Gas‐Phase Photolysis of Ethyl Iodide at 2537 and 2288 Å. Reactions of Hot Ethyl Radicals with Added Hydrocarbons

1967 ◽  
Vol 47 (8) ◽  
pp. 2849-2855 ◽  
Author(s):  
R. E. Rebbert ◽  
P. Ausloos
Keyword(s):  
Gas Phase ◽  
Ethyl Iodide ◽  
Ethyl Radicals

The Gas Phase Radiolysis of Ethyl Iodide*

1963 ◽  
Vol 38 (5_6) ◽  
pp. 285-294 ◽  
Author(s):  
Ralph N. Schindler ◽  
M. H. J. Wijnen
Keyword(s):  
Gas Phase ◽  
Ethyl Iodide

The mercury (63P1) photosensitized hydrogenation of ethylene. Kinetics of the reaction C2H5 + H2 = C2H6 + H

1968 ◽  
Vol 46 (20) ◽  
pp. 3275-3281 ◽  
Author(s):  
L. E. Reid ◽  
D. J. Le Roy
Keyword(s):  
Gas Phase ◽  
Molecular Hydrogen ◽  
Mercury Vapor ◽  
Experimental Conditions ◽  
Working Pressure ◽  
Extinction Coefficients ◽  
Secondary Reactions ◽  
Ethyl Radicals ◽  
Kinetics Of ◽  
Hydrogenation Of Ethylene

A quantitative study has been made of the reaction of ethyl radicals with molecular hydrogen in the gas phase in the temperature range 240 to 320 °C. The mercury (63Pi) photosensitized decomposition of hydrogen in the presence of ethylene was used to generate ethyl radicals. Extinction coefficients for the absorption of 2537 Å by mercury vapor were measured and Beer's law was shown to be obeyed under the experimental conditions used. The corrections required to allow for the nonuniformity of radical concentrations in the cell were small. After delineating the experimental conditions necessary to minimize secondary reactions, the rate constant (cm3 mole−1 s−1) for the reaction C2H5 + H2 = C2H6 + H was found to be given by log10k = 12.57 − 13.7/θ. Experiments in the presence of added carbon dioxide showed the absence of hot radical effects at the working pressure of 92 Torr of hydrogen.

Spin relaxation of muonium‐substituted ethyl radicals (MuCH2ĊH2) in the gas phase

1996 ◽  
Vol 105 (17) ◽  
pp. 7517-7535 ◽  
Author(s):  
Donald G. Fleming ◽  
James J. Pan ◽  
Masayoshi Senba ◽  
Donald J. Arseneau ◽  
Robert F. Kiefl ◽  
...  
Keyword(s):  
Gas Phase ◽  
Spin Relaxation ◽  
Ethyl Radicals

High-temperature dissociation of ethyl radicals and ethyl iodide

2012 ◽  
Vol 44 (7) ◽  
pp. 433-443 ◽  
Author(s):  
Xueliang Yang ◽  
Robert S. Tranter
Keyword(s):  
High Temperature ◽  
Ethyl Iodide ◽  
Ethyl Radicals

THE POLYMERIZATION OF ETHYLENE SENSITIZED BY ETHYL IODIDE

1956 ◽  
Vol 34 (1) ◽  
pp. 41-53 ◽  
Author(s):  
V. B. Sefton ◽  
D. J. Le Roy
Keyword(s):  
Thermal Decomposition ◽  
Mercury Vapor ◽  
Chain Termination ◽  
Ethyl Iodide ◽  
Predominant Formation ◽  
Equilibrium Processes ◽  
Ethyl Radicals ◽  
Radical Disproportionation

The polymerization of ethylene sensitized by the thermal decomposition of ethyl iodide in the presence of mercury vapor has been studied at 250°, 275°, and 300 °C. C14-labelled ethyl iodide was used in a number of experiments. The increase in the rate of decomposition of ethyl iodide in the presence of ethylene and the formation of butyl iodide are accounted for by equilibrium processes of the type RI + Hg = R + HgI. The important features of the reaction were established from the identity, quantity, and activity of the various products. The predominant formation of olefins is attributed to the isomerization and decomposition of large radicals. Very little of the butane is formed by the combination of ethyl radicals. Radical disproportionation is the most important chain termination step.

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.

Reactions of thiyl radicals. XII. Triplet mercury photosensitized decomposition of ethyl sulfide in the gas phase

1976 ◽  
Vol 54 (8) ◽  
pp. 1290-1295 ◽  
Author(s):  
Conrad S. Smith ◽  
Arthur R. Knight
Keyword(s):  
Quantum Yield ◽  
Gas Phase ◽  
Quantum Yields ◽  
Second Step ◽  
Primary Process ◽  
Reaction Products ◽  
Process Comparison ◽  
Thiyl Radicals ◽  
Ethyl Radicals ◽  
High Sulfide

The triplet mercury photosensitized decomposition of ethyl sulfide vapour has been studied at 25 °C. The reaction products include C2H4 (Φ0 = 0.075), C2H6 (Φ0 = 0.043), C4H10 (Φ0 = 0.011), C2H5SH (Φ0 = 0.068), 4-methyl-3-thiahexane (Φ0 = 0.011), and C2H5SSC2H5 (Φ0 = 0.175). The overall decomposition quantum yield is 0.38 at high sulfide pressures. The initial decomposition gives principally ethyl radicals and ethylthiyl radicals; a second step which yields ethylene and ethanethiol may account for up to 20% of the primary process. Comparison of the direct and sensitized decompositions indicates that both likely originate in the triplet manifold of ethyl sulfide.Primary decomposition quantum yields have been accurately redetermined for the direct, 254 nm, photolysis of methyl sulfide (0.51), methylethyl sulfide (0.46), and ethyl sulfide (0.49).

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