Non-equilibrium steady state in closed system with reversible reactions: Mechanism, kinetics and its possible application for energy conversion

Mathematical model of the first-order reversible reaction with shifted equilibrium are considered. It is shown that in the case of Ox ↔ Red first-order reaction, a new equilibrium is not achieved (achieved indefinitely). The system only absorbs and releases heat as a result of the endothermic and exothermic reactions, respectively. As an experimental model for the first-order reaction, we used a simple electrochemical cell with the equilibrium system Cu2+ ↔ Cu+ in the copper(II) chloride electrolyte. The mechanism of the observed electrochemical process is proposed and kinetics was studied. Due to the diffusion of ions between the electrodes and reversible reactions the cyclicity of the process is supported. Thus, the cell is a system for which external heat is a source of energy due to local equilibrium at the anode. On the basis of experimental data, possible applications of this phenomenon were proposed.

Abstract licence: CC BY-NC

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