氟氯酰(ClF₃O)是一种极强的氟化剂和氧化剂, 极易与水和有机物发生爆炸性反应。 目前关于氟氯酰与水以及有机物等物质的反应机理不多见, 氟氯酰与水以及有机物等物质由反应物变成产物的过程有待研究。 采用ICCD瞬态光谱测量系统, 实时拍摄到无氧和有氧环境下氟氯酰和正癸烷反应的瞬态发射光谱; 采用量子化学理论方法对氟氯酰和正癸烷的反应机理进行了探索研究, 理论计算与试验结果相一致。 瞬态发射光谱试验结果表明, 在无氧环境下, 氟氯酰和正癸烷反应会产生CH和C₂自由基, 证实了无氧时氟氯酰确实能与正癸烷发生反应, 显示出氟氯酰的高活性; 在有氧环境下, 则会产生OH, CH和C₂自由基。 CH自由基强度最大的发射峰位于431.4nm, 归属于 A² Δ-X² П电子态之间的跃迁; C₂自由基强度最大的发射峰位于516.3 nm, 归属于 A³ П_g- X³ П_u电子跃迁; OH自由基强度最大的发射峰位于309.5 nm, 归属于 A² Σ⁺ -X² П_i电子跃迁。 量子化学理论计算结果表明, ClF₃O与正癸烷的反应始于ClF₃O中具有较多负电荷的F原子向正癸烷分子中间的H原子进攻生成HF, 该引发反应活化能很低, 并大量放热。 在无氧环境下, 氟氯酰与正癸烷可能发生氟代反应, 反应产物为ClFO、 HF和相应的氟代烷烃等。 氟代烷烃可能会发生脱氢反应生成C₁₀H₂₀F, 接着裂解为C₄H₉及氟代烯烃C₆H₁₁F; C₄H₉进一步分解为C₂H₅和C₂H₄, 最终形成CH和C₂自由基等。 有氧环境下反应初始步骤与无氧条件下相同, 当反应进行到一定程度, 产生烷烃自由基之后, O₂参与反应, 形成过氧自由基, 过氧自由基继续分解, 产生OH, CH和C₂自由基。 在氧气参与下, 反应过程中产生大量的OH自由基, 加速反应的进程, 宏观上表现为正癸烷被引发爆燃与燃烧。 这些自由基和中间体对于揭示氟氯酰和正癸烷反应的微观机理具有重要的指示意义。 氟氯酰和正癸烷的反应机理与试验结果均证实: 小自由基CH、 OH和C₂是氟氯酰与正癸烷反应过程中的重要中间产物, 这对于认识氟氯酰与正癸烷反应的微观过程非常重要, 也为氟氯酰的武器化应用奠定了一定的理论基础。

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 the A² Δ-X² Π electronic transition of the CH radical. The peak at 516 nm produced by the A³ П_g- X³ П_u electronic transition of the C₂ radical was also observed. The peak at 309 nm corresponds to the A² Σ⁺ -X² П_i 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.