An important guide that highlights the multiphase chemical processes for students and professionals who want to learn more about aerosol chemistry
Atmospheric Multiphase Reaction Chemistry provides the information and knowledge of multiphase chemical processes and offers a review of the fundamentals on gas-liquid equilibrium, gas phase reactions, bulk aqueous phase reactions, and gas-particle interface reactions related to formation of secondary aerosols. The authors - noted experts on the topic - also describe new particle formation, and cloud condensation nuclei activity. In addition, the text includes descriptions of field observations on secondary aerosols and PM2.5.
Atmospheric aerosols play a critical role in air quality and climate change. There is growing evidence that the multiphase reactions involving heterogeneous reactions on the air-particle interface and the reactions in the bulk liquid phase of wet aerosol and cloud/fog droplets are important processes forming secondary aerosols in addition to gas-phase oxidation reactions to form low-volatile compounds. Comprehensive in scope, the book offers an understanding of the topic by providing a historical overview of secondary aerosols, the fundamentals of multiphase reactions, gas-phase reactions of volatile organic compounds, aqueous phase and air-particle interface reactions of organic compound. This important text:
- Provides knowledge on multiphase chemical processes for graduate students and research scientists
- Includes fundamentals on gas-liquid equilibrium, gas phase reactions, bulk aqueous phase reactions, and gas-particle interface reactions related to formation of secondary aerosols
- Covers in detail reaction chemistry of secondary organic aerosols
Written for students and research scientists in atmospheric chemistry and aerosol science of environmental engineering, Atmospheric Multiphase Reaction Chemistry offers an essential guide to the fundamentals of multiphase chemical processes.
Table of Contents
Preface xiii
1 Historical Background of Atmospheric Secondary Aerosol Research 1
1.1 Introduction 1
1.2 Secondary Inorganic Aerosols 1
1.2.1 Sulfate 2
1.2.2 Nitrate 3
1.3 Secondary Organic Aerosols 4
1.3.1 Photochemical Smog 5
1.3.2 Blue Haze 6
References 7
2 Fundamentals of Multiphase Chemical Reactions 13
2.1 Introduction 13
2.2 Gas-Liquid Phase Equilibrium and Equilibrium in Liquid Phase 13
2.2.1 Fundamentals of Thermodynamics 14
2.2.1.1 Internal Energy and Enthalpy 14
2.2.1.2 Entropy 16
2.2.1.3 Gibbs Energy 18
2.2.1.4 Chemical Potential 19
2.2.2 Chemical Equilibrium and Equilibrium Constant 21
2.2.2.1 Chemical Equilibrium 21
2.2.2.2 Equilibrium Constant of Gas-Phase Reaction 22
2.2.2.3 Equilibrium Constant of Liquid-Phase Reaction 24
2.2.2.4 Temperature Dependence of Equilibrium Constant 26
2.2.3 Gas-Liquid Equilibrium and Henry’s Law Constant 29
2.2.4 Hydration of Carbonyl Compounds and Effective Henry’s Law Constant 31
2.2.5 pH and Equilibrium in the Aqueous Solution 32
2.2.5.1 Dissociation Equilibrium of Pure Water and pH 32
2.2.5.2 Ion Dissociation and Equilibrium in Aqueous Solution 33
2.3 Reactions in the Liquid Phase 35
2.3.1 Thermodynamics and Activity Coefficients of Nonideal Solutions 35
2.3.1.1 Salting-in, Salting-out 38
2.3.2 Chemical Kinetics of Aqueous-Phase Reaction 39
2.3.2.1 Diffusion Process and Chemical Reaction Kinetics 39
2.3.2.2 Transition State Theory of Solution Reaction and Thermodynamic Expression 42
2.3.3 Cage Effect and Aqueous-Phase Solvent Effect 46
2.3.3.1 Cage Effect 46
2.3.3.2 Solvent Effect in the Aqueous Phase 48
2.4 Uptake Coefficient and Resistance Model 51
2.4.1 Accommodation Coefficient and Uptake Coefficient 52
2.4.2 Resistance Model 54
2.5 Physical Chemistry of Interface Reaction 56
2.5.1 Langmuir-Hinshelwood Mechanism and Eley-Rideal Mechanism 56
2.5.2 Resistance Model Including Interface Reaction 59
2.5.3 Surface Tension of Air-Water Interface and Thermodynamics of Accommodation Coefficient 65
2.5.3.1 Surface Tension 65
2.5.3.2 Thermodynamics of Accommodation Coefficient at Air-Water Interface 68
2.6 Chemical Compositions and Physical Characters of Particles 71
2.6.1 Elemental and Molecular Composition of Particles 72
2.6.1.1 Inorganic Elements and Compounds 72
2.6.1.2 Organic Compounds 74
2.6.1.3 van Krevelen Diagram 77
2.6.2 Molecular Composition and Vapor Pressure 78
2.6.3 Gas-Particle Partitioning and Volatility Basis Set Model 84
2.6.3.1 Gas-Particle Partitioning and SOA Formation Yield 84
2.6.3.2 Volatility Basis Set Model 88
2.6.3.3 Gas-Aqueous Phase Partitioning of Hydrophilic Compounds 90
2.6.4 Phase State of Particles and Mass Transfer 93
References 95
3 Gas-Phase Reactions Related to Secondary Organic Aerosols 107
3.1 Introduction 107
3.2 Ozone Reactions 107
3.2.1 Properties and Reactions of Criegee Intermediates 108
3.2.1.1 Direct Detection of Criegee Intermediate and Molecular Structure 110
3.2.1.2 Formation of CH2OO in Ozone-Ethene Reaction 115
3.2.1.3 Formation of syn- and anti-CH3CHOO in Ozone-Alkene Reactions 118
3.2.2 Alkenes and Dialkenes 130
3.2.2.1 Ethene 130
3.2.2.2 >C3 Alkenes 132
3.2.2.3 1,3-Butadiene 134
3.2.3 Isoprene 135
3.2.4 Cycloalkenes 139
3.2.4.1 Cyclohexene 139
3.2.4.2 1-Methylcyclohexene 141
3.2.4.3 Methylenecyclohexane 144
3.2.5 Monoterpenes 144
3.2.5.1 α-Pinene 145
3.2.5.2 β-Pinene 148
3.2.5.3 Limonene 150
3.2.6 Sesquiterpenes 155
3.3 OH Radical-Induced Oxidation Reactions 160
3.3.1 Alkanes 160
3.3.1.1 Reactions of Alkyl Peroxy Radicals 165
3.3.1.2 Reactions of Alkoxy Radicals 165
3.3.2 Alkynes 170
3.3.3 Alkenes, Dialkenes, and Cycloalkenes 171
3.3.3.1 Alkenes 171
3.3.3.2 1,3-Butadiene 173
3.3.3.3 Cycloalkenes and Methylene cyclohexane 174
3.3.4 Isoprene 175
3.3.4.1 Fundamental Processes of OH-Induced Oxidation Reaction 175
3.3.4.2 HOx Radicals Regeneration Reaction 178
3.3.4.3 Formation of Isoprene Hydroxy Hydroperoxide (ISOPOOH) and Isoprene Epoxydiol (IEPOX) 179
3.3.4.4 Formation of Hydroxy Isoprene Nitrates 180
3.3.4.5 Reactions of Methyl Vinyl Ketone and Methacrolein 182
3.3.5 Monoterpenes 183
3.3.5.1 α-Pinene 183
3.3.5.2 β-Pinene 185
3.3.5.3 Limonene 187
3.3.6 Monocyclic Aromatic Hydrocarbons 189
3.3.6.1 Benzene 189
3.3.6.2 Toluene 192
3.3.7 Polycyclic Aromatic Hydrocarbons 195
3.3.7.1 Naphthalene 196
3.3.7.2 Other Polycyclic Aromatic Hydrocarbons 198
3.3.8 Carbonyl Compounds: OH Radical Reactions and Photolysis 199
3.3.8.1 Glyoxal 199
3.3.8.2 Methylglyoxal 202
3.3.8.3 Glycolaldehyde 204
3.3.8.4 Hydroxyacetone 207
3.4 NO3 Oxidation Reactions 209
3.4.1 Isoprene 209
3.4.2 Monoterpenes 213
3.4.2.1 α-Pinene 213
3.4.2.2 β-Pinene 214
3.4.2.3 Limonene 215
3.4.3 Monocyclic and Polycyclic Aromatic Hydrocarbons 217
3.4.3.1 Phenol, and Cresol 217
3.4.3.2 Naphthalene 218
3.4.3.3 Other Polycyclic Aromatic Hydrocarbons 219
References 219
4 Aqueous-Phase Reactions Related to Secondary Organic Aerosols 245
4.1 Introduction 245
4.2 OH Radical Reactions 246
4.2.1 UV Absorption Spectrum of OH Radicals in Aqueous Solution 246
4.2.2 Formation of OH Radicals in Cloud/Fog Droplets and Deliquescent Aerosols 248
4.2.3 Reaction Rate Constants of OH Radicals in the Aqueous Phase 254
4.2.4 Reactions of Formaldehyde and OH Radical Chain Reaction 257
4.2.5 OH Radical Reactions and Photolysis of ≥C2 Carbonyl Compounds 262
4.2.5.1 Glyoxal and Glyoxylic Acid 262
4.2.5.2 Methylglyoxal, Pyruvic Acid, and Acetic Acid 264
4.2.5.3 Glycolaldehyde and Glycolic Acid 267
4.2.5.4 Methacrolein and Methyl Vinyl Ketone 268
4.2.6 Oligomer Formation Reactions from ≥C2 Carbonyl Compounds 270
4.2.6.1 Glyoxal and Methylglyoxal 272
4.2.6.2 Methyl Vinyl Ketone and Methacrolein 273
4.3 Nonradical Reactions 275
4.3.1 Diels-Alder Reaction 276
4.3.2 Hemiacetal and Acetal Formation Reactions 277
4.3.2.1 Glyoxal 279
4.3.2.2 Methylglyoxal 280
4.3.2.3 1,4-Hydroxycarbonyl Compounds 281
4.3.3 Aldol Reaction 281
4.3.3.1 Acetaldehyde 282
4.3.3.2 Methylglyoxal 283
4.3.3.3 Methyl Vinyl Ketone and Methacrolein 284
4.3.4 Esterification Reactions 285
4.4 Formation Reactions of Organic Sulfates 287
4.4.1 C2 and C3 Carbonyl Compounds 287
4.4.2 Monoterpenes 288
4.4.3 Isoprene 291
4.4.4 Monocyclic and Polycyclic Aromatic Hydrocarbons 291
4.5 Formation Reactions of Organic Nitrogen Compounds 292
4.5.1 Organic Nitrates 292
4.5.2 Imidazoles 293
References 295
5 Heterogeneous Oxidation Reactions at Organic Aerosol Surfaces 309
5.1 Introduction 309
5.2 Aging of Organic Aerosols in the Atmosphere 309
5.3 Reactions of Ozone 313
5.3.1 Oleic Acid and Unsaturated Long-Chain Carboxylic Acids 314
5.3.2 Squalene 316
5.3.3 Polycyclic Aromatic Hydrocarbons 318
5.4 Reactions of OH Radicals 320
5.4.1 Squalane and Long-Chain Alkanes 320
5.4.2 Levoglucosan, Erythritol, and Hopane 325
5.4.3 Saturated Dicarboxylic Acids 326
5.4.4 Squalene and Long-Chain Unsaturated Carboxylic Acids 328
5.4.5 Polycyclic Aromatic Hydrocarbons 330
5.5 Reactions of NO3 Radicals 332
5.5.1 Levoglucosan, Squalane, Long-Chain Alkane, and Alkanoic Acid 332
5.5.2 Squalene and Oleic Acid 334
5.5.3 Polycyclic Aromatic Hydrocarbons 334
References 336
6 Reactions at the Air-Water and Air-Solid Particle Interface 343
6.1 Introduction 343
6.2 Molecular Pictures and Reactions at the Air-Water Interface 344
6.2.1 Thermodynamics of Adsorption 345
6.2.1.1 OH, HO2, and O3 346
6.2.1.2 Organic and Inorganic Compounds 348
6.2.2 Microscopic Picture of Molecules 349
6.2.2.1 Air-Pure Water Interface 350
6.2.2.2 Hydrophilic Organic Compounds 352
6.2.2.3 Amphiphilic Organic Compounds (Surfactants) 356
6.2.2.4 Hydrophobic Organic Compounds 357
6.2.2.5 NH3 and SO2 358
6.2.3 Reactions of O3 and Organic Compounds 359
6.2.3.1 Oleic Acid 360
6.2.3.2 Sesquiterpene Criegee Intermediates 360
6.2.3.3 Polycyclic Aromatic Hydrocarbons 361
6.2.4 Reactions of OH Radicals and Organic Compounds 362
6.2.4.1 Carboxylic and Dicarboxylic Acids 362
6.2.4.2 Organic Sulfur Compounds 364
6.3 Air-Sea Salt Particle, Seawater, and Sulfate/Nitrate Aerosol Interface 365
6.3.1 Microscopic View of Interface of Air and Alkaline Halide Aqueous Solution 366
6.3.2 Reactions at the Interface of Sea Salt and Alkali Halide Aqueous Solution 368
6.3.2.1 Reaction with O3 369
6.3.2.2 Reaction with OH Radicals 371
6.3.2.3 Uptake of HO2 Radicals 372
6.3.2.4 Reaction with N2O5 372
6.3.2.5 Reaction with HNO3 373
6.3.3 Reactions of Organic Compounds at the Air-Seawater and Air-Sea Salt Interface 375
6.3.4 Microscopic View of the Interface of Air and Sulfate/Nitrate Aqueous Solution 377
6.3.4.1 Sulfate Ion (SO4 2-) 377
6.3.4.2 Nitrate Ion (NO3 -) 378
6.4 Reactions on Snow/Ice Surface 379
6.4.1 Formation of NOy in the Photochemical Reaction of NO3 - 379
6.4.2 Formation of Inorganic Halogens on the Snow Ice and Sea Ice Surface 382
6.4.2.1 Reaction with O3 382
6.4.2.2 Reaction with OH Radicals 383
6.4.2.3 Reactions with N2O5 384
6.5 Interface of Water and Mineral Dust, Quartz, and Metal Oxide Surface 385
6.5.1 Microscopic View of Adsorbed Water on Mineral Surface 386
6.5.2 HONO Formation Reaction from NO2 on the Mineral Surface 390
6.5.2.1 Dark Reaction 390
6.5.2.2 Photochemical Reaction 392
6.5.3 Reaction of Organic Monolayer on Mineral Surface 394
References 396
7 Atmospheric New Particle Formation and Cloud Condensation Nuclei 415
7.1 Introduction 415
7.2 Classical Homogeneous Nucleation Theory 415
7.2.1 Homogeneous Nucleation in One-Component Systems 415
7.2.2 Homogeneous Nucleation in Two-Component Systems 419
7.3 Atmospheric New Particle Formation 422
7.3.1 New Particle Formation Rate and Growth Rate 422
7.3.2 Sulfuric Acid in New Particle Formation 425
7.3.3 Basic Substances in New Particle Formation 427
7.3.4 Organic Species in New Particle Formation 430
7.3.5 Other Species in New Particle Formation 433
7.3.5.1 Iodine Oxides 433
7.3.5.2 Atmospheric Ions 434
7.3.6 Field Observation of Nanoclusters 435
7.4 Aerosol Hygroscopicity and Cloud Condensation Nuclei 436
7.4.1 Köhler Theory 436
7.4.2 Nonideality of Solution in a Droplet 441
7.4.3 Hygroscopicity Parameter, 𝜅 442
References 446
8 Field Observations of Secondary Organic Aerosols 453
8.1 Introduction 453
8.2 Global Budget of Aerosols 453
8.3 Analysis Methods of Ambient Aerosol Compositions 458
8.3.1 Positive Matrix Factorization 458
8.3.2 Mass Spectrum Peak Intensity and Elemental Ratio 459
8.3.3 Elemental Composition 460
8.4 Marine Air 461
8.5 Forest Air 465
8.5.1 Amazon Tropical Forest 465
8.5.2 Finland Boreal Forest 469
8.6 Urban/Rural Air 472
8.6.1 Characterization of Ambient Aerosols 472
8.6.1.1 PMF Analysis 472
8.6.1.2 Mass Signal Intensity Ratio and Elemental Ratio 474
8.6.1.3 Particle Size Distribution 477
8.6.1.4 Elemental Composition 478
8.6.2 Molecular Composition 479
8.6.2.1 Dicarboxylic Acid 480
8.6.2.2 Plant Origin VOC Tracers 481
8.6.2.3 Anthropogenic VOC Tracer 484
8.6.2.4 Organic Sulfate 485
8.6.2.5 Organic Nitrates and Imidazoles 486
8.6.2.6 High-Molecular-Weight Compounds and Oligomers 489
References 493
Index 509
