Nernst equation:

quantitative relationship amongst three

quantities- electrode p vn as
Nernst in 1889 derived a
active mass or molar concentration of the
ionic species. h i s
system temperature and
Nernst equation.

Let the reversible reduction electrode reaction be:

M+ ne M
is equal to tne
When the reaction is spontaneous, decrease in the free energy of the system (- AG)
maximum energy obtainable from the system (Wmax).

- AG = Wmax

= (nF)xE --- (1)

where, nF is the coulombs of charge that is transferred during the reaction;

n is the number of moles of electrons transferred in the reaction

and Fit one faraday of electricity (96500 C nole-),
E is the electrode potential ivoltage (V) or energy available per coulomb (i C)].

For reactants and products of the reaction at unit activity, standard change in free energy,

- AG = nFE° -(2)
where, E is the standard electrode potential.

Change in free energy is related to equilibrium constant of the reaction, Kea, by van't Hoff reaction
isotherm:
AG
RTInKeg + RTInQ -(3)
where, Q is the reaction quotient,
Ris molar gas constant
and Tis the temperature ofthe system expressed in Kelvin.

Also, standard change in free energy, AG° = -

RT InKeg
'. AG AG° + RTIn[M -(4)
[M*]
By definition, [M] = 1. Substitution of AG and AG° in
equation (4) gives,
' - nfE = - nFE+ RT Inn 1

(M"] -(5)
RT 1
OrE =E In - -(6)
nF [M"]

2
 E = E° 2.303RT log [M*
Or
nF --(7)

Substituting the values of R 8.314J molH K1

& F 96,500Coulomb mol 1

E =E + 0.0591 log [M*

at 298 K
(8)
Equation (7) [or (8)] is suggested to be Nernst equation for electrode potential.

For a cell reaction of the type,

xX+yY pP+qQ
Nernst equation for cell potential,

RT Products] RT[P°IQJ" 2.303 RTlogPPIqj

Ecell Ecel nnF [Reactants] Ecell nF XI[Y] Ece nF

or
Ecell Ecell [Reactants] RTX"YI 2.303 RT [XT Y
nF [Products]
Ecell
RinOP(al
nF
Ecell +
nF
o