Thermocells convert heat energy directly into electrical energy through charge-transfer reactions at the electrode–electrolyte interface. To perform an analytical study on the behavior of thermocells, the Onsager flux relationship was applied to thermocells, which used aqueous copper II sulfate and aqueous potassium ferri/ferrocyanide as the electrolyte. The transport coefficient matrices were calculated for each electrolyte and applied to several simulations, which were subsequently validated through experimental testing and comparison to previous literature results. The simulation is shown to correctly predict the short circuit current, maximum power output, and power conversion efficiency. Validation demonstrates that the simulation model developed, using the Onsager flux equations, works for thermocells with different electrode materials (platinum, copper, charcoal, acetylene black, and carbon nanotube), electrode spacing, and temperature differentials. The power dependence of the thermocell on concentration and electrode spacing, with respect to the Seebeck coefficient, maximum power output, and relative efficiency, is also shown.