Ben-Amotz Dor, Widom B
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393, USA.
J Chem Phys. 2007 Mar 14;126(10):104502. doi: 10.1063/1.2464081.
General expressions are obtained for the thermodynamic properties of nonideal gases of arbitrary composition. These include the equation of state and solvation thermodynamic functions of mixtures with any number of components, expanded to first order in total number density. The results are expressed in terms of binary second virial coefficients which are in turn related to binary interaction potential energy functions. Solvation thermodynamic functions (at both constant pressure and constant volume) are decomposed into solute-solvent and solvent-reorganization contributions, thus indicating how each of the latter quantities may be experimentally measured. Moreover, the results are used to identify solute-induced changes in solvent thermodynamic functions, as well as nonideal (excess) contributions to chemical reaction equilibria and solvation heat capacities. The effects of a solute on the reorganization energy and chemical potential of a nonideal solvent are shown to differ qualitatively from both the corresponding ideal gas and high density fluid results.
得到了任意组成的非理想气体热力学性质的一般表达式。这些表达式包括状态方程以及任意数量组分混合物的溶剂化热力学函数,这些函数在总密度上展开到一阶。结果用二元第二维里系数表示,而二元第二维里系数又与二元相互作用势能函数相关。溶剂化热力学函数(在恒压和恒容下)被分解为溶质 - 溶剂和溶剂重组贡献,从而表明如何通过实验测量后者的每一个量。此外,这些结果用于确定溶质引起的溶剂热力学函数变化,以及对化学反应平衡和溶剂化热容量的非理想(过剩)贡献。结果表明,溶质对非理想溶剂的重组能和化学势的影响在性质上与相应的理想气体和高密度流体结果都不同。