Thermal Decomposition of Nitromethane and Reaction between CH3 and NO2

被引:39
作者
Matsugi, Akira [1 ]
Shiina, Hiroumi [1 ]
机构
[1] Natl Inst Adv Ind Sci & Technol, 16-1 Onogawa, Tsukuba, Ibaraki 3058569, Japan
关键词
SHOCK-WAVES; DISSOCIATION; TEMPERATURE; KINETICS; RADICALS; TUBE; MECHANISM; OXIDATION; PRESSURE; RANGE;
D O I
10.1021/acs.jpca.7b03715
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The thermal decomposition of gaseous nitromethane and the subsequent bimolecular reaction between CH3 and NO2 have been experimentally studied using time-resolved cavity-enhanced absorption spectroscopy behind reflected shock waves in the temperature range 1336-1827 K and at a pressure of 100 kPa. Temporal evolution of NO2 was observed following the pyrolysis of nitromethane (diluted to 80-140 ppm in argon) by monitoring the absorption around 400 nm. The primary objectives of the current work were to evaluate the rate constant for the CH3 + NO2 reaction (k(2) ) and to examine the contribution of the roaming isomerization pathway in nitromethane decomposition. The resultant rate constant can be expressed as k(2) = (9.3 +/- 1.8) x 10(-10)(T/K)(-0.5) cm(3) molecule(-1) s(-1), which is in reasonable agreement with available literature data. The decomposition of nitromethane was found to predominantly proceed with the C-N bond fission process with the branching fraction of 0.97 +/- 0.06. Therefore, the upper limit of the branching fraction for the roaming pathway was evaluated to be 0.09.
引用
收藏
页码:4218 / 4224
页数:7
相关论文
共 44 条
[1]   Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries [J].
Alecu, I. M. ;
Zheng, Jingjing ;
Zhao, Yan ;
Truhlar, Donald G. .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2010, 6 (09) :2872-2887
[2]   Thermal Dissociation and Roaming Isomerization of Nitromethane: Experiment and Theory [J].
Annesley, Christopher J. ;
Randazzo, John B. ;
Klippenstein, Stephen J. ;
Harding, Lawrence B. ;
Jasper, Ahren W. ;
Georgievskii, Yuri ;
Ruscic, Branko ;
Tranter, Robert S. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2015, 119 (28) :7872-7893
[3]   Low temperature oxidation of methane: the influence of nitrogen oxides [J].
Bendtsen, AB ;
Glarborg, P ;
Dam-Johansen, K .
COMBUSTION SCIENCE AND TECHNOLOGY, 2000, 151 (01) :31-71
[4]   INVESTIGATION INTO THE PRESSURE-DEPENDENCE BETWEEN 1 AND 10 TORR OF THE REACTIONS OF NO2 WITH CH3 AND CH3O [J].
BIGGS, P ;
CANOSAMAS, CE ;
FRACHEBOUD, JM ;
PARR, AD ;
SHALLCROSS, DE ;
WAYNE, RP ;
CARALP, F .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1993, 89 (23) :4163-4169
[5]  
Boyer E., 2006, 44 AIAA AER SCI M EX, P361, DOI [10.2514/6.2006-361, DOI 10.2514/6.2006-361]
[6]   Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections [J].
Chai, Jeng-Da ;
Head-Gordon, Martin .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (44) :6615-6620
[7]   Photodissociation dynamics of nitromethane and methyl nitrite by infrared multiphoton dissociation imaging with quasiclassical trajectory calculations: Signatures of the roaming pathway [J].
Dey, Arghya ;
Fernando, Ravin ;
Abeysekera, Chamara ;
Homayoon, Zahra ;
Bowman, Joel M. ;
Suits, Arthur G. .
JOURNAL OF CHEMICAL PHYSICS, 2014, 140 (05)
[8]   Kinetic modeling of the interactions between NO and hydrocarbons in the oxidation of hydrocarbons at low temperatures [J].
Faravelli, T ;
Frassoldati, A ;
Ranzi, E .
COMBUSTION AND FLAME, 2003, 132 (1-2) :188-207
[9]  
Forst W., 2003, UNIMOLECULAR REACTIO
[10]  
Frisch M.J., 2010, GAUSSIAN 09