Elements of Environmental Engineering: Thermodynamics and Kinetics, Third Edition

by Valsaraj; Kalliat T.

• ISBN13: 9781420078190
• ISBN10: 1420078194
• Edition: 3rd
• Format: Hardcover
• Copyright: 2009-06-09
• Publisher: CRC Press

Summary

Revised, updated, and rewritten where necessary, but keeping the clear writing and organizational style that made previous editions so popular, Elements of Environmental Engineering: Thermodynamics and Kinetics, Third Edition contains new problems and new examples that better illustrate theory. The new edition contains examples with a practical flavor such as global warming, ozone layer depletion, nanotechnology, green chemistry, and green engineering. With detailed theoretical discussion and principles illuminated by numerical examples, this book fills the gaps in coverage of the principles and applications of kinetics and thermodynamics.

Table of Contents

Preface	p. xi
Author	p. xv
Introduction	p. 1
Energy, Population, and Pollution	p. 1
Environmental Standards and Criteria	p. 2
The Discipline of Environmental Engineering	p. 2
Chemical Thermodynamics and Kinetics in Environmental Engineering	p. 4
Applications of Thermodynamics and Kinetics	p. 4
Equilibrium Partitioning	p. 4
Fate and Transport Modeling	p. 5
Design of Separation Processes	p. 8
Units and Dimensions	p. 11
Structure of the Book	p. 12
References	p. 12
Basic Chemical Thermodynamics	p. 13
Equilibrium	p. 13
Fundamental Laws of Thermodynamics	p. 14
Zeroth Law of Thermodynamics	p. 15
First Law of Thermodynamics	p. 16
Second Law of Thermodynamics	p. 17
Third Law of Thermodynamics	p. 18
Enthalpy and Heat Capacity	p. 22
Thermodynamic Standard States: Enthalpies of Reaction, Formation, and Combustion	p. 23
Combination of First and Second Laws	p. 25
Chemical Equilibrium and Gibbs Free Energy	p. 26
Free Energy Variation with Temperature and Pressure	p. 26
Concept of Maximum Work	p. 28
Gibbs Free Energy and Chemical Potential	p. 29
Gibbs-Duhem Relationship for a Single Phase	p. 30
Standard States for Chemical Potential	p. 31
Thermodynamics of Surfaces and Colloidal Systems	p. 32
Surface Tension	p. 32
Curved Interfaces and the Young-Laplace Equation	p. 33
Surface Thickness and Gibbs Dividing Surface	p. 35
Surface Thermodynamics and Gibbs Equation	p. 36
Gibbs Adsorption Equation	p. 37
Problems	p. 37
References	p. 41
Multicomponent Equilibrium Thermodynamics	p. 43
Ideal and Nonideal Fluids	p. 43
Concentration Units in Environmental Engineering	p. 44
Dilute Solution Definition	p. 45
Fugacity	p. 45
Fugacity of Gases	p. 46
Fugacity of Condensed Phases (Liquids and Solids)	p. 46
Activities of Solutes and Activity Coefficients	p. 47
Ionic Strength and Activity Coefficients	p. 49
Fugacity and Environmental Models	p. 51
Ideal Solutions and Dilute Solutions	p. 55
Vapor-Liquid Equilibrium: Henry's and Raoult's Laws	p. 55
Henry's Law	p. 55
Raoult's Law	p. 56
Vapor Pressure of Organic Compounds, Clausius-Clapeyron Equation	p. 58
Vapor Pressure over Curved Surfaces	p. 63
Liquid-Liquid Equilibrium	p. 66
Octanol-Water Partition Constant	p. 66
Linear Free Energy Relationships	p. 69
Nonideal Solutions	p. 69
Activity Coefficient for Nonideal Systems	p. 69
Excess Functions and Activity Coefficients	p. 70
Activity Coefficient and Solubility	p. 70
Correlations with Hydrophobicity	p. 72
Special Structural Features of Water	p. 73
Hydrophobic Hydration of Nonpolar Solutes	p. 75
Hydrophobic Interactions between Solutes	p. 78
Hydrophilic Interactions for Solutes in Water	p. 79
Molecular Theories of Solubility: An Overview	p. 80
Structure-Activity Relationships and Activity Coefficients in Water	p. 82
Theoretical and Semi-Empirical Approaches to Aqueous Solubility Prediction	p. 83
First-Generation Group Contribution Methods	p. 83
Excess Gibbs Free Energy Models	p. 86
Second-Generation Group Contribution Methods: The UNIFAC Method	p. 86
Solubility of Inorganic Compounds in Water	p. 88
Adsorption on Surfaces and Interfaces	p. 88
Gibbs Equation for Nonionic and Ionic Systems	p. 89
Equilibrium Adsorption Isotherms at Interfaces	p. 90
Adsorption at Charged Surfaces	p. 101
Problems	p. 103
References	p. 116
Applications of Equilibrium Thermodynamics	p. 119
Air-Water Phase Equilibrium	p. 119
Estimation of Henry's Constant from Group Contributions	p. 123
Experimental Determination of Henry's Law Constants	p. 125
Effects of Environmental Variables on Kaw	p. 126
Air-Water Equilibrium in Atmospheric Chemistry	p. 136
Wet Deposition of Vapor Species	p. 137
Wet Deposition of Aerosol-Bound Fraction	p. 138
Dry Deposition of Aerosol-Bound Pollutants	p. 143
Dry Deposition Flux of Gases from the Atmosphere	p. 144
Thermodynamics of Aqueous Droplets in the Atmosphere	p. 147
Air/Water Equilibrium in Waste Treatment Systems	p. 150
Soil-Water and Sediment-Water Equilibrium	p. 152
Partitioning into Soils and Sediments from Water	p. 153
Adsorption of Metal Ions on Soils and Sediments	p. 155
Adsorption of Organic Molecules on Soils and Sediments	p. 159
Biota/Water Partition Constant (Bioconcentration Factor)	p. 164
Air-to-Aerosol Partition Constant	p. 167
Air-to-Vegetation Partition Constant	p. 171
Adsorption on Activated Carbon for Wastewater Treatment	p. 172
Problems	p. 175
References	p. 183
Concepts from Chemical Reaction Kinetics	p. 189
Progress toward Equilibrium in a Chemical Reaction	p. 190
Reaction Rate, Order, and Rate Constant	p. 193
Kinetic Rate Laws	p. 194
Isolation Method	p. 195
Initial Rate Method	p. 195
Integrated Rate Laws	p. 195
Reversible Reactions	p. 198
Series Reactions and Steady-State Approximation	p. 201
Parallel Reactions	p. 207
Activation Energy	p. 208
Activated Complex Theory	p. 210
Effect of Solvent on Reaction Rates	p. 213
Linear Free Energy Relationships	p. 215
Reaction Mechanisms	p. 216
Chain Reactions	p. 216
Reactions in Solutions	p. 219
Effects of Ionic Strength on Rate Constants	p. 219
Environmental Catalysis	p. 221
Mechanisms and Rate Expressions for Catalyzed Reactions	p. 222
Homogeneous Catalysis	p. 224
Heterogeneous Catalysis	p. 228
General Mechanisms of Surface Catalysis	p. 228
Autocatalysis in Environmental Reactions	p. 234
Redox Reactions in Environmental Systems	p. 237
Rates of Redox Reactions	p. 240
Environmental Photochemical Reactions	p. 244
Enzyme Catalysis	p. 247
Michaelis-Menten Kinetics and Monod Kinetics	p. 247
Problems	p. 254
References	p. 264
Applications of Chemical Kinetics in Environmental Systems	p. 267
Types of Reactors	p. 267
Ideal Reactors	p. 267
Batch Reactor	p. 269
Continuous-Flow Stirred Tank Reactor	p. 269
Plug-Flow Reactor (PFR) or Tubular Reactor	p. 270
Design Equations for CSTR and PFR	p. 271
Relationship between Steady State and Equilibrium for a CSTR	p. 276
Nonideal Reactors	p. 277
Dispersion Model	p. 277
Tanks-in-Series Model	p. 278
Dispersion and Reaction	p. 280
Reaction in a Heterogeneous Medium	p. 281
Kinetics and Transport at Fluid-Fluid Interfaces	p. 284
Diffusion and Reaction in a Porous Medium	p. 286
The Water Environment	p. 290
Fate and Transport	p. 290
Chemicals in Lakes and Oceans	p. 290
Chemicals in Surface Waters	p. 293
Biochemical Oxygen Demand in Natural Streams	p. 295
Water Pollution Control	p. 299
Air Stripping in Aeration Basins	p. 299
Oxidation Reactor	p. 303
Photochemical Reactions and Wastewater Treatment	p. 309
Photochemical Reactions in Natural Waters	p. 311
The Air Environment	p. 313
F&T Models	p. 313
Box Models	p. 313
Dispersion Models	p. 319
Air Pollution Control	p. 324
Adsorption	p. 324
Thermal Destruction	p. 327
Atmospheric Processes	p. 330
Reactions in Aqueous Droplets	p. 330
Global Warming and Greenhouse Effect	p. 337
Ozone in the Stratosphere and Troposphere	p. 347
Soil and Sediment Environments	p. 357
F&T Modeling	p. 357
Transport in Groundwater	p. 358
Sediment-Water Exchange of Chemicals	p. 364
Soil-Air Exchange of Chemicals	p. 366
Soil and Groundwater Treatment	p. 369
P&T for NAPL Removal from Groundwater	p. 370
In Situ Soil Vapor Stripping in the Vadose Zone	p. 373
Incineration for ex Situ Treatment of Soils and Solid Waste	p. 375
Applications of Chemical Kinetics in Environmental Bioengineering	p. 376
Enzyme Reactors	p. 380
Batch Reactor	p. 381
Plug-Flow Enzyme Reactor	p. 382
Continuous Stirred Tank Enzyme Reactor	p. 383
Immobilized Enzyme or Cell Reactor	p. 387
In Situ Subsoil Bioremediation	p. 391
Kinetics of Bioaccumulation of Chemicals in the Aquatic Food Chain	p. 393
Applications in Green Engineering	p. 398
Environmental Impact Analysis	p. 399
Life Cycle Assessment	p. 405
Problems	p. 406
References	p. 420
Properties of Selected Chemicals of Environmental Significance	p. 425
Standard Free Energy, Enthalpy, and Entropy of Formation for Compounds of Environmental Significance	p. 431
Selected Fragment (bj) and Structural Factors (Bk) for Octanol-Water Partition Constant Estimation	p. 433
Concentration Units for Compartments in Environmental Engineering	p. 435
Dissociation Constants for Environmentally Significant Acids and Bases	p. 437
Bond Contributions to Log Kaw for the Meylan and Howard Model	p. 439
Regression Analysis (the Linear Least-Squares Methodology)	p. 441
Error Function and Complementary Error Function Definitions	p. 445
Cancer Slope Factor and Inhalation Unit Risk for Selected Carcinogens	p. 447
U.S. National Ambient Air Quality Standards	p. 449
Index	p. 451
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