Modeling spreading-pressure-dependent binary gas coadsorption equilibria using gravimetric data

The present work proposes an approach to building nonideal coadsorption models in a thermodynamically consistent fashion, including the effects of pressure and spreading pressure, from simple gravimetric measurements. This is an "inverse problem" of parameter determination from appropriate and limited experimental data.The approach relies on the nonideal adsorbed solution theory, which includes activity coefficients and their dependence on spreading pressure, and on an original form of the excess Gibbs energy of mixing. A fully analytical development leads to explicit relations between the infinite dilution activity coefficients and three sets of independent information: the parameters of this excess Gibbs function, the limiting slopes of measured binary gravimetric curves at two different total pressures, and the properties of the single-component isotherms. From there, the four parameters of the model may be determined quasi-analytically and uniquely. The method is exemplified with the coadsorption of CO(2) and CH(4) on activated carbon, and a heterogeneous set of data. On one hand, the total adsorbed mass of the two components is measured at 1 bar by "incremental gravimetry." On the other hand, data obtained from independent batch-type equilibration measurements at 2 bar allow a comparison of calculated and measured data for the individual component concentrations. It is emphasized, however, that only total adsorbed mass data are needed for application of the method.