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ОбложкаThe mechanisms of reactions influencing atmospheric ozone / J.G.Calvert et al. - Oxford; New York: Oxford university press, 2015. - xvii, 590 p.: ill., tab. - Bibliogr.: p.497-547. - Auth. ind.: p.549-573. – Sub. ind.: p.575-590. - ISBN 978-0-19-023302-0
Шифр: (И/Д23-M45) 02
 

Место хранения: 02 | Отделение ГПНТБ СО РАН | Новосибирск

Оглавление / Contents
 
Acknowledgments About the Authors

I    Ozone in the Atmosphere .................................... 1
I-А  Introduction ............................................... 1
I-B  Historical Perspective of Atmospheric Ozone ................ 3
I-C  Properties of the Earth's Atmosphere ....................... 7
     I-C-l  Chemical and Physical Properties .................... 7
     I-C-2  Meteorology and Its Effects on Atmospheric Ozone ... 14
I-D  Summary of Ambient Measurements of Tropospheric Ozone ..... 16
     I-D-1  Measurements of Surface Ozone in Background and
            Remote Locations ................................... 16
     I-D-2  Measurements of Surface Ozone in Polluted Urban
            Areas .............................................. 25
I-Е  Summary of Measurements of Stratospheric Ozone ............ 31
I-F  Ozone and Its Mechanisms of Formation and Destruction in
     the Atmosphere ............................................ 33
     I-F-l  Ozone Formation and Destruction in the Unpolluted
            Stratosphere ....................................... 33
     I-F-2  Stratospheric Ozone Depletion: The Role of
            Halocarbons ........................................ 38
        I-F-2.1  Stratospheric Ozone Depletion and the
                 Montreal Protocol ............................. 40
     I-F-3  Ozone Formation in the Troposphere ................. 44
     I-F-A  Ozone Destruction in the Troposphere ............... 47
I-G  Major Sources of the Atmospheric Trace Gases
     (NOx and VOCs) ............................................ 48
I-H  Ozone and Climate ......................................... 54
     I-H-l  Contribution of Ozone to the Natural Greenhouse
            Effect ............................................. 54
     I-H-2  Contribution of Ozone to Radiative Forcing of
            Climate Change ..................................... 57
     I-H-3  Impact of Climate Change on Ozone .................. 58
I-I  About the Material Covered in This Book ................... 59

II    Mechanisms of Ozone Reactions in the Troposphere ......... 61
II-A  Introduction ............................................. 61
II-B  Ozone Photodecomposition and the Mechanism of HO
     Radical Formation ......................................... 61
     II-B-1  Absorption Cross Sections of Ozone ................ 62
     II-B-2  Quantum Yields of O(1D) Formation in Ozone
             Photodecomposition ................................ 63
     II-B-3  Estimated Photolysis Frequencies j[O(1D)] for
             Ozone Photodecomposition .......................... 65
     II-B-4  Comparison of Measured and Calculated j[O(1D)]
             Values ............................................ 65
II-C  Mechanisms of the Ozone Reactions with Organic
     Compounds ................................................. 67
     II-C-1  Ozone Reactions with the Acyclic Mono-Alkenes ..... 67
     II-C-2  Ozone Reactions with the Cyclic Alkenes ........... 84
     II-C-3  Ozone Reactions with the Dienes ................... 86
II-D  Mechanisms of O3 Reactions with Unsaturated Oxygenates ... 87
     II-D-1  Ozone Reactions with the Unsaturated Alcohols ..... 87
     II-D-2  Ozone Reactions with the Unsaturated Ethers ....... 88
     II-D-3  Ozone Reactions with the Unsaturated Aldehydes .... 93
     II-D-4  Ozone Reactions with the Unsaturated Ketones ...... 94
     II-D-S  Ozone Reactions with the Unsaturated Organic
             Acids ............................................. 95
     II-D-6  Ozone Reactions with the Unsaturated Esters ....... 96
II-E  The Mechanisms of Reactions of the Criegee
     Intermediates ............................................. 96
     II-E-1  The Fragmentation Reactions of the Criegee
             Intermediates ..................................... 96
       II-E-1.1  Suggested Fragmentation Modes of the CH2OO4
                 Intermediate .................................. 97
       II-E-1.2  Suggested Fragmentation Modes of the CH3HOO4
                 Intermediate .................................. 97
       II-E-1.3  Suggested Fragmentation Modes of the
                 (CH3)2OO4 Intermediate ......................... 97
     II-E-2  The Mechanism of HO Radical Formation in the
             Reactions of Ozone with theAlkenes ................ 98
     II-E-3  Reactions of the Stabilized Criegee
             Intermediates ..................................... 99
       II-E-3.1  The CH2OO and CH3CHOO Reactions with Water
                 Vapor ........................................ 107
       II-E-3.2  Reaction of Criegee Intermediates with
                 Other Trace Gases ............................ 108
II-F  Use of SARs in Ozone-Alkene Reactions ................... 108
     II-F-1  Estimation of Rate Coefficients for the
             Reactions of Ozone with the Alkenes .............. 108
     II-F-2  An SAR Method of Estimating the Yield of HO
             Radical Formed in the Alkene-Ozone Reactions ..... 110

III    The Oxides of Nitrogen: Their Relation
       to Tropospheric Ozone .................................. 114
III-A  Overview of Tropospheric "Odd Nitrogen" Chemistry ...... 114
III-B  Reactions of NO with O3 and with HO2 ................... 116
III-C  The Photodecomposition of NO2 and j(NO2)
       Determination .......................................... 117
III-D  Evaluation of the Mechanisms of the Major Reactions of
       NO2 with Trace Gases in the Troposphere ................ 120
     III-D-1  Reaction of NO2 with HO:HON02 Formation ......... 120
     III-D-2  Reactions of NO2 with HO2, RO2 and RC(O)O2
              Radicals: Reversible Peroxynitrate and
              Peroxyacetyl nitrate Formation .................. 121
       III-D-2.1  Loss Processes for HONO2, Organic Nitrates,
                  Peroxynitrates, and Peroxyacyl Nitrates:
                  Photolysis, Reaction with HO, and
                  Deposition .................................. 121
     III-D-3  The Heterogeneous Formation of HONO and Its
              Subsequent Losses ............................... 125
     III-D-4  The Reaction of NO2 with O3 The Formation of
              NO3 Radical ..................................... 126
     III-D-5  NO2 + NO3 Reactions: N2O5 Formation and
              Dissociation .................................... 126
       III-D-5.1  Heterogeneous Reactions of N2O5 with
                  H2O and Halide Ions ......................... 126
III-E  Evaluation of the Mechanisms of NO3 Radical Reactions .. 127
     III-E-1  The Photodecomposition of NO3 [j(NO3] ........... 127
     1II-E-2  Mechanism of the Reaction of NO3 with NO ........ 130
     III-E-3  Rates and Mechanisms for Reactions of NO3 with
              the Alkanes ..................................... 130
     III-E-4  Rates and Mechanisms for Reactions of NO3 with
              Haloalkanes ..................................... 131
     III-Е-5  Rates and Mechanisms for Reactions of NO3 with
              Alkenes, Haloalkenes, and Alkynes ............... 133
       III-E-5.1  Rates and Mechanisms for Reactions of NO3
                  with Alkenes ................................ 133
       III-E-S.2  Rates and Mechanisms for Reactions of NO3
                  with Haloalkenes ............................ 142
       III-Е-5.3  Rates and Mechanisms for Reactions of NO3
                  with Alkynes ................................ 144
     III-E-6  Rates and Mechanisms for the Reactions of NO3
              with Aromatic Hydrocarbons ...................... 146
     III-Е-7  Rates and Mechanisms for Reactions of NO3 with
              the Oxygenates .................................. 146
       III-E-7.1  Rates and Mechanisms for the Reactions of
                  NO3 with Alcohols ........................... 148
       III-E-7.2  Rates and Mechanisms for the Reactions of
                  NO3 with Ethers ............................. 151
       III-Е-7.3  Rates and Mechanisms for the Reactions of
                  NO3 with Aldehydes .......................... 154
       III-Е-7.4  Rates and Mechanisms for the Reactions of
                  NO3 with Ketones ............................ 157
       III-Е-7.5  Rates and Mechanisms for the Reactions of
                  NO3 with Organic Acids ...................... 159
       III-Е-7.6  Rates and Mechanisms for the Reactions of
                  NO3 with Esters ............................. 160
       III-E-7.7  Rates and Mechanisms for the Reactions of
                  NO3 with N-Atom-Containing Oxygenates ....... 160
     III-E-8  Use of SARs to Estimate NO3 Rate Coefficients ... 161
       III-E-8.1  SAR-Based Estimates of Rate Coefficients
                  for NO3 Reactions with the Alkanes and
                  Haloalkanes ................................. 162
       III-E-8.2  SAR-Based Estimates of Rate Coefficients
                  for NO3 Reactions with Saturated,
                  Oxygenated Compounds (Aldehydes, Alcohols,
                  Ethers, Ketones, Esters, and Saturated
                  Multifunctional Species) .................... 163
       III-E-8.3  SAR-Based Estimates of Rate Coefficients
                  for NO3 Reactions with the Alkenes,
                  Haloalkenes, and Alkynes .................... 166
       III-E-8 4  SAR-Based Estimates of Rate Coefficients for
                  NO3 Reactions with Unsaturated Oxygenated
                  Compounds (Alcohols and Ethers) ............. 167
       III-E-8.5  SAR-Based Estimates of Rate Coefficients
                  for NO3 Reactions with Unsaturated Carbonyl
                  Compound (Aldehydes, Ketones, Esters) ....... 169

IV    The Hydroxy! Radical and Its Role in Ozone Formation .... 172
IV-A  Introduction ............................................ 172
      IV-A-1  Measurement of HO Radical Concentrations ........ 173
IV-B  Mechanisms of HO Radical Reactions with Alkanes ......... 178
IV-C  Mechanisms of HO Radical Reactions with Haloalkanes ..... 185
IV-D  Mechanisms of HO Radical Reactions with Alkenes ......... 191
     IV-D-1  HO Reactions with Mono-Alkenes ................... 191
     IV-D-2  Mechanism of HO Addition to Alkenes ..............
     IV-D-3  HO Reactions with Dienes ......................... 206
IV-E  Mechanisms of the HO Radical Reactions with the
     Alkynes .................................................. 208
     IV-E-1  Reaction of HO with Acetylene (Ethyne,HC≡CH) ..... 208
     IV-E-2  Reaction of HO with Propyne (Methyl Acetylene,
             CH3≡CH) .......................................... 208
     IV-E-3  Reaction of HO with 1-Butyne (HC≡CCH2CH3) and
             2-Butyne (CH3C≡CCH3) ............................. 208
     IV-E-4  The Mechanism of HO Addition Reaction with
             Alkynes .......................................... 208
IV-F  Mechanisms of the HO Reactions with Aromatic
      Hydrocarbons ............................................ 209
IV-G  Mechanisms of the HO Reactions with the Alcohols ........ 211
     IV-G-1  HO Reactions with Acyclic Alcohols ............... 211
     IV-G-2  HO Reaction with Diols ........................... 227
     IV-G-3  HO Reactions with Saturated Alcohols ............. 228
     IV-G-4  HO Reactions with Aromatic Alcohols .............. 228
     IV-G-5  HO Reactions with Unsaturated Alcohols ........... 228
     TV-G-6  HO Reactions with Halogen-Atom-Substituted
             Alcohols ......................................... 229
IV-H  Mechanisms of Reactions of HO with Ethers ............... 230
     IV-H-1  HO Reactions with Acyclic Ethers ................. 230
     IV-H-2  HO Reactions with Difunctional Ethers ............ 251
     IV-H-3  HO Reactions with Vinyl Ethers ................... 251
     IV-H-4  HO Reactions with Cyclic Poly ethers ............. 251
     TV-H-S  HO Radical Reactions with Halogen-Atom-
             Substituted Ethers ............................... 251
IV-I  Mechanisms of Reaction of HO Radical with the
     Aldehydes ................................................ 253
     TV-I-1  HO Radical Reactions with Acyclic Aldehydes ...... 263
     IV-I-2  HO Radical Reactions with Unsaturated Aldehydes .. 263
     IV-I-3  HO Radical Reactions with Aromatic Aldehydes ..... 265
     IV-I-4  HO Radical Reactions with Halogen-Atom-
             Substituted Aldehydes ............................ 265
IV-I  Mechanisms of HO Radical Reactions with Ketones ......... 265
     IV-J-1  HO Radical Reactions with Acyclic Ketones ........ 266
     IV-J-2  HO Radical Reactions with Hydroxyketones ......... 276
     IV-J-3  HO Radical Reactions with Unsaturated Ketones .... 276
     IV-J-4  HO Radical Reactions with Halogen-Atom-
             Substituted Ketones .............................. 276
IV-K  Mechanisms of Reaction of HO Radical with Organic
      Acids and Acid Anhydrides ............................... 276
IV-L  Mechanisms of Reaction of HO Radicals with Esters ....... 277
     IV-L-1  HO Radical Reactions with Acyclic Esters ......... 277
     IV-L-2  HO Radical Reactions with Unsaturated Esters ..... 279
     IV-L-3  HO Radical Reactions with Halogen-Atom-
             Substituted Esters ............................... 279
IV-M  Mechanisms of Reactions of HO Radical with N-containing
     Oxygenates ............................................... 280
IV-N  Summary of HO Radical Reactions with Organic Compounds .. 296
IV-O  Structure-Activity-Relations (SARs)for Estimating HO
     Rate Coefficients ........................................ 296

V    Mechanisms of Reactions of HO2 and RO2 Radicals .......... 315
V-A  Introduction ............................................. 315
V-B  Reactions of HO2 with NO and RO2 with NO ................. 317
     V-B-l  Kinetics of the HO2 + NO and the RO2 + NO
            Reactions ......................................... 317
     V-B-2  Products and Mechanisms of the HO2 + NO and RO2
            + NO Reactions .................................... 320
V-C  Reactions of HO2 + NO2 and RO2 + NO2 ...................... 324
V-D  Reactions of HO2 + HO2 and HO2 + RO2 ...................... 326
V-E  Reactions of HO2 with NO3 and RO2 with NO3 ................ 331
V-F  Reactions of HO2 with RO2 and HO2 with ClO,
     BrO, IO .................................................. 332
V-G  Reactions of HO2 with O3 and RO2 with O3 .................. 335
V-H  Reactions of RO2 with RO2 and RO2 with R'O2 ............... 336
     V-H-1  Introduction ...................................... 336
     V-H-2  Kinetics of RO2 Reactions with RO2 and RO2 with
            R'O2 .............................................. 337
     V-H-3  Products of the RO2 Reaction with RO2 and RO2
            with R'O2 ......................................... 340
V-I  R02 Unimolecular Reactions ............................... 343
     V-I-l  RO2 → QOOH Isomerization .......................... 343
     V-I-2  Decomposition Reactions of the a-Hydroxy-Peroxy
            Radicals .......................................... 346

VI   Mechanisms of Reactions of the RO Radicals ............... 347
VI-A Introduction ............................................. 347
VI-B Modes of Alkoxy Radical Reactions in the Atmosphere ...... 348
     VI-B-1  Alkoxy Radical Reactions with O2 ................. 348
     VI-B-2  Unimolecular Decomposition Reactions of the
             Alkoxy Radicals .................................. 349
       VI-B-2.1  Unimolecular Decomposition of RR'R"CO•
                 Radicals ..................................... 349
       VI-B-2.2  Unimolecular Decomposition of Acyloxy
                 Radicals [RC(O)O•] ........................... 352
       VI-B-2.3  Unimolecular Isomerization Reactions of the
                 Alkoxy Radicals .............................. 352
       VI-B-2.4  Unimolecular Decomposition of RCHCIO•
                 Radicals ..................................... 357
       VI-B-2.5  Unimolecular Decomposition of RC(O)OCH(0•)R'
                 Radicals ..................................... 357
       VI-B-2.6  Chemical Activation in the Chemistry of
                 Alkoxy Radicals .............................. 358
VI-C Reaction Rate Coefficients and Atmospheric Fate of
     Selected Alkoxy Radicals ................................. 360
     VI-C-I  Reaction of the Methoxy Radical (CH3O•) .......... 360
     VI-C-2  Reaction of the Ethoxy Radical (C2H5O•) .......... 361
     VI-C-3  Reactions of the 1-Propoxy Radical (n-Propoxy
             Radical, n-C3H7O•) ................................ 361
     VI-C-4  Reactions of the 2-Propoxy Radical [iso-Propoxy
             Radical, CH3CH(0•)CH3] ............................ 362
     VI-C-5  Reactions of the 1-Butoxy Radical (n-Butoxy
             Radical CH3CH2CH2CH2O•) ........................... 363
     VI-C-6  Reactions of the 2-Butoxy Radical [sec-Butoxy
             Radical, CH3CH(O•)CH2CH3] ......................... 364
     VI-C-7  Reactions of the 2-Methyl-2-Propoxy Radical
             [tert-Butoxy Radical, (CH3)3CO•] .................. 365
     VI-C-8  Reactions of the 2-Methyl-l-Propoxy Radical
             [iso-Butoxy Radical, (CH3)2CHCH2O•] ............... 365
     VI-C-9  Reactions of the 1-Pentoxy Radical (n-Pentoxy
             Radical, CH3CH2CH2CH2CH2O•) ....................... 366
     VI-C-10 Reactions of the 2-Pentoxy Radical [CH3CH2CH2CH
             (0•)CH3] .......................................... 366
     VI-C-11 Reactions of the 3-Pentoxy Radical [CH3CH2CH(O•)
             CH2CH3] ........................................... 367
     VI-C-12 Reactions of the 2,2-Dimethyl-l-Propoxy Radical
             [Neopentoxy Radical, (CH3)3CCH2O•] ................ 367
     VI-C-13 Reactions of the 2-Methyl-2-Butoxy Radical
             [CH3CH2(O•)(CH3)2 ................................. 368
     VI-C-14 Reactions of the 2-Methoxy-l-Butoxy Radical
             [CH3CH2CH(CH3)CH2O•] .............................. 368
     VI-C-15 Reactions of the 2-Hexoxy Radical
             [CH3CH2CH2CH2CH(O•)СН3] ........................... 368
     VI-C-16 Reactions of the 3-Hexoxy Radical [CH3CH2CH(O•)
             CH2CH2CH3] ........................................ 369
     VI-C-17 Reactions of the 1-Hexoxy Radical [n-Hexoxy
             Radial, CH3CH2CH2CH2CH2CH2O•] ..................... 369
     VI-C-18 Reactions of the 2-Methyl-2-Pentoxy Radical
             [CH3CH2CH2C(O•)(CH3)2 ............................. 369
     VI-C-19 Reactions of the 4-Methyl-l-Pentoxy Radical
            [CH3)2CHCH2CH2CH2O•] ............................... 370
     VI-C-20 Reactions of the 5-Methyl-2-Hexoxy Radical
             [(CH3)2CHCH2CH2CH(O•)CH3] ......................... 370
     VI-C-21 Reactions of the 2-Methyl-2-Hexoxy Radical
             [CH3CH2CH2CH2C(O•)(CH3)2 .......................... 370
     Vl-C-22 Reactions of the 2,5-Dimethyl-2-Hexoxy Radical
             [CH3)2CHCH2CH2C(O•)(CH3)2] ........................ 370
     VI-C-23 Reaction of the Cyclopentoxy Radical ............. 371
     VI-C-24 Reactions of the Cyclohexoxy Radical ............. 371
     VI-C-25 Reactions of the 4-Methyl-Cyclohexoxy Radical .... 371
     VI-C-26 Reactions of Other Five- and Six-Carbon Alkoxy
             Radicals ......................................... 372
     VI-C-27 Reactions of the 2-Hydoxy-Ethoxy Radical
             (HOCH2CH2O•) ..................................... 372
     VI-C-28 Reactions of the CH3OCH2O•
             Radical .......................................... 372
     VI-C-29 Reactions of the CH3CH2OCH(0•)CH3
             Radical .......................................... 373
     VI-C-30 Reactions of the CH3C(O)CH2O•
             Radical .......................................... 374

VII  The Impact of Inorganic Trace Gases on Ozone in the
     Atmosphere ............................................... 375
VII-A  Introduction ........................................... 375
VII-B  Sources and Sinks of Atmospheric Carbon Dioxide (CO2)
     and Carbon Monoxide (CO) ................................. 375
     VII-B-1  Levels of Atmospheric CO2 and the Global
              Carbon Cycle: A Brief Overview .................. 375
     VII-B-2  Atmospheric Budget and Chemistry of Carbon
              Monoxide ........................................ 376
       VII-B-2.1  Sources of CO to the Atmosphere ............. 376
       VII-B-2.2  Loss of CO via Reaction with HO:
                  A Significant Source of HO2 ................. 376
VII-C  Tropospheric Chemistry of Inorganic Halogen Species .... 376
     VII-C-1  Sources of Inorganic Halogens to the
              Troposphere ..................................... 377
     VII-C-2  Tropospheric Inorganic Halogen Cycles ........... 377
     VII-C-3  Reactions of Cl Atoms with the Hydrocarbons ..... 380
       VII-C-3.1  Reactions of Cl Atoms with Alkanes .......... 380
       VII-C-3.2  Reactions of Cl Atoms with Haloalkanes ...... 380
       VII-C-3.3  Reactions of Cl Atoms with Alkenes .......... 383
       VII-C-3.4  Reactions of Cl Atoms with Aromatic
                  Hydrocarbons ................................ 384
     VII-C-4  Reactions of Cl Atoms with Oxygenates ........... 385
       VII-C-4.1  Reactions of Cl Atoms with Alcohols ......... 385
       VII-C-4.2  Reactions of Cl Atoms with Ethers ........... 388
       VII-C-4.3  Reactions of Cl Atoms with Aldehydes ........ 392
       VII-C-4.4  Reactions of Cl Atoms with Ketones .......... 392
       VII-C-4.S  Reactions of Cl Atoms with Organic Acids .... 394
       VLl-C-4.6  Reactions of Cl Atoms with Esters ........... 396
       VII-C-4.7  Reactions of Cl Atoms with N-Atom-
                  Containing Oxygenates ....................... 399
     VII-C-S  Structure-Activity Relations (SARs)for
              Reactions of CI Atoms with Organic Species ...... 400
       VII-C-S.l  SARs in the Reaction of CI Atoms with
                  Alkanes ..................................... 400
       VII-C-S.2  SARs in the Reaction of CI Atoms with
                  Saturated Alcohols and Ethers ............... 400
       VII-C-5.3  SARs in Reactions of CI Atoms with
                  Saturated Carbonyl Compounds ................ 401
       VII-C-S.4  SARs in Reaction of CI Atoms with
                  Unsaturated Compounds ....................... 405
     VII-C-6  Reactions of Br Atoms with Organic Compounds:
              An Overview ..................................... 405
       VII-C-6.1  Reactions of Br Atoms with Alkanes .......... 406
       VII-C-6.2  Reactions of Br Atoms with Alkenes and
                  Alkynes ..................................... 406
       VII-C-6.3  Reactions of Br Atoms with Aromatic
                  Hydrocarbons ................................ 407
       VII-C-6.4  Reactions of Br Atoms with Alcohols and
                  Ethers ...................................... 407
       VII-C-6.5  Reactions of Br Atoms with Aldehydes ........ 407
       VII-C-6.6  Reactions of Br Atoms with Ketones, Acids,
                  and Esters .................................. 409
       VII-C-6.7  Polar Surface Ozone Depletion Events:
                  A Special Case .............................. 409
     VII-C-7  Reaction of Iodine Atoms with Organic
              Compounds ....................................... 411
VII-D  Atmospheric Reactions of Sulfur Compounds .............. 412
     VII-D-1  Sources of Atmospheric Sulfur Compounds ......... 412
     VII-D-2  Loss Processes for SO2 and SO3 .................. 412
     VII-D-3  Atmospheric Oxidation of Reduced Sulfur
              Species: H2S, CH3SH, CH3SCH3, CH3SSCH3 ........... 414
       VII-D-3.1  Atmospheric Oxidation of H2S ................ 414
       VII-D-3.2  Atmospheric Oxidation of CH3SH
                  (Methanethiol, Methyl Mercaptan) ............ 414
       VII-D-3.3  Atmospheric Oxidation of CH3SCH3 (Dimethyl
                  Sulfide, DMS) ............................... 418
       VII-D-3.4  Atmospheric Oxidation of CH3SSCH3
                  (Dimethyl Disulfide) ........................ 420
     VII-D-4  Atmospheric Chemistry of COS and CS2 ............ 421
       VII-D-4.1  Atmospheric Chemistry of Carbonyl Sulfide
                  (OCS) ....................................... 421
       VII-D-4.2  Atmospheric Chemistry of Carbonyl
                  Disulfide (CS2) ............................. 423

VIII Photodecomposition of Light-Absorbing Oxygenates and
     Its Influence on Ozone Levels in the Atmosphere .......... 425
VIII-A  Introduction .......................................... 425
VIII-B  Photolysis Frequency (j-Value) of Molecules and
     Their Photochemical Lifetimes (1/j) ...................... 425
VIII-C  The Mechanisms of  Photodecomposition of Aldehydes .... 428
     VIII-C-1  Mechanism of Photodecomposition of
               Formaldehyde ................................... 428
     VIII-C-2  Mechanisms of Photodecomposition of Higher
               Acyclic Aldehydes .............................. 433
     VIII-C-3  Photodecomposition Pathways of Aldehydes
               Containing Additional Functional Groups ........ 435
        VIII-C-3.1  Photodecomposition of Unsaturated
                    Aldehydes ................................. 435
        VIII-C-3.2  Photodecompositions of HO- and Halogen-
                    Atom-Substituted Aldehydes ................ 437
        VIIl-C-3.3  Photodecomposition of Acyclic Dials
                    (Dicarbonyls) ............................. 438
VIII-D  Mechanisms of Photodecomposition of Ketones in the
     Troposphere .............................................. 440
     VIII-D-1  Mechanisms of Photodissociation of Acetone
              within the Troposphere .......................... 442
     VIII-D-2  Mechanisms of the Atmospheric
              Photodecomposition of Larger Acyclic Ketones .... 446
       VIII-D-2.1  RC(O)R' + hv → RCO +  R': Process (I) ...... 446
       VIII-D-2.2  Ketone Photodissociation into Enol and
                   Alkene Products: Process (II) .............. 447
     VIII-D-3  Photodecomposition ofKetene (CH2=C=0) .......... 448
     VIII-D-4  Photodecomposition of Some HO- and Halogen-
               Atom-Substituted Ketones ....................... 448
     VIII-D-5  Photodecomposition Pathways for Some
               Difunctional Ketones ........................... 449
     VIII-D-6  Photodecomposition of Carbonyl Halides,
               Formyl Halides, and Acetyl Halides ............. 451
VIII-E  The Photodecomposition of N-Atom-Containing
     Compounds ................................................ 451
     VIII-E-1  Photodecomposition oftheAlkyl Nitrates ......... 452
     VIII-E-2  Photodecomposition of the Peroxyacyl Nitrates
               (RC(O)OON02) ................................... 453
     VIII-E-3  The Role of HONO in Ozone Generation in Urban
               Atmospheres .................................... 454
     VIII-E-4  Photodecomposition of Other N-Atom-Containing
               Oxygenates and Other Photochemically Active
               Trace Gases .................................... 455
VIII-F  Summary of Photochemical Processes in the
     Troposphere .............................................. 457

IX   Chemical Mechanisms for Air Quality Modeling and
     Their Applications ....................................... 465
IX-A  Development of Mechanisms for Air Quality Modeling ...... 465
     IX-A-1  Requirements for Mechanisms for Air Quality
             Modeling, Their Development, and an Overview
             of the Types of Mechanisms Available ............. 465
     IX-A-2  Computer-Generated and Detailed Explicit
             Mechanisms ....................................... 468
     IX-A-3  Condensed Mechanisms (EKMA, Carbon Bond,
             SAPRAC, RADM/RACM) ............................... 469
IX-B  Methods of Assessing the Influence of VOCs and NOx on
     Ozone Generation Using Computer Models ................... 473
     IX-B-1  Process Analysis and the Sensitivity of Ozone
             Formation to VOC and NOx ......................... 473
     IX-B-2  O3, PAN, HNO3, H2O2, HO and HO2 Isopleths:
             VOC and NOx Sensitivity .......................... 476
     IX-B-3  Methods of Sensitivity and Process Analysis for
             Mechanism Assessment ............................. 477
     IX-B-4  NOx and VOC Sensitivity and Indicator Ratios for
             NOx and VOC ...................................... 480
IX-C  Computer Assessment of the Effects of [H20],
     Temperature, and Clouds on O3 Generation ................. 481
IX-D  Simulation of the Effects of CH2O, CO,
     SO2, NO3 and N2O5 on O3 Generation ........................ 484
IX-E  Measures of Ozone Formation Reactivity .................. 487
     LX-E-1  Incremental Reactivity: MIR and MOIR ............. 487
       IX-E-1.1  Maximum Ozone Incremental Reactivity: MOIR ... 487
       IX-E-1.2  Maximum Incremental Reactivity: MIR .......... 487
       IX-E-1.3  Comparison of MOIR and MIRValues ............. 488
     IX-E-2  Photochemical Ozone Creation Potential (POCP) .... 489
IX-F  Modeling of Secondary Inorganic Aerosol and Organic
     Aerosol Formation ........................................ 490
IX-G  Potential Deficiencies of Atmospheric Chemistry
     Mechanisms as Implemented in Air Quality Models .......... 493
IX-H  Future Development of Atmospheric Chemical Mechanisms
     for Air Quality Modeling ................................. 496

References .................................................... 497
Author Index .................................................. 549
Subject Index ................................................. 575

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Документ изменен: Fri Jan 20 10:25:17 2017. Размер: 35,565 bytes.
Посещение N 181 c 13.09.2016