In drop profile analysis tensiometry, the ratio of drop surfaces area S to volume V is large, i.e., S/V >> 1. In such a case, the concentration of a surfactant within the drop bulk decreases due to adsorption at the drop surface. In contrast, in bubble profile analysis tensiometry, we have S/V << 1 so that depletion due to adsorption is negligible. A protocol is presented to determine the correct adsorption parameters of surfactants from surface tension data measured by bubble and drop profile analysis tensiometry. The procedure is applied to experimental data measured for selected surfactants of different adsorption activities: C10OH, CTAB, Tween 20, and the equimolar mixture SDS + DoTAB. The results show that for surfactants with higher surface activity, the differences between the surface tensions measured with the drops and bubbles profile analysis tensiometry, respectively, are larger, while for less surface-active surfactants, such as SDS, the results obtained from drop and bubble profile experiments are very close. The correction procedure is based on the same set of adsorption parameters used to fit both the experimental data obtained from drop-based measurements (which involve the depletion effects) and those data measured in a way that depletion effects are negligible.
In mixed solutions of anionic and cationic surfactants, called catanionics, ion pairs are formed which behave like non-ionic surfactants with a much higher surface activity than the single components. In equimolar mixtures of NaCnSO4 and CmTAB, all surface-active ions are paired. For mixtures with n + m = const, the interfacial properties are rather similar. Catanionics containing one long-chain surfactant and one surfactant with medium chain length exhibit a strong increase in surface activity as compared with the single compounds. In contrast, catanionics of one medium- and one short chain surfactant have a surface activity similar to that of the medium-chain surfactant alone. Both the Frumkin model and the reorientation model describe the experimental equilibrium data equally well, while the adsorption kinetics of the mixed medium- and short-chain surfactants can be well described only with the reorientation model.
The surface tension of C13DMPO aqueous solution drops in hexane vapor is studied using the drop profile method. The hexane was injected into the measuring cell at three different conditions: before the formation of the solution drop, at a certain moment during the adsorption process, and after reaching the equilibrium of surfactant adsorption. The surface tension values for all experiments at the same concentration and different injection situations ultimately coincide with each other after attaining the final equilibration stage. The equilibrium surface tension isotherms of C13DMPO solutions, and the adsorption of both components—surfactant and hexane—were calculated. It was shown that the presence of surfactant leads to an increased hexane adsorption.