Analyzing the surfactant classification confusion through the HLD formulation equation

The qualitative presentation from Winsor on an interfacial balance of interactions between the surfactant and the oil and water phases has been transformed into a multivariable linear equation so-called hydrophilic-lipophilic deviation (HLD). This relation involves at least 6 independent variables (surfactant head and tail specifications, water salinity, oil nature, temperature, and pressure) with a MacLaurin series first order approximation, i.e., a linear multivariable expression. After 40 years of practical experience, it can be said that the HLD relation matches well the experimental data, with only very few exceptions with complex mixtures. Herein, we clear the confusion concerning the meaning and the mathematical handling of the surfactant parameter in the HLD equation. We start with a presentation of simple surfactant systems with only 4 parameters (water salinity, oil nature, surfactant nature, and temperature) as was done 40 years ago. Later, we present a critical discussion on the surfactant term, concerning binary surfactant systems, and on strategies for applications in ternary surfactant mixtures. We have found that the surfactant parameters can only be compared in a series of surfactants with the same head group, where the surfactant parameter is a linear function of the surfactant tail length.