%0 Journal Article %1 Leather:2010p3169 %A Leather, Kimberley E %A McGillen, Max R %A Percival, Carl J %D 2010 %J Physical Chemistry Chemical Physics %K Aerosol Atmospheric Calculated Chamber, Chemistry, Formation, Hydroxyl, Mechanisms, Molecular-Properties, Oh Organic Ozone, Parameters, Products, Rate %N 12 %P 2935--2943 %R 10.1039/b919731a %T Temperature-dependent ozonolysis kinetics of selected alkenes in the gas phase: an experimental and structure-activity relationship (SAR) study %U http://www.rsc.org/publishing/journals/CP/article.asp?doi=b919731a %V 12 %X The kinetics of the reactions of ozone with several alkenes have been measured at atmospheric pressure between 217 and 301 K using EXTRA (EXTreme RAnge chamber). This work represents the first kinetic determinations of the system and focuses on the temperature-dependence of alkene ozonolysis, which is an important tropospheric process impacting upon climate and human health, yet few studies have investigated these reactions as a function of temperature. Temperature-dependent rate coefficients have been established for 3,3-dimethyl-1-butene, 2,4,4-trimethyl-1-pentene and 4-methyl-1-pentene at 217-301 K and atmospheric pressure. The derived Arrhenius expressions are as follows: k = (2.68(-1.23)(+2.23)) x 10(-15) exp-(16.29 +/- 1.20/RT), k = (7.31(-4.05)(+9.39)) x 10(-15) exp-(15.33 +/- 1.84/RT) and k = (5.21(-1.85)(+2.85)) x 10(-15) exp-(15.66 +/- 0.87/RT) cm(3) molecule(-1) s(-1) for 3,3-dimethyl-1-butene, 2,4,4-trimethyl-1-pentene and 4-methyl-1-pentene, respectively. A strong linear correlation has been observed between a simple structure - activity relationship (SAR) and the activation energy, E-a, possessing an R-2 value of 0.90. However, no significant correlation was observed for the A-factor. Notwithstanding, with accurate predictions of the SAR for E-a and log k(298), values for the A-factor can be retrieved, and hence the prediction of k at any temperature. The newly acquired data agree well with the original SAR and suggest that the factors controlling the rate of ozonolysis reaction are captured accurately by the SAR index.

@article{Leather:2010p3169, abstract = {The kinetics of the reactions of ozone with several alkenes have been measured at atmospheric pressure between 217 and 301 K using EXTRA (EXTreme RAnge chamber). This work represents the first kinetic determinations of the system and focuses on the temperature-dependence of alkene ozonolysis, which is an important tropospheric process impacting upon climate and human health, yet few studies have investigated these reactions as a function of temperature. Temperature-dependent rate coefficients have been established for 3,3-dimethyl-1-butene, 2,4,4-trimethyl-1-pentene and 4-methyl-1-pentene at 217-301 K and atmospheric pressure. The derived Arrhenius expressions are as follows: k = (2.68(-1.23)(+2.23)) x 10(-15) exp[-(16.29 +/- 1.20/RT)], k = (7.31(-4.05)(+9.39)) x 10(-15) exp[-(15.33 +/- 1.84/RT)] and k = (5.21(-1.85)(+2.85)) x 10(-15) exp[-(15.66 +/- 0.87/RT)] cm(3) molecule(-1) s(-1) for 3,3-dimethyl-1-butene, 2,4,4-trimethyl-1-pentene and 4-methyl-1-pentene, respectively. A strong linear correlation has been observed between a simple structure - activity relationship (SAR) and the activation energy, E-a, possessing an R-2 value of 0.90. However, no significant correlation was observed for the A-factor. Notwithstanding, with accurate predictions of the SAR for E-a and log k(298), values for the A-factor can be retrieved, and hence the prediction of k at any temperature. The newly acquired data agree well with the original SAR and suggest that the factors controlling the rate of ozonolysis reaction are captured accurately by the SAR index.}, added-at = {2010-06-22T19:38:37.000+0200}, affiliation = {Univ Manchester, Ctr Atmospher Sci, Sch Earth Atmospher {\&} Environm Sci, Manchester M13 9PL, Lancs, England}, author = {Leather, Kimberley E and McGillen, Max R and Percival, Carl J}, biburl = {https://www.bibsonomy.org/bibtex/241d0a289f5c5923ccc6dd777a0216cf0/gsmith}, date-added = {2010-04-29 08:40:55 -0400}, date-modified = {2010-04-29 08:41:06 -0400}, doi = {10.1039/b919731a}, interhash = {7f34aea2cb64da20ab30f40ae17c261a}, intrahash = {41d0a289f5c5923ccc6dd777a0216cf0}, journal = {Physical Chemistry Chemical Physics}, keywords = {Aerosol Atmospheric Calculated Chamber, Chemistry, Formation, Hydroxyl, Mechanisms, Molecular-Properties, Oh Organic Ozone, Parameters, Products, Rate}, language = {English}, local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Physical%20Chemistry%20Chemical%20Physics/2010/Physical%20Chemistry%20Chemical%20Physics,%2012,%202935-2943%202010.pdf}, month = Jan, number = 12, pages = {2935--2943}, pmid = {000275385700017}, rating = {0}, read = {Yes}, timestamp = {2010-06-22T19:39:00.000+0200}, title = {Temperature-dependent ozonolysis kinetics of selected alkenes in the gas phase: an experimental and structure-activity relationship (SAR) study}, uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p3169}, url = {http://www.rsc.org/publishing/journals/CP/article.asp?doi=b919731a}, volume = 12, year = 2010 }