本文用量子化学从头计算法研究了Cr/O2/Ar气相体系所发生的两个反应的机理.在MP2/SDD水平上优化了反应物、过渡态、中间体和产物的几何构型.在同一水平上计算了能量,同时进行零点能校正,并且计算出反应的热效应、熵变、活化能和绝对速率常数,并与文献数据进行了比较.计算结果与文献数据比较吻合,表明量子化学计算是研究铬等痕量元素气相反应机理和计算热力学及动力学参数的一种有效手段.
参考文献
| [1] | D J Swaine.Trace Elements in Coal[M].London: Butterworths,1990:278. |
| [2] | Arthur Fontijin;Alan S Blue;A S Narayan et al.GasPhase Oxidation Kinetics of Toxic Metals at Incinerator Temperatures[J].Combust Sci and Tech,1994,101:59-73. |
| [3] | Kashireninov OE.;Fontijn A. .Modeling of chromium combustion in incineration: Thermochemistry of Cr-C-H-Cl combustion in air and selection of key reactions[J].Combustion and Flame,1998(4):498-506. |
| [4] | Sliger R N;John C K;Nick M M .Towards the Development of a Chemical Kinetic Model for the Homogeneous Oxidation of Mercury by Chlorine Species[J].Fuel Processing Technology,2000,65-66:423-438. |
| [5] | David P B;Jasmina H;Oleg E K et al.Laser-Induced Fluorescence and Mass Spectrometric Studied of the Cu+HCl Reaction Over a Wide Temperature Range[J].Journal of Physical Chemistry,1996,100:17835-17839. |
| [6] | A S Narayan;Aleksandar G Slavejkov;Arthur Fontijin.The Metals-HTP Technique: Kinetics of the Cr/O2/Ar Reaction System from 290 to 1510 K[M].Twenty-Fourth Symposium (International) on Combustion The Combustion Insititute,1992:727-733. |
| [7] | J Mark Parnis;S A Mitchell;Peter A Hackett .Transition Metal Atom Reaction Kinetics in the Gas Phase: Association and Oxidation Reaction of 7S3 Chromium Atoms[J].Journal of Physical Chemistry,1990,94:8152-8160. |
| [8] | M J Frisch;G W Trucks;H B Schlegel.Gaussian 98 (Revision A9) Gaussian Inc[M].Pittsburgh PA,1998 |
| [9] | Komornicki A;Mciver J W .Rapid Geometry Optization for Semiempirical Molecular Orbital Method[J].Chemical Physics Letters,1971,10:303. |
| [10] | Bartley B;Ebbinghaus;The Chromium Oxides;the Chromium Oxyhydroxides, and Volatility Calculations in Waste Incineration Processor .Thermodynamics of Gas Phase Chromium Species:[J].Combustion and Flame,1993,93:119-137. |
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