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Lqud caton and anon
Sovent extracton has become a very powerfu method of separaton for
varous reasons.One amongst them s, t s very smpe, rapd, seectve and
senstve. Ths method does not need any knd of sophstcated nstrument
exceptng a separatng funne. The organc chemsts have rendered
yeomans servce to anaytca chemsts by syntheszng an array of gands
wth dfferent functona groups contanng varyng donor atoms. The
sovent extracton doman s domnated by the extracton by cheaton or
compound formaton. It has receved maxmum attendaton due to an array
of reagents avaabe for the purpose of separatons n sovent extracton.
Ion exchange s another method whch s qute effectve for the purpose of
separatons at macro and mcrogram concentratons. On account of
dscovery of pate theory one coud easy predct and desgn the coumn
from optmum condtons of sorpton and carry out the separatons. The
effcency of on exchange separaton coud be easy mproved by
ncreasng coumn heght or n other words ncreasng the number of
theortca pates (HETP) whe n sovent extracton, effcency of separaton
coud be accompshed by mutpe extractons or counter current
Lqud on exchangers as the name mpes combnes the advantages of
both sovent extracton as we as of on exchange technques. The greatest
advantage of qud on exchanger s that one coud regenerate the resn
and use t agan and agan. Therefore theprocess becomes economca. Ths
s one of the reasons why most of ndustra processes for recovery of
metas from mneras prefer the use of qud caton exchanger ke LIX 64 N
or qud anon exchangers ke Aanne 336 or Amberte LA-1.
The sovent extracton method has made great strdes n ast four decades.
A number of monographs have been pubshed deang wth varous aspects
of sovent extracton.Some of them put emphass on the theory of cheats
extracton whe others have dwet on rgorous treatment of extracton
equbra or on the mechansm of extracton. Few of them have
ramfcaton wth aspect of sovent extracton. The chemca engneerng
aspect pertanng to desgn and deveopment have been covered by
worthwhe monographs. The handbook of sovent extracton s an exceent
source of nformaton on a aspects of the extracton. The modern
chemstry of supramoecues n sovent extracton s very we covered n a
recent research monograph by the author.
The frst dscovery of extracton method dates back to 1842 when Pegot
dscovered anove method for the extracton of uranum(VI) wth
ethyacetate or dethy ether. Ths was foowed by ntensve study on the
sovent extracton of ron (III) wth dethy ether from hydrochorc acd.
Serous attempts were made to repace exposve dethy ether wth an
equvaent sovent wthout much success. The sovent extracton methods
were put on frm footng by Nernst by formuatng an equaton satsfyng
thermodynamc consderaton of concentraton as we as the actvty
coeffcent of soute both n aqueous and the organc phase. When dthzone
was frst dscoverd by Fsher there was a great exctement as by |ust
controng pH of the souton one coud extract as many as sx metas wth
dthzone n choroform or carbon tetrachorde as duents. Ths was
foowed by the dscovery of the cupferron. It was an dea reagent for both
ron (III) and copper (II) at varyng condtons of extractons. Snce t was
used for extracton of both copper as we as ron t was desgnated as
cupferron. Sande and hs group dscovered dmethy-gyoxme whch was a
rea andmark n the chemstry of organc gands. In spte of deveopment
of sophstcated nstruments for the anayss of metas, dmethy gyoxme,
contnues to en|oy favoured pace for the compexaton of ncke, paadum
and bsmuth. Oxne was aso an equay promsng gand.
An extensve account of extracton equbra was gven by many chemsts.
They presented a vvd pcture of the extracton behavour and enumerated
varous parameters whch nfuenced the process of extracton. They
attempted to cassfy varous extracton systems. The sgnfcance of the KD
or D n predctng stabty of a compex was ascertaned rgorousy by
equaton n overa extracton. The authortatve revews are a andmark n
extracton chemstry whch dea wth varous factors nfuencng the process
of extracton and the possbty of usng them n anaytca chemstry
whch was favoured by many workers. Ouanttatve nterpreton of
extracton equbra and factors promotng separaton were revewed n
anaytca chemstry.
Tabe 1.1 Internatona Sovent Extracton Conferences (ISEC)
S. No. Year Pace where hed Name of sponsorng country
1 1965 Harwe U.K.
2 1966 Gothenburg Sweden
3 1968 |erusaem Israe
4 1971 Hague Netherands
5 1974 Lyon France
6 1977 Toronto Canada
7 1980 Legh Begum
8 1983 Denver USA
9 1986 Munch Germany
10 1988 Moscow Russa
11 1990 Kyoto |apan
12 1993 York U.K.
13 1996 Mebourne Austraa
14 1999 Barceona Span
15 2002 |ohannesberg South Afrca
16 2005 Montrea Canada
The separaton scence pays a sgnfcant roe n anaytca chemstry. In
the past many
methods have been deveoped usng arge number of sophstcated
nstruments. It factated quanttatve anayss of metas from mgram
(10-3) to ato eve (10-18). The methods were rapd and senstve. They
ncuded absorpton spectroscopy, fuorosence technque, pasma
spectroscopy ncudng atomc absorpton method and numerous
eectroanaytca and radochemca methods. However, nspte of these
methods beng so senstve and seectve, for the purpose of quanttatve
anayss the demand grew for anayss of extra pure materas specay
those free from nterferng components. Some methods coud not furnsh
reabe resuts f n case nanogram (10-9) mpurtes were present. Ths ed
to search for reabe methods for the purpose of soaton and purfcaton
of compounds before one coud undertake the task of nstrumenta
quanttatve anayss. Many separaton methods are descrbed n
authortatve monographs. Each of them s mportant n a true sense. An
account of varous separaton methods ke chromatography, reversed
osmoss, eectrophoress, dayss are avaabe n the monographs. They
ndcate how an exceent nstrumenta method of anayss can be used f
suppemented by an effcent separaton technque. A coormetrc
methods need premnary separaton of mpurtes. In the presence of such
mpurtes t woud nfuence the process of anayss.Some books present
nformaton on the specased methods for the soaton and determnaton
of rare metas or the radoactve sotopes. Ony few methods were an
excepton to ths rue of pre-separaton as are atomc absorpton
spectroscopy or nductvey couped pasma atomc emsson spectroscopy
whch generay do not need premnary treatment of sampe souton for
separaton. Amongst separaton methods so far utzed, sovent extracton
occupes the most favoured poston.
The sovent or qud-qud extracton methods have been broady cassfed
on the bass of process of extracton. Based on ths the four broad
categores of extracton were gven as extracton by cheaton or
compound foowed by a method of extracton by sovaton or on par
formaton and the bendng of these two methods nto synergc extracton.
The ma|or share of success for the extracton procedure goes to extracton
by cheaton. As descrbed earer the dscovery of dthzone, cupferron,
dmethygyoxme or 8- hydroxyqunone have permtted extractve
separaton of arge number of eements. Ths group of extracton aso
ncudes acd akyphosphorc acd dervatves (.e. qud caton
exchangers). Unfortunatey none of the cheaton methods had appcatons
n the ndustra scae operaton. However, for anaytca chemsts the
methods were a bessng, as many cheatng agents ke say 2-
thenoytrfurocetone1 or 8-hydroxy2qunone permtted smutaneous
extracton and drect photometrc determnatons n one snge operaton.
Even wth newy dscovered tha or aza crown ethers11 the drect
extracton and coormetrc determnaton of metas was the most popuar
mode of anayss.
In nucear energy programmes, the greatest contrbuton pertans to
sovaton system. The versate sovatng sovents ke TBP, TBPO, TOPO or
smpe compounds ke dethy ether, ethy aceate or MIBK whch factated
separatons of varous eements ke uranum, thorum, putonum or
cafornum. The method of substochometrc extracton was qute
satsfactory for anayss of varous sotopes of eements. Even common
transton metas ke zrconum, hafnum, nobum and tantaum or seres of
transton eements or the eements ke uranum or thorum were
separated wth sovatng sovents ke TBP. In such a system more the basc
sovent t offered better the extracton. TBP>TBPO>TOPO (order of
The ast-named compound provded better extractons. Apart from bascty
the eectron densty sorroundng the donor atom was of utmost
CH3-CH2- O -CH2 CH3 C-CH2-CH2- O -CH2-CH2-C
dethy ether (I) dchoro ether (II)
In the above exampe oxygen s the donor atom the eectron densty
around t n
compound (II) beng arge the repuson ncrease to retard the process of
extracton. Apart from ths the presence of satng out agents aso enhance
extracton e.g. urany ntrate from ntrc acd meda contanng thum
ntrate gave better extracton as the atter ncreased the anonc
concentraton vz. NO-
The addton of thum ntrate decreased the deectrc constant of the
aqueous phase
thereby promotng extracton due to better assocaton of ons and fnay
by removng the water moecues from the coordnaton sphere of the meta
to gve room for the sovent moecue. Many worthy separatons have been
carred out n the sovaton system on pot pant scae.
The synergc extracton s a system deang wth combnaton of the two
e.g. urany ntrate was better extracted wth mxture of TBP as we as H-
DEHP (bs-2
ethy hexy) phosphorc acd. Ths was because the stabsaton factor
ncreases due to
|ont acton of process of sovaton as we as cheaton eadng to the
synergc extracton.
Large number of systems coud show synergc extracton. Unfortunatey
none of the synergc extracton systems have been used n ndustry for
recovery of on or purfcaton of metas by such system on pot pant scae.
Another way of cassfcaton of extracton process s argey based upon a
knd of acdc or basc sovents used for extracton e.g. extracton wth (H-
DNNS) dnonynapthenc suphonc acd s an exampe of acdc extracton
whe extracton wth hgh moecuar weght amnes (HMWA) s usuay
termed as basc extractons. In fact both systems vz. acdc or basc
extractants have one thng n common namey the extracton proceeds by
on par formaton.An anonc speces assocates wth sutabe caton to form
an uncharged speces whch ready undergoes quanttatve extracton . An
authortatve revew on sovent extracton by on par formaton have
appeared outnng nfuence of varous parameters
nfuencng process of extracton. A revew artce by Smth and Coeman or
by Green and Khopkar are rea andmarks n the chemstry of extracton by
on par formaton. The other revews have brought out rea exampes of
the sovent extracton wth hgh moecuar weght amnes.
At ths |uncture, t s worthwhe to expan the sgnfcance of the words
"Lqud caton exchangers". Now, a acdc akyphosphorc acds, napthenc
acd, caporc acd or smar fatty acds are exampes of qud caton
exchangers. Ths s because the extracton proceeds n same manner as
one n sod caton exchange reacton n coumn. If o- refers to organc
phase, R = gand and M s meta wth vaencyn.
|H2 R|0 + Mn+ (Mn R)0 + 2H
In ths exampe we note that a proton was repaced by meta on Mn+ wth
the vaencyas n ether n resn phase n caton exchange reacton n
coumn or n sovent extracton n the organc phase. In vew of the fact that
the exchange proceeds wth reference to caton and snce extractants were
mosty used n qud form, we desgnate these process as "qud caton
exchange reacton". A fatty acds have protons whch were exchanged by
meta ons
As far as the sgnfcance of qud anon exchanger was concerned, a
hgh moecuar weght amnes (HMWA) were termed as qud anon
exchangers. These amnes mght be prmary, secondary, tertary or
quaternary and dependng upon the knd of extracton one, two, three or
four hydrogen atoms are repaced by anonc speces to form the compex
e.g. f R3 NH+ was tertary amne and underwent reacton wth anon n the
foowng manner
a uncharged compex was formed. Now ths sat of amne when contacted
wth anonc choro compex .
So we have an on par wth caton as (R3NH+) wth uncharged anon as
2-) formng on whch s a pared compex. Such extracton s common n
purex process for recovery of uranum e.g. the suphate compex durng
extracton wth HMWA. Snce we use amne n qud form and snce the
reacton proceeds wth the exchange of anon, the whoe product was
caed qud anon exchangers. There are many amnes as TOA, TIOA, TLA,
MDOA, etc. Further we have synthetc amnes ke Prmene |M-T (prmary),
Amberte LA-2 (tertary) or Aquat 336 (quaternary) amne. Hgher the
basc amne, better was the process of extracton. On these assumptons
the extractabty vares wth rse n extracton from prmary> secondary>
tertary> quaternary amnes.
Before undertakng extensve dscusson on the appcatons of qud on
exchangers n anaytca chemstry t s worthwhe to undertake descrpton
of some recent work on mportant facets of sovent extractons wth qud
on exchangers whch were noted n the ast few years durng extracton
studes. An nterestng revew on extractons nvovng organophosphorous
compounds or suphur contanng aky suphoxdes, hgh moecuar weght
amnes and qunone compounds51 was pubshed. An attempt was made
to draw an anaogy between amne extractons of metas and ther anon
exchange sorpton on the sod anon exchange resn n coumn. A usefu
chart was prepared stng the extracton of many eements wth
quaternary amnes from a mnera acd soutons mosty based on the
vaue of the dstrbuton constants aong wth nvestgatons on the
mechansm of extracton. An exhaustve account on extracton of seected
metas wth aky amne or ther correspondng sats as we as extractons
wth aky organophosphorous compounds
was carred out. The extracton of anonc choro compexes of ron, cobat,
ndum and gaum were extracted wth quaternary ammonum compounds
n aromatc hydrocarbons. Ths reveaed that the process represents anon
exchange phenomena as was seen n coumnar work. Another revew
appeared amost the same tme n 1964 on extracton of metas wth hgh
moecuar weght amnes. A smar authortatve revew appeared on
extractons wth quaternary ammonum compounds of the transton
eements as we as nner transton eements . A typca exampe cted was
the synergstc extractons nvovng two extractants vz. cheatng agent
and aphatc or aromatc amne . The roe of organc poymers as on
exchanger was stressed n another revew . A paper chromatographc
studes were carred out usng wth Amberte SA-2 and SB-2 paper strps
and mxtures of cheatng extractants ke 2-thenoytrfuoro acetone (TTA)
to separate severa mut-component mxture of the metas. A genera
revew on extractons n anaytca chemstry comprsed of the norganc
compounds and organometac compexes by water mmscbe sovents.
Another revew was presented on extractons
n chemstry n the past three years (1959-1961). A arge number of papers
presented n Conference on Separaton Scence and Technoogy ncuded
severa hgh moecuar weght amnes . A specfc reference merts menton
of qud caton exchangers ke LIX 65N (2- hydroxy 5-nony benzophenone
oxme) from the vewpont of extracton equbra and strppng n process
of extracton.
The hgh moecuar weght amnes or qud anon exchangers factated
severa separatons; the mportant beng separaton of uranum and
transuranum eements. The most nterestng factor of these extractons
was that not ony they factated separaton of the chemcay smar
eements ke zrconum and hafnum87 or nobum and tantaum or
gaum, ndum and thaum but they aso provded seectve methods for
ther separatons specay of eements n two dfferent oxdaton states. For
nstance t provded the best too for the separaton of U(IV) from U(VI) or
T(I) from T (III) n the organc acd soutons. An endeavour s made at ths
pont to hghght some of the mportant separatons so easy
accompshed by use of qud anon exchanger. The separaton of cadmum
and znc was effected by Amberte LA-2. The bromo or odo compexes at
pH-3.0 showed promsng separatons. Large number of qud anon
exchangers ke MDOA66 .e. methydodecy octy amne or TOA was used
for the extractve separaton of cobat n
hydrochorc acd or thocyanate meda wth Amberte LA-168 factatng
the cean-cut separaton of ncke. The separaton of chromum n two
oxdaton states vz. Cr (VI) and Cr (III) was factated by use of MDOA, TBA
(trbuty amne) or Aquat 336S (a quaternary amne) n choroform. The
method permtted drect photometrc determnate of bue perchorc acd at
525 nm. The most chaengng task was to separate znconum from
hafnum . Ths was carred out by use of TOA from 8M hydrochorc acd
wth xyene as duent by process of mutstage counter current extracton .
In comparson wth qud caton exchangers not much work has been
carred out on extracton of anthandes by amnes or qud anon
exchangers. Ony tetervaent anthandes were extractabe factatng
separatons of anthandes from actndes. Another andmark n the
chemstry of qud anon exchangers was separaton of nobum and
tantaum . The amnes used were MDOA, or TIOA from 9M hydrochorc acd
and ony Nb was extracted but not Ta , thus factatng ther separaton
wth MDOA n xyene. Wth TBA aso, separatonwas possbe from 9M
hydrochorc acd when Nb was extracted and not Ta . Oxaate
speces were best extracted n TBA . Some of the extracton coud be
carred out wth TOA n kerosene at pH-1.0 wth tartarc or oxac acds
promotng formaton of ther anonc speces. A arge number of transuranc
eements ncudng uranum (VI) were seperated. The U (VI) separaton was
exceent n suphate meda athough good separaton was aso possbe
from ntrate , chorde as we as acetate soutons . The work n akane
meda factated the separaton of anonc carbonate compexes. Severa
exampes coud be cted to show usefuness of qud anon exchangers n
anaytca chemstry.
Lqud caton exchangers consst of arge number of extractants. They
ncude aky
phosphorc acds ke HDEHP, dervatves of suphonc acds ke HDNNS
naptheene) suphonc acds or severa fatty acds ke caproc acds. The
extractants behave amost ke a cheatng agent wthout formaton of rng
or cycc structured compounds. Kmura had done exhaustve work on
extracton of severa transton metas by extractons wth H-DEHP as
extractant. Maxmum amount of work was done by Peppard et a. on the
extractve separaton of anthandes by HDEHP from hydrochorc acd.
Uranum (VI) was best extracted from suphurc acd wth HDEHP n
kerosene . The satng out agents promoted extracton whe TBP, TOPO
ead to synergestc extracton of uranum wth HDEHP .e., bs (2 ethyhexy)
phosphorc acd . Other ess common transuranc metas were aso
quanttatvey extracted wth bs 2-ethy hexy phosphorc acd. There were
severa exampes nvovng extracton of copper wth caproc acd or wth
napthnc or other fatty acds. The dscusson on mechansm of extracton or
extracton equbra s gven n subsequent chapters.
The most sgnfcant advantage was the possbty of separaton of
eements at mcrogram concentraton. These methods factated the
separaton of the chemcay smar metas. No other method n sovent
extracton aows separaton of eements n two dfferent oxdaton states.
Further, the group separaton of anthandes or actndes was qute
smpfed by these extractants. The fexbty of ad|ustment of pH or
controng reagent concentraton or choce of duent or organc carboxyc
acds factated the seectve separatons of arge number of eements. On
account of the advantage of regeneraton of exchangers, the process
became most economca. In severa nstances common sovents such as
kerosene or aromatc hydrocarbons served the purpose of the duent. Most
of the extractants were commercay avaabe n pure form, so further
purfcaton was not necessary. The extracton equbra was attaned n a
few seconds. The strppng of the metas was possbe wth dute mnera
acds or water. The dfference n strppng behavor was fuy expoted for
meta separaton. The ony dsadvantage was the formaton of thrd phase
durng extracton. To mtgate ths probem one had to use modfers. Such
modfersconssted of decano, or smar poyhydroxy acoho. Thrd phase
formaton was specay a serous probem n ndustra separatons, whch
deayed separaton. The phases were easy separated n the presence of
the modfers.
No other extractant was so frutfuy used for the meta separaton as was
qud on
exchangers. Athough cheatng extractants were numerous whch
factated exceent separatons at tracer eves n aboratory, they were
proved to be useess on ndustra scae n the pot pant operaton. Even
the sovatng sovents (wth the excepton of TBP and to some extent MIBK)
were found to be worthess for arge scae separatons. However, qud
caton exchangers ke LIX-64N, Versatc acd, SRS-100 had extensve
appcatons for the separaton of copper. The napthanc or caproc or nony
suphonc acds were used on a arge scae. Smary the separaton of
cobat or ncke was accompshed on mass scae wth Keex-100 as the
extractants. Not ony qud caton exchangers but aso qud anon
exchangers were used n ndustry. The extracton of znc, cadmum,
patnum, vanadum, chromum, as we as zrconum and nobum was
acheved by qud on exchangers. A over the word specay n South
Afrca, Europe, Canada, Engand and Austraa there are bg pants for
recovery of metas. In comparson neggbe progress was made for ther
use n asan countres ke |apan, Chna and Inda. However, wth knowedge
of mechansm of the extracton equbra and knetcs of extracton, one
coud deveop seectve methods for the separaton of metas wth these
reagents. Ths s because a processes were economca and reproducbe.
Sovent extracton s a most versate too of separaton on account of ts
senstvty and speed of operaton. The technque needs no sophstcated
exceptng a smpe pH meter or spectrophotometer. An evouton has
occured snce 1850 for the deveopment of extractants for the purpose of
separaton. A arge number of authortve research monographs have
appeared n the market. The hstory of deveopment dates back to 1842
when procedure for extracton of uranum was deveoped. Ths was qucky
foowed by a seectve method for sovent extracton of ron. Then new
extractants ke dthzone, cupferron, dmethygyoxme and 8-
hydroxyqunone were synthessed. Some attempts were made to
understand the mechansm of the extracton. At the same tme, the sub|ect
of separaton scence grew we wth the possbty of anayss from mto
nanogram concentraton of meta. A most sutabe way of cassfcaton was
based on process of extracton. It was wdey accepted by anaytca
chemsts athough the one nvovng categorsaton of acdc, neutra and
basc extractants was aso qute satsfactory. Enormous amount of work
was carred out n the chemstry of cheatng extractants.
Ths was foowed by use of sovatng sovents permttng argescae
separaton. The synergc extracton system dd not progress due to paucty
of ts appcaton n ndustra operatons but extracton by on par
formaton nvovng basc extractants ke hgh moecuar weght amnes or
acdc extractants ke aky phosphorc acd or fatty acds came to the
forefront due to ther appcatons n ndustra separaton. The aky
phosphorc acd extracton mechansm was smar to cheaton but dd not
form any cycc structure. Amnes or basc qud anon exchangers had wde
utty n chemstry. Some new facts of extractons encountered are brefy
deat wth. Lqud anon exchangers have growng demand n separaton
chemstry on account of prepondrance of anonc compexes of mnera
acds or organc carboxyc acds whe qud caton exchanger had wde
appcabty n chemstry of anthandes for ther separaton. Many more
qud exchangers were sted wth ony one demert of thrd phase
formaton n hgh moecuar weght amnes but t was crcumvented wth
the use of modfers. Numerous ndustra appcatons were possbe, more
detas of whch w be provded n the ast chapter of ths monograph. In
one can state that athough these exchangers have very wde appcabty
and used n advanced countres ke USA, UK, Canada, Europe, t has not
become popuar n most
Asan countres excudng |apan. However, t s hoped that as the
fundamenta chemstry deveops they woud fnd very wde appcabty n
pot pant operaton n Inda.
Solvent extraction and separation of element with the li!id
ion exchan"er# S$%$ &hop'ar (p!)lisher#new a"e
Ion exchan"e separation in anal+tical chemistr+# ,lof
Sam!elson (p!)lisher#-ohn wile+ and sons*
Ion exchan"e and solvent extraction vol$#./ 01aco) %arins'+
and 2i3ha' %arc!s
Anal+tical chemistr+# 4ar+ Christian 5
edition (p!)lisher#
-ohn wile+ and sons*