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ChemWiki:TheDynamicChemistryEtextbook>AnalyticalChemistry>Electrochemistry>NernstEquation

Nernst Equation

TheNernstEquationenablesthedeterminationofcellpotentialundernonstandardconditions.Itrelatesthemeasuredcellpotentialtothereaction
quotientandallowstheaccuratedeterminationofequilibriumconstants(includingsolubilityconstants).

Introduction
TheNernstEquationisderivedfromtheGibbsfreeenergyunderstandardconditions.
E

= E

o
reduction

(1)

oxidation

isalsorelatedtoEundergeneralconditions(standardornot)via
G = nF E

(2)

with
isthenumberofelectronstransferredinthereaction(frombalancedreaction),
istheFaradayconstant(96,500C/mol),and
Eispotentialdifference.
Understandardconditions,equation2isthen
n

= nF E

(3)

Hence,when E o is positive, the reaction is spontaneous and when E o is negative, the reaction is nonspontaneous. From thermodynamics, the
GibbsenergychangeundernonstandardconditionscanberelatedtotheGibbsenergychangeunderstandardequationsvia
o

G = G

SubstitutingG

= nF E

andG

= nF E

+ RT ln Q

(4)

intoequation4,wehave:
nF E = nF E

+ RT ln Q

(5)

DividebothsidesoftheequationabovebynF ,wehave
E = E

RT

ln Q

(6)

nF

Equation6canberewrittenintheformoflog10 :
E = E

2.303RT

log Q

(Generalized Nernst Equation)

nF

AtstandardtemperatureT=298K,the

2.303RT
F

termequals0.0592Vandthisequationturnsinto:
E = E

0.0592 V

log Q

(Nernst Equation @ 298 K)

http://chemwiki.ucdavis.edu/Analytical_Chemistry/Electrochemistry/Nernst_Equation

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NernstEquationChemwiki

The equation above indicates that the electrical potential of a cell depends upon the reaction quotient Q of the reaction. As the redox reaction
proceeds, reactants are consumed, and thus concentration of reactants decreases. Conversely, the products concentration increases due to the
increased in products formation. As this happens, cell potential gradually decreases until the reaction is at equilibrium, at which G = 0 . At
equilibrium,thereactionquotientQ = Keq .Also,atequilibrium,G = 0 andG = nF E ,soE = 0 .
Therefore,substitutingQ

andE

= Keq

= 0

intotheNernstequation,wehave:
0 = E

RT

nF

ln Keq

(7)

Atstandardconditions,theequationabovesimplifiesinto:
0 = E

0.0592 V

log Keq

(8)

Thisequationcanberearrangedinto:
nE
log Keq =

(9)

0.0592 V

TheequationaboveindicatesthattheequilibriumconstantKeq isproportionaltothestandardpotentialofthereaction.Specifically,when:
,reactionfavorsproductsformation.
,reactionfavorsreactantsformation.
ThisresultfitsLeChtlier'sPrinciple,whichstatesthatwhenasystematequilibriumexperiencesachange,thesystemwillminimizethatchangeby
shiftingtheequilibriumintheoppositedirection.

K > 1, E

K < 1, E

> 0
< 0

Example1
o
TheE cell

= +1.10 V

fortheZnCuredoxreaction:
2+

Z n (s) + C u

(aq)

Zn

2+
(aq)

+ C u(s) .

Whatistheequilibriumconstantforthisreversiblereaction?
SOLUTION
Under standard conditions, [C u2+ ] = [Z n 2+ ] = 1.0 M and T = 298 K. As the reaction proceeds, [C u2+ ] decreases as [Z n 2+ ] increases.
Letssayafteroneminute,[C u2+ ] = 0.05 M while[Z n2+ ] = 1.95 M .AccordingtotheNernstequation,thecellpotentialafter1minuteis:
E = E

0.0592V

log Q
n

0.0592V
E = 1.10V

1.95 M
log

0.05 M

E = 1.05 V

Asyoucansee,theinitialcellpotentialisE = 1.10 V ,after1minute,thepotentialdropsto1.05V.Thisisafter95%ofthereactantshavebeen

consumed.Asthereactioncontinuestoprogress,moreC u2+ willbeconsumedandmoreZ n 2+ willbegenerated(ata1:1ratio).Asaresult,the
cellpotentialcontinuestodecreaseandwhenthecellpotentialdropsdownto0,theconcentrationofreactantsandproductsstopschanging.
Thisiswhenthereactionisatequilibrium.Fromfromequation9,theKeq canbecalculatedfrom
2 1.10 V
log Keq =

0.0592 V

log Keq = 37.2

37.2

Keq = 10

37

= 1.58 10

o
ThismakesensefromaLeChtlier'sPrinciple,sincethereactionstronglyfavorstheproductsoverthereactantstoresultinalarge E cell
of1.103
o
V.Hence,thecellisgreatlyoutofequilibriumunderstandardconditions.ReactionsthatarejustweaklyoutofequilibriumwillhavesmallerE cell
values(neglectingachangeinn ofcourse).

References
1. Atkins,PeteranddePaula,Julio.PhysicalChemistryfortheLifeSciences.NewYork:W.H.FreemanandCompany.p.214222.
2. Sherwood,Lauralee.HumanPhysiology6thedition.ThompsonCorp.2007.p.77
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