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faradayandnernst

Electrochemistry:NernstEquationandFaraday'sLaw

Let'sreviewwhatoccursinagalvaniccell:
ThezincelectrodeislosingmassasZnmetalisoxidizedtoZn2+ ionswhichgo
intosolution.
TheconcentrationoftheZn2+ solutionisincreasing.
Anions,negativeions(e.g.Cl),areflowingfromthesaltbridgetowardthe
anodetobalancethepositivechargeoftheZn2+ ionsproduced.
ThecopperelectrodeisgainingmassasCu2+ ionsinthesolutionarereducedtoCu
metal.
TheconcentrationoftheCu2+ solutionisdecreasing.
Cations,positiveions(e.g.K+ ),areflowingfromthesaltbridgetowardthe
cathodetoreplacethepositivechargeoftheCu2+ ionsthatconsumed.
Areactionmaystartatstandardstateconditions,butasthereactionproceeds,the
concentrationsofthesolutionschange,thedrivingforcebehindthereactionbecomes
weaker,andthecellpotentialeventuallyreacheszero.

**Whenthecellpotentialequalszero,thereactionisatequilibrium.
NernstEquationCanbeusedtofindthecellpotentialatanymomentinduringa
reactionoratconditionsotherthanstandardstate.

https://www.chem.tamu.edu/class/majors/tutorialnotefiles/nernst.htm

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faradayandnernst

E=cellpotential(V)underspecificconditions
E =cellpotentialatstandardstateconditions
R=idealgasconstant=8.314J/molK
T=temperature(kelvin),whichisgenerally25 C(298K)
n=numberofmolesofelectronstransferredinthebalancedequation
F=Faraday'sconstant,thechargeonamoleofelectrons=95,484.56
C/mol
lnQc=thenaturallogofthereactionquotientatthemomentintime
Reactionquotient(Qc)Themathematicalproductof
theconcentrationsoftheproductsofthereactiondividedbythe
mathematicalproductoftheconcentrationsofthereactants.
Sincethetemperatureisgenerally25 C(298K),threeofthetermsintheaboveNernst
equationcanbeconsideredconstants:R,T,andF.Substitutingthevaluesofthese
constants,resultsinthefollowingequation:

Forthereaction:

Thereisatransferof2electrons,son=2.

AtequilibriumE=0andQc=Kc:

TheNernstequationcanberearrangedasfollows:

https://www.chem.tamu.edu/class/majors/tutorialnotefiles/nernst.htm

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faradayandnernst

Thisequationcanbeusedtocalculatetheequilibriumconstantforanyoxidation
reductionreactionfromitsstandardstatecellpotential.

SampleCalculation
Calculatethecellpotentialforthefollowingsystem:

Writethehalfreactionswiththehalfcellpotentials:

Multiplythereactionstogetthelowestcommonmultipleofelectrons:

Faraday'sLawTheamountofsubstanceconsumed
orproducedatoneoftheelectrodesinanelectrolytic
cellisdirectlyproportionaltotheamountof
electricitythatpassesthroughthecell.
Bydefinition,onecoulomb(C)ofchargeis
transferredwhenaoneampere(amp)currentflows
foronesecond(s):

https://www.chem.tamu.edu/class/majors/tutorialnotefiles/nernst.htm

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faradayandnernst

Michael
Faraday

Faraday'sConstantThechargeonamoleof
electrons:
F=96,454.56C

https://www.chem.tamu.edu/class/majors/tutorialnotefiles/nernst.htm

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