TY - UNPB
T1 - Coulombic surface-ion interactions induce non-linear and chemistry-specific charging kinetics
AU - Boon, W.
AU - Dijkstra, M.
AU - van Roij, R.
PY - 2022
Y1 - 2022
N2 - While important for many industrial applications, chemical reactions responsible for 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 non-linear 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.
AB - While important for many industrial applications, chemical reactions responsible for 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 non-linear 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.
UR - http://www.scopus.com/inward/record.url?eid=2-s2.0-85141614769&partnerID=MN8TOARS
U2 - 10.48550/arXiv.2210.15426
DO - 10.48550/arXiv.2210.15426
M3 - Preprint
SP - 1
EP - 10
BT - Coulombic surface-ion interactions induce non-linear and chemistry-specific charging kinetics
PB - arXiv
ER -