ヘキサン-ヘキサン異性体2成分混合系の溶液構造 : I. Kirkwood-Buff積分と揺らぎによる解析
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概要
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The Kirkwood-Buff (KB) integrals Gij (i, j : hexane or hexane isomers) have been calculated for the four hexane-hexane isotner (2-methylpentane, 3-methylpentane, 2, 2-dimethylbutane, or 2, 3-dimethylbutane) binary mixtures over the whole concentration range at 25℃ using the thermodynamic properties. The KB integral differences from ideal solutions proposed by Matteori ΔG〓 and by Shulgin and Ruckenstein ΔG〓 have also been estimated. Moreover, the concentration AK(Ax;)2> and density <(ΔN)2>/N fluctuations and their correlations <(ΔNΔxi)> have been obtained from both Gij and the number densities of the solutions using Nishikawa procedure. The three Gij values for all systems are different from those for ideal systems, and obviously contain the ideal parts. The G〓 values are nearly the same as the A G〓 ones for all systems over the whole concentration range, and the concentration dependences of A G〓 resemble those of Gij for all systems. However, the magnitudes of Δ G〓 are fairly different from those of Gij. The ΔG〓 values are smaller than ΔG〓 for the hexane-2-methylpentane and -3-methylpentane systems over the whole concentration range, while larger 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. The three fluctuations for all systems are not distinguishable from those for ideal systems, and they are not suitable for discussing the solution structures of these systems.
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