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THE MECHANISMS OF ATMOSPHERIC OXIDATION OF THE OXYGENATES This page intentionally left blank 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 OxfordUniversityPress,Inc.,publishesworksthatfurther OxfordUniversity’sobjectiveofexcellence inresearch,scholarship,andeducation. Oxford NewYork Auckland CapeTown DaresSalaam HongKong Karachi KualaLumpur Madrid Melbourne MexicoCity Nairobi NewDelhi Shanghai Taipei Toronto Withofficesin Argentina Austria Brazil Chile CzechRepublic France Greece Guatemala Hungary Italy Japan Poland Portugal Singapore SouthKorea Switzerland Thailand Turkey Ukraine Vietnam Copyright©2011bybyJ.G.Calvert,A.Mellouki,J.J.Orlando, M.J.Pilling,andT.J.Wallington PublishedbyOxfordUniversityPress,Inc. 198MadisonAvenue,NewYork,NewYork10016 www.oup.com OxfordisaregisteredtrademarkofOxfordUniversityPress Allrightsreserved.Nopartofthispublicationmaybereproduced, storedinaretrievalsystem,ortransmitted,inanyformorbyanymeans, electronic,mechanical,photocopying,recording,orotherwise, withoutthepriorpermissionofOxfordUniversityPress. 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.