Self-reaction of HO2 and DO2: negative temperature dependence and pressure effects
| dc.contributor.author | Mozurkewich, M. | |
| dc.contributor.author | Benson, S.W. | |
| dc.date.accessioned | 2010-06-22T13:52:53Z | |
| dc.date.available | 2010-06-22T13:52:53Z | |
| dc.date.issued | 1985 | |
| dc.description.abstract | The negative temperature dependence, pressure dependence, and isotope effects of the self-reaction of HO2 are modeled, using RRKM theory, by assuming that the reaction proceeds via a cyclic, hydrogen-bonded intermediate. The negative temperature dependence is due to a tight transition state, with a negative threshold energy relative to reactants, for decomposition of the intermediate to products. A symmetric structure for this transition state reproduces the observed isotope effect. The weak pressure dependence for DO2 self-reaction is due to the approach to the high-pressure limit. Addition of a polar collision partner, such as ammonia or water vapor, enhances the rate by forming an adduct that reacts to produce deexcited intermediate. A detailed model is presented to fit the data for these effects. Large ammonia concentrations should make it possible to reach the high-pressure limit of the self-reaction of HO2. | en |
| dc.identifier.citation | Int. J. Chem. Kin., 17, 787-807. | en |
| dc.identifier.uri | http://hdl.handle.net/10315/4266 | |
| dc.language.iso | en | en |
| dc.publisher | Wiley-Blackwell | en |
| dc.rights | The definitive version is available at www3.interscience.wiley.com | en |
| dc.rights.article | http://www3.interscience.wiley.com/cgi-bin/fulltext/109607466/PDFSTART | en |
| dc.rights.journal | http://www3.interscience.wiley.com/journal/5000443/home?CRETRY=1&SRETRY=0 | en |
| dc.title | Self-reaction of HO2 and DO2: negative temperature dependence and pressure effects | en |
| dc.type | Article | en |