Selective counterion condensation in ionic micellar solutions

Small-angle neutron scattering experiments have been carried out on micellar solutions of cationic surfactants of cetyltrimethylammonium bromide (CTABr) and chloride (CTACl) in the presence of varying concentrations of salts KBr and KCl. In these systems, while the size of micelles strongly increases with the addition of KBr, the effect of addition of KCl in comparison is much less pronounced. It is found that in equimolar surfactant to salt micellar solutions of CTABr/KCl and CTACl/KBr, the micellar sizes are larger in CTACl/KBr than those in CTABr/KCl. The measurements have been done for different equimolar surfactant to salt concentrations and at different temperatures. We explain these results in terms of selective counterion condensation on the micelles. That is, while the condensation of Cl- counterions on the CTABr micelles in CTABr/KCl takes place around the condensed Br- counterions of CTABr, the Cl- counterions of CTACl in CTACl/KBr are replaced by Br- counterions of the salt. Similar results have also been obtained on micellar solutions of anionic surfactants of sodium dodecyl sulfate and lithium dodecyl sulfate in the presence of salts LiBr and NaBr, respectively.