Electrochemistry

Chapter 19
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Electrochemicalprocessesareoxidation-reductionreactions
inwhich:

theenergyreleasedbyaspontaneousreactionis
convertedtoelectricityor

electricalenergyisusedtocauseanonspontaneous
reactiontooccur
0

2+ 2-

2Mg(s)+O2(g)2MgO(s)
2Mg2Mg2++4e-

Oxidationhalf-reaction(losee-)

O2+4e-2O2-

Reductionhalf-reaction(gaine-)
19.1

Oxidationnumber
Thechargetheatomwouldhaveinamolecule(oran
ioniccompound)ifelectronswerecompletelytransferred.
1. Freeelements(uncombinedstate)haveanoxidation
numberofzero.

Na,Be,K,Pb,H2,O2,P4=0
2. Inmonatomicions,theoxidationnumberisequalto
thechargeontheion.

Li+,Li=+1;Fe3+,Fe=+3;O2-,O=-2
3. Theoxidationnumberofoxygenis usually2.InH2O2
andO22-itis1.

4.4

4. Theoxidationnumberofhydrogenis+1exceptwhen
itisbondedtometalsinbinarycompounds.Inthese
cases,itsoxidationnumberis1.
5. GroupIAmetalsare+1,IIAmetalsare+2andfluorineis
always1.
6.Thesumoftheoxidationnumbersofalltheatomsin
amoleculeorionisequaltothechargeonthe
moleculeorion.

HCO3Oxidationnumbersofall
theatomsinHCO3-?

O=-2

H=+1

3x(-2)+1+?=-1
C=+4
4.4

BalancingRedoxEquations
TheoxidationofFe2+toFe3+byCr2O72-inacidsolution?
1. Writetheunbalancedequationforthereactionionionicform.
Fe2++Cr2O72-Fe3++Cr3+
2. Separatetheequationintotwohalf-reactions.
+2

Oxidation:
Reduction:

+3

Fe2+Fe3+
+6

+3

Cr2O72-Cr3+

3. BalancetheatomsotherthanOandHineachhalf-reaction.
Cr2O72-2Cr3+
19.1

BalancingRedoxEquations
4. Forreactionsinacid,addH2OtobalanceOatomsandH+to
balanceHatoms.
Cr2O72-2Cr3++7H2O
14H++Cr2O72-2Cr3++7H2O
5. Addelectronstoonesideofeachhalf-reactiontobalancethe
chargesonthehalf-reaction.
Fe2+Fe3++1e6e-+14H++Cr2O72-2Cr3++7H2O
6. Ifnecessary,equalizethenumberofelectronsinthetwohalfreactionsbymultiplyingthehalf-reactionsbyappropriate
coefficients.
6Fe2+6Fe3++6e6e-+14H++Cr2O72-2Cr3++7H2O

19.1

BalancingRedoxEquations
7. Addthetwohalf-reactionstogetherandbalancethefinal
equationbyinspection.The number of electrons on both
sides must cancel.
Oxidation:

6Fe2+6Fe3++6e-

Reduction: 6e-+14H++Cr2O72-2Cr3++7H2O
14H++Cr2O72-+6Fe2+6Fe3++2Cr3++7H2O

8. Verifythatthenumberofatomsandthechargesarebalanced.
14x12+6x2=24=6x3+2x3
9. Forreactionsinbasicsolutions,addOH-toboth sidesofthe
equationforeveryH+thatappearsinthefinalequation.
19.1

GalvanicCells
anode
oxidation

cathode
reduction

spontaneous
redoxreaction

19.2

GalvanicCells
Thedifferenceinelectrical
potentialbetweentheanode
andcathodeiscalled:
cell voltage
electromotive force (emf)
cell potential
CellDiagram
Zn(s)+Cu2+(aq)Cu(s)+Zn2+(aq)
[Cu2+]=1M&[Zn2+]=1M
Zn(s)|Zn2+(1M)||Cu2+(1M)|Cu(s)
anode
cathode
19.2

StandardReductionPotentials

Zn(s)|Zn2+(1M)||H+(1M)|H2(1atm)|Pt(s)
Anode(oxidation):

Zn(s)Zn2+(1M)+2e-

Cathode(reduction): 2e-+2H+(1M)H2(1atm)
Zn(s)+2H+(1M)Zn2++H2(1atm)

19.3

StandardReductionPotentials
Standard reduction potential (E0)isthevoltageassociated
withareduction reactionatanelectrodewhenallsolutes
are1Mandallgasesareat1atm.

ReductionReaction
2e-+2H+(1M)H2(1atm)
E0=0V

Standardhydrogenelectrode(SHE)

19.3

StandardReductionPotentials
0
Ecell
=0.76V

0
Standard emf (Ecell
)

0
0
0
Ecell
=Ecathode
- Eanode

Zn(s)|Zn2+(1M)||H+(1M)|H2(1atm)|Pt(s)
0
Ecell
=EH0+/H 2- EZn0 2+/Zn
0 2+
0.76V=0 - EZn
/Zn
0 2+
EZn
/Zn=-0.76V

Zn2+(1M)+2e-ZnE0=-0.76V

19.3

StandardReductionPotentials
0
Ecell
=0.34V

0
0
0
Ecell
=Ecathode
- Eanode
0 =E 0
Ecell
Cu

2+
/Cu

EH 0/H+

0 2+ -0
0.34=ECu
/Cu
0 2+
ECu
/Cu=0.34V

Pt(s)|H2(1atm)|H+(1M)||Cu2+(1M)|Cu(s)
Anode(oxidation):

H2(1 atm)2H+(1M)+2e-

Cathode(reduction): 2e-+Cu2+(1M)Cu(s)
H2(1atm)+Cu2+(1M)Cu(s)+2H+(1M)

19.3

E0isforthereactionas
written

ThemorepositiveE0the
greaterthetendencyforthe
substancetobereduced

Thehalf-cellreactionsare
reversible

ThesignofE0 changes
whenthereactionis
reversed

Changingthestoichiometric
coefficientsofahalf-cell
reactiondoes notchange
thevalueofE0

19.3

Whatisthestandardemfofanelectrochemicalcellmade
ofaCdelectrodeina1.0MCd(NO3)2solutionandaCr
electrodeina1.0MCr(NO3)3solution?
Cd2+(aq)+2e-Cd(s)E0=-0.40V

Cdisthestrongeroxidizer

Cr3+(aq)+3e-Cr(s)E0=-0.74V

CdwilloxidizeCr

Anode(oxidation):

Cr(s)Cr3+(1M)+3e- x2

Cathode(reduction): 2e-+Cd2+(1M)Cd(s)

x3

2Cr(s)+3Cd2+(1M)3Cd(s)+2Cr3+(1M)
0
0
0
Ecell
=Ecathode
- Eanode
0
Ecell
=-0.40(-0.74)
0
Ecell
=0.34V

19.3

SpontaneityofRedoxReactions
G=-nFEcell
G

=-nFE 0

cell

n=numberofmolesofelectronsinreaction
J
F=96,500
=96,500C/mol
Vmol

0
G0=-RT lnK =-nFEcell

(8.314J/Kmol)(298K)
RT
0 =
lnK =
lnK
Ecell
nF
n (96,500J/Vmol)
0
Ecell
=
0

Ecell

0.0257V
lnK
n

0.0592V
logK
=
n

19.4

SpontaneityofRedoxReactions

0
G0=-RT lnK =-nFEcell

19.4

Whatistheequilibriumconstantforthefollowingreaction
at250C?Fe2+(aq)+2Ag(s)Fe(s)+2Ag+(aq)
0.0257V
lnK
Ecell =
n
0

Oxidation:

2Ag2Ag++2e-

Reduction: 2e-+Fe2+Fe

n=2

E0=EFe0 2+/Fe EAg0 /Ag

+
E0=-0.44(0.80)
E0=-1.24V

0
Ecell
x n
-1.24V x 2
=exp
K=exp
0.0257V
0.0257V

K=1.23x10-42
19.4

TheEffectofConcentrationonCellEmf
G=G0+RTlnQ

G=-nFE

G0=-nFE 0

-nFE=-nFE0 +RTln Q
Nernst equation
E=E0 -

RT
lnQ
nF

At298
E=E 0 -

0.0257V
lnQ
n

E=E 0 -

0.0592V
logQ
n

19.5

Willthefollowingreactionoccurspontaneouslyat250Cif
[Fe2+]=0.60Mand[Cd2+]=0.010M?
Fe2+(aq)+Cd(s)Fe(s)+Cd2+(aq)
Oxidation:

CdCd2++2e-

Reduction: 2e-+Fe2+2Fe
E0=EFe0 2+/Fe ECd0

2+
/Cd

E0=-0.44(-0.40)
E0=-0.04V

n=2

0.0257V
lnQ
n
0.010
0.0257V
ln
E= -0.04V 2
0.60
E=E 0 -

E=0.013
E>0

Spontaneous
19.5

Batteries

Drycell
Leclanch cell

Anode:
Cathode:

Zn(s)Zn2+(aq)+2e2NH+4(aq)+2MnO2(s)+2e-Mn2O3(s)+2NH3(aq)+H2O(l)

Zn(s)+2NH4(aq)+2MnO2(s)Zn2+(aq)+2NH3(aq)+H2O(l)+Mn2O3(s)
19.6

Batteries

MercuryBattery

Anode:
Cathode:

Zn(Hg)+2OH-(aq)ZnO(s)+H2O(l)+2eHgO(s)+H2O(l)+2e-Hg(l)+2OH-(aq)
Zn(Hg)+HgO(s)ZnO(s)+Hg(l)
19.6

Batteries

Leadstorage
battery

Anode:
Cathode:

Pb(s)+SO42-(aq)PbSO4(s)+2ePbO2(s)+4H+(aq)+SO42-(aq)+2e-PbSO4(s)+2H2O(l)

Pb(s)+PbO2(s)+4H+(aq)+2SO2-4 (aq)2PbSO4(s)+2H2O(l)
19.6

Batteries

SolidStateLithiumBattery

19.6

Batteries

Afuel cellisan
electrochemicalcell
thatrequiresa
continuoussupplyof
reactantstokeep
functioning

Anode:
Cathode:

2H2(g)+4OH-(aq)4H2O(l)+4eO2(g)+2H2O(l)+4e-4OH-(aq)
2H2(g)+O2(g)2H2O(l)
19.6

Chemistry In Action:BacteriaPower
CH3COO-+2O2+H+2CO2+2H2O

Corrosion

19.7

CathodicProtectionofanIronStorageTank

19.7

Electrolysisistheprocessinwhichelectricalenergyisused
tocauseanonspontaneouschemicalreactiontooccur.

19.8

ElectrolysisofWater

19.8

ElectrolysisandMassChanges

charge(C)=current(A)xtime(s)
1molee-=96,500C

19.8

HowmuchCawillbeproducedinanelectrolyticcellof
moltenCaCl2ifacurrentof0.452Aispassedthroughthe
cellfor1.5hours?
Anode:
Cathode:

2Cl-(l)Cl2(g)+2eCa2+(l)+2e-Ca(s)
Ca2+(l)+2Cl-(l)Ca(s)+Cl2(g)

2molee-=1moleCa
C
s 1mole- 1molCa
molCa=0.452
x1.5hrx3600 x
x
s
hr 96,500C 2mole=0.0126molCa
=0.50gCa
19.8

Chemistry In Action:DentalFillingDiscomfort

2+

Hg2/Ag2Hg30.85V
2+

Sn/Ag3Sn-0.05V
2+

Sn/Ag3Sn-0.05V