Standard partial molar volumes in water of mono- and polyhydric aliphatic alcohols in wide ranges of temperature and pressure
Cibulka, I., Hnědkovský, L. and Hynčica, P. (2007) Standard partial molar volumes in water of mono- and polyhydric aliphatic alcohols in wide ranges of temperature and pressure. Journal of Molecular Liquids, 131-132 . pp. 206-215.
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New results of a systematic study of partial molar volumes at infinite dilution (standard partial molar volumes) in water of several hydroxyderivatives of aliphatic hydrocarbons are summarized. The experiments were performed using an automated vibrating-tube densimeter designed for the measurements of density differences Δρ=ρ(solution)−ρ(water) in the temperature range from 298 K to 573 K and at pressures up to 30 MPa. The set of solutes comprises monohydric alcohols derived from methane, ethane, propane, and isomers of butane, and selected polyhydric (from two to five hydroxyl groups) derivatives of ethane, propane, n-butane, n-pentane, 2,2-dimethylpropane and n-hexane. Analogues of isothermal compressibility and isobaric expansivity for standard partial molar volume have also been evaluated from experimental data.The results are discussed from the point of view of regularities within homologous series. The effect of the number of hydroxyl groups and their position on the aliphatic chain is examined. Particular attention is focused to the sign inversion of the derivatives of standard partial molar volume with respect to temperature and pressure that is observed for solutes with large number of hydroxyl groups. A simple group contribution method has proved to be capable to predict this behaviour qualitatively, the effect is not, however, strictly additive.
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