Environmental Organic Chemistry E-Book

René P. Schwarzenbach

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 2069

Veröffentlichungsjahr: 2016

Beschreibung

Examines in a pedagogical way all pertinent molecular and macroscopic processes that govern the distribution and fate of organic chemicals in the environment and provides simple modeling tools to quantitatively describe these processes and their interplay in a given environmental system

• Treats fundamental aspects of chemistry, physics, and mathematical modeling as applied to environmentally relevant problems, and gives a state of the art account of the field
• Teaches the reader how to relate the structure of a given chemical to its physical chemical properties and intrinsic reactivities
• Provides a holistic and teachable treatment of phase partitioning and transformation processes, as well as a more focused and tailor-made presentation of physical, mathematical, and modeling aspects that apply to environmental situations of concern
• Includes a large number of questions and problems allowing teachers to explore the depth of understanding of their students or allowing individuals who use the book for self-study to check their progress 
• Provides a companion website, which includes solutions for all problems as well as a large compilation of physical constants and compound properties

Leseprobe

ENVIRONMENTAL ORGANIC CHEMISTRY

Third Edition

René P. SchwarzenbachPhilip M. GschwendDieter M. Imboden

Copyright © 2017 by John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey.Published simultaneously in Canada.

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, [phone], fax [phone], or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, [phone], fax [phone], or online at http://www.wiley.com/go/permission.

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Library of Congress Cataloging-in-Publication Data is available.

ISBN: 978-1-118-76723-5

CONTENTS

Preface

About the Companion Website

Chapter 1 General Topic and Overview

1.1 Introduction

1.2 Assessing Organic Chemicals in the Environment

1.3 What is This Book All About?

1.4 Bibliography

Part I Background Knowledge

Chapter 2 Background Knowledge on Organic Chemicals

2.1 The Makeup of Organic Compounds

2.2 Intermolecular Forces Between Uncharged Molecules

2.3 Questions and Problems

2.4 Bibliography

Chapter 3 The Amazing World of Anthropogenic Organic Chemicals

3.1 Introduction

3.2 A Lasting Global Problem: Persistent Organic Pollutants (POPs)

3.3 Natural but Nevertheless Problematic: Petroleum Hydrocarbons

3.4 Notorious Air and Groundwater Pollutants: Organic Solvents

3.5 Safety First: Flame Retardants All Around Us

3.6 How to Make Materials “Repellent”: Polyfluorinated Chemicals (PFCs)

3.7 From Washing Machines to Surface Waters: Complexing Agents, Surfactants, Whitening Agents, and Corrosion Inhibitors

3.8 Health, Well-Being, and Water Pollution: Pharmaceuticals and Personal Care Products

3.9 Fighting Pests: Herbicides, Insecticides, and Fungicides

3.10 Our Companion Compounds: Representative Model Chemicals

3.11 Questions

3.12 Bibliography

Chapter 4 Background Thermodynamics, Equilibrium Partitioning and Acidity Constants

4.1 Important Thermodynamic Functions

4.2 Using Thermodynamic Functions to Quantify Equilibrium Partitioning

4.3 Organic Acids and Bases I: Acidity Constant and Speciation in Natural Waters

4.4 Organic Acids and Bases II: Chemical Structure and Acidity Constant

4.5 Questions and Problems

4.6 Bibliography

Chapter 5 Earth Systems and Compartments

5.1 Introduction

5.2 The Atmosphere

5.3 Surface Waters and Sediments

5.4 Soil and Groundwater

5.5 Biota

5.5 Questions

5.7 Bibliography

Chapter 6 Environmental Systems: Physical Processes and Mathematical Modeling

6.1 Systems and Models

6.2 Box Models: A Concept for a Simple World

6.3 When Space Matters: Transport Processes

6.4 Models in Space and Time

6.5 Questions and Problems

6.6 Bibliography

Part II Equilibrium Partitioning in Well-Defined Systems

Chapter 7 Partitioning Between Bulk Phases: General Aspects and Modeling Approaches

7.1 Introduction

7.2 Molecular Interactions Governing Bulk Phase Partitioning of Organic Chemicals

7.3 Quantitative Approaches to Estimate Bulk Phase Partition Constants/Coefficients: Linear Free Energy Relationships (LFERs)

7.4 Questions

7.5 Bibliography

Chapter 8 Vapor Pressure (

p

i

*)

8.1 Introduction and Theoretical Background

8.2 Molecular Interactions Governing Vapor Pressure and Vapor Pressure Estimation Methods

8.3 Questions and Problems

8.4 Bibliography

Chapter 9 Solubility (

C

sat

i

w

) and Activity Coefficient (γ

sat

iw

)in Water; Air–Water Partition Constant (

K

i

aw

)

9.1 Introduction and Thermodynamic Considerations

9.2 Molecular Interactions Governing the Aqueous Activity Coefficient and the Air–Water Partition Constant

9.3 LFERs for Estimating Air–Water Partition Constants and Aqueous Activity Coefficients/Aqueous Solubilities

9.4 Effect of Temperature, Dissolved Salts, and pH on the Aqueous Activity Coefficient/Aqueous Solubility and on the Air–Water Partition Constant

9.5 Questions and Problems

9.6 Bibliography

Chapter 10 Organic Liquid–Air and Organic Liquid–Water Partitioning

10.1 Introduction

10.2 Thermodynamic Considerations and Comparisons of Different Organic Solvents

10.3 The Octanol–Water System: The Atom/Fragment Contribution Method for Estimation of the Octanol–Water Partition Constant

10.4 Partitioning Involving Organic Solvent–Water Mixtures

10.5 Evaporation and Dissolution of Organic Compounds from Organic Liquid Mixtures–Equilibrium Considerations

10.6 Questions and Problems

10.7 Bibliography

Chapter 11 Partitioning of Nonionic Organic Compounds Between well-Defined Surfaces and Air Or Water

11.1 Introduction

11.2 Adsorption from Air to Well-Defined Surfaces

11.3 Adsorption from Water to Inorganic Surfaces

11.4 Questions and Problems

11.5 Bibliography

Part III Equilibrium Partitioning in Environmental Systems

Chapter 12 General Introduction to Sorption Processes

12.1 Introduction

12.2 Sorption Isotherms and the Solid–Water Equilibrium Distribution Coefficient (

K

i

d

)

12.3 Speciation (Sorbed versus Dissolved or Gaseous), Retardation, and Sedimentation

12.4 Questions and Problems

12.5 Bibliography

Chapter 13 Sorption from Water to Natural Organic Matter (NOM)

13.1 The Structural Diversity of Natural Organic Matter Present in Aquatic and Terrestrial Environments

13.2 Quantifying Natural Organic Matter–Water Partitioning of Neutral Organic Compounds

13.3 Sorption of Organic Acids and Bases to Natural Organic Matter

13.4 Questions and Problems

13.5 Bibliography

Chapter 14 Sorption of Ionic Organic Compounds to Charged Surfaces

14.1 Introduction

14.2 Cation and Anion Exchange Capacities of Solids in Water

14.3 Ion Exchange: Nonspecific Adsorption of Ionized Organic Chemicals from Aqueous Solutions to Charged Surfaces

14.4 Surface Complexation: Specific Bonding of Organic Compounds with Solid Phases in Water

14.5 Questions and Problems

14.6 Bibliography

Chapter 15 Aerosol–Air Partitioning: Dry and Wet Deposition of Organic Pollutants

15.1 Origins and Properties of Atmospheric Aerosols

15.2 Assessing Aerosol–Air Partition Coefficients (

K

i

PMa

)

15.3 Dry and Wet Deposition

15.4 Questions and Problems

15.5 Bibliography

Chapter 16 Equilibrium Partitioning from Water and Air to Biota

16.1 Introduction

16.2 Predicting Biota–Water and Biota–Air Equilibrium Partitioning

16.3 Bioaccumulation and Biomagnification in Aquatic Systems

16.4 Bioaccumulation and Biomagnification in Terrestrial Systems

16.5 Baseline Toxicity (Narcosis)

16.6 Questions and Problems

16.7 Bibliography

Part IV Mass Transfer Processes in Environmental Systems

Chapter 17 Random Motion, Molecular and Turbulent Diffusivity

17.1 Random Motion

17.2 Molecular Diffusion

17.3 Other Random Transport Processes in the Environment

17.4 Questions and Problems

17.5 Bibliography

Chapter 18 Transport at Boundaries

18.1 The Role of Boundaries in the Environment

18.2 Bottleneck Boundaries

18.3 Wall Boundaries

18.4 Hybrid Boundaries

18.5 Questions and Problems

18.6 Bibliography

Chapter 19 Air–Water Exchange

19.1 The Air–Water Interface

19.2 Air–Water Exchange Models

19.3 Measurement of Air–Water Exchange Velocities

19.4 Air–Water Exchange in Flowing Waters

19.5 Questions and Problems

19.6 Bibliography

Chapter 20 Interfaces Involving Solids

20.1 The Sediment–Water Interface

20.2 Transport in Unsaturated Soil

20.3 Questions and Problems

20.4 Bibliography

Part V Transformation Processes

Chapter 21 Background Knowledge on Transformation Reactions of Organic Pollutants

21.1 Identifying Reactive Sites Within Organic Molecules

21.2 Thermodynamics of Transformation Reactions

21.3 Kinetics of Transformation Reactions

21.4 Questions and Problems

21.5 Bibliography

Chapter 22 Hydrolysis and Reactions with Other Nucleophiles

22.1 Nucleophilic Substitution and Elimination Reactions Involving Primarily Saturated Carbon Atoms

22.2 Hydrolytic Reactions of Carboxylic and Carbonic Acid Derivatives

22.3 Enzyme-Catalyzed Hydrolysis Reactions: Hydrolases

22.4 Questions and Problems

22.5 Bibliography

Chapter 23 Redox Reactions

23.1 Introduction

23.2 Evaluating the Thermodynamics of Redox Reactions

23.3 Examples of Chemical Redox Reactions in Natural Systems

23.4 Examples of Enzyme-Catalyzed Redox Reactions

23.5 Questions and Problems

23.6 Bibliography

Chapter 24 Direct Photolysis in Aquatic Systems

24.1 Introduction

24.2 Some Basic Principles of Photochemistry

24.3 Light Absorption by Organic Compounds in Natural Waters

24.4 Quantum Yield and Rate of Direct Photolysis

24.5 Effects of Solid Sorbents (Particles, Soil Surfaces, Ice) on Direct Photolysis

24.6 Questions and Problems

24.7 Bibliography

Chapter 25 Indirect Photolysis: Reactions with Photooxidants in Natural Waters and in the Atmosphere

25.1 Introduction

25.2 Indirect Photolysis in Surface Waters

25.3 Indirect Photolysis in the Atmosphere (Troposphere): Reaction with Hydroxyl Radical (HO

•

)

25.4 Questions and Problems

25.6 Bibliography

Chapter 26 Biotransformations

26.1 Introduction

26.2 Some Important Concepts about Microorganisms Relevant to Biotransformations

26.3 Initial Biotransformation Strategies

26.4 Rates of Biotransformations

26.5 Questions and Problems

26.6 Bibliography

Chapter 27 Assessing Transformation Processes Using Compound-Specific Isotope Analysis (CSIA)

27.1 Introduction, Methodology, and Theoretical Background

27.2 Using CSIA for Assessing Organic Compound Transformations in Laboratory and Field Systems

27.3 Questions and Problems

27.4 Bibliography

Part VI Putting Everything Together

Chapter 28 Exposure Assessment of Organic Pollutants Using Simple Modeling Approaches

28.1 One-Box Model: The Universal Tool for Process Integration

28.2 Assessing Equilibrium Partitioning in Simple Multimedia Systems

28.3 Simple Dynamic Systems

28.4 Systems Driven by Advection

28.5 Bibliography

Appendix A Mathematics

Appendix B Physical Constants and Units

Appendix C Physical Properties of Organic Compounds

Appendix D Temperature Dependence of Equilibrium Constants and Rate Constants

Appendix E Estimation of Gas-Phase Hydroxyl Radical Reaction Rate Constants of Organic Chemicals

Index

EULA

List of Tables

Chapter 1

Table 1.1

Chapter 2

Table 2.1

Table 2.2

Table 2.3

Table 2.4

Table 2.5

Chapter 3

Table 3.1

Chapter 4

Table 4.1

Table 4.2

Table 4.3

Table 4.4

Table 4.5

Table 4.6

Table 4.7

Table 4.8

Table 4.9

Table 4.10

Chapter 5

Table 5.1

Table 5.2

Table 5.3

Table 5.4

Table 5.5

Table 5.6

Table 5.7

Table 5.8

Table 5.9

Table 5.10

Chapter 6

Table 6.1

Table 6.2

Table 6.3

Chapter 7

Table 7.1

Table 7.2

Table 7.3

Table 7.4

Chapter 8

Table 8.1

Table 8.2

Chapter 9

Table 9.1

Table 9.2

Table 9.3

Table 9.4

Table 9.5

Table 9.6

Chapter 10

Table 10.1

Table 10.2

Table 10.3

Table 10.4

Table 10.5

Table 10.6

Table 10.7

Chapter 11

Table 11.1

Table 11.2

Chapter 13

Table 13.1

Table 13.2

Table 13.3

Chapter 14

Table 14.1

Table 14.2

Chapter 15

Table 15.1

Table 15.2

Table 15.3

Table 15.4

Chapter 16

Table 16.1

Table 16.2

Table 16.3

Table 16.4

Table 16.5

Chapter 17

Table 17.1

Table 17.2

Table 17.3

Chapter 19

Table 19.1

Table 19.2

Chapter 21

Table 21.1

Chapter 22

Table 22.1

Table 22.2

Table 22.3

Table 22.4

Table 22.5

Table 22.6

Table 22.7

Table 22.8

Table 22.9

Chapter 23

Table 23.1

Table 23.2

Table 23.3

Table 23.4

Table 23.5

Table 23.6

Chapter 24

Table 24.1

Table 24.2

Table 24.3

Table 24.4

Table 24.5

Table 24.6

Chapter 25

Table 25.1

Chapter 26

Table 26.1

Table 26.2

Table 26.3

Chapter 27

Table 27.1

Table 27.2

Table 27.3

Table 27.4

Table 27.5

Table 27.6

Table 27.7

Table 27.8

Table 27.9

Table 27.10

Table 27.11

Table 27.12

Table 27.13

Chapter 28

Table 28.1

Table 28.2

Table 28.3

Table 28.4

Table 28.5

Table 28.6

Appendix A

Table A.1

Appendix B

Table B.3

a

Table B.3

b

Appendix C

Table C.1

Table C.2

Appendix D

Table D.1

Table D.2