High-Temperature Rate Constants for CH3OH + Kr Products, OH + CH3OH mg src="http://pubs.acs.org/images/entit
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- 作者：N. K. Srinivasan ; M.-C. Su ; J. V. Michael
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：May 17, 2007
- 年：2007
- 卷：111
- 期：19
- 页码：3951 - 3958
- 全文大小：169K
- 年卷期：v.111,no.19(May 17, 2007)
- ISSN：1520-5215
文摘
The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308nm (corresponding to a total path length of ~4.9 m) has been used to study the dissociation of methanolbetween 1591 and 2865 K. Rate constants for two product channels [CH3OH + Kr 
mages/entities/rarr.gif"> CH3 + OH + Kr (1)and CH3OH + Kr mages/entities/rarr.gif"> 1CH2 + H2O + Kr (2)] were determined. During the course of the study, it wasnecessary to determine several other rate constants that contributed to the profile fits. These include OH +CH3OH mages/entities/rarr.gif"> products, OH + (CH3)2CO mages/entities/rarr.gif"> CH2COCH3 + H2O, and OH + CH3 mages/entities/rarr.gif"> 1,3CH2 + H2O. The derivedexpressions, in units of cm3 molecule-1 s,-1 are k1 = 9.33 × 10-9 exp(-30857 K/T) for 1591-2287 K, k2 =3.27 × 10-10 exp(-25946 K/T) for 1734-2287 K, kOH+CH3OH = 2.96 × 10-16T1.4434 exp(-57 K/T) for 210-1710 K, kOH+(CH3)2CO = (7.3 ± 0.7) × 10-12 for 1178-1299 K and kOH+CH3 = (1.3 ± 0.2) × 10-11 for 1000-1200 K. With these values along with other well-established rate constants, a mechanism was used to obtainprofile fits that agreed with experiment to within <±10%. The values obtained for reactions 1 and 2 arecompared with earlier determinations and also with new theoretical calculations that are presented in thepreceding article in this issue. These new calculations are in good agreement with the present data for both(1) and (2) and also for OH + CH3 mages/entities/rarr.gif"> products.