Abstract
A new model is proposed for liquid water. It is obtained by consideration of the two transitions (melting and boiling) which define the liquid phase. These transitions are discussed with the aid of two analogies to well-known phenomena in polymer physical chemistry. In analogy to the helix-coil transition in polypeptides and polynucleotides, the melting of ice is viewed as a process consisting essentially of the destruction of the orderly interconnected small rings of hydrogen bonds characteristic of the crystal. The fact that the breakup of interconnected small rings is cooperative, even when unaccompanied by the breaking of bonds which are not parts of rings, is clearly seen by inspection of the theory for the putatively analogous helix-coil transition. The condensation of water vapor is viewed in analogy to gelation in reversibly polymerizing systems, an analogy which interprets its cooperativity. Taken together, these interpretations of the phase transitions indicate that the liquid can be viewed as an infinitely and randomly branched “gel” of (rapidly interchanging) hydrogen bonds in which closures of rings (primarily large rings) are present at random but in which there is no significant preference for an ordered array of small rings. These concepts also lead naturally to an interpretation of the triple point and sublimation. The random gel model is seen to be consistent with most of the known properties of liquid water. In particular, the radial distribution function, infrared and Raman spectra, dielectric properties, density maximum, and properties of the supercooled region are discussed briefly here.
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gibbs, J.H., Cohen, C., Fleming, P.D. et al. Toward a model for liquid water. J Solution Chem 2, 277–299 (1973). https://doi.org/10.1007/BF00651977
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DOI: https://doi.org/10.1007/BF00651977