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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Mechanism and Rate of Thermal Decomposition of Hexachlorocyclopentadiene and Its Importance in PCDD/F Formation from the Combustion of Cyclodiene Pesticides
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Mechanism and Rate of Thermal Decomposition of Hexachlorocyclopentadiene and Its Importance in PCDD/F Formation from the Combustion of Cyclodiene Pesticides

机译：六氯环戊二烯的热分解机理及速率及其在环二烯农药燃烧中PCDD / F的重要性

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Thermal decomposition of hexachlorocyclopentadiene (HCCP) has been studied in inert gas and under oxidative conditions in a silica flow reactor at a residence time of 5.0 s between 690 and 923 K and 1 atm pressure. Pyrolysis was initiated by Cl bond fission to form pentachlorocyclopentadienyl radical; two such radicals then combined to undergo a series of intramolecular rearrangements and Cl fissions, producing principally octachloronaphthalene (8ClNP) and Cl-2. This process has been studied by quantum chemical calculation, and a reaction potential energy surface has been developed. The rate constant of initial Cl atom fission has been calculated by canonical variational transition state theory as k = 1.45 x 10(15) exp(-222 +/- 9 kJ mol(-1)/RT) s(-1) between 500 and 2000 K A minimal kinetic model was developed to model the decomposition and major products. Oxidative decomposition was studied in nitrogen with O-2 contents of 1, 6, 12, and 20 mol %. Increasing O-2 to 6-8% increased the rate of decomposition of HCCP and decreased the yield of 8ClNP. Above 823 K, hexachlorobenzene (HCB) and CO became major products. The oxidative reaction has also been studied quantum chemically. At high O-2 content (>similar to 10%), the rate of decomposition of HCCP declined as did yields of 8ClNP and HCB, but CO yields increased.
机译：已经在惰性气体中研究了六氯环戊二烯（HCCP）的热分解，在二氧化硅流反应器的氧化条件下，在590和923k和1atm压力之间的停留时间为5.0秒。通过Cl键裂变引发热解，形成五氯环戊二烯基。然后将两种这样的基团组合以进行一系列分子内重排和Cl裂缝，主要生产八氯萘萘（8ClNP）和Cl-2。已经通过量子化学计算研究了该过程，并且已经开发了反应势能表面。初始CL原子裂变的速率常数已经通过规范变分过渡状态理论计算为k = 1.45×10（15）exp（-222 +/- 9 kJ mol（-1）/ Rt）s（-1）之间的500建立了2000年KA最小动力学模型，以模拟分解和主要产品。在氮中研究了氧化分解，其中O-2含量为1,6,12和20mol％。 o-2至6-8％的增加增加了HCCP的分解率，降低了8CLNP的产量。以上823 k，六氯苯（HCB）和CO成为主要产品。还研究了氧化反应也研究了量子化学。在高O-2含量（>类似于10％）时，HCCP的分解率下降，如8ClNP和HCB的产率，但CO屈服增加。

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