Abstract

AbstractA physicochemical parameter, represented by the symbol Σs*, based on molar solubility in water and molar attraction constants of Small, has been developed to express quantitatively the relative hydrophobicity, or nonpolar character, of the hydrocarbon molecule. The value of Σs* can be calculated for a hydrocarbon from its chemical structure. The scale of Σs* is consistent within each group of aromatic, cyclic, and noncyclic hydrocarbons. Reverse osmosis data have been obtained at 250 psig for single‐solute aqueous feed solution systems involving low concentrations of 39 different hydrocarbons (including 13 aromatics, 10 cyclic, and 16 noncyclic compounds) and several samples of cellulose acetate membranes of different surface porosities. The effect of operating pressure on membrane performance has also been studied for two aromatic hydrocarbon solutes. The values of Σs* for the solutes used were in the range of 425 to 924 for aromatic hydrocarbons, 521 to 931 for cyclic hydrocarbons, and 369 to 960 for noncyclic hydrocarbons. The reverse osmosis data have been correlated with Σs* for each group of hydrocarbons studied. In all cases, positive solute separations were obtained, and the ratio [PR]/[PWP] was less than 1. With respect to each film, solute separation increased with increase in Σs*, and decreased with increase in operating pressure. Also, solute separation decreased in the order aromatic hydrocarbon > cyclic hydrocarbon > noncyclic hydrocarbon at any given value of Σs*. At a given operating pressure, for low values of Σs* (∼500 or less) solute separation increased with progressive decrease in average pore size on the membrane surface. For high values of Σs* (∼800 or more), solute separation initially increased with decrease in average pore size, then passed through a maximum and minimum with further decrease in average pore size, and again increased with still further decrease in average pore size. The results are discussed on the basis of preferential sorption of solute at the membrane–solution interface under the experimental conditions studied.

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