Principles of Environmental Thermodynamics and Kinetics, Fourth Edition

497 Pages·2018·12.37 MB·English

by  Melvin, Elizabeth M., Valsaraj, Kalliat T

Principles of
Environmental
Thermodynamics
and Kinetics
Fourth Edition

Principles of
Environmental
Thermodynamics
and Kinetics
Fourth Edition
Kalliat T. Valsaraj and Elizabeth M. Melvin
CRC Press
Taylor & Francis Group
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Library of Congress Cataloging-in-Publication Data
Names: Valsaraj, K. T. (Kalliat T.) author. | Melvin, Elizabeth M., author.
Title: Principles of environmental thermodynamics and kinetics / Kalliat T.
Valsaraj and Elizabeth M. Melvin.
Other titles: Elements of environmental engineering
Description: Fourth edition. | Boca Raton : Taylor & Francis, CRC Press,
2018. | Revised edition of: Elements of environmental engineering /
Kalliat T. Valsaraj. 2009. | Includes bibliographical references and index.
Identifiers: LCCN 2017040508 | ISBN 9781498733632 (hardback : alk. paper)
Subjects: LCSH: Environmental engineering. | Thermodynamics. | Chemical
reactions.
Classification: LCC TD153 .V35 2018 | DDC 628--dc23
LC record available at https://lccn.loc.gov/2017040508
Visit the Taylor & Francis Web site at
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and the CRC Press Web site at
http://www.crcpress.com
Contents
Preface .......................................................................................................................xi
Acknowledgments ...................................................................................................xiii
Authors .....................................................................................................................xv
Chapter 1 Introduction ..........................................................................................1
1.1 Energy, Population, and Pollution .............................................1
1.2 Environmental Standards and Criteria .......................................2
1.3 The Discipline of Environmental Engineering ..........................3
1.4 Chemical Thermodynamics and Kinetics in
Environmental Engineering .......................................................4
1.4.1 Applications of Thermodynamics and Kinetics ...........5
1.4.1.1 Equilibrium Partitioning ...............................5
1.4.1.2 Fate and Transport Modeling ........................5
1.4.1.3 Design of Separation Processes ....................8
1.5 Units and Dimensions ................................................................9
1.6 Structure of this Book ..............................................................12
References ..........................................................................................13
Chapter 2 Basic Chemical Thermodynamics and Kinetics .................................15
2.1 Single-Component Thermodynamic Equilibrium ...................15
2.1.1 Equilibrium .................................................................15
2.1.2 Fundamental Laws of Thermodynamics ....................16
2.1.2.1 Zeroth Law of Thermodynamics ................17
2.1.2.2 First Law of Thermodynamics ....................18
2.1.2.3 Second Law of Thermodynamics ...............19
2.1.2.4 Third Law of Thermodynamics ..................21
2.1.2.5 Combination of First and Second Laws ......26
2.1.2.6 Enthalpy and Heat Capacity .......................26
2.1.2.7 Thermodynamic Standard States,
Enthalpies of Reaction, Formation, and
Combustion .................................................27
2.1.3 Chemical Equilibrium and Gibbs Free Energy ..........30
2.1.3.1 Free Energy Variation with
Temperature and Pressure ...........................30
2.1.4 Concept of Maximum Work .......................................32
2.1.5 Gibbs Free Energy and Chemical Potential ...............34
2.1.5.1 Gibbs-Duhem Relationship for a Single
Phase ...........................................................35
2.1.5.2 Standard States for Chemical Potential ......36
2.1.6 Thermodynamics of Surfaces and Colloidal Systems ....37
2.1.6.1 Surface Tension ...........................................37
v
vi Contents
2.1.6.2 Curved Interfaces and the Young-
Laplace Equation ........................................38
2.1.6.3 Surface Thickness and Gibbs Dividing
Surface ........................................................40
2.1.6.4 Surface Thermodynamics and
Gibbs Equation and Gibbs Adsorption
Equation ......................................................41
2.1.6.5 Gibbs Adsorption Equation .........................42
2.2 Multicomponent Equilibrium Thermodynamics .....................42
2.2.1 Ideal and Nonideal Fluids...........................................43
2.2.1.1 Concentration Units in Environmental
Engineering .................................................44
2.2.1.2 Dilute Solution Definition ...........................44
2.2.2 Fugacity ......................................................................45
2.2.2.1 Fugacity of Gases .......................................46
2.2.2.2 Fugacity of Condensed Phases
(Liquids and Solids) ....................................46
2.2.2.3 Activities of Solutes and Activity
Coefficients .................................................46
2.2.3 Ideal, Dilute Solutions ................................................49
2.2.3.1 Vapor-Liquid Equilibrium: Henry’s and
Raoult’s Laws .............................................49
2.2.3.2 Vapor Pressure of Organic Compounds:
Clausius-Clapeyron Equation .....................53
2.2.3.3 Vapor Pressure over Curved Surfaces .........58
2.2.3.4 Liquid-Liquid Equilibrium .........................61
2.2.4 Nonideal Solutions .....................................................65
2.2.4.1 Activity Coefficients for Nonideal
Systems .....................................................65
2.2.4.2 Activity Coefficient and Solubility .............66
2.2.4.3 Ionic Strength and Activity Coefficients .....68
2.2.4.4 Correlations with Hydrophobicity ..............71
2.2.4.5 Structure-Activity Relationships and
Activity Coefficients in Water .....................80
2.2.4.6 Theoretical and Semiempirical
Approaches to Aqueous Solubility
Prediction ....................................................82
2.2.4.7 Solubility of Inorganic Compounds
in Water .......................................................86
2.2.5 Adsorption on Surfaces and Interfaces .......................86
2.2.5.1 Gibbs Equation for Nonionic and Ionic
Systems .......................................................86
2.2.5.2 Equilibrium Adsorption Isotherms at
Interfaces .....................................................87
2.2.5.3 Adsorption at Charged Interfaces ...............98
Contents vii
2.3 Concepts from Chemical Reaction Kinetics ..........................100
2.3.1 Progress Toward Equilibrium in a Chemical
Reaction ....................................................................102
2.3.2 Reaction Rate, Order, and Rate Constant .................104
2.3.3 Kinetic Rate Laws ....................................................106
2.3.3.1 Isolation Method .......................................106
2.3.3.2 Initial Rate Method ...................................106
2.3.3.3 Integrated Rate Laws ................................106
2.3.4 Activation Energy .....................................................119
2.3.4.1 Activated Complex Theory .......................120
2.3.4.2 Effect of Solvent on Reaction Rates .........125
2.3.4.3 Linear Free Energy Relationships.............127
2.3.5 Reaction Mechanisms...............................................128
2.3.5.1 Chain Reactions ........................................129
2.3.6 Reactions in Solutions ..............................................132
2.3.6.1 Effects of Ionic Strength on Rate Constants ...132
2.3.7 Environmental Catalysis ...........................................133
2.3.7.1 Mechanisms and Rate Expressions for
Environmental Catalysis ...........................134
2.3.7.2 Homogeneous Catalysis ............................136
2.3.7.3 Heterogeneous Catalysis ...........................140
2.3.7.4 General Mechanisms of Surface Catalysis ....140
2.3.7.5 Autocatalysis in Environmental Systems ....144
2.3.8 Redox Reactions in Environmental Systems ............147
2.3.8.1 Rates of Redox Reactions .........................151
2.3.9 Environmental Photochemical Reactions .................154
2.3.10 Enzyme Catalysis .....................................................159
2.3.10.1 Michaelis-Menton and Monod Kinetics .....159
2.4 Chemical Kinetics and Reactor Design .................................166
2.4.1 Types of Reactors .....................................................166
2.4.1.1 Ideal Reactors ...........................................167
2.4.1.2 Nonideal Reactors .....................................176
2.4.1.3 Dispersion and Reaction ...........................179
2.4.1.4 Reaction in Heterogeneous Medium ........181
2.4.1.5 Diffusion and Reaction in a
Porous Medium .........................................185
Problems ...........................................................................................190
References ........................................................................................217
Chapter 3 Applications of Equilibrium Thermodynamics ................................223
3.1 Fugacity and Environmental Models .....................................223
3.2 Air-Water Phase Equilibrium ................................................227
3.2.1 Estimation of Henry’s Constant from Group
Contributions ............................................................231
viii Contents
3.2.2 Experimental Determination of Henry’s
Constants ..............................................................232
3.2.3 Effects of Environmental Variables on K .............234
AW
3.3 Air-Water Equilibrium in Atmospheric Chemistry ................244
3.3.1 Wet Deposition of Vapor Species .............................246
3.3.2 Wet Deposition of Aerosol-Bound Fraction .............246
3.3.3 Dry Deposition of Aerosol-Bound Pollutants ..........250
3.3.4 Dry Deposition Flux of Gases from the
Atmosphere ..............................................................251
3.3.5 Thermodynamics of Aqueous Droplets in the
Atmosphere ..............................................................254
3.3.6 Air-Water Equilibrium in Waste Treatment
Systems ...................................................................257
3.4 Soil-Water and Sediment-Water Equilibrium ........................260
3.4.1 Partitioning into Soils and Sediments from Water .....261
3.4.2 Adsorption of Metal Ions on Soils and Sediments .....262
3.4.3 Adsorption of Organic Molecules on Soils and
Sediments .................................................................266
3.5 Biota-Water Partition Constant ..............................................272
3.6 Air-to-Aerosol Partition Constant..........................................275
3.7 Air-to-Vegetation Partition Constant .....................................279
3.8 Adsorption on Activated Carbon for Wastewater
Treatment ...........................................................................281
Problems ...........................................................................................283
References ........................................................................................293
Chapter 4 Applications of Chemical Kinetics in Environmental Systems .......299
4.1 Water Environment ................................................................299
4.1.1 Fate and Transport ....................................................299
4.1.1.1 Chemicals in Lakes and Oceans ...............299
4.1.1.2 Chemicals in Surface Waters ....................303
4.1.1.3 Biochemical Oxygen Demand in
Natural Streams ........................................305
4.1.2 Water Pollution Control ............................................309
4.1.2.1 Air Stripping in Aeration Basins ...............309
4.1.2.2 Oxidation Reactor .....................................314
4.1.2.3 Photochemical Reactions and
Wastewater Treatment ...............................320
4.1.2.4 Photochemical Reactions in Natural
Waters .......................................................321
4.2 Air Environment ....................................................................323
4.2.1 Fate and Transport Models .......................................323
4.2.1.1 Box Models ...............................................323
4.2.1.2 Dispersion Models ....................................330
Contents ix
4.2.2 Air Pollution Control ................................................335
4.2.2.1 Adsorption ................................................335
4.2.2.2 Thermal Destruction .................................339
4.2.3 Atmospheric Processes .............................................341
4.2.3.1 Reactions in Aqueous Droplets .................342
4.2.3.2 Global Warming and the
Greenhouse Effect .....................................349
4.2.3.3 Ozone in the Stratosphere and
Troposphere ..............................................359
4.3 Soil and Sediment Environments...........................................369
4.3.1 Fate and Transport Modeling ...................................369
4.3.1.1 Transport in Groundwater .........................369
4.3.1.2 Sediment-Water Exchange of
Chemicals .............................................376
4.3.1.3 Soil-Air Exchange of Chemicals ..............379
4.3.2 Soil and Groundwater Transport ..............................381
4.3.2.1 Pump-and-Treat for NAPL Removal ........382
4.3.2.2 In Situ Soil Vapor Stripping ......................386
4.3.2.3 Incineration for Ex Situ Treatment ...........388
4.4 Applications in Environmental Bioengineering ....................389
4.4.1 Enzyme Reactors ......................................................393
4.4.1.1 Batch Reactor ............................................394
4.4.1.2 Plug Flow Enzyme Reactor ......................395
4.4.1.3 Continuous Stirred Tank Enzyme
Reactor ....................................................397
4.4.1.4 Immobilized Enzyme of Cell Reactor ......401
4.4.1.5 In Situ Subsoil Bioremediation .................405
4.4.2 Kinetics of Bioaccumulation in the Aquatic
Food Chain ...............................................................407
4.5 Applications in Green Engineering .......................................413
4.5.1 Environmental Impact Analysis (EIA) .....................414
4.5.2 Life Cycle Assessment .............................................420
Problems ...........................................................................................421
References ........................................................................................433
Appendix A: Properties of Selected Chemicals of Environmental
Significance ...........................................................................................................439
Appendix B: Standard Free Energy, Enthalpy, and Entropy of
Formation for Compounds of Environmental Significance .............................447
Appendix C: Selected Fragment (b) and Structural Factors (B ) for
j k
Octanol–Water Partition Constant Estimation .................................................449
Appendix D: Concentration Units for Compartments in Environmental
Engineering ...........................................................................................................451