Some Aspects of Solvation

  • H. J. V. Tyrrell


A simple fluid such as a liquid rare-gas can best be described in Bernal’s term1 as a heap of randomly arranged atoms. Such a heap has, paradoxically, a ‘structure’ characterized by a range of coordination numbers and controlled very largely by the repulsive forces between the particles. The radial distribution curve of such a fluid shows a marked peak corresponding to the nearest neighbours of the central atom; subsequent peaks for second-nearest neighbours and so on rapidly become indistinguishable as the distance from the central atom increases. For all atoms the correlation time τc, defined approximately as the time required for the atom to rotate through one radian or to move a distance equal to its diameter, will be the same. In more complex fluids, particularly those where strong specific interactions, such as hydrogen bonding, can occur, the orientation of one particle with respect to its neighbours will not be random, some configurations corresponding to slightly lower energies than others. The most extreme example of this is, of course, water. Its physical properties are unusual for a substance of low molecular weight, and attempts to interpret these properties in terms of association have a long history. In their simplest form they involve an equilibrium between monomeric water H2O and ‘bulky’ or ‘ice-like’ water (H2O) n ; a very full account appears in a recent book2 on the structure of water.


Solvent Molecule Regular Solution Apparent Molal Volume Hydration Number Solvation Number 
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© A. J. Downs, D. A. Long, L. A. K. Staveley 1971

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  • H. J. V. Tyrrell

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