电解质溶液微扰理论研究

提出了以中性硬球-带电硬球混合物为参考体系,以溶液中各种粒子之间的静电、色散、诱导等作用为微扰项的电解质溶液微扰理论。与前人的理论相比较,本文避开了长程库仑力的发散问题,可以部分反映粒子直径差异对体系热力学性质的影响。用本文方法计算的内能数据与MC值比较接近。

PERTURBATION THEORY OF ELECTROLYTE SOLUTION

A perturbation model for electrolyte solution has been developed. A mixture of charged hard spheres and neutral hard spheres is used as the reference system of perturbation expansion and the interactions between various particles including repulsion force, dispersion, induction and electrostatic force are taken as the perturbation terms. The expressions of Helmholtz free energy and internal energy are deduced. Comparing with the methods in the literature, the reference system and expansion of perturbation terms of our model are more reasonable. The long - range term is simpler and the effect of the size difference between particles can be partly shown. The internal energy results calculated with our perturbation model are close to MC data.