Solubilization kinetics of oils by ionic and nonionic micelles: theoretical model

TL;DR

This paper develops a theoretical model to analyze the kinetics of oil solubilization by ionic and nonionic micelles, highlighting differences in diffusion-controlled processes and potential barriers affecting hydrocarbon uptake.

Contribution

It introduces a Fickean diffusion model and Poisson-Boltzmann calculations to explain the distinct solubilization behaviors of ionic versus nonionic micelles.

Findings

Nonionic micelles exhibit barrier-free, diffusion-controlled solubilization.

Ionic micelles show slower rates due to potential barriers.

The model aligns well with experimental diffusion retardation data.

Abstract

Experimental data on solubilization kinetics found in literature were analyzed by using the model proposed earlier (1). The rates of oil molecular exchange between the micellar core and the surrounding aqueous solution were determined. It was concluded that the solubilization of hydrocarbon molecules by nonionic surfactants of ethylene oxide type is essentially barrier-free, that is, is diffusion controlled. It is quite different for ionic surfactants, where the rate is one-two orders of magnitude slower, indicating the existence of a potential barrier for hydrocarbons to get inside the micelles. A Fickean diffusion model of solubilization has been proposed to explain these trends. For ionic micelles, the hydrocarbons are predicted to be excluded from the micellar double layer region because of their low dielectric constant. The Poisson-Boltzmann model was used to model this effect; the diffusion retardation factors were compared with the experiment and a fair agreement was seen. For nonionic groups, such as oligoethylene oxide, on the other hand, no such barrier was predicted to exist. The analysis of this paper is performed only for the case of the 'slow' solubilization; it does not cover the case of the rapid, 'catastrophic' solubilization observed in the other group of experiments; the distinction between the slow and fast mechanisms is discussed and a possible explanation is suggested.