Unimolecular decomposition of formic acid in the gas phase--on the ratio of the competing reaction channels.
Unimolecular decomposition of formic acid in the gas phase--on the ratio of the competing reaction channels.
复制标题
DOI：
10.1021/jp045072h
复制
发表时间：
2005-06
期刊：
影响因子：
--
通讯作者：
Ko Saito;Takanori Shiose;O. Takahashi;Y. Hidaka;Fuhito Aiba;K. Tabayashi
中科院分区：
文献类型：
--
作者：
Ko Saito;Takanori Shiose;O. Takahashi;Y. Hidaka;Fuhito Aiba;K. Tabayashi
利用两种激波管对甲酸在气相中的热分解进行了重新研究。单分子分解通过主脱水通道(K1)和次要脱羧基通道(K2)进行。这一结果与我们以前的研究(J.Chem.太棒了。1984、80、4989)。在1300~2000K的温度范围内，在(0.5~2.5)×10~(-5)mol·cm~(-3)的总密度范围内，脱羧基处于衰减区。实验结果与传统过渡态理论和莱斯-拉姆斯佩格-卡塞尔-马库斯理论的理论计算值进行了比较。
The thermal decomposition of formic acid was reinvestigated in the gas phase using two types of shock tubes. It was confirmed that the unimolecular decomposition proceeds through a main channel of dehydration (k1) and a minor decarboxylation channel (k2). This result is in good agreement with our previous study (J. Chem. Phys. 1984, 80, 4989). Furthermore, it was confirmed that the dehydration process is in the second-order region and that the decarboxylation is in the falloff region, in the temperature range of 1300-2000 K and over the total density of (0.5-2.5) x 10(-5) mol cm(-3). The experimental ratios between the two channels, k2/k1, are compared with those of theoretical calculations by conventional transition state theory and the Rice-Ramsperger-Kassel-Marcus theory.