Kinetic Concepts in Reversed Micellar Systems

O’Connor, Charmian J.; Lomax, Terence D.; Ramage, Robyn E.

doi:10.1007/978-1-4613-3494-1_4

Cited by 1 publication

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“…4 As can be observed in Figures 1 and 2, the respective k obs in the reverse micelles are at the most twice or three times higher than in pure n-hexane for the same amine concentration. The plots in Figures 1 and 2 are characteristic for bimolecular reactions, 24 that is, the rate of the reaction goes through a maximum in micelles.…”

Section: Effects Of Aot Concentrationmentioning

confidence: 99%

Kinetics and mechanism for the reaction of 1-chloro-2,4-dinitrobenzene with n-butylamine and piperidine in AOT/n-hexane/water reverse micelles

Zingaretti¹,

Boscatto²,

Chiacchiera³

et al. 2003

Arkivoc

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The kinetic profile of the S N Ar reaction of 1-chloro-2,4-dinitrobenzene with n-butylamine and piperidine in AOT/n-hexane/water reverse micelles were investigated as a function of variables such as AOT and amine concentration and the amount of water dispersed in the reverse micelles,The reactions in the micellar medium are faster than in the pure solvent. The pseudo-first order rate constants of the reactions go through a maximum when the AOT concentration is increased. Micellar interface saturation and no further micellar catalysis occurs at c.a. 0.1M of AOT. At higher AOT concentration dilution of the reactants in the micelles is the responsible of the rate decrease. In micellar medium a significant lost in the catalysis is observed compare with pure n-hexane. Thus, the reactions effectively take place at the interface of the aggregates. The kinetic behavior can be quantitatively explained taking into account the distribution of the substrate and the nucleophile between the bulk solvent and the micelle interface. A plausible mechanism to explain the results is proposed. Both the reactants distribution constants, between the micellar pseudo-phase and organic solvent, and the intrinsic second-order rate coefficients of S N Ar reactions in the interface were evaluated.

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Section: Effects Of Aot Concentrationmentioning

confidence: 99%