A Level REDOX 1

9/20/2016 ALevelREDOX1.
Oxidation&ReductionreactionsIntroductiontooxidationstate,assigningoxidationnumber,naminginorganiccompoundsGCEK
DocBrown'sAdvanced
PhysicalTheoreticalInorganic
Chemistry
REDOXREACTIONS
CHEMISTRYRevisionNotes
Part1
Sections1to4Definitionsanddescribingredoxreactions
Thedefinitionsofoxidationandreductionaregivenandexplainedinterms
ofelectronlossorgain,andthentheideasappliedtolotsofexamplesfrom
inorganicchemistryreactions.Theconceptofoxidationstate(oxidation
number)isthenintroduced.Simpleionsaredealtwithfirst,then,viathe
conceptofelectronegativity,howtoworkoutoxidationstateformore
awkwardexamplesisexplained!Therulesconcerningoxidationnumber
aregivenandshouldbelearnedassoonaspossible!Examplesofhowto
nameinorganiccompoundsthatrequireRomannumeraloxidationstatesinthenamearealsogivenonthispage.
REDOXsectionindex:1.Basicredoxdefinitions*2.Introducingoxidationstate(withsubindex)*3.Oxidation
staterulesguidelines&inorganicexamples*4.Naminginorganiccompounds*5.Usingoxidationstatesto
describeredoxchangesinagiveninorganicreactionequation(withsubindex)*6.Constructingfullinorganic
redoxequationsfromhalfequations(withsubindex)*7.Redoxtitrations*8.Organicsynthesisreductions(with
summarytable)*9.Organicsynthesisoxidations(withsummarytable)*10.OtherOrganicRedoxReactions(with
subindex)*11.Carbon'sox.stateinselectedorganiccompoundsandfunctionalgrouplevel*Youareadvisedto
studysections1.to6.instrictorderandcoverstherequirementsofASA2*SeealsoEquilibriaPart7Redox
ReactionsforHalfcellequilibria,electrodepotential,standardhydrogenelectrode,Simplecellsandnotation,
ElectrochemicalSeries,Ecellforreactionfeasibility,'batteries'andfuelcellsystemsetc.
RedoxreactionsinInorganicChemistrysections14
Theveryimportantconceptsofoxidation,reduction,oxidationstate/numberandtheir
applicationtoredoxreactionsareexplainedusingavarietyofexamplesinsections14.Howto
combinehalfcellequationstowriteafullionicredoxequationsisfurtherexplainedinPart2
sections56.ApplicationofredoxconceptstocellswillbedescribedinEquilibriaPart7"Redox
Equilibria".
1.Oxidationandreductiondefinitions
Thebasic,butinadequatedescriptionsofoxidationandreductionintermsofoxygenarefirstdescribed,followed
bysomesimpleexamplesofthemuchmoreimportantelectrontransferdefinitions.Itisadvisabletostudysection1.
beforeproceedingtosection2.onoxidationstate/number.Pleasenotethatinthefirstpartsofsection1.theequationsare
notmeanttobebalanced,butjustfocusontheparticularoxidationorreductionchangeandlaterthefullbalancedredox
equationsaregiven.
Theexamplesarenotalwaysmeanttobebalancedorcomplete,buttheydoshowtheessentialoxidationorreduction
change.
OXIDATION
REDUCTION
Gain/additionofoxygenbyanatom,moleculeorione.g.
Loss/removalofoxygenfromacompoundorione.g.
http://www.docbrown.info/page07/redox1.htm
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9/20/2016 ALevelREDOX1.Oxidation&ReductionreactionsIntroductiontooxidationstate,assigningoxidationnumber,naminginorganiccompoundsGCEK
1.S==>SO2
Burningsulphuroxidised.
2.CH4==>CO2+H2O
Burningmethanetowaterandcarbondioxide,C
andHbothgainO.
3.NO==>NO2
Nitrogenmonoxideoxidisedtonitrogendioxide,
rapidinairwithNOfromcarexhaustfumes.
4.SO32==>SO42
Oxidisingthesulphiteiontothesulphateion
e.g.bychlorine/bromineoxidisingagents.
Loss/removalofelectronsfromatom,ionormolecule
e.g.
1.CuO==>Cu
Lossofoxygenfromcopper(II)oxideto
formcopperatomsinmetalextractionwithor
displacementbymorereactivemetal.
2.Fe2O3==>Fe
Iron(III)oxidereducedtoironinblastfurnace
usingcarbonorcarbonmonoxide.
3.NO==>N2
Nitrogen(II)oxidereducedtonitrogen.
4.SO3==>SO2
Sulphurtrioxidereducedtosulphurdioxide.
Gain/additionofelectronsbyanatom,ion,ormolecule
e.g.
1.Fe==>Fe2++2e
Anironatomloses2electronstoformthe
iron(II)ione.g.intheinitialchemistryofiron
rustingorinanironacidreaction.
2.Fe2+==>Fe3++e
Theiron(II)ionloses1electrontoformthe
iron(III)ion,e.g.viachlorineormanganate(VII)
oxidisingagents.
3.2Cl==>Cl2+2e
Thelossofelectronsbychlorideionstoform
chlorinemoleculese.g.the+veanodereaction
inelectrolysisofchloridesortheactionofavery
strongoxidisingagent.
1.Cu2++2e==>Cu
Thecopper(II)iongains2electronstoform
neutralcopperatomse.g.inelectrolysisatthe
vecathodeorwhencopperisdisplacedfromits
saltbyamorereactivemetal.
3+
2.Fe +e==>Fe2+
Theiron(III)iongainsanelectronandisreduced
totheiron(II)ione.g.byaddingzinctoacidified
iron(III)saltsolution.
3.2H++2e==>H2
Hydrogenionsgainelectronstoformneutral
hydrogenmoleculese.g.inthevecathode
reactionintheelectrolysisofacidsorina
metalacidreaction.
Anoxidisingagentisthespeciesthatgivestheoxygen
orremovestheelectrons
Areducingagentisthespeciesthatremovestheoxygen
oractsastheelectrondonor
REDOXREACTIONSinanoverallreaction,oxidationandreductionmustgotogethere.g.in
termsofoxygenandthesearecompleteandbalancedequations
1.copper(II)oxide+hydrogen==>copper+water
CuO(s)+H2(g)==>Cu(s)+H2O(g)
Heatedcopperoxideisreducedtocopper(Oloss)whenhydrogenispassedoverit,
hydrogenisoxidisedtowater(Ogain),
hydrogenisthereducingagent(removesOfromCuO),
andcopperoxideistheoxidisingagent(donatesOtohydrogen).
2.iron(III)oxide+carbonmonoxide==>iron+carbondioxide
Fe2O3(s)+3CO(g)==>2Fe(l)+3CO2(g)
Intheblastfurnacetheiron(III)oxideisreducedtoliquidiron(Oloss),
thecarbonmonoxideisoxidisedtocarbondioxide(Ogain),
COisthereducingagent(Oremover/acceptorfromFe2O3),
andFe2O3istheoxidisingagent(OdonatortoCO)]
3.nitrogen(II)oxide+carbonmonoxide==>nitrogen+carbondioxide
2NO(g)+2CO(g)==>N2(g)+2CO2(g)(e.g.incarexhaustcatalyticconverter)
Nitrogen(II)oxideisreducedtonitrogen(Oloss),
carbonmonoxideisoxidisedtocarbondioxide(Ogain),
andCOisthereducingagent(Oremover/acceptor)
andNOistheoxidisingagent(Odonor).
4.iron(III)oxide+aluminium==>aluminiumoxide+iron
Fe2O3(s)+2Al(s)==>Al2O3(s)+2Fe(s)(theThermitreaction)
Iron(III)oxideisreducedandistheoxidisingagent(itstheoxygenloseri.e.oxygendonor),
andthealuminiumisoxidisedandisthereducingagent(itstheoxygengainer/acceptor/remover).
Redoxreactionanalysisbasedonthemoreimportantandadvancedelectrondefinitions
andnotethattheelectrongainmustequaltheelectronlossinthecompleteandfullybalancedequation
e.g.
1.magnesium+iron(II)sulphate==>magnesiumsulphate+iron
Mg(s)+FeSO4(aq)==>MgSO4(aq)+Fe(s)
Thisisthe'ordinarymolecular'equationforatypicalmetaldisplacementreaction,butdoesnotreally
showwhatreallyhappensintermsofatoms,ionsandelectrons,soweuseionicequationsliketheone
shownbelow.
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ThesulphateionSO42(aq)iscalledaspectatorion,becauseitdoesn'tchangeinthereactionandcanbe
omittedfromtheionicequation(below).
Also,noelectronsshouldshowupinthe'real'balancedequationbecausethenumberofelectronslostby
somereactantspeciesequalstheelectronsgainedbyotherreactantspecies.
Mg(s)+Fe2+(aq)==>Mg2+(aq)+Fe(s)
Themagnesiumatom,Mg,loses2electrons(oxidation)toformthemagnesiumion,Mg2+,
theiron(II)ion,Fe2+,gains2electrons(reduced)toformironatoms,Fe,
Mgisthereducingagenti.e.theelectrondonortotheFe2+ion,
andtheFe2+ionistheoxidisingagenti.e.theelectronremoveroracceptorfromtheMgatom.
2.zinc+hydrochloricacid==>zincchloride+hydrogen
Zn(s)+2HCl(aq)==>ZnCl2(aq)+H2(g)
ThechlorideionClisthespectatorionsotheionicredoxequationis...
Zn(s)+2H+(aq)==>Zn2+(aq)+H2(g)
Zincatomsareoxidisedtozincionsbylosingtwoelectrons,
andzincisthereducingagenti.e.theelectrondonortothehydrogenion,H+.
Hydrogenionsaretheoxidisingagenti.e.twohydrogenionsgain/acceptoneelectroneachfromaZnatom,
andsoarereducedtoformhydrogenmolecules.
3.copper+silvernitrate==>silver+copper(II)nitrate
Cu(s)+2AgNO3(aq)==>2Ag(s)+Cu(NO3)2(aq)
ThenitrateionNO3isthespectatorionsotheionicredoxequationis
Cu(s)+2Ag+(aq)==>2Ag(s)+Cu2+(aq)
inwhichcopperatomsareoxidisedbythesilverionsbyatwoelectronloss,
theseelectronsaretransferredfromthecopperatomstothesilverions,
sotheyarereducedbyoneelectrongaineachtosilveratoms.
Thesilverionsaretheoxidisingagent(eacceptor),
andthecopperatomsarethereducingagent(edonor).
Oneother,andverylimiteddefinition,isintermsofhydrogen,butsuchredoxdefinitionshavelittleusethesedays
exceptinthereduction(Hgain)reactionsofunsaturatedorganiccompoundssuchasalkenes,aldehydes,ketones,
carboxylicacidsandthereductionnitroaromaticcompoundstoamines.However,thatisnottosaytheyare
unimportantreactions,infactallfourreactionsbelowareallofconsiderableindustrialsignificance.
reductionishydrogengain:e.g.
(alkene)ethene+hydrogen==>ethane(alkane)
C2H4+H2==>C2H6(reductionofanalkene)
nitrogen+hydrogen==>ammonia
N2+3H2==>2NH3(reductionofnitrogen)
oxidationishydrogenloss:e.g.
ammonia+oxygen==>nitrogen(II)oxide+water
4NH3+5O2==>4NO+6H2O(oxidationofammonia)
methane+oxygen==>carbondioxide+water
CH4+2O2==>CO2+2H2O(oxidationofmethane)
Electrondefinitionsofoxidationorreductionarethemuchmoreusefulandimportantforadvancedlevel
chemistryasistheveryimportantassociatedconceptofoxidationstate/numberwhichisexplainedinsection2.
Definitionsandanalysisofredoxreactionsintermsofoxygenorhydrogenmaynotgetyouthemarksat
advancedlevel!So,LEARNandUSEthefollowingassoonaspossibleinyouradvancedredoxanalysis.
1.Oxidationiselectronlossbyaspeciesorincreaseintheoxidationstate/numberofanelementinthe
speciesinvolvedwhichcanbetheelementitself,oracovalentcompoundorioncontainingtheelement(ditto
for2.,3.and4.).
2.Reductioniselectrongainbyaspeciesordecreaseintheoxidationstate/numberofanelementinthe
speciesinvolved.
3.Anelectronacceptorisanoxidisingagentandthereforegetsreducedinitsaction,sothereisadecreasein
theoxidationnumber/stateofoneoftheatomsoftheoxidisingagent.
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4.Anelectrondonorisareducingagentandthereforegetsoxidisedintheprocess,sothereisanincreasein
theoxidationnumber/stateofoneoftheatomsofthereducingagent.
Youalsoneedtoconceiveof'redox'reactionsasacombinationoftwohalfcellreactions/equations(see
EquilibriaPart7formoreonhalfcellpotentialsandredoxequilibria.
Onehalfreactionwillbeanoxidationandtheother'half'willbeareduction.
Howtoputthetwotogethertogivesthefullionicredoxequationtocompletelysummarisearedoxreactionin
simplecasesisgiveninsection2.below,andseesections5.and6.forlotsofmorecomplexexamples).
2.Introducing,explaininganddefiningoxidationstateandexamples
Insimplecases,particularlysimpleions,theoxidationstatecanbedefinedasthenumberofelectronswhich
mustbeaddedorremovedtoleavetheelementinitselectricallyneutralelementalstatewhichisthen
consideredtobeinazerooxidationstatee.g.
chlorine,ClorCl2,oxidationstatezero(0),theelementitselfinanelectricallyneutralstate.
chlorideion,Cl,oxidationstateminusone(1),becauseoneelectronmustberemovedtoleavethe
electricallyelementitself.
sulfur,SorS8,oxidationstatezero(0),theelementitselfinanelectricallyneutralstate.
sulfideion,S2,oxidationstateminustwo(2),becausetwoelectronsmustberemovedtoleavetheelectrically
elementitself.
sodium,Na,oxidationstatezero(0),theelementitselfinanelectricallyneutralstate.
sodiumion,Na+,oxidationstateplusone(+1),becauseoneelectronmustbeaddedtogivetheelectrically
atomoftheelementsodium.
iron,Fe,oxidationstatezero(0),theelementitselfinanelectricallyneutralstate.
iron(III)ion,Fe3+,oxidationstateplusthree(+3),becausethreeelectronsmustbeaddedtogivetheelectrically
atomsoftheelementiron.
Note:
Importantsignconventions:
Thesign(+/)foranoxidationstateisquotedfirste.g.
3,2,1,0,+1,+2,+3etc.(obviouslynosignforzero)
Inthesymbols/formulaeofions,thenumericalvalueoftheionchargeisquotedfirste.g.
PO43,S2,I,NH4+,Mg2+,Al3+etc.(nonumberifchargeis+/one)
Inanelectricallyneutralcompoundormolecule,thesumoftheoxidationstatesmustaddupto
zero.
Ifitdoesn't,thenyouhavegotsomethingwronginyouranalysis.
BUT,the'zerosumrule'providesawayofworkingoutanotherunknownoxidationstateofanatom,ifyou
knowtheoxidationstatesoftheotheratomsinthespecies.
Inthecaseofions,thesumoftheoxidationstatesequalstheoverallchargeontheion.
Whendealingwithatomsandsimpleions,redoxanalysisisusuallyquitestraightforwarde.g.thethree'electron
analysed'examplesinsection1.aboveandtheexamplesbelowwheretheconceptofoxidationstate/number
isnowfurtherintroducedviadetailedexamplesforsimpleionsormolecules.Itisbesttostudytheminthe
ordergiven.
Afterthis,themoreawkwardsituationsaredealtwith.
Section2reactionsubindex:2.1metal+acid*2.reactivemetal+nonmetal*2.3*halogenhalogen
displacement*2.4metalmetaldisplacement*2.5whataboutmorecomplexmolecule/ionsituations?
Ex2.1Reactingametalwithanacid
magnesium+sulphuricacid==>magnesiumsulphate+hydrogen
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Mg(s)+H2SO4(aq)==>MgSO4(aq)+H2(g)
SincethechlorideionSO42isaspectatorioni.e.itdoesn'tchangechemicallyorphysicallyinstate,sothe
ionicredoxequationis
Mg(s)+2H+(aq)==>Mg2+(aq)+H2(g)
Magnesiumatomsareoxidisedtomagnesiumionsbythelossoftwoelectrons.
Hydrogenionsarereducedbyelectrongaintoformhydrogenmolecules.
Theoxidationstatesoftheelementsareshownin()forthespeciesinvolvedintheactualchemicalchangeand
wouldbequotedasfollows:
Mg(0)+2xH(+1)==>Mg(+2)+2xH(0)andthehalfcellreactionsare...
theoxidation:Mg(s)==>Mg2+(aq)+2e(ox.stateincreasesby2unitsperMgatom)
thereduction:2H+(aq)+2e==>H2(aq)(ox.statedecreasesby1unitperH+ion)
Theoxidationstateformagnesiumisincreasedbytwounitsperatom,isbalancedbytheoxidationstateoftwo
hydrogens(asH+ion)decreasingbyoneuniteach.
Havingnowquotedsomeoxidationstates,nowisthetimetoexplaintheconceptfurtherandconnectitwith
electrontransfersinsimpleionicredoxreactionsliketheoneabove.
Importantpointsandideastotakeforwardintosection2.2onwards...
Theoxidationstatedefinesthetheoreticalelectronchangeneededtoconverttheoxidisedorreduced
'state'oftheelementinanion(orinamoleculelater),backtoits'elementalstate'wheretheoxidation
stateisconsideredaszero(0).
Conventionsreminderstobestrictlyadheredto...
Inquotingoxidationstates,thesignisplacedbeforethenumber(e.g....2,1,0,+1,+2...etc.),
andthereisalwaysanumberafterthesign.
Forions,thechargesigncomesafterthenumber(e.g....3,2,,+,2+,3+...etc.),butthecaseofa
single+/chargenonumberisrequired,the'1'isassumed.
The'freeelement'isconsideredtohaveanoxidationstateofzero(0)i.e.notcombinedwithanother
elementinanionicorcovalentcompound.Itcanofcoursebecombinedwithitselfe.g.H2,butitsstillinazero
ox.state.
So,intermsofthemagnesiumacidreaction....
Themagnesium(Mgatom)isthereducingagentorelectrondonor,soitsoxidationstateisincreased.
Magnesiumisinthe+2oxidationstateinitsion(Mg2+)andtheoreticallyneedstogaintwoelectronsto
returntoelementalmagnesiumatoms(Mg).
Thehydrogenion(H+)istheoxidisingagentorelectronacceptor,soitsoxidationstateisdecreased.
Hydrogenisinthe+1oxidationstateinitsion(H+)andtheoreticallyneedstogainoneelectronperionto
returntoelementalhydrogenmolecules(H2).
Thetotal/netelectrontransfersoroxidationstatechangesmustbezeroi.e.forexampleabove
Foreverymagnesiumatomlosingtwoelectrons,twohydrogenionsgainanelectroneach,i.e.
magnesium'sox.stateincreasesbytwounitsbalancedbytwohydrogens(ions)eachdecreasingtheir
oxidationstatebyoneunit.
Oxidation(eloss)=increaseinox.stateandreduction(egain)=decreaseinox.state.
So,numerically,electronslost=electronsgained
andincreaseinoxidationstates=decreaseinoxidationstates.
Ex2.2Heatingreactivemetalswithnonmetals
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Whenreactivemetalsareheatedwithreactivenonmetals,ioniccompoundsarereadilyformedexothermicallyina
combustionreaction.MgS,Li2O,Na2O2,themajorproductofburningsodiuminexcessair/oxygen,andCa3P2
respectively.
Notethatstrictionicformulaearealsogiventomaketheredoxanalysisclearer.
Ineachcasethemetalisthereducingagent(electrondonor/loser,oxidisedinprocess),
andthenonmetalistheoxidisingagent(electronacceptor/gainer,reducedinprocess).
Ex2.2.1:2Al(s)+3Cl2(g)==>2Al3+(Cl)3(s)(or2AlCl3,aluminiumchloride,itisanioniclattice)
Oxidationstatechanges:
Aluminiumatom==>aluminiumion:oxidation,eloss,oxidationstatechange..
2xAlincreasing,eachfrom(0)to(+3),losing3electronsperatom,
chlorinemolecule==>chlorideion,reduction,egain,ox.statechangeis..
6xCldecreasing,eachfrom(0)to(1),gaining1electronperatom(or2epermolecule),
andthehalfreactions*arewrittenas:
(i)oxidation:Al==>Al3++3eand(ii)reduction:Cl2+2e==>2Cl
adding2x(i)+3x(ii)givesthefullequation(iii)2Al+3Cl2==>2AlCl3
Intermsofthefullbalancedequation,6electronslosti.e.ariseof6ox.state'units',whichisbalancedby6
electronsgainedi.e.adecreaseof6ox.state'units'.
*Notethesealsocalledhalfcellpotentialequations,andisawayofrepresentingthe'separate'oxidationor
reductioninequationform.
Ex2.2.2:Mg(s)+S(s)==>Mg2+S2(s)(orMgS,magnesiumsulphide)
Magnesiumatom==>magnesiumion:oxidation,eloss,oxidationstatechange...
1xMgincreasingfrom(0)to(+2),losestwoelectronsperMgatom,
whichis'electronically'balancedbythe...
sulphuratom==>sulphideion:reduction,egain,ox.statechange...
1xSdecreasingfrom(0)to(2),gainingtwoelectronsperSatom,
andthehalfreactionsarewrittenas:
(i)oxidation:Mg==>Mg2++2eand(ii)reduction:S+2e==>S2
adding(i)+(ii)givesthefullequation(iii)Mg+S==>MgS
Ex2.2.3:4Li(s)+O2(g)==>2(Li+)2O2(s)(or2Li2O,lithiumoxide)
Lithiumatom==>lithiumion:oxidation,eloss,ox.statechangeforlithiumisfrom0to+1
4xLiincreasing,eachfrom(0)to(+1),losingoneelectronperLiatom,4electronschangeintermsofthe
balancedequation
twooxygenmolecules==>twooxideions:reduction,egain,ox.statechange,ox.statechangeof0to2
2xOdecreases,eachfrom(0)to(2),gainingtwoelectronsperOatom(orfourelectronsperO2molecule),
andthehalfreactionsare:
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(i)oxidation:Li==>Li++2e(formationofthelithiumion)
(ii)reduction:O2+4e==>2O2(formationoftheoxideion)
addingandbalancinggives4x(i)+(ii)givingthefullequation
(iii)4Li+O2==>2Li2O
Intermsofthefullbalancedequation,4electronslosti.e.ariseof4ox.state'units'bythelithiumatoms,which
isbalancedby4electronsgainedi.e.adecreaseof4ox.state'units'bytheoxygenatoms.
Ex2.2.4:2Na(s)+O2(s)==>(Na+)2O22(s)(orNa2O2,sodiumperoxideisthemajorproductinexcessair/oxygen)
Oxidationstatechanges:Thisisverysimilartoexample2.2.3
Sodiumatom==>sodiumion:oxidation,eloss,ox.statechangeisfrom0to+1
2xNaincreases,eachfrom(0)to(+1),losingoneelectronperNaatom,
oxygenmolecule==>peroxideion:reduction,egain,ox.statechange...
2xOdecreases,eachfrom(0)to(1),gainingtwoelectronsperOatom(ortwoelectronsperO2molecule),
(i)oxidation:Na==>Na++e(formationofsodiumion)
(ii)reduction:O2+2e==>O22(formationoftheperoxideion)
addingandbalancing2x(i)+(ii)givesthefullequation
(iii)2Na+O2==>Na2O2
Intermsofthefullbalancedequation,2electronslosti.e.ariseof2ox.state'units'forthesodiumatoms,which
isbalancedby2electronsgainedi.e.adecreaseof2ox.state'units'oftheoxygenatomsoftheoxygen
molecule.
Ex2.2.5:6Ca(s)+P4(s)==>2(Ca2+)3(P3)2(s)(or2Ca3P2,calciumphosphide)
Calciumatom==>calciumion:oxidation,eloss,ox.statechange...
6xCaincreasing,eachfrom(0)to(+2),losingtwoelectronsperCaatom,
phosphorusmolecule==>phosphideion:reduction,egain,ox.statechange...
4xPdecreasing,eachfrom(0)to(3),gainingthreeelectronsperPatom(ortwelveelectronsperP4
molecule),
(i)oxidation:Ca==>Ca2++2eand(ii)reduction:P4+12e==>4P3
addingandbalancing6x(i)+(ii)givesthefullequation(iii)6Ca+P4==>2Ca3P2
Youcanalsoworkoutthisexamplebasedon(iv)P+3e==>P3,
inwhichcasethebalancedequationisbasedon3x(i)+2x(iv)==>Ca3P2.
Ex2.3Ahalogendisplacementreaction
A'morereactive'**halogendisplacingalessreactivehalogen(X>Y).
7/16
halogenX+Yhalidesalt==>Xhalidesalt+halogenY
X2(aq)+2KY(aq)==>2KX(aq)+Y2(aq)
sincethepotassiumion(K+)isaspectator,theionicredoxequationis
X2(aq)+2Y(aq)==>2X(aq)+Y2(aq)
wherehalogenXismorereactivethanhalogenY(F>Cl>Br>I).
X2istheoxidisingagentorelectronacceptor,Xhasanox.stateof(0)inthehalogenmoleculeandacceptsan
electronfromY,andsoXgetsreducedtoox.state(1)intheXion.
Yisthereducingagentorelectrondonor,Yhasanox.stateof(1)inthehalideionanddonatesanelectrontoX2,
andsoYisoxidisedtoox.state(0)intheY2molecules.
sointermsofoxidationstates:2xX(0)+2xY(1)==>2xX(1)+2xY(0)
andthehalfcellreactionsare...
(i)reduction*:X2(aq)+2e==>2X(aq)and(ii)oxidation*:2Y(aq)==>Y2(aq)+2e
adding*(i)+(ii)gives(iii)X2(aq)+2Y(aq)==>2X(aq)+Y2(aq)
*Notethattheequationscanbewrittenonthebasisofhalfmoleofthehalogenmolecule,
*i.e.(iv)1/2X2(aq)+e==>X(aq),(v)Y(aq)==>1/2Y(aq)+e
and(iv)+(v)givestheequallyvalidbalancedequation(vi)1/2X2(aq)+Y(aq)==>X(aq)+1/2Y2(aq)
**MorereactiveheremeansthehalfcellpotentialforX2/XismorepositivethanforY2/Y,
i.e.X2isastrongeroxidisingagentthanY2.(seeEquilibriaPart7).
Ex2.4Ametaldisplacingalessreactivemetal
A'morereactive'*metaldisplacingalessreactivemetal.
copper+silvernitrate==>silver+copper(II)nitrate
Cu(s)+2Ag+(aq)==>2Ag(s)+Cu2+(aq)
Onecopperisoxidisedbylosingtwoelectrons,soitsox.numberchangesandincreasesfrom(0)to(+2).
Twosilverionsarereducedbygainingoneelectroneach,sotheiroxidationstatedecreasesfrom(+1)to(0).
andthehalfcellreactionsare...
(i)reduction:Ag(aq)+e==>2X(aq)and(ii)oxidation:Cu(s)==>Cu2+(aq)+2e
adding2x(i)+(ii)givesthefullbalancedequation.
*Morereactiveheremeansthehalfcellpotentialforthemorereactivemetalisthelesspositiveormorenegative
potential,orinotherwords,theAg/Ag+ismorepositivethanforCu/Cu2+,i.e.Ag+isastrongeroxidisingagentthan
Cu2+.(seeEquilibriaPart7).
Ex2.5Whataboutoxidationstateandthe'notsosimple'situations?
HowinredoxtermsdowedealwiththestructureandreactionsofelectricallyneutralcovalentmoleculeslikeH2Oor
morecomplexionslikePO43whichareheldtogetherwithcovalentbondsbutcarryanoverallelectricalcharge?
Thesesituationswillberedoxanalysedbyextendingtheconceptofoxidationnumberoroxidationstate
introducedinsection2.1,butfirstarecapofthesimpleionsituation.
Aspointedoutalready,forsimpleionsofoneatom,youcanthinkofitastheelectronchangerequiredto
returntheatomtoanuncombinedelectricallyneutralatomormolecule,becausethisrelatesnumericallytothe
relativeelectronlossorgaininvolvedinformingtheionfromthefreeelemente.g.
8/16
Magnesiumisinthe+2oxidationstateinioniccompoundscontainingthemagnesiumionMg2+
Mg2++2e==>Mg,e.g.inmagnesiumchloride,MgCl2orMg2+(Cl)2
Phosphorusisinthe3oxidationstateinioniccompoundscontainingthephosphideionP3
P33e==>P,e.g.insodiumphosphide,Na3P.or(Na+)3P3
Oxygenisinthe2oxidationstatee.g.inioniccompoundscontainingtheoxideionO2
O22e==>1/2O2
Importantconventions,remindersandtrendsbeforeproceedingtothe'notsosimple'situations:
Inwritingoxidationstates,the+orsigniswrittenbeforethenumberandthereisalwaysasign
exceptforzero(0)fortheuncombinedelementitself.
Thereisalwaysasignfortheelectricalchargeonanion(chargedparticle)symbol/formula,sinceitcan't
bezerobydefinition,butnonumberiswrittenforasingle+/charge,butmusthave2,3etc.fordoubleor
triplechargesetc.,andthenumbercomesbeforetheelectricchargesignonanion.
Thesetwoconventionsmustbestrictlyadheredtoe.g.ionformulaAl3+,ox.stateis+3.
Sometimes()areneededinionicformulae,e.g.thecorrectionicformula(Na+)3P3isNOTthesameas
theincorrectNa+3P3,becausethereisnosuchionasNa+3whichimpliesthreesodiumatomscombined
carryinganoverallchargeofsingle+,ratherthanthecorrectthreeseparatecorrectNa+ions,eachwitha
singlepluscharge.
Now,veryimportantlyconceptuallyforthemoreawkwardcases...
themoreelectropositiveelementstendtohaveapositiveoxidationstateinacompoundbecause
mostmetalsmorereadilyloseelectronsthannonmetals,
andthemoreelectronegativeelementstendtohaveanegativeoxidationstateinacompound
becausemostnonmetalsmorereadilygainelectronscomparedtometals.
Thisidea,basedontherelativeelectronegativityofanelement(tablebelow),isexploitedinawayinthenext
section3.toderivetheoxidationstateofanyelementinanymoleculeorionconsistingofatleasttwoatoms.
BUTbeware,initiallyyoumayhavetoconceiveofamolecule/molecularionasifitiscomposedofa
combinationofsimpleoneatomions,evenifthat'snotthecaseinrealityitdoeshelptoworkthrough
theabstractnatureofthistopic!
Itsausefulconceptualisationofthe'redox'situationi.e.amethodofproblemsolvingatthestartofdealingwith
the'notsosimple'chemicalspecies.So,readoninsection3where,bytheend,hopefullyyouwillbeableto
analysespecieswithoutthinking'falsely'intermsofcombiningsimpleionsthatdon'treallyexistinthesituation.
Youmayneedtorefertothetabulatedvaluesofelectronegativitybelow.
Electronegativityisthepowerofanatomtoattractelectronchargefromanotheratomitiscovalentlybonded
to.SomePaulingvaluesofelectronegativityarequotedbelow.
element
Na Mg Al Mn Fe H Si P C S
I Br Cl N O F
electronegativity 0.9 1.2 1.5 1.5 1.8 2.1 1.8 2.1 2.5 2.5 2.5 2.8 3.0 3.0 3.5 4.0
Generallyspeakingelectronegativityincreasesfromlefttorightacrossaperiodoftheperiodictableand
decreasesdownagroupoftheperiodictable.
3.Oxidationstaterulesandguidelinesandapplicationtoinorganicmolecules/ions
Itsreallyimportantthatyouhavestudiedatleastsection2.5beforereadingthissection,andhavesomeidea
ontherelativeelectronegativityofelementscommonlyencounteredinyourinorganicchemistry.Itwillgreatlyhelp
inunderstandingtheassignmentofoxidationstatesofelementsinthequotedcompoundsonthesethreewebpages.
Furthermore,asmuchaspossibleofthefollowingguidelinesandexamples,3.1to3.4shouldbelearnedas
quicklyaspossibleandtheywillhelpyouthroughoutyourchemistrystudies.
Oxidationstatesinnaminginorganiccompoundswithrespecttooxidationstateisexplainedinsection4.butthey
areunavoidablyquotedinhereinsection3.
9/16
3.1:Atomsinelements,i.e.notcovalentlyorionicallycombinedwithatomsofanotherelements,areconsideredto
haveanoxidationstateofzeroor0irrespectiveofthephysical,molecularorallotropic*stateoftheelement,
e.g.inXe(g),Fe(s),H2(g),Cl2(g),Br2(l),O2(g),O3(g),P4(s),S8(s),C60(afullerene),Cn(graphite)etc.
*Allotropesaredifferentphysicalformsofthesameelementinthesamephysicalstatee.g.solidcarbon
(graphite,diamond,fullerenes),gaseousoxygen(dioxygen,trioxygenozone).Thedifferentformsarisefrom
differencesinthebondingBUTtheyareallinox.stateofzero)
3.2:Irrespectiveofbeinginanionicorcovalentcompoundorthephysicalstateofthecompound,forneutral
moleculesorsimple/complexmolecularionsofselectedelementsthefollowing'rules'3.2.1to3.2.4apply...
BUTpleasenotethat...
thetotaloxidationnumbersofallatomsinacompoundiszero(moredetailsguideline3.3),
thetotaloxidationnumbersofallatomsinanionequalstheoverallchargeontheion(see
guideline3.4)andwatchthesignconventionsforionchargeandoxidationstate/number,
themostelectronegativeelementinthecompoundorioncarriesthenegativeoxidationstate(see
aboveforPaulingvaluesofelectronegativity),
thereareimportantexceptionstotheusualoxidationstateofanelementmentioned,intermsofthe
advancedchemistryyouwillencountersowatchoutandawaywego!
Ex3.2.1:fluorine:Fisalways(1)inallcompounds,
becauseithasthehighestelectronegativityofanyelementandonlyoneelectronshortofastablenoble
gasstructureelectronicallye.g.formationoffluorideionF[2.7]+e==>F[2.8]
The(1)staterelatestoeithergaininganelectrontoformthefluorideion,F,e.g.inionicsodiumfluoride,
NaF(Na+Clionicbond,Nais+1),
orsharewithoneotherelectrontoformacovalentbonde.g.inthemoleculeshydrogenfluoride,HF(+H
Fpolarbond,His+1),ortetrafluoromethane(carbontetrafluoride),CF4(+CFpolarbond,Cis+4).
Ex3.2.2:hydrogenHis(+1)inmostcompounds.
Thisrelatestotheoneouterelectroneitherbeinglostintheformationofahydrogenion,H+,asinacids,
orbeingsharedwithanotherelectrontoformacovalentbondpair,whenbondingwithamore
electronegativeatom.
e.g.HCl(+HClpolarbond,Clis1),H2O(+HOpolarbond,Ois2),NH3(+HNpolarbond,N
is3).
Oneexceptionisintheformationofhydrideswithmetalswherehydrogen'sox.stateis(1)
e.g.inionicsodiumhydride,Na+H,Nais+1)orthecovalentberylliumhydride,BeH2(+BeH
polarbond,Beis+2)becausemostmetalsaremoreelectronegativethanhydrogen.
Thissituationhappensiftheotheratomofthebondhasaverylowelectronegativity,i.e.withvery
electropositivemetalsoflowionisationenergysuchasGroup1(Li,K,Rb,Cs),Group2(Ca,Sr)and
alsoinmanycovalentmetalhydridesoflesselectropositivemetalsthanGps1/2,butstillless
electronegativethanhydrogene.g.berylliumBeH2andaluminiumAlH3.(+AlHpolarbond,Alis
+3)
Ex3.2.3:oxygen:Ois(2)inmostcompounds,sinceitisthe2ndmostelectronegative
element.
Thisreadilyrelatestotheformationoftheoxideion,O2withelectropositivemetals(verylow
electronegativity)e.g.MgO(Mg2+O2ionicbond,Mgis+2),Al2O3(Al3+O2ionicbond,Alis+3)etc.,
wherethetwoelectrongainbyoxygenO[2.6]givingthestablenoblegasconfigurationof[2.8]inthe
O2oxideion,
orbysharingtwoelectronsfromotherlesselectronegativeatomstoformtwosinglebondsoronedouble
bonde.g.water,H2O,+HO2H+(His+1),orcarbondioxide,CO2,2O=C4+=O2(Cis+4)
moleculesrepresentedintermsofpartialchargesofthepolarbondsduetotheelectronegativity
difference.
BUTtherearetwoimportantoxidationstateexceptionsforO
10/16
(i)InperoxidesH2O2(covalent,His+1))orNa2O2(ionic,Nais+1)/O22,whereitis(1)
Heretwooxygenatomsarelinkedtogethere.g.HOOH,
whichchangesthesituationcomparedtoHOH.
and(ii)Ois(+2)inF2O
becausetheelectronegativityoffluorineishigherat4.0thanoxygenat3.5
soyougetaFO2+FpolarbondasFisalways1.
(Thereisalsothecurioussituationregardingthe'superoxideion'O2asinKO2(Kis+1),whereeach
oxygenhasanaverageoxidationstateof0.5,sincetheionistheequivalentofandioxygenmoleculeplus
oneelectron.)
Ex3.2.4:chlorineClis1inmanysimplecompoundscombinedwithalesselectronegative.
Thisisrelatedelectronicallytotheformationofthechlorideionbychlorinegainingoneelectron.
e.g.Cl[2.8.7]+e==>Cl[2.8.8])e.g.insodiumchlorideNaCl(Na+Clbond,Nais+1).
orsharingwithoneelectronfromalesselectronegativeelementincovalentlybonding
e.g.HCl(+HClpolarbond,His+1),PCl5(+PClpolarbond,Pis+5)
BUTwhencombinedwiththemoreelectronegativeOorF,Clhasa(+)oxidationstate
e.g.Clis(+1)inchlorine(I)oxide,Cl2O(+ClOpolarbond,Ois2)
or(+3)inchlorine(III)fluoride,ClF3(+ClFpolarbond,Fis1)
Theredozensofsimilarsocalled'interhalogencompoundswherethemostelectronegativehalogen
carriesthenegativeoxidationstateandthepositiveoxidationstateofthelesselectronegative
halogenisshownwith(Romannumerals)anditretainsits'elemental'name.
Therearealsoawholeseriesof'chlorateions'and'oxides',wherethemoreelectronegativeoxygen
resultsinchlorinehavingoxidationstatesof(+1),(+3),(+4),(+5)andthemaximumpossible(+7).The
latteristhemaximumox.stateforanyhalogen,andisdictatedbyusingall7outerelectronsinbonding
e.g.
chlorate(I),ClO,chlorate(III),ClO2,chlorate(V),ClO3,chlorate(VII),ClO4,
Thesesortofionexamplesareexplainedinmoredetailinsection3.4
Notethatthenameofanonmetallicoxyanionchangesfrom...ideto...atewhenthenonmetalis
combinedwithoxygentoformthepolyatomicanionandtheoxidationstateisdenotedafterthe
namebya(Romannumeralsnumber)inbrackets.
chlorine(IV)oxide,ClO2(chlorinedioxide),bromine(IV)oxide,BrO2,
Thesesortofmoleculeexamplesareexplainedinmoredetailinsection3.3
(formoredetailsandexamplessee3.4chargeonionsand3.5maximumoxidationstatepatterns)
Theseguidelinesforchlorinealsoapplytobromineandiodine.
3.3:Sincecompoundshavenonetoverallelectricalcharge,thesumoftheoxidationstatesofalltheatomsin
acompoundisalsozero,again,thisiseasytofollowinsimpleioniccompoundse.g.
Ex3.3.1:Magnesiumoxide,MgO,Mg2+O2,
OneMg2+balancesoneO2,or...
oneMginthe+2ox.statebalancesoneOinthe2ox.state.
Ex3.3.2:Aluminiumsulphide,Al2S3,ionically(Al3+)2(S2)3,
two3+ionselectricallybalancethree2ions,or
twoAl'sinthe+3ox.statebalancethreeS'sinthe2ox.state.
11/16
Butitisnotsoeasyatfirstincovalentmoleculesbecauseyouneedtoknowhowtoassigntherelevant
oxidationstates.Thisisagainisreadilydonebyusingthedifferenceinelectronegativityguideline,and,
particularlyatthestart,thinkinginasortof'ionic'conceptualway,eventhoughtheatomsinsuchanionare
covalentlybondedtogetherandthe'ionic'natureisreallyduetotheoverallnetelectricalchargecarriedbythe
particle.
Incovalentmoleculesthemostelectronegativeelementscarrythenegativeoxidationstatese.g.using
theguidelines3.2.1to3.2.4...
Ex3.3.3:Water,H2O
Twohydrogensinthe+1statebalanceoneoxygeninthe2statebecause
oxygen'selectronegativityishigherthanhydrogen's.
Inotherwords,theassignmentofoxidationstateswillcoincidewithbondpolarity+HO2H+
basedonelectronegativitydifferencesandyoucancrudelythinkofwatermadeupoftwoH+ions
andoneO2ion,eventhoughinrealitywaterisneutralcovalentmolecule!
Ex3.3.4:Phosphorusoxychloride,POCl3.
Thetwomostelectronegativeelementsareoxygenandchlorineandtheywillcarrythenegative
oxidationstatesof2and1respectively.
YoucanthinkofthiscovalentcompoundasifitismadeupofonePat(+5),oneOat(2)andthree
Clat(1),so(+5)+(2)+(3x1)=0.
NotethatbyusingtheguidelinesyoucandeducethatPisinthe+5ox.stateeventhoughthereis
norulespecifiedtophosphorusquotedhere.
Ex3.3.5:Pureliquidsulphuricacid,H2SO4
Fromtheguidelineshydrogenis+1,oxygenis2,sosulphurwillbesulphurinthe+6ox.state.
so,(2x+1)+(+6)+(4x2)=0
Noteagain,thatbyfollowingtheguidelinesyoucandeducethatSisinthe+6ox.stateeventhough
thereisnorulespecifiedforsulphur.
3.4:Insimpleionsofoneatomtheoxidationstateisnumericallythesameasthechargeontheion.
Ex3.4.1:SodiumasNa+hasanox.stateof(+1),oxygenastheoxideionO2hasanox.stateof(2),for
aluminiumintheionAl3+itis(+3),chlorineasthechlorideionCl(1),sulfurasthesulfideionS2(2)etc.
Forionsofatleasttwoatoms,thechargeonanionisnumericallyequaltothesumoftheoxidation
numbersofalltheatomsintheion.
ThereforeyoucannowdealwithnonelectricallyneutralmolecularionslikePO43inthesamewayoutlinedfor
neutralcovalentmoleculesin3.3,BUTyoumusttakeintoaccounttheoverallchargeontheion.
Ex3.4.2:Forionslikephosphate(V),PO43
Oxygenismoreelectronegativethanphosphorus,so..
Pis+5,Ois2,andtherefore+5+(4x2)=3intotal,=3foroverallchargeontheion.
YoucanconceiveofitmadeupofonefictitiousP5+combinedwithfourfictitiousO2ions,evenifthey
don'texisthere,but(5+)+(4x2)=3.
NoteagainthattheRomannumeralinbracketsdenotesthepositiveoxidationstateofphosphorus,
the2ofoxygeniscorrectlyassumed(moreonnamingions/compoundslater).
Ex3.4.3:Inthe'inorganic'carbonateion,CO32,againoxygenisthemostelectronegativeelement.
Cis+4andOis2and(1x+4)plus(3x2)givesatotalof2,sotheionchargesurplusis2.
However,theoxidationstateofcarboninorganicmoleculesismoretricky,but,suchknowledgeisnot
usuallyrequiredforUKAdvancedlevel.
Therearewaysofusinghalfcellequationstogetroundtheproblemofconstructingredoxequations
involvingtheoxidationandreductionoforganicmolecules,seee.g.theoxidationofalcoholswith
acidifiedpotassiumdichromate(VI).
Forthoseinterested,therearesomeexamplesofoxidationstatesinorganicmoleculesPart3.
Ex3.4.4:Thecompoundpotassiumnitrate,KNO3
Inthenitrateion,NO3,togiveanoverallchargeof1ontheion,nitrogenmustbe+5andoxygenat2.
So,overallinthecompound:oneofKat(+1)andoneofNat(+5)isbalancedbythreeofOat(2).
12/16
Ex3.4.5:Thechlorate(V)ion,ClO3
Oxygenisinthe2oxidationstate,sowith3O'sat(2)each,thechlorinemustbeinthe(+5)stateto
givetheionanoverallchargeofasingleminus.
Ex3.4.6:Thedichromate(VI)ion,Cr2O72
With7O'sat(2),total14,the2Cr'smustequalatotalof+12togivethe2surpluschargeontheion,
sothechromiumisinthe(+6)ox.state.
Ex3.4.7:Transitionmetalcomplexionse.g.[CrCl2(H2O)4]+,
H2Oisneutral,2H(+1)andO(2),soyoucanfocusontheClandCr.
ThetwochlorideligandsareClions(ox.state1),contributingatotalchargeofa2,
thereforetheCrmustbeinthe+3statetogiveanoverallchargeofasingle+onthecomplexion.
Thiscomplexmightbecalledthetetraaquadichlorochromium(III)ion.
Otherexamplesoftransitionmetalcomplexes
[TiCl6]2,titaniumisina+4ox.state(Clis1),(6x1)+(+4)=2overall.
[VO]2+(aq),or[VO(H2O)5]2+(aq),vanadiumisin+4ox.state(His+1,Ois2),
3.5:Themaximumoxidationstatepossibleisoftenthenumberofouterelectronsinthevalencyshell.
ForGroups1to7andeventheNobleGases(group0/8)thereis,notsurprisingly,anicesimplepatternrelated
totheGroupnumberofthePeriodicTablee.g.
Groups14:Nais+1e.g.inNaCl,Cais+2e.g.inCaO,Alis+3e.g.inAlCl3,Cis+4e.g.inCO2,
Groups58:Pis+5e.g.inH3PO4,Sis+6e.g.inSO42,Clis+7e.g.inClO4,andXeis+8e.g.inXeO4.
AfterKandCaonPeriod4ofthePeriodicTablecomethe3dblockofmetals,wherethingsarenotsoclearcut.
Uptomanganese,themaximumox.stateisstilldictatedbythenumberofvalencyelectronse.g.
Sc+3inScCl3,Ti+4inTiO2,V+5inVO43,Cr+6inK2Cr2O7,Mn+7inMnO4,
(xrefouterelectronconfigurationintermsof3dx4s2),
butforFe,Co,Ni,CuandZnthepatterniscomplex,andgenerallyoneofdecreasingmax.ox.state,
e.g.effectivelyamax.of+3forFesinceonlyafewunstablecompoundswithover+3ox.stateexist(e.g.
FeO42[ferrate(VI)oxyanion],Comax.+3andusuallyincomplexions,forCuthereareafewunstable
complexionsshowingthe+3state,buteffectivelythemax.is+2ine.g.CuSO4etc.andZnonlyexhibits
the+2ox.stateinitscompoundse.g.ZnO,ZnCl2etc.
ApartfromSc(+3)andZn(+2),alltherestofthe3dblockaretruetransitionmetalsexhibitingvariable
oxidationstates,afactthatisimportantinthecatalyticactivityoftherecompoundse.g.theuseofV2O5in
theContactProcessformakingsulphurtrioxideinthemanufactureofsulphuricacidortheiron(III)ion
catalysisofiodideoxidationbyperoxodisulphate..
3.6:OtherPeriodicTable'patterns',e.g.forthoseelementsencounteredatUKadvancedASA2andIBacademic
level.
ForGroup1(+1)andgroup2(+2)elementsthereisonlyonestableoxidationstate,
Group3mainly+1and+3,
Group4mainly+2and+4,
Group5mainly3,+3and+5,(thoughseethevariationfornitrogeninsection3.7below)
Group6mainly2,+4and+6,
Group7canbeveryvariablefrom1allthewayto+7(see3.2.4forClandBrexamples).
3dBlockTransitionmetalsshowvaluesfrom+1to+7dependingontheelement.
Scandium(+3)andzinc(+2)haveonlyonestableoxidationstateincompoundsandarenottrue
transitionmetalelements.
Fromtitaniumtocopper,alloftheelementsexhibitatleasttwostableoxidationstatesinsimple
compoundsorcomplexionsandareconsideredtruetransitionmetals.
Lastlya'curiosity',nickel(0)carbonylisNi(CO)4,asortofneutralcomplexformedonheatingnickelin
carbonmonoxide(C+2,O2)soNiisinazeroox.state!
13/16
3.7:Oxidationstatecanbequitevariableevenforasingleelemente.g.nitrogen'soxidationstateinvarious
compoundsorions:
forammoniaNH3,ammoniumionNH4+,ammoniumchlorideNH4Cl,
nitrideionN3andmagnesiumnitrideMg3N2itis(3)
forhydrazineN2H4itis(2),
forazocompoundsRN=NRitis(1),Risusuallyaromatic,
fornitrogenN2itis(0),
fornitrogen(I)oxideN2O(+1),
fornitrogen(II)oxideNO(+2),
forsodiumnitriteNaNO2,nitrite/nitrate(III)ionNO2andnitrogen(III)oxideN2O3itis(+3)
fornitrogen(IV)oxideNO2(+4)
fornitrogen(V)oxideN2O5,nitroniumcationNO2+,nitrateionNO3,NaNO3andHNO3itis(+5)
andjusttocomplicatemattersfurtherinammoniumnitrateNH4NO3,
nitrogen'soxidationstateis3and+5.
Thissequenceillustrateswhytheconceptofoxidationnumber/stateissoimportantinredoxchemistrye.g.the
nitrogencycle,whichisallaboutelectrontransferviaenzymes!
4.Oxidationstatesandnaminginorganiccompounds
4.1:Differentcompoundsorionscanbeformedfromthesametwo(ormore)differentelements,soatleast
oneoftheelementsisinadifferentoxidationstateineachcompoundorion.
Thereforethereisaneedtoindicatethiswhenwritingthenameofthecompoundorion.
(Romannumerals)areusedtoindicatethevalueoftheoxidationstatebutwithnopreceding+sign.
Someexampleshavealreadybeendealtwithinsection3.4,sosection4.actsasacollectiverecapand
extensionofusingRomannumeralnotationdepictingdifferentoxidationstatesofthesameelementintwoor
morecompounds.
Apositiveoxidationstateisassumed,andifyouhaveworkedthroughtheguidelinesinsection3.you
shouldhavenotroubleinanalysingtheexamplesbelowandconnectingthe(II)etc.inthenamewithan
oxidationstateanalysisofthecompoundorion.
TheRomannumeralsnumberisplacedin()afterthename,butwithnospacebetweenit.
Sometimes,especiallyintransitionmetalcomplexes,youmightevenseetheRomannumeralsina
formula,
e.g.theoctahedralcomplex[CrIIICl2(NH3)4]+(canyouseewhyCrisinthe+3state?)
andthisiscalledthetetraamminedichlorochromium(III)ion,
butthis'superscript'notationisrarelyencountereduntilundergraduatelevelstudies,
sowewillstartwithsomesimplernamingexamples!
4.2:FormetallicornonmetallicelementsthenameoftheelementisusedifNOTinananion
Someoftheoldnamesarestillincommonuse,buttrytousethecorrectsystematicnamee.g.
copper(I)oxideCu2Oandcopper(II)oxideCuO
(oncecalledcuprousoxideandcupricoxide)
iron(II)chlorideFeCl2andiron(III)chlorideFeCl3
(oncecalledferrouschlorideandferricchloride)
14/16
iron(II)oxideFeO,iron(III)oxideFe2O3anddiiron(II)iron(III)oxide,Fe3O4
(oncecalledferrousoxideandferricoxideandtriirontetroxide)
Historicnote:...ouswastheloweroxidationstate,...icthehigher.
vanadium(II)sulphateforVSO4orV2+SO42andvanadium(III)sulphateV2(SO4)3
sulphur(IV)oxideSO2(sulphurdioxide)andsulphur(VI)oxide,SO3(sulphurtrioxide)
nitrogen(I)oxideN2O(dinitrogenoxide)nitrogen(II)oxideNO(nitrogenmonoxide),nitrogen(IV)oxideNO2
(nitrogendioxide)andnitrogen(V)oxideN2O5(nitrogenpentoxide).
transitionmetalcomplexcationse.g.
diaquatetraamminecopper(II)ion,[Cu(H2O)2(NH3)4]2+
(waterandammoniaareelectricallyneutralligandsattachedtothecentralCu2+ion)
4.3:Forelements(metalornonmetal)combinedwithoxygenorothermoreelectronegativeelement,giving
ananion,theionnameendsin...atewiththeprefixderivedfromtheelementsname.Insuchcasestheoxygen
carriesthenegativeoxidationstateof(2)orchlorine(1)e.g.
vanadate(V)ion,VO43,
manganate(VI)ion,MnO42,manganate(VII)ion,MnO4,(wascalledthepermanganateion)
sulphate(IV)ion,SO32(sulphite)andsulphate(VI)ion,SO42(sulphate)
nitrate(III),NO2(nitrite)andnitrate(V),NO3(nitrate)
Historicnote:...itewastheloweroxidationstate,...atethehigher.
chlorate(I),ClO,chlorate(VII),ClO4etc.oxygenismoreelectronegativethanchlorine.
(oncecalledthehypochloriteionandtheperchlorateionrespectively)
transitionmetalcomplexanionse.g.
tetrachlorocuprate(II)ion,[CuCl4]2(oxidationstatesCu+2,Cl1)
15/16
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