An electron spin resonance study of the reactions of hydrogen atoms with halocarbons

1986 ◽  
Vol 64 (11) ◽  
pp. 2192-2195 ◽  
Author(s):  
William E. Jones ◽  
Joseph L. Ma

The absolute rate constants for the reaction of H atoms with methyl- and vinyl-halides have been determined using esr spectroscopy and a conventional gas flow system. The rate constants determined at 298 ± 2 K at a pressure of 0.55 Torr are methane, (1.7 ± 0.3) × 10−17; ethane, (2.3 ± 0.5) × 10−17; methylfluoride, (4 ± 3) × 10−15; methylchloride, (8 ± 2) × 10−16; methylbromide, (2.1 ± 0.6) × 10−14; vinylfluoride, (1.47 ± 0.02) × 10−13; vinylchloride, (1.66 ± 0.08) × 10−13; and vinylbromide (4.07 ± 0.73) × 10−13 in units of cm3 molecule−1 s−1.


1972 ◽  
Vol 50 (14) ◽  
pp. 2374-2377 ◽  
Author(s):  
J. A. Howard ◽  
J. E. Bennett

Absolute rate constants for the self-reaction of cyclopentylperoxy, cyclopentenylperoxy, and sec-butylperoxyradicals have been determined over a 125 °C temperature range. Arrhenius plots derived from these rate constants suggest that the mechanism for this reaction is more complex than the currently accepted Russell mechanism.



1980 ◽  
Vol 58 (7) ◽  
pp. 677-680 ◽  
Author(s):  
Edward Furimsky ◽  
James A. Howard ◽  
Jennifer Selwyn

Isopropylperoxy radicals at low temperatures exist in equilibrium with di-isopropyl tetroxide. The thermodynamic parameters for this equilibrium are very similar to the values of ΔH0 and ΔS0 for the tert-butylperoxy radical – di-tert-butyl tetroxide equilibrium. Differences in second-order rate constants for mutual destruction of secondary and tertiary alkylperoxy radical appear to result from differences in rate constants for unimolecular decomposition of secondary and tertiary alkyl tetroxides.Isopropylperoxy radicals have the same termination rate constant in the gas phase and in solution.





1975 ◽  
Vol 53 (16) ◽  
pp. 2361-2364 ◽  
Author(s):  
John Charles Tait ◽  
James Anthony Howard

A kinetic electron spin resonance study of the self-reaction of SF5 and a spectroscopic and kinetic e.s.r. study of the reaction of SF5 with 1,1-di-t-butylethylene are reported. This radical undergoes self-reaction by a second-order process and the rate constants are given by the Arrhenius equation log 2k1(M−1 s−1) = (10.3 ± 0.5) − (1.7 ± 0.5)/θ where θ = 2.303RT kcal mol−1. It adds to 1,1-di-t-butylethylene to give (t-Bu)2CCH2SF5 which decomposes by a first-order process with rate constants that obey the expression log k2(s−1) = (13 ± 0.4) − (10 ± 0.2)/θ. Both these rate constants are pertinent to kinetic studies of the photoinduced addition of SF5C1 to olefins.



1973 ◽  
Vol 46 (5) ◽  
pp. 1134-1155 ◽  
Author(s):  
J. C. Westfahl

Abstract Oxidation of a series of phenolic antioxidants, or compounds related to antioxidants, was carried out using ferricyanide ion in dimethylsulfoxide solution. The free radicals produced were studied by ESR spectroscopy. Most of the antioxidants examined contained one or more 3,5-di-tert-butyl-4-hy-droxybenzyl groups. Based on their behavior on oxidation, the compounds can be divided into two classes. One class forms a relatively unstable primary radical which decomposes to give 2,6-di-tert-butyl quinone methide.



1975 ◽  
Vol 53 (5) ◽  
pp. 623-627 ◽  
Author(s):  
J. H. B. Chenier ◽  
J. A. Howard

A kinetic electron spin resonance spectroscopic study of the reaction of tertiary alkylperoxy radicals with α-tetralin hydroperoxide is reported. The absolute rate constants for this hydrogen atom transfer process (k1) are given by the equation log (k1/M−1 s−1) = (6.0 ± 0.5 ) − (4.5 ± 0.5 )/θ, where θ = 2.303 RT kcal mol−1.A significant isotope effect is obtained when the hydroperoxidic hydrogen is replaced by deuterium, e.g. k1H/k1D at 21° = 9.Other alkyl hydroperoxides, e.g. triphenylmethyl, s-butyl, and 9,10-dihydro-9-anthracyl have approximately the same reactivity to t-ROO• as α-C10H11OOH.



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