Quantitative analysis of micellar effect on the reaction rate of alkaline fading of phenolphthalein
Abstract
Quantitative treatment of the kinetic data of the reaction between phenolphthalein dianion and hydroxide ion in aqueous solutions containing variable concentration of various surfactants is presented. Following surfactants are used: Brij-35 (nonionic), sodium n-dodecyl sulfate (anionic), cetyltrimethylammonium bromide (cationic) and 3-(dimethyl-n-dodecylammonio)-propansulfonate (zwitterionic). The quantitative treatment is carried out basing of Piszkiewicz’s, Berezin’s, and Pseudophase Ion-Exchange (PIE) models. It is revealed that the Berezin’s model is a more applicable one for describing the effect of nonionic, anionic, and zwitterionic micellar systems. The values of the corresponding kinetic parameters are discussed. The effect of cetyltrimethylammonium hydroxide on the reaction is also examined and quantitatively described by the PIE model. The research of systems based on a cationic surfactant shows previously unknown effect called by us as “diverting influence”.
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Roshchina E.V., Eltsov S.V. Micellar effects in the kinetics of reaction between phenolphthal-ein and hydroxide ion. (1) The effect of nonionic and anionic surfactants // Visn. Hark. nac. univ. 2013. №1085. Ser. Him. Issue 22 (45). P.119–126. (In Russian)
Laguta A.N., Eltsov S.V. Micellar effects in the kinetics of reaction between phenolphthalein and hydroxide ion. (2) The effect of cationic and zwitterionic surfactants // Visn. Hark. nac. univ. 2013. №1085. Ser. Him. Issue 22 (45). P.127–135. (In Russian)
Laguta A.N., Eltsov S.V. Micellar and salt effects in kinetics of the reaction between phenol-phthalein and hydroxyl ion // Visn. Hark. nac. univ. 2014. №1136. Ser. Him. Issue 24 (47). P.19–30. (In Russian)
Bunton C. A., Savelli G. Organic Reactivity in Aqueous Micelles and Similar Assemblies. // Adv. Phys. Org. Chem. 1986. Vol. 22. P. 213–309.
Romsted L. S. Introduction to Surfactant Self Assembly. // in Supramolecular Chemistry: From Molecules to Nanomaterials, Wiley. 2012. P. 1–23.
Zakharova L., Valeeva F., Zakharov A., Ibragimova, A., Kudryavtseva L., Harlampidi H. J. Micellization and catalytic activity of the cetyltrimethylammonium bromide–Brij 97–water mixed micellar system. // Coll. Int. Sci. 2003. Vol. 263. P. 597–605.
Martinek K., Yatsimirski A. K., Osipov A.P., Berezin I. V. Micellar effects on kinetics and equilibrium of synthesis and hydrolysis of benzylideneaniline: A general kinetic conception of micellar catalysis. // Tetrahedron 1973. Vol. 29. P. 963–969.
Cheong M.-Y., Ariffin A., Khan M. N. A Comparative Analysis of Pseudophase Ion-Exchange (PIE) Model and Berezin Pseudophase (BPP) Model: Analysis of Kinetic Data for Ionic Micellar-mediated Semi-ionic Bimolecular Reaction. // Bull. Korean. Chem. Soc. 2007. Vol. 7. P. 1135–1140.
Garcia-Rio L., Leis J. R., Mejuto J. C., Navarro-Vazquez A., Perez-Juste J., Rodriguez-Dafonte P. Basic Hydrolysis of Crystal Violet in β-Cyclodextrin/Surfactant Mixed Systems. // Langmuir 2004. Vol. 20. P. 606–613.
Samiey B., Cheng C.-H., Wu J. Effects of Surfactants on the Rate of Chemical Reactions. J. Chem. 2014. Vol. 2014. P. 1–14.
Piszkiewicz D. Micelle catalyzed reactions are models of enzyme catalyzed reactions which show positive homotropic interactions. // J. Am. Chem. Soc. 1976. Vol.98. No.10. P. 3053–3055.
Piszkiewicz D. Positive cooperativity in micelle-catalyzed reactions. // J. Am. Chem. Soc. 1977. Vol. 99. No. 23. P. 1550–1557.
Piszkiewicz D. Cooperativity in bimolecular micelle-catalyzed reactions. Inhibition of cataly-sis by high concentrations of detergent. // J. Am. Chem. Soc. 1977. Vol. 99. No. 5. P. 7695–7697.
Berezin I. V., Martinek K., Yatsimirski A. K. Physicochemical foundations of micellar cataly-sis. // Russ. Chem. Rev. (Usp. Khim.) 1973. Vol. 42. P. 787–802.
Mchedlov-Petrossyan N. O., Romanenko A. V., Nikishina L. E. Acid–base equilibria of phe-nolpthalein in aqueous solutions. / Zhurn. Anal. Khim. 1984. Vol. 39. No. 8. P. 1395–1403.
Mishchenko K.P., Ravdel A.A. Kratkiy spravochnik fiziko-khimicheskikh velichin. Lenin-grad: Khimiya, 1974, 200 p. (In Russian)
Berthod A., Garcia-Alvares-Coque C. Micellar liquid chromatography. Dekker, N. Y., 2000, 603 p.
Sesta B. Physicochemical properties of decyldimethylammonium propanesulfonate and its homologous compounds in aqueous medium. // J. Phys. Chem. 1989. Vol. 93. P. 7677–7680.
Mittal K. L., Lindman B. Eds., Surfactants in Solution, Plenum: N. Y., 1984, 2.
Bunton C.A., Robinson L., Micellar effects upon the reaction of P-nitrophenyl diphenyl phos-phate with hydroxide and fluoride ions. // J. Org. Chem. 1969. Vol. 4. P. 773–780.
Bunton C.A., Moffatt J. R. Ionic competition in micellar reactions: a quantitative treatment. // J. Phys. Chem. 1986. Vol. 90. No. 4. P. 538–541.
Mchedlov-Petrossyan N. O., Vodolazkaya N. A., Yakubovskaya A. G., Grigorovich A. V., Alekseeva V. I., Savvina L. P. A novel probe for determination of electrical surface potential of surfactant micelles: N,N'-di-n-octadecylrhodamine. // J. Phys. Org. Chem. 2007. Vol. 20. P. 332–344.
Eltsov S. V., Barsova Z. V. Ionization of long-chain fatty acids in micellar solutions of surfac-tants // Kharkov University Bull. 2008, № 820, Chem. Series. Issue 16 (39) P. 292–298 (In Russian).
Laguta A.N., Eltsov S.V., Mchedlov-Petrossyan N.O., Kinetics of alkaline fading of methyl violet in micellar solution of surfactants: Comparing Piszkiewicz’s, Berezin’s, and Pseudo-phace Ion-exchange models, Int. J. Chem. Kin., in press.
Bunton C. A., Gan L.–H., Moffatt J. R., Romsted L. S., Savelli G. Reactions in micelles of cetyltrimethylammonium hydroxide. Test of the pseudophase model for kinetics. // J. Phys. Org. Chem. 1981. Vol. 85. P. 4118–4125.
Bunton C. A., Mhala M. M., Moffatt J. R. Nucleophilic reactions in zwitterionic micelles of amine oxide or betaine sulfonate surfactants. // J. Phys. Org. Chem. 1989. Vol. 93. P. 854–858.
Bunton C. A. Reactions in micelles and similar self-organized aggregates. // in New Compre-hensive Biochemistry. 1984. Vol. 6. P. 461–504.
Bunton C.A., Carrasco N., Huang S.K., Paik C.H., Romsted L.S., Reagent distribution and micellar catalysis of carbocation reactions. // J. Am. Chem. Soc. 1978. Vol. 100. P. 5420–5425.
