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首页> 外文期刊>RSC Advances >Mechanism investigation on the reactions of ClF3O and n-decane by combining density functional theory and spontaneous emission spectroscopy
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Mechanism investigation on the reactions of ClF3O and n-decane by combining density functional theory and spontaneous emission spectroscopy

机译：结合密度泛函理论和自发发射光谱研究ClF3O与正癸烷反应的机理

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The mechanism of the reactions of ClF _(3) O and n -decane had two stages. The first stage was the initial reaction between ClF _(3) O and n -decane. The initial reactions were investigated using a density functional theory (DFT) method. The results showed that the critical part of the mechanism of the initial reaction was the roaming of the HF intermediate. A H atom on n -decane was abstracted by a F atom on ClF _(3) O to produce HF. The formed HF roamed around and then broke to give ClFO, fluorinated decane and a new HF molecule. The initial reactions were considered to be barrier-less reactions and extremely exothermic. The average released energy of the initial reactions was 412.9?kJ mol ~(?1) , which was great enough to cause thermal decomposition of n -decane. The second stage included the reaction between ClFO and n -decane and the thermal decomposition of n -decane. The secondary reactions involving ClFO were also studied using a DFT method. ClFO was less reactive than ClF _(3) O. The average energy barrier of the reactions of ClFO and n -decane was 116.3 kJ mol ~(?1) and the average released energy was 266.5 kJ mol ~(?1) . Thermal decomposition of n -decane was evidenced by the emission spectra of the characteristic radical intermediates CH and C _(2) , which were observed using an intensified charge-coupled device (ICCD) system. The main gaseous products of the thermal decomposition of n -decane, as identified using gas chromatography, were hydrogen, ethylene and acetylene. The experimental results showed that the thermal decomposition of n -decane was an important secondary reaction following the initial reactions.
机译：ClF_（3）O和正癸烷的反应机理有两个阶段。第一步是ClF_（3）O和正癸烷之间的初始反应。使用密度泛函理论（DFT）方法研究了初始反应。结果表明，初始反应机理的关键部分是HF中间体的漫游。正癸烷上的一个H原子被ClF_（3）O上的一个F原子抽象产生HF。生成的HF到处漫游，然后分解得到ClFO，氟化癸烷和一个新的HF分子。最初的反应被认为是无障碍反应并且极度放热。初始反应的平均释放能量为412.9？kJ mol〜（？1），足以引起正癸烷的热分解。第二阶段包括ClFO与正癸烷之间的反应以及正癸烷的热分解。还使用DFT方法研究了涉及ClFO的二级反应。 ClFO的反应性不如ClF_（3）O。ClFO与正癸烷反应的平均能垒为116.3kJ mol〜（？1），平均释放能为266.5kJmol〜（？1）。正癸烷的热分解由特征自由基中间体CH和C _（2）的发射光谱证明，这些光谱是使用增强电荷耦合器件（ICCD）系统观察到的。用气相色谱法鉴定，正癸烷热分解的主要气体产物是氢气，乙烯和乙炔。实验结果表明，正癸烷的热分解是继初始反应之后的重要二级反应。

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