Radical Production in the Radiolysis of the Hydrocarbons

Weber, Edward N.; Forsyth, Paul F.; Schüler, Robert H.

doi:10.2307/3570273

Cited by 54 publications

(18 citation statements)

References 11 publications

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“…Other pertinent yields for the same system include a total G of 3.3 Tor sec-hexyl and n-hexyl iodide formation 16 and an iodine uptake, G(--Tz), of 3.8 measured by Schuler and co-workers. 25 3. BRANCHED HYDROCARBONS A discussion of reaction (1.2) in branched compounds can be illustrated for the quaternary substituted carbon atom in neopentane and neohexane (2.2dimethyl-butane).…”

Section: +Hzmentioning

confidence: 99%

Correlation of the radiation chemistry of liquid hydrocarbons with the energetics of molecular-ion reactions

Williams¹

1961

Trans. Faraday Soc.

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Exothermic reactions involving alkane parent ions are considered to precede the neutralization process in the liquid state. Thermochemical calculations show that carbon-carbon scission is energetically preferred for branched alkane ions whereas the corresponding dissociation of linear hydrocarbon ions is less favoured. Hydrogenatom detachment from a parent ion is not a facile process but the removal of molecular hydrogen to produce an olefin ion is exothermic in trans-vinylene group formation. A reaction of the parent ion with a molecule is often exothermic and can lead to dimer formation. These considerations afford a rational basis for the interpretation of the radiation chemistry of hydrocarbons as a function of molecular structure ; an explanation is derived for the occurrence of either cross-linking or degradation in irradiated vinyl polymers.

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Section: +Hzmentioning

confidence: 99%

Correlation of the radiation chemistry of liquid hydrocarbons with the energetics of molecular-ion reactions

Williams¹

1961

Trans. Faraday Soc.

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“…Depending upon conditions, each variable can have important effects in radiation chemistry A L T H O U G H the radiation chemistry of hydrocarbons has been studied in some detail at relatively low temperatures (6,8,79,24), corresponding studies have not been reported at high temperatures. The effects of radiation intensity have been studied by comparing cobalt-60 radiation with the mixed radiation from the Brookhaven atomic reactor.…”

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confidence: 99%

High Temperature Radiation Chemistry of Hydrocarbons

Lucchesi¹,

Tarmy²,

Long³

et al. 1958

Ind. Eng. Chem.

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An experimental study of the cracking of hydrocarbons initiated by nuclear radiation emphasizes effect of such process variables as temperature, feed composition, and phase. The effects of radiation intensity have been studied by comparing cobalt-60 radiation with the mixed radiation from the Brookhaven atomic reactor.Depending upon conditions, each variable can have important effects in radiation chemistry.A-Lthough the radiation chemistry of hydrocarbons has been studied in some detail at relatively low temperatures (6, 8, 19, 24), corresponding studies have not been reported at high temperatures. This lack of data contrasts with the situation in photochemistry, where hydrocarbons have been studied over a wide temperature range (18). Data on high temperature effects of radiation-i.e., near or at incipient cracking conditions-are of general theoretical and great practical interest because they give insight into the possible utility of nuclear radiation for commercial processes. ExperimentalRadiation Sources. Most of the experiments reported were done in the cobalt-60 radiation laboratory at the Esso Research Center, Linden, N. J.(2). The radiation from the 3200-curie source is pure gamma radiation from cobalt-60 (1.17 and 1.33 m.e.v. per disintegration); and a small beta contribution (0.31 m.e.v. per disintegration), with a 5.26-year decay half life ( 16).The graphite-moderated reactor at Brookhaven National Laboratory was used as the source of high intensity, mixed pile radiation (4). One of the available experimental holes (W-45) was used for the experiments.Radiation Intensities and Dosimetry. The cobalt-60 source consists of a hollow cylinder of cobalt, 13.5 inches long and 3 inches in outside diameter (l8/4 inches in inside diameter), encased in an aluminum shell. The source strength as of June 28, 1955, was 3130 curies.The radiation intensities at various distances from the axis of the source were obtained by calculation using the standard "point source" and standard "pipe source" calculation ( 22), and by actual measurement. The dose ratedistance relationship was determined experimentally, iron(II-III) dosimetry as

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“…The very low hydrogen yields from pure C 6 H 6 may be due mainly to failure to split off hydrogen atoms, rather than to rapid reaction with them. The yield of radicals from C 6 H 6 detected by ordinary methods is somewhat low; G =0.33–0.89 by iodine [ 47 ] and DPPH disappearance [ 40 ]. Possibly it is also of about this same magnitude in mixtures where C 6 H 6 exhibits a protective effect.…”

Section: Resultsmentioning

confidence: 99%

Gamma irradiation of hexafluorobenzene

Florin¹,

Wall²,

Brown³

1960

J. RES. NATL. BUR. STAN. SECT. A.

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Mi xt ures of hexafluo robenze ne a,nd benze ne were irra di ated in li quid phase by means of a C060 cram ma o urce at 20° a nd a t '2 18° C. P crfiuoro hep tane a nd va ri ous b inar.v mix t ures involvi~g perflu o roh epta nc, h exaflu or obe ll ze ne, be nze ne, a nd cyclo hexane were a lso in'ad iated at 20° C. H exafluorob e nzene rese mb led benze ne ve ry closely in its behav ior up o n r a dio \ys is. Ge nerall y t he fluor oc arbon-h ydrocarbon mix t ur es evolved mu ch mo rc SiF4 (indi cat in g th e form at ion of J-IF, which r eac ts with th e glass vesse l) than th e pure flu orocarbon co mpon ents. The polym er from hexaflu o robe nze ne-benzrne mixtures was p r oba~ly ri ch in cyclohexadi ene a nd cycloh exe ne un its , I'cse mbiin g t hat from pu re benzene, a nd Its co mposition rat io exhib ited a strong "alte rn at in g" te nd e ncy. Th e res ults a re di scussed in te rms of fr ee-radi cal and excited-state mechanisms. r\ t 218 0 C hexaflu o robenzene a nd a lso its mixtures with benze ne showed qua litat ive difl'erences from th eir beha vior a t 20° C, a ltho ug h t he G va lues for SiF4 and p o lymer rema in ed mode rat e.

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Radical Production in the Radiolysis of the Hydrocarbons

Cited by 54 publications

References 11 publications

Correlation of the radiation chemistry of liquid hydrocarbons with the energetics of molecular-ion reactions

Correlation of the radiation chemistry of liquid hydrocarbons with the energetics of molecular-ion reactions

High Temperature Radiation Chemistry of Hydrocarbons

Gamma irradiation of hexafluorobenzene

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