Mineral dissolution kinetics as a function of distance from equilibrium – New experimental results

We revisit a fundamental question in mineral dissolution kinetics, namely: is the function of dissolution rate versus the distance from equilibrium continuous, or does the “switch” between two different reaction mechanisms cause a discontinuity, i.e., a kinetic bifurcation? Based on new insight from experimental results, including direct observations of retreating crystal surfaces with vertical scanning interferometry (VSI), we present evidence that a discontinuity does indeed exist. Through a carefully designed near-equilibrium albite dissolution experiment, we show how a non-steady-state dissolution rate observed on a crystal surface reflects reactivity inherited from earlier episodes of undersaturation. This outcome forces us to re-think the common practice of extrapolating overall dissolution rates measured far-from-equilibrium to near-equilibrium conditions.