Theoretical Analysis of the Necessary and Sufficient Conditions for the Formation of Adsorption Azeotropes in Binary Gas Mixtures.

This work theoretically assessed the necessary and sufficient conditions for the formation of an adsorption azeotrope in a binary gas mixture when this mixture exhibits either intersecting or nonintersecting single gas isotherms. The thermodynamically consistent dual process Langmuir (DPL) model with equal component i saturation capacities qi,js on site j and the general DPL model with nonequal qi,js on site j were used for this purpose. Analytical expressions derived for both DPL models, in terms of the single gas isotherm DPL model parameters, were used to find examples or to determine theoretically when an adsorption azeotrope forms in a binary gas mixture for both intersecting and nonintersecting single gas isotherms. For the general DPL model, it was determined that neither necessary nor sufficient conditions exist for the formation of an adsorption azeotrope in a binary gas mixture. This means that an adsorption azeotrope can form irrespective of whether the corresponding single gas isotherms intersect or not. For the thermodynamically consistent DPL model, it was determined that the intersection of the single gas isotherms is a sufficient condition for the formation of an adsorption azeotrope in a binary gas mixture, but it is not a necessary condition. This means that intersecting single gas isotherms guarantee the formation of an adsorption azeotrope in the corresponding binary gas mixture, while nonintersecting single gas isotherms can also result in the formation of an adsorption azeotrope in the corresponding binary gas mixture. Overall, this analysis provides a well-posed resolution to the question of necessity and sufficiency for the formation of adsorption azeotropes in binary gas mixtures and the intersection of their corresponding single gas isotherms based on two physically sound formulations of the very popular DPL model.