Ozonolysis fragment quenching by nitrate formation: The pressure dependence of prompt OH radical formation. Presto, A., A. & Donahue, N., M. J. Phys. Chem. A, 108:9096-9104, 2004. abstract bibtex The gas-phase reaction of ozone with alkenes is known
to be a significant source of OH radicals in the troposphere. The
pressure dependence of the OH yield in ozone-alkene reactions is
both important and controversial; the poor understanding of the
pressure-dependent OH yield for different ozone-alkene reactions is
a major obstacle to developing an accurate simulation of
tropospheric chemistry. Using a high-pressure flow reactor, we have
investigated the ozonolysis of a series of alkenes in the presence
of NO2. The four alkenes studied were 2,3-dimethyl-2-butene (TME),
trans-5-decene, cyclohexene, and alpha-pinene, which provide
significant differences in size (C6 vs C10) and structure (linear
vs cyclic) to elucidate the influence of these competing effects on
OH formation. OH yields from TME and trans-5-decene ozonolysis
decrease with increasing pressure, but OH yields from cyclohexene
(0.64 +/- 0.20) and alpha-pinene (0.89 +/- 0.20) are
pressure-independent and consistent with the literature. Acetone
production increases relative to TME consumption as pressure
increases; this observation, supported by density functional
calculations, is consistent with acetone and nitrate radical
production from the SCI + NO2 reaction. Both the pressure
dependence of OH formation from the linear alkenes (TME and
trans-5-decene) and the pressure-independent OH yields observed for
cyclohexene and alpha-pinene can be explained by changes in the
extent of collisional stabilization of the carbonyl oxide (Criegee)
intermediate with increasing pressure.
C1 Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA.
Carnegie Mellon Univ, Dept Chem Engn, Pittsburgh, PA 15213 USA.
@article{
title = {Ozonolysis fragment quenching by nitrate formation: The pressure dependence of prompt OH radical formation},
type = {article},
year = {2004},
pages = {9096-9104},
volume = {108},
id = {b0b15c2a-8b9c-346a-89ec-e240552259f3},
created = {2014-10-08T16:28:18.000Z},
file_attached = {false},
profile_id = {363623ef-1990-38f1-b354-f5cdaa6548b2},
group_id = {02267cec-5558-3876-9cfc-78d056bad5b9},
last_modified = {2017-03-14T17:32:24.802Z},
read = {false},
starred = {false},
authored = {false},
confirmed = {true},
hidden = {false},
citation_key = {Presto:JPCA:2004a},
source_type = {article},
private_publication = {false},
abstract = {The gas-phase reaction of ozone with alkenes is known
to be a significant source of OH radicals in the troposphere. The
pressure dependence of the OH yield in ozone-alkene reactions is
both important and controversial; the poor understanding of the
pressure-dependent OH yield for different ozone-alkene reactions is
a major obstacle to developing an accurate simulation of
tropospheric chemistry. Using a high-pressure flow reactor, we have
investigated the ozonolysis of a series of alkenes in the presence
of NO2. The four alkenes studied were 2,3-dimethyl-2-butene (TME),
trans-5-decene, cyclohexene, and alpha-pinene, which provide
significant differences in size (C6 vs C10) and structure (linear
vs cyclic) to elucidate the influence of these competing effects on
OH formation. OH yields from TME and trans-5-decene ozonolysis
decrease with increasing pressure, but OH yields from cyclohexene
(0.64 +/- 0.20) and alpha-pinene (0.89 +/- 0.20) are
pressure-independent and consistent with the literature. Acetone
production increases relative to TME consumption as pressure
increases; this observation, supported by density functional
calculations, is consistent with acetone and nitrate radical
production from the SCI + NO2 reaction. Both the pressure
dependence of OH formation from the linear alkenes (TME and
trans-5-decene) and the pressure-independent OH yields observed for
cyclohexene and alpha-pinene can be explained by changes in the
extent of collisional stabilization of the carbonyl oxide (Criegee)
intermediate with increasing pressure.
C1 Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA.
Carnegie Mellon Univ, Dept Chem Engn, Pittsburgh, PA 15213 USA.},
bibtype = {article},
author = {Presto, A A and Donahue, N M},
journal = {J. Phys. Chem. A}
}
Downloads: 0
{"_id":{"_str":"5411bfbb480d3bb058002a18"},"__v":0,"authorIDs":[],"author_short":["Presto, A., A.","Donahue, N., M."],"bibbaseid":"presto-donahue-ozonolysisfragmentquenchingbynitrateformationthepressuredependenceofpromptohradicalformation-2004","bibdata":{"title":"Ozonolysis fragment quenching by nitrate formation: The pressure dependence of prompt OH radical formation","type":"article","year":"2004","pages":"9096-9104","volume":"108","id":"b0b15c2a-8b9c-346a-89ec-e240552259f3","created":"2014-10-08T16:28:18.000Z","file_attached":false,"profile_id":"363623ef-1990-38f1-b354-f5cdaa6548b2","group_id":"02267cec-5558-3876-9cfc-78d056bad5b9","last_modified":"2017-03-14T17:32:24.802Z","read":false,"starred":false,"authored":false,"confirmed":"true","hidden":false,"citation_key":"Presto:JPCA:2004a","source_type":"article","private_publication":false,"abstract":"The gas-phase reaction of ozone with alkenes is known\nto be a significant source of OH radicals in the troposphere. The\npressure dependence of the OH yield in ozone-alkene reactions is\nboth important and controversial; the poor understanding of the\npressure-dependent OH yield for different ozone-alkene reactions is\na major obstacle to developing an accurate simulation of\ntropospheric chemistry. Using a high-pressure flow reactor, we have\ninvestigated the ozonolysis of a series of alkenes in the presence\nof NO2. The four alkenes studied were 2,3-dimethyl-2-butene (TME),\ntrans-5-decene, cyclohexene, and alpha-pinene, which provide\nsignificant differences in size (C6 vs C10) and structure (linear\nvs cyclic) to elucidate the influence of these competing effects on\nOH formation. OH yields from TME and trans-5-decene ozonolysis\ndecrease with increasing pressure, but OH yields from cyclohexene\n(0.64 +/- 0.20) and alpha-pinene (0.89 +/- 0.20) are\npressure-independent and consistent with the literature. Acetone\nproduction increases relative to TME consumption as pressure\nincreases; this observation, supported by density functional\ncalculations, is consistent with acetone and nitrate radical\nproduction from the SCI + NO2 reaction. Both the pressure\ndependence of OH formation from the linear alkenes (TME and\ntrans-5-decene) and the pressure-independent OH yields observed for\ncyclohexene and alpha-pinene can be explained by changes in the\nextent of collisional stabilization of the carbonyl oxide (Criegee)\nintermediate with increasing pressure.\nC1 Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA.\nCarnegie Mellon Univ, Dept Chem Engn, Pittsburgh, PA 15213 USA.","bibtype":"article","author":"Presto, A A and Donahue, N M","journal":"J. Phys. Chem. A","bibtex":"@article{\n title = {Ozonolysis fragment quenching by nitrate formation: The pressure dependence of prompt OH radical formation},\n type = {article},\n year = {2004},\n pages = {9096-9104},\n volume = {108},\n id = {b0b15c2a-8b9c-346a-89ec-e240552259f3},\n created = {2014-10-08T16:28:18.000Z},\n file_attached = {false},\n profile_id = {363623ef-1990-38f1-b354-f5cdaa6548b2},\n group_id = {02267cec-5558-3876-9cfc-78d056bad5b9},\n last_modified = {2017-03-14T17:32:24.802Z},\n read = {false},\n starred = {false},\n authored = {false},\n confirmed = {true},\n hidden = {false},\n citation_key = {Presto:JPCA:2004a},\n source_type = {article},\n private_publication = {false},\n abstract = {The gas-phase reaction of ozone with alkenes is known\nto be a significant source of OH radicals in the troposphere. The\npressure dependence of the OH yield in ozone-alkene reactions is\nboth important and controversial; the poor understanding of the\npressure-dependent OH yield for different ozone-alkene reactions is\na major obstacle to developing an accurate simulation of\ntropospheric chemistry. Using a high-pressure flow reactor, we have\ninvestigated the ozonolysis of a series of alkenes in the presence\nof NO2. The four alkenes studied were 2,3-dimethyl-2-butene (TME),\ntrans-5-decene, cyclohexene, and alpha-pinene, which provide\nsignificant differences in size (C6 vs C10) and structure (linear\nvs cyclic) to elucidate the influence of these competing effects on\nOH formation. OH yields from TME and trans-5-decene ozonolysis\ndecrease with increasing pressure, but OH yields from cyclohexene\n(0.64 +/- 0.20) and alpha-pinene (0.89 +/- 0.20) are\npressure-independent and consistent with the literature. Acetone\nproduction increases relative to TME consumption as pressure\nincreases; this observation, supported by density functional\ncalculations, is consistent with acetone and nitrate radical\nproduction from the SCI + NO2 reaction. Both the pressure\ndependence of OH formation from the linear alkenes (TME and\ntrans-5-decene) and the pressure-independent OH yields observed for\ncyclohexene and alpha-pinene can be explained by changes in the\nextent of collisional stabilization of the carbonyl oxide (Criegee)\nintermediate with increasing pressure.\nC1 Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA.\nCarnegie Mellon Univ, Dept Chem Engn, Pittsburgh, PA 15213 USA.},\n bibtype = {article},\n author = {Presto, A A and Donahue, N M},\n journal = {J. Phys. Chem. A}\n}","author_short":["Presto, A., A.","Donahue, N., M."],"bibbaseid":"presto-donahue-ozonolysisfragmentquenchingbynitrateformationthepressuredependenceofpromptohradicalformation-2004","role":"author","urls":{},"downloads":0},"bibtype":"article","biburl":null,"creationDate":"2014-09-11T15:28:59.082Z","downloads":0,"keywords":[],"search_terms":["ozonolysis","fragment","quenching","nitrate","formation","pressure","dependence","prompt","radical","formation","presto","donahue"],"title":"Ozonolysis fragment quenching by nitrate formation: The pressure dependence of prompt OH radical formation","year":2004}