The mass flux at the surface of a drop in an immiscible host liquid is dictated by the composition of the drop surface. In a binary system, this composition is essentially constant in time and equals the solubility of the drop constituent in the host liquid. This situation has been treated in a classic study by Epstein and Plesset (J. Chem. Phys., vol. 18, 1950, pp. 1505–1509). The situation is very different for ternary and higher-order systems in which, due to the mutual interaction of the drop constituents, their concentration at the drop surface markedly differs from the respective solubilities and depends on time. This paper presents a thermodynamically consistent analysis of this situation, for both growing and dissolving drops, with and without an initial concentration of the drop constituents in the host liquid. In some cases the results, which have important implications e.g. for solvent extraction processes in the chemical and environmental remediation industries, show major deviations from the predictions of approximations in current use, including simple extensions of the Epstein–Plesset theory.
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