Fundamentals of Environmental Engineering

N= 622 < 10% mo! ee Lom x19 MC R= 8314) mol Kt 1.987 cal mol K+ = (208265 L atm mol! K f= 6626 % IW 5 pstant ke 1381 X WP d K F = 9689 10° C mat? © = 2.998 X 1 mst miteivity by = BBS XID C2 gy 5 = 9.806 ms? = 4.184 joules () = 96.485 ky mot! 23.061 keal mot? L197 % 10"? kd mot! 10 = 101325 x 10° Pa = 10m = 10% m e 2 PK. » Surface Tension Dielectric lonization Viscosity against Air Constan term's) Gem ev tem 01787 W756 8.28 Sonsiy 0749 863 47338, 999.726 ovis oraz hs 14.536 9991950139 07349 Rs as 988.228 o.n01002 07275 207 M1669 997.069 oxo ooni97 mss 139965 95671 ooooT97s bons ™m 1.830 Muliptication Prefix Symbot Factor clin Syma Ww? cent 0 rill we micro o~ ano ie pico le emo oe atte Fundamentals of Environmental Engineering James R. Miheleic Contributors Martin T. Auer David W. Hand Richard E. Honrath, Jr. Judith A, Perlinger Noel R. Urban Department of Civil and Environmental Engineering ‘Michigan Technological Universy Michael R. Penn Department of Civil and Environmental Engineering Untvesy of Wisconsin: Plateile ® John Wiley & Sons, Inc.EDITOR Wayne Anderson [MARKETING MANAGER Katherine Hepburn SENIOR PRODUCTION MANAGER Lucile Buonocore SENIOR PRODUCTION EDITOR Monique Coletl DESIGN DIRECTOR Madelyn Lenwe COVER DESIGNER Michal Jung ILLUSTRATION EDITOR Sigmund Malinowski ILLUSTRATION STUDIO JAK Graphics, “Tis book i printed on aci-ree paper: ©) ‘The paper in this book was manufictured bya mill whose forest manasement programs inde setae yi arestng os imborinde Suid ld brea ected sumbers fre ut each ea docs ot xced te amount of new grec ne Copyright © 199, John Wiley & Son, Ine, Al rights reserved. Nop of his pbizaton may beer sre ina tiesto anined inary tom ory ny meas mechan phocytes cr tvs, kept ne Sens 1 eke ee Unie Sea, py Ac. ios eer ie pre writen permit he blob uration og pyen fhe mpopne pres ees Cop ane Cet, 22 Reno Dive, Daves A925 O78 1 a (97% 46-8600, Requests the Pablierrprmsion shale aes the ins Depart a Wit & Som, eI Rive ee (21) 766 on ar anya. HI Rer ste. Hoboken M1 rn ‘To order books o fr customer service pleat, call 1(800)-CALL-WILEY (225.5945), Library of Congres Cataloging i Publication Dat: Mice James Fondamental of envioamental engnerng/ James R Mieke contributors, Martin T. Auer... fetal . * em Includes iblogapical ferences an index ISBN 0-47-2653 (loa pape) 1. Beloiaengneeving. 2 Environmental cence. 1. Aver, ‘Martin T, I. Title. : [GESSONSA 1958 enter 839309 ap wos76s4 Preface In our local community many grade-school and high-school classes “adopt” a local stream. Working with their teachers and personnel from Michigan Tech’s Environmental Outreach Center, students first learn about water quality and land issues in the classroom, then go into the field to measure the stream’s flow and perform some field measurements of selected chemical and biological water quality parameters. One day I read these comments on the “Adopt a Stream’ program provided by a third grader from the town of Bessemer. The third grader wrote: “During “Adopt a Stream” we asked a ton of questions. Most were hard ‘ones to answer. The teachers asked two tons of questions. Even I asked a ton of questions. I wanted to mosily know how long it takes nonpoint source pollution to go underground and travel into the water and pollute it.” How insightful this third grader was! [ seem to remember that I did not learn about nonpoint source pollution: and how surface waters can be hydraulically ‘connected to groundwater until late in my college career. The fact is that today, ‘engineers and scientists who work on what seem to be increasingly complex environmental problems require a vast knowledge of the fundamentals of chemis- ‘ry, biology, and physical processes. Fundamentals of Environmental Engineering is the outgrowth of a team- teaching effort for a course required of all civil and environmental engineering, undergraduates at Michigan Tech. Other students taking this course major in fields such as chemical and geological engineering, chemistry, and biology. The intention of the course is to provide a bridge for a student to move from the fundamentals studied in first- and second-year math and basic science courses to their introductory and upper level engineering courses, which apply those fundamentals. Fundamentals of Environmental Engineering provides coverage of the basics required for design, operation, analysis, and modeling of both natural and engineered systems. Also, the fundamentals presented here are a necessity for solving both small-town and global environmental problems. Chapters include (1) reporting concentrations in air, water, and soil; (2) chemistry (kinetics, thermodynamics, equilibrium processes in air, soil, and water, and photochemistry); (3) physical processes (mass and energy balances, reactor engineering, mass transport, Stokes’ law, and Darcy's law); and (4) biology (ecosystem structure and function, energy and material flow, population dynamics and modeling ‘growth, oxygen demand and oxygen sag in surface water, wastewater treatment,iv. Preface eutrophication of lakes, eoxytem health, and public welfare). Fundamentals of Environmental Engineering also emphasizes the connections among the ferent specially areas of environmental enginering-the conto to this effort have expertise in inking water and wastewater Westmont as qual engineering, groundwater engineering, solid and hazardous wast anagemest and remediation, surface water qual cnvtonmental chemistry, ecology, snd assessing environmental rk. Ths the book presents those requvedfumeginon tals alongwith lose to one hundred applications fora diverse st of relent environmental situations ining multimedia ues encompassing engineered treatment and chemical fate and transport in a water and sail Dar mea not oreplace the many exellent books that cover a patclr Lope or chapter of this text Rather i Co presen all the sientte fundamental none een focunderstand format fran undergraduate audience ‘ur student reviewers went well beyond pointing out typographical errors. ‘they provided many insight comments that make this text more “stadeat friendly" One request wast note etl equations, Weave don this lc, ing a next those equations we fet were of major importance Web Site Additional resources for instructors and students to support ths text can be found at www.wiley.com/college/miheleic, Acknowledgments The flowing Mihigan Tech students majoring in el eget, envion- men engeeing Shon nd Doe’ pied meee cen improv the techs cnent ind ena a ac. Tye tot Evan Berhnd Ely Bent esi gh taone eon kay Fateron,Raghraman Vnitpahy sd Suse Weve See Bags Man Tels Depart of Welogia Senses prod hee on the logy caper and Kinerh lentes ices sete ee the gues tt capes woud a fo hank or che ena cancing colnet Wigan Tech rl comments sap ed sxchnge of sus ry of with ete ineaportedinen et ean Baildon Catone lob ios Ne Hr, Aloe apes ne een ae tron Final woul et thank Mak Mie Dons Ween a ne tomer of he Deptt of Chi Enpinceneg. Unseen Gere, New Zend ho made cael ae ea a redo. Tou Ihe to think he long reviewer forte lp inte development of ths text Win D. Burgos, Fowoshant Seat Unio Ith Costes, Conon Unvented Stn over eos Pe James R. Mihelcie ‘South Shore of Lake Superior Preface ¥ About the Authors Dr. James R. Miheleie is Associate Professor of Civil and Environmental Engi- neering at Michigan Technological University. He teaches introductory courses in environmental engineering and advanced courses in environmental biochem- istry, solid and hazardous waste management, biological processes, and water chemistry. He has been awarded the Department of Civil and Environmental Engineering Howard E. Hill Outstanding Faculty of the Year Award and has also been a finalist for the Michigan Tech Teacher of the Year Award. Dr. ‘Mihelcic’s research interests include environmental microbiology; optimizing biological treatment processes and understanding biological transformations in ‘wastewater, soil, and groundwater; studying bioavailability of hydrophobic organic chemicals discharged to soil and aquatic environments; and development of estimation methods that predict environmental properties such as sediment~ ‘water partition coefficients, bioconcentration, and biodegradability from knowledge of chemical structure. Dr. Martin T. Auer is Professor of Civil and Environmental Engineering at Mich- igan Technological University with 18 years of service on the faculty. He teaches introductory courses in environmental engineering and advanced coursework in surface water quality engineering and mathematical modeling of lakes, reservoirs, and rivers. Dr. Auer’s present research activity includes studies of pollution problems in Onondaga Lake, New York and the New York City reservoir system and an investigation of cross-marginal transport processes in Lake Superior. Dr. David W, Hand is Associate Professor of Civil and Environmental Engi neering at Michigan Technological University. He teaches senior-level courses in drinking water treatment, wastewater treatment engineering, and air stripping! adsorption processes. Dr. Hand’s present research focus is on the development ‘of a mathematical model that describes the performance of the International ‘Space Station's portable water treatment system, the development and application of photocatalytic oxidation processes for the removal of pollutants from ‘water and air, and the development of environmental engineering software tools for pollution prevention practices. Dr. Richard E. Honrath, Jr. is Associate Professor of Civil and Environmental Engineering at Michigan Technological University. He teaches courses on the fundamentals of environmental engineering science, current topics in air quality engineering, and advanced atmospheric chemistry. Dr. Honrath’s research interests include the photochemistry of nitrogen oxides and ozone in the troposphere, with a focus on measurement and modeling studies of the hemispheric scale impacts of human activities on tropospheric composition and chemistry. Dr. Michael R. Penn is Assistant Professor of Civil and Environmental Engi neering at the University of Wisconsin-Platteville with teaching responsibilities for undergraduate courses in introductory environmental engineering, wastewater treatment and water quality, groundwater hydrology, solid and hazardous ‘waste management, and hydrology. He taught comparable courses in a previouswi Preface position at Wilkes University in Wilkes-Barre, Pennsylvania, Dr. Penn received his Ph.D. from Michigan Technological University on completion of research on nutrient cycling in lakes and sediments. His current research interests focus on involving undergraduates in surface and groundwater contaminant fate and transport investigations. Dr. Judith A. Perlinger is Assistant Professor of Civil and Environmental En- sineering at Michigan Technological University. She teaches courses on funda- ‘mentals of environmental engineering science, environmental and water chemistry, and environmental organic chemistry. Dr. Perlinger’s research interests include the transport and transformation of xenobiotic organic chemicals in the environment. Most recently her research has focused on kinetic and mechani aspects of reductive transformations of these compounds in anaerobic environ- ‘ments such as groundwater aquifers and lake sediments. Dr. Noel R. Urban is Assistant Professor of Civil and Environmental Engineering at Michigan Technological University. His research focuses on the biogeochem- istry of nutrients and minor metals in wetlands and lakes. Dr. Urban’s teaching activity centers around environmental chemistry, Back Row (L-R): Mike Penn, Richard Honrath, Jim Mielec, Noel Urban Contents Chapter 1 Student Preface: Why Do I Need Fundamentals? J Chapter 2 Units of Concentration un 2.1 Mass Concentration U: 241 MassMass Units 12 212 Mass/Volume Units: mg/L and ygim? 13 22. Volume/Volume and Mole/Mole Units 4 221 Using the Ideal Gas Law to Convert ppm, to pgim? 15 23. Partial-pressure Units 18 24 Mole/Volume Units 21 25. Other Types of Units 22 251 Normality 22 252 Concentration as a Common Constituent 25 253 Reporting Particle Concentrations in Air and Water 28 254 Representation by Effect 31 26 Common Concentrations Encountered in Wastestreams, Surface and Groundwaters, and the Atmosphere 32 Chapter Problems 36 References 1 a Chapter 3 Chemistry “ 31 The Difference Between Activity and Concentration 43 3.11 Tonie Strength 48 3.12. Calculating Activity Coefficients for Electrolytes 45 3.13 Calculating Activity Coefficients for Nonelectrolytes 47 3.2 Chemical Kinetics 49 321 The Rate Law 49 322 Zero- and First-order Reactions 52 323. Pseudo-firs-order Reactions. 55 324 Half-Life and Its Relationship to the Rate Constant 56Contents 32.5 Effect of Temperature on Rate Constants 58 3.26 Catalysts 61 33 Chemical Thermodynamics and Equilibrium 63 33.1 Calculation of Change in Free Energy at Standard Conditions 65 332. Calculating Changes in Free Energy under Nonstandard “Ambient” Conditions 68 333 Free Energy and Its Relationship to the Equilibrium Constant 72 33.4 Effect of Temperature on the Equilibrium Constant 15 34 Equilibrium Processes 75 34.1 Volatilization 76 342 Air-Water Equilibrium 80 34.2.1 Henry's Constant with Units for a Gas Dissolving ina Liquid 82 3422 Dimensionless Henry's Constant for a Species ‘Transferring from a Liquid to aGas 84 343° Acid-Base Chemistry 86 343.1 pH 86 343.2 Definition of Acids and Bases and ‘Their Equilibrium Constants 87 3433 ‘The Carbonate System, Alkalinity, ‘and Buffering Capacity 92 3.44 Precipitation-Dissolution 97 345. Sorption and Ion Exchange to Solid Surfaces 102 345. Introduction 102 345.2 Sorption and Adsorption 103, 3453 lon Exchange 119 35 Oxidation/Reduction 120 3.6 Photochemistry and the Atmosphere (Urban Smog and the Ozone Hole) 122 361 Introduction 122 3.6.2 Stratospheric Ozone Chemistry 125 363. Tropospheric Ozone Chemistry 128 Chapter Problems 129 References 136 Chapter 4 Physical Processes 4.1 Mass Balances 139 4.11 The Control Volume 141 412 413 414 445 416 Contents ix ‘Terms of the Mass-Balance Equation for a CMFR. 141 412.1 Mass Accumulation Rate, ddr 141 41.22 Mass Flux in, ry, 148 4123. Mass FlUX Out, gu, M45 41.24 Net Rate of Chemical Reaction, Miacion 146 4.125 Steps in Mass-Balance Problems 147 Reactor Analysis: The CMF 147 ‘The Batch Reactor 155 ‘The Plug-Flow Reactor 155 4.15.11 Comparison of the PFR to the CMFR_ 158 415.1 Response to Inlet Spikes 160 41512. Selection of CMER or PFR_ 161 Retention Time and Other Expressions for VQ. 162 Energy Balances 165 424 422 Forms of Energy 165 ‘Conducting an Energy Balance 167 Mass-Transport Processes 174 43.1 432 433 ‘Advection and Dispersion 174 43.1.1 Definition of the Mass-Flux Density 175 43.1.2 - Calculation of the Advective Flux 175 43.13 Dispersion 176 43134 Fick's Law 176 43132 Molecular Diffusion 179 431.33 Turbulent Dispersion 181 43.134 Mechanical Dispersion 182 ‘The Movement of a Particle in a Fluid: Stokes’ Law 183 432.1 Gravitational Settling 184 4322 Calculation of the Minimum Particle Size Removed 187 4322.1 Distance Settled during Retention Period 188 43222 Settling Velocity Greater than the Overflow Rate 189 432.23 Equivalence of the Two Methods 189 4323 Other Applications of Force Balances on a Particle 192 Flow of Water Through a Porous Medium: Darcy's Law for Groundwater Flow 192 433.1 Head and Hydraulic Gradient 194 4332 Porosity 194 4333. Darcy’sLaw 194 4334 The Darcy Velocity Versus the True Horizontal Velocity 196 Chapter Problems 198 References 207x Contents Chapter 5 Biology Sa 52 33 54 38 56 Ecosystem Structure and Function 210 S11 Major Organism Groups 212 Population Dynamics 217 52.1 Units of Expression for Population Size 217 522 Models of Population Growth 218, 522.1 Exponential or Unlimited Growth 219 Logistic Growth: The Effect of Carrying Capacity 221 522.3 Resource Limited Growth: The Monod Model 224 5.2.24 The Yield Coefficient: Relating the Rate of Growth to the Rate of Substrate Utilization 227 Respiration: The Decay Coefficient 229 Biokinetic Coefficients 229 Batch Growth: Putting It All Together 230 522.8 Growth Models and Human Population 233 Energy Flow in Ecosystems 237 53.1 Energy Capture and Use: Photosynthesis and Respiration 237 532 Trophic Structure in Ecosystems 242 53.3. Thermodynamics and Energy Transfer 246 Biochemical Oxygen Demand (BOD), Theoretical Oxygen Demand (THOD), and Chemical Oxygen Demand (COD) 248 54.1 Definition of BOD, CBOD, and NBOD 248 Sources of BOD 249 ‘Theoretical Oxygen Demand 251 BOD Kinetics 256 ‘The CBOD Rate Constant 258 Measurement of BOD 260 ‘The BOD Test: Limitations and Alternatives Such as Chemical ‘Oxygen Demand 264 Dissolved Oxygen and BOD in Rivers 265 55.1. Oxygen Saturation 269 552 The Oxygen Deficit 270 553. The Oxygen Mass Balance 270 554 The Dissolved-oxygen Sag Curve and the Critical Distance 272 ‘Material Flow in Ecosystems 273 56.1 Hydrologic Cycle 277 562 Carbon Cycle 281 5.63 Oxygen Cycle 283 5.64 Nitrogen Cycle 283 5.65. Phosphorus Cycle 287 5.66 Sulfur Cycle 288 57 58 Contents xi Lakes: Nutrients and Eutrophication 291 5.7.1 Thermal Stratification of Lakes and Reservoirs 291 5.7.2. Organic Matter, Thermal Stratification, and Oxygen Depletion 293 5.13. Nutrient Limitations and Trophic State 295 5.74 Modeling and Managing Eutrophication 296 5.75. Lake and Reservoir Restoration and Management 299 Ecosystem Health and Public Welfare 300 5.8.1 Bioconcentration and Bioaccumulation 300 582 Toxicity 304 5.83. Indicator Organisms 308 Chapter Problems 310 References 320 Solutions to Chapter Problems 323 Index 331Chapter 1 Student Preface: Why Do I Need Fundamentals? James R. Mihelcic Judith A. Perlinger fundamentals that they question(s). For exam ‘a physical/chemical treatmer ‘balances, reactor desigit and cal and physical treatment processes. Today, the profession of environmental engineering draws upon many disci- plines, including civil, environmental, chemical, mechanical, and geological en- ering; geology; chemistry; microbiology; toxicology; atmospheric sciences; ‘meteorology; and ecology. The civil engineering profession encompasses many specialty areas (i, structural, geotechnical, water resources, transportation, construction management, environmental), all of which have an environmental component to them, For example, an engineer may be designing the concrete structure of a reactor that another engineer sized or may be involved in traffic planning in an urban area that has a goal of meeting stringent air-emission regulatory limits. Also, many practicing engineers find themselves specifically working on ‘an environmental engineering problem at some point in their career.2 Chapter 1 Student Preface: Why Do I Need Fundamentals? ‘Today's environmental problems are complex and are no lorger confined to one particular medium. For example, no longer is it acceptable to treat contant. inated water by stripping the contamination into the air and thereby causing an air-pollution problem. Furthermore, an individual must now understand how chemicals move across boundaries of air, water, and soil, and how entry across each of these boundaries can influence a chemical’s transport, fate, potential risk, and treatment. Not only is the study of environmental engineering the study of the effects of humans on the environment, but to some extent the effects of the environment on human activities. One definition of environmental engineering is that itis a fied in which one ‘applies the basic fundamentals of mathematics, physics, chemistry and biology to the protection of human health and the environment. At the 1996 Environmental Engineering Education Conference (AEE, 1997) representatives from industry and academia stressed the necessity for environmental engineers io have a strong background in the fundamentals of chemistry, biology, and physical processes, The purpose of Fundamentals of Environmental Engineering is 10 demonstrate hhow fundamentals learned in mathematics, physics, chemistry, and biology are applied to environmental problems. SITUATION 1 MUNICIPAL WASTEWATER TREATMENT. ‘Municipal wastewater contains relatively large amounts of organic matter, solids, and nutrients such as nitrogen and phosphorus, As discussed in later chapters, all of these items may adversely impact the chemical and biological balances of a river or lake if they are improperly discharged. In addition, urtreated wastewater may spread disease among humans by exposure during drinking, bathing, or swimming. The purpose of municipal wastewater treatment is to first collect and transport the wastewater to a treatment plant, where itis treated to remove dissolved and particulate organic matter, solids, nutrients, and pathogens to levels that will not cause an adverse impact on human health and the environment. ‘These goals are met by constructing a treatment plant that employs physical, chemical, and biological treatment processes. Figure 1-1 shows an overhead photo of a large treatment plant used by a major USS. city. There are many tanks and buildings in the photo, and each of them has some specialized job for pump- ing or treating the wastewater and sludge generated during treatment, Each of these specialized unit processes employs some fundamental aspect(s) of chemical, biological, or physical processes. For example, solids are removed by the physical process of gravity settling; organic matter is removed by a physical process like gravity settling if itis in a particulate form and by a biological process if itis dissolved and readily assimilated by microorganisms; and phosphorus can be removed by chemical and/or biological methods. In addition, there may be a need. to determine how much of the potential pollutants in the wastewater a lake or river can safely assimilate. This requires knowledge of the chemist-y and biology of the receiving water as well as of how physical processes such as mixing and transport influence the pollutants. SITUATION 1 Municipal Wastewater Treatment 3 Figure 1. Aerial photo of a wastewater treatment plant used to treat municipal wastewater. Each reactor incorporates some combination of chemical, biological, or physical processes 10 {reat the wastewater, (John Edwards/Tony Stone Images/New York, Inc) Fundamentals of Environmental Engineering provides a reader with the tools, to begin answering questions such as: How do I design, construct, and operate a treatment plant to treat a specific ‘wastewater, given that T must treat a certain volume of wastewater daily, and the influent wastewater has specific pollutant characteristics? How large a reactor must I construct, and can 1 speed up a chemical or biological reaction in order to construct a smaller, and less expensive reactor? IFT have several types of reactors to choose from, which one works best for a given treatment objective? : How do daily and seasonal variations in the flow of wastewater supplied by households and industry influence the design and operation of a particular treatment process? ‘Are there special considerations of the receiving water body that influence the plant design? For example, there may be a more strict phosphorus discharge standard for a more-nutrient-sensitive water body. ‘Can 1 use the same biological treatment reactor to remove both organic carbon ‘and inorganic nitrogen?4 Chapter 1 Student Preface: Why Do I Need Fundamentals? How much of a particular waste can I discharge to a receiving water body; h do mixing and transport influence the fate of the waste; and will this di charge adversely affect the chemistry or biology of the water body? How do I optimize a particular treatment process to more efficiently treat a particular waste? Should I biologically treat a particular waste in the presence of oxygen (aer- obically) or in the absence of oxygen (anaerobically), and how do these methods differ? ‘What are the most efficient methods of supplying needed oxygen to an aerobic biological reactor? How do temperature changes during the summer and winter affect chemical or biological treatment processes or naturally occurring recovery processes of a lake or river? SITUATION 2 ACID RAIN came to the forefront as a major environmental issue in the late 1960s ‘and early 1970s. Acid rain has a much lower pH than natural rainwater (e.g., PH 32-45), although, as we will investigate in Chapter 3, rainwater not impacted by anthropogenic emissions is already slightly acidic (pH 5.6). Acid rain is pri- ‘marily the result of humans discharging excessive amounts of sulfur dioxide (SO;) ‘and nitrogen oxides (NO and NO;, which can be combined together and de- SEO sensitive seis present prem aces E53 Potential probiem areas igure 1-2. Global map showing extent of acid rain problem. (Adapted from Rodhue, 1989, “Acidification in a Global Perspective,” with permission of the Royal Swedish ‘Academy of Sciences.) SITUATION 2 Acid Rain 5 seribed as NO,) into the atmosphere. After emission to the atmosphere, these ‘oxides are chemically transformed into the strong acids, sulfuric acid (H,SO.) and nitric acid (HINO,), that then return to the earth as either wet (ic. rai ‘snow, fog) or dry deposition. These emissions result primarily from the combustion of fossil fuels e.g, coal, oil) for electricity generation using coal, transportation, and home heating, Figure 1-2 shows the extent of the world’s areas with ‘current of potential acid-deposition problems. This figure shows that acid rain is a large-scale problem, Figure 1-3 shows a simplified schematic of how sulfur and nitrogen oxide emissions may be transported to a terrestrial or aquatic system. The distances of ‘transport can occur on a local or regional scale. Acid deposition may cause ex- tensive damage to buildings and historical monuments and has been implicated in the decline of mountainous forests and the death of fish populations and other ‘aquatic organisms. In the 1960s and 1970s, a popular method selected to control ‘emissions at the local scale was the construction of tall stacks that released the gaseous emissions high in the air. This lessened high concentrations of pollutants at the ground level near the stack but resulted in transport of the problem to regions downwind, It is now clear that this method to control emissions was shortsighted. Because of political, technical, and economic reasons, little was done about reducing acid-deposition precursors until passage of the 1990 Clean ‘Air Act Amendments. A section of this law (called Title IV) finally attempted to significantly reduce emissions of acid-rain precursors (especially SO; emi #0, on hy éepton Figure 1-3. Simplified schematic that demonstrates how sulfur and nitrogen oxide ‘emissions may be transported to terrestrial or aquatic ecosystems.© Chapter 1 Student Preface: Why Do I Need Fundamentals? sions). This caused individuals to incorporate other solutions to the problems such as substittition of lower sulfur-content fossil fuels (some coal contains 1-5% sulfur), removal of sulfur from fuels prior to combustion, reduction in demand for electricity and gasoline through energy conservation methods, and treatment Of stack gases through removal of SO; and NO,. Ifyou were an engineer or scientist, how would you solve the following aspects of the acid-rain problem? You might be developing a national poliey to deal with the problem, or an employee at a coal-fired power plant attempting to reduce its emissions in order to meet new air regulations. Fundamentals ef Environmental Engineering provides a reader some tools required to answer questions such as 1. How do I design, construct, and operate a physical, chemizal, or biological ‘treatment method to scrub SO, and NO, from stack gas’? 2. If I scrub acid-rain precursors from the stack gas, do I create a water- pollution or sol lowaste problem which I will then have to treat as well? ‘3. What is the atmospheric chemistry of acid-rain production, and how fast do the reactions take place? 4. How are air emissions mixed and transported downwind, and do such pro- ‘cesses influence air quality on a foval of regional scale? 5. What is the effect, if any, of acid deposition on a particular forest, ake, or tural area provided that Ihave some knowledge about the underlying geology, chemistry of a watershed or lake, and biotic community? 6. How does the design and implementation of a loc tation system influence air quality on the local o al or regional transpor- regional scale? SITUATION 3 FATE OF CHLORINATED ALIPHATIC HYDROCARBONS IN SOIL, AND GROUNDWATER ‘The U.S, chemical industry manufactures approxi inated aliphatic hydrocarbons annually. A. chlori chain hydrocarbon consisting of hydrogen and carb for some of the hydrogens. These chemicals are used as degreasing agents for metal parts and inthe production of electronic parts, including the microchips in ‘our computers. They are also used for dissolving rubber, extracting other chem. icals (eg. coffee production) dry cleaning, as intermediates in manufacturing ‘other chemicals, and are also found in many household products, ircluding paints, paint removers, and spill cleanup agents. Table 1-1 lists the 20 most abundant organic constituents reported in groun Water at solid and hazardous waste disposal sites in the United States along with their common use and chemical formulae. Of these 20 chemicals, all but 7 are chlorinated aliphatic hydrocarbons. Some of the others include benzene, toluene, and ethylbenzene, which are components of fuel products like gasoline, diesel ately 20 million tons of chlo- inated aliphatic is a straight on with chlorines substituted, ‘Table 1-1. Twenty Most Abundant Organic Constituents Identified in Groundwater at 479 U.S. Waste Disposal Sites ‘Chemical Formula Use Chemical Rank Se pees ee ccczoud BSSSSSSSESRS 2 3 BGP e 284s eeae ig 2a2e Fokeee 2ate eevitea 2bde apbeuee rele are Bos 3: BSgLEEE ZERE Bugis Pele anny ud BEtSGER ZBae Sgisaas fs he eetseee bese Ee2E25 2 § LE Sadeghi pebie Epreesae gees EASGSEZSSESS ae eedl fR2 3 2822 632 ¢ fad deh as ie $225 32) 2227 e885 38 8 BESESSSIESBE 1 2 3 4 5 6 1 8 9 10 u 2 GHLOH Phenol 3 4 15 16 0 GH ca, Used in chemical synthesis Refrigera Chlorobenzene Vinyl chloride ‘used in plastics industry ca, Dry clesning, metal degreasing, velerinary medicine Used in vacuum pumps Carbon tetrachloride CuH.0, CoH Bis(2-ethythexy!) phthalate Naphthalene GCkHs Gals Used in manufacturing mothballs and motor fuel, component of coal tar Solvent 1\12-Trichloroethane Chioroethane 18 19 20 ‘Raspted from Barbee, 1994, Refrigerant, solvent, used to produce tetraethyl lead ‘Moe information on uses and chemical properties can be found in Verechueren (1996) and Merck and Co, oe (1989).Chapter 2 Units of Concentration James R. Mihelcic Richard E. Honrath, Jr. ‘Noel R. Urban In this chapter a reader will become familar withthe different units sed to ‘mieaauire pollutant levels in aqueous (.e., wates), soilediment, and atmo: spheric systems. In addition, the last section in the chapter will familiarize the reader with typical magnitudes and units of concentrations that are encountered in various engineered and natural systems. x ‘Chemical concentration is one of the most important determinants in almost all aspects of chemical fate, transport, and treatment in both environmental and ‘engincered systems. This is because concentration is the driving force that con- trols the movement of chemicals within and between different environmental media, as well as the rate of many chemical reactions. In addition, the severity of adverse effects, such as toxicity and bioconcentration, are often determined by concentration. Concentrations of chemicals are routinely expressed in a variety of units. The choice of units to use in a given situation depends on the chemical, where itis located (e.., ait, water, or soil/sediments), and often on how the measurement will be used. It is therefore necessary to become familiar with the units used and ‘methods for converting between different sets of units. Representation of con- ‘centration usually falls into one of the categories listed in Table 2-1. Important prefixes to know include pico (10, abbreviated as p), nano (10%, abbreviated as n), micro (abbreviated as u, 10~*), milli (m, 10~), and kilo (k, 10°?) 2. MASS CONCENTRATION UNITS Concentration units based on chemical mass include mass chemical/total mass and ‘mass chemical/total volume, Examples of these are shown below. In these descrip- tions, mis used to represent the mass of the chemical referred to as chemical i n12 Chapter 2 Units of Concentration Table 2-1. Common Units of Concentration Used in Environmental Measurements ean ‘Typical Units Representation Example (Defined Below) Mass chemicaltotal mass ‘mgkg in soil ‘mg/kg, pp Mass chemicaltotal volume pinata oraie gn Phe Volume chemicaltotal volune vole fection in sir py Moles chemicattotal ome moles in water Mu ————— 2.1.1 Mass/Mass Units ‘Mass/mass concentrations are commonly expressed as parts per milion, 8 a arts per nillion, parts per billion, parts per trilion, and so on. For example, 1 mg ofa solute placed in 1 ke of solvent equals 1 ppm. Parts per million by mass (referred to as ppm or ppm,) is defined as the number of units of mass of chemical per million units of total ‘mass. That i PPMa = 8 of fin 10° g total opp This definition is equivalent to the following general formula, which is used to calculate ppm, concentration from measurements of chemical mass in a sample Of total Mass Mra 22) Note that the factor 10° in Equation 2-2 is really a conversion factor. It has the implicit units of ppma/mass fraction (mass fraction = my/m,) as shown in Equation 23: my PPM My = MA x 196 —_PPMn__ Pe Yass fraction tae In Equation 2-3, m,/tsq1 is defined as the mass fraction, and the conversion factor of 10*is similar to the conversion factor of 10° that is used to convert fractions to percentages. For example, the expression 025 = 25% ean be thought of as 0125 = 0.25 X 100% = 25% 4) ‘Similar definitions are used for the units ppb, ppt, and % by mass, That is, 1 pb, equal 1 part per billion or 1g chemical per billion (10°) g total, so thatthe number of ppb,, in a sample is equal to m,/myoxa) X 10°. And 1 Ppt. usually means 1 part per trillion. However, be cautious about interpreting ppt values because 21 Mass Concentration Units 13 they may refer to either parts per thousand or parts per trillion (10). Mass/mass concentrations can also be reported with the units explicitly shown (e, ma/ke, ng/kg). In soils and sediments, 1 ppm, equals 1 mg of pollutant per kg of solid (mg/kg) and 1 ppb, equals 1 jg/kg, Percent by mass is analogously equal to the number of g pollutant per 100 g total. ‘A one-kg sample of soil is analyzed for the chemical solvent trichloroethylene (TCE), The analysis indicates that the sample contains 5.0 mg of TCE. What is the TCE concentration in ppmy and ppb,? SOLUTION Simg TCE _ 0.005 g TCE (ICE = To kg 10" g soil eons BTCE 2 106 = 5 ppttig, = 5,000 ppb gol Note that in soil and sediments, mg/kg equals ppm, and pgikg equals pPbye 2.12 Mass/Volume Units: mg/L and xg/m? In the atmosphere it is common to use concentration units of mass/volume ait such as mg/m’ and g/m’. In water, massivolume concentration units of mg/L and pg/L are common. In most aqueous systems, ppg is equivalent to mg/L. ‘This is because the density of pure water is approximately 1,000 g/L. This is demonstrated in Example 22. The density of pure water is actually 1,000 g/L at SC. At 20°C the density has decreased slightly to 9982 g/L. In addition, this ‘equality is strictly true only for “dilute” solutions, in which any dissolved material does not contribute significantly to the mass of the water, and the total density remains approximately 1,000 g/L. Most wastewaters and natural waters can be considered dilute, except perhaps seawaters and brines. One liter of water is analyzed and found to contain 5.0 mg TCE. What is the ‘TCE concentration in mg/L and ppm.,? SOLUTION 50 mg TCE role 1.0L H,014 Chapter 2 Units of Concentration To convert to, ppitg, which is a massimass unit, itis nec ne SS unit, it is necessary to convert the volume of water to mass of water, by dividing by the density of water, approximately 1,000 g/L: ee = 50mg TCE, 1.0L H,0 [rcp] = SO me TCE, LOL HO (tcE] 1.0L H,0 ~ 1,000 gH,0 50 mgTCE 50x 10s TCE 1 To Ae TCE. 10" ppm _ 000 g total 2 total ‘ass fraction = 50 ppm | See that in most aqueous stems that are due, mg/l. is eguivten Aso, in tis problem the TCE concentration is wel above ie aeano drinking water standard for TCE of g(r 3 ppb) which was er eco human health, Five ppb is small value Thnk of if one teams he Rene human population 3 iio peopl, ths means that 2ndivduas sieges of your eases constitute aman concentration of pp CONCENTRATION IN AIR: ‘What is the carbon monoxide (CO) concentration expressed in fm? of ‘gas mixture that contains 10-* mole of CO? ° ee SOLUTION denne eat 16 (atomic weight of O). : : ec [co] « 12X10" mole CO, 28 g CO TO Ctotal — * mole CO X10 ECO, Whug 10 _ 2.800 ug TWLtoal ge ee 2.2 VOLUME/VOLUME AND MOLE/MOLE UNITS Unis of volume faction or mole action ae fe tre frequent sed fr gas concentra: Sons. The mst commen volume fraction units ae pom (owe Sr een volume) (refered oa pom or pms) hich dete ne y, ppmy = > x 108 ese 2.2 Volume/Volume and Mole/Mole Units 15 In Equation 2-5, Vi/Viga i the volume fraction and the factor 106is a conversion factor, with units of 10° ppmy/(volume fraction). ‘Other common units for gaseous pollutants are ppby (parts per 10° by volume). ‘The advantage of volume/volume units is that gaseous concentrations reported in these units do not change as a gas is compressed or expanded. Atmospheric concentrations expressed as mass/volume (¢.., ug/m?) decrease as the gas ex- pands, since the pollutant mass remains constant but the volume increases. Both mmass/volume units, such as wg/m?, and ppm units are frequently used to express gaseous concentrations (see Equation 2-9 for conversion between jghm’ and pom) 2.21 Using the Ideal Gas Law to Convert ppmy to xg/m? “The Ideal Gas Law can be used to convert gaseous concentrations between mass/ volume and volume/volume. The Ideal Gas Law states that pressure (P) times volume occupied (V) equals the number of moles (n) times the gas constant (R) times the absolute temperature (T) in degrees Kelvin or Rankine. This is written in the familiar form of PV = nRT 2-6 Here R, the universal gas constant, may be expressed in many different sets of units. Some of the most common values are displayed below: (0.08205 L-atm/mole-K 8.205 x 10° m-atm/mole-K 82.05 cm?-atm/mole-K 1.99 x 10"? keal/mole-K 8314 J/mole-K 1.987 cal/mole-K 62,358 cm?-torr/mole-K 62,358 cm’-mmHg/mole-K [Because the gas constant may be expressed in a number of different units, always be careful ofits units and cancel them out to ensure the use of the correct value of ‘The Ideal Gas Law states that the volume occupied by a given number of molecules of any gas is the same, no matter what the molecular weight or composition of the gas, as long as the pressure and temperature are constant. The deal Gas Law can be rearranged to show that the volume occupied by n moles of gas is equal to vent en At standard conditions (P ~ 1 atm, T = 27315 K), one mole of any pure gas will occupy # volume of 224 L. This result ean be derived by using the corre-16 Chapter 2 Units of Concentration ‘sponding value of R (0.08205 L-atm/mole-K) and the form of the Ideal Gas Law provided in Equation 2-7. At other temperatures and pressures, this volume var ies as determined by Equation 2-7. Ags mntre contains 001 mole of suur oxide 60.) and 0999 mole of i ‘Whats the SO, concentration expresed in unis of pag? SOLUTION ‘The concentration in ppmy is determined using Equation 2-5. Vso, Vocus [s0,] = = x 10° ‘To solve, convert the number of moles of SO, to volume using tl of $0; to volume using the Ideal Gas Law (Equation 2-6) and the otal number of moles to volume Then dive the ‘0 expressions Vso, = 0.001 mole SO, x a 1 = (999+ 001) te oat EE RT = (1.000) mote total x 87 (1.000) total x 5 Substitute these volume terms for ppmy, to obtain Rr 0.001 mote so, x 27 ole > x 10° 1.000 mote totat x RE P 0.001 L SO. 1.000 L total ———————————— ee x 10% = 000 ppmy. __ Note that in Example 24, the terms (RTP) cancel out This demonstrates an important point that wseful in calculating volume faction er mole ecto concentrations. For gases volume ratios and mote ratios are equivalent, That clear from the Ideal Gas Law, because at constant temperaireond pressure the 22. Volume/Volume and Mole/Mole Units 17 ‘yolume occupied by a gas is proportional to the number of moles. Therefore, Equation 2-5 is equivalent to Equation 2-8 moles i oles al * 1 2-8)R Ppmy = See that the solution to Example 2.4 could have simply been found by using. Equation 2-8 and determining the mole ratio. Therefore, in any given problem, cither units of volume or units of moles can be used to calculate ppmy. ‘Being aware of this fact will save unnecessary conversions between moles and ‘volume, The mole ratio (moles moles total) is sometimes referred to as the mole fraction, X. ‘Example 2.5 and Equation 2-9 show how to use the Ideal Gas Law to convert concentrations between jug/m? and ppmy. “The concentration of SO, is measured int air tw be 100 ppby. What is this concentration in units of wgim*? Assume the temperature is 28°C and pressure is 1 atm, Remember that T(K) is equal to TC) plus 273.15. SOLUTION To accomplish this conversion, use the Ideal Gas Law to convert the volume of 0; to moles of $O., resulting in units of moles/L. This can be converted to ‘sim? using the molecular weight of SO, (MW = 64). This method will be used {o develop a general formula for converting between ppmy and ym. First, use the definition of ppby to obtain a volume ratio for SO3: 100 m* SO; 10" a air solution 100 ppby Now convert the volume of $0: in the numerator to units of mass. This is done in two steps. First, convert the volume to a number of moles, using a rearranged format of the Ideal Gas Law (Equation 2-6) (n/V = PIRT) and the given temperature and pressure: 100mSO, 10? m air solution * RT 100 m? SO, atm ~ 10m air solution “ ‘m? atm’ aan 1-(2228) 09 mole 4.05 x 10% mole SO; im air18 Chapter 2 Units of Concentration In the second step, convert the moles of SO; to mass of SO; using the molecular weight of SO,. 405 x 10° mole $0» ,- 64 g 805, 10° ug _ 260 pg air mole SO," gm ee Example 2.5 demonstrates that a useful conversion for converting air concentra: tions between units of ug/nt’ and ppmty can be written as 1,000 P Ppmy x MW x HOP? oop Where MW is the chemical species molecular weight; R equals 0.08205 L-atm/ mole-K; T's the temperature in degrees K; and the 1,000 is a conversion {acer (1,000 L = mm). Note that for 0°C, RT has a value of 224 L-aim/mole, while ot 20°C RT has a value of 24.2 L-arm/mole. 23 PARTIAL-PRESSURE UNITS In the atmosphere, concentrations of chemicals in the gas and particulate phases may be determined separately. A substance will exist in the gas phase if the ‘atmospheric temperature is above the substance’s boiling (or sublimation) point oF if its concentration is below the saturated vapor pressure of the chemical at specified temperature (vapor pressure is defined in Section 3.4.1), The major and minor gaseous constituents of the atmosphere all have boiling points well below ‘atmospheric temperatures. Concentrations of these species typically are ex. pressed either as volume fractions (e..,%, ppmy, oF ppby) or as partial presgurce (units of atmospheres, atm). Table 2-2 summarizes the concentrations of the most abundant atmospheric gaseous constituents. ‘The total pressure exerted by a gas mixture may be considered as the sum of the partial pressures exerted by each component of the mixture. The partial pressure of each component is equal to the pressure that would be exerted if all of the other components ofthe mixture were suddenly removed, Partial pressure commonly written as P, where i refers to the particular gas being considered For example, the partial pressure of oxygen in the atmosphere Po, is 0.21 atm. Remember that the Ideal Gas Law states that, at a given temperature and ‘volume, pressure is directly proportional to the number of moles of gas present; therefore, pressure fractions are identical to mole fractions (and volume frac. tions). For this reason, partial pressure can be calculated as the product of the ‘mole or volume fraction and the total pressure. For example, PB volume fraction, or mole fraction, x P, = [ppmy), x 10-* x Pra) wnt) 210) 23° Partial Pressure Units 19 ‘Table 2-2. Composition of the Atmosphere* Contain Cnc conpont___(esanoramis) gm) Sonne me room ott om 33 wre Ga coy ts > ‘Neon (Ne) 0.0018 : tun some 7 tne ey oom Xenon) ota ue hyo ota bin i de C40) ona tai ‘Ozone (0) 0.000002 Data from Graedel and Crutzen, 1953, ‘Values represent concentrations in dry ar at remote locations. In addition, rearranging Equation 2-10 shows that ppmy values can be calcu- Jated from partial pressures as follows: ppmy = ~~ x 10° 1k i ypes that cn be wed spr pesur an be ded othe ist ot wt pes ttt Tha eer volume (Eun 2), moe (Eton 28, tal eee (Equation 1) ean be ei my cleat i iphenys (PCBS) inthe ai J concentration of gas-phase polyeoisted biphen si thove ate Superior naman be 0 pograne prea ntr(). At the para res (an) of BS? Asse the mere BO, the atmosphere pressure sm, andthe average molecular weight of PCBS m5, soLuTION a ‘Techni srsture PCs lng home tana poi re? 1. The paral pressure defined asthe mol ot Volume the ttl ga pres it nd the numer of moles of PCBs in ter of ‘hen ue the Teal Gas Lav (Equation 2 fo calla that one mole of as at20 Chapter 2 Units of Concentration ee ke x X= chlorine or hydrogen Fare 21. Chemica Struct of Polychlorinated Biphenys (PCBS). PCBs area aeompounds produced commercial by ehloriaing biphenyl Che eas ee plsed at any oral ten avaiable se, wth 29 poe PCH congas ee stability of PCBs caused them to have a wide range of uses, including serving ag Coolants n transformer and sx hyraliuide and solvents Hower th seat ‘Properties that resulted in this stability also resulted in a chemical that did not de; ide casily, bioaccumulated in the food chain, and was also hazardous to Lumans and m= wii, Assoringy in 976 Congres pasted the Tox Sulmances Gated (TSCA) tat banned the mansactureof PCBs and PCBconsinng eee SCA so extalised sti reuitins regarding the ftuc ase and ale o Rebs PCBs ae ‘typically sold as mixtures that are commonly referred to as Arochlors. For example the ‘Aochior 126) mint consis of 0% clone by meg, which meantne aa ‘tisin he mature repay sisted wih 63 eons ye ai Im contrat Aroclor 142 const of 42% chlorine by weighs, of Pets with 1-0 substituted clones per biphenyl molec it primarily consists (°C and 1 atm occupies 22.4 L and substitute thi to determine the mole fraction of PCBs: value into the frst expression PE mole ag By gam 0 i air © 325g pe re as x 1097 BLEPCB ye 224 L mole PCB c mole ai mole air Multiplying the mole fraction by the total pressure (1 atm) (see Equation 2-1 fies the PCB put rewure £34210 army, Oe Paton 2-10) What would be he pra prsre (tm) oferbon dioxide (CO) barometer reads 290 nce of He the tle ham SOS ope he ne Perature is 10°F? Use Table 22 to obtain the concentration of COs in dry air, SOLUTION ‘Te part presut concentration isin Table 2. re or dy ai are for dey irs the part reste mus fit be cored fr the mokture presenti thea te Sena 24 Mole/Volume Units 21 CO; concentration is 350 ppmy. The partial pressure will be this volume fraction times the total pressure of dry air. The total pressure of dry air is the total at- rmospheric pressure (29.0 in Hg) minus the contribution of water vapor. The vapor pressure of water can be looked up at 70°F to be 0.36 Ibfin?. Thus the total pressure of dry air is Hg ‘ep peso CO, wuld te 10° volfrae pry x [rsa inte x 8] Vol fraction * P, 29.9 inFlg, 350 ppmy * 33 x 10~* atm 24 MOLE/VOLUME UNITS Units of moles per liter (molarity, M) are often used to report concentrations of compounds dissolved in water. Molarty is defined as the number of moles of compound per liter of solution. Thus a 10™ M solution of copper contains 10-* roles of copper per liter of solution. Concentrations expressed in these units are read 28 molar. Thus, the copper solution would be described as being 10~* molar. ‘Molarity, M, should not be confused with molality, m. Molaity is usualy used in equilibrium calculations and throughout the remainder of this book. Molality is the number of moles of a solute added to exactly one liter of solvent. Thus, the actual volume of a molal solution is slightly larger than one liter. Molality is ‘more likely tobe used when properties ofthe solvent, suchas boiling and freezing Point, are a concern. Therefore, itis rarely used in environmental situations. Convert the concentration of trichloroethene (TCE) (5 ppm) to units of molarity. ‘The molecular weight of TCE is 131.5 g/mole. SOLUTION Remember, in water, ppg is equivalent to mg/L, so the concentration of TCE is 5.0 mg/L. Conversion to molarity units requires only the molecular weight: mgTCE , 1g , Lmole _ 38 X 10 moles L “i@mg * ise Gi an 5044 \aupter z Units of Concentration Often, concentrations below 1 M are expressed in units of milimoles per liter, or millimolar (1 mM = 10°? moles/L) or micromoles per liter or miomnet (7 aM ~ 10°* moles/L). Thus, the concentration of TCE could be expresses ae 0.038 mM or 38 1M, ‘The concentration of alachlor, a common herbicide, in the Mississippi River as found to range from 0.04 to 0.1 ug/L. What is the concentration range in mole? The molecular formula for alachlor is C,,H0;NCI (MW ~ 270), SOLUTION ‘The lowest concentration range in nmole/L, can be found as follows: 0.04 pg a ole 10% g 10” nmole _ 0.15 nmol rm ‘mole L Similarly, the upper limit (0.1 ug/L.) can be calculated to be 0.37 nmoV/L. Hence ‘the concentration range of alachlor is 0.15-0.37 nmol/L, ——— 2.5 OTHER TYPES OF UNITS ‘Sometimes concentrations are expressed as “normality,” as a “common constit- nent,” or represented by “effect.” The following three sections describe thees ‘methods to express concentration in further detail 2.5.1 Normality Normality (equivalens/L) is typically used in defining the chemistry of water, Rbecially in instances where acid/base and oxidatiowreduction reactions are tsk in place. Its also used in determining the accuracy of a water analysis, as dem, Gastated in Example 2.12, and in calculating dosages of chemicals during some Pater treatment processes (e.g, softening hard water). Normality is alse need ‘the analytical measurement of water constit- {onts. For example, “Standard Methods for the Examination of Water sud Syastewater” (American Public Health Association (APHA), 1992) has many Sramples where concentrations of chemical reagents are prepared and reported in units of normality and not molarity, Reporting concentration on an equivalent bass is useful because if two chem ‘cal speces react and the two specie reacting have the same strength on an equ. 25. Other Types of Units 23 « Lamb volume of reactant number 1 wil act wih amt. volume Sfraetant umber Tacitus chemisy the mmber of equteatspormele Of acd equal the numberof mole of the eid can potently Som For ample HCI has | equvalenvmol, 180, has? equiatentslnole, and HPO, fas 3equivalentsnole. Likewise, the number of equivalents per mole of «base ethan ire wine ole oe Tay NOH has 1 equivalenvmole, CaCO; has 2 equivalets/mele, and POX” ha alent “Sp otntnroctin eco he nme of es hed ew my cts spe doa aso Fr vane tember of alents of Na* is 1 (where e~ equals an electron) Because: Na —> Na* +e”. Likewise, the number of equivalents for Ca®* is2 pay oS = a equivalent weight (units = gleqy) of a species is defined as the molecular, Weight of he species dded by he number of equtelens inte pets (mole! Toole gly) of HCI, H,SO,, NaOH, CaCOs, and aqueous CO;? ‘What isthe equivalent wei SOLUTION ‘The equivalent weight is found by dividing the molecular weight by the number of equivalents. 143558, leq _ 3658 cay WE OF HCL = le mole ~ eqy Qx1)+32+ (4X16) g , Zeqv _ 49g eqy wt of H,SO, = ‘mole mmole ~ eqv B+W+ig, leq _ 40 eqy wt of NaOH = B= 1S E18 a mole” mole ~ eqv 40+ 12+ G16), 2eqv_ 50g cay wot Caco, = Oe ee mining the equivalent weight of aqutous CO, requires abit of thinking tnd some ew information, Aeouseafon die i ot an ald unl ithe Grates in water and forms carbonic ai (CO, + H0 ~» HCO.) So aqueos COs really has 2 equmole. Thus on can se that the equivalent weight of aque ous xrbon donde 24+ @XIO 8, Dew 2p mole mole ~ eqv44 Chapter 2 Units of Concentration SOLUTION IM Hct = Lm HCI, eq _ 1 eqy L mole L N Lmole HaS0, 2 1M H,S0, = LMOle HeS0. , 2 eqy _ 2 eqy_ L mole ~~ 2N ‘Note that on an equivalent basis, a I-M soluti i i ew tn an evn bass lution of sulfuric acid is twice as strong Ee ete ya apni oe the titration, the equivalent weight of liter of water. Oxyge’s equivalent weighs ne lecular weight of O; (32 p/mote) by 4 equimole. is that the sum of all cati or et ir is following example shows how this is done, The label o1 bottle: 7 d Be neutrality. Another way to state this ofthe mineral Water resulted in the lowing cat inthe folowing cation and eons beng esd wih corresponding concentrations (a mg/L ee [Ca**] = 29; Iso? [Mg?*] = 20; =47 [Fr] (Na) = 115; 0.09; IK*] = 33; [oj =77 Is the analysis correct? 25. Other Types of Units 25 SOLUTION First convert all concentrations of major ions to an equivalent basis. Ths is done by first multiplying the concentration in mgyL by a unit conversion (g/,000 mg) tad then dividing by the equivalent weight of each substance (fig/eqv). The con- entrations of all cations and anions are then summed up on an equivalent basis. ‘A solution with less than 5% error is generally considered acceptable. Cations Anions 195 10° ew [sor] = 25% 7 cq 167 x a eq pr SB ew S210" cay ory = LAI ew pry = SAO oe ‘The total amount of cations equals 9:87 x 10~* eqviL, and the total amount of anions equals 3.2 x 10~* equ/L. ‘The analysis is not within 5%. The analysis resulted in over 3 times more cations than anions on an equivalent basis. Therefore, it can be concluded that either (a) one or more of the reported concentrations are incorrect (assuming all ‘major cations and anions are accounted for), or (b) one or more important anions \were not accounted for by the chemical analysis (c.., bicarbonate, HCOs, would bbe a good guess for the missing anion, as itis a common anion in most natural waters). 2.5.2 Concentration as a Common Constituent Concentrations can be reported as a common constituent, and can therefore include contributions from a number of different chemical compounds. Nitrogen ‘and phosphorus are chemicals that have their concentration typically reported as a common constituent, For example, the phosphorus in a lake or wastewater may be present in inorganic forms called orthophosphates (ie., HsPO., HPO; HPO#-, PO}- and PO}~ and HPO;? complexes), polyphosphates (c.g, HaP;O>, H,P,035), metaphosphates (¢.g., HP,O3~), and/or organic phosphates. Because phosphorus can be chemically converted between these forms and can thus be found in several of these forms, it makes sense at some times to report the total P concentration, without specifying which form(s) are present. Thus each concentration for every individual form of phosphorus is converted to mg PIL using26 Chapter 2 Units of Concentration the MW of the individual species, the MW of P (32), and simple stoichiometry ‘These converted concentrations of each individual species can then be added to determine the total phosphorus concentration. The concentration is then reported in units of mg/L. as phosphorus (written as mg P/L, mg/L as P, or mail P), Nitrogen can also exist in many different chemical forms in aqueous systems. ‘These forms include ammonia (NH and NH), nitrate (NOs), nitrite (NOs), and organic nitrogen (e.g, amino acid like alanine (CH,CHNH;COOH) or gly. cine (H,NCH;COOH), amines, tc.). To express the concentration of total nitrogen (all forms of nitrogen combined), the concentration of each individual species Of nitrogen is converted to mg N/L (MW = 14), as is done in Example 2.13. Thus the concentration could be reported as mg NO5/L or mg NO;-NiL (mg of NO} as nitrogen/L), ‘A water contains two nitrogen species. The concentration of NH is 30 mg/L. NH, and the concentration of NO is 5 mg/L NO3. What is the total nitrogen con centration in units of mg N/L? SOLUTION Use the appropriate molecular weight and stoichiometry to convert each indi vidual species to the requested units of mg N/L, then add the contribution of each species. 30mg NH, , mole NH, mole N 14g _ 24.7 mg NHN L 17g ™ mole NH, * mole N L SmgNOF ,, mole NOS, _moleN 14g L @g “mole NOs ™ mole N ‘Total nitrogen concentration = 24.7 + 1.1 = ‘The “alkalinity” and “hardness” of a water are typically reported by deter- ‘mining al of the individual species that contribute to either alkalinity or hardness, then converting each of these species to units of mg CaCOy/L, and finally sum, ring up the contribution of each species. Thus, hardness is normally expressed as mg/L as CaCO. ‘The hardness of a water is caused by the presence of divalent cations in water. Ca?" and Mg?” are by far the most abundant divalent cations in natural waters, ‘though Fe", Mn**, and Sr?* may contribute as well. These cations are released 25. Other Types of Units 27 ‘Table 2-3. Scale to Quantify the Hardness of Water Hardness (3s mg/l. CCOs) Hardness Evaluation =50 Solt 50-150 ‘Moderately hard 151-300 Hard >300 Very hard From Hammer and Harmer, 1996, from the dissolution of minerals. For example, calcium carbonate can react with the natural acidity found in rain water to release hardness (shown as Ca**) and alkalinity (here in the form of HCO5) according to the following reaction: CaCO, + HCO, > Ca? + 2HCOs @-12) ‘There is no adverse health effect from drinking hard waters; however, they can hinder soap formation and produce scale in boilers and piping. This increases the cost to society because of increased soap usage and plugging up of boilers and pipes with scale. Furthermore, hard waters can leave a “slimy” feeling on your body after bathing, so they are not aesthetically pleasing to some consumers. ‘The (otal hardness of a water can be found by summing the contributions of all divalent cations after convertiag their concentrations to a common constituent. Then the resulting value can be compared to the scale shown in Table 2-3 to evaluate the hardness of the water. In Michigan, Wisconsin, and Minnesota untreated waters usually have a hardness of 121-180 mg/L as CaCOs, In Tinois and fowa water is harder with many values greater than 180 mg/L as CaCO. ‘The conversion of concentration of specific cations (from mg/L) to hardness (as mg/L CaCO) ean be accomplished by the following expression, where M?* represents a divalent cation. Me inmg ,__0___™8.caco, @ay L “ eqvwtofM™ ingleqy ~ L 8 ae ‘The origin of the 5 Equation 2-13 comes from the fact that the equivalent ‘weight of calcium carbonate is 50 (100 grams CaCO? equivalents). The equivalent weights (in units of gleqy) of the following divalent cations are Mg = 24/2; Ca, 40/2; Mn, 55/2; Fe, 56/2; Sr, 88/2. Water has the following chemical composition. [Ca**] = 15 mg/L; [Mg*] = 10 mg/L; (SO%-] = 30 mg/L. What is the total hardness in units of mg/L as CaCO,?SOLUTION {ind the contribution of hardness from each diva valent cations are not included in the calcula 15 mg Ca?* eee eee “wes © tilts OF Concentration (50 g CaCO, eo Peay /50 g CaCO, 24g Mee 2eqv Ss modertely hard Also note at fect EPesnt hey would be indent hegre alter removing all particle larger than 2.5 jms refers to particles less than 2.5 jum in size In aquatic systems and in the analytical de phase is distinguished by filtration using a fit \wpically determines the cutoff between the “deaheae phases. Therefore, in analytical chemistry, the ‘Separate metals into a “dissolved” and ‘part Inthe areas of drinking water, divided into a "aisolved” on ton of eatin and evapora can be futher broken down into shows the analytical difference between total solids ion, 38 mg [ot as Caco, 2 mg “Eas Caco, mination of metas, the sola opening of. um Th ee acd “partclte® 45 um cit can be late” phase, ae wastewater, and land eachat, soli f ate, soi ares pended” fraction. This done ty nana Procedures. Each of the ' two types of solids a “Axed” and “volatile” fracion. Figure 2.2 dissolved solids, and volatile and volatile suspended solids Total solids (TS) are determined by placing known volume in a drying dish at ind evaporatin ‘otal suspended solids, total a wellmized vater sample of the water at 103-105" The lent cation, Anions and all non. mg/L as CaCO;, Note this water iron (Fe™) or manganese (Mn?) 25. Other Types of Units 29 ricesmlein sa) wtsin ot atc aL ee ‘ier a te dig, emp wth ct acer fe Forme and ms tenet S30C on > Pree statein a> wisinat rece any ote noi ae mt Figure 2-2. The analytical difference between total solids (TS), total suspended solids (TSS), volatile suspended solids (VSS), and total dissolved solids (TDS). increase in the weight of the drying dish is due to the total solids. Total solids can thus be determined by dividing the increase in weight gain of the drying dish by the sample volume. Concentrations are typically reported in mg/L, ‘Total dissolved solids (TDS) and total suspended solids (TSS) are determined by first filtering a well-mixed samplé of known volume through a glass-fiber filter (Z-yu size opening). The suspended solids are the particles caught on the filter. ‘The concentration of TSS can be determined by drying the filter at 103-105°C, determining the weight increase in the filter, and then dividing this weight gain by the sample volume (results in mg/L). Suspended solids (collected on the filter) may adversely impact aquatic ecosystems by impairing light penetration or act as a source of nutrients or oxygen-depleting organic matter. Also, a water high in suspended solids may be unsuited for human consumption or swimming. The ‘TDS are determined by collecting the sample that passes through the filter, drying this filtrate at 180°C, and then determining the weight gain of the drying dish. This weight gain divided by the sample volume is the concentration of TDS (results in mg/L). Dissolved solids may adversely affect the taste of a water and ccan also lead to scale formation. This is because dissolved solids tend to be less organic in composition and consist of dissolved cations and anions. For example, ‘one would expect that hard waters would also be high in dissolved solids. TS, TDS, and TSS can be further broken down into a “fixed” and ‘‘volatile” fraction. For example, the volatile portion of the TSS is termed the volatile suspended solids (VSS) and the fixed portion is termed the fixed suspended solids (ESS). Determining the volatile fraction of a sample is done by taking each sample just discussed and igniting it in a furnace at 500°C (50°C). The weight loss {due to this high-temperature ignition provides the volatile fraction, and the fixed fraction is what sample remains after ignition. Figure 2-3 shows how to relate the various solid determinations used in water treatment, wastewater, and leachate situations, In wastewater treatment plants, the volatile fraction is a good approx-30 Chapter 2 Units of Concentration Ts =| tps | + | 1ss Tvs = | vps| + | vss + + Fps | + | Fss Figure 23. Matrix showing how the various measurements of solids in aqueous samples cat be reltd: For example, the T98 and VSS ae meme he determined by difference. Sa HESS cn be TFs imation ofthe organi mater content of the solid, Thus, determina ’ : . Thus, determination of vo- atile solids in a biological aeration tank (e.g., 3, el tothe umber of microorganins inthe uni Nt YS) cm Be elated ‘An aic-sampling program sampled 100.00 L of air fo of air for particles. The followin ras of patces were collected for particular size fractions: I2eg tatoos one Part size > 25 um and 6 mg retained with particle size <23an, What ae the i snd toa pended pret (ISP) coment of i a SOLUTION By definition, PM, the concentration of part . Pasi the concentration of particles between 0. and25 mor iin this case the mass of particles retained size < 2.5 um. Therefore, 4 6 my 1/L 10° 0. PMs = 88 Ong _ Ong 100,000 L . ne me mm qsp = 2met Gime, 1L 10° yp _ 180 up 100,000 L my mg m Note that these particulate concentrations are relati tions are relatively high. The sample was ‘most likely collected from an urban area where TSP concentrations range i trations range from A laboratory provides the following analysis obtained from a 50-mL. sample of wastewater. Total solids = 200 mg/L, total suspended solids ‘ i Suspended solids = 40 mg/L, and volatile suspended solids What 120 mg/L. (a) What i 25 Other Types of Units 31 {s the concentration of total dissolved solids of this sample? (b) If this sample was filtered through a slassfiberfiter, then the filer was placed in a muffle Turnace at 550°C overnight, what would be the weight of the solids (in mg) re- ‘maining on the filter after the night in the furnace? (c) Is this water sample turbid, and approximately what percent ofthe solids are composed of organic matter? SOLUTION (a) Refer to Figure 2-3 to see the relationship between the various forms of solids. TDS equals TS ~ TSS; thus, TPSEET LoL (8) The solids remaining on the filter are suspended solids (dissolved solids ‘would pass through the filter). Because the filter was subjected to a temperature of 550°C, the measurement was being made for the volatile and fixed fraction ofthe suspended solids, that is, the VSS and FSS. However, during the ignition phase, the volatile fraction is burned off, while what zemains on the filter is the inert or fixed fraction of the suspended solids. ‘Thus, this problem is requesting the fixed fraction of the suspended solids. Accordingly, the 5O-mL sample had FSS = 40 mg/L. Therefore, ss = 40:8 _ wt of SS remaining on filter after ignition x L ‘mL. sample 50 mL ‘The unknown, x, can be solved for and equals 2 mg. (©) The sample is turbid. This is because the suspended matter, which is measured as TSS, causes the sample to appear turbid. Of course, if one allows the sample to sit for some time period, the suspended solids would settle land the sample might appear to be nonturbid. The solids found in this ‘sample contain at least 60% organic matter. The total solids concentration is 200 mg/L and of this, 120 mg/L are volatile suspended solids. Therefore, because volatile solids consist primarily of organic matter (e.g., organic carbon, nitrogen, phosphorus, etc), itcan be concluded that approximately {60% (120/200) of the solids are organic. 2.54 Representation by Effect In some eases, the actual concentration of a specific substance is not used at all, especially in instances where mixtures of ill-defined chemicals are present (e.g., raw sewage). Instead, the strength of the solution or mixture is defined by some ‘common factor on which all the chemicals within the mixture depend (€.g., ox- yygen depletion from biological and chemical decomposition of the chemicals that ‘make up the raw sewage). Thus, the strength of a wastewater is determined, not94 Unapter 2 Units of Concentration by measuring concentrations of a specific chemical(s), but by some direct effect the sample constituents have, fun method is used a5 a measure of the strength of municipal wastewater inifenileffuent and other wastes. For many organie-bearing wastes, biological ae chemical degradation ofthese wastes results inthe depletion of oxypen row the stream that can result in ish kill ifthe dissolved oxygen concentaayog drops too low. Instead of identifying the hundreds be present, itis more convenient to report tl 2.6 COMMON CONCENTRATIONS ENCOUNTERED IN WASTESTREAMS, SURFACE AND GROUNDWATERS, AND THE ATMOSPHERE. Section isto familiarize the reader with the relative magnitude of concentrations that are typically encountered in the environmental sien, ang Engineering field, as well as the type of units commonly used in air, water 'ese examples, the chemical concentrations are {ery low. That is, the systems are “dilute” even though the chemical concentra, tions may still be of concern to human health and the environment, {Miface and Groundwater, Aqueous-phase (ce. in water) concentrations typically are expressed cither as mass or moles per volume. Concentrations of dissolved chemical species in water range from as low as pa/L. (ps stands fog picograms or 10. g) of contaminants to mg/L of major ions, The natural chery yoeks and minerals, which then release inorganic and organi: chemical spevios ints solution. ‘There are other processes that can influence the chemistry of nat, Ural waters. For example, the chemistry of lakes in New Zealand is related to the lithology of the catchment area, the lake's proximity tothe ea, and toalesey cerce, the origin ofthe lake (ie, was the lake formed by voleaic activity glee! array oy constructed by humans) (Viner, 1987). In second case, the chemistry of lakes situated in the Antarctic is profoundly influenced by the extreme cota and arid conditions of that region. Also lakes in the Adirondack Mountains of New York are influenced by the transport of air pollutants such as aed rafn ‘able 24 summaries the ranges of concentrations for some typical pollutants as well as for some natural constituents of surface waters. Major anions encoun, fered in natural waters include CI", SO3", HCO; , and COR, while major cations include Na", K*, Ca?*, and Mg?*. Minor anions present in natural watorsnclode £ ‘ 2.6 Concentrations in Wastestreams and the Environment 33 ‘Table 2-4. Range of Concentrations Encountered in Natural Waters Gobaunce Ran, Fog Lakes Rivers _Groudeaier Oven TEE ye. Ch He, 25) 001-100 ug 001-10 pal 02-10 ag. 001-100 ng Cree sonnei ar-Soong 001-10 npr. 0001-10 ppt Sls lve) ee -! 1-120 mg/L 800 mg/L et 0.1-20 mg/L 1-120 mg/L Es Os t0mg/l, O2-30meL O1-S0mgrL 35,000" mgrL ral wi ate de H*, Fe**, Fe**, Mn?*, and AP*. Oren ches tat contrite drinking water spies and ex tio effects have drinking water standards or guidelines ranging from 0.0008 wa rat ez! arsenic concentrations in Southern C: lifornia’s | tral anc : i ee eg ae ronhazardous tions of most constituents (e.g., ni- Sco alate mania ne reated municipal sewage may have concentrations of five-day bio es nel SS) alent Saag ee Tea eh a tan Eaten ‘Table 2-5. Arsenic Concentrations in Southern California's Central and West Basin Groundwater Supplies ‘Number of Wel wt Aree For Ranges ndwater Number Wells z ne — Tested <05 mg/L 05-19 wei 2-5 neil Swell ” nia 2 3 8 19 Wer 33 i B 1 ‘Adapted fom Ried, 19942% Cnapter 2 Units of Concentration Table 2-6. Dry Weather Leachate Concentration from the Goff Mountain Landfill, West Virginia Parameter Range (mg/L) Average (mg/L) Chemical oxygen demand (COD) 4500-8310 7,090 ‘Total organie carbon (TOC) 169-2800 1270 ‘Total suspended solids (TSS) 130-189 1160 Volatie suspended solids (VSS) 108-149 120 NH,-N = 296 Po}-P = Below analytical detection Alkalinity (as mg/L. CaCO) = 1420 ‘Adapted from Campbell ta, 1995, reduce levels of BOD,, TSS, and Pby 85 to 95%, Though still mall on a relative Concentration basis, concentrations inthe 1-10-mg/L range ae high for weg other environmental situations, Atmosphere.’ Table 2-2 showed that the concentrations of the major atmo spheric gaseous constituents were quit larg. Infact, the concentration tomveee i the atmosphere is approximately 210,00 ppm. However, the concenee oon of pollutants can be much smaller. Concentations of particulates and of oon pollutants found i the atmosphere ae frequently expressed in unital as eee the atmosphere are usually much lower than concentrations encountered in munigpsl,sereae, find soilsediment systems. Human exposure to air pollutants cane dgtieoc however, as we breathe a large amount of ai approximately 20 m* per di following two paragraphs provide a brief description of typical eoncoareneee pollutants encountered in a wide variety of instances where ais quai fant to humans and the environment. {Concentrations of toa suspended particulate matter inthe atmosphere mey ‘Tange from less than one to several hundred. g/m*. Concentrations of airborne Particles in Mexico City ean average close to 600 jgln? for total ‘suspended of 10 umm or less (these smaller particles are termed PM,) (Villalobos Pictrat ct al, 1995). Pollutant concentrations are only a small fraction of this total. For ratatatals (8s Cu, Hg, Pb, Zn, Ca, et.) a5 well as numerous trace organic Pollutants, concentrations range from 0.001 ng/m® to 10 ng/im? In Canada, ground-level ozone (O:) levels have exceeded 190 ppb in some Populated areas (also in some USS. and European cities), while the acceptable Canadian air-qui avs in some areas, Rural and remote areas in Canada have ozone concentrations thar peak in the 20-30 ppb range (Fuentese and Dann, 1994). Inthe 1960s catoee Tae atide (CO) levels averaged approximately 25-40 ppm in large U's eee ks Washington, Chicago, Denver, and Los Angeles. Fortunately these valine had been reduced to 9-15 ppm by the 1980s, However, one study determined Chapter Chemical Problem Mirex 10 Phenol 1 Chlordane 16 Formaldehyde 19 Toxaphene 3 PAH 2% (Chemical class, which includes.) Naphthalene Anthracene Benzo(a)pyrene Toluene a Chemical Formula ‘Chemical Structure aq a ya CuCl ba 7 aa a on con CY qa a CioHeChy a. Cd. g cH,0 ao os Cols Cute Coote CoH “E488 igure 2-4, Chemical structure of compounds used in chapter problems.36 Chapter 2 Units of Concentration sa a Bema ah Sot pm, tse omcnne ores een ee maldehyde concentrations re eae ee in tao st es ei Gt trae ss Meat Hg ‘averages 0.01 ngim’, which are quite low. : Tec ones ae sca he ra disintegrations per second, a. CHAPTER PROBLEMS ee & particular mediums) to match the given concentration tale ts toe “ori pete Ge eae ae yer eae pal oemran iene SER tet OO om 0 ms mt utes peo oi i) oxygen dissolvedin water; (i trogen oxide in air; (vi) alkalinity 22, A typical loaf of bread contains 120 contains 120 mg of sodium in ezch 1-ounce slice. (a) What is the concentration of sodium in the bread in ppm? (b) Is the ‘answer to part (a) in units of ppm,, or ppmy? Which makes sense and why? Shen ee Cues ai strate 7 Battin ne te ay Sits in pl or te eran cat serge te om nntcae se grasa Tesi a enone eet sa tu dei eo st aon em ett plan to household the residual eoncenteadon chlorine demand in mg/L? fn 020 mall whats the ead Chapter Problems 37 24. A water sample contains 10 mg NO5/L. What is the concentration in (a) ppm, (b) moles/L, (c) mg NO-NIL, and (4) ppb? 25. A liquid sample has a concentration of iron (Fe) of 5.6 mg/L. The density of the liquid is 2,000 gm/L. What is the Fe concentration in ppm? 2.6, Coliform bacteria (e.g., E. coll) are excreted in large numbers in human ‘and animal feces (approximately 50 million coliforms per gram of feces!) ‘Untreated domestic sewage may contain greater than 3 million coliforms per 100 mL. Water that meets a standard of less than one coliform per 100 mL is considered safe for human consumption. Is a one-liter water sample that contains 9 coliforms safe for human consurnption? 2-7, The treated effluent from a domestic wastewater-treatment plant contains ammonia at 9 mg N/L and nitrite at 0.5 mg N/L. Convert these concentrations to mg NHy/L and mg NO3/L. 2-8. A chemist reports that the concentration of nitrite (NOZ) plus nitrate (NO) in a groundwater sample from an agricultural region is 0.850 mM. Nitrite and nitrate are often clevated in groundwater in agricultural regions due to nitrogen fertilization. Regulations require that the total concentration ({NO;] + [NOz]) be below 10.0 mg/L. as N to avoid methemo- slobinemia, or blue-baby syndrome, which can be fatal. (a) What is the concentration of ([NOz] + [NOs } expressed as {mg/L as NJ? (b) What is the concentration expressed as ppm, as N? (c) What is the concentration expressed as % by mass as N? 29, Concentrations of nitrate exceeding 44.3 mg NO3/L are a concern in drinking water due to the infant disease, methemoglobinemia. Nitrate levels can bbe enhanced by improper use of synthetic and natural fertilizers, irigation practices, livestock-handling operations, and industrial-waste handling. Due to the presence/absence of animal wastes, fertilizer application, and ‘groundwater recharge pattems, nitrate concentrations near three rural wells were reported as 0.01 mg NO; N/L, 13 NO¥ NIL, and 20 NO; NIL. Do any of these three wells exceed the 44.3 ppm level?” 210, Mirex (MW = 540) is a fully chlorinated organic pesticide that was manufactured to control fire ants. It was also used as a fire retardant and in pyrotechnics, Due to its structure, Mirex is very unreactive; thus, it persists in the environment. Lake Erie water samples have had Mirex measured as high as 0.002 jg/L and lake trout samples with 0.002 e/g (Journal of Great Lakes Research, 19:145-157, 1993). (a) What is the aqueous concentration of Mirex in units of () ppb, (i) ppt, (ii) umoles/L? (b) What is the concentration of Mirex in fish in (i) ppm, (i) ppb? 2.1L. Chlorophenols impart unpleasant taste and odor to drinking water at concentrations as low as 5 mg/m’. They are formed when the chlorine disin- fection process is applied to phenol-containing waters. What is the59 Lnapter 2 Units of Concentration Unpleasant taste and odor threshold in units of (a) mg/l, (b) ua/L,(e) ppm, (@) ppb? 2-12, The LC is used in determining toxicity to aquatic species, Its the aqueous Concentration of atest chemical that results in 50% mortality in the test species (LC = lethal concentration) during a predetermined time period. The LC measured for fathead minnows, during a 96-h exposure test 151 mgiL. for caffeine (C,HyoN,O:) and’ 44.1 mg/L. for trichloroethene (TCE) (CaCLH). Is the LCs) exceeded if the aqueous concentration of caffeine is 6.2 x 10™* M and TCE is 45 x 10-* M? 2-13. Chloroacetic acids are byproducts of the breakdown of hydrofluorochlo- rocarbons (HFCs), which have been implicated in the depletion of the ozone layer. HFCs are the current replacement products for freons, The concentration of monochloroacetic acid in rain water collected in Zurich, was 7.8 nmoliL. Given that the formula for monochloroacetic. acid is CH,CICOOH, calculate the concentration in g/L, 2-14, In 1981, concentrations of Pb, Cu, and Mn in rainwater collected in Mine neapolis were found o be 9.5, 2.0, and 86 ug/L, respectively. Express these Soncentrations as nmole/L, given that the atomic weights are 207, 63.5, and 55, respectively, 2S. The dissolved oxygen (DO) profile in a biological reactor (i.e, aeration tank) at a domestic wastewater-treatment plant is 0.5 mgiL in the anoxic zone and 8 mg/L near the end of the 108-ft-long tank. What are these two, DO concentrations in units of (a) ppm, (b) moles/L? 216, The average concentration of chlordane, a chlorinated pesticide now banned in the United States, in the atmosphere above the Arctic circle in Norway was found to be 0.6 pg/m? (Ochme et al, 1996). In this measure. ‘ment, approximately 90% of this compound is present in the gas phase, the ‘remainder is adsorbed to particles. For this problem, assume that all of the compound occurs in the gas phase, the humidity is negligibly low. and the average barometric pressure is 1 atm. Calculate the partial pressure. of chlordane. The molecular formula for chlordane is CjgCl,H, The average air temperature through the period of measurement was —5°C. 2-17. What is the concentration in (a) ppm, and (b) percent by volume, of carbon monoxide (CO) that has a concentration of 103 mg/m? The problem con, ditions are temperature = 25°C and pressure =-1 atin, 2-18, Ice resurfacing and edging machines use internal combustion engines that sive off exhaust containing CO and NO,, The Detroit News (March 5, 1995) Feported that average CO concentrations measured in local ice rinks were as high a8 107 ppm and as tow as 36 ppm. How do these concentrations compare to the U.S. outdoor-air-quality 1-h standard of 35 mpi? Aseoe the temperature equals 20°C. 2-19. The concentration of formaldehyde in a mobile home was found to be 07 ppm. Ifthe inside volume of the home is 800 m’, what mass of form, Chapter Problems 39 in unite of gram? Assume T = 256K, ee es eae P= atm. The molecular weight of formaldehyde is 30 i sumer day 0, The concentration of ezoe (0) in Los Angeles on a hot su 2 ae Fe ta) 125 phy, What othe Oy comcntalon in ni of (a) g/m’, and (b) number of moles of O; per 10* moles of air? is ied wi i and 2g of 21. nylon i et Wit nat 1g ivoen a2 ot 2h yon (O-) The pressure in the room is LO alm and the temperature Sees hat fs ongen concentration inte aloo unis of pr ac Jou?) What sth volume othe ballon alr’ Howto, et 2-22. A gas mixture contains 1.5 x 10~* mole CO and has a total of 1 mole. Gilat athe CO socenation in pp? : concentration of 001 pom, . “Clans might have a sulur dioxide (60, concntati 778 tile "polluted alr might have a concentration of 2 ppm. Exposure 10 Soh eves over 1pm may lea fo reahing contin ne wpe osimtny pte Cone thse we consneoonsto ga-Asune 8 temperntr of 28 capacity of our uns 24, Caton nnoxide (CO tes the angen ayn apc four lng 20h Cor campete wih omer fr one of te four esses of Your Hoo’ femoplbis oleae foe CO has about «Ames one fay torte ten han eye, Exe 9 pt CO fr 3 mn as en toon to ina oncs iy ts tmetinterval criminal hs, mo te hevly pled ates maybe mre pone to ardent. Ar moore we aetente kt eden he CO concentrations €5 mpm? Assume iM tbperatre of 98 Tie ane of Miclgan's Depertaea of Eavrounonal Quay “nd that tothe concen sl tha exceed wp ean pose Syst erg nts cin 10° g of toxaphene, what are the toxaphene soil and Michigan action level Sefaratons epee innit of pp?) Does hissample pose test so proundnter is lta? aco a dase of organic chemicals 2.26 Paeytic aromatic hydrocarbons (PAHS) ae ac that consist of two or more fused benzene rings iced ina inet, nel, orto avangoment They ae sociated wih the combustion offs fitand sme ic circ encnoget oF mutanopnie Undeveloped ek tay fan tol PAH concentra thvolletS ugk, wh ween are ay hav solconcenratons that ang rom 60 p@/EG 300 pp ig Wha tthe conrntraon of PAHs ntndevetoped ares a tal of aa ti »il samples collected 2.0. The concentration af toluene (Ci) in sdsutce 5 here undegouod songs sn spr removel nite te tluce cour iat wats mg/g What se ene concenvation ppm? 2258,40° Chapter 2 Units of Concentration 228. The following table contains atypia chemical analy chemical ana ofa surface water («) Using the four most abundant cations and tree ost sbusdan ee tound in tis specie suace water, show ether thesnaioeiesere ot (0) What s the hardness ofthis watcrin ums ot apt Caco SS aT ‘ainy | Allytenzne onste "Oa aus ‘ (detergent) . anes | Neos 2 ee oo os noe phasors Caiman — %3 Settum 358 Selntun xD Shoe mM ter xD Groat a 6 Gover 01 Salle as Gite ND Total daotva ste 2) onde 7 ee ND ———————oOoos ND “Token fom Hammer, 1975 "Not: All values ae reported in mg/L. ND means the chemical was nondetectable 2-28. While visting Zagreb, Croatia, Mr. Arthur Van de Lay vi ‘Art Museum and then takes inthe great architecture ofthe ata café in the ol tov and orders abt of chemical concentration of this water is [Na"] = Os mg [Kejeons 2+) 24) ae mL [Ma] = 19 mg, [Ca] ~ 35 mei, [Cr] = 08 gil SOF] 2 Mampi (HCO;]~ 18 mgt, [NOs] = 38 mi. The pt ofthe water is: ati the hardness of this water in mg/L. CaCO? chemical analysis correct? a the Mimara ity. He stops ral water. The reported 2-30. A laboratory provides the following solids anal lowing solids analysis for a wastewater sample: TS = 200 mg/L; TDS = 30 mg/L; FSS = 30 mg/L. (a) What is the total Suspended solids concentration ofthis sample? (b) Does this sample have appreciable organic matter? (Why or why not?) 2.31. A 100-mL water sample is collected from a municipal wastewater treatment plant's biological aeration treatment reactor. The sample is placed in a dirying dish (weight = 0.5000 g before the sample is added), and then placed ‘an oven at 104°C until all the moisture is evaporated. The weight ofthe dish is recorded as 0.5625 g, A similar 100-mL sample is filtered and the 100-mL liquid sample that passes through the filter is collected and placed in another drying dish (weight of dish before sample is added is also 0.5000 g). This sample is dred at 104°C and the dried dish’s weight is re. corded a 0.5325 g, What isthe concentration (in mg/L.) of (a total solids? (©) total suspended solids? (c) total dissolved solids? and (d) volatile sus. pended solids? (Assume that in the aeration basin, VSS = 0.7*TSS.) ore References 41 REFERENCES ‘American Public Health Association (APHA). 1992, Standard Methods for the ‘Examination of Water and Wastewater, American Public Health Association, ‘Washington, D.C. Campbell, M. P., D. P. Smith, and A. D. Levine. 1995. Biological treatment of hazardous waste landfill Ieachate: A comparative study of fied film reactors. In Innovative Technologies for Site Remediation and Hazardous Waste Man- agement, Pittsburgh, Pa. han, C.C, J.D. Spengler, H. Orkaynak, and M. Lefkopoulou, 1991. Commuter exposures fo VOCS in Boston, Massachusetts J. Air & Waste Management ‘Association. 41:1594—1600. binghaus, R., H. H. Kock, S. G. Jennings, P. MeCartin, and M. J. Orren. 1995. ‘Measurements of atmospheric mercury concentrations in northwestern and central Europe—Comparison of experimental data and model results. Atmo- spheric Environment. 29(2)3333-3344. Femmandes-Bremauntz, A. A.,andM.R. Ashmore. 1995. Exposure of commuters to carbon monoxide in Mexico City—I. Measurement of in-vehicle concentrations. Atmospheric Environment, 29(4):525-532 Fuentes, J. D, and T. F. Dana, 1994, Ground-level ozone in eastern Canada: Seasonal variations, trends, and occurrences of high concentrations. J. Air & ‘Waste Management Association. 41019-1026. Graedel, T. E., and P. J. Crutzen. 1993. Atmospheric Change: An Earth System Perspective. W. H. Freeman, New York Hammer, M. J. 1975. Water and Waste-Water Technology. John Wiley & Sons, New York. Hammer, MJ. and M. J. Hammer, Jr. 1996, Water and Wastewater Technology. Prentice Hall, Englewood Ciffs, NJ. Liu, K. S., 8. B. Hayward, J. R. Girman, B. A. Moed, and F. Y. Huang. 1991 "Annual average radon concentrations in California residences, J. Air & Waste Management Association. 41:1207-1212, McGeorge, L. J., 8. J. Krietzman, C. J. Dupuy, and B. Mintz. 1992, National Survey of drinking water standards and guidelines for chemical contaminants. J. American Water Works Association. 84(3):72-76. Ried, J. 1994, Arsenic occurrence: USEPA secks cleaner picture. J. American Water Works Association. 86(9):44-51 Villatobos-Pietrni, R.,S. Blanco, and S. Gomez-Arroyo. 1995. Mutagenicity as- ‘sessment of airborne particles in Mexico City. Atmospheric Environment. 29(4):517-524, Viner, A. B. 1987. Inland Waters of New Zealand. Department of Scientific and Industrial Research, Wellington, New Zealand.Chapter 3 Chemistry James R. Mihelcic Noel R. Urban Judith A. Perlinger David W. Hand ‘In this chapter a reader will eview several important chemical principles” and apply them to understanding the chemistry of pollutants ina variety of engineered and natural systems. The chapter begins with a brief review of ‘the difference between concentra iss followed by cover. age of chemical kinetics; thermodynamics and it relationship to equilibrium ‘processes; specific équilibrium processes betveén chemicals in the water, air and solid phase oxidation/reduction processes; and a discussion of photo- ‘chemistry using the examples of the ozone hole and urban ozone. ‘Chemistry is important to environmental engineering and science because the ultimate fate of many pollutants discharged to air, water, soil, and treatment {acilities is controlled by their “reactivity” and “chemical speciation.” Likewise, cost-effective design, construction, and operation of many waste-treatment unit processes is dependent on the fundamental chemical processes that may take place in a particular treatment process, Also, individuals who predict (ic., model) how pollutants move through groundwater, surface water, soil, the atmosphere, fr a reactor are interested in whether a chemical degrades over time and how they can mathematically describe the rate of chemical disappearance or equilibrium in their overall model. 3. THE DIFFERENCE BETWEEN ACTIVITY AND CONCENTRATION ‘Activity can be thought of as the effective or apparent concentration in water or that portion of the true mole-based concentration of a species that participates in a chemical reaction. In most environmental situations, activity and concentra- eB77 Uuapter 3 Chemistry tion are used interchangeably rchangeably. Places wh seawater, some briny groundwaters, This section explains the differen shows how to relate them. re they bein to die gealy fer peat ince tndsome hit conentated wares c= beeen activity and concenaion The remainder of Chapter 3 assum Te lr 3 assumes that activity (design 8) and concentration (designated by [ SEA ne ie Notation for concentration (L} bracke, marae we te In an ideal system, the molar fi the molar free en: mole fraction (mole fraction defined i not include the effect of other dissol which also affect a solute’s mi lergy of a solute in water depends on the ved species or the composition of the water, it a lar ree energy. Chemica lent bonding van der Waals interactions, volume enna ah and long range eletrotati frees (hes 1 me ) ‘conduct (Egtton 3) omN species ican electrolyte meen sen spose isa noneectrlyte \ . for tow ionierengts pas, Torhighionc strengths, forall onic enti, renin, eeosyn wethe Guneters asthe Daves P (cram) (crsimiay Con ‘approximation: _spproximation: paral €quaion35) (Caution 3.6 coefficients for electrolytes and in Chapter 2). However, this fraction docs 3.1 The Difference Between Activity and Concentration 45 ‘All these complexities are then superimposed on solute-solvent interactions. cof activity instead of concentration accounts for these nonideal effets. Activity jerelated to concentration by use of activity coefficients. Activity coefficients are etermined by first finding the solution's ionic strength. Then one of several avations, developed specifically for ether electrolytes (ie, ions) or nonelectro- fe (uncharged species), are used to determine the activiy coefficient ofeach Piividual species. Figure 3-1 summarizes this two-step process. 3.11 Tonic Strength ‘The ionic strength of a solution (referred to as f or jz) has units of molesiter and can be determined from the following expression: i 3 ZC? a) where C; is the molar concentration of an ionic species in solution, and zis the Charge of the ion. In most natural waters the ionic strength is derived primarily from the major “background” cations and anions that make up natural waters. ‘These latter were listed in Section 2.6. Freshwaters typically have an ionic strength of 0,001 t0 0.01 M and seawaters have an ionic strength of approximately (07 M. The ionic strength of aqueous systems rarely exceeds 0.7 M. It can be correlated to easily measured water-quality parameters such as total dissolved solids (TDS) or specific conductance as shown below: w= 25 x 105 x (TDS), where TDS is in mg/L. 62) 6 x 10™ X (specific conductance) 3 where specific conductance is in ymhofem and is measured with a conductivity meter. 3.4.2 Calculating Activity Coefficients for Electrolytes ‘When describing equilibrium relationships, aqueous chemical concentrations are reported as either [concentration] or {activity}. As mentioned previously, both have units of moles/iter when used in chemical-equilibrium relationships. Activ- ity and concentration are related by an activity coefficient, y, as follows: (c= nIcl ae the con- ‘where {C) is the activity of species / in units of moles per liter, {Ci centration of species i in moles per liter, and + is the activity coefficient fori cy Suapier 9 Chemistry ity and Concentration 47 3.1 The Difference Between A SESELLIN tides Noe hat xy an act cof ae deren, tied (species like Na*, » HgCl”, etc.) the activi mth ways equal oof les thin 1. Figure 3.2 demonstrate te oem uncrowded and crowded dance floor hi the netng and crowded dance floor how an increas in ionic reo on tivity of the reacting species. This can be thought of as redtne ees cocthcient gales (20h 88 O, COs, trichloroethene, Benzene) the activity. is always equal to or greater than 1. 2 ) the activity Also, note that in an ; inan equilibrium reaction quotient (se covffiients ae raised tothe molrstoichiometre power ene sity ther relationships include the Debye-Hickel and extended Debye-Hitckel Ree Stumm and Morgan, 1996, for a summary). Note that activity coefficients for electrolytes depend on the absolute value of the charge, as is discussed in ‘Example 3-1 Calculate the ionic strength and all the individual activity coefficients for a L-liter solution in which 0.01 mole of FeCl, and 0.02 mole of H,SO, are dissolved. SOLUTION log y, = Az ni? ‘After the two compounds are placed in water they will completely dissociate to Tey os) form: 0.01 M Fe**, 0.04 MH", 0.08 M CI-, and 0.22 M SO,2>. The ionie strength is piven by Equation 31: Y0.01(3+)? + 0.04(+1)? + 0.03(—1)? + 0.02(—2)"] = 0.12 M the solvent, which is usually water. The Davies approxim: Note that this ionic strength is relatively high but still below that of seawater. ‘approximation is useful for solutions with yu < 0.5 Mz | ‘The Daves aprosination am on 3.6) i = ye used to determine each species’s activity coefficient: Ad pl? log y, = — Az wi? _ "03 n 66 YH") = 078, (Cr) = 078, (S027) = 036, 7(Fe™*) = 0:10 [Asis apparent from this example, the activity coeficents of ions with higher valence deviate much more from 1.0 for a given ionic strength, That i, for electrolytes, use of activity coefficients is much more important for ions with a higher valence, because they are strongly influenced by the presence of other ions. Thus, while ata particular ionic strength it may not be important to calculate activity Coefficients for monovalent ions, it may be very important for di, tr, and tetra- velent ions 3.1.3. Caleulating Activity Coefficients for Nonelectrolytes fe usually estimated from empirical Activity coefficients for nonionic species ded dance floor. Here a dancer ca lancer can easily find expressions such as: thee partner and this snot se is not strongly ineneed by the es Disko s crowded dance oor. ta is stanton a donc aes a on er mt dry inca by conc asion ee ‘umber of background ions (i.e, iodo of other fons atempting to en apparent conceiation decreed a he ions (ie, high ionic strength). — ogy, = ks en where ks is referred to as the “salting out” coefficient and has units of Limole. ‘Table 3-1 lists some salting-out coefficients for several organic chemicals of en- a large number of background vironmental interest. Examples of salting-out coefficients are 0.208 for toluene, 0.140 for chloroform, and 0.132 for O;.s° \napter 5 Chemistry Table 31 Salting-out Coefficients (at 20°C) for Several Organic Chemical mnie Chemicals : Saling ow Orzmic Chemical coe fu Me Epeer op Sain 1,1,1-Trichloroethane a pra oass ec 7 14 Dichloreetane ous Gowe1967 Dichloromethane Gessett, a our Gasset 1987 a ee Nn ous Serbs tas 983 ee oz Setanta ceyink and Jenkins, 1980 ‘i An air stripper is being used to remove benzene wen water. Assume the ionic strength of seawater is Oot Me. What i the ac Activity eon for benzene ‘water The slingout coetient for benzene Oras eva 04 i sh souunion Because benzene se benzene is a nonelectrolyte, use Equation 3-7 to det coefficients. This expression is used for solutions of both — low and high ionic log y = ks. log y = 0.195 (0.001 M) results in y (freshwater) og = 0.195 (0:7 M) results in y (seawater) = 1.4 Note that if 4 < 0.1 M, the activi deviate much from a value of 1. Therefore, = This result of activity coefficients being greater than Visualizing atmospheric oxygen dissolving in a water o: high ieee igh ionic strength. A water with a high ionic strength has many ions dissolved in it. The ions dissolved payater are covered with a shell of hydrated water and these hydration shells in Nyety tightly packed together wien compared to the water molecules in the {ik solution, which take up the remainder of the solution, Because ofthis tight Frckng, nonclecrolytes, such as onygen inthis case dissolve less well i this Pint of hydrated water than the bulk volume of more loosely associated non- Tydrated water. Therefore, a given total volume of water (hydrated plus non- tydrated water) can accept less nonelectroyte. Thus, the concentration of the total volume of water is less than the activity 32 CHEMICAL KINETICS “There are two very different approaches used in evaluating a chemical’ fate and treatment: kinetics and equilibrium. Kinetics (Section 3.2) deals with the rates of reactions, and equilibrium (Sections 3:3 and 3.4) deals with the final result or stopping place of reactions. If reactions happen very rapidly relative to the time frame of our interest, the final conditions that result from the reaction are likely to be of more interest than are the rates at which the reaction occurs. In this case, ‘an equilibrium approach is used. Examples of rapid reactions include acid-base reactions, complexation reactions, and some phase-transfer reactions (e.g., vol- alization, dissolution). ‘Other reactions either occur relatively slowly or are prevented from reaching equilibrium (e.., via subsequent reactions of the products of the first reaction). In such cases, the kinetic approach is used to understand how fast the reaction ‘will occur. Biologically mediated reactions, light-driven (photochemical) reactions, redox reactions, and decay of radioactive elements all are examples of reactions that generally do not reach equilibrium quickly and thus require the kinetic approach. It is extremely important to be able to decide which approach to take in solving chemical problems. Both the equilibrium and kinetic approaches are based on thermodynamics. [As is discussed in Section 33, only reactions that result in thermodynamically favorable changes in their energy state can occur. This change in energy state is, called Gibbs free energy change and denoted AG. Itis this change in energy state that defines the equilibrium condition. However, not all reactions that occur ‘would result in a favorable change in Gibbs free energy, and the magnitude of this energy change seldom is related to the rate of the reaction. For a reaction to occur, it generally is necessary that atoms collide, and that this collision has the right orientation and enough energy to overcome the “activation energy” required for the reaction, These energetic relationships are shown in Figure 3-3 3.2.1 The Rate Law Rate laws are used to predict the rates of chemical (abiotic) and biological (biotic) processes. The rate law expresses the dependence of the reaction rate on mea- surable, environmental parameters. Of particular interest is the dependence of50 Chapter 3 Chemistry Activation Energy Restate ree Eeecty Love ao Reaction Figure 3-3. The energetic relationship required for a reaction to occur, the rate on the concentrations of the cence the reaction rate include temper ing microorganisms), The rate of an irreversible reaction, reactants Other parameters that may in ature andthe presence of ells (velo a a aes + OH — win +o 4 bt For the reaction dep a ation die ae 9 ect one molec of DCM mus cote nd cule of OF. This reaction i termed a Bhuny root les in nature are constantly moving at a 7 iperature. As a result of this motion, mol les are onstantlycolng, but only smal faction of caisene on ecu ate he more molecules of DCM in axed volume (ie, the concn ae ish the eater the proba that sain Fence anc ill occur. Similarly, the more molecules of OH— ae i nd ia les of OH- there are, the reser Probability ofa olson between a molcle of DCM and OM aiken raction of the collisions actually result in a reaction, Proportional to the number of collisions per unit time. — on this discussion, the rate of an irreversible binary reaction should be mr tration of each chemical species and can be writ- R= k{DCMIION-} lem _ dcr) dt dt dt dt Ga where 2 is the rate of reaction, kis the rate constant for this [DCM] isthe concentration of dichloromethane, [OH] is the eran the concentration of 32 Chemical Kinetics 1 hydroxide ion, [CM] is the concentration of chloromethanol, and (CI-} is the ‘concentration of chloride ion, The minus signs in Equation 3-8 indicate that the xroducts’ concentrations are decreasing over time. ‘The bold portion of Equation 3-8 is referred to as the rate aw for the reaction. ‘The rate law expresses the dependence of the reaction rate on the concentrations of the reactants. The rate law in this case would be called first order with respect, to DCM and first order with respect to OH™. The term first order indicates that each species is raised to the first power. The rate law is second order overall because it involves the product of two species, each raised to the first power. Because the reaction was depicted as being irreversible, it was assumed that the concentration of products did not influence the rate of the forward reaction. ‘To generalize these terms, a hypothetical rate law can be constructed for a generic irreversible reaction of a moles of species A reacting with b moles of species B to yield products, P. The rate law is written R= Ay By ‘This reaction would be termed ath order with respect to A and bth order with respect to B. The overall order of the reaction would be (a + b). This reaction is termed an elementary reaction because the reaction order is controlled by the stoichiometry of the reaction. That is, a equals the molar stoichiometric coefficient ‘of species A, and b equals the molar stoichiometric coefficient for B. ‘The order of a reaction should be determined experimentally, however, be- ‘cause it often does not correspond to the reaction stoichiometry. This is because the mechanism or steps of the reaction do not always correspond to that shown in the reaction equation ‘The collision-based reaction of the hydrolysis of dichloromethane can be con- trasted with some biological transformations of organic chemicals that occur in either treatment plants or natural environments where soils and sediments are present. In some of these situations, zero-order transformations are observed. ‘This can be due to several items, including the rate-limiting diffusion of oxygen from the air to the aqueous phase, which may be slower than the demand of ‘oxygen by the microorganism biodegrading the chemical. Another explanation for observing zero-order kinetics is the slow, rate-limiting movement of a chemical (required by the microorganisms for energy and growth) that has a low water solubility (ppb and ppm range) from an oil or sol/sediment phase into the aque- ‘ous phase where the chemical is then available for the organism to utilize. 2,-D is one such chemical that has been observed to have zero-order kinetics of biodegradation. It is a herbicide, commonly used by farmers and households (itis found in many dandelion weed killers). 24-D can be transported to a river or lake by horizontal runofi or vertical migration to groundwater that is then hydraulically connected to a lake or river. Ithas been found to disappear in lake water according to zero-order kinetics (Subba-Rao, 1982): ‘The rate law for this type of reaction can be written as 4.40) dt . oo) : G-10)© \mapter 3 Chemistry This reaction is termed zero-order because it does not de “ond ero: tse it does not depend on the concent ‘concentration 3.2.2 Zero- and First-order Reactions Pow Sommaire tne isc meeehmtad edgar ert C> products 3. Prod Gu) ‘The rate law for describin the decrease in concent ceed e ‘cutration of chemical Cwith time ofa -Hcr a G2) Here [C] is the concentration of “C." ion of "Cy" ‘dependent on the order ofthe reaction, a integer (e.g., 0, 1, 2). : time, k isa rate constant that h iat has units ind the reaction order, n, is typically an ru 4a a a! i tar=teyee Sead ttc fy “wa x 280 ening! Time time Figite 3-4. Summary of zero and frstorder rate expressions Note the between each of these expressions, | 3.2 Chemical Kinetics 53 ‘zero-order Reaction nis zero, Equation 3-12 becomes ac] a G13) ‘isis the rte law describing a zero-order reaction. This the rate-law expression ‘ned in Equation 3-10 to describe the transformation of 2.4-D. Here, the rate of, Uisappearance of C with time is zero order with respect to “C” and the overall Seder of the reaction is zero order. Equation 3-13 can be rearranged and inte {rated forthe following conditions; at time zero the concentration of “C" equals Gand at some future time, r, the concentration equals C: (iaa=-+f'a Integration of Equation 3-14 yields: [C] = [Co] ~ ke G1) G15) ‘A reaction is zero order if concentration data are plotted versus time and the result isa straight line, This is illustrated in Figure 3-4. The slope of the resulting line isthe zero-order rate constant k, which has units of concentrationltime (ee, molesfiter-day). First-order Reaction If'n = 1, Equation 3-12 becomes Cl 2 4c) dt G1GR This ts the rate law for a frs-order reaction, Here the rate of disappearance of C with time is fist order with respect to (C] and the overall order of the reaction is first order. Equation 3-16 can be rearranged and integrated forthe same two conditions used in Equation 3-14 to obtain an expression that describes the concentration of C with time: (C} = (Cale™ GAD Here kis the first-order reaction rate constant and has units of time (e.,hr™, day”), A reaction is ist order when the natural logarithm of concentration data plotted versus time results is straight line. The slope of this resulting straight in is the first-order rate constant, k, as ilustrated in Figure 34.Suapter 3 Chemistry the amount ofthe radioisotope Tn, decay is proportional to would be wien a MORE Pretent. Therefore, the rate law for cedure dee Eas) ey ae > WALES om Thee ler with respect to ""’Cs and is first orc 1S. First, when comparing the concentration over tim a | 32 Chemical Kinetics 55 SOLUTION ‘This is a first-order reaction, so use Equation 3-17, Let [COs] equal th CO concentration. When 99% of the CO goes away, [CO] = 0.01[CO,]. There- fore, 0.01[CO¢] = [COgle* where k = 1.2 h~, Solve for ¢, which equals 3.8 h. 32.3 Pseudo-first-order Reactions ‘There are many circumstances in which the concentration of one participant in reaction remains constant during the reaction. For example, ifthe concentration of one reactant initially is much higher than the concentration of another, itis impossible for the reaction to cause a significant change in the concentration of the substance with the high initial concentration. Alternatively, if the concentration of one substance is buffered at a constant value (e.g, pH in a lake does not ‘change because it is buffered by the dissolution and precipitation of alkalinity: ‘containing solid CaCO;), then the concentration of the buffered species will not ‘change even if the substance participates in a reaction. A pseudo-firstorder reaction is used in these situations. It can be modeled as if it were a first-order reaction. Consider the irreversible elementary reaction: aA + DB eC + dD @-19) ‘The rate law for this reaction is R= HAriBy 6-20) If the concentration of A does not change significantly during the reaction for ‘one of the reasons provided above (ie. [Ao] >> [Bol or [A] = [Aa], the concentration of “A” may be assumed to remain constant and can be incorporated into the rate constant, k. The rate law then becomes: | R= kay where k’ is the pscudo-first-order rate constant and equals k[4o}*. This manip- ulation greatly simplifies the rate law for the disappearance of substance B: 5) _ “a7 omy @2) eB If b is equal to 1, then the solution of Equation 3-22 is identical to that for Equation 3-17. In this case, the pseudo-first-order expression can be written as (B] = [Bole** G2)30 Chapter 3 Chemistry Tats Sibersee is located in the German city of Nuemnberg. The lake's water stan cs been diminished because of high hydrogen sulfide concentrations (ihe seabiees, mel) that originates from a nearby leaking landfill. To combat the Problem, the city decided to aerate the lake in an attempt to. TES {0 nonodorous sulfate ion according to the following oxidation serene HAS + 20, + 802° + 2H". Jt has been determined experimentally that the reaction follows first-order Kinetics with respect to both oxygen and hydrogen sulfide concentrations M5) «1,510, The present rate of aeration maintains the oxygen concentration panei The rate constant (k for the reaction was determined exper be 1.000 Limole-day. Ifthe aeration completely inhibited anerebse respiration 71g Bus stopped the production of sulfide, how long would ittake to reanca HLS concentration in the lake frou 500 uM to 1 pNk? the lake at SOLUTION rip dissolved oxygen ofthe lake is maintained at a constant value and therefore onde ant, T cn be combined with the rate constant to make a pseudo hice order rate constant. Thus [HS] = [H4,5,Je-** where k= {O,). : L000 L 2 mg aoe tensa te ‘The time, t,can be calculated to equal 100 days 324 Half-Life and Its Relationship to the Rate Constant react tseful to express a reaction in terms of the time required to react one- half of the concentration initaly present. The “halfie” is used forth Purpose rele, tn i defined as he time required forthe concentration of he net decrease by one-half (eg. [C] = 0:{Ca)). The relationship between helene, Fie, fetction rate constant depends on the order of the reacton se dham os Figure 34, 32 Chemical Kinetics $7 life can be related to the zero-order rte or vero-oner resins, th aif can be rested to th constant by subsitetng(C] = 05% [Cl ito Equation 315 asical = [Cal ~ kin 2» ‘quation 3.24 can be solved forthe halite: fy = 2G 625) wn = ie, for a istorder resto, the half can be elated tothe fst order eae &, by substituting [C] = 0.5[Co) into Equation 3-17: 05Cy = Coe 6-26) ‘The halflife for a first-order relationship then is given by: ad @2nR ana" inantin groundwater. stn pfs ra a Sentient rs mero scm ttn Wu een ie St heen te sn ae ar nares ear oa chemicals? SOLUTION order rte constants, ely scp cmcenraionependent, std ae cet Ths to sete problem, conver hai tos Hst-ordes rate constant with the use of Equation 3-27. 0.693 searene Kyce Krotaeoe58 Chapter 3 Chemistry operat Src cummin fC ik a non pn on ete soe sol Aum tha ie only reaction by which "Cs was lost from the soil was ireuh tn ct gues om el a ihren ce a oe eas Cae ln Oo end ee Batra men SOLUTION Since the half-life ear, the 1 Eaqatiog applte equals 30 years, the rate constant k can be determined from 6 ba 6008 yet 3.2.5 Effect of Temperature on Rate Constants ‘Typially rat constants are determined and en termined and compiled fr temperatures of eer 29 or 29C. Howes, gosndvaens cal he empeaucecrunde ne urls waters, wasteaters andsospeverally hae geet eae from 0°Cto PC. Thus, when aciferenttemperntare nese or scientist must fist determine ifthe effect of temperature is iapeneee ey secondly, ifimportn, how to converte rte cons or there ag bss ol mos acon are dependent on tempera, In Sten 's mentioned that the rate of molecular motion was a function of porate, ‘Thus, the higher the temperature, the faster the moles sane ag nan increase in the numberof colsions per uit ne A higher ec abo incense eno the colson, Aa ea gear hace ae colisions results in a chemical ection Consequently, eo crn Acton that depend on colsions of two or more moleee eile ena increase in temperature. In contrast, eactons mot penton 32 Chemical Kinetics 59 collisions (e.8, radioactive decay) will not be influenced in this manner. In addition, biological processes (enzyme catalyzed) have some optimal temperature range, above or below which the enzyme becomes destroyed (ic., denatured). ‘That is, biological processes will show an increase in reaction rate Wi in temperature up to a certain point, after which the rate will begin to decrease further increases in temperature. ‘An example demonstrating the importance of temperature effects on a rate constant is the decomposition of peroxyacetyl nitrate (PAN). PAN is formed in the atmosphere by the oxidation of hydrocarbons in the presence of nitrogen oxides (NO,). PAN is an eye irritant to humans, a plant toxicant, and can act as a reservoir of NO, during urban-smog formation. The rate constant for the at- mospherie thermal decomposition of PAN is strongly temperature dependent. ‘The first-order rate constant increases from 5.0 X 10°65" at PC to 1.6 X 10-25 at 35°C (Finlayson-Pitts and Pitts, 1986). The result is that the half-life of PAN drops from 2,300 min at 0°C to only 7.2 min at 35°C. ‘The Arrhenius equation is used to adjust rate constants for changes in temperature, Its written as (6-28) ke Aeeaeny ‘where kis the rate constant ofa particular order, A is termed the preexponential factor (same units as &), E, is the activation energy (kcal/mole), R is the gas constant, and Tis temperature (K). The preexponential factor is related to the ‘umber of collisions per time; therefore, the preexponential factor is different {or gas-and liquid-phase reactions. The preexponential factor, A, also has a small dependence on temperature for many reactions; however, most environmental situations span a relatively small temperature range. The activation energy, E, is the energy required for the collision to result in a reaction. A plot of in(k) versus 1/T can be used to determine E, and A, as shown in Figure 3.5. After E, ‘and. A are known for a particular reaction, Equation 3-28 can be used to adjust ‘rate constant for changes in temperature. ‘The Arrhenius equation is the basis for another commonly used relationship ‘between rate constants and temperature used for biological processes over nar- row temperature ranges. The carbonaceous biochemical oxygen demand (CBOD) rate constant, ky, known at a particular temperature, is typically converted to other temperatures using the following expression: ken = kn XO7-TD G29 ‘where © is a dimensionless temperature coefficient. In fact, © equals exp(Ea + [R x TI x 72} as ean be seen from the Arthenius equation. @ is temperature COxe G31)66 Chapter3 Chemistry in which one mole of solid carbon reacts with ‘oxygen to produce one mole of gaseous carbon jn a closed container maintained at a constant t GEL atmosphere, 394.37 kt of energy would be released. This value tould be {Gtermined from the amount of heat that had to be removed from the contsingy {0 maintain it at a constant temperature. This energy is termed the free en ‘one mole of gaseous dimolecular dioxide. If this reaction proceeded temperature of 25°C and a pressure under standard conditions, concluded that the reaction cannot proceed as written, but could, in fact, proceed spontaneously in the opposite direction under standay rd conditions, Zhe change in free energy for a reaction at standard conditions, AG, can de determined asthe sum ofthe free energies of formation of the products multiplied by their stofchiometric coefficients, minus the sum of the free en- exgies of formation of the reactants multiplied by ther stoichiomene coefficients: AG? = SHAG Pegataany ~ ZitiA GPyrecans) (3-32) 2 Eauation 332 1, refers tothe stoichiometric coefficient foreach species, i which is obtained from a balanced chemical reaction; AG® is obtained for ait dual species, from tabulated values as provided in Table’ 2 LAG is positon, Under standard conditions, the reaction could not proceed in the forwaed ae tion, but could proceed in the reverse direction. Likewise, if AG ie nega lnder standard conditions, the rection could proceed spontan can procee which the reaction will proceed. Acid rain isthe result of burning fossil fuels. The sulfur contained in fossil fuels Faulzed to sulfur dioxide, SO., during combustion, Inthe atmosphere, SO; dissolves in water droplets where it forms sulfurous acid, HSO,, The culforees ie ‘ances in the cloud water (substances such acid, H,S0,, Could the following two If the free-energy change was positive, it could be inergy of Formation (AG{) and 2. Values ofthe Change in Free Energy’ Se ae Table ea of Formation (AF) for Some Common Chemical Species at 25 in Formation ‘Change in Free Energy of Formation Change in Heat of Species (AG) (ka/mote) (AH?) (kifmole) Hit = = ALOFD (6) 1 00; (8) 354 Fe(OH) (© Fe (9) HC a) 106) +612 Hele) 206 HS @ “398 HS (0) =116 HS" (aa) 330 (aa) ~ni Ma (9) = Ma(OH): (9) san MnO 6) = Ma00H (6) “Wea NH (@®) 03 NH, (a9) wax. NHL (aq) 207 NO,” (aq) ° Os(@) “117 0 (a0) 389 Ott radical (@) a) OF (a) 285, 1,0 () -28, H0@) 1280 HPO, (ag) 1300 HPO. (eq) —1250 Po (aa) =1380 0, 190 509 es oa pce lx prepa eh paral (Sete aps ne us pn le os pe Si ‘Secon oid sted th parent (fret specie exiting oy on re the was ae bed ic aioe (er ee i cmd ir Stumm and Morgan 198 Tf tee, CR G99) wu come Al as ave ‘deed ots sions es)(93 Chapter 3 Chemistry e Fecions, the combustion of FeS; (pyrite) inthe coal to yield SOs, and the oxi. dation of SO; by Fe** in the clouds to dation of SO; by Fe to yield H:S0, proceed spontaneously at PPESxe) + 550m) —> FeO) + 450g MSOs) + 2Fe™ gay + HeOQ) —> HySO cg) + 27g +H SOLUTION The relevant free energies of Tm {energies of formation at standard conditions are tabulated ow together with the stoichiometric coetcients from theabove twoequationg | ‘Compound G} (kS/mole) (ne, moles) FeSu9 160 2 * 0 FeByy 148 r 50g 00 4 HS) 534 1 Fema an) 2 H0q 237 tc HSOuuy a5 I Feoo -789 2 Hog o 2 Use Equation 3.32 to deter mine the change in ree ene i for bo easton. For pte combustn nT MTR standard condon AG? = [AGjre0, + 44GI50, Ace = PAG Irs, + S5AG%o,] [143 + 4(—300)) ~ [2(-160) + 5.5(0)] = —1,623 1 Similarly, for sufurie acid production i = (AGins0, + 2G fr + 2AGH] ~ (ACIs0, + 28G Fro + AGP} AGE = [-745 + 2-789) + 2(0)} ~ (-$34) + 2(-4.60) + (~237)) = —123 EI Both reactions result in a decrease in free ener ” is negative). There. a in free rey (e., AG? is negati fore, bth reactions can proceed spontaneously as written at standond ech ions. 332 Calculating Changes in Free En: under Nonstandard “Ambient” Conditions Section 33.1 considered ol onsidered only the free-energy chan Seon one BY change fr reaction occurring un- HS.) + 2Fe qa) + 2H" 33. Chemical Thermodynamics and Equilibrium 71 SOLUTION “Assume ideal conditions, so concentration equals activity. Example 3.8 provided 3 AG" equal to ~123 KJ for the reaction of interest. Therefore, . H,SO4)(Fe** PLA" AG = AG + RX Tx in SpE HIBW , 834d 0S moke-K™ J AG at ambient conditions is negative; therefore, the oxidation of sulfurous acid to sulfuric acid could proceed under the stated conditions. Equation 3-33 corrects AG® for concentrations that are not equal to “standard conditions”; however, it does not correct it for temperature. Because most tabulated values for AG® are at 25°C, ifthe ambient temperature is ot equal to 25°C, an additional correction is necessary to obtain a value for AG? at the new temperature. For the curious, the derivation of this temperature correction is presented in the Advanced Topic box below. An example that demonstrates the use of temperature correction of equilibrium constants is postponed until Sect 334 because the material covered in that section allows a simplification to be made. ‘This temperature correction is based on the definition of Gibbs free energy: G=H-Txs @ From this definition, it is clear that the change in free energy per unit change in temperature (ie., AG/87) is equal to ~S: ag o) ‘The derivative of this expression with respect to temperature again yields that (@AG"AT) equals ~AS*. (Note that by measuring the change in standard free energy with change in temperature, one could determine the magnitude of the standard change in entropy.) The important implication of these relationships is72 Chapter 3 Chemistry that AG® is dependent ot F TAG" is dependent on temperature, Further transformation of Equation b Yields wel poneralzton tar aon Yelisa wet onertanton at alns an to carea Aoi esc aeae so ee 2 1 (aac —_ daa eee: i 0 eT (MS). Laci nsy and AH® can be substituted for (AG® + TAS*) to obtain ae ee ~AH® ar re @ A simple substation ito Equa cinpl bon ino Equation diss the van Ho equation tats dl tation ). Integration of Equation alized correction in AG® fr changes in tmportares no” © the generalized fe?) - Here AG} and AG¥ are the values of AG® at temperatures T, and 7, ‘one must correct AG? for e Vale of 80 a es eaoy echange in temperature and then seth eae nT In practice, le corrected ee ee Free Energy and Its Relationship to the Equilibrium Constant in the previous sectic rit % sof te ope at te point of auilibium (point C) is zero, In other words, oo ree energy is zero at equilibrium. If the change in fre ener ) igual etl ging) termine a reaction’s equilibrium constant, K: inorder AG=0=AG"+ RTInK G39 AG? = -RT In kK @37) At equilibrium, O = K, $0 K was substituted for t ‘wo previous equations. According to Equation 3.97 teas eat 2 in he 3-37, there isa special relation- | 33 Chemical Thermodynamics and Equilibrium 73 snip between the concentrations of ll ofthe species at equilibrium and the value SfAG°. This relationship is 638) ‘At 25°C all of the terms on the right-hand side of Equation 3-38 are constant, and hence the value of the quotient @ at equilibrium (ie., K) is a constant. ‘Equation 3-38 is useful because it can be used to solve for unknown equilibrium constants as long as the reaction temperature, stoichiometry, and values for ‘3G? are known. The equilibrium expression, or equilibrium quotient, is called the equilibrium constant and is usually denoted by the symbol K. ‘Do not confuse the equilibrium constant, K, with the reaction rate constant, k.Note that K is constant for a specific reaction (as long as temperature is constant) and ils units are dependent on reaction stoichiometry. Later on in this chapter, equilibrium constants will be defined for reactions that describe acid-base chemistry (K, and K,); precipitationidissolution reactions (K,,); and airhwater exchange (Henry's constant). The equilibrium constant for the reaction provided in Equation 3-34 is given by the reaction quotient, Q: CHI _ x laylapP oc G39R ‘The equilibrium constant is useful because it provides the ratio of the concentration (or activity) of individual reactants and products for any reaction at equilibrium. Reduced ferrous iron (Fe**) can be oxidized to ferric iron (Fe™) in the presence ‘of oxygen according to the following reaction. AEE ug) + Ong) + 10 HzOq) —> 4Fe(OH) xy + 8H oq) ‘This reaction produces the reddish-brown stain seen in many sinks and bathtubs ‘where the water is aerated as it exits the faucet. This chemical reaction is also used during water treatment to remove iron from water. During water treatment, alter the Fe(OH); precipitate is formed from aerating the water, the precipitate is then removed by either settling tanks or filtration. ‘The equilibrium constant for this reaction at 25°C is 10". What equilibrium concentration of reduced iron is present in a system of water at 25°C and pH = 7 ({H*] = 10-7 M) that has air bubbied through it? Assume ideal conditions (i., activity and concentration are the same).74 Chapter3 Chemistry SOLUTION ‘Set up the equilibrium expression 107 = [Fe(OH us} {H* FH xeo)lOP Remember that [1,09] = [Fe(OH enember tat (OF) = 1 gaseous oxygen, so use the partial pressure of onygen in sit O21 eee aqueous phase oxygen concentration I th I the reaction was ‘would use the aqueous molar O, concentration; rien With On yu -—_lo-s [Fe (021 atm] 10" Solve for Fe] = 67X10" M, ea ‘ re : Wher dees ate le Ho xan aural ystems that ae ner neutral pi a at In fc some mi 4 “chelating” agent tht compen on in oder parent Fe?* available for microbial use. Ee win beyoteit nantes of H*, Fe**, and Fe"* provided in Example 3.9, ene tee) SOLUTION In Example 38 AG® was determined to equal Hence the equilibrium constant is determi equals zero at equilibrium: (023 kk) | (mole ~ K) GON 1 a * (83147) » GD» ag 108 Remember that K is me ‘emember that K is merely the reaction quotient, Q, at equilibrium. Hence ros = (SSO.)Re* Pp E [.S0,(0Fe*F[H.O} From this expression the rato thatthe problem requested can be found (S05) __[Fe*“Ppa*p (S0,] ~ KiFe* FF] 123 kJ for the reaction of interest. ined from Equation 3-38 because AG k= op AO. ind the reaction is written using | 34 Equilibrium Processes 75 Filling in the appropriate values the ratio is [H,S0,] _ [10°F [10~P [H,SO,] ~ 10*[10*F (1) Clearly this reaction proceeds extremely far to the right such that virtually all of the sulfur is oxidized to sulfuric acid under the assumed conditions inside of clouds. — 10 334 Effect of Temperature on the Equilibrium Constant Most tabulated equilibrium constants are recorded at 25°C. The van't Hoff relationship is used to convert equilibrium constants to temperatures other than those for which the tabulated values are provided. Van’t Hoff discovered that the equilibrium constant (K) varied with absolute temperature and the enthalpy of a reaction (AH°), Van’t Hoff proposed the following expression to describe this: dink _AH® at” RT 3-40) Here AH? is found from the heat of formation (AH) forthe reaction of interest determined at standard conditions (see Table 32 for some typical values). Most temperatures encountered in environmental problems are relatively small. ‘Therefore, the temperature differences are not that large. If AH” is assumed to not change over the temperature range being investigated, Equation 3-40 can be tegrated oy Ka) Ae (12 oleh G-) = Equation 3-41 can be used to calculate an equilibrium constant for any temperature (Le, temperature two, 7) ifthe equilibrium constant is known at another absolute temperature (temperature one, T;, which is usually 20 or 25°C). Re- member, though that, as stated previously, itis assumed that AH® (usually measured at 25°C) remains constant over the temperature range of interest. Later in this chapter, Example 3.25 demonstrates the use of Equation 3-41. Similarly, if AG? was known at a specific temperature, the equilibrium constant at that temperature could be calculated using Equation 3-3. 34 EQUILIBRIUM PROCESSES In environmental systems, some important equilibrium processes include those between pure compounds and air (volatilization); chemicals dissolved in water ‘and air (Henry's law); acids and bases; dissolved and precipitated chemicals; and9 Chapter 3 Chemistry 341 Voltieaon Pata presre 242 Ale-Water Equitrom Henrys Contant hort MOAGH-Bue Byam As jm Adit» Conopte Dae +H Asi) 0 in Dasity Cimcon (&;) Base +10 <> Conjugate Acid + OH 344 Preptation Disoution Solid Chemical <> Disolied Chemical ot pt ution Sold Chemical "4Chemical Solubility Product (K, i * (Ky) 245 Srpton-onExchan ‘oli Sacer Si Water Parton (Kp Ra Fendt Pormeters (tinea, Scctiy Cetin, Séparaion aco ‘Sched ncn . onsale ure 3-10, The equilibrium processes described in Section 34 chemicals dissolved ir Gssolved in the water and adsorbed on a sold (sdsorption and io exchange). Figure 3-10 outlines t ines these equilibrium: tach ofthese ec anes these equilibrium processes. Tis section sevice 34.1 Volatilization ns etre of enol protien that th ne medium. For example, at ofthe mercy fit emitted a a poltane hat ec ey seldom ae confined to just charged ino the envronsat amaging effects ocr in nes _qterit moves through the atmosphere, is deposited into a lake, and then under- a biological transformation process called methylation. This process resulted seSpproximately 1,300 fishing advisories in lakes Uhroughout the United States 1995. is 2%, ya shown in Figure 31, pss sch as DDT, which a it wwe tanned in the United States, is stil sprayed on fields in Central America where itihen volatilzes. Airborne DDT can then be transported to the United States; xt a result DDT is found in remote lakes and fish in the northernmost reaches ‘the lower 48 states, including Isle Royale National Park (MI), located in Lake Superior. Also, lead that was jitally used in paint and gasoline is now found primarily in the sol where it ill an pose health hazard to children who ingest The contaminated soil. Finally, Examples 3.8 and 39 showed how acid rain orig- nates with the burning of fossil fuels, with the subsequent emission of air pol- jutants. In all these examples, pollutants are emitted to the atmosphere and cause damage after they are deposited on land or surface waters. Figure 3-11, Volailization of chemicals can result in regional and long-range transport ofthe chemicals to places faraway where adverse environmental effects can be {etected. Persistent organi pollutants (POPs) become concentrated inthe food chain where they ean cause tore effects on animal reproduction, development, and jimmunologeal function. The US. State Department has termed POPs “one ofthe great environmental challenges the word face." POPS include polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-doxins and furans, and pesticides such as DDT, toxaphene, chlordane, and heptachlor. Though banned for use in many developed ‘countries, they ar stil manufactured for export and remain widely used and turegulated in developing countries. These chemical volatilize more easily inthe warm Surface temperatures found in the southern United States and subtropical and tropical regions, then condense and deposit in hgh latitudes where temperatures are cooler (Wenia and MacKay, 1996). This procss of exporting toxic chemicals to other counties that then return by atmospheric transport has been termed “the circle of poison,10 Cnapter3 Chemist pter3 Chemistry 3A Equilibrium Processes 79 ‘A key step inthe transfer of : f ransfer of pollutants between different en 3 is voltizaton. All iquids and solids exist in equiloriun oh oe Phat, Volalizaon (snanymous wih eapoaton) ithe efor Ee | i lui sate tots gaseous Sblination a ot word used | ‘sation, Everyone has first | sat Everyone has fi sthand experience with this phenomenon with water. The | famixture of miscible (.e., mutually soluble) liquids, rather than a pure liquid was present, the denominator in Equation 3-43 would be the concentration of $e Raia! gud (4) in moe tractons, Xt = Bol _ Pa Kas G4 Equation 3-44 is known as Raoult’s law. The equation constant, K, equals the saturated vapor pressure. Raoult’s law is useful whenever a mixture of chemicals (eg gasoline, diesel fuel, kerosene) is spilled. ‘The vapor pressure for all compounds increases with temperature, and at the boiling point of the compound the vapor pressure equals atmospheric pressure. ‘There are many consequences of this statement. First, atmospheric concentrations of volatile substances can be expected to be higher in summer than in winter, in the day versus in the night, and in warmer (southern) locations compared to northern locations. Second, for any structurally similar group of liquid icals exposed to the air, the equilibrium gas-phase concentrations will de- more readily than water. The fumes fr it 5 ese commonly used products oe ‘The chemical 1,4-dichlorobenzene (1,4-DCB) is used in an enclosed area. At20°C (68°F) the saturated vapor pressure of DCB is 53 X 10™* atm, What would be the concentration in the air of the enclosed area (units of g/m*) at 20°C? The molecular weight of 1,4-DCB is 147 g/mole. SOLUTION ‘Rearrange the Ideal Gas Law (PV = nT) to solve for the concentration of DCB in the air: Qo — HO om nl P 53x 10am Equation 3-42 indicates that liquid water er oes a iquid water is in equilibrium with gaseous water pole = K (793K) (Ge. water vapor). The equilibrium constant (called the soured ‘vapor partial Pressure) for this reaction is *esction is x 10-5 BOIS 5, 1,000 L 147 g On a Friday afternoon, a worker spills one liter of tetrachloroethene (PCE) on a laboratory floor. The worker immediately closes all the windows and doors and and hence the equilibrium constant turns off the ventilation in order to not contaminate the rest of the building. The of atmospheres,34° Equilibrium Processes 81 ) anc the temperature in the 25°C 81.62 glo’, nd the molec weight of PCE ga ea OPE sowution PCE isa volatile chemical. The PCE remenrat chemical The problem asks how much of th Figure 3-12. Schematic of an air-sparging process used to treat contaminated {groundwate. Injected air strips chemicals from the saturated zone into the overlying unsaturated zone. Vapors stripped into the unsaturated zone must then be removed by ‘a method such as vacuum extraction and trested above ground with activated carbon, biofltration, or thermal oxidation. into the water until it reaches its equilibrium (or saturation) concentration. En- gincers use this equilibration between air and water to maintain the necessary concentration of oxygen in sewage-treatment plants and to calculate how much organic waste can safely be discharged to surface waters. Another important application of air-water partitioning is inthe stripping of gases or volatile substances from water. Air sparging is used to strip volatile pollutants from ground. Water to the unsaturated zone (vadose zone) where they can be treated and sir-stripping towers can be designed to make drinking water safe by stripping hazardous chemicals out of water. Figure 312 isa schematic of an ai-sparging process for treating contaminated groundwater, and Figure 313 depicts an a stripping tower used to treat a drinking-water supply contaminated with volatile organic chemicals. ‘The Henry's constant, Ky (some authors use the term #1), is used to describe 4 chemicals equilibrium between the air and water phases. Henry's law i just 2 special case of Raoull’s law (Equation 3-44) applied to dilute systems. Remem- ber, most environmental situations are dilute. Because the mole fraction of a dissolved substance in a dilute system is a very small number, concentrations such as moles/L are typically used rather than mole fractions. Note that Equation 3-44 may also be useful because it can be used to estimate Henry's constants in the absence of reliable experimental data. That is, a Henry's eonstant fora particular chemical can be determined by dividing the saturated vapor pressure of the chemical by its aqueous solu Water into the atmospher oxins for many years into the Fox River iver ne the PCBs and dioxins sorbed onto the sedi {he river or were carried downstream. Today, tents and settled to the bottom of ; the majority of discharges of these82 Chapter 3 Chemistry gure 343, Phow of sitting tower wed 2 Wausau, Won, halogenated sovens (Gchloosthene and Peelorcethene fom 2 inking: water Ieweats about 5 millon talons per dy, ich S about one-aio the Gi’ water needs (Courtesy Dave Find) The units of Henry's constant vary depending on whether a reaction is writen 4 gas phase going 10 ao phy oe hae ate oF aqueous phase going wo ges hae don, Henry's constants may abo be unis, Thus fs et Proper units, understand why particular units Seer i, understand why parte ‘are used, and be able to convert 342.1 Henry's Constant with Uns fora Gas Disobing ina Liquid ‘The following reaction describes the trans sibes the tans of gas (in this the atmosphere to water (depicted in Figure S10, M8 OBEN) fom 6-45) B-46)Ro 34 Equilibrium Processes 83 “The value of the Henry’s constant, Ky, at 25°C for oxygen is 1.29 x 10-* moles! -atm, Note that in this case the units of Ky are moles/L-atm. The reaction was writen as gas going to aqueous because in this case we are concerned with how the composition of the gas affects the composition of the aqueous solution. The preceding expression shows that the equilibrated dissolved oxygen saturation oncentration in surface waters is a function of the partial pressure of oxygen in the atmosphere and the Henry's constant. Calculate the concentration of dissolved oxygen (units of moles/L and mg/L) in a water equilibrated with the atmosphere at 25°C. The Henry's law constant for “oxygen at 25°C is 1.29 x 10°? mole/L-atm, SOLUTION ‘The partial pressure of oxygen in the atmosphere is 0.21 atm. Equation 3-46 can be rearranged to yield: + mole «mole ore oe 1% Pa =O) = (109102 BE) a am 279 ‘Thus the solubility of orygen at this temperature is 2.7 x 10 moles/L If this is rultiplied by the molecular weight of oxygen (32 g/mol), the solubility can be reported as &7 mg/L. ‘The value forthe concentration of dissolved oxygen in water equilibrated with the atmosphere is 144 mg/L at °C and 92 mg/L at 20°C. This demonstrates that ‘oxygen solubility in water is dependent on the water temperature (one reason trout lke colder waters). The reason for this is that for the reaction described in Equation 345, the change in heat of formation (A4*) at standard conditions is ~3.9 kcal. Because AH? is negative, Equation 3-45 could be written as Org) > Orjaq) + heat a7 ‘An increase in the temperature (or adding heat to the system) will, according to LeChatelier’s principle, favor the reaction that tends to diminish the increase in temperature. The effect is to drive the reaction in Equation 3-47 to the left, which consumes heat, diminishing the temperature increase in the process. ‘Therefore, more oxygen will be in the gas phase at an increased temperature, and thus the solubility of dissolved oxygen at the increased temperature will be lower.84 Chapter3 Chemistry 342.2 Dimensionless Henry's i fenry’s Constant Srom a Liquid to a Gas {In the case where an individual isi 1 | Ite i is interested in the transfer ofa chemi inthe aqueous phase to th atmosphere, the chemical iene a et ind liquid phase chemical is described on writen in revere Equation 3-45, Examples of | Volatile onganic chemicals (e ural transfer of chemicals from a lake of ri for the chemical trichloroethene (TCE). for a Species Transfering TC gy — TCE, In this case the equilibrium expression is written as : (TCE, “Tre Toble $3. Unit Conversion of Henry’s Constants (Hand et a) ea) vo ues) X RT x 556 BOUHLO ‘i ry ‘R= 0320s StL mol K "Equations reprinted from Hand et aL in Water Quay ermision. Copyright 1998 American Water Works Saar 34 Equilibrium Processes 85 ee eee ne tr Te nN eet lias Se ee a eee carne ip te eae ‘The Henry’s constant for the reaction transferring oxygen from air to water is 1.29 X 10? moles/L-atm at 25°C. What is the dimensionless Ky for the transfer ‘of oxygen from water fo air at 25°C? SOLUTION ‘The problem is requesting a Henry's constant forthe reverse reaction, therefore, the Henry's constant provided equals [1.29 x 10"? moles/L-atm]” = 775 L-atm! role for the reaction of aqueous oxygen going to gaseous oxygen. Using the Ideal Gas Law: 71S L-atm ‘mole 0.08205 Lat =2 are) oR) Ky, (dimensionless) ( Note that the units on the dimensionless Henry's constant of 32 are really mole/L of air divided by mole/L of water, which equals L of water per L of air. Hexachlorobenzene (CCl) is a chemical produced mainly as an unwanted by- produet during the production of pesticides and other organic chemicals. This ‘compound is widely distributed in the environment and bioaccumulates strongly. ‘The dimensionless Henry's law constant for this compound is 0.054. If the concentration in the air above Lake Michigan is measured to be 50 pmole/m? and the concentration in the water of Lake Michigan is measured to be 100 pmole/ LL, would hexachlorobenzene (HCB) tend to move from the water into the air (or from the air into the water?86 Chapter 3 Chemistry SOLUTION Ree roe 7 my Kea Which is the reaction of transfer Seg eee he aso of eng tration can be predicted from the air ‘concentration: eels 50 pmole mi = Bopmoles , _m_ _ 093 pmoles 0.054 eee On Ce rae ium. Therefore, HCB will continue the water to the air until equilibrium is established. othe eae ee 343° Acid-Base Chemistry Aci base calculations are required in instances where neutralization ofan acidic or basic solution is required, and for nu is necessary to maintai tan olan inate oo uty voll si at an nn ig the fate and westent of many chemical species ts Hem ca conta 343.1 pit By definition, the pH of solution i pH = ~Iog(Ht*) snp ee eee incl ea! ep at conetaton ote dpe a approximately 5.6 due to the presence of lessee aeprorinily the presence of dissolved carbon dioxide from the ‘The concentrations of OH™ and H* ae oe ‘are related to one another through the n of water: eee On Gs) ‘Table 34. Dissociation Constant for Water st Various Temperatures ‘Femperature, °C Ke pH of Neutra Solution 0 0.12 x 10 741 15 045 x 10" 718 20 (0468 x 10" 708 2 LoL x 10-** 7.00 30 LaT x 10-" 692 ‘anes of K, obtained from Stumm and Morgan, 1996 “The equilibrium (also called dissociation) constant (K,,) for Equation 3-51 equals 10° at 25°C. Thus, K, = 10" = [JOH] sR ‘This allows the determination of the concentration of H* or OH” ifthe other is known. The van't Hoff relationship (see Section 3.34) can be used to determine the K,, at other temperatures. Table 3-4 shows the K, at various temperatures of environmental significance. Note that at 25°C [H*] equals {OH}; thus [H"] = 1077 and the pH of a neutral water would equal 7.00. However, at 15°C, {H*] equals 10-7" and thus the pH of a neutral solution at this temperature would equal 7.18. 34.3.2 Definition of Acids and Bases and Their Equilibrium Constants ‘Acids and bases are substances that react with hydrogen ions (H"). An acid is defined as a species that can release or donate a hydrogen ion (also called a proton). A base is defined as a chemical species that can accept or combine with a proton. ‘The reaction of a monoprotic (monoprotic means the acid can donate one proton and the base can accept one proton) acid, HA, with a base, B~, is illustrated in Equation 3-53. Ifthe reaction is reversible, then according to the preceding def- ition, A~ isa base and HB is an acid. It is always the case that an acid donates ‘a proton to a base, and in the process itself becomes a base. For acid-base pairs like those shown in Equation 3-53, A~ is termed the conjugate base of acid HA, and HEB is termed the conjugate acid of base B~. HA + BY <> A> + HB G53) One of the remarkable features of water is that it can act as both an acid and ‘base. This feature makes acids and bases important to humans and to all living organisms. Note that in Equation 3-54 where a base is added to water, water acts as.an acid and donates a proton to base (B): Bo + H,0 — HB + OH G54)88 Chapter3 Chemistry However, in the case where an acid is added to water, water accepis a proton from the acid (HA) and acts as a base: HA + H,0 > H,0* + A- 55) This substance HO is nothing other than a water molecu! le with a proton attached and looks like: ae Jn point of fact, no free H ions actually exist in water. They are always combined With one or more water molecules. However, forthe sake of simplicity the water mojeeules attached to the H” are generally ignored and Equation 3-55 is generally written as HASH + A> 6-56) The forward reaction of Equation 3-56 is termed the dissociation or deprotona- tion of the acid, HA. The reverse reaction is termed the protonation of the bace duis can undergo such reactions and this becomes the basis fr distinguishing {heir relative strengths. Acids that have a strong tendency to dissociate (Reaction 3.56 goes far to the right) are called strong acids, while acids that have less of 2 tendency to dissociate (Reaction 3-56 goes a litle to the right) are called weak acids. ‘The strength of an acid is stant for the dissociation reaction. picted in Equation 3-56 is ted by the magnitude of the equilibrium con- ‘The equilibrium constant for the reaction de- TA] oo THAT @snp At equilibrium, a strong acid will dissociate and show high concentrations of Hi and A and a smaller concentration of HA. This means that when a sreng acid is added to water, the result is a much lager negative free-energy change than when adding a weaker acid. Thus for strong acids the equilibrium constant, Ke will be large (and AG would be very negative). Similarly, the K. for meal acid would be small (and AG would be less negative), Chemists have adopted the habit of taking the negative logerithm of equlib- um constants and concentrations and denoting them by the prefix “pt Fer example, pH equals ~log(H*). Hence pK isthe negative logarithm of hee nerd dissociation constant (Le, pK, = ~log(K,)). Table 3-5 shows values of equili. ‘lum constants for some acids and bases of environmental importance. Tatte 3.6 shows thatthe pK, of a weak acid is larger than the px, ofa stong sci ‘The pK, ofan acid is related tothe pH at which the acd wll issosiate Strong acs are those that have a pK, below 2. They can be assumed to disooiet 3.4 Equilibrium Processes 89 ‘gable 3-5. Some Common Acids and Bases and Their Equilibrium Constants ‘When Added to Water at 25°C i. meme — . Oe eee 0 ic a H,PO,” Dihydrogen Se qugoot sie coor gis cae dioxide and ao = moor ign 18 Ogee wor wpimymae ge iis NEL ‘Ammonium 7 on a ‘Carbonate 37 oo mee uaweee sro moan i Values obtained from Stamm and Margan, 1996. completly in wate inte pi rnge 35-14 HC, HINO, Su and HOO. rv) ng als commonly conten noel tans he wes her conjugate bases (CT, NOs SO." and C10, ae so weak hat th rang of 014 hey a med to eer exist wih tached protons.” hugh mot natal waters eit vs ne ene of 68, the pH cof water is restricted to 0-14. The pH is restrcted to this range because another special characterise of water, The dissociation reaction for wate acting as an acid ean be written as HO Ht + OF os oor 0K, for water J equilibrium constant for hs ection a 25° is 10, othe pK, isa Hence water a very weak aid beaine i has& very high pe The thpression forthe equim quotients x, = Hor . [H,0] prryorr) = 10" 59)90 Chapter 3 Chemistry This is the same expression as Equation 3-52 : nas Equation 3-52. When the cor 1M or 10 then the consntaton of Ok mee Mater never les than zero? The concentration of water is fence the maximum possible concentration of hydrogen ion centration of H* What percentage oft mm al anmona (ie, Ny PH or The pk fo NILe woe Hei 19 = NHL) INH] 2 + NHL) is present as NH ata _| K, sozurion “The problem i requesting INH ONAL] + (NAGH * 100% ten ren anc atta oid ec Pression for the NH,*/NH, system Provides the second required ‘equation: “s = (NEI) _ pH, ]007) INHG] INH] ‘Thus, at pH = 7, [NH,*] = 200) the fet expression polly INH]. This expression can be substituted into 10-* [NH] eR TAF) * 100% = 05% Note that a this neutral Note ta tal pH, slost all of the total ammonia ofa sjtem SjAmmonium fon (NH) I tony O54 exes NI The eet ia mast toric to aquatic lie is NH. It storie to oer concentrations above 0.2 mg/L. Thus wastevatrdchages wa ces at most of theft ammonia nthe les tox NH” form This oad acne 34 Equilibrium Processes 91 some wastewater discharge permits for ammonia specify that the pH of the dis- harge must also be less than 9. ‘One nonbiological method to remove ammonia from water is to run the water through an air-stripping tower. NH) is in equilibrium with NHisq,, However, the other form of ammonia, NH," is not in equilibrium with the gaseous phase, ‘Thus, in order to strip ammonia from water, to what pH must the water be adjusted to ensure efficient removal of total ammonia? The pK, for NH," is 93. SOLUTION ‘We must ensure that most of the total aqueous ammonia (NH + NH,*) isin the form of NH which is the only aqueous species in equilibrium with gaseous ammonia, NE. The amount of NH.) at different pHs can be determined, as, was done in Example 3.17 at pH = 6 the %NFliy is 0.052% at pH = 8 the %NHaq, is 4.8% at pH = 10 the %NFea) is 83.3% at pH = 11 the %NHyjay is 98% Because only NH) is in equilibrium with NH, an operator would typically calculate the lime dosage to raise the pH to approximately 11 before running the ‘wastestream through an air-stripping tower. ‘What is the pH of a river immediately after a train wreck releases 400 liters of concentrated (14 M) hydrochloric acid over a period of 1 hour? The river flow rate (Q) is 100 ms, and assume that the stream is pristine and dilute (i.e., no other acids or bases are present). The pK, for HCl is ~3. SOLUTION ‘Assume the acid is mixed evenly into the volume of water that flows past the train in one hour. In one hour, a volume of river water that flows past the train wreck equals 3,600s SSPE x 1h = 36 x 10° mr v=axr% Chapter’3- Chemistry ‘The total concentration of the acid in this volume is then Cotaaa = Vl % Coney (400 LYM M) Volver 6X 10F my * orT = 1S x 10°F The total acd concentration equals the torn of the ad (CEs alow th ad consentaton tb sow te lated tothe concentration of H= and fey = FU]. aga fricy = 1° As eon from its equibium cavlbriam constant (pK, = Will completely disociate: Three ates face on the added sid therefore seas ium [C1"] >> [FICI). A mass bal- = THCY] + [Cr] = [Cr] = 16 x 10-5 zat a gt oe en (se pepstetepe oo dissociates to yield one H* and one CI. wu -ntration of H* also is 1. ea rr a pio ‘This is the pH of the ‘impacted river. oo oe ee sum of sociated and undssoia uation forthe equilibrium conse ed ee 3) HClisa very: ‘strong acid and 3.4 Equilibrium Processes 93 Aumesphere Water Cooana Upon dissolving in water, dissolved CO, undergoes a hydration reaction by reacting with water to form carbonic acid: Czy + HO HCO, K = 10" a ‘This reaction has important implications for the chemistry of water in contact with the atmosphere. First, the water in contact with the atmosphere (e.., rain) has the relatively strong acid, carbonic acid, dissolved in it “Thus, the pHT of rain water, not impacted by anthropogenic emissions, will be below 7. In fact, the pH of “umpolluted” rain water is approximately 5.6. Thus, acid rain, which typically has measured pH values of 35 to 45, is approximately 10-100 times more acidic than natural rain water, but not 10,000 times more acidic if natural rain water had a pH of 70. In addition, because natural rain ‘water is slightly acidic and the partial pressure of carbon dioxide in soil may also be high fcom biologial activity, water that contacts rocks and minerals candi solve ions into solution. Thus, inorganic constituents dissolved in fresh water, and the dissolved salts in the oceans, have their origin in minerals and the atmosphere. Carbon dioxide from the atmosphere provides an acid that can react with the bases of rocks, releasing the rock constituents into water where they can remain either dissolved (see Equation 2-12 for example) or precipitate into a solid phase. Figure 3-15 shows how the dissolution of limestone by groundwater can remove large amounts of rock and form a surface topography known as karst to- ography. This topography consists of sinkholes, large solution cavities (caves ‘and caverns), and small lakes and ponds. Some ofthese cavities serve as conduits for groundwater transport. Mammoth Cave National Park (Kentucky) (the ‘world’s longest cave with 330 miles mapped so far!), Carlsbad Caverns National ark (New Mexico), Wind Cave National Park (South Dakota), and Moravian Karst National Park (Czech Republic) were all created by the dissolution of limestone by slightly acidic water. When waters rch in dissolved carbon dioxide94 Chapter 3 Chemistry Fare 245, Kart opprapy sh stoving he detlpment ft cvs sa ks ad poh Toppa ste el of dca iene ea sic of natural ern ates Ret meson othe National Pak Areas, by Ellwood, Brooks, B., © 1996, with permicccw a Men Inc,, Upper Saddle River, NJ. te! and calm ion drip from the ci om the elng of caves some ofthe dissolved ea dioxide degasses, which concentrates the calc i a ish the ditfernce between COs and tue H.C, Therefor the tem HCO, has een deboed eet nee ee oid by Coney tense te HCO, aks ee aa a a6 lus, the concentration of H,CO,* in waters equil rat ‘mosphere is approximately 10-° M. ee HCO," —> HCO,” + HY Ky = 10" G0) ‘and bicarbonate is in equilibrium with carbonate ion as follows: HCO — COP + HY Ky = 19713 6-63) Note that by our definition of an acid and base, bicarbonate can act as either an acid or a base. In addition, bicarbonate an¢ sido In addition, bicarbonate and carbonate are common bases in ‘The total inorganic carbon content of a water sample is defined as ‘Total inorganic carbon = [H,COs*] + [HCO,"] + [COZ] (64) of tural waters (pH 6-9), H,CO,* and CO,?- are smal rnc Sho 2 8 On a 34 Equilibrium Processes 95 Figure 3-16. Stalagmite and stalactte formation in Carlsbad Caverns National Park (New Mexico). These formations are formed from the dissolution and subsequent precipitation of minerals such as calcite (CaCOs). (Raymond G. Barnes/Tony Stone ImagesNew York, Ine.) tions (Equations 3-62. and 3-63) that the total inorganic carbon of a system can be measured by first acidifying a water sample so that almost all of the total inorganic carbon is converted H,CO;*. This compound is in equilibrium gaseous CO,, and therefore can be air-stripped and the gaseous CO; measured. Alkalinity. Alkalinity is a measure of a water’s capacity to neutralize acids. The alkalinity of natural waters is “usually” due to naturally occurring salts of weak acids. Bicarbonate is the dominant weak acid in most natural waters (pH of 6-8), with minor contributions from carbonate and hydroxide, OH™. Accordingly, the alkalinity of these waters can be defined as Alkalinity (moles/L) = [HCOs"] + 2{COs*] + [OH] ~ [H"]_ -65)Ro Note that there is the integer of 2 in front of the carbonate term because one mole of carbonate can consume 2 moles of acidity, H*. Also, in most natural ‘waters of neutral pH (pH 6-8), the concentration of bicarbonate is significantly sreater than that of carbonate or hydroxide; therefore, the total alkalinity can be Approximated by the bicarbonate concentration. In some natural waters and industrial waters, other salts of weak acids that ‘may be important in determining a solution's alkalinity are borates, phosphates, ammonia, or organic acids. For example, anaerobic digester supernatant and79 HCO,- + H* ‘The equilibrium quotient for this reaction is Ky = 10-8 = et iCO5*] Many lakes in Michigan's Uj . CaCO¢y > Ca?* + COP” (G-66) ipper Peninsula have low concei oe) tom en nd le cone of ee: centration of bicarbonate Here the subscript (5) denotes that the species isa solid. The equilibrium constant for such a reaction i referred to asthe solubility product, K,,. For the reaction in Equation 3-66, the K,, would be given by ‘of the conceatrations of HCO,- ~ is very smell at these pHs, oreo Ko [GCOr) = [Ca?*][COF] 679 Chapter 3 Chemistry E 3 34 Equilibrium Processes 99 ‘Table 3-6. Examples of Some Common Precipitate—Dissolution Reactions, the Associated K,,, and the Significance in Environmental Engineering Eaqulitvium Equation Ky alwe Significance Ge0O, (6) —> Ca? + COP 33X10 Hardness removal, scaling MgCOs(6)—>Mg*+COZ- 3.510 Hardness removal, scaling CHOH)(6)<—> CaP? 20H 63X10 Hardness removal Mg(OH); (6)*<—> Mg? +20H- 6910" Hardness removal Cu(OH): (8) —> Cut? + 20H 78x10 Heavy metal removal Za(OH): (8) —> Zn" + 2084 32% 10 Heavy metal removal ‘AUOH);(@)<—> AP? + 30H" 63. 10°" “Coagulation Fe(OH), (8) <—> Fe + 30H" 6 X10" Coagulation, iron removal 150, (s) <> Ca®* + SOP” 44x 1075 ‘Flue-gas desulfurization ‘Ramp with permission ofthe McGraw Hil Companies from Sawyer et al, Chemistry for Environmental Engineering, 1998, McGraw-Hill Companies, K, obtained from Morel tnd Hering 1953 of all metals equals 9.6 X 10°*? The Ky, for formation of metal hydroxide pre- ipitates are 5.0 x 10°, 32 x 10°, 69 x 10", and 7.8 X 10, respectively. — SOLUTION gure 3.17. Scale formation ina wate : icra ormton ina water Stibaton pie, (She TenyScene Photo The metals all have the following generic reaction where Me isthe divalent cation Me(OH)ax) = Me* + 20H Because the activity (which we are a ‘Therefore, first set up the K,, = [Me**][OHF for each metal cation and solve ssuming equals concentration nL is defined to be equal to one (Rule ? of Seer’, as rh qeucentration) of a solid for [OH™]. The equilibrium concentration of each divalent cation was given as i equal to the product ofthe concentranen en a2 eauilibrium constant 9.6 x 10°* moles/L and each individual K,, was provided, Then use the disso- the equillorum conten, tWo dissolved ions. Thus, if iation constant 52) fo solve for [H"), wi - the ition constant for water (Equation 3-52) {H1°), which can be con : concentration of one of the s the Sur conn nd ne of the species is known, verted to pH. This resulting pH is where precipitation of the cations will begin genic Zn > Cd > Mg. How many kg of hydroxide sludge with a water content of 95% (5% solids) are generated daily for a wastewater plant treating 1 MGD of a copper waste with 10” M Cu?*? Assume all the Cu is removed as Cu(OH), (MW = 97.5).100 Chapter 3. Chemistry SOLUTION 10° gal 3.78 moles Cut* mole Cu -» moles mole Cu(OH) 915; day gl X10 EE 5, ole CH OH, £ kg. mole Cu* mole Cu( ORs * 70005 = 370 kg dry sludge ,. 100 kg total sludge _ 7.400 kg wet sludge day Ske dry solids day Wha i reuie to reduce a high concent 8 high concentration of doled Mg 48 mg/L? The Kp forthe flowing eacon 10 et ME down to Mg(OH) ayy <> Mg?* + 20H- SOLUTION tomolevL Bm [Mg] = 8ms 8, 1 mole iar 1000 mg * "24g ‘Then, the equilibrium relationship is written as rors = [Me ORF TMg(OF),] Substituting values for al the known parameters 19-16 _ [00018][0H-F 1 Solve for [OH] = 6.2 x 10-5 M. This results in [H*] At hs pH any segs in exes of 0 ha 179. will precipitate out as 10%” M;so pH = Mg(OH)ay) because the solubility of Mg?” would be exceedel, Of CaSO (MW = 136 gimole) ina solution wi the sl - mole) in solution with no other sourees of C* or SOx". CaSOxy isa component of gypnim, which a5 drywall, Landfills containing construction reluse often eve eechats ain 34 Equilibrium Processes 101 high concentrations of Ca?* and SO?” as a result of the dissolution of this sub- Hance. The solubility produet (K.,) for CaSOqa is 10°*”. SOLUTION ‘The solubility is the amount (moles/L) of the calcium sulfate that can dissolve in water. From the stoichiometry, for CaSOq, each x motes that dissolve in water produces 1x moles of Ca** and 1x moles of SO,*. Thus the solubility would be qual to the concentration of Ca®* or the concentration of SO?” in a solution in equilibrium with the solid CaSOq, Because the concentrations of both ions would be equal, the equilibrium relationship can be written as, Key = 104 = [Ca [S077] (edt) Solve for x, which equals 10-* M. This is the maximum concentration of Ca?* ‘and SO, that will result if one attempts to dissolve solid calcium sulfate into ‘one liter of water. That is, only 10"? mole (0.68 g) of calcium sulfate can be dissolved in the one liter of wates. After that, no additional solid can be dissolved in the water. Any additional solid added to the water will not dissolve but will remain as a precipitate, This value is termed the chemical’s solub ‘Typically, as temperature is increased, the solubility of a solid electrolyte will also increase (for solid electrolytes, Kp gets higher). However, notable excep- tions to this rule are CaCOsp,C2s(P Og, CaSOay, and FePO,ey where the K,, decreases with higher temperatures 0 the solubility decreases. This is shown inthe following reaction for FePO, FePOqy = Fe + PO? + heat ‘The AH® for this reaction is ~18.7 kcal so heat is released by this reaction as just shown, ‘What is the solubility of Ca,(PO,)aiy at 25°C and 10°C? The K,, is 13 x 107% at 25°C. The AH} for Cax(PO.)a is -986.2 keal/mole, for Ca** is =129.77 kcal/mole, and for PO,” is ~306.9 kcal/mole. SOLUTION ‘The equilibrium quotient (Equation 3-39) for this reaction at 25°C is 13 x 10- = (Ce P[PO?-F102 Chapter 3 Chemistry From the reaction stoichiometry, for every x moles of Cas(PO, in for every x moles of cy that dissolves Be moles of Cae slated and 2 moles of Po oe eee the solubility of Cay(PO,)z.) at 25°C is found as follows. ° 13 x 10°? = xp ¥ can be solved for as 1.9 x 10°” M, the solubility if Cas(PO,)oy) at i, lubility of Ca;(PO,)2,4) at 25°C. ‘The solubility of Cay(PO.) at 10°C can be found similar, except the Kip at 10°C must be determined. For this the van't Hoff relationship (Equation 3-41) is required along with the heat of formation (AH). 7 Feu lng (AH), At 10°C the AH® for the re- AH? = [3(-129.77) + 2(-306.9)] ~ {(1)(—986.2)] = -16.91 keal Remember that this assumes that the values of AH. (1 °C) dic ales of 19 (measured a 25) di atl a 19°C. Equation 3-41 canbe tan ay cawef a a TT, Sulsituting values in resus in Ky at 10°C wat 10°C equal to 5.89 x 10°", The solubilit at 10°C can then be found as was done before for 25°C. Tresolbilty 5.89 x 10-% = (3xf'[2xy° le that ety (€2, chloroform, benzene, PCBS) ako increases wih intoniog ener OO —aeee 3.45 Sorption and Ion Exchange to Solid Surfaces 34.5.1 Introduction The process of rpg adoption, and in exchange ae important ia the mosphere, inst warns ingroumdnate aera ina tems It shomiats tsome sedated wit ee ee thy cn be deposited to lind by pation selon ne ena ec association of chemicals with particles can influence the toxicity of a chemical, For example spon of suminan on pees reg desu teeing wit a i ues (ih sees wey ote aa ee parce organise tah theater fos heey ee Sate the wate fost expo to addondl seme eo sorption ont partes tt ete to the bowom oes Raa 34 Equilibrium Processes 103 ants from the lake water but could concentrate chemicals in the sediments. In subsurface systems like the unsaturated zone and groundwater there is obviously ‘ tremendous surface area, derived from solids, onto which chemicals can sorb. Substances that sorb to subsurface solids are not as likely to be transported Guickly in the subsurface, or at least their movement will be slower relative to the movement of water and substances that do not sorb appreciably. In addition, some substances sorb so strongly that bacteria cannot remove them from the solids and break them down (Mihelcic et al., 1993). Hence sorption can adversely influence bioremediation of contaminated soil and groundwater. In addition, sorption and ion-exchange processes are used to treat water and gases that are contaminated with a wide assortment of organic and inorganic pollutants 34.5.2 Sorption and Adsorption “Adsorption isthe physical and/or chemical proces in which a substance accu- ‘mulaes ata solid-liquid interface. The solid can be a natural material (eg, surface soil, harbor or river sediment, aquifer material) ort can be of anthropogenic origin (c.g, activated carbon). The word “sorption” is used to describe th teraction of organic solutes with soils and sediments. Sorption isthe combined process of adsorption of a solute at a surface and partitioning ofthe solute into the organic carbon that has coated the surface ofa particle. The sorbate (or adsorbate) is the substance being transferred at the interface from the liquid to the solid phase. The sorbent (or adsorbent) is the solid phase onto which the adsorbate ‘ccumulates, Though sorption and adsorption can also take place from the vapor phase, the following discussion will deal only with sorption and adsorption from the liquid phase. Figure 3-18 shows a schematic ofthe sorption process. ‘Why does adsorption occur? From a thermodynamic viewpoint molecules always prefer to be in a lower energy state. A molecule adsorbed onto a surface has a lower energy state on a surface as compared to being inthe aqueous phase. ‘Therefore, during the process of equilibration, the molecule is driven to the sur- ae bry te iS ns igure 3-18. Sorption of an organic chemical typically takes place when the organic solute (the sorbate) adsorbs either onto reactive surface sites (adsorption) or partitions {nto organic matter that has coated the particle (the sorbent). This process influences the mobility, natural degradation, and engineered remediation of organic pollutants.104 Chapter3. Chemistry face and a lower energy state. Attraction of a molecule toa sur ‘a molecule toa surface can be cau esata re at cnt aoa ca principle governing the interactions between most adsorbates and adsorben, ‘These forces include dipole-dipole interactions, dispersion interactions or Lon. don-ran der Wal fore, an hydrogen bonding, During srpton tosis an sediments, a phenomenon termed hydrophobic partitioning ean also accom th aléeton wats parace e Simply put, if equilibrium is achieved between the or : tween the organic chemical (the sorbate) and the solid surface (the sorbent), an eqiriem constant Kens ne used to relate the aqueous- and solid-phase concentrations of a chemical (ie, [Coo] = K{Caysou]). Understanding this will allow you to do Examples 3-27 to 3.29. The remainder of this section discusses sorption at it a sses sorption and adsorption in more The Freundlich Isotherm Equation. Although some say the Freundlich therm equation is empirical, it can be derived from thi i rom thermodynamic relationshi assuming a heterogeneous surface. It is written as — eee: (3-68)Po here ¢ isthe equilibrium solid-phase concentration ( ‘ concentration (mg soroatelg sorbent), C he equilibrium liquid-phase concentration (mg/l), Xi the Frecedich noc Parameter (mg sorbate/g sorbent)(L waterlmg sorbate)", and lin is the Freundlich intensity parameter (antes) In gas-phase systenss Could ees sent the gas-phase concentration of the chemical : igure 219 shows the Freundich therm equation pote fr diferent val Us of hn, Note that for vals of Unless than one the othe eee favorable for sorption because low values ofthe sorbate gutta cornea, ‘ion ild age values ofthe solid-phase concentration Ths mean tee bate prefers to be sorbed onto the sre However, Ngherajucne one amie Cine Figure 3-19. Freundlich isotherm plotted for different values of Un | 34 Equilibrium Processes 105 trations the sorptive capacity of the solid decreases as the active sorption sites become saturated with sorbate molecules. For Un values greater than one the isotherm is considered to be unfavorable for sorption because high values of the Figuid-phase sorbate concentration are required to get sorption to occur on the sorbent. However, it shows that as sorption occurs, the surface is modified by the sorbing chemical and made more favorable for additional sorption. Ifthe {Un value equals one, the isotherm is termed a linear isotherm. A linear isotherm js commonly observed with dilute aqueous phases and natural sorbents, as is discussed later in this section. In order to determine the Freundlich parameters (K, 1/n) for a particular chem- jcal solute and sorbent, the Freundlich isotherm is linearized by taking the log of both sides of the Equation 3-68, which results in 1 log q = + log € + log K Go) One reason for using Equation 3-69 is tht it can be fited to experimentally determined q and C data in order to determine the specific Freundlich parameters (K and tin) specific to a particular chemical solute and sorbent. Values of K and Un for a wide range of synthetic adsorbents and chemicals are provided by Sontheimer et al. (1988). The Freundlich isotherm parameters are used in Example 331. Linear Isotherm Equation. In many soil and sediment systems (aquatic or subsurface) the concentration of the chemical of concern is relatively low (ie., a dilute system). In these situations it has been observed on numerous occasions that In is very close to one. For the case where I/n equals 1, the Freundlich isotherm equation (Equation 3-68) can be written as KxC G-70)R where Kis the equilibrium constant between an aqueous- and solid-phase solute and has units such as emigm or L/kg. In this case, K is referred to as a soil- or sediment-water partition coefficient. The soil-water partition coefficient is sometimes referred to as a partition coefficient (K,) or distribution coefficient (Ka). Equation 3-70 is useful because if equilibrium is obtained between a chemical in the aqueous (or gascous) phase and solid phase, and K and either the solid or aqueous (or vapor) phase concentration is known, the remaining unknown concentration can be solved for. The problem with this K is that itis chemical and sorbent specific. Thus, although K can be measured for every relevant system, this would be time-consuming and costly. Fortunately, when the solute is aneu- tral, nonpolar organic chemical, the soil-water partition coefficient can be nor- alized for organic carbon, where it then becomes chemical-specifc, but no longer sorbent-specifc406 Chapter 3. Chemistry Soll: Water Partition Coefficients Normalized to Organic Carbon (K.,) and Octanol-Water Partition Coefficients (K,.). It has been shown that fo) nd and sediments wth fraction organic carbon (,.) greater than 0001 (0190) ang {ow eaulibrium slate concentrations (= 10"? molar or the aqueous solubty) the sil-water patton coefficient (K) can be normalized to te solls stone carbon content. K can be normalized for a olor sediments fraction of sean carbon 38 follows: fac G7 Here Kai called the soil-water partition coefficient normalized to organic Rot, Kee has units of emg organic carbon (or Likg organic carbon) aif, § the fraction organic carbon for a specific soil or sediment (1% organie exrbog, caval an f.< of O01). A sand-gravel aquifer might have 0.1% or less ornamie Sarpon uc less than or equal to 0.001), asurace soil might contain 1-5% organic carbon, and lake sediments may be even higher, especially if they siesey pile water body where the sediments are high in biological solids (eg, algae) Ithas been found by many that for systems with a relatively high among Sfreanie carbon (greater than 0.1%), K,. can be directly correlated to pasar, ter called the octanol-water partion coefficient, K,., of chemical, The octanol-water partition coefficient of a specific chemical can be deter srined by a relatively esy-to-understand experiment, fan organic chemical, seraed in a sealed container that contains equal volumes of octanol (C,H;,OH) a cuater after equilibration and separation ofthe water andthe octanol Phare he concentration ofA is measured in these two phases. The equilibrium coment for this system isthe octanol-water partition coefficient, or Ke, and equals inate from Nalues of Kw range Over many orders of magnitude; therefore, Kis usually Teported as log Kow- Table 3-7 lists some typical values of lop K.."for a wide Nariety of chemicals. Values of Ka. for environmentally significant chemicals Tauee from approximately 10! to 107 (log Ky, range of 1-7), The higher the value, the greater the tendency of the compound to partition from the water into ag ‘przanic phase. Chemicals with high values of K,,.. are hydrophobic or “water fearing.” Such compounds will have a very high tendency to sor to particles the environment, The magnitude of an organic chemicals K,., can tell alot about the chemical’s titimate fate in the environment. For example, the values in Table 3.7 indicate that very hydrophobic chemicals such as 2.3,78-TCDD are likely to bioseere ‘ulate inthe lipid portions of humans and animals, Conversely, chemicals cach 4s benzene, trichloroethene (TCE), tetrachloroethene (PCE), and toluene art 34 Equilibrium Processes 107 Table 3-7. Examples of log K, for Some Envionmentally Significant Goemials Chea Laake, or 07s Bunane 28 Taclrotine ie Teetoroctene 2 Tatene an ne bat Neptalene 336 1,2,4,5-Tetrachlorobenzene 4.05, Fhematene 6 eve so 278 TCDD bet ues obtained from Bak : : re relatively feel Wend a roundvaer contaminants ec thy ae rb sin env rsh nig vento nw Ivng ager. This en comparton to pyrene or 237.8 7CDD, whch are tice cna cr salient sant hel ea tt Re cates vl ih shal ake ee cy phobic chemicals hat haves high Ky, wil eatracted toa “ike pase; in ths Gite topo tral ea mail hat te puter ne nv foment ge 9:2) ws Nw Ka ah st ely elt fr 7 Chemical data st that spans many tages of bydrophobiy. Ke has hemi ast Note tat the elation own in Equation 3.73 was fo these data, The heavy lines represent the ~90% confidence interval on the corelaion. Baker et al. (1997). Copyright WEF, reprinted with permission,108 Chapter 3 Chemistry correlated to'other environmental properties such as bioconcentration factors (Gee Chapter 5, for example) and aquatic toxicity. Estimating Kye. K’s are sometimes normalized to organic matter (therefore, Kon). When obtaining organic normalized soil-water partition coefficients from the literature a user must be careful of whether the soil-water partition coeff cient (K) was normalized to organie carbon (K..) or organic matter (Kn). This is because organic carbon is not the same as organic matter (om). Organic matter consists of organic carbon, organic nitrogen, organic sulfur, organic phosphorus, and so on. Thus, the amount of organic matter in a sample would be expected tobe greater than organic carbon, In fact, it has been found that approximately 50 to 59% of organic matter is organic carbon; thus, the ratio of organic matter to organic carbon is approximately .7 to 20 (Nelson and Summer, 1982). The advantage of using Kj. rather than K,, or Ky is that “chemical-specific” values can be obtained from the literature or predicted. Thus, after asoil or sediments specific f.. is determined (see Nelson and Summer for how this is done), the “site- and chemical-specific” K can be obtained from Equatioa 3-71. Over 70 correlations are availabe in the literature to predict K.. (sce Baker etal, 1977, for a discussion of them) from knowledge of other properties of the chemical or its chemical structure. The data in Figure 3-20 were correlated and the following relationship for estimating K., from Ka, was obiained (Baker et a, 1997): log Kae 1908 log Ka +0094 (n= 72,7= 0.91) 3-73) zg ‘The 95% confidence interval for a value of log K,. obtained from this correlation is wan ‘The correlation provided in Equation 3-73 was developed from a critically eval- uated data set of 72 chemicals that represented 11 different classes of organic chemicals. These 11 chemical classes were aromatic amines; aromatic acids; pesticides; phthalates; chlorinated alkanes; chlorinated alkenes; alkyl-substituted aromatics; polychlorinated biphenyls; chlorinated aromatics; phenols and chlorinated phenols; and polycyclic aromatic hydrocarbons. The correlation accounts for 91% of the variability in the data for chemicals with log K,, Fanging from 1.7 to 7.0. The data set is available in Baker et al. (1997), Individuals seeking values of K,. should first consult a data set that has dergone a quality check or use an appropriate, statistically validated correlation (like Equation 3-73) to estimate the value of Kye; Kye can then be related to 34 Equilibrium Processes 109 the site-specific K by knowledge of the system's organic carbon content using Equation 3-71. ‘The log Ky» for anthracene is 4.45. What is anthracene’s soil-water partition ‘coefficient normalized to organic carbon along with the 95% confidence interval? SOLUTION ‘Use an appropriate correlation such as is provided in Equation 3-73. Note that this correlation requests the log Ky, NOt Key! Jog Kee = 0,903(4.45) + 0.094 = 4.11 em*/g organic carbon Therefore, Kye = 10" emg organic carbon. TFor ths estimated value, the 95% wuniideuce interval on log Ke: is given by 2) } = 20.66 cm"/g organic carbon ‘Thus log Kee = 4.11 * 0.66 em'Vg or Ko, = 1.29 X 10* em'/g and the 95% confidence interval is [2.82 x 10%, 5.89 x 10°. That i, a user can be 95% confident that the true value of K,, les somewhere between this range. Note that a user of this correlation has 95% confidence that the estimated value of log Koc is ‘within only approximately 2/3 base-10 log units. This is actually pretty good for aK,_ correlation, ‘Anthracene has contaminated harbor sediments, and the solid portion of sedi- ‘ments is in equilibrium with the pore water. If the organic carbon content of sediments is 5% and the solid sediment anthracene concentration is 50 g/kg sediment, what is the pore water concentration of anthracene at equilibrium? SOLUTION From Example 3.26, the log K.. for anthracene was estimated to be 4.11 em*/g, organic carbon. An organic carbon (QC) content of 5% means that foc = 0.05.110 Chapter3 Chemistry ‘Therefore, using Equation 3-71, the sediment specific partition coefficient, K, is equal to co _10en? 005200 _ py i“ gsediment — g OC . g sediment — (664 cm?/g sediment ‘The equilibrium aqueous-phase concentration, C, is then derived from the equilibrium expression given in Equation 3-70: 50 ug x kg C= gix = Kesediment “1000 g , em? , 1,000 mL. _ 0.078 wg 644 em ober L z sediment Note that the aqueous-phase concentration of anthracene is relatively low compared to the sediment-phase concentration (50 ppb in the sediments and 0.078 ppb in the pore water). Thisis because anthracene is hydrophobic. Its water solubility is tow (and Kay is high) so it wants to partition to the solid phase. Also, the solid phase is high in organic carbon content. A sand-gravel aquifer would ‘be much lower in organic carbon (f,. very low); therefore, less of the anthracene ‘would partition from the aqueous to the solid phase. Equilibrium constants for inorganic species with solid surfaces are also used. For example, assume that lead leaches from mine tailings into a stream that passes through a small wetland. The lead sorbs tothe organic soil of the wetland with a K value of 10* Likg, Predict the concentration of Pb in the soil (in 8/2) after 25 years of exposure to leachate with a Pb concentration of 25 ug/L. SOLUTION Initially, the concentration of Pb in the soil may have been close to zero, and ‘much of the inflowing Pb would have been removed from the water by sorption ‘onto the soil. Eventually, however, enough Pb will have sorbed onto the soil such that the soil isin equilibrium with the Pb in the inflowing water. It is this equilibrium concentration that the problem requests, From the definition of K in Equation 3-70: re) * PPosmiwal 34 Equilibrium Processes 11 Hence the concentration of sorbed Pb is simply equal tothe partition coefficient (K) times the dissolved concentration (25 ug/L). The sorbed concentration ‘would be 10" L/kg x 25 pg/L = 25 x 10° ygikg or 250 ugig. ‘A typical value of fac for particles suspended in the upper waters (termed the epilimnion) of Lake Superior is 0.2. What is the ratio of sorbed to dissolved PCB in these upper waters? Assume the log Kg. (cm'/g organic carbon) for PCB equals 6. SOLUTION Use an equilibrium expression to determine the ratio of sorbed to dissolved PCB (ie. giC). Therefore [PCByorved] eal 2 Prey 7 10 X02 = 2X 10% emg total (One must examine the units in order to understand this ratio. The units ofthis ratio (K) are cm*lg of particles. Thus, the units of sorbed PCB are mg/kg, and the units of dissolved PCB are mg/L. Thus, on every kilogram of suspended particles there are 2 X 10° times more PCB than there is in every liter of water. In Lake Superior there are typically only 0.5 mg of suspended solids per liter of water; therefore, in each liter of water only one-tenth of the PCB gets sorbed conto particles. This result can be obtained by multiplying the ratio of2 x 10 L/k, by the concentration of suspended solids (05 mg/L. x 10°* kg/mg) to yield the dimensionless ratio of 0.1. However, sedimentation of these suspended particles is one method by which PCBs are removed from the water column, ‘The retardation factor can be defined as the ratio of the average linear velocity of groundwater over the velocity of a chemical whose movement is retarded because of sorption to the solid material in the aquifer. Thus, if the retardation factor equals 10, the average velocity of the chemical would be about 10 times slower than the average velocity of the groundwater. The retardation factor is defined as 1+ o K 75)412 Chapter3 Chemistry crise ion Carbon tesebloride = = Tenachorotiene BEEE concenratoninjeced concentration) ‘iRetive Conceateation peered ae Fire 32, Rests of» eld ale sd tht show ie atone oredaton hema slute anspor in the sabsace, The stay was ondactel Ontario The svengepomdeser sc atheah, ea te Sle mses tts Sng ha eames irate edn tleA met el ctl Ste ‘erat tg pte de eins ao ese ee sate sos pas snd move the ane veg a ace Shamita eh the monring wel ence en ae Ietchlorotone (aka ened tos erator ea a RCE) ‘Thus, one might expect that carbon tetrachloride isles hydrophobic than ° tcncloretien: Rovere he or cctna ce eae con tease epred 27 ond he ae ea thce K afaron (tapes tyne Aman Tse Cheah ean a2 Prysial Property Daa (ATCHEDIPPR) Peony eee si th gr sear demonsrs how rasta etree eg Bee? WH Sts emoaneat ao shows sone oie tig al aR anon eae nicl eso en esheets oe ah ‘he subsurtacaver somples vont In thin, he erp eon content ofthe aur sey tow (0.02%) so sorption seen nae the Soninant neni oling arden, cg a ana ie inthe reported veo te otolnaterprton seinen Gea tceclorethene sgh more byrophe Po cena A Sr sg that th mater soi curen ernie asa cane TINS tetrachloroethene is 484 mg/L. These values contr lict the reported values for K, 7 shih en eo eve tat eon entire ae Kon Coren doen Ker ae lee of a I te Gee amore dened undertone hc obra Ko reprise ie eo nc en a 34 Equilibrium Processes 113 where 7 i the volume of voids/total volume and py is the soil bulk mass density (both values are discussed further in Chapter 4). The retardation factor is useful for predicting the relative movement of chemicals as shown in Example 3.30. Figure 3-21 shows how the groundwater contamination plume from two chemicals with different sorptive properties (therefore, different retardation factors) will spread at different rates because of sorption. Thus, hydrophobic chemicals, ‘which sorb more strongly, will typically move through the subsurface at a slower rate than a less hydrophobic chemical. ‘A ypical value of subsurface porosity is 0.3 and soil bulk mass density is 21 glem?. If the subsurface material’s fraction of organic carbon is 0.01 (1% ‘organic carbon), determine the retardation factors for toluene (log Koy = 2.73) and 1,3,5-trichlorobenzene (log Kay = 4.49). SOLUTION First determine the Kye of each solute, Use an appropriate correlation for these chemicals such as Equation 3-73. For toluene, log Kj- = 0:908(2.73) + 0.094 = 2.56 - 360 cm? Koc = 1 = aan carbon 3.6 cm? Ke Koc X foc = 300001) = a 903(4.49) + 0.094 = 4.15 For 1,35-TCB, log Kye 14,100 em? ie i organic carbon Ml em? aquifer material K = Kye X foe = 14,100(0.01) Use Equation 3-75 to determine the retardation factor. For toluene, 21g wane =1 fit tt] 26 Os: ‘Similarly, the retardation factor for 1,3,5-TCB equals 990. ‘This shows that the toluene moves about 26 times slower than water and 13,5-TCB 990 times slower than water. Note that how much a chemical's move-114 Chapter3 Chemistry ment is retarded (or slowed) relative to the velocity of the groundwater is primarily influenced by the hydrophobicity of the chemical and the amount of organic carbon contained in the soil or aquifer. This problem also suggests that toluene will move more quickly vertically through the unsaturated zone with rain recharge compared to 1,3,5-TCB. Also both chemicals should move slower than the groundwater when moving horizontally toward a downgradient well. ——— ee Activated Carbon. Activated carbon particles are charcoal granules that have been carefully prepared from the pyrolysis of organic materials such as bitumi- ‘nous coal, peat, lignite, wood, and coconut shells, In this process, the carbon: ‘ccous materials are converted to mixtures of gas, tars, and ash. The tar is burned off and the gases are allowed to escape, creating a highly porous charcoal material that contains a very high internal surface area (500-1,000 m*/g). The special pyrolysis process provides active or adsorption sites on the internal surfaces of the charcoal where adsorption of chemicals can occur. This provides an ideal adsorbent; high surface area and active sites. Activated carbon adsorbents are used for water treatment, industrial solvent recovery, and treatment of contaminated air streams. Figure 3-22 depicts one of these applications. Activated carbon can be broken into two types: powdered activated carbon (PAC) and granular activated carbon (GAC). PAC consists of very small particles that are typically less than 005 mm in diameter, The typical size range (does) cconaminntes Poe tne 9 —> (reel Way ‘Spent Carbon ‘Figure 3-22. Adsorption using activated carbon is the most widely used treatment technology for the purification of air and water. Its also widely used by industry for Purifying gases and liquids, and recovering solvents from by-product streams that are ‘used in various production processes. This figure shows a schematic diagram ofa fixed bed activated carbon system. Contaminated liquid is pumped through a bed of activated AP* > Ca?*>Na* and PO? > $02 > C Rule 2. At tow aqueous concentrations (<1,000 trations (<1,0 mg/L TDS) and typical su- face and groundwater temperatures the exten of exchange nts ooh increasing atomie number (decreasing hydrated radius) of the exchangin ion as follows: ig hydrated radius) of the exchanging Cs*> Rb >K* >Na*>Li* and Bu?" > Sr?* > Ca? > Mg? > Bet diminish; in some cases the ion of lower valence has the higher exchange poten, salad ions are being held more tightly by the resin, f (greensand, clay, peat, aluminosilicates (zeolites) and syntheiic organic resins (tog ne ano can es ion cons re its ane at ue GPA): nea i sin change ‘HT and Na*), because the density is different for each form of the resin, se 3.5 OXIDATION/REDUCTION Some chemical reactions aca becase clectrons ae tansered betmeen die ent chemical specie. The pei ioning leon) ie leone sin hile he speieacmpingeecuon) (hs csmsonacenne aecn Those reactions ae elle oldaonfeduton recone ota oo ne eat ear aernym sates "LEO goes GER" or ln of cleaner dation, gain of elerrons equal reuton, Ondatoninieg ee iese ca 35 Oxidation/Reduction 121 the fate and speciation of many metals and organic pollutants in natural systems, and many treatment processes employ redox chemistry. The most commonly used treatment processes involving redox reactions are probably aerobic biolog- ‘cal processes where organic compounds are oxidized to CO, and oxygen is reduced to water. These processes are discussed in depth in Chapter 5. ‘Another reason for understanding redox chemistry is that the oxidation state ‘of a chemical may control its mobility in the environment or its toxicity. For ‘example, hexavalent chromium (Cr**) is bright orange in color. One use of it ‘was a reagent in the leather-making industry. It is considered very hazardous to humans, Trivalent chromium (Cr) is green in color and is much less hazard- ‘ous. There are many sites around the country where soil and groundwater have been contaminated by chromium waste products from tanneries. Accordingly, ‘many tanneries have switched from the use of hexavalent to trivalent chromium, ‘This is because of consideration of worker safety as well as potential impact on chromium discharged to the environment. The substitution of a less hazardous form of chromium in the leather tannery industry is an example of “pollution prevention.” ‘Ammonia nitrogen (oxidation state of ~3) can be converted through nitrifi- cation and denitrification to Ns gas (Oxidation state of 0). In addition important atmospheric pollutants include NO (oxidation state of +2) and NO» (oxidation state of +4). This conversion of nitrogen to different compounds occurs through ‘many redox reactions. In addition, acid rain is caused by emissions of SO; (sulfur oxidation state of +4), which is oxidized in the atmosphere to sulfate fon, S02 (sulfur oxidation state of +6). It is sulfate ion that returns to the Earth's surface in dry or wet deposition as sulfuric acid. In the remainder of this section we discuss two examples of common redox reactions, the COD test and oxidation of organic matter. ‘The chemical oxygen demand (COD) testis used to characterize the strength of a wastewater. In this test, a sample containing an unknown amount of organic matter is added to a 250-ml. flask. Also added to the flask are AgSO, (a catalyst to ensure complete oxidation of the organic matter); a strong acid (H,SO,), dichromate (Cr,0,?>, a strong oxidizing agent); and, MgC, (to provide Hg” jon that complexes chloride ion, C-). Chloride ion interferes with the test and is present in high amounts in many wastewater samples. This is because it can be oxidized to CP by dichromate as well as by organic matter. However, the complexed form of CI” is not oxidized. Thus, if uncomplexed CI” is allowed to be oxidized to CP, it would result in a false-positive COD value if not accounted for. ‘The sample and all the reagents are combined and the sample is refluxed for 3 h. Then the sample is cooled to room temperature and the dichromate that remains in the system is determined by titration with ferrous ammonium sulfate. The following reactions explain the COD test where glucose has been assumed to represent the organic matter present in the sample: CHi20g + 6H,0 > 6CO, + 24H" + 24e™ 78) Ge + 14H + Cr,07> > 201°" + THO B-79)122 Chapter3 Chemistry Equations 3.78 and 3.79 are termed hal-reactions. Equation 3:78 the bal: reaction forthe oxidation of gluco, and Equation 379 the haltceaton for theredction of hexavalent comm to tivlen chromium. Electrons ae wc tena The ove easion x fou by Ht malig Enon 579 9 # 0 balance the numberof electrons in both reaction allowed by adn ba half-reactions to obtain: a CiHaO¢ + 32H” + 4Cr.0;?* + 6CO, + 8CP* + 22H,0 3-80) Note that the glucose is oxidized (donates electrons) and the chromium is reduced (accepts electrons) from the hexavalent form (Cr*) to the trivalent form (Ce). Thus, the COD test determines how much of the hexavalent chromium is reduced during the COD test. The amount of hexavalent chromium is then related to the amount of organic matter that was oxidized. Engineered biological remediation of natural and synthetic organic chemicals 'ypically consists of adding oxygen to convert the compounds to end products such as carbon dioxide and water. In addition, discharge of wastes to surface ‘waters may contain organic matter that will react in the receiving lake or river. ‘Chapter 5 covers the oxidation of organic matter and the associated consumption of oxygen. If the organic matter is assumed to be represented by glucose, the glucose can be ordled to carbon dioxide and oxygen is reduced to water as CaFlizO, + 6H,0 —> 6CO; + 24H" + 2407 G81 Oxia + 4H + de” <9 2H,0 82) wih an overall reaction of ater multiplying Equation 382 by 6 to Blane the Cally, + 602449) —> 6CO, + 6H,0 G83) Note that in thi teaton the mole of gcse (ihe elecuon donor) donate 24 total electrons, which are accepted by the 6 moles of oxygen (the electron acceptor). i ee 3.6 PHOTOCHEMISTRY AND THE ATMOSPHERE (URBAN SMOG AND THE OZONE HOLE) 3.6.1 Introduction ‘The stratosphere is the region of the atmosphere 15 to 50 km above the Earth's surface. The troposphere is the region from ground level to 15 km. O: level sm. Ozone concentrations in the stratosphere are in the ppmiy range. This ozone filters out some 3.6 Photochemistry and the Atmosphere 123 of the harmful ultraviolet (UV) rays that are emitted by the Sun. Tropospheric ‘zone concentrations reach several hundred ppby in polluted urban areas, At these concentrations, zone (called smog) can be harmful to humans and plans. Figure 3.23 shows the effect on visibility from smog in Los Angeles. In this section tre disouss the general chemistry of tropospheric ozone (ie. urban smog) and {depletion of stratospheric ozone (ie, the ozone hole). A more detailed chemical description is available elsewhere (Baird, 1995) This chemistry is interesting in that it uses photochemical reactions that are catalyzed by chemicals occurring naturally inthe envisonment or are emitted by human activities. Photochemistry is extremely important in the study of atmospheric chemistry as well 2s some photochemical reactions that occur in the upper waters of lakes and rivers. An example of photochemistry in our daly lives isthe fading of fabric dyes that have teen exposed to sunlight. Another example is photosynthesis, which is perhaps the most important photochemical reaction to the world (photosynthesis is discussed in Chapter 5). “The diferent types of light can be differentiated according to the size oftheir wavelengths. Table 3-10 shows the entire electromagnetic spectrum, Photochem jeal reactions from UV light help control the chemistry of the azone hole and trban smog, infrared light is important in understanding the greenhouse eect, 1s will be shown in Example 4.11 Light can be envisioned to consist of small bundles of energy called photons. “These bundles of energy can be absorbed or emitted by matter. The energy of a photon, E (units of joules), is equal to 84) where fk equals Planck’s constant (6.626 X 10™ J.) ¢ is the speed of light GX 10? mis), and A isthe light’s specific wavelength. Equation 3-84 shows that greater energy is contained in photons witha shorter wavelength. ‘This “light energy” can be absorbed by a molecule. A molecule that absorbs light energy has its energy inereased by rotational, vibrational, and electronic excitation. The motecule then typically has a very short time (small fraction of a second) to either use the energy in a photochemical reaction or lose it (most Tikely as heat). All atoms and molecules have a favored wavelength at which they absorb light. That is, an atom or molecule will absorb light with a specific range ‘of wavelength. Greenhouse gases such as water vapor, CO;, N,O, and CH, absorb energy emitted by the Earth as infrared light, while the major components of the atmosphere (Nz, Oa, Af) are incapable of absorbing infrared light. 1 this “capture” of energy released by the Earth that partially contributes to the warming of the Earth’s surface. Anthropogenic emissions of greenhouse gases such as CO;, CH,, and CFCs have increased the amount of this energy that is “captured.” “Another example of molecules absorbing light energy isin the filtering ofthe ‘UV light that enters the Earth's atmosphere. O; molecules located above the2A Chapter3 Chemistry sepa ty of mountains in Los Angeles on 1 day of good air ualty is poor due to high levels of ozone (6). ‘Coast Air Quality Management District) 3.6 Photochemistry and the Atmosphere 125 ‘Table 3.10. The Electromagnetic Spectrum ‘Wavelength (am) Range =50 rays 50-400 Untraviolet (UV) 400-750 Visible (400-450 = violet, and 620-750 = red) 3150 Infrared stratosphere filter out (or absorb) most of the incoming UV light in the 120-220- ‘nm range, and other gases such as N; filter out the UV light with wavelengths smaller than 120 nm, This means that no UV light with a wavelength below 200 nm reaches the surface of the Earth, All of the UV light in the 220-290-nm range is filtered out by ozone (O,) molecules inthe stratosphere with a litle help from Oz molecules. However, O, alone filters a fraction of UV light in the 290-320-nm range and the remainder makes it to our planet’s surface. Over- ‘exposure to this portion of the light spectrum can result in malignant and non- ‘malignant skin cancer and adversely affect the human immune system and plant ‘and animal growth. Most of the UV light in the 320~400-nm range reaches the Earth's surface, but fortunately this is the least harmful type of UV light to the Earth’s biological systems. 3.62. Stratospheric Ozone Chemistry ‘The “ozone layer” is actually a misnomer because there is no actual layer in the stratosphere. Instead the middle part of the stratosphere (15~35 km) contains ‘most of the protective ozone, Ozone concentrations never exceed 10 ppmy in the stratosphere, so there is never really a lot around. In fact, if all of the ozone in the stratosphere were moved to the Earth’s surface at 1-atm pressure, it would form a layer only approximately 0.3 mm thick. Thus, when people talk about the “ozone layer” they mean that most of the stratospheric ozone is located in the lower half ofthe stratosphere, about 15-35 km above the Earth's surface. Some- times the thickness of the ozone layer is measured by Dobson units (DU). One ‘DU equals 0.001-mm thickness of pure ozone at the density Oy would have at J-atm pressure. Ozone concentrations near the equator are approximately 250 DU, above North America about 350 DU, and in subpolar regions approximately 450 DU. This difference in the amount of Os between the equator and polar regions is caused by stratospheric winds that transport O, away from the equator toward both polar regions. ‘The “ozone hole” that appears each spring over the Antarctic lasts for several ‘months and has resulted in measured O; levels as low as 90 DU. Their relative closeness to the southern polar region is one reason why countries such as Aus- tralia and New Zealand are world leaders in treating the “ozone layer” as an important public health issue.126 Chapter 3 Chemistry Ozone Cycling in the Stratosphere. In the stratosphere, ozone is created, destroyed, and then recreated by several natural chemical reactions. However, the introduction of some anthropogenic chemicals has disrupted ozone’s natural ey. cle. This has resulted in enhanced destruction rates of Os, which has led to te. duced ozone levels. ‘Stratospheric O, is formed by the reaction of atomic oxygen (O) with dimolecular oxygen (0,) according to the following reaction: 0+0+0, 6-85) ‘The O required in Equation 3-85 is derived from the reaction of O, with UV Photons (A = 241 nm) according to the following reaction: 0; + UV photon > 20 G89, However, inthe stratosphere the majority of oxygen exists as Os, so only a litle Oisavalable. Therefore, eventhough there is litle O in the steatosphere relative {0 O,, small amounts of © created here will react with the abundant O; to form ‘ozone (Os) according to Equation 3-85. Equations 3-85 and 3-86 explain the natural formation of ozone inthe stratosphere. They also provide insight as to why the concentration of ozone is much, much higher in the stratosphere (ppmy levels) versus the twoposphece (ppby, levels). This is because the stratosphere contains much more O than the trope. sphere, where O is not produced by natural mechanisms in large amounts except under human-induced conditions of smog formation (discussed later in this section) Ozone is destroyed naturally in the stratosphere by the reaction of ozone with {UY photons with A = 320 mi 0; + UV photon — 0, + OF @sn Here, the molecule with the * superscript is defined as being in an “excited state because of a change in its electron configuration, The molecule in this “excited state” has more energy compared to its “ground state,” which is defined as the lowest energy state of a molecule. These “excited” oxygen molecules can either ) react with O; to form more Os, or (2) destroy O to create O,. Fortunately, the activation energy required for this destruction of ozone is quite high (18 kI/mole), so this natural destruction reaction occurs at a very slow rate. Catalytic Destruction of Ozone. The destruction of ozone in the atmosphere ‘occurs in the presence of catalysts (referred to as “X” in Equations 3-88 and 3-89 below). These catalysts are either nonchlorine-containing chemicals that are produced by natural processes over the world’s oceans, or are “halogen-containing” (usually chlorine) catalysts emitted by human activities. Iti the accelerated emis- ions of these chlorine-containing catalysts by human activities that has resulted ‘decreases in stratospheric ozone, reported in the news as the “ozone hole.” 3.6 Photochemistry and the Atmosphere 127 ‘The catalytic destruction of ozone occurs in a two-step process: X +0, XO + 0; G88) XO+0>X +0; 89) ‘The overall reaction for this two-step process is +0520; 6-90) refers toanafom of molecule hat has ooe uapsitedcectron. Pe es teciea es ae tres ae all be dete tng ohana pene es hn He atl SS rae rt Not haan equine 388389 the eta (X) an ee Fe ek ets care cot ee ta a es ne pogenic catalysts can assist in the destruction of close to 10" ozone molecules ae ei ee esuved fom the aatophere! lonclorine Catalysts, One ofthe mos commen natura ctalyss she fee Thlal of ic onde (NOD, whichis rood when an NO mole risen th suatuphere and happets to eat wih ne ofthe ected atomic ongen motels (O", whose formation was described by Equation 3-67 Although most fhe 0 and OF react to form Ny and ame reactions do produce NOt Nor canbe sbstued fr X nt Equations. ond 29 flow: NOs + 0; > NOw + Oy sn NOs + ONO" + 0, 692) ‘The overall reaction of Equations 3-91 and 3-92 results in the destruction of Os as provided by Equation 3-90. rine Catalyst, Freeadcl chlorine toms are very flint cay in the destruction of ozone, Thus the pretest threat wo rtosphere Oi from ‘horine containing chemical, Bromine confining chemical ea problem tnd me) acount for up to 5% ofthe Oy deplete, but heir chemistey& not Steused het If donne radicals (CH) re resent inthe stoner, O, de stocon wil cur ezrdng tothe twostepeacton (Equations 88 and 385) followed by the O; destruction reaction (Equation 3-90) as follows: Che + 0, > CIO* + Oy 93) Clos +O Ck +0, 94) Remember that the overall reaction is written as 0, +0420; 95)128 Chapter3 Chemistry Fortunately, 99% of stratospheric Cl is stored in nonreactive forms such as HCI and chlorine nitrate (CIONO;). The amount of stratospheric chlorine hes increased in recent decades, however, and during the Antarctic spring a lot at this stored chlorine is released into the active catalytic forms, Cle and ClO.. A ‘naturally occurring ehlorine-containing chemical is chloromethane (CH,C), Which is formed over the world’s oceans and may be transported up into the Stratosphere, CHCl molecules can react with UV photons (A of 200-280 nm) to Produce chlorine-free radicals, Ck. The major anthropogenic source of chlorine 's from the movement of chlorofluorocarbons (CFCs) into the stratosphere snd subsequent release of chlorine free radicals. CFCs (known commercially 05 ieons) were widely used inthe northern hemisphere beginning in the 1930s, The three most commonly used CFCs were CFC-12 (CFCly, used extensively as a coolant, refrigerant, and imbedded in rigid plastic foam), CFC-11 (CFC, used {c blow holes in soft plastic such as cushions, carpet padding, and car seats); and CRC-13 (CF,CL-CFCl,, used to clean circuit boards). CFCs are relatively stable in the troposphere, but after being transported up into the stratosphere they can Undergo photochemical reactions that release the catalytic chlorine free radical, (Ch. For example, the breakdown of CFC-12 occurs as follows: (CF:Ch + UV photon (200-280-nm range) > CF, + Ck (3-96) Another Cl can subsequently be released from the CF;Ch. 36.3 Tropospheric Ozone Chemistry Tropospheric ozone is also known as urban ozone or smog. Itis not emitted by any smokestack or tailpipe, but is instead produced by a complex chemical pro. cess that involves hundreds of chemical reactions. In the troposohere high osore levels can adversely affect the human respiratory system, agricultural crops and forests, and degrade materials such as rubber. Figure 3-23 showed how tropospheric ozone affects visibility in cities throughout the world Ozone production in the troposphere requires a source of nitrogen oxides, Sunlight, and reactive hydrocarbons, The process i facilitated by natural features Such as mountains, which can trp the emissions and limit thir dilution by clean incoming air, or by a feature that causes the formation of air iaversions, which trap pollutants close to ground level (e., being located near a large body of Water). This local geography along with dense human populations contribute to the urban ozone problems of cites such as Los Angeles, Denver, Mexico City, and Rome. In addition, long-range transport of pollutants can carry an ozone, Producing chemical soup to unfortunate regions that are located downwind. A Simplified three-step reaction for tropospheric ozone production can be written as follows: 2NO +.0,—>2NO; G97) NO; + h—> NO+ + 0 3-98) 0+0,4+M—>0,+M. B99) | Chapter Problems 129 erect ne ec cae N; + O, = 2NO (3-100) “foul” the catalyst and destroy its effectiveness. Traffic planners can develop and crore akon ri tera, pein CHAPTER PROBLEMS id to a one-ter water 341. How many grams of NaCl would you need to adi sample (pH = 7) so the ionic strength equaled 0.1M? in the destruction of a pollutant has a 3.2, A first-order reaction that results in the destruction of tate constant of 0.VGsy (a) How many day wl it ake for SO% ofthe chemical to be destroyed? (b) How long will it take for 99% of the chemical to be destroyed? (c) How long will it take for 99.9% of the chemical to be destroyed? rachloro- A strain of bacteria has been isolated that can cometabolize tet os (TCA). This strain of bacteria can be used for the bioremediation36. 36. 37. Chapter 3 Chemistry of hazardous-waste sites contaminated with TCA. Assume that the biodegradation rate is independent of TCA concentration (ie., the reaction is zero order). In'a bioreactor it is observed that the rate for TCA removal ‘was 1 g/L-min. What water retention time would be required to reduce the concentration from 1 mg/L in the influent to 1 g/L in the effluent of a reactor? Assume the reactor is completely mixed, ‘Assume that PO,?~ is removed from municipal wastewater through precipitation with Fe** according to the following reaction: PO,” + Fe** —» FePO us. “The rate law for this reaction is {pox dt KFe™ [P02] (a) What is the reaction order with respect to PO,~? (b) What order is, this reaction overall? Phosphate ion reacts in water (o form monohydrogen phosphate according, to the following equation: PO? + H,0 <> HPO? + OH- (@) Given that this is an ideat system, temperature is 298 K, and the total ‘combined phosphate and monohydrogen phosphate is 10-* M, what percentage of the total concentration is in the phosphate ion form at pH = 112 (b) Will the reaction proceed as written at pH = 9 when [PO2-] 10°** M, and (HPO?] = 10° M, and if not, in which direction will proceed? (c) Will the reaction proceed as written if 10"! M NaCl solution is added to the system in part (b), and if not, in which direct proceed? Ammonia, NHs, is a common constituent of many natural waters and ‘wastewaters. In treating water containing ammonia at a water-treatment plant, the ammonia reacts with the disinfectant hypochlorous acid, HOC, in solution to form monochloroamine, NH,C1 as follows: NH, + HOC|— NH,CI + 1,0 ‘The rate law for this reaction is {NH} r= ~UHOCIINE,) (2) What is the reaction order with respect to NH? (b) What order is his reaction overall? (c) Ifthe HOC! concentration is held constant and equals. 10™M, and the rate constant equals 5.1 x 10° L/mole-s, calculate the time required to reduce the concentration of NH, to one-half its original value. A treatability study is run to investigate the rate at which a hazardous chemical can be treated. The following data are collected at 25°C. Chapter Problems 131 Concentration of Chemical Time (ug/L) (ays) 10 0 ost 1 056 3 036 5 022, 7 oad 10 (@) Is this a zero- or first-order reaction? (b) What is the rate constant for this reaction? (c) What is the halflife for this reaction? (d) If @ for this reaction is determined to be 1.1, what is the rate constant at 30°C? . A water-treatment plant is designed to remove dissolved manganese (Mn’*) and iron (Fe®*) from the water. The water is aerated to oxidize these reduced species and cause formation of a solid precipitate that can then be filtered out ofthe water. The reaction for Mn is 4Mn?* + Osgq) + 80H” > 4MnOOH yy + 2,0 (a) Ifthe [Mn®*] equals 25 x 10~® M, pH is maintained at 7, temperature is 25°C, and the oxygen concentration is maintained at a constant value by blowing air equilibrated with the atmosphere into the solution, will the reaction proceed forward as written? To determine the order of the reaction and the rate constant, a laboratory experiment is conducted that yields the following results. Time (min) (Ma?*](u) 0 25 3 7 6 Md 2 625 (b) Is this reaction first or zero order? (c) What is the rate constant? Nitrogen dioxide (NO) concentrations are measured in an air-quality study and decrease from 5 ppm to 2 ppm in 4 min with a particular light intensity. (a) What is the first-order rate constant for this reaction? (b) What is the half-life of NO, during this study? (c) What would the rate constant need to be changed to in order to decrease the time required to lower the NO; concentration from 5 ppm to 2.ppm in 1.5 min? You are provided the following rate constants for the hydrolysis ofa variety of organic chemicals. Chloroform (7.13 x 10-!/min) and trichloroethane (1.24 x 10~*/min). (a) Calculate the half-lives in years for the hydrolysis Of these chemicals. (b) Which chemical will persist longest in the environ- ‘ment given that hydrolysis is the only destruction reaction? ‘IL If the rate constant for the degradation of biochemical oxygen demand (BOD) at 20°C is 0.23/day, what is the value at 5°C and 25°C? Assume that © equals 1.1.132 Chapter 3 Chemistry 3-12. In enviroriments where dissolved oxygen concentration is low, nitrate sometimes serves as an alternate electron acceptor in the oxidation of reduced species. Is it possible to oxidize sulfide with nitrate in natural waters under the following conditions at 25°C? H* + NO,” + HS" + H,0 —»S02> + Ni” ‘The concentrations (moles/L) are [H*] = 10%, [NOs] = [HS“] [S027] = [NH] = 10 AG" for the preceding reaction is 2031.19 ki/mole ‘The reddish-colored mercury oxide (HgO) can decompose according to the following reaction: HO.) > He) + 1/202) Is this decomposition reaction a potential source of atmospheric mercury pollution at room temperatures of 25°C? 3-14, Will the foll tions? 343. reaction proceed spontaneously under standard condi- Fe 4 dH + Ong > Fe" + 240 3.15. Is the following reaction thermodynamically feasible under standard conditions? AG} for NOs) = 20.69 kcal/mole; NOx) = 1226 kcal/mole; Ong = 0 keal/moale 2NOw) + Ong) > ZNO) 3.16. An engineer plans to treat wastes from a manufacturing process that uti- lizes chromium in a conerete tank. However, chromium may cause dete- rioration of concrete according to the following reactions: 2Fe™ + (Fe, Mg):SiOys > Fe:MgSiOus + 2Fe* + Mg 3Fe™* + CrOS- + 8H* > 3Fe™* + Cr+ + 41,0 CP + 30H > COM) ‘The second reaction regenerates the Fe™* required for the first reactio ‘and the process can continue until no more conerete or Cr0,?~ are avai able. Loss of Mg and Fe from the concrete in the frst reaction can produce a more porous concrete that crumbles readily (a) Is the reaction shown in step 2 thermodynamically feasible? (b) Given the following concentrations in the reactor, will the integrity of the reactor be in danger? (Fe**] = 10°" M, [Fe] = 0.1 uM, [CrO,? 10°* M, [Cr°"] = 10 nM, pH = 53. 37. (a) What is the solubility (in moles/L) of CaF, in pure water at 25°C? (b) What is the solubility of CaF, if the temperature is raised 10°C? (©) Does the solubility of CaF, increase, decrease, or remain the same if the ionic strength is raised” (Explain your answer.) 318, The chemical 1,4-dichlorobenzene (1,4-DCB) is sometimes used as a dlis- lavatories. At 20°C (68°F) the vapor pressure is 5.3 x Chapter Problems 133 10™* atm. (a) What would be the concentration in the air in units of g/m”? ‘The molecular weight of 1,4-DCB is 147 g/mole. (b) An alternative disinfectant is I-bromo-4-chlorobenzene (1,4-CB). The boiling point of 14-CB is 196°C, whereas the boiling point of 1,4-DCB is 180°C. Which compound ‘would cause the highest concentrations in the air in lavatories? (Explain your answer.) 319. rhe boiling temperatures of chloroform (an anesthetic), carbon tetrachloride (commonly used in the past for dry cleaning), and tetrachloroethene (previously used as a degreasing agent) are 61.7°C, 765°C, and 121°C. The vapor pressure of a chemical is directly proportional to the inverse of the ‘chemicals boiling point Ia large quantity of these compounds were spilled in the environment, which compound would you predict to have higher concentrations in the air above the site? (Explain your answer.) ‘What would be the saturation concentration (moleiL) of oxygen (O,) in a river in winter when the air temperature is 0°C if the Henry’s law constant at this temperature is 2.28 X 10 mole L~ atm™*? What would the answer be in units of mg/L? 3.20. 3-21. Polychlorinated biphenyls (PCBs) are a mixture of over 200 individual ‘compounds. These pollutants have been spread widely throughout the environment. If the concentration of PCB-105 (one of the individual compounds) was 300 pmole/m? in the air above a large lake and the concentration in the surface water of the lake was 100 pmole/L, would this compound tend to move from the water into the air or from the air into the water? (Assume the air temperature is 25°C.) The Henry's law constant for this compound is 10 mole/L-atm. 3.22, On a cloudy, windy day in August the temperature above Lake Superior reached 25°C. The barometer read 760 mmHg, and a scientist aboard an EPA research vessel measured an oxygen concentration (partial pressure) of 0.18. If there is no water vapor in the air, the oxygen partial pressure would have been 0.2. Assuming that nitrogen, oxygen, and water vapor are the only important contributors to the gas pressure, calculate the equilib rium constant at 25°C for the reaction: HO eis —> Haw, 3.23, Ifthe partial pressure of earbon dioxide at25°Cis 10-** atm and its Henry's constants 10" moles/L-atm, what is the molar concentration of dissolved carbon dioxide in rainwater equilibrated withthe atmosphere? What is the Henry's constant for carbon dioxide in dimensionless form? 3-24, The log Henry constant (units of L-atm/mole and measured at 25°C) for trichloroethene is 1.03; for tetrachloroethene it is 1.44; for 12-di- methylbenzene it is 0.71; and for parathion it is ~3.42. (a) What are the dimensionless Henry's constant for each of these chemicals? (b) Rank the ‘chemicals in order of ease of stripping from water to air.

Fundamentals of Environmental Engineering

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