Thermodynamics and Efficiency of a CuCl(aq)/HCl(aq) Electrolyzer

• Published in: Electrochimica acta 2014-10, Vol.143 (C), p.70-82
• Main Authors: Hall, Derek M., Akinfiev, Nikolay N., LaRow, Eric G., Schatz, Richard S., Lvov, Serguei N.
• Format: Article
• Language: English
• Subjects: Copper-chlorine (Cu-Cl) hybrid thermochemical cycle; CuCl(aq)/HCl(aq) electrolytic cell; Decomposition potential; Voltage, Current, Thermodynamic and overall efficiencies
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2014.08.018

The high ionic strength and complex speciation of the anolyte solution within the CuCl(aq)/HCl(aq) electrolytic cell have impeded predictions of the energy requirements for the cell's electrolytic reaction at 25°C and 1bar. After collecting experimental open circuit potential (OCP) data and comparing the values obtained with predictions from prospective thermodynamic models, an approach to predict thermodynamic values and the overall efficiency was formulated. The compositions of the experimental measurements ranged from 2-2.5mol of CuCl(aq) with 8-9mol of HCl(aq) per kilogram of water in anolyte solution and 8-9mol of HCl(aq) per kilogram of water in catholyte solution. From the OCP data, it was found that activity coefficient and speciation effects were critical in predicting the Gibbs energy, entropy and thermodynamic (intrinsic maximum) efficiency of the electrolytic cell. At equilibrium, all thermodynamic functions of the anolyte redox reactions were the same after activity coefficients and speciation effects were taken into account. The electrochemical reactions’ Gibbs energy and entropy were found to be 9700J/mol and 2.18J/(mol K) at 25°C and 1bar, which indicated that the reactions required a small amount of electrical and thermal energy to proceed. With thermodynamic values for the electrolytic reaction and experimental data from a CuCl(aq)/HCl(aq) electrolytic cell, the voltage, current, thermodynamic and overall efficiency were calculated. The overall efficiency ranged from 15 to 95% depending on the current density.