Analysis of the bromide ion distribution in the water pool of reverse micelles of hexadecyltrimethylammonium bromide in chloroform/n-dodecane and isooctane/n-hexanol by chemical trapping

Chemical trapping of bromide ions in reverse micelles prep are d with hexadecyltrimethyl ammonium bromide, CTAB, in 12-dodecane/CHCl3 and isooctane/n-hexanol has been obtained for 2,4,6-trimethylbenzenediazonium (1-ArNa2+) and 2,4-dimethyl-4-hexadecylbenzenediazonium (16-ArN2+) tetrafluoroborates. Quantitative analysis of the reaction products of 1-ArN2+ and 16-ArN2+ with water and bromide ion, the corresponding phenol and bromo derivatives, and comparison with appropriate standard curves yielded the local concentrations of Br- in the water pool, [Br](f), and micellar interface, [Br](b), in reverse CTAB micelles prepared in n-dodecane/CHCl3 and isooctane/n-hexanol, The determination of [Br](b), in reverse micelles by chemical trapping with 16-ArN2+ can be obtained after correction for probe distribution between the reverse micelle and the organic solvent, especially in the case of n-dodecane/CHCl3, This correction was possible after demonstrating that 16-ArN2+, upon dediazoniation in wet n-dadecane/CHCl3, yields exclusively the corresponding bromo derivative. A Poisson-Boltzmann (PB) equation above a water/detergent molar ratio, W/S, of 14 appropriately describes the values of [Br](f). Comparison of the experimental values of [BT](b) with those predicted by PB with changing W/S suggest that 16-ArN2+ extends from the interface 0.6-1.2 nm with increasing W/S. Both PB calculations and experimental data indicate that the degree of counterion dissociation from CTAB reverse micelles in n-dodecane/CHCl3 reaches a value of ca. 0.2 above W/S 15.