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Volumn 69, Issue 11, 2004, Pages 3899-3906

The nature of the micellar Stern region as studied by reaction kinetics. 2

Author keywords

[No Author keywords available]

Indexed keywords

AMMONIUM COMPOUNDS; BENZENE; HYDROPHOBICITY; PHENOLS; POSITIVE IONS; REACTION KINETICS;

EID: 2442692879     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049959l     Document Type: Article
Times cited : (22)

References (53)
  • 9
    • 2442665959 scopus 로고    scopus 로고
    • note
    • The difference between reaction rates and reaction rate constants should be noted. Due to compartmentalization, concentrations of reactants inside micelles can be higher so that, notwithstanding lower reaction rate constants, reaction rates can still be higher than observed in bulk water.
  • 10
    • 0032560981 scopus 로고    scopus 로고
    • Examples of surfactants equipped with catalytically active headgroups can be found among others in the following: (a) Otto, S.; Engberts, J. B. F. N. ; Kwak, J. C. T. J. Am. Chem. Soc. 1998, 120, 9517-9525.
    • (1998) J. Am. Chem. Soc. , vol.120 , pp. 9517-9525
    • Otto, S.1    Engberts, J.B.F.N.2    Kwak, J.C.T.3
  • 14
  • 26
    • 2442669704 scopus 로고    scopus 로고
    • note
    • c = 0). It should also be noted that micellar rate constants for substrates bound to spherical micelles can only be determined as long as the surfactant concentration is below the concentration at which wormlike micelles start to form. This poses an upper limit on the concentration range in which relevant results can be obtained.
  • 28
    • 0024298964 scopus 로고
    • Kraut, J. Science 1988, 242, 533-540.
    • (1988) Science , vol.242 , pp. 533-540
    • Kraut, J.1
  • 31
    • 2442648406 scopus 로고    scopus 로고
    • note
    • In our opinion, the conclusion in ref 25 that the rate-retarding effect brought about by the micelles is not a salt effect is unwarranted. The conclusion has been based on activation parameters of the reaction occurring in the micelle. However, these activation parameters will include effects of the thermodynamics of micellization changing with temperature.
  • 33
    • 0346306014 scopus 로고    scopus 로고
    • Recently, similar attempts at including both "headgroup mimics" and "tail mimics" in model solutions for the micellar Stern region have been made. However, these tertiary solutions either (i) do not distinguish between the rate effects of headgroup mimic and tail mimic (refs 25 and 40) or (ii) seem to reproduce the rate of a single reaction only (Tada, E. B.; Ouarti, N.; Silva, P. L.; Blagoeva, I. B.; El Seoud, O. A.; Ruasse, M.-F. Langmuir 2003, 19, 10666-10672).
    • (2003) Langmuir , vol.19 , pp. 10666-10672
    • Tada, E.B.1    Ouarti, N.2    Silva, P.L.3    Blagoeva, I.B.4    El Seoud, O.A.5    Ruasse, M.-F.6
  • 35
    • 0002664833 scopus 로고
    • Chapman, N. B., Shorter, J., Eds.; Plenum: London
    • Exner, O. In Correlation Analysis in Chemistry; Chapman, N. B., Shorter, J., Eds.; Plenum: London, 1978; pp 439-540.
    • (1978) Correlation Analysis in Chemistry , pp. 439-540
    • Exner, O.1
  • 37
    • 0034677585 scopus 로고    scopus 로고
    • Hydrophobic interactions are rather dependent on size and shape of the hydrophobic (parts of) molecules involved; see e.g.: Southall, N. T.; Dill, K. A. J. Phys. Chem. B 2000, 104, 1326-1331. We therefore restricted our choice of alcohols for our mimicking solution to linear alcohols. The actual choice of linear alcohol is expected to be unimportant as all short-chain linear alcohols retard the hydrolysis reactions of activated amides in similar ways following an additivity scheme (see ref 35 and the following: Buurma, N. J.; Pastorello, L.; Blandamer, M. J.; Engberts, J. B. F. N. J. Am. Chem. Soc. 2001, 123, 11848-11853).
    • (2000) J. Phys. Chem. B , vol.104 , pp. 1326-1331
    • Southall, N.T.1    Dill, K.A.2
  • 38
    • 0035814371 scopus 로고    scopus 로고
    • Hydrophobic interactions are rather dependent on size and shape of the hydrophobic (parts of) molecules involved; see e.g.: Southall, N. T.; Dill, K. A. J. Phys. Chem. B 2000, 104, 1326-1331. We therefore restricted our choice of alcohols for our mimicking solution to linear alcohols. The actual choice of linear alcohol is expected to be unimportant as all short-chain linear alcohols retard the hydrolysis reactions of activated amides in similar ways following an additivity scheme (see ref 35 and the following: Buurma, N. J.; Pastorello, L.; Blandamer, M. J.; Engberts, J. B. F. N. J. Am. Chem. Soc. 2001, 123, 11848-11853).
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 11848-11853
    • Buurma, N.J.1    Pastorello, L.2    Blandamer, M.J.3    Engberts, J.B.F.N.4
  • 44
    • 2442658503 scopus 로고    scopus 로고
    • note
    • The 1-propanolysis of 1a-f is expected to make a negligible contribution to the observed rate constants (see ref 35).
  • 49
    • 2442643378 scopus 로고    scopus 로고
    • note
    • It is expected that the micellar rate constants as reported in refs 40 and 41 will be reasonably well reproduced by the model solutions reported here. This is expected because water concentrations are less than 30 M in all the presented model solutions.
  • 50
    • 2442670994 scopus 로고    scopus 로고
    • note
    • T(30) probe can be used mainly for the interactions with the alkyl tails whereas le is mainly suitable for the interactions with the ionic headgroups. This results in a 2 x 2 matrix with one row strongly dependent on TMAB molality and one row mainly dependent on 1-propanol molality, yielding a reasonable first indication of the Stern region as a reaction medium.


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