Additivity Rule of the Partial Molal Volume. 4. Its Proof Based on the Postulate of Independent Volume Changes for Unit Reactions

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Abstract
The additivity rule of the partial molal volume is proved to be equivalent to the postulate of independent volume changes for unit reactions which states that the (configurational) volume changes are determined by the reaction sites and not affected by the other sites in the composite molecule. The postulate of independent volume change leads to the reduction of the multiple body distribution function to the product of the pair distribution functions between the nearest‐neighbor sites in the composite molecule. The postulate is applied to the model system of n‐alkane solution composed of hard spheres. The calculated result based on a proper pair cavity distribution function well reproduces the characteristics of the additivity rule of the partial molal volume of n‐alkanes, and predicts molecular dimensions of n‐alkane in a reasonable manner.

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