Difference in screening effect of alkali metal counterions on H-AOT-based W/O microemulsion formation

The purpose of this study was to estimate the screening of electrostatic repulsions between the polar headgroups of AOT^- by alkali metal counterions and to explore the relationships between the screening effect and the phase behavior of H-AOT-basedW/Omicroemulsions. The screening effectwas evaluated bymeans of criticalmicelle concentration (CMC) data using the pyrene 1:3 ratio method with aqueous solutions containing M-AOT (whereM⁺ =Li⁺ , Na⁺ , K⁺ , Rb⁺ and Cs ⁺ ) to form normal micelles, and by counterion binding constants, determined from plots of CMC versus counterion concentration. The order of the screening effect was found to be K⁺ ≈ Rb⁺ Cs ⁺ Na⁺ Li⁺ . Interestingly, the order does not follow the hydration size dependence of the alkali metal counterions. An aqueous MOH solution containing a given concentration/H-AOT/isooctane was emulsified at a water content (w₀ = [water]/[H-AOT]) of 10 to produce H-AOT-based W/O microemulsions. The phase behavior and size variation were investigated by FT-IR and DLS measurements. The emulsified mixture separates into two phases at lower MOH concentration due to an insufficient screening effect. When the concentration is increased to a level sufficient to intensify the screening effect, W/O microemulsions are formed without phase separation at lower KOH and RbOH concentrations compared to CsOH.Aperiod of standing after the emulsification and a higher concentration ofNaOHcompared toKOH, RbOH, and CsOHare required to formW/O microemulsions.W/O microemulsions are not formed in the case of LiOH. These results indicate that the formation of a W/O microemulsion with H-AOT is strongly correlated with the order of the screening effect. A possible cause for the difference in the screening effect is proposed based on hydration of the polar headgroups and counterions, as evidenced by FT-IR spectral data, i.e., symmetrical sulfonate stretching and O-H stretching.