Abstract

The process of micellization of sodium alkyl sulfates (SAS : sodium decyl- (SDS) and dodecylsulfate (SDDS)) of formation in aqueous solution without or with alcohols including propanol-1, propanol-2 and butanol-1 and their adsorption behavior at air-liquid interface were investigated with both the tensiometry and the conductometry at 298 K. The effect of chain length of alcohol on micellar and interfacial properties were discussed. Some parameters including surface excess concentration (Γmax), minimum area per surfactant molecule (Smin) at air-liquid interface, degree of ionization of micelle, and standard free energy of adsorption and micellization, etc. are estimated. It was experimentally established that the introduction of 0.5-1.0 mol/dm3 of alcohols into surfactant solutions contributes to the process of micellar formation of SAS and increases the stability of the micellar phase, as evidenced by the observed synergistic effect on the critical micelle concentration (CMC). The addition of different alcohols changes the values of Γmax, Smin, CMC of SDS and SDDS and induces an increase in degree of ionization (β) of micelle relative to that in pure water. When alcohols are introduced into SDS and SDDS solutions, the degree of ionization of micelles at a constant length of the alkyl radical of surfactant moderately increases with increasing alcohol content in the solution and ranges from 0.50-0.73 and 0.38-0.75, respectively. Also, the effect of alcohol was discussed. The obtained thermodynamic parameters were used to confirm these behaviors of interfacial adsorption or micellization. An increase in chain length of alcohol promotes the micellization process. The CMC values decrease with increasing length of the alkyl radical of alcohols. Propanol-1, compared to propanol-2, somewhat reduces the value of SDS and SDDS CMC to a greater extent. Standard free energy of micellization ∆G0mic, also confirms the micellization behavior. Standard free energy of adsorption (∆G0адс) indicates that an increase in the chain length of alcohol in aqueous solution is favorable to the adsorption of SDS and SDDS at air-liquid interface. A comparison of the values of the standard free energy of adsorption and micelle formation in sodium alkyl sulfates – alcohols – water systems showed that adsorption is the most thermodynamically advantageous process in the studies systems, and the packing of surfactant “molecules” in micelles is less dense, compared to packing in a mixed adsorption layer.

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