The Reaction of Hydrogen Atoms with Solid Olefins at – 195°C

Klein, Ralph; Scheer, Milton D.

doi:10.1021/j150566a033

Cited by 41 publications

(18 citation statements)

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“…Firstly, the activation energy for H-atom abstraction by H atoms is sufficiently large (-7 kcal) (11) that this reaction could not occur a t 77 OK. We have, however, found that the bimolecular process giving H D does occur a t low temperatures. Further, Klein and Scheer (12) found that H atoms could diffuse rapidly a t 77 without reaction through a layer of aliphatic hydrocarbons -lo4 A thick. This would mean t h a t if thermal H atoms were reactive intermediates, RHD would be of this order.…”

Section: Discussionmentioning

confidence: 99%

The Ranges of Interactions in the Radiolysis of Solid Hydrocarbon Mixtures

Dyne¹,

Denhartog²

1966

Can. J. Chem.

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\Ve describe a novel technique for measuring the ranges of interaction in the radiolysis of hydrocarbon mixtures, e.g. the distance between donor and acceptor molecules in a n energy transfer process. Thin layers, 20 to 1000 A thick, of solid C-CGDI? sandwiched between other materials which activate or deactivate the hydrocarbon, are irrad~ated. The yields of DZ and H D are measured a s a function of the layer thickness. These yields change rapidly when the layer thickness is comparable with the range of the interaction.We find: (a) the activation of c -C~D I ? by n-C~H14 has a very short range consistent with a n ion-molecule reaction between nearest neighbor molecules; (b) the deactivation by CCI4 or benzene has a longer range (180 A or more) consistent with the average separation of positive ions and electrons in an irradiated hydrocarbon; (c) the intermediates in the bimolecular reaction giving H D in layers of CGDlz and CGIllZ have a short range ( < 100 A) and cannot be thermal hydrogen atoms.

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Section: Discussionmentioning

confidence: 99%

The Ranges of Interactions in the Radiolysis of Solid Hydrocarbon Mixtures

Dyne¹,

Denhartog²

1966

Can. J. Chem.

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“…Fro111 AHl(cyclopentane) = -18.46 kcal/mole and AHf(cyclopentene) = 7.87 kcal/mole (5) Values of 4-5 kcal/mole for E-1 in gas phase reactions have been generally found (8), although the reaction of H atoms with olefins in the solid state suggest a lower value of 1.5 kcal/mole (9). Even with this lower value, D(C-H) in cyclopentane ivould have to be 104 kcal/mole.…”

Section: Resultsmentioning

confidence: 99%

Free Radicals by Mass Spectrometry: Xxxii. Thermal Decomposition of Cyclopentyl Radicals

Palmer¹,

Lossing²

1965

Can. J. Chem.

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At low pressures and elevated telnperatures cyclopentyl radicals are found to dissociate mainly by two modes of reaction: about 34% by loss of H atom to form cyclopentene, and about 66% by a C-C bond rupture to form ethylene and allyl radicals. Under the conditions employed no evidence for a third possible mode, the loss of H t to form cyclopentenyl radical, could be found. I t is estimated that an incidence of 2Yo of the latter could have been detected.

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“…The use of liquid helium as an indispensable refrigerant for attaining temperatures close to absolute zero is based on important recent developments in the fields of low-temperature chemistry ( Klein and Scheer, 1958) and free-radical research (Broida, 1957;Minkoff, 1959). The temperature domain below the glassy transformation of H. Fernandez-Moran.…”

Section: Low-temperature Preparation Techniques For Electron Microscopymentioning

confidence: 99%

MacroMolecular Complexes

2012

Chemistry International -- Newsmagazine for IUPAC

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The Reaction of Hydrogen Atoms with Solid Olefins at – 195°C

Cited by 41 publications

References 1 publication

The Ranges of Interactions in the Radiolysis of Solid Hydrocarbon Mixtures

The Ranges of Interactions in the Radiolysis of Solid Hydrocarbon Mixtures

Free Radicals by Mass Spectrometry: Xxxii. Thermal Decomposition of Cyclopentyl Radicals

MacroMolecular Complexes

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