Arrhenius parameters for rearrangements of the neophyl, 1-indanylmethyl, 2-allylbenzyl, and 2-(2-vinylphenyl)ethyl radicals relative to hydrogen abstraction from tributylstannane

1984 ◽  
Vol 106 (14) ◽  
pp. 3964-3967 ◽  
Author(s):  
James A. Franz ◽  
Russell D. Barrows ◽  
Donald M. Camaioni
Keyword(s):  
Hydrogen Abstraction ◽  
Arrhenius Parameters ◽  
Ethyl Radicals

Kinetics of radical exchange in the reaction of CF3 radicals with tin tetramethyl

1976 ◽  
Vol 54 (10) ◽  
pp. 1617-1623 ◽  
Author(s):  
T. N. Bell ◽  
P. J. Young
Keyword(s):  
Exchange Reaction ◽  
Rate Constant ◽  
Additional Data ◽  
Hydrogen Abstraction ◽  
Arrhenius Parameters ◽  
Abstraction Reaction ◽  
Reaction Proceeds ◽  
Kinetics Of

The reaction of CF3 radicals with SnMe4 leads to hydrogen abstraction and also radical exchange.[Formula: see text]We propose the exchange reaction proceeds via a five coordinate intermediate. The Arrhenius parameters for the exchange reaction are,[Formula: see text]Additional data for the H abstraction reaction[Formula: see text]combined with previous data yields an improved rate constant for abstraction,[Formula: see text]

Hydrogen abstraction by perfluoroethyl radicals from methylfluorosilanes

1976 ◽  
Vol 54 (15) ◽  
pp. 2359-2364 ◽  
Author(s):  
Thomas N. Bell ◽  
Toshitsugu Yokota ◽  
Alden G. Sherwood
Keyword(s):  
Hydrogen Abstraction ◽  
Arrhenius Parameters

Arrhenius parameters have been measured for hydrogen abstraction by C2F5 radicals (produced from the photolysis of perfluoropropionic anhydride) from methylfluorosilanes and tetramethylsilane.[Formula: see text]The results are discussed in relation to those of similar reactions involving the CF3 and the CH3 radical, and interpreted in terms of polar effects.

SOME HYDROGEN ABSTRACTION REACTIONS OF PERFLUOROETHYL RADICALS

1966 ◽  
Vol 44 (2) ◽  
pp. 171-177 ◽  
Author(s):  
G. O. Pritchard ◽  
J. R. Dacey ◽  
W. C. Kent ◽  
C. R. Simonds
Keyword(s):  
Hydrogen Abstraction ◽  
Arrhenius Parameters

With perfluoroazoethane as a photolytic source of C2F5 radicals, the hydrogen abstraction reactions of C2F5 with deuterium, ethane, cyclohexane, acetone, and trifluoroacetaldehyde have been studied, and the Arrhenius parameters derived. The H-atom abstraction reactions of the three perfluoroalkyl radicals, CF3, C2F5, and C3F7, are discussed.

Pyrolysis of triethylgallium by the toluene carrier technique

1979 ◽  
Vol 57 (24) ◽  
pp. 3178-3181 ◽  
Author(s):  
Michellene C. Paputa ◽  
Stanley James W. Price
Keyword(s):  
Thermal Decomposition ◽  
Pressure Range ◽  
Hydrogen Abstraction ◽  
Significant Extent ◽  
Rate Determining Step ◽  
Surface Catalysis ◽  
Gas System ◽  
One Step ◽  
Gallium Hydride ◽  
Ethyl Radicals

The pyrolysis of triethylgallium has been studied in a toluene carrier gas system in the temperature range of 464.7 to 700.7 K and a pressure range of 0.82 to 3.73 kPa. From the data obtained from this work, the following mechanism for the thermal decomposition of the metal alkyl is proposed:[Formula: see text]where [1] is the rate determining step. After runs below 606 K were corrected for the contribution of a concurrent residual reaction, a least-squares analysis of experimental results from 567 to 651 K based on both product and residual alkyl analysis gave[Formula: see text]at 1.60 kPa.The rate constant, k1, is very slightly pressure-dependent as revealed by tests at 648.0 K (80% and 45% decomposition). Studies indicate there is no detectable surface catalysis effect. Similarly, no effect was observed for changes in concentration or contact time.The mechanism for the formation of polymeric gallium hydride in reaction [4] is not clearly defined and may consist of more than one step. Reaction [5] is slow but based on the C2H4:H2 ratio must occur to a significant extent (40–80%) during a run. Further decomposition occurs between runs, causing a build-up of H2 in the reaction vessel.Experimental data for the hydrogen abstraction by ethyl radicals from toluene[Formula: see text]yield the equation[Formula: see text]

Reactions of methyl radicals. V. Hydrogen abstraction from hydrogen sulfide

1983 ◽  
Vol 36 (11) ◽  
pp. 2195 ◽  
Author(s):  
H Arican ◽  
NL Arthur
Keyword(s):  
Hydrogen Sulfide ◽  
Rate Constant ◽  
Hydrogen Abstraction ◽  
Methyl Radicals ◽  
Arrhenius Parameters ◽  
Temperature Range

Hydrogen abstraction from H2S by CH3 radicals, produced by the photolysis of azomethane, has been studied in the temperature range 334-432 K. The rate constant, based on the value 1013.34 cm3 mol-1 s-1 for the recombination of CH3 radicals, is given by log k4 = (11.00 � 0.01) - (8760 � 80)/19.145T where k4 is in cm3 mol-1 s-1 and E is in J mol-1. The previous data reported for this reaction are discussed and best values for its Arrhenius parameters are recommended. The results indicate that CH3 radicals react faster than CF3 radicals with H2S; this confirms the importance of polar effects in the hydrogen abstraction reactions of CF3 radicals.

Sign in / Sign up

Export Citation Format

Share Document