Hydration of bromide at reverse micelle interfaces studied by X-ray absorption fine structure

Abstract

Nanoconfined water exhibits various interesting properties, which are not only of fundamental importance but also of practical use. Because reverse micelles (RMs) provide versatile ways to prepare nanoconfined water, the understanding of their physicochemical properties is essential for developing efficient applications. Although the water properties in the RMs could be affected by its interaction with the RM interface, the details have not been well understood. This study focuses on the local structures of Br^- in hexadecyltrimethylammonium bromide (HTAB) RMs formed in chloroform and 10% hexanol/heptane. The dependence in Br^- hydration on the molar ratio of water to HTAB (w) is investigated using X-ray absorption fine structure (XAFS). These systems cover a wide range of w values (0-30) and allow us to study the impact of this parameter on the local structure of Br^- at the RM interface, which comprises water, surfactant headgroups, and organic solvent components. The presence of multiple scattering paths complicates the XAFS spectra and makes it difficult to analyze them using standard fitting methods. The linear combination of the spectra corresponding to the individual scattering paths captures the molecular processes that occur at the RM interface upon increasing w. The maximum hydration number of Br^- is found to be 4.5 at w > 15, suggesting that although most of the ions remain at the interface as partly hydrated ions, some of them dissociate as completely hydrated ones.

Keywords: Chloroform; Hexadecyltrimethylammonium bromide; Hexanol/heptane; Reverse micelle interface; Water/surfactant ratio; X-ray spectrometry.