Reduction Potential - Nernst Equation

Nernst Equation

The and pH of a solution are related. For a half cell equation, conventionally written as reduction (electrons on the left side):

The half cell standard potential is given by:

where is the standard Gibbs free energy change, is the number of electrons involved, and is Faraday's constant. The Nernst equation relates pH and :

where curly brackets indicate activities and exponents are shown in the conventional manner. This equation is the equation of a straight line for as a function of pH with a slope of volt (pH has no units.) This equation predicts lower at higher pH values. This is observed for reduction of O2 to OH− and for reduction of H+ to H2. If H+ were on the opposite side of the equation from H+, the slope of the line would be reversed (higher at higher pH). An example of that would be the formation of magnetite (Fe3O4) from HFeO−
2 (aq):

3 HFeO−
2 + H+ = Fe3O4 + 2 H2O + 2 ]

where = −1.1819 − 0.0885 log[HFeO−
2] + 0.0296 pH. Note that the slope of the line is −1/2 the −0.05916 value above, since = −1/2.

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