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8/21/2016 introducingtransitionmetals

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:

metal 1stIE 2ndIE 3rdIE

Ca 590 1150 4940

Fe 762 1560 2960

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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