<b>Differences in Electron Spin Resonance Spectra and Annealing Characteristics of Radicals Produced in Polycrystalline and Glassy Alkyl Iodides by γ-Radiolysis</b>

Fenrick, Harold W.; Filseth, S.V.; Hanson, Allen L.; Willard, John E.

doi:10.1021/ja00906a003

Cited by 20 publications

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“…are identical with that observed by others (6,13) There is a significant difference between our and is attributed to the C2H ,' radical. The g facvalues and those of Arnikar and Willard (3) for tors being different for CC1,' and C2H; radithe yields of iodine and hydrogen iodide from cals, their e.s.r.…”

Section: Resultssupporting

confidence: 92%

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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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Section: Resultssupporting

confidence: 92%

“…For personal use only. duction in reactions [3] and [16] is equivalent to G(C2H5'), the excess of G(1) over G(C2H5') must result from the two other reactions [lo] and [13]. In the case of pure ethyl iodide, this excess can come only from reactions [lo] and [13b] and accounts for g(1) = G(I),,, -G(C,-H,') = 1.…”

Section: Iodine Formationmentioning

confidence: 99%

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

Leblanc¹,

Thyrion²,

Herman³

1968

Can. J. Chem.

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“…Although their measurement requires interaction of the salt with the porous separator, evidence has been presented in the case of PbCl2 to indicate independence of experimental results on the nature of the separator. 4 In that study the transference number of Clwas found to be within 1% of 0.75 for each of three different separators: an "ultrafine" porosity Pyrex frit (max pore diam, 0.9µ); apiece of unglazed porcelain; and a wad of asbestos fibers packed tightly between "coarse" porosity Pyrex frits.…”

Section: Double-layer Effect On "External Transportmentioning

confidence: 88%

Double-layer effect on "external transport numbers" in molten lead chloride

Laity¹,

Sjoblom²

1967

J. Phys. Chem.

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“…It is established, for example, that all of the glassy alkyl halides and some of the polycrystalline halides yield predominantly the radical which results from rupture of the carbon-halogen bond.38~39~40~41 The polycrystalline iodides with even number of C atoms do not yield significant amounts of this radical but give an esr signal indicating an iodine-containing y-Irradiation of straight chain paraffin hydrocarbon~42~~~~44 and radical . 39,40,41 …”

Section: Free Radical Reactionsmentioning

confidence: 99%

Generation and Study of Reaction Intermediates in Organic Solids

Willard

1969

Molecular Crystals

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This paper reviews : ( I ) methods by which bond rupture, and ionization, can be produced in organic solids; (2) methods of detecting trapped reaction intermediates ; (3) illustrative experiments dealing with the yields and the decay of trapped electrons and free radicals. Factors to be considered in deciding whether trapped electrons a d radicals decay by random reaction with potential reacting partners, by combination with sibling partners, or by combination with other predestined partners are discussed. It is shown that radical decay rates do not show consistent correlation with viscosity.

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Differences in Electron Spin Resonance Spectra and Annealing Characteristics of Radicals Produced in Polycrystalline and Glassy Alkyl Iodides by γ-Radiolysis

Cited by 20 publications

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

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

Double-layer effect on "external transport numbers" in molten lead chloride

Generation and Study of Reaction Intermediates in Organic Solids

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