OxidationReduction

and
Electrochemistry
DavidA.Katz
DepartmentofChemistry
PimaCommunityCollege

OxidationReductionReactions
Inanoxidationreduction (Redox)reaction,
electronsaretransferredfromonespeciesto
another.
Forexample,inasinglereplacementreaction
Cu(s) +2AgNO3(aq) 2Ag(s) +Cu(NO3)2(aq)
TheCuatomsloseelectronstoformCu2+inthe
Cu(NO3)2(aq)andtheAg+ gainselectronstoform
metallicAg

OxidationReductionReactions
Thiscanbemoreeasilyobservedbywritingthenet
ionicequationforthereaction:
Cu(s) +2Ag+ (aq) 2Ag(s) +Cu2+(aq)
ThemetallicCuatomsareuncombined,sotheyare
consideredtohaveanoxidationnumberofzero.
TheinitialcombinedAg+ ionsareina+1oxidationstate.
EachCuatomwilllose2electronsto2Ag+ ions
TheresultingAgatomsareconsideredtohavean
oxidationnumberofzero

OxidationReductionReactions
Cu(s) +2Ag+ (aq) 2Ag(s) +Cu2+(aq)

OxidationNumbers

Inordertokeeptrack
ofwhatloses
electronsandwhat
gainsthem,welist
theoxidation
numbersofeach
element.

OxidationandReduction

Aspeciesisoxidized whenitloseselectrons.
Here,zinclosestwoelectronstogofromneutralzinc
metaltotheZn2+ ion.

OxidationandReduction

Aspeciesisreduced whenitgainselectrons.
Here,eachoftheH+ gainsanelectronandthey
combinetoformH2.

OxidationandReduction

Thespeciesthatcontainstheelementthatis
reducedistheoxidizingagent.
H+ oxidizesZnbytakingelectronsfromit.

Thespeciesthatcontainstheelementthatis
oxidizedisthereducingagent.
ZnreducesH+ bygivingitelectrons.

AssigningOxidationNumbers
1. Elementsintheirelementalformhavean
oxidationnumberof0.
2. Theoxidationnumberofamonatomicion
isthesameasitscharge.

AssigningOxidationNumbers
3.Theoxidationnumberofmetalsdepends
ontheirpositionintheperiodictable

GroupIAelementsare+1
GroupIIAelementsare+2
GroupIIIAelementsare+3
GroupIVAmetalsareusually+2or+4
GroupVAmetalsareusually+3or+5

AssigningOxidationNumbers
4.Nonmetals tendtohavenegative
oxidationnumbers,althoughsomeare
positiveincertaincompoundsorions.
Oxygenalwayshasanoxidationnumberof
2,exceptintheperoxideioninwhichithas
anoxidationnumberof1.
Hydrogenisalways1whenbondedtoa
metal
Hydrogenis+1whenbondedtoa
nonmetal.

AssigningOxidationNumbers
4.Nonmetals (continued).
Fluorinealwayshasanoxidationnumberof
1.
Thehalogens(Cl,Br,andI)haveanoxidation
numberof1whentheyarenegative
Thehalogens(Cl,Br,andI)willhave
positiveoxidationnumbersinoxyanions
(ClO,ClO2,ClO3,etc.)

AssigningOxidationNumbers
5.Thesumoftheoxidationnumbersina
neutralcompoundis0.
6.Thesumoftheoxidationnumbersina
polyatomicionisthechargeontheion.

BalancingOxidationReductionEquations
Oxidationreductionequationsmaybedifficultto
balance.
Generally,theeasiestwaytobalancetheequation
ofanoxidationreductionreactionisviathehalf
reactionmethod.
Thisinvolvestreatingtheoxidationandreduction
astwoseparateprocesses,balancingthesehalf
reactions,andthencombiningthemtoattainthe
balancedequationfortheoverallreaction.

BalancingRedox Equationsbythe
HalfReactionMethod
1. Assignoxidationnumberstotheelements
intheequation
2. Determinewhatisoxidizedandwhatis
reduced.
3. Writetheoxidationandreductionhalf
reactions.

BalancingRedox Equationsbythe
HalfReactionMethod
4.Balanceeachhalfreaction.
a.
b.
c.
d.

BalanceelementsotherthanHandO.
BalanceObyaddingH2O.
BalanceHbyaddingH+.
Balancechargebyaddingelectrons.

5.Multiplythehalfreactionsbyintegersso
thattheelectronsgainedandlostarethe
same.

BalancingRedox Equationsbythe
HalfReactionMethod
6.Addthehalfreactions,subtractingthings
thatappearonbothsides.
7.Makesuretheequationisbalanced
accordingtomass.
8.Makesuretheequationisbalanced
accordingtocharge.

BalancingRedox Equationsbythe
HalfReactionMethod

ConsiderthereactionbetweenMnO4 andC2O42:
MnO4(aq) +C2O42(aq) Mn2+(aq) +CO2(aq)(acidicsolution)

BalancingRedox Equationsbythe
HalfReactionMethod
First,assignoxidationnumbers(rememberoxygenis
2)
+7

+3

+2

+4

MnO4 +C2O42 Mn2+ +CO2

Theoxidationnumberofmanganesegoesfrom+7to+2,itis
reduced.
Theoxidationnumberofcarbongoesfrom+3to+4,itis
oxidized.

BalancingRedox Equationsbythe
HalfReactionMethod
Determinetheoxidizingandreducingagents
+7

+3

+2

+4

MnO4 +C2O42 Mn2+ +CO2

TheMnO4 istheoxidizingagent
TheC2O42 isthereducingagent

BalancingRedox Equationsbythe
HalfReactionMethod
Theoxidationhalfreactionis
C2O42 CO2
Balancethehalfreaction
C2O42 2 CO2
Thisbalancesboththecarbonatomsand
theoxygenatoms

BalancingRedox Equationsbythe
HalfReactionMethod
Balancethechargebyadding2electronsto
therightside.
C2O42 2CO2 +2e

BalancingRedox Equationsbythe
HalfReactionMethod
Thereductionhalfreactionis
MnO4 Mn2+
Themanganeseisbalanced
Inordertobalancethe4oxygens,weadd4
watermoleculestotherightside.
MnO4 Mn2+ +4H2O

BalancingRedox Equationsbythe
HalfReactionMethod
MnO4 Mn2+ +4H2O
Theadditionofwaterontherightsideofthe
equationincludedhydrogenatoms.
Tobalancethe8hydrogens,add8H+ tothe
leftside.
8H+ +MnO4 Mn2+ +4H2O

BalancingRedox Equationsbythe
HalfReactionMethod
8H+ +MnO4 Mn2+ +4H2O
Balancethecharges,add5e totheleftside.
5e +8H+ +MnO4 Mn2+ +4H2O

BalancingRedox Equationsbythe
HalfReactionMethod
Beforethetwohalfreactionscanbeadded
together,thenumberofelectronslostmustbe
equaltotheelectronsgained:
C2O42 2CO2 +2e
(2e lost)
5e +8H+ +MnO4 Mn2+ +4H2O(5e gained)
Toattainthesamenumberofelectronsoneach
side,multiplythefirstreactionby5andthe
secondby2.
5C2O42 10 CO2 +10 e
10 e +16 H+ +2MnO4 2Mn2+ +8 H2O

BalancingRedox Equationsbythe
HalfReactionMethod
5C2O42 10CO2 +10e
10e +16H+ +2MnO4 2Mn2+ +8H2O
Addthesehalfreactions
10e +16H+ +2MnO4 +5C2O42
2Mn2+ +8H2O+10CO2 +10e
Cancelouttheelectronsfrombothsidestoget
16H+ +2MnO4 +5C2O42 2Mn2+ +8H2O+10CO2

BalancingRedox Equations
inBasicSolution
Ifareactionoccursinbasicsolution,useOH
andH2OinsteadoftheH+ andH2Ousedinacid
solution
Theeasiestmethodistobalancetheequation
asifitoccurredinacid.
Oncetheequationisbalanced,addOH toeach
sidetoneutralizetheH+ intheequationand
createwaterinitsplace.
Ifthisresultsinwateronbothsidesofthe
equation,subtractwaterfromeachsideasa
finalstep.

BalancingRedox Equations
inBasicSolution
Completeandbalancethefollowingredoxequation
thattakesplaceinbasicsolution
CN (aq)+MnO4 (aq) CNO (aq)+MnO2(s) (basic
solution)

First,assignoxidationnumbers(rememberoxygenis2)
+23+72+432+42

CN (aq)+MnO4 (aq) CNO (aq) +MnO2(s)

Note:InananionsuchasCN,C,whichcomesfirst,wouldbepositiveandN
wouldbenegative.Ifnegative,Nwouldbe3.

BalancingRedox Equations
inBasicSolution
+23+72+432+42

CN (aq)+MnO4 (aq) CNO (aq) +MnO2(s)

Theoxidationnumberofcarbongoesfrom+2to+4,itis
oxidized. (Clost2e)
Theoxidationnumberofmanganesegoesfrom+7to+4,itis
reduced.(Mngained3e)
MnO4 istheoxidizingagent
CN isthereducingagent

BalancingRedox Equations
inBasicSolution
Thereductionhalfreactionis
MnO4 MnO2
Balancethehalfreaction
MnO4 MnO2
Balancetheoxygenatoms,addH+ andH2O
4H+ +MnO4 MnO2+2H2O

BalancingRedox Equations
inBasicSolution
Balancethecharges,add3e totheleftside
3e +4H+ +MnO4 MnO2+2H2O

BalancingRedox Equations
inBasicSolution
Theoxidationhalfreactionis
CN CNO
SincetheCatomsarebalanced,balancethe
oxygen.
AddH2OtotheleftsideandH+ totherightside.
H2O +CN CNO +2H+

BalancingRedox Equations
inBasicSolution
H2O+CN CNO +2H+
Balancethecharge,add2e totherightside
H2O+CN CNO+2H++2e

BalancingRedox Equations
inBasicSolution
Beforethetwohalfreactionscanbeadded
together,thenumberofelectronslostmustbe
equaltotheelectronsgained:
H2O+CN CNO +2H++2e (2e lost)
3e +4H+ +MnO4 MnO2+2H2O(3e gained)
Toattainthesamenumberofelectronsoneach
side,multiplythefirstequationby3andthe
secondby2.
3 H2O+3 CN 3 CNO +6 H++6 e
6 e +8 H+ +2 MnO4 2 MnO2+4 H2O

BalancingRedox Equations
inBasicSolution
Addthehalfreactions
3 H2O+3 CN +8 H+ +2 MnO4
3 CNO +6 H++2 MnO2+4 H2O
CancelouttheH+ andH2Otoget
2 H+ +3CN +2MnO4 3 CNO +2 MnO2+H2O

BalancingRedox Equations
inBasicSolution
Thisreaction,however,takesplaceinbasicsolution
2 H+ +3CN +2MnO4 3 CNO +2 MnO2+H2O
Add2OH tobothsidestocancelouttheH+
2OH +2 H+ +3CN +2MnO4 3 CNO +2 MnO2+H2O+2OH
(RememberthatH+ +OH H2O)

2H2O+3CN +2MnO4 3 CNO +2 MnO2 +H2O+2OH

Thebalancedequationis
3CN +2MnO4 +H2O 3 CNO +2 MnO2 +2OH

AHistoryofElectricity/Electrochemistry

Thales of Miletus (640546 B.C.) is

credited with the discovery that
amber when rubbed with cloth or
fur acquired the property of
attracting light objects.
The word electricity comes from
"elektron" the Greek word for
amber.
Otto von Guericke (16021686)
invented the first electrostatic
generator in 1675. It was made of
a sulphur ball which rotated in a
wooden cradle. The ball itself was
rubbed by hand and the charged
sulphur ball had to be
transported to the place where
the electric experiment was
carried out.

ThalesofMiletus

OttovonGuericke

 Eventually,aglassglobereplacedthe
sulfursphereusedbyGuericke

Later,largediskswereused

 EwaldJrgenvonKleist(17001748),
inventedtheLeydenJarin1745to
storeelectricenergy.TheLeydenJar
containedwaterormercuryandwas
placedontoametalsurfacewith
groundconnection.
In1746,theLeydenjarwas
independentlyinventedbyphysicist
PietervanMusschenbroek(1692
1761)and/orhislawyerfriend
AndreasCunnaeusinLeyden/the
Netherlands
Leydenjarscouldbejoinedtogether
tostorelargeelectricalcharges

 In1752,BenjaminFranklin(17061790)
demonstratedthatlightningwas
electricityinhisfamouskiteexperiment
In1780,Italianphysicianandphysicist
LuigiAloisio Galvani(17371798)
discoveredthatmuscleandnervecells
produceelectricity.Whilstdissectinga
frogonatablewherehehadbeen
conductingexperimentswithstatic
electricity,Galvanitouchedtheexposed
sciaticnervewithhisscalpel,whichhad
pickedupanelectriccharge.Henoticed
thatthefrogslegjumped.

CountAlessandroGiuseppeAntonioAnastasio
Volta(1745 1827)developedthefirstelectric
cell,calledaVoltaicPile,in1800.
Avoltaicpileconsistofalternatinglayersoftwo
dissimilarmetals,separatedbypiecesof
cardboardsoakedinasodiumchloridesolution
orsulfuricacid.
Voltadeterminedthat
thebestcombinationof
metalswaszincand
silver
Voltaselectricpile(right)
AVoltaicpileatthe
SmithsonianInstitution,(far
right)

In1800,EnglishchemistWilliamNicholson
(17531815)andsurgeonAnthonyCarlisle
(17681840)separatedwaterintohydrogen
andoxygenbyelectrolysis.

JohannWilhelmRitter(17761810)repeated
Nicholsonsseparationofwaterintohydrogen
andoxygenbyelectrolysis.Soonthereafter,
Ritterdiscoveredtheprocessof
electroplating.Healsoobservedthatthe
amountofmetaldepositedandtheamount
ofoxygenproducedduringanelectrolytic
processdependedonthedistancebetween
theelectrodes

HumphreyDavy(17781829)utilizedthe
voltaicpile,in1807,toisolateelemental
potassiumbyelectrolysiswhichwassoon
followedbysodium,barium,calcium,
strontium,magnesium.

WilliamNicholson

JohannWilhelm
Ritter

HumphreyDavy

MichaelFaraday(17911867)beganhiscareerin1813asDavy's
LaboratoryAssistant.
In1834,Faradaydevelopedthetwolawsofelectrochemistry:
TheFirstLawofElectrochemistry
Theamountofasubstancedepositedoneachelectrodeofan
electrolyticcellisdirectlyproportionaltotheamountofelectricity
passingthroughthecell.
TheSecondLawofElectrochemistry
Thequantitiesofdifferentelementsdepositedbyagivenamountof
electricityareintheratiooftheirchemicalequivalentweights.

Faradayalsodefinedanumberofterms:
Theanode isthereforethatsurfaceatwhichtheelectriccurrent,accordingto
ourpresentexpression,enters:itisthenegative extremityofthe
decomposingbody;iswhereoxygen,chlorine,acids,etc.,areevolved;andis
againstoroppositethepositiveelectrode.
Thecathode isthatsurfaceatwhichthecurrentleavesthedecomposing
body,andisitspositive extremity;thecombustiblebodies,metals,alkalies,
andbasesareevolvedthere,anditisincontactwiththenegativeelectrode.
Manybodiesaredecomposeddirectlybytheelectriccurrent,theirelements
beingsetfree;theseIproposetocallelectrolytes....
Finally,Irequireatermtoexpressthosebodieswhichcanpasstothe
electrodes,or,astheyareusuallycalled,thepoles.Substancesarefrequently
spokenofasbeingelectronegative orelectropositive,accordingastheygo
underthesupposedinfluenceofadirectattractiontothepositiveornegative
pole...Iproposetodistinguishsuchbodiesbycallingthoseanions whichgoto
theanode ofthedecomposingbody;andthosepassingtothecathode,
cations;andwhenIhaveoccasiontospeakofthesetogether,Ishallcallthem
ions.
thechlorideofleadisanelectrolyte,andwhenelectrolyzed evolvesthetwo
ions,chlorineandlead,theformerbeingananion,andthelatteracation.

JohnFredericDaniell(17901845),professorofchemistryatKing's
College,London.
Daniell'sresearchintodevelopmentofconstantcurrentcellstook
placeatthesametime(late1830s)thatcommercialtelegraph
systemsbegantoappear.Daniell'scopperbattery(1836)became
thestandardforBritishandAmericantelegraphsystems.
In1839,Daniellexperimentedonthefusionofmetalswitha70
cellbattery.Heproducedanelectricarcsorichinultravioletrays
thatitresultedinaninstant,artificialsunburn.Theseexperiments
causedseriousinjurytoDaniell'seyesaswellastheeyesof
spectators.
Ultimately,Daniellshowedthattheionofthemetal,ratherthan
itsoxide,carriesanelectricchargewhenametalsaltsolutionis
electrolyzed.
Left:AnearlyDaniellCell
Right:Daniellcellsused
bySirWilliamRobert
Grove,1839.

VoltaicCells
Inspontaneous
oxidation
reduction(redox)
reactions,
electronsare
transferredand
energyis
released.

VoltaicCells
Ifthereactionis
separatedintotwo
parts,wecanuse
thatenergytodo
workbymaking
theelectronsflow
throughan
externaldevice.
Thistypeofsetup
iscalledavoltaic
cell.

VoltaicCells
Thisisatypicalvoltaic
cell
Astripofzincmetalis
immersedinasolution
ofZn(NO3)2
Astripofcoppermetal
isimmersedina
solutionofCu(NO3)2
Thetwosolutionsare
connectedbyasalt
bridge containing
NaNO3
Theoxidationoccursat
theanode(Zn)
Thereductionoccursat
thecathode (Cu)

VoltaicCells

Thesaltbridgeisusedto
preventelectronsflowing
directlyfromthezinctothe
copper
ThesaltbridgeconsistsofaU
shapedtubethatcontainsa
saltsolution,sealedwith
porousplugs,oranagargel
solutionofthesalt
Thesaltbridgekeepsthe
chargesbalancedandforces
theelectrontomovethrough
thewire
Cationsmovetowardthe
cathode.
Anionsmovetowardthe
anode.

VoltaicCells
Inthecell,electrons
leavetheanodeand
flowthroughthe
wiretothecathode.
Astheelectrons
leavetheanode,the
cationsformed
dissolveintothe
solutionintheanode
compartment.
Eventually,ifthecell
isusedforalong
time,theanode
(zinc)willdissolve

VoltaicCells
Astheelectronsreach
thecathode,cationsin
thecathodeare
attractedtothenow
negativecathode.
Theelectronsaretaken
bythecation,andthe
neutralmetalis
depositedonthe
cathode.
Eventually,ifthecellis
usedforalongtime,all
thecopperionswill
plateontothecopper
cathode

ElectromotiveForce(emf)
Wateronly
spontaneously
flowsonewayina
waterfall.
Likewise,electrons
onlyspontaneously
flowonewayina
redoxreaction
fromhigherto
lowerpotential
energy.

ElectromotiveForce(emf)
Thepotentialdifferencebetweentheanode
andcathodeinacelliscalledthe
electromotiveforce(emf).
Itisalsocalledthecellpotential,andis
designatedEcell.

CellPotential
Cellpotentialismeasuredinvolts(V).
J
1V=1
C
WhereJ=Joules
C=Coulombs
Recallthat1electronhasachargeof1.6x1019 C

StandardReductionPotentials
Thecellpotential
isthedifference
betweentwo
electrode
potentials.
Byconvention,
electrode
potentialsare
writtenas
reductions
Reduction
potentialsformost
common
electrodesare
tabulatedas
standardreduction
potentials.

StandardHydrogenElectrode
Electrodepotentialsarereferencedtoastandard
hydrogenelectrode(SHE).
Bydefinition,thereductionpotentialfor
hydrogenis0V:
2H+ (aq,1M) +2e H2 (g,1atm)

StandardCellPotentials
Thecellpotentialatstandardconditionsis
calculated
=Ered (cathode) Ered
Ecell
(anode)
SubstancereducedSubstanceoxidized

Becausecellpotentialisbasedonthe
potentialenergyperunitofcharge,itis
anintensiveproperty.

CellPotentials

Oxidation: Ered = -0.76 V

Reduction: Ered = +0.34 V

CellPotentials
= Ered
(cathode) Ered
(anode)
Ecell
=+0.34V (0.76V)
=+1.10V
Generally, most of the common cells used, on the average,
generate approximately 1.5 V

OxidizingandReducingAgents
Thestrongest
oxidizershavethe
mostpositive
reduction
potentials.
Thestrongest
reducershavethe
mostnegative
reduction
potentials.

OxidizingandReducingAgents
Thegreaterthe
differencebetweenthe
two,thegreaterthe
voltageofthecell.

FreeEnergy
G foraredoxreactioncanbefoundby
usingtheequation
G =nFE
where:
n isthenumberofmolesofelectronstransferred
F isaconstant,theFaraday.
1F =96,485C/mol=96,485J/Vmol
E =ThestandardcellpotentialinV

Understandardconditions,
G =nFE

NernstEquation
Rememberthat
G =G +RT lnQ
Thismeans
nFE =nFE +RT lnQ
DividingbothsidesbynF,wegettheNernst
equation:
RT
lnQ
E =E
nF
or,usingbase10logarithms,
2.303RT
logQ
E =E
nF

NernstEquation
Atroomtemperature(298K),and
R=8.314J/molK
F=96,485J/Vmol

2.303RT
F

=0.0592V

ThefinalformoftheNernstEquationbecomes

0.0592
E =E
n

logQ

WaltherHermannNernst(18641941)

Nernst'searlystudiesinelectrochemistrywereinspired
byArrhenius'dissociationtheoryofionsinsolution.
In1889heelucidatedthetheoryofgalvaniccellsby
assumingan"electrolyticpressureofdissolution"which
forcesionsfromelectrodesintosolutionandwhichwas
opposedtotheosmoticpressureofthedissolvedions.
Also,in1889,heshowedhowthecharacteristicsofthe
currentproducedcouldbeusedtocalculatethefree
energychangeinthechemicalreactionproducingthe
current.Thisequation,knownastheNernstEquation,
relatesthevoltageofacelltoitsproperties.
IndependentlyofThomson,heexplainedwhy
compoundsionizeeasilyinwater.Theexplanation,
calledtheNernstThomsonrule,holdsthatitisdifficult
forchargedionstoattracteachotherthroughinsulating
watermolecules,sotheydissociate.

ConcentrationCells

NoticethattheNernstequationimpliesthatacellcouldbe
createdthathasthesamesubstanceatbothelectrodes.
Forsuchacell,Ecell wouldbe0,butQ wouldnot.
Therefore,aslongastheconcentrationsaredifferent,
E willnotbe0.

ApplicationsofOxidation
ReductionReactions

Why Study Electrochemistry?

Batteries
Corrosion
Industrial production
of chemicals such
as Cl2, NaOH, F2
and Al
Biological redox
reactions

The heme group

BATTERIES

Primary, Secondary, and Fuel Cells

Batteries
Most commercial batteries produce 1.5 V. To get a higher
voltage, batteries are joined together.

Dry Cell Battery

Primarybattery usesredoxreactions
thatcannotberestoredbyrecharge.

Anode (-)
Zn Zn2+ + 2eCathode (+)
2 NH4+ + 2e-2 NH3 + H2

Alkaline Battery
Nearly same reactions as in common dry
cell, but under basic conditions.

Anode(): Zn+2OH ZnO +H2O+2e

Cathode(+):2MnO2 +H2O+2e Mn2O3 +2OH

AlkalineBatteries

Lead Storage Battery

Secondary
battery
Usesredox
reactionsthat
canbereversed.
Canberestored
byrecharging

Lead Storage Battery

Anode (-) Eo = +0.36 V
Pb + HSO4- PbSO4 + H+ + 2eCathode (+) Eo = +1.68 V
PbO2 + HSO4- + 3 H+ + 2e- PbSO4 + 2 H2O

Ni-Cad Battery
Anode (-)
Cd + 2 OH- Cd(OH)2 + 2eCathode (+)
NiO(OH) + H2O + e- Ni(OH)2 + OH-

Fuel Cells: H2 as a Fuel

Fuelcell reactantsare
suppliedcontinuouslyfrom
anexternalsource.
Carscanuseelectricity
generatedbyH2/O2 fuel
cells.
H2 carriedintanksor
generatedfrom
hydrocarbons.

HydrogenAir Fuel Cell

HydrogenFuelCells

H2 as a Fuel

Comparisonofthevolumesofsubstancesrequired
tostore4kgofhydrogenrelativetocarsize.

Storing H2 as a Fuel

OnewaytostoreH2 istoadsorbthegasontoa
metalormetalalloy.

Electrolysis
Usingelectricalenergytoproducechemicalchange.
Sn2+(aq)+2Cl(aq) Sn(s)+Cl2(g)

Electrolysis of Aqueous NaOH

ElectricEnergyf ChemicalChange
Anode (+)
4 OH- O2(g) + 2 H2O + 4e-

Cathode (-)
4 H2O + 4e- 2 H2 + 4 OH-

Eo for cell = -1.23 V

Anode

Cathode

Electrolysis
ElectricEnergyf ChemicalChange
Electrolysisofmolten
NaCl.
Hereabattery
+
pumpselectrons
Anode
fromCl toNa+.
NOTE: Polarityof
electrodesisreversed
frombatteries.

electrons
BATTERY

Cathode
Cl-

Na+

Electrolysis of Molten NaCl

SeeFigure20.18

Electrolysis of Molten NaCl

electrons

Anode (+)

BATTERY

2 Cl- Cl2(g) + 2e-

+
Anode

Cathode
Cl-

Na+

Cathode (-)
Na+ + e- Na

Eo forcell(inwater)=Ec Ea
= 2.71V (+1.36V)
= 4.07V(inwater)
ExternalenergyneededbecauseEo is().

Electrolysis of Aqueous NaCl

electrons

Anode (+)
2 Cl- Cl2(g) + 2e-

BATTERY

Cathode (-)
2 H2O + 2e- H2 + 2
Eo for cell = -2.19 V

OH-

Note that H2O is more

easily reduced than
Na+.

+
Anode

Cathode
Cl- Na +
H 2O

Also,Cl isoxidizedinpreferencetoH2O
becauseofkinetics.

Electrolysis of Aqueous NaCl

Cells like these are the source of NaOH and Cl2.
In 1995: 25.1 x 109 lb Cl2 and 26.1 x 109 lb NaOH

AlsothesourceofNaOClforuseinbleach.

Electrolysis of Aqueous NaI

Anode (+):
2 I- I2(g) + 2eCathode (-): 2 H2O + 2e- H2 + 2 OHEo for cell = -1.36 V

Electrolysis of Aqueous CuCl2

Anode (+)

electrons

2 Cl- Cl2(g) + 2e-

BATTERY

Cathode (-)
Cu2+ + 2e- Cu

+
Anode

Cathode

Eo for cell = -1.02 V

Note that Cu is more
easily reduced than
either H2O or Na+.

Cl- Cu2+
H2O

Electrolytic Refining of Copper

ImpurecopperisoxidizedtoCu2+ attheanode.Theaqueous
Cu2+ ionsarereducedtoCumetalatthecathode.
Thecopperatthecathodeisover99%pure

Producing Aluminum
2Al2O3 +3Cf 4Al+3CO2

CharlesHall(18631914)developedelectrolysisprocess.
FoundedAlcoa.

Corrosionand

CorrosionPrevention