Kirkwood-Buff積分および関連パラメータからみたシクロヘキサン－ヘキサン、－テトラデカン、1,2-ジクロロエタン、－アセトン、2-プロパノール混合系の溶液構造
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The Kirkwood-Buff(KB) integrals Gij(ij:cyclohexane or solvent)have been calculated for cyclohexane binary liquid mixtures over the whole concentration range at 298.15 K using the thermodynamic properties such as isothermal compressibilities, excess molar volumes, and excess molar Gibbs energies. Successively, their related parameters such as the KB integral differences from idela solutions, concentration and density fluctuations, linear coefficients of preferential solvations, and excess numbers of molecules are estimated from the KB integrals. for the systems whose solvents are hydrocharbons such as hexane and tetradecane the KB integrals and their related parameters change monotonically which changing concentration, and their magnitudes are comparatively small. These facts suggest that van der Waals interaction is predominant and no spcific interactions exist in the cyclohexane-hydrocarbon systems. On the other hand, for the systems whose solvents have the polar atoms or groups such as -Cl, -CO, and -OH anmely, 1,2-dichloroethane, acetone, and 2-propanol, these values change drastically with changing concentration, and the maxima for G11 and G22 and the minima ofr G12 appear at certain concentrations. These phenomena are due to self-associations of respective components. In particular, for the systems whose solvents are kelones and alcohols, self-associations of respective components are more propressed. These results indicate that both the dipole-dipole attractive force between ketone melecules and the hydrogen bond between alcohol ones play an important role in the systems and these solvents prefer to associate themselves. Consequently, cyclohexane molecules also tend to collect together for lack of solvents around them.
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