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InorgChem d-Block Elements

TRANSITION ELEMENTS are elements, which forms at least one compound in which the element has in incompletely filled inner d su!shell "lements with at least one o#idation state in which the element has incompletely filled inner d su!shell $i.e. w/1 to 9 e%& 'candium $'c& ( )inc $*n& are not transition elements as !oth has only one o#idation state 'c+, ( *n2,, which !oth has no incompletely filled d su!shell d-BLOCK ELEMENTS are elements whose highest energy electron / last filled electron is found in the d or!ital "lement atoms with electronic configuration - .$n+1&s2nd x /irst transition series0 'c, 1i, 2, 3r, 4n, /e, 3o, 5i, 3u, *n

Electronic configuration:
6toms of d !loc7 elements are characteri)ed !y inner !uilding of d su!shells 4ost contains the configuration - .nd x$n+1&s2 "#cept0 3r $*829&0 -6r.+d59s1 and 3u $*829&0 -6r.+d1:9s1 1he 2, ions of d !loc7 elements ha;e no e% in the ;alence s or!ital 3onfiguration0 - .nd x

Typical properties of Transition elements:

Properties similar to s !loc7 elements 4etals <ood conductor of electricity ( heat 4P =P Properties different from s !loc7 elements >ard, strong, high 0 'trong ( closely pac7ed struct. due to delocali)ation of 9s ( +d e% 'imilar chemical properties0 ?utermost su!shell 8 9s2 2aria!le o#idation state0 'uccessi;e @" are close 6!ility of formation of comple#es0 6;aila!ility of low lying d ;acant or!itals 3pds are colored0 'plitting of d su!shell into different energy le;els after comple# formation 3atalytic !eha;ior0 6!ility to form comple#es ( the e#istence of ;aria!le o#idation states 'c ( *n do not e#hi!it typical properties of transition elements

Variation of Properties
Ionization Enthalpy:
d =loc7 elements has 9d su!shell filled !efore +d su!shell =efore filling, 9s has lower energy than +d 6fter filling d or!ital, +d has lower energy than 9s e% in d or!ital screens 9s as it is more penetrating Ahen d !loc7 metal ioni)es, the 9s e% are first remo;ed Bifference in energy !tw +d ( 9s su!shells is small, successi;e @" increases gradually 6cross the 1st transition series, @" increases slightly 6dditional e% is added to inner +d su!shell and screens the 9s e%, which is !eing ioni)ed 'creening effect cancels most the increase in "53 1st @" of 'c C *n > 1st @" of D ( 3a as the "53 inc. Bue to the small ( gradual increase in @", transition elements ha;e similar chemical properties

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Metallic Radius:
/actors affect the metallic radius of d !loc7 metals0 "53 on the outermost e%0 inc. from 'c to *n Eepulsion !tw the d electrons0 inc. from 'c to *n 6ll d !loc7 metals ha;e smaller atomic radii than s !loc7 in same period due to the inc. of "53 6cross the period from 'c to *n, 6tomic radius dec. slightly from 'c to 3r0 'light increase of "53 3r to 5i ha;e nearly constant atomic radius0 @ncreasing "53 ( repulsion cancelled out 6tomic radius inc from 5i to *n0 Eepulsion !tw e% increases as * increases ?;erall ;ariation in atomic radius is small $:.12 % :.16 nm&0 e% is in inner +d su!shell

Ionic Radius:
2ariation of ionic radius of d !loc7 elements is similar to that of atomic radius 6ll d !loc7 metals ha;e smaller ionic radii than s !loc7 due to the inc. of "53 6cross the period, the ionic radius from 'c to 3u dec. slightly as the slightly inc. of "53 @onic radius of *n2, is slightly larger than e#pected as the full filled +d1: produces a larger electronic repulsion

Melting Point & Hardness:

4P ( >ardness of metal 4etallic !ond strength d =loc7 elements usually ha;e higher 4P ( hardness =oth s ( d e% are delocali)ed to the electron sea and ta7e part in the metallic !ond 'trong metallic !ond 4ost d !loc7 elements are closely pac7ed $3oordination num!er 8 12& 6tomic radii of d !loc7 elements are smaller 4P =P as only small fraction of metallic !onds has to !e !ro7en in melting !ut all metallic !onds are !ro7en in !oiling $i.e. =oiling 8 6tomi)ation& /actor affecting the 4P ( hardness of 'c to *n 'maller atomic radius 'tronger metallic !ond 4ore unpaired d e% 4ore delocali)ed e% in metallic !ond 'tronger metallic !ond 3loser pac7ing of atoms 'tronger metallic !ond >alf filled or full filled d su!shell are e#tra sta!le 6cross the period from 'c to *n, the 4P ( hardness @ncreased from 'c to 2 as the no. of unpaired d e% inc. ( atomic radius dec. 4etallic !ond strength increases Becreased from 2 to 4n as 3r ( 4n has e#tra sta!le +d5 4etallic !ond strength dec. @ncreased to a ma#. at /e, 3o, 5i as unpaired d e% are more in;ol;ed in metallic !ond Becreased from 3u to *n as !oth has e#tra sta!le +d1:

d =loc7 elements usually ha;e higher densities than s !loc7 elements as the atoms are closely pac7ed 1he density increases from 'c to 3u as the relati;e atomic mass increases while atomic radii are appro#imately constant *n has a lower density than 3u as the +d ( 9s e% are less in;ol;ed in metallic !ond Farger atomic radius

6cross the period from 'c to *n, "53 increases "lectronegati;ity generally increases "ase of formation of metal ions dec. 4etallic character dec. d =loc7 elements are less electropositi;e / more electronegati;e than s !loc7 elements d =loc7 cations are less li7ely to form than s !loc7 4n has a lower electronegati;ity than e#pected Bue to low ioni)ation enthalpies0 "#tra sta!ility of 4n2,0 -6r.+d5 *n has particularly low electronegati;ity


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Bue to low ioni)ation enthalpies0 "#tra sta!ility of *n2,0 -6r.+d1: 1he standard electrode potential $" & has a similar ;ariation with electronegati;ity Ahen "53 on the outermost e% increases, " !ecomes more positi;e or less negati;e

!idation "tates:
1ransition metals show ;aria!le o#idation states0 'c ,1, ,2, ,+ 'c+, 1i ,1, ,2, ,+, ,9 1i2,, 1i+,, 1i?2 2 ,1, ,2, ,+, ,9, ,5 22,, 2+,, 2?2,, 2?2, 3r ,1, ,2, ,+, ,9, ,5, ,6 3r2,, 3r+,, 3r9,, 3r?+ 4n ,1, ,2, ,+, ,9, ,5, ,6, ,7 4n2,, 4n$?>&+, 4n?2, 4n?92%, 4n?9% /e ,1, ,2, ,+, ,9, ,5, ,6 /e2,, /e+, 3o ,1, ,2, ,+, ,9, ,5 3o2,, 3o+,, -3o/6.2% 5i ,1, ,2, ,+, ,9 5i2,, 5i+,, 5i2?+, 5i?2 3u ,1, ,2, ,+ 3u,, 3u2, *n ,1, ,2 *n2,
G 3omple# only 4ost sta!le state ?#idation states

1he e#istence of ;aria!le o#idation states due to gradual increases rather than sharp rapid rise of successi;e @" of transition metal 6cross the 1st transition series, /rom 'c to 4n, the highest possi!le ?5 8 1otal no. of e% in +d ( 9s 4a#imum ?5 found in 4n$2@@& =y remo;al of all +d ( 9s electrons from 4n /rom 4n onwards, the highest ?5 decreases as the no. of unpaired e% decreases 'ta!ility of a particular ?5 is related to e#tra sta!le state of half/full filled d or!ital 4n2, ( /e+, are particularly sta!le as they ha;e -6r.+d5 config. *n2, is particularly sta!le as it has -6r.+d1: config. "nthalpy of formation of an ion0 >f 8 >atom , @" , >hyd 6n ion of lower >f is energetically sta!le 6n energetically sta!le ion $e.g. 3u,& may !e unsta!le w.r.t. disproportionation0 3u$s& 3u,$aH& >f 8 ,6:6 7Imol%1 3u$s& 3u2,$aH& >f 8 ,971 7Imol%1 $less sta!le& Bisproportionation0 23u,$aH& 3u$s& , 3u2,$aH& > 8 %291 7Imol%1 ?ccurs spontaneously ( energetically fa;ora!le

#ormation of $olored $pds:

4ost s !loc7 metals form colorless cpds !ut most d !loc7 metals form colored cpds "#ception0 'c+,, 1i9, 3u,, *n2, Ahen transition metal forms cpd, 1he electrons in s shell is remo;ed d shell !ecomes the outermost shell 1he d or!itals may split into different energy le;els in cpd 1he splitting is due to the electronic repulsion !tw d e% and FP e% of anion / ligand @f the metal ion has d shell neither full filled nor empty, e% in lower energy le;el can Jump to a higher or!ital 6!sor!s electromagnetic radiation of a particular freHuency 6!sorption in the ;isi!le light region ma7es the ion colored 3olor of aHueous ion0 'c+, 3olorless 1i+, Purple 1i9, 3olorless 22, 2iolet 2+, <reen 2?2, =lue 2?2, Kellow 2?+% Eed 2, +, 3r =lue 3r <reen 4n2, Pale pin7 4n$?>&+ =rown 4n?2 =lac7 4n?92% <reen 4n?9% Purple /e2, <reen /e+, Kellow 2, 3o Pin7 5i2, <reen 3u, <reen 3u2, =lue *n2, 3olorless 'ome transition metals show colored flame when !urned as the e#citation of e%

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Eadiation in ;isi!le spectrum is emitted when the e% falls !ac7

Reaction %ith %ater:

d =loc7 metals usually react slowly with water 1he low reacti;ity of d !loc7 metals is due to its high @" ( >atom "#ception0 'c , hot water 'c$?>&+$aH& , >2$g&

Vanadium & Manganese

2anadium is a soft ( sil;ery white metal 3ommon o#idation states0 ,2, ,+, ,9, ,5 Kellow 2?2,, =lue 2?2,, <reen 2+,, 2iolet 22, respecti;ely 2anadium can react w/o#idi)ing acids >5?+ ( >2'?9 2anadium$2&0 Bio#o;anadium$2& ion 2?2, is produced !y dissol;ing ammonium polytrio#o;anadate$2&0 5>92?+$aq& , 2>,$aq& 2?2,$aq& , 5>9,$aq& , >2?$& 2?+%$aq& , 2>,$aq& 2?2,$aq& , >2?$& 5either 25, nor -2$>2?&6.5, e#ists as the charge density is e#tremely high >ydrolysis occurs0 25,$aq& , 2>2?$aq& 2?2,$aq& , 9>,$aq& @t is a sta!le o#idation state of 2 2anadium$2& o#ide, 22?5, is an amphoteric o#ide0 22?5$s& , 2>,$aq& 22?2,$aq& , >2?$& 22?5$s& , 6?>%$aq& 22?9+%$aq& , +>2?$& 2anadium$@2&0 ?#o;anadium$@2& ion 2?2, can !e produced !y reacting 2?2, with metal0 *n$s& *n2,$aq& , 2e% 2?2,$aq& , 2>,$aq& , e% 2?2,$aq& , >2?$& 5either 29, nor -2$>2?&6.9, e#ists as the charge density is e#tremely high 2anadium$@@@& ( 2anadium$@@&0 2+, and 22, ions can !e produced !y reducing 2?2, !y metal0 2?2,$aq& , 2>,$aq& , e% 2+,$aq& , >2?$& 2+,$aq& , e% 22,$aq& =y adding e#cess *n granules or *n amalgam in acidic condition $conc. >3l&, 2?+%$aq& 2?2,$aq& 2?2,$aq& 2+,$aq& 22,$aq& =oth 2+, and 22, ions are reducing and readily o#idi)ed !y air or water

4anganese is a hard, pin7ish grey metal 3hemically acti;e and rapidly attac7ed !y hot water, steam or acid0 4n$s& , 2>2?$& 4n$?>&2$s& , >2$g& 4n$s& , >2?$g& 4n?$s& , >2$g& , 4n$s& , 2> $aq& 4n2,$aq& , >2$g& 3ommon o#idation state0 ,2, ,9, ,7 4anganese$@@&0 1he pale pin7 4n2, ion is ;ery sta!le in acids $partly due to +d5 config.& @t forms comple# -4n$>2?&6.2, in water and undergoes slight hydrolysis -4n$>2?&6.2,$aq& -4n$?>&$>2?&5.,$aq& , >,$aq& @n al7aline medium, 4n2, would !ecomes white 4n$?>&20 -4n$>2?&6.2,$aq& , 2?>%$aq& -4n$?>&2$>2?&5.$s& , 2>2?$& 1he 4n$?>&2 in al7aline is readily o#idi)ed !y ?2, >2?2, ?3l% to unsta!le 4n$?>&+$s& and finally to 4n?2$s&0 94n$?>&2$s& , ?2$g& , 2>2?$& 94n$?>&+$s& 24n$?>&+$s& , $n%+&>2?$g& 4n2?+n>2?$s& 24n2?+n>2?$s& , ?2$g& 94n?2$s& , $2n&>2?$& 24n$?>&2$s& , ?2$g& 24n?2$s& , 2>2?$&


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4anganese$@2&0 4n?2 is a dar7 !rown amphoteric solid w/strong o#idi)ing property0 4n?2$s& , 9>,$aq& , 2e% 4n2,$aq& , 2>2?$& 4n?9 can o#idi)e 3l% in >3l$aq&0 4n?2$s& , 9>3l$aq& 4n3l2$aq& , 2>2?$& , 3l2$g& 4n?9 can !e o#idi)ed !y strong o#idi)ing agent in !asic medium0 +4n?2$s& , 6?>%$aq& , 3l?+%$aq& +4n?92%$aq& , +>2?$& , 3l%$aq& 24n?2$s& , 9?>%$aq& , ?2$g& 24n?92%$aq& , 2>2?$& 4anganese$2@@&0 4n2?7 is acidic co;alent compound Purple manganate$2@@& ion 4n?9% is a powerful o#idi)ing agent0 6cidic medium0 4n?9%$aq& , 8>,$aq& , 5e% 4n2,$aq& , 9>2?$& 6l7aline medium0 4n?9%$aq& , 2>2?$& , +e% 4n?2$s& , 9?>%$aq& 4n?9% can react w/iron$@@@& ion0 4n?9%$aq& , 8>,$aq& , 5/e2,$aq& 4n2,$aq& , 9>2?$& , 5/e+,$aq&

6 comple# $coordination compound& is formed when a central metal ion/atom is attached !y ligands in which the no. of ligands is greater than the normal ;alance of the central ion/atom 1he metal ion/atom acts as an electron pair acceptor $Fewis acid or electrophile& 1he metal ion/atom ought to !e has high positi;e charge density to attract the ligands 1he ligand acts as an electron pair donor $Fewis !ase or nucleophile& COMPLEX0 6 central metal ion/atom surrounded !y and dati;ely !onded to other ligands LIGAND0 6n ion or molecule containing at least one atom ha;ing a lone pair of electrons which can !e donated to the central cation or atom to form a dati;e co;alent !ond COORDINATION NUMBER of the central ion is the num!er of ligands !onded to the central ion d =loc7 metal has strong tendency towards comple# formation as the a;aila!ility of low lying ;acant or!itals ena!les metal ions to accept FP e% from ligands

3oordination compounds are named according to the nomenclature recommended !y @LP63 @onic coordination compounds0 3ation is name !efore the anion 1he ligands and central metal are named together as one word ?rder of ligands0 6nionic, 5eutral, 3ationic "#ample0 -Pt3l2$5>+&9.2, 8 Bichlorotetraammineplatium$@2& 5ames of anionic ligands end in %o 5ames of neutral ligands are the names of the molecules, e#pt 5>+, >2?, 3?, 5? 5ames of common ligands0 LIGAND PREFIX LIGAND PREFIX =romide =r% =romo 6mmonia 5>+ 6mmine 3hloride 3l% 3hloro Aater >2? 6Hua 3yanide 35% 3yano 3ar!on mono#ide 3? 3ar!onyl /luoride /% /luoro >ydro#ide ?>% >ydro#o 'ulphate$2@& '?92% 'ulphato 6mide 5>2% 6mido @f the no. of a particular ligand is more than one, the num!er is indicated w/<ree7 prefi#0 Aithin each type of ligand, the ligands are arranged in alpha!etical order, ignoring the num!ering prefi#es NUMBER PREFIX NUMBER PREFIX 1wo Bi /i;e Penta 1hree 1ri 'i# >e#a /our 1etra @f the comple# is anionic, the name of the metal ends in %ate

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"#ample0 -/e$35&6.+% 8 >e#acyanoferrate$@@@& 5ames of common metals in anionic comple#es0 METAL NAME METAL NAME 1itanium 1itanate 5ic7el 5ic7elate 3hromium 3hromate 3opper 3uprate 4anganese 4anganate *inc *incate @ron /errate Platinum Platinate 3o!alt 3o!altate @f the comple# is cationic or neutral, the name of the metal is unchanged "#ample0 -3r3l2$>2?&9., 8 BichlorotetraaHuachromium$@@@& 5eutral coordination compounds0 1he name of the comple# is the name of the cpd

(onding & "ta)ility:

Figand contains FP e% which forms dati;e !onds with the central metal Bifferent ligand has different tendency to donate their unshared electrons to form dati;e !ond 1he strength of the dati;e co;alent !ond of differs as the ligands differ 6 ligand can !e replaced !y another ligand which form more strong dati;e !ond i.e. the ligand that of higher tendency to donate the electrons Ahen a stronger ligands present, the wea7er ligand would !e replaced0 -/e$>2?&6.2,$aq& , 635%$aq& -/e$35&6.9%$aq& , 6>2?$& -5i$>2?&6.2,$aq& , 65>+$aq& -5i$5>+&6.2,$aq& , 6>2?$& @n the displacement of ligands of the comple#, usually there would !e color change 1he formation of comple# or displacement of ligand is a stepwise reaction @n -3u$>2?&6.2,$aq& , 95>+$aq& -3u$5>+&9$>2?&2.2,$aq& , 9>2?$&0
-3u$>2?&6.2,$aq& , 5>+$aq& -3u$5>+&$>2?&5.2,$aq& , 5>+$aq& -3u$5>+&2$>2?&9.2,$aq& , 5>+$aq& -3u$5>+&+$>2?&+.2,$aq& , 5>+$aq& -3u$5>+&$>2?&5.2,$aq& , >2?$& -3u$5>+&2$>2?&9.2,$aq& , >2?$& -3u$5>+&+$>2?&+.2,$aq& , >2?$& -3u$5>+&9$>2?&2.2,$aq& , >2?$& D1 8 1.911:9mol%1dm+ D2 8 +.161:+mol%1dm+ D+ 8 7.771:2mol%1dm+ D9 8 1.+51:2mol%1dm+

[-3u$5> & $> ?& . ] = D D D= [-3u$> ?& . ] [ 5> ]

2+ + 9 6 2 2 2+ 9 1 2 +

D1, D2, D+, D9 are called stepwise sta!ility constant 1he eHuili!rium constant of o;erall reaction0

D+ D 9

D is called the sta!ility constant of the comple# and it gi;es a measure of the sta!ility of the comple# ion 1he comple#es with large sta!ility constant is sta!le

1he spatial arrangement of ligands around the central metal is related to the coordination num!er 1he coord. no. is determined !y0 'i)e of the central metal 5o. and nature of ;acant or!itals for forming dati;e !onds F <enerally the coord. no. is constant for a particular metal atom / ion F F 3ommon coordination num!ers0 2, 9, 6 4 F F 3oordination num!er 8 60 @n comple#es with coord. no. of 6, the structure usually is octahedral0 F +, +% "#ample0 -3r$5>+&6. and -/e$35&6. F F 4 3oordination num!er 8 9 F F F @n comple#es with coord. no. of 9, the structure usually is tetrahedral0 "#ample0 -*n$5>+&9.2, and -3o3l9.2% 4 F 6 few four coordinated comple#es are ha;ing sHuare planar structure0 F F "#ample0 -3u$5>+&9.2, and -3u3l9.2% 1he -3u$5>+&9.2, and -3u3l9.2% comple# should !e si# coordinated and in octahedral structure, !ut the two >2? is loosely !onded and ignored usually >2? 53 35 @somerism occurs in the comple#es0 3u 'tructural isomers0 Bifferent ligands coordinated to the central metal 35 53 >2?


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"#ample0 -3o$5>+&5=r.2,'?92% and -3o$5>+&5'?9.,=r% <eometrical isomer0 Bifferent geometrical arrangement of ligands 'Huare planar comple#es0 a a ! ! 4 4 and -4a2!2.0 a ! ! a a a c c 4 4 and -4a2!c.0 a ! ! a d ! c d ! d 4 4 4 , and -4a!cd.0 a a ! a c c

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?ctahedral comple#es0 a ! a a 4 and -4a9!2.0 ! a a a ! ! a a 4 and -4a+!+.0 ! a a a

! ! 4 a a ! ! 4 a !

$atalytic action:
d =loc7 elements and their cpds are common catalysts in industry ( !iological systems =y pro;iding suita!le reaction surfaces, or =y forming unsta!le intermediates 3ommon catalysts0 22?5 or 2?+%0 3ontact process, 2'?2$g& , ?2$g& +'?+$g& /e or /e2?+0 >a!er process, 52$g& , +>2$g& 25>+$g& 4n?20 Becomposition of hydrogen pero#ide, 2>2?2$& 2>2?$& , ?2$g& 5i0 4anufacture of margarine, E3>83>2 , 2>2$g& E3>23>+ Pt0 4anufacture of nitric$2& acid, 95>+$g& , 5?2$g& 95?$g& , 6>2?$&

Heterogeneous catalysis:
@n heterogeneous catalysis, the catalyst and reactants are in different phases Lsually, the catalyst are finely di;ided solids 1he heterogeneous catalyst pro;ides a suita!le reaction surface for reactants to come close together and react "#ample, catalysis of gaseous reaction on solid surfaces li7e >a!er process ?utlined mechanism0 1he gaseous reactant diffuse to the catalyst 1he catalytic surface adsor!s one reactant $3at , E1 3at%E1& 1he catalytic surface adsor!s another reactant $3at , E2 3at%E2& =ond !rea7ing ( forming !tw catalyst ( reactants $3at%E1 , 3at%E2 3at%E2%E1%3at& 1he products desor!ed and diffused away $3at%E2%E1%3at E1%E2& 1he a!undance of ;alence e% and a;aila!ility of ;acant or!itals in d !loc7 elements facilitate the surface adsorption of reactants 1he adsorption !rought the reactants within close pro#imity to cataly)e reaction

Homogeneous catalysis:
@n homogeneous catalysis, the catalyst and reactants are in same phase 1he catalyst form an intermediate with the reactants to cataly)e reaction Eeaction mechanism is changed such that "6 is lower "#ample0 '2?82%$aq& , 2@%$aq& 2'?92%$aq& , @2$aq& is slow due to 7inetic factors /e+, can cataly)e the reaction as /e2,$aq& , e% /e2,$aq&0 2@%$aq& , 2/e+,$aq& @2$aq& , 2/e2,$aq& 2/e2,$aq& , '2?82%$aq& 2'?92%$aq& , 2/e+,$aq& /e+, o#idi)es iodide ions and gi;es /e2,, !ut /e2, reduces pero#odisulphate$2@& and gi;es /e+, 1he catalyst is unchanged at last