Organic sorbate-organoclay interactions in aqueous and hydrophobic environments: sorbate-water competition

Sorption of nitrobenzene, phenol, and m-nitrophenol from water and n-hexadecane was measured on Na-montmorillonite and organoclays in which 41 and 90% of the exchange capacity of the Na-clay was occupied by hexadecyltrimethylammonium. The strength of sorbate-sorbent interactions in n-hexadecane for all three sorbents was in the following order: nitrobenzene < phenol < m-nitrophenol. The magnitude of the distribution coefficients suggests that the contribution to solute uptake of partitioning between n-hexadecane and the organic pseudophase of the dried organoclays is minor, whereas the major contribution is from adsorptive sorbate-sorbent interactions. Sorption isotherms obtained in different solvents were compared using a sorbate activity scale. In the organoclays, the stronger the tendency of a sorbate to interact with sorption sites, the less pronounced is the reduction in the activity-based sorption due to competition with water. The order of this reduction for the different sorbates is nitrobenzene > phenol > m-nitrophenol. The weakening of sorbate-sorbent interactions resulting from water-sorbate competition might be mitigated by interaction between the organic sorbate and sorbed water molecules. Since the more strongly interacting organic compounds are less susceptible to suppression of sorption in the presence of water, hydrating organoclays may result in an increased differentiation between "weakly" and "strongly" interacting ("nonpolar" and "polar") compounds in the organoclay phase.