摘要
本文报道用过渡态理论计算化学反应速率常数,将实验没定的O(~3P)和醇类分子化学反应速率常数由实验条件(293-503K)外推到200-2000K范围内,以便将这些数据应用到大气和燃烧化学研究中去.外推结果以三参数Arrhcnius公式表示.结果为: 1.O(~3P)+CH_3OH k_1(T)=4.80×10^(-19)T^(2.17)exp(-3.63kcal.mol^(-1)/RT) 2.O(~3P)+C_2H_5OH k_2(T)=1.27×10^(-19)T^(2.88)exp(-2.97kcal.mol^(-1)/RT) 3.O(~3P)+i-C_3H_7OH k_3(T)=2.38×10^(-23)T^(3.99)exp(-0.44kcal.mol^(-l)/RT) 4.O(~3P)+n-C_3H_7OH k_4(T)=5.06×10^(-20)T^(3.00)exp(-1.7kcal.mol^(-1)/RT) 5.O(~3P)+n-C_4H_9OH k_5(T)=9.70×10^(-21)T^(3.20)exp(-0.58kcal.mol^(-1)/RT) 6.O(~3P)+t-C_5H_(11)OH k_6(T)=9.01×10^(-20)T^(2.97)exp(-2.25kcal.mol^(-1)/RT) 7.O(~3P)+i-C_5H_(11)OH k_7(T)=6.11×10^(-25)T^(4.44)exp(-1.65kcal.mol^(-1)/RT)
Using transition-state theory, we calculated the rate constants of reactions O(~3P) atom and alcohol molecules to extrapolate the experimentally measured results to temperature range 200—2000K in order to use these data in study of atmospheric and combustion processes. Then the calculated results are fitted to three parameters Arrhenius expressions as follows.
1. CH_3OH k_1(T)=4.80×10^(19)T^(2.71)exp(-3.63kcal.mol^(-1)/RT)
2. C_2H_5OH k_2(T)=1.27×10^(19)T^(2.88)exp(-2.97kcal.mol^(-1)/RT)
3. i-C_3H_7OH k_3(T)=2.38×10^(-23)T^(3.99)exp(-0.44kcal.mol^(-1)/RT)
4.n-C_3H_7OH k_4(T)=5.06×10^(-20)T^(3.00)exp(-1.7kcal.mol^(-1)/RT)
5. n-C_4H_9OH k_5(T)=9.70×10^(-21)T^(3.20)exp(-0.58kcal.mol^(-1)/RT)
6. t-C_5H_(11)OH k_6(T)=9.01×10^(-20)T^(2.97)exp(-2.25kcal.mol^(-1)/ RT)
7. i-C_5H_(11)OH k_7(T)=6.11×10^(25)T^(4.44)exp(-1.65kcal.mol^(-1)/RT)
