Irradiation temperature effects on hydrogen atom reactions upon radiolysis and photolysis at 4.2 and 77 K of neopentane containing various additives as studied by electron spin resonance

1979 ◽  
Vol 83 (12) ◽  
pp. 1590-1596 ◽  
Author(s):  
M. Iwasaki ◽  
H. Muto ◽  
K. Toriyama ◽  
M. Fukaya ◽  
K. Nunome
Keyword(s):  
Electron Spin Resonance ◽  
Hydrogen Atom ◽  
Electron Spin ◽  
Temperature Effects ◽  
Irradiation Temperature ◽  
Spin Resonance

An Electron Spin Resonance Study of Hydrogen Atom Reactions with Butenes Trapped in Aqueous Sulfuric Acid Glasses

1974 ◽  
Vol 52 (19) ◽  
pp. 3410-3414 ◽  
Author(s):  
Howard Reginald Falle ◽  
Frederick Peter Sargent
Keyword(s):  
Electron Spin Resonance ◽  
Sulfuric Acid ◽  
Hydrogen Atom ◽  
Electron Spin ◽  
Qualitative Agreement ◽  
Electron Spin Resonance Study ◽  
Torsional Motion ◽  
Spin Resonance ◽  
Percentage Ratio ◽  
Spin Resonance Study

Hydrogen atom reactions with butenes trapped in sulfuric acid glasses yield sec-butyl radicals by addition and methallyl radicals by abstraction. The character of the e.s.r. spectra due to the CH3ĊHCH2CH3 radicals depends on whether cis-2-butene or trans-2-butene was the precursor. Computer simulated spectra indicate that the most probable conformation for the CH3ĊHCH2CH3 radicals derived from cis-2-butene and trans-2-butene are 'oblique' and 'trans', respectively. Qualitative agreement between the simulated and experimental spectra is achieved by adding together the spectra computed for CH3ĊHCH2CH3 and [Formula: see text] in the percentage ratio 40:60. In computing the spectra for CH3ĊHCH2CH3, it is assumed that the radicals are distributed over a range of conformations and can undergo torsional motion.

A Kinetic Electron Spin Resonance Study of the Transfer of a Hydrogen Atom from α-Tetralin Hydroperoxide to a Tertiary Alkylperoxy Radical

1975 ◽  
Vol 53 (5) ◽  
pp. 623-627 ◽  
Author(s):  
J. H. B. Chenier ◽  
J. A. Howard
Keyword(s):  
Electron Spin Resonance ◽  
Hydrogen Atom ◽  
Electron Spin ◽  
Hydrogen Atom Transfer ◽  
Electron Spin Resonance Study ◽  
Absolute Rate ◽  
Alkyl Hydroperoxides ◽  
Spin Resonance ◽  
Alkylperoxy Radicals ◽  
Spin Resonance Study

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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