Addition of methyl radicals to carbon monoxide: Chemically and thermally activated decomposition of acetyl radicals

1974 ◽  
Vol 6 (6) ◽  
pp. 855-873 ◽  
Author(s):  
K. W. Watkins ◽  
William W. Word
Keyword(s):  
Carbon Monoxide ◽  
Methyl Radicals ◽  
Thermally Activated

THE PHOTOLYSIS OF DEUTERATED ACETONE AND OF DEUTERATED ACETONE–HYDROGEN MIXTURES

1960 ◽  
Vol 38 (11) ◽  
pp. 2161-2170 ◽  
Author(s):  
J. F. Henderson ◽  
E. W. R. Steacie
Keyword(s):  
Carbon Monoxide ◽  
Excited Molecule ◽  
Methyl Radicals ◽  
Hydrogen Mixtures

The photolyses of acetone, acetone-d6, and acetone-d6 – hydrogen mixtures were investigated at 471 °K. The rates of formation of methane, ethane, and carbon monoxide and the ratio [Formula: see text] were independent of the fractional amount of acetone which photolyzed, as measured by 100[CO]/[A]0, which was varied from <1% to 18%. When the acetone-d6–hydrogen mixtures were photolyzed, [Formula: see text] and [Formula: see text] were observed to be functions of [A]0 and [H2]0. It is postulated that some of the CD4 and CD3H was formed by a reaction between methyl radicals and an excited molecule which contained both C—D and C—H bonds.

Primary process(es) in the mercury-photosensitized decomposition of dimethyl ether at 2537 Å

1968 ◽  
Vol 46 (16) ◽  
pp. 2693-2697 ◽  
Author(s):  
R. Payette ◽  
M. Bertrand ◽  
Y. Rousseau
Keyword(s):  
Carbon Monoxide ◽  
Quantum Yield ◽  
Light Intensity ◽  
Dimethyl Ether ◽  
Molecular Hydrogen ◽  
Room Temperature ◽  
Primary Process ◽  
Methyl Radicals ◽  
Hydrogen Atoms ◽  
Radical Recombination

The mercury-photosensitized decomposition of dimethyl ether has been studied at room temperature and at pressures ranging from 10 to 200 Torr.The formation of an excited dimethyl ether (DME) molecule has been verified by following the rates of formation of methane, ethane, and carbon monoxide with various ether pressures.The study of the variation of the quantum yield of molecular hydrogen formation with absorbed light intensity at high ether pressures has shown that the primary process involves the dissociation of ether molecules into hydrogen atoms and methoxy methyl radicals:[Formula: see text]The results presented in this paper indicate that the excited DME molecule can originate in a radical recombination between hydrogen atoms and methoxy methyl radicals.

THE PHOTOLYSIS OF ACETONE IN THE PRESENCE OF HYDROGEN BROMIDE

1955 ◽  
Vol 33 (2) ◽  
pp. 383-390 ◽  
Author(s):  
M. J. Ridge ◽  
E. W. R. Steacie
Keyword(s):  
Carbon Monoxide ◽  
Hydrogen Bromide ◽  
Methyl Radicals ◽  
Methyl Radical

The presence of hydrogen bromide during the photolysis of acetone sharply inhibits the yields of carbon monoxide, ethane, and volatile methyl radical derivatives as measured by the function (CH4 + 2C2H6). The observed effects can be explained on the assumption that both acetyl and methyl radicals react rapidly with HBr.

Studies of the reactions of hydroxyl radicals. II

1966 ◽  
Vol 291 (1424) ◽  
pp. 85-93 ◽  
Keyword(s):  
Hydrogen Peroxide ◽  
Carbon Monoxide ◽  
Hydroxyl Radicals ◽  
Room Temperature ◽  
Order Reaction ◽  
Methyl Radicals ◽  
Third Order ◽  
Experimental Conditions ◽  
Homogeneous Decomposition ◽  
Methane Carbon

The homogeneous decomposition of hydrogen peroxide has been used as a source of hydroxyl radicals. In part I values were reported for the relative rates of reaction of hydroxyl radicals with methane, carbon monoxide, formaldehyde and hydrogen peroxide. In this paper these values are confirmed for different experimental conditions and more consideration is given to details of subsequent reactions. The reaction of methyl radicals with oxygen has previously been shown to occur by a third order reaction both at 200 °C (Hoare & Walsh 1957) and at room temperature (Christie 1958). Present results show that the reaction is second order at 525 °C as suggested by Barnard & Honeyman (1964). In the absence of added oxygen, methyl radicals combine to give ethane which in turn reacts with hydroxyl radicals twelve times more rapidly than does methane.

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