The Gas-phase Photochemical Decomposition of the Simple Aliphatic Ketones.

Davis, Wallace.

doi:10.1021/cr60126a002

Cited by 39 publications

(16 citation statements)

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“…I t has been shown (12,3) that in the photoIysis of acetone between 130" and 300" the production of methyl radicals and the formation of methane and ethane are accounted for by the following reactions:…”

Section: Introductionmentioning

confidence: 99%

THE REACTIONS OF CH₃ AND CD₃ RADICALS WITH HYDROGEN AND DEUTERIUM

Majury¹,

Steacie²

1952

Can. J. Chem.

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The reaction of CH3 and CD3 radicals with hydrogen and deuterium have been investigated, acetone being used as a source of methyl radicals. 'The results indicate (1) that the substitution of D? for H.: has a considerable effect, (2) the substitutiorl of CD3 for CH3 has relatively little effect. (3) I t IS concluded that, contrary to the results of Burton et al., the activation energy of the reaction CH3 + H?+ CHI + H is 9.7 zt 0.6 kcal. INTRODUCTIONI t has been shown (12, 3) that in the photoIysis of acetone between 130" and 300" the production of methyl radicals and the formation of methane and ethane are accounted for by the following reactions:CH,. C 0 . C H 3 + 2 C H 3 + CO(1)CH3+CH3.CO4CH3--tCH4+CH2.C0.CHB.Assuming a steady concentration of methyl radicals, it follows thatIn the presence of hydrogen the methyl radicals also react as follows* where (RCH,)4 represents the rate of production of methane by reaction (4).The fate of the H-atom produced in reaction (4) is presumed to be H+CI-I3.CO.CH3+Hz+ CH2.CO.CH3. For personal use only.

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Section: Introductionmentioning

confidence: 99%

THE REACTIONS OF CH₃ AND CD₃ RADICALS WITH HYDROGEN AND DEUTERIUM

Majury¹,

Steacie²

1952

Can. J. Chem.

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“…2, 3, 7, 8, 9, 10, 1 1 could well replace those given by Herr and Noyes (6). These latter have been republished in so many monographs (30,31) and reviews (32,33) that they have gained an authority never claimed by the authors (who suggested their quantum yields were accurate to +-10%). Only Fig.…”

Section: Discussionmentioning

confidence: 91%

The stationary-state approximation in the photolysis of acetone

Nicholson¹

1983

Can. J. Chem.

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A mechanism has been written for the photolysis of acetone at 313 nm and 253.7 nm and the differential equations involved solved rigorously. Testing this mechanism has revealed inconsistencies between different sets of experiments that were not previously obvious. The stationary-state approximation is valid up to ca. 0.5% decomposition but its practical usefulness is minimal. Graphs are given showing the variation of all significant quantum yields with temperature, pressure, and light intensity.

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“…The variables in the system that have been studied are: Since there have been extensive reviews of the photochemistry of acetone (18,80,81,105), only the salient features will be discussed here. At temperatures above 100°C.…”

Section: A the Calculation O F The Primary Quantum Yieldmentioning

confidence: 99%