Spectroscopically Quantifying the Influence of Salts on Nonionic Surfactant Chemical Potentials and Micelle Formation

The influence of two salts (NaSCN and Na₂SO₄) on the micellization of a nonionic surfactant (1,2-hexanediol) is quantified using Raman multivariate curve resolution spectroscopy, combined with a generalized theoretical analysis of the corresponding chemical potential changes. Although the SCN^- and SO₄^2- anions are on opposite ends of the Hofmeister series, they are both found to lower the critical micelle concentration. Our combined spectroscopic and theoretical analysis traces these observations to the fact that in both salt solutions the ions have a greater affinity for (or are less strongly expelled from) the hydration shell of the micelle than the free surfactant monomer, as quantified using the corresponding chemical potentials and Wyman-Tanford coefficients. This probe-free experimental and theoretical analysis strategy may readily be extended to micelle formation processes involving other surfactants, salts, and cosolvents, as well as to other sorts of aggregation and binding processes.