Abstract A method that champions the approaches of two independent research groups, to quantitate the chromatographic stationary phase surface available for lipophilic ion adsorption, is presented. For the first time the non-approximated expression of the electrostatically modified Langmuir adsorption isotherm was used. The non approximated Gouy–Chapman (G–C) theory equation was used to give the rigorous surface potential. The method helps model makers, interested in ionic interactions, determine whether the potential modified Langmuir isotherm can be linearized, and, accordingly, whether simplified retention equations can be properly used. The theory cultivated here allows the estimates not only of the chromatographically accessible surface area, but also of the thermodynamic equilibrium constant for the adsorption of the amphiphile, the standard free energy of its adsorption, and the monolayer capacity of the packing. In addition, it establishes the limit between a theoretical and an empirical use of the Freundlich isotherm to determine the surface area. Estimates of the parameters characterising the chromatographic system are reliable from the physical point of view, and this greatly validates the present comprehensive approach.