%0 Journal Article %1 RaventosDuran:2007p1832 %A Raventos-Duran, M. Teresa %A Percival, Carl John %A McGillen, Max R %A Hamer, Paul D %A Shallcross, Dudley E %D 2007 %J Physical Chemistry Chemical Physics %K Absorption-Spectroscopy, Atmospheric Boundary-Layer, Chemistry, Constants, Gas-Phase, Ho2, Organic Peroxy-Radicals Pressure-Dependence, Product Rate Self-Reaction, Yield, %N 31 %P 4338--4348 %R 10.1039/b703038j %T Kinetics and branching ratio studies of the reaction of C2H5O2+HO2 using chemical ionisation mass spectrometry %U http://www.rsc.org/publishing/journals/CP/article.asp?doi=b703038j %V 9 %X The overall rate coefficient for the reaction Of C2H5O2 with HO2 was determined using a turbulent flow chemical ionization mass spectrometer (TF-CIMS) system over the pressure range of 75 to 200 Torr and temperatures between 195 and 298 K. The temperature dependence of the overall rate coefficient for the reaction between C2H5O2 and HO2 was fitted using the following Arrhenius expression: k(T) = (2.08(-0.62)(+0.87)) x 10(-13) exp (864 +/- 79)/T cm(-3) molecule(-1) s(-1). The upper limits for the branching ratios for reactive channels leading to O-3 and OH production were quantified for the first time. A tropospheric model has been used to assess the impact of the experimental error of the rate coefficients determined in this study on predicted concentrations of a number of key species, including O-3, OH, HO2, NO and NO2- In all cases it is found that the propagated error is very small and will not in itself be a major cause of uncertainy in modelled concentrations. However, at low temperatures, where there is a wide discrepancy between existing kinetic studies, modelling using the range of kinetic data in the literature shows a small but significant variation for C2H5O2, C-2,H5OOH, NOx and the HO2: OH ratio. Furthermore, a structure-activity relationship (SAR) was developed to rationalise the reactivity of the reaction between RO2 and HO2.

@article{RaventosDuran:2007p1832, abstract = {The overall rate coefficient for the reaction Of C2H5O2 with HO2 was determined using a turbulent flow chemical ionization mass spectrometer (TF-CIMS) system over the pressure range of 75 to 200 Torr and temperatures between 195 and 298 K. The temperature dependence of the overall rate coefficient for the reaction between C2H5O2 and HO2 was fitted using the following Arrhenius expression: k(T) = (2.08(-0.62)(+0.87)) x 10(-13) exp [(864 +/- 79)/T] cm(-3) molecule(-1) s(-1). The upper limits for the branching ratios for reactive channels leading to O-3 and OH production were quantified for the first time. A tropospheric model has been used to assess the impact of the experimental error of the rate coefficients determined in this study on predicted concentrations of a number of key species, including O-3, OH, HO2, NO and NO2- In all cases it is found that the propagated error is very small and will not in itself be a major cause of uncertainy in modelled concentrations. However, at low temperatures, where there is a wide discrepancy between existing kinetic studies, modelling using the range of kinetic data in the literature shows a small but significant variation for [C2H5O2], [C-2,H5OOH], [NOx] and the HO2: OH ratio. Furthermore, a structure-activity relationship (SAR) was developed to rationalise the reactivity of the reaction between RO2 and HO2.}, added-at = {2010-06-22T19:38:37.000+0200}, affiliation = {Univ Manchester, Sch Earth Atmospher {\&} Environm Sci, Manchester M60 1QD, Lancs, England}, author = {Raventos-Duran, M. Teresa and Percival, Carl John and McGillen, Max R and Hamer, Paul D and Shallcross, Dudley E}, biburl = {https://www.bibsonomy.org/bibtex/21c1f2ca885c10232d712cce772b1e1e5/gsmith}, date-added = {2010-03-11 11:14:44 -0500}, date-modified = {2010-03-11 11:16:00 -0500}, doi = {10.1039/b703038j}, interhash = {6fd7378322523626b13807746a659eaf}, intrahash = {1c1f2ca885c10232d712cce772b1e1e5}, journal = {Physical Chemistry Chemical Physics}, keywords = {Absorption-Spectroscopy, Atmospheric Boundary-Layer, Chemistry, Constants, Gas-Phase, Ho2, Organic Peroxy-Radicals Pressure-Dependence, Product Rate Self-Reaction, Yield,}, language = {English}, local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Physical%20Chemistry%20Chemical%20Physics/2007/Physical%20Chemistry%20Chemical%20Physics,%209,%204338-4348%202007.pdf}, month = Jan, number = 31, pages = {4338--4348}, pmid = {000249100500033}, rating = {0}, timestamp = {2010-06-22T19:38:47.000+0200}, title = {Kinetics and branching ratio studies of the reaction of C2H5O2+HO2 using chemical ionisation mass spectrometry}, uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p1832}, url = {http://www.rsc.org/publishing/journals/CP/article.asp?doi=b703038j}, volume = 9, year = 2007 }