含铬废物焚烧中CrOCl_2+OH→CrO_2Cl+HCl基元反应研究

Study on elementary reaction CrOCl_2+OH→CrO_2Cl+HCl in chromium waste incineration

含铬废物焚烧过程中形成具有不同氧化价态的多种铬氧化物,其毒性有较大差异,尤其是六价铬化合物具有极强的致癌作用。利用量子化学的方法研究了铬/氢/空气/氯焚烧体系中CrOCl2+OH→CrO2Cl+HCl反应的反应机理。通过Gaussian98软件在B3LYP/6-311+G(3df,2p)理论水平上,优化出各驻点的几何结构并得到经过零点能校正后的各驻点能量,通过过渡态搜索和内禀反应坐标分析确定该反应为基元反应。分别计算了正、逆反应的活化能,并采用传统过渡态理论计算了该反应的正向反应速率常数。

Chromium waste incineration can produce chromium compounds with different valence. They are of different toxicity, among which hexavalent chromium compounds are highly carcinogenic. The reaction mechanism of reaction CrOCl2＋OH→CrO2Cl＋HCl in Cr/H/Air/Cl chromium waste incineration was studied by quantum chemistry method. The geometry structures of reactants, products, transition state and intermediates were optimized and frequencies and energies with zero point energy correction of these stationary points were calculated by Gaussian 98 at B3LYP/6-311 4- G（3df,2p） theory level. The reaction was confirmed as an elementary reaction through transition state search and intrinsic reaction coordinate analysis. The activation energies of forward and reverse reaction were also obtained. Forward reaction rate constant was calculated by traditional transition state theory.