应用量子化学密度泛函理论方法,分别采用不同的基组计算汞-溴体系中的分子几何构型、振动频率和反应焓变,并与NIST数据库及相关文献数据进行了比较,最后得出采用B3PW91/Stevens组合计算得到的结果与实验值最为符合.在此基础上,研究了煤燃烧过程中汞与溴化氢的反应机理,优化得到反应过程中各驻点(反应物、过渡态和产物)的几何构型,计算了活化能并校正了零点能.利用经典过渡态理论,计算了反应的指前因子A及不同温度下的反应速率常数.计算得到的相关参数为深入研究煤燃烧过程中汞的排放控制及动力学模型提供了可靠的参考依据.
参考文献
| [1] | CHERYL HOGUE .MERCURY RULE OVERTURNED[J].Chemical and engineering news: "news edition" of the American Chemical Society,2008(7):6-0. |
| [2] | 火电厂大气污染物排放标准[S].北京:中国环境科学出版社,2012. |
| [3] | 王泉海,陈世凯,吴小君.溴元素对烟气中汞的形态和分布的影响[J].燃烧科学与技术,2011(02):160-164. |
| [4] | 朱燕群,周劲松,蔡小舒,岑可法.燃煤过程中不同烟气组分对汞形态转化的影响[J].浙江大学学报（工学版）,2007(02):356-360. |
| [5] | Widmer N C;West J.Thermochemical study of mercury oxidation in utility boiler fuel gases[A].Air&Waste Management Association.Salt Lake City.Utah,2000 |
| [6] | Helble J J;Fujiwara N .Kinetic modeling of homogeneous mercury oxidation:The importance of NO and H2O in predicting oxidation in coal-derived systems[J].Environmental Science and Technology,2001,35(18):3701. |
| [7] | Niksa S;Fujiwara N;Fujita Y et al.A mechanism for Hg oxidation in coal-derived exhausts[J].Journal of the Air And Waste Management Association,2002,52(08):894. |
| [8] | Xu Minghou;Qiao Yu;Zheng Chuguang .Modeling of homogeneous mercury speciation using detailed chemical kinetics[J].Combustion and Flame,2003,132(1-2):208. |
| [9] | Jennifer Wilcox;Terumi Okano .Ab initio-based Mercury Oxidation Kinetics via Bromine at Postcombustion Flue Gas Conditions[J].Energy & Fuels,2011(Mar./Apr.):1348-1356. |
| [10] | Cao Yan;Wang Quanhai et al.Investigation of mercury transformation by HBr addition in a slipstream facility with real flue gas atmospheres of bituminous coal and powder river basin coal[J].Energy and Fuels,2007,21(05):2719. |
| [11] | SHOU-HENG LIU;NAI-QIANG YAN;ZHAO-RONG LIU .Using Bromine Gas To Enhance Mercury Removal from Flue Gas of Coal-Fired Power Plants[J].Environmental Science & Technology: ES&T,2007(4):1405-1412. |
| [12] | Goodsite M E;Plane J M C;Skov H .A theoretical study of the oxidation of HgO to HgBr2 in the troposphere[J].Environmental Science and Technology,2004,38(16):1772. |
| [13] | 朱维良,蒋华良,陈凯先,嵇汝运,曹阳.分子间相互作用的量子化学研究方法[J].化学进展,1999(03):247-253. |
| [14] | Parr R G;Yang W T.Density functional theory of atoms and molecules[M].Oxford:Oxford Science Publication,1989:1. |
| [15] | Frisch M J;Trucks G W;Schlegel H B.Gaussian 03,Revision,D.01[M].Wsllingford CT:Gaussian,2004:1. |
| [16] | Malt'sev A A;Selivanov G K;Yampolsky V I et al.Far infrared absorption spectra of mercury dihalide vapours[J].Nat Phys Sci,1971,231:157. |
| [17] | Klemperer W;Lindeman L .Infrared spectrum of sercuric chloride and bromide[J].Journal of Chemical Physics,1956,25(03):397. |
| [18] | Clark R J H;Rippon D M .Vapour phase Raman spectra of mercury(Ⅱ) choride,mercury(Ⅱ) bromide and mercury (Ⅱ) iodide.ν(∑g+) band contours and the mercury-halogen bond polarisability derivatives[J].Journal of the Chemical Society,Faraday Transactions Ⅱ,1973,69(02):1496. |
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