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“78194_C000.tex” — page i[#1] 22/4/2009 19:43
“78194_C000.tex” — page ii[#2] 22/4/2009 19:43
“78194_C000.tex” — page iii[#3] 22/4/2009 19:43
CRC Press
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 Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
Author . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Energy, Population, and Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Environmental Standards and Criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 The Discipline of Environmental Engineering. . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.4 Chemical Thermodynamics and Kinetics in Environmental
Engineering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4.1 Applications of Thermodynamics and Kinetics . . . . . . . . . . . . . . . . 4
1.4.1.1 Equilibrium Partitioning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4.1.2 Fate and Transport Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.4.1.3 Design of Separation Processes . . . . . . . . . . . . . . . . . . . . . . . 8
1.5 Units and Dimensions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.6 Structure of the Book . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

2 Basic Chemical Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

2.1 Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2 Fundamental Laws of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.1 Zeroth Law of Thermodynamics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.2 First Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.3 Second Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.4 Third Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.5 Enthalpy and Heat Capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.6 Thermodynamic Standard States: Enthalpies of Reaction,
Formation, and Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.7 Combination of First and Second Laws . . . . . . . . . . . . . . . . . . . . . . . . 25
2.3 Chemical Equilibrium and Gibbs Free Energy . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.3.1 Free Energy Variation with Temperature and Pressure . . . . . . . . 26
2.4 Concept of Maximum Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.5 Gibbs Free Energy and Chemical Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.5.1 Gibbs–Duhem Relationship for a Single Phase . . . . . . . . . . . . . . . . 30
2.5.2 Standard States for Chemical Potential . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.6 Thermodynamics of Surfaces and Colloidal Systems . . . . . . . . . . . . . . . . . . 32
2.6.1 Surface Tension. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.6.2 Curved Interfaces and the Young–Laplace Equation . . . . . . . . . . 33
2.6.3 Surface Thickness and Gibbs Dividing Surface . . . . . . . . . . . . . . . . 35

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 vi Contents

2.6.4 Surface Thermodynamics and Gibbs Equation . . . . . . . . . . . . . . . . 36

2.6.5 Gibbs Adsorption Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

3 Multicomponent Equilibrium Thermodynamics. . . . . . . . . . . . . . . . . . . . . . . . . . 43

3.1 Ideal and Nonideal Fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.1.1 Concentration Units in Environmental Engineering . . . . . . . . . . . 44
3.1.2 Dilute Solution Definition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.2 Fugacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.2.1 Fugacity of Gases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.2.2 Fugacity of Condensed Phases (Liquids and Solids) . . . . . . . . . . 46
3.2.3 Activities of Solutes and Activity Coefficients . . . . . . . . . . . . . . . . . 47
3.2.4 Ionic Strength and Activity Coefficients . . . . . . . . . . . . . . . . . . . . . . . 49
3.2.5 Fugacity and Environmental Models . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.3 Ideal Solutions and Dilute Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.3.1 Vapor–Liquid Equilibrium: Henry’s and Raoult’s Laws . . . . . . 55
3.3.1.1 Henry’s Law. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.3.1.2 Raoult’s Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.3.2 Vapor Pressure of Organic Compounds, Clausius–Clapeyron
Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.3.3 Vapor Pressure over Curved Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.3.4 Liquid–Liquid Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.3.4.1 Octanol–Water Partition Constant . . . . . . . . . . . . . . . . . . . . 66
3.3.4.2 Linear Free Energy Relationships. . . . . . . . . . . . . . . . . . . . . 69
3.4 Nonideal Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.4.1 Activity Coefficient for Nonideal Systems . . . . . . . . . . . . . . . . . . . . . 69
3.4.1.1 Excess Functions and Activity Coefficients . . . . . . . . . . 70
3.4.2 Activity Coefficient and Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4.3 Correlations with Hydrophobicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.4.3.1 Special Structural Features of Water . . . . . . . . . . . . . . . . . . 73
3.4.3.2 Hydrophobic Hydration of Nonpolar Solutes . . . . . . . . 75
3.4.3.3 Hydrophobic Interactions between Solutes . . . . . . . . . . . 78
3.4.3.4 Hydrophilic Interactions for Solutes in Water . . . . . . . . 79
3.4.3.5 Molecular Theories of Solubility:
An Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.4.4 Structure–Activity Relationships and Activity
Coefficients in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.4.5 Theoretical and Semi-Empirical Approaches to Aqueous
Solubility Prediction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.4.5.1 First-Generation Group Contribution Methods. . . . . . . 83
3.4.5.2 Excess Gibbs Free Energy Models. . . . . . . . . . . . . . . . . . . . 86
3.4.5.3 Second-Generation Group Contribution
Methods: The UNIFAC Method . . . . . . . . . . . . . . . . . . . . . . 86
3.4.6 Solubility of Inorganic Compounds in Water . . . . . . . . . . . . . . . . . . 88
3.5 Adsorption on Surfaces and Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

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 Contents vii

3.5.1 Gibbs Equation for Nonionic and Ionic Systems . . . . . . . . . . . . . . 89

3.5.2 Equilibrium Adsorption Isotherms at Interfaces . . . . . . . . . . . . . . . 90
3.5.3 Adsorption at Charged Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116

4 Applications of Equilibrium Thermodynamics. . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

4.1 Air–Water Phase Equilibrium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
4.1.1 Estimation of Henry’s Constant from Group
Contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.1.2 Experimental Determination of Henry’s Law Constants . . . . . . 125
4.1.3 Effects of Environmental Variables on Kaw . . . . . . . . . . . . . . . . . . . . 126
4.2 Air–Water Equilibrium in Atmospheric Chemistry . . . . . . . . . . . . . . . . . . . . . 136
4.2.1 Wet Deposition of Vapor Species. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
4.2.2 Wet Deposition of Aerosol-Bound Fraction . . . . . . . . . . . . . . . . . . . . 138
4.2.3 Dry Deposition of Aerosol-Bound Pollutants . . . . . . . . . . . . . . . . . . 143
4.2.4 Dry Deposition Flux of Gases from the Atmosphere . . . . . . . . . . 144
4.2.5 Thermodynamics of Aqueous Droplets
in the Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
4.2.6 Air/Water Equilibrium in Waste Treatment Systems . . . . . . . . . . 150
4.3 Soil–Water and Sediment–Water Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . 152
4.3.1 Partitioning into Soils and Sediments from Water . . . . . . . . . . . . . 153
4.3.2 Adsorption of Metal Ions on Soils and Sediments . . . . . . . . . . . . . 155
4.3.3 Adsorption of Organic Molecules on Soils
and Sediments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.4 Biota/Water Partition Constant (Bioconcentration Factor) . . . . . . . . . . . . 164
4.5 Air-to-Aerosol Partition Constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
4.6 Air-to-Vegetation Partition Constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
4.7 Adsorption on Activated Carbon for Wastewater Treatment . . . . . . . . . . . 172
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183

5 Concepts from Chemical Reaction Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189

5.1 Progress toward Equilibrium in a Chemical Reaction . . . . . . . . . . . . . . . . . . 190
5.2 Reaction Rate, Order, and Rate Constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
5.3 Kinetic Rate Laws. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
5.3.1 Isolation Method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
5.3.2 Initial Rate Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
5.3.3 Integrated Rate Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
5.3.3.1 Reversible Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
5.3.3.2 Series Reactions and Steady-State Approximation . . . 201
5.3.4 Parallel Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
5.4 Activation Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
5.4.1 Activated Complex Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
5.4.2 Effect of Solvent on Reaction Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
5.4.3 Linear Free Energy Relationships . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215

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 viii Contents

5.5 Reaction Mechanisms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216

5.5.1 Chain Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
5.6 Reactions in Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
5.6.1 Effects of Ionic Strength on Rate Constants . . . . . . . . . . . . . . . . . . . 219
5.7 Environmental Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
5.7.1 Mechanisms and Rate Expressions for Catalyzed
Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
5.7.2 Homogeneous Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
5.7.3 Heterogeneous Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
5.7.4 General Mechanisms of Surface Catalysis . . . . . . . . . . . . . . . . . . . . . 228
5.7.5 Autocatalysis in Environmental Reactions . . . . . . . . . . . . . . . . . . . . . 234
5.8 Redox Reactions in Environmental Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
5.8.1 Rates of Redox Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
5.9 Environmental Photochemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
5.10 Enzyme Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
5.10.1 Michaelis–Menten Kinetics and Monod Kinetics. . . . . . . . . . . . . . 247
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264

6 Applications of Chemical Kinetics in Environmental Systems . . . . . . . . . . 267

6.1 Types of Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
6.1.1 Ideal Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
6.1.1.1 Batch Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
6.1.1.2 Continuous-Flow Stirred Tank Reactor . . . . . . . . . . . . . . . 269
6.1.1.3 Plug-Flow Reactor (PFR) or Tubular Reactor . . . . . . . . 270
6.1.1.4 Design Equations for CSTR and PFR . . . . . . . . . . . . . . . . 271
6.1.1.5 Relationship between Steady State
and Equilibrium for a CSTR . . . . . . . . . . . . . . . . . . . . . . . . . . 276
6.1.2 Nonideal Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
6.1.2.1 Dispersion Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
6.1.2.2 Tanks-in-Series Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
6.1.3 Dispersion and Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
6.1.4 Reaction in a Heterogeneous Medium. . . . . . . . . . . . . . . . . . . . . . . . . . 281
6.1.4.1 Kinetics and Transport at
Fluid–Fluid Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
6.1.5 Diffusion and Reaction in a Porous Medium. . . . . . . . . . . . . . . . . . . 286
6.2 The Water Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
6.2.1 Fate and Transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
6.2.1.1 Chemicals in Lakes and Oceans. . . . . . . . . . . . . . . . . . . . . . . 290
6.2.1.2 Chemicals in Surface Waters . . . . . . . . . . . . . . . . . . . . . . . . . . 293
6.2.1.3 Biochemical Oxygen Demand in
Natural Streams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
6.2.2 Water Pollution Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
6.2.2.1 Air Stripping in Aeration Basins . . . . . . . . . . . . . . . . . . . . . . 299
6.2.2.2 Oxidation Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303

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 Contents ix

6.2.2.3 Photochemical Reactions and Wastewater

Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
6.2.2.4 Photochemical Reactions in Natural Waters . . . . . . . . . . 311
6.3 The Air Environment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
6.3.1 F&T Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
6.3.1.1 Box Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
6.3.1.2 Dispersion Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
6.3.2 Air Pollution Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
6.3.2.1 Adsorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
6.3.2.2 Thermal Destruction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
6.3.3 Atmospheric Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
6.3.3.1 Reactions in Aqueous Droplets . . . . . . . . . . . . . . . . . . . . . . . 330
6.3.3.2 Global Warming and Greenhouse Effect . . . . . . . . . . . . . 337
6.3.3.3 Ozone in the Stratosphere and Troposphere . . . . . . . . . . 347
6.4 Soil and Sediment Environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
6.4.1 F&T Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
6.4.1.1 Transport in Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
6.4.1.2 Sediment–Water Exchange of Chemicals . . . . . . . . . . . . 364
6.4.1.3 Soil–Air Exchange of Chemicals . . . . . . . . . . . . . . . . . . . . . 366
6.4.2 Soil and Groundwater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
6.4.2.1 P&T for NAPL Removal from Groundwater . . . . . . . . . 370
6.4.2.2 In Situ Soil Vapor Stripping in the Vadose Zone . . . . . 373
6.4.2.3 Incineration for ex Situ Treatment of Soils
and Solid Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375
6.5 Applications of Chemical Kinetics in Environmental
Bioengineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
6.5.1 Enzyme Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
6.5.1.1 Batch Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
6.5.1.2 Plug-Flow Enzyme Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
6.5.1.3 Continuous Stirred Tank Enzyme Reactor . . . . . . . . . . . . 383
6.5.1.4 Immobilized Enzyme or Cell Reactor . . . . . . . . . . . . . . . . 387
6.5.1.5 In Situ Subsoil Bioremediation. . . . . . . . . . . . . . . . . . . . . . . . 391
6.5.2 Kinetics of Bioaccumulation of Chemicals in the Aquatic
Food Chain. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
6.6 Applications in Green Engineering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
6.6.1 Environmental Impact Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
6.6.2 Life Cycle Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420

Appendix 1 Properties of Selected Chemicals of Environmental

Significance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
Appendix 2 Standard Free Energy, Enthalpy, and Entropy of
Formation for Compounds of Environmental
Significance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431

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 x Contents

Appendix 3 Selected Fragment (bj ) and Structural Factors (Bk ) for

Octanol–Water Partition Constant Estimation. . . . . . . . . . . . . . . . 433
Appendix 4 Concentration Units for Compartments in
Environmental Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
Appendix 5 Dissociation Constants for Environmentally Significant
Acids and Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
Appendix 6 Bond Contributions to Log Kaw for the Meylan and
Howard Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
Appendix 7 Regression Analysis (the Linear Least-Squares
Methodology). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
Appendix 8 Error Function and Complementary Error Function
Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Appendix 9 Cancer Slope Factor and Inhalation Unit Risk for
Selected Carcinogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
Appendix 10 U.S. National Ambient Air Quality Standards . . . . . . . . . . . . . . . 449

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451

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 Preface

Energy and environmental concerns are the most important issues for the current
generation. These problems are related to the increased demand for available resources
but human beings have become adept at meeting these challenges. Unfortunately, our
attempts to resolve our problems also contribute to the degradation of the environment.
The consequences of environmental pollution can be disastrous, with many examples
that demonstrate the severity of the problem. The present-day debate about global
warming, climate change, water quality, air quality, and solid waste disposal are
examples.
Our prescription for alleviating environmental problems requires that we train stu-
dents in the science and engineering of environmental issues. A well-trained cadre of
professionals is required to make sure that sound science is involved in the formula-
tion of public policy. To this end, the present-day environmental professional needs
broad interdisciplinary training across the disciplines of physics, chemistry, biology,
and engineering.
Environmental engineering is interdisciplinary. It is a challenge to develop courses
that will provide students with a thorough, broad-based curriculum that includes
every aspect of the environmental engineering profession. Traditionally, environmen-
tal engineering has been a subdiscipline of civil engineering with primary emphasis
on municipal wastewater treatment, sewage treatment, and landfill management prac-
tices. During the second half of the twentieth century more emphasis was placed on
end-of-pipe treatment in manufacturing operations to control release of water, air,
and solid wastes. With the realization that environmental problems are not confined
to end-of-pipe treatment, the attention turned toward pollutant fate and transport in
the general environment, waste minimization, pollution prevention, and green engi-
neering. Thus stand-alone programs in environmental engineering began to appear in
many universities.
Environmental engineers perform a variety of functions, the most critical of which
are process design for waste treatment or pollution prevention, fate and transport
modeling, green engineering, and risk assessment. Physical chemistry is an essential
element of environmental engineering. In particular, chemical thermodynamics and
chemical kinetics, the two main pillars of physical chemistry, are crucial to environ-
mental engineering. Unfortunately, these topics are not covered in the environmental
engineering curricula in most universities. Chemical engineers take separate courses in
thermodynamics and kinetics. They also take several prerequisites in chemistry, such
as physical chemistry, organic chemistry, inorganic chemistry, and analytical chem-
istry. Most environmental engineering programs do not require such a broad spectrum
of chemistry courses, but rely on an introductory chemistry course for environmen-
tal engineers. However, such a course lacks the proper depth in the two important
aspects of physical chemistry. I believe that an additional course should be taught that

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 xii Preface

introduces these subjects and lays the foundation for more advanced courses in envi-
ronmental process design, environmental transport modeling, green engineering, and
risk assessment. To accomplish this objective I wrote the first edition of this textbook
in 1995. It is based on a course entitled “Chemical Thermodynamics and Kinetics
for Environmental Processes” that I have been offering to environmental engineering
majors and as a single semester required course for the Accreditation Board for Engi-
neering and Technology (ABET)–accredited BS degree program in environmental
engineering. It is also taught in the chemical engineering department at Louisiana
State University (LSU). Students taking this course also take a fundamental ther-
modynamics course in the mechanical engineering department at LSU, which deals
primarily with the laws of thermodynamics, concepts of heat engines, and mechan-
ical applications of thermodynamics. They also take an introductory environmental
engineering course preceding this.
This is an undergraduate textbook, but portions of it are also suitable for an
introductory graduate-level course. A basic understanding of physics, chemistry, and
mathematics (especially differential calculus) is assumed. In writing this third edition,
I have considered the comments of several instructors who have used the past editions
of the book. In response to their requests, I have eliminated redundant material and
refocused the chapters. Sections such as green engineering, biological processes, life
cycle analysis, etc., have been added. I have provided a larger number of examples
and problems in this edition. The examples are chosen to represent important appli-
cations, but, since the choice is subjective, I do admit that some may be more relevant
than others. The problems are of varying levels of difficulty and they are ranked 1,
2, and 3, with 1 indicating the “least difficult” and 3 indicating the “most difficult”
or “advanced.” These are represented by subscripts beside the problem number. In a
typical single semester course, I follow the general outline as follows:

Lecture Number Sections Covered

2 lectures 1.1–1.6
3 lectures 2.1–2.5, 2.6.1
9 lectures 3.2.1, 3.2.2, 3.2.5, 3.3.1, 3.3.2, 3.3.4.1, 3.4.1, 3.4.2, 3.5.1, 3.5.2
9 lectures 4.1.1–4.1.3, 4.2.1–4.2.4, 4.2.6, 4.3.1, 4.3.3, 4.4–4.6
6 lectures 5.2, 5.3.3, 5.4.1, 5.5.1, 5.7.1, 5.9, 5.10.1
14 lectures 6.1.1, 6.2.1.1–6.2.1.3, 6.2.2.2, 6.3.1.1, 6.3.3.2, 6.3.3.3, 6.4.1.2,
6.5.1.1–6.5.1.3, 6.6.2

In writing this book, I have received help and encouragement from a number of
people. Special thanks to Louis Thibodeaux, a friend and colleague of mine at LSU,
with whom I have collaborated for over two decades in environmental engineering
research. I extend special thanks to David J. Wilson for being a great role model as
an educator and researcher, especially for his infectious enthusiasm for teaching. My
present and past graduate students, in particular, Nick Ashley and R. Ravikrishna,
have contributed in many ways by working out problems and pointing out errors in
the previous editions.

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 Preface xiii

This work would not have been possible without the unconditional love and support
from my family (my wife, Nisha, and my two children, Viveca and Vinay).
This book is dedicated to my beloved father, who was always there for me when I
needed him, but did not live to see his son’s achievements, and my dear mother, who
is a source of inspiration to me in my life.

Kalliat T. Valsaraj

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 Author
Kalliat T. Valsaraj is the Charles and Hilda Roddey
distinguished professor and the Ike East professor
in chemical engineering in the Cain Department of
Chemical Engineering at Louisiana State University
in Baton Rouge. He is currently the chair of the depart-
ment of chemical engineering. He received his MSc
in chemistry from the Indian Institute of Technology,
Madras, in 1980, and his PhD in physical chemistry
from Vanderbilt University, Nashville, TN, in 1983.
His research encompasses various areas of environ-
mental, chemical, and materials engineering. He is
the author of 152 peer-reviewed journal articles, 4
books, 25 book chapters, 47 reports and monographs,
and 2 patents. His research has been supported by
federal agencies (the National Science Foundation, the Department of Defense, the
Department of Energy, the Environmental Protection Agency, and the Department of
Interior), state agencies, and industry. He is a Fellow of the American Institute of
Chemical Engineers. He is also a member of the American Chemical Society, the
American Association for the Advancement of Science, the American Society for
Engineering Education, the Association for Environmental Engineering and Science
Professors, Sigma Xi, the Air and Waste Management Association, and the Soci-
ety for Environmental Toxicology and Chemistry. He serves on the editorial review
boards of several journals: Environmental Toxicology and Chemistry, Journal of the
Air and Waste Management Association, Environmental Monitoring and Assessment,
and Scientific Journals International (Chemical and Bioengineering Division).

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 1 Introduction
Pollution is an inevitable consequence of advances in human endeavors to improve
the quality of life on this planet. As civilized societies learned to organize, humans
realized methods to purify water for drinking purposes, dispose of excrement, build
sanitary sewers, and perform municipal wastewater treatment to prevent communica-
ble diseases. They also realized how air pollution can adversely affect human health
and the necessity to control the same. Thus, the history of pollution is as old as the
human species itself.
The twentieth century has been a period of rapid technological advances, which
has helped us to harness the available natural resources. Along with these advance-
ments, we have also created myriad environmental pollution problems. Pollution is
undesirable and expensive, but it is an inevitable consequence of modern life. The
reality is that we cannot eliminate pollution altogether, but we can certainly mitigate
it through recycle, reuse, and reclamation.

1.1 ENERGY, POPULATION, AND POLLUTION

Energy consumption has increased dramatically as the population has exploded.
Increased utilization of natural resources is necessary to sustain the various industries
that drive the economy of industrialized nations. Unfortunately, increased industrial
activity has also produced anthropogenic pollutants. The harnessing of nuclear power
has left us the legacy of radioactive waste. Increased agricultural activity in both
developed and developing nations has been necessitated in order to sustain the bour-
geoning world population. Intensive agricultural uses of pesticides and herbicides
have contributed to the pollution of our environment. Some of the major environmental
problems that one can cite as examples of anthropogenic origin are (a) increased car-
bon dioxide and other greenhouse gases in the atmosphere, (b) depletion of the earth’s
protective ozone layer due to man-made chlorofluorocarbons, (c) acid rain due to
increased sulfur dioxide as a result of fossil fuel utilization, (d) atmospheric haze and
smog, polluted lakes, waterways, rivers, and coastal sediments, (e) contaminated
groundwater, and (f) industrial and municipal wastes.
The environmental stress (impact) due to the needs of the population and the better
standard of living is given by the master equation (Graedel and Allenby, 1996)

GDP EI
EI = P × × , (1.1)
Person GDPunit per capita

where EI is the environmental impact, P is the population, and GDP is the gross
domestic product.
P in the above equation is unarguably increasing with time and that too in geometric
progression. The second term on the right-hand side denotes the general aspiration

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 2 Elements of Environmental Engineering: Thermodynamics and Kinetics

of humans for a better life, and is generally increasing as well. The third term on the
right-hand side denotes the extent to which technological advances can be sustained
without serious environmental consequences. The third term can be made as small
as possible to limit the overall environmental impact and enable the transition to a
sustainable environment. Both societal and economic issues are pivotal in determining
whether we can sustain the quality of life while at the same time mitigating the
environmental consequences of the technologies that we adapt.
The quality of our life is inextricably linked to industrial growth and improvements
in agricultural practices. Chemicals are used in both sectors, to sustain innovations in
the industrial sector and to improve agricultural efforts at maintaining a high rate of
crop production. Thus, the chemical manufacturing industry has been at the forefront
of both productivity and growth. During the twentieth century, the chemical manufac-
turing industry has shown phenomenal growth. Overwhelming arrays of chemicals
have been produced each year. Over the whole period of human history, one estimate
suggests that approximately six million chemical compounds have been created, of
which only 1% are in commercial use today. Many of the compounds are important for
sustaining and improving our health and well-being, since they are starting materials
for various products that we use everyday.

1.2 ENVIRONMENTAL STANDARDS AND CRITERIA

There exist several Congressional statutes in the United States that are instrumental
in setting standards for drinking water, ambient water quality, and ambient air quality.
The Environmental Protection Agency (EPA) takes several steps before a stan-
dard is set for a specific compound in a specific environment. These include factors
such as the following: occurrence in the environment; human exposure and risks of
adverse health effects in the general population and sensitive sub-populations; ana-
lytical methods of detection; technical feasibility; and impacts of regulation of water
systems, the economy, and public health.
Environmental quality standards refer to maximum contaminant concentrations
allowed for compounds in different environmental media. These concentrations are
expected to be protective of human health and useful for ecological risk management.
It has long been recognized that a realistic assessment of the effects of chemicals
on humans and ecosystems is mandatory for setting environmental quality standards.
The implication is that our concerns for the environment should be driven by sound
science. A prudent policy with regard to environmental regulations should con-
sider the weight of evidence in favor of acceptable risk against potential benefits.
In fact, risk assessment should be the paradigm that is the basis for current and future
environmental legislation.

1.3 THE DISCIPLINE OF ENVIRONMENTAL ENGINEERING

Environmental awareness is the first step in understanding pollution problems. On the
one hand, we should better understand the potential impacts, so that we can focus our
resources on the most serious problems. On the other hand, we should also understand

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 Introduction 3

the technologies better, so that we can improve their effectiveness and reduce their
costs. These activities are within the discipline of environmental engineering.
Environmental engineering is the study of the fate, transport, and effects of
chemicals in the natural and engineered environments and includes the formulation
of options for treatment, mitigation, and prevention of pollution in both natural and
engineered systems.
It has only been in the latter half of the twentieth century that environmental engi-
neering grew to a mature field with depth and focus. Environmental engineering is
an interdisciplinary field. It involves the applications of fundamental sciences, that
is, chemistry, physics, mathematics, and biology, to waste treatment, environmental
fate and transport of chemicals, and pollution prevention. The main pillars that
support an environmental engineering curriculum are physics (statics and fluids),
chemistry (organic, inorganic, kinetics, thermodynamics, and material and energy bal-
ances), mathematics (calculus and algebra), and biology (toxicology, microbiology,
and biochemistry)—see Figure 1.1. Statics, fluids, and energy and material balances
are prerequisites for several engineering disciplines (chemical, civil, petroleum, and
biological). For environmental engineering, two main pillars are from chemistry
(chemical thermodynamics and kinetics). Chemical thermodynamics is that branch of
chemistry that deals with the study of the physico-chemical properties of a compound
in the three states of matter (solid, liquid, and gas). It also describes the potential for
a compound to move between the various phases and the final equilibrium distribu-
tion in the different phases. Chemical kinetics, on the other hand, describes the rate
of movement between phases and also the rate at which a compound reacts within
a phase.

Environmental engineering practice

(Process design, chemical fate modeling, risk analysis, economics)

Water treatment, air pollution, hazardous waste

treatment, environmental fate and transport,
hydrology, geosciences, ecology, microbiology

Organic, Toxicology,
kinetics, Statics, microbiology,
thermodynamics Calculus biochemistry
fluids

Chemistry Physics Mathematics Biology

FIGURE 1.1 Pillars of environmental engineering.

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 4 Elements of Environmental Engineering: Thermodynamics and Kinetics

1.4 CHEMICAL THERMODYNAMICS AND KINETICS

IN ENVIRONMENTAL ENGINEERING
The environment may be conceptualized as consisting of various compartments.
Table 1.1 summarizes the total mass and surface areas of various compartments in
the natural environment. The transport of materials between the compartments on
a global scale depends only on forces of global nature. However, on a local scale
the partitioning and transport depend on the composition, pressure, temperature, and
other variables in each compartment.
There are four distinct environmental compartments: hydrosphere, atmosphere,
lithosphere, and biosphere (Figure 1.2). These may be in continuous contact with a
sharp boundary between them (air–water) or may be discontinuous (e.g., soil–water).
In some cases, one phase will be dispersed in another (e.g., air bubbles in water,
fog droplets in air, aerosols and dust particles in air, colloids suspended in water,
oil droplets in water, and soap bubbles in water). Some compartments may have
the same chemical composition throughout, but differ significantly in their spatial
characteristics (e.g., the lower troposphere versus the upper stratosphere, a stratified
deep water body, or a highly stratified atmosphere). The biosphere, which includes
all plant and animal species, is in contact with the three other compartments in the
overall scheme. Reactions and transformations occur in each phase, and the rate of
exchange of mass and energy between the compartments is a function of the extent
to which the respective compartments are in nonequilibrium.

1.4.1 APPLICATIONS OF THERMODYNAMICS AND K INETICS

1.4.1.1 Equilibrium Partitioning
Chemical thermodynamics is central to the application of the equilibrium-partitioning
concept to estimate pollutant levels in environmental compartments. It assumes that
the environmental compartments are in a state where they have reached constant

TABLE 1.1
Composition of Natural Environment
Compartment Value

Air (atmosphere) (mass) 5.1 × 1018 kg

Water (hydrosphere) (mass) 1.7 × 1021 kg
Land (lithosphere) (mass) 1.8 × 1021 kg
Land (area) 1.5 × 1014 m2
Water (area) 3.6 × 1014 m2
Source: Weast, R.C. and Astle, M.J. (Eds). 1981. CRC
Handbook of Chemistry and Physics, 62nd ed.
Boca Raton, FL: CRC Press, Inc.; Stumm, W.
and Morgan, J.J. 1981. Aquatic Chemistry, 2nd
ed. New York, NY: John Wiley & Sons, Inc.

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 Introduction 5

Atmosphere

Biosphere

Hydrosphere
Lithosphere

FIGURE 1.2 Equilibrium between various environmental compartments, reactions within

compartments, and material exchange between the compartments.

chemical composition, temperature, and pressure and have no tendency to change

their state. Equilibrium models only give us the chemical composition within the
individual compartments and not how fast the system reached the given equilibrium
state. Although, admittedly, a time-variant (kinetic) model may have significant
advantages, there is general agreement that equilibrium partitioning is a starting
point in this exercise. It is a fact that true equilibrium does not exist in the envi-
ronment. In fact, much of what we observe in the environment occurs as a result
of the lack of equilibrium between compartments. Every system in the environment
strives toward equilibrium as its ultimate state. Hence, the study of equilibrium is a
first approximation toward the final state of any environmental system.

1.4.1.2 Fate and Transport Modeling

The environment is a continuum in that as pollutants interact with various phases,
they undergo both physical and chemical changes and are finally incorporated into
the environment. Fate models, based on the mass balance principle, are necessary
to simulate the transport between and transformations within various environmental
media. This is called the multimedia approach. The mass balance principle can be
applied through the use of a multimedia fate and transport model to obtain the rates
of emissions and the relative concentrations in each compartment. A number of such
models already exist, some of which are described in Table 1.2.
Consider a chemical that is released from a source to one of the environmental
compartments (air, water, or soil). To assess the effect of the pollutant to the ecosystem,
we need to first identify the various pathways of exposure. Figure 1.3 illustrates
the three primary pathways that are responsible for exposure from an accidental
release. Direct exposure routes are through inhalation from air and drinking water

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 6 Elements of Environmental Engineering: Thermodynamics and Kinetics

TABLE 1.2
Descriptions of a Few Multimedia Fate and Transport Models that are
Currently in Use
Model Acronym Description

CalTOX A fugacity-based model to assist the California Environmental Protection

Agency to estimate chemical fate and human exposure in the vicinity of
hazardous waste sites
ChemCAN A steady-state fugacity-based model developed for Health Canada to
predict a chemical’s fate in any of the 24 regions of Canada
HAZCHEM A fugacity-based model developed as a regional scale model for the
European Union Member States
SimpleBOX Developed by RIVM, the Netherlands, it uses the classical concentration
concept to compute mass balances
Source: The multi-media fate model: A vital tool for predicting the fate of chemicals, SETAC Press,
1995.

from the groundwater aquifer. Indirect exposure results, for example, from ingestion
of contaminated fish from a lake that has received a pollutant discharge via the soil
pathway. Coupling the toxicology with a multimedia fate and transport model thus
provides a powerful tool to estimate the risk potential for both humans and the biota.
Risk assessment is typically divided into the assessment of cancer and noncancer
health effects. Animal toxicology studies or human epidemiological data are used to
establish a unit risk level for cancer. A dose–response model then relates the response
to the dosage to which the subjects are exposed. Most cancer dose–response models
conservatively assume a no-threshold model, so that the risk is extrapolated from high
to low dosages assuming that there is some response at any dosage above zero.

Air pathway

Source

Lake
Receptors
Soil pathway

Groundwater pathway

FIGURE 1.3 Environmental risks and exposure pathways.

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 Introduction 7

The risk alluded to is the incremental lifetime cancer risk (ILCR), and is given by

ILCR = SF × CDI, (1.2)

where SF is the slope factor for the chemical and CDI is the chronic daily intake
of the chemical by the defined exposure route. A listing of the SFs can be found
in Appendix 9. The CDI requires the use of a multimedia fate model to obtain the
concentration value that goes into its determination. Thus, knowledge of the SF and
the CDI allows the determination of the lifetime cancer risk.
If the excess cancer risk from the inhalation route is to be estimated, we can also
write the following equation:

Riskair = IUR × Cair , (1.3)

where IUR is the inhalation unit risk (in per μg/m3 ) (see Appendix 9) and Cair is the
average exposure concentration in air. For example, for formaldehyde the unit risk
is 1.3 × 10−5 μg−1 /m3 , and if someone is exposed to a concentration of 0.77 μg/m3
over a lifetime (70 years), the lifetime risk is 1 in 105 . For noncancer risk assessment
in air, we use a hazard quotient (HQ):

Cair
HQ = , (1.4)
RfC

where RfC is the reference concentration (see Appendix 9 for definitions). If HQ is

<1, the risk is acceptable.
Within the regulatory framework, it is now mandatory to assess the potential harm-
ful effects on humans and the environment from the use of new chemicals and from
the continued use of existing ones. Examples are the Toxic Substances Control Act
(TSCA) in the United States, the Canadian Environmental Protection Act (CEPA) in
Canada, and the 7th amendment in the European Union (EU). Once risk is estab-
lished, the next step will be to isolate the pollutant from the ecosystem to minimize
the risk.
In the above context, the following specific questions will need to be addressed:

(i) What is the final equilibrium state of the pollutant in the environment, that is,
which of the environmental compartments is the most favorable, how much
resides in each compartment at equilibrium, and what chemical properties
are important in determining the distribution?
(ii) How fast does the pollutant move from one compartment to another, what
is the residence time in each compartment, and how fast does it react within
each compartment or at the boundary between compartments?

The answer to the first question employs the tools of chemical thermodynamics
and the second question requires the applications of concepts from chemical kinetics.
Multimedia fate and transport (F&T) models are recognized as a necessary com-
ponent for risk assessment, chemical ranking, management of hazardous waste sites,

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 8 Elements of Environmental Engineering: Thermodynamics and Kinetics

optimization of testing and monitoring strategies, determination of global disper-

sion, and recovery times. To construct F&T models, one needs to obtain a range of
physico-chemical parameters: thermodynamic, kinetic, and toxicological.

1.4.1.3 Design of Separation Processes

Environmental engineers design separation processes for the isolation of contaminants
from waste streams before they are discharged to the environment. Both physical and
chemical separation processes are used in environmental engineering. For example,
particulate separation from air and water involve physical separation techniques that
use mechanisms such as aggregation, coagulation, impaction, centrifugal force, and
electromotive force, to name a few. The removal of dissolved gases and vapors from
air and water involve, on the other hand, chemical separation methods. Whereas
mixing of chemicals to form a mixture is a spontaneous process, and, as we will see
in Chapter 2, a thermodynamically favorable process, the reverse, namely, separation
into the component species, requires the expenditure of work. The overall objective
of an environmental separation process is not only to isolate the pollutant, but also to
recycle and reuse where possible the materials separated and separation agents that
were used during the operation.
Invariably, environmental separation processes involve contact between two or
more phases and the exchange of material and energy between them. As an example,
consider the removal of organic contaminants from water by contacting with a solid
phase such as powdered activated carbon. The process has two distinct stages. In

(a) (b)
PF PF
CF CF
PR PR

(c)
PF

CF

(d) (e)
PF PF
CF CF

PR PR

FIGURE 1.4 General separation techniques. CF, contaminated feed, PF, pollutant-free
stream, PR, pollutant-rich stream. (a) Separation by phase creation; (b) separation by phase
addition; (c) separation by barrier; (d) separation by solid agent; and (e) separation by field
gradient. (Modified from Seader, E.D. and Henley, E.J. 1986. Separation Process Principles.
New York: John Wiley & Sons, Inc.)

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 Introduction 9

stage I, those contaminants in water with a greater affinity for the carbon are concen-
trated on the carbon by a process called adsorption. The removal depends not only
on the rate of transport of compounds from water to carbon (the realm of kinetics),
but also on the ultimate capacity of the carbon bed (the realm of thermodynamics). In
stage II, we have to regenerate the medium within the reactor so that it can be reused.
Moreover, in stage II, we need information on how fast the pollutant can be recov-
ered from the activated carbon, and also the fate and transformation of the adsorbed
pollutant (that is, the kinetic aspects).

TABLE 1.3
Applications of Chemical Thermodynamics and Kinetics in Environmental
Processes
Typical Equilibrium Thermodynamic
Process Representation Property Kinetic Property

Solubility in water A (pure)  A (water) Saturation solubility, Ci∗ Dissolution rate

Absorption in A (air)  A (water) Henry’s law constant, KH Absorption rate
water
Precipitation from A (water)  A (crystal) Solubility product, Ksp Precipitation rate
water
Volatilization from A (water)  A (air) Henry’s law constant, KH Volatilization rate
water
Evaporation from A (pure)  A (vapor) Vapor pressure, Pi∗ Evaporation rate
pure liquid

Acid/base A  A− + H+ Acidity or basicity Acidification rate

dissociation constant, Ka or Kb
Ion exchange A+ + BX  BA + X+ Ion-exchange partition Ion-exchange rate
constant, Kexc
Oxidation/reduction Aox + Bred  Ared + Box Equilibrium constant, Ki Redox reaction rate

Adsorption from A (water)  A (surface) Soil/water partition Adsorption rate

water constant, KSW
Adsorption from A (air)  A (surface) Particle/air partition Adsorption rate
air constant, KAP

Uptake by biota A (water)  A (biota) Bio-concentration factor, Rate of uptake

KBW
Uptake by plants A (air)  A (plant) Plant/air partition Rate of uptake
constant, KPA

Chemical reaction A + B  Products Equilibrium constant, Keq Rate of chemical

reaction
Photochemical A + (hν)  Products Equilibrium constant, Keq Rate of photolysis
reaction
Biodegradation A + (enzymes)  Products Equilibrium constant, Keq Michaelis–Menten
reaction and Monod
kinetics constants

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 10 Elements of Environmental Engineering: Thermodynamics and Kinetics

Separation techniques can be classified broadly into five categories as shown in

Figure 1.4 (Seader and Henley, 1998). In every one of these processes, the rate of
separation is dependent on selectively increasing the rate of diffusion of the contami-
nant species relative to the transfer of all other species by advection (bulk movement)
within the contaminated feed. Equilibrium limits the ultimate compositions of the
effluent streams (pollutant-rich and pollutant-free). The rate of separation within the
reactor is determined by the mass transfer limitations (“driving force”), whereas the
extent of separation is determined by equilibrium thermodynamic factors. Both ther-
modynamic and kinetic (transport) properties are thus instrumental in environmental
separations.
The above discussions of applications in environmental engineering show that
for both natural and engineered systems, two types of issues are paramount—an
equilibrium study to describe the final distribution of pollutants within different com-
partments and a kinetic study to describe the rate of transformations of chemicals
within each compartment and the rate of movement of chemicals between compart-
ments. A list of processes common to both natural and engineered systems is given
in Table 1.3. It summarizes the associated thermodynamic and kinetic properties that
are necessary for understanding each process.
In summary, we can look at chemical thermodynamics in environmental engineer-
ing as the essential element by which we connect observations on simplified systems
to the segment of the environment (natural or engineered) that we are interested
in. To put it in context, Figure 1.5 appropriately places the role of thermodynam-
ics in our endeavor to understand and design processes in natural and engineered
systems.

Thermodynamic models
Model (chemical properties)
parameters Mathematical models
(dynamics, mass balances)

Reproduction Design
Evaluation Optimize
Regression Predict
Feedback
Adjust Control

Observations System
(experimental (chemical plant,
data on environmental
simplified systems) compartment)

FIGURE 1.5 Role of chemical thermodynamics in understanding natural and engineered

systems. (Modified from http://www.codata.org/codata02/04physci/rarey.pdf.)

“78194_C001.tex” — page 10[#10] 10/4/2009 19:22

 Introduction 11

1.5 UNITS AND DIMENSIONS

The SI (International System of Units) is the standard set of units for engineering and
science. The International Union of Pure and Applied Chemistry (IUPAC) produced
a document (Cohen et al., 2007) entitled Quantities, Units and Symbols in Physi-
cal Chemistry, which recommended a uniform set of units for all measurements in
physical chemistry. This document should be consulted for a more elaborate discus-
sion of the various units. However, in a number of cases, environmental engineers
still prefer to use the CGS (centimeter–gram–second) system of units. Table 1.4 gives
the seven base quantities and their symbols that SI units are based on. All other
physical quantities are called derived quantities and can be algebraically derived
from the seven base quantities by multiplication or division.

TABLE 1.4
Base Quantities, Units, and Symbols in SI Units
Physical Quantity Name Symbol

Length Meter m
Mass Kilogram kg
Time Second s
Electric current Ampere A
Thermodynamic temperature Kelvin K
Amount of substance Mole mol
Luminous intensity Candela cd
Source: Mills, I., Cvitas, T., Homann, K., Kallay, N., and
Kuchitsu, K. (Eds). 1988. Quantities, Units and Symbols
in Physical Chemistry, IUPAC Physical Chemistry Divi-
sion. Oxford: Blackwell Scientific Publications.

TABLE 1.5
Relations between SI and CGS Units for Some Derived Quantities
Derived Quantity Unit CGS Symbol Equivalent SI Unit

Force Dyne dyn 105 newtons (N)

Pressure Bar bar 105 pascals (Pa)
Atmosphere atm 101,325 Pa
Torr torr 133.32 Pa
Millimeter of mercury mm Hg 133.32 Pa
Pounds per square inch psi 6.89 × 103 Pa
Energy, work, heat Erg erg 10−7 joules (J)
Calories cal 4.184 J
Liter atmospheres L atm 101.325 J
Concentration Molar (mol/L) M 103 mol/m3
1 mol/dm3
Viscosity Centipoise cP 10−3 kg/m s

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 12 Elements of Environmental Engineering: Thermodynamics and Kinetics

The physical quantity amount of substance is of paramount importance to environ-

mental engineers. The SI unit for this quantity is the mole defined as the amount of
substance of a system that contains as many elementary entities as there are atoms in
0.012 kg of carbon-12. IUPAC recommends that we should refrain from calling it the
“number of moles.” Much of the published literature is based on the more familiar
CGS units. The relations between the common CGS and SI units for some important
derived quantities of interest in environmental engineering are given in Table 1.5.
A description of the most common units in environmental engineering is given
in Appendix 4 and the reader should familiarize himself or herself with these before
proceeding further.

1.6 STRUCTURE OF THE BOOK

The book is divided into six chapters. It can be broadly divided into two sections. The
first section (Chapters 2–4) is on chemical thermodynamics whereas the second sec-
tion (Chapters 5 and 6) is on chemical reaction kinetics. Chapter 2 is an introduction to
the thermodynamics of homogeneous phases composed of single or multiple species.
It also introduces the important concepts of free energy and chemical potential that
are of paramount importance in dealing with equilibrium systems in environmen-
tal engineering. A concise description of surface thermodynamics is also included in
Chapter 2. Chapter 3 is an extension of the thermodynamics of homogeneous systems
to heterogeneous and multicomponent systems. The important concepts of activity
and fugacity and nonideal solutions and gases are dealt within this chapter. Chapter 4
deals with the applications of the concepts developed in Chapters 2 and 3 on air–water,
soil–water, and air–soil equilibria to illustrate the concept of equilibrium partitioning
between compartments in environmental engineering. Applications of equilibrium
thermodynamics in waste treatment operations are also described. Chapter 5 gives a
short summary of the essential aspects of chemical reaction kinetics. Concepts such
as reaction rates and activation energies are introduced and discussed. The concepts
developed in Chapter 5 are used to illustrate the applications of chemical kinetics
in environmental waste treatment processes and biological systems in Chapter 6.
Applications of reactor models and transport theory are exemplified in Chapter 6.

REFERENCES
Cohen, E.R. et al. 2007. Quantities, Units and Symbols in Physical Chemistry, 3rd ed.
Cambridge, UK: The Royal Society of Chemistry (for IUPAC).
Graedel, T.E. and Allenby, B.R. 1996. Design for the Environment. Upple Saddle River, New
Jersey: Prentice Hall.
Mills, I., Cvitas, T., Homann, K., Kallay, N., and Kuchitsu, K. (Eds). 1988. Quantities, Units and
Symbols in Physical Chemistry, IUPAC Physical Chemistry Division. Oxford: Blackwell
Scientific Publications.
Seader, J.D. and Henley, E.J. 1998. Separation Process Principles. New York, NY: John Wiley
& Sons, Inc.
Stumm, W. and Morgan, J.J. 1981. Aquatic Chemistry, 2nd ed. NewYork, NY: John Wiley &
Sons, Inc.
Weast, R.C. and Astle, M.J. (Eds). 1981. CRC Handbook of Chemistry and Physics, 62nd ed.
Boca Raton, FL: CRC Press, Inc.

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 2 Basic Chemical
Thermodynamics
The discussion in Chapter 1 indicated that knowledge of equilibrium between different
compartments is important in environmental engineering. The fundamental principles
of thermodynamics are germane to the understanding of equilibrium in environmental
systems. There are four laws of thermodynamics that epitomize the entire subject of
thermodynamics.
In this chapter the discussion of thermodynamics is limited to its basic laws, since
a number of excellent references are available elsewhere (e.g., Lewis and Randall,
1961; Denbigh, 1981). Phase equilibrium, as it relates to bulk phases (single com-
ponent, homogeneous), will be discussed in this chapter, followed by an expanded
discussion of multicomponent and heterogeneous systems in Chapter 3. Since most
of the applications of thermodynamics in environmental engineering are confined to
a narrow range of temperatures (∼ −40◦ C to +40◦ C) and atmospheric pressure, we
need not focus on extreme temperatures or pressures. A brief review of the concept
of equilibrium and the fundamental laws of thermodynamics is presented, followed
by the introduction of the concepts of free energy, chemical potential, and the Gibbs–
Duhem relationship. The effect of surface area on the total thermodynamic property
of a system is negligible except when the subdivision in phases is exceedingly small,
which occurs in many environmental systems. Therefore, an introductory discussion
of surface thermodynamics is also included.

2.1 EQUILIBRIUM
The natural environment is a complex system. However, an environmental system can
be assessed by assuming that equilibrium exists between the different environmental
phases and that the properties are time-invariant. Equilibrium models are easy to
apply since they need only a few inputs. They are sometimes grossly inappropriate
and have to be replaced with kinetic models, which assume time-variant properties
for the phases. Kinetic models are complex and require a number of input parameters
that are poorly understood and sometimes unavailable for environmental situations.
Before beginning a discussion of the laws of thermodynamics, we need to define
some terms. To quote Lewis and Randall (1961), “Whatever part of the objective
world is the subject of thermodynamic discourse is customarily called a system.” The
system may be separated from the surroundings by a physical boundary like the walls
of a container, or maybe concrete. A system may be closed if there is no mass transfer
either to or from the surroundings, or open if either matter or energy can transfer
to and from the surroundings. For example, the Earth is an open system in contact
with the atmosphere around it with which it exchanges both matter and energy. A
system is said to be isolated if it cannot exchange either mass or energy with its

13

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