Mechanisms of Atmospheric Oxidation of the Oxygenates

1634 Pages·2011·197.522 MB·English

by  Jack Calvert, Abdelwahid Mellouki, John Orlando, Michael Pilling, Timothy Wallington

THE MECHANISMS OF
ATMOSPHERIC OXIDATION
OF THE OXYGENATES
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THE MECHANISMS OF
ATMOSPHERIC OXIDATION
OF THE OXYGENATES
JACK G. CALVERT, ABDELWAHID MELLOUKI,
JOHN J. ORLANDO, MICHAEL J. PILLING,
and TIMOTHY J. WALLINGTON
3
3
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Copyright©2011bybyJ.G.Calvert,A.Mellouki,J.J.Orlando,
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LibraryofCongressCataloging-in-PublicationData
Themechanismsofatmosphericoxidationoftheoxygenates/byJ.G.Calvert...[etal.].
p.cm.
Includesbibliographicalreferences.
ISBN978-0-19-976707-6
1.Atmosphericchemistry.2.Oxidizingagents—Environmentalaspects.3.Photochemical
oxidants—Environmentalaspects.4.Oxidation—Environmentalaspects.
I.Calvert,JackG.(JackGeorge),1923–
QC879.9.073M432011
551.51'1—dc22 20100022483
1 3 5 7 9 8 6 4 2
PrintedintheUnitedStatesofAmerica
onacid-freepaper
Contents
Acknowledgments viii III-B AcyclicEthers 290
AbouttheAuthors xi III-C Multi-FunctionalEthers 340
III-D UnsaturatedEthers 372
I THEOXYGENATES:THEIR III-E CyclicEthers 382
PROPERTIES,SOURCES, III-F AromaticEthers 420
ANDUSEASALTERNATIVE
III-G Halogen-Substituted
FUELS 3
Ethers 434
I-A RolesofOxygenatesin
III-H RateCoefficientCorrelationsand
AtmosphericChemistry 3
Structure–ActivityRelationships
I-B PhysicalPropertiesofthe
(SARs) 523
Oxygenates 6
I-C SourcesofOxygenatesinthe
Troposphere 19 IV RATECOEFFICIENTSAND
I-D AmbientConcentrationsofthe MECHANISMSFORTHE
OxygenatesintheLower ATMOSPHERICOXIDATIONOF
Troposphere 74 THEALDEHYDES 539
I-E UseofOxygenatesasFuels IV-A Introduction 539
orFuelAdditives 96 IV-B AcyclicAldehydes 540
I-F TreatmentofKineticData IV-C Hydroxyaldehydes 585
andEstimationof IV-E UnsaturatedAldehydes 598
AtmosphericLifetimesof IV-F Derivedfrom
Oxygenates 111 AtmosphericOxidation
oftheAromaticandBiogenic
II RATECOEFFICIENTSAND Hydrocarbons 618
MECHANISMSFORTHE IV-G Halogen-Substituted
ATMOSPHERICOXIDATIONOF Aldehydes 634
THEALCOHOLS 116
II-A Introduction 116
V RATECOEFFICIENTSAND
II-B AcyclicAlcohols 117
MECHANISMSFORTHE
II-C Diols 183
ATMOSPHERICOXIDATIONOF
II-D UnsaturatedAlcohols 185
THEKETONES 651
II-E AromaticAlcohols 236
V-A Introduction 651
II-F Halogen-Substituted
V-B Alkanones 652
Alcohols 256
II-G Hydroperoxidesand V-C Hydroxyketones 691
Peroxides 279 V-D Diketones 700
V-E UnsaturatedKetones 706
III RATECOEFFICIENTSAND V-F CyclicKetones 726
MECHANISMSFORTHE V-G KetonesDerivedfrom
ATMOSPHERICOXIDATIONOF BiogenicHydrocarbons 731
THEETHERS 289 V-H Halogen-Substituted
III-A Introduction 289 Ketones 741
v
vi Contents
VI RATECOEFFICIENTSAND IX MECHANISMSOF
MECHANISMSFORTHE PHOTODECOMPOSITIONOFTHE
ATMOSPHERICOXIDATIONOF SUNLIGHT-ABSORBING
THEORGANICACIDS 747 OXYGENATES 974
VI-A Introduction 747 IX-A Introduction 974
VI-B AcyclicOrganicAcids 748 IX-B Mechanismsof
VI-C DibasicOrganicAcids 762 Photodecompositionofthe
VI-D UnsaturatedOrganic AcyclicAldehydes 983
Acids 763 IX-C Photodecompositionof
VI-E Keto-Acids 766 AldehydesContaining
VI-F OrganicAcidsDerivedfrom AdditionalFunctional
AromaticCompoundsand Groups 1024
fromTerpenes 768 IX-D PhotodecompositionofAcyclic
VI-G Halogen-SubstitutedOrganic Ketones 1089
Acids 769 IX-E PhotodecompositionofCyclic
VI-H AcidAnhydrides 772 Ketones 1143
IX-F PhotodecompositionofKetones
ContainingAdditional
VII RATECOEFFICIENTSAND
FunctionalGroups 1175
MECHANISMSOFATMOSPHERIC
IX-G Photodecompositionofthe
OXIDATIONOFTHEESTERS 774
AcylHalidesandCarbonyl
VII-A Introduction 774
Halides 1223
VII-B Acyclic,Saturated
IX-H Photodecompositionof
MonofunctionalEsters 775
NitrousAcid,AlkylNitrites,
VII-C DifunctionalEsters 841
Nitroalkanes,andthe
VII-D CyclicEsters(Lactones) 846
Nitroso-Compounds 1233
VII-E UnsaturatedEsters 848
IX-I PhotodecompositionofNitric
VII-F AromaticEsters 866
Acid,PeroxynitricAcid,andthe
VII-G Carbonates 868
AlkylNitrates 1276
VII-H Lactates 870
IX-J Photodecompositionofthe
VII-I Halogen-Substituted PeroxyacylNitrates 1298
Esters 871
IX-K Photodecompositionof
HydrogenPeroxideandthe
VIII RATECOEFFICIENTSAND AlkylHydroperoxides 1306
MECHANISMSFORTHE IX-L PhotodecompositionofSome
ATMOSPHERICOXIDATIONOF AromaticOxygenates 1311
THEN-ATOM-CONTAINING IX-M SummaryofPhotochemical
OXYGENATES 886 Processes 1349
VIII-A Introduction 886
VIII-B Amides 887
X THEINFLUENCEOF
VIII-C AminoAlcohols 902
OXYGENATESONTHE
VIII-D AlkylNitrates 904
ATMOSPHERICCHEMISTRYOF
VIII-E SaturatedDinitrates 924 URBAN,RURAL,ANDGLOBAL
VIII-F UnsaturatedDinitrates 928 ENVIRONMENTS 1358
VIII-G HydroxyalkylNitrates 929 X-A ImportanceofOxygenatesin
VIII-H CarbonylNitrates 932 AtmosphericChemistry 1358
VIII-I AlkylNitrites 934 X-B RepresentationofOxygenatesin
VIII-J Nitroalkanes 943 ChemicalMechanismsand
VIII-K Nitroalkenes 955 Models 1359
VIII-L Nitroaromaticsand X-C RoleofOxygenatesin
Nitroarenes 956 SecondaryOrganicAerosol
VIII-M PeroxyacylNitrates 962 Formation 1372
VIII-N N,N-Dimethylnitrosamineand X-D RoleofOxygenatesinthe
N,N-Dimethylnitramine 970 UpperTroposphere 1377
Contents vii
X-E RoleofOxygenatesin App-V Ketones 1516
TransportofPollutants App-VI OrganicAcids 1523
(e.g.,PAN) 1383 App-VII OrganicAcid
X-F RoleofOxygenatesasProxies Anhydrides 1525
forVOCEmissions 1384 App-VIII Esters 1526
App-IX Nitrogen-Containing
References 1391 Oxygenates 1532
APPENDIX STRUCTURESOFTHE
OXYGENATES 1480 AuthorIndex 1543
App-I Alcohols 1480
App-II Ethers 1490 SubjectIndex 1595
App-III Aldehydes 1508
App-IV AcylHalidesandCarbonyl
Halides 1515 CompoundIndex 1598
Acknowledgments
The authors thank several agencies and their members for support of this research
effort:BrentK.Bailey,ExecutiveDirectoroftheCoordinatingResearchCouncil(3650
MansellRoad,Suite140,Alpharetta,GA30022),andthemembersoftheCoordinating
ResearchCouncil’sAtmosphericImpactsCommitteewhogavetheauthorstheirsupport
and monitored this study: Rory S. MacArthur, Chevron EnergyTech. Co., Richmond,
CA; James C. Ball, Ford Motor Co. (Retired), Dearborn, MI; Daniel C. Baker, Shell
GlobalSolutions(U.S.),Houston,TX;RobertCassidy,NissanTechnicalCenterNorth
America, Irvine, CA: David P. Chock, Ford Research and Advanced Engineering,
Dearborn, MI; Alan M. Dunker, General Motors R&D Center, Warren, MI; Alan J.
Krol, BPAmerica, Naperville, IL; Mani Natarajan, Marathon Petroleum Co., LLC,
Findlay, OH; David Patterson, Mitsubishi Motors R&D of North America, Cypress,
CA;CharlesH.Schleyer,ExxonMobilResearchandEngineering,Paulsboro,NJ;Ken
Wright, ConocoPhillips Petroleum Co., Bartlesville, OK. Special thanks are extended
to Steven Japar andAlan Dunker for their thorough reviews of chapters I through IX
andchapterX,respectively.WeacknowledgethesignificanthelpofLoisMott(CRC)
forhercarefuleditingofthemanuscript.
The authors acknowledge their research organizations and educational institutions
forthesupportoftheirparticipationinthisresearch:InstitutdeCombustionAérother-
mique Réactivité et Environnement (ICARE) of the Centre National de la Recherche
Scientifique (CNRS), Orleans, France; National Center for Atmospheric Research
(NCAR),AtmosphericChemistryDivision,Boulder,CO;FordMotorCompany,Phys-
ical and Environmental Sciences Department of the Scientific Research Laboratories,
Dearborn, MI; Oak Ridge National Laboratories, Environmental Sciences Division,
Oak Ridge, TN; and The School of Chemistry, University of Leeds, Leeds, U.K.
viii
Acknowledgments ix
NCARisoperatedbytheUniversityCorporationforAtmosphericResearch,underthe
sponsorshipoftheU.S.NationalScienceFoundation.
The authors thank their many coworkers who provided them with important new
information and other assistance: Geert Moortgat and Hannelore Keller-Rudek, Max-
PlanckInstitute,Mainz,Germany,forprovidingreprintsandspectraldatafromthefiles
of Mainz SpectralAtlas; James Burkholder (Aeronomy Laboratory, National Oceanic
and Atmospheric Administration, Boulder, CO) for providing original spectral data.
The authors acknowledge the help of several library staffs in obtaining many of the
reprintsofthepublisheddatathatwerereviewedandreferencedinthisstudy:National
Center for Atmospheric Research, Boulder, CO; Institut de Combustion, Aérother-
mique,RéactivitéetEnvironnement(ICARE)andtheCentreNationaldelaRecherche
Scientifique (CRNS), Orleans, France; the Oak Ridge National Laboratories, Oak
Ridge, TN (especially Larkee Moore, Mary Jacqueline, and William Meyers); The
Ohio State University, Columbus, OH (Dr. Belinda L. Hurley, Jose Biaz); Pennsyl-
vania State University, College Station, PA; and Case Western Reserve University,
Cleveland,OH.JackCalvertthankstheDepartmentofEnergy,OfficeofScience,Bio-
logicalandEnvironmentalResearchProgramforhisVisitingScientistappointmentin
the Environmental Sciences Division, Oak Ridge National Laboratories, Oak Ridge,
TN, and Gary K. Jacobs for hosting this appointment. Tim Wallington thanks James
Anderson,LeandroBenvenutti,andSherryMueller(FordMotorCompany)forhelpful
discussions.