Fig. 5: Steady-state mixed-potential-driven catalysis occurs in a closed, isothermal, and isobaric system.
From: Theoretical framework for mixed-potential-driven catalysis
Surroundings are enclosed by rigid adiabatic walls, completely isolated from the external world, a common experimental approximation. At steady-state, the “internal” entropy created in the reaction system (\({{{{{\rm{T}}}}}}{{{{{{\rm{d}}}}}}}_{{{{{{\rm{i}}}}}}}{S}_{{{{{{\rm{sys}}}}}}}/{{{{{\rm{d}}}}}}t\)) which exactly balances the “exchange” entropy to the surroundings (\(-T{{{{{{\rm{d}}}}}}}_{{{{{{\rm{e}}}}}}}{S}_{{{{{{\rm{sys}}}}}}}/{{{{{\rm{d}}}}}}t\)), and would be dissipated as heat (\({{{{{\rm{d}}}}}}Q/{{{{{\rm{d}}}}}}t\)) in the surroundings. At any particular time, in the mixed-potential-driven catalysis, Gibbs free energy drop of the net reaction (\(-\Delta {G}_{{{{{{\rm{r}}}}}}}\)) undergoes transformation into the overpotentials (\(|{\eta }_{1}^{{{{{{\rm{mix}}}}}}}|\) and \(|{\eta }_{2}^{{{{{{\rm{mix}}}}}}}|\)), which serve to accelerate each of half-reactions, and are ultimately dissipated as Joule heat to the surroundings through the exchange entropy.
