大正则系综
压缩性
统计力学
正则系综
组分(热力学)
热力学
数学
偏摩尔性质
统计物理学
统计理论
统计系综
压缩系数
分布(数学)
物理
数学分析
摩尔体积
统计
蒙特卡罗方法
作者
John G. Kirkwood,Frank P. Buff
摘要
A general statistical mechanical theory of solutions is developed with the aid of the theory of composition fluctuations in the grand canonical ensemble. It is shown that the derivatives of the chemical potentials and osmotic pressure with respect to concentrations, the partial molar volumes, and compressibility may be expressed in terms of integrals of the radial distribution functions of the several types of molecular pairs present in the solution. Explicit coefficients of a q-fraction expansion of the thermodynamic variables are presented in a detailed treatment of the two-component system.
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