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用流动微波放电—化学发光方法测定O(~3p)原子与CH_3COCH_3和CH_3COC(CH_3)_3的化学反应速率常数k=3.37±1.00×10~(-12)exp(-7.03±0.22kcal.mol~(-1)/RT) (丙酮+0(~3p),T=373-503K)和k=4.61±2.60×10~(-11)exp(-5.46±0.44kcal·mol~(-1)/RT) (3.3-2甲基-2-丁酮+O(~3p),T=303-503K)并就测定的O(~3p)原子与一系列酮分子反应速率常数进行了讨论,估算了O(~3p)原子与各类C—H键反应速率的Arrhenius参数。发现与羰基相邻的C—H键与O(~3p)反应的活化能要略大于非相邻的同类键反应的活化能。还根据Evans-Polanyi关系式,对这些键的键能进行了讨论。
The rate constant of chemical reaction of O (~ 3p) atom with CH_3COCH_3 and CH_3COC (CH_3) _3 was determined by mobile microwave discharge-chemiluminescence (K = 3.37 ± 1.00 × 10- (-12) exp (-7.03 ± 0.22kcal.mol ~ (-1) / RT) (acetone +0 (~ 3p), T = 373-503K) and k = 4.61 ± 2.60 × 10 ~ (-11) exp (-5.46 ± 0.44kcal · mol -1 RT) (3.3-2 methyl-2-butanone + O (~ 3p), T = 303-503K). The reaction rate constants of O (~ 3p) Arrhenius Parameters of O (~ 3p) Atom Reaction Rates with Various C-H Bonds. It is found that the activation energy of the C-H bond adjacent to the carbonyl group is slightly larger than the activation energy of the non-adjacent homologous bond reaction. The bond energies of these keys are also discussed according to the Evans-Polanyi relation.