화학공학소재연구정보센터
Journal of the Electrochemical Society, Vol.163, No.7, H576-H583, 2016
Monte-Carlo Simulation of the Ionic Transport of Electrolyte Solutions at High Concentrations Based on the Pseudo-Lattice Model
The theoretical understanding of the ionic transport in electrolyte solutions is not yet well-established at high concentrations, such as at C/mol.L-1 > 1. In our present study, two transport phenomena-self-diffusion and ionic conduction-of the electrolyte solution at high concentrations ( roughly 0.05 <= C/mol.L-1 <= 3) are computationally simulated by a kinetic Monte-Carlo scheme. A "swap mechanism" in the three-dimensional pseudo-lattice is proposed to model the movement of ions and solvent, in which only the nearest-neighbor interaction is considered. The energy difference between the before-and after-swap states, based on which the stochastic Monte-Carlo process occurs, is found to be expressed in only two energetic terms; the coulombic repulsion between ions with the identical sign, +epsilon(ii), and the heat of dissolution of the ionic crystal, Delta H-diss. The self-diffusion coefficients of both ions and solvent decrease with the increase in the ionic concentration, which qualitatively agree with the experimental observation. The asymmetric bell-shape of the specific conductivity, sigma, principally originates from the coulombic repulsion. The ionic concentration at which the maximum sigma occurs well coincides with that of the experimentally observed results. The Delta H-diss-dependency reveals that, ceteris paribus, sigma marks the highest at around -2kT < Delta H-diss < 0, out of the range of which sigma is attenuated by either the ion-ion or ion-solvent interaction. Finally, the limitations in the model are addressed. (C) 2016 The Electrochemical Society. All rights reserved.