Abstract
The premise for carrying out the present work was the hypothesis that in binary solu~ tions of nonelectrolytes the structural changes associated with the formation of molecular compounds and with the development of concentration fluctuations are best characterized with the aid of thermodynamic functions that express the relationship between the values of the energy of the intermolecular interaction in the pure liquids and in solution. In order to confirm this hypothesis we calculated several such functions for a number of solutions of nonelectrolytes over a broad range of concentrations according to the method of E. S. Rudakov. Analysis of the respective isotherms showed that of all the thermodynamic functions studied, the deviations from additivity of the partial energies for switching off the interaction xiAFic provide the most complete picture of the composition of the molecular compounds for~ed and the changes in the concentration fluctuations. Regardless of the nature of the intermolecular interaction in the system, the formation of molecular compounds is always manifested on one of the isotherms of the xiAFic in the form of a negative extremum, and the maximum in the development of the concentration fluctuations is manifested in the form of a positive ex tr emum.
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