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用流动放电-化学发光技术测定了O(~3p)原子与乙醚和异丙醚总包二级反应速率常数。反应速率常数与温度关系可表达为k_1=(1.91±0.70)×10~(-11)exp[-(2.14±0.16)kcal·mol~(-1)/RT]·cm~3·molec.~(-1)·s~(-1) [O(~3p)+乙醚] k_2=(3.25±0.80)×10~(-11)exp[-(2.57±0.20)kcal·mol~(-1)/RT]·cm~3·molec.~(-1)·s~(-1) [O(~3p)+异丙醚] 还讨论了醚分子中氧原子对α-位C—H键能及其反应活化能的影响。结果表明,氧原子使α位C—H键能减弱而降低了反应活化能。
The second order reaction rate constants of O (~ 3p) atom with ether and isopropyl ether were measured by flow discharge - chemiluminescence. The relationship between the reaction rate constant and the temperature can be expressed as k_1 = (1.91 ± 0.70) × 10 ~ (-11) exp [- (2.14 ± 0.16) kcal · mol -1 / RT] cm ~ 3 · mol ~ (-1) · s ~ (-1) [O (~ 3p) + ether] k_2 = (3.25 ± 0.80) × 10 ~ (-11) exp [- (2.57 ± 0.20) kcal · mol -1 /RT]*cm~3·molec.~(-1)~s~(-1)[O (~ 3p) + isopropyl ether] The discussion of the C-H bond energy of α-position of oxygen atom in ether molecule And its reaction activation energy. The results showed that the oxygen atoms reduced the α-C-H bond and decreased the activation energy.