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OxidationReductionReactions:Redox

RedoxReactions
Redoxreactions,oroxidationreductionreactions,haveanumberofsimilaritiestoacidbasereactions.Fundamentally,
redoxreactionsareafamilyofreactionsthatareconcernedwiththetransferofelectronsbetweenspecies.Likeacid
basereactions,redoxreactionsareamatchedsetyoudon'thaveanoxidationreactionwithoutareductionreaction
happeningatthesametime.Oxidationreferstothelossofelectrons,whilereductionreferstothegainofelectrons.
Eachreactionbyitselfiscalleda"halfreaction",simplybecauseweneedtwo(2)halfreactionstoformawhole
reaction.Innotatingredoxreactions,chemiststypicallywriteouttheelectronsexplicitly:
Cu(s)>Cu2++2e
Thishalfreactionsaysthatwehavesolidcopper(withnocharge)beingoxidized(losingelectrons)toformacopperion
withaplus2charge.Noticethat,likethestoichiometrynotation,wehavea"balance"betweenbothsidesofthe
reaction.Wehaveone(1)copperatomonbothsides,andthechargesbalanceaswell.Thesymbol"e"representsa
freeelectronwithanegativechargethatcannowgooutandreducesomeotherspecies,suchasinthehalfreaction:
2Ag +(aq)+2e>2Ag(s)
Here,twosilverions(silverwithapositivecharge)arebeingreducedthroughtheadditionoftwo(2)electronstoform
solidsilver.Theabbreviations"aq"and"s"meanaqueousandsolid,respectively.Wecannowcombinethetwo(2)half
reactionstoformaredoxequation:

Wecanalsodiscusstheindividualcomponentsofthesereactionsasfollows.Ifachemicalcausesanothersubstanceto
beoxidized,wecallittheoxidizingagent.Intheequationabove,Ag+istheoxidizingagent,becauseitcausesCu(s)to
loseelectrons.Oxidantsgetreducedintheprocessbyareducingagent.Cu(s)is,naturally,thereducingagentinthis
case,asitcausesAg+togainelectrons.
Asasummary,herearethestepstofollowtobalancearedoxequationinacidicmedium(addthestarredstepina
basicmedium):
1.Dividetheequationintoanoxidationhalfreactionandareductionhalfreaction
2.Balancethese
BalancetheelementsotherthanHandO
BalancetheObyaddingH2O
BalancetheHbyaddingH+
Balancethechargebyaddinge
3.Multiplyeachhalfreactionbyanintegersuchthatthenumberofelostinoneequalsthenumbergainedintheother
4.Combinethehalfreactionsandcancel
5.**AddOHtoeachsideuntilallH+isgoneandthencancelagain**
Inconsideringredoxreactions,youmusthavesomesenseoftheoxidationnumber(ON)ofthecompound.The
oxidationnumberisdefinedastheeffectivechargeonanatominacompound,calculatedaccordingtoaprescribedset

ofrules.Anincreaseinoxidationnumbercorrespondstooxidation,andadecreasetoreduction.Theoxidationnumber
ofacompoundhassomeanalogytothepHandpKmeasurementsfoundinacidsandbasestheoxidationnumber
suggeststhestrengthortendencyofthecompoundtobeoxidizedorreduced,toserveasanoxidizingagentor
reducingagent.Therulesareshownbelow.Gothroughthemintheordergivenuntilyouhaveanoxidationnumber
assigned.
1.Foratomsintheirelementalform,theoxidationnumberis0
2.Forions,theoxidationnumberisequaltotheircharge
3.Forsinglehydrogen,thenumberisusually+1butinsomecasesitis1
4.Foroxygen,thenumberisusually2
5.Thesumoftheoxidationnumber(ONs)ofalltheatomsinthemoleculeorionisequaltoitstotalcharge.
Asasidenote,theterm"oxidation",withitsobviousrootfromtheword"oxygen",assumesthatoxygenhasanoxidation
numberof2.Usingthisasabenchmark,oxidationnumberswereassignedtoallotherelements.Forexample,ifwe
lookatH2O,andassignthevalueof2totheoxygenatom,thehydrogensmusteachhaveanoxidationnumberof+1
bydefault,sincewaterisaneutralmolecule.Asanexample,whatistheoxidationnumberofsulfurinsulfurdioxide
(SO2)?Giventhateachoxygenatomhasa2charge,andknowingthatthemoleculeisneutral,theoxidationnumber
forsulfurmustbe+4.Whataboutforasulfateion(SO4withatotalchargeof2)?Again,thechargeofalltheoxygen
atomsis4x2=8.Sulfurmustthenhaveanoxidationnumberof+6,since+6+(8)=2,thetotalchargeontheion.
Sincethesulfurinsulfatehasahigheroxidationnumberthaninsulfurdioxide,itissaidtobemorehighlyoxidized.
Workingwithredoxreactionsisfundamentallyabookkeepingissue.Youneedtobeabletoaccountforallofthe
electronsastheytransferfromonespeciestoanother.Thereareanumberofrulesandtricksforbalancingredox
reactions,butbasicallytheyallboildowntodealingwitheachofthetwohalfreactionsindividually.Considerforexample
thereactionofaluminummetaltoformalumina(Al2O3).Theunbalancedreactionisasfollows:

Lookingateachhalfreactionseparately:

Thisreactionshowsaluminummetalbeingoxidizedtoformanaluminumionwitha+3charge.Thehalfreactionbelow
showsoxygenbeingreducedtoformtwo(2)oxygenions,eachwithachargeof2.

Ifwecombinethosetwo(2)halfreactions,wemustmakethenumberofelectronsequalonbothsides.Thenumber12
isacommonmultipleofthree(3)andfour(4),sowemultiplythealuminumreactionbyfour(4)andtheoxygenreaction
bythree(3)toget12electronsonbothsides.Now,simplycombinethereactions.Noticethatwehave12electronson
bothsides,whichcancelout.Thefinalstepistocombinethealuminumandoxygenionsontherightsideusingacross
multiplytechnique:

Takingcareofthenumberofatoms,youshouldendupwith:

OneofthemoreusefulcalculationsinredoxreactionsistheNernstEquation.Thisequationallowsustocalculatethe
electricpotentialofaredoxreactionin"nonstandard"situations.Thereexisttablesofhowmuchvoltage,orpotential,a
reactioniscapableofproducingorconsuming.Thesetables,knownasstandardpotentialtables,arecreatedby
measuringpotentialat"standard"conditions,withapressureof1bar(1atm),atemperatureof298K(or25C,or
roomtemperature)andwithaconcentrationof1.0Mforeachoftheproducts.Thisstandardpotential,orE,canbe
correctedbyafactorthatincludestheactualtemperatureofthereaction,thenumberofmolesofelectronsbeing
transferred,andtheconcentrationsoftheredoxreactantsandproducts.Theequationis:

Perhapsthebestwayofunderstandingthisequationisthroughanexample.Supposewehavethisreaction:
Fe(s)+Cd2+(aq)>Fe2+(aq)+Cd(s)
Inthisreactioniron(Fe)isbeingoxidizedtoiron(II)ion,whilethecadmiumion(Cd2+)inaqueoussolutionisbeing
reducedtocadmiumsolid.Thequestionis:howdoesthisreactionbehavein"nonstandard"conditions?
Thefirstthingtoanswerishowdoesitbehaveinstandardconditions?Weneedtolookatthestandardpotentialfor
eachhalfreaction,thencombinethemtogetanetpotentialforthereaction.Thetwo(2)halfreactionsare:
Fe2+(aq)+2e>Fe(s),E=0.44V
Cd2+(aq)+2e>Cd(s),E=0.40V
Noticethatbothhalfreactionsareshownasreductionsthespeciesgainselectrons,andischangedtoanewform.
Butinthecompletereactionabove,Feisoxidized,sothehalfreactionneedstobereversed.Quitesimply,thepotential
forthehalfreactionofironisnow0.44V.Togetthepotentialfortheentirereaction,weaddupthetwo(2)half
reactionstoget0.04Vforthestandardpotential.

Thequestionnowis:whatisthetotalpotential(involts)foranonstandardreaction?Supposeagainthatwehavethe
samereaction,exceptnowwehave0.0100MFe2+insteadofthestandard1.0M.WeneedtousetheNernstequation
tohelpuscalculatethatvalue.IfyougototheRedoxHalfReactionCalculator,youshouldnoticethatthereactionis
selectedandtheappropriatevaluesareenteredintotheboxes.Sincewedon'thaveanyspecies"B"or"D",wehave
enteredzerofortheirconcentrations.TheconcentrationofthesolidFeis1.0M(actually,concentrationsofsolidsand
solvents(liquids)don'tenterintotheNernstequation,butwesetthemto1.0sothatthemathematicsworksout).Ifyou
clickonthe"Evaluate"button,youshouldlearnthatthestandardpotentialis0.44V,whilethenonstandardpotentialis
0.5V.Ifyouscrolldownonthecalculator,youcanenter0.5asthefirsthalfreaction.Weagainchangethesignsince
we'reactuallyreversingtheFereaction
Usingthecalculatoragain,wecalculatethenonstandardpotentialoftheCdreaction.Supposewenowhavea
concentrationofCd2+of0.005M,whatisitspotential?Thecalculatorshouldreturnastandardpotentialof0.4Vanda
nonstandardpotentialof0.47V.Placethisvalueintheboxforthesecondhalfreaction,thenclickon"Evaluate".You
shouldlearnthatthenetnonstandardpotentialis0.03V,slightlylessthanthevalueofthenetstandardpotential.Since
thisvalueislessthanthenetstandardpotentialof0.04V,thereislessofatendencyforthisreactiontotransfer
electronsfromreactantstoproducts.Inotherwords,lessironwillbeoxidizedandcadmiumwillbereducedthanat
standardconditions.
Testyouruseoftheredoxcalculatorbycalculatingthenetstandardpotentialforthisreaction:
2Ag+(aq,0.80M)+Hg(l)>2Ag(s)+Hg2+(aq,0.0010M)
Answer:0.025V.Sincethevalueispositive,thereactionwillworktoformtheproductsindicated.Negativevaluesofthe
potentialindicatethatthereactiontendstostayasreactantsandnotformtheproducts.Thenetstandardpotentialfor
thisreactionis0.01Vsincethenonstandardpotentialishigher,thisreactionwillformproductsthanthestandard
reaction.
Freeenergyandthestandardpotentialcanalsoberelatedthroughthefollowingequation:

Where:
G=changeinfreeenergy
n=numberofmoles
Ifareactionisspontaneous,itwillhaveapositiveEo,andnegativeG,andalargeKvalue(whereKistheequilibrium
constantthisisdiscussedmoreinthekineticssection).
Theenergyreleasedinanyspontaneousredoxreactioncanbeusedtoperformelectricalworkusingan
electrochemicalcell(adevicewhereelectrontransferisforcedtotakeanexternalpathwayinsteadofgoingdirectly
betweenthereactants.Thinkofthereactionbetweenzincandcopper.Insteadofplacingapieceofzincdirectlyintoa
solutioncontainingcopper,wecanformacellwheresolidpiecesofzincandcopperareplacedintwodifferentsolutions
suchassodiumnitrate.Thetwosolidsarecalledelectrodes.Theanodeistheelectrodewhereoxidationoccursand
massislostwhereasthecathodeistheelectrodewherereductionoccursandmassisgained.Thetwoelectrodesare
connectedbyacircuitandthetwo(2)solutionsareconnectedbya"saltbridge"whichallowsionstopassthrough.The
anionsarethenegativeionsandtheymovetowardstheanode.Thecationsarethepositiveionsandtheymove
towardsthecathode.
Thefollowingisadiagramofanelectrochemicalcellwithzincandcopperactingastheelectrodes.

Anexternalelectriccurrenthookeduptoanelectrochemicalcellwillmaketheelectronsgobackwards.Thisprocessis
calledelectrolysis.Thisisused,forexample,tomakesomethinggoldplated.Youwouldputthecopperinasolutionwith
goldandaddacurrentwhichcausesthegoldionstobondtothecopperandthereforecoatingthecopper.Thetime,
current,andelectronsneededdeterminehowmuch"coating"occurs.Thekeytosolvingelectolysisproblemsislearning
howtoconvertbetweentheunits.Usefulinformation:1A=1C/sec96,500coulombscanproduceone(1)moleofethe
electronsneededisdeterminedbythechargeoftheioninvolved
ExampleProblem:Ifyouaretryingtocoatastripwithaluminumandyouhaveacurrentof10.0A(amperes)runningfor
onehour,whatmassofAlisformed?
Thesolutionofthisprobleminvolvesalengthlyunitconversionprocess:

PracticeRedoxProblem:balancethefollowingredoxreactioninacidicsolution:
S(s)+NO3(aq)>SO2(g)+NO(g)
Theredoxsolutionisavailable.
PracticeElectrolysisProblem:Ittakes2.30minusingacurrentof2.00Atoplateoutallofthesilverfrom0.250Lofa
solutioncontainingAg+.WhatwastheoriginalconcentrationofAg+insolution?
Theelectrolysissolutionisavailable.

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