Comment on 鈥淜inetics of the reactions of Cl atoms with 2-buten-1-ol, 2-methyl-2-propen-1-ol, and 3-methyl-2-buten-1-ol as a function of temperature鈥?by Rodriguez et al. (J. Atmos. Chem. (2008) 59:187鈥?97)
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- 作者：Timothy J. Wallington and Abdelwahid Mellouki
- 关键词：Chlorine atoms ; Unsaturated alcohols
- 刊名：Journal of Atmospheric Chemistry
- 出版时间：May, 2009
- 出版年：2009
- 期刊代码：37_01677764
- 类别：ch
- 卷：63
- 期：1
- 页码：93-94
- 数据来源：sp
摘要
The Arrhenius expressions and the data plotted in Figure 2 of Rodriguez et al. 2008 give rate coefficients of approximately 2 脳 10-8 cm3 molecule-1 s-1 at 255 K. Such values are approximately two orders of magnitude larger than expected from simple collision theory (Finlayson-Pitts and Pitts 1986). The rate coefficients reported at sub-ambient temperatures are substantially greater than the gas kinetic limit and are not physically plausible. The rate coefficients reported by Rodriguez et al. imply a long range attraction between the reactants which is not reasonable for reaction of neutral species such as chlorine atoms and unsaturated alcohols. We also note that the pre-exponential A factors (10-23-10-20) and activation energies (−15 kcal mol-1) are not physically plausible. We conclude that there are large systematic errors in the study by Rodriguez et al. (Atmos Chem 59:187–197, 2008).