Abstract
The amount of adsorption at equilibrium is commonly used for reporting solid/solution isotherms, despite the admonishment by the International Union of Pure and Applied Chemistry (IUPAC) against equating the surface excess (i.e., the measurable quantity for sorption, signifying the competitive sorption of adsorbate and solvent) with the actual amount adsorbed. The consensus, more generally stated, is that the surface excess cannot be divided into individual isotherms for sorbate and solvent unless simplifying model assumptions are introduced. Here we show, contrary to the IUPAC report, that there exists a simple method for assigning the total isotherm to the sorbate's actual amount adsorbed and to the individual solute isotherm. This requires a combination of isotherm and volumetric measurements. For dilute sorbates, we establish criteria to show if the total isotherm is dominated by the amount of sorption at the interface, in agreement with the common assumption in the practical literature. In the absence of the volume data, we propose an approximate yet more versatile method based on the specific surface area to carry out order-of-magnitude analysis to examine whether the actual amount adsorbed dominates surface excess. Application of our methods to the adsorption of sodium decyl sulfate on polystyrene latex, malachite green on activated carbons, and thiophenes on a metal-organic framework all demonstrated the dominance of the actual amount adsorbed, significantly simplifying isotherm analysis in terms of the underlying interactions (i.e., surface-sorbate and net self-interactions at the interface), eliminating the need for excess surface quantities. Analysis of fully miscible solvent-sorbate isotherms (e.g., the mixtures of organic solvents adsorbed on mesoporous silica and carbonaceous adsorbents) indicates the contributions from both sorbate and solvent isotherms.