 3 - 2 6 1 , 333 B evan, E . J . 312 B e v an , J . G . 134 Bingley, R . 135, 169 B i r n b a u m , K. 265 B ish o p , J . 277, 3 6 4 , 369, 370 B lac k ,]. 48, 55, 114116, 148 B l o n d e a u , L. 50 B oliv ar, S. 23, 26, 366 B o l lm a n n , J . E. 161, 365, 367, 3 6 8 B o sc h , C . 390 B o sc h , R . 310 Bose, G . M . 3 4 ,4 3 ,4 4 B o u g u e r , P. 17, 18 B o u lto n , M . 108, 113 B o u s s i n g a u l t , J . B. 2 3 , 26 Bowles, W . 1 8-20, 40, 93, 94 Boyle, R . 5 B r a b o u r n e , L o r d 416 Brande, W . T . 203, 227 B ra n d t, G. 35-37 B r a u e r , E. 387, 388 B ra y , W . 9 B r a n t , J . R . 1 8 8 -1 9 2 , 301, 317, 318, 3 2 0 B r a n t , V. 79 B r e i t h a u p t , A. 236 B r e g u e t, A. L. 348 B r e g u e t, A. 348 B risso n , M . J . 67, 68, 181 B ro c h , O . J . 285,298 B rock, W H . 188 B ro d ie, S ir B e n j a m i n 294 B ro o k e , H . I. 273 B r o w n ri g g , W . 16, 20, 29, 3 0 , 31-3 3, 38, 39, 44 B r u g n a te l li , L. 153 B u c h a n a n , P. D. 215 Buffon, C o m t e d e 24, 25, 4 9 , 51, 56-59 B u r y , M r s . S. 198 B u tle ro v , A. M . 250
B a b in g t o n , W . 135, 142 Baker, D. 371 B a lb in u s, B 3 Ban ks, S i r j o s e p h 21, 22, 65, 79, 81, 82, 114, 144, 150, 158, 162 B a r a b o s h k in , N. N . 403, 406 B a r b a , A. 5 B a r ro w , H. 206, 207 B a ru el, J . P. 1 9 0 ,1 9 1 ,2 3 9 ,3 6 6 B a u m , A. 44, 46, 4 7 , 48, 52, 55, 56, 58, 66, 75, 94 Beadle, C. 312 B echer, J . J . 6 B e cqu e rel, A. C . 209, 349 B e cqu e rel, E. 350 Bellaigue, G . d e 198 Benito, F. 25, 94 Bergm an, T . O . 35, 50, 51, 52, 77, 96, 115, 184, 259
435
C ab ezas, D o n J . 99 C a d e t, L. C. 66-68 C allen d ar, H . L. 3 5 7 ,3 5 8 - 3 6 0 ,3 6 2 C an n izz aro , S. 337-339 C a r d a n , H . 4, 5 C arlo s III, K in g 19, 20, 93, 94, 96, 99, 100, 103, 104 C arlo s IV, K in g 104, 105 C a ro , N. 390 C aro th e rs, W . H . 400 C a ry , W. 1 6 1 -1 6 4 ,1 6 8 ,2 0 6 C asan ov a, G. J. 33 Castillejos, M a rq u e s d e los 15, 95, 9 6 C a th e rin e the G reat, E m p ress 7 1 ,1 2 2 C erd ia, V iceroy P ed ro M essia de la 25, 93 C h a b a n e a u , P. F. 8 0 ,9 2 ,9 3 , 9 6 - 1 0 3 , 106, 112, 120, 125, 188, 245, 317 C hald ecott, J . A. 84, 117, 148, 161, 162, 168, 183, 348 C h a p ta l, J . A. C. 189 C h a rles X , K ing 192 C harlotte, Q u e e n 144 C h a sto n , J . C . 173,286 C hatelier, H . L. L e 346, 350-355 C h a te n a y , L. 188 C h a v an ea u , see C h a b a n e a u C henevix, R. 155, 156, 158, 159, 162, 183 C hernyaev, I. I. 406 C hild ren, J . G . 1 4 3 ,1 4 5 ,1 7 5 C hugaev, L. A. 404, 4 0 5 C lark e, E. D. 2 7 3 ,2 7 4 -2 7 6 C lark e, F. W . 376 C la u s, C. E. see K laus C lerk, Sir I). 309 Cleve, P. T . 262 C lo u d , J. 367, 372 C o c h ran e, C a p ta in C. S. 2 6 ,1 0 6 C ock, T. 1 3 2 ,1 3 8 -1 4 1 ,1 6 0 ,1 6 2 ,1 7 3 , 174, 189, 195, 198, 201, 20S-208, 212, 214, 216, 239, 276, 291, 318, 367 C ock, W. J . 205, 289, 290, 292 C ollet-Descotils, H. V. 150-152, 159, 183, 184, 185-187 Collins, P. 227 C o n d a m in e , C. M . de la 17 C ook, Sir E rn est 230 C oo p er, Sir A stley 135, 138, 162, 197-199, 212, 214 C oo p er, T . 367 C ortinovis, D o n A. M . 2 C o sta , E. M . d a 20 C ottin g to n , I . E . 164 C ousins, C . A. 413
C o u s sm a k e r, A. B. 406, 410, 411, 413, 415 C o u tu rie r 188, 190, 317, 318 C ox , E. 370 C rell, L. F. F. von 60, 62, 63, 76, 81, 89, 114, 115, 116, 123, 148 C ro n ste d t, A. F. 35, 65, 94 C rookes, S ir W illia m 3 13 ,3 87 C ro slan d , M . 185 C ross, C . F. 312 C ullen, W . 114 C u o q , P. A. 1 8 8 -1 9 0 ,3 1 7 ,3 1 8 C u th b e rts o n , J . 113 D aim ler, G . 3 0 9 ,3 1 0 ,3 2 4 D alry m p le, A. 82 D alto n, J . 1 4 5 ,2 0 3 ,2 5 4 ,2 5 5 ,2 7 6 D aniel, H . 127 ,1 28 D aniell, J. F. 208, 211-213, 220, 348 D a r c e t,J . 24, 126 D a rw in , H. 360 D a u b e n y , C . G. B. 203 D a u m y , J . 86- 88, 112 D avila, D o n P. F. 93 D avy, E d m u n d 2 2 0 ,2 2 1 ,2 2 2 ,2 2 8 , 231, 260, 264 D avy, E d w a r d 306, 307 D avy, S ir H u m p h r y 133, 139, 142, 143, 147, 155, 175, 203, 208, 219-221, 228, 231, 260, 306, 343, 425 D eb ra y , J . H . 271, 277, 278, 279 , 280-286, 290-292, 295, 296, 299, 319, 320, 322, 323 D eering, E. C . 4 1 3 ,4 1 5 ,4 1 6 D e la la n d e see L a la n d e D e la n o u e ,J . 102 D elisle see lIsle D elplace, G . 304, 305 D em idov, C o u n t A n a to le 2 9 1 ,4 0 3 D em idov, C o u n t N ikolai 2 3 6 ,2 4 2 ,2 4 3 281, 319, 320 D escotils see C ollet-D escotils D esm ou tis, H. 190, 280, 318 Deville, H. S. C. 2 7 1 ,2 7 7 ,2 7 8 , 279-286, 290-293, 295, 297, 298, 300, 319, 320, 322, 323, 334, 346 D ickson, J . 243 D b e rein e r, F. 245, 246 D b e rein e r, J . W . 2 1 8 ,2 2 1 -2 3 1 , 244-247, 333, 334, 349 D olland , G . 203 D o m b e y .J . 24 D o m i see D a u m y D ow se, J 160 D rijfhout, H . H . 329
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437
438
439
Paal, C. L. 394 P arav ey 2 P arker, YV. 114 Parkes, S. 165, 167 Parsons, T . 168 P artin gton , J . R. 392 Pattison, H. L. 168 Paul, G r a n d D u k e of R ussia, later T s a r P a u l i 7 0 ,7 1 ,2 4 4 P au l I, T s a r see Paul, G r a n d D u k e o f R ussia P au sa n iu s 2 Pauw els, A. 330 Pauw els, F e rd in a n d 330 Pauw els, F rancois 330 Pavesi, A. 338 Pavlovna, G r a n d D uchess M a r ia 2 4 4 , 245 P ayen, A. 189 P eachy, S. J . 265 Pellat, A. 203 Pelletier, B. 7 9 ,8 5 ,8 9 ,1 1 2 ,1 2 3 Pelouze, T. 260, 262, 282 P enaflorida, C o u n t of s e e M u n ib e , F. J. de Pepper, J. 167, 168 Pepys, W . H . 1 3 4 ,1 3 5 ,1 3 9 ,1 4 2 , 143-145, 208 Percier, C. 105 Percy, J . 215, 294 Prouse, J. F. de L a 109 Petrie, Sir F lin d ers 301 Petrie, YV. 3 0 1 ,3 0 3 ,3 0 4 Pettenkofer, M . 327 Peyrone, M . 261, 262 Pfeffer. YV. 387 Philip V, K in g of S p a in 17 Phillips, F. C. 398 Phillips. P. 229, 230, 232 Phillips, R. 1 3 4 ,1 3 5 ,1 3 9 ,1 4 2 Phillips. VV. 134,135 Pistrucci, B. 207 Pius VI, P ope 100, 101 Pleischl, A. M . 2 2 5 ,2 2 6 Pliny 2 Poggendorff, J .C . 249, 250, 257, 322, 333 Pope, Sir YVilliam 265 Pouillet, C. S. M . 349, 350 Poussett, W . M . 200, 201 Powell, A. R. 3 4 4 ,4 1 3 .4 1 5 .4 1 7 Prentice, M . 304, 305 Priestlev, J . 65, 69-72, 110, 113, 114, 118, 141, 148. 273 Pringle, Sir J o h n 110 P roust, J. L. 96, 103, 104, 105, 150, 151, 188, 253, 254, 317
440
Scheele, K. W . 35, 148 Scheffer, H. T . 35-37, 39, 44, 48, 52, 75 Scherer, A. N. von 126 Schofield, F. H. 361 S ch u m a ch er, C. H. 206, 207 Schw eigger, J . S. C. 2, 222 Scott, D. A. 9 Seebeck, T . J . 349 Seguin. A. 84,85, 117, 118 S ello n .J. S. 293, 294, 313, 314, 320 Senderens, J. B. 394, 397 Seubert, K. F. O . 3 42 S helburne, Earl of 113 Sickingen, C o u n t K arl von 57, 60, 6 1, 62-64, 66, 69, 88, 98, 110-112, 114-116, 118, 119. 148, 150, 155 S ie b e n , G. 328 S ie b e n , W . 3 2 8 ,3 2 9 Siem ens, Sir W illiam 3 5 4 ,3 5 5 , 356-358 Sillim an, B. 272, 273, 275, 276. 305, 372 S im m s, F. R. 310 Skita, A. 395 Skoblikoff 262 S m eato n, W . A. 21, 56, 81, 263 Sm ee, A. 2 1 1 ,2 1 2 ,2 1 3 - 2 1 5 ,4 2 4 S m ith, C. S. 39,121 S m ith, E. F. 258 S m ith. J . 167, 168 S m ith, L ieu tenan t W . R. B. 195 Snyder, S. 368 Sobolevsky, P. G. 234, 237-241, 243, 244, 245, 248 Spengel, H . 307 Sperry, F. L. 376 Squire, W . S. 385 Staite, W . E. 301, 307 S t a s .J .S . 2 8 5 ,2 9 8 ,2 9 9 S ternberg, C o u n t K a s p a r 3 S todart, J . 201 Stokes, C<. 204 Streicher, J. S. 173 Strom eyer, F. 264 Suckow , G . A. 60, 62 Sw an, J . W . 307-309 Sylvester, C. 165. 168, 348 Sysoev, V. 237 T ait, P. G. 350 T e n n a n t, C. 165, 167 T e n n a n t, S. 66, 116, 120, 136, 147-153, 158-160, 165, 173-175, 183-186, 200, 273, 274, 348 T h e n a rd . L. J. 224, 225. 227, 228, 230, 277
T h iers, L.. A. 284 T h o m p s o n . B see R u m fo rd , C o u n t T h o m so n , S ir J . J . 343, 357, 358 T h o m so n . T . 124, 169, 255, 256, 274 T h o rp e , S ir E d w a rd 366 T h y , N. C. de see M illy, C o m te de T ik an ov itch , M . 407 T illet, M . 6 4 ,1 2 3 T illoch, A. 135. 137, 144 T resca. H. 2 96-298 T ro m m sd o rff. J . B. 156 T ro p s c h . H . 397 T ro u g h to n , E. 169 T s c h irn h a u s , C o u n t E. YV. von 67 T u rg o t, A. R J 24. 25, 60 T u r n e r, E. 229, 266 T y n d a ll ,) . 355 Ulloa, D o n A. de 12. 13, 16, 18, 19, 33, 34, 35 U re, A. 266 d Urfe, M a rq u is e 33 U sselm an , M . C. 148, 149, 159, 160, 164, 169 V alentini, N1. B 3 V a n M a r u m , M . 113 V arley, S. 144 V arvinsky, I. 235 V au q u elin , N. L. 104, 151, 152, 156, 159, 178, 179, 183-187, 189-191, 225, 231, 235, 259, 260, 317 V avon, G . 395 V ictoria, Q u e e n 207 V ilialonga, D o n J . de 15 Virgil 275 Virgili, J. F. y 15, 103 Vogel, R. 330 V oskressenskii, A. A. 339 V ro n c en k o 246 W a g n e r. P. A. 412 W a h l, W. H . 373 W ales, A. E. 148 W all, G e n e ra l R. 38 W alleriu s, J . G. 35 W alpole, R. 29 VVa rb u rto n , H. 147, 160, 170, 203 W a rg e n tin , P. W . 35 W arte n w e ile r, F. 416 W a tso n , W . 17, 18, 31. 32. 33, 34, 37, 39, 43, 44, 65, 110 W 'edgew ood, J o h n 128
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W edgew ood, J o s ia h 118, 127 W edg ew o od , J o s ia h II 128 VVehnelt, A. R. 309 W eiss, F. 245 W e nd lin g on , J . 93 W e rn e r, A. 263 W h ea tsto n e, C. 208 ,3 06 W hew ell, Rev. W . 208 W h ip p le, R. S. 360 W h ite r, L. 128 W ilde, P ro sp er de 394 W ilkinson, S irG eoffrey 432 W illiam son, A. W . 357 Willis. T . 116 Willis, W . 311 W illsttter, R 395. 396 W ilson, B. 420 W inkler, C. 385 W hler, F. 2 5 7 ,2 5 8 ,2 5 9 ,2 6 1 ,3 1 6 , 326, 327, 337 Wolf, T . 7 W ollaston, Rev. F. 149, 162 W ollaston, F. H. 168 W ollaston, F. J. H . 168
W o lla sto n , VV. H . 119, 120, 136, 146, 147-154, 156-175, 185, 186, 189, 191, 194, 195, 197. 199, 200-203, 205, 206, 208, 215, 225, 238-240, 243, 249, 255, 256, 273, 274, 291, 301, 302, 317, 318, 333, 348, 422 W ood, C. 2 8 .2 9 ,3 9 .4 4 ,5 5 W o o d , W . 28 W o o d h o u se , J . 2 70-272 W right, J . 210 W rtte m b e r g , D u k e of 63 W u rtz , C. A. 1 0 2 ,2 6 2 ,2 6 5 ,3 0 0 Y acobi, B .S . s e e ja c o b i
Z ea, F. A. 365, 366 Zeise, W . C. 264, 265 Z elinsky, N. D. 396 Z in in , N. N. 339, 340 Z ub ice, D o n F. de E. de see E lh u y a r Zubice, D o n J . J . de E. de see E lh u y a r Zvyagintsev, O . E. 403, 407
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Subject Index
A cadem ie des Sciences, co m m u nicatio ns to, o n p la tin u m 55-73, 75-91 m etric s ta n d a rd s 296 A ir N itrates C o rp o ra tio n 391 A ja x -N o rth ru p 286 A laska, p latin u m m ining in 381 A ldehydes, h y d ro g e n a tio n 395, 396, 400 A llen a n d H a n b u ry s 138 Alloy data, first co m p ilatio n of 74 Alluvial deposits, gold 1, Z 15-17, 21, 381 p latin u m m etals 111, 13-27 iridium 382 see also Alaska, Brazil, C a n a d a , C olom b ia, E cuador, M in es, R ussia, S o u th Africa A m erica n C y a n a m id C o m p a n y 391 A m erica n P la tin u m W o rk s 372 A m m onia, nitric acid p ro d u c tio n 2 3 1 ,3 8 4 ,4 2 3 oxidation 391-394 p latin u m p rec ip ita tio n b y 37, 48, 51, 65 synthesis 390 A nalytical chem istry 259 A ng lo -C o lo m bian D ev elop m en t C o m p a n y 367 A nodes, c a rb o n im p re g n ated w ith p la tin u m 374 p latin u m -clad 425 A p p aratu s, palladium , b y j o h n s o n 198, 200 p latin u m 26, 291 p latinum , by, A ch ard 76 Bishop 369, 370 C u o q a n d C o u tu rie r 189 J a n e ty 84, 188 P roust 105 Q u e n n e ss e n 319 W o llaston 162 to isolate alkali m etals 143 Arsenic, for m elting p la tin u m 36, 39, 59, 75-91, 117. 237 Artificial fibres 312 A skesian Society 135 A ssaying 39, 64, 135, 160, 161, 195 A tom ic theory 253-269, 333-345 A utom o b ile ignition 3 0 9 ,3 1 9
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Cells, B u n s e n 373 p rim ary 208210 se e a ls o F u e l cells, G r o v e cells C h a in , p a l l a d i u m , G e o r g e I V s 197 p latinum 194, 237 C h a li c e , p l a t i n u m 100 C h e m i c a l S oc iety 207 F a r a d a y m e d a l m a d e of p a l l a d i u m 208 C h e m ic a l a n d M etallurgical C o rp o ra tio n 414 see a ls o C o n s o l i d a t e d G o l d Fie lds C h e m i c a l sy m b o ls 256 C h e m i s c h e W e r k e H l s 431 C h i l e s a l tp e t r e 387 Choc 14-19, 2 1-2 3, 27, 9 3 -1 0 7 , 291, 3 6 6 se e also C o l o m b i a t w - d i c h l o r o d i a m m i n e p l a t i n u m ( I I ) 262, 4 2 7 , 429 C isplatin 2 6 2 ,4 2 7 ,4 2 9 C ladding, g o ld lin e d p l a t i n u m 349 p l a t i n u m c la d c o p p e r 112, 124, 279 p l a t i n u m c la d silver 197 se e also D o u b l C o a l, g a sific a tio n 397 C oinage, p latin u m . C o lo m b ia n 106 R u s s i a n 2 4 1 -247 , 280 C o i n s , c o u n te r fe it g o ld 20, 105, 183 C o l o m b i a 7-1 0, 13-27, 106, 161, 291, 3 6 5 367 f o u n d i n g of t h e R e p u b l i c 2 3 ,2 6 ,9 7 m o n o p o l y in p l a t i n u m 27 o u t p u t of p l a t i n u m , see p r o d u c t i o n of platinum se e a ls o C h o c C o m i t I n t e r n a t i o n a l des P o i d s et M e s u r e s 297 C o m m i s s i o n of W e i g h t s a n d M e a s u r e s 1 18, 179 see a ls o S t a n d a r d s C o m p a n i a M i n e r a C h o c P a c ifico 367 C o m p to ir L yon-A lem and 321,329 C o n d u c t o r s , thick film 428 C o n s o l i d a t e d G o l d F ie ld s 367, 412, 414. 4 1 5 C o n t a c t process, for s u l p h u r i c a c id m anufacture 229 -2 3 3 , 386 in R u s s i a 404 C o n t a c t s , ele ctrical 295, 306, 310, 328, 4 2 2 Copper se e C la d d in g , D o u b l C o r r o s i o n p r o t e c ti o n 425, 429 C o u r t a u l d s 312 C r u c ib l e s , i r id i u m 313 p latinum 77, 79, 85, 88, 125, 162, 188, 239, 259, 291, 306, 319, 322 for g r a v im e t r i c a n a ly s is 373
for i so la tin g a l u m i n i u m 258 for m e l t i n g o p t ic a l g las s 2 0 3 . 4 2 3 t h e first 76 C u o q C o u t u r i e r et C i e 189, 190 see a ls o D e s m o u t i s C ups, palla d iu m 192 C u tlery , p la tin u m 81, 144, 168, 188, 237, 306 D a v y M c K e e 432 DEGL'SSA 326 -3 3 1 D e sm o u tis Q u e n n e s s e n 190, 250, 291, 301, 3 1 8 - 3 2 1 , 403 D e u tsc h e G o ld u n d S ilb er S c h eidean stalt 3 2 6 -3 3 1 D bereiner Feuerzeug 226 D b e r e i n e r s T r i a d s 333 D oubl 8 6 ,1 1 2 ,2 7 8 see also C l a d d i n g D redges 382, 404, 406 D u P o n t , E. I. 394 D y e s t u f f 385, 400 E cole P o ly tec h n iq u e 182 E c u a d o r 7, 12 27 E erstegeluk P la tin u m 415 see a ls o P o t g i e t e r s r u s t P l a t i n u m E g y p t, a r ti f a c t s w i t h p l a t i n u m 1 E le c t r i c l a m p s 306, 307, 319, 328, 375, 424 E le c t r o c h e m i s t r y 208-216 E le c t r o d e p o s i ti o n , se e E l e c t r o p l a t i n g E le c t r o d e s , p latinum 208 p l a t i n u m in fuel cell 377, 428 see a ls o A n o d e s E l e c t r o g r a v i m e t r i c a n a l y s i s 373 E lectroplating 2 1 0 -2 1 5 ,4 2 4 w ith p a lla d iu m 374 p latinum 295, 374 rhodium 424 ruthenium 424 E n g elh ard Industries 371 E sm era ld a s 6-8 E x h a u s t g a s c o n tr o l 429, 430 E x h ib i t io n s , C h i c a g o 1893 305 L o n d o n 1819 188, 189 1851 2 1 5 ,3 0 1 ,3 1 8 ,3 2 1 1862 293, 303, 318, 319 P a r i s 1855 291, 302, 319 1867 283, 295, 304 1878 2 9 9 , 3 0 5 , 3 1 9 1889 319 P h i l a d e l p h i a C e n t e n n i a l E x h ib i t io n , 1876 370 E x p lo s iv e s, n itr ic a c i d for 387
444
Fertilisers, a m m o n iu m salts 231 C hile s altpetre 387 nitrates 423 F ib re optics 4 2 3 ,4 2 6 F isch er-T rop sch synthesis 397 F orsch u n g sin stitu t fr E d e lm etalle 330 F ra n c e 179-192. 317-321 early work on p la tin u m 43, 60 Revolution 81. 112. 179 see also A ca d m ie des Sciences Fuel cells 2 0 9 .2 1 0 ,4 2 7 M o n d s 377, 379 see also G ro v e cells G as tu rb in e b lad es 429 G erm an y , early w ork on p la tin u m 41 see also R oyal P ru ssia n A c a d e m y of Sciences G ib b s P hase R u le 267 Glass, decorated w ith p la tin u m 237 .3 27 optical, m elted in p la tin u m crucibles 87, 203. 423 G old sources, see Alluvial deposits G oldsm iths, work on p la tin u m using arsenic 75-91 W orshipful C o m p a n y of 160, 167 G re e n Pickslay & Co., Sheffield cutlery 202 G r o s salt 262 G ro ve cells 2 95 ,3 75 see also F u e l cells G u n s 163, 237 H ab er-B o sch process 392 H a t to n G a r d e n 195-217 H erae u s 317, 321-325, 403 H y d ro ca rb o n s, aro m a tic 398 H ydrogen, ab sorption by p a lla d iu m 266, 321, 428 catalytic co m b in a tio n w'ith oxvgen 223, 225 g enerators 268 H y d ro g en c y anid e m a n u fa c tu re 394 H y d ro g en iu m 266 Ignition tubes 328 I.G. F a rb e n in d u strie 394 Im perial C h e m ic a l In d u stries 393, 394 Indians, S o u th A m e ric a n 7 In tern ation al B u rea u of W e ig h ts an d M e asures 284 In tern ation al M e tric C o m m iss io n 283
In te rn atio n a l N ickel C o m p a n y 376 I n tern a tio n al T e m p e r a tu r e S cale 362 Irid iu m , c h e m istry 173, 320 discovery 66, 150-153 filam ents in electric light b u lb s 308 m elting 1 7 3 ,2 7 4 ,2 7 6 ,2 9 3 ,3 1 3 p rec ip ita te d d u rin g p la tin u m refining 48, 51, 120, 244 p ro perties 183-187, 190 refining 258 sources, see A lluvial deposits Irid iu m alloys, p la tin u m -irid iu m 173, 186, 282, 284, 295, 303 see also P la tin u m alloys p la tin u m -irid iu m -rh o d iu m 280 steel-iridium 202 pro perties 186 recovery 190 Irid iu m com plexes, a m m o n iu m ch lo ro irid ate 66, 120 chlorides 244 Isom erism in p la tin u m salts 261 Izvestiya of the Platinum Institute see R ussia Jew ellery, p la tin u m 7, 16, 101, 187, 188.237 from E sm e ra ld a s 6 -1 0 J o h a n n e s b u r g C o n so lid a te d 1 n vestm en t T ru st 415 J o h n s o n V iatth ey & Co. 161, 175,250, 289-314, 306-330, 350-358, 3 6 ^ 3 7 9 , 392-397, 403, 406, 407, 410, 415, 417 see also M a t t e S m elters, M a tth e y R u s te n b u rg R efiners J o h n s o n M a tth e y Inc. 427 K etones, h y d ro g e n a tio n 395, 396 K la u s salt 262 K ru p p G ru so n w e rk 414 L ea d c h a m b e r process 3 6 9 ,3 8 6 L e a rn e d Societies, E ng lish 133-145 see also A c a d e m ie des Sciences, A sk esian Society, C h e m ic a l Society, R oy al P ru ssia n A c a d e m y of Sciences, R oy al Society of L o n d o n , R o y a l S w ed ish A c a d e m y of Sciences; S p a in , A c a d e m y of Sciences; U n ite d States, A c a d e m y of Sciences L e c tu re on P la tin u m , F a r a d a y s 292, 336
445
446
O cc u rre n c es, see Alluvial deposits, M in e s O rfo rd C o p p e r C o m p a n y 376 O rg a n o m e ta llic c o m p o u n d s 191,257, 264-266, 326 O s m irid iu m 10, 235 O sm iu m , discovery 150-153 pro perties 183-187, 190 refining 258 sources, see Alluvial deposits O s m iu m catalysts 391 O s m iu m tetroxide 249 O xygen, catalytic c o m b in atio n w ith h yd ro gen 225 discovery by Priestly 69 m elting p la tin u m 69, 117 P alladium . ab sorption of h yd ro gen 266-268, 321, 428 discovery 146, 153-155 m elting 274 p roperties 183-187, 191-192, 196-200, 208 refining, see R efining of p allad iu m sources, see Alluvial deposits P a llad iu m alloys 205 g oid -p a lla d iu m 169 silver-palladium 197, 268, 430 silver-palladium -X 197 silver-palladium diffusion tu b es 268 P allad iu m catalysts, black 396 colloidal 395 co m p o u n d s 432 finely divided 395 su p p o rted 397 P allad iu m com plexes 191, 257, 260, 326 Patents, autom obile, p latin u m ignition tubes 309 electroplating 215 h y d ro genation of aldehydes a n d ketones 395 nitric acid 231 ,3 89 p la tin u m g au ze catalyst for 390 oleum , over platinised p u m ice 385 pho to grap hy , p latin u m 311 refining p la tin u m 292 refining p latin u m , D e b ra y s 2 79 ,3 19 relay for telegrap h 307 resistance th e rm o m e te r 359 siphon, p la tin u m 319 smelting sulphides to m a tte 414 sulphuric acid boilers 230, 303, 304 therm ionic valve, p la tin u m c a th o d e 309 viscose rayo n 312 Pauw els F reres 330
P e n nibs 169,202 P erio dic ta b le 333 -3 44 P h a rm a ce u tica ls, ca ta ly sts for 397 P h o to g ra p h y 245, 311, 319 P latfo rm in g 398 P la tin a del P in to 15, 33, 35, 37, 43, 90 P la tin o ty p e C o m p a n y 311 P latin um , a d u lte ra tin g gold, see C o in s clad ding , see C la d d in g d isp ersion stre n g th e n e d 432 finely divided 221 first sam p les in E u r o p e 24 first scientific e x p erim en ts 19, 2 9 -5 3 first sep ara tio n from its m in eral 43 first use of th e n a m e 5 0 ,5 2 leaf 189 m alleable, see M a lle a b le p la tin u m m elting, see M e ltin g p rec ip ita tio n by a m m o n iu m chloride, see A m m o n ia R o o m 105-107 sources, see A lluvial deposits spo ng e 391 strip 388 tensile stre n g th 119, 172, 183 w orkings, earliest 1, 5 5-72 P la tin u m alloys, a n tim o n y -p la tin u m 120 a rse n ic -p la tin u m 120 b ism u th -p la tin u m 120 c o b a lt-p la tin u m 120 c o p p e r-p la tin u m 25, 102, 120, 237 c o p p e r-irid iu m -p la tin u m 120 c o p p e r-p la tin u m -z in c 88 g o ld -p la tin u m 39, 161, 304 irid iu m -p la tin u m 120, 173, 277, 282, 284, 289, 295, 303, 304, 308, 310 ir id iu m -p la tin u m -rh o d iu m 280, 323 le ad -p la tin u m 120, 124, 299 steel-p latinu m 201 tin -p la tin u m 120 zin c -p la tin u m 120 d isp ersion stre n g th e n e d 432 native from C o lo m b ia 10 native from R u ssia 235 P la tin u m catalysts, acetylene h yd ro g e n a tio n , for 394 A d a m 's , p la tin u m o xide 397 black 222, 395-397, 400 colloidal 395 finely divided 395 gasolene engines, for 429 g au zes 390-394, 423, 426 lead -tolerant 430 nitric acid p ro d u ctio n , for 3 87 -3 93
447
R efining of p a lla d iu m by, B r a n t 191 C ock 205 J o h n s o n 196 J o h n s o n M a tth e y 379 R efining of p latin u m , p ro d u c e d by, A c h a rd , using arsenic 75 B o llm a n n in U .S.A . 367 B r a n t 188 C h a b a n e a u 98 C lo u d 367, 372 C oilet-D escotils 185 D a u m y 86 Deville a n d D e b ra y 279 D b e re in e r a n d W eiss 245 H e r a e u s 322 J a n e ty , using arsenic 78, 85 J a n e t y s m e th o d in R u s sia 237 J o h n s o n M a tth e y 379 L lsle, de 56 M a m y s h e v in R u ssia 236 G e o rg e M a tth e y using lead 299 Milly, de 63 M o rv ea u , de 59 M u s s in -P u s h k in 122 P elletier 89 P elletier a n d I n gen-ho usz 112 P etten k ofer 327 Pow ell-D eering process 4 1 3 ,4 1 8 Ridolfi 123 R o c h o n 88, 89 Sickingen, C o u n t von 6 0,63 , 116 Sobolevsky 237 W o lla sto n 159, 170 cu p ellatio n 30, 41, 42, 48, 55 early p o w d e r m e tallu rg y 56 solvent ex tractio n 421 in R u ssia 408 in S o u th A frica 414 R e is e ts second ch lo ride 261 see also -d ic h lo ro d ia m m in e p la tin u m (II ), C isp latin R h o d iu m , discovery 146, 158 m elting 276 electro p latin g 424 pro perties 184187, 190 sources, see A lluvial deposits R h o d iu m catalysts, co m p lex for b u ty ra ld e h y d e p ro d u c tio n 432 R h o d iu m com plexes, c h lo ro p e n ta m m in e rh o d iu m ch lo ride 262 R ic a rd o C o n s u ltin g E n g in ee rs 429 F rie d ric h R oessler S h n e 326 see also DEGUSSA R olls R o y c e 429
448
R o y a l P r u s s i a n A c a d e m y of S c ie n c e s 4143 c o m m u n i c a t i o n s to, o n p l a t i n u m 43, 70, 75, 125 R o y a l Society of London, B akerian L ec tu re 110, 160, 170, 203, 355 C o p l e y M e d a l 39, 152 c o m m u n i c a t i o n s to, on, a to m ic theory' 255 palladium 155, 159 platinum 20, 2 8 -5 3 , 110, 149, 152, 230 p l a t i n u m m e t a ls 201 p a l l a d i u m p r e s e n t e d to 169 p l a t i n u m p r e s e n t e d to 33, 38, 240 R o y a l S w e d i s h A c a d e m y of Sciences, c o m m u n i c a t i o n to, o n p l a t i n u m 37, 44, 50, 51 first c o m m u n i c a t i o n to, o n c a ta ly s is 232 R u s s i a 235 -2 5 2 , 256, 291, 295, 4 0 3 - 4 0 9 m o n o p o ly in p l a t i n u m 236,404 o u t p u t of p l a t i n u m , see p r o d u c t i o n of platinum P l a t i n u m I n s t i t u t e 405 Izvestiya o f 4 0 5 - 4 0 7 refin ing of p l a t i n u m 281, 370, 408, 409 R u ssia n R evolution 321,403 S t a t e A s s o c ia t io n of P l a t i n u m M i n e s of t h e U r a l s 406 see a lso U r a l s R u s t e n b u r g P l a t i n u m M i n e s 412, 417, 420 see also M a t t e S m e lte r s, M a t t h e y R u s t e n b u r g R e fin e rs, P o tg ie te rs r u s t, S o u t h Africa, W a t e r v a l P l a t i n u m M ining C o m p a n y R u t h e n 247 R uthenium , discovery 186, 247 sources, se e A lluv ial d e p o sits R uthenium com pounds 375 p o t a s s i u m c h l o r o r u t h e n a t e 249 p o t a s s i u m r u t h e n a t e 300
alluvial d e p o s i t s 4 1 1 . 4 1 8 m in e s 4 1 4 - 4 2 1 se e also M e r e n s k y Reef, P o t g i e t e r s r u s t , R ustenburg p l a t i n u m o u t p u t , see P r o d u c t i o n of platinum S o u th A m e ric an G o ld a n d P la tin u m C om pany 367 Spain, A c a d e m y of S c i e n c e s 65, 103 early w o r k o n p l a t i n u m 40, 188-191 P la tin u m age 93-107 Sp en cer C h a p m a n a n d M essel 385 S p e r r y l i t e 376 S p i n n e r e t s for a rtificial fib res 312, 371 Standards 118 A v o i r d u p o i s P o u n d 207 Im perial S ta n d a rd T ro y P o u n d 206 Intern a tio n a l P rototype K ilogram 299 kilogram m e 180, 283, 2 9 5 - 2 9 9 m etre 180, 188, 2 8 3 - 2 8 5 , 2 9 5 - 2 9 9 S t a t e m o n o p o li e s in p l a t i n u m , C olom bia 27 R u ssia 236, 404 Ste el, t e m p e r a t u r e of m o l t e n 360 S te el alloys 201, 202 Stills, p l a t i n u m 2 91,369 Sugarbow l, p la tin u m 79 S u lp h u ric acid 1641 6 8 , 3 0 1 306 bo ilers, se e B o ile rs co n tact process 2 2 9 - 2 3 3 , 386, 404 price 167 stills, see Stills S u p e r a l l o y s 429 S w e d e n , e a rly w o rk o n p l a t i n u m 3537, 50 se e also R o y a l S w e d i s h A c a d e m y of Sc ie n c e s S y n t h e t i c A m m o n i a a n d N itra t e s L t d . 392 se e also I imperial C h e m i c a l I n d u s t r i e s
S a l - a m m o n i a c , for p r e c i p i t a t i n g p l a t i n u m 29 -53, 5 5-73 , 98, 122, 126, 137, 138, 140, 150-170, 183, 186, 190, 238, 243 S e e b ec k effect 349 S ilver lustre 127 Siphon, p latin u m 189, 319 S m u g g lin g , in L a t i n A m e r i c a 14, 1 9-21, 24, 26, 27, 30, 81, 103, 149, 291 in R u s s ia 2 3 6 , 2 4 7 Snuffboxes, p l a t i n u m 16, 79, 81, 85, 216 S o d i u m , d isco very 143 S o ldering , p l a t i n u m 79, 84, 189 S o u t h A frica 411 421
T e a pots, p l a t i n u m 81, 100 T e a set, p l a t i n u m d e c o r a t i o n o n 129 T eleg rap h y 209, 295, 306, 307, 422 T elesc ope, e y ep iec e s 169 m irrors 34, 36, 88 o p tic a l g la s s 203 T em p era tu re m easurem ent 347-362 se e also P y r o m e t e r s , T h e r m o c o u p l e s , T herm om eters T h e r m i o n i c valves 308 T herm ocouples, irid iu m :irid iu m -rh o d iu m 423 irid iu m .p la tin u m -irid iu m 350 iro n -p la tin u m 350
449
p la tin u m -p a lla d iu m 349 p la tin u m :rh o d iu m -p la tin u m 349, 353, 423 r h o d iu m -p la tin u m :rh o d iu m -p la tin u m 423 T h e rm o ele ctric effect 349-351 T h e rm o m e te rs, bi-m etallic 168, 348 p la tin u m resistance 324, 354360, 423 T u b e s , p latin um , fusion w elded 293 U n io n C a r b id e 432 U n io n P la tin u m M ining C o m p a n y 420 see also R u s te n b u rg P la tin u m M in e s U n ite d A lkali C o m p a n y 392 U n ite d S tates of A m erica 367-382 A ca d e m y of Sciences 373 see also A laska U nited T echnologies C o rp o ra tio n 427 U n iv e rsal-M atth ey P ro du cts 400
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A Hsitory of Platinum

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A Hsitory of Platinum

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A History of Platinum Allied Metals

A History of Platinum and its Allied Metals

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

Ju liu s Caesar S ealiger 1484-1558

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

Early European Literature

1982 Johnson Matthey

Rum ours from the New W o r ld

1982 Johnson Matthey

T h e r e is a ta n ta lis in g reference to this in R o b e rt B oy les T h e Sceptical C h y m is t p u b lis h e d in L o n d o n in 1661. After q u o tin g A c o s t a s p a r a g r a p h he ad ds :

1982 Johnson Matthey

1982 Johnson Matthey

The P re-C olu m b ian Indians of E cu ad o r and C olom bia

1982 Johnson Matthey

An Early Use of Powder M etallurgy

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

Don A n to n io d e Ulloa 1716-1795

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

Antonio de U llo a s Voyage of D iscovery

1982 Johnson Matthey

1982 Johnson Matthey

Th e Irish Naturalist William Bowles

1982 Johnson Matthey

AXT1CUOS VOLCANES DE ESPAA.

Counterfeiting and Smuggling

1982 Johnson Matthey

1982 Johnson Matthey

Lu VAcadmie R oyale des Sciences en Juin 1 7 8 $ ; F ar M L.

1982 Johnson Matthey

Photograph b\ courtesy of the of the B ritish M u se u m

1982 Johnson Matthey

Jean Baptiste Boussingault 1 8 0 2 -1 8 8 7

T h e Source of the Alluvial Platinum

1982 Johnson Matthey

Samples of Platinum sent to E u ro p e

1982 Johnson Matthey

Don Jos C eleslino Mutis 1 7 3 2 -1 8 0 8

1982 Johnson Matthey

Platinum after Independence from Spain

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

1982 Johnson Matthey

After describing his few e x p e rim en ts h e co n c lu d e d :

William W atso n s Contributions

1982 Johnson Matthey

1982 Johnson Matthey