Properties of the adsorption layer in a binary liquid mixture near the critical point

A method for the determination of parameters of the surface layer (thickness and refraction index) at the liquid-vapor interface in binary liquid mixtures was developed. The parameters of the surface layer for the C₇H₁₄-C₇F₁₄ liquid mixture in the vicinity of the critical point, which was studied by means of ellipsometry in [1], were calculated using the proposed method. The temperature dependences of the thickness and refraction index that were determined in the homogeneous isotropic layer approximation at the interface liquid-vapor, show structural peculiarities that were not observed earlier. Their appearance is explained by the possible influence of hydrodynamic processes at the boundary.     

Probability distribution of singly and multiply scattered light near the critical point of a binary mixture

The probability density function p(I) is theoretically and experimentally investigated in the case of single, double, and multiple light scattering near a second-order transition (demixing of the binary mixture nitrobenzene and n-hexane). Experimentally we find no differences between the statistics of singly, doubly or multiply scattered light, and as expected from theory, p(I) shows an exponential variation. These results justify the use of either heterodyne or homodyne techniques for studying single or multiple scattering close to a critical point. We also describe a particularly simple way of determining whether homodyne or heterodyne detection occurs.     

Spectral measurements of the depolarized multiple scattered light from a binary mixture near its critical point

We report the first spectral measurements of the depolarized multiple scattered light from a binary mixture near its critical point. Spectral analysis of the depolarized light allows to separate rigorously the multiple scattering from the light scattered by the anisotropy fluctuations. The results are in very good agreement with a recent theory by Oxtoby-Gelbart.     

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.     

Anomaly in electric resistance of binary liquids near the critical point

Electric resistance in critical solutions of nitrobenzene inn-hexane,n-heptane andn-octane was measured. The resistance near the critical point was studied and divergence in the temperature derivative measured.     

Autocorrelation function of scattered light for a binary fluid near the critical mixing point

Using a time-to-amplitude conversion method the second order correlation function of the central component in light scattered by a binary fluid was measured very close to the critical point. At kξ?7 deviation from a exponential decay of the concentration fluctuations turns out to be smaller than one percent.     

Solutions of the Percus-Yevick and hyper-netted chain equations near the gas-liquid critical point

An intuitive approach is used to develop a theory of the transverse current correlation function in simple liquids. The memory function obtained on the basis of this approach is expressed in terms of the velocity autocorrelation function for the kinetic part and in terms of the radial distribution function, the interatomic potential and a time-dependent term which describes the relative motion of two atoms in the liquid for the potential part. The results for the memory function and the frequency spectrum are found to be in satisfactory agreement with the computer simulation studies of Levesque et al.     

Spectrum of depolarized light scattered from nitroethane-isooctane mixture near its critical point

We present the results of a study of the spectrum of depolarized light scattered from the critical nitroethane—isooctane mixture which has a very weak critical opalescence. Near the critical point only slight narrowing of the spectrum is observed.     

A scaling equation of state near the critical point and the stability boundary of a liquid

A new scaling equation of state is proposed to describe the equilibrium thermodynamic properties of liquids near the critical point. In distinction from the existing scaling equations, which are parametric, the new equation is nonparametric and is expressed directly in terms of the physical quantities (pressure, temperature, and so on). It creates a number of advantages for the traditional representation and data processing. The equation gives rise to a binodal, spinodal, and a curve of thermal capacity divergence (pseudospinodal). The equation is expressed in terms of reduced variables (the ratio of the deviation of a thermodynamic variable from its critical value to the critical value) and contains 3 system-dependent adjustable constants. With the help of this equation, we conducted an approximation of the experimental PVT data in the critical region of ⁴He, C₂H₄, and H₂O with a pressure error of 0.4% and carried out a calculation of the C _v ⁴He thermal capacity with no more than 4% error using a three-system constant determined from the PVT data.