HYDROGEN FORMATION IN THE RADIOLYSIS OF TOLUENE<sup>1</sup>

Ingalls, R. B.

doi:10.1021/j100905a031

Cited by 15 publications

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“…Only a small number of H• atoms contribute to the H 2 yield in the case of benzene and its derivatives, since H• atoms readily add to the aromatic ring . Irradiation of toluene and its deuterated analogues demonstrates that the H 2 is formed from the H• atoms of both the side-chain and the aromatic ring . However, the contribution of the toluene methyl group to H 2 formation is greater than that of the aromatic moiety.…”

Section: Resultsmentioning

confidence: 98%

“…44 Irradiation of toluene and its deuterated analogues demonstrates that the H 2 is formed from the H• atoms of both the side-chain and the aromatic ring. 45 However, the contribution of the toluene methyl group to H 2 formation is greater than that of the aromatic moiety. Unimolecular processes account for about 38% of H 2 formed from the ring, while 62% is due to bimolecular reactions.…”

Section: ' Results and Discussionmentioning

confidence: 99%

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Role of the Low-Energy Excited States in the Radiolysis of Aromatic Liquids

2011

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The contribution of the low-energy excited states to the overall product formation in the radiolysis of simple aromatic liquids--benzene, pyridine, toluene, and aniline--has been examined by comparison of product yields obtained in UV-photolysis and in γ-radiolysis. In photolysis, these electronic excited states were selectively populated using UV-light excitation sources with various energies. Yields of molecular hydrogen and of "dimers" (biphenyl, bibenzyl, dipyridyl for benzene, toluene, pyridine, respectively, and of ammonia and diphenylamine for aniline) have been determined, since they are the most abundant radiolytic products. Negligibly small production of molecular hydrogen in the UV-photolysis of aromatic liquids with excitation to energies of 4.88, 5.41, 5.79, and 6.70 eV and the lack of a scavenger effect suggest that this product originates from short-lived high-energy singlet states. A significant reduction in "dimer" radiation-chemical yields in the presence of scavengers such as anthracene or naphthalene indicates that the triplet excited states are important precursors to these products. The results for toluene and aniline suggest that efficient dissociation from the lowest-energy excited triplet state leads to noticeable "dimer" production. For benzene and pyridine, the lowest-energy triplet excited states are not likely to fragment into radicals because of the relatively large energy gap between the excited state level and corresponding bond dissociation energy. The "dimer" formation in the radiolysis of benzene and pyridine is likely to involve short-lived high-energy triplet states.

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Section: Resultsmentioning

confidence: 98%

Section: ' Results and Discussionmentioning

confidence: 99%

Role of the Low-Energy Excited States in the Radiolysis of Aromatic Liquids

2011

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“…+ H-] -H2 + C8H8 (1) the possibility of the reaction occurring in two stages being included in equation 1, in which the brackets enclose species which have not been separated by diffusion from the solvent cage in which they were formed. However, in the liquid state the majority of the H2 is produced by bimolecular reactions of the excited molecules, reaction 4 Moreover, the experimental results make it necessary to assume that the excited molecules do not react with radical scavengers. On passing from liquid to solid p-xylene Oh, decreases sharply to a value which varies slightly with temperature.…”

Section: Fig 2•-mentioning

confidence: 99%

“…Activity coefficients for MgCl2 and KC1 calculated from the partial pressures of MgCl2 monomer and KC1 monomer30 are shown in Fig. 4. The agreement with the results of other investigators15-20 for MgCl2 in the liquid composition range 0 to 42.9 mole % KC1 is better than 10% while the activity coefficients calculated for KC1 in the range 67.2 to 100 mole % KC1 agree to better than 5% with previously reported results.15•17 In Table IV the activities obtained at 1075°are compared (30) I. Prigogine and R. Defay, "Chemical Thermodynamics," Longmans, Green and Company, London, 1954, p. 410. with those computed from the model of Flood and Urnes.21 It appears from the above comparisons that the proposed vapor phase model leads to activities which are in substantial agreement with other work.…”

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confidence: 99%

The Radiolysis of the Xylene Isomers and Ethylbenzene

Verdin¹

1963

J. Phys. Chem.

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The G-values f o r the formatLon of H2 and CH4 in tne 6 0~o y-radiolysis of the xylene isomers and ethylbenzene have been compared. The presence of iodine does not a f f e c t OH2, but reduces GCH4 t o a limiting value. Por p-xylene %2 and the unscavengeable CH4 yield a r e independent of temperature from 20' t o 1 1 0 ' C, whereas the t o t a l CH4 yield increases s i x f o l d over thds range. The H2 and CH4 yields a r e greatly reduced i n t h e solid s t a t e , and i n the liquid s t a t e benzene shows a protective effect on the wields of both gases. The formation of CH4 and C2 -hydrocarldbns was c o~. with the C6 -and C, -products f o r p-xylene and ethylbenzene, and isom,:isation has been shown t o occur t o a negligible exte:.~. The production of high molecular weight products was measured f o r the xylenes, and i s independent of dose r a t e and temperature f o r liquid p-xylene, but i s decreased i n t h e s o l i d s t a t e . The r e s u l t s are q u a l i t a t i v e l y consistent with the reactions of radicals and exc i t e d molecules. L E G A L N O T I C E

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“…Die vorliegenden Messresultate, die an Mischungen von Benzol mit Toluol und ihren Deuteroverbindungen erhalten wurden, sollen abklaren, inwiefern diese Hypothese auch differenziertcren Versuchsbedingungen standhalt und inwiemeit andere Iieaktionsmoglichkeiten ausgeschlossen werden konnen. Toluol werden nach INCALLS 24% des Wasserstoffs in solchen Reaktionen gebil-det[6]. Will man die Analyse der Dimerprodukte als Informationsquelle beziiglich strahlungschemisch induzierter Prozesse verwendcn, so muss festgestellt werden, ob diese Produkte nicht iiber Reaktionen primar gebildeter Molekeln vom Benzyn-Typus entstehen.…”

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Strahlungschemie der Kohlenwasserstoffe. 12. Mitteilung. Benzol‐Toluol und deuterierte Verbindungen

Hoigné

Gäumann

1964

Helvetica Chimica Acta

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Further information on the radiation chemistry of aromatic liquids has been obtained by a detailed analysis applied mainly to the dimeric products formed by the gamma irradiation of mixtures of benzeneltoluene and their deutero‐compounds (benzene‐d6toluene‐d0 and benzene‐d0/toluene‐α‐d3). The diphenylmethane‐type of molecules are not formed by a reaction of dehydroaromatic species (benzyne). The different products are generally produced according the expected mixture law when corrections for the competing chemical reactions are allowed for. In the perdeutero‐benzenel/toluene system however an energy transfer from benzene‐d6, to toluene must be postulated to explain the yields obtained. The isomer distribution of the three phenyltoluenes can be compared with the statistical values.

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HYDROGEN FORMATION IN THE RADIOLYSIS OF TOLUENE¹

Cited by 15 publications

References 0 publications

Role of the Low-Energy Excited States in the Radiolysis of Aromatic Liquids

Role of the Low-Energy Excited States in the Radiolysis of Aromatic Liquids

The Radiolysis of the Xylene Isomers and Ethylbenzene

Strahlungschemie der Kohlenwasserstoffe. 12. Mitteilung. Benzol‐Toluol und deuterierte Verbindungen

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HYDROGEN FORMATION IN THE RADIOLYSIS OF TOLUENE1

Cited by 15 publications

References 0 publications

Role of the Low-Energy Excited States in the Radiolysis of Aromatic Liquids

Role of the Low-Energy Excited States in the Radiolysis of Aromatic Liquids

The Radiolysis of the Xylene Isomers and Ethylbenzene

Strahlungschemie der Kohlenwasserstoffe. 12. Mitteilung. Benzol‐Toluol und deuterierte Verbindungen

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HYDROGEN FORMATION IN THE RADIOLYSIS OF TOLUENE¹