定标粒子理论计算非水溶液的盐效应常数

本文应用定标粒子理论计算了非电解质溶质在盐(NaI、或KI)和环丁砜组成的非水电解质溶液中溶解度的盐效应常数。硬球作用项采用Masterton-Lee的方法。软球作用项采用胡英等的径向分布函数处理方法, 并考虑进了偶极-偶极、偶极-诱导偶极、电荷-偶极和电荷-诱导偶极等相互作用。分子的硬球直径σ和能量参数∈/k由经验方程计算。由理论值和实验结果比较得出: 当σ_2取0.563 nm、离子半径取电子密度标度时, 理论值与实验值符合得较好。

CALCULATION OF SALT EFFECT COEFFICIENTS OF NONAQUEOUS SOLUTION BY SCALE PARTICLE THEORY

The salt effect coefficients (k_s) of nonelectrolyte solute dissoving in nonaqueous electrolyte solutions, which is composed of salt (NaI,or KI) and sulfolane, was calculated by the scale particle theory. Considering the distribution behavior of the particles in solution and the forms of molecular interactions,we calculated K_s in different ways. 1. The term of hard sphere interaction (k_α) was calculated by Masterton -Lee's equation. The term of soft sphere interaction (k_β) was treated by Y. Hu's radial distribution funtion method, ie take the first coordination circle as in-order, and out of the circle as random mixing. Fur-thermore, we take the following interaction form into calculation: dipole-dipole, dipole-induced dipole, dipole-charge of ion and charge-induced dipole. The results shown that the treatment method used is better than others. 2. The molecular hard sphere diametere σ and energy parameter ∈/k were obtained from various empirical equations. These equations contain some parameters which can be got easily. By comparing the calculated k_s with the experimental results, when σ_2=0.563 nm and ion's diameter is in electronic density scale, the agreement between theory and experimental result is good.