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Spontaneity of Redox Reactions Under Conditions other than Standard State The concentrations of the half-cell species affect Ecell [ions] = 1 M; Pgases = 1 atm: E°cell [ions] ≠ 1 M; Pgases ≠ 1 atm: Ecell (potential changes) The cell potential drops as the reactants are comsumed and the reaction approaches equilibrium G = nFEcell ) when G = 0,Ecell = 0 G = G + RT ln Q nFEcell= nFE +RTlnQ ) Ecell=E RTlnQ From Chapter 15.4, we have We can rewrite this as cell cell nF E=E 0.0257VlnQ or E=E 0.0592VlogQ nn Nernst Equation e.g., Will the following reaction occur spontaneously at 298 K if [Fe2+] = 0.60 M and [Cd2+] = 0.010 M ? Cd(s) + Fe2+(aq) Cd2+(aq) + Fe(s) Solution: n = 2 and Q = 0.010 / 0.60 = 0.0167. Also, from Table 18.1, Cd2+(aq) + 2e– → Cd(s), E° = -0.40 V Fe2+(aq) + 2e– → Fe(s), E° = -0.44 V Thus E = (-0.44 V + 0.40 V) – (0.0257 V / 2)(-4.094) = +0.01 V Yes, since E > 0, this reaction is spontaneous.PDF Image | Electrochemistry
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