Abstract

The apparent molar volumes, heat capacities, relative enthalpies, and isentropic compressibilities of symmetrical trialkylamine oxides and cyclohexyldimethylamine oxide were measured in water at 25 °C. The data were in most cases analyzed with a mass-action model which was previously developed (J. Phys. Chem. 87, 1397 (1983)) for micellar systems. Trimethylamine oxide shows no sign of micellization while the three next members of this homologous series and cyclohexyldimethylamine oxide form aggregates with relatively low aggregation numbers. The thermodynamic data were compared with those of assymmetrical amine oxides to investigate the effect of geometry on the micellar properties. The thermodynamic properties of the solutes in the pre-micellar region show a very good group additivity which is independent of geometry. On the other hand, with symmetrical isomers, the CMCs are much larger, the aggregation numbers smaller and the thermodynamic functions of micellization larger. These geometrical factors can be taken advantage of for thermal energy storage.

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