Necessary conditions of the equivalence of canonical and grand canonical ensembles in Coulomb system thermodynamics Available to Purchase

It was found that the equivalence of the grand canonical and canonical ensembles for the Coulomb systems is possible only when charged particles of different types in calculating the physical quantities are considered as formally “independent” ones, and the quasi-neutrality condition is used in the final stage of calculations. The phase equilibrium condition is obtained and the expression is derived for the isothermal compressibility of matter as a two-component Coulomb system, which corresponds to the known limit relations for static structure factors. On this basis, it is demonstrated that the critical point of matter, considering as the Coulomb system is determined from the condition of vanishing mean square of fluctuations of the total charge per unit volume.