Abstract
Micellar solutions of the anionic surfactant sodium dodecyl sulfate (SDS) markedly decrease the rate of alkaline hydrolysis of substrates such as N-alkyl-4-cyanopyridinium ions and p-nitrophenyl alkanoates. For the lower homologs, the magnitude of the rate decrease is a sensitive function of the length of the alkyl chain of the substrate. However, the observed rates of alkaline hydrolysis for the higher homologs converge to a limiting value which is virtually independent of further increase in the alkyl chain length or of the SDS concentration. In this limit of essentially complete substrate incorporation, the observed rate constants for alkaline hydrolysis are directly proportional to the concentration of added NaCl and are nearly second-order with respect to added NaOH in the absence of buffer. These results, which demonstrate that the intrinsic second-order rate constant for alkaline hydrolysis in the micellar pseudophase of SDS is not zero, can be analyzed in terms of the free sodium ion concentration dependence of the local “pH” at the SDS micellar surface.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
Similar content being viewed by others
References
This is paper 6 of the series Ion Exchange in Micellar Solutions.
F.M. Menger and C.E. Portnoy, J. Amer. Chem. Soc., 89, 4698 (1967).
E.J. Fendler, R.P. Liechti and J.H. Fendler, J. Org. Chem., 35, 1658 (1970).
G.J. Buist, C.A. Bunton, L. Robinson, L. Sepúlveda and M.Stam, J. Amer. Chem. Soc., 92, 4072 (1970).
J.L. Kurz, J. Phys. Chem., 66, 2239 (1962).
C.A. Bunton and L. Robinson, J. Phys. Chem., 74, 1062 (1970).
P. Mukerjee and K. Banerjee, J. Phys. Chem., 68, 3567 (1964).
M.S. Fernandez and P. Fromhertz, J. Phys. Chem., 81, 1755 (1977).
C.A. Bunton and L. Robinson, J. Org. Chem., 34, 773 (1969).
I.M. Cuccovia, E.H. Schröter, R.C. de Baptista and H. Chaimovich, J. Org. Chem., 42, 3400 (1977).
M.T.A. Behme, J. G. Fullington, R. Noel and E.H. Cordes, J. Amer. Chem. Soc., 87, 266 (1965).
E.F.J. Duynstee and E. Grunwald, Tetrahedron, 21, 2401 (1965).
H. Nogami, S.Awazu, Y. Kanakubo, Chem. Pharm. Bull., 11, 13 (1963).
H. Nogami, S. Awazu and M. Iwatsura, Chem. Pharm. Bull., 81 1251 (1963).
C.A. Bunton, L. Robinson and L. Sepúlveda, J. Amer. Chem. Soc., 91, 4813 (1969).
C.N. Sukenik, B. Weisman and R.G. Bergman, J. Amer. Chem. Soc., 97, 445 (1975).
J.K. Landquist, J. Chem. Soc. Perkin I, 454 (1976).
F.H. Quina, Tese de Livre-Docência, Instituto de Quimica, Universidade de São Paulo (1977).
M. Politi, I.M. Cuccovia, H. Chaimovich, M.L.C, de Almeida, J.B.S. Bonilha and F.H. Quina, Tetrahedron Lett., 115 (1978).
F.H. Quina, M.J. Politi, I.M. Cuccovia, E. Baumgarten, S.M. Martins-Franchetti and H. Chaimovich, J. Phys. Chem., 80, 361 (1980).
E.M. Kosower and J.W. Patton, Tetrahedron, 22, 2081 (1966).
H. Chaimovich, M.J. Politi, J.B.S. Bonilha and F.H. Quina, J. Phys. Chem., 83, 1951 (1979).
H. Chaimovich, R.M.V. Aleixo, I.M. Cuccovia, D. Zanette and F.H. Quina. In “Solution Behaviour of Surfactants - Theoretical and Applied Aspects”, K.L. Mittal and E.J. Fendler, Eds. Plenum Press, New York (1981).
J. Th. G. Overbeek and D. Stigter, Ree. Trav. Chim., 75, 1263 (1956).
E.K. Rideal, Proc. Roy. Soc. (London) A209, 431 (1951); J.T. Davies and E.K. Rideal, ibid. A194, 417 (1948).
F.H. Quina and H. Chaimovich, J. Phys. Chem., 83, 1844 (1979).
L.S.Romsted, Ph.D. Thesis, Indiana University, Bloomington (1975).
K.Shinoda and T. Soda, J. Phys. Chem., 67, 2072 (1963); P. Mukerjee, ibid., 66, 1733 (1962).
P.Mukerjee, J. Phys. Chem., 66, 943 (1962).
C.A.Bunton, K. Ohmenzetter and L. Sepúlveda, J. Phys. Chem., 81, 2000 (1977).
C.A.Bunton and L.S. Romsted, in “The Chemistry of Functional Groups”, Supplement B: “The Chemistry of Acid Derivatives”, Part 2, S. Patai, Ed. Wiley, New York (1979), p. 945.
Guthrie, J.P., Can. J. Chem., 51, 3494 (1973).
I.M. Cuccovia, Tese de Doutoramento, Instituto de Quimica, Universidade de São Paulo (1980).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1982 Plenum Press, New York
About this chapter
Cite this chapter
Quina, F.H., Politi, M.J., Cuccovia, I.M., Martins-Franchetti, S.M., Chaimovich, H. (1982). Alkaline Hydrolysis in Micellar Sodium Dodecyl Sulfate; The “Binding” of −OH to Anionic Micelles. In: Mittal, K.L., Fendler, E.J. (eds) Solution Behavior of Surfactants. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-3494-1_25
Download citation
DOI: https://doi.org/10.1007/978-1-4613-3494-1_25
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4613-3496-5
Online ISBN: 978-1-4613-3494-1
eBook Packages: Springer Book Archive