Part V – May 1968 - Papers - Near-Equilibrium Kinetics of the Dissociation of Cupric Oxide

The dissociation of cupric oxide to cuprous oxide and oxygen was studied with a microbalmce technique at 700" to 750°C. In this temperature range the dissociation pressure of the reaction 2CuO= Cu2O + 1/2 O2 was: The theory of near-equilibriwm reaction rates predicts a linear relationship between reaction rate and the Gibbs free-energy change for small values of AF/RT. This correlation is found to be valid for AF/RT = -0.1 or approximately 200 cal per mole away from equilibrium. THE theory of reaction rates near equilibrium as developed from classical thermodynamics suggests a small range of linear behavior between the overall reaction rate and the free-energy change accompanying the process. The extent of this linear correlation is generally unknown, even to the order of magnitude. The idea of linearity is also found in the formal mathematics of coupled transport phenomena, e.g., chemical diffusion, thermal diffusion, thermoelectricity, and so forth. The linear array of forces and fluxes which leads to various main and cross coefficients is predicated upon linearity between reaction rates and the bulk thermodynamics which govern the process. The general case in reaction kinetics is well-known: the magnitude of the free-energy change does not cor- relate with observed reaction kinetics, irrespective of whether the process occurs by diffusion or chemical reaction or both. The real need is to investigate specific reaction paths near equilibrium in order to learn of the limitations in attempting to correlate reaction rates and thermodynamics. It is the main purpose of this paper to examine the dissociation kinetics of cupric oxide under conditions of known driving force where the dissociation process is likely to occur by chemical reaction. A secondary objective is to obtain equilibrium data for the CuO-Cu20-O2 system. In a prior paper Edmiston and race' investigated reduction kinetics of wustite in H2-H2O gas mixtures. The present study was carried out in oxygen according to the following reaction: