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- W2017747852 abstract "Most of the time, the two OH chemical bonds of a water molecule in the liquid are both inserted in H-bond chains. These temporary insertions are non-ergodic and, according to the thermodynamic of mobile disorder of Huyskens and Siegel, their influence on the Gibbs free energy G h is ruled by the fractions of time γ during which the molecule escapes from their influence and is able to evaporate. The general equation is: G h = n RT ln γ . In water-alcohol mixtures mixed H-bond chains are formed and γ w = [1 + K w1 C + K w1 K w2 c 2 ], C being equal to the sum of the concentrations C w + C A . On this basis equations are derived predicting the solubility of water at 25°C in cyclohexane-alcohol mixtures as a function of the concentration of the alcohol. The insertion constants are fitted and one obtains a 6% agreement with the experimental values. At 25°C in the primary alcohols K w1 ≈ 8.5 dm 3 mol −1 and K w2 ≈ 0.3 dm 3 mol −1 . In pure water K w2 is somewhat smaller: 0.2 dm 3 mol −1 . In the secondary alcohols and the tertiary alcohols, the second insertion constant of water K w2 is significantly higher (respectively 0.35 and 0.40 dm 3 mol −1 ). These values agree with other experimental observations and lead to a correct prediction of the peculiarities of the experimental ternary diagrams water-alcohol-cyclohexane. They explain why ethanol is miscible with water in all proportions whereas from 1-butanol, phase demixing is observed." @default.
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- W2017747852 date "1995-12-01" @default.
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- W2017747852 title "The two non-ergodic insertion constants of the water molecule in H-bond chains at 25°C and their influence on the ternary diagrams water-alcohol-alkane" @default.
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- W2017747852 doi "https://doi.org/10.1016/0167-7322(95)00873-x" @default.
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