Measuring reaction rates at equilibrium with the isotope doping method

Abstract

Since the time of J. H. van't Hoff [1], it has been known that chemical equilibrium is dynamic, meaning that at equilibrium, chemical reactions do not cease, but instead the forward and backward reaction rates are equal. The constant concentrations at equilibrium preclude the use of concentrations to measure reaction rates at equilibrium. Therefore, with the exception of a few special cases, no reaction rates at equilibrium have been published in the literature of chemistry, physics, or chemical engineering. Here we report dissolution and precipitation rates at equilibrium for quartz and barite with the isotope-doping method. Experimental data show that dissolution and precipitation rates are equal at equilibrium, indicating the principle of detailed balance (PDB) appear to be applicable at these experimental conditions. The PDB has been a cornerstone for irreversible thermodynamics and chemical kinetics for a long time, and its wide application in geochemistry has mostly been implicit and without experimental testing of its applicability. Nevertheless, many extrapolations based on PDB without experimental validation have far reaching impacts on society's mega environmental enterprises. The isotope doping method appears to able to test its applicability for a variety of minerals at a wide range of conditions.