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Title: Mechanism of product formation during the photolysis of ketene

Abstract

The photolysis of ketene has been studied with both /sup 14/CH/sub 2/CO and CHTCO, and a new mechanism is suggested for the reactions of triplet methylene in pure ketene. The isotopic experiments are consistent with the set of reactions, (6) plus (8) to (11), /sup 3/CH/sub 2/ + /sup 3/CH/sub 2/ ..-->.. C/sub 2/H/sub 2/ + 2H (8), H + CH/sub 2/CO ..-->.. CH/sub 3/ + CO (9), /sup 3/CH/sub 2/ + CH/sub 3/ ..-->.. C/sub 2/H/sub 4/ + H (10,11), CH/sub 3/ + CH/sub 3/ ..-->.. C/sub 2/H/sub 6/ (6); and not with the earlier proposal of (3) to (6), /sup 3/CH/sub 2/ + CH/sub 2/CO ..-->.. CH/sub 3/ + CHCO (3), CHCO + CHCO ..-->.. C/sub 2/H/sub 2/ + 2CO (4), CH/sub 3/ + CHCO ..-->.. C/sub 2/H/sub 4/ + CO (5). The formation of atomic hydrogen rather than molecular hydrogen in (8) has important consequences for interpretation of the flash photolysis of ketene.

Authors:
;
Publication Date:
Research Org.:
Univ. of California, Irvine
OSTI Identifier:
5507879
DOE Contract Number:  
E(04-3)-34
Resource Type:
Journal Article
Journal Name:
J. Phys. Chem.; (United States)
Additional Journal Information:
Journal Volume: 83:16
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBON 14; ISOTOPE EFFECTS; KETENES; PHOTOLYSIS; METHYLENE RADICALS; REACTION KINETICS; TRITIUM; EXPERIMENTAL DATA; ISOLATED VALUES; LABELLED COMPOUNDS; BETA DECAY RADIOISOTOPES; BETA-MINUS DECAY RADIOISOTOPES; CARBON ISOTOPES; CHEMICAL REACTIONS; DATA; DATA FORMS; DECOMPOSITION; EVEN-EVEN NUCLEI; HYDROGEN ISOTOPES; INFORMATION; ISOTOPES; KINETICS; LIGHT NUCLEI; NUCLEI; NUMERICAL DATA; ODD-EVEN NUCLEI; ORGANIC COMPOUNDS; ORGANIC OXYGEN COMPOUNDS; PHOTOCHEMICAL REACTIONS; RADICALS; RADIOISOTOPES; YEARS LIVING RADIOISOTOPES; 400500* - Photochemistry; 400302 - Organic Chemistry- Isotope Effects- (-1987)

Citation Formats

Russell, R L, and Rowland, F S. Mechanism of product formation during the photolysis of ketene. United States: N. p., 1979. Web. doi:10.1021/j100479a005.
Russell, R L, & Rowland, F S. Mechanism of product formation during the photolysis of ketene. United States. doi:10.1021/j100479a005.
Russell, R L, and Rowland, F S. Thu . "Mechanism of product formation during the photolysis of ketene". United States. doi:10.1021/j100479a005.
@article{osti_5507879,
title = {Mechanism of product formation during the photolysis of ketene},
author = {Russell, R L and Rowland, F S},
abstractNote = {The photolysis of ketene has been studied with both /sup 14/CH/sub 2/CO and CHTCO, and a new mechanism is suggested for the reactions of triplet methylene in pure ketene. The isotopic experiments are consistent with the set of reactions, (6) plus (8) to (11), /sup 3/CH/sub 2/ + /sup 3/CH/sub 2/ ..-->.. C/sub 2/H/sub 2/ + 2H (8), H + CH/sub 2/CO ..-->.. CH/sub 3/ + CO (9), /sup 3/CH/sub 2/ + CH/sub 3/ ..-->.. C/sub 2/H/sub 4/ + H (10,11), CH/sub 3/ + CH/sub 3/ ..-->.. C/sub 2/H/sub 6/ (6); and not with the earlier proposal of (3) to (6), /sup 3/CH/sub 2/ + CH/sub 2/CO ..-->.. CH/sub 3/ + CHCO (3), CHCO + CHCO ..-->.. C/sub 2/H/sub 2/ + 2CO (4), CH/sub 3/ + CHCO ..-->.. C/sub 2/H/sub 4/ + CO (5). The formation of atomic hydrogen rather than molecular hydrogen in (8) has important consequences for interpretation of the flash photolysis of ketene.},
doi = {10.1021/j100479a005},
journal = {J. Phys. Chem.; (United States)},
number = ,
volume = 83:16,
place = {United States},
year = {1979},
month = {8}
}