The Effect of Moderators on the Reactions of Hot Hydrogen Atoms with Methane

Estrup, P. J.; Wolfgang, Richard

doi:10.1021/ja01496a001

Cited by 59 publications

(38 citation statements)

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“…Excellent agreement between theory and experiment has been obtained for the energetic reactions of tritium with methane (9) and with other compounds (10). However, the assumption that the important recoil processes in condensed phases can be des cribed by billiard ball mechanics appears to be incorrect.…”

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confidence: 89%

Recoil chemistry of carbon-11 in liquid hydrocarbons

Clark

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confidence: 89%

Recoil chemistry of carbon-11 in liquid hydrocarbons

Clark

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“…Previous gas-phase experiments have led to a hypothesis for the reactions of highenergy recoil atoms with hydrocarbons that is able to explain the observed effects quite satisfactorily (1)(2)(3)(4)(5)(6)(7)(8)(9). The most iinportailt characteristics of this hypothesis are that the tritium atoms react (a) as neutral atoms-the predominailt charge state for a n~oviiig hydrogen nucleus a t energies froin 10'ev down; (b) \\~hile possessing kinetic energy greatly in escess of average therinal energies, and hence are able to both react in a very few collisions and to undergo reactions that are highly endotherinic and/or have high activation energies.…”

Section: Tritium Reactions At High Kinetic Energymentioning

confidence: 99%

“…In pure cyclopropane, abstraction, reactions such as [4] and [5] are the only important reactions that can occur for H atoms or radicals, except recombination as in [GI.…”

Section: Reactions Of Hydrogen Atoms and Radicalsmentioning

confidence: 99%

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Hot Atom Reactions and Radiation-Induced Effects in the Reactions of Recoil Tritium With Cyclopropane

Lee¹,

Musgrave²,

Rowland³

1960

Can. J. Chem.

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Recoil He3 (71, p) tritium atoms have been reacted with cyclopropane in the gas phase under a variety of experimental conditions. The labeled hydrocarbon and molecular hydrogerl products have been separated by gas chromatography and assayed by gas proportional counting.The obser\;ed products show a strong dependence upon irradiation dose-cyclopropane is very inert to\\ra~-cl reactions with hydrogen atoms and organic radicals, and the labeled olefinic products react preferentially, in effect as scavengers, \vith the reactive species from radiolysis of the parent molecule.Energetic tritium atoms are able to react \\.ith cyclopropane to give labeled cyclopropane a s a product without causing isonierization or decomposition of the molecule. The relative yields of cyclopropane and propylene are dcpendent LIPOII the average collisional de-excitation times, indicating that a fraction of the labeled cyclopropane molecules are decomposing in times of approxirnatel), 10-"seconds. Cyclopropane, propylene, ethylene, hydrogen, and srnall amounts of allene and methylacetylene are observed as "hot" products in the presence of gaseous free radical scavengers. Many additional compounds are found as the result of free radical and/or radiolysis reactions in the absence of scavengers.The "hot" reactions are explained in terms of the single-step interactions of high kinetic energy tritium atorns with the c).clopropane molecules-the energy for endothermic and high activation energy processes is obtained from the recoil energy. The kinetic energy of the recoil atom a t reaction is estimated to be of the order oc 130 Itcal/mole for some of the observed labeled compo~~nds.

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“…NMR spectra of the 1,2-diiodopentane 138 28. NMR spectra of pure cis-2-pentene 139 29. NMR spectra of dl-2,3-diiodopentane I 210 30.…”

Section: Comparison Of the Relative Sensitivities Of The Wolfmentioning

confidence: 99%