UNIT ()PERATIONS AND \ | PROCESSES IN ENVIRONMENTAL ses ae koe | ENGINEERING ERIM OH TECN)N Reynolds/Richardsi wariss | ne 4 ao 5 ssseme UNIT OPERATIONS | "AND PROCESSES IN. ENVIRONMENTAL \,_ ENGINEERING _ aeee |= PWS Series in Engineering Der Anderson, Thermodynamics Askeland, The Science and Engineering of Materials, Third Edition Baliga, Power Semiconductor Devices Bolluyt/Stewart/Oladipupo, Modeling for Design Using SitverScreen Borse, FORTRAN 77 and Numerical Methods for Engineers, Second Edition ‘Clements, 68000 Family Assembly Language Clements, Microprocessor Systems Design, Second Edition Clements, Principles of Computer Hardware, Secand Edition Das, Principles of Foundation Engineering, Second Edition Das, Principles of Geotechnical Engineering, Second Edition Das, Principles of Soi! 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ISBN 0.534-0488+-" Water — Pu 4. ‘Sewage — Purification — Problems. exercises. etc TD430.R48 1905 628.162 — de20 n. 2. Sewage — Purificanon 3. Water — Purifice:.cr L Richards. Paul A. a i — Problems. exercises Title. j Pr Sponsoring Editor: Jonathan Plant roduction Coordinator: Robine Andrau Marketing Development Manager: Nathan Wilbur Manufacturing Coordinator: Wendy Kilborn Interior Designer: Robine Andrau Interior Illustrator: Car Brown Printed and bound in the United States of America 97 9 99—1098 76543 Typesener: Besi-set Typesetier Ltd.. Hong Kong Cover Designer: Jjuisa Gecha Cover Printer: Coral Graphic Services. Inc. Text Printer/Binder Crawiordsville R.R. Donnelley & Sonsvi Contents 4 WATER QUANTITIES AND WATER QUALITY 67 Water Quantities 67 Water Quality 78 Problems 91 5 WASTEWATER QUANTITIES AND WASTEWATER ‘ QUALITY 93 Wastewater Quantities 93 Wastewater Quality 102 Measurement of Waste Organic Materials 106 Effluent Requirements | | Problems 113 6 lop WATER AND WASTEWATER TREATMENT 3 } : PLANTS [14 , ( a] Water Treatment Plants 114 i Wastewater Treatment Plants 119 Design Flow Rates and Parameters 125 7 PRELIMINARY UNIT OPERATIONS i . AND PROCESSES [28 Water Treatment 128 Wastewater Treatment 134 Problems 163 8 * wok | COAGULATION AND FLOCCULATION 166 oo Theory of Coagulation 166| ih Contents Preface xiii I CHEMICAL CONCEPTS | Inorganic Chemistry | Physical Chemistry 6 Organic Chemistry 12 Priority Pollutants 16 Problems 7 2 BIOLOGICAL CONCEPTS 19 Bacteria 19 / Other Microbes and Some Larger Organisms 28 Pathogens and Waterborne Communicable Diseases 30 Bacterial Analyses 30 / Biochemical Kinetics. Growth Kinetics, and Temperature Effects 32 Problems 36 3 MASS BALANCES, FLOW MODELS, AND REACTORS 38 Mass Balances 38 Flow Models . 42 Reactors 47 Problems 64Contents Miscellaneous Filters 322 Problems 325 i AMMONIA REMOVAL 327 Physical Operations 327 Chemical Processes 335 Biological Processes 337 * Problems 348 12 ADSORPTION 350 Adsorption 350 Column Contacting Techniques and Equipment 353 Fixed-Bed Adsorption Columns 358 Moving-Bed Countercurrent Adsorption Columns 368 Fluidized Beds 371 Test Columns 371 Design Considerations 371 Problems 373 13 ION EXCHANGE 376 Theory 377 Contacting Techniques and Equipment 380 Design Procedures 381 4 Softening and Demineralization 382 Ammonia Removal 384 Design Considerations 390 Problems 392 Nei cgi aSConsents vi Coagulants 174 Coagulant Aids 178 jar Tests 178 Chemical Feeders 179 Rapid Mixing and Flocculation 180 Lime-Soda Softening 206 Coagulation and Flocculation in Water Treatment 210 Coagulation and Flocculation in Wastewater Treatment 212 Problems 216 9 SEDIMENTATION 219 Type | Settling 220 Type ll Settling 231 Type Ill and Type IV Settling 239 Actual Sedimentation Basins 247 Sedimentation in Water Treatment Plants 255 Sedimentation in Wastewater Treatment Plants 257 Inclined-Settling Devices 264 Inlet and Outlet Hydraulics 268 Protiems 277 10 FILTRATION 284 Single-Medium Filters 284 Multimedia Filters 307 Filter Layout, Appurtenances, and Details 310 Filtration in Water Treatment 315 Filtration in Wastewater Treatment 318 Upflow Filtration 321toh Contents 16 OXYGEN TRANSFER AND MIXING 498 Oxygen Transfer 498 Mixing 508 Compressor Requirements 509 Problems 519 17 TRICKLING FILTERS AND ROTARY BIOLOGICAL CONTACTORS 523 Trickling Filters 523 Biological Filtration 528 Filter Performance 530 Flowsheets for Intermediate- and High-Rate Trickling Filters 54! Filter Details 542 Operational Problems 543 Rotary Biological Contactors 544 Problems 554 STABILIZATION PONDS AND AERATED LAGOONS 557 Stabilization Ponds 558 Aerated Lagoons 563 Problems 570 19 ANAEROBIC DIGESTION 573 Process Fundamentals 575 Low-Rate Digesters 578 High-Rate Digesters 583Contents ix 14 MEMBRANE PROCESSES 395 Dialysis 395 Electrodialysis 397 Reverse Osmosis 401 Problems 409 15 ACTIVATED SLUDGE 411 Microorganisms 415 Biochemical Kinetics 419 Food-to-Microbe Ratio (F/M) and Mean Cell Residence Time (6.) 425 Plug-Flow and Dispersed Plug-Flow Reactors 427 Completely-Mixed Reactors 435 cr Other Activated Sludge Process Modifications 440 Pure Oxygen Activated Sludge 449 . Temperature Effects 450 Other Kinetic Relationships 452 Space or Volumetric Loading Relationships 459 Empirical Relationships 459 Reactor Basins 461 Biochemical Equations 463 Sludge Production 467 Oxygen Requirements 468 Nitrification 471 Activated Sludge Coefficients 475 Rate Constants and Coefficients from Continuous-Flow Biological Reactors 480 Operational Problems 484 Problems 490Contents Sludge Treatment 708 Composting 717 Problems 720 23 OTHER UNIT OPERATIONS AND PROCESSES 723 Water Treatment 723 Wastewater Treatment 724 Problems 739 24 DISINFECTION 740 Chlorination 743 Ozonation 749 Chlorine Dioxide 751 UV irradiation 752 High pH Treatment 754 Appendix A Conversions and Measures 757 Appendix B International Atomic Weights of Eements 760 Appendix C Density and Viscosity of Warer 762 Appendix D Dissoived Oxygen Saturation Values in Water 764 Appendix E laboratory Biological Treatment Studies 766 Glossary 769 Answers to Selected Problems 783 Index 79!Coments Two-Stage Digesters 585 Egg-Shaped Digesters 585 Digester Operation 587 Digester Volume 587 Moisture-Weight Relationships 592 Sludge Quantities and Solids Concentrations 592 Digester Heat Requirements 595 Digester Gas Utilization 600 Fertilizer Value of Dried Sludge 601 Fluid Properties of Sludge 601 Sludge Thickening 603 Sludge Dewatering 604 Problems 606 20 AEROBIC DIGESTION 610 Aerobic Biochemical Equations 613 Kinetics of Aerobic Biological Oxidation 614 Design Considerations 614 Probiems 626 21 SOLIDS HANDLING 629 Wastewater Treatment Plant Sludges (Organic) 629 Wastewater Treatment Plant Sludges (Chemical) 657 Water Treatment Plant Sludges 658 Problems 663 22 LAND TREATMENT OF MUNICIPAL WASTEWATER AND SLUDGES 666 Wastewater Treatment 666Preface Water Treatment Chapter Topic 7 Screening. Presedimentation, Aeration. Adsorption. Prechlorination 8 Coagulation and Flocculation 9 Sedimentation 10 Fikration 12 Adsorption 24 Disinfection 13 Ton Exchange 14 Membrane Processes 21 Solids Handling 3 Iron and Manganese Removal, Volatile Contaminant Renova! from Groundwater Wastewater Treatment Chapter Topic 7 Screening and Shredding. Grit Removal. Flow Equalization. Quality Equalization 9 Sedimentation 15 Activated Sludge 16 Oxygen Transfer and Mixing 17 Trickling Filters and Rotary Biologica! Contactors 18 Stabilization Ponds and Aerated Lagoons 24 . Disinfection 19 Anaerobic Digestion 20 Acrobic Digestion 21 Solids Handling 2 Land Treatment of Municipal W: astewater and Sludges 23 Fotauon. Oii Separation. Septic Tans. and Soli Adsorption Systems Advanced Wastewater Treatment Chapter Topic 8 mn and Flocculation 9 non 11 Ammonia Stripping 10 Filtration 12 Adsorption 14 Membrane Process 13 Ton Exchange 11 Amm Removal by lon Exchange. Breakpoint Chiorination, and Biolegica! Means 23 Anaerobic Contact Process. Submerged Anaerobic Filter. Biological Phosphorus Removal. Aquatic Svstems awePreface Unit Operations and Processes in Environmental Engineering. Second Edition is for an advanced undergraduate course or a graduate-level course in environmental engineering. It has been written primarily for the civil/ environmental engineering curriculum: however, it may be used in other fields. such as chemical engineering. where water and wastewater treatment are taught. The book presents water and wastewater treatment under a single cover. using the unit operation and process approach. The funda- mentals of each operation and process are first presented in each chapter: then the application in the water treatment and wastewater treatment fields is given. Some operations or processes. such as activated sludge. are used in only one field and are presented accordingly. The undergraduate civil engineer's background in chemistry. mathematics. and fluid mechanics. and a prior introductory course in environmental engineering. are adequate preparation for use of the text. In nearly all the chapters. numerous example problems are given along with practice problem sets at the ends of the chapters. since an engineering discipline is most rapidly learned by problem solving. The book is oriented toward engineering design based on fundamentals. Chapters | through 5 present background material on chemical concepts. biological concepts. mass balances. flow models. reactor fundamentais. water quantities. water quality. wastewater quantities: and wastewater quality. The instructor may vary the depth of. coverage of these chapters according to the background of his or her class. Chapter 6 should then be covered Decause it has typical Howsheets of water. wastewater. and advanced wastewater treatment plants. After Chapter 6. the chapters need not be covered in sequentiai order: each chapter is written to be complete within itself. This presentation allows the instructor to select chapters or parts of the chapters in any sequence desired. If the instructor wants to cover water treatment in the first part of a semester and wastewater treatment in the latter part. he or she may choose the sequence of the chapters or parts ot the chapters accordingly. The material coverage for a water treatment approach. a wastewater treatment approach. and an advanced wastewater treatment approach would include the following chapters or parts of chapters and major topics. xiii| | Preface Solids handling is best covered as a separate subject because it involves both physical and chemical trearments. A third approach to using the book is to cover the topics in the order of their occurrence — from the most widely used treatment topics first to the least common treatment topics last. In using this approach. the instructor -may choose the sequence of topics to his or her own liking. The book contains more material than can be conveniently covered in a one-semester, three-credit-hour course: thus. the instructor may choose to limit the depth of coverages of some topics. However, the material that is not covered in class can serve as a valuable reference source for the student. Based on feedback from users of the first edition. all homework problems have been reviewed. Some problems have been deleted. other problems have been revised, and numerous new problems have been added. Over 60 percent of the homework problems in the second edition are new. There are over 300 homework problems in the second edition. compared to about 100 in the first edition. The glossary includes most terms that are covered in an introductory environmental engineering course. The Appendix contains tables that give common conversion factors. atomic numbers and weights. properties of water, dissolved oxygen concentrations at various temperatures. chloride concentrations and atmospheric pressures. and three diagrams for laboratory biological treatment reactors. along with instructions. Although the book is intended as a textbook. it will be usefu! as a reference book for practicing engineers and for engineers who wish to do self-study. The examples in the metric system (International Svstem of Units, abbreviated SI) will help practicing engineers. as well as students. 10 use this dimensional system. A Solutions Manual. which includes full worked-out sojutions to the homework problems. is also available for instructors. The authors appreciate the ris or Dana L. Montet in preparing the Solutions Manual. The authors 2iso gratefully acknowledge the thorough seading of the manuscript and t=z meaning‘ul suggestions by the following reviewers: Frederic C. Blanc Richard O. Mines. Jr. Northeastern University Robert P. Carnahan University of South Florida Ronald A. Chadderton Villanova University John D. Dietz University of Central Florida Austin Grogan University of Central Florida Universi of South Florida Vito Punzi Villanova University Aarne Vesilind Duke University irvine W. Wei Northeastern University Tom D. Reynolds Paul A. Richards—_—— 2 Preface [f the instructor wants to cover the chapters based on the fundamental principle involved — that is. physical. chemical..or biological — he or she may choose the chapters accordingiv. The material coverage tor this approach would include the following chapters’ or parts of chapters and major topics. Physical Treatment Chapter Topic ° Screening, Presedimentation. Aeration. Adsorption. Screening and Shredding. Gnt Removal. Flow Equalization. Quality Equalization 9 Sedimentation 10 Filtration lL Ammonia Stripping 12 Adsorption 14 Dialysis and Reverse Osmosis 16 Oxygen Transfer and Mixing 3 Volatile Contaminant Removal from Groundwaters. Flotation. Oil Separation. Septic Tanks 3h UV Disinfection Chemical Treatment Chapter Topic * Neutralization $ Coagulation and Flocculation 3 fon Exchange 14 Electrodialvsis a4 Disinfection ul Ammonia Removal bv Ion Exchange and Breakpoint Chlorination 4 Chiorine and Ozone Disinfeczion Biological Treatmem Chapter Topic 15 Activated Sludge Vv Trickling Filters and Rotary Biological Contactors 18 Stabilization Ponds and Aerated Lagoons 19 Anaerobic Digestion | 20 Aerobic Digestion ~ | u _ Ammonia Removal by Nitrification- Denitrification : 2 Land Treatment of Municipai Wastewaters and Sludges ef 3 Anaerobic Contact Process. Submerged Anaerobic Filter, Biological | Phosphorus Removal. Aquatic Svstems, Septic Tank and Soil : Absorption SystemsBel INORGANIC CHEMISTRY CHEMICAL CONCEPTS The purpose of this chapter is to review basic inorganic chemistry and present an introduction to physical chemistry and organic chemistry as telated to the field of water and wastewater treatment. : The basic chemical identities that compose all substances are the elements. The various elements vary from each other in atomic weight. size. and chemical properties. The symbols for the elements are used in writing chemical formulas and equaticns. The atomic weight is the weight of an element relative to carbon-12. which has an atomic weight of 12. The valence is the combining power of an element relative to that of the hydrogen atom. which has an assigned value of 1. Thus. an element with ~3 valence can replace three hydrogen atoms in a compound. and an element with -3 valence can react with three hydrogen atoms. The equivalent weight of an element is equal to its atomic weight divided by the valence. For example. the equivalent weight of calcium (Ca7*) is 40.0 ym divided Sy the valence of +2. to give 20.0 gm. The molecular weight ot a compound equals the sum of the atomic weights of the combined elements and is usually expressed in grams. The equivalent weight of a compound is that weight of the compound which contains 1 gram atom of available hydrogen or its chemical equivalent. Equivalent weight also equals the molecular weight/Z. where Z is a positive integer whose value depends upon. the chemical context. For acids. Z is equal to the moles of H™ obtainable from 1 mole of the acid. For H2SO:. Z = 2. so the equivalent weight is [(1 x 2) + 32 + (10 x 4).2] = 49.0gm. For bases. the value of Z is equal to the number of moles of H7 with which 1 mole of the base reacts. Thus for Ca(OH)2, Z = 2. For salts. Z is the oxidation or valence state of the ions. For BaCl>. Z = 2 because Ba™> is equivalent to 2 moles of H~. For Al-(SOu)s. Z = 6 because 2AI*? is equivalent to 6 moles of H™. For oxidizing or reducing agents. Z is equal to the change in oxidation or valence state. For K2Cr-O- in acid conditions. it undergoes a change in valence state of 3 x 2 or Z = 6. In a large number of different molecules. certain groupings of atoms act together as a unit and are termed radicals. Radicals are given special names for identity. Some common radicals encountered in water and wastewater engineering are the hydroxyl (OH7), bicarbonate (HCO;), carbonate (CO5?), orthophosphate (PO;*). sulfate (SOs), ammonium (NHS), nitrite (NOZ), nitrate (NOZ), and hypochlorite (OCI~) ions. The hydroxyl group 1Concentration Units Hydrogen fon Concentration CHAPTER i Chemical Concepts (OH) is one of the most frequent that occurs. Radicals themselves are not compounds, but they join with other elements to form compounds. Usually, the concentration of ions or chemicals in solution is expressed as the weight of the element or compound in milligrams per liter of water. abbreviated mg/f. Sometimes. the term parts per million (ppm) is used rather than mg/E. If the specific gravity is unity. conversion gives (1 mg/£} (m€/1000 mg) (€/1000 m£) or 1:10°. Thus 1 mg/£ equals to } part per-million. Usually, the specific gravity is so close to 1 that this conversion can be assumed. Chemical dosages are usually expressed as pounds per million gallons (kilograms per million liters); however. older books may refer to grains per gallon. One grain per gallon equals to 17.1 mg/€. The concentrations of elements are usually stated in milligrams of that particular element. and it is usually understood that the solution contains the stated number of milligrams. For example, a water that contains 36.2 mg/€ of sodium contains 36.2mg of sodium ion (Na~) by weight per liter. In special cases. the concentration expressed is not for a specific element. For example. hardness that is due to Ca~? and Mg~° is frequently stated in unit weights of CaCO . This facilitates computations invoiving hardness by using a single term rather than two terms. one for Ca~- and one for Mg**. The alkalinity of water may be due to one or more of the following ions: HCOz.COz*. and OH~. These also are frequently expressed as mg/€ as CaCO;. 10 simplify certain computations. All nitrogen com- pounds — that is. ammonia. nitrite. and nitrate — are usually expressed as mg/¢ nitrogen — that is. mg{-N. Also. all phosphates are usually expressed as mg/£ phosphorus — that is. mg/{-P. Sometimes concentrations are expressed as milliequivalents per liter (meq/f). These are obtained by dividing mg/{ bv the milliequivalent weight — that is. the equivalent weight expressed as milligrams. . In order to standardize tests so that common. procedures are used. the book titled Standard Methods for the Examinatior of Water ang Wastewater (APHA. 1992) is used for al] analyses done routinely. Pure water (H-O: dissociates to a slight degree to vield a concentration of hydrogen ions. H~, equal 10 107 mole’. The dissociation is represented by H.0 =H™ + OH™ a Since water dissociates to produce one hydroxyl ion. OH” . for each hydrogen ion. H*, there are also 10-7 mole/€ of hydroxyl produced. Since for pure water the amount of hydroxyl ions is equal to the amount of hydrogen jons. pure water is considered neutral. The acidic or basic nature of water is Telated to the concentration of hydrogen ions and is expressed by the symbol. pH. where 1 pH = ey (1.2)Chemical Equilibria Inorganic Chemistry 3 Since the logarithm of | over 107” is 7, the pH at neutrality is 7. The slight ionization of water is represented by (H*][OH7] = kK, = lo-" (3) where K,, is the ionization constant for pure water. When an acid is added to water. it ionizes in the water and the hydrogen ion concentration increases. resulting in a lower pH. Consequently. the hydroxyl ion concentration decreases. For example. if an acid is.added to increase the [H™] to 107°. the pH is 2 and the [OH] must decrease to 107'*. since [10~*][10-")} = 107" (Lai Likewise. if a base is added to increase the (OH™| to 107>, the (H™] decreases to 10~'' and the pH is 11. It is important to remember that the (H7] and [OH™] can never be reduced to zero, no matter how acidic or basic the solution may be. The pH scale ranges from 0 to 14. where pH 0 to 7 is acidic and pH 7 to 14 is basic or Acidic Range Basic Range reo OOo. I i 1 0 7 14 Frequently. the basic side is referred to as alkaline. The pH may be measured by an electronic electrode or pH indicators that exhibit significant coior change. Adjustment of pH is used to optimize coagulation. softening. and disinfection reactions and is used in corrosion control, In wastewater treatment. the pH must be maintained in a favorable range for optimum biological activity. Most chemical reactions are reversible to some degree. and the concen- trations of reactants and products determine the final equilibrium. Consider the equation aA - bB=-C - dD pF where A.B = reactants C. D = products Ain increase in A or B shifts the reaction to the right. and an increase in C or D shifts it to the left. The relationship may be expressed by the mass- action equation C}[DI* ach =K (1.6) where [ ] = molar concentrations K = equilibrium constanteet Ways to Shift Equilibria CHAPTER | Chemical Concepts Strong acids and bases in dilute solutions approach 100% ionization. while weak acids and bases are poorly ionized. An equilibrium relationship that is very important in water chemistry is the carbonic acid-bicarbonate-carbonate system. Carbonic acid dissociates as follows: HCO; = H™ + HCO; (7 and for this system, the mass action equation is : [HYCO] =p = gas x 9 mos" [H:CO,] K, A5 x 1077 at 25°C (1.8) The bicarbonate ion [HCO5] dissociates as follows: HCO; = H™ + CO;? (9 and for this system, the mass action equation is = Kz = 4.69 x 107") at 25°C (1.10) The previous discussion is for homogenous chemical equilibria. wherein al! reaciants and products occur in the same physical state. Heterogeneous equilibria occur between substances in two or more states. For example. at PH greater than 10. solid calcium carbonate in water reaches a stability with calcium and carbonate ions in solution since the dissociation is CaCO, = Ca7> ~— COz* (ai Equilibrium between crystals of a compound in the solid state and its ions in solution may be treated mathematically as if the equilibrium were homogenous in nature. For Eq. (1.11). the equilibrium equation according 10 mass action is (Ca7“}iCO [CaCO] The concentration of a solid substance can be treated as a Consiant A. in the mass action equation: therefore. [CaCO ] may be treated as K, to give {Ca~*][COx*] = K.K = K,, = 8 x 107° at 25°C (1.43) =k (1.12: The constant. K,,. is termed the solubility product constant. lf the product of the ionic molar concentrations is less than the solubility: product constant. K,p,, the solution is undersaturated. Conversely. if the product is greater than the solubility product. K,,. the solution is super- saturated. For this case. crvstals form and precipitation progresses until the ionic concentrations are reduced to those of a saturated solution. From Eg. (1.13). the solubility of calcium carbonate is about 7 mg‘f Chemical reactions in water or wastewater treatment rely on shifting equi- libra to bring about desired changes or desired results. The most common2H and Alkalinity Inorganic Chemtsry 3 ways to shift equilibria are the production of insoluble substances, weakly ionized compounds, or gaseous end products, and oxidation and reduction Teactiuny. An example of production of an insoluble substance is in water soften- ing. where slaked lime, Ca(OH);. is added to remove Ca~*. Ca** + 2HCOS + Ca(OH); = 2CaCO;; + 2CO; (Lid Other reactions occur in softening. but this one illustrates the production of an insolubie compound. The solubility product constant of the CaCO; is 5 x 107" at °C. An example of production of a poorly ionized compound is the neutrali- zation of acid or caustic wastes. Many textile mill wastewaters have NaQH present and are neutralized by using H»SO, as follows: 2H~ + SOs? + 2Na™ + 20H™~ — 2H-O + 2Na~ - SOF? (1.15) The combination of [H~] and [OH™] produces water that is poorly ionized. Production of a gaseous product is illustrated by adding chlorine at the breakpoint as follows: 3Cl + 2NH: — Nz t - 6H™ = 6CI- (1.16) Here. the gaseous nitrogen produced. N-. causes the reaction to go to completion. An example of using oxidation-reduction reactions to compléte the reaction is the adding of chlorine to cyanide ion. CN~. in electroplating wastes. to give 5Cl; ~ 2CN~ + 8OH™ — 10CI> ~ 2CO. = N;* ~4H;0 (1.17) This reaction goes to completion because chlorine is reduced while the cyanide ion is oxidized to CO, and HO. Also. this reaction goes to comple- tion because a gaseous product. N:. is formed. Alkalinity is 3 measure of the capacity of a water to neutralize acids — that is. to absorb hydrogen ions without significant pH changes. It is determined in the !aborators by titrating the water with a standardized sulfuric acid solution. usuaily 0.02N H,SO,. The three chemical forms that cause alkalinity in natural waters are bicarbonate. carbonate. and hydroxyl ions: HCO}. CO;*. and OH~. The COS*. HCO;. and OH™ are related to the CO: and H7™ ion concentration (or pH) as shown by the following equilibrium reactions (Sawyer er al., 1994), CO, + H,O = H2CO; = HCO; + H* (1.18) M(HCO;)- = M** - 2HCOF (1.19) HCO; = CO3* +H" (1.20) CO;? + H.O = HCO; + OH™ (1.21)I } | i & i ed PHYSICAL CHEMISTRY _ Chemical Kinetics CHAPTER i Chemical Concepts From these equations. it can be seen thar CO: and the three forms of alkalinity are al! part of one svstem that exists in equilibrium since all equations have HCO;. A change in the concentration of any one member of the system will cause a shift in the equilibrium. cause a change in concentration of the other ions. and result in a change in pH. Conversely. a change in pH will shift the equilibrium and result in a change in concentration of the other ions. Figure 4.6 shows the relationship between CO. and the three forms of alkalinity in a water with a total alkalinity of 100mg/€ as CaCO; over the pH range commonly found in water and wastewater engineer- ing. As can be seen. for most natural waters the pH is from 5 to 8.5: thus the HCO; content represents the major portion of the alkalinity. Substances that offer resistance to a pH change are referred to as buffers. Since the pH range for natural waters and wastewaters is from about 5 to 8.5. the main buffering system is the bicarbonate-carbonate system. If an acid is added. a portion of the H™ ions combine with HCO; to form un-ionized H»CO;. and only the H~ remaining free affect the pH. If a base is added. then some of the OH™ ions react with HCO; to form CO3°. and only the OH™ remaining free affect the pH. Both chemical reactions and biological processes depend upon the natural buffering action to control PH changes. In coagulation. when the alkalinity naturally present is insuf- ficient. calcium hydroxide. Ca(OH)-. and sodium carbonate. Na-COs. can be added to furnish alkalinity to react with the coagulant. The main areas of physical chemistry that are utilized in water and waste- water engineering are concerned with chemical kinetics. gas laws. and colloidal dispersions. Chemical kinetics is concerned with the rate at which reactions occur. The types of reactions discussed in this section are irreversible reactions occurring in one phase wherein the reactants are dispersed uniformly throughout the liquid. In irreversible reacuons. the stoichiometric combi- nation of the resctants leads to almost compie:e conversion to products. Most reactions in water and wastewater engineering are sufficiently irre- versible to allow ifis assumption for the kinetic interpretation of experimen- tal data. Of the reactions discussed in this text. the first-order kinetics occur the most frequently in water and wastewater engineering. Zero-order reactions occur af w rate that is independent of the con- centration of the reactant or product. so the disappearance of the reactants is linear with time. Consider the following conversion of a single reactant into a single product. A(reactant) — B(product) (1.22) If C represents the concentration of A. the rate at which A disappears with respect to time is -s>=ke=-r (1.23)Physical Chemistry 7 where dC co . aye : 7a r = rate of change in the concentration of A with time, mg e-day ‘ or hour k = reaction constant. mg ¢-dav or hour Rearranging Eq.-(1.23) for integration gives * “ | c= -&] ae (1.24) we 0 where C = concentration of A at any time. r, mg:¢ Ca = initial concentration of A. mg'é t = time. days or hours Integration gives 7 C{ = ~k «251 af or C- CG, = kr (1.261 or ar C=O,- kt (1.27) 4 Equation (1.27) is a linear equation of the type v = b + mix. soit will plot a straight line on arithmetic graph paper. as shown in Figure 1.1: If the data plots a straight line. the réaction is zero-order and the slope of the line is equal to k. First-order reactions occur if 2 rate that is proportional to the concen- tration of one reactant. Again consider the conversion of a singie reactant to a single product. A(reactant) — P(product) Time, £ ——~ FIGURE 1.1 Plot of Data for a Zero-Order Reaction