水及有机溶剂中离子溶剂化焓的理论计算

A CALCULATION OF ION SOLVATION ENTHALPY IN AQUEOUS AND NONAQUEOUS SOLUTIONS

离子溶剂化热力学的理论研究是一项令人感兴趣的工作.在Born理论的基础上人们先后提出了多种较详细的计算离子溶剂化热力学量的模型或公式,并对离子在不同溶剂中的溶剂化自由能进行了理论计算.本文从离子-溶剂间的相互作用力出发,分别考虑了离子溶剂化过程中造腔作用、静电吸引、静电排斥及非静电相互作用对离子溶剂化焓的贡献,得到了一个具有一定意义的、计算离子溶剂化焓的理论公式。

In the light of the interactions between particles, this paper is a calculation ofthe standard solvation enthalpies for ions Li^+, Na^+, K^+, Rb^+, Cs^+, Ag^+, Cl^-, Br^-and I^- in solvents as H_2O, MeOH, FA, DMF, DMSO, MeCN, PC and SL. Thecontributions from the cavity formation process, electrostatic attraction, electrostaticrepulsion and those from nonelectrostatic interactions are considered. The accordancebetween the calculated values and those from literature is good except Li^+.