Prediction of Solubility of Nonpolar Gases in Micellar Solutions of Ionic Surfactants

The solubilities of methane, carbon dioxide, ethane, and propane have been determined experimentally at 1 atm partial pressure and 25°C in aqueous solutions of sodium dodecyl sulfate and cetyltrimethylammonium bromide. For this purpose a specially developed apparatus is used, which is relatively simple compared to those reported in the literature hitherto. Above the CMC, the solubility of each gas increases linearly with surfactant concentration indicating micellar solubilization. The degree of solubilization is greatest for propane and decreases in the order propane > ethane > carbon dioxide > methane. Both the length of the alkyl chain and the properties of the head-group region (i.e., the micelle-water interfacial tension) are observed to determine the intramicellar solubility. A method for estimating the solubilities is also proposed based on the rationale that the micellar phase may be represented by a droplet of a "model solvent" into which the solubilizate molecule dissolves as it would in a bulk solvent. The mixture of the solute species and the model solvent is assumed to behave as a regular solution. Accordingly, a characteristic solubility parameter is estimated for the model solvent from the interaction potential between two adjacent surfactant molecules in a micelle. The solubility computed using the regular solution approximation is further corrected for the Laplace pressure that acts across the curved micelle-water interface and generally reduces the intramicellar solubility. It is concluded that for small nonpolar solutes, micellar solubilities may be reasonably well predicted by assuming that the model solvent has a solubilizing capacity (i.e., solubility parameter) close to that of a bulk equivalent alkane. Copyright 1997 Academic Press. Copyright 1997Academic Press

[1]  Radwan,et al.  Solubilization of Gases by Polyethoxylated Octyl Phenols , 1990, Journal of colloid and interface science.

[2]  J. Scamehorn,et al.  Solubilization in Surfactant Aggregates , 1995 .

[3]  B. Joensson,et al.  Solubilization of uncharged molecules in ionic surfactant aggregates. 1. The micellar phase , 1992 .

[4]  Nagamune Nishikido Thermodynamic equations expressing the synergistic solubilization effect by surfactant mixtures , 1991 .

[5]  M. Grätzel,et al.  Kinetics and Catalysis in Microheterogeneous Systems , 1991 .

[6]  M. J. Rosen,et al.  Surface concentrations and molecule interactions in cationic−anionic mixed monolayers at various interfaces , 1989 .

[7]  Y. Moroi,et al.  Solubilization of 4-n-alkylbenzoic acids into dodecylsulfonic acid micelle: Examination of laplace pressure of micellar interior , 1988 .

[8]  Y. Moroi,et al.  Thermodynamics of solubilization into surfactant micelles: Effect of hydrophobicity of both solubilizate and surfactant molecules , 1988 .

[9]  A. D. King,et al.  The solubility of carbon dioxide and nitrous oxide in aqueous solutions of cetyltrimethylammonium bromide, sodium dodecyl sulfate, sodium 1-heptanesulfonate, and sodium perfluorooctanoate , 1988 .

[10]  F. Puisieux,et al.  Micellar solubilization in aqueous binary surfactant systems: Barbituric acids in mixed anionic + nonionic or cationic + nonionic mixtures , 1988 .

[11]  Aniruddha B. Pandit,et al.  Intensification of multiphase reactions through the use of a microphase—II. experimental , 1988 .

[12]  B. Jonsson,et al.  Phase equilibria in a three-component water-soap-alcohol system. A thermodynamic model , 1987 .

[13]  A. D. King,et al.  The solubility of gases in aqueous solutions of sodium 1-heptanesulfonate and sodium perfluorooctanoate , 1986 .

[14]  J. Rathman,et al.  Thermodynamics of mixed micelle formation , 1986 .

[15]  J. Bocquet,et al.  The case of a synergistic solubilization effect: the partitioning of 1-pentanol in aqueous solutions of mixed ionic hydrocarbon and fluorocarbon surfactants , 1986 .

[16]  A. D. King,et al.  The solubility of gases in aqueous solutions of decyltrimethyl- and cetyltrimethylammonium bromide , 1985 .

[17]  J. Israelachvili Intermolecular and surface forces , 1985 .

[18]  Y. Shchipunov Adsorption at the interface of two immiscible liquids and association of surface-active substances in bulk phase. 1. Application of the modified gibbs equation , 1984 .

[19]  A. D. King,et al.  The solubility of gases in solutions containing sodium alkylsulfates of various chain lengths , 1983 .

[20]  P. Mukerjee,et al.  Micelle-water distribution coefficients of nitroxides. Correlation with dodecane-water distributions and interfacial activity , 1982 .

[21]  B. Kozankiewicz,et al.  Investigation of micelles, microemulsions, and phospholipid bilayers with the pyridinium N-phenolbetaine et(30), a polarity probe for aqueous interfaces , 1981 .

[22]  H. Wennerström,et al.  Thermodynamics of ionic amphiphile—water systems , 1981 .

[23]  P. Mukerjee Solubilization in micellar systems , 1980 .

[24]  Charles Tanford,et al.  The hydrophobic effect , 1980 .

[25]  Eli Ruckenstein,et al.  Aggregation of Amphiphiles as Micelles or Vesicles in Aqueous Media , 1979 .

[26]  B. Lindman,et al.  Micelles. Physical chemistry of surfactant association , 1979 .

[27]  K. Mittal,et al.  Solution Chemistry of Surfactants , 1979 .

[28]  P. Mukerjee,et al.  Benzene derivatives and naphthalene solubilized in micelles. Polarity of microenvironments, location and distribution in micelles, and correlation with surface activity in hydrocarbon-water systems , 1978 .

[29]  H. Høiland,et al.  Partial molal volumes and partial molal compressibilities of n-alkanes in sodium dodecanoate solutions , 1978 .

[30]  M. B. King,et al.  The solubilities of carbon dioxide, hydrogen sulphide and propane in some normal alkane solvents—II: Correlation of Data at 25°C in Terms of Solubility Parameters and Regular Solution Theory , 1977 .

[31]  T. Ackermann Regular and Related Solutions , 1973 .

[32]  P. Mukerjee Odd-even alternation in the chain length variation of micellar properties , 1970 .

[33]  J. S. Rowlinson,et al.  Molecular Thermodynamics of Fluid-Phase Equilibria , 1969 .

[34]  J. Corkill,et al.  Partial molar volumes of surface-active agents in aqueous solution , 1967 .

[35]  D. Stigter On the Adsorption of Counterions at the Surface of Detergent Micelles1 , 1964 .

[36]  J. Prausnitz,et al.  Thermodynamics of Gas Solubility in Mixed Solvents , 1964 .

[37]  K. Shinoda,et al.  Colloidal Surfactants: Some Physicochemical Properties , 1963 .

[38]  D. E. Lamb,et al.  Measurement of concentration fluctuations with an electrical conductivity probe , 1960 .

[39]  Bean Hs Solubilisation by surface active agents. , 1960 .

[40]  E. Hutchinson,et al.  Solubilization : and related phenomena , 1955 .

[41]  J. Mcbain,et al.  The Effect of Potassium Oleate upon the Solubility of Hydrocarbon Vapors in Water , 1941 .

[42]  Joel H. Hildebrand,et al.  Solubility of Non-Electrolytes , 1936, Nature.