Kinetics of isomerization of the free cis-stilbene radical anion into its trans isomer in hexamethylphosphoric triamide. Spectroscopic and electron spin resonance identification of cis-stilbene radical anion in tetrahydrofuran

1977 ◽  
Vol 99 (8) ◽  
pp. 2642-2647 ◽  
Author(s):  
H. C. Wang ◽  
G. Levin ◽  
M. Szwarc
1990 ◽  
Vol 68 (4) ◽  
pp. 640-643
Author(s):  
Mary Jane Walzak ◽  
John R. Harbour

Electron spin resonance spectroscopy (ESR) has been used to investigate the electrochemical and photolytic behaviour of particulate C.I. Pigment Red 122. Heterogeneous electrochemical reduction and oxidation of the pigment resulted in different reversible ESR signals with the radical cation giving a signal of ΔHpp = 2.3 G and g-factor of 2.0033 and the radical anion giving ΔHpp = 3.2 G and g-factor 2.0039. On exposure to light the inherent ESR signal, which was determined to be a two-component signal, increased in intensity by a factor of 2.4 but did not change in linewidth or g-factor. This light-induced signal was reversible and decayed to initial levels in the dark. The mechanism of these reactions is discussed. Keywords: ESR, pigment, electrochemistry, photo effects.


The electron spin resonance method was employed to study the nature, concentration and kinetics of the disappearance under varying conditions of radicals produced in polyethylene by fast electron irradiation at 77°K. The predominant radical species at 77°K is the alkyl radical —CH 2 —ĊH—CH 2 —. On being warmed to room temperature it disappears rapidly, revealing a more stable un­identified radical. The kinetics of the decay at room temperature of both radicals was observed. Their stabilities were found to vary in polyethylene samples of differing physical and chemical properties. G values for these radicals are given. Comparison was made with spectra obtained under similar conditions with two pure paraffins and a pure olefin to evaluate the effect of crystallinity branching, molecular weight and unsaturation. In the olefin there is evidence for a build-up of allyl radicals due to the encounter of an alkyl radical with main chain unsaturation. This supports the view that alkyl radicals are mobile, and cross-linking occurs when two such radicals meet.


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