Total Overpotential Calculation for Concentration Dependent Kinetics
When using the Concentration dependent kinetics option in the Porous Electrode Reaction and Electrode Reaction nodes, the equilibrium potential is typically a constant referring to a reference state, and the concentration dependence of the kinetics is accounted for only in the pre-exponential terms according to
where
A result of this is that, when the pre-exponential factors CO,m and CR,m differ due to concentration gradients, there can at zero activation overpotential be a net charge-transfer current density flowing over the electrode–electrolyte interface. This local current density should obviously give rise to a heat source. The solution is to add a concentration overpotential term to the total overpotential when calculating the heat sources.
When using the Concentration dependent kinetics option, the overpotential, used in the irreversible heat term above, is calculated as follows:
where
If the number of electrons is not available,
is assumed.