The enthalpies of transfer from water to aqueous surfactant solutions, ΔH(W→W+S), of polar additives have been determined as a function of the surfactant concentration at fixed additive concentration. The surfactants used are sodium dodecylsulfate (NaDS), dodecyltrimethylammonium bromide and dodecyldimethylamine oxide (DDAO). The additives used are iso-butanol t-butanol, butoxyethanol, phenol, benzene, tributylphosphine oxide (TBPO), octyldimethylphosphine oxide (ODPO), octydimethylamine oxide (ODAO), DDAO and NaDS. A maximum was observed in the plots of ΔH(W→W+S) vs. fsms curves for ODPO and ODAO in NaDS while a small minimum was observed for TBPO. The experimental data are rationalized on the basis of the pseudo-phase transition model for the micellization process and a mass action model for the distribution of the additive between aqueous and micellar phases. The standard free energies, enthalpies and entropies of transfer of the additives from the aqueous to the micellar phases are reported. The effect of different butanol isomers on the thermodynamics of solubilization in the micellar phase has been derived. The enthalpies of transfer of benzene are always negligible with respect to those of phenol while the free energies of transfer are always comparable. Studies of symmetrical and asymmetrical additives show that asymmetry causes an increase of the free energy of transfer due to the decrease of the entropy. The thermodynamics of transfer of NaDS from the aqueous to the DDAO micellar phases and of DDAO from the aqueous to the NaDS micellar phases are compared to the thermodynamics of micellization of the two surfactants; the formation of mixed micelles seems to be energetically unfavored with respect to the pure micelles. © 1990 Plenum Publishing Corporation.
