Structure of liquid solutions near the critical point

Specific features of the structure of the critical state of binary liquid solutions leading to an anomalous behavior of the Rayleigh line due to a dramatic increase in concentration and density fluctuations are considered. It is shown that an experimental treatment must deal with two fluctuation regions near the critical point of solvent vaporization. In the first region, one can achieve a sufficient degree of accuracy by using theories like self-consistent field theory. In the second region, which is closer to the critical point than the first region, scaling theory of second-order phase transitions may be applied. It is found that the anomalous behavior of the Rayleigh line associated with kinetic coefficients is determined by the equilibrium thermodynamic properties and by the radius of fluctuation correlation (r_c). A general theory is developed for calculating thermodynamic potentials, especially the chemical potential and its concentration derivative in the fluctuation region. The results of these calculations are compared with the experimental data briefly described in the paper. Translated fromZhurnal Struktumoi Khimii, Vol. 39, No. 4, pp. 655–668, July–August, 1998.