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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >HNC/HCN ratio in acetonitrile, formamide, and BrCN discharge
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HNC/HCN ratio in acetonitrile, formamide, and BrCN discharge

机译：乙腈，甲酰胺和BrCN排放物中的HNC / HCN比

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Time-resolved Fourier transform (FT) spectrometry was used to study the dynamics of radical reactions forming the HCN and HNC isomers in pulsed glow discharges through vapors of BrCN, acetonitrile (CH_3CN), and formamide (HCONH_2). Stable gaseous products of discharge chemistry were analyzed by selected ion flow tube mass spectrometry (SIFT-MS). Ratios of concentrations of the HNC/HCN isomers obtained using known transition dipole moments of rovibrational cold bands v_1 were found to be in the range 2.2-3%. A kinetic model was used to assess the roles the radical chemistry and ion chemistry play in the formation of these two isomers. Exclusion of the radical reactions from the model resulted in a value of the HNC/HCN ratio 2 orders of magnitude lower than the experimental results, thus confirming their dominant role. The major process responsible for the formation of the HNC isomer is the reaction of the HCN isomer with the H atoms. The rate constant determined using the kinetic model from the present data for this reaction is 1.13 (±0.2) × 10~(-13 cm~3 s~(-1).
机译：时间分辨傅立叶变换（FT）光谱用于研究通过BrCN，乙腈（CH_3CN）和甲酰胺（HCONH_2）的蒸气在脉冲辉光放电中形成HCN和HNC异构体的自由基反应的动力学。通过选定的离子流管质谱仪（SIFT-MS）分析了放电化学的稳定气态产物。发现利用旋转振动冷带v_1的已知过渡偶极矩获得的HNC / HCN异构体的浓度比在2.2-3％的范围内。使用动力学模型评估自由基化学和离子化学在这两种异构体形成中的作用。从模型中排除自由基反应会导致HNC / HCN比值比实验结果低2个数量级，从而证实了它们的主导作用。形成HNC异构体的主要过程是HCN异构体与H原子的反应。使用动力学模型从当前数据确定的该反应的速率常数为1.13（±0.2）×10〜（-13 cm〜3 s〜（-1）。

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