Instantaneous Emission Spectra and Mechanism Study on the Reaction of ClF3O and n-Decane
YAN Hua1, LIU Xing-hua2, DING Yong3, ZHAO Zhi1, LUO Yong-feng1, WU Yu-hong1, YAN Peng1, DONG Lu1, WANG Da-xi4
1. Academe of the Rocket Force, Beijing 100094, China
2. School of Science, Hainan University, Haikou 570228, China
3. Sichuan Honghua Industry Limited, The Second Branch, Emeishan 614200, China
4. College of Science, the Petroleum University of China, Beijing 102200, China
Abstract：Chlorine trifluoride oxide (ClF3O) has stronger corrosive and oxidizing properties than other chlorine fluorides such as ClF3. It can react with numerous materials, e.g., water and hydrocarbons. The reaction between ClF3O and organic hydrocarbons may occur at quite a low temperatures and cause an explosion. So far, however, no detailed information about the reactions is available. Using an intensified charge-coupled device (ICCD) system, transient emission spectra of the reaction of ClF3O and n-decane were measured in a spectral range of 200～850 nm. Using density functional theory (DFT) method were performed to investigate the reaction mechanism of ClF3O and n-decane. All calculated results are consistent with the experimental data, which indicates that the present results are credible. The emission spectra of CH and C2 radical intermediates were observed in the reactions of ClF3O and n-decane under a no-oxygen environment, and this shows that ClF3O is a highly reactive compound. The detection of the CH, C2 and OH radical intermediates shows clearly that a large amount of energy was released during the reaction between ClF3O and n-decane under an oxygen environment. The primary peak was found at 431 nm corresponding to theA2Δ-X2Π electronic transition of the CH radical. The peak at 516 nm produced by theA3Пg-X3Пu electronic transition of the C2 radical was also observed. The peak at 309 nm corresponds to theA2Σ+-X2Пi electronic transition of the OH radical was also found. The results of the calculations showed that the F atom on ClF3O attacks the H atom on n-decane to initialize the reactions, and a F atom on ClF3O abstracted h atom on n-decane to produce HF. The initial reactions were considered to be barrier-less reactions and extremely exothermic. Under a no-oxygen environment, a fluorination reaction occurred between ClF3O and n-decane, and the products were ClFO, HF and corresponding fluoroalkanes. Fluoroalkanes may undergo dehydrogenation to form C10H20F. Then it is cleaved into C4H9 and C6H11F, then C4H9 further decomposed into C2H5 and C2H4, and finally formed CH and C2 radical. The initial steps of reaction in the aerobic environment were the same as in an anaerobic condition. When the reaction proceeded to a certain degree, after producing alkane radicals, O2 formed peroxic radicals, and peroxic radicals continue to decompose to form CH, C2 and OH radical intermediates. In the presence of oxygen, many OH radicals were produced in the reaction process, which accelerated the process of reaction. Macroscopically, n-decane was initiated by deflagration and combustion. Results show that the main emission bands are attributed to OH, CH and C2 radicals produced during the reaction process of ClF3O and n-decane, which reveals that small OH, CH and C2 radicals are important intermediate products in the reaction process of ClF3O and n-decane. This is very important for understanding the micro-process of reaction of ClF3O and n-decane. It also play an important theoretical foundation for the application of the weapon of ClF3O.
闫 华，刘兴华，丁 勇，赵 志，罗永锋，武玉红，颜 澎，董 露，王大喜. 氟氯酰与正癸烷反应的瞬态光谱和机理探索研究[J]. 光谱学与光谱分析, 2022, 42(05): 1522-1528.
YAN Hua, LIU Xing-hua, DING Yong, ZHAO Zhi, LUO Yong-feng, WU Yu-hong, YAN Peng, DONG Lu, WANG Da-xi. Instantaneous Emission Spectra and Mechanism Study on the Reaction of ClF3O and n-Decane. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(05): 1522-1528.
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