
%0 Journal Article
%A Arthur, NL 
%A Newitt, PJ 
%T Reactions of trifluoromethyl radicals. V. Hydrogen abstraction from methyl acetate and methyl (<sup>2</sup>H<sub>3</sub>)Acetate
%J Australian Journal of Chemistry
%D 1980/07/01
%V 33
%N 7
%P 1437-1446
%K 
%R https://doi.org/10.1071/CH9801437
%U https://www.publish.csiro.au/paper/CH9801437 
%X Hydrogen abstraction by CF3 radicals from CH3COOCH3 and CD3COOCH3 has been studied in the temperature range 78-242&#176;, and data have been obtained for the reactions:  CF3 + CH3COOCH3 &#8594; CF3H+[C3H5O2]              (3) CF3 + CH3COOCH3 &#8594; CF3H+CH2COOCH3             (4) CF3 + CD3COOCH3 &#8594; CF3D+CD2COOCH3             (6) CF3 + CD3COOCH3 &#8594; CF3H+CD3COOCH2             (7)  The corresponding rate constants, based on the value of 1013.36 cm3 mol-1 S-1 for the recombination of CF3 radicals, are given by (k in cm3 mol-1 s-1 and E in J mol-1): logk3 = (11.52±0.05)-(35430±380)/19.145T             (3)logk4 = (11.19±0.07)-(34680±550)/19.145T             (4)logk6 = (11.34±0.06)-(46490±490)/19.145T             (6)logk7 = (11.26±0.05)-(36440±400)/19.145T             (7)At 400 K, 59% of abstraction occurs from the acetyl group, and 41 % from the methoxy group. The kinetic isotope effect at 400 K for attack on the acetyl group is 25, due mainly to a difference in activation energies. 
