...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >High-temperature shock tube and modeling studies on the reactions of methanol with d-atoms and CH_3-radicals
【24h】

High-temperature shock tube and modeling studies on the reactions of methanol with d-atoms and CH_3-radicals

机译：高温激波管及甲醇与d原子和CH_3-自由基反应的模型研究

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The shock tube technique has been used to study the hydrogen abstraction reactions D + CH_3OH → CH_2O + H + HD (A) and CH _3 + CH_3OH → CH_2O + H + CH_4 (B). For reaction A, the experiments span a T-range of 1016 K ≤ T ≤ 1325 K, at pressures 0.25 bar ≤ P ≤ 0.46 bar. The experiments on reaction B, CH _3 + CH_3OH, cover a T-range of 1138 K ≤ T ≤ 1270 K, at pressures around 0.40 bar. Reflected shock tube experiments, monitoring the depletion of D-atoms by applying D-atom atomic resonance absorption spectrometry (ARAS), were performed on reaction A using gas mixtures of C_2D _5I and CH_3OH in Kr bath gas. C_2D_5I was used as precursor for D-atoms. For reaction B, reflected shock tube experiments monitoring H-atom formation with H-ARAS, were carried out using gas mixtures of diacetyl ((CH_3CO)_2) and CH_3OH in Kr bath gas. (CH_3CO)_2 was used as the source of CH _3-radicals. Detailed reaction models were assembled to fit the D-atom and H-atom time profiles in order to obtain experimental rate constants for reactions A and B. Total rate constants from the present experiments on D + CH_3OH and CH_3 + CH_3OH can be represented by the Arrhenius equations kA(T) = 1.51 × 10~(-10) exp(-3843 K/T) cm~3 molecules~(-1) s~(-1) (1016 K ≤ T ≤ 1325 K) and kB(T) = 9.62 × 10-12 exp(-7477 K/T) cm~3 molecules~(-1) s~(-1) (1138 K ≤ T ≤ 1270 K). The experimentally obtained rate constants were compared with available rate data from the literature. The results from quantum chemical studies on reaction A were found to be in good agreement with the present results. The present work represents the first direct experimental study on these bimolecular reactions at combustion temperatures and is important to the high-temperature oxidation of CH_3OH.
机译：激波管技术已用于研究氢提取反应D + CH_3OH→CH_2O + H + HD（A）和CH _3 + CH_3OH→CH_2O + H + CH_4（B）。对于反应A，在0.25 bar≤P≤0.46 bar的压力下，实验跨度为1016 K≤T≤1325 K的T范围。反应B的实验CH _3 + CH_3OH，在0.40 bar左右的压力下，其T范围为1138 K≤T≤1270K。使用Kr浴气体中C_2D _5I和CH_3OH的气体混合物对反应A进行反射激波管实验，以应用D原子原子共振吸收光谱法（ARAS）监测D原子的消耗。 C_2D_5I用作D原子的前体。对于反应B，使用Kr浴气体中的二乙酰基（（CH_3CO）_2）和CH_3OH的气体混合物，进行了用H-ARAS监测H原子形成的反射激波管实验。 （CH_3CO）_2被用作CH _3-自由基的来源。组装了详细的反应模型以适合D原子和H原子的时间曲线，以获得反应A和B的实验速率常数。本实验中D + CH_3OH和CH_3 + CH_3OH的总速率常数可以表示为Arrhenius方程kA（T）= 1.51×10〜（-10）exp（-3843 K / T）cm〜3分子〜（-1）s〜（-1）（1016 K≤T≤1325 K）和kB（ T）= 9.62×10-12 exp（-7477 K / T）cm〜3分子〜（-1）s〜（-1）（1138 K≤T≤1270 K）。将实验获得的速率常数与文献中可获得的速率数据进行比较。发现反应A的量子化学研究结果与当前结果高度吻合。目前的工作代表了在燃烧温度下对这些双分子反应的首次直接实验研究，对CH_3OH的高温氧化非常重要。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号