溶剂化的热力学集团展开理论

把二元溶液的过剩内能（excess energy）分成溶剂-溶剂、溶剂-溶质及溶质-溶质相互作用部分。利用集团展开方法给出了二元溶液在正则系综的配分函数的表达式，利用该表达式得到了溶质的偏摩尔内能(partial molar energy)和偏摩尔熵(partial molar entropy)的表达式。在无限稀溶液情形，过剩偏摩尔内能的溶剂-溶剂部分又称重组织内能（reorganization energy），它反映了溶质存在时对其周围溶剂分子之间的相互作用能的影响。研究表明，在溶质的粒子数密度相对较大时，溶质分子之间的相互作用将影响过剩偏摩尔内能的溶剂-溶剂部分，对于稀溶液，过剩偏摩尔内能的溶剂-溶剂部分与溶质的摩尔分数成线性关系。对低密度二元溶液，溶质的过剩偏摩尔内能和过剩偏摩尔熵也与溶质的摩尔分数成线性关系。

Virial Expansion Theory for Thermodynamics for Solvation

A theory for solvation thermodynamics of binary solution is developed by Virial expansionmethod. The excess energy of binary solution is divided into three interactive terms of solvent - solventsolvent - solute and solute - solute. Using the approach of Virial expansion the partial function of canonicalensemble for a binary solution is expressed. The expression of partial molar energy and entropy of soluteare obtained by this expression. Under the condition of infinite dilution，the solvent - solvent term ofthe excess partial molar energy can also be called as reorganization energy. It shows that the presentationof solute affects interactive energy of solvent molecules around solute molecules. The study in this papershows that when the molar fraction of solute particles is relatively higher，the interaction among solutemolecules would affect the solvent - solvent term of excess partial molar energy. For diluted solution，thesolvent - solvent term of excess partial molar energy is linear to the molar fraction of solute. For binarysolution with low density，the excess partial molar energy and excess partial molar entropy of solute is alsolinear to the density of particles.