Enthalpy measurements in aqueous SDS/DTAB solutions using isothermal titration microcalorimetry
Date of Original Version
Isothermal titration microcalorimetry has been used to measure enthalpies of aggregate formation and binding, at 25°C, for aqueous solutions of the single surfactants sodium dodecyl sulfate (SDS) and dodecyltrimethylammoniumbromide (DTAB) and mixtures of these at 1 wt % total surfactant concentration, over accessible composition ranges. The enthalpy of formation for SDS micelles is 0.6 kJ g-1 mol-1, and that for DTAB micelles is -2.1 kJ g-1 mol-1. This calorimetric experiment also produces a direct measurement of the critical micelle concentration (cmc) for each surfactant. The enthalpy of formation for 5:95 SDS/DTAB mixed micelles is -5.5 kJ g-1 mol-1 total surfactant and -6.7 kJ g-1 mol-1 total surfactant for 85:15 SDS/DTAB mixed micelles. Vesicles at an SDS/DTAB ratio of 62:38 have an enthalpy of formation of -13.4 kJ g-1 mol-1 total surfactant, indicating a strong enthalpic contribution to their free energy of formation. The enthalpies of aggregate formation are in good agreement with predictions from a molecular-thermodynamic model. Within the context of regular solution theory (RST), the interaction energy parameter is -51.7 kJ g-1 mol-1, again in excellent agreement with the prediction from the molecular-thermodynamic model. Monomer solutions of each surfactant show a measurable enthalpy of dilution with a positive deviation from ideality. Using RST, the activity coefficients for SDS and DTAB monomers in water are 1.035 and 1.025, respectively. The enthalpy of dilution of concentrated micellar solutions (∼5 cmc) of each surfactant up to its cmc is zero, implying that these solutions behave "ideally" over this concentration range. The enthalpy of binding of DTAB monomers to SDS micelles is -28.4 kJ g-1 mol-1, to 20:80 SDS/DTAB mixed micelles is -36.4 kJ g-1 mol-1, and to 62:38 SDS/DTAB vesicles is -28.6 kJ g-1 mol-1. The enthalpy of binding of SDS monomers to DTAB micelles is -24.7 kJ g-1 mol-1.
Meagher, Robert J., T. Alan Hatton, and Arijit Bose. "Enthalpy measurements in aqueous SDS/DTAB solutions using isothermal titration microcalorimetry." Langmuir 14, 15 (1998): 4081-4087. doi:10.1021/la970941y.