Abstract
A study of hydrogen
abstraction from CH3COOCD3 by CH3 radicals in
the temperature range 113-232�, and by CF3 radicals in the range
83-212�, has yielded data on the reactions: CH3+CH3COOCD3
→ CH4+CH2COOCD3 (1)CH3+CH3COOCD3
→ CH3D+CH3COOCD2 (2) CF3+CH3COOCD3
→ CF3H+CH2COOCD2 (3) CF3+CH3COOCD3
→ CF3D+CH3COOCD2 (4) The corresponding
rate constants, based on the values 1013.34 and 1013.36
cm3 mol-1 s-1 for the recombination of CH3
and CF3 radicals, respectively, are given by (k in cm3 mol-1 s-1 and E in J mol-1): logk1 = (11.31�0.12)-(43500�1030)/19.145T (1) logk1 = (11.31�0.12)-(53460�640)/19.145t (2) logk3 =
(11.12�0.06)=(34260�450)/19.145T
� (3) logk4 =(10.93�0.12)-(38650�900)/19.145T (4)These results lead
to kinetic isotope effects at 400 K for attack on the acetyl group of 11, for
the CH3 reaction, and 24, for the CF3 reaction, thus
confirming the values we obtained previously. For attack on the methoxy group,
the kinetic isotope effects are 8 and 4, for the CH3 and CF3
reactions, respectively.
Cited by
2 articles.
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