表1 由2-氯酚形成PCDD/Fs过程中包含的基元反应的Arrhenius方程 Reactions Arrhenius formulas

2-CP+H→2-CPR+H2 k(T) = (1.10×10-11) exp(-6437.64/T)

2-CP+OH→2-CPR+H2O k(T) = (3.43×10-12) exp(-2661.33/T)

2-CP+O(3P)→2-CPR+OH k(T) = (4.75×10-12) exp(-3513.60/T)

2-CP+Cl→2-CPR+HCl k(T) = (2.09×10-11) exp(118.87/T)

IM1+H→IM3+HCl k(T) = (3.12×10-12) exp(-2891.38/T)

IM1+OH→IM3+HOCl k(T) = (1.02×10-11) exp(-6442.22/T)

IM1+Cl→IM3+Cl2 k(T) = (1.04×10-11) exp(-1861.28/T)

IM3→DD+Cl k(T) = (3.58×1011) exp(-13706.87/T)

IM3→IM4 k(T) = (4.26×1011) exp(-11885.95/T)

IM4→1-MCDD+H k(T) = (2.35×1013) exp(-15078.04/T)

IM2+H→IM5+H2 k(T) = (2.00×10-20) exp(-2885.70/T)

IM2+OH→IM5+H2O k(T) = (6.81×10-21) exp(-487.51/T)

IM5→1-MCDD+Cl k(T) = (5.05×1011) exp(-13763.30/T)

IM5→IM6 k(T) = (3.74×109) exp(-6677.26/T)

IM6→1,6-DCDD+H k(T) = (2.22×1013) exp(-15257.27/T)

2-CPR+2-CPR→IM7 k(T) = (3.86×10-15) exp(-5527.18/T)

IM7+H→IM8+H2 k(T) = (1.28×10-11) exp(-2222.77/T)

IM7+OH→IM8+H2O k(T) = (1.14×10-12) exp(-4313.22/T)

IM8→IM9 via TS15 k(T) = (1.39×109) exp(-2074.71/T)

IM8→IM9 via TS16 k(T) = (6.28×103) exp(-5740.21/T)

IM9→IM10 k(T) = (2.11×1012) exp(-14722.61/T)

IM10→4,6-DCDF k(T) = (4.11×1013) exp(-11176.13/T)

IM7→IM11 k(T) = (3.71×1010) exp(-6831.91/T)

IM11+H→IM9+H2 k(T) = (1.25×10-13) exp(-106.32/T)

2-CPR+2-CPR→IM12 k(T) = (1.56×10-16) exp(-4904.96/T)

IM12+H→IM13+HCl k(T) = (9.27×10-12) exp(-4210.06/T)

IM12+OH→IM13+HOCl k(T) = (7.35×10-12) exp(-7395.10/T)

IM12+Cl→IM13+Cl2 k(T) = (3.29×10-11) exp(-2140.44/T)

IM13→IM14 k(T) = (2.11×1010) exp(-4657.53/T)

IM14→IM15 k(T) = (2.04×1012) exp(-14193.42/T)

IM15→4-MCDF+OH k(T) = (2.34×1013) exp(-9511.18/T)

3. 2,3,7,8-TeCDD的降解机理

2,3,7,8-TeCDD是210中二噁英中毒性最强的，光-Feston试剂是污水处理中常用的一种方法。张庆竹采用高水平量子化学方法阐述了2,3,7,8-TeCDD在光-Feston试剂作用下的降解机理，提出了几种可能的反应途径。在B3LYP/6-31G(d)水平上计算了反应驻点(包括反应物、中间体、过渡态和产物)的信息。提出了两种可能的反应机理：开环-加成