Kinetic study of the photochlorination of 2,3-dimethylbutane and other alkanes in solution in the presence of benzene. First measurements of the absolute rate constants for hydrogen abstraction by the "free" chlorine atom and the chlorine atom-benzene .pi.-complex. Identification of these two species as the only hydrogen abstractors in these systems

1985 ◽  
Vol 107 (19) ◽  
pp. 5464-5472 ◽  
Author(s):  
Nigel J. Bunce ◽  
Keith U. Ingold ◽  
James P. Landers ◽  
J. Lusztyk ◽  
J. C. Scaiano
Keyword(s):  
Kinetic Study ◽  
Chlorine Atom ◽  
Rate Constants ◽  
Hydrogen Abstraction ◽  
Free Chlorine ◽  
Absolute Rate ◽  
Pi Complex ◽  
The Absolute

The reactions of O(3P) with 2-propanone, 2-butanone, and 3-pentanone

1986 ◽  
Vol 64 (7) ◽  
pp. 1408-1414 ◽  
Author(s):  
John M. Roscoe
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Substrate Concentration ◽  
Activation Energies ◽  
Absolute Rate ◽  
The Absolute

The reactions of O(3P) with 2-propanone, 2-butanone, and 3-pentanone have been studied kinetically as a function of temperature and substrate concentration. The absolute rate constants for these reactions in the gas phase, in the units M−1 s−1, obey the following relations.[Formula: see text]The activation energies for these reactions are comparable to those for the reactions of O(3P) with alcohols, but the preexponential factors for the reactions of O(3P) with these ketones are significantly smaller than those for the analogous reactions with alcohols. The available data indicate that the reactivity of O(3P) toward ketones shows a variation with polar effects of substituents which is similar to that found for the reactions of OH with ketones.

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