Estimating the activation energy of bond hydrolysis by time-resolved weighing of dissolving crystals

Abstract

Abstract Bond-breaking activation energy E B is nowadays a key parameter for understanding and modeling crystal dissolution processes. However, a methodology to estimate E B based on classical dissolution experiments still does not exist. We developed a new method based on the calibration of a Kossel type dissolution model on measured dissolution rates obtained by mass (or volume) variations over time. The dissolution model does not depend on the geometry of the crystal surface but only on the density of the different types of sites (kink, step, terrace, bulk). The calibration method was applied to different experimental setups (flow through and batch) with different ways of estimating the dissolution rates (solute concentration in the fluid, surface topography) for calcite crystals. Despite the variety of experimental conditions, the estimated bond-breaking activation energies were very close to each other (between 31 and 35 kJ/mol) and in good agreement with ab initio calculations.