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RT Inkeg RT Inq: P and of The

The Nernst equation quantitatively relates the electrode potential (E) of a cell to concentrations of reactants and products. It was derived by Nernst in 1889 based on thermodynamic principles relating free energy change (ΔG) to maximum work obtainable (Wmax). The Nernst equation shows that electrode potential (E) equals standard electrode potential (E°) plus an additional term involving the temperature (T), number of moles of electrons transferred (n), Faraday's constant (F), and the logarithm of the active ion concentration or reaction quotient (Q). For a cell reaction involving multiple reactants and products, the Nernst equation relates the cell potential (Ecell) to concentrations and the standard cell

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86 views2 pages

RT Inkeg RT Inq: P and of The

The Nernst equation quantitatively relates the electrode potential (E) of a cell to concentrations of reactants and products. It was derived by Nernst in 1889 based on thermodynamic principles relating free energy change (ΔG) to maximum work obtainable (Wmax). The Nernst equation shows that electrode potential (E) equals standard electrode potential (E°) plus an additional term involving the temperature (T), number of moles of electrons transferred (n), Faraday's constant (F), and the logarithm of the active ion concentration or reaction quotient (Q). For a cell reaction involving multiple reactants and products, the Nernst equation relates the cell potential (Ecell) to concentrations and the standard cell

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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

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