ChemInform Abstract: Rate Constants for Abstraction of Hydrogen from Ethylene by Methyl and Ethyl Radicals Relative to Abstraction from Propane and Isobutane

ChemInform ◽  
1989 ◽  
Vol 20 (16) ◽  
Author(s):  
S. I. AHONKHAI ◽  
X.-H. LIN ◽  
M. H. BACK
Keyword(s):  
Rate Constants ◽  
Ethyl Radicals

COMBINATION AND DISPROPORTIONATION OF ETHYL RADICALS: INFLUENCE OF THE REACTION H+C2H5 = C2H6

1955 ◽  
Vol 33 (5) ◽  
pp. 821-829 ◽  
Author(s):  
Moyra J. Smith ◽  
Patricia M. Beatty ◽  
J. A. Pinder ◽  
D. J. Le Roy
Keyword(s):  
Light Intensity ◽  
Excellent Agreement ◽  
Mercury Concentration ◽  
Rate Constants ◽  
Room Temperature ◽  
Low Light ◽  
Ethylene Concentration ◽  
Light Intensities ◽  
Ethyl Radicals ◽  
Hydrogenation Of Ethylene

The mercury (3P1) photosensitized hydrogenation of ethylene has been studied at room temperature as a function of ethylene concentration, mercury concentration, and light intensity. In addition to combination and disproportionation, ethyl radicals have been shown to take part in the reaction[Formula: see text]The conditions favoring this reaction have been established and anomalous values previously found for the ratio of ethane to butane have been explained. The value obtained for the ratio of the rate constants for the disproportionation and combination of ethyl radicals, 0.15 ±.01, is in excellent agreement with the values obtained by other methods. Hexane formation is of some importance at low light intensities and high ethylene concentrations, and is adequately accounted for by the reactions[Formula: see text]

Determination of absolute rate constants of addition of ethyl radicals to olefins

1977 ◽  
Vol 13 (2) ◽  
pp. 204-208 ◽  
Author(s):  
V. E. Myshkin ◽  
A. G. Shostenko ◽  
P. A. Zagorets ◽  
K. G. Markova ◽  
A. I. Pchelkin
Keyword(s):  
Rate Constants ◽  
Absolute Rate ◽  
Ethyl Radicals

Temperature Dependence of Disproportionation–Combination Ratios for Alkyl Radicals in Liquid Methane

1971 ◽  
Vol 49 (17) ◽  
pp. 2861-2867 ◽  
Author(s):  
Hugh A. Gillis
Keyword(s):  
Activation Energy ◽  
Temperature Dependence ◽  
Gas Phase ◽  
Rate Constants ◽  
Room Temperature ◽  
Transition States ◽  
Alkyl Radicals ◽  
Liquid Methane ◽  
Ethyl Radicals

The ratios of rate constants for disproportionation to combination have been measured for ethyl radicals and for i-propyl radicals in liquid methane between −181 and −94 °C. The radicals were generated by γ-radiolysis of dilute methane solutions of ethylene-d4 or propylene-d6. The activation energy for combination was found to exceed that for disproportionation by 290 ± 30 cal mol−1 for ethyl radicals and by 255 ± 25 cal mol−1 for i-propyl radicals. In both cases the disproportionation—combination ratio in the liquid, extrapolated to room temperature, is greater than that in the gas phase by a factor of about 2.5. These results are interpreted as indicating that disproportionation and combination reactions proceed by way of different transition states.

The Temperature Dependence of the Ratio kd/kc for Ethyl Radicals

1975 ◽  
Vol 53 (8) ◽  
pp. 1237-1244 ◽  
Author(s):  
D. G. Hooper ◽  
M. Simon ◽  
M. H. Back
Keyword(s):  
Liquid Phase ◽  
Transition State ◽  
Gas Phase ◽  
Rate Constants ◽  
Low Temperatures ◽  
Experimental Error ◽  
Hydrogen Atoms ◽  
Direct Photolysis ◽  
Temperature Range ◽  
Ethyl Radicals

The ratio of the rate constants for disproportionation and combination for ethyl radicals, kd/kc[Formula: see text]has been measured over the temperature range 298–173 K in the gas phase. Ethyl radicals were produced by direct photolysis of ethylene followed by addition of hydrogen atoms to ethylene. At low temperatures the only important reactions of the radicals were combination and disproportionation. The ratio kd/kc was obtained from measurements of the rates of formation of ethane, butane, and butene. No change in the ratio kd/kc was observed over the temperature range studied, leading to the conclusion that Ed − Ec = 0, within the experimental error. The significance of this result is discussed in relation to other measurements in both gas and liquid phase and to the nature of the transition state for this reaction.

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