Kinetic study of the reactions of tert-butyl radicals in the liquid phase in the presence and absence of oxygen

1996 ◽  
Vol 92 (19) ◽  
pp. 3497 ◽  
Author(s):  
Andrew R. Costello ◽  
John R. Lindsay Smith ◽  
Moray S. Stark ◽  
David J. Waddington
1981 ◽  
Vol 46 (8) ◽  
pp. 1941-1946 ◽  
Author(s):  
Karel Setínek

A series of differently crosslinked macroporous 2,3-epoxypropyl methacrylate-ethylenedimethacrylate copolymers with chemically bonded propylsulphonic acid groups were used as catalysts for the kinetic study of reesterification of ethyl acetate by n-propanol in the liquid phase at 52 °C and in the gas phase at 90 °C. Analysis of kinetic data by the method of nonlinear regression for a series of equations of the Langmuir-Hinshelwood type showed that kinetic equations which describe best the course of the reaction are the same as for the earlier studied sulphonated macroporous styrene-divinylbenzene copolymers. Compared types of catalysts differ, however, in the dependence of their activity on the degree of crosslinking of the copolymer used.


1994 ◽  
Vol 49 (24) ◽  
pp. 4563-4578 ◽  
Author(s):  
David Parra ◽  
Javier Tejero ◽  
Fidel Cunill ◽  
Montserrat Iborra ◽  
José F. Izquierdo

1989 ◽  
Vol 67 (2) ◽  
pp. 245-249 ◽  
Author(s):  
Hayder A. Zahalka ◽  
Yoel Sasson

Kinetic data are reported regarding the esterification of 1,4-dichlorobutane with sodium formate catalyzed by quaternary ammonium salts as a model for reactions in series, under solid–liquid phase transfer conditions. The process was found to follow a consecutive first-order mechanism of the general type A → R → S. The reactivity of the quaternary ammonium salts with regard to the counteranion was Cl− > Br− > 1− > HSO4−. The reaction rate was linearly dependent on catalyst concentration up to 12 mol% of catalyst relative to the substrate. Above this concentration the rate was constant and independent of the amount of the catalyst. The activation energy of the two consecutive steps was found to be similar (21 kcal/mol). Therefore, the product distribution (R/S) is not appreciably affected by temperature. A mechanism termed "Thin aqueous boundary layer" is suggested for nucleophilic displacement reactions under solid–liquid phase transfer conditions. Keywords: phase transfer catalysis, series reactions, kinetic study.


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