
TY  - JOUR
A1  - Arthur, NL 
A1  - Newitt, PJ 
T1  - Reactions of Methyl Radicals. III. Hydrogen Abstraction from Methyl Acetate and Methyl [<sup>2</sup>H<sub>3</sub>]Acetate
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1979
VL  - 32
IS  - 8
SP  - 1697
EP  - 1708
KW  - 
UR  - https://doi.org/10.1071/CH9791697 
N2  - A study of hydrogen abstraction by CH3 radicals from CH3COOCH3 in the temperature range 116-224&#176;, and from CD3COOCH3 in the range 117-234&#176;, has yielded data on the reactions: CH3 + CH3COOCH3 &#8594; CH4 + [C3H5O2] (4) CH3 + CH3COOCH3 &#8594; CH4 + CH2COOCH3 (5) CH3 + CH3COOCH3 &#8594; CH4 + CH3COOCH2 (6) CH3 + CD3COOCH3 &#8594; CH3D + CD2COOCH3 (7) The corresponding rate constants, based dn the value of 1013.34 cm3 mol-1 s-1 for the recombination of CH3 radicals, are given by (k in cm3 mol-1 s-1 and E in J mol-1): logk4 = (11.56 &#177; 0.12) - (44430 &#177; 970)/19.145T     (4) logk5 = (11.17 &#177; 0.22) - (42900 &#177; 1760)/19.145T     (5) logk6 = (11.44 &#177; 0.16) - (46980 &#177; 1290)/19.145T     (6) logk7 = (11.39 &#177; 0.04) - (52110 &#177; 330)/19.145T     (7) At 400 K, 64% of abstraction occurs from the acetyl group, and 36% from the methoxy group. The kinetic isotope effect at 400 K for attack on the acetyl group is 9.6; this is mainly due to a difference in activation energies since the quotient of A factors is close to unity. 
ER  -

