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NCERT Exemplar · Q20

Q.Under what condition is ECell=0E_{Cell} = 0 or ΔrG=0\Delta_r G = 0?

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The cell potential ECellE_{Cell} and the Gibbs free energy change ΔrG\Delta_r G become zero when the cell reaction reaches equilibrium — that is, when the concentrations of reactants and products are such that the reaction quotient QQ equals the equilibrium constant KK.

The Nernst equation is the bridge between electrochemistry and thermodynamics. For a cell reaction, it tells us how the voltage changes as the reaction proceeds. The key idea is simple: a battery runs because the reaction is not yet balanced — there’s a driving force. Once the reaction reaches equilibrium, that driving force vanishes, and both ECellE_{Cell} and ΔrG\Delta_r G drop to zero.

Let’s see why, step by step.

  1. Start with the Nernst equation for a cell. For a general cell reaction:

aA+bB→cC+dDaA + bB \rightarrow cC + dD

the cell potential at any point is:

ECell=ECell∘−RTnFln⁡QE_{Cell} = E^\circ_{Cell} - \frac{RT}{nF} \ln Q

where Q=[C]c[D]d[A]a[B]bQ = \frac{[C]^c [D]^d}{[A]^a [B]^b} is the reaction quotient, nn is the number of electrons transferred, FF is Faraday’s constant, RR is the gas constant, and TT is the temperature.

  1. Recall the thermodynamic link. The Gibbs free energy change for the cell reaction is:

ΔrG=−nFECell\Delta_r G = -nF E_{Cell}

This is a direct relation — if ECell=0E_{Cell} = 0, then ΔrG=0\Delta_r G = 0, and vice versa. So the condition is the same for both.

  1. What happens as the reaction proceeds?

    As the cell discharges, reactants are consumed and products build up. The value of QQ increases. The Nernst equation shows that ECellE_{Cell} decreases as QQ grows. This continues until the system can go no further — that is, until chemical equilibrium is reached.

  2. At equilibrium, QQ becomes KK.

    At equilibrium, the reaction quotient equals the equilibrium constant: Q=KQ = K. Plugging this into the Nernst equation:

ECell=ECell∘−RTnFln⁡KE_{Cell} = E^\circ_{Cell} - \frac{RT}{nF} \ln K

But we also know from thermodynamics that at equilibrium:

ΔrG∘=−RTln⁡K\Delta_r G^\circ = -RT \ln K

And since ΔrG∘=−nFECell∘\Delta_r G^\circ = -nF E^\circ_{Cell}, we get:

ECell∘=RTnFln⁡KE^\circ_{Cell} = \frac{RT}{nF} \ln K

Substituting this back:

ECell=RTnFln⁡K−RTnFln⁡K=0E_{Cell} = \frac{RT}{nF} \ln K - \frac{RT}{nF} \ln K = 0 …

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