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THEGENERALFEATURESOF
TRANSITIONMETALCHEMISTRY
Thispageexplainswhatatransitionmetalisintermsofits
electronicstructure,andthengoesontolookatthegeneral
featuresoftransitionmetalchemistry.Theseincludevariable
oxidationstate(oxidationnumber),complexionformation,
colouredions,andcatalyticactivity.
Youwillfindsomeofthiscoveredquitebrieflyonthispagewith
linkstootherpartsofthesitewherethetopicsarecoveredin
moredetail.
Theelectronicstructuresoftransitionmetals
Whatisatransitionmetal?
Thetermstransitionmetal(orelement)anddblockelementare
sometimesusedasiftheymeanthesamething.Theydon't
there'sasubtledifferencebetweenthetwoterms.
We'llexploredblockelementsfirst:
dblockelements
YouwillrememberthatwhenyouarebuildingthePeriodicTable
andworkingoutwheretoputtheelectronsusingtheAufbau
Principle,somethingoddhappensafterargon.
Atargon,the3sand3plevelsarefull,butratherthanfillupthe
3dlevelsnext,the4slevelfillsinsteadtogivepotassiumand
thencalcium.
Onlyafterthatdothe3dlevelsfill.
Note:Ifyouaren'tsureaboutatomicorbitalsandelectronic
structures,youreallyneedtofollowthislinkbeforeyougo
on.Ittakesyoutoapageexplainingatomicorbitalsandthen
ontootherpagesaboutelectronicstructures.
Ifyoudofollowthelink,usetheBACKbuttononyour
browser(ortheHistoryfileorGomenu)toreturnquicklyto
thispage.
TheelementsinthePeriodicTablewhichcorrespondtothed
levelsfillingarecalleddblockelements.Thefirstrowofthese
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isshownintheshortenedformofthePeriodicTablebelow.
Theelectronicstructuresofthedblockelementsshownare:
Sc [Ar]3d14s2
Ti [Ar]3d24s2
V [Ar]3d34s2
Cr [Ar]3d54s1
Mn [Ar]3d54s2
Fe [Ar]3d64s2
Co [Ar]3d74s2
Ni [Ar]3d84s2
Cu [Ar]3d104s1
Zn [Ar]3d104s2
Youwillnoticethatthepatternoffillingisn'tentirelytidy!Itis
brokenatbothchromiumandcopper.
Note:Thisissomethingthatyouarejustgoingtohaveto
accept.Thereisnosimpleexplanationforitwhichisusable
atthislevel.Anysimpleexplanationwhichisgivenisfaulty!
Peoplesometimessaythatahalffilleddlevelasin
chromium(withoneelectronineachorbital)isstable,andso
itissometimes!Butyouthenhavetolookatwhyitis
stable.Theobviousexplanationisthatchromiumtakesup
thisstructurebecauseseparatingtheelectronsminimises
therepulsionsbetweenthemotherwiseitwouldtakeup
somequitedifferentstructure.
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Butyouonlyhavetolookattheelectronicconfigurationof
tungsten(W)toseethatthisapparentlysimpleexplanation
doesn'talwayswork.Tungstenhasthesamenumberofouter
electronsaschromium,butitsouterstructureisdifferent
5d46s 2.Againtheelectronrepulsionsmustbeminimised
otherwiseitwouldn'ttakeupthisconfiguration.Butinthis
case,itisn'ttruethatthehalffilledstateisthemoststable
itdoesn'tseemveryreasonable,butit'safact!Thereal
explanationisgoingtobemuchmoredifficultthanitseems
atfirstsight.
Neithercanyouusethestatementthatafulldlevel(for
example,inthecoppercase)isstable,unlessyoucancome
upwithaproperexplanationofwhythatis.Youcan'tassume
thatlookingniceandtidyisagoodenoughreason!
Ifyoucan'texplainsomethingproperly,itismuchbetterjust
toacceptitthantomakeupfaultyexplanationswhichsound
OKonthesurfacebutdon'tstanduptoscrutiny!
Transitionmetals
Notalldblockelementscountastransitionmetals!Thereare
discrepanciesbetweenthevariousUKbasedsyllabuses,but
themajorityusethedefinition:
Atransitionmetalisonewhichformsoneormorestable
ionswhichhaveincompletelyfilleddorbitals.
Note:ThemostrecentIUPACdefinitionincludesthe
possibilityoftheelementitselfhavingincompletedorbitals
aswell.Thisisunlikelytobeabigproblem(itonlyreally
ariseswithscandium),butitwouldpayyoutolearnthe
versionyoursyllabuswants.Bothversionsofthedefinition
arecurrentlyinuseinvariousUKbasedsyllabuses.
IfyouareworkingtowardsaUKbasedexamandhaven'tgot
acopyofyoursyllabus,followthislinktofindouthowtoget
one.UsetheBACKbuttononyourbrowsertoreturnquickly
tothispage.
Onthebasisofthedefinitionoutlinedabove,scandiumandzinc
don'tcountastransitionmetalseventhoughtheyaremembers
ofthedblock.
Scandiumhastheelectronicstructure[Ar]3d14s2.Whenitforms
ions,italwayslosesthe3outerelectronsandendsupwithan
argonstructure.TheSc3+ionhasnodelectronsandso
doesn'tmeetthedefinition.
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Zinchastheelectronicstructure[Ar]3d104s2.Whenitforms
ions,italwayslosesthetwo4selectronstogivea2+ionwith
theelectronicstructure[Ar]3d10.Thezincionhasfulldlevels
anddoesn'tmeetthedefinitioneither.
Bycontrast,copper,[Ar]3d104s1,formstwoions.IntheCu+ion
theelectronicstructureis[Ar]3d10.However,themorecommon
Cu2+ionhasthestructure[Ar]3d9.
CopperisdefinitelyatransitionmetalbecausetheCu2+ionhas
anincompletedlevel.
Transitionmetalions
Hereyouarefacedwithoneofthemostirritatingfactsin
chemistryatthislevel!Whenyouworkouttheelectronic
structuresofthefirsttransitionseries(fromscandiumtozinc)
usingtheAufbauPrinciple,youdoitonthebasisthatthe3d
orbitalshaveahigherenergythanthe4sorbital.
Thatmeansthatyouworkontheassumptionthatthe3d
electronsareaddedafterthe4sones.
However,inallthechemistryofthetransitionelements,the4s
orbitalbehavesastheoutermost,highestenergyorbital.When
thesemetalsformions,the4selectronsarealwayslostfirst.
Youmustrememberthis:
Whendblockelementsformions,the4selectronsare
lostfirst.
Note:TheproblemhereisthattheAufbauPrinciplecanonly
reallybeusedasawayofworkingouttheelectronic
structuresofmostatoms.Itisasimplewayofdoingthat,
althoughitfailswithsome,likechromiumorcopper,of
course,andyouhavetolearnthese.
Thereis,however,aflawinthetheorybehinditwhich
producesproblemslikethis.Whyaretheapparentlyhigher
energy3delectronsnottheonestogetlostwhenthemetal
ionises?
Ihavewrittenadetailedexplanationofthisonanotherpage
calledtheorderoffilling3dand4sorbitals.Ifyouarea
teacheroraveryconfidentstudentthenyoumightliketo
followthislink.
Ifyouaren'tsoconfident,Isuggestthatyouignoreit.Make
surethatyoucanworkoutthestructuresoftheseatoms
usingtheAufbauPrincipleontheassumptionthatthe3d
orbitalsfillafterthe4s,andlearnthatwhentheatomsionise,
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the4selectronsarealwayslostfirst.Justignorethe
contradictionsbetweenthesetwoideas!
TowritetheelectronicstructureforCo2+:
Co [Ar]3d74s2
Co2+ [Ar]3d7
The2+ionisformedbythelossofthetwo4selectrons.
TowritetheelectronicstructureforV3+:
V [Ar]3d34s2
V3+ [Ar]3d2
The4selectronsarelostfirstfollowedbyoneofthe3d
electrons.
Note:Youwillfindmoreexamplesofwritingtheelectronic
structuresfordblockions,byfollowingthislink.
UsetheBACKbuttononyourbrowsertoreturnquicklyto
thispage.
Variableoxidationstate(number)
Oneofthekeyfeaturesoftransitionmetalchemistryisthewide
rangeofoxidationstates(oxidationnumbers)thatthemetals
canshow.
Note:Ifyouaren'tsureaboutoxidationstates,youreally
needtofollowthislinkbeforeyougoon.
UsetheBACKbuttononyourbrowsertoreturnquicklyto
thispage.
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Itwouldbewrong,though,togivetheimpressionthatonly
transitionmetalscanhavevariableoxidationstates.For
example,elementslikesulphurornitrogenorchlorinehavea
verywiderangeofoxidationstatesintheircompoundsand
theseobviouslyaren'ttransitionmetals.
However,thisvariabilityislesscommoninmetalsapartfromthe
transitionelements.Ofthefamiliarmetalsfromthemaingroups
ofthePeriodicTable,onlyleadandtinshowvariableoxidation
statetoanyextent.
Examplesofvariableoxidationstatesinthetransition
metals
Iron
Ironhastwocommonoxidationstates(+2and+3)in,for
example,Fe2+andFe3+.Italsohasalesscommon+6oxidation
stateintheferrate(VI)ion,FeO42.
Manganese
Manganesehasaverywiderangeofoxidationstatesinits
compounds.Forexample:
+2 inMn2+
+3 inMn2O3
+4 inMnO2
+6 inMnO42
+7 inMnO4
Otherexamples
Youwillfindtheaboveexamplesandotherslookedatindetailif
youexplorethechemistryofindividualmetalsfromthetransition
metalmenu.Thereisalinktothismenuatthebottomofthe
page.
Explainingthevariableoxidationstatesinthetransition
metals
We'lllookattheformationofsimpleionslikeFe2+andFe3+.
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Whenametalformsanioniccompound,theformulaofthe
compoundproduceddependsontheenergeticsoftheprocess.
Onthewhole,thecompoundformedistheoneinwhichmost
energyisreleased.Themoreenergyreleased,themorestable
thecompound.
Thereareseveralenergytermstothinkabout,butthekeyones
are:
Theamountofenergyneededtoionisethemetal(thesum
ofthevariousionisationenergies)
Theamountofenergyreleasedwhenthecompound
forms.Thiswilleitherbelatticeenthalpyifyouarethinking
aboutsolids,orthehydrationenthalpiesoftheionsifyou
arethinkingaboutsolutions.
Themorehighlychargedtheion,themoreelectronsyouhave
toremoveandthemoreionisationenergyyouwillhaveto
provide.
Butoffsettingthis,themorehighlychargedtheion,themore
energyisreleasedeitheraslatticeenthalpyorthehydration
enthalpyofthemetalion.
Note:WhatIamtalkingabouthereinageneralwayare
BornHabercycles.Youwillfindthesecoveredinthe
energeticssectionofChemguide,ormychemistry
calculationsbook.
Thinkingaboutatypicalnontransitionmetal(calcium)
CalciumchlorideisCaCl2.Whyisthat?
IfyoutriedtomakeCaCl,(containingaCa+ion),theoverall
processisslightlyexothermic.
BymakingaCa2+ioninstead,youhavetosupplymore
ionisationenergy,butyougetoutlotsmorelatticeenergy.There
ismuchmoreattractionbetweenchlorideionsandCa2+ions
thanthereisifyouonlyhavea1+ion.Theoverallprocessis
veryexothermic.
BecausetheformationofCaCl2releasesmuchmoreenergy
thanmakingCaCl,thenCaCl2ismorestableandsoforms
instead.
WhataboutCaCl3?Thistimeyouhavetoremoveyetanother
electronfromcalcium.
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Thefirsttwocomefromthe4slevel.Thethirdonecomesfrom
the3p.Thatismuchclosertothenucleusandthereforemuch
moredifficulttoremove.Thereisalargejumpinionisation
energybetweenthesecondandthirdelectronremoved.
Althoughtherewillbeagaininlatticeenthalpy,itisn'tanything
likeenoughtocompensatefortheextraionisationenergy,and
theoverallprocessisveryendothermic.
Itdefinitelyisn'tenergeticallysensibletomakeCaCl3!
Thinkingaboutatypicaltransitionmetal(iron)
Herearethechangesintheelectronicstructureofirontomake
the2+orthe3+ion.
Fe [Ar]3d64s2
Fe2+ [Ar]3d6
Fe3+ [Ar]3d5
The4sorbitalandthe3dorbitalshaveverysimilarenergies.
Thereisn'tahugejumpintheamountofenergyyouneedto
removethethirdelectroncomparedwiththefirstandsecond.
Thefiguresforthefirstthreeionisationenergies(inkJmol1)for
ironcomparedwiththoseofcalciumare:
Thereisanincreaseinionisationenergyasyoutakemore
electronsoffanatombecauseyouhavethesamenumberof
protonsattractingfewerelectrons.However,thereismuchless
increasewhenyoutakethethirdelectronfromironthanfrom
calcium.
Intheironcase,theextraionisationenergyiscompensated
moreorlessbytheextralatticeenthalpyorhydrationenthalpy
evolvedwhenthe3+compoundismade.
Theneteffectofallthisisthattheoverallenthalpychangeisn't
vastlydifferentwhetheryoumake,say,FeCl2orFeCl3.That
meansthatitisn'ttoodifficulttoconvertbetweenthetwo
compounds.
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Theformationofcomplexions
Whatisacomplexion?
Acomplexionhasametalionatitscentrewithanumberof
othermoleculesorionssurroundingit.Thesecanbeconsidered
tobeattachedtothecentralionbycoordinate(dativecovalent)
bonds.(Insomecases,thebondingisactuallymore
complicatedthanthat.)
Themoleculesorionssurroundingthecentralmetalionare
calledligands.
Simpleligandsincludewater,ammoniaandchlorideions.
Whatallthesehavegotincommonisactivelonepairsof
electronsintheouterenergylevel.Theseareusedtoformco
ordinatebondswiththemetalion.
Someexamplesofcomplexionsformedbytransition
metals
[Fe(H2O)6]2+
[Co(NH3)6]2+
[Cr(OH)6]3
[CuCl4]2
Othermetalsalsoformcomplexionsitisn'tsomethingthatonly
transitionmetalsdo.Transitionmetalsdo,however,formavery
widerangeofcomplexions.
Note:Youwillfindmuchmoreaboutcomplexionsby
followingthislink.Itwilltakeyoutoapartofthesitedealing
exclusivelywithcomplexions.
Ifyoudofollowthelink,usetheBACKbuttononyour
browser(ortheHistoryfileorGomenu)ifyouwanttoreturn
tothispageagain.
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Theformationofcolouredcompounds
Somecommonexamples
Thediagramsshowaproximatecoloursforsomecommon
transitionmetalcomplexions.
Youwillfindtheseandothersdiscussedifyoufollowlinksto
individualmetalsfromthetransitionmetalmenu(linkatthe
bottomofthepage).
Alternatively,youcouldexplorethecomplexionsmenu(follow
thelinkinthehelpboxwhichhasjustdisappearedoffthetopof
thescreen).
Theoriginofcolourinthetransitionmetalions
Whenwhitelightpassesthroughasolutionofoneoftheseions,
orisreflectedoffit,somecoloursinthelightareabsorbed.The
colouryouseeishowyoureyeperceiveswhatisleft.
Attachingligandstoametalionhasaneffectontheenergiesof
thedorbitals.Lightisabsorbedaselectronsmovebetweenone
dorbitalandanother.Thisisexplainedindetailonanother
page.
Note:Youwillfindadetailedexplanationoftheoriginof
colourincomplexionsandthefactorswhichcauseitto
changebyfollowingthislink.Thatpageisonthepartofthe
sitedealingwithcomplexions.
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UsetheBACKbuttononyourbrowserifyouwanttoreturnto
thispageagain.
Catalyticactivity
Transitionmetalsandtheircompoundsareoftengoodcatalysts.
Afewofthemoreobviouscasesarementionedbelow,butyou
willfindcatalysisexploredindetailelsewhereonthesite(follow
thelinkaftertheexamples).
Transitionmetalsandtheircompoundsfunctionascatalysts
eitherbecauseoftheirabilitytochangeoxidationstateor,inthe
caseofthemetals,toadsorbothersubstancesontotheir
surfaceandactivatethemintheprocess.Allthisisexploredin
themaincatalysissection.
Transitionmetalsascatalysts
IronintheHaberProcess
TheHaberProcesscombineshydrogenandnitrogentomake
ammoniausinganironcatalyst.
NickelinthehydrogenationofC=Cbonds
Thisreactionisattheheartofthemanufactureofmargarine
fromvegetableoils.
However,thesimplestexampleisthereactionbetweenethene
andhydrogeninthepresenceofanickelcatalyst.
Transitionmetalcompoundsascatalysts
Vanadium(V)oxideintheContactProcess
AttheheartoftheContactProcessisareactionwhichconverts
sulphurdioxideintosulphurtrioxide.Sulphurdioxidegasis
passedtogetherwithair(asasourceofoxygen)overasolid
vanadium(V)oxidecatalyst.
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Ironionsinthereactionbetweenpersulphateionsand
iodideions
Persulphateions(peroxodisulphateions),S2O82,arevery
powerfuloxidisingagents.Iodideionsareveryeasilyoxidisedto
iodine.Andyetthereactionbetweentheminsolutioninwateris
veryslow.
Thereactioniscatalysedbythepresenceofeitheriron(II)or
iron(III)ions.
Note:Youwillfinddetailedexplanationsofthesereactions
inthecatalysissectionofthesite.Youcouldusefullystart
withthetypesofcatalystspage.
UsetheBACKbuttononyourbrowsertoreturnquicklyto
thispage.
Questionstotestyourunderstanding
Ifthisisthefirstsetofquestionsyouhavedone,pleasereadthe
introductorypagebeforeyoustart.YouwillneedtousetheBACKBUTTON
onyourbrowsertocomebackhereafterwards.
questionsonfeaturesofthetransitionmetals
answers
WHEREWOULDYOULIKETOGO now?
Tothetransitionmetalmenu...
TotheInorganicChemistrymenu...
ToMainMenu...
JimClark2003(lastmodifiedJune2015)
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