Adsorption isotherms for fluids with strong interparticle repulsions

We derive adsorption isotherms for an adsorbate of hard-sphere particles with “sticky” interactions at any fluid density being adsorbed onto a plane, “sticky” surface. The theory is based on the Percus-Yevick theory for bulk fluids and explicitly includes the equilibrium between the adsorbed fluid and the bulk adsorbate. The theory predicts a surface condensation at low temperatures and low bulk densities in good agreement with surface condensations found in experimental studies of adsorption of gases onto graphite. An approximate law of corresponding states for these transitions is developed. At higher bulk densities and room temperatures, the adsorption isotherms can show a maximum, in accord with recent experimental work.