
Chemistry of the Upper and Lower Atmosphere
Theory, Experiments, and Applications
By:Â Barbara J. Finlayson-Pitts, James N. Pitts Jr
Hardcover | 10 November 1999
At a Glance
1 Pages
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- Serves as a graduate textbook and "must have" reference for all atmospheric scientists
- Provides more than 5000 references to the literature through the end of 1998
- Presents tables of new actinic flux data for the troposphere and stratospher (0-40km)
- Summarizes kinetic and photochemical date for the troposphere and stratosphere
- Features problems at the end of most chapters to enhance the book's use in teaching
- Includes applications of the OZIPR box model with comprehensive chemistry for student use
Industry Reviews
Preface | p. xvii |
About the Authors | p. xix |
Acknowledgments | p. xxi |
Overview of the Chemistry of Polluted and Remote Atmospheres | |
Regions and Characteristics of The Atmosphere | p. 2 |
Air Pollution and the Chemistry of Our Troposphere | p. 3 |
Historical Perspectives: Ancient and Medieval Times | p. 3 |
"London" Smog: Sulfur Dioxide, Acidic Aerosols, and Soot | p. 3 |
"Los Angeles" Smog: Ozone and Photochemical Oxidants | p. 4 |
Acid Deposition | p. 8 |
Chemistry of the Natural Troposphere: Remote Atmospheres | p. 9 |
Chemistry of the Stratosphere | p. 10 |
Global Climate Change | p. 11 |
Indoor Air Pollution | p. 13 |
Discussion Topic and OZIPR Model | p. 13 |
Discussion Topic: "Background Ozone" | p. 13 |
OZIPR Model | p. 13 |
The Atmospheric System | |
Emissions | p. 15 |
Oxides of Nitrogen | p. 17 |
Volatile Organic Compounds (VOC) | p. 18 |
Carbon Monoxide | p. 20 |
Sulfur Compounds | p. 20 |
Total Suspended Particles (TSP), PM10, and PM2.5 | p. 21 |
Lead | p. 25 |
Meteorology | p. 26 |
Lapse Rate: Temperature and Altitude | p. 26 |
Potential Temperature | p. 28 |
Temperature Inversions | p. 28 |
Removal from the Atmosphere: Wet and Dry Deposition | p. 30 |
Typical Ambient Concentrations and Air Quality Standards | p. 33 |
Units of Concentrations and Conversions | p. 33 |
Criteria and Noncriteria Pollutants and Air Quality Standards | p. 35 |
Effects on Visibility and Materials | p. 37 |
Economics | p. 38 |
Atmospheric Chemistry: Risk Assessments and Public Policies for Air Pollution Control | p. 38 |
Spectroscopy and Photochemistry: Fundamentals | |
Basic Principles | p. 43 |
Molecular Energy Levels and Absorption and Emission Spectroscopy | p. 43 |
Fates of Electronically Excited Molecules | p. 50 |
Absorption of Light | p. 52 |
Basic Relationships | p. 52 |
The Beer - Lambert Law | p. 53 |
Atmospheric Photochemistry | p. 55 |
Solar Radiation and Its Transmission through the Atmosphere | p. 55 |
Calculating Photolysis Rates in the Atmosphere | p. 61 |
Procedure for Calculating Photolysis Rates | p. 76 |
Example: Photolysis of Acetaldehyde at the Earth's Surface | p. 81 |
Photochemistry of Important Atmospheric Species | |
Molecular Oxygen | p. 86 |
Absorption Spectra | p. 86 |
Photochemistry | p. 89 |
Ozone | p. 90 |
Absorption Spectra | p. 90 |
Photochemistry | p. 91 |
Nitrogen Dioxide | p. 95 |
Absorption Spectra | p. 95 |
Photochemistry | p. 96 |
Nitric ACID | p. 98 |
Nitrous ACID | p. 99 |
Peroxynitric ACID | p. 100 |
Nitrate Radical | p. 100 |
Dinitrogen Pentoxide | p. 101 |
Nitrous Oxide | p. 101 |
Organic Nitrates and Peroxyacetyl Nitrate | p. 102 |
Organic Nitrates | p. 102 |
Peroxyacetyl Nitrate | p. 103 |
Sulfur Dioxide and Sulfur Trioxide | p. 103 |
SO[subscript 2] | p. 103 |
SO[subscript 3] | p. 105 |
Hydrogen Peroxide and Organic Hydroperoxides | p. 107 |
Aldehydes and Ketones | p. 107 |
Chlorine Nitrate (ClONO[subscript 2]) and Bromine Nitrate (BrONO[subscript 2]) | p. 111 |
HCl and HBr | p. 113 |
The Halogens | p. 114 |
ClO, BrO, and IO | p. 114 |
ClOOCl | p. 114 |
OClO | p. 115 |
HOCl, HOBr, and HOI | p. 115 |
Nitrosyl Chloride (ClNO) and Nitryl Chloride (ClNO[subscript 2]) | p. 117 |
Halogenated Methanes and Ethanes | p. 117 |
Kinetics and Atmospheric Chemistry | |
Fundamental Principles of Gas-Phase Kinetics | p. 130 |
Definitions | p. 130 |
Termolecular Reactions and Pressure Dependence of Rate Constants | p. 133 |
Temperature Dependence of Rate Constants | p. 138 |
Laboratory Techniques for Determining Absolute Rate Constants for Gas-Phase Reactions | p. 141 |
Kinetic Analysis | p. 142 |
Fast-Flow Systems | p. 142 |
Flash Photolysis Systems | p. 145 |
Pulse Radiolysis | p. 146 |
Cavity Ring Down Method | p. 147 |
Static Techniques | p. 148 |
Laboratory Techniques for Determining Relative Rate Constants for Gas-Phase Reactions | p. 149 |
Reactions in Solution | p. 151 |
Interactions of Gaseous Air Pollutants with Atmospheric Aqueous Solutions | p. 151 |
Diffusion-Controlled Reactions of Uncharged Nonpolar Species in Solution | p. 152 |
Reactions of Charged Species in Solution | p. 153 |
Experimental Techniques Used for Studying Solution Reactions | p. 155 |
Laboratory Techniques for Studying Heterogeneous Reactions | p. 156 |
Analysis of Systems with Gas- and Liquid-Phase Diffusion, Mass Accommodation, and Reactions in the Liquid Phase or at the Interface | p. 158 |
Knudsen Cells | p. 165 |
Flow Tube Studies | p. 167 |
Falling-Droplet Apparatus | p. 167 |
Bubble Apparatus | p. 168 |
Aerosol Chambers | p. 168 |
Liquid Jet Apparatus | p. 169 |
DRIFTS | p. 171 |
Surface Science Techniques | p. 171 |
Other Methods | p. 172 |
Compilations of Kinetic Data for Atmospheric Reactions | p. 172 |
Rates and Mechanisms of Gas-Phase Reactions in Irradiated Organic-NO[subscript x]-Air Mixtures | |
Sources of Oxidants in the Troposphere: OH, O[subscript 3], NO[subscript 3], HO[subscript 2], and Cl | p. 179 |
OH | p. 179 |
O[subscript 3] | p. 180 |
NO[subscript 3] | p. 180 |
HO[subscript 2] | p. 180 |
Cl | p. 180 |
Lifetimes of Typical Organics in the Troposphere | p. 181 |
Reactions of Alkanes | p. 182 |
Hydroxyl Radical (OH) | p. 182 |
Nitrate Radical (NO[subscript 3]) | p. 184 |
Chlorine Atoms (Cl) | p. 184 |
Reactions of Alkyl (R), Alkylperoxy (RO[subscript 2]), and Alkoxy (RO) Radicals in Air | p. 185 |
Alkyl Radicals (R) | p. 185 |
Alkylperoxy Radicals (RO[subscript 2]) | p. 185 |
Alkoxy Radicals (RO) | p. 188 |
Summary of R, RO[subscript 2], and RO Radical Reactions in the Troposphere | p. 191 |
Reactions of Alkenes (Including Biocenics) | p. 191 |
Hydroxyl Radical (OH) | p. 191 |
Ozone (O[subscript 3]) | p. 196 |
Nitrate Radical (NO[subscript 3]) | p. 201 |
Chlorine Atoms (Cl) | p. 205 |
Nitrogen Dioxide (NO[subscript 2]) | p. 206 |
Reactions of Alkynes | p. 206 |
Hydroxyl Radical (OH) | p. 206 |
Reactions of Simple Aromatic Hydrocarbons | p. 207 |
Hydroxyl Radical (OH) | p. 207 |
Nitrate Radical (NO[subscript 3]) | p. 212 |
Chlorine Atoms (Cl) | p. 212 |
Reactions of Oxygen-Containing Organics | p. 213 |
Reactions of OH, NO[subscript 3], and Cl | p. 213 |
Hydroperoxyl Radical (HO[subscript 2]) | p. 216 |
Reactions of Nitrogenous Organics | p. 217 |
Peroxyacetyl Nitrate and Its Homologs | p. 217 |
Alkyl Nitrates and Nitrites | p. 220 |
Amines, Nitrosamines, and Hydrazines | p. 221 |
Chemistry of Remote Regions | p. 225 |
Emissions of Biogenic Organics | p. 225 |
Chemistry | p. 231 |
Upper Troposphere | p. 239 |
Arctic | p. 241 |
Atmospheric Chemistry and Biomass Burning | p. 244 |
Chemistry of Inorganic Nitrogen Compounds | |
Oxidation of No To NO[subscript 2] and the Leighton Relationship | p. 265 |
Oxidation of NO[subscript 2] | p. 266 |
Daytime Gas-Phase Reaction with OH | p. 266 |
Nighttime Reactions to Form NO[subscript 3] and N[subscript 2]O[subscript 5] | p. 267 |
Reactions of NO and NO[subscript 2] with Water and Alcohols | p. 268 |
Other Reactions of NO[subscript 2] | p. 272 |
Atmospheric Chemistry of Hono | p. 273 |
Formation of HONO | p. 273 |
Atmospheric Fates of HONO | p. 274 |
Reactions of NO[subscript 3] and N[subscript 2]O[subscript 5] | p. 276 |
Reactions of NO[subscript 3] | p. 276 |
Reactions of N[subscript 2]O[subscript 5] | p. 279 |
Atmospheric Chemistry of HNO[subscript 3] | p. 281 |
Formation | p. 281 |
Tropospheric Fates | p. 281 |
"Missing" NO[subscript y] | p. 286 |
Ammonia (NH[subscript 3]) | p. 286 |
Acid Deposition: Formation and Fates of Inorganic and Organic Acids in the Troposphere | |
Contribution of H[subscript 2]SO[subscript 4], HNO[subscript 3], HONO, and Organic Acids | p. 294 |
Solubility of Gases in Rain, Fogs, and Clouds: Henry's Law and Aqueous-Phase Equilibria | p. 295 |
Oxidation of SO[subscript 2] | p. 296 |
Field Studies | p. 296 |
Oxidation in the Gas Phase | p. 298 |
Oxidation in the Aqueous Phase | p. 301 |
Oxidation on Surfaces | p. 324 |
Relative Importance of Various Oxidation Pathways for SO[subscript 2] | p. 325 |
Organic Acids | p. 326 |
Oxidation of Sulfur Compounds Other Than SO[subscript 2] | p. 328 |
Reactions of Dimethyl Sulfide (CH[subscript 3]SCH[subscript 3]) | p. 329 |
Dimethyl Disulfide (CH[subscript 3]SSCH[subscript 3]) | p. 334 |
Methyl Mercaptan (CH[subscript 3]SH) | p. 334 |
Hydrogen Sulfide (H[subscript 2]S) | p. 335 |
Carbon Disulfide (CS[subscript 2]) | p. 335 |
Carbonyl Sulfide (COS) | p. 336 |
Particles in the Troposphere | |
Physical Properties | p. 349 |
Some Definitions | p. 349 |
Size Distributions | p. 351 |
Particle Motion | p. 362 |
Light Scattering and Absorption and Their Relationship to Visibility Reduction | p. 365 |
Reactions Involved in Particle Formation and Growth | p. 375 |
Nucleation, Condensation, and Coagulation | p. 375 |
Reactions of Gases at Particle Surfaces | p. 379 |
Reactions in the Aqueous Phase | p. 380 |
Relative Importance of Various Aerosol Growth Mechanisms | p. 380 |
Chemical Composition of Tropospheric Aerosols | p. 380 |
Inorganic Species | p. 381 |
Organics | p. 393 |
GAS-Particle Distribution of Semivolatile Organics | p. 412 |
Adsorption on Solid Particles | p. 413 |
Absorption into Liquids | p. 417 |
Octanol - Air Partitioning Coefficients | p. 420 |
Airborne Polycyclic Aromatic Hydrocarbons and Their Derivatives: Atmospheric Chemistry and Toxicological Implications | |
Nomenclature and Selected Physical and Spectroscopic Properties of Polycyclic Aromatic Hydrocarbons (PAHs) and Polycyclic Aromatic Compounds (PACs) | p. 440 |
Combustion-Generated PAHs and PACs | p. 440 |
Structures and IUPAC Rules for Nomenclature | p. 440 |
Solubilities and Vapor Pressures | p. 451 |
Gas - Particle Partitioning, Sampling Techniques, and Ambient Levels of Selected PAHs and PACs | p. 453 |
Absorption and Emission Spectra of Selected PAHs and PACs | p. 461 |
Biological Properties of PAHs and PACs I: Carcinogenicity | p. 466 |
Historical Perspective: Benzo[a]pyrene, the "Classic Chemical Carcinogen" | p. 466 |
Carcinogenicity of PAHs, Cancer Potencies, and Potency Equivalence Factors | p. 467 |
Carcinogenicity of Nitroarenes and Other Nitro-PACs | p. 473 |
Biological Properties of PAHs and PACs II: Mutagenicity | p. 475 |
Short-Term Tests for Genetic and Related Effects | p. 475 |
The Ames Salmonella typhimurium Reversion Assay | p. 475 |
The Salmonella TM677 "Forward Mutation" Assay | p. 483 |
Human Cell Mutagenicities of PAHs and PACs | p. 484 |
Bacterial and Human Cell Mutagenicities of Polluted Ambient Air | p. 486 |
Bacterial Mutagenicity of Urban Air: A Worldwide Phenomenon | p. 486 |
Sources, Ambient Levels, Transport, and Transformation: Some Case Studies | p. 491 |
Bioassay-Directed Chemical Analysis for PAHs and PACs in Fine Ambient Aerosols Using a Human Cell Assay | p. 497 |
Bioassay-Directed Chemical Analysis for Vapor-Phase and Particle-Phase PAHs and PACs in Ambient Air Using Bacterial Assays | p. 502 |
Atmospheric Fates of Particle-Associated PAHs: Heterogeneous Reactions | p. 504 |
Background | p. 504 |
Theoretical and Experimental Structure - Reactivity Relationships | p. 505 |
Field Studies of Atmospheric Reactions: Transport and Transformation | p. 507 |
Photochemical Reactions of Particle-Associated PAHs | p. 510 |
Gas - Particle Reactions | p. 513 |
Atmospheric Fates of Particle-Associated Nitroarenes | p. 518 |
Reactions of Gas-Phase PAHs: Atmospheric Formation of Mutagenic Nitroarenes | p. 519 |
Combustion-Generated Primary Emissions of Nitroarenes | p. 519 |
Atmospheric Formation of Nitro-PAHs and Nitro-PACs | p. 520 |
Analytical Methods and Typical Atmospheric Concentrations for Gases and Particles | |
Gases | p. 548 |
Optical Spectroscopic Techniques | p. 548 |
Mass Spectrometry | p. 561 |
Filters, Denuders, Transition Flow Reactors, Mist Chambers, and Scrubbers | p. 567 |
Methods for, and Tropospheric Levels of, Specific Gases | p. 569 |
Generation of Standard Gas Mixtures | p. 607 |
Particles | p. 608 |
Sampling and Collection of Particles | p. 608 |
Measurement of Physical Characteristics: Mass and Size | p. 612 |
Measurement of Chemcial Composition | p. 619 |
Real-Time Monitoring Techniques for Particles | p. 626 |
Generation of Calibration Aerosols | p. 632 |
Homogeneous and Heterogeneous Chemistry in the Stratosphere | |
Chemistry of the Unperturbed Stratosphere | p. 657 |
Stratosphere - Troposphere Exchange (STE) | p. 658 |
Chapman Cycle and NO[subscript x] Chemistry | p. 660 |
High-Speed Civil Transport (HSCT), Rockets, and the Space Shuttle | p. 662 |
HSCT | p. 662 |
Space Shuttle and Solid Rocket Motors | p. 667 |
Chlorofluorocarbons | p. 669 |
Types, Nomenclature, and Uses | p. 669 |
Lifetimes and Atmospheric Fates of CFCs and Halons | p. 670 |
Gas-Phase Chemistry in the Stratosphere | p. 673 |
Antarctic "Ozone Hole" | p. 675 |
Polar Stratospheric Clouds (PSCs) and Aerosols | p. 680 |
Effects of Volcanic Eruptions | p. 690 |
Ozone Depletion in the Arctic | p. 696 |
Ozone Destruction in the Midlatitudes | p. 700 |
Contribution of Brominated Organics | p. 701 |
Sources and Sinks of Brominated Organics | p. 701 |
Bromine Chemistry in the Stratosphere | p. 702 |
Contribution of Iodine-Containing Organics | p. 706 |
Summary | p. 707 |
Scientific Basis for Control of Halogenated Organics | |
International Agreements on Phaseout of Halogenated Organics | p. 727 |
Ozone Depletion Potentials (ODP) | p. 730 |
Trends in CFCs, Their Replacements, Stratospheric O[subscript 3], and Surface UV | p. 733 |
Trends in CFCs and Their Replacements | p. 733 |
Trends in Stratospheric O[subscript 3] | p. 736 |
Trends in Surface Ultraviolet Radiation | p. 741 |
Tropospheric Chemistry of Alternate CFCs | p. 744 |
Kinetics of OH Reactions | p. 744 |
Tropospheric Chemistry | p. 746 |
Summary | p. 753 |
Global Tropospheric Chemistry and Climate Change | |
Radiation Balance of the Atmosphere: The Greenhouse Effect | p. 763 |
Global Absorption and Emission of Radiation | p. 763 |
Radiative Transfer Processes in the Atmosphere | p. 766 |
Dependence of Net Infrared Absorption on Atmospheric Concentrations | p. 769 |
Contribution of Trace Gases to the Greenhouse Effect | p. 770 |
Infrared Absorption by Trace Gases | p. 770 |
Trends in Trace Gas Concentrations | p. 773 |
Radiative Forcing by Greenhouse Gases and Global Warming Potentials | p. 783 |
Aerosol Particles, Atmospheric Radiation, and Climate Change | p. 788 |
Direct Effects | p. 789 |
Indirect Effects of Aerosol Particles | p. 799 |
Some Other Factors Affecting Global Climate | p. 814 |
Absorption of Solar Radiation by Clouds | p. 814 |
Feedbacks: Water Vapor, Clouds, and the "Supergreenhouse Effect" | p. 819 |
Solar Variability | p. 821 |
Volcanic Eruptions | p. 822 |
Oceans | p. 822 |
Observations of Climate Changes | p. 823 |
Observed Temperature Trends | p. 823 |
Other Climate Changes | p. 828 |
The Future | p. 828 |
Indoor Air Pollution: Sources, Levels, Chemistry, and Fates | |
Radon | p. 844 |
Oxides of Nitrogen | p. 846 |
Levels of NO[subscript x] | p. 846 |
HONO and HNO[subscript 3] | p. 847 |
CO and SO[subscript 2] | p. 849 |
Volatile Organic Compounds | p. 850 |
Ozone | p. 859 |
Indoor VOC-NO[subscript x]-O[subscript 3] Chemistry | p. 859 |
Particles | p. 861 |
Applications of Atmospheric Chemistry: Air Pollution Control Strategies and Risk Assessments for Tropospheric Ozone and Associated Photochemical Oxidants, Acids, Particles, and Hazardous Air Pollutants | |
Tropospheric Ozone and Associated Photochemical Oxidants | p. 871 |
Environmental Chambers | p. 872 |
Isopleths for Ozone and Other Photochemically Derived Species | p. 882 |
Models | p. 886 |
Reactivity of VOC | p. 907 |
Typical Reactivity Scales | p. 907 |
Application to Control of Mobile Source Emissions | p. 909 |
Field Observations of VOC, NO[subscript x], and O[subscript 3] | p. 913 |
Alternate Fuels | p. 918 |
Reformulated Gasolines | p. 918 |
Compressed Natural Gas (CNG) | p. 919 |
Liquefied Petroleum Gas (LPG) | p. 920 |
Alcohol Fuels and Blends with Gasoline | p. 920 |
Hydrogen | p. 921 |
Electric Vehicles | p. 921 |
Control of ACIDS | p. 921 |
Control of Particles | p. 923 |
Atmopsheric Chemistry and Risk Assessments of Hazardous Air Pollutants | p. 925 |
Enthalpies of Formation of Some Gaseous Molecules, Atoms, and Free Radicals at 298 K | p. 943 |
Bond Dissociation Energies | p. 945 |
Running the OZIPR Model | p. 947 |
Some Relevant Web Sites | p. 949 |
Pressures and Temperatures for Standard Atmosphere | p. 951 |
Answers to Selected Problems | p. 952 |
Subject Index | p. 957 |
Table of Contents provided by Syndetics. All Rights Reserved. |
ISBN: 9780122570605
ISBN-10: 012257060X
Published: 10th November 1999
Format: Hardcover
Language: English
Number of Pages: 1
Audience: Professional and Scholarly
Publisher: ACADEMIC PR INC
Country of Publication: US
Dimensions (cm): 28.58 x 22.33 x 4.6
Weight (kg): 2.91
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