Calorimetric, Viscosimetric, and Light Scattering Studies of the Aggregation of, and the Solubilization of Water by, Triton X-35 in n-Heptane.

The behavior of a nonionic surfactant TX-35 in solution in n-heptane in the presence and absence of added water has been examined using the microcalorimetric, viscosimetric, and quasielastic light scattering experimental methods. In this paper, we were interested in the aggregation process of the poly(oxyethylene) glycol alkylphenyl ether in n-heptane and in the solubilization of water in the reverse micelle of the surfactant (micellar solubilization). The analysis of the differential molar enthalpies of dilution of TX-35 in dried n-heptane has shown the occurrence of a gradual exothermic aggregation process on a very wide range of concentration which takes place at particular concentration so-called "operational CMC". This operational CMC value has been confirmed by viscosities measurements. The differential molar enthalpies of hydration of TX-35 were also measured and found to be exothermic. The maximal hydration ratio (w0) was found to be equal to 3.2 mol H2O per mole of TX-35 before the point of phase separation. The measurements of the variation of the amount of water contained in TX-35 solutions at different concentrations in n-heptane also show the occurence of a gradual aggregation process and confirm the value of the maximal hydration ratio already determined by microcalorimetry. In the absence of added water, from the quasielastic light scattering experiments, a mean diameter of the aggregates close to 45 Å has been determine, while in the presence of water, a mean diameter of 61 Å was detected and remained unchanged with increasing the hydration ratio indicating that the size of the aggregate is more influenced by the presence of water than by the amount. In the presence of water, it is relevant to discuss aggregates of lamellar or filament shape. Copyright 1999 Academic Press.