III Nernst Equation

It relates the reduction potential of an electrochemical reaction to the standard electrode potential,
temperature, and activities (concentrations) of the chemical species undergoing reduction and oxidation

Derive Nernst Equation for EMF of a Cell Ecell = Eºcell – 0.0592 log10 {[M]a / [M2+]a}
n
❖ Consider an electrode consisting of a metal in contact with a solution of its own cations
❖ As an example, we may consider a zinc rod in contact with a solution of zinc sulphate (Zn2+ ions)
❖ The following equilibrium will be established considering that the reaction from left to right
involves reduction
Zn2+(aq) + 2e- ⇋ Zn WH. Nernst, German chemist
❖ The equilibrium constant of the reaction is given by (1920, Nobel Prize, Nernst Heat Theorem)
K = [Zn]a / [Zn2+]a ---------- (1)
❖ Let E be the EMF produced by the cell reaction. If ΔG is the free energy change
of the reaction and n is the number of electrons involved in the reaction, then
ΔG = -nFEcell ---------- (2)
❖ Under standard conditions, standard free energy change ΔG0 is given by
ΔG0 = -nFEºcell ---------- (3)
❖ According to Vant Hoff reaction isotherm ΔG = ΔG0 + RT ln K 1
III Nernst Equation
❖ Substitution of eqn (1), (2) and (3) in the above equation, we get
ΔG = ΔG0 + RT ln K
-nFEcell = -nFEºcell + RT ln {[Zn]a / [Zn2+]a}

Dividing throughout by –nF, we get

Ecell = Eºcell – RT ln {[Zn]a / [Zn2+]a}
nF
Converting to natural log, we get
Ecell = Eºcell – 2.303RT log10 {[Zn]a / [Zn2+]a}
nF
When T= 298K, F= 96500C R=8.314 JK-1mol-1, then the expression 2.303RT = 0.0592

Ecell = Eºcell – 0.0592 log10 {[Zn]a / [Zn2+]a}

n

This known as the Nernst equation

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 II Applications of Nernst Equation
❖ The Nernst equation can be used to calculate:
o Single electrode reduction or oxidation potential at any conditions
o Standard electrode potentials
o Comparing the relative ability as a reductive or oxidative agent
o Finding the feasibility of the combination of such single electrodes to produce electric potential
o EMF of an electrochemical cell
o Unknown ionic concentrations
o The pH of solutions and solubility of sparingly soluble salts can be measured with the help of
the Nernst equation
❖ Limitations of Nernst Equation:
o For solutions having very high concentrations, the ion concentration is not equal to the ion activity
o In such cases, experimental measurements must be conducted to obtain the true activity of the ion
o It cannot be used to measure cell potential when there is a current flowing through the electrode,
because the flow of current affects the activity of the ions on the surface 3
II Nernst Equation
In Daniel cell, the electrode potential for any given Cu2+ and Zn2+ ion concentration, the equation
can be written as:

❖ E(cell) depends on the concentration of both Cu2 + and Zn2 + ions.

❖ It increases with an increase in Cu2 + ion concentration and a decrease in the Zn2 + ion concentration.
❖ By translating the natural logarithm into the above final E(cell) equation, it reduces to base 10 and
substitutes the values of R, F, and T= 298 K.
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