A technique of modeling of phase and chemical equilibria by equations of state for systems containing supercritical components and ionic species is considered. Attention is focused on the structure of equation of states with inclusion of non-electrolyte and electrostatic contributions. A hole quasichemical model was applied to illustrate the technique and to show how an EOS can be modified for systems with chemical reactions and electrostatic interactions in the liquid phase. The concentration dependency of the density and dielectric permittivity was taken into account in describing the electrostatic contribution that is required for thermodynamic consistency of the results of modeling. A method of assessing the appropriate relationships for mixtures containing supercritical components is suggested, alongside with the way to estimate the "true" composition of mixtures where ionic species are formed due to chemical reactions. The raised questions are discussed with respect to the following systems: solutions of acid gases in water-alkanolamine mixtures and water-ammonia-carbon dioxide system in a broad interval of temperatures and pressures. (C) 2010 Elsevier B.V. All rights reserved.