Effect of temperature on the surface phase behavior and micelle formation of a mixed system of nonionic/anionic surfactants

The adsorption and micellar behavior of diethylene glycol mono-n-tetradecyl ether (C14E2), sodium 3,6,9,12-tetraoxaoctacosanoate (TOOCNa), and their mixture at a 1:1 molar ratio have been studied by film balance, Brewster angle microscopy (BAM), and surface tensiometry at different temperatures. The monolayers of pure C14E2 and its mixture with TOOCNa show a first-order phase transition with a conspicuous cusp point in their respective adsorption isotherms. This is further confirmed by the observation of bright two-dimensional condensed phase domains visualized by BAM just after the appearance of the phase transition. It is interesting to note here that for C14E2, condensed domains are observed up to 19 °C, while in the mixed system, they are observed up to 22 °C. To understand why in the mixed system the domains are observed at higher temperatures than for pure C14E2, we have measured the temperature dependency of the equilibrium surface tension at ⩾cmc (γcmc) values of both the pure and the mixed systems. The γcmc values of pure C14E2 remain almost constant, while those of pure TOOCNa and its mixture with C14E2 decrease appreciably with increasing temperature. It is concluded that higher degree of dehydration of the ethylene oxide (EO) chain reduces the head-group size of TOOCNa, which outweighs the combined effect of the repulsive interactions between the head-groups and the thermal motion of the adsorbed molecules. Furthermore, C14E2 being inserted into the TOOCNa monolayer reduces the electrostatic repulsions between the charged heads, and consequently, the adsorbed monolayers attain closer molecular packing. As a result, the γcmc values of both pure TOOCNa and its mixture with C14E2 decrease with increasing temperature. This facilitates the formation of condensed domains in the mixed system at higher temperatures, whereas none of the individual members can show any indicative feature of phase transition under the same experimental conditions.