ヘキサン-ヘキサン異性体2成分混合系の溶液構造 : II. 選択的溶媒和の一次係数と過剰分子数による解析

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The linear coefficients of preferential solvations 〓 and the excess numbers of molecules Δn〓 (i, j = 1, 2, 1: hexane, 2: hexane isomers) have been calculated for the four hexane-hexane isomer (2-methylpentane, 3-methylpentane, 2, 2-dimethylbutane, or 2, 3-dimethylbutane) binary mixtures over the whole concentration range at 25℃ using the Kirkwood-Buff (KB) integrals and the number densities. The differences of the 〓 values from ideal solutions proposed by Matteori and by Shulgin and Ruckenstein Δ〓 and Δ〓 have also been estimated. The Δ〓 values are nearly the same as the Δ〓 ones for all systems over the whole concentration range, and the concentration dependences of Δ〓 resemble those of 〓 for all systems. The Δ〓 values are positive for the hexane-2-methylpentane and -3-methylpentane systems over the whole concentration range, while negative for the hexane-2,2-dimethylbutane and - 2,3-dimethylbutane systems. Moreover, the Δn〓 and Δn〓 values are negative and positive, respectively for the hexane-2-methylpentane and -3- methylpentane systems over the whole concentration range, while positive and negative, respectively for the hexane-2,2-dimethylbutane and-2,3-dimethylbutane systems. These facts suggest that the former and latter systems prefer to form self- and hetero-associations, respectively, and are in good agreement with our previous results.
群馬大学教育学部の論文