Ionic Intermediates in γ-Irradiated Organic Glasses at - 196°

Guarino, John P.; Hamill, William H.

doi:10.1021/ja01059a006

Cited by 87 publications

(21 citation statements)

References 2 publications

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“…The polystyrene cell contributes an absorption band with a maximum at 410nm at room temperature39) The spectrum observed at 77K with ~G =0.91 x104 was similar to that of Ref. 8 (0.83 × 104 at room temperature at 60 ns).…”

supporting

confidence: 72%

Inverted micelles of AOT as electron scavengers in 3-MP at 77 K in the absence and presence of water

Heijman

Horikx

Nauta

et al. 1984

Radiation Physics and Chemistry (1977)

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Abstract--Pulse radiolysis of bis (2-ethylhexyl)sulfosuccinate (AOT) solutions in 3 methylpentane (3 MP) at 77 K leads to the formation of a species absorbing at around 450 nm. This absorption is believed to result from the scavenging of electrons by AOT inverted micelles. The electron scavenging capacities of an AOT solution depend on the aggregation number of the micelles. The addition of water leads to less et~cient electron capture which is explained by an increase of the aggregation number. This increase is of the same order of magnitude as measured by other techniques at room temperature.

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supporting

confidence: 72%

Inverted micelles of AOT as electron scavengers in 3-MP at 77 K in the absence and presence of water

Heijman

Horikx

Nauta

et al. 1984

Radiation Physics and Chemistry (1977)

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“…Froin this they assumed that in the absence of solute, G(trapped electron) was approximately 3.0. They estimated a minimum oscillator strength f 0.8 for trapped electrons in MTI-IF (3). f is expected to be close t o unity and has been found to eclual O.S to 0.9 for F centers in alkali halides (4).…”

Section: Introductionmentioning

confidence: 97%

Electron Spin Resonance Determination of the Radiolytic Yields of Trapped Electrons and Other Species in an Organic Glass

Smith¹,

Pieroni²

1965

Can. J. Chem.

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The radiolytic yields, a t liquid nitrogen temperature, of trapped electrons and radicals or radical-ions in 2-methyltetrahydrofuran and the yields of these species plus the biphenyl anion in solutions containing biphenyl have been determined by e.s.r. These measurements were also carried out after photolysis of the trapped electrons. The combined results are interpreted in terms of the identity of the intermediates and the reactions which they undergo. "Dual e.s.r. cavity" techniques have enabled greater accuracy and precision than is nor~nally obtained when concentrations of paramagnetic species are determined by e.s.r.

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“…Thermalized electrons can undergo dissociative capture with ethyl iodide and carbon tetrachloride (12,15,19,20) in the following reactions:…”

Section: Discussionmentioning

confidence: 99%

Radiolysis of ethyl iodide and carbon tetrachloride mixtures at 77°K

Leblanc¹,

Thyrion²,

Herman³

1968

Can. J. Chem.

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The radical yields of C2H5' and CCI,' observed by electron spin resonance of CCI4 + C,H51 mixtures irradiated by y rays at 77 "K are compared with yields of HCI, I,, and HI measured after thawing. The dissociative capture of thermalized electrons by CC14 is extremely effective and accounts for most of the observed radicals. The difference between yields of HC1 and CCI3' results from charge transfer from C2H51' to CC1,'. The formation of iodine proceeds both from neutralization processes of C1-ions with positive ions formed from C2H51, and from ion-molecule reactions.On compare les rendements radicalaires observes par la resonance tlectronique paramagnttique aux rendements en HCI, I, et H I observes apris rkchauffement de melanges de CC14 et de C2H51 soumls aux irradiations des rayons y. La capture d'electrons thermalids est tris efficace dans le cas du CC14 et fournit la plus grande partie des radicaux observts. L'Ccart entre les rendements en HCI et CCI,' est dii au transfert de charge que subit C2H51+ avecCCI,'. Les reactions de neutralisation de C1-avec une entit6 positive issue de C2H51 et les reactions ion-molCcule sont a la base de la production d'iode. IntroductionIt has been shown that some y-irradiated halogenated alkanes form anions efficiently by electron capture, as indicated by the corresponding visible and U.V. spectra of the ionic species in organic glasses at -196 O C (1). In the same way, Hamill and his co-workers (1) have established a scale of relative efficiency of electron capture for a whole series of solutes dissolved in suitable solvents; these measurements were based on competitive reaction abilities of solutes for thermalized electrons produced within the medium; however, they were confined to low solute concentrations.It seems worthwhile to extend such a study over a wider range of concentration in a mixture of two solutes chosen from the Hamill scale. However, at high concentration the technique of measuring the optical spectrum of organic glasses at 77 OK does not give sufficient precision, therefore another experimental approach was preferred: the e.s.r. spectrum of radicals in frozen solutions and the subsequent chemical analysis of reaction products enabled us to establish a reaction scheme in such a system. In addition, irradiation in the solid phase has the advantage of limiting the reactions, especially of formed products, by preventing diffusion of bulky fragments in the solid.

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Ionic Intermediates in γ-Irradiated Organic Glasses at - 196°

Cited by 87 publications

References 2 publications

Inverted micelles of AOT as electron scavengers in 3-MP at 77 K in the absence and presence of water

Inverted micelles of AOT as electron scavengers in 3-MP at 77 K in the absence and presence of water

Electron Spin Resonance Determination of the Radiolytic Yields of Trapped Electrons and Other Species in an Organic Glass

Radiolysis of ethyl iodide and carbon tetrachloride mixtures at 77°K

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