Initiation Mechanisms and Kinetics of Pyrolysis and Combustion of JP-10 Hydrocarbon Jet Fuel
Initiation Mechanisms and Kinetics of Pyrolysis and Combustion of JP-10 Hydrocarbon Jet Fuel
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DOI：
10.1021/jp8081479
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发表时间：
2009-03-05
影响因子：
2.9
通讯作者：
Goddard, William A., III
中科院分区：
文献类型：
--
作者：
Chenoweth, Kimberly;van Duin, Adri C. T.;Goddard, William A., III
为了研究与单组分碳氢喷气燃料 JP-10（外三环[5.2.1.0(2,6)]癸烷）热解相关的引发机制和动力学，我们采用 ReaxFF 反作用力场进行了分子动力学 (MD) 模拟。我们发现主要分解反应涉及（1）乙烯从 JP-10 解离，导致形成 C-8 烃中间体，或（2）产生两种 C-5 烃。 ReaxFF MD 与作为温度函数的产物分布的实验结果非常一致。根据JP-10的消耗速率，我们计算出该材料热分解的活化能为58.4 kcal/mol，这与JP-10中应变促进的C-C键断裂机制一致。这与 62.4 kcal/mol 的实验值吻合良好。此外，我们对导致 JP-10 氧化的反应事件进行了 ReaxFF MD 研究。在这里，我们发现从 ReaxFF 获得的热力学能量与量子力学计算之间总体一致，说明了 ReaxFF 在研究碳氢化合物氧化方面的有用性。这些结果与现有实验观察结果的一致性表明，ReaxFF 可以为重要碳氢化合物燃料的复杂热分解和氧化过程提供有用的见解。
In order to investigate the initiation mechanisms and kinetics associated with the pyrolysis of JP-10 (exotricyclo[5.2.1.0(2,6)]decane), a single-component hydrocarbon jet fuel, we carried out molecular dynamics (MD) simulations employing the ReaxFF reactive force field. We found that the primary decomposition reactions involve either (1) dissociation of ethylene from JP-10, resulting in the formation of a C-8 hydrocarbon intermediate, or (2) the production Of two C-5 hydrocarbons. ReaxFF MD leads to good agreement with experiment for the product distribution as a function of temperature. On the basis of the rate of consumption of JP-10, we calculate an activation energy of 58.4 kcal/mol for the thermal decomposition of this material, which is consistent with a strain-facilitated C-C bond cleavage mechanism in JP-10. This compares well with the experimental value of 62.4 kcal/mol. In addition, we carried out ReaxFF MD studies of the reactive events responsible for oxidation of JP-10. Here we found overall agreement between the thermodynamic energies obtained from ReaxFF and quantum-mechanical calculations, illustrating the usefulness of ReaxFF for studying oxidation of hydrocarbons. The agreement of these results with available experimental observations demonstrates that ReaxFF can provide useful insights into the complicated thermal decomposition and oxidation processes of important hydrocarbon fuels.