• Journal of the Korean Chemical Society
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• v.8 no.2
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• pp.68-74
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• 1964

Water has the melting point, the boiling point, the heat of fusion, and the heat of vaporization all much higher than would be normally expected from the hydrogen compounds of the other members of the oxygen family. Another unique characteristic of ice-Ⅰ is its volume decrease which takes place in its melting. A number of significant efforts have been made in the past to explain these properties quantitatively. The authors, reasoning from the unusually great free surface energy of water and the characteristic volume change on melting, propose the structural model of liquid water as follows. On melting, fluidized vacancies of a molecular size are introduced. Thereupon, for the unusually great surface energy density, molecules surrounding the vacancies become to have close packed arrangement. But molecules not in direct contact with vacancies should still possess the original structure i. e., ice-Ⅰ. When a molecule adjacent to a vacancy jumps into the vacancy, the molecule attains the gaslike degree of freedom. Using the above model, the authors had developed the liquid partition function of water by applying the theory of significant structures in liquids. Molar volume, vapor pressure, entropy of fusion and entropy of vaporization were calculated over a wide temperature range. The results show good agreement with experimental observations.