Abstract
While important for many industrial applications, chemical reactions responsible for the charging of solids in water are often poorly understood. We theoretically investigate the charging kinetics of solid-liquid interfaces and find that the time-dependent equilibration of surface charge contains key information not only on the reaction mechanism, but also on the valency of the reacting ions. We construct a nonlinear differential equation describing surface charging by combining chemical Langmuir kinetics and electrostatic Poisson-Boltzmann theory. Our results reveal a clear distinction between late-time (near-equilibrium) and short-time (far-from-equilibrium) relaxation rates, the ratio of which contains information on the charge valency and ad- or desorption mechanism of the charging process. Similarly, we find that single-ion reactions can be distinguished from two-ion reactions, as the latter show an inflection point during equilibration. Interestingly, such inflection points are characteristic of autocatalytic reactions, and we conclude that the Coulombic ion-surface interaction is an autocatalytic feedback mechanism.
- Received 4 November 2022
- Accepted 15 December 2022
DOI:https://doi.org/10.1103/PhysRevLett.130.058001
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