Abstract

The paper attempts to explain the mutual influence of nonpolar and electron-donor groups on solute hydration,
the problem of big importance for biological aqueous systems. Aprotic organic solvents have been used as
model solutes, differing in electron-donating power. Hydration of acetonitrile, acetone, 2-butanone, and
triethylamine has been studied by HDO and (partially) H2O spectra. The quantitative version of difference
spectra method has been applied to determine solute-affected water spectra. Analysis of the data suggests
that solvent-water interaction via the donor center of the solute is averaged between water-water interactions
around the solute. Such behavior can be simply explained by the model of solute rotating in a cavity of water
structure, which is formed by clathratelike hydrogen-bonded water network. On the basis of the band shape
of solute-affected HDO spectra and the corresponding distribution of intermolecular distances, the criterion
for hydrophobic type hydration has been proposed. From that point of view, all the studied solutes could be
treated as hydrophobic ones. The limiting band position and the corresponding intermolecular distance of
affected water, gained with increasing electron-donating power of solutes, has been inferred from the data
obtained. These observations are important for interpretation of vibrational spectra of water as well as for
volumetric measurements of solutions. The simple model of hydration, proposed to better justify the results,
connects the values obtained from the methods providing microscopic and macroscopic characteristics of the
system studied.

Citations

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