Some Features of Temperature and Pressure Dependences
of Partial Molar Volumes of Electrolytes in Aqueous Solutions
and the TammannGibson Rule

S. L. Lyubimov and B. R. Churagulov

Faculty of Chemistry, Moscow State University, Moscow, 119899 Russia

Received October 18, 1995

Abstract—An approach based on the Tammann–Gibson rule was used to explain qualitatively the anomalies
in the pressure dependence of the partial molar volumes of electrolytes in aqueous solutions in a wide range
of concentrations. The model predicts that the partial molar volume of electrolytes in infinite-dilution
solutions of inorganic 1-1 acids decreases as pressure increases; it also predicts a change in the sign of the deriv-
ative (/ p)_T from positive to negative with increasing concentration in binary water–salt systems with auto-
complexation and the existence of a minimum in the versus p dependence for some ternary water–salt–salt
systems with acidocomplexation under conditions of significant excess of anions. A considerable decrease in
the value with increasing temperature (and even a change of the positive to the negative sign of ), the
presence of shallow maxima in the versus dependence at temperatures near 320 K, and variations in the
value of T_max with pressure and concentration were also explained.

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