The reaction of free alkyl radicals in the gas phase

1947 ◽  
Vol 2 ◽  
pp. 104 ◽  
Author(s):  
C. E. H. Bawn ◽  
C. F. H. Tipper
Keyword(s):  
Gas Phase ◽  
Alkyl Radicals

Bimolecular Homolytic Substitutions at Nitrogen: An Experimental and Theoretical Study on the Gas-Phase Reactions of Alkyl Radicals with NF3

2015 ◽  
Vol 21 (44) ◽  
pp. 15826-15834 ◽  
Author(s):  
Paola Antoniotti ◽  
Paola Benzi ◽  
Stefano Borocci ◽  
Chiara Demaria ◽  
Maria Giordani ◽  
...  
Keyword(s):  
Gas Phase ◽  
Theoretical Study ◽  
Gas Phase Reactions ◽  
Alkyl 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.

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