Separation of mineral electrolytes according to size exclusion mechanism using neutral nanoporous polystyrene sorbents and carbonaceous materials has been examined in detail on hand of HCl and CaCl2 solutions, taken separately and in the mixture. Phase distribution coefficients of the above electrolytes have been measured under static conditions at different concentrations. The k-values and their dependence on the concentration were correlated with the elution curves of the components from a chromatographic column. Both the static and dynamic data suggest a strong dependence of the hydration number and effective size of ions on the concentration. Self-concentration of HCl in small pores and that of CaCl2 outside of small pores exhibits itself in both static and chromatographic experiments and results from the relocation of the components largely within the volume of the initial mixture. Additional apparent "retention" of HCl in the porous volume of the sorbent in concentrated electrolyte mixtures was shown to be caused by the competition between all ions of the system for hydration water. Increased separation selectivity and enhanced self-concentration effects for more concentrated mixtures point to preparative and industrial perspectives of size exclusion chromatography (SEC) of complex electrolyte mixtures on nanoporous neutral sorbents.