Activity Coefficients of Aqueous Mixed Ionic Surfactant Solutions from Osmometry
- 237 Downloads
Osmotic techniques for measuring thermodynamic activities, such as isopiestic equilibration, are well established for multicomponent solutions, especially mixed salt solutions. Surprisingly, these techniques have not yet been applied to mixed ionic surfactants, despite the numerous practical applications of these systems and the importance of the Gibbs free energy for micelle stability. In this study, mass-action equations are developed for the osmotic coefficients of solutions of ionic surfactant CA + ionic surfactant CB, with common counterion C. Extended Debye–Hückel equations are used for the ionic activity coefficients. The equilibrium constants for mixed micelle formation are evaluated by Gibbs–Duhem integration of critical micelle concentrations. Fitting the derived equations to the osmotic coefficients of aqueous sodium decanoate + sodium dodecylsulfate solutions measured by freezing-point osmometry is used to evaluate the activities of the total surfactant components. Very large departures from ideal solution behavior are indicated, including stoichiometric surfactant activity coefficients and micelle activity coefficients that drop below 0.05 and 10−8, respectively, relative to unity for ideal solutions. Osmometry offers many interesting and unexplored possibilities for studies of mixed surfactant thermodynamics.
KeywordsActivity coefficients Freezing point depression Mass-action model Micelles Surfactants Osmotic coefficient
Acknowledgment is made to the Natural Sciences and Engineering Research Council for the financial support of this work.
- 3.Robinson, R.A., Stokes, R.H.: Electrolyte Solutions, 2nd edn. Butterworths, London (1959)Google Scholar
- 4.Pitzer, K.S., Brewer, L.: Thermodynamics, 2nd edn. McGraw-Hill, New York (1961). (revised version of 1st edn by Lewis, G. N., Randall, M.)Google Scholar
- 10.Pitzer, K.S.: A consideration of Pitzer’s equations for activity and osmotic coefficients in mixed electrolytes. J. Chem. Soc. Faraday Trans. I 80, 3451–3454 (1984)Google Scholar
- 32.Scamehorn, J.F. (ed.): Phenomena in Mixed Surfactant Systems, vol. 311. American Chemical Society, Washington, DC (1986)Google Scholar
- 33.Clint, J.H.: Micellization of mixed ionic surface active agents. J. Chem. Soc. Faraday Trans. I 71, 1327–1334 (1975)Google Scholar
- 36.Holland, P.M., Rubingh, D.N. (eds.): Phenomena in Mixed Surfactant Systems, vol. 501. ACS Symposium SeriesAmerican Chemical Society, Washington, DC (1992)Google Scholar
- 38.Sharma, P., MacNeil, J.A., Bowles, J., Leaist, D.G.: The unusual importance of activity coefficients for micelle solutions illustrated by an osmometry study of aqueous sodium decanoate and aqueous sodium decanoate + sodium chloride solutions. Phys. Chem. Chem. Phys. 13, 21333–21343 (2011)CrossRefGoogle Scholar