Heat evolution of micelle formation, dependence of enthalpy, and heat capacity on the surfactant chain length and head group

Micelle formation by many surfactants is endothermic at low temperatures but exothermic at high temperatures. In this respect, dissociation of micelles (demicellization) is similar to dissolving hydrocarbons in water. However, a remarkable difference between the two processes is that dissolving hydrocarbons is isocaloric at about 25°C, almost independently of the hydrocarbon chain length, whereas the temperature (T*) at which demicellization of different surfactants is athermal varies over a relatively large range. We have investigated the temperature dependence of the heat of demicellization of three alkylglucosides with hydrocarbon chains of 7, 8, and 9 carbon atoms. At about 25°C, the heat of demicellization of the three studied alkylglucosides varied within a relatively small range (ΔH D=-7.8 ± 0.4 kJ/mol). The temperature dependence of ΔH_demic indicates that within the studied temperature range the heat capacity of demicellization (ΔC_P,demic) is about constant. The value of ΔC_P,demic exhibited an apparently linear dependence on the surfactant's chain length (ΔC_P,demic/n_CH2=n47 ± 7 kJ/mol K). Our interpretation of these results is that (i) the transfer of the head groups from micelles to water is exothermic and (ii) the temperature dependence of the heat associated with water-hydrocarbon interactions is only slightly affected by the head group. This implies that the deviation of the value of T* from 25°C results from the contribution of the polar head to the overall heat of demicellization. Calorimetric studies of other series of amphiphiles will have to be conducted to test whether the latter conclusion is general.