Table Of ContentChemistry for Environmental Engineering and Science
!
The McGraw-Hill Series m Civil and Environmental Engineering
Engineering Economy Niison: Design of Concrete Structures Wmer Resources and Environmental
Blank andTarquin: Engineering Economy Nowak and CoHins; Reliability of Structures Engineering
Humphreys: Jeten's Cost and Optimization Taly: Design of Modern Highway Bridges George Tchobanogloas, University of
Taly: Reinforced Masonry Structure Design California. Davis, Consulting Editor
Engineering
Riggs, Bedworth, Randhawa: Engineering
Bailey and Ollis: Biochemical Engineering
Economics Survevme
Steinet: Engineering Economic Principles Anderson and Mikhail: Surveying: Theory and Fundamentals
Practice Benjamin: Water Chemistry
Wolf and DeWitt: Elements ofPhotogrammetry Bishop: Pollution Prevention: Fundamentals
Bannerjee: The Boundary Element Methods In (with Applications in CIS) and Practice
Canter: Environmental Impact Assessment
Engineering
Barnes: Statistical Analysis for Engineers and Statics. Dynamics, and Mechanics of Materlab Chanlett: Environmental Protection
Scientists: A Computer-Based Approach (IBM) Barber: Intermediate Mechanics of Materials Chapra: Surface Water Quality Modeling
Ledbed: Formulas/or Structural Dynamics Beer and Johnston: Vector Mechanics for Chow, Maidment, Mays: Applied Hydrology
Milton and Arnold: Introduction to Probability Engineers: Statics Crites and Tchobanoglous: Small anil
Decentralized Wastewater Management
and Statistics: Principles and Applications for Beer and lohnston: Vector Mechanics for
Engineering and the Computing Sciences Engineers: Dynamics Systems
Reddy: Introduction to ¡he Finite Element Beer and Johnston: Vector Mechanics for Davis and Cornwell: Introduction to
Method Engineers: Statics and Dynamics Environmental Engineering
Rosenkrantz: Introduction to Probability and Beer and Johnston: Mechanics of Materials deNevers: Air Pollution Control Engineering
Statistics for Scientists and Engineers Young: Roark's Formulas for Stress and Strain Eckenfelder: Industrial Water Pollution
Zienkiewicz and Taylor: The Finite Element Control
Method: Basic Concepts and Linear Cwftruction Eneinfirn?, ""d Project Bweis, Ergas, Chang, Schroeder:
Applications Management Bloremedlatlon Principles
Raymond E. Levitt, Stanford University, Freeman: Hazardous Waste Minimization
Consulting Editor LaGrega, Buckingham, Evans: Hazardous
Çengel and Tamer: Fundamentals of Thermal- Waste Management
Fluid Sciences Barrie and Paulson: Professional Construction Linsley, Franzini, Freyberg, Tchobanoglous:
Finncmore and Fraiiïini: Fluid Mechanics with Management Water Resources Engineering
Engineering Applications Bockrath: Contracts and the Legal McOhee: Water Supply and Sewage
Streeter, Bedford, Wylie: Fluid Mechanics Environment for Engineers and Architects Metcalf & Eddy, Inc.: Wastewater
White: Fluid Mechanics Callahan, Quackcnbush, Rowlings: Engineering: Collection and Pumping of
Construction Project Scheduling Wastewater
Ç-eotechnical Enemeerini Gtiíñs and Fan: Construction Planning for Metcalf & Eddy, Inc.: Wastewater
Atkinson: Introduction to the Mechanics of Engineers Engineering: Treatment and Reuse
Soils and Foundations Hinze: Construction Contracts Peavy, Rowe, Tchobanoglous: Environmental
Bowies: Foundation Analysis and Design Oberlender: Project Management for Engineering
Bowles: Engineering Properties of Soils and Engineering and Construction Rittmann and McCarty: Environmental
Their Measurement Peurtfoy, Ledbetter, Schexnayder: Construction Biotechnology: Principles and Applications
Planning, Equipment, and Methods Rubin: Introduction to Engineering and the
Peurifoy and Oberlender: Estimating Environment
Chapra and Canal«: Numerical Methods for Construction Costs Sawyer, McCarty, Parkin: Chemistry for
Environmental Engineering and Science
Engineers
Heath: Scientific Computing: An Introductory Trgnsprtrtaiinn Engineering Sturm: Open Channel Hydraulics
Survey Edward K. Morlok, University of Tchobanoglous, Theisen, Vigil: Integrated
Pennsylvania, Consulting Editor Solid Waste Management: Engineering
Principles and Management Issues
Structures
Gaylord and Stailrneyer: Design of Steel Banks: Introduction to Transportation Wentz: Safety, Health, and Environmental
Structures Engineering Protection
Laursen: Structurât Analysis Horonjeff and McKeWey: Planning and Design
Leet and Bemai: Reinforced Concrete Design of Airports
Leet and tiang: Fundamentals of Structural Kanafani: Transportation Demand Analysis Budynas: Advanced Strength and Applied
Analysis Meyer and Miller: Urban Transportation Stress Analysis
Dally and Riiey: Experimental Stress Analysis
Leonard: Tension Structures: Behavior and Planning
Analysis Wells: Airport Planning and Management Ugural: Stresses in Plates and Shells
Lin and Cai: Probabilistic Structural
Dynamics: Advanced Theory and Applications
m
WÊÊm %m
m
Chemistry for Environmental
Fifth Edition
Clair N. Sawyer
Late Professor of Sanitary Chemistry
Massachusetts Institute of Technology
Perry L. McCarty
Silas H. Palmer Professor Emeritus of Civil and Environmental Engineering
Stanford University
Gene F. Parkin
Professor of Civil and Environmental Engineering
University of Iowa
Mc
Gram»
Hill
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McGraw-Hill Higher Education gg
A Division of The McOraw-HÜl Companies
CHEMISTRY FOR ENVIRONMENTAL ENGINEERING AND SCIENCE
FIFTH EDITION
Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the
Americas, New York, NY 10020. Copyright © 2003 by The McGraw-Hill Companies, Inc. All rights reserved.
Previously published under the titles of Chemistry for Environmental Engineering. Copyright © 1994,1978 by
The McGraw-Hill Companies, Inc. Ail rights reserved. Chemistry for Sanitary Engineers. Copyright © 1967,
1960 by McGraw-Hill, Inc. Ail rights reserved. No part of this publication may be reproduced or distributed
in any form or by any means, or stored in a database or retrieval system, without the prior written consent of
The McGraw-Hill Companies, Inc., including, but not limited to, in any network or other electronic storage or
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Some ancillaries, including electronic and print components, may not be available to customers outside
the United States.
This book is printed on acid-free paper.
International 1 2345 67 8 90QPF/QPF09 87 65432
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ISBN 0-07-248066-1
ISBN 0-07-119888-1 (ISE)
Publisher: Elizabeth A. Jones Designer: K. Wayne Harms
Sponsoring editor: Suzanne Jeans Cover designer: Scan Communications Group, Inc.
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Library of Congress Catatogmg-in-Publicatkm Data
Sawyer, Clair N.
Chemistry for environmental engineering and science / Clair N. Sawyer, Perry L. McCarty, Gene F. Parkin.
—5th ed.
p. cm.—-(The McGraw-Hill series in civil and environmental engineering)
Includes index.
ISBN 0-07-248066-1 (acid-free paper)—ISBN 0-07-119888-1 (ISE)
i. Environmental chemistry. 2. Environmental chemistry—Laboratory manuals.
3. Sanitary engineering. 4. Sanitary engineering—Laboratory manuals. I. McCarty, Perry L. II. Parkin, Gene P.
III. Titte. IV. Series.
TD193 .S28 2003
628'.01'54—dc21
2002025494
CIP
INTERNATIONAL EDITION ISBN 0-07-119888-1
Copyright © 2003. Exclusive rights by The McGraw-Hill Companies, Inc., for manufacture and
export. This book cannot be re-exported from the country to which it is sold by McGraw-Hill.
The International Edition is not available in North America.
www.mhhe.com
TO OUR FAMILIES Martha, Annette, Kyle, and Eric who sacrificed much for this
current effort.
CONTENTS
2.7 Oxidation-Reduction Equations 18
Preface xiü
2.8 Metals and Nonmetals 24
2.9 The Gas Laws 24
1
2.10 Solutions 27
PART
2.11 Equilibrium and Le Chatelier' s
Fundamentals of Chemistry
Principle 29
for Environmental Engineering
2.12 Activity and Activity Coefficients 30
and Science 1
2.13 Variations of the Equilibrium
Relationship 32
CHAPTER 1 2.14 Ways of Shifting Chemical
Introduction 3 Equilibria 42
2.15 Amphoteric Hydroxides 45
1.1 Water 4
Problems 46
1.2 Wastewater and Water Pollution
Control 5 References 51
1.3 industrial and Hazardous Wastes 6
1.4 Air Pollution and Global Environmental CHAPTER 3
Change 7 Basic Concepts from Physical
1.5 Summary 9 Chemistry 52
3.1 Introduction 52
3.2 Thermodynamics 52
CHAPTER 2
3.3 Vapor Pressure of Liquids 63
Basic Concepts from General
3.4 Surface Tension 64
Chemistry 10
3.5 Binary Mixtures 66
2.1 Elements, Symbols, Atomic Weights, Gram
3.6 Solutions of Solids in Liquids 69
Atomic Weights 10
3.7 Membrane Processes: Osmosis
2.2 Compounds, Formulas, Formula Weights,
and Dialysis 71
Gram Molecular Weights, Mole, Equivalent
3.8 Principles of Solvent Extraction 74
Weights, Equivalent 11
3.9 Electrochemistry 76
2.3 Avogadro's Number 13
3.10 Chemical Kinetics 86
2.4 Valency, Oxidation State, and
3.11 Catalysis 96
Bonding 13
3.12 Adsorption 97
2.5 Nomenclature 16
2.6 Chemical Equations; Weight Relationships Problems 106
and Conservation of Mass and Charge 17 References 112
VÎ
Contents vu
CHAPTER 4 5.14 Phenols 251
Basic Concepts from Equilibrium 5.15 Alcohols, Aldehydes, Ketones,
Chemistry 114 and Acids 254
4.1 Introduction 114 5.16 Simple Compounds Containing
Nitrogen 256
4.2 Limitations of Equilibrium
Calculations 114 Heterocyclic Compounds
5.17 Heterocyclic Compounds 258
4.3 Ion Activity Coefficients 116
5.18 Dyes 260
4.4 Solution to Equilibrium Problems 118
The Common Foods and Related Compounds
4.5 Acids and Bases 121
5.19 General 260
4.6 Buffers 160
5.20 Carbohydrates 260
4.7 Buffer Index 162
5.21 Fats, Oils, and Waxes 266
4.8 Complex Formation 164
5.22 Proteins and Amino Acids 269
4.9 Solubility of Salts 174
Detergents
4.10 Oxidation-Reduction Reactions 190
5.23 Detergents 275
4.11 Computer Methods for Solving Equilibrium
Problems 198 5.24 Soaps 275
Problems 199 5.25 Synthetic Detergents 276
References 211 Pesticides
5.26 Pesticides 279
5.27 Chlorinated Pesticides 279
CHAPTER O
Basic Concepts from Organic 5.28 Organic Phosphorus Pesticides 281
Chemistry 212 5.29 Carbamate Pesticides 282
5.1 Introduction 212 5.30 s-Triazines 283
5.31 Biological Properties of Pesticides 283
Aliphatic Compounds
5.2 Hydrocarbons 216 5.32 Pharmaceutically Active and Endocrine-
Disrupting Chemicals 284
5.3 Alcohols 222
Behavior of Organics in the Environment
5.4 Aldehydes and Ketones 227
and in Engineered Systems
5.5 Acids 231
5.33 Introduction 288
5.6 Esters 235
5.34 Fate of Organics 289
5.7 Ethers 236
5.35 Structure- and Property-Activity
5.8 AUcyl Halides and Other Halogenated
Relationships 303
Aliphatic Compounds 237
Problems 307
5.9 Simple Compounds Containing
References 313
Nitrogen 242
5.10 Cyclic Aliphatic Compounds 245
5.11 Mercaptans or Thioalcohols 245 CHAPTER 6
Basic Concepts from Biochemistry 315
Aromatic Compounds
5.12 Introduction 246 6.1 Introduction 315
5.13 Hydrocarbons 247 6.2 Enzymes 316
viii Contents
8.9 Effect of Radiation on Humans 394
6.3 Cofactors 318
6.4 Temperature Relationships 318 Problems 396
References 397
6.5 pH 321
6.6 Major and Trace Elements 322
6.7 Biodegradation 322
6.8 Biochemistry of Carbohydrates 324
PART
6.9 Biochemistry of Proteins 325
Water and Wastewater
6.10 Biochemistry of Fats and Oils 326
Analysis 399
6.11 General Biochemical Pathways 328
6.12 Energetics and Bacterial Growth 336
CHAPTER 9
6.13 Novel Biotransformations 339
Introduction 401
6.14 Molecular Biology and Genetic
Engineering 345 9.1 Importance of Quantitative
6.15 Biochemistry of Humans 352 Measurements 401
9.2 Character of Environmental Engineering
Problems 355
and Science Problems 402
References 359
9.3 Standard Methods of Analysis 402
9.4 Scope of a Course in Analysis
CHAPTER 7 of Environmental Samples 402
Basic Concepts from Colloid 9.5 Expression of Results 403
Chemistry 360
9.6 Other Items 408
7.1 Introduction 360 Problems 408
Colloidal Dispersions in Liquids 364
I.A
7.3 Colloidal Dispersions in Air 373 CHAPTER 10
Problems 375 Statistical Analysis of Analytical
References 375 Data 410
10.1 Introduction 410
CHAPTER 8 10.2 Rounding Numerical Data 411
Basic Concepts from Nuclear 10.3 Definitions 412
Chemistry 376 10.4 Distribution of Experimental Data 416
8.1 Introduction 376 10.5 Errors 419
8.2 Atomic Structure 377 10.6 Hypothesis Testing 426
8.3 Stable and Radioactive Nuclides 379 10.7 Detection Limits 430
8.4 Atomic Transmutations and Artificial 10.8 Lognormal Distribution 433
Radioactivity 385 10.9 Regression Analysis 437
8.5 Nuclear Reactions 387 10.10 Quality Assurance and Quality
8.6 Nuclear Fission 388 Control 446
8.7 Nuclear Fusion 390 Problems 446
8.8 Use of Isotopes as Tracers 390 References 451
Contents
CHAPTER 11 CHAPTER 14
Basic Concepts from Color 523
Quantitative Chemistry 452
14.1 General Considerations 523
11.1 General Operations 452 14.2 Public Health Significance 524
11.2 The Analytical Balance 455 14.3 Methods of Determination 524
11.3 Gravimetric Analysis 457 14.4 Interpretation and Application of
11.4 Volumetric Analysis 458 Color Data 526
11.5 Colorimetry 466 Problems 527
11.6 Physical Methods of Reference 527
Analysis 472
11.7 Precision, Accuracy,
CHAPTER X*3
and Statistical Treatment
Standard Solutions 528
of Data 474
Problems 474 15.1 General Considerations 528
References 475 15.2 Preparation of LOON
and 0.020 NH S0 .
2 4
CHAPTER 12 Solutions 530
15.3 Preparation of 1.00 N
Instrumental Methods of
and 0.020 NNaOH
Analysis 477
Solutions 532
12.1 Introduction 477
Problems 534
12.2 Optical Methods of Analysis 478 Reference 535
12.3 Electrical Methods of
Analysis 490
CHAPTER 16
12.4 Chromatographic Methods
pH 536
of Analysis 503
12.5 Other Instrumental Methods 512 16.1 General Considerations 536
Problems 516 16.2 Theoretical Considerations 536
References 517 16.3 Measurement of pH 538
16.4 Interpretation of pH Data 540
CHAPTER 13 Problems 540
Turbidity 518 References 541
13.1 General Considerations 518
CHAPTER 17
13.2 Environmental Significance 519
Acidity 542
13.3 Standard Unit of Turbidity 520
13.4 Method of Determination 520 17.1 General Considerations 542
13.5 Application of Turbidity 17.2 Sources and Nature
Data 521 of Acidity 542
Problems 522 17.3 Significance of Carbon Dioxide
Reference 522 and Mineral Acidity 544
X Contents
17.4 Methods of Measurement 544 20.6 Disinfection with Chlorine Dioxide 583
17.5 Application of Acidity Data 547 20.7 Disinfection with Ozone 584
Problems 547 20.8 Application of Disinfectant Demand
Reference 548 and Disinfectant Residual Data 585
Problems 585
CHAPTER 18 Reference 586
Alkalinity 549
CHAPTER 21
18.1 General Considerations 549
Chloride 587
18.2 Public Health Significance 550
18.3 Method of Determining Alkalinity 550 21.1 General Considerations 587
18.4 Methods of Expressing Alkalinity 551 21.2 Significance of Chloride 588
18.5 Carbon Dioxide, Alkalinity, and pH 21.3 Methods of Determination 588
Relationships in Natural Waters 557 21.4 Application of Chloride Data 590
18.6 Application of Alkalinity Data 558 Problems 591
18.7 Other Considerations 559 References 592
Problems 560
Reference 562 CHAPTER 22
Dissolved Oxygen 593
CHAPTER 19
22.1 General Considerations 593
Hardness 563
22.2 Environmental Significance of Dissolved
19.1 General Considerations 563 Oxygen 595
19.2 Cause and Source of Hardness 564 22.3 Collection of Samples for Determination
19.3 Public Health Significance 566 of Dissolved Oxygen 596
19.4 Methods of Determination 566 22.4 Standard Reagent for Measuring Dissolved
Oxygen 597
19.5 Types of Hardness. 568
22.5 Methods of Determining Dissolved
19.6 Application of Hardness Data 569
Oxygen 599
Problems 569
22.6 Dissolved-Oxygen Membrane Probes 601
Reference 570
22.7 Application of Dissolved-Oxygen
Data 602
CHAPTER 20
Problems 602
Residual Chlorine and Chlorine
References 603
Demand 571
20.1 General Considerations 571
C H A P T E R 23
20.2 Chemistry of Chlorination 574
Biochemical Oxygen Demand 604
20.3 Public Health Significance of Disinfection
23.1 General Considerations 604
Residuals 578
23.2 The Nature of the BOD Reaction 605
20.4 Methods of Chlorine Residual
Determination 580 23.3 Method of Measuring BOD 610
20.5 Measurement of Chlorine Demand 583 23.4 Rate of Biochemical Oxidations 616
