VERNON L. SNOEYINK University of Illinois, Urbana

DAVID JENKINS University of California, Berkeley

JOHN WILEY & SONS, New York' Chichester' Brisbane' Toronto' Singapore


© 1980, by John Wiley

& Sons. Inc.

All rights reserved. Published simultaneously in Canada. Reproduction or translation of any part of this work beyond that permitted by Sections 107 and 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons.
Library of Congress Cataloging in Publication Vata: Snoeyink, Vernon L. Water Chemistry

Includes bibliographies and index. 1. Water chemistry. 1. Jenkins, David. 193,5...joint author. II. Title.

QD169. W3S66 546' .22'024628 ISBN 0-471-05196-9


Printed in the United States of America

30 29 28 27 26 25 24
Printed and bound by Quinn - Woodbine, Inc ..

To Jeannie, Todd, and Craig Joan, Daniel. and Sarah

This book is a first-level text on water chemistry that places special emphasis on the chemistry of natural and polluted waters and on the applied chemistry of water and wastewater treatment. It provides a comprehensive coverage of the dilute aqueous solution chemistry of acidbase reactions. complex formation, precipitation and dissolution reactions, and oxidation-reduction reactions. Although it is written primarily for students and those individuals who are currently working in environmental or sanitary engineering, much of its contents should also prove to be of value to chemists, biologists, ecologists, and geochemists. We assume that the readers will have a good background in general chemistry; additional knowledge in the fields of analytical and physical chemistry is useful but not essential. The material in the text has been satisfactorily taught to advanced undergraduates and first-level graduate students in environmental engineering with one year of elementary chemistry as a background. This book provides an integrated coverage of chemical kinetic and equilibrium principles and applies them to water chemistry in its broadest sense, that is, to natural and polluted water and to water and wastewater treatment processes. Special attention is paid to the effects of temperature and ionic strength on reactions. In the first introductory chapter, the characteristics of the various types of water of concern are presented along with a discussion of the concentration units unique to water chemistry. Chapters 2 and 3 provide the background in chemical kinetics and thermodynamics necessary for the subsequent coverage of water chemistry. If the text is to be used for teaching students with background in physical chemistry, Chapters 2 and 3 may be read for review purposes only. Chapters 4 to 6, and 7 deal, respectively, with acid-base, complexation, precipitation·dissolution, and oxidation-reduction chemistry. In each of these chapters we first present the necessary principles for understanding the systems to be encountered and then the necessary tools to solve problems; following this, we present one or more applications of the topic in the water or wastewater areas. The graphical solution of equilibrium problems is stressed throughout the book. The acid-base chemistry chapter concludes with a detailed discussion of the carbonate system. The complexation chapter deals at length with the organic and inorganic complexes of metal ions found in natural waters. Phosphate chemistry and heterogenous calcium carbonate equilibria and kinetics are presented as applications of the principles of precipitation·dissolution presented in Chapter 6. In Chapter 7, the topics of corrosion, iron chemistry, chlorine chemistry, biologically important redox reactions, and prinCiples of electrochemical measurements are presented to iIIus-



trate the importance and practical application of the principles of oxidation:reduction reactions. Numerous example problems are presented throughout the discussion as aids to the understanding of the subject matter. Many problems are presented at the end of the chapters_ The answers to these problems are given in an appendix so that readers can test their knowledge_ References to more detailed treatments of selected topics are given at the end of each chapter. The Water Chemistry Laboratory Manual by D. Jenkins, V. 1. Snoeyink, J. F. Ferguson, and J. O. Leckie, 3rd ed" John Wiley & Sons, Inc., New York, 1980, initially published by the Association of Environmental Engineering Professors, contains many experiments that are based on the principles presented in this book. The laboratory manual is written for use in the same type of course for which this text is written. The nomenclature and format of these two texts are designed to make them companion volumes for an integrated lecture-laboratory course. Our thanks are due to the students and many other persons who aided in the preparation of this book: to J. F. Fitzpatrick, R. A. Minear, and R. R. Trussell, who were selected by the publishers to review the-text; to the University of California at Berkeley and the University of Illinois at Urbana-Champaign for their generous leave policies that enabled us to devote our time to writing this book; and to Miss Cathy Cassells, Mrs. Ruth Worner, Mrs. Flora Orsi, and especially to Mrs. Virginia Ragle for their typing services in the preparation of the manuscript.

Vernon L. Snoeyink U*'ana, Illinois David Jenkins Berkeley, California

CHAPTER ONE - INTRODUCTION 1.1. 1.2. 1.3. Properties of Water Composition of Several Types of Water Methods of Expressing Concentration Additional Reading 3



CHAPTER TWO - CHEMICAL KINETICS 2.1. 2.2. 2.3. In trod uction Collisions of Reacting Species Orientation of Reactants The Rate Law Reaction Mechanism Effect of Temperature on Reaction Rate Catalysis Empirical Rate Laws Problems Additional Reading


25 26 27 36


2.5. 2.6. 2.7. 2.8.
2.9. 2.10.

40 44


CHAPTER THREE - CHEMICAL EQUILIBRIUM 3.1. 3.2. Introduction The Dynamic Nature of Chemical Equilibrium The Thermodynamic Basis of Chemical Equilibrium Enthalpy and the Temperature Dependence of the Equilibrium Constant Nonideal Behavior of Ions and Molecules in Solution Problems Additional Reading

58 58








4.1. 4.2. 4.3. 4.4. 4.4.1. 4.4.2. 4.4.3. 4.4.4. 4.5. 4.6.

86 86 86

Introduction Definition of Terms Rate of Reaction Equilibrium Calculations-A General Approach Mass Balances Equilibrium Relationships The Proton Condition The Charge Balance or Electroneutrality Equation Strong Acid-Strong Base Calculations Weak Acid-Weak Base Calculations Graphical Procedure for Equilibrium Calculations-pCpH Diagrams Determination of Temperature and Ionic Strength Effects on Equilibria Using pC-pH Diagrams Multiprotic Acid-Conjugate Base Equilibrium Calculations

95 95



102 108


125 134 136 136

4.1.1. 4.11.\1.

Ionization Fractions and Distribution Diagrams

Mixtures of Acids and Bases-pH Calculation Strong Acid-Strong Base Mixtures Weak Acid-Strong Base and Strong Acid-Weak Base Mixtures pH Buffers and Buffer Intensity Buffer pH Buffer Intensity The Carbonate System The Carbonate Species and Their Acid-Base Equilibria Calculation of Carbonate Species Concentrations in Open and Closed Systems Alkalinity and Acidity Alkalinity and Acidity Endpoints Analytical Definition of Alkalinity and Acidity




4.12.). 4.12.2. 4.13. 4.13.1. 4.13.2. 4.13.3. 'J 4.13.4. , '.

156 156 162 173


5.COORDINATION CHEMISTRY 5.5. 5.2.3. Complexes with Other Inorganic Ligands Complexes with Organic Ligands The Nature of Copper in Water and Wastewater Complexation by NTA Metal Ion Association with Humic Substances Problems Additional Reading CHAPTER SIX . 6.2.2. Problems Additional Reading IS2 IS5 197 IS7 IS7 200 201 20S 217 223 225 226 231 241 242 243 243 244 244 245 246 247 247 248 251 252 253 254 258 Ligands~_ CHAPTER FIVE .15. 5. 6. 5. Introduction Nomenclature and Definition of Terms Reaction Rate Complex Stability and Equilibrium Calculations Metal Ion Hydrolysis-H 2 0 and OH.3.8.S.4.7. 5.3. 6. 6. 6. 5. 5.3.Contents xi 4.7. 6. 5.2.3. 6.PRECIPITATION AND DISSOLUTION 6.4.1. 5.1. Introduction Precipitation and Dissolution Kinetics Nucleation Crystal Growth Agglomeration and Ripening Dissolution Equilibrium Calculations The Solubility Product Effect of Temperature on Solubility The Common Ion Effect Conditional Solubility Product Log Concentration Diagrams Solubility of Salts of Weak Acids and Bases .6. 6.7. 6. 6.

6. 6. Effect of Complexation on Solubility Competitive Effects of Several Ligands Precipitation of Fe(OH)". 7. 6.-pH Predominance Area Diagrams 338 343 344 348 .-pC-pH and Predominance Area Diagrams Aluminum Phosphate Precipitation Calcium Carbonate Solubility and Water Stability Calcium Carbonate Solubility in Open and Closed Systems The Effect of Complex Formation on the Solubility of CaC03(') Phosphate Chemistry Reactions of Phosphates Magnesium Ammonium Phosphate Precipitation Iron Phosphate Precipitation from Wastewater Problems Additional Reading 262 270 271 279 282 282 295 298 298 306 310 6.10.8.OXIDATION . 7.!' 7. 7.!' .) and FeC03(.!.8.!' 6.-pC Diagrams The p.5.6.4. 7. Graphical Representation of Redox Equilibria The p..2. Introduction Redox Stoichiometry Redox Equilibrla Direction of Reaction Free Energy and Potential of Half-Reactions Combination of Haff-Reactions The Nernst Equation Formal Potentials The Electron Balance and Equilibrium Calculations Electron Activity and p.2. 7.!. 6.9. 7.3.S. 7.3. 7.3.REDUCTION REACTIONS 7. 6. 313 315 316 316 316 322 322 324 330 331 336 336 CHAPTER SEVEN . 7.!' 7. 7.xii Contents 6.

7.6.11. 7.2. Ionization Fractions Appendix 2.4.3. 7.3. 7.9. 7. ·7.6. Useful Data Index 431 435 442 453 .5.6. 7.6.5. 7.4.8. 7. 7.12. 7.2. 7.8.1.Contents xiii 7. 7. 7. 7. 7. Answers to Problems Appendix 7. Other Predominance Area Diagrams The pE-pH Diagrams Incorporating Solids Corrosion 354 358 363 363 366 368 371 374 378 378 382 386 387 388 390 399 404 405 407 412 414 414 422 426 430 The Corrosion Cell The Galvanic (or Electromotive) Series Corrosion Reactions Concentration Cells Corrosion Control Iron Chemistry Iron in Groundwaters Acid Mine Drainage Chlorine Chemistry Forms of Aqueous Chlorine Chlorine Equilibria Chlorine Reactions with Inorganic Species Chlorine Reactions with Organic Substances Biologically Important Redox Reaelions The Nitrogen Cycle Electron Acceptors in Microbial Systems Microbial Yields Electrochemical Measurements Potentiometric Measurements Amperometric (Polarographic) Measurements Problems Additional Reading Appendix 1.3.1. 7.10.8. 7.




2. since hydrogen and oxygen each have 3 isotopes. The hydrogen atoms carry a positive charge while the oxygen atom is negatively charged. The American Heritage Dictionary of the English Language 1 concisely draws the distinction we want to make in its first three definitions of the word water. 3.1. nearly odorless and tasteless liquid. However. American Heritage and Houghton. Any of various forms of water such as rain. PROPERTIES OF WATER Although the title of this book is Water Chemistry. the contents deal only slightly with the chemistry of H2 0. H2 0 is a strongly dipolar molecule. In common with the usage adopted by the sanitary! environmental engineering profession and other branches of the scientific community. weight per gallon (15°C) 8.0000." This book is largely directed toward a consideration of the type~ of waters exemplified by definitions 2 and 3. 1447. p. In the water molecule both hydrogen atoms are located on the same side of the oxygen atom. L . However. it would be remiss if we did not consider the important properties of water that make it such a dominant aspect of our environment. Any body of water such as a sea. 1969. there exist 18 possible molecular weights for water. boiling point 100°C (212°F). "Water (wa'taI. or stream. Most water molecules have a molecular weight pf 18. Because of this distribution of charge. river. 1. essential for most plant and animal life and the most widely used of all solvents. H20. This book is about the interactions between these compounds. wot'ar) n. Melting point O°C (32°F). we use the word water to mean the dilute aqueous solution! suspension of inorganic and organic compounds that constitutes various types of aquatic systems. William Morris.INTRODUCTION 1.337 pounds. A clear colorless. lake. specific gravity WC) 1. ed. With a few exceptions it is only in this introductory chapter that we feel compelled to even talk about the properties of H20. The water molecule dipoles 1 The American Heritage Dictionary of the English Language. their bonds with the oxygen atom are 105° apart.

The minerals that make up the earth's crust are largely inorganic solids in which positively charged and negatively charged ions exist in a lattice structure. I! solid H2 0 were denser than liquid H20. At atmospheric pressure and room temperature (25°C) the heavier molecules. with its dipolar character. we find that many of its physical properties are anomalous.2 Introduction attract each other and form aggregates through bonds that are known as "hydrogen bonds". It is thought that these aggregates in water at room temperature can reach sizes of up to about 100 H20 molecules. that is. hydrogen sulfide. H2S. Its freezing point is lower than would be expected. The last property-that in which H2 0 forms a less dense solid than the liquid from which it forms-has far-reaching ramifications. the maximum density is at 4°C. The polarity of water is an important factor in determining its solvent properties. has the power to surround a positively charged ion with the negatively charged part of its molecule (or conversely surround the negatively charged crystal ion with the positively charged part of its molecule). Nemethy and G. Water is a liquid that becomes a gas only when the temperature is increased to 100°C and above. Chern. 36: 3382 (1962). Lakes would freeze from the bottom upward and. H2S (molecular weight 34). consequently. are all gases. an open-structured substance that is less dense than the liquid water from which it forms. H2Te. It is far denser than its related species at any given temperature. Water. thereby isolating the ion from its surrounding ions 2 G. life in its present form in aquatic systems would not exist because n<. Scheraga. and H2Te (molecular weight 130). A Model for/the Thermodynamic Properties of Liquid Water." J. .ttural bodies of water would freeze solid whenever the temperature fell below the freezing point of water. attracted to each other by electrostatic bonds. H2 Se (molecular weight 81). H2Se. 1. and hydrogen telluride. I! we compare it with the dihydrides of the elements in the same family of the periodic table as oxygen. Water is the dihydride of oxygen. All of these properties (and many more) are caused by the hydrogen bonding between H2 0 molecules. Its surface tension and dielectric constant are much higher than would be predicted from the properties of the other dihydrides.. and it freezes to form ice. Phys. hydrogen selenide. "Structure of Water and Hydrophobic Bonding in Proteins.' The hydrogen bonding in water is responsible for many of the unusual properties possessed by this substance. ice would form at the bottom of natural bodies of water rather than at the top. H.

COMPOSITION OF SEVERAL TYPES OF WATER The general compositiori. The ocean is an approximately 1.500 1. of the various types of water in the hydrosphere can best be discussed within the framework of the hydrologic cycle.2.13 percent. Water dissolves some (small or large) amount of virtually every solid or gas with which it comes in contact.1 M solution of anions plus cations.-) Bromide (Br-) Other solids Total dissolved ~olids 19. "Chemistry-The Oceans as a Chemical System" in H. In the last analysis the solvent properties of water make necessary the several dictionary definitions of the word water. 1. In this table the category TABLE I-I Major Constituents of Seawater mglkg (ppm) 10. Comparative and Descriptive Oceanography. surrounded (or hydrated) by water molecules. M. Composition of Sea Water. 2 of The Sea. The solvent powers of water are exerted in these systems leading to such general phenomena as corrosion and scaling. Of the total amount of water on the earth the oceans account for the vast majority: 97. The ion. The polar ice caps and glaciers contain 2. 1963. Vol. and streams contain only 0.500 965. groundwater accounts for 0.-) Bicarbonate (HCO. Hill. Wiley-Interscience. Inc. . New York. 3-25.350 400 380 Constituent Sodium (Na+) Magnesium (Mg2+) Calcium (Ca'+) Potassium (K+) Chloride (CI-) Sulfate (SO. D. can then leave the crystal lattice and move out into solution-it becomes a dissolved ion. such as concrete.Composition of Several Types of Water 3 and neutralizing the forces of attraction that maintain the integrity of the crystal structure.24 percent. lakes. and refined metals such as iron and copper).02 percent of the total. On a smaller scale water circulates in man-made systems (conduits and pipes made from synthetic minerals. its average composition is given in Table 1-1.000 2. In the global cycle of water on the earth (the hydrologic cycle). Reprinted by permission of John Wiley & Sons.700 142 65 34 Water (balance) 34.61 percent.517 Source: E. pp. water contacts the gases in the atmosphere (including air pollutants and volcaniC emissions) and the minerals in the top few kilometers of the earth's crust. and the rivers. Goldberg.

0243 g/cc.05-2) x x x x x 6x 10-' 10-' 10-' 10-' 10-' 10-' 10-' 10-' 10-' 10-' 10-' 10. Nauk. water evaporates and then is transported over land masses. The dissolved salt content of sea water (total dissolved solids of approximately 34. published in Washington.03 1.4 Introduction of "other solids" incorporates a wide variety of species that includes just about' every element present in the earth's crust. SiO. Cr (0.781 0." Akad.07 mg/liter). the water has a chance to equilibrate with the gases in the atmosphere. 01 Commerce.2 1.0) 8.).17 mg/ liter).O CO. Percentage by Volume 78. which is significantly greater than pure water.0001 mg/liter). and Hg (0. .8 0. Rn 1. B (4.0003 X X X X X X 0. Li (0.OS mg/liter)) to minute (Cd (0.05-2) X 10-' 6 x 10-" 1.S mg/liter).0093 0.5 mg/liter).8 x 10-3 5.S. A:r H. 0) x 10-' 8fx 10-' (0. It should be realized that the mean composition of the earth's atmosphere is subject to considerable variation.D28 0.1 x 10-' (O.00005 mg/liter).9 0. 1961. Because of this. U. SSSR. water passes through" the earth's lower atmosphere. SO" NO" and so TABLE 1-2 Mean Composition of the Atmosphere Gas N. P (0.1-1. Ne He CH.4 mg/liter). and F (1.20 Source: B. 1-1. 03 Xe NO.209 0.OS-I) x 10-' 1 x 10-' 5 X 10-' 5 X 10-' (0. Geoliz Moskva (translated by the Israel Program lor Scientific Translations. snow.S-1) 1 5 5 (0. Of/ice 01 Technical Services.).O H. Mirtov.4 1.8 5. "Gaseous composition of the atmosphere and its analysis. The mean composition of the lower atmosphere is shown in Table 1-2. and I (O.5 x 10.500 mg/liter) is sufficient to raise ils specific gravily at 20°C to a value of 1.2 x 10-' 1. (S. From the oceans.93 0.1 (0. 209 pp.3 mglliter)) to small (N (0. Dept.1 20.1-2. especially in the levels of some of the minor constituents such as CO" CO. Prikl. In this category average concentrations range from moderate (Sr (8 mglliter). Inst. where il can be deposiled as one or another form of precipitation (rain.7 (0. hail.5 Partial Pressure (aIm) 0. N. During its passage from the ocean to the land surface. Kr CO SO. etc. A.00003 mglliter)) to miniscule (Pa (2 x 10-' mg/liter)and Ra (l x 10-10 mg/liter)).

' S. which are products of combustion processes and are associated with the air pollution that accompanies urban-industrial communities_ The major atmospheric constituents.+ HC03 S042CINO.6 0. Eastern N.14 0.6 0. 41 pp. 1957-1959.M. 10.1 4.7 0. Jan.1 2. and 0" are both sparingly soluble in water (17. Belgium. .NOjTotal dissolved solids pH 2. 1964.4 4 0. Res. 7:00 P. Na+. J. and Bulk Precipitation at Menlo Park.65 0.0 6. U. Menlo Park.5 3. at 25°C).01 0.2 4.0 38 5.0 0. and SO" are very soluble (1450 and 94. Even so. Feth.100 mg/kg. On the Relation Between pH and the Chemical Composition in Atmospheric Precipitation.57 0.2 0.M. Fisher.02 0. Average of 180 samples.2 0. respectively. Rain. H.97 0. Whitehead. A.2 0. N. can be very acidic.3 mg/kg. Station S26U. at 250C)3 but some of the minor constituents..3 0. 1. Average composition of rain from August 1962 to July 1963 at 27 points in North Carolina and Virginia. for example.8 1. Chemical Composition of Rain.0 2.6 17 0. Al (III) Ca2+ Mg2+ Na+ K+ NH.6 0.5 and 39.0 0. 9 to 8:00 A. H.Composition of Several Types of Water 5 forth. respectively.62 I.7 0. Calif.3 0. Dry Fallout. Calif.6 3 1. CI-. 39 pp. 69:3319-<3333 (1964). 3 The solubility of gas is expressed as the weight of gas (mg) dissolved in I kg of water at a total pressure (partial pressure of the indicated gas plus the vapor pressure of water at 25°C) of 760 mm Hg (760 torr or I atm).56 0. Jan.2 8. Feth. 24. 1958. Rain and snow that are generated from an atmosphere containing high concentrations of combustion-generated SO.S. Geological Survey Water Supply Paper 1535K.36 0. S. and J. Highway 50. Geological Survey Water Supply Paper 1535). and Mg2+ than precipitation that falls in the interior of a great land mass. 2.2 6. 20.. Carolina and Southeastern Virginia: U.8 5.S. Nevada (east of Lake Tahoe) altitude 7100 ft.0 0. W.S.4 5 Constituent SiO. the figures in Table 1-3 show that rainwater is indeed an extremely dilute solution TABLE 1-3 Composition of Rain and Snow (in mgniter) 2 0. 1964.0 7 0. Geophys. 3 and 4.42 0.18 0. Chemical Composition of Snow in the Northern Sierra Nevada and Other Areas. Snow. Nov. M. Tellus. The composition of precipitation is quite variable and greatly influenced by atmospheric contaminants.0 0.23 0.2 9. Roberson.0 4 7.02 0. E.. Chemical Composition of Rainfall. European Atmospheric Chemistry Network. Gambell and D.8 0. J. ROiJE'rs. CO. Precipitation near the oceans contains more SO/-. 1958.0 3 1. Spooner Summit.2 0.11 1. 550-556 (1972). Granat. and C. U. W.4 0.

6 B 1. They are illustrated by Type A. Surface waters that originate in basins where the major rocks are granite contain very small amounts of dissolved minerals.5) is significantly lower than that of the seawater from which it was generated. in Table 1-4.41 34 14.'- ClNO. N. Dayton. Well Water. Oakland.09 92 34 8.SO. we can expect .5 to 6. Average data for 1976. East Bay Municipal Utility District. indicating the remarkable efficiency of the distillation process that results in the production of "fresh water" from seawater. Ohio. San Francisco and Oakland (from the Sierra Nevada Mountains).6 2. Niagara Falls. water falls onto the land surface and comes in contact with rocks. .6 0..6 18.4 339 84 9. mg/liter SiO. The time and intimacy of contact between water and rocks also influences the composition of the solution.Y. Since the composition of the land surface and the extent and nature of biological activity (including man's activity) vary from one place to another.Total dissolved solids Total hardness as CaCO. The reactions can be viewed in general terms as a giant global acid-base titration in which the acids of the rainwater (CO" SO" and NO. Niagara River.2 0. for example. TABLE 1-4 Typical Analyses of Surface and Groundwaters in the United States Constituent.1 6.6 13 434 369 Na+ K+ HCO.5 1. A. C.1 165 123 C 10 0. Fe(I1I) Ca2+ Mg2+ A 9. This is a reflection of the equilibration that has taken place with atmospheric CO.1 2. not more than approximately 30 mg/liter.that waters of a variety of compositions will result from these reactions. Seattle (from the Cascade Mountains). the water supplies of New York City (from the Catskill Mountains).02 36 8.0 1. and soils and the animal and plant inhabitants of the land surface.0 0. Note that the pH of "unpolluted" precipitation (5.2 119 22 13 0. B. Calif.07 4.2 1.6 Introduction of dissolved salts. sediments. These are an important group of waters. Pardee Reservoir. and many rivers and lakes in New England are of this type.5 0. In precipitation. Chemical reactions take place that further modify the composition of the water.) titrate the bases of the rocks.3 1. Rainwater is poorly buffered so that it cannot maintain its neutral pH in the presence of even these small amounts of acid-producing gases.

and many smaller places along the lakes and rivers of the St. 264: 507-525 (l966). Example C in Table 1-4 is a groundwater from 30 to 60-ft-deep wells used for the public water supply of Dayton." Am. In an earth unpopulated by living things the natural waters formed by water -air -earth interactions would now flow back to the ocean carrying their various dissolved constituents and suspended clay and silt particles. The second general type of surface water (Table 1-4. For the moment let us assume that we have a sterile earth. Garrels.) leaving behind a clay mineral. J. This water. They usually require softening to make them acceptable for general domestic use and most industrial uses. The reaction also helps to regulate the CO. It has been proposed by Mackenzie and Garrels' that in the oceans the reverse of the reaction that weathered the rocks takes place.-bearing water and rocks and soils in the ground and the length of time for dissolution. T. CaH. Lawrence River Basin. and total mineral content. . bicarbonate ion. M. -).Composition of Several Types of Water 7 which· is the yearly average composition of the outlet of Pardee Reservoir of the East Bay Municipal Utility District. I-I).. may be added to the water in the soil by the activities of soil microorganisms. "Chemical Mass Balance Between Rivers and Oceans. Siever has summarized this global chemical scheme in the form of a series of chemical engineering processes (Fig. that is less rich in silica than the parent rock. Although the detailed arguments in support of this view are beyond the scope of this book. typified by that of the Great Lakes (except Lake Superior) is of intermediate hardness (calcium plus magnesium). or kaolinite. and HCO. illite. Mackenzie and R. Additionally. Cleveland. Ohio. These particles of clay minerals can be washed down the rivers along with the dissolved salts into the ocean.0. It is thought that this reaction controls the pH of the ocean at about pH 8. the water supply for much of the East Bay Area of the San Francisco Bay region. 4 F. Cations. for example. The dissolution of these minerals from the rocks causes them to degrade and eventually to form clay minerals. CO. alkalinity (HCO. montmorillonite. Detroit. it is believed that the constancy of the concentrations of SiO" K+. Niagara the ocean is attributable to this reaction. This type of water is widely used as public water supplies for cities such as Chicago. and MgH are leached out of the rocks along with silica (SiO. Na+. Type B) originates from basins other than the granite basins described above. This is because of the intimate contact between the CO. Cations such as K+. Buffalo. and dissolved silica and clay minerals react to generate new rocks. content of the earth's atmosphere. Groundwaters generally have higher dissolved mineral concentrations than surface waters. On the land surface the acids of the ahnosphere have attacked the bases of the rocks to produce a water containing dissolved minerals. Sci . Milwaukee. which are laid down at the bottom of the ocean. Waters such as this are widely distributed throughout the heartland of the United States. .

the concentrations of the major dissolved constituents (Ca2+. Mg'+. (See Fig. This increased activity can dissolve more minerals than would be possible with precipitation from unpolluted air. Cl-. Chemical engineering analogy to the surface geochemical cycle. HC0 3-. The interlocking nature of these reactions on a global scale has some important consequences for the composition of natural waters. Now let us inhabit the earth with plants and animals.) vary over a rather narrow range because of the buffering action of these reactions. S-29 (1968). Their activities are important in altering the composition of natural waters at all stages of the hydrologic cycle." Sedimentology. For ex· ample. It has resulted in depressed pH values and increased mineral contents in the poorly buffered lakes in the Scandinavian coun· tries (polluted air from the industrial areas of northern Europe drifts north to Scandinavia) and in New England and Eastern Canada (polluted air from industrial sections of the United States drifts into New England and Canada). the composition of the ocean is fairly constant with respect to these major dissolved components.q. 1·2. From R. Reprinted by per· mission of Blackwell Scientific Publications Limited. "Sedimentological Consequences of Steady·State Ocean.) For the same reason. SiO". Man's activities affect water quality in a variety of other ways including .8 Introduction t water L£d Sedimentary IZLZ:l Crystalline c::::J FllJid phases Fig. 1·1. 11.Atmosphere. Siever. SOI-. Na+. We have already seen that man's industrial activities can increase the acidity of the atmosphere and the water that comes in contact with it through precipitation.

are disproportionately greater than increases in Ca'+. Thus Table 1-5 shows that increases in CI. The data are mostly from the United States from various sources. since the upstream salt loads produced by irrigated agriculture and natural runoff make the water unusable for many purposes in the downstream regions. The individual components that make up these dissolved minerals are not present in the same ratio that one would typically expect from the dissolution of rocks by water. N. The contribution of these dissolved salts by municipal use has an important influence'on the degree to which wastewater can be recycled for reuse. and SO. Davies and R. NH4+ and NO. M. and agricultural wastes into the surface~ and groundwaters. Hydrogeology.and Na+. Significant contributions of dissolved salts also arise from irrigated agriculture. . Typically. Fig. DeWiest. . Reprinted by permission from John Wiley & Sons. An excellent example of the striking effect that water returned from agricultural irrigation can have on water quality is given in Table 1-6. 1966. Again the quantities and concentrations of the specific types of dissolved minerals are in different ratios than would be expected for the dissolution of the minerals of rocks. Mg2+. which shows the water quality in the Upper Colorado River Basin as one progresses from the headwaters in western Colorado downstream through Utah to Arizona. 1·2. Inc. From S.'-.Composition of Several Types of Water 9 the discharge of municipal. a single municipal use of a water will contribute about 300 mg/liter of total dissolved minerals to a water. New York. Cumulative curves showing the frequency distribution of various constituents in terrestrial water. C. John Wiley. Domestic wastes contribute increases in the mineral and organic matter content of natural waters. industrial. The high salinity (TDS) of this river has led to both interstate and international disputes (between Mexico and the United States).

In the latter case. If sufficient dilution is not provided.5 mglliter. and domestic and agricultural sources contain a wide variety of organic compounds (see Tables 1-7 and 1-8).7 Others SiO. J. Neal. H. and 1 to 2 mglliter of phosphorus bound to organic compounds.(total) P04' .) Total solids pH (in pH units) Source. Hardness (as CaCO. mglliter Constituent Cations Average Minimum 8 7 0 1 Trace Maximum Na+ K+ NH.HCO. The impact of these organic materials from wastewater on natural water quality takes a variety of forms. nitrogen.1 -44 12 7 7.NO. and <0.+ Ca2+ Mg2+ 66 10 15 18 6 74 10 1 100 28 24 25 15 79 81 320 -0. By comparison natural surface water concentrations of organic carbon. Typical domestic wastewater contains about 100 to 300 mglliter of organic carbon.80/P04' . 1964. 10 to 30 mglliter of organic nitrogen. Public Health Service Report 999-WP-9. the dilution provided to the wastewater by the receiving water is important because the concentrations of biodegradable organic matter in undiluted wastewater require many times more oxygen for their aerobic degradation than is present in water saturated with dissolved oxygen in contact with the earth's atmosphere.6 101 15 36 50 15 200 25. Biodegradable organic compounds can either be removed in a waste treatment plant or they can be degraded by the natural water flora and fauna.5 9 6 -36 128 -1.10 Introduction TABLE 1-5 Increment Added by Municipal Use of Water.9 2 265 57 50 40 22 261 217 541 0 Anions ClNO. <1.) Alkalinity (as CaCO. "Advanced Waste Treatment by Distillation:' AWTR-7. Based on 22 U_S_ Cities (Tap Water to Secondary Effluent) Added Increment. U. Wastewaters from industry. and phosphorus are approximately 1 to 5.(ortho) 6 -4_7 0. the degradation of this organic . respectively.S.

Near Camero. Utah Hite.6 3. L. Iorns.12 120 142 178 182 184 56 70 73 76 400 660 658 580 Near Asco. H. Data largely from W.2 3.. Near Dorsero. Col. C. Utah Lees Ferry.TABLE 1-6 Quality of Water in Upper Colorado River Basin Average Station Location Flow.5 4.1 9. Geological Survey Professional Paper 441.08 0. and G. V.0 6. 1965.6 2. Washington. D. cfs Cer+ ." U. 53 48 O.8 12 25 26 25 5.Mg'+ Na+ K+ HC0372 SO/- Cl- TDS Boron Hot Sulfur Springs.9 40 62 79 79 74 1.ll Source.3 54 84 II 91 334 a a 0. 244 2399 4138 7639 14167 17550 16 48 3.C.0 77 93 281 230 235 1. Col. "Water Resources of the Upper Colorado River Basin.4 3.S. - . Hembree. Oakland. Ariz.04 0. Col.

and A. Even water treated by disinfection for public supply contains microorganisms. H. Natural waters themselves are never free of organisms. Toxic materials (both inorganic and organic) can modify or eliminate biological processes occurring in natural waters.2 232 311 75 percent Source.0 5. England.2 31. A. This change can have far -reaching consequences for the chemistry of many species (see Chapter 7).0 1. 4:302 (1961). Sewage Purif. M.8 0. Because the individual anabolic and catabolic reactions executed by microorganisms are too numerous to discuss individually. Painter. Bywaters. For example. Inst. or they may have undesirable health effects if they are not removed during drinking water purification. Organics of all types may react with water treatment chemicals. and new organics that have undesirable effects may be produced." J.0 55. We can divide these activities into two types: those that yield usable energy for the organism (catabolism) and those in which the organism expends energy (anabolism).5 1. Copyrigbt © Institute of Water Pollution Control. Viney.12 Introduction TABLE 1-7 Sewage Composition of Stevenage.0 28.0 21. . Organics of industrial origin may cause taste and odor. The importance of organisms in natural water relates to the types of chemical transformations that they catalyze.0 3. The presence of nonbiodegradable (persistent) organics in wastewaters affects water in ways that depend on the nature of the materials.5 14.. reprinted by permission. the products of microbial degradation (humic materials) can give the water a brown color and can modify metal ion behavior (see Chapter 5). we will give a few examples to illustrate how they influence natural water quality. matter can consume all the oxygen present and convert the water from an oxic state to an anoxic condition. "Composition of Sewage and Sewage Effluents. Raw Milligrams as Carbon per Liter Constituent Fatty acids Fatty acid esters Proteins Amino acids Carbohydrates Soluble acids Amides Anionic surface-active agents Creatinine Amino sugars Muramic acids Total identified Total organic carbon Proportion identified 71.

methoxy phenol nitrobenzene toluene o-cresol phenyl cyclohexane 2..dimethoxybenzene isopropylbenzene o.3-dimethyloctane n-dodecane 1. For example. Environmental Protection Agency.3.S. The occurrence of photosynthesis in natural systems also means that we may not treat them as equilibrium systems. Region VI.) and CaCO". The microbial reduction of sulfate to sulfide could be accompanied by a reduction in the dissolved heavy metal content in a natural water. and the reduction of carbon dioxide to methane. the reduction of nitrate to ammonia and nitrogen gas. All 0"1 these reactions can exert a profound effect on water quality especially when it is realized that the affected chemical species also engage in many other chemical reactions. "Industrial Pollution of the Lower Mississippi River in Louisiana/' Report of the U. The anabolic activities of aquatic organisms also affect water quality. Dallas. Photosynthesis is the reaction in which organisms utilize radiant energy (sunlight) to drive an oxidation-reduction reaction in which carbon dioxide is reduced to organic matter by water with the production of oxygen. . the sulfide ion forms precipitates with many heavy metals.Composition of Several Types of Water 13 TABLE 1-8 Typical Organic Compounds of Industrial Origin Found in Lower Mississippi River Water" acetophenone a--camphanone dicyclopentadiene 1. the reduction of sulfate to sulfide. we must find the steady state that results from the superimposition of the photosynthetic (nonequilibrium reaction) upon the chemical equilibria. HC0 3-. This reaction is fundamentally important in natural systems because its occurrence dictates that the aquatic system cannot be treated as a closed system.2. Mg(OH)". and CO. Other energy-producing reactions of organisms involve the reduction of oxygen to water.e .'-) from solution. Substances whose solubility is inversely related to pH (e. Photosynthesis is ultimately responsible for most of the organic matter present on the earth and in natural waters. Photosynthesis uses an external (i. Because photosynthetic organisms consume inorganic carbon (C0 2 . like many other biological reactions it affects water quality..) may precipitate from a photosynthesizing natural water. Tex . Photosynthesis produces oxygen so that we would expect oxic conditions in a water containing actively photosynthesizing organisms.3-dimethylnaphthalene 2.g . April 1972. they reduce the alkalinity and increase the pH of waters in which they grow.5-trichlorophenol vinyl benzene xylene ·4-ethyl pyridine ethylbenzene a Source.• nonchemical) source of energy to drive a reaction that is energetically impossible in a closed system.

v/v. thereby modifying natural water organics. Since the construction of cell material requires the use of elements such as nitrogen. For example. NO. 1. respectively. These waters and the degraded minerals that result from their production flow into the ocean where a reverse reaction to the weathering that produced them occurs.14 Introduction Photosynthetic aquatic organisms withdraw inorganic carbon from solution to provide building blocks for the organic compounds they synthesize. . and oxygen. phosphorus. the growth of organisms in natural waters will modify the concentrations of these so-called nutrient elements. This discussion will also provide definitions and methods of calculation that will be useful in the later chapters of this book. and potassium beside carbon. that is. 5 Note: For gaseous constituents in solution or for the various components of a mixture of gases. The growth of algae in a productive natural water can nearly completely deplete the nitrogen and phosphorus concentrations of the water.' An ocean of the present composition results and new rocks are produced. METHODS OF EXPRESSING CONCENTRATION Several different methods of expressing concentration are commonly used in various branches of water chemistry and it is appropriate to present these here. Mass Concentration There are two basic ways to express the mass concentration of dissolved species (solutes) in solution. They can be interconverted if the density of the solution is known. the units mg/liter and ppm (parts per million) are. the chemical reactions of atmosphere and the solids in the rocks of the land surface form dilute mineral solutions that we call surface water and groundwater. weight of solute in a given weight of solution. the w/v and w/w units most often used to express the concentration of various materials in waters and wastewaters. or the volume of a constituent at standard temperature and pressure in a unit volume of solution. The second is a w/w basis. hydrogen. i organic composition of all of these solutions.xpressing concentration are widely used in water chemistry. 5 Both of these methods of '. is also in common usage. 1. Nonphotosynthetic organisms build their cell material from organic compounds.3.-) and phosphorus (POl-). In summary. The first is to state concentration in units of mass of solute in a unit volume of solution-the so-called w/v (weight/ volume) basis. +.3. the situation often exists where the amount and rate of growth of aquatic photosynthetic organisms is controlled by the concentrations of nutrients such as nitrogen (NH. in fact. Man's activities and the activities of organisms growing in and around natural waters modify both the inorganic a'.1.

.:.t.:s". -) and find that 100 ml of solution contained 36 mg NH. We can express the components as constituents other .i0.:"'-". " mass of substance (mg) " mgII Iter = ppm = volume of solution (liter) mass of substance (mg) mass of solution (kg) = " f " d enslty 0 solutIOn. In both types of concentration expression the mass component of the concentration term can take a variety of forms. +/liter * (~:) = concen t ra t Ion In -Iiter · " mg and =:. there has been a tendency to use the mg/liter unit rather than ppm. these concen· tration units are us en interchangeably by practitioners in the field.s--. these two methods of concentration expression are identicaL that is.::o. X 124 riJ.g. Possibly.te!~1?!'.o:. for the analysis and expression of concentration of the constituents of sludges and sediments. + 1000 ml 100 ml x liter 360 mg NH. the mg/kg (ppm) unit is usually used because.::.. a mass of a material in a known volume of solution is analyzed rather than a mass of solute in a known mass of solution.m=a:. this is because the mg!liter method represents the way in which most constituents are analyzed. p Concentration in ppm ( If p ~ _--.lll~~_"Elg:~aJru:.)'-c volume of solution (liter) " -. that is. if we were to analyze a solution of ammonium nitrate (NH4NO.g NO. However. In recent years. for example..>_~n ~~~_~!Ifli. we could compute that the solution contains: 36 mg NH."nsitY~fl~..-"(k". however. in this type of analysis. ~~~~~~.100 ml 1000 ml liter 1240 mg NO.::fc:s:. The simplest form is when specific components of a solution are expressed in terms of the specific components themselves.Methods of Expressing Concentration 15 If the "density of the solution is unity. + and 124 mg NO.=c.lucct". Indeed.-. -!liter Each component of the solution is expressed as the form in which it appears in solution.) for ammonium ion (NH4+) and for nitrate ion (NO. samples are usually weighed out rather than measured out volumetrically.concentration In (mg) " hter I X p ~:1 = (liter -kg J =I kg/liter. Concentration in ppm For wastewaters and most natural waters (with the exception of seawater and brineS).:cn".

tl!~<:l.~!9~ ~~_~e a}!!9l!!ll9i!!. It is also important to remember that the expression of various constit· uents in terms of a common constituent is merely a convenience and has nothing to do with the nature of the constituent In a specific water. which we analytically express as phosphorus. More common to chemistry in general is the use of molarity.3.trci-.d mg NHt -Nlliter = 360 mg NH. The units /Lg.~-----. But there are various types of phosphates.atomsfliter are often found in oceanographic literature.rih~onsiTIuent~"Ii'-i.-'...rtrC. Molar Concentration and Activity The previous discussion has centered around the topic of expressing the mass of constituents either _as "themselves" or as some common constituent for the sake of convenience. There is no phosphorus in water or wastewater.-w~wQ.-----.. -Nfliter ~-~.-Nfliter = 1240mgN03-/hter x 62mgN0 = 280 mg NO. -~ ~--- ~~~~~ntr~!E-~~3~ ___a . .~-. -.----.----.-P/liter.-N _ .~-'~------~-~.2. where 31 is the atomic weight of phosphorus. the moles of Holute per volume of solutiQn /'" ~-----~----:. NO = 2.~E?__:g!.16 Introduction ~~~~_~~~~ nitr~.. . we would be led to believe that -"--'----~~-.-fliter.. -Nlliter. If we had read this incorrectly and assumed that the standard was stated in terms of mg NO..~Ij!!. if we were to . 10 mg NO. and carbon. 1.0 /Lg-atom per liter of phosphatephosphorus is 31 /Lg PO.~-./'------~'-~ ...I). we would be in trouble because the water would be unusable for most purposes. 14mgN 8 NH + 1 mg 4 3 280 mg NHt -Nlliter .. Often people speak of the amount of phosphorus in water or wastewater. .~~~'--. -Nlllter 62mg 3 instead of the 10 mg NO. the EPA Drinking Water Standards recommend an upper limit on nitrate for public water supplies of 10 mg/liter. For example.sed'wideiyTn water chemistry../llter X 14mgNO..• containing the common constituent is present in a water and it is desired ~the~'Co'i1C.<-~-- common constituent is useful when a variety of affferent components all . If there were. In this instance the nitrate is expressed as N.---.---..'. especially for nitrog'. 14mgN mgNO.!!r:~m:~'Uh~y'sQ. This method is used frequently by oceanographers to express the concentration of micronutrients in seawater.25 mg NO..--'~--.. For example.. For example 1.+ /liter = X than those in which they appear in solution.(. It is important to indicate clearly whieh method of concentration expression is being used or considerable errors can result..:pho~rus.

. 1. Cases may arise where a single substance has two different equivalent weights because of its involvement in two different types of reaction. defined as .. the normality... Equivalents and Normal Concentration The expression of solute concentration as equivalents/liter. .-.-' !o.~ (3)t9. ~~p-p~r '--'--'---. are based on molar concentrations. normal concentration.~~~ ~s..-~ '. or actual.. .SiibS!ciilcer~-~.'--'--<' .ec:ll~~nOJM-9. Knowing this.•~ .<_'-'--'-~~'._ .' -.t(y):-The active concentration-that concentration we use in many thermodynamic equations-is called the activity of the substance (see Chapter 3). .h~~rn~~~9~2~®.~. is mass of substance per liter equivalent weight ~-------~--"'----------------------." __ .t th.--".~~----.'-e:· t~ilviiy·co~iliCie.-.. ..~ nJlE}ber ()f_el"E'!2I1s.~· Norma Ilty = ..-~ ~~~~_~_~_9~1LgJ. In the very dilute aqueous systems such as fresh natural waters we can use concentrations in terms of molesniter directly in equilibrium expressions.3. .:.~ ~-'-.. that is... many problems are easier to solve.._ ' . The methods are those based on (I) the charge of an ion. This is because the equilibrium const~~~C.olProfonioih:ydro~ynonsJr<.. . The advantage in using normality is that when two substances react to produce other substances.s-it~-:b~ the law of mass action in which quantities of reacting species are expressed in terms of moles. In 1!10re cOI?-centrated solutions iL~~Q~t t~~~~!!ls..'"_.__ .--.. -'.-. ..=-num!Ler. . and molality...'-..t.Methods of Expressing Concentration 17 in liters. Equivalent Weight Based on Ion Charge..rnslerreajno.'~~ __ ----_ .with ih.ll1ifi. weassumefl1cltUle·re. Expression of solute concentrations in terms of equivalentslliter or normal concentrations requires a knowledge of the nature of the reaction being considered. h . the number of equivalents of each reacting species is equal to the number of equivalents of product..' '. with which we deal in great detail later in this text. is based on a definition that is related to the type of reaction in which the solution constituents are involved..__ " ."'---. A one normal solution of a substance is a solution that contains one equivalent weight of a substance per liter of solution.--.•• J. ~---~-~-------- active concentration. I EqUlva ent welg t = The equivalent weight is molecular weight h lonc arge and the number of equivalents per liter.:~n~fer::.:·iS"l. 1. of the substance and the analytical. --'-.3.]d. Three methods of definition of equivalent weight are commonly encountered in water and wastewater chemistry...----~ ~ . (2) the . the moles of solute per mass of solvent in kilograms.

"-b~.-. provide one .-~ ----.-..9!I!l~!i!y~s!~~~g thE! number of equivalentslliter of charge units. the "moles of charge unitslliter") are useful in checking the accuracy of water analysis.. 155 mg Ca3(PO.-.Ssolutioi!xe5iC:it9is~Yhe-equiv.. . participates in the dissolution reaction.'sihat participate inpre~ipitation­ di. Another way stating the same definition is "that weight of a substance that will either replace one OH.erm ~!l_.18 Introduction We use these definition~qt._.lliter given that Ca3(PO.on~3:jQ!~~_C?~J--~o~_ ~e<:t~. Normahty = 30 mg/meq positive and six negative charges... Gram equivalent weight gram molecular weight ion charge 60g/mole 2eq/mole 30g/eq = 30mg/meq 60 mgiliter ./-_~_... Equivalent Weight Based on Acid-Base Reae/ions.'ideniical quantity..-"the 'N<3ight of as .f wJthj)ne_. To satisfy the law of electroneutrality.---.-..--.~pe. The equivalent .).~i.. the total amount of negative charge).~~------- ~ ~------ __ -'_"-----"_.'...H:_~10 _ f. ___ f ~ or II . ---~..p-.. Because each Ca3(PO..nj..i~~i. and for determining the nu.-. We illustrate the use of this concept in Chapter 4.)...T.I-... Example 1-1 Find the normality of the following solutions: 1. 60 mg COl~/liter.)._~- ~-. given that C032~ participates in the precipitation reaction.-r- ___ ./"'.'-~--.67 mgmeq 2.67 g/eq =51.. Gram equivalent weight 2 meqiliter 2..e units (or th. forms six 3lOg/mole 60. _______ ".1.~_- ___ ' ___ .--'TT a substance that win either replac-e orie nf'-\liydrogenlOii) (proton) in an a~~~~. 155 mgiliter / Normahty = 51 .!~aIEmJs and !...._---weight of a substance in acid-base reactions is defined-r..---.)..67 mg/meq 6 eqmoe / I 3 meqlliter . The molecular weight of CO.--"--. Solution I. is 310.-.--. .-----~---.5IC~. the total amount of positive charge) must equal the total number of equivalents! liter of negatively charged ions (Le.iiiier of chaq:... Ca2+ + C032-7' CaC03 (s) 2. The molecular weight of Ca3(PO.~.Tit~~-... the total number of equivalentslliter of positively charged ions (Le.• __ '_ ~ _ __ _ __ - '_.(hydroxyl ion) from a base.

_ ' _ ._ "'_. h molecular weight .__/ Example . I E qUiva ent welg t = n .Methods of Expressing Concentration 19 OH.5 mg/meq I meqlliter 36. = 0. + HPO. Thus Gram equivalent weight = gram mol~ul~r weight 1 eq mo e = 60 g/eq = 60 mg/meq Normality 45 mglliter . Solution I._ _ " _ .PO." Generalizing.5 mg HCllliter.~_" __ ~""_' _ _ _.'. -----------~--. = I meq/liter One OH~ resufts from this reaction. _-where n is the number of protons or hydroxyl ions that react.5 mglliter NormalY-365/ I . we find Gram equivalent weight = gram molecular weight I eq/mole 36. 36. with respect to the reaction H. One H+ reacts per HC! form a base.+ OR- 4. _ _ -'.1-2 Find the normality of the following solutions: I. ~_~ _________. 45 mg C032~fliter. 49 mg H3POJIiter. Gram equivalent weight = gram molecular weight 2eq/mole 49 g/eq = 49 mg/meq 49 mglliter 49mg/meq 9Sg/mole 2eq/mole Normality 3.r ______ ~ ____ .75 meqlllter 60 mgmeq I ..- with respect to the reaction CO. Therefore.--~. '" 2H+ 3..5g/mole I eq/mole 't _ 36..5 g/eq = 36. with respect to the reaction HCI + NaOH '" NaCI + H2 0 2. 45 mg COl-fliter." .' " __ "' _ _. ____ .for a reaction. __ .+ 2H+ '" H2 CO. we can say .~- + H20". •.~. with respect to the reaction CO. or react with one OH. mgmeq 2. HCO.. 2H+ react per H3 P04 • Therefore.

-~---.--. This can be a source of confusion.has a charge of 2. in the half reaction for the reduction of oxygen to water.O the equivalent weight of oxygen is Gram equivalent weight = gram molecular weight / I 4eqmo e 32 g/mole 4 eq/mole = 8 / g eq . + 4H+ + 4e.has I equivalent/mole for the acid-base reaction.'. each with the same mass concentration of CO. For example. HCO.within each HCO. ._-------substance per mole of electrons transferred. HCO. An acid or a base can have more than one equivalent weight. For example.h-> CaCO". 1-2. 4.'.. a value that is of one-half the molecular weight. and each CO.. -'-. Another type of reaction that may cause some confusion is the combined reaction.= CaCO".. I G ram eqUlva ent = gram molecular weight 2 eqmoe / I 60g 2eq/mole = 30 g/eq = 30 mg/meq Normahty . it has. but it can be dealt with if one is aware of it. Thus.-----. and the normality of two CO. and 2 equivalents/mole for the precipitation step in Eq. In Eq. Ca" (1-2) (I-I) + CO. In much of the water chemistry literature." one equivalent of electrons.'.'-. I-I it is the CO. . ~---~. However. ~--"""'~~---------------." On" mole at electrons is ~-----------.5 meqnlter .is defined as~ of -'.-.20 Introduction Two H+ react with each COl~. For oxidationreduction reactions.} (1-3) Since Ca'+ participates only in the precipitation reaction. and correspondingly CaCO" is treated as though it has only one equivalent weight.-> 2H.---'-.2 equivalents/mole for reactions I-I and 1-3. 1-1. the equivalent weight . -----.'.. = 30 45 mgniter mgmeq / = 1.had an equivalent weight of 30 for one reaction and 60 for another. 0.-----.-> H+ + CO. the reaction Ca" + HCO. in Example 1-2 the ion CO. Thus .that reacts to form the precipitate.. .'and the precipitation reaction.'-.. Equivalent Weight for Oxidation-Reduction Reactions. differed by a factor of 2. Eq.} + H+ is the sum of the acid-base reaction. 3. CO.

respectively.. Note that if Fe'+ and Fe'+ were to participate in a precipitation-dissolution reaction. D. To do this we assume that in all cases e ch mole of o.'u~be.. Simil~ ~~~pUi.. + 4H+ + 4eand -7 2H. 0.O One mole of Fe2+ or Fe'+ reacts or is produced per mole of electrons so that the equivalent weights of each of these species are the same as the molecular weights.xpress the concentration of available chlorine in various compounds (see Chapter 7).--- .'. are other reactions for 0.ld~jhe ----. tll~.. for an overall oxidation-reduction reaction. We then say that the concentration of organic matter is moles 4eq mg 0. Fe3 +. ---------.r!n9:j'-'~t~~!>eJ .-. let us assume that 0.3. -~~~- ~----~--------.x .'s car. (There .4.O we need to determine the number of electrons transferred per mole of species..'-. In the BOD test. the oxidizing agent dichromate. but they will not take place under the conditions of interest in the BOD or COD tests.25 X 10-' moles of 0..~uiv~J~!!. + 4H+ -7 4Fe'+ + 2H./eq..jH~ci. is oxidized to ferric ion.. det".9:?_9C used to~<:!~~~t!e!is . 4Fe'+ + 0. 1.25 x 10-' ..O. be-used to .'yi'. by oxygen. is used in place of oxygen.------.:!!.:. It is common in water chemistry to express the results of oxidationreduction reactions [such as those that take place in the biochemical oxygen demand (BOD) or chemical oxygen demand (COD) tests] in terms of oxygen much the same way that we earlier expressed ammonia and nitrate in terms of nitrogen.2!. We do this by separating the overall reaction into half-reactions.. Fe2 +.4.='---~~--~ -~"'-.Methods of Expressing Concentration 21 Similarly.Lh~_Cls'lllIl!E!j~~J~heE. In the COD test.tio.~----- oJ-f!.¥gen can accept 4 moles of electrons as in Section 1. such as the one in _ which ferrous ion. in which the number of electrons transferred is other than 4.ntration of organic matter in "mg/lite_r as 0 20" .oLeq_'&~5d"'!lls/lite~. had been used in place ofCrzPl::.LJ{~2.. react with the organic matter in I liter of water.3.x 8000 liter mole eq = 8 mglliter as 0.~e (hgJjLO.-"cO]lce.: of ~g:iiiter x 8000.) ~~1l<>:~_<!!..same numl:>er of eq/liter of it wouldre'Gct..-----.. Cr.JJ. the equivalent weights would be one half and one third of the molecular weights.' O. Th~ihe ". MassNolume Concentrations as 0.

For the total alkalinity reaction we are concerned with the CO. CO. (1.5.6. CaCO. Therefore.4) The equivalent weight of CaCO. it probably arose because early sanitary engineers were attracted by the prospect of normalizing concentrations to CaCO" a substance commonly used and referred to in water chemistry..3. it commonly appears in older literature.. is the w/w version of meq/liter. for ~dness.'.. In this method of expression. the concentration of a substance as "mg/liter as CaCO. (1·5) Each mole of CaCO.--. we treat Mg2+ the same as CaH. with respect to Ca'+ in precipitation or dissolution reactions. in this system is defined on the basis of "charge" or "acid-base reactions" (i. equivalent of CaCO.3.. epm The term equivalents-per million." is determined by the equation Number of equivalents of substance per liter x SO X lO'mg CaCO. especially in geochemistry. + Ca2+ l (1-6) .'.and OH-) concentrations in water and wastewater engineering and water chemistry is the calcium carbonate system.). r *- Equivalent weight of CaCO.22 Introduction 1. It is a term that was once commonly used but rarely is found in current literature. For example. 10' ml = 10' g and I epm = I meq/liter 1.3. Since I meqlliter and 10-' eq/liter When solution density = = = 10-' eq/liter = ~---------. or 2 equivalents of Ca2+. + 2H+ -> H. Mass Concentration as CaCO.-. yields I mole.-.e . This method of expressing concentration has the identical advantages (and disadvantages) to the "equivalents" method. cases I and 2 in Section 1. A very widespread system for expressing hardness (calcium and magnesium) and alkalinity (HCO. 100 glmole 2 eq/mole = SO geq I Because Mg2+ is also divalent and its properties as a hardness ion are based on charge just as are those of Ca'+. epm.CO.- 10-' eq/ml I eqllO' ml I glml.3. Equivalents per Million.portion of CaCO.

. + H+ -7 Ca2+ + HCO." again as shown in Eq. and C. New York. 1·4. This point is overlooked in much of the water chemistry literature.Additional Reading 23 and. Stumm. J. 1978. Hydrogeology..4.lnterscience. Minerals and Equilibria. S. CaCO. N. Aquatic ChemistrY. H. . and J. for this reaction.+ H+ -7 H2 CO. In the following reaction. New York. once again has an equivalent weight of so. (1·7) (1·8) Each mole of these bases reacts with 1 mole of H+. M. Wiley.are part of alkalinity and react as follows. each mole contains one equivalent of capacity for reacting with H+ and we convert the moleslliter (= eqlliter) of these species to "mglliter as CaCO. New York. For this reason the reader should always examine the basis used to express concentrations as "mglliter as CaCO. 1966. Calcium carbonate does not always have an equivalent weight of SO g/mole. L. M .and HCO. 1970. Harper. John Wiley.. Garrels. has an equivalent weight of lOa g/eq. Christ. CaCO. OH. W. Morgan. therefore. reacts with I mole of H+. New York. C.D . Holland. R..+ H+ -7 H2 0 HCO. Solutions. Wiley. however. since 2H+ react per mole of CaCO" for this reaction CaCO. and R.Interscience.. DeWiest. 1965. The Chemistry of the Atmosphere and Oceans." 1. Thus.- I mole of CaCO.. ADDITIONAL READING Davies. Other bases such as OH. .

Pearson. 1 . determines the design and performance of treatment processes and the behavior of natural water systems. by equilibrium calculations alone we can predict that it woud be impossible for sulfide to exist in water that contained dissolved oxygen. However. we find that solutions of Fe(II) salts at low pH values are stable indefinitely even when a stream of pure In this chapter we concern ourselves only with systems that are uniform in concentration throughout. Selleck. Berkeley. A. E. the chemical oxidation of organic compounds by chlorine and ozone. for example. However. reaction rates control such diverse reactions as precipitation. and magnesium hydroxide. Suisun Bay-Lower San Joaquin River Area. data collected in South San Francisco Bay in 1962 showed that sulfide could be detected in waters that contained up to 3 mg/liter dissolved oxygen. Storrs. calcium carbonate. South San Francisco Bay Area. dissolution. are reactions whose rates control the design and efficiency of treatment processes.' In natural waters. In water and wastewater treatment. University of California. and the chemical oxidation of iron(II) and manganese(I1). The subject is of considerable concern to the aquatic chemist because in many instances the rate at which a reaction proceeds toward equilibrium. rather than the equilibrium condition.CHEMICAL KINETICS 2. "A Comprehensive Study of San Francisco Bay. and oxidation-reduction and concentrations exist that are not those that would be predicted by equilibrium calculations.' This occurrence is possible because the reaction rate between oxygen and sulfide in dilute aqueous sol1:ltion is not rapid. 63-3. and E. 1961-62." SERL Report No. 2nd annual report.1. P. R. the precipitation of calcium phosphates. N. San Pablo Bay Area. 1963. The oxidation of Fe(ll) to Fe (III) by molecular oxygen is a reaction that equilibrium calculations predict will go to completion in waters where dissolved oxygen is present. INTRODUCTION The topic of chemical kinetics deals with the rate and mechanism of chemical reactions. . These nonequilibrium situations are particularly common for reactions involving oxidation-reduction and precipitation-dissolution_ For example. In process design the degree and type of mixing are important in addition to the rate at which chemical species react in uniform systems.

In this example we see that pH exerts a profound effect on whether equilibrium conditions or kinetic considerations better describe the system. when we mix ·hydrogen and oxygen gases together. 2.2. However. In Fe(1I) solutions with pH values> 7 to 8 the rate of oxidation of Fe(1I) to Fe(I1I) is so rapid that it is limited by the rate at which oxygen can be supplied by dissolution from the gas phase. not only is the rate of formation and dissolution of this thermodynamically predicted solid slow. From our investigation of chemical kinetics we should understand why some oxidation-reduction reactiops proceed very slowly in the absence of microorganisms while in their presence they occur rapidly. If natural water phosphate levels were controlled by equilibrium of the water with the thermodynamically stable calcium phosphate solidcalcium hydroxyapatite.Collisions of Reacting Species 25 oxygen gas is bubbled through them. Wiley-Interscience. thermodynamic or equilibrium predictions would lead one to conclude that ammonia would be oxidized to nitrate in oxygenated water. less than 0. In similar fashion for an unoxygenated water in equilibrium with the earth's atmosphere. . a rapid conversion of ammonium ion to nitrite and then to nitrate will take place. 1970. Morgan. we would predict that nitrate in water should be converted to nitrogen gas. CasOH(P04j. yet the presence of a little platinum or a spark in a mixture of these two gases will produce water with explosive violence. collisions between reacting species are necessary for chemical reactions to occur. Although 3 W. This reaction. Stumm and J.1 percent Fe(1I) will oxidize each day. 534-S38. 3 At pH < 4. COLLISIONS OF REACTING SPECIES With a few exceptions. pp. In their absence sodium nitrate solutions are perfectly stable. there is no reaction. J. Aquatic Chemistry.-phosphate levels would be so low that we would not be concerned with phosphate as a nutrient for photosynthetic aquatic organisms. In this chapter and in succeeding chapters we will examine the reasons for these observations in an effort to better understand the chemistry of aqueous systems. such as radioactive decay. For example. which is called denitrification. but also calcium phosphate solids of higher solubility form and then transform very slowly into hydroxyapatite. Yet an aerated sterile solution of ammonium chloride is stable indefinitely. However. The information derived from chemical kinetics should help us understand why. if we introduce microorganisms of the genre Nitrosornonas and Nitrobacter. levels of phosphate exist in receiving waters that are far in excess of those predicted by equilibrium with hydroxyapatite because. which contains 78 percent nitrogen gas. again only takes place in the presence of suitable microorganisms.

N. Because of this.3. .. and this can significantly affect the rate at which collisions occur. Why Do Chemical Reactions Occur? Prentice-Hall." In a gas phase when two reacting species collide and subsequently rebound they can become separated by a great distance in a very short period of time. However. We can increase the number of collisions between reacting species by increasing the temperature. The number of collisions between species other than the solvent in a solution is only slightly greater than in the gas phase. it is more likely that these are usually responsible for chemical reactions. for the same concentration and temperature. where less than 0. 1965. reacting species.26 Chemical Kinetics collisions bring the reacting species close enough together for reaction to occur. especially ionic species. J. 'K. Differences between liquid phase reactions and gas phase reactions occur largely because of the so-called "cage effect.ion combine very rapidly to form the precipitate AgCl(s) when present in a 4 J. the reactants are deflected so that another collision between the reactants can occur. For example. ORIENTATION OF REACTANTS Reactions between species that require no special orientation during collision to result in a reaction tend to be more rapid than reactions between species that must be properly aligned for a collision to result in a reaction. we can also increase the number of collisions by increasing the pressure. Chemical Kinetics. 1965. in solution the solvent molecules that surround the colliding species serve to trap them subsequent to collision by immediately colliding with the rebounding species. in air at ordinary laboratory conditions. successive collisions of the same molecules tend to occur in a solvent. If the reacting medium is a compressible gas.' Thus. A similar line of reasoning can be followed for substances reacting in solution. New York. Collisions between two species (a bimolecular collision) are a far more common occurrence than the simultaneous collision of three (trimolecular) or more species. However. Laidler. Campbell. Indeed. 2. For example. Englewood Cliffs. McGraw·Hill. 4 We can reason that on the basis of the much greater frequency of bimolecular collisions. This so-called "orientation effect" partially explains why many collisions between reacting species are not successful in producing a reaction. reactions in solution should occur at approximately the same rate as in the gas phase. frequently interact with the solvent.J. Three molecules collide simultaneously (lrimolecular collision) at a rate of about 10' times per second. in many instances. A. not all collisions successfully produce a chemical reaction. one molecule hits another (bimolecular collision) approximately 10' times per second. the spherical Ag+ ion and the spherical CI. 2nd ed.1 percent of the gas volume is occupied by gas molecules.

The Rate Law 27 supersaturated solution. Englewood Cliffs. d~~l = where -k[Al'[Bl'[P1P[Qlq . Orientation effect..(acetate) ion occur that do not result in reaction because the only collision that can result in reaction is between Na+ and the oxygen end of CH3 COO. q • . reactants ---> P + 2Q .7 A collision between Ncr+ and any other part of the acetate ion cannot form a sodium acetate precipitate. Why Do Chemical Reactions Occur? Prentice-Hall.. = constants 6 . Many collisions between the spherical Na+ ion and the linear CH3 COO. k = reaction rate constant. Campbell.. N. CH3 COO- ~ H 0 H C H C 0 8 CH3 COONa. A very large percentage of the collisions between . . 1965. concentrations far in excess of those encountered in dilute aqueous solution. 2_1). 2-1... J. The formation of solid sodium acetate' from supersaturated sodium acetate solutions is slow by comparison and the supersaturated solutions can exist for long periods of time without a precipitate forming.J ..) Fig. 2. (2-1) d~~l = time rate of change in molar concentration of species A. 2-1). A.. and a. b. products we can write the rate law. sodium acetate will not precipitate unless the concentrations of Na+ and CH3 COO. these species is successful in producing reaction because each is spherical and no special orientation is required (Fig.(Fig..4_ THE RATE LAW We can show experimentally that for the general irreversible reaction A + 2B + . . However. . p.each exceed approximately 15 moles per liter.

.1 x 106 (liters/mole sec) at 25°C.=! d[Q] .28 Chemical Kinetics In this book. the order with respect to B is b. NH2CI.. as follows. [ ] is used to signify concentration in moleslliter.2 dt . New York. Morris. C. that is. NH. the exponents of the product concentration. the relative number of moles of species reacting and the relativ~ number of moles of products being formed as the reaction proceeds. The following example illustrates several points that are important for a good understanding of the rate law. and so forth... and so forth. if d[A] = -k[A][B]' dt then we would say that the reaction was first order with respect to A.. If the reaction is irreversible. HOCl. and I mole of P is formed for every mole of A that reacts.. in solution to form monochloroamine. a The rate law was determined to be a J. _ -d[P] - dt _. For example. and so forth. . I.2) because I mole of A reacts for every 2 moles of B that react. We can determine the reaction order from the rate law. Example 2-1 Ammonia. It reacts with the disinfectant hypochlorous acid. we can state that d[A] _! d[B] dt .. k.CI + H. It is important to note that reaction order is generally not determined by the stoichiometry of the overall reaction. q. chapter in Principles and Applications of Water Chemistry. + HOCI --> NH. are usually zero. then p. and third order overall. (2·3) while the order with respect to A is a.. The overall reaction order is a+b+p+q . Laboratory experimentation is necessary to de· termine the order. was found by experiment to be 5.O The rate constant. Using our knowledge of the stoichiometry of the reaction.. second order with respect to B. 1967. We may use concentration units other than moleslliter in the rate law but in doing so we should use the same concentration unit for each species and realize that both the numerical value and units of the reaction rate constant will differ from those found when molecular concentrations are used. John Wiley. NH31 is a common constituent of many natural waters and wastewaters. (2.2 dt .

) 1 t Since 1 mole NH.1. Equation 2·2 can be written more explicitly as d[H~C1J ~ -k[HOC1J'[NH.lliter ~ [NH. the reaction rate becomes (d[HOC1J) (dO"w The new reaction rate is 2S percent of the initial reaction rate. (l) k ~ d[HOC1Jldt [NH.J' where a = I and b = 1. This derives from a rearrangement and dimensional analysis of Eq.1Xconcentration. (d[HOCIJ) . Solution o.][HOCl] ( 1 ) (I) [NH. [HOC1J 1 [NH.1).~kyx (dt)orlglnal When x and yare each reduced by 50 percent.l' molelliter sec (molelliterXmolelliter) liter mole sec b. The rate of reaction is then. we can state (2) k'~( mg NH.J t Setting k' = rate constant when concentrations are expressed in mg! liter. the rate constant can be written.000 mg NH. Let the initial concentrations of NH3 and HOCl be x and y.lliter. 2·2 thus.lliter ~ 17. k ~ d[HOC1J dt . c.000 . for re~ctions with an overall order of 2. The overall reaction order is a + b ::::: 2. (3) mg NH. The experienced eye will immediately recognize a second-order reaction from the units of the rate constant which. respectively.The Rate Law 2.lliter )(.J (0) What is the overall reaction order? (b) What percent decrease in reaction rate occurs if the concentration of each ~eactant is reduced by SO percent? (c) Determine the value of the rate constant when concentrations are expressed in units of mgl liter rather than moleslliter. 29 d[H~C1J ~ -k[HOC1][NH.J x 17. are always liter! mole sec or more generally (time. When the concentrations of HOCl and NH3 are both expressed as molelliter.

we have I k= Since k = 5. we must integrate the rate expression with respect to time. the reaction is zero order. We will do thisfor several values of the reae!ion order. the initial concentration of A. 2-6 and solving the integral.1 X k' [NH.000 t I I 17.000 [NH. and (c). n.5 [A]o when t = t 1{2' Then t '12 =-k-When n = 1. [A] ° . d[A] = -k[A] dt (2-6) ·0.J t lOs liter/mole sec.J x 17. the reae!ion is first order.7 x 10' 300 liter/mg sec Integrated forms of the rate law are very useful for analyzing rate data to determine reaction rate constants and reaction order. [AI Jd[A] = -J kdt [AI. 2-5 by setting [A] = 0.4) Upon integrating.5[A]o Rearranging Eq. t1{" or time for 50 percent of the initial concentration to react can be obtained from Eq. (b). and we can write. k' = S. both with respee! to A and overall. When n = 0. Let Us first consider the irreversible reaction A --> products which has the rate law d[A] = -k[A]n dt To determine the behavior of [A] as a function of time. we obtain [A] = [A]o -kt (2·5) where [A]o = the concentration of A at t = 0.I x 10' 1. The half-life. and d[A] - dt = -k[A]O = -k (2. that is.30 Chemical Kinetics Combining (a).

then we can write d[AJ = -k[AJn dl and integrating. we obtain d[AJ J([AJ)n Jk dl = 0 [A) (2-9) [A1o or t ~II) CAJ~-1) t ~II) or CA:S-1) = -kl n ~ I CAJIS-1 - l [AJ n-1) = -kl (2-10) If n = 2.693 =-k- If the reaction is greater than first order. for example. when [AJ = 0. the reaction is second order. Let us now proceed to the slightly more complex case of the irreversible reaction in which two reactants react to give products.kt (2-8) (2-7) Examination of Eq. which has a slope of -k. from Eq. we find the half-life to be 11/2 0.5 [AJa. 2-11. and we can write (2-11) and the half-life is I 1'12 =.kl or [AJ= [AJa e. we would determine the rate constant k by plotting II[AJ versus I to yield a straight line with a slope of k in accordance with Eq. 2-7 suggests that the rate constantk may be determined experimentally from a plot of In [AJ versus t.k[AJa For a second-order reaction involving one reactant. Also.The Rate Law 31 we find In [AJ = In [AJa . 2-8. We can write A + B -> products (2-12) . both with respect to A and overall.

or dX = -d[A] = k[A][B] dt dt (2·19) .14. we can see that for each molecule of A which reacts. 2.20) Integrating.X) (2. There are two general situations we must examine. 2·16. 2·12. 2·16 and 2·17 in Eq. and substituting for X from Eqs. one molecule of B will react. it is useful to use the substitution [A] = [A]o-X [B] = [B]o . The concentra· tions of A and B will therefore decrease at the same rate.32 Chemical Kinetics which has the rate law d[A] dt = d[B] = -k[A]'[B]b dt (2. rearranging. we obtain dX d[A] -=--- dt dt (2. Differentiating Eq.17) where X is the concentration in moleslliter of each species that has reacted. the reaction is second order overall and first order with respect to both A and B.".--. d[A] = -k[A][B] dt (2· 14) From the reaction stoichiometry in Eq.X (2·16) (2. 2. 2·11.19. d[A] = -k[A][B] dt . We can therefore substitute [A] for [B] to give d[A] = -k[A]' dt (2. 2·16 and 2·17. will yield the same expression as Eq. and since they were initially equal this means they will always be equal. When a = b = I and [A]o = [B]o.~ and substituting for [A] and [B] from Eqs. we obtain . we obtain dX cit = k([A]o X)([B]o .18) From Eq.15) which. These are when [A]o = [B]o. and when [A]oi' [B]o' For the first case. when integrated.13) When a = I and b = I.

the integrated form of the rate law will also be different.[A]. namely the pseudo fjrst-order reaction. For example. For example.). k can be determined as k = slope/([B]. for the reaction 2A + B "'"' prod ucts For the initial condition of [A]. it is often possible to assume that the water is present in large excess. It is important to note that Eq. + ([B] '. . and [A]. are known. we must plot 1/[B]' versus t and obtain the slope which is equal to Sk.)k.[A] ) kt (2-21) A plot of experimental data in the form In ([B]/[A]) versus t will yield a straight line with a slope of ([B].e-k't (2-2S) When reactions taking place in dilute aqueous solution have water as one of the reactants. 2-12. This equation can be integrated to give [A] = [A]. if reactant B is present in large excess over reac"tant A. [A] [A]. and since [B]. the hydrolysis of one molecule of the disaccharide sucrose to yield two molecules of monosaccharides (one . = (2-22) 2[B].The Rate Law 33 In l!ll = In [B].' . then d[A] dt = -k[A][B] = -k'[A] (2-27) where k' = k[B] and k' is a pseudo first-order reaction rate constant. . Then k = slope/So One other reaction order will be considered here.[A]. 2-21 is only yalid for the reaction stoichiometry given in Eq. The reaction A + B "'"' products which has the rate law d[A] dt = -k[A][B] (2-25) (2-26) can be treated as a first-order reaction if one of the reactants is present in such excess that its concentration is virtually unchanged during the course of the reaction. For example.' + Skt (2-24) To obtain k from experimental data for a reaction that follows this rate law. If the stoichiometry is different. and a rate law of = -k[A]'[B] d[B] dt (2-23) the integrated form of the rate expression is I I [B]' = [B].

however. Given that the reaction is irreversible. It readily decomposes to oxygen and water in the presence of a manganese dioxide catalyst (see Section 2-7).] versus t is curvilinear. let us test whether the reaction is first or second order. we can make use of the equations applicable to irreversible reactions by controlling the reaction conditions used to collect rate data so that the assumption of irreversibility can legitimately be made. once products formed. In each of the situations already discussed.] versus t is linear and j/[H. Example 2-2 Hydrogen peroxide. First. we assumed that the reactions were irreversible. Even if the reaction is reversible there will be little back reaction during this time period because the products that participate in the back reaction are present only in small quantities. no -reverse reaction to form the reactants occurred. Figure 2-2 shows that In [H. Very few reactions are strictly irreversible. we find that Mn021!l 2H 20 2 -----? 2H 2 0 + O2 Determine the rate constant and order of this reaction. H20 2t is an oxidizing agent that often finds use in water purification processes.O. that is. A common experimental technique used in the study of reaction rates is to make each of the reactants in turn present in large excess. For a first-order reaction the plot of In [H20 2J! versus t should he straight line while for a second-order reaction the plot of 1/[H20 21 versus t should be linear. Additional Reading) for procedures on handling more com· plex problems and for a more detailed treatment of the topic of rate equations. The reader is referred to other texts (see Section 2·10. The following example illustrates a procedure for determining the reaction order and rate constant. The dependence of the reaction rate on the concentration of the other reactants can then be studied. Solution The data in Table 2-1 were obtained during an experiment to determine the rate constant and order of the reaction. but because the H2 0 concentration remains essentially constant in dilute aqueous solution it can be considered as a pseudo first·order reaction. One way of doing this is to collect rate data only during a very short time period following the mixing of reactants.34 Chemical Kinetics molecule each of glucose and fructose) can be written as H20 + C12H22011 ~ C6H120 6 + C6H120 6 sucrose glucose fructose Experiments show this reaction to be second order overall. Thus the reaction can be treated as first order with respect to H20 2 • .O.

77 -4.0071 In [H. t.9 101 141 The rate constant can be determined from" the slope of the plot of In (H20 versus t.45 -3.05 -4.023 0.and second·order plots for Example 2·2.45)] 20-0 -0.013 0. .£ -4 OJ E -5 0 10 20 30 Time.2 55. min Fig. s Iope = 2 1 "'In [A] 6.25 43.O. min 40 50 60 140 120 100 80 ~I~ 60 400L---~ll0----~2~0----~3~0~---4~0----~50=---~60 Time. minutes 35 [H. First.] -3.018 0.t -k I [-4.O. t.The Rate Law TABLE 2-1 Time. 2-2.34 -4.032 0. 2-27.03/min k k ~ ~ + 0.] M 0.05 .0099 0.62 -4.O.03 x SO/sec 5 x IO-'fsec -3 (a) First-order p!ot .95 II[H.( -3. From Eq.6 76.] 0 10 20 30 40 50 31.

and (2) the scatter of data points owing to experimental error makes it difficult to judge whether the straight line fit for one assumed order is better than another. '-/ CH. Thus. CH. if the reaction A -> products is elementary and monomolecular. respectively. . Elementary reactions may be monomolecular. Indeed we can define a particular type of reaction-the elementary reaction-which has the special property that its reaction order can be determined from its stoichiometry.5. REACTION MECHANISM We have noted previously that the order of a reaction cannot necessarily be determined from an examination of the stoichiometry of the reaction. and if the data are carefully collected and the experiment is properly designed.CH = CH. the procedure gives fairly reliable results. CH. (The data used in this example were collected by one of us when he was an undergraduate. Thus A + A'"-~ products or A + B -> products The rate laws are. .36 Chemical Kinetics This trial-and-error approach to finding reaction order has definite limitations because (I) it is difficult to apply if the reaction order is not an integer. where a single species reacts and its concentration alone determines the rate of the reaction. Elementary reactions that are bimolecular involve the interaction of two molecules which may be two molecules of the same species or molecules of different species. ) 2. Most reaction orders are integers. Generally stated.. however.CH. the reader is left to judge for himself whether the data were carefully collected. d[A] dt and = -k[A]' .. the rate law will be d[A] dt = -k[A] Radioactive decay is an example of such a reaction as is the decomposition of the gas cyclopropane to propylene. . while the design of the experiment was most likely well done.

CH3Br + bromomethane 1iodide CH31 + iodomethane -k[CH3 Br]W] Be bromide d[CH.] dt = k[H"g)][I"g)] The formation of hydrogen bromide from hydrogen gas and bromine gas can be stoichiometrically stated as H2(g) + Br2(g) ~ 2HBr(g) = The rate law is found by experiment to be ! d[HBr] 2 dt k[H"g)][Br"g)l''' I + k' [HBr. We can determine the reaction order with respect to each reactant (and product) and the influence of the concentration of all species . when written stoichiometrically. experimentation may well reveal a complicated rate law that indicates a complex mech· anism. Overall reactions.Reaction Mechanism 37 d[A] = d[B] = -k[A][B] dt dt Examples of such reactions are the decomposition of nitrogen dioxide to nitric oxide and oxygen in the gas phase. are composed of a series or a sequence of elementary reactions. bimolecular and first order with respect to both [I"g)] and [H"g)]' The rate law is 2& = ~ = I d[RI] -d[I.] = More complex reactions than these are the rule rather than the exception.g)]/[Br"g)] The reaction is evidently not elementary.] -d[H. However. 2NO.Br] dt d~. may lead one to believe that they have simple mechanisms. -> 2NO + 0. For example. contrast the following two reactions: The formation of hydrogen iodide from hydrogen gas and iodine gas is stoichiometrically represented as The reaction is elementary. ' d[NO.] dt = -k[NO ]' and the formation of iodomethane from bromomethane. Such complex reactions as these. however.

Haldane. When the reaction depicted in Eq. London. glucose.H 120. and fructose. 1930. . let us examine the results from a biochemical experiment in which the rate of hydrolysis of sucrose by the enzyme saccharase is investigated.[P] « k 1[S] and defining the total amount of enzyme as [E]. 9 R. -d[S]/dt = constant. glucose + C. To illustrate these points further. Our first step will be to determine ES in terms of the total amount of E-containing species and substrate concentration.. Chern... S. in "Emymes" by J. that is. while at higher sucrose concentrations the rate of hydrolysis approached a maximum rate that was apparently independent of sucrose concentration.H12 0.[P] (k 2 Assuming k . catalyzes the reaction: saccharase C 12H22 0 sucrose 11 + H2 0 ~ C. ES must be formed. [P].[E][P] = rate of ES removal k 2 [ES] + k3[ES] Thus. d[ES]/dt = 0.=:ES. = Dividing through by [E] and rearranging yields [E] = [ES] + k3) k. The reaction scheme proposed is kJ k3 S + E. 2-3). This enzyme. Saccharase und Raffinase wirkung des Invertins. Physiol. and Rate of ES formation k. B.=:P . -d[S]/dt = k[S].. we can derive the expression. + E k2 k4 (2-29) We can reason that the rate of reaction should be related to the concentration of ES complex because. that is." Zis.[E][S] + k. for the reaction to take place. This rate behavior can be rationalized by assuming that the sucrose and enzyme react to form a complex which then may either revert to sucrose and enzyme or react to form the products. because the reactions in Eq. Kuhn "Uber Spezifitat der Enzyme II. = [E] + [ES]. 2-29 is at steady state. 125: 28 (1923). or biological catalyst (of which we shall speak in more detail later). Longman. fructose The data of Kuhn' showed that the initial rate of hydrolysis of the substrate sucrose (-d[S]/dt) was a function of the substrate concentration [S] when the saccharase enzyme concentration [E] was constant (Fig. At low substrate concentrations the rate of hydrolysis appeared to be proportional to sucrose concentration.38 Chemical Kinetics on the rate of the overall reaction if we know the sequence and rates of the elementary reactions that make up the overall reaction. 2-29 are elementary.[S] + k.

Reprinted by permission of the Longman Group Limited. 15 00 10 5 oL---~--~~~~~~--~~-J 0. 2-3. that is. + k.. analysis of Eq.!::!' ~ 39 -. gives a rectangular hyperbola---<l curve of the form depicted in Fig. S.20 0. This lends support to the contention that our kinetic model is descriptive of the reaction mechanism. :§ Qig . + k. a property that agrees with one of . Adapted from R.. The value of Vm" is the maximum rate of reaction.-~ C o.10 0. this rectangular hyperbolic expression provides a useful model for microbial growth kinetics.)lk " we obtain ..':0 . "Enzymes.30 Sucrose concentration. 2-3. if we set Km = (k.. 2-30 shows that V = Vm. when [ESJ [EJ.' The reaction then is zero order with respect to [SJ. . V = Vm" [SJ Km + [SJ (2-30) A plot of V versus [SJ using this expression. V. [SJ [ESJ = [(k.. the Michaelis-Menten equation. [EJ.2 '0 ~~ >''::.05 0. As we shall see later in this chapter. When Vm" is reached. Further. Haldane. Kuhn in J.f sucrose hydrolysis by yeast saccharase as a function of substrate concentration.Reaction Mechanism 35 30 . then the maximum rate of reaction Vm" will occur when all of the enzyme is present as [ESJ. London. further increases in [SJ have no effect on reaction rate.25 0. At this point we should examine the two constants that determine the shape of the V versus [SJ curve. Rate o. the rate attained at high values of [SJ. 1930.---- 25 20 ~E '0. B. moles/liter Fig. When [SJ > > Km . is proportional to [ESJ.. .15 0." Longmans Greene and Co .J + [SJ If we now assume that the rate of reaction.)lk .

k = Ae(-EafRn (2-31) Equation 2-31 can be linearized as follows./2 and [8] =[8]112' for example. and is indicative of the strength of the bond between enzyme and substrate. In the substrate concentration range where K m » [8]. 2. EFFECT OF TEMPERATURE ON REACTION RATE Experiments have shown that chemical reaction rates increase with increasing temperatures. If V = Vm. 2-30 predicts that V = V m" [8] Km = K' [8] This is the expression for a reaction which is first order with respect to [8]. the Michaelis-Menten constant.. 2-3. We call this value of the substrate concentration [8]. 2-3). Arrhenius formulated the empirical rate law.2 M of substrate to allow an enzyme to operate at half of its maximum rate.12. The lower the value of Km. Values of Km for single substrate-enzyme reactions are generally between 10-2 and 10-5 M. Above a certain temperature the structure of the enzyme becomes altered (denaturation) and its catalytic properties are reduced and eventually destroyed. these reactions have temperature optima.6. an expression that fits the experimentally observed behavior in Fig. the effect of temperature on reaction rate is related to its effect on the reaction rate constant. ./2 = Vmax [8]"2 Km + [8]. Rather than show a consistent increase with increasing temperature. 10 In many instances./2 (see Fig. Rr (2-32) 10 One exception is the effect of temperature on enzymatically catalyzed reactions. Eq. The significance of this range of values is that it only requires 10-5 to 10. This can be shown using Eq. the greater is the affinity hetwe"n enzyme and substrate. 2-3. The value of Km is equal to the value of [8] when V = Vm. Thus we see that the same reaction can be either zero or first order depending on the concentration of reactants. Vmax 2 or Km = [8].40 Chemical Kinetics our initial experimental observations. is variously called the half-velocity constant./2 This constant.. Ink =lnA _ E. Km.

a straight line with a slope of . activated complex activated complex -) products We can illustrate the relative average energy levels of reactants. products. To do this. . However. we assume that the reaction A + B . Figure 2-4 shows that the complete reaction proceeds. where A = E. in this example.. as well as ilH.IR). is released when the activated complex decomposes Activated complex Reactants Products Extent of reaction Fig.. = R T = = the pre-exponential factor.. This energy. unstable intermediate known as a transition complex or an activated complex A + B . the activation energy and is also treated as a constant for a particular reaction the ideal gas constant the temperature in 'K It is possible to relate the experimentally observed and empirically stated effect of temperature on reaction rate to a theoretical description of the effect of temperature on the energy level distribution of reacting species.. Activation energy. or frequency factor. and activated complex by a diagram such as that presented in Fig. with a release of energy. the heat of reaction.... 2-4.Effect of Temperature on Reaction Rate 41 so thai a plot of In k versus liT should give. 2-4.E.IR and an intercept on the liT axis of In (A)/(E. products proceeds through a high-energy. ilH. and is usually treated as a constant that is independent of temperature for a particular reaction.. the intermediate formation of the activated complex requires the input of an average amount of energy E" the activation energy of the forward reaction.

Simply stated. an energy input of (fl. 2·5 we can see that. Figure 2·4 is based on the average energy levels of reactants. as the stipulated energy level is raised.) is required to form the activated complex of which only E.42 Chemical Kinetics into the products of the reaction. The effect of temperature on the distribution of energy levels for a given species can be described by the Maxwell·Boltzmann theory. We can now postulate that only molecules with an energy level equal to or greater than E are capable of forming the high energy·level transition complex. OK constant From this equation and from Fig. and the activated complex. To understand how the idea of a high. Further examination of Eq.H + E . Making this postulate draws our attention to the similarity E Energy Fig. is released when A and B are reformed. for a given temperature. the value of N will decrease as the value of E is increased. products. 2·33 reveals that for a given energy level. For the reverse of this reaction to proceed. which relates the variation of the number of molecules with an energy equcll to or greater than a given energy level to the absolute temperature.) is the activation energy of the reverse reaction. .H + E.5). Reactant energy distribution. we must examine the distribution of energy levels in a reactant at a given temperature (see Fig. Thus N =NoD exp (. The quantity (fl. 2. a smaller and smaller fraction of the total molecules are included in N.:) where (2·33) E = = = = = = No N R T D a stipulated energy level (see Fig. 2-5. 2·5) total number of molecules number of molecules with energy equal to or greater than E gas constant absolute activated complex is related to the effect of temperature on the reaction rate. increasing the temperature should exponentially increase the population of molecules present at or above this energy level.

Why Do Chemical Reactions Occur? Prentice.5 Rate Constant.400 -7.Hall. 11 e-E~IRr is The Maxwell-Boltzmann theory strictly applies to molecules in the gas phase.] ~ 5. k 35.4 Determine the activation E!nergy for this reaction and the value of the pre· exponential factor.35 3. liT ~ 0.2 x 10' M. Englewood Cliffs. .2 298.56 x 10-' M and [KI] ~ 1.888 -7.053 OK (1') T .4 10-' 10. 2·31). Example 2-3 The rate constant k for the reaction between hydrogen peroxide and potassium iodide to form iodine and water.400 callmole II. was found to v~ry as follows with temperature when the reactant concentrations were held constant at [H. 2-31 and 2-33 and provides some theoretical basis for the empirically derived Arrhenius equation.. Temperature.24 x 10' liter/mole sec 11. 4 kcal/mole ~ Using Eq.15 3. A. Campbell. °C 44.5 1. : : ': 2H20 + I2iaq ) + 2K+. 2-6 that when In k yields InA ~ -7 + 1.3 277." The procedure for determining the values of E.7 308.1 4.Effect of Temperature on Reaction Rate 43 between Eqs.60 ~ See Fig. See 1.63 2. 2-32 and observing from Fig. ~ 11. E. 2-32.(l/T) -E.02 6. 2-6.73 A ~ 1. N. 99 cal/mole OK. for a discussion of this topic.7 15.7 ~ 3.99 x 305.47 3. In k -6.66 1. since dimensionless.00327 °K-' The units of A are the same as the units of k (see Eq. but the same concepts apply equally well to the distribution of the velocities among molecules in a solution.IR ~ -5750 OK.401 -6. ~ !'. H20 2 + 2KI + 2H+ :. From this figure.J .0 25. 1965. Solution Plot the data according to Eq.On k)/!'.x 10' I 317.319 -8. Temperature.118 -9.9 288. slope Since R ~ 1.25 3.8 11. and A for a reaction is illustrated in the following example.98 U7 X X X X X 10-' 10-' 10.O.

I.2 3.RT Without catalyst Reactants W. Arrhenius plot for Example 2-3.7 Fig.44 Chemical Kinetics -6 -7 -8 -9 -10L-__ 3. 2.5 3. For example. we can show that if the rate of a reaction (at 25'C) is increased by a factor of two upon the addition of a catalyst. = Ea . 2·6.0 • ~ ____ ~ __ ~ ____ ~ __ ~ ____ ~ __ ~ 3. 2-7).th -"'\ catalyst Products Extent of reaction Fig.4 3.3 3. 2·7.1 InA . Effect of a catalyst on activation energy.1 3.7. Ink. .6 3. the activation energy is reduced by 409 cal/mole. With no catalyst. They act by modifying the reaction pathway or the nature of the activated complex so that the reaction may proceed through an activated complex with a lower activation energy (Fig. CATALYSIS Catalysts are substances that increase the rate of reaction.

H.2k _ E.O" and tripo.O". Ink... becoming part of the activated complex. B9th types of chemical catalysts as well as the specific biological catalysts known as enzymes are important in aquatic chemistry.1 409·cal/mole 298 X In (t) = E. Its concentration is not changed by the overall reaction. Hydrogen ion (H+) and hydroxyl ion (OH-) are common catalysts in aquatic systems. or heterogeneous when the catalyst is present as a distinctly separate phase.2 RT I k . The effect of their catalysis is manifested by changes in reaction rate that occur with changes in pH. = In (2k . 1-2. For example. t. _ E..409 kcal/mole. not its extent. one of the major constituents of household synthetic detergents is the salt of con· densed phosphoric acid such as pyrophosphoric acid.H.2 . that is. 45 2.1 = - Thus E. These compounds react with water in a reaction known as hydrolysis to form orthophosphoric acid thus: H 0 0 0 (2·34) H " o + HO-P--D-PI--DH ~ 2[HO-P--DH] II II II / I I OH OH OH Pyrophosphoric acid Orthophosphoric acid 4NaOH + NaO-P--D-P--D-P--DNa ~ 3[NaO-P-ONa] + 2 0 o 0 0 0 / I I I I H Na Na Na Na Pentasodium tripolyphosphate Trisodium phosphate iii i H" (2·35) . A catalyst may participate in the reaction by. is not altered.99 X = E'. attributable to the presence of a catalyst the heat of the reaction.P. Iyphosphoric acid.1 n n 1 - RT RT RT In (t) 1. ) = InA 1 Ea.E'.. is decreased by 0.. We can therefore deduce that a catalyst will only influence the rate of a reaction. HsP.I . Although there is a change in E. . for example.E'.Catalysis With a catalyst. A+ B+ ~atalyst = products + catalyst Catalysts may be generally classified as homogeneous when the· catalyst is uniformly distributed on a molecular level throughout the reacting medium.

:. the liquid under investigation must be deoxygenated. As Fig. 14th ed . In the typical washing machine environment of 65°C and pH 9.'. Na.S34/hr at pH = 0 to 0. usually a time period of significantly less than I day. The rate constant is highly dependent on [H+j and varies from 0. a 5 percent decomposition of pyrophosphate would take several days so that in the typical wash cycle of 10 to IS min.=: 2S0.46 Chemical Kinetics The condensed phosphates contribute approximately SO to 60 percent of the total phosphate in domestic wastewater.+ 0..5 to 8 and temperatures between 10 to 20'C. so it is important that the condensed phosphates are stable (i.. no condensed phosphates ever survive biological waste treatment processes-<lgain a maximum period of about I day. The reason for these observations is again catalysis but in this instance catalysis by enzymes. An example of such an enzyme is pyrophosphate phosphohydrolase.e . American Public Health Assoc .SO" which reacts with oxygen to form sodium sulfate. do not undergo hydrolysis as in Eqs.O. many years at pH 7.. Most domestic wastewaters have pH values in the range 6.O. It takes about 10 minutes to 12 Standard Methods for the Examination of Water and Wastewater. However. 85. 2S0. Ca2+ and Mg'+. The recommended method" for accomplishing deoxygenation is to add sodium sulfite. Na. The rate equation for the hydrolysis of pyrophosphate is -d[P. which catalyzes the hydrolysis of inorganic pyrophosphate to 2 moles of orthophosphate.1 to 0. 2-8 shows. hydrolysis will be insignificant.0318 at pH = 1.00272lhr at pH 3. Prior to the test. Moreover. Most microorganisms possess an enzyme (a specific biological catalyst) that will mediate the hydrolysis of inorganic condensed phosphates.'-j/dt = k[P. and prevent their interaction with the surfactant. and over a century at pH 10. . 1975. we observe that much of the condensed phosphate in domestic wastewater has reverted to orthophosphate by the time that the wastewater reaches the treatment plant. p. the time for 5 percent hydrolysis of a pyrophosphate solution at 10°C is about I year at pH 4. The hydrolysis of condensed phosphates is catalyzed by H+. They are used in the commercial synthetic detergent formulation to complex the hardness ions. Orthophosphates do not perform this complexing function as well as the condensed phosphates. The effiCiency with which aeration devices transfer oxygen to water or to wastewater is measured by determining the rate at which the device increases the dissolved oxygen concentration of the liquid.'thereby depleting the solution of dissolved oxygen. 2-34 and 2-35) during the cleansing process.3. 2-8 we would predict that pyrophosphates would be quite stable under these conditions.'-j. This reaction is extremely slow in the absence of a catalyst. From Fig.SO" thus: .

KhandelwaL A. p.01 mglliter cobalt ion allows the complete removal of dissolved oxygen in IS to 20 seconds. The introduction of 0. K. Phosphorus and Its Compounds.y Hour Minute o Temperature "'c Fig." A further example of catalysis by metal ions is the effect of cupric ion. American Chemical Society. "Chemical Fixation of Oxygen. Van Wazer. Water Works Association. 3CW + 0. "Kinetics of Ozonation of Cyanides.14 In wastes from industries such as metal plating and coal carbonization. Adapted from J. D. -> 3CNOThe rate of this reaction is more than doubled in the presence of Cu'+. I.Catalysis 47 Century pH 10 Year Month D. Vol. 39: 1121-1127 14 (I 947). Baiduhn. 13 D. ozone. 1. Advances in Chemistry Series 21. .J. Cu2+. Grove. and C. Washington. 2·8. cyanide can be oxidized to cyanate by ozone. R. Reprinted by permission of John Wiley & Sons. reduce the concentration of dissolved oxygen from 10 to 7 mgiliter when catalysts are not present. Inc.. 454. 1966. New York. p. S." Ozone Chemistry and Technology." J. Am.C" 1959. Time for 5 percent hydrolysis of pyrophosphate (sodium salt) in a 1 percent (approximate) solution. Pye. Interscience. K. on the oxidation of cyanide. Jr.

The Beckman Model 900 carbon analyzer consists of a quartz tube heated to 950'C. The objective here is a simplification of complex situations. EMPIRICAL RATE LAWS Our discussion up to this point has dealt with the use of kinetics to describe the rates of chemically well·defined reactions and to explore the mechanism of reactions. test) and the amount of dissolved oxygen consumed in this time period is measured. Tl1elfc5D.) is present].--~----.O..-"---~----------' . The BOD.-----------------.) catalyst in the determination of organic carbon.~. concentration is determined by an infrared detector./"'-.. = dissolved oxygen (mglliter) dilution factor where dilution factor = volume sample!(volume of sample + volume -----------------./----_.. In the BOD test.measurement determines only one point on the curve that ~-.waters and in receiving -..8..48 Chemical Kinetics The rate law for the reaction in the presence of an excess and constant ozone concentration is It shows no dependence on Cu2 + concentration above a certain minimum concentration indicating that its effect is purely catalytic. nated with cobalt nitrate.ed o~yg~n (D. The first concerns treatment of data from the ~ oxygen demand (BOD test tha~yariously to_c:l".."~h of wastewater.~~ dissol'. not the discovery of exact mechanism from kinetic analysis. the degree of organic pollution ~.-~ dilution water).~~~_e.. containing asbestos that has been impreg. A sample of 20 ILl is injected into a stream of oxygen that passes over the heated catalyst that enhances the oxidation of organic carbon to CO. Two examples of this use of kinetic formulations that are relevant to aquatic systems will be given here.----~ ~-----~~"--. An example of heterogeneous catalysis related to the field of water chemistry is the use of cobaltic oxide (Co..-----" -the rate at which the organic matter in wastewater can be degr_aded ny ~~C{~~~f9-b~~_~~~~(HHons [Le.he. At 950'C the cobalt nitrate decomposes to cobaltic oxide. The CO. The fractional order of the reaction indicates a complex mechanism. to provide an empirical mathe· matical framework in which data from complex reactions can be analyzed. is then calculated as "-""" BOD ... a diluted sample of wastewater is incubated for a period (5 days at 20'C in the standard BOD.O. 2. Kinetic formulations can be used in what one might call the opposite sense-that is.. .

.ct toorgClllic oL~.-ai. Nevertheless. measuring oxygen uptake has often been expressed as ".>"e_n. we can usefully employ the empirical first·order relationship to formulate the "BOD curve" (see Fig. 2-9. .!!C~nt19~~d~!...ID--"'ll.Empirical Rate Laws 49 relates dissolved oxygen uptake to time... dation) is of importance in waste treatment plant design and receiving water management.<>ducts....rga!l.~c:tS.lR. It must be recognized that this is a totally empirical statement because the nature of the degradable organic matter in wastewater is not well·defined and certainly the individual microbial degradation rates of all organic compounds in water are not known. the overall time course of the consumption of oxygen for degradation of carbonaceous organic matter in the BOD test has many of the characteristics of a first· order reaction.pr_e..O.Q. 2·9). +J1g9±g"igized£r.11¥-J..of dissolved mgtte.sence of an excess.:: . we obtain (2·37) where Lo k = = the original concentration of biodegradable organic matter rate constant/day 5 Time.r. then for a first. t..!lcjiorlin . The reaction monitored by ..ord?r reaction we can write dL -=-kL dt (2.!h". days Fig..36) Integrating. If!~J (days). Since the rate of BOD exertion (or organic matter degra. "First-order" representation of first·stage carbonaceous BOD. and the rate o~~)l~t~.!'_!.~tatedt()befi!sCor~"ty(


Chemical Kinetics

Because L cannot be measured directly, the equation must be modified to replace L with a parameter that can be measured as a function of time. We can achieve this modification by setting .
y =Lo-L


where ~~igJ~~~h!l.e~.t..9&~, !,. The value of y can be assessed by determining dissolved oxygen consumption at any time, through measurements of (Iissolved oxygen concentration of the sample,


Substituting Eq. 2·38 in Eq. 2.37, we obtain

Lo - L


y = Lo - Loe- kt

y = Lo(l - e- kt )

which is the classical first-order empirical rate equation for BOD. Various procedures exist for analyzing y versus t data to obtain the constants k and Lo. One of these, the Thomas slope method, is presented here. 's This procedure involves developing a straight line equation that approximates the relationship of y and t. If we expand the (1 - e- kt ) portion of Eq. 2-40, we obtain

I- eThe quantity [kt(i


= kt

[I -

kt 2

+ (kt)' 6

(kt)' 24

+ ...J


+ kt/6)-']

has a similar expansion,

(I +

kt)-' =kt



+ (kt)'

_ (kt)"

+ ...)




Comparing these two expansions, we see that a minor difference appears only in the fourth term; on this basis we can say

Lo (1 - e'-kt)

Lo [ kt ( I +

~t) -'J


(2-44) Rearranging Eq. 2-44, we obtain an equation of a straight line

!..)' (Y /3 = (L k)-1/3 + ( 6k'/3) t L 6/3


H. A. Thomas, Jr., "Graphical Determination of BOD Curve Constants," Water and Sewage Works, 97: 123 (1950).

Empirical Rate Laws


Letting" (2-46) and (2-47) it can be shown that (2-48) and
1 Lo = ka'


With experimental data relating y and time, we can plot (1Iy)'/3 versus time. However, experimental values of y > O.9Lo should not be used in fitting the straight line because Eq. 2·42 is significantly different from Eq. 2-41 in this range. Fitting the plot with a straight line and determining the intercept, a, and the slope, b, Eqs. 2·47 and 2·48 can be used to give k and L~ The following example illustrates the procedure. We must be careful to bear in mind as we proceed with these calculations that they are empirically based. It is neither wise nor proper to read any more significance into them than that; it is certainly improper to infer, as many have done, that we" can deduce anything about the reaction mechanism from these calculations. Example 2-4
Standard Methods 16 states that the rate constant (base 10) for the oxygen uptake of a mixture of glucose (150 mg/liter) and glutamic acid (150 mg/liter) should be between 0.16 to D.IS/day when proper seeding with microorganisms is practiced. The data in Table 2-2 were obtained at 20°C on a candidate seed material by a University of California graduate student. Does the seed satisfy the above specifications?
TABLE 2-2 Time, t, days


BOD, y, mg/liter 122 117 184 193 203 205 207

0.0082 0.017 0.Ql6 0.021 0.025 0.029 0.034

0.202 0.25 0.25 0.276 0.292 0.307 0.324

2 3 4 5 6 7

Standard Methods for the Examination of Water and Wastewater, 14th ed., American Public Health Association, 1975, p. 548.


Chemical Kinetics

From Fig. 2·10, a plot of (tty)'" versus t according to Eq. 2·45. we find a From Eq. 2·48, k(base e) or k(base 10)
~ ~

0.182 and b












0.31. From Eq. 2·49, 234mglliter

1 1 Lo ~ ka' ~ 0.71(0.182)'

Since k is much greater than 0.16 to O.IS/day, the seed is

The second widespread use of empirical kinetic expressions in the wastewater and water pollution control fields is in the kinetics of growth of mixed microbial cultures on single or multiple substrates. Typical examples are the growth of activated sludge solids on wastewater BOD





0.29-0.182 = b


b ~D.D216


!:. 0.24


0.20 0.18 ~0.182 =a

0.16 L.._-'-_ _"-_-'-_ _'-_-'-_ _'-_-'---'




Fig. 2-10. Plot of {t/y)1/3 versus t to determine k and Lo for Example 2·4.

Empirical Rate Laws


and the growth of algae on nutrients such as nitrate and phosphate. The . French microbiologist Monod" derived a relationship between the growth rate of a pure culture of bacteria and the concentration of the substrate that limited the growth of the bacteria (the so·called growth limiting substrate).
M = M m " [S] K, + [S]



M = growth rate = (lIX)(dXldt) Mmax = maximum growth rate X = microbial mass or number concentration K, = substrate concentration when M = Mm.,J2

The relationship, expressed in Eq. 2-50, bears a striking resemblance to the Michaelis-Menten expression developed previously for enzyme substrate interaction. Indeed, some workers believe that the analogy is not coincidental, stating,that microorganisms are 'bags full of enzymes' so that it is not surprising that their growth rate is related to the behavior of the catalysts that mediate the many reactions that contribute to growth. The growth-rate-substrate relationship is expressed empirically in applications such as biological wastewater treatment. In these processes we grow a mixed and variable population of microorganisms (e.g .. activated sludge) on a mixed and variable substrate (e.g .. domestic sewage). We have the same problem that arose in attempting to assess the kinetics of the BOD reaction. We do not have a definitive measure of growth-limiting substrate concentration, Neither do we have a welldefined measurement of microorganism concentration. Without going into the rationale for their selection, the parameter used for microorganisms is usually the mass of suspended solids or the mass of volatile suspended solids in the activated sludge suspension, For growth-limiting substrate we usually use BOD or COD concentration, These parameters are readily measured, but they are collective parameters that indicate rather than specify exactly what we should be measuring. As a consequence the empirical nature of the microbial growth expression is comp6unded. In spite of this, however, the expression has useful appltcation in the design and prediction of performance of biological waste treatment plants. For example, the data in Fig, 2-11 show the relationship between the growth rate and substrate concentration, expressed as soluble COD, for an activated sludge unit operated on a protein/beef extract substrate, The growth rate is a first-order function of the degradable organic matter concentration, We can see that for the range of conditions studied, there

J. Monod, "La Technique de Culture Continue, Theorie et Applications:' Ann. Inst. Pasteur, 79: 390-410 (1950),


Chemical Kinetics


M= k, (s,



" e
~ ~


k, -= 0.22 liter, mg day

" " !J

~ e • , "




Nondegradable COD

14 mg/liter


• • •
0 0 5 10 15


Soluble effluent COD,S"

Fig. 2·11. First·order relationship between the activated

sludge growth rate and the degradable effluent soluble COD concentration. From D. W. Eckhoff and D. Jenkins, "Activated Sludge Systems, Kinetics of the Steady and Transient States," SERL ,Rept. 67-12, University of California, Berkeley.

was a linear relationship between M and [S] indicating that we are in the region where K, » [S] and M = k'[S]. Such an observation is indeed commonplace for activated sludge systems treating wastewaters at the practically employed rates of treatment. The curve in Fig. 2-11 would allow us to state that if we wished to produce an effluent with a soluble COD of less than 20 mglliter from the activated sludge treatment of this waste, we should design the treatment plant to accommodate an activated sludge growth rate of less than about 1.2/day,





1. The rate constant of a first-order reaction is 2.5 x 1O-6/sec, and the initial concentration is 0.1 M. What is the initial rate in moleslliter sec, moles/cc sec, and in moles/cc min?
2. A first·order reaction is 40 percent complete at the end of 50 minutes. What is the value of the rate constant in sec-1? In how many minutes will the reaction be 80 percent complete?
If the initial rate of a second·order reaction at 20°C is 5


10-7 moleslliter sec, and the initial concentrations of the two reacting substances are each 0.2 M, what is the k in liters/mole sec? If the activation energy is 20 kcallmole, what is k at 30'C?

4. -A reaction
2A --> 3P

is first order with respect to A. If the half-life of A (time for 50 percent to react) is t1 seconds, and the reaction is irreversible, (a) Write an expression for the reaction rate constant in terms of t l' (b) Using the expression for the reaction rate constant determined in part (a), develop an expression for the time required for 90 percent of A to react. 5. Evaluate the following data to determine whether the reaction A ---? products is first or second order. Calculate the rate constant and be certain to give its units.
A (mMiliter)

Time (sec)

1.00 0.50 0.25 0.10 0.05
S. The forward rate law for the reaction W + OR- "" H20 is given as

11 20


d[W] ~ d[OR-] ~ -k[W][OR-] dt dt
The rate constant, k, at 20°C was found to he 1.3 x 1011 liters/mole sec. Assuming NaOH is rapidly added and mixed with Hel in aqueous solution such that the initial concentrations of H+ and OH- are 10- 4 M, how much time is required for one half of the acid and hase to react? (Assume for this calculation that the reaction is irreversible.)

S6 7.

Chemical Kinetics The temperature dependence of the reaction rate is frequently expressed quantitatively using parameters other than Ea. For example, the following expression for the reaction rate constant for the BOD test is often used:
kT2 =k 20(OY Tz-293)

where T2 is the temperature in OK and temperature. (a) Show that
8 ~ eXPRT,T,


is the rate constant at that


and thus that () is a function of T1 and T2' (b) Determine E, if 8 ~ 1.047 and T, ~ 293°K. (c) If T2 = 283°K and () remains the same, what is the value of Ea?

B. In the field of biology the term Q" where
Q _
10 k(T+10)


is frequently used. Although Q10 does vary with Ea and temperature. if Ea is approximately a constant for certain types of reactions. Q10 values can be used to good advantage. If the temperature is 25°C. what is Ea if Q10 = 1.8? 9. A recent study has shown that monochloramine. NH 2 Cl. "decay" in wastewater is very slow, especially in comparison with free chlorine, HOCI and OCI-. The exposure of NH 2CI to light was found to increase the rate of decay significantly. When light was completely excluded from the sample, 20 percent decay took place in 8 hours and the data conformed to the first-order rate law. (a) Assuming (1) a treatment plant is discharging effluent containing 2 mgt liter NH,Cl. as Cl,; (2) a 1:10 dilution (one part effluent plus nine parts receiving water) is achieved with complete mixing; (3) the receiving water is not exposed to light; and (4) a level greater than 0.002 mg/liter N1i,CI, as Cl v is deleterious to trout, how long after discharge will it take for the receiving water to become "acceptable" for trout? (b) Assuming that each l2-hour period of no light is followed by a l2-hour period of light during which the applicable first-order reaction rate constant is 0.3/hr, how long will it take for the receiving water to become acceptable for trout?

10. The effluent from a secondary clarifier has a pH of 8.3, an ammonia (NH3 ) concentration of 34 mgniter, and is dosed with 10-3 M HOCI. The reaction is reversible but assume conditions are such that only the forward reaction must be considered.
It has a rate law,

NH,Cl + H,O


~ -k[NH,][HOCI]

Additional Reading
where k = 5.5 X 106 liters/mole sec at 15°C. (a) Calculate the time for 90 percent of the HOCI to react. (b) If k ~ I x 10' liters/mole sec at 40°C, what is the activation energy?



BOD data have been determined as follows:

/ (days) I 2 3 4 5 7 10 12

Y (mglliter)

0.705 1.060 1.540 1.700 1.880 2.310 2.570 2.805

Find Lo and k (both base e and base 10) assuming a first·order reaction.



Campbell, J.A .. Why Do Chemical Reactions Occur? Prentice-Hall, Englewood Cliffs, N.J.. 1985.
Frost, A. A" and R. G. Pearson,.Kinetics and Mechanisms. John Wiley. New York, 1961.
Hammes, G. G., Princ;ipJes of Chemical Kinetics. Academic Press, New York. 1978.

King, E. L.. How Chemical Reactions Occur. W. A. Benjamin, Menlo Park, Calif .. 1964. Laidler, K. J.. Chemical Kine/ics. McGraw-Hill, New York, 1965.
Skinner, G. B., Introduction to Chemical Kinetics. Academic Press, New York, 1974.

3.1. INTRODUCTION In this chapter we will describe methods that will allow us to anSwer the questions "Will this reaction go?" and, if so, "How far can it proceed?" These are extremely important questions to pose prior to setting about the investigation of any chemical or biochemical system. If a reaction is impossible, there is absolutely no sense whatsoever in attempting to determine its rate, its mechanisnl, or its use in a water or waste treatment process. If, for example, you were to be approached by a salesman trying to sell you a chemical that would prevent carbon dioxide and nitrogen from combining with chloride to form dangerous hydrogen cyanide and hypochlorous acid during treatment of a particular wastewater, you could. by using techniques similar to those developed in this chapter, tell him that the reaction was not possible with or without the chemical and send him on his way. And you couid do this conclusively without conducting a single experiment! The techniques we will develop are based on the branch of science known as thermodynamics. The theoretical aspects of thermodynamics are extremely precise and orderly; its mathematical basis is complex. We, however, are only interested in what thermodynamics can do for us as a tool in solving problems of chemical equilibrium. We are in a situation similar to the automobile driver using a road map. Not many drivers thoroughly understand the principles of geometry and plane trigonometry that were used to draw the map. However, most know how to read a map and in doing so could manage reasonably well to get from Urbana to Berkeley.



Let us examine the hypothetical. elementary, reversible reaction taking place at constant temperature, aA + bB ;;=! cC + dD

The reactants A and B combine to form the products C and D. In this reaction, a moles of A combine with b moles of B to form c moles of C and d moles of D. If we were to introduce A and B into a suitable reaction

The Dynamic Nature of Chemical Equilibrium ra) 59 rb) c a A . C. 3. (a) Initially only A and Bare pr:esent. C.I(b).' From this discussion we learn that the equilibrium state can be approached from both directions. we have seen previously in Chapter 2 1 Strictly speaking. Course of reaction between A. After a while A. The ratio is the so·called equilibrium constant. we would obs~rve a concentration·time change such as that depicted in Fig.g c 8 " ~ c B . not a static situation. time·invariant levels. the equilibrium constant is defined in terms of activity. The forward and reverse reactions proceed at such a rate that the ratio of concentrations of products to reactants (as described by the equilibrium constant. The concentrations of A and B decrease until they reach values that do not change with time. 3.can be used. and D concentrations all reach constant. vessel and at time intervals analyze the contents of the reaction vessel.2). v. B. When we investigate the rate at which the equilibrium condition is approached.~ 8 Time Time 8 Fig. [C]'[D]d [A]'[B]b = K (3. Another way of stating this is that a chemical reaction is at equilibrium if its forward rate of reaction. while the concentrations of C and D increase from zero to time-invariant values. If we were to add only the products of the reaction. or active concentrations. Eq. v (.. we say that the reaction is at equilibrium cmd we call the concentrations of species present at thai time equilibrium concentrations. [C]'[D]d/[A]'[B]b is the same as that attained in the previous experiment when A and B were initially present. we can deduce that the equilibrium condition is a dynamic one. such as the molar concentration. and D. is equal to the rate of the reverse reaction.2) The unit of concentration as indicated by [ ] is molelliter. as discussed later in this chapter. C and D. B. Concentration. but other concentration units also . For example. remains constant. to the reaction vessel under the same experimental conditions. The interaction of reactants and products does not cease when equilibrium is reached. K. 3·I(a). 3·1. we would obtain a concentration versus time profile such as in Fig. often can be used as a good approximation of activity for species in dilute aqueous solutions. If the ratio of the concentration of products to reactants. (b) initially only C and D are present. .

However. = k2 = = k 2 [C)'[D]d (3-6) K (3-7) The equilibrium constant is thus the ratio of the rate constants of the forward and the reverse reactions--<I fact that underscores the dynamic nature of equilibrium! 3.. . The reaction will proceed until the opposing reaction rates are equal.g. e. k. Elving. they will combine. if only A and B are present.60 Chemical Equilibrium that if the reaction in Eq. in Treatise on Analytical Chemistry. the forward rate of reaction. For example. Interscience. By knowing the position of chemical equilibria. The first is to do an experiment and the second is to calculate the answer using previously determined equilibrium data. Vol. Kolthoff. T. the second approach is far superior if time is of the essence. To explore the various techniques that can be used to answer the 2 If the chemical reaction is not elementary. and Vf=V r (3-5) Therefore. can be expressed by the rate law. M. Although the first way may be more enjoyable to those who like puttering around in the laboratory. I.[A]'[B]b (3-3) and the reverse rate by v" v. we can determine whether it is possible for certain reactions between reactants at given concentrations to proceed. v r. There are two general ways to answer questions like these. we can provide answers to questions such as: Will calcium carbonate tend to precipitate or dissolve in this water? Can I possibly oxidize sulfide with nitrate? and so on. 3-1 is elementary. and P.. Part I.. J. as soon as the reaction of A and B produces C and D. vr = k. See. and by the reverse reaction produce A and B. eds . THE THERMODYNAMIC BASIS OF CHEMICAL EQUILIBRIUM A knowledge of the position of chemical equilibria is of the utmost importance to us in water chemistry. the forward rate of reaction will proceed at a finite rate while there will be no reverse reaction because no C and D are present. derivation of K from rate constants is still possible but is more complex. S. New York.[A]'[B]b and [C]'[D]d [A]' [B]b k. Lee. 1959. = k 2 [C)'[D]d (3-4) Initially.3. Wiley. I.

Our treatment. in additien to. G =H -TS (3-8) where G = Gibbs free energy. The entropy is a sort ef internal manifestatien ef energy that can be visualized in several ways. fer example. The tetal free energy. G T. C and D that are present and G A. we weuld find semething like that depicted by the selid line at the left side ef the diagram in Fig. 3-1. Fer example.g" wellfermed crystals) have lew entropy while randemly arranged systems (e. perferm "useful werk. censider the reversible reactien previeusly examined in Eq. Energy. werking with clesed systems. The free energy is that part ef the tetal energy that is available to. entropy is eften defined as describing the degree ef erder er organization in ci system. the criterien fer equilibrium is that the tetal free energy ef the system (G T ) is a minimum. a gas) have high entropy.The Thermodynamic Basis of Chemical Equilibrium 61 question "Will this reactien ge?" we must delve a little into. kcal The enthalpy is the tetal energy centent ef an element or cempeund. we will present enly that which is useful and immediately applicable for our purpose. a reactien vessel and calculate the tetal free energy ef the system as a functien ef extent ef reactien as the reactien proceeded. Fer thermedynamic purpeses a clesed system is ene to. Fer clesed systems at censtant pressure and censtant temperature. 3-2. G s. For a more comprehensive coverage of the topic. and G 0 represent the free energy/ mele ef each substance. then G T =nAG A+ nsG s + neGe +nDG D . add A and B to. we usually are interested in systems at censtant temperature and pressure. hewever. The product TS is that part ef the tetal energy which is net available fer useful work.g. the student is referred to. B.. Highly structured materials (e. the thermedynamic basis ef equilibrium. OK S = entropy. Since. may flew across its beundaries. G e. Fer example. if n A. we can make extensive use ef the thermedynamic expressien fer free energy. n s. aA + bB <2 cC + dD If we were to." that is. kcalloK . ef thermedynamics will be brief. ether'than pressure-velume werk. H = enthalpy. ether texts (see Sectien 3-7). which matter cannet be added er remeved. is the sum ef the free energies ef each ef the reactien cempenents. Mest ef the reactiens with which we are cencerned in water chemistry take place in a clesed system er can be analyzed as theugh they take place in a clesed system. kcal T = abselute temperature. n e and no represent the number ef meles ef A.

Variation of Gibbs free energy for the chemical reaction aA + bB. 3-1) and G I is the free energy per mole. 1. 3-2. Also. Conversely. 2. at a certain extent of reaction. as long as the value of G T decreases./ .G is positive and thus G T would increase if the reaction were to proceed).G where tl. Thus we may state that the equilibrium condition of a reaction is the point at which G T is a minimum. In each case the reaction only proceeds spontaneously.G is > 0 (Le.. This point can be spontaneously reached from either the product or reactant side. calculation of the total free energy of the system as the reaction proceeded to form A and B would produce a curve of the form shown by the dashed line on the right-hand side of Fig. We can therefore state that if... . b./ C and D present --// ~~ Minimum G T• " reaction at equitibrim Extent of reaction Fig.g . the reaction cannot proceed spontaneously as written. it may proceed spontaneously in the opposite direction to which it is written." o ~ ~ Only reactants A and B present . and it is the equilibrium point of the system. the change in G T is proportional to tl. Because of this there exists.G is negative and thus G T decreases as the reaction proceeds). or without any external help. 3-2.62 Chemical Equilibrium ~'-' . a point where G T is at a minimum. and d in Eq. tl. c."" (3-9) where is the stoichiometric coefficient (e. tl.G = (~ VIG) "od"" ..= cC + dD. tl. VI tl.k" Only products ~ . if we were initially to add only C and D to the reaction vessel.'. the reaction may proceed spontaneously as written. Only reactants are present at the far left side of the diagram and only products at the far right side. It can be shown that as any reaction proceeds an incremental amount. a./ .G is < 0 (Le . we may deduce that reaction in the direction that decreases G T is spontaneous while reaction in the direction that increases G T is not spontaneous or will not occur in a closed system.. Conversely.( ~ VIG) ".

by convention. we can measure changes in free energy..G for the general reaction given by Eq.78kcallmole The minus sign indicates that free energy is released or given off. we can determine that the formation of calcite (CaCO". the free energy per mole of each reactant and product at the standard state condition of 25'C and I atm total pressure. . 3-1.du.. The first step in determining t. and oxygen has the following free energy. we use the relationship t. calcium.. t.e.' = free energy/mole of Equation 3-10 is developed.)} from carbon. Table 3·1 presents a summary of t. the reaction is at equilibrium and will not proceed spontaneously in either direction.. all are assigned free energy values of zero kcallmole. This free energy change is called the standard free energy of formation. H+ at a concentration of I molel liter in an ideal solution and at standard state conditions has been assigned a free energy of zero. to establish a baseline for ionic substances in solution. . {D}d n {A}' {B}b (3-1O) t. calcite t.G for a reaction provide us with a powerful tool to predict whether or not reactions are possible. AG = 0 (i.t. To calculate t.'.G.!n more detail later. This convention is necessary because it is impossible to measure absolute values of free energy.The Thermodynamic Basis of Chemical Equilibrium 63 3.' values for some substances commonly encountered in water chemistry. At standard state every element is assigned. The term G. Values of t.78 kcal of free energy per mole.G.G' + RT I {C}.'.G. We can also deduce that to break down I mole of calcite into I mole of Ca metal. 02(9)' CgraPhlte{S)' and so forth.G' { } = = (~ v/G. and I t moles of oxygen would require the input of +269. or active concentration (discussed later in this section) species i at 25'C and I atmosphere pressure G.' = -269.. assigning a value of zero to elements at standard state allows us to measure the free energy change involved in forming compounds at standard state from their component elements at standard state. However. for example. d free energy of zero per mole.( ~ v. I mole of graphite.o) .G/1 """". (3-11) activity.G is to determine G. Thus H2(g}. Thus. C(graphite) + ~02(9) + CatS) --7 CaC0 3 (S). G T is at a minimum).G where = t. Also.' is called the standard free energy per mole of species i.

372 -11.976 -6.63 -116.78 -144.889 -167." Species Ccifa~) tl. Christ.45 -151.74 -49.o kcallmole CaC03 {s)' calcite CaOes) C{s).TABLE 3-1 Thermodynamic Constants for Species of Importance in Water Chemistry.52 -166. -132. 1965.43 -3.34 3. Minerals.0 -54.18 -161.o kcallmole -129.41 3. a For a hypothetical ideal state of unit molality.9 0 -54.00 -26.3 -124.90 -4.31 -126. M.22 -4.93 0 -37.(aQ) ReOia'll CO&~q) CH 3COO-.00 -49.595 -54.1 -108. Ohio.0 -165.957 -57. 64 .0 0 0 -20.7979 -68. Chemical Rubber Publishing Company.3174 -216. Solutions. which is approximately equal to that of unit mclarity.4 -197.41 -221.00 -140.4 I:lG.26 -92. acetate Hctaq) H 2{g) FeliQ) Ferat) Fe(OH)3(. Cleve· land.H.84 0 0 -21.' Mnfa-l~1l Mn02(s) M9fi~1l Mg(OH)"" NOiaq) NH3 (g) NH 3 (aq) NHtaq) HNOS{aq) 02(aq) 02(9) OH("aq) H2O(9) H 20 W SO~Caq) HS~q) H2 S(g) H 2 S(aq) Source.01 -7.30 -2.4 0 -94. Garrels and C.22 -89.99 -199. Condensed from the listing of R.0 -11.9 0 -94.690 -177. L.27 -26.4 -111. and Equilibria.54 graphite CO 2 (g) CO 2 (a'lJ CH 4(9) H2CO. and Handbook of Chemistry and Physics.140 -149. Harper & Row.372 -3.0 -53.892 -6.69 -17. New York.6357 -56.18 -269.2 -110.31 -12.815 -9.32 -31.04 -19.77 -288.37 -19.05 -98.

First.31 ~G' = -2..let us use this information to determine the free energy change associated with the reaction in which calcite dissolves in acid. + RT In {i} where (3-lS) G.) and H+ reacting to form their component elements.The Thermodynamic Basis of Chemical Equilibrium 65 Now. these elements then recombine to form Ca2+ and HC03 -. to form the calcium and bicarbonate ions.) + H+ --> --> ---7 --> Ca + C + ~O"g) H+ Ca2+ HC03 - +269. if we react 1 mole of H+ with 1 mole of calcite to produce 1 mole of Ca2+ and 1 mole of HC03 .71 This computation allows us to see two things. from the free energies of formation of reactants and products by using Eq. Thus (3·13) where VI is the stoichiometric coefficient of species i. {i} = = the free energy per mole of substance i in a state other than standard measured relative to our established datum the active concentration. we can see it is possible to determine the overall standard free energy change for the reaction as 2S'C. (3-12) Even though it does not occur physically.) in acid. free energy is released because ~G' is negative.18 -140. 3-12 (3-14) Equation 3-13 has limited usefulness because it only refers to the situation when all reactants and products are at standard state.78 o -132. Or for Eq. H+. ~G'. with respect to the dissolving of CaCO". or activity. Second. and more generally. Thus CaCO"" H+ Ca H+ + C + to"g) CaCO". 3-ll with ~Gt. we can visualize this reaction as taking place by CaCO". We can relate the free energy of a single substance at a state other than standard to its free energy of formation at standard state by the expression G. of species i .1 being used in place of G I'. = tlG t. We are almost always interested in systems whose components are at other than standard state.

co"" .} 3 (5) Since. {i} = S. {i} is related to the molar concentration. e.HCOl ..Caco + RT In {HCO.ca2-t.caco3ts ) we can state - - e. [ij. For pure solids or liquids in equilibrium with a solution.ilG£. by {i} = 'Y1[ij where 'Y. is the mole fraction.66 Chemical Equilibrium The value of the activity of a substance is dependent on the choice of standard state conditions-the conditions that result in unit activity-just as the value of e. {i} = 'Y.-} + e. Returning to our example of the dissolution of CaCO"" in acid. As the total pressure decreases.c.Gt." is dependent on the choice of standard state. from Eq.} Collecting terms.RT In {H+} ..Go + RT In {HCO. 'YI approaches I.. the following interpretation of activity is used throughout this book: I.} (3-16) This is a specific form of Eq.RT In {CaCO". approaches I and {i} approaches [i]. I. 3-13.G(.+ AGr.X. U} = 2. 3-9 and 3-IS.. = activity coefficient.G = e. 3.. Consistent with the choice of standard state conditions used to develop Table 3·1 and in most publications on aqueous chemistry.ilGf.H+ .ca2-t.G"HCOJ. 3-10 applied to the acid dissolution of . X I where X I is the mole fraction.P I where P I is the partial pressure of the gas in atmospheres. we can write .Gf.+ RT In {HCO.. For the solvent in a solution.RT In {W} .H+ .+ 6.-}{Ca2+} {W}{CaCO".G. For gases in equilibrium with a solution.-} + RT In {Ca2 +} .. For mixtures of liquids. 312. 4. llGo = AGf. 'Y. we obtain ilG = 6.G = e. 'YI approaches I.RT In {CaCO". and combining Eqs.6.e. As the solution becomes more dilute. The activity generally is assumed to be I for the dilute solutions of concern to us. {i} = 'Y.G1." + RT In {Ca2+} .G(.Gf. whereX.G('HCO. the activity of a gas can be approximated closely by its partial pressure.e. For ions and molecules in solution.c. Eq. As the solution becomes dilute (most cases of interest to us).H+ .6. When reactions take place at atmospheric pressure.

3·22 into Eq. Q. IlG = IlG' + RT In Q (3·20) When the value of Q is identical to that of the equilibrium constant K. since the activity of pure solid is unity and assuming that the activity coefficients of the ionic component are equal to I. the system is at equilibrium and IlG = 0. 3. we call this term the reaction quotient. Eq.) reaction. we can state. where Q = {HC03-HCa2+} {W} {CaCO". 3·12. we obtain Q IlG = -RTlnK +RTlnQ =RTln K (3·23) Equation 3·23 allows us to develop another set of criteria to determine whether reactions are possible or not because the ratio of QIK will determine the sign of IlG for a reaction. .17) In examining Eqs. because the magnitude of the logarithmic term is not equal to the equilibrium constant except at equilibrium. we can then write 0= IlG' +RTlnK or (3·21) (3·22) IlG'= -RTInK Substituting Eq. that is. 3·10 and 3·19 (or Eqs. {C}'{D}d Q = {A}a {B}b (3. for the reaction aA + bB ~ cC + dD . HoWever. 3·10.19) or in dilute solution. [CJ' [D]d Q = [A]a[B]b Combining Eqs. we obtain IlG = IlG' + RT In [HC03 -][Ca2+] [H"] (3. 3·16 and 3·17.20.The Thermodynamic Basis of Chemical Equilibrium 67 CaCO".)} or in dilute solution (3·18) Q = [HC03-][Ca'+] . 3·16 and 3·18). we can see that the logarithmic term has a form that is reminiscent of the equilibrium constant for the reaction as written in Eq. and the general form of the equation. For dilute solutions. [H"] More generally.

G' = = (1)(0) + (1)(-37.98 x 10-3 x 298 xlog [(10-')(5 xlO-')] = +1.03 Because AG > 0. From Table 3·1 -56.09 kcal __ ----"19:c.09 + 2. the reaction is not spontaneous as written and can proceed spontaneously only in the opposite direction.G = = = [W][OH-] This equilibrium constant is usually given the special designation Kw' tl. 3·13.G 25°C. Example 3-1 1. .987 x 10-3 x 298 K = -RT In K = In K = .09 = +19.G is positive and the reaction is impossible as written. If QIK < I. Determine the equilibrium constant for the reaction in which liquid H20 dissociates to H+ and OH.60 From Eq.G tl. If QIK = I. 2.. Is this reaction proceeding as written when [W] 10-' M? = 10-' M and [OW] = 5 x Solution 1. H+ and OH.96 X 10-15 I x 10-") Based on the selection of standaz:d state conditions given previously in this section and neglecting ionic strength effects.68 Chemical Equilibrium I. 3·20. then tl. then tl.. tl. K can be written as follows for dilute solutions. K 2.60) . From Eq.. then tl.0~9:.G = 0 and the system is at equilibrium..69) 19. The use of the tables of free energy values and the determination of whether a reaction is at equilibrium is illustrated in the following examples.(1)(-56. H2 0"" W + OW 2.3 x 1. that is.24 ('" = 9.G' tl. 3. If QIK > I. tl.32..69 o -37.G' + RT In [W][OH-] 19.are combining to form H2 0 molecules._ _ 1.G is negative and the reaction is spontaneous as written.

364 log K ~7. We now have sufficient information to provide answers to the question posed earlier in the chapter about sulfide stability in the presence of nitrate.2 x 10' ~ 10'" K [H+]'[Fe(OH)".ol'(Po..) H'[Fe 2+]' It is important to note that we may only use gaseous oxygen as a reactant in this equation if it is in true equilibrium with the solution. Give the form of the equilibrium constant making the assumption that activity coefficients have a value of l.7 -166.)H'[Fe'+]' [H+]' (Po. correspondingly. that is. if the equilibrium O2(9) .(0) -5( --{j6.3 o -56.7) -7. Example 3-~ Find the' equilibrium constant for the reaction at 25°C.O (!teal/mole) H. Atmospheric oxygen is in equilibrium with the dissolved oxygen.::: O.0 o ~ ~ 4 X 0 + 2( -166.3) .2( -20. Therefore. ..The Thermodynamic Basis of Chemical Equilibrium .G must be positive.0) . Fe(OH)"" W aGO aGo RT InK K ~ ~ Fe2+ O 2(9) -20.0'(0) + 5H.9 6. 2Fe'+ + . aG.We can solve this problem alternatively using aG 69 ~RTlnQ.O "" 2Fe(OH)"" + 4W in which ferrous iron is oxidized by molecular oxygen to ferric hydroxide in aqueous solution.6..9 ~ -RT InK 2.]' (XH.o.. the reaction as/written is not possible. O~erwise we should use the value of IlGt for 02{aQ)' 02(aQ) as a reactant and. Solution From Table 3-1..3RTlogK ~ 1. K ~ ~ Q K [W][OH-] 10-" ~ (10-')(5 X 10-') ~5 X 10-" Since QIK > I..(aq) is satisfied. .

)[HS ][W) and since [NH:) 10. In the slrict chemical sense this overall reaction is a composite of ll. H2 0(l) HSNO. From Table 3-1.01 -56.34 -19 +3.+ NH: nitrate bisulfide sulfate ammonium We must find out whether the reaction is spontaneous as written.-. if in Iwo reactions the product of one reaction serves as a reaclant in the other.'and + 11.41 o -177. [HS-) 10' 10-'. in acid.'-) ~ ll.G ~ll. is that they are additive. and [H+) ~ Q (10-')(10-') (10 ')(10 ')(10 ') Therefore.01 -26. The reaction is H+ + NO.) '" Ca'+ + CO. An important property of standard free energy changes.'.41 ~ -116. [NO.Go+RTlnQ _ Q .8 .35 Because 6. For example.[NO.25 [NH.Go. 3-13. the reaction will proceed spontaneously as written at the reactant concentrations indicated.Go values of the two reactions.+][SO.-) ~ 10-'.69) SO/NH4+ From Eq.. ~ 10-'.Go (kca!) CaCO".38 -14.34)-(-26.69 +3.) + H+ '" Ca H + HCO.H+ -56. ll.9 ~ -105.3 log 10' -116. In our previous example of the dissolution of CaCO. Assume that ionic strength effects are negligible (these effects will be discussed later in this chapter).987 x 10-' x 298 x 2. [80.O "'SO.+ H.4 M of reacting species and pH 8 ([H+] = 10.GO~(-19-177.09 .70 Chemical Equilibrium Example 3-3 Is it possible at 25°C to oxidize sulfide in natural waters with nitrate? Typical concentrations that exist are 10.+ HS. ll. the lJ.25 + 10.G ~ ~ -116.G is negative.8 M). lJ.Go value for the combined reactions is the sum of the ll.'-) 10-'. we wrote the equation CaCO".25 + 1.

Note further that it is the value of tlG.H.' we circumvent this problem by assigning Ht a value of zero to all elements in their most stable form at 25'C and I atm pressure. which controls the direction of a reaction.14..'. if tlH is positive.4. We can determine values of enthalpy of specie~based on these assignments and call these the enthalpy of formation.24) Similarly to tlG'. For a reversible reaction in a closed system it is relateq to tlG' by (3. each in their standard states.71 kca!. tlH' for a reaction can be calculated from tlH' where Vi = ( t vHt) p"du". we can compute the tlHf' values of various compounds from the assigned H' values of their component elements. tlH' is equal to the amount of heat taken up or released when a moles of A and b moles of E. Just as we could not determine the absolute value of G.=: cC + dD. If tlH is negative. The term tlH' is of most interest to us. aA + bE . in ideal solution (y = J) also is assigned an 11' value of zero. 3.38 .( t v. tlH. we also cannot measure H. it is not necessary that each of the individual reactions have a negative (positive) value of tlG. . H+. are completely converted to c moles of C and d moles of D.' the stoichiometric coefficient the enthalpy of species i in kcallmole at standard conditions of 25'C and I atm pressure For the general reaction. Similarly to the computations for tlG. each in their standard states.09 = -2.') """'" (3·25) = = H. heat is evolved and the reaction is called exothermic.'. not tlG'. In aqueous solution I molelliter of the hydrogen ion. a function of tlG' and Q.'. . ENTHALPY AND THE TEMPERATURE DEPENDENCE OF THE EQUILIBRIUM CONSTANT The enthalpy change of a chemical reaction (tlH) is the amount of heat that is released or taken up during the course of the reaction. A selection of these tlHt values is given in Table 3·1. As with G.Enthalpy and the Temperature Dependence of the Equilibrium Constant 71 with a: standard free energy change of tlG' = 11. If tlG for the composite reaction is negative (positive). Whether the composite reaction is spontane'ous depends upon the value of tlG for that reaction.' values. heat is taken up and the reaction is called endothermic.

which states that --=-- dinK dT ilW RT' (3-26) If we assume that. and H+ are such that the system is at equilibrium. oversaturated or undersaturated) with respect to CaC03 (S} (1) as it enters the residence and (2) as it leaves the water heater? Solution Let us tackle this problem using the equation as the basis for our solution.!. Application of the Van't Hoff relationship is illustrated in the following example.e. over a limited temperature range. (3-27) ilHo In K = . We are told that at 25°C the concentrations of Ca2+.!. . for reactions are most commonly used in water chemistry to determine the effect of temperature on the position of equilibrium. which was calculated in Section 3·3.71 kcal. or = ilW R (.72 Chemical Equilibrium Standard enthalpy change values. _T. First we will calculate the value of the equilibrium constant using the tl. K.Ho is not a function of temperature. 6.) T.o value for this reaction of -2. integration of Eq_ 3-26 yields In K. HCO:}-. . ilHo.o values from Table 3·l. Example 3-4 A municipal water supply enters a residence at 15°C and is heated to SO°C in the home water heater.RT + constant (3-28) or K = C' exp -t!.G. A useful expression in this regard is due to Van't Hoff. If the water is just saturated with respect to CaC03 (S} at 25°C.HO) ( liT" (3-29) where C' is a constant. what will be the condition of the water (i.. and then determine the value of the equilibrium constant at 15°C and at SO°C using llH.

IS5.99 K1 = 10+ 1.5 n .5 kcal Let K.71 10gK.) 333 K3 At 15°C the equilibrium constant is greater. llW = -129. the water at 15°C contains less Ca2 + and HC03.18 -RTlnK. '(T').77 . The water had a value of Q that met equilibrium conditions at 25°C and the value of this quantity will not change as temperature decreases. llW = -S. .45 . if we may assume that [H+1 remains constant.77 -IS5. 3·27.than allowed by equilibrium.99 Let K at 25°C = K" then Calculate llW from Eq. than that at 25°C. from Eq. _T1 1.(-288. and at 6Cf'C it is less.- /lHO(1 I) R T3 T. By similar reasoning. that is. = 1. = K at 15°C (288°K). it is undersaturated.18 . 3 --- _In K + In 10+""" 3 _ -S. Thus the term Q = [Ca2+][HC03-] [H+] is greater than K at SO°C and less than K at 15°C. Therefore. and K3 = InK -InK 1 2 = llW R (l.Enthalpy and the Temperature Dependence of the Equilibrium Constant 6.1.45 o -129. From Eq.5 . (T3).. at 60°C the water is oversaturated with respect to CaC03(S) and CaC03!s) will be deposited within the heater. InK 1 -1nK 3 = ...98 x 10 I (_1___1_) 288 298 Similarly.) T2 3 -I K 10+.98 x 10 = 10+1.48 (_1__ 298 J.+ n .0) K at SO°C (333°K).1. = -2. 3·25..H(o kcallmole 73 CaC03 (s) W Cafa~ll HC03~q) -288. Note that these conclusions have some bearing on the life of home water heaters. 3-27.99 _ -S.

One could have sensed that K would decrease as the temperature increases from the value of t.96 .:=: H2S0 4 ({) HZ(g) + !02(g) . 4. thus decreasing the equilibrium constant.74 Chemical Equilibrium We see from the example that the equilibrium constant for CaCO".=: Ca'+ + HC03 . electrostatic interactions betw.Ho for HZS0 4{{l given the following reactions: lIW (keal) 1. 2.Ho.5.31.) + H* . NONIDEAL BEHAVIOR OF IONS AND MOLECULES IN SOLUTION In very dilute aqueous solutions." ~ -193./~-'~ ~~~_'?t. SIS) + 02(g) ~ 80 2 (9) 802(g) + !02. we lIH. Since heat is produc~d as the reaction goes to the right.5 .32 Solution Adding reactions (I) through (4) and the lIW values. The t.5 times larger than at 25°C.68.HO values for a series of consecutive reactions can be added.. in the equation.concentration.::::': H 20 C {) -70.een the ions also increase and the ~~'--~?'"'~~-.4 .Jz~~9t. Thus.96 15°C is approximately 1.~ {i} = -~ rdi] (3-30) . This is an example of the general situation that for exothermic reactions..23. 3. Example 3-5 Find the standard enthalpy of formation.92 keal 3.::::': S03(9) 803(9) + H20({1.Go values. the equilibrium is shifted to the right and the equilibrium constant increases. ions behave independently of one another and it is valid to assume that activity coefficients of ions have values of unity.32 ~ -193. an increase in temperature will shift the equilibrium in the direction of less complete reaction.92 kea!. which is negative..SO. If we take heat away from the reaction by lowering the temperature. 3·25.. at 60°C it is less than t as large as at 25°C.14 -68.5 -31. 6.Ho value for the overall reaction.le~". Os he conce tr tion of io in~­ creases. just as were t. raising the temperature tends to drive the reaction to the left.. to yield an overall t.~~gnJ-~it:E1.' for H. However. Applying Eq. . we obtain ~sl + 202(9) + H2(g) ~ H2 S04«(1 where lIW obtain ~ -70. for endothermic reactions. an increase in temperature will shift the equilib· rium in the direction of more complete reaction.@g~~clo>:~1 .

.43 X 10-3 X 2'J + [10-' X I'J + [10-' X 2'J + [1. Chern. Brine a: 5800 mg/Iiter NaCI.. fL. [CO. S. . 24.~jJl~l and chemical equilibrium is affected. and 0.. 2.Nonideal Behavior of Ions and Molecules in Solution 75 the activity coefficient.'-J = 10-' M.02 X 10-3 x I']) Example 3·7 Which of the following brines has the greater ionic strength? 1. 16. For brine a.lOrih6 general reaction. Brine b: 3100 mg/liter MgSO. Randall.-----------~ Application of this equation is shown in the following two examples.099 x I' 3 + 0. 35.099 M 1') =0.. Solution The atomic weights are Na. Am. Mg. Example 3·6 Compute the ionic strength of.Randall' to describe the intensity of the electric field in a solution: fL = ~2: (CIZl) (3-32) where C I = concentration of ionic species. ~~-----To calculate activity coefficients of ions in aqueous solution.099 x G. [Na+J = 1... "I" becom~..=': cC + dD it becomes necessary to write the equilibrium constant and reaction quotient in the form Q orK = {C}'{D}d (ycfCJ)«Yo[D])d {A}'{B}b = (yJA])'(YB[B])b (3-31) ~ . [HCO. 32. Lewis and M. Soc. 43: IllI (1921). CI. i ZI = charge of species i ~~--------------.. a solution containing the following concentration of ions: [CaHJ = 10-' M. a. we must employ the quantity ionic strength.1 '" = teO.099 =0.-J = 10-' M [SO/-J = IO-'M.02 x IO-'M Solution '" = H[lO-' X 2'J + [10-' '" = 1.A + bB :.5. J. [Na+J = 5800mg/Iiter 58.500mg/mole [CI-J = 5800 mg/Iiter 58. 23.. For example'.500 mg/mole 0... N. which was devised by Lewis and ..099M 0.

Figure 3-3 is a presentation of data given by Lind' on the conductance versus ionic strength of various surface and groundwaters. Geological Survey Professional Paper 700 D. . In this expression TDS is the total dissolved solids in mg/liter..I + 0.. 1970. Am. Water Works Assoc ..026 They both have virtually the same ionic strength.. 28: 1500 (1936).. Russell. Rather than work through laborious calculations of ionic strength for more complex solutions than those given in the examples.~~_siliQ§).. Ionic strength appears in each of the various expressions used to calculate activity coefficients in aqueous solutions... Langelier presented the approximation. was ..104 ~O. it is usually precise enough for most purposes in water chemistry to use an approxi~ mation of ionic strength derived from a correlation with specific conducance or T~i§..--. The conductance of a solution is a measure of the ability of a solution to conduct a current. U." Ph. 5 W..-~--.6 X 10. -~. L.--' . Thesis... C. Electrical current is transported through solutions via the movement of ions. --------- --- This is similar to the expression that can be derived from the data in Fig.S.5 x specific conductance (". ----'------------~--. The DeBye-Hiickel theory of interaction of ions in aqueous solution incorporates both the electrostatic interactions between ions and the thermal motion of the ions. D272-D280. 120. Dec.-. If the conductance of a water sample is known.. Berkeley.. 1976.D. 3·3. Langelier. Russell' derived the following correlation between ionic strength and conductance for 13 waters of widely varying composition. pp.000 mg/mole g [SO '-] ~ 3100 mglliter .. '" = 1.. Lind. this figure can be used to provide a crude estimate of ionic strength.-----.. "Chemical Aspects of Groundwater Recharge with Wastewaters. and conductivity increases as ion concentration increases. called the DeBye-Hiickel limiting law..mho/cm) . University of California.... J.026 x 2' 0.---.(0. 5 '" = ~------------~ 2. "The Analytical Control of Anti-Corrosion Water Treatment" J.026 M 0..026 M x 2') ~0. [M H] ~ 3100 mglliter 120..5 x 10-5 X TDS (3·33) for several waters he examined.000 mg/mole !L ~ . F. 6 L. The basic equation.76 Chemical Equilibrium For brine b. It is a property attributable to the ions in solution.

After C. developed for ionic strengths of less than approximately 5 x 10. pmho/cm Fig.' J. pp. Lind.J. the extended DeBye-Huckel approximation of the DeBye-Huckel limiting law.0 Specific conductance. is AZl {L1J2 -log y.1.'/2 ~ (3-35) where . U.3 and can be stated as -log y. 1/2 ~ (3-34) An alternative equation.S. = 1 + Ba . Specific conductance as a means of estimating ionic strength.I. J.Nonideal Behavior of Ions and Molecules in Solution 77 50 • • 10 • • • 'b x ~ £ 0.I.5Z. D272-D280. = 0. 1970. c 0 ~ e 'c S! 1. 3·3. Geological Survey Professional Paper 700D. which is applicable for ionic strength of less than approximately 0.

7 0.10 1 .488 a constant that relates to the solvent: for water at 25°C.3 0. 'iI1~~ HP02Guntelberg Jtl) 4 <pproximat!on / ~ y r/ .509 for water at 15°C.9 0. A = 0. A = 0.: ~coJ N.' 0. 3·35) and the Gun· telberg approximation (Eq.0000 1 111111 1.50 for water at O°C. A = 0. These curves were calculated using Eq.00 1 W '/ F- (t4) - 1 I h II if' ~ § // '/ // GUntelberg approximation r----= - I / 0. 3-4.78 Chemical Equilibrium A = B = aj = a constant that relates to the solvent: for water at 25°C.4 0. 0.~ A~ f j II (t3) Il0..324 X 10' a constant that relates to the diameter of the hydrated ion: for monovalent ions. this is usually about 3 to 4 X 10-' Figure 3·4 shows the variations of activity coefficients as a function of ionic strength for some ions commonly found in water.2 0.5 0.0 1 gOO.Hit. 3·35. 3·36).. for example.6 0. with the exception of H+." Mg2> Ca~7Z Z:GUn~~~rg approximation / L//OH' F' f ffCl-j ~>"COl Fe J< / / I0. B = 0. B = 0. Activity coefficients of aqueous ions based on the extended DeBye-Huckel equation (Eq.326 X 10' for water at O°C.328 X 10' for water at 15°C..1 o Fig. .' l- .0 0. B = 0.000 1 / / I I 0.

Eq.' = {W}{COl-} {HCO.1/2 (3·38) (3-39) 10 _ 0.SZ. However. and 3·36 cannot be verified directly. Solution K = 0. mentally the activity coefficient of a single ion..1/2 -log y. Eq. The equilibrium constant. as. 3·34. 3. 1/2 gy± I +p. of the molar concentrations of carbonate to bicarbonate at 25°C in a solution with an ionic strength of 10---3 • Also find the pH. however. y±.'p.5 IZ~_I p.SZ. for the reaction HCO.326 X 10' x 3 x 10 ')p.[HCO.-[CO l-j YHCO. There is. a mean activity coefficient.35. Therefore. and Z+ = charge of the positive ion Z_ y± = = charge of the negative ion mean of the two activity coefficients Example 3-8 Find the ratio.2.'" H+ + COlis 1O-~10.5. [H+J = 10. Eqs.'/2 (3·36) Equation 3·36 is also called the Giintelberg approximation of the DeBye-Huckel theory and is also commonly used to calculate y for ions of various charge at temperatures other than 15°C. = I + (0.10 moleslliter.5 IZ~_I p. 3·35 beco".1/2 1+ p.'p. and measure experimentally. 3-39 is the Guntelberg approximation..3.1/2 ~ where Eq. it is possible to define. } YH. it is impossible to determine experi. at equilibrium. -Iogy± = 0.1/2 0. 3·4.. 3·38 is the DeBye-Huckellimiting law. There have been other extensions of the theory to make it apply at higher ionic strengths. j . Ka. It is also plotted in Fig.Nonideal Behavior of Ions and Molecules in Solution 79 For mimovalent ions at 15°C. Because anions cannot be added to a solution without an equivalent number of cations (and vice versa). no satisfactory theory that provides a good estimate of the activity coefficient for ionic strengths of greater than about 0. (3·37) The DeBye-Huckel and Guntelberg relationships can be extended to the mean activity coefficient thus:.[H+j Yco.

Eq. Failey. = 0.. in seawater ionic strength is approximately 0.0158 0. M.132 for oxygen in NaGI solution' and. 3-40 predicts that the activity coefficient of oxygen will be logy = 0. F.3) 1/2 'YcOi.24 . Because values of k.= 0. nonionic or molecular solutes have activity coefficients of approximately I for ionic strengths of less than 0.. Chern.96 x 10-") = 10.. Rev" 4: 285 (1927). 0. .132 x 0.'-J (0.7.= O. if k. An empirical equation of the form log y = k.80 Chemical Equilibrium the DeBye--Huckellimiting law.7 = 0.= 0.01 to 0.0924 y = 1.02 The theory for predicting the activity coefficients of nonelectrolytes in aqueous solution is not as well developed as for electrolytes.0066 then y == 1. The salting-out coefficient k.1.02 As the ionic strength increases.132 x 0.58 J If we had not taken activity coefficients into account the ratio would have been [CO/-]/[HC03~] Also pH = -log {Wj = -log(YH' [H+J) = -log(0. for example. ~sing -log Yw = -log YHCO. For example.05 = 0..S x 22 x 00.86) [CO .96 -log 'Ycol..5 x 'YHC0 3-= 1 '(10 -~ "'= 0.15.96)[HCO. generally fall in the range from 0.96)(10-")(0. must be experimentally determined. log Y = 0.. Randall and C.05.86 'YH+ = 10-"" = (0. (3·40) is generally used to relate activity to ionic strength. = 0.

203 = {O"".21.Nonideal Behavior of Ions and Molecules in Solution 81 The activity coefficient is greater than one. ks' of 0.29 X 10. and for (3) Pacific Ocean water (ionic strength = 0. that 'Y must be greater than 1.3.203 2. (2) the Sacramento River water (specific conductivity = 450 p. for the reaction O2 (9) ~ 02(aQ) is 1.vapor pressure (mmHg) \ X 760 ) 02 = [0"".007. Henry's constant.4 M (or 8. Knowing POz we can calculate [02(aQ)] from the equilibrium constant. KH . .} = 1. {i} = 'Y.4 mg!1iter) The ionic strength estimate for Sacramento River water: From Fig." Example 3-9 Given that the equilibrium constant. If the oxygen dissolved in the seawater is in equilibrium with the atmosphere. The effect of decreasing the solubility of molecular species. P O2 = ( atmospheric pressure (mmHg) .out coefficient. {02{aQ)} [02(aQJ.] eGO 7~.3 at 25°C and assum~ng a salting. This phenomenon is illustrated by Example 3-9. determine the molar dissolved oxygen activity and concentration at 25°C for (1) distilled water.7). 3-3 for a specific conductance of 460 I'mho. In dry air the volume fraction of oxygen is 0.21) = = 0.29 x 10-3 Po. We can visualize that this is indeed possible if we think of the condition of the water in seawater. I' = 0. if the dissolved oxygen activity is constant while the dissolved oxygen concentration decreases as the salt concentration increases. there will be a significant quantity of the H2 0 present as water of hydration associated with the ions present in the seawater.} = 1.8 mm Hg. by increasing salt concentration is known as the "salting-out effecl. At 25°C the vapor pressure of water is 23.62 x 10. we see from the equation. Because there is so much salt present.29 x 10-3 x 0. Therefore.mho).[ij. such as dissolved oxygen.132.8) (0. K = {O"". Given that ~ is the volume fraction of O2 in dry air. -i the activity of oxygen in the water is controlled only by the partial -J\'" pressure of oxygen in the atmosphere. Oxygen dissolves less well in water which is bonded to ions so that a given total volume of water will dissolve a smaller concentration of oxygen at equilibrium if it contains much sail. Solution Dissolved oxygen in distilled water: Since p. It is not a function of salt content of the water. = 0.

+ . PROBLEMS The heat of combusion of a substance is defined as the enthalpy change that occurs when 1 mole of a substance reacts with elemental oxygen to form liquid water and gaseous CO2 .S.007 k.62 x 10.) .75 mglliter for the ocean water. X [0 21aq)1 = 2..6 keal CO.4 mgllUer.75 mg/liter For both waters the activity of oxygen is the same at 2. X and 0. The same analysis conducted using a membrane·covered..621.2410- 2. Express the answer in terms of kcallmole and kcal/g. ARt.132 y = 1. specific oxygen electrode will produce an identical reading in both solutions because it responds to activity rather than concentration. = 0.0.002 = 2..7 and logy =0. --> CO". = 0.4mgniter 4 For Pacific Ocean water.M 8..=0.82 Chemical Equilibrium Let us assume that the partial pressure of oxygen is the same over the Pacific Ocean as it is over the Sacramento River (a reasonable assumption). Calculate the standard enthalpy of formation. for CO(g) using the following information: CIS) 2.007 log y = 0.62 X 10.132 y = 1. For Sacramento River water.0 kcal -67. It is significant to note that a dissolved oxygen test conducted on the two wat· ers using the wet chemical method (Winkler method) will produce a result of 8.132 For Sacramento River water.4 mglliter for the river water and 6. p.. We might ask how a fish feels with respect to the dissolved oxygen content of these two waters.7 xO.11 x 10. I.24 Now since k.62 x 10.4 4 1. + 02(g) --7 CO 2(g) tlHo I1W = = -94. = 0.. Does it care about dissolved oxygen activity or dissolved oxygen concentration? We leave the reader to ponder this question..1 = = 2. Because of this the dissolved oxygen activity will be the same in both solutions. [0". CH 4 (g) at 25°C and a constant pressure. Determine the heat available from the combustion of met4ane. 3.132 p.002 For Pacific Ocean water.4 M or 8.4 M = 6.

[NH3J ~ 10.+ C02(aQ) + H20 (tl The bacteria function as a catalyst in the reaction but do not alter the amount of energy that can be obtained from the reaction. Ammonia. If a man had a mass of 70 kg with the heat capacity of water (l call g.6. is present in solution at equilibrium when the pH is 1O. moles/liter.) 4: An important reaction in muscular activity is the oxidation of lactic to pyruvic acid.Problems 3. The reaction can be represented as follows: CR. (a) Find the equilibrium constant. Calculate ilHO for the reaction given that the tlHO of combustion (see Problem 1) is -279 kcallmole for pyruvic acid and -326 kcallmole for lactic acid (lactic acid ~ CH3CHOHCOOH.JCOO- + 202(aQ) ~ RCO.GO) for all maintenance and synthesis of new bacterial cells when I mole of acetate ion undergoes aerobic oxidation by bacteria.Ho for vaporization at 37°C is 575 cal/g.0? (Neglect ionic strength effects. How much water would he need to evaporate in a day to maintain constant temperature? (6.~HNOJ(aq) is at equilibrium in aqueous solution.J. ~([N03-J + [HN0 3J) is present as HN0 3 at pH ~ I? (Use standard free energy tables to make your calculations and assume that all activity coefficients have a value of 1.oC).5 M. K.J. There is a certain amount of inefficiency involved. pyruvic acid ~ CH3COCOOH).0') 8. Mg{OHh(sl is precipitated according to the following reaction Mg2+ + 20H. and [NH4+J ~ 10-' M.ordance with the following reaction NH3\aqj + H 20 ~NH4+ +OH- (a) Calculate the equilibrium constant. 6.0. Calculate the amount of energy available (that is.) How much MgH. what percent of CT.'" Mg(OH)".N~ {where C T •NO. Note: Not all of the availcrble energy is used for synthesis and maintenance. H. NH. in which direction is the reaction going? 7.average man produces about 2500 keal of heat a day through metabolic activity. S. is the reaction at equilibrium? If not. K w .) 9. what would be the temperature rise in a day if no heat were lost? Man is actually an open system. at 25 and 40'C for the following reaction. and the main mechanism of heat loss is the evaporation of water. for this reaction at 2SoC. pH ~ 9. Assuming that the reaction H+ + NO. at some time. 83 An. is a base and will readily accept a proton in acc.J . (b) If. .O '" W + OH(b) Is the reaction exothermic or endothermic? .

decomposes in a soIu!ion that is in equilibrium with the atmosphere in accordance with the following reaction. Sci.5 X 10. The reaction of divalent manganese with O 2 in aqueous solutions is given as follows: \ Delfino and Lee (Environ.PO.84 Chemical Equilibrium 10. The following quantities of salts were added to a volume of water to make 1 liter of solution: I X 10-' moles NaCI 2 X 10-' moles CaCI. using the Giintelberg approximation of the DeBye-Huckel law. calculate the pH at which the reaction will be at equilibrium if [MnO.out" M.'-J/[H.'" S'. 2 x 10-' moles BaCI. (a) What is the ionic strength of the solution? (b) A small amount of phosphate salt is added to the same solution with negligible change in ionic strength. Assume that the gas is in equilibrium with the water. for H2S. (Ka.l = 10-7 and K a•2 = 10-14 for H2S where Ka. 13. originally contained 0. CT.4 mgt liter.'" H+ + HPO. will the precip· itate continue to form after the measurement on the tenth day? (b) What should the Mn2+ concentration be at equilibrium? 12. (a) Assuming that the pH remains constant during aeration.+ 4H+ ~ 4Mn02(S) + 2H2 0 + 302(9) The equilibrium constant for this reaction is 10+68. (a) If [MnO.-J ~ 10-" M and pH ~ 7. H2 S(g) ~ H2S(aq) (b) The ·partial pressure of H2S(9) overlying the water if the total soluble sulfide concentration. Note that KH = K for the reaction. Given K = 10-7•2 for the reaction H.'- Calculate [H+][HPO. ks' for a nonelectrolyte in the same solution if its activity is 10-3 M and its concentration is 9. Calculate (a) Henry's constant.6 mgt liter of Mn2+.1 is the equilibrium constant for H2S(aq) ~ HS. called 'K.) II.+ H+ and Ka. KH .S""J + [HS-J + [S'-J.5.PO. (c) Calculate the "salting.5.-J ~ IO. pH = 8..S ~ [H.. December 1968) found that a lake water sample devoid of oxygen. 4Mn04. .4 M.-J. and Technol. The sample was aerated (atmospheric conditions) and after 10 days of saturation with atmospheric O 2 the Mn2+ concentration was 0.+ H+. Permanganate.2 is the equilibrium constant for HS. is I X 10-3 M and the solution pH is 8. is the reaction at equilibrium or proceeding to the right or the left? (b) If the reaction is not at equilibrium for the conditions in part (a). Mn04-.

5 atm. He03-. In order to cut costs at the lime sooftening plant.. G.9 kcal. The reaction 02(9) :. W. 4th ed .8 92... and H+ are each 10. In what direction does the following reaction proceed initially? CO 2 (aQ) + H 20.+ H+. (a) Calculate the free energy of formation and the enthalpy of formation for the reactant and the product and compare to the values listed in Table 3·l. 2nd ed .. and 100°. McGraw.:::: CoOtS} + CO 2(g) The decision is made to store the sludge in a container open to the atmosphere prior to recalcination.. J. 50. . NaRC0 3 • and He} are mixed instantaneously so that the concentrations of C02(~q). revised by K. Brewer. will any of the CaC03(S) decompose according to the given reaction? 16. Physical Chemistry.:=: HC0 3 . 85 At" 25°C. 'C 25 50 100 Vapor Pressure. Ral)dall. mmHg 23. K (= KH • Henry's constant) = 1.29 x 10-3 at 25°C and AH' = -3. is the reaction at equilibrium? Why? 3. Moore. Thermodynamics. N.7. (b) Calculate the equilibrium constant at 50'C. calculate the equilibrium concentration of O 2 in water at 25. for atmospheric pressure.5 760 and that dry air is 21 percent O 2 by volume.J . and M. (d) Given that 9.. 1961. (c) Given that the vapor pressure is as follows: Temperature. Prentice-Hall. S.Hill.5 mg 02/liter is found in solution at 25°C. Englewood Cliffs. aqueous solutions of CO 2{aq)..5 M initially.Additional Reading 14. N. K = 10-6 •3 15.. Knowing that P C02 = 10-3 . the operator decides to recalcinate the calcium carbonate sludge according to the reaction CaC0 3 (s):.::'! 02(aQ) has an equilibrium constant. Pitzer and L.• 1972. ADDITIONAL READING Lewis.

coordination chemistry. In water treatment. H+. Some metal ions behave as acids. and complexation reactions involve acid·base reactions. The chapters that follow and deal with precipitation. Special attention will be given to techniques for calculating the composition of solutions of acids and bases. or a proton as it is commonly called. the substance B.1. DEFINITION OF TERMS The most commonly used definitions of an acid and a base are those of Bransted and Lowry. These definitions state that an acid is a substance which can donate a hydrogen ion.2. and that a base is a substance which can accept a proton. It is essential for understanding the carbonate system that has an important influence on the pH of natural waters and may govern the solubility of certain metal ions. oxidation-reduction. the dosages of chemicals required to reduce hardness (calcium and magnesium) are partially governed by the acid-base properties of the solution being treated. The substance HA is an acid because it can donate a proton. B- + HA "" HB + Aacid z base2 (4-1) a proton is transferred from HA to the anion B-. . The concentrations of metal ions in water are governed to a great extent by acid-base phenomena. Thus the concentration of hydroxide ion may determine the concentration of many metal ions. and oxidation-reduction chemistry will make use of many of the principles developed in this chapter. In this chapter we will consider in detail acid-base reactions using relevant examples from water treatment processes and natural water chemistry to illustrate the various a base because . 4. INTRODUCTION A thorough examination of acid-base chemistry is important in the study of aqueous chemistry. Many precipitationdissolution. ferric ion has an acid strength comparable to phosphoric acid and much of its chemistry is governed by its acidic properties.ACID-BASE CHEMISTRY 4. for example. In the general reaction.

04-. are formed as the reaction proceeds to the right. Substances that can function as both an acid and a base.Definition of Terms 87 it can accept the proton.+ HCO. or OH-·3H 20. there is good evidence that at least three additional water molecules are somewhat more loosely attached to the hydrated proton so that another representation of the proton in water would be H.. Because of its amphoteric properties water undergoes auto-ionization thus. such as HCO. In the reaction between the carbonate ion and water. although the formula H.O+ often is used to emphasize that acid-base reactions are proton exchange reactions. In aqueous solution the proton is bonded quite strongly to a water molecule so that it is more correct to use the symbol H. HCI + H20 .=': OR.O + H20. HB. the proton donor. the base that forms when the proton is given up. rather than H+ to represent it in equations.O+. Furthermore..O.=': H.+ H20. also is hydrated. HA.O+ or H. Water can be both an acid and a base. HB and B. they are amphoteric.O.O+ + CIbasel base2 (4-2) water is a base because it accepts a proton from HCI. The hydroxyl ion.=': H. A-.conjugate base pair. H. and A-. OH-. are caJled ampholytes. It is common to use H+ as a shorthand notation for H... by neglecting ionic strength effects we can write The auto-ionization reaction can be written also as H. having three water molecules bonded to it. and OH.O+ + OHwith the resulting equilibrium constant. Note that the reaction is reversible so that a new acid.O.-.. in the following reaction.O. CO. For example. Similarly.2. and a new base.are an acid. H20 . that represent H. (4-5) . + or H+·4H.and H.+. In this reaction.basel acid 1 (4·3) the water molecule donates a proton to the carbonate ion and is therefore an acid.O. the hydrated proton or hydronium ion. are called an acid-conjugate base pair.=':H+ + OHThe equilibrium constant for this reaction is K= {W}{OH-} {H20} (4-4) But because {H20} = I in dilute solution (see Section 3·3).

Eq. K. In this text we will follow common practice and use H+ and OH.e.Go = + 19. indicate that the acid has a strong tendency to donate a proton to water. values near the dividing line. 4-3). Strong acids tend toward complete dissociation while weak acids are incompletely ionized. The dividing line between what the chemist refers to as a strong acid and a weak acid lies somewhere in the region of iodic acid (pK. 4-5.60) . 4-4.H 2 0 - Ll.- - ~ Gf. G"OH. In Example 3-1. In doing this.09 kcal was calculated for Eq. perchloric. the free energy of the hydrated hydroxyl ion is the free energy of OH. respectively. it is a strong base.Go = -56. K w .. On occasion we will use HaO+ to emphasize that acid-base reactions are truly proton exchange reactions. GO = ~ G~H30+ - + .o values from Table 3-1 yields the identical value for Ll. The acids are listed in the order of decreasing strength while the bases are in the order of increasing strength. i.88 Acid-Base Chemistry K = {HaO+}{OW} {H. i.g. For acids with pK.g. dissociation is incomplete for high concentrations but tends toward completion for low .. and K. Table 4-1 is a listing of some K.. Large values of K.09kcal (4-6) Thus using the shorthand notation of H+ for HaO+ and omitting water molecules from both sides of Eqs. 4-2). indicate that . As shown in Example 3-1.O}' or when {H.2(-56.Go of + 19.Go. refers to the reaction in which a base accepts a proton from a water molecule (e. Conversely. The equilibrium constant. The equilibrium constant. for these reactions from free energy calculations. K" for an acid refers to the reaction in which an acid donates a proton to a water molecule ( the free energy of the water molecules hydrating it.69 + (-37. and making the same calculation for Eq.8). plus the free energy of the water molecules bonded to it. Similarly.O} I and neglecting ionic strength effects. nitric.e. K = [HaO+][OW] = Kw We can derive the value of the equilibrium constant. and Kb values of relevance to water chemistry. Large values of K.G.. we should recall that the free energy of the proton is zero. a Ll. hydrochloric. Eq.69) = +19. = 0. 4-5 does not affect the free energy change for the reaction.6. small values of K.a substance has a strong tendency to accept a proton from water. and HaO+ would be classified as strong acids while the remainder of the list are weak acids. The free energy of the hydrated proton is the free energy of the proton. Thus. K = I X 10-14 at 25°C when Ll. respectively.. zero. it is a strong represent the hydrated proton and hydroxyl ion.09 kcal. denote weak acids and bases. D. using Ll. of the acids listed.

{CN }{H2 0} {H30+}{CN-} 2 2. I. Kw = 1. hydroxide. 2H2 0 "" H30+ + OH-. K.K. As illustrated in Table 4-1.) and the conjugate base of a weak acid is a strong base (large K b ). HCN. At 2S'C. the dividing line between strong and weak bases is in the neighborhood of dihydrogen silicate. Using the notation pX to signify -log X. the conjugate base of a strong acid is a weak base (small K. water.14 {H+}{OH-}.0 x 10. acid HCN + H20 ""H30+ + CN-. sulfide. for an acid if Kb for the conjugate base is known. and the cyanide ion. or conversely. we can write pH + pOH = pKw = 14 where pH= -log{W} pOH = -log {OH-} pKw = -logKw When ionic strength effects are negligible. This effect is known as the leveling effect of the solvent. (pKb = 1. {HCN}{H20}{CN }{H20} {H2 0}2 Because {H20} = L (4-8) where Kw is the equilibrium constant for ionization of water. Thus. An important relationship exists between the K. amide. we obtain the overall equation. forms the basis for the definition of the pH scale. K. conjugate acid K _ {HCN}{OH-} • . K=K. and oxide are strong bases whereas the remaining entries are weak bases.. we can write equations for the donation of a proton to water by HCN and for the acceptance of a proton from water by CN-.4). Equation 48 enables us to calculate Kb for the conjugate base of an acid if K. Using hydrocyanic acid. of the bases listed. The Kw equation. (4-7) K =K K = {H30+}{CN-}{HCN}{OH-} = {H3 0 +}{OH-} . and is dependent upon the relative affinities of the conjugate base and H2 0 for the proton. value for its conjugate base. is known. pH = -log [W] pOH = -log [OH-] . CN-. CNbase + H2 0"" HCN + OH-. = {HCN}{H 0} conjugate base By adding (]) and (2). value of an acid and the K. as an example of an acid-conjugate base pair. which describes the dissociation of water.Definition of Terms 89 concentrations. Similarly.

Perchloric acid Hydrochloric acid Conjugate Base -log K.O 10. HSO.8 10.COOAI(H.O). CH.OH'+ F- 21 17 17 14 14 13.5 4. ~ pK.1 Sulfuric acid Nitric acid Hydronium ion Iodie acid Bisulfate ion Phosphoric acid Ferric ion Hydrofluoric acid Nitrous acid Acetic acid Aluminum ion RIO.'H.2 3.9 CIO.O).Fe(H.>+ HF Iodate ion Sulfate ion Dihydrogen phosphate ion Hydroxo iron(III) complex Fluoride ion Nitrite ion Acetate ion RNO.O).SO.CIHSO.H.1 2.>+ NO.H.3 9.2 12 11. HCI H.COOH AI(H.5 9.8 9.PO.NO.O). H30 + Acidity and Basicity Constants for Substances in Aqueous Solution at 25°C -log K.8 2 2.9 1!. RNO.2 TABLE 4-1 Acid HCIO. Perchlorate ion Chloride ion Bisulfate ion Nitrate ion Water -7 --3 --3 -0 0 0.OH'+ Hydroxo aluminum(Im complex . Fe(H.PO.7 4. ~ pK.

HsOC032- Bisulfide ion Monohydrogen phosphate ion Hypochlorite ion Cyanide ion Borate ion Ammonia Trihydrogen silicate ion Phenolate ion Carbonate ion Phosphate ion Dihydrogen silicate ion Sulfide ion Hydroxide ion Amide ion Oxide ion a.H. C.+ Carbon dioxide and carbonic acid Hydrogen sulfide Dihydrogen phosphate Hypochlorous acid Hydrocyanic acid Boric acid Ammonium ion Orthosilicic acid Phenol Bicarbonate ion Monohydrogen phosphate Trihydrogen silicate Bisulfide ion Water 6.4 4.3 12.PO.7 4.3 9.SiO.O NH3 OH- Ammonia Hydroxide ion POiH2 SiO/S'OHNH.7 1.NH3 H3 SiO.5 9.1 7.4 HPO/OCICNB(OH).5 9.1 3.RsOH HC03- HPOiHaSi04 - HSH.9 6.8 6.S H.2 7.0'- a a -9 -10 ~ .3 12.3 7.3 9.9 10.C0 3' H.6 14 14 -23 -24 HC03HS- Bicarbonate ion 7.B03 NH.5 4.C.7 4.7 6.3 9.7 4.7 1.HOCI HCN H.

62.H' = + 13. It is. 0. At 25'C. Because this proton transfer enables the system to attain a lower free energy.323 _1_) = 5. however.69 ..(-56.OH.36 (~ 298 . Table 4-2 is a tabulation of K was a function of temperature and of the corresponding pH values of a neutral solution.G' = -26.323) -'4) . that pH 7 only represents neutrality at 25'C because the pH scale has its origin in the Kw equation and Kw is a function of temperature. quite helpful to think of acid strength in terms of the standard free energy change of the reaction in which I mole of protons is transferred from the acid to water. pH = pOH and pH = pKw/2 = 7.36 kcal Using the Van't Hoff relationship. the solution is said to be neutral. pH values abov. From the relationship. fhe reaction H2 0 .500)'{2 = 6.92 Acid-Base Chemistry When {W} = {OW}.H' = 0 + (-54. we can calculate Kw at 50'C as follows.96) .H+ + tJ.H.H' = 1l. As previously indicated. under standard conditions.73 X 10-'4 Thus. however. 3-27. Eq.G' = -0.69) tJ. the reaction tends to proceed readily in the direction written and accordingly nitric acid is a very strong acid.43 -56.Hf.0 X 10 KW•50 0 + 1.1l1..has an enthalpy of reaction (from Table 3-1).= H+ + OH.H' ( I I R 298 .In 1.3RT log K . In an aqueous solution where [H+] = [OH-].Hf.02 kcal Thus. for nitric acid. or [W] = [OW]. For example.02 kcal of free energy are released for each mole of proton-s transferred from nitric acid to water.G' = -2. ll. Conversely.ll. For example.(-68.(-26. 1l.e 7 indicate thsxt [OH-] > [H+] and the solution is said to be basic or alkaline.o 1l.32) 1l.=: H30+ + N03- ll.987 X 10-3 13. at 50'C. neutrality is attained at pH = 7. neutrality is at pH = -log (K W. K" of an acid gives an indication of its strength. HN0 3 + H 2 0:. Values of pH below 7 signify that [H+] > [OH-]: and the solution is said to be acidic. using values given in Table 3-1. the equilibrium constant. It is important to realize.41) . In Kw •50 o = In Kw •25 ° -f! _ ( 1l.

2 D. The H+ and OH.45 X 0. Mechanisms of Inorganic Reactions in Solution: An Introduction. k. sec. New York. (4·9) is elementary.03 By comparison the free energy change for dissociation of the bisulfide ion. 3rd ed.1 kcal. Reaction rates of this magnitude are consistent with a diffusion·controlled reaction in which the ions diffuse to the point of contact and then react instantaneously. Since the reaction in Eq.98 X 10 ' X 298 = 1.47 X 2. McGraw·Hill.3 X -0.14 10-14 10-14 pKw 14.00 13. B.47 X 10.' has the fastest reaction rate known in aqueous solution.95 x 10-14 10-14 10-14 10. 1968. 4.4 X 10" liter/mole.76 Source.2 • ' K = 1.47 7.+ H20 . . = 2. we can write Forward rate = k. 1958.5 x IO-'/sec. HS. Reinhold. and k. [If+}[OH-] = (4·10) (4·11) Reverse rate 1 k2 [H20] For an exception see the discussion of the reaction H2 CO.68 x 1.01 x 1. S.00 6. = 1O. RATE OF REACTION Acid·base reactions in aqueous solutions generally proceed extremely rapidly. at 25°C.}.12 X 0.Rate of Reaction 93 TABLE 4·2 °C 0 15 20 25 30 40 Ion Product of Water Kw 0.3. Harned and B.35 14. a large positive number.18 7.. W + OH. Benson.' The reaction. Owen.= Section 4·13. =<= H+ + HC03 .O+ + S'is + 19.08 7. log K = -2.17 14..93 14.ions have exceptionally high mobilities. H...92 6.53 pH of a "neutral" solution ({W} ~ (OR-}) 7. ~ 1. there is little tend· ency for this reaction to proceed as written and bisulfide is a weak acid (J(.14 . The Physical Chemistry of Electrolyte Solutions.02 1..= H2 0 k2 (4·9) with k. accordingly.83 13. London.

s.3 x UP Assuming. and k.also is extremely rapid. Even though the reaction rates of weak acids and bases are slower. Example 4-1 The dissociation of HaS is given by k.O] or k.5 molelliter) 1. = 4.that the reaction is irreversible. [WJ[OW] (mole'lliter') (4-13) Substituting for k. [H. where k. H. pK.4 X 10+" liter/mole. "D.5 moleslliter here because in the rate law. (4-12) [WJ[OH-] k. The rate of reaction of H+ with bases other than OH. sec. Benson.99 X 10-'4 == 10-'4 When ionic strength effects are negligible the concentration product equals Kw.O] k. (2. Mechanisms of Inorganic Reactions in Aqueous Solution: An Intro- duction. dissociate relatively slowly. . McGraw-Hill. = 7. It is necessary to use 55.S "" H+ + HS- k.5 x 1O-5/sec)(55. the concentration of water in moleslliter has been used whereas in the equilibrium constant. 0.S] dt 3 = -k 1 [H S] 2. they can be considered essentially instantaneous as is shown by the following example for the weak acid H.94 Acid-Base Chemistry = At equilibrium.[H.1. with a high affinity for protons. since other bases diffuse more slowly. and using 55_5 moles/liter as the concentration of water. London. The rate at which acids dissociate or give up a proton is a function of the affinity of the acid for the proton. Weak acids. Similarly. = k. forward rate reverse rate.3 we obtain the concentration product of water. KWI we use the mole fraction for the concentration of water. how long will it take for 50 percent of the HaS to dissociate? sec-1 • 4 Solution The rate law d [H. therefore. although not quite as fast as its reaction rate with OH-. weak bases have slower reaction rates than strong bases. 1968.

SJI = concentration at t = t. HA.S]. the rate at which HS. or leave to.+ H30+ Let us assume that the system is homogeneous and closed (Le" no species containing A can enter from.>.. or a salt of its conjugate base. Mass Balances In acid-base reactions the reacting species are conserved.4.. -4. we can concern ourselves primarily with the determination of species concentrations at equilibrium. EQUILIBRIUM CALCULATIONS-A GENERAL APPROACH Because acid-base reactions in solution generally are so rapid. MA (where M is a cation) is added to water.S were bubbled into a solution.1.6 X 10-4 sec From this value we would expect the dissociation of H:. If H:.>. [H:. acid·base equilibrium calculations are of central importance in the chemistry of natural waters and in water and wastewater treatment processes.integrated between time = 95 0 and time = t to give I [H. 4. and that precipitation or dissolution of such species cannot occur).>.4. the acid ionizes partially or completely. 4.would be produced would be controlled by the efficiency of the mixing device.SJo = concentration at t = 0.and H+ to be at equilibrium in a well~mixed solution only a fraction of a second after it is added. [OH-j.---------- where C T •A is the number of moles of "species containing A" per liter and . When HA is added to water.S].A ~ ~ [HAj + [A-j -~. As we shall see later in this text. (4-14) .>. A mass balance ~g)'~~~ CT. HA + H2 0:o= A. where n [H.Equilibrium Calculations-A General Approach can be . we desire to know [H+j. The purpose of this section is to develop a general approach to the solution of acid-base equilibrium problems and to apply this approach to a variety of situations involving strong and weak acids and bases.-. Thus In.S into HS. even for the most efficient mixing system. Usually.t k' [H:.-<-~~-. and . ~ .3 X 10+3 t ~ 1. and the concentration of the acid and its conjugate base that result when an acid or a base is added to water. Let us consider first the equations that describe a solution which results when an acid. the atmosphere.

~~-- CT•A = __ [HA] .. C.M = [W] ~_~ ~ or. r.... -~ 4. Equilibrium Relationships The second group of equations we need to consider describe equilibrium relationships._ ~"'... .. A- + H20"" HA + OH+ [MA] (4-15) A mass balance on M gives. ..' _r O" -._ _ _ ''"--..'. [A-] + ..-• _. (4-16) where C T •A = ~ '-.. . _ _ _ 'ov O_ .96 Acid-Base Chemistry is equal to the analytical concentration of HA or the number of moles of H!\ added per liter.."r••_____ "--' .. .J where CT...--~--~ When MA and HA both are added to a solution. _ ..•• . sum of the moles of HA and MA added per liter of solution.. A-..2. .. it dissociates MA"" M+ + A- and the base. . .. ••••• where CT..-_~._. --.-. ..~. K _ [HA][OW] b [A ] 5 (4-20) This mass balance assumes that M+ does not form complexes with A-or other solutes-on assumption that is legitimate for the alkali metals but may not be valid for alkali earth and transition metals (see Chapter 5). neglecting ionic strength effects._" __ . __ ~_. .-__ '. When C moles of the salt MA are added per liter. In aqueous solution.~ (4-17) "-.. For the example of HA added to pure water the following equilibria are pertinent..M is the number of moles of M per liter.-_~~_ ~'T""-.4.M =[~.. given that MA__dissociatescompletely. . Kw = [W][OH-] = 10-14 at 25'C The dissociation of HA is described by [W][A-] [HA] (4-18) Ka = (4-19) The same equations are valid if the salt MA is added to solution. .__________ [A-] [HA] + o~'-·.. . C}.~_. reacts with water.~ ._'. The basicity constant.-" . . ________ .•• ._.___ c.5 C = CT.A = '---------"~-'~--_._-.. we obtain for the dissociation of water. [HA] and [A-] are the molar concentrations of the acid and conjugate base in solution at equilibrium.. A mass balance on A yields C T--•A = __ --.

O+.4. A-. OH-. Since Kw = K.K b . PRL = H2 0 and MA (or. 4-19. Example 4-2 Determine the proton condition when HA is added to water.are H3 0+. A-. Eqs. H20. In later sections and chapters it is used to solve natural water problems.O+] = [OW] Again the species at the PRL. HA. A-. The species having protons in excess of the PRL are equated with the species having less protons than the PRL. The proton mass balance is established with reference to a "zero level" or a "reference level" for protons (the proton reference level. A-. and H20. Species with protons> PRL·= H3 0+. OH-. It is an essential component of equilibrium problem solving if either H+ or OH. . Species with protons < PRL = OH-. All species are involved in reactions with H+ or OH-. equivalently. 4. H20. and HA. Proton Condition [H. and A-. It is used in this section only to solve problems related to solutions made up in the laboratory. A-. Solution The species present are H30+. H20. H2 0. Proton Condition [HA] + [H. the species at the PRL do not appear in the proton condition. Species with protons > PRL = HA. The Proton Condition The proton condition is a special type of mass balance equation on protons.3. The species that involve reactions with H+ or used in place of Eq. The PRL is established as the species with which the solution was prepared. Solution The species present are H30+. H. do not appear in the proton condition. Example 4-3 Determine the proton condition when the salt MA is added to water.Equilibrium Calculations-A General Approach 97 could . PRL = HA. OH-. Species with protons < PRL = OH-.and does not affect the proton condition).O+] = [OH-] + [A-] Note that HA and H2 0. and HA. 4-19 and 4-20 cannot both be used because they are not independent. since M+ completely dissociates from A.are involved in the equilibria. PRL). M+.

N. [P043-] is counted three times. and P04 3-. H2 P04 .-] + 2[HPOf-] + 3[PO. H2 0. H3P0 4 • in pure water. HCOa-. PRL ~ H. formed in. In a solution the total number of positive charges must equal the total number of negative charges. or removed from a solution without the addition. Butler.O+] ~ [OW] + [H2PO. of an equal number of ions of the opposite charge. H2 0. Ionic Equilibrium. . and CO/-.. OH-.98 Acid·Base Chemistry Example 4·4 State the proton condition for a solution of phosphoric acid.4. Na+. H2P04 -. since P04 3. Ions of one charge cannot be added to.. OH-. PRL ~ HC03-. ~ Species with protons> PHL = H+. or removal. The Charge Balance or Electroneutrality Equation The basis of the charge balance is that all solutions must be electrically neutral. Proton Condition [H.PO" H20. Species with protons < PRL OW. Solution The species present are H30+. Addison. Solution The species present are H+. C032-.has three less protons per molecule than the PRL. However. HaP04 .'-] Note that the concentration of [HPOl-} is counted twice because it has two less protons per molecule than the PRL.4. HPO/-. these more·complicated situations are more readily solved by obtaining the proton condition from a combination of the charge balance and the mass balance. 6 The details of this approach are given in J. = = Species with protons> PRL H30+ I Species with protons < PRL OH-. Proton Condition A proton or hydroxyl mass balance also may be used to arrive at the proton condition. Example 4·5 State the proton condition for sodium bicarbonate. H2 0. NaRCO s • added to water. H2 CO. HPOl-. Similarly.. 1964. 4. as is shown in Section 4·4·4.Wesley.. A Mathematical Approach. Reading. Mass. formation. H2CO. and POl-.' This approach can be applied to the more complicated situation that arises when both MA and HA are added to the same solution.

The species present are. A-.Equilibrium Calculations-A General Approach Example 4-6 Determine the charge balance when HA is added to water. H+.PO. Charge Balance [Na+] + [H+] = [OH-] + [H. Since all waters must be electrically neutral.POn + 2[HPO. H2 0. H J P04 . H+. we can deduce that a complete water analysis must produce a result in which . OH-. HA. Total positive charges = (H+J. Charge Balance [W] + [H+] = [OW] + [A-] Example 4-8 Write a charge balance statement for Na2HP04 dissolved in water.'-] + 3[POt-] Note that the molar concentration of HPO/. Solution Total positive charges = [Na+] + [H+]. Total negative charges = [OW] + [H. Total positive charges = [M+] + [H+]. Total negative charges = [OH-] + [A-]. and H+. Solution The species present are M+. Total negative charges = [OW] + [A-]. H 2 0. the charge balance equation has significant practical application in the analysis of waters. Charge Balance Total positive charges = total negative charges or Example 4-7 Determine the charge balance when MA is added to water. 99 Solution The species present are HA.'-] + 3[POt-].carries three negative charges per molecule. Na+. Besides being essential to the solution of equilibrium problems. OH-. since HPO/carries two negative charges per molecule while P043 . HPOl-. A-. -] + 2[HPO. and H 20. multiplied by two and the molar concentration of P04 3. and multiplied by three in the charge balance. H2P04 -.

8 (the pH of the water sample). bicarbonate = 286. An acceptable water analysis will have this equation agreeing to within ±S percent for wastewater or seawater analyses and ± 2 percent for water analyses. Water Co.04 Cl- 98 80. since it is not charged at pH = 7. calcium = 65 mg CaH/liter (162.70 8.~.76 0. and chloride = 98 mg Cl-/liter./liter. Meq Cone. For complex solutions this is generally the best way to determine proton conditions. magnesium = 18. sodium = 76 mg Na+lliter. Note that SiOl does not enter into the computation.Q.2 23 40 24.Is the water analysis satisfactory from the point of view of analytical accuracy? Solution Arrange anions and cations in separate columns as in Table 4·3. showed: pH = 7.8.49 8.'28 HCO.5 96 61 I 2 I 2.58 4.5 mg as CaC03 /liter). when C moles of MA are added per liter of solution. Californi.286.30 3. Then multiply by the charge/ion to obtain mmoles of charge units/liter.2 mg MgHliiter (75 mg as CaC03 Iliter).9 bf the Manhattan Bf?och.100 Acid·Base Chemistry the total number of positive charges = the total number of negative charges. also called the milliequivalentslliter (meq/liter) of charge units. Compute millimoleslliter (mmoles/liter) of individual anions and cations by dividing the concentrations by the appropriate molecular weight.charge) .7 35. mgt mgt Charge! Charge! mgt mgt Charge! Charge! Cations liter mmole ion liter· Anions liter mmole ion liter 76 65 18. Mass Balances (I) CT.3 I 2 2 3. assuming complete dissociation of MA. The analyses check with excellent accuracy.04 l (+ charge) l (.25 1.are negligible. sulfate = 28 mg S042 -/liter. The charge balance and mass balance equations can be combined to give the proton condition. we obtain the following results. silica = IJl mg 8iO.. Sum the meqlliter of positive and negative charges and compare sums for agreement. and that Wand OR.M = [M+] = C (2) C T•A = [HA] + [A -] = C TABLE 4·3 Anion-Cation Balance Meq Cone. Example 4-9 An analysis of water from Well No. Larger deviations than this indicate either errors in analysis or an overlooked species.7 mg HC03 -lliter. For example.

Example 4-10 State the equations necessary to arrive at the concentration of each species in I. and (3) to eliminate M+. then activities. Since we have four unknowns. HA. ionic strength effects are negligible. H2 0 (2) Kw = 10-" = {W}{OH-} Equilibrium Consiant. If we cannot assume that activities and molar concentrations are identical. five independent equations are required. [OH-j. OH-. therefore. or graphically. Solution a.A to arrive at the proton condition. b. The equilibrium constants then can he converted from constants based on activities to constants based on concentrations. { }. (2). The species present are [Wj. and CT. We have five unknowns. Mass Balance on A (I) CT. and H+. to yield the concentration of each species present. . The species present are Na+. = {W}{A-}/{HA} = Proton Condition (or Charge Balance) (4) [Wj Wl + [OH-j If we make the assumption that activity coefficients of all species are unity. C. are equal to molar concentrations. A-. [HA] + [H+] = [OH-] Using the equilibrium equations in combination with mass and charge balances and the proton condition.A = [HAj + [A-j = 10-3 Equilibrium Constant. then the activity coefficient must be calculated using the relationships given in Section 3-6. it is now possible for us to proceed with the solution of acid·base problems and to arrive at the concentration of each species present in such systems. four independent equations are required. and [A-j. [ J. . HA (3) K. 10-3 M solution of NaA. [HAj. and the solution procedure is the same.Equilibrium Calculations-A General Approach 101 Charge Balance (3) [W] + [H+] = [A-] + [OW] We can combine (I). and knowing Ka and Kw we can solve equations (1) to (4) simultaneously. 10-3 M solution of HA. 2. that is.

= [Na+] = 10. Charge Balance (5) [Na+] + [WI = [A-] + [OH-] The proton condition.". The following three examples illustrate how the equations describing a strong acid or a strong base solution can be solved. and CT •CI = [Cl-] Although this assumption is valid for most strong acid or strong base calculations of interest. = 10' [WJ[Cl-l/[HCl] when activity coefficients have a value [Cl-] » [HCl] or [HCl] is approximately 0. For example.5. When the pH is very low « -2). However. HCl is present in solution at all pH values.102 Acid·Base Chemistry Mass Balance on Na+ (I) CT. H20 (3) Kw = 10-" = {W}{OH-} = {W}{A-} {HA} Equilibrium Constant. it is extremely rare in water chemistry that we are concerned with pH values less than about I. it is completely ionized. may be used instead of (5) Analytical and graphical procedures for solving these equations are given in the sections that follow. STRONG ACID-STRONG BASE CALCULATIONS We can assume that when a strong acid is added to water. when HCl 'J(. of unity. a mass balance on Cl gives CT. HA (4) K . [HA] + [WI = [OR-I.3 Mass Balance on A (2) CT.CI = [HCl] + [Cl-] Since K.3 Equilibrium Constant. = 10') is added to pure water.CI and must be taken into account. the number of HCl molecules becomes a significant fraction of CT. 4.A = [HA] + [A-] = 10. .

[CI-] = 10-'. = 10-" = [W][OH-] Mass balance on CI 3. In mass balance: Because Hel is a strong acid. Find [W]. so assume [HCI] Thus 7. [OW] = 10-12 • satisfy it to within 5 percent. HCI "" W + CI-.O"" W + OW. [W] =-[CI-] + [OW] Assumptions 5. From (7) and (2) K 10-" 12 [OW] = [H:] = 10-' = 109. Solution The unknowns are W. OW. that is.Strong Acid-Strong Base Calculations 103 Example 4-11 10-' moles of HCI are added to I liter of distilled water at 25'C. Kw 2. From (5) and (6) 8.!lance) 4. Equilibria l. Check the proton condition to find whether the concentrations that have been determined. and CI-. HC!. [W] = 10-'.12 . Assume that activity coefficients are unity. H.CI = [CI-] + [HCI] = 10-' Proton Condition (Charge B!. What is the pH of the solution? Demonstrate that [HCI] is negligible. assume that [CI-] » Thus 6. K = 10' = [W][CI-] [HCI] . [W] 10-' = = [CI-] + [OW] 10-' + 10. CT. [OH-] and [CI-] for this solution. In proton condition: Solution is acid.

However. The criterion of agreement to within 5 percent is arbitrary. or any equations for which assumptions were made. are added to I liter of distilled water at 25°C.104 Acid-Base Chemistry The proton condition is satisfied since the right. = 10' = [W][Cn [HC1I _ [10-'][10-'1 10' [HC1I [HC1I = 10-' [CI-I = 10-'» 10-' If the proton condition. it would be necessary either to make a different simplifying assumption or to solve the equations without making an assumption. = [NO. we will make the assumption. hand side are virtually identical.) 2.. -I = 10-' Proton Condition (Charge Balance) 3. Equilibria I. CT. Based on the result of Example 4-11.O '" W + OH-. [WI = [NO. What is the pH of the solution? Assume that activity coefficients are unity.-I + [OH-] . in subsequent calculations that strong acids and strong bases are dissociated completely. Kw = 10-" = [W][OH-I Mass Balance on NO. accuracy better than 5 percent is rarely needed or justified. Solution The unknowns are H+. (assuming complete dissociation of HNO. To demonstrate that [HC1I is negligible compored to [CI-I and so justify our simplifying assumption in the mass balance: K . NO.hand side and the left. in view of the variation in reported equilibrium constants (reported values for a single reaction usually vary by more than 5 percent) and because of the purpose for which the calculations are generally made. H. and N03 -. Example 4-12 10-' moles of the strong acid HNO. 10_ The pH of the solution is pH =2 II. did not check within 5 percent. without verification. OH~.

Thus [NO. Check the assumption in the proton condition: [W] 10-7 ~ ~ [NO.-].-] 5.-]. a. We then can solve for [H+] and use its value to solve for other species concentrations. and indeed to solutions where assumptions are not made. II.-] » [OW]. From (3) and (4) From (5) and 0) [OH-] ~ [H:] ~ 10-7 ~ 10-7 7. so we must resign ourselves to solving the equations without making an assumption in the proton condition. Therefore. we obtain 10---14 [W] ~ 10. In proton condition: The solution is acid. we will now assume that [OW] » [NO. Using our new assumption in the proton condition. we find that 9. From (I) and (8) K w ~ [WHOW] ~ [W]' ~ 10-14 ~ [W] ~ 10-7 [W] 10-7 ~ ~ and [OW] 10-7 10. so assume that [NO. having failed with our assumption that [NO.Strong Acid-Strong Base Calculations lOS Assumptions 4. Check this new assumption in the proton condition: [NOn + [OH-] 10-7 + 10-7 The new assumption does not check any better than the original one. The usual approach to this solution. is to solve first for unknown concentrations in the proton condition (charge balance) in terms of [H+] and constants. Substituting (I) and (2) in (3) to eliminate [OW] and [NO. We now must try to make another assumption. K 10. The best approach is to assume the opposite situation from the assumption that did not work.-] [W] » ~ [OW] which is equivalent to assuming that [W] » [OW].7 + [W] or .14 6.-] + [OW] 10-7 + 10-7 The assumption does not check since the right·hand side is 100 percent greater than the left-hand side.

CT.10-" ~ 0 which can be solved using the quadratic formula [W] ~ --7""-- -b ±Vb' . Kw ~ [W][OW] ~ 10-14 ~ Mass balance on Na+ (assuming complete dissociation of NoOH). [W] + [Na+] ~ [Na+] ~ 10-' [OH-] Assumptions 4. we obtain ~ 1. the solution is basic. Equilibria I.N.14.O "" W + OW.618 x 10-'. ~ » [WJ). so assume [Na+]» [W] (This is equivalent to assuming [OW] [Na+] 5.Io-'[W] . ~ 10 10-10 + 10-' ~ Check assumption in the charge balance 10-' . Charge Balance 3. Assume that activity coefficients are unity.79 A similar set of assumptions and a similar calculation procedure can be used to calculate the species concentrations in the solution of a strong base as shown in the following example.4 M NaOH solution at 25'C. and [Na+]. or pH 6. H. 2. Solving. In charge balance. and c = -10. Thus [OH-] ~ From (2) and (4) [Na+] ~ [OH-] 10-' pOH~4 6. Example 4-13 Calculate pH and pOH in a 10. [OW].4ac 2a For this problem. [W] ~ ~ ~ 10-" ~ 10-10 [OW] 10-' pH 7. a = L b [W] ~ = -10.106 Acid-Base Chemistry [W]' . Solution The unknowns are [W].7 .

14 = {H+}{OH-} = YH+[H+]YOW[OH-] Using the Giintelberg approximation of the DeBye-Hiickel law (Eq.90 The value..12 ) can be neglected because it is approximately 10 orders of magnitude less than [W] (= 10-') and [CI-] (= 10-').5(l'[H+] + (. In each of the preceding examples.I) '[CI-] + (.2 X 10-12 M These values can be compared with pH = 2 and [OH-] = 1.12 when the effect of ionic strength was neglected.52: CIZl I 10-' M (3-32) = 0. the mass balance and proton condition (charge balance) equations are unaffected because these are based on concentration rather than activity.hand side of the equation. An eITor on the order of 10 percent in [H+] and 20 percent in [OH-] resulted from neglecting ionic ..log (0. that is. we must make changes in all of the equilibrium expressions we use_ Since the K..log YH+ = -log Yow = YH+ = YOH- = 0.045 . JL = HI X 10-' + I x 10-') = 10-' M 0.0 x 10.9)(10-') 14 1.5(1) '(10-')'/2 I + (10 ')'/2 0. we are concerned only in these examples with the Kw equation_ This becomes 10. ionic strength effects were neglected. equation is eliminated by a simplifying assumption. which are based on concentrations rather than activities.05 = 10. strong acids and strong bases are completely dissociated. 0.I + JL 1/2 CT.9)(0.J)'[OH-]) [OH-] (= 10. [H+] = 10-'.log {W} = .Strong Acid-Strong Base Calculations 107 The assumption checks.5Z'JL"' -Iogy-=c:. since the left·hand side of the equation is only a fraction of a percent larger than the right.c. However. does not change because it was calculated using only the mass balance and proton conditions. Let us now recalculate the pH for Examples 4-11 and 4-13 taking ionic strength into account. . [OH-] X 10-') = 2.log (YH+ [W]) = . pH = . JL = 0. 3-36) to express activity coefficients as a function of ionic strength.+ YH+YOH" [H] 14 = 10(0.9 and from Kw.CI (3-36) We can calculate Y if JL is known. In these examples. For Example 4-11.

this value does not change because only the mass balance and proton condition were used to calculate it.4 + I x 10. Therefore.4 so that including the effect of ionic strength we obtain pOH = 4. to I liter of water at 25°C. {OH-} = I'OH- [OH-] = 0.004 compared to pOH = 4.6.99 x 10.4)11' I + (10.4 ) = 10. Example 4-14 Calculate the concentration of all species in a solution prepared by adding 10-2 mole of acetic acid. or Kb equilibrium equations that complete dissociation takes place. Neglect ionic strength effects. For Example 4.0 wherf ionic strength effects were neglected.13.= 0. and can be neglected in the calculation of fL. We conclude that in solutions with an ionic strength of 10-2 moleslliter and equilibria involving only monovalent ions. 4. where [Na+] = 10.])'[OH-] + I' [Na+]) Using [H+] = 10-10 . we can see that [H+] is very small compared to [OH-] and [Na+].4 M = -log I'H+ I'H+ -log I'ow (0. Typical calculations for weak acid and weak base systems are illustrated in the following example.4 14 = l.4 .COOR (HAc). We therefore might conclude that at ionic strengths of 10. CR.5(1 = X 10.99 From Example 4·13 we found [OH-] = 10. fL = 0. but we are not able to make the simplifying assumption in theK.5(I'[H+] + (. Also.996 compared to pH = 10 when ionic strength effects were neglected. WEAK ACID-WEAK BASE CALCULATIONS Weak acids and weak bases do'not ionize (or protolyze) completely in aqueous solution. Therefore. {H+} = 10{OH-} 14 = 100. we can safely neglect the effects of ionic strength on equilibria involving only monovalent ions.4 molelliter. which was obtained by neglecting the effect of fL. concentrations of solution components for weak acid or base solutions is similar to that used for strong acids and strong bases.108 Acid·Base Chemistry strength effects.10 and pH = 9.4 fL = 0.01 X 10.4 )'/2 = 4.99 x 10.9 X 10-3 = I'OH.5)(1')(10. . The approach used to solve for the. the effect of ionic strength can be significant.

6. 8. In the charge balance assume that [Ac-] » [OH-]. 10-•. 7 10-" = [W][Ac-l/[HAc] = 2. [HAc]. [HAc] [HAc] = [W][Ac-] K. we find.Ao = [Ac-) = 10-' The solution is acid and therefore [OH-) is small. When we think about this assumption a little more.O "" W + OH-. we can see . [W] = [Ac-] 7. in the proton condition. Checking our assumptions. [W] = [Ac-] + [OH-] 10-' = 10-' + 10-" This assumption is acceptable because the two sides of the equation are virtually equal. Equilibria I. In the mass balance we find 10-' = [Ac-] + [HAc] 10-' = 10-' + 5 This equation is hopelessly unbalcmced so that the assumption of [Ac-] » [HAc] is not acceptable. and [Ac-]. ~.Ao = [HAc] + [Ac-] = 10-' Charge Balance (or Prolan Condition) 4.Weak Acid-Weak Base Calculations 109 Solution The unknowns are [W]. Thus four equations are required. H. Kw = = 10-•. we can make the following assumptions: HAc is an acid so it dissociates to produce [H+] and (Ac-J. HAc "" W + Ac-. From (5) and (6). K. 5. From (I) and (8). = [10-'). [OH-]. CT.7 = 10+0 •7 = 5 M 10. [OH-] = [H:] = K 10-" 10-' = 10-" 9. From (2) and (7). [W] = [Ac-] + [OH-] To solve equations (1) to (4). In the mass halance assume [Ac-] » [HAc]. Then . [WJ[OH-] Mass Balance on Ac 3.

In the proton condition.47 x 10-< From (6) and (2) From (2) and (2) [OH-] ~ 4. ~ 10-3 . our approach would have been to obtain a solution without making any assumptions in the mass balance. we find that to eliminate [HAc] and [Ac] to solve fot 10-'-' ~ [W][W] 10' [WI 13. household bleach. From this example we can see that even though one of our first assumptions was not valid.47 x 10 1O.24 x 10-" This assumption is acceptable because the right-hand side of the equation is virtually equal to the left·hand side. which by our criterion of < 5 percent error is just acceptable. Example 4-15 Sodium hypochlorite (NaOCl).5 percent. .47 X 10.4 + 2. in the mass balance we obtain 10-' 10-' ~ ~ [HAc] + [Ac] 10-' + 4.47 X 10. we obtain [WI ~ [Ac-] + [OH-] X 4. and checking tlie assumptions" allowed us to correct the assumptions to obtain a solution with the desired degree of accuracy.t4 4 14.will he present compared to the quantity of HAc. the <Ipproach of "making assumptions.24 x 10-" IS. 2. Checking our new assumptions. ~ 10-' ~ [HAc] (1) Substituting (6) and (1) into [WI. is a commonly used disinfectant. This would have led to a quadratic equation in [H+]." ~ 4.4 ~ 4. which could have been solved as in Example 4-12.110 Acid-Base Chemistry that it was a poor one because we know that HAc is a weak acid so that only a small amount of Ac. The mass balance becomes 11. C uo 12.47 x 10. If the second assumption in the mass balance had not yielded the desired accuracy.47 10.10-')110-'] x 100 ~ 4.4 . So let us now 'make the opposite assumption in the mass balance equation that [HAc] » [Ac-]. obtaining a solution.4 The error of this balance is [00-' + 4.

OCI-. and HOel. NaOCI --> Na+ 4-1). the most effective disinfectant species. determine the concentrations of the "free chlorine" species. K b = [HOCIJ[OW]i[OCI-] = 10-'5 (Table 1. if ionic strength effects are taken into account? Solution The unknowns are H+. [W]. the proton condition becomes [HOCI] 10.O '" W + OH-. What is the concentration of HOCI. Arbitrarily assuming that [OCI-] » becomes Assuming that [HOCI] » [HOCI]. HOCI and OCI-. 2. H. 5.6 x 10-" M pH = 9. Mass balance on eel: 7." = 5. Kw Mass balance on Na+: =0 [W][OW] 10-" CT •N.25 7 Complete dissociation can be assumed in most instances for salts of the alkali and alkaline earth metals. OH-.5 _ [W](lO-3) 10 [W] . 3. Proton condition: [HOCI] + [W] Equations (3) = [OW] to (7) will be used to solve this problem. = [WJ[OCI-j/[HOCI] = = .) 6. = [Na+] = 10. we obtain -T. in a freshiy prepared solution of lO-3 M NaOCI in distilled water. Assumptions 8. IO.+ H20". 4. OCI. Na+. dissociation is completeT so [NaOCI] = O. the mass balance on OCI [OCI-] = 10-3 9.Weak Acid-Weak Base Calculations a. Exceptions are discussed in Chapter S. = [OH-] Substituting (4). K.(10 "([W]) = 10-9. . (8) and (9) in (3) and solving for [W]. Alternatively. HOCI + OW.3 (Assume that NaCCI is completely dissociated. III Neglecting ionic strength effects. Thus five equations are required. a. HOCI '" W + OCI-. Neglecting ionic strength effects. h. the necessary equations are Equilibria + OCI-.T5 (Table 4-1).

the mass balance on Na. except that cKa and cKw have replaced Ka and Kw.5 + 10-3 error =( 1.78 x 10. and the two equilibrium relationships. Check the assumption in the proton condition: 1.6 x 10-10\ error ~ ( 1.52: C. pOH ~4. 17. In this problem the degree of dissociation is very close to that calculated in part (a). For a precise calculation. (6). {HOCI} _ 'YH+[W]Yoc. X The assumption is acceptable. ~ 1O-7 •5YHoc. 'Kw~ IO.Z? I (3-32) 8 It is an approximation because ionic strength affects the degree of dissociation of HOCl.5 5.H /(yH'YoH") ~ [H+][OH-j.75 12. making the iterative calculation unnecessary.78 x 10. To account for ionic strength effects.5 M Check the assumption in the mass balance on OCI: 10.-[OCI-] 'YHOC' [HOCI] 15.5 M .!(YH'Yoc. h. 13. The ionic strength of the solution can be calculated to a good approximations using the ionic concentrations computed in part (a): fL = 0. the mass balance On OCI. 14.5 + 5.5 ~ {W}{OCn .112 IL Acid-Base Chemistry From (4) and (10) Kw I [OH-] ~ [WI ~ 10-"" ~ . The approach to the solution of the equations is identical to that used in part (a).-) ~ [H+][OCI-]![HOC1].003 percent The assumption is acceptable.6 X 10-10 ~ 1. (7). 78 x 10. we need the following five equations: (5).78 X 10. Then 10-"= {W}{OH-} 'YH+[W]'YOH-[OH-] Kw~ ~ 16. .78 X 10-. From (9) and (11) [HOCI] ~ ~ 10-"" ~ 1.78 X 10 5) X 100 ~ 0. These equations are identical to the five equations used in part (a). a new ionic strength should be calculated and a new solution should be obtained. 'K. the proton condition.78 X 10.\ 10 3 -. after the solution to part (b) is obtained.3 [HOCI] + [OCI-] 100 = 1. K ~ 10-7. respectively. 78 percent 10-3 = 1.

since we notice significant effects at 10-2 moles/liter but not at 10-3 moles/liter. OH-.H+.02 X 10-10 L81 x 10-' 9. and again we see that the ionic strength correction had little effect and could have been neglected. Activity coefficients for the ions . I! should be remembered that in each of these situations we have been dealing with equilibria involving only monovalent ions-for ions of higher charge the ionic strength value at which activity coefficient corrections TABLE 4-4 Effect of Ionic Strength of Species Concentrations in 10-3 M NaOCI Solution.46 cKw = 10. M W.6 X 10-10 L78 x 10-' 9. (7).Weak Acid-Weak Base Calculations I' ~ t([W](I)2 ~ ~ 113 + [OH-](-I)2 10 + [OCI-j(-l)' c3 + [Na+](l·)2) 3) t(5. (6). 20.75 .77 OCI-.)'/2 l' ~ 0. OCI-.M Ionic Strength Effects (I' ~ 10-3 molelliter) 10-3 10-3 L81 x 10-' 6. and Na+ can be calculated using the Giintelberg approximation of the DeBye-Huckel law. since the ionic strength at which activity coefficients for neutral molecules deviate significantly from unity is of the order of 0. (15).96 L53 X 10-' (3·36) 19. Accounting for Not Accounting for Ionic Strength Effects Na+.23 4. and (16) as in part (a) yields the values shown in Table 4·4.25 4. Thus we can narrow down even further the range at which ionic strength effects become significant.M OH-. 96 2L Solving equations (5).5(10-3)'/2 I + (10 . It is assumed that the activity coefficient of HOCI is unity. The chlorine solution in Example 4-15 has an ionic strength' of 10-3 molesiliter.M pH pOH 10-3 10-3 L78 x 10-' 5. It can be seen that there is very little change in [HOCI]. Using the activity coefficients and equations (15) and (16) yields cKa = 10-7 . O.6 x 1010-3 M + L 78 x 10-' + IO + 10- 18.M HOCI.13 .1 M.5Z2 ftl12 -log')'= I 1/2 +1' 0.

3·4). However. it is important to master the computation method because the basis of the graphical procedure lies in the compu· tation method. We will also neglect ionic strength effects. At this stage we wish to eliminate such equilibria from consideration.o! (Table 4-1) OH~. GRAPHICAL PROCEDURES FOR EQUILIBRIUM CALCULATIONSpC-pH DIAGRAMS Graphical procedures are available that allow equilibrium calculations to be carried out much more readily than by the computations we have been discussing. and the diagram that results.e Equilibria HCN K = a [W][CN~J .) in the atmosphere above a solution. or for a mixture of the acid and its conjugate base. For this example. Graphical procedures for acid-base systems consist of setting up equilibrium and mass balance equations Oll a double logarithmic plot of -log concentration (pC) and pH. is added to I liter of distilled water at 25°C in a closed system with no atmosphere. The activity coefficient of a trivalent ion in a solution with an ionic strength of 1O~3 M is approximately the same for a monovalent ion in a solution with an ionic strength of 1O~1 M (see Fig. let us first consider the situation when a weak acid is added to water. The approach we use. Note that the free chlorine at pH 9. are valid equally for addition 01 the conjugate base of the weak acid. To develop the graphical procedure. 1. We make the last stipulation because HCN"Q) is volatile and will tend to equilibrate with HCN. The distribution of the species HOCI and OCI~ and their variation with pH is a key factor in disinfection capability because the effectiveness of these two species as a bactericide is markedly different (HOCI being about 80 to 100 times more effective than OCI~ for some organisms). The diagram so produced is examined to determine the pH at which the proton condition (or charge balance) is satisfied. HCN. The equations that describe the system a. (4-21) H+ + Kw = Mass Balance [WJ[OH~] =I X 1O~14 (4-22) C T •eN = [HCN] + [CN~] = 1O~3 (4-23) .. 1O~3 moles. [HCN] H2 0 . All of the species concentrations then can be read off from the graph at this pH value..3 CN~.25 is almost entirely present in the form of OCI~.114 Acid·Base Chemistry become significant falls to about 1O~3..o! W + 1O~9.7.

4-1). . } Line@ 10 [H" I 12LL~--~~----~----~------~------L-----~------J Fig. pK. pH O~_____2T-_____4T-____-T6______~8r-~'~~'~'9~3~1rO______1T2____--.CN = 10-3 M. 4-1. which in logarithmic form is log K" or pOH The slope of this line is dpOH =-1 dpH and when pH = = 14 = log [Wf + log [OH-] pH (4-26) 0. Fig. CT. The second equation plotted on the diagram is the K" expression. pOH = 14.eN = 3 Equation 4-25 is not a function of pH so it plots as a horizontal line at pC = 3 (see line 1. which in logarithmic form is (4-25) -log CT. = 9.eN = pCr.~ System point (£) o 6 '2 1 Line 8 c ~ GJ ~ "I o ~ 8 Line@.3 at 25'C.14 2 Line CT. The pC-pH diagram for cyanide-hydrocyanic acid.d~~~L---~~~~ 4 n " c· .eN ®\ 3~"~L~in~e7CDf1~~~--~--~~------~.Graphical Procedures for Equilibrium Calculations-pC-pH Diagrams 115 Proton Condition (Charge Balance) [W] = [CN-] + [OH-'] (4-24) The first equation we plot on the diagram is the mass balance.

Now let us examine the region of the graph where [H+] » K" or pK. Tackling [CN-] first.3 this region is at pH values above 9. 4-1 as line 3. -log [H+] = O. Since pK. = 9. > pH. » [H+] . Equation 4·28 becomes and (4-29) This is the equation o(a straight horizolltal line at pC = 3. or pH > pK.CN [W] = [CN-] which in logarithmic form is log C UN + log K. Rearranging.concentration lines are common to the graphical solution of all acid-base problems (and many other types of equilibrium problems) so that it would be handy to prepare pC-pH diagrams with these lines already plotted on them. The first step would then be to plot pC T on the diagram. The next lines to be plotted are for [CN-] and [HCN]. we obtain _ [W][CN-] (4-27) KaCT.log [W] = pH so d (-log [WJ) dpH and when pH = 0. 4-21 and 4·23 to eliminate [HCN] and produce K.) (4-28) Now let us examine the region oUhe graph where K.CT. To plot these quantities in the pC-pH diagram.CN [CN ] = ([W] + K. It should be drawn on the diagram in the region of pH > 9. From the slope and intercept we can plot this line on Fig.log [W] = + log [CN-] .. Now. by definition. we can combine Eqs.3. . first we must derive expressions relating each of them to pH and constants.116 Acid·Base Chemistry From this slope and intercept we can plot this line on Fig.3 (line 4). The H+ and OH. . Equation 4-28 becomes K. 4-1 as line 2.

3. > pH.eN . [HCN] p[HCN] = = I s opeWhen pH = K. the socalled "system poin!. and rearranging." In the region around pH 9. We can solve Eqs.eN pCr.3 we must draw a dashed line.eN[W] [W] +K. Since approximations were made to derive both sections of the p[CN-] line. . = 3 With this slope and coordinate we can plot the p[HCN] line in the region pH > 9.Graphical Procedures for Equilibrium Calculations-pC-pH Diagrams 117 or (4-30) The slope is d(p[CN-]) dpH When pH = -I pK. 4-21 and 4-23 to eliminate [CN-] with the result that K .3 (line 7). In the region where [H+] « K" pH > pK" Eq.[HCN]) [HCN] [HCN] In the pH region where [H+] = CT. pH + pC T.eN[W] (4-33) pK. Again we must forego drawing in the p[HCN] lines in the immediate vicinity of pK..eN = 3 (4-32) We can draw a horizontal straight line at pC = 3 for HCN in the pH region below pK. we may not draw either section of the line through pH 9.3 (line 5). this equation becomes = = [HCN] p[HCN] C T. = 9. (line 6).3 p[HCN] = pC TeN .eN . With this slope and coordinate we can plot the [CN-] line in the region pH < 9. d(p[HCN]) + 1 dpH CT.pK. We will return to the exact behavior of the lines in this region after development of the [HCN] line. (4-31) » K" pK. = [WHC T. = 9_3 p[CN-] = pC TeN = 3 . 4-31 becomes.

.eN + 0. . To use the diagram for determining equilibrium concentrations of various species._ From Eq. pH = pK. except in the immediate vicinity of pH = pK. which is located 0. we find CT. when considering Eq. Therefore we have a common point through which both the [HCN] and the [CW] lines must pass. let us examine the position of these two graphs at the point pH = pK. 4-1 now is complete.) and [HCN] = [CN-]. pOH.1. p[HCN] and at pH = = pC. If more accuracy is desired in this region.3). [CN-j. Example 4-16 What is the pH. because of the assumptions that were made_ To complete the graph in Fig_ 4-1. at pH = pK. It is only at points where proton conditions are satisfied that the diagram can be used to obtain equilibrium concentrations. p[CN-] = The diagram in Fig.. 4-27 and 4-31.118 Acid-Base Chemistry We now have lines for [HCN] and [CN-] plotted as a function of pH for the entire pH range. . 0. pC TeN + 0. They can be drawn through this point as a smooth curve that starts at about one pH unit either above or below pK = pK . + 1. 4-34 and 4-35 we can see that at the point (pC = (pC TeN + .3 log units vertically below P~. additional points can be calculated by substituting pH values in Eqs. 4-31 at pH [HCN] or in logarithmic form p[HCN] = = pK.04 pCT. pC TeN + 0. when pH = pK" or when [H+] = K" we obtain [CN-] or = C T •eN 2 p[CN-] = .eN at pH = pK.3 (4-35) From Eqs.3 = (4-34) Similarly. = 9. and [HCNj in a 10-3 M HCN solution at 25°C which is closed to the atmosphere so that no HeN can volatilize? Neglect ionic strength effects.3.CN + 0. The [HCN] and the [CN-] lines both pass through this point. we must examine it (as illustrated in the following examples) to find the pH where the proton condition or charge balance is satisfied. This point can be entered on the diagram.04 pK. eN 2 . 4-27. For example.

·8. The temperature is 25°C.1 + 10-3. NaOCI. [Na+] = Gr.·8. [CN-] = 10-"'. pK. however. and [OW] = 10-. since the error is a small fraction of I percent. NaCN. pOH. 4·1) can be used to determine the pH of 10-3 M solutions of sodium cyanide. This point satisfies our simplified proton condition.4 mole of sodium hypochlorite.B . we find that 10-10. [HOCI]. Checki'ng our assumption in the proton condition. Construct a pC .Graphical Procedures for Equilibrium Calculations-pC-pH Diagrams 119 Solution The proton condition for HCN in H2 0 is We must use the same technique 9f approximation that was employed in the computation procedure to find the point in the diagram where the proton condition is satisfied. 4·2.5 X 10-' = 3.OCI = [HOCI] + [OCI-] = 5 pC r. [H+] = 10-•.9 The assumption is acceptable. 4·1. C r. [HCN].9 = 10-3 . and [Na+] in a 10-3 M NaCN solution. At ili~_~=IO~~~~=I~M~=I~~~1=IO~~ From a mass balance on sodium. and [OCI-] in a solution to which 10.4 = 1. and 5 x 1O-'.2 and we can read off all the other species concentrations at pH 6.1. The same diagram (Fig.Na = 10-3 M.pH diagram for HOCI following the procedure described previously. Fig. flying blind in this instance because we have the diagram to guide us in our selection of assumptions.2 .5. We are not.ocl x 10-' + 10. we can see that [CN-] » [OH-] and [H+] = [CN-]. have been added per liter of solution. Solution I. The temperature is 25°C. is satisfied. which when neglecting [OH-J becomes [H+] = [CN-]. This point occurs at pH = 10. neglect ionic strength effects. we see that [HCN] » [WI and the approximate proton condition [HCN] = [OH-]. Point A occurs at pH = 6. Example 4·17 Find the pH. Solution The proton condition for NaCN in H20 is [HCN] + [W] = [OH-] Examining Fig. neglect ionic strength effects.2: [HCN] = J(J3. HOCI. [CN-]. since 10-'" » 10-. Examining point A in Fig. and of mixtures of HCN and NaCN. 4·1 at point E. Example 4·18 Find the pH. = 7.nlOle of hypochlorous acid. Our assumption that [CW] » [OW] is justified. In the diagram.

[OCI-] = Hi4 M. . At this pH.2 I 8 10el-1 [H+ J 10 {OWl 12 Fig. the charge balance is preferred over the proton condition for finding the point of neutrality because it is easier to write.ocl 1. For situations where an acid and its conjugate base are added. [OH-] = 10--5 . 4-2. 3 = 5. The pC-pH diagram for hypochlorite-hypochlorous acid: Cr.4 M.~ I o g c • 0 c 8 ~ 6 {HOell . 25'C.99 X Hi' M. The charge balance for our mixture is [Na+[ + [H+] = [OH-] + [OCI-] Examining Fig.3 X 10:-' M. [Na+] » [H+] and [OCI-] » [OH-] so that the charge balance simplifies to [Na+] = [OCI-]. we must examine the diagram for the point at which electroneutrality is met.Na = 4 We can draw the [Na+] line in the diagram as a horizontal line at peT = 4. Because we added both an acid and a conjugate base we must account for the cation (Na+) accompanying the conjugate base in our diagram. 2 = 6. and [HOCI] = 10--4 . [Na+] = Hi'M. [H+] = 10--'" = 1. we can see that at point A. a condition that is met at pH 7. To solve for the species present.-T---~r---~r---~· 2 peT. = [Na+] = 10-4 M peT.5 X 10. = 2.120 Acid-Base Chemistry pH 2 6 12 O~----T-----T-----T-~. 4-2.8 [Na+ 4 "" c.7.0 x 10--' M.QCI = 3. A mass balance on Na+ yields CT•N.

which is close to pKb= pKw . at this pH of 5. (3) read off values of . For example.. We have now made all possible combinations of assumptions in the charge balance and could by this process of elimination eventually find the correct set of assumptions.99 xlO. We can expect trouble here.q)] + [OH-]. 4-3 reveals that in the region where the proton condition is satisfied (an approximate pH of 6. [OH-] = 10-' and'IOCI-] = 10-. 4-2. There are instances when assumptions in the proton condition are not possible. a condition that is satisfied at point C in Fig. At this pH of 10.8. 121 I error = = X 10-' + 1. just to the left· hand side of [W] = [NH~. [H+] = 10-5 . If we make the assumptions that [Na+] » [H+] and [OH-] » [OCI-]. However. or the analytical concentration of a base is close to its Kb value or the K.!nnce reduces to [Na+] = [OH-].81 10 .5. The approach to this type of problem is illustrated in the following example.3 = 4.99 10-'+5. 4-2.0 X 10-7 (I X X X 10-7 ) -(I x 10-'+1. then the charge ba. (2) guess the point in the diagram (e.' + 1.7. It also becomes difficult to make simplifying assumptions in the proton condition for both acids and bases when their analytical concentration approaches 10-7 M.·8 so that the assumption of [OH-] » [OCI-] is not acceptable. The proton condition is [W] = [NH~.Graphical Procedures for Equilibrium Calculations-pC-pH Diagrams Checking the charge balance.)] + [OW] Examination of Fig. One of the more common situations encountered is when the analytical concentration of an acid is close to its K. Construction of the pC-pH diagram follows previously described procedures (see Fig. = 4. then the charge balance becomes [H+1 = [OCI-1.pK.4•5 M NH4 CI solution Solution Note that pC T•NH.8 and Na+ = 10-' so that [Na+] » [H+1 and our assumption is not valid.0 I X 10-8 =I X 10-' + 5.q)]) where [W] = [NH".99 X 10 8 X 100 O. = 14 . it is not pOSsible to neglect [OW] or [NH3(aq)1 with respect to each other. 4-3).S percent so that the assumptions are acceptable.. We have several alternatives: (l) use a computational procedure.7 to 7).9. We can prove that these are the only viable set of assumptions to make in the charge balance by using the pC -pH diagram to check the validity of other possible assumptions.g. Example 4-19 Determin~ all species concentrations present in a 10. value of its conjugate acid. we obtain. value or the Kb value of its conjugate base. a condition that is met at point B in Fig. if we assume [H+] » [Na+] and [OCI-] » [OH-].

8 and [NH.+] = 10-'·'. [H+] = 10-6 . and [OH-] = 10. 4-3. Example 4·26 later in this chapter deals with another situation in which approximations in the charge balance are not possible.7 . [OH-] and [NH3(aQ)] from the diagram at several pH values in the critical region and then construct a pH versus P([NH. we find that pH = p([NH. With experience.pH diagram for a 10-'·' M NH.6 •65 . NH3 8 c 0 u c [ NH 3{aq) J 6 INH.". 4·3. 3-27) can be used to convert 25'C equilibrium constants to the values at the desired temparature. The Van't Hoff relationship (Eq. The modification of a 25'C·based pC-pH diagram for temperatures other than 25'C merely entails the use of equilibrium constants for the appropriate temperature in the equilibrium expressions used to construct the diagram.". ____~2_______4T-____~6r-____~8~__~9·r3-Tl0~____~lT2______~14 2 " 'g 0 ~ c· 4 C T .'.122 Acid·Base Chemistry pH o~ pK.] + [OH-]) at pH = 6.8.".2 ~ 8 IH' I 10L-----~----~QL----~-------L----~~----~------~ Fig.CI solution at 25'C. DETERMINATION OF TEMPERATURE AND IONIC STRENGTH EFFECTS ON EQUILIBRIA USING pC-pH DIAGRAMS The pC ·pH diagrams can be used for systems having temperatures other than 25'C and ionic strengths other than zero. [NH. The pC.'. 4. Construction of pC-pH diagrams for ionic strengths other than zero requires the use of activities rather than concentrations in all equilibrium . alternative 2 is acceptable and speedy.I . Alternative 3 is illustrated in Table 4·5 and by the dashed line in Fig. Using this alternative.] + [OW]) line so that the proton condition can be solved exactly in the diagram.] = 10.

. we then (4-37) -log [OH-] = 14.8 10.5 8.. 3-4.6 [NH.0 7. let us construct the pC -pH diagram for a 10-3 M hypochlorous acid solution at 15°C with an ionic strength of 0.CI Solution (See Fig.1 7.0 6.Effect of Temperature and Ionic Strength on Equilibria From pC -ph Diagrams 123 TABLE 4-5 Proton Condition Solution for a 10.6 5 l. 4-3) pH pOH [OH-] p[NH3(aQ)} 9 [NH3(aQ)} ([OH-] 9 + [NH .7 10-7 10. = 0. In this example.0 8.5 7.8 2..75.2 x 10-1 10.83 and 'YOH- = 0.0 3.1 M.1 x 1010.3 6.8 7.8 3.5 8.p'H At p.5 X 10-15 (see Table 4-2). that 'YHC can compute that 'Kw = 7. Mass balance and charge balance (or proton condition) equations are based on concentration and therefore are not corrected for activity.15 and = 0.5 6.. 4-4..14 .8 10.p'H This equation plots as line 2 in Fig.6 x 10.3 5.6 B.2 X 10.6 6. for HOCI at 15'C is 10-7 .1 6.6 7."j) 5. The constant K.CCI = 3 (4-38) Equation 4-38 plots as line 3 in Fig.6 8.2 x 10.7 8.6 5 1.6 -expressions.8 .5 7.2 X 10.6 X 10.6 x x x x x x 1010. 4-4.0 6. equilibrium constants and pH values based on concentration measurements will be denoted as 'K and p'H while the constants and pH values based on activity will be referred to as K and pH.7 3. 5 1". Kw at 15'C is 4. Thus C T •OCI = 10-3 = [HOCI] + [OCI-] and pCr..4 •5 M NH. or temperature.p'H = -logKw + log 'YH+ + log 'YaH' .0 7.8 B.8 6. .2 X 10.1 we find from Fig.l X 102. As an example of these two types of corrections.8 10.6 X 10. defined as p'H = -log [W] (4-36) This is plotted as line I in Fig. "j) 9 p([OH-] + 8. The mass balance equations are defined in terms of concentrations and do not need correction for p.3 7. The line for [OH-] is derived as follows: Kw = {H+}{OH-} = 'YH+[W] 'YOH-[OW] Kw 'YH+ 'Yow 'K w = [W][OW] = -log [OH-] = p'K w . The master variable in the pC-pH diagram is p'H. 4-4.5 6.1 5.7 2.

The lines for [OCI-] and [HOCI] are constructed using the 'K. in Fig.83.1. respectively.p'R diagram for ROCI-OCl. The [OCI-] and [HOCI] lines (lines 4 and 5. 4·39 to obtain ' 15°C. 3·4. When p. 'YH+ = 0.76. The pC. = 0. at 15°C = 10-7 .4." we can substitute these values in Eq. from Fig..= 0. (4·41) . p. ~ 0. equation and therefore will reflect the modification of this equation to account for temperature and ionic strength effects on K. = 10-7 .-[ OCI-] 'YHoel[HOCI] Ka'YHOCI '}'H+'YOCI- (4·39) 'K. Since K. CT.1.124 Acid-Base Chemistry p'H [OWl 10 Fig. and 'YHoel = I. . 4·4) can then be derived from the equations cKa [H+] + 'K. {H+}{OCI-} {HOCI} [H+][OCI-] [HOCI] 'YH+[H+]'Yoe.QCI (4·40) and [HOCI] = C T•oel [H+] [H+] + 'K. 4·4. 'Yoe. K.

S04 :0= HS04. [HA-j. [OH-]) when 10-' moles of the weak acid H. H. Consider.A (pK.. The equilibria are H.Aj. for example. The remaining equation necessary to describe the system is either the proton condition or the charge balance.. The procedure is somewhat more complex because we have additional species to consider as well as additional equilibrium statements.A. by combining the mass balance. The pC-pH diagram in Fig. we can construct a pC-pH diagram in a similar fashion to that used for a monoprotic acid. Kw = [W][OH-j = 10-14 (4-42) K. Eq. sulfuric acid. CT. = 8) are added to I liter of water at 25° a weak acid. pC = -log C T •OC .Conjugate Base Equilibrium Calculations 125 The system point is (pCH = p'K. [HA-J. = 10-' H. pC = -log C T •OC . and [A'-j.1 = 4 and pK. [WJ..+ H+.Multiprotic Acid. and equilibrium constants. . Eqs..4 10-' (4-43) (4-44) The mass balance on species containing A is (4-45) and is plotted in Fig. To illustrate the procedure.S04 is classified as a strong acid while HS04 . [A'-j.~ [W][HA-j 10.. 4-4 can now be used to obtain concentrations as previously demonstrated. 4-45.--. we will determine the pH and concentrations of all species present ([H..+ H+.AJ. bisulfate ion K. 4. H.. and the two equilibrium relationships. For the general case of a multiprotic acid added to water.1 == 10'.Aj as a function of [H+j.9. . we obtain [H. sulfate ion K. 4-5 as a horizontal straight line at pCT. First for H. MULTIPROTIC ACID-CONJUGATE BASE EQUILIBRIUM CALCULATIONS A multiprotic acid can donate more than one proton. We will next develop lines for each of the A-containing species: [H.A.[H.A = 2. 4-43 and 4-44.Aj -'--. We will neglect ionic strength effects.::.1 . no correction for ionic strength is necessary.)' instead of (pH = pK.O :0= H+ + OH-. Since these equations are based on concentration rather than act~vity.) in the absence of corrections for ionic strength..S04' which can donate two protons. HS04 -:o= SO/.

.![W]) ~ (K". pK". .A. 4-5 as line I.1 »K"" or pH < pK'. 4·46 becomes CT.47) O~----~--~r-----r-----r-----T-----T---~ 2 4 6 8 10 12 14 ..A (I + (K".A] line in the pC-pH diagram. 4-5... 10 Fig..A = [H. K.126 Acid-Base Chemistry or [H. = 8.1 = 4.A] = 2 This is plotted in Fig.pK.l < pK".A] = CT.A] or pCT.. 4-46 at various pH values so that we can plot an [H. so that Eq. pH 10-' (4.A = p[H.pH diagram fora 1O-'M solulionof H. The pC. In the region where [H+] »K.t[Wl')) (4-46) We must now examine the behavior of Eq.

A] versus pH.A + 2 log [H+] . [H+]' or in logarithmic form log [H.A] = CT.) and pH 8 (= pK.A] = pCT.. .)) .log K". .A + 2pH . This line is plolted as line 2 in Fig. This line is plolted in Fig. and [HA-] = [H. » [H+] or pK".2' Eq. < pH.3 (4-50) Thus at pH = pK"" p[H.A])ld pH = + 1.log K".1ogarithmic form log [H.A + log [H+] -log K". > [H+] > K'. < pH < pK. To complete the curve for p[H. . . or p[H. this is the equation of a straight line with a slope of +2 that passes through the point (pH = pK"" p[H. we can write [H.A + pH . dashed lines are plolted. < pK".A] = pCT.A] .pK".A] = pC T the first system point.pK".). 4-5 between pH 4 (= pK". Eq.A] plots at a point 0.A] = pCT. In the region K".).). we must make adjustments here. and pK". (4-48) Since d(p[H..A 4-46 becomes [W] K '" or in.. and pH = pK".A])/d pH = +2. (4-49) Since d(p[H.3 units below the intersection of lines I and 2. 4-43 we can show that when pH = pK"" [H+] = K".A] = pCT.2' or pK".K".A (I/K". » K".. at pH values in the region of pK". p[H.pK".A + pK".Multiprotic Acid-Conjugate Base Equilibrium Calculations 127 In the region K". In the vicinity of pH = pK".A] = log CT. we must determine its behavior in the pH regions near pK". since our assumptions break down in these regions.pK". [H2A] = CT. . slope of + I that passes through the point (pH = pK"" p[H. 4-46 becomes [HA]=C T.A 2 or in logarithmic form.. . or p[H. 4-5 as line 3 in the region pH > pK". this is the equation of a straight line with a .A + 0.. Dashed lines are again plolted in the region where pH approaches pK". From Eq. Since.A] = log CT. [A'-] is negligible.

pC T. 2. 4-46 exact! y [H. 4-5.A] value by solving Eq.l' pCT. = 10-8 .A] = log CT.1 = 4 and pKa . The diprotic acid diagram has two system points.A) and (pK . we can use Fig.A] plots at a point 0.A to 1 liter of distilled water. To find the desired pH. This pC-pH diagram differs in two major ways from that for a monoprotic acid: 1.A] = CT'A( 1 + (10 '/10 8)1+(10 12/10 = 1~) CT'A( 2 /IO+~ = CT.128 Acid-Base Chemistry When [H+] = K". The position of the [HA-] and [A'-] lines can be determined in a similar fashion by making approximations in the following equations developed by substituting the equilibrium expressions in the mass balance and solving for [HA-] and [A'-J.A p[H. (pK'. Example 4-20 Find the pH of the 25°C solution resulting from the addition of (J) 10-' moles of H.'. 4-5. respectively. we can determine the p[H..A] = 6. in terms of C TA [H+] and . \ . The use of the diagram is illustrated in the following example.3 units below the intersection of lines 2 and 3 in Fig. These lines plot as shown in Fig. constants.2 = 8. Here pK a.A] and [A -] have regions where the slopes (d pCld pH) are +2 and -2.3 + log (5 x 10-') Thus at pH 8 = pK"" p[H. (4-51) and (4-52) It would be a useful exercise for the student to construct lines for pH versus p[HA-] and p[A'-] using these equations and appropriate assumptions. 4-5 in conjunction with the proton condition for H2A..A to 1 liter of distilled water and (2) 10-' moles of Na. Solution 1.A(5 x 10-') log [H.A)' The lines for [H. respectively.

Checking the proton condition.05." [H.GOOH which we will represent as H2Su.' . 2.05. [OH-] .Multiprotic Acid-Conjugate Base Equilibrium Calculations [WI ~ 129 [HA -] + 2[A'-] + [OH-] (4-53) Examining the diagram. except that the same simplifying assumptions cannot be made in the general equation obtained by combining the mass balance and equilibrium equations for pKa.Su showing variations of [H+].95 • Checking the assumptions in the proton condition.A). (4-54) Examining the diagram.05 + 10-8 + 10-10. and that 2[Su2+] and [OH-] are negligible compared to [HSu-]. we see that at pH 10.95 The equation is valid to within a fraction of 1 percent. 2[A'-] and [OH-] are negligible compared to [HA-]_ Therefore.A] and [H+] are negligible in comparison to [HA-]." [OH-] ~ 10-10 . For H2Su the proton condition is [W] ~ [HSu-] + 2[Su'-] + [OH-] Examining the diagram.Su]. [W] ~ 10-10 . 1O~3. Note that because of the close proximity of the pKa values the lines for [H 2Su] and [Su 2-] have no straight line portions between pKa.2' The approach to obt?ining the position of these lines in the diagram is similar to that shown previously for the acid H2A.A] ~ 10-. [H. and Su2. At this pH.o5 = 10-3. and [Su'-] with pH.l = 4. The structure of succinic acid (pKa. see Eq. . [HSu-]. Example 4-21 The dibasic acid succinic acid is an important metabolic intermediate formed in plant and animal cells. It is written as.GOOH dH. we see that there is much less than 5 percent eITor and therefore our assumptions are acceptable. [HA-] ~ 10-'. and [A'-] ~ 10-'. 4-5 together with the proton condition for Na2A to find the pH.l and pKa. we see that at pH 3.Su] ~ 10-'. At this pH. [W] ~ 10-3 . HSu-. [A'-] ~ 10-'. condition is satisfied only at pH 3. we can see that at pH 3. 10.2 Solution Figure 4-6 is a pC-pH diagram for H. [OH] ~ 10-'. [H+] ~ [HSu-].2 (e.2. [H.2. We can use Fig.·05. Thus the protol).. Therefore.2 and pK a . the proton condition is satisfied only at pH 3. .2 = 5. [HA-] ~ [OH-] . Find the concentrations of all species in a molar solution of succinic acid (H2Su).g .l < pH < pK a . 4-46 for the general acid H. and that 2[H. and [OH-] ~ 10-10 . 05 . the approximate proton condition [W] ~ [HA-] is satisfied_ At this pH. The approach to obtaining a solution for concentrations of H2Su. At this pH. .in this region is to substitute values of H+ into the general equation for each of these species and to solve for the concentration at each pH.A] ~ 10-10 . the proton condition is satisfied only at pH 10. [H. [HA-] ~ 10-3 .5 at 25'C) is GH.

8 The assumptions are acceptable. we obtain 10-3 . the pC-pH diagram for phosphoric acid.. ~ 10-'.-] = (4-55) 10-.-] [H. 4-7 for C uo.PO. Equilibria Kw = 10-14 = [H+][OH-] [W][H.ic acids to multiprotic acids. neglecting ionic strength effects. Applicable equations are.5 . 4-6. ~ 4.. The advantage of the graphical procedure over computational method becomes gre'ater and greater as the number of equilibria increases. As an example. pK.10 .1 pK.... pK.2 and pK. ~ 7..PO. ~ 5. (pK.. [HSu-] = 10-3. .3 at 25'C).3 • Checking our assumptions in the proton condition. 2 + 2 X 10. and [Su2-] = 10-5 . The pC-pH diagram for 10-' M succinic acid (H.PO" is shown in Fig.' [H.1.130 Acid-Base Chemistry pH Fig.2. H.3 + 10..8u). ~ 12.PO.1 (4-56) (4-57) = 10-7..1 ~ 2..2 = 10-3 .] K = [W][HPO.2.5 at 25'C.-] '. The pC -pH diagram for a triprotic acid can be developed by extending the procedure used to plot the diagrams for monoprotic and diprot.

-]. [HPOl-1.K".pH diagram for a 10-' M phosphate solution.W1') + (K".PO.) + 1 + (K.K.2 I 24 Fig.) + (4·61) (4 62) .K".I. pK".PO. The pC. Species CT..![W]) + (K"."![WP) (4·60) [H. and [PO.) + ([W1/K".PQ. 4·7.C ( 1 \ .K".po. [H+1.I.( ([W1/K".PO.PO.PO'( 1 + (K".K.s-l (4·59) The equilibria and mass balance can be combined and solved for [H. = 12.Multiprotic Acid.W]) + (K".'-l = CT.PO.1.PO..T. pK"..]. ([W1~/K"./[W1i) [PO.3 at 25'C..( ([W1'IK". and constants to yield [H.l + ([W1/K".. [H.K"..l + [H.. = 7.s-l in terms of CT.PO..K. ([W1'/K.2. pK"..) + 1) (4·63) pH 2 4 6 8 '-' 10 0- '~ c c' 12 E ~ 8 ~ .K"./[W1'i) [HPO '-1 .) + 1 + fK".Conjugate Base Equilibrium Calculations 131 (4·58) Mass Balance on PO.-l = CT'PQ. -1 + [HPOl~l + [PO. . = 10-' = [H.PO. = 2.l'= CT. .

The pC -pH diagrams have so far been used only for solutions containing one acid and its conjugate base(s). The use of Fig. The system points are (pK.and H+ in a 10-3 M Na2HP04 solution. 10-9 .PO.3 moles of ammonium acetate. the slope of the [H.'-] = 10-6 .-] + 2[H. NH4Ac.Po) and (pK "" pC T. Checking the proton condition.·9 M. oJ.·9 M.] versus pH line is 0 when pH < pK.J and 10-' moles HAc. [Na+] = 2 X 10-' M. and these species -equilibrate as follows: .2 X X 1. C T.26 _ (1.32 10-' 10-'») X 10-' -1.1 = 10-4 .. [OH-] = 10-. per liter of water.Na = [Na+] = 2C T .PO. and [PO.. [H'] = 10-9 ...PO. OH. acetic acid. and [PO. Solution Using Fig.PO. (pK '. +2 when pK." pC T. 1 + 10-4·9 + 2 X 10. [H+] + [H. At this pH.'-] is much less than [OW].PO. Example 4-22 Determine the concentration of each phosphate species.] = [OW] + [POlo] (4-65) we see that at pH 9. [HPOl-] 10-' M.PO. < pH < pK".1 < pH < pK.32 error = X X 10-' = 1. and +3 when pH > pK".9 percent The assumption is just acceptable.] = 10-1'-' M.. [H.11 . per liter of -distilled water.1 M. [H.-] = [OH-]. 9 + 10-6.. 4·7./ and Ac-.. the mass balance on Na+. and that [H'] and 2[H..PO.) Solution NH4Ac dissociates to NH.).132 Acid·Base Chemistry These equations can be examined for their behavior with respect to pH in various regions.1.OH (NH..] are much less than [H. 4-7 is illustrated in the following example...1' +1 when pK.PO..1' pCT.PO. (Note that this solution is identical to that which would be obtained by adding 10-' moles of NH.-] = 10-.26 1. For example. These'diagrams are equally applicable to mixtures of acids as is shown by the following example.. [H. M.Po).26 X 10 ' 100 4. P04 = 2 X 10-3 (4·64) and the proton condition. Example 4-23 Determine the pH of a solution prepared by adding 10.

+] K .)] and that [HAc] » [H+] and [NH.7. we see that at pH 7.Multiprotic Acid-Conjugate Base Equilibrium Calculations 133 K = 10 -. [HAc] =[NH~. .. [NH4tj '~ ~ " o· ~ 4 0 ~ 0 6 [NH.)] . Because C TNH3 = CT.2 I m 10 Fig. the lines are superimposed. some of ..Ac solution at 25°C.i 8 0 0 ..7 = [W][Ac-] [HAc] Mass-Balances We can plot the pC-pH diagrams for these two acid-conjugate base pairs on the same diagram (Fig. The pC-pH diagram for a 1O-'M NH.3..Ac is the same for each pair. 4·8. [NH. HAc = 4. 4·8). pH O~----~----~----~r-----~-----T----~r---~ 2 4 6 8 10 12 14 2 [Ac-]. = [H+][NH~.] » [OH-r so that the proton condition is satisfied. . pK a . pK a . The proton condition is Examining the diagram. = 10 -'.NH4+ = 9..

Graphical presentation of a values as a function of pH-the so-called distribution diagrams---are helpful in graphical solutions of equilibrium problems. For example. Eqs. A table of a versus pH is given in Appendix 1. = [H+][OCl-]/[HOCI] (= K. 4-28 and 4-31 for the HCN-CNsystem. K . of 7. in Eqs. 4-69 and 4-70. (4-66) (4-67) = 10-7. we can introduce the concept of an ionization fraction (or a value). 4-51 and 4-52 for the diprotic acid H.q .10. IONIZATION FRACTIONS AND DISTRIBUTION DIAGRAMS On several occasions in the previous section we developed equations that express the amount of an acid or its conjugate base as a fraction of the total analytical concentration (e. that the equations were increasing in complexity as the number of protons in the acid increased.oe. obtain [HOCl] Cr. (4-68) Solving for [HOCl]lCToe . which has a pK. multiplication of the analytical concentration by the appropriate ionization fraction at a particular pH value will directly produce the concentration of the species at that pH. 4-67 in 4-66 to eliminate [OCI-] yields CT = [HOCI] + [W] [HOCl] . The reader should also have noted.) 4. we .oe. Tables of a values as ex function of pH may be used to aid computations.5 = [W][OCI-] [HOCl] Substituting Eq. consider HOCI. to develop pC-pH diagrams and noted that there were pH regions (close to the pK values) where our assumptions broke down. 4-46. = [HOCl] + [OCI-] . Neglect ionic strength effects. that is. To simplify the situation..134 Acid-Base Chemistry fl ~ \ I. and similarly for OCI-. in addition to its simplicity of expression. We used these equations.oe. is that it is independent of the analytical concentration.5 at 25°C. with simplifying assumptions. The ionization fraction can be determined from the mass balance and equilibrium equations.-)) should be used in place of K. 4-60 to 4-63. [OCI-] CT. = ao (4-69) = [H+] + K. (4-70) The subscript on a refers to the number of protons that the species has released. [W] [H+] + K./(YH'Yoe. C Toe .A and Eqs. the fraction of CT. Eqs. K. If ionic strength effects are important.oe. for the phosphoric acid system). 'K. probably with some trepidation. Therefore. which is [HOCl]. K. . The major advantage of the ionization fraction..

~ [HOCI] CT.Ionization Fractions and Distribution Diagrams 135 Using Eqs.1 ~ 7. 0 0 0 4 6 pKa. 4-10.2 (b) 8 10 12 pKa . P04 0.S and H. at 25°C.1 4 6 pH pKa . Distribution diagrams for the multiprotic acids. and (b) H.1 =2.PO.5 10 12 14 25'C. . 0 0 2 4 pH pK a = 7.0 " .OCI 1. such curves can be obtained using either the table or the general equations for IX in Appendix I. 0. (.S " " 1.0 CT.2 = 7. 410. ~ [H.5 'fl ~ ... 4-9).and IX. \ .0 = [H3 P0 4 CT. 4-69 and 4-70. H. Distribution diagrams for (a) H.. .S] 0:-1 = [HS-J 1.1 8 10 pH (a) 12 14 pKa. . 0 oS 1. 0 0 0 2 pKa. P04 1 C(2 = [HP042 -] C T.3 14 ~ 12. or alternatively the table of IX versus pH in Appendix I. we can determine lX. 0. 4-9.3 Fig.5 .. Distribution diagram for HOC1-'OC1.2 = 14 16 18 0'0 " ~ oS 1.S C" 0:2 = [s2-] CT.5 g ~ .s. are shown in Fig. at various pH values and plot them in a distribution diagram as IX versus pH (Fig. 'fl ~ ~. 1.PO.

their dissociation in aqueous solution is assumed to be complete.11. and treatment schemes involve reactions between acids and bases.ow we have concerned ourselves with situations in which acids.[N +J _ number of moles a .Na - . and salts are added to each other. acid-base titrations such as those used for the determination of acidity and alkalinity. Many important analytical methods. MIXTURES OF ACIDS AND BASES-pH CALCULATION Until . [Na+J + [H+J = [CI-J + [OH-J .1 moleslliter xvolumeadded I liter +volumeadded Mass Balances on volume Charge Balance 4. have been added singly to distilled water. Strong Acid-Strong Base Mixtures The calculation of solution pH after the addition of a strong acid to a solution containing a strong base. Solution Because Hel is a strong acid and NaOH is a strong base. What is the pH after addition of (I) 5 ml. the dissolution of minerals by ground waters bearing CO" and so on. make simplifying assumptions. conjugate bases. for example. is very similar to the calculations used in Section 4-5 for determining pH in solutions of strong acid or strong base. 4.CI = [Cl-J = number of moles total volume C T. We must now address situations in which we have to predict the nature and extent of composition changes that occur when acids. and then check the assumptions.1. natural processes. the addition of metal ion coagulants.11.1 M NaOH? The solution temperature is 25°C. or vice versa. (2) 10 ml and (3) 20 ml 0. 3 • CT. or lime for softening or water stabilization in water treatment. The equations needed to solve the problem are Equilibrium L Kw = 10-1< = [W][OH-J IUter x 10 -3 molesfliter I liter +volumeadded 0. The following example will serve as an illustration. Example 4-24 A 0. the production of acid rain. and salts of conjugate bases.and Na+ 2. The general approach is to write equations that describe the solution after the acid and base are mixed. Neglect ionic strength effects.136 Acid-Base Chemistry 4. the neutralization of acid wastes by in-plant base addition or by discharge and dilution in surface waters. find the solution to the equations.1 M NaOH solution is added to 1 liter of 10-3 M HCl solution.

005 +[W] ~ 10-3 - 5 X 10-' 10-' 1.005 ~ 5 x 1.Mixtures of Acids and Bases-pH Calculations 137 a.0.10-3 1. we would expect the solution to be basic with [OH-] » [H+]. Neglecting [OH-] (~ IO.0l ~ 10.005 At this pH.3 10-"" and the charge balance is satisfied to well within Substituting (2) and (3) into (4) and using a volume of NaOH added of 0.IXO. (O.H + . we can make a simplifying assumption. ~ 5xlO-'M pH ~3.H [W] [H+j ~ 1O~3 IO.1)(0. b.02 liter / (0. [OH-] 5 percent error. which is a quadratic in [H+]. c. Thus [OW] ~ 2 x 10.005) 1.IO.02 + + 1. 1.005 liter x 10-' molelliter ~ 5 x 10-' moles) we would expect the solution to be acid so that [H+] » [OH-].IXO. we find that (4) and using a volume of NaOH added of 0.005 liter (5 mI). Substituting (2) and (3) in (20 ml).02 Since the amount of strong base added exceeds the amount of acid present.80 x 10-' where pOH pH ~3.02) [H+] ~ [OW] 10. The volume added is 0. we therefore have a salt solution with a pH of 7. and (3) in (4). NaOH + Hel ~ Noel + H2 0).99 .3 . At this point we have added a quantity of base equal to the amount of acid present (the stoichiometric amount to satisfy the reaction.005 This equation.01 liter (10 ml).H /[H+]) in (5). However.02 9.OI) + [W] ~ [OH-] + 10LOt 1. (2). we obtain < (0. could be solved exactly.01 or 3 and from equation (I) pH ~ 7.005 or [H+]'. we obtain [H+]~5XIO-' 1..3 1. Since the amount of strong acid present (l liter X 10-3 mole/liter = 10-3 moles) exceeds the amount of base added (0. Substituting (I).

1 0.9 ml acid to lower the pH from the initial value of approximately 13 to pH 10. ~ ~ [Na+J ~ 00-' MXl liter)!(l liter ~ + V). (2).10 .1.SO.75 ~ 1.1OIyH+ ~ 10-1010.4 Assume that 1. .83 ~ 1.'-J + [OH-J. C T•SO. 3. It must be partially neutralized by the addition of H2 S0 4 prior to discharge.20 x 10.~ 10.need not be included in the charge balance because at pH 10 its concentration is negligible. The required final pH is 10. Solution Equations I.33 x 10.1 ml would lower the pH by 3 units to pH 7. {H+} ~ 10. 2.138 Acid·Base Chemistry Example 4-25 Spent regenerant solution from an ion exchange process contains 10.1 .33 2. What volume of aIM H2 S0 4 solution must be added per liter of waste? The temperature is 25°C and the ionic strength is approximately 0. CT•N. [OH-J ~ 1O.'-J 0 MXV)IO liter 10.1.4 (activity coefficients from Fig. We can perform the calculation shown in Example 4-25 many times over and from the data construct a curve of pH versus acid added.4 10. + V).2 x 10 then -10 «0 +V) 10. If ionic strength effects had not been taken into account. [Na+J 4.1 = Vacfd 50 rol We can see then that it took 49.0 is satisfied and the pH =7 t when V"" x 2 ~ 1000 ml x 0. [SO.20 x 10.0499 liter 49.) Substituting from 0).1 moles of NaOH per liter. the same answer would have been obtained for this problem. --> Na. 10-" ~ {W}{OH-}.4 IYoH.000lV V ~ X a ~ 0. + [WJ ~ 2[SO.4 0 + V) 0. but a further increment of only 0. and (3) in (4). (Note HS04.~ 0 10 z: V) + 1.0999 ~ ~ 0.9 ml We should note that the stoichiometric statement 2NaOH + H.S04 + 2H.33 x 10.2V .{OH-} ~ 10-'. we obtain oO~\) + 1. 3·4). [WJ ~ 1O.

. However.---.-. 4. the carbonate system. 4·11. as in Example 4·25. At first we will examine some simple situations . This curve is known .2 20 0.. Although we will take up the subject of buffers in more detail in Section 4·12.----. A consideration of such systems will lead us to an understanding of pH buffers and eventually to one of the important pH buffering systems in natural water.-----.-. In Fig... Titration of I liter of 0. The solution is thus poorly buffered for pH. 12 10 8 / ' Equivalence point pH - \ 7' ~ ~--------------- 64- - 2 0 I 10 ~ l 30 0.----.---..11. the importance of these types of systems far outweighs that of the strong acid-strong base and Strong Acid-Weak Base Mixtures The situation with these mixtures becomes slightly more complicated than for strong acid.-. is plotted.Mixtures of Acids and Bases-pH Calculations 139 expressed either as ml added or as the equivalent fraction. it is worthwhile to note that a strong acid alone would be a poor choice of neutralizing agent for a waste which is primarily a strong base. Weak Acid-Strong Ba. It is apparent that in the region of the equivalence point. process control to any desired pH in this region would be very difficult...strong base mixtures because we cannot always assume complete dissociation of the weak acid or weak base.4 I 40 0. . The solution. equivalent fraction Fig.. or the point of stoichiometric addition. the number of equivalents of H+ added per mole of base present.2. .. is poor at resisting changes in pH for incremental additions of acid.---.8 I 50 1. Most natural waters indeed behave like mixtures of weak acids and the salts of strong bases.6 0. Because of the wide fluctuation of pH for small additions of acid near the equivalence point. f. the pH of a strong base solution to which a strong acid is being added (or vice versa) is very sensitive to the amount of acid added. which is a mixture of a strong base and its salt. as ci titratJoir curve. 4·" the titration curve for addition of H2 S04 to the spent regenerant solution. that is.1 M NaOH with I M H 2 S0 4 at 25°C.0 mt of 1M H2 S04 f. 14..

CT. What is the solution pH after 0. We will use two approaches: the first using pCpH diagrams and the second a trial-and-error method.01 liters of 0. = [Na+] = (0. Example 4-26 A solution contains 10-3 moles of acetic acid. K. 1. = = = = [W][Ac-]i[HAc]. We must resort to finding values of ([Na+J + [H+]) from the diagram in the region around pH 4_3 and then plotting -log ([Na+] + [WD versus pH. The solution for the charge balance is obtained by inspection of the pC-pH diagram. Solution Since the volume of base added per liter is very small. CT. values would both change when NaOH is added. and 0.1 M NaOH and 0. 4. but a different pC -pH diagram would have to be constructed after each addition. and ml added versus pH) and show the relationship between the titration curve and the pC-pH diagram.3. . HAc. .5 x 10-+ and [OH-] « [Ac-]. .0025 liter: From (2) [Na+] = O. and (4) to plot a pC-pH diagram for the acetic acidacetate system (CT. 9 The general equations are as follows. The graphical procedure could still be used. [W][OH-].4 M.Ac = 10-3 M) (Fig.3. neglect ionic strength effeds.1 V)/(1 liter + V). 0. The temperature is 25°C. it is reasonable to assume that its addition causes no volume change.IV = 2. Ii added versus pH.IV M. We then can determine the pH where -log ([Na+] + [H+D = -log [Ac-].5 x 10-+ + [W] = [OH-] + [Ac-] Now assuming [H+] «2. Kw 5. equation (5). 3. = number of moles added/sample volume = 10-4. C TN. we must first determine Na+ from equation (2) and then substitute this value in the charge balcmce. 6 .140 Acid-Base Chemistry illustrated by examples. C Uo and C TN.005.Ao = [HAc] + [Ac-] = (10-')/(1 liter + V). The approximate solution of the charge balance does not work because [Na+) and [H+] are the same order of magnitude. (3). [Na+] + [W] = [OH-] + [Ac-]. .0025. 2.< 10-" [Na+] = V(1)(O. the charge balance becomes [Ac-] = 2. and C TN. Checking our assumption. To determine the solution pH after each NaOH addition. 4-12). The charge balance solution in the pC-pH diagram can be found at pH 4.5 x 10-+ M The charge balance becomes 2. which is the solution 'If the volume change had not been neglected.I)/1 liter = O. For V = 0. We use equations (I). we find that [Na+1 = 10-3 .5 x 10. which is not much greater than [H+] = 10-4.03 liter of 1M NaOH have been added per liter? From these data sketch a titration curve (equivalent fraction." = [HAc] + [Ac-] = 10-3 M.

The pC-pH diagram and titration curve for 10.1) ~ 5 x 10-' M .n" 0. and at this pH our second assumption that [OH-] « [Ac-] 'is acceptable.M HAc-Ac. From the diagram see that this ·occurs at pH = 4. .7.5 Infl"t. /' + [Ac-] If we assume that [H+] « 5 x 10-' and [OH-] « [Ac-].5 I I I : I 15 I 20 r o • z 10 '" IV po. 4·12. tlie charge balance ~ 5 x 10-' + [W] [OH-j becomes [Ac-] = 5 x 10-4. For V ~ 0.'I +[H'1I1 I I I [Ac-I (Na+] 4 6 I I I I 1 8 I 25°C.005 liter: From (2) we [Na+] The charge balance becomes ~ (0. Our assumptions are O~--~----~-r--~--~~--~~--~----~ 2 4 6 8 10 12 14 2 (HAc] ([N.005)(0.4. a solution that is met at pH valid at this pH. pH = 4.Mixtures of Acids and Bd~es-pH Calculations 141 to the charge balance.on)11 I 5 oL----J__ 2 I I ~~~L--L ____~_____L_____L____~o 8 10 12 3 4 6 14 Fig.0 1 1.

01)(0. Assuming [HAcl » [H+].1)(0. f = (0.S where f = number of equivalents NaCH added moles of (HAc + Ac ) number of equivalents NaCH addedlliter CT. As we shall see later.002Sliter.010. For V ~ 0.OOSliter.8 For V ~ 0. equation (5). Any addition of base corresponding to f < 0.added ~ the number of equivalents of HAc initially present.03 liter of I M NaOH. pH ~4.5 will produce a solution pH between that of the original HAc solution and the pKa. pH ~ 12. and all of any strong acid added to such a mixture can be assumed to react with Ac-. the number of equivalents of OH.+ H. From the pC . pH ~ pK . the following important observations can be made.2S.3 ~ CT.4 ForV = O. all of these observations are of great importance to the subject of pH buffers.01)11 X 10-3 = 1.03)(1) ~ 3 x 10-' The charge balance.Ac moleslliter of NaAc.03 liter. we obtain [HAc] + [WI ~ [OW] which is the proton condition for a solution containing CT.1) ~ 10. When f ~ O. By comparing these two plots.pH diagram the charge balance is satisfied at pH 12.S. [Na+] ~ (0.O or Ac. f ~ (1)(0. . f ~ (0. Note that this occurs at a pH value equal to the pK a of the acid. In other words all of the NaOH added to such a mixture can be assumed to react with HAc. pH ~4.010 liter.7 ForV ~ 0. together with the pC-pH diagram. f = (O.SO. I.0. For V ~ 0. the influence of [H+1 and [OH-} on pH changes caused by the addition of base are negligible.Ac The titration curve was plotted in Fig. becomes 3 x 10-2 If we assume that [H+] + [WI ~ [OH-] + [Ac-] « 3 x 10-' and [OH-] » [Ac-I.--> Ac. summarizing: For V ~ 0. that is. we find that the charge balance is satisfied at pH 7.142 Acid-Base Chemistry The addition of S x 10-' M NaOH has produced S x 10-' M NaAc so that the solution fs an equimolar mixture of undissociated HAc and Ac-." Substituting [HAc] + [Ac-] for [Na+] in the charge balance.002S)/1 X 10-3 ~0. 4·12.8 in the pC-pH diagram where [HAc] ~ [OH-]. the charge balance becomes [OH-] ~ 3 x 10-'.03)11 X 10-3 ~ 30. Finally t note that because Qur assumptions were acceptable. HAc + OH. pH =7.. We now have sufficient data to sketch the titration curve. from (2) [Na+] ~ (0.OO5)!f x 1O-3 =0.S.1)(0.I)(O.+ H+ --7 HAc so that for strong base addition the [Ac-1 concentration is equal to the analytical concentration of strong base added.

3. we find [NH4+] ~ [OH-] at pH ~ 10.3 M NaAc solution. Roughly sketching the pC-pH diagram (Fig. It is useful to compare the strong acid. When f ~ 1. After 1 equivalent fraction of strong acid has been added. Solution pH Estimate Before HCI addition.4 liter of 10-3 M HCI and (2) 0.3 M NH 4CI solution with that for a 10-3 M NH3(aq) solution to which 10-3 mole HClIliter have been added to verify this statement.strong base in Fig.0.1O Again using the pC-pH diagram (Fig. the pH is that of a 10. we will have a 10. Note that the strong acid.5 before HCI is added. This can either be read from a pC·pH diagram or calculated as in Example 4-14. This pH is the equivalence point. 4-13) to solve for the CI approximate pH. Here the resistance of·the solution to pH change on the addition of strong base (or strong acid) is small-the solution is very poorly buffered. At this pH (= pK a) the change of pH for a given addition of strong bo'se is small-the solution is very well buffered.5. we obtain PRL Proton Condition [NH/] + [H+] = [OH-] Assuming [NH/] » [H+]. At this pH value the curve has an inflection point in the opposite direction to that at f = 0. Example 4-27 What is the pH of a 10-3 M NH"".8 liter of 1O~3 M HCI? Estimate the pH before attempting to calculate it exactly.Mixtures of Acids and Bases-pH Calculations 2.3 M NH 4 solution. 411 with the curve for a weak acid. solution following the addition of (1) 0. The pH increases very slowly as it approaches the pH of the solution being added. 4.strong base system has no good pH region of buffering corre· sponding to that of the weak acid·strong base system. 143 At f ::'0 0. The pKa of NH4+ at 25°C is 9.strong base titration curve in Fig. 4-13).5 the titration curve has an inflection point. . 4·12. Neglect ionic strength effects. 5. this will be the pH of a 1O~3 M NH3 [aq) solution. neglecting dilution. we can rapidly estimate the pH. 3. We will now examine a strong acid-weak base system using a trialand-error method of solution. we find 10 The reader should compare the proton condition for a 10.

)] =[H+] at pH '" 6. 2.8 X 10-') = 0 8 (10 ') • and the pH will be between 9. Cr. A sketch of the pC-pH diagram for 10 -.)] + [OH-] = [W] Assuming that [NH""J » [OH-] Find [NH. so that the pH will be between the initial pH and pH 9.144 Acid.4 liter of 10-' M Hel have been added.4 X 10-' =04 10 ' ..O Proton condition [NH~. PRL NH..3.. i = = number of moles addedltotal volume (10-' moleslliter)(V)/(l liter + V liter). The pH will now be calcuiated exactly.1.3 and 6.+. H.. M NH. i = pK" or between 10. = where V = the volume of Hel solution added. When 0.Base Chemistry pKo 2 4 6 B 10 12 14 2 4 NH. . Mass Balances 1.NHl = [NH 3{aq)] + [NH4+] = number of moles/total volume 10-' moles/(I liter + V liter).5 and (0.3.8 liter of 10-' M Hel has been added.1. Cr. 4-13. and fairly close to 9. When 0. v T 0 ~ 6 NH4 + B 10 OW H' Fig.

·5.444 x 10 -.387XO. For V ~ 0. the procedure used here applies equally well to higherorder polynomials for which the quadratic formula is not applicable. K.799 and pH = 8.443)(0.7. ". Although this formula may have worked well for this example.556 X ~ ..556 x 10 -') + [H +] ~ [H+] + 0. In the next section we shall see that there is an even easier approximate solution to such problems.285 x 10-' 10-' ~ 0. [NH.285 X 10-' ~ 0.71 X 10-' from (I). '" 0.+] 4.5 ~ 0.275 X 10. x 10-' (0. From Appendix I.31 10-' X 10-' M (from (I» and the charge balance is 10. [H+] ~ 10-.5 + 0. For V ~ 0.". Kw IO- H [H+][OH-] Charge Balance 5.4 and [H+] ~ 10-'''.285 x 10-' ~ 9.(0.8 liter. charge balance to obtain [NH3]/CT.: + 0.14 10-'.Mixtures of Acids and Bases-pH Calculations 145 Equilibria 3.~~.NHJ and a.][H+]/[NH. that can be used with acceptable accuracy in most instances. +] + [H+] ~ [OH-] + [CI-] = Knowing ao = [NH4+]/C T . ~ 0. + [H+] ~ [H+] + (I + V) Since we know Vr and no is a function only of [H+] and constants.71 x 10-') + 10-'. '" 0.4 liter.5.387 (0. From Appendix I. Try pH ~ 9. C T • m.NH3' we can substitute in the IO. ~ ~ 10-'" ~ ~ [NH.14 '" (0.14 [H+] +0.71 x 10-') + 10-'" 0. we have an equation with one unknown which we can solve by trial and error using the table of a values versus pH in Appendix l.443.H IO-'V ".31 x 10-' ~ The equation is not satisfied. The charge balance in Example 4-27 could also have been solved using the quadratic formula. By trial·and·error. ~ 0. C T • NH. . based on the assumption of complete reaction.C T • NH. we find this equation to be satisfied with a reasonable degree of accuracy when no = 0.31 The equation is satisfied.71 x 10-') + [II+] Try pH ~ ~ 10.

12." Similar problems are encountered in chemical processes where acids (e. constituents such as SiO. H+. With wastewater containing 25 mg NH:-Nil iter.alkalinity (or 179 mglliter of alkalinity as CaC03 ). Constant and well-regulated pH is essential for the proper functioning of the many biological and chemical processes involved in water and wastewater treatment. significant operation problems can be caused by low pH values.0 to 6. as we shall see later.. The pH of about 95 percent of the naturally occurring waters is within the range of 6 to 9. pH BUFFERS AND BUFFER INTENSITY As we have previously stated. Just as the bulfering of water results in resistance to pH depression upon the addition of strong acid.57 mM/liter of HC0 3. most waters and wastewaters are usually well buffered in the pH range of 6.=" N03 . If any of these processes consume most of the alkalinity in a water or wastewater. or strong base. Although pH buffers (solutions that resist change in pH on the addition of strong acid. For example.+ H2 0 + 2H+ produces 2 moles of strong acid (H+) for every mole of NH: oxidized.g . OH-) are the most commonly talked about buffers. they are by no means the only type. 11 . In treatment processes such as See Section 4·13 for a discussion of alkalinity. Other examples are metal ion buffers.• alum. and K+ are also regulated within very narrow limits. poorly buffered water areas of the northeastern United States.57 mM/liter of strong acid. which will destroy 3. In most situations this does not present a problem because. ferric chloride) are used as coagulants and precipitants in water and wastewater treatment. we can show that pH elevation is resisted upon the addition of strong base. in extended aeration activated sludge plants located in the low alkalinity. this amounts to the production of 25 mg Niliter x 2 mM H+ 14 mg N/mM mM N 3. It is now thought that the mineral composition of many natural waters is regulated by a buffer system involving silicates (clay minerals such as kaolinite). For example.146 Acid-Base Chemistry 4. a buffer solution is a solution that in some way has the ability to maintain a stable composition when various components are added or removed. In treatment plants in this region the oxidation of ammonia to nitrate (nitrification) by the reaction NH: + 20 2 .6 by the carbonate system. severe depressions of pH (to values of 4 to 5) can occur. and oxidationreduction potential buffers. There are instances when this is not so. the efficiency of the activated sludge process decreases markedly when the pH falls below about 6.

or the degree of resistance of a buffered solution to pH change_ 4_12. of the acid should be very close to the desired pH of the buffer solution for maximum buffer intensity. are Mass Balances CT. we arrive at a similar expression for [HA]. The most common method of preparing a buffered solution is to add a mixture of a weak acid and its conjugate base. (4-77) Equations 4-76 and 4-77 can be substituted into Eq. hydrated lime (Ca(OH). = [Na+] C N".' = C H• + C N". we obtain [A-] = [W] . it is often necessary to raise the pH of ir solution to about I L Field scale operating data have shown that the amount of the base.[OH-] + C N !. = W][W] [HA] (4-73) (4-74) Kw = [W][OH-] Charge Balance [Na+] + [W] = [A-] + [OH-] (4-75) Combining Eqs.the solution and a base that reacts with any strong acid added to the solution. Equilibria K. (4-76) and combining Eqs. Buffer pH A solution buffered at a particular pH value will contain an acid that reacts with any strong base added to . neglecting ionic strength. the pK. 4-71 and 4-76. The equations describing the system. moles/liter of its conjugate base A-are added to the distilled water.". Let us examine the general case when C H• moles/liter of the weak acid HA and C N". 4-73 to obtain a general expression for pH of the buffer. .). required to affect this pH elevation is a direct function of the alkalinity and buffer capacity of the solution_ In this section we will look at the procedure for determining the pH of a buffer solution and then consider methods to predict and determine the buffer intensity.pH Buffers and Buffer Intensity 147 water softening and phosphate removal by calcium phosphate precipitation. = [HA] = + [A-] (4-71) (4-72) C T .1. 4-72 and 4-75 to eliminate [Na+].

What is the pH of each of these buffers after addition of 10-' moles of NaOH per liter of solution if C r = 10. or in logarithm form. = = [A-J.148 Acid-Base Chemistry [W] = K (CHA '(C N. 'K. (b) Examination of Table 4-1 shows that both H.7 should be a good buffer at pH 4.3 M in each case? (a) Examination of Table 4·1 shows that acetic acid. Ka 10- . When ionic strength effects are important. of 4. should be used instead of K. in Eqs. 4-79 or 4·80 to determine the ratio of C HAc/C NaAc: [H+] 10. 4-78 to 4-80.S"" and H.have pK. The concentrations of add and conjugate base are determined by the required ability of the buffer to resist pH changes upon addition of strong acid or base. (4-79) where C HA = [HA] and C N. and almost invariably for prepared buffers. C HA CN. H2P0 4 - . C HA » ([OH-] . or the buffer intensity. C NaAC Note that establishing the buffer pH determines the ratio but not the concentration of acetic acid and sodium acetate to use. . What ratio of acid to conjugate base should be used in ea<. From an examination of the equilibrium constants in Table 4-1.P04..[W]) and CN'A» (-[OW] + [W]). Assuming that [H+] and [OH-] are small compared to C HAc and C NaAc' we can use Eq. besides which it is toxic and evil-smelling.0. H2 S(aq) is volatile and would be difficult to keep in solution.7. determine which acid-conjugate base pair should --be used 'to buffer a solution at (i) pH 4. + [OH-] .7 and (ii) pH 7. HAc.0 C"Ao -=--=--=1 47 Solution 1.) Equation 4-78 then becomes [H+] = K. Therefore.[W]) .h of these buffers? 2. pK. Example 4-28 1. . with a pK. (The pC-pH diagram can be used to determine when this condition is met. + log ( CN"') C HA pH or [salt] pH = pK. + log [acid] (4-80) This equation is commonly used for the preparation of buffer solutions at a given pH. values near 7.[OH-] + [W]) (4-78) For most buffer solutions.

1 x 10-'-10-'=5. + log [HAc] 6 x 10-' =4. Buffer Intensity Buffer intensity.I+J).02=7..3.) On this basis [HAc] = 5 x 10-' . = [H. (4-80).7+log 4x 10' = 4.2-0. After the addition of 10-' mole NaOHlliter. the assumption of complete reaction is valid. 4-79 becomes 2.P04 = 10-3 M and CN~HPo)CNa~po4 = 0. =12.[H+J) and [Ac-] » ([OH-] + [. Thus [HAc] decreases. (Our check to determine whether this approach is valid is to determine if the as· sumptions used to develop Eq.2=7. is defined as the moleslliter of strong base. The reader may wish to prove this using the approach given in Example 4·27. This condition is met for phosphoric acid wherepK a. H. {3. we obtain [Ac-] pH = pK.2 + log 5.pH Buffers and Buffer Intensity 149 is the better choice..9 x 10-' pH=7. Thus .PO.12.2.2 =4.-] are much greater than [H+] and [OH-] at this pH so our assumption of complete reaction is valid. and [H.7 + 0.added reacts completely with HAc.=7.mount of OH.18 Again [H. (b) Knowing that C T.2 value describing the equilibrium.9 x lO-'M.63. and pK. we find that CN'H. that is. = [HPO. Because [H+] and [OH-] are very small with respect to [HAc] and [Ac-] in this region. For pK.1 x lO-'M andCN"HPO. Eq.PO.1 x 1O-'M. are valid at the final pH of the solution.1 x 10 ' =7.9 Because [H+] and [OH-] are much smaller than [HAc] and [Ac-] at pH = 4. or buffer capacity. (or OH-) which when added to a solution causes a unit change in pH. [HAc] » ([OH] .3 was prepared using C HAC = C NaAc = 5 X 10-'. [HPO. (a) The initial solution with C T • Ac = 10.10-' = 4 x 10-'.-] = 3..added per liter. we can assume that the small o..-] = 6."" HPO.-] and [HPO. 4. 4-80.2. Phosphoric acid is a triprotic acid and we are interested in the pK a.9x lO-'M.9 x 10-' + 10-' =4.-] =6. 4.PO. and [Ac-] increases by the amount of OH. Applying Eq. and [Ac-] = 5 x 10-' + 10-' = 6 x 10-'. C s.9...1 =2. pKa.PO.-] = 3.PO.+ H+ We can consider this equilibrium in isolation from the two other equilibria if the pKa values 'differ by more than about 2 pH units. as it is often called.2.1.

For example. at the equivalence point of the titration of HAc with a strong base. Q . We can generally conclude that the buffer intensity is a maximum at pH = pK" that is. 6 8 f 10 (m] of 0. when [HAc]'oltJ" = C B. Although we have learned all of these facts previously.0 1.2 0 2 0. when [Ac-] = [HAc] and that 13 is at a minimum when f = I. It is in this aspect of buffer design that the computational method for deter· mining 13 is most usefuL To develop a general equation for 13. 2S C. Experimental measurement involves determining a titration curve that shows the course of pH change with moles of strong acid or base added.~ 10 ~ a.4 0.d pH (4·81) where C A is the molesfliter of strong acid (or H+) added. The slope of a titration curve is d pHldV where V = ml of X normal acid or base added. the titration curve for 10-3 M HAc (Fig. 4·14 together with a plot of 13 derived from slope measurements on this curve.8 1. The slope of the titration curve can be converted into 1/13 by multiplying by the factor C'. liters)/(normality of titrant))(lD' mlfliter) C' (d pHldV) = d pHldC B = 1/13 Therefore. "0 6 E b 5 4 2 0 0.ISO Acid·Base Chemistry 13 = d dCB dC A pH = .2 x "'- 0 1.6 0.12) is reproduced in Fig. where C' Thus = «sample volume. a knowledge of the absolute value of 13 helps us to design buffers at a given pH with the desired capacity to resist pH change. The buffer intensity can be determined experimentally and by computation at individual pH values. the reciprocal of the slope of the titration curve is proportional to the buffer intensity. Titration and buffer intensity curves for HAc-Ac. let us consider a solution containing 12 Titration curve 15 10 8 :I: .1 M NaOH) 1O~:) M Fig.4 4 Equivalent fraction. 4.

4-85.AK.[OW] (4-85) + [W] Substituting in Eq. (4-89) Then _ d [A-] = d ((-K. and the salt of its conjugate base NaA to which C A moles/liter of strong acid (HC!) are added. ([W] +K. the equilibria are K. (4-88) and [HA] = [W]CT.CT.A)/([W] +K. If we neglect ionic strength effects.)2 (4-90) . 4-82 and 4-84.A [W] +K.[K] .pH Buffers and Buffer Intensity lSI a monoprotic acid. HA. "" [W]W] [HA] (4-82) (4-83) Kw = [H+][OW] Mass Balances and (4-84) Charge Balance [Na+] or using CA = [Cl-] CA = [Na+] Since (4-86) + [W] = [A-] + [OH-] + [Cl-] .» d [W] d [W] + CT. 4-86 for C A from Eq. we obtain = _ f3 (d [Na+] d [W] +d d [W] _ d [A -] _ d [OH-]) ( d [W]) [W] d [W] d [W] d pH (4-87) Evaluating each of the differentials. we obtain d [Na+] d [W] o d [W] d[W]=1 From Eqs.

3 d [W]/[W] (4·92) Substituting the values of the differentials in Eq. Kw a + I + ([W] +K.~. 4·95 can be written (4·96) /3 = /3H. we find that /3 = .A and lX. together with the table of lX values in Appendix I allows the rapid computation of /3 as a function of pH.O + f3HA (4·97) We can also use a similar derivation of /3 for a multiprotic acid.3 ( [W] + [OW] + (~~:~ ~T..A' substituting into Eq. 3( [W] + [OH~] + [HA][A ~] ) [HA] + [A ] (4·94) Knowing that lX.) In the event that ionic strength effects are important.3[W] ([H:. = [A~]/CT. H"A. 4·88. 4·87. we can derive a third way of expressing /3: (4·95) This equation.( CT. l! the pK. values are separated by more than 2 pH units.3[W] [~:]2 (4·93) = 2.3d [W] (4·91) -2.3[W] dpH d (-log [W]) d[W] d (In [W])/-2. I! no weak acid·conjugate base pair were present. the derived . and 4·89 gives an alternative expres· sion for /3: /3 = 2 . = [HA]/CT.152 Acid. and cK w in place of K W' Substituting from Eqs.3[W] + 2.o = 2.. 4·84. cK.AK.:K.)2 + [W]2 ) (-2. 4·94. 4·83 Kw [OW] = [W] Then d [OW] d [W] d[W] d[W] d(-Kw/[W]) = Kw d [W] [Wl' -2.)2) + 2.3[H] +) = 2. should be used in place of K.Base Chemistry From Eq. derivation by the above procedure would have yielded the buffer intensity attributable to water: /3H.3 ([H] + [OH~]) so that Eq.

where and C T •A ~ [HoA] + [Ho_. and so forth.pH Buffers and Buffer Intensity 153 equation produces results within 5 percent error of the correct value of ~" .. A derivation similar to the previous equations yields the equations applicable to such a solution. More than one acid-conjugate base pair may be used to buffer a solution.A and ""A are the IX values for HA and A-. or in terms of a values.HAc = 4.. [W] + [OW] + [HA][A -] [HA] + [A] + [HB][B-] [HB] + [B ] + . ..J. Determine the individual contributions of the acetic acid (f3HAc) and of water (/3H# to the total buffer intensity (f3) and plot their variation with pH. Hydrogen Ion Concentration. neglect ionic strength effects') 12 J.3( [W] + [OH-] + .3 M acetic acid solution at several pH values to determine the variation of /3 with pH. Example 4-29 Compute the buffer intensity of a 10. P~ 2 3 ( .) (4-100) or P ~ PH.A ] + [Ho_..O + PHA + PHB + .. New Concepts in a Systematic Treatment. How do the computed values of f3 compare with the values measured from the titration curve in Fig.A ] + [Ho_. ) (4-98) or in terms of a values. N.A -] + [Ho->A'-] + . Ricci. 4·14? (Ka.A' ] Thus P ~ 2. Princeton University Press.Aand CT.7. 1952. (4-99) ..B and "O. [HoA][Ho-.A -] [HoA] + [Ho_.. (4-101) (4-102) where HA and HB are of total concentration CT. E. Princeton.A -][Ho->A'-] + [Ho_.

61 2.1 4. 4-15 shows that {3H.58 x 10 -'molelliter {3H"'= 2.3 x x x x x x x x x x x x 0.8 2.80 0.7 1.3 x x x x x x x x x x x x f3HAc {3 6.00 0..0 Computation of C<o C<. including multiprotic systems.00 10-' 10-' 10-' 10-' 10-3 10.80 0.5 4.50 0.9 . is to be neutralized to pH 6 prior to discharge. determine values determine 0'0 and <X1 from Appendix 1.6 4.75 x 10 -. NaHC03 • or soda ash.1 3.9 5..3 2.3 3. f3.33 0.CT.3 5.09 0.91 0.9 2.strong base system. [H+] = 10-1.66 0.75 xlO -'molelliter {3 = 0.5 xO. Fig.91 0. Na2COJ. could be used to increase the buffer intensity of the solution so that the desired final pH could be TABLE 4-6 pH 4.7 {3HP = 2.o is predominant at very high and very low pH but that it contributes very little to f3 in (he pH range 5 to 9 for a 10-3 M buffer solution.0 11. f3H~ has a minimum at pH = pK.9 2.9 2.3(0.4 4.5 6.3 5. Exam pie 4-30 A strongly acidic pharmaceutical waste.8 M.7 1.20 0.3 5.00 0.0 5.58 0.99 1.7 7. Examination of Fig.3 2.8 1. Also. Example 4-29 {3H.conjugate base systems.o and {3HAo are plotted in Fig.8 4.) = 4. When {3HP and f3HAc are summed to give {3.0 5.3 2.6 2. It should be noted that /3H.2 5.2 10-' 10-' 10-' 10-' 10-' 10-' .J2 and is symmetrical about this pH.1 3.5 x 10-') =5. + 5.75 5.50 0.2 10-' 10-' 10-5 10-5 10-' 10-' 5. This same phenomenon is also observed for other acid.1 1. There will be a maximum at each pKa for the multiprotic species. Using these a {3 = {3H.3 x x x x X 10-' 10-' 10-' 10-' 10-' a x 10-' x 10-' x 10-' x 10-' a 0 10-' 10-' 10-' 10-' 10-' 10. Continuous neutralization with SO percent caustic soda.154 Acid-Base Chemistry Solution For selected pH values.p is the buffer intensity of a strong acid.66 0.01 0.0 3.o' 4. 4·15 shows that {3HAc has a maximum at pH = pKa and is symmetrical about this pH.33 0. A laboratory study showed that the addition of sodium bicarbonate. NoOH.7 2.21 X 10 -'molelliter See Table 4-6.7 9.00 0..00 1.3 1.01 0.7 2. 4-15. resulted in an effluent pH that varied widely in the range 4 to 11 because of the low buffer intensity of the water. = 6.6 2.46 X 10 -.3([H+] + [OH-]) + 2.7 4.00 0.3aoa.3 (10-'" + 10.20 0.6 4. The values 01 {3H.o + {3HAo = 2..09 0.99 1.HAo At pH 4.

co..75 X 10-' = 2. and '" = 0 = 6.] at pH 13 =6 This example is based upon information given by R. achieved in the neutralization process.334)C T + (0...42 x 10-' mole NaHCO. Y. 0. The H+ concentration neutralized by NaHC0 3 via the reaction HCO.-----.)/CT. calculate the NaOH and NaHCOa required to achieve the neutralization. must be added per liter of waste to achieve the desired buffer intensity. '" 0. CT.1. 6 moles H+/liter (1.334XO)C T .58 x 10-' mole H+!1iter be neutralized..+ H+ . Chen..666XO.cO.58 x 10-' mole!1iter). required using Eq. 4-99: . Next we calculate the required NaOH. W. Okey.334 .C TCO." presented at the 32nd Purdue Industrial Waste Conference.r----. Adjustment of the solution to pH 6 requires that (1.I x 10-') = 1..3([H+] + [OH-] + "o".co) X 10-' M Thus 1. In the waste there are 10.CO. K.CT.'-]!CT.-]/C T •CO. = 1. . f3 = 2. Sycip..666 = = [CO.75 mM/liter is necessary if the neutralization system is to continuously produce an effluent with a pH sufficiently close to 6.CO.Co.. + ". H. 13 Solution Calculate the NaHCO.3(10-' + 10-8 + (0. 1978.pH Buffers and Buffer Intensity 155 8r-----r-----r-----r----.-----.) From Appendix I at pH [HCO.. "0 = 0. Ind. Buffer intensity versus pH for 10-' M HAc-Ac-. is equal to [H. b pH x 10-' .co. Z. and A. 4-15..42 [H. Neglect ionic str~ngth effects. "Techniques for Continuous Neutralization of Strong Acid Wastes. Lafayette. Given that a f3 of

~ (0. from supersaturated waters involves a heterogeneous reaction between gas and liquid phases. carbonate.13. aqueous or dissolved CO.CT.. bicarbonate. Carbonates and bicarbonates form complexes and ion pairs with metals such as Ca'+ and Mg'+. produced) and biosynthesis by autotrophs or photosynthetic organisms (CO. consumed).0 and f3 to 0.42 9. (For the moment we will neglect the equilibria between carbonate species and metal ions and the involvement of .666)(1. The carbonate species also buffer natural watt'rs. THE CARBONATE SYSTEM We will now turn our attention to a discussion of what is the most important acid-base system in water: the carbonate system.4 M = 1.. Carbon dioxide is a participant in the biological processes of respiration (CO. The Carbonate Species and Their Acid-Base Equilibria The various components of the carbonate system are interrelated by the following equilibria. precipitates is one of the bases of the precipitation process for water softening. The formation of CaCO.48 X 10..-. In addition. 4. respectively) are based largely on the specific properties of the carbonate system. Carbonate ion participates in heterogeneous equilibria with solids containing carbonate.46 X 1O.O Total H+ requiring neutralization Neutralization by NaHCOs NoOH required 1. and carbonate-containing solids-comprise one of the major acid-conjugate base systems in natural waters.48 X 10-' M Thus 1..C0 3 . OW + H+ .CO. H..75 mMlliter.2 mole NaOH/liter are required to adjust the solution pH to 6. CO. 4. CO.156 Acid-Base Chemistry [H..58 X 10-' M -9. the carbonate species almost always has a bearing on the type and quantity of chemicals required to treat water and wastewater. individual species are of interest to us because they participate in important reactions other than strictly acid-base interactions.46 X 10.(. Because of this the analytical techniques for measuring the capacity of a water to neutralize strong acid and strong base (alkalinity and acidity.1. from the atmosphere into water and the release of CO.. The dissolution of CO.4 molelliter X 10 -') NaOH required to neutralize the H+ via the reaction.CO. The chemical species lhat make up the carbonate system-gaseous CO" CO. notably calcium carbonate. H. The dissolution of carbonatebearing minerals is a major source of inorganic carbon-containing species in natural waters. Because of their almost universal occurrence and involvement in reactions. HCO.( •• .] ~ ~ a.42 x 10-3 mole NaHCO)liter and 1.13.'-. carbonic acid.

71 -1.. pKa.O .30 60 1. A closed system with solid present. ·C Reaction 5 1.22 -2.46 10.. = 10-10.CO.-. Buswell. We must examine our system to see whether it can be treated as I.'-. 4.CO.. H.5 (4. K =KH= 10-1. HC03 . A closed system with no solid present.10 -1..14 8. An open system with no solid present.l = 10-6 . pX.22 8. M.09 -2.:: Ca 2+ + HeOl -. .43 8.52 10 1.:: C0 2laQ . K.. C02(91 +HP. "Calcium Carbonate Saturation Index and Alkalinity Interpretations. Water Works Assoc. I.38 10.74 1.51 -2. CO 2{g) ~ CO 2(aQ).99 40 1.103) CO". 2. = 10-3 •5 K... pKH 2.20 6. Lorson and A.. H~O.106) (4. E.+ H+. p(K.47 6. CaCOJ(S) + H+ . During titration the sample is warmed and vigorously bubbled with air to equilibrate the sample with the atmosphere. where K H is Henry's constant. 34: 1664 (1942).107) K.= H. + H.3D 10. 3. we must first make a decision concerning the nature of the system. The use of simple sketches helps us to decide the nature of our system.34 -1. When we are presented with a problem involving the carbonate system.49 8." J.) 6.....q. pK •. An open system with solid present. For example. . A water sample containing carbonate species is titrated with a strong acid..8 6. Am..33 8..40 Source: From T.= H+ + CO.47 10.= W + HCO.2 4..35 10.+H+. H.38 8.CO.The Carbonate System 157 carbonate·containing solids (see Chapters 5 and 6)).IK •. This step is important because carbonate species can be involved in homo· geneous solution equilibria as well as heterogeneous gaslliquid and Iiquidfsolid equilibria.34 6. HeO J.28 25 1.27 15 1. TABLE 4·7 Temperature Dependence of Some Important Carbonate Equilibrium Constants Temperature.42 10. 1 3.= H+ + HCO.-. .:: Ca2+ + CO/-.15 -2.34 10. Km = 10-'" (4·104) (4·105) (4.¢ COl. The temperature dependence of the constants we will use most· frequently is presented in Table 4-7.64 6.21 20 1041 6.56 8. S. ~ HeO l . CaC03(5).

). may escape) and is not in equilibrium with any carbonate-containing solid. CaCO". The system can be sketched as in the following figure. The system is considered to be closed to the atmosphere (although some CO. The system is open to the atmosphere and not in equilibrium with a carbonate· containing solid.158 ACid-Base Chemistry The system can be sketched as in the following figure. The system is closed to the atmosphere and tends to be in equilibrium with a carbonate-containing solid. The system can be sketched as in the following figure. til 2. 3. The titration is conducted rapidly in a nearly full container with little shaking. The hypolimnion of a stratified lake is in contact with sediment containing calcite. . A water sample containing carbonate species is titrated with strong acid.

The system is open and in equilibrium with the atmosphere with a P co. . The system can be sketched as in the following figure. It is not in equilibrium with a carbonate-containing solid. co. and water take place in the vigorously aerated aeration basin of an activated sludge plant. Nitrification (oxidation of ammonia to nitrate) and oxidation of organic matter to CO. of the aerating gas.The Carbonate System 159 Epilimnion Hypolimnion r 5.

C0 3] is only 0.6 X 10-3 [CO"".C0 3] = I/K m we find that . for H.] + [H.C0 3 ]l/[H. and neglecting ionic strimgth effects.]' Because it is difficult to distinguish between CO"aq. 4·104 we can conclude that the concentration of hydrated carbon dioxide.] and [W][HC03-] [H.. H. is a hypothetical species only.C0 3] m 1. predominates over the concentration of carbonic acid.C03] + [CO"aq.C03 ] = K.3 The implications of this development are important because they point .CO.C03] + [CO"ad = [H. K".C0 3 • K = 10-. and H.]/[H.CO.104. we can determine the ionization constant. (l/Km) +I - -K a" Since -=--= I Km I I 10-. as follows: Since [H. the equilibrium constants for ionization of H.16 percent of [CO"aq. CO 2{aq).) is used to represent H.·6 = 10-6 .] Thus [H. Km Ka" K' = 10-3 •5 10-.CO. a hypothetical species (H.CO.] (4·108) where H.C03 plus CO".·6 631 -»1 Km therefore.]) (4·109) Now multiplying the numerator and denominator of Eq.C0 3] and knowing that [CO". 4·108 in the Ka " equation. and H.160 Acid-Base Chemistry From Eq. = (l/~m) = K.C03 can be wrjtten as [W][HC0 3 -] [H. Substituting Eq. 4·109 by [H. we obtain Ka" = [W][HC03 -] ([H.CO.C03 ] ([CO"". K.CO.q.C0 3 ] K.' We will follow this convention. ([W] [HC03 -])/[H. Using Eqs..C0 3 by analytical procedures such as acid·base titration.·6 = [H.q. 4·103 and 4.

. the strong base that was added to the solution was not neutralized.1 M NaOH (strong base) and swirl the flask to mix. 5 ). The explanation for this behavior lies in the slow (relative to other deprotonation reactions) rate of hydration of aqueous CO. M. is extremely rapid.O This reaction. A simple experiment will illustrate the problem.. "The Hydration of Carbon Dioxide.C03 is a fairly strong acid.. Now add I to 2 ml of 0.O "" H. The CO". H. like most acid-base reactions.. content. By chilling the solution as we did in our experiment. species. solution. The reason for the slow hydration rate lies in the change of molecular configuration that must occur in CO. Kern. the available H. 3 .C03 + OH. Chern. For . CO". is 10-•. Educ ." Take 200 ml of chilled distilled water and add a piece of dry ice (solid CO.CO. The result is that the pH increases momentarily until the slower CO. we can write (4-110) Although equilibrium calculations justify the use of the hypothetical species.] » [H.+ H.q.C0 3 has a rate constant of 0..The Carbonate System 161 out that H.q. molecule is This experiment is taken from D. The solution will be momentarily (seconds) blue. green at pH 7. is the major dissolved CO. but there is very little of it in solution. If we recall our earlier discussions on kinetics. a value that would give the impression that carbonic acid is a very weak acid. The reaction.C03 that participates in acid-base reactions with OHH.C03 is consumed at a faster rate than it can be produced.some reason then. we realize that slow reaction rates are not characteristic of acid-base reactions.C0 3]. (K. 37: 14 (1960).03 at 20 to 25°C.q. there are some kinetic consideratio. + H. hydration reaction can supply more H.. The indicator will turn yellow in the chilled CO. it is the minor species H." 14 J. These color changes indicate that after the addition of strong base the pH of the solution was at pH above 8 for a significant time and then gradually returned to below pH 6. However. K"l' for H. the rate is slowed even further. This point is emphasized because the composite first dissociation constant.0025 to 0. = 10-3 . then return to its original yellow color through an intermediate shade of green. of minerals'by CO" carbonic acid has some of the properties of a strong acid.. As we shall see later when we examine the dissolution.. Therefore. for a measurable time period.) to it to increase its dissolved CO.!s that must be addressed. hydration. or remained unreacted. on the addition of excess OH-. Because of the preceding equilibrium calculations and because [CO".CO.q. and blue at pH 8 and above. . Add 3 to 4 drops of bromothymol blue indicator. which is yellow below pH 6. HC03 .C03 to react with the OH-. From our equilibrium discussions we know that CO".

[H. 4-16.... 5 Therefore. From Eq.] = 4.5 atm of CO" and when this is in equilibrium with CO".CO.] (4-112) Because [H. Calculation of Carbonate Species Concentrations in Open and Closed Systems In working problems concerned with carbonate equilibria in waters. Throughout this text we will use the hypothetical species H.K. gas in the atmosphere above the solution. let us examine homogeneous (no precipitates).2.5 .C03 has the form.] =10. with waters of hydration attached. HO "-C=O HO / with associated waters of hydration. O=C=O. from Eqs.1 [W] 5 . The normal atmosphere contains 10-3. First. 4-103 and 4-110. This procedure often leads to complex equations.CO.[W][HC0 3-] [H. but we should keep in mind its true nature.] versus pH plots as a horizontal straight line at -log C = 5 as shown in Fig.13.CO. 5 atm (Fig. -log [H.C03 • We will treat it as a diprotic acid. We intend to present both ways of attacking the problem because it is only by having a fundamental knowledge of the system that one can develop the ability to make rational simplifications. we obtain (4-111) Let us now construct a pC -pH diagram for the carbonate system open to an atmosphere containing P ca. we can take one of two general approaches.CO.. to represent CO""' plus H. The first method is to treat the problem rigorously.162 Acid-Base Chemistry linear. 4-16). = 10-3 .CO. In these systems the carbonate species in solution are in equilibrium with the CO. open systems.] = 10-5 . Our first step is to determine the concentration of each carbonate species as a function of pH. we know that K . while H.CO. The second method is to make simplifying assumptions to provide an easy but approximate solution. [H. [HCO -] 3 = 1O.1 - . For [HC0 3 -]. 4-111.

Total concentration of carbonates. 4·16.we know that (4·114) Combining Eq.2pH This equation yields the line for [CO.2 .K•. Similarly. 4·111 and the equations for K •. for CO.pH + 11.C~' versus pH for an open system at 25°C.3 (4. + pK. 2 yield [CO 32-] -log [CO.6 .'-] = = 1O-'K •.3 pH 2 3 4 5 6 7 8 9 10 11 12 13 14 O~-r--r--r--r--r~~-r~r--r~r-Tn~~~~ 2 3 4 10 11 Fig. 2 [H+]2 (4-115) 5 + pK•.The Carbonate System 163 and -log [HC0 3 -] = 5 . . Knowing that (4·116) we can obtain the concentration of the individual species at various pH 6. andK•. .'-] shown in Fig.3 = . .'.pH + 6. 4-16. 4-16. . CT.2pH = 21.113) This equation yields the line for [HC03 -] shown in Fig..

] predominates for pH < pK.CO. The proton conditions for the closed system are H2 CO. Let us first determine the composition of 10-5 M solutions of H2CO. . 4-116. The diagram is shown in Fig.. Examination of Fig. 4-17. and plot -logC r . determine C r .co. versus pH.164 Acid-Base Chemistry from Fig.] 5 6 = [CO. 4-16. as a nonvolatile diprotic {. as a function of pH using Eq. Thus construction of the pC-pH diagram follows the same steps taken in Section 4-8 for the diagram of the hypothetical diprotic acid H2A (Fig.CO. in both systems. = .'-] predominates for pH > pK". < pH < pK. The pC-pH diagram for a 10-5 M carbonate solution at 25' C. and sodium carbonate.) acid. we can treat H2CO. Note that [H. 4-5).'-] + [OW] pH 234 7 8 9 10 11 12 13 14 4 <0 0- c· 5 ~ '~ 0 • 0 c 0 0 c 6 7 8 T m 0 9 10 11 12 Fig.. Na2CO. 4-17.. with a .2' and [CO. increases rapidly as pH increases above pK"l' Now let us tackle the closed system. Since the constraint that the system be in equilibrium with a certain partial pressure of CO2 has been removed.: or approximately [W] = [HCO.l' [HC0 3-] predominates for pK. sodium bicarbonate. The resulting curve is shown in Fig...-] NaHC0 3 : [H+] + [H. 4-16. NaHC0 3 .co. 4-16 also reveals that C r .

= 10. When atmospheric CO. 7 10.-]. 4·17) [H'] [OH-] [H.5 = 10-5 M [W] = [HCO.5 . 7 10.CO. and C.8 .7 . 10-5 M Na.CO.10 .4 10-5 10-7 . The calculations are slightly more complex for the open system.'-] + [OH-] or approximately [H+] = [HCO.7 . Because CO 2 can enter the solution or be evolved.5 . 10. 0 10-5 .co J is an unknown. 6 10-5 10.7 7.CO.4.CO.9 . [H.6 . Henry's law gives [H.'. 5 .CO.6 CT. 5 10. 3 10-7 .'-] 10-8 .C~ 10-5 M H.4 .3 6.4 10. 7 10-6. 6 10. respectively.] = KHP co.8 .-] [CO. 3 10.0 10-9 10-5 Open System [H+] [OW] [H. TABLE 4·8 Comparison of Composition and pH of Open and Closed Carbonate Systems Solution Closed System (Fig. 1 CT. 5 The proton condition is X 10-3.] [HCO. -] + 2[CO. 3 10-4 .] + [HCO.4 .: or approximately [W] + 2[H.0 pH 5.-] [CO.0 10. 10-5 M NaHCO.10.CO. 7 10. B.4 10-5 .iliter. 10-5 M NaHCO.CO. 4·17. 3 10- 5 10.6 .1.CO.5 . 7 10. is in equilibrium with distilled water.C~ 10-5 M H.t. 9 10. 3 pH 5. Cr.5.] = [OH-] Na. each in equilibrium with the atmosphere. 4·16. To make comparisons with the closed· system solution. The concentrations of the various species in these solutions as taken from Fig. (2) distilled water + 10-5 mole NaHCO.5 .C031 [HCO. and is satisfied at point A on Fig. 4·17 are tabulated in Table 4-8. -] = [OH-] I These proton conditions are met at points A. 10-5 M Na. 1 10.6 9. 1 10.CO.CO.CO. Examination of the figure shows that C T •CO.7 6.4 . 7 10. 10-1. let us consider (I) distilled water. in Fig.iliter. and (3) distilled water + 10-5 mole Na. 6 10-6 .The Carbonate System 165 or approximately [H. Solution 10.4 10. The solution compo· sition is given in Table 4·8.'-] 10-5 10-5 10-5 10-5 .3 10-5 .

In the open system [H.5 atm).0003 atm (10-3. [Na+] » [H+] and [HC0 3 -] » 2[CO. we find the charge balance is satisfied at pH 6. If we were to bubble a 10-5 M Na. We can conclude that equilibration of closed solutions of NaHC03 and Na. 3. 4-117 results but [Na+] is now 2 X 10-5 M. For freshly distilled water the pH should be only slightly below neutrality while after contact with the atmosphere containing 10-3 •5 atm (P eo).'-] + [OH-]. which is applicable to open systems.6. It would be a useful exercise for the reader to experimentally determine the pH value of distilled water immediately after preparation and then again after standing the distilled water overnight in a beaker open to the atmosphere.C03 solution with air containing P eo. the same charge balance.8. The species concentrations at this pH.. When 10-5 M Na. = 0.C0 3 solutions in the open system contain higher C T •eo.3 (point B) where [Na+] = I X 10-5 = [HC0 3-].] remains constant.166 Acid-Base Chemistry The addition of 10-5 mole NaHC03 /liter of distilled water followed by equilibration with the atmosphere at 25°C results in the following charge balance (4-117) where [Na+] = I x 10-5 • Figure 4-16. than the NaHC0 3 and Na.C03 with the atmosphere will cause a depression in pH. [H+] « 10-5 . then over a prolonged period its pH would drift down from 9 to about 6. Using Fig.C0 3 is added to distilled water. concentration is constant in the closed system but varies with pH in the open system. the pH will drift down to the neighborhood of 5. 4-16. where [Na+] = 2 X 10-5 = [HC0 3 -]. and [HC0 3 -] » 2[CO. The C T•eo.CO.7.C03 solutions in the closed system. shows that this equation is satisfied at pH 6. are also given in Table 4.6. 4. 4-16.'-] + [OH-]. Comparison of the closed and open systems in Table 4·8 reveals the following important distinctions l. Let us now turn our attention to the calculation of solution composition following the addition of strong acid or strong base to the closed carbonate system. their pH values are significantly lower. The concentrations of the various species at this pH are presented in Table 4-8. Eq. 2. Even though the NaHC0 3 and Na. The pH of a 10-5 M CO""' solution and of a distilled water solution that is equilibrated with the atmosphere is equal. The results and methods that we derive from this exercise will . taken from Fig.

I. C T •CO .[WJ 1O-~3 which is the charge balance for a M NaHC03 solution. and the appropriate pC -pH diagram. 2. Example 4-31 Calculate the solution pH. From the pC. 2 X 10-3 mole HN0 3 per liter of solution.-J = 10-' C T•N. solution composition.-] + [CO.= [H..[NO. the charge balance.-J = [HCO.. .'-J = 10-' Charge Balance [Na+J . 10-3 mole HN03 per liter of solution. is known. Cr. of titrant for a solution containing 10. we can write 10-' = [HCO.CO. NO.J + [WJ = [CO. (2) assessing pH and solution composition when acidic wastes are discharged to receiving waters.pH diagram for a closed system with CT. we need the mass balance. We can also substitute [H.-J + 2[CO. Solution 1.coJ .[W] After substituting from mass balances on [Na+] and [N03 -]. = [NO. Mass Balances = [Na+J = 2 x 10-' CT. Assume that a negligible volume change occurs as a result of the addition of HN03 and that the system is closed. The eqUivalent fraction is calculated as f = number of equivalents of HNOa addedJIiter C T •C03 1x 1O~3 3 1 x 10 To determine the solution composition.-J + [CO.'-] + [OH-] ..'-J + [OW] which is the proton condition for a solution prepared by adding only NaHC03 to distilled water.The Carbonate System 167 prove useful in (I) calculating solution composition during water treatment operations where strong acids or bases are 'added to carbonate-bearing waters in processes such as coagulation and stabilization.cos = 10--3 .J + [HCO. and (3) calculating the pH and solution composition at various stages of the alkalinity and acidity titrations.CO.3 M Na 2C0 3 to which are added l. We will demonstrate methods of calculating the solution pH and composition following strongacid or strong-base addition when the analytical concentration of carbonates.'-] for 10-' in the charge balance to obtain [H.-J + 2[CO.COjJ + [HCO. and the equivalent fractions.'-J + [OH-] .

" [H. 4·18.] + [HCO.~ c u 0 5 6 7 • u c ~ T 8 9 0 10 11 12 Fig.'-] pH 3 4 5 6 7 8 9 10 11 12 13 14 2 3 4 " c· 0.'-] 10-5 2. The pC·pH diagram for a carbonate solution. and [CO.168 Acid-Base Chemistry M. The solution composition is [W] ~ 10-8 . [CO. Fig.'-] » [OH-]." [OW] [HCO.-] ~ ~ 10-5 . this proton condition is met at pH 8. 4-18.] [H.CO.3 We determine the solution composition as in part (1).] » [H+]. Mass Balances C T •N. ~ [H.5. ~ [Na+] ~ 2 x 10-' Cr •No3 = 2 X 10. 10-'. 0 . . The equivalent fraction is calculated as 1 = number of equivalents of HN0 3 added/liter = 2 X 10.] ~ ~ 10.GO.3 where [H.CO.C03 = -3 Mat 25'C. -] + [CO.3 C T•CO. C T .3 = 2 C T•C03 1 X 10.CO.

[W] This is the proton condition of a 10-3 M H2 CO. pHHCO.C0 3 .] = 10-'. The application of pC-pH diagrams for closed system problems is most useful when the initial solution pH corresponds to a pure carbonate solution (i. -] = 10-"'. it can be shown that if one equivalent fraction of strong base is added to a solution containingC r .The Carbonate System 169 Charge Balance [Na+] . It is satisfied at pH 4.'-] + [OH-]. results.[W] Substituting mass balances on Na+ and N03 .in the charge balance. pHHCO. .CO. Solution 1.-] and [ solution of Na. the pH of a solution with the same Cr.-. moleslliter of H. we can write o= or [HCO.'-] + [OW] .co. the initial pH does not correspond to pHco " pHHCO. our coverage of these simple examples has hopefully instilled into the reader's mind the nature of the assumptions that can be made in various pH regions of the carbonate system. Similarly.'. calculate the pH after addition of: I. Cr.and the amount of acid or base added does not correspond to f = I or 2. 10-' mole HClIliter.-] + 2[CO.. or pHco.'-] + [OW] . Generally.col and has a pH of 7.-] + 2[CO. if two equivalent fractions of strong base are added.'-] = 10-10.. 4-18).-] = [HCO.'-. No weak acids or weak bases are present other than the carbonate species. 3 x 10-' mole NaOH!liter. solution. 2. pHco. and [CO. where [fi+] = [HCO.7 in the pC-pH diagram (Fig. however.0.'. but other anions and cations aTe present.-] »2[CO.. [H. Such cases are the exception. plico.C03 solution) and the amount of strong acid or strong base added is equal to one or two equivalent fractions. when strong acid or strong base is added to solutions containing carbonates.[NO. We will solve this problem using one exact solution and one approximate method of solution. but made up with only NaHC03 results. Example 4-32 A solution contains 10-3 M Cr.for an NaHCO. solution.. Neglecting ionic strength effects. [OH-] = 10-"'. [HCO. The solution composition is [H+] = 10-'-'.e.. for an H. the pH of a .for an Na. solution and pHco.

] + 2[C0 3'-] + [OH-] .[W] 2[C0 3'-] + [OH-]. C A + .'-] + [OH-] + C A [HC03-] + 2[C0 3' .170 Acid-Base Chemistry Equilibria [W][OH-] ~ Kw ~ 10-" [HC03-j[W] ~ K ~ 10-'.[H+] 8. Thus [H. ~ = 2[SO. are in solution.. ~ 8.CO.7 X 10-' M and [HC0 3-] ~ a. + [W] or C.2 = 10. CB + [K+] + 2[Ca2+] . . ~ 0.C A ~ ~ [HC0 3-] + 2[CO.3 x 10-' = [HCOn + [HCOn ~ Assuming that 7. .'-] + [OH-] .' [C0 3'-j[W] [HC03 ] Ka .] + [HC0 3 + [C0 3 '-] -] " For example.3 X [W] 8. ~ 10.3 x 10-' M. To calculate [CO.3 X 10-' + 2(4..1663 and a.'-] + [Cl-] + [Be] [Na+] 16 For example.3 ~ [H.10-' = 7.. are in solution.[W] From Appendix L ao ~ 0...16 Cbarge Balance C.3 X 10-' ~ ~ After the addition of 10-' mole HCl/liter: Exact Solution The final charge balance after adding 10:' M HC!.] '. and [HC0 3-] » In the mass balance. we obtain 7.'-.3 x 10-' 2[CO. CT. . we enter the values for [HC0 3-] and [H+] in the K". equation to find [CO '-] ~ K.] + [HC0 3-] + [CO..8337..CO. if SO. -C A [HC03.C T •CO..CO.3 x 10-'» [H+]. [HCOn 3 10-". -10-' ~ 8.3 [H. CI-.3 X 10-' .'-].1 X 10-' M The initial charge balance is then C.1 X 10-') + 10 -.3 x 10-' ~ 8.. if Na+. Ca2 + + .CO. C. ." Ca = moleslliter of positive charge units other than [H+].C0 3 = 10-3 ~ [H. K+.CA 7. Be.] + [OH-] .3 10' X 10-' 4.'-] CA = moles/liter of negative charge units other than those of the carbonates and [OH-]. ~ 1.10 .] aOC T •CO.3 Mass Balances Cuo..

CO. (The bases OH. Approximate Solution The strong acid added (10.3 x 10-' M = 8.7 X 10-4 M = 10. however.) HCO.7 X 10-' 7. which is present at significant concentration.CO.CO.] = initial [H.7 x FromK •. alternatively. = 6." M 10-"·' x 7. The approximate solution is slightly different.6.-] = initial [HCO.CO.' X 2. (W] IO-4 Final (H.3 X 10 ' = IO-6. " (COr] Checking our assumptions.] + [H+] added + IO-4 = 2.4 pH = 10-6.'-] is negligible 10-' = (H. 2.] and (HCO.] + 7.+ H+ -> H. From K •.' x 2. This problem can be solved in the same fashion as given in (l). the solution obtained in this way can be checked using the set of equations that describe the system..-] =7.and COl.'-] + (OH-] = 2 X 10-6 •71 + 10. we obtain (H ] - + _ 10-6. Addition of 3 x 10. Final [HCO. The assumption of complete reaction can be made when the concentration of the predominant acid and its conjugate base pair is much greater than the H+ or OHconcentrations." = From K.[H+]added 10-' = 7.".-] .4 mole HClIliter) is assumed to react completely with only the strongest base. Whether this estimate will be valid can generally be judged very easily using the appropriate pC-pH diagram and the estimated pH.3 (H.7 X 10-' Using these values in theK a.3 x IO-' » 2 (CO. (HCO.-].7 x IO-'!7.CO.4 moles NaOHlliter.". HCO.1 equation because it includes both [H2 CO.are stronger.3 x 10-' = 1. (OH-] = 10-'·".The Carbonate l!ystem assume that (CO. and it is as follows: ." We can see that the assumptions are valid.'-] = 10-6.3 x IO-'IIO-6 .73 This approximate solution is in excellent agreement with the exact solution.3 x 10. but their concentrations are at least 2 orders of magnitude lower.] X 171 10-' = 2.. 10-6 .7 •27 and since (CO. 1 .3-.

Substitution into the charge balance and mass balance shows that the values obtained are satisfactory..10-•.3 X 10-4 ~ 4. (the [WI is negligible). we should examine the Ka . 23 and [OH-] = 10-4 . H.] . then any remaining OHreacts with HCOa-.equivalent amount of NaOH 1. + OH--> HCO.4 M). _ 10-'" _ [H. ~ 3 x 10.7. We assume that the strong base first reacts stoichio· metrically with all of the H.7 8. x 8. The approximate solution approach is especially useful in certain practical problems.7? Solution At pH 8.and COl-.4 .4 Final [HCO. such as the one illustrated in the following example.CO.O and HCO. pHHco3-' essentially all of the carbonates are in the form of HC0 3-.CO.2.CO.6 .CO.3 moles/liter.3 and a CT .7 x 10-' ~ 0 ~ [OH-] remaining after reaction with H.7 X 10.3. equation. [HCO. At pH 6.'-] + [CO.-] formed from H.-] + [HCO.7 x 10-' .-j Final [HCO.CO. A wastewater containing 1 X 10-2 M H2 S04 is to be discharged to the stream. 9. Example 4-33 A stream has a pH of 8. Therefore. since we assume that it has all reacted with the added OH-.-+ H.-] Final [CO.47 From K a" and Kw.3 X 10-' + 1.7 x IO-'M X 10. C03 of 3 x 10.3 x 10-' ~ 1.IH 2CO.[OH-] reacted withH.'- ~ ~ ~ 8.1.] ~ ~ initial [H.'. HC0 3 . thus the reactions. -] _ K".CO.[HCO.-] to [H. the ratio of [HCO.} =10.+ H. Also we can deduce that our final solution will not contain a significant amount of H2 CO.4 M) greater than the initial IH2COj] (= 1..7 From K"" [H+] ~ 10.2 equation for relationships between concentrations of the major form CO.7 X 10.] can be determined from the K".10. 53. that is.172 Acid·Base Chemistry Approximate Solution The strong base is added in an amount (3 X 10.4 - 1.3 x 10-' pH ~ 10-9 •47.7 x 10-'/1.CO.3 X 10-'. the weaker acid.'-] formed + 1.-] reacted with OH.O are both important. respectively. .'-] ~ 1. if the pH may not drop below 6.+ OH-->CO..3 x 10-' ~ initial [CO.[WI .1.1 x 10. and the corresponding dilution ratio.CO. Final [H.5 . initial [HCO.CO.] . What is the most waste that can be discharged per liter of stream water. 7 . ~ [OH-] added .

:'t~~tC!~. and organic bases.CO. Acidity is a measure of the capacity of a. I~~~iiYii~cittr. We can define alkalinity and acidity in two ways: operationally and a~alytically (or mathematically).4 mole of HCO. Let us first examine the operational definition of alkalinity and then proceed to see how this is related to the mathematical definition when the components of the solution contributing to the alkalinity are only carbonate species and OH-.' to H+.'?:t .S.CO.~~_§~~~~1 borates. ~ 3 X 10-' ~ [R.s. u. In the determination of total alkalinity a known volume of sample is titrated with a standard solution of a strong acid to a pH value in the approximate range of 4 to 5 and usually in the range 4.::. phosphates. since this will convert 10. Assuming a complete reaction between H+ and HC0 3 -.043 or 0. .H.14 H+ + HCO. 2H+ + C01. This endpoint is commonly indicated by the color change of the indicator methyl orange.] + [RCO.043 liter of waste may he addedlliter of stream water. ". water to neutralize strong base.¢ H 2CO.] [HCO.L . we obtain mole H+ can be added per liter of stream water.al1Y ati~ib. [H. a~~i'~and·"i:i~<3Iici~~.'.13.. pre.-] ~ CiS) (3 x 10-') ~8.¢ H2 CO._Y{~lL9~ Jg~_sp"sj"s.5 to 4.CO.] with the mass balance. the mass balance be~omes 173 C T •CO.6 8. in_§Il)(l)1 c~~t~C.Q.:.11.-]I[H. is very small.!~iils!!iIEiT()~J?E~ l!9. Alkalinity and Acidity Alkalinit is a measure of.~-.Q.:Ii:a:~~IX· .4 8.itr~.6 x 10-' 2 x 10 ' 0.q!l~LQ!t..6 X X 10.6 x 10 -4M xlO-'M ~G:~)(3 x 10-') ~2. Thus 8.--.._s.:XJtQ!!-~J?~£~_. at pH 6. therefore. hi-najiiraTwate~sthis capacity is..the capacity of a water to neutralize strong d '!9.3.7. The waste is 10-' M H2SO" or 2 x 10-' M H+. the total alkalinity is often referred to as the methyl orange alkalinity. __ C::. 4. of!~n .8. amin~nia'...CO.-] Combining the ratio [HCO. The H+ added is the stoichiometric amount required for the following reactions: H++OH-¢H 20 H+ + H.CO.The Carbonate System Since [CO/-j.

co.solution).=: H 20 1 (i.02 N H2 S0 4 to titrate it further to the methyl orange endpoint.0. The value of to titrate it to the phenolphthalein endpoint and 22. caused by the masking effect of the buffering of water (i. CT.e. arid (2) the pH of a solution to which has been added the stoichiometric amount of H+ required to complete only the following reaction: W + OR. the carbonate species will be present all as CO. 200 ml of the water require 1.:. They represent. what are the total and carbonate alkalinities of the sample in meqlliter and the total alkalinity in mglliter as CaC0 3? .co. Caustic alkalinity can be determined by calculation if the carbonate and total alkalinity are known..e..'· (the caustic alkalinity)·cannot be determined readily in the laboratory because of the poorly defined eRdpoint.. Example 4·34 A sample of water from the overflow of the recarbonation basin that follows a precipitation/softening process has a pH of 9.·.· is about pH 8.'-. This is the carbonate alkalinity.3 while pHco. The amount of acid required to reach pHco . respectively.02 N H. This endpoint can be determined with a pH meter or by the color change of the indicator phenolphthalein so that it is often referred to as the phenolphthalein alkalinity. solution wlth a C TCO. the solution at the endpoint of the titration should be an H2CO.· and pHco. (I) the pH of solution to which has been added the stoichiometric amount of H+ required to complete the following two reactions: W + OR. is generally between pH 10 and II and varies with . C TCO . of the solution being titrated.1 ml of 0. or as the form that results when CT.CO l ' It is possible to determine experimentally the amount of acid required per liter of solution to lower the pH of a solution to pHHco..9 ml of 0... These are pHHco.molar solution of CO 2. as pHco" and we call the solution a CT.'·.. Assuming the sample contains no calcite particles. that equals the . Since we will assume that the alkalinity titration is a closed system (no atmosphere). the solution will have the pH of a CT.solution).co..molar HC03. and H20. H20).-molar C032.:.=: H2 0 In the lalter case. For the carbonate system we can theoretically identify two more significant pH values that occur during the course of an alkalinity titration. the reaction H+ + OH.174 Acid·Base Chemistry The pH at the true endpoint of the total alkalinity titration should be that of a solution of H2CO. We refer to the pH of such a solution . moles of Na2C03 is added to H20 (i. the pH of aCT.

-.'.3) and we then required an acid volume of Vmo to reach about pH 4.4 meqlliter x 50 mg CaCO...+ H+ --> HCO. it imme· diately became colorless (or if the pH was below about 8. we would know that the original solution contained only CO.3 (V mol.02 eqlliter x 1000 meq/eq x 1/(200 ml sample volume) 0. . . make some deductions about the initial composition of a solution from the alkalinity titrations.18).alone.Carbonate alkalinity = the meq of acid/liter of sample required to reach the ~ ~ *-') . If the initial solution required V p ml of acid to reach pH 8.-~~------~-.and CO. we can. If we make the previous approximation of complete reaction and combine it with the assumption that the alkalinity of a water is due solely to carbonate species and OH-..Lp]{-L3J().and HCO.'. It should be emphasized that .3. If the volume of acid to reach pH 8. r 1\ The Carbonate System 175 phenolphthalein endpoint l. -.3 but no further acid addition was required to reach pH 4. ~~~~..... We can also deduce that each mole of CO.+ W --> H20 ~---"'~- and ~ CO.- .~ ~ is complete.02 eqlliter X 1000 meq/eq x 1/(200 ml sample volume) = 2.91~jU<3aj. Thus we assume that ~ti2!!s OH.l ml X 0. By similar reasoning we can show that if Vp > Vmo' then the major alkalinity species are OH.3 to approximately pH 4. does not exist because there is no pH range over which these two species are concurrently the major alkalinity species (see Fig. the original solution would have contained only HCO..3 and another H+ as it is titrated from pH the major species contributing to alkalinity.present will consume one H+ when the solution is titrated to pH 8..'. The third possible combination of major alkalinity·causing species. OH.3 to pH 4. if Vmo > V" then the major alkalinity species are CO.4 meq/liter 2. 4.'. the alkalinity was due to OH.'tiop HCO.3 (Vp) was equal to the volume of acid required to proceed from pH 8.3.imeq ~ 120 mglliter as CaCO..+ W --> the major alkalinity species.3... to a good approximation. -- ~~()tl. when we put phenolphthalein indicator into the solution..'-.11 meqlliter Total alkalinity = the meq of acid required/liter of sample to reach the methyl orange endpoint ~ 24 ml x 0. If.and HCO.

'-. X N X V-1*2 [ J < I X 10-3 M. When V.3 M.'-] ~ V. is added. COiHCO. rol Vroo = volume of titrant from the phenolphthalein endpoint to the methyl orange moleslliter. These relationships are tabulated in Table 4-9. ml x normality of titrant in eqlliter x ( I I I) samp eva ume. [OH-] ~ (Y.and COl-. Vp = ml acid required to titrate the COi. V. ml V = sample volume.-] ~ V m. the HCO.. - H. . X N X V-1 [OH-] ~ V.CO.- x ~ eqH+ ' 1.OHcoB and HCO. ~22.according to the reaction: H+ + COl.) X N X V-1 [CO. thus the acid added in eqlliter = the concentration of C032. I H+ is added for each CO. . M [CO.CDJ > 2 however. [CO.~ !.11 x 1O-'molelliter -> [CO.-] ~ (Ym.originally present plus the HCO.V.5. eqlliter Note: The accuracy of the OH.'-] ~ V.V m.lml V m. results will be significantly in error if CT. X 10. From Table 4·9. rol N = normality of titrant.'-] Since H + ~ + HCO.- Where: Vp = volume of titrant to the phenolphthalein endpoint. Example 4-34 (continued) We can now determine the major alkalinity species from the titration values. m I mole CO . X N X V-I .02 X 11200 0.1 x 0..) X N X V-1 = Vmo ~ 0 Vmo = 0 Vroo > Vp V.concentrations obtained from this table depend upon the value of CT.C03' Accuracy is acceptable for CT. [CO.'-] ~ V. .9ml Since Vmo > Vp • the major species present are HC03.- TABLE 4-9 Approximate Concentrations of Carbonate Species and Hydroxide from Alkalinity Titration Data Condition Vp Predominant Form of Alkalinity Approximate Concentration.~ He03 -. X N X V-1 ""2 [HCO.176 Acid-Base Chemistry the concentrations obtained by this procedure are approximate and significant errors are introduced if the solution pH is greater than about 9.'-] ~ V ~ X N X V-1 'i-:J.and COl.

In the analysis of waters the two endpoints used in acidity determinations are pH 8.1) 0.-> HC03.and is generally between 10 and I L The carbon dioxide acidity endpoint is at pHHco. [HCO J -] = (V mo . carbon dioxide acidity is referred to as phenolphthalein acidity and mineral acidity is often called methyl orange acidity. of the sample. For a water in which acidity is contributed solely by H+ and carbonate species.+ H20 20H. The mineral acidity endpoint is at pHco" about pH 4 to 5.18 X 1O-3 molelliter 1 We can make similar definitions and calculations concerning acidity measurements.3.7 is used instead of pH 4 to 5.'. 14th ed . about 8.. respectively.02 X 1 200 2.'. is added to pure water.endpoint is ill defined. to the color changes of the indicators phenolphthalein and methyl orange.""e sample to the phenolphthalein endpoint will be converted to H2CO. when the sample is titrated to the methyl orange endpoint.3 and pH 4 to 5 correspond. .co.1. 1975.+ H2 CO. "" C0 3 + 2H20 2The species present at the endpoint pH are those which result when Na2C03 equal to theCT. the endpoint of the total acidity titration is at a pH where a stoichiometric amount of OH.-. See Standard Methods. pH 3. As in the caustic alkalinity determination the pH co.The Carbonate System 177 formed by titration of . This pH is pH co.+ W "" H20 OH-'+ HC03.'7 Using the assumption of complete reactions. Since the endpoints at pH 8. from Table 4·9.Vp)ml x normality of titrant in eq/liter X 1 mole HC0 3 -leq X X IIsample volume in ml ~ ~ (22. Thus.3 (pHHco3-) and pH 4-5 (pHco).9 . we can deduce that adding base to achieve a pH of 4 to. Addition of strong base to pH 8.has been added to complete the following three reactions: OH. 5 will allow the completion of the reaction H+ + OH-> H20 and the carbonate species will be in the form that exists when CO2 is added to pure water.3 will complete the reactions and H2CO.+ H20 17 For wastewaters in which weak acids and bases other than the cc:rbonate system are present."" C032. + OH.

1 rl1 1 ~"' "I I 1 1 Strong .: >- I _1.' the total I t Strong 1 8:g • N. must be added to lower the pH from pH eo .-. the carbonate alkalinity endpoint_ An additional equivalent fraction must be added to lower the pH from pHHeo. Relationship of the pC-pH Diagram to the titration curve for the carbonate system at 25° C.. acid addition base addition I I Caustic alkalinity Fig.t.178 Acid-Base Chemistry Figure 4-19 shows the relationships between the acidity and alkalinity titratioh curves and the pC -pH diagram_ It shows that I equivalent fraction of strong acid. pHHeo. (f = I).'.to pH eo. .

8 + 12.1 M Hel to lower its pH to 4.l N NaOHl25D ml sa~ple. ~ ~------------..2 ml x 100 meqlliter xl/250 ml sample volume = 4. In doing so the following reactions will essentially be completed.2 = 23.2 ml of 0."o) of 0.- + OH.1 N NaOHl250 ml sample to complete the second reaction and raise the pH to 8.3. .CO. What are (!) the total alkalinity arid total acidity. total acidity = (5..+ H.'.-> H. where CT. the HC0 3 . a further 5. H+ + OH.8 ml of 0. and (3) the approximate concentrations of the major carbonate species? / mi Solution 1. This will require an additional 12.during the total acidity titration.1 N titrant was required to titrate to the CO 2 acidity endpoint and 12.The Carbonate System 179 alkalinity endpoint. we can deduce this from the information given.7.52 meqlliter 18 • Note that total acidity can also be calculated with the aid of Fig. That is. (2) the carbon dioxide acidity.Q H.8 7 + 5. 4·19.t 1 Total acidity = 23:8 ml x 100 meqiliter x 250 ml sample volume = 18 9. total acidity = CO 2 acidity + I eq fraction = CO 2 acidity + CT. In addition.2 W.2 ml of D. The pH of the sample is approximately 6.I to pHC032-. Total alkalinity = 12.-> HCO. thus mineral acidity is absent and we can disregard the first reac· lion. an amount equivalent to the strong acid required in the total alkalinity titration.7) requires the addition of 5-Jl ml 0.COl .88 meqlliter Total acidity is equivalent to the amount of strong base which must be added per liter to raise the pI. and HCO.O + OR.8 ml of 0. The total amount of base added then is 5. It takes 5.present in the sample (which ti· trated as total alkalinity) will need to be converted to C0 32.8 + 12. which is approximated by pH 4.+ H. Total alkalinity is based on the volume of titrant required to lower the pH of the sample to the methyl orange endpoint. Sin~e 5.1 N titrant was required to titrate to the total alkalinity endpoint.1 N· NaOH to raise its pH toJU" the same volume of the water requires the addition of 1"2.formed via the second reac· tion to CO/-. These relationships show that for the carbonate system () .3 in this problem.52 meqiliter.coJ = CO 2 acidity + total alkalinity.-> CO.8 j:\lU250 ml sample./-------------------------------------------Example 4-35 Two hundred and fifty ml of a freshly sampled well water (approximately pH 6.8 mU25D ml is required to conver! the HC0 3 .3. To complete the third reaction.8 + 5.O Although we are not given the volume of titrant to pHc~2-.2) x lOa eqiliter x (1/250 sample volume) = 9.

B ml ~ x 100 meqlliter x 2!0 ml sample volume much less dependent. rather they vary with the C T •CO.8 for 150 mqlliter (3 meqlliter) and pH 4.2 X 100 X 250 ~ 4.3) and V mo ~ 2.8 ml x normality of titrant in meqlliter X X lIml sample volume I mole H. ~ a (initial pH < = species is HC03 -.B8 mMlliter Since the mineral acidity ~ a (initial pH> 4. in the initial solution. in solution.leq of OH- ~ 5. 4-20. Since V. [H 2CO.-. If we treat the titrations as closed systems. acidity 3.5 for 500 mg/liter (10 meq/liter)" shows that this variation is significant indeed for pH eo .IBO 2.3.1 for total alkalinities of about 50 mg/liter (1.B ~ x 100 X 250 I 2.. 4-20 and the statement in Standard Methods (14th ed.are not truly fixed values. This appears to be a reasonable approach if the solution is not shaken vigorously and if the titration is conducted rapidly.4.3.3) and base (5. the C T •CO. the major acidity species is H2 CO.] = 5. at the endpoint will be the same as theC T •co .32 meq/li ter 12.. Also note that 1 OHis required to convert each H2 CO." The actual values that correspond to pHco" pHHco. pH 4. 8.) that "the following pH values are suggested as the endpoints for the corresponding alkalinity concentrations as calciUm carbonate: pH 5. The equivalence point pH is the theoretical pH at which a titration is complete while the endpoint pH is an approximation of the equivalence point pH. Alkalinity and Acidity Endpoints We have been careful in the preceding discussion of alkalinity and acidity titrations and calculations to refer to the pH of the various endpoints" as "approximate values.32 mM 4. whilepHHco. The variation in equivalence point pH values is shown in Fig. and pReo..'. CO.13. . to HC0 3 -. Figure 4-20 shows that PReOlalso is strongly dependent on C T •CO.B ml) is required to reach pH 8.0 meq/liter).2 mt the major total alkalinity . Reference to Fig.CO. 19 The reader should keep in mind the difference between endpoint pH and equivalence point pH. Acid-Base Chemistry Carbon dioxide acidity corresponds to the amount of base required to raise 'pH to. ~ 5. Thus [HC0 3 -1 Vmo ml x normality of titrant in meq/liter x lIml sample x I mole HCO 3 -Ieq of H + I ~ 12.

2). especially the one employing the pC·pH diagram (e. Here we will examine approximate methods for their calculation. we assume that there is present an H2 CO. At the total alkalinity (and mineral acidity) equivalence point.12.Co.. which is the approximate proton condition for an H.1 - _ [H+][HCO. Therefore.l'12 For a total alkalinity of 50 mgiliter as CaCO. [H+] = (K".The Carbonate System lSI 10-5L-__ ~~ ____ ~ 2 ____ 4 ~LL ____ pH -L~ __~__L-____~~____.] Considering only the K . at the endpoint.5 and 9. solution. [HCO.CO. solution of concentration CT.-] [H.65 pH = 4. (l meqiliter) and an original sample pH between 7. will produce a 10-' M H..] and assuming [H+] = [HCO.CO. The equivalence point pH values can be calculated exactly using previously presented methods. .CO...65 . X 10-')112 = 10. The pH values for alkalinity and acidity titration endpoints in a closed system as a function of the initial total carbonate concentration.coa which is equal to CLeo.4. see Section 4.-] = I x 10-' M Titration to pHeo.1 equation K = C T •eo.' 6 8 10 12 14 Fig.CO. For pHeo" we will check the rationale behind the Standard Methods statement quoted previously. solution with an [H+] of [H+] = (l0-6. of the sample prior to titration. 4·20.CT. [H.g.-].

Since at pHHea.ea.6. with C T. If a sample is warmed and bubbled with nitrogen gas (free of CO. andK".CO. since it is governed solely by the small amount of CO. pHea. the equivalence point would be the pH. concentration at the endpoint.'-] Substituting for these terms fromK...) C T. [H. X 10-10 .' we find that (KwK". the solution is boiled to expel CO" and then. respectively. Thus for C T. [H+] < [OH-] .C03 1/' + (K a.ea.'-] or approximately..1 K a. values.' we have an HCO..5 and for total alkalinity of 500 mg/liter as CaCO.CO. has led to alkalinity titration methods (employed in Europe) in which the majority of the acid is added.1 and is independent of alkalinity.equivalence point (for carbonate alkalinity and carbon dioxide acidity) is at about pH 8. perhaps indicating that some allowance has been made for the escape of CO.ea. with CT. -] [H+] = ~ C T. after cooling. (10 meq/liter). since at pH > 7.182 Acid-Base Chemistry Similarly. generated from the last small acid addition plus the CO. (3 meq/liter).CO. where [H.3 and varies relatively less than PHea.CO. > IO-'M.. ~ 4.3 For the range of alkalinities in which most natural waters fall (10" to .solution.] = [OW] + [CO. = 4.2 The Standard Methods endpoint values are higher than the closed system pHea. The variation of pHea. = 10-' M. for a total alkalinity of 150 mg/liter as CaCO. during the titration that would result in a lower H. the proton condition is [H+] + [H. The pHHea.] ~ a and [H+] = [OW] which at 25°C is pH 7..] = [OH-] + [CO.ea. pH= 8. [H+] ~ (10." K w . we obtain PHea. we find Solving for [H+] and recognizing [HCO. The pH of the endpoint is then at about pH 5. the small amount of remaining acid is added.')'12 ~ 10-8.ea. in the atmosphere.2 )'12 The first term becomes insignificant compared to the second term when CT.) during titration.

their proton conditions.] and [H+] are negligible so that [HCO. and between total acidity.. the proton condition is 2[H. > 10-'.· will be very close to 8. pH co .'· can most easily be determined by using the pC. At extremely low alkalinities. The various alkalinity and acidity measurements are defined in term" of the proton conditions of the equivalence points to which the alkalinity and acidity determinations dre the determination of initial pH and either total alkalinity or total acidity will allow the computation of CT.CO. C T •C03 For values of C T. < 10-'.5. we find K. Thus the presence of alkalinity with respect to a particular endpoint indicates an excess of species containing less protons than the reference (or endpoint) species over species containing more protons than the reference species.-] + [W] = [OH-] At pH » 7. Alkalinity requires the addition of strong acid (H+).'.co.and H+ as buffering components. Since at pH co . Acidity requires the addition of strong base (OH-). [H. the pH will be less than 8.'-]· = CT.] + [HCO. [W] = (KwK. and if two of these quantities are measured. pHHCO. see Table 4-11. H+. and all species. which contribute to the alkalinity and acidity.'.'· we have a CO. H+. . there is a definite relationship between total alkalinity. The pH co. and the associated mathematical definitions of acidity and alkalinity for a water containing only the carbonate species.3. which is tantamount to removing and CT.alone. Analytical Definition of Alkalinity and Acidity Alkalinity and acidity are defined on the basis of the constituent bases and acids. 4·20.The Carbonate System 183 10-' M ·or 50 to 500 mg/liter as CaCO.. 4·20 shows. pH. and OH.13.). as shown in Fig... Thus the presence of acidity with respect to a particular endpoint indicates an excess of species containing more protons than the reference species over species containing less protons than the reference species. the third can be calculated. when CT. Table 4·10 summarizes the various equivalence points... Each of the mathematical definitions of alkalinity and acidity can be expressed in terms of a values.pH diagram. Since many natural waters can be treated as though they were solely buffered by carbonate species. pH.3. respectively.).co. Substituting from and K wand recognizing [CO.CO. 4. and OH-.-] = [OH-]. From these expressions we can see that for systems which are buffered by carbonate species.CO. For such systems. as Fig. OH.endpoint (for caustic alkalinity and total acidity) is between pH 9-11 and varies significantly with CT.

-] + 2[CO.-] + 2[H.[ (a.O C0 32H.[H+] Total acidity ~ [H+] + [HCO.CT.CO.] . (a.2[CO.[HCO. cKw should be used in place of Kw.] . (0:.[H.] .[OH-] Caustic alkalinity ~ [OW] . '" TABLE 4-10 Alkalinity and Acidity Equations and Equivalence Points Equivalence Point pHco> pHHCO.H.[H+] .[H+] a~ + [~:] [H+] H.'-] + [OW] ~ Definition (Alkalinity and Acidity in eqlliter) Total alkalinity Mineral acidity ~ ~ [HCO.[C0 3 2 -] . -] .] [OH-] TABLE 4-11 Alkalinity and Acidity in Terms of CT.'-] + [OW] ~ Carbonate alkalinity ~ [CO.COl (0:0 - 20:~ + [H+] a~ + [H+] - [~:] ~ [W] Carbon dioxide addity Mineral acidity [H+] - ~:] . -] + 2[H.CO. and C"co. -] .-] + 2[CO.[OH-] [H+] + [H.'-] + [OH-] . + CT.[W] .O [W] ~ Proton Condition [ Kw + 20:~ - CT. (a 2 - Oi Values Parameter Total alkalinity Carbonate alkalinity Caustic alkalinity Total acidity ~:] .CO.CO.- Reference Species H2 CO. + 20:2) Note: If ionic strength effects are important.] [W] [CO.CO.'-] . + 2a~ +] .[W] [H+] .[OW] pH cOl- + [HCO..2[H. and the a values should be calculated using '1(a rather than Kilo .[W] Carbon dioxide acidity = [H+] + [H2CO.O HCO.'-] + [OH-] .COl {a.

Knowing pH = 7.-] From K a.83 x 10-' x 0.969. and OHr The pH on sampling is 7.CO.83 X 10-' 2.74 10-' M 2- _ 2.5.02 eqlliter x 11100 ml sample volume ~ 2. we obtain [H+] ~ 10-'-' 10-'" C T.9 mg Clliter Therefore.02 N HCI to lower the pH of 100 ml to 4. What is the major component of the alkalinity? (Neglect ionic strength effects.The Carbonate System 185 Example 4·36 What is the total inorganic carbon concentratio'n (in mg carbonlliter) in a water buffered by the carbonate system.) + [H:] .8. '" O.] [HCO. ."O C T • CO. ] ~8. 2.ies contributing to alkalinity is thus HC0 3 -.7 ml X 0.8 x IO-'M The major spec.969 ~2. x 0. We found that the total alkalinity = 2.) Total alkalinity (eqlliter)~ 13. Example 4·37 We can use the mathematical definition of alkalinity to provide an exact solution to the Example 4-34 worked previously by the approximate method of complete reactions.83 x 10-3 moleniter X 12.".031 ~ 8.(a.COJ(a1 + 2(2) K From Appendix 1.74 X 10-' ~ CT.031.969 ~ C T. + 2a. ~ ~ [OW] ~ [H.7 10.8 x 10 -5 M x 2. Thus 2.74 X IO-'eqlliter From Table 4·11.74 X [CO.74 x 10-' 2. ao ~ 0.000 mg carbon/mole ~ 33.7 !Ill 0.74 X 10-' 0.CO.0. a.4 x 10-3 eq/liter and the initial pH was 9. Total inorganic carbon concentration = To determine the major component of alkalinity.[H+] ===C T . ~ ~ 2.COJ = -~-~­ a. and a.3 x 10-10•3 10 '.83 X 10 -.8 and the water requires 13. we must determine the concen· trations of each of the alkalinity species in the original sample. H+. ~ 0.CO. 2.2.

5 line and total alkalinity 1.CT.J = 0 X [HCO. where [H.= (0.'-] = a. moleslliter) can be represented by . Thus 10.CO} A water has a pH of 8.8 meqlliter.17 X 10-' [H. + 2a. X X 10 This diagram.952)(2.'-] = l. Total alkalinity = X 10-' These values check well with those obtained previously using the approximate equations in Table 4-9.C T. of a water are given. CT. = 1.5 and a total alkalinity of 1.-] = a. at the intersection of the pH 8.048)(2.17 X I~O_~~.048.0.8 X 10-' M (see point A).14 Total alkalinity = 2.9 Cr.952 + 2(0.9 2.8 meqlliter. In the Deffeyes diagram coordinate system. Solution From Fig. pH.952 and a. the addition of strong acid (C" moleslliter) and strong base (C s.18 [CO.CO J = - 10. and pH has been used by Deffeyes to construct a diagram relating alkalinity to C T.l [" and total alkalinity. CT. 10-') =2. at a series of constant pH values.9 X 2.048) + 10.28 x 10 -') = I. can be used for a wide variety of calculations involving the addition and removal of various species from the carbonate system.CO. What is its The temperature is 25°C. = 0.-] = 2.186 Acid-Base Chemistry From Table 4-11.4 x 10-' = C T .l X IO-'M IO-'M The relationship between alkalinity.cO.CO. If two of the three characteristics. shown in Fig.28 X 10-3 Now [ + [~:] - [H+] At pH 9.28 and from Ka". from Appendix I. the third characteristic can be determined using the 4-21. = 4. = 0. CT.] = 10. Example 4·38 e T. 4-21. = (0.(0.

LJNaHC03 Ca COl Na2C03 j CA CO. & Ocean.. 4·21. mM CT. 1 _J 11 LJ 1 Dilution Fig.0 2. S. COl C. Reproduced by permission of Limnology and Oceanography. From K.0 1. The Deffeyes diagram for 25°C. 187 11' _J _J It . 10: 412(1965).0 Total carbonate carbon. Deffeyes. Lim.

'-. The water characteristics.9 meqlliter. The point pH 9. The addition or removal of CO..75 X 10-' mole of Wlliter.-N produces 3 moles of H+ (strong acid) or 14 g NH. meqlliter in the diagram to point C. the desired final water. The characteristics of the treated water are thus pH = 6. = 1. 1. and alkalinity to the same extent and therefore results in a 450 downward movement in the diagram. and CT. The required additions are 20 This is an important point that the reader can verify using the alkalinity equations.65 mM.5 X 10-' glliter)/(l4 g/mole) or 0. is added or removed per mole of meqlliter alkalinity and pH 8. Thus 3.-N produce 3 moles H+.5 mglliter as CaCOj(50 mg/meq)) = 1.0 andCT. 4·21.0 mM? Solution The original water sample contains (82.CO. and the product of dmmonia oxidation is N2 gas.0 are located at point B on Fig.0 and the C T • C03 to 2.4. CA. .65 meq/liter of total alkalinity.0 is treated with C12 {gl to oxidize NH3(aq) to nitrogen gas (breakpoint chlorination).CO.5 mglliter as CaCO. Dilution decreasesCT. are added or removed per mole of CO. since 1 equivalent of alkalinity and I mole of C I. and a pH of 8.5 mg NH. N. what is the pH. we can use the Deffeyes diagram to solve rather complex problems.C~ = 2. Carbonate addition or removal causes a 60 (211) movement from the horizontal. is to move vertically downward from point B.' given that negligible dilution takes place by the addition. andeT. since this is a closed system diagram and strong acid and base addition affect alkalinity without influencing C T.-.-Nlliter produces 3 x (3.5 mg NH3-Nlliter.col-following treatment? What combination of NaOH and NaHCO.CO.. It is also an important consideration in sampling because CO2 release or uptake after a sample is taken hut before total alkalinity is measured will not affect the total alkalinity value.75 X 10-3 mole H+/liter of solution. 0 Example 4·39 A water with an alkalinity of 82.0 mM lies above an upward 45° movement in the diagram from point C. must be used to adjust the pH of the treated water to 9.188 Acid·Base Chemistry vertical movement in the diagram. without affecting alkalinity.Co. since 2 equivalents of alkalinity and I mole of C T. total alkalinity = 0. The effect of addition of 0. If the initial ammonia concentration is 3. '0 Bicarbonate addition or removal causes a 45° movement.75. total To adjust the sample composition to the point. causes horizontal movement in the diagram because this influences CT.Io' + 6W + 6CI- Thus I mole of NH. + 3CI. we first satisfy the CT. Table 4-8. The reaction of chlorine with NHa to produce N2{g) is 2NH. . Armed with these tools. 0.coJ requirement of the final water by adding NaHC03 to point D and then adding NaOH (C a ) to move vertically upward from point D to point E.

0. and the concentrations of [H+]. By employing these relationships. The diagram in Fig.02 N NaOH to raise its pH to 8. Eq. The same volume of water requires 4 ml 0.35) NaOH could be added instead to produce the same effect.SO.02 eqlliter x 3 I~O ml I~O ml sample volume 2 x 10.02 eq/liter x sample volume Carbon dioxide acidity = 4 ml x ~ 8 x 10-' eqlliter . C T .mineral acidity = C T.] + [HCO.CO. [OH-]. Compute the total inorganic carbon content. and [CO. [HC0 3-]. and (0.35 roM Na. to lower the pH of 100 ml to 4. The relationship in Eq.] + [H+] .02 N H. Total alkalinity ~ 10 ml = x 0.].[CO.[OW] . C03 In each of these equations both of the capacity parameters can be readily determined by titration with a strong acid or base.3 to 4.'-] + [OH-] .'-] = C T. [H.'-] ~ ~ CT. Solution Titrations are for total alkalinity and carbon dioxide acidity.carbonate alkalinity Proof From Table 4·10.75'mM ~ Since NaOH + NaHCO. Example 4-40 A 25°C water sample requires 10 ml 0.-] + [CO.3 and Eq. 4·120 applies to waters with pH below 4.c0J' the initial pH. (4.0. C03 Similarly.CO.(CtoD) NaOH(DtoE) ~0. we can compute C T.35mM 189 ~0.'-] in the initial water sample assuming that alkalinity and acidity are solely due to the carbonate system.3. [HC03-] + 2[CO.75 .[H+] + [H. 4-19 also shows these relationships. Total alkalinity + carbon dioxide acidity = C T .3.CO.3. C03 (4·119) (4·120) and Carbon dioxide acidity .118) [H. H+ and OH-. 4-119 is useful for waters in the pH range 8. and individual alkalinity or acidity species based solely on the two appropriate titration Carbonate System NaHCO. -> Na.CO.3.eq/liter 0. 4-118 is applicable for waters with pH > 8.CO" 0.4 roM Further examination of the expressions in Table 4·10 allows the follow· ing useful relationships to be established: Total alkalinity .C03 ' the initial pH.

75.) + [~:] X [H +] 10-' ~ 2.coJ (= 2. In addition the analytical definition of acidity and alkalinity must be changed to incorporate these bases.715.. Alternatively.. ~ 2.CO.col 2 X 10-' [H.O "'" B(OH)..8 10-. Fig. 4·119.] [HCO. 4-21. + 2a. The following reactions are important in this regard in waters and wastewaters."'" HPO.8 From Table 4·11. + H. the pH Thus 6.190 Acid·Base Chemistry From Eq.3.+ H+ 9. From Appendix 1.71 ~ » [OH--] .[H+].co.285..8 X lQ--3).'. knowing the total alkalinity (= 2 x 10-3 ) and having calculated Cr.8 X 10' 0.14 10-'( a. ande r. to find [CO. (25°C) Silica (silicic acid): H. "'" H. from Appendix 1.-] a. we can use [HC0 3 --1 and [H+] as calculated together with K .CO l C"co. we cannot use these calculations and diagrams without modifications.f:: .+ H+ Hydrogen sulfide: H.~2 X IO-'M Within the limits of accuracy of Appendix 1.SiO. ~ 0. ~ ~ 0. However.1 9.are present that react with protons in the pH range of the alkalinity and acidity titrations.'-] ~ 5 X 10-'. + H+ Acetic acid: HAc"'" Ac.3 4. At pH 6.+ H+ Dihydrogen phosphate: H.3 7.7 . Total alkalinity + carbon dioxide acidity = C T. "0 ~ 0.. Total alkalinity 2 Assume 2a2 X X IO-'M ~ C.7. we can use the Deffeyes[H+] « a1.8 X IO-'M ~ a.(a..2 7. If bases other than the carbonates and OH. since the pH is less than 8. ". +2 a.P04. a2 = O. ~ 2.+ H+ Boric acid: H.SiO.CT.S"q. "'" HS. to obtain the pH of 6.) + [H+] . -log K.BO.+ H+ Ammonium ion: NH4+ "'" NH.

and NH.[H+] CT.l60 X 10-' mg = 0.copr.44 X 10-5 M . For very complex systems for which a detailed chemical analysis is not available. eqiliter = [OH-] + [HCO.CT. propionic acid and butyric acid.." = 8 mgiliter as SiO.] + f'[Ac-] . as well as carbonates. 4-122.copr. by the carbonate system.33 x 10-' M At pH 9.. eq/liter [OH-] + a.SlCr.AC . Anaerobic digester supernatant often contains high concentrations of bases similar to acetate.-] + [B(OH).col + [OR -1 + iX. and by the hydroxide? Here pKa. + a. Many natural waters contain silicates and organic bases that contribute to the total alkalinity. from Appendix L ". and the silica content was 8 mg/liter as SiOl' What fraction of the total alkalinity is contributed by the the endpoint of the titration. ammonia.'-] + [NH. mg CaCO.imole = 1.CX1. and phosphates. and phosphates.lmeql X 10-' eq/meq = 4 X 10-' eqiliter From Eq. if the system is chemically defined we can show that these substances will contribute to alkalinity if. -] + 2[CO. ammonia. HPO. no attempt is made to work with the mathematical definition of alkalinity. B(OH). Total alkalinity = !X. In terms of a values this expression becomes Total alkalinity. + -] + [HPO.-.5.Sf .' l + 2a2.65.s/ = 9.S'C T •S. + a. will each be completely converted to their conjugate acids.-. However.SiO. Wastewaters contain substantial quantities of organic bases. Example 4-41 The East Bay Municipal Utility District.AC' is the fraction of C T•M present as Ac.CT.[W] (4-121) where f' is the fraction of [Ac-] titrated at the total alkalinity endpoint. H.C T •PO .NH3 + (a1. We can modify the total alkalinity definition to include these species so that Total alkalinity. was 9.SC T •S + a"PQ." = 4. (4-122) + lX'1. for example'.65. values similar to that of acetic acid.Ac)CT. Solution Totalalkalinity(eqiliterl = (20 mgiliter as C~~O.[H+] = where a:.NH3CT. during the titration.. obtains water from the Mokelumne River..CO.The Carbonate System 191 Many other organic acids important in water chemistry have pK.AC .'-] + [H. 10-" [OH-] = [H~] K = 10-"" = 10-4. In January 1968 the total alkalinity of the treated and distributed water was 20 mglliter as CaCOa• the pH.. some of the base is converted to the conjugate acid.

2 percent 10.44 X 10-' eqiliter 0.77 x 10-') = ( 4 X 10' Alkalinity due to hydroxide = 0. Calculate the pH of the following potassium hydroxide. l.0percent Alkalinity due to carbonate and bicarbonate =100 .CT.Si = 0. HCI04 • solutions: 2. Ka = 10. 4. OCI~. in this water a significant fraction of the total alkalinity (almost 20 percent) is due to the silicate system.9 •22 If 10-' moles of the herbicide NaAsO" are added to 1 liter of distilled water at 25°C. PROBLEMS (a) 10-3 M.192 Thus Acid-Base Chemistry Silica in the form of H 3Si0 4- = a. '" H+ + AsO.COO Na) is added to 1 liter of distilled water. (b) 10-' M.eq/liter X 0.44 x 10-') = ( 4 x 10' x 100 = II.6.33 x 10.77 X 4 10-' eqlliter 100 = 19. what is the resulting pH? Determine by solving the appropriate set of equations analytically. what percentage of the total amount of propionic acid is ionized at 25°C? Aqueous free chlorine is hypochlorous acid. 5. 4.8 percent Therefore. Arsenious acid is a weak acid RAsO.87 for propionic acid. KOH. HOCI. Many interesting aspects of the carbonate system occur in connection with heterogeneous systems containing carbonate solids and soluble carbonate complexes. 3.0) = 69.14. with the relative amounts depending on the pH of the solution. what is the solution pH? Solve the appropriate set of equations analytically and graphically and compare the results. (a) A solution of 10-' mole of sodium propionate (CH. These topics are dealt with in the next two chapters.-. (b) 10-' M. If the pKa = 4. (b) Propionic acid is a common constituent of anaerobic digesters.58 x 1.4 = 0.(19. .77 x Alkalinity due to silicate = 0. and hypochlorite ion. If the pH of the digester contents is 7. Calculate the pH of the following perchloric acid. solutions: (a) 10-' M.CH.2 +11.

15. Assume that no weak acids are present in the scrubber water.Problems 193 (a) .1 (c) ao. are added to I liter of distilled water? The temperature = 25°C. results from NOx removal from a stack gas. 2.) Hint: What is the predominant carbonate 'species at pH 8. [Include both approximate (±0. What is the pH of a 10-3 M KHSO.5 x 10.6. and a3 for H}.CO. and lX. per liter if p. Assume that activity effects are negligible and the temperature is 25°C.05) and exact values. 3-4 for activity coefficients. 14.5 X 10.04 at pH 8.7. (a) How much Na2C03 must be added to neutralize this solution prior to discharge? (The final pH is 8. solution at 25'C.) 8.0. al.3. p.3? (b) What is the buffer intensity of the final solution? . at pH 4. 12. 10-' moles NH. at pH 6. '" O? What is the pH of a 25'C solution c'ontaining 10-3 moles NaHC03 and 2 x 10-3 mole NH. What pH results when 10-' mole of NaH. calculate (a) lX. what is the pH of a solution prepared by adding 10-' mole of NaOCI to I liter of water? (b) What is the pH at which 50 percent of the total free chlorine is present as HOCI? (c) What is the pKb for OCI. = 10.01. (See Tables 4-2 and 4-7 for equilibrium constants.PO.and to what reaction does this constant apply? Neglect ionic strength effects. temperature = 25°C.7 mole of NH". a. What is the pH of a solution that is prepared by adding 10.Ac and 10-' moles NaOH are added to I liter of water at 25'C. Neglect ionic strength effects and the temperature is 25°C. and 2. A solution of (0) Write the (b) Write the (c) Write the 10-2 mole of No2HP04 is added to 1 liter of solution. 7. assume that jJ.7 mole NaOH are added to I liter of distilled water at 25'C. a. p. 10. What is the pH if p.CO. 9. 6.Nal andCT•P04 ' proton condition. a2. mass balances for Ncr and P04 • Cr. HF. Calculate the a values as required in Problem 4-10 given that the ionic strength is 0. ~ IO-'? A nitric acid solution.2 after the addition.5 mole of Na. pH = 2. (b) "" and for H.. for hydrofluoric acid. to I liter of water? The temperature ~ 15'C. ~ 7. charge balance. ~ O. (See Fig..5 for HOCI at 25'C. Compare the value obtained when ionic strength effects are taken into account with that calculated when it is neglected.) Compare this value with that obtained if the temperature is 25°C.2.. What is the pH if p. 11.Given that pK. ~ O? 13. '" O? Using either the table or the equations in Appendix 1..

" what is the "new" pH of the total alkalinity equivalence point? 20. in solution in equilibrium with atmospheric CO2 ? (b) What is the pH of the total alkalinity equivalence point.-] = 3 [CO..SO" and the pH of the stream should not be permitted to drop below 6. (a) As the pH is lowered during the alkalinity titration.CO.? (Neglect dilution effects. A sample of natural water that lias been equilibrated with CaC03 (s) is isolated from its surroundings. (a) HC!. pH = 8. pHco.5 units of 8.1 mole H2S0 4 /liter? Assume that the H2 S0 4 will react only with the Na2COa and that the pH after neutralization is 8.1 pH unit. (c) Na. Indicate whether the c. An industrial wastewater is to be discharged to a receiving stream with a pH of 8. or have no effect on the total alkalinity or total acidity and state very briefly why.. (c) If 50 percent of the CO2 formed during the titration" escapes. at what pH is the CO. decrease.xddition of small quantities of the following will increase..+ ~N"" +8H+ +6CIThe maximum amount of ammonia that will be used in the experimehts is 12. 3CI. (d) CO.. A natural water has the following partial analysis: 21. (0) What is the maximum dilution ratio (volume waste/volume stream water) that can ~e used for discharge of the wastewater? (b) What is the buffer intensity of the solution at pH 6.S units of the initial pH of 8.3.) 18.SO. Neglect ionic strength effects. A sample of natural water contains 1 X 10-3 M C03 2.194 16..3 [HCO.. Determine the buffer intensity of this solution. The wastewater contains 5 X 10-' M H. in moleslliter is required to neutralize a pickle liquor solution containing 10. since the pKa of NH/ is 9.) Give your answer to nearest 0. An experiment is to be conducted on breakpoint chlorination (the oxidation of ammonia by chlorine) in which it is desired to maintain the pH constant within O.)] = 3 X X 10-' M 10-5 M [CaH ] = 5 X 10-' M [MgH] = I X 10-4 M [SO. (Note: There is a detailed discussion of the breakpoint chlorination reaction in Chapter 7.5 mg as Nlliter (0.and 3 x 10-3 M HC03 -. Acid·Base Chemistry How much soda ash. (e) Na.3? 19.'-] = I X 10-' M . Na2C03.0 during the reaction. The breakpoint reaction between C1 2 and NH3 proceeds as follows: 17. the temperature = 25°C. Neglect ionic strength effects.3 and a total alkalinity = 2 X 1O~3 eq/liter. + 2NH. Select an appropriate acid· conjugate base pair and determine the concentration of it that will control the pH to within 0.89 x 10-3 moleslliter). (b) FeCI.3.3 and the pH of interest is pH 8). Make the assumption that all of the ammonia is in the NH4+ form (0 reasonable assumption.

Calculate [H+J. N" Ionic Equilibrium-A Mathematical Approach. ADDITIONAL READING ACID·BASE EQUILIBRIA Butler.-] ~ 1 x 10. 24. carbonate. [Cl-] ~ 1 x 10-' M [80. The P(I cannot be rais~d above 9.02NH2S04 is required to titrate a lOO·ml sample to the total alkalinity endpoint? What is the total alkalinity in eq/liter and in mglliter as eaC0 3? (b) A waste containing 10. In some regions carbonate.-J.? 25.4 M (a) What is the solution pH and COl. [HCO. The ionic strength of the solution is 10.Additional Readings (0)" 195 What volume of O.2 M and the temperature is 40'C.3. Reading.7? The lake has a volume of 20 X 10' ft'.'-] neglecting ionic strength effects and compare with the values obtained when corrections are made for ionic strength effects.0. and total alkalinity (in eqlliter and in mg! liter as GaC03)? (c) What is the mineral. CO" and total acidity (in eqlliter)? (d) What is the pH if 5 X 10. What volume of acid rain. carbonate.1 pH unit)? (e) What is [W].(to the nearest 0.13.4 mole OR. Acid rains.concentration? (b) What is the caustic.5. pH = 4. A partial water analysis is given as follows: co. CO2 . J.coJ? (d) What is pHco2 and pHco 3 2. [HCO.3 is 6 ml and an additional 8 ml is required to'titrate to pH 4.'-]. and [CO. and an alkalinity of 30 mglliter as CaCO. (a) What is the caustic. Addison-Wesley. and total alkalinity in meqlliter? (b) What is the mineral. resulting from conversion of industrial S02 emissions to H2S04 . a pH ~ 7. [CO.(as NaOH) are added per liter of the above sample? 23. The titrant volume required to titrate to pH 8. ~ 44 mg/liter [HCOj-] ~ 2 x 10-' M .3 and the exact procedure and compare the results.15. .bearing minerals are lacking in the earth and the lakes in these regions have a low alkalinity.2 moles NaOH/liter is to be discharged to this water. is required to lower the pH of a lake to 6.02 N H2 S04 . What is the maximum number of liters of waste that can be added to each liter of the natural water? 22.-] and [H.CO. 4.] in the original sample? Calculate using both the approximate method described in Section 4.0. A solution has a carbonate alkalinity of 1 meqlliter and a total alkalinity of 6 meqlliter. Fifty ml of a natural water sample is titrated with 0. and total acidity in meqlliter? (c) What is CT. can cause significant pH depressions in such lakes and may result in fish kills. Mass" 1964. [OH-]. Use the constants given in Tables 4·2 and 4·7 for your calculations.

J. Minerals and Equilibria. Princeton.Interscience. New York.J . Princeton University Press. Ricci. H. G . CARBONATE EQUILIBRIA Garrels. Solutions.. L. R.. E. VoL 2. A" Chemical Analysis: An Advanced Text and Reference McGraw· Hill.196 Acid-Base Chemistry l Laitinen. J. N. Kolthoff and P.. Christ. J. eds" WileyInterscience.. 1952. Aquatic Chemistry." Chapter 8 in Treatise on Analytical Chemistry. I. M. 1965. New York. L. New York. 1960. 1970 . New Concepts in a Systematic Treatment. New York. Morgan. Harper. Hydrogen Ion Concentration. Part I. "Graphic Presentation of Equilibrium Data. Stumm. W.. Elving. Sillen. and J. 1959. and C. Wiley. M.

The effect of complexation on solubility is the major topic in Chapter 6.1. the toxicity and possibly the biostimulatory properties of metals. These effects include such things as the modification of solubility (see Section 6-5). the titrimetric finish of the chemical oxygen demand (COD) test uses the complexing agent I. A discussion of complex formation in several dilute aqueous systems is presented to illustrate important points. generally reducing the free metal ion concentration so that effects and properties which depend on free metal ion concentration are altered. cationic. or anionic. the central ions and ligands can exist individually as well as combined in complexes. Ca'+ and Mg'+ concentration. employs the complexation of these metals with the chelating agent ethylenediaminetetraacetic acid (EDTA). with a number of ions or molecules.IO-phenanthroline to detect the presence of Fe2+ and so indicate the endpoint. 5. called ligands. Usually. usually metals. The total possible number of attachments to a central atom or central ion or the total possible . depending upon the charges of the central ions and the ligands. INTRODUCTION Complex formation is important in the chemistry of natural waters and wastewaters from several standpoints. Complexes modify metal species in solution. the approaches to calculating species distribution in more complicated systems are discussed together with the results of such computations.COORDINATION CHEMISTRY 5. surrounding them and attached to them. The determination of hardness. and the adsorption of metals from ~olution. chloride analysis by. The objective of this chapter is to present sufficient background information to enable the student to underslCl{ld the principles of complex formation and stability. NOMENCLATURE AND DEFINITION OF TERMS Coordination compounds or complexes consist of one or more central atoms or central ions. Methods for calculating the concentrations of complexes in fairly simple systems are presented.2. the mercurimetric method depends on the formation of the complex HgCl~{ao) between Hg2+ and the chloride ion. The complex can be nonionic. the modification of surface properties of solids. Complex formation is used extensively in water analysis.

3-. Mechanisms of Inorganic Reactions. 1 2 3 Substances that can accept a pair of electrons are called Lewis acids and substances that can donate a pair of electrons are called Lewis bases. Thus we can regard the central species as an electron acceptor and the ligand as an electron donor. Pearson. FeCl. For example.' Since metal ions have an affinity for accepting electrons. F.IO-phenanthroline in the complex Ni(phenanthroline). tetra-.3+. John Wiley.O). AI(H.'-. Ni(CO)r. there are no characteristic suffixes for cationic and neutral complexes. Molecules and ions with free electron pairs tend to form complexes whose strength is a function of their ability to donate or share that pair of electrons. (II). Ni(II) has a coordination number of 4 in its complex with carbonyl (CO).198 Coordination Chemistry number of coordinated species is referred to as the coordination number.' There are a few basic rules to follow in naming complexes. with 1. sulfatocalcium(II).O and "am mine" for NH3.O). and so forth. tetraamminecopper(1I) ion. These rules are illustrated by the following examples: Fe(CN). MgC03'. Exceptions to this are the terms "aquo" for H. the suffix" -0" is used. they all form coordination compounds. Cu(NH3). . 1967. hexacyanoferrate(lI) ion. The characteristic suffix for anionic complexes is "-ate". with a tend· ency that increases as the electron-accepting affinity of the metal ion increases. .3 Ligands are named as molecules if they are neutral.'. but 4 for chloride. If they have a positive charge. (-I). lron(III) has coordination numbers of 6 for water. and cyanide. carbonatomagnesium(lI).-. (I). Basolo and R.. The coordination number of a metal ion may vary from one ion to another. hexaaquoaluminum(III) ion. if the group is negative. New York. See F.2+. CaSO. Basolo and R. The oxidation state of the central metal ion is generally given in parentheses following the name of the complex. The prefixes "di-. Fe(CN). The superscript "0" on the magnesium and calcium complexes indicates the complex is uncharged. The central species is a Lewis acid and the ligands are Lewis bases. Ligands are attached to the central species by coordinate covalent bonds in which both of the electrons participating in the bond are derived from the ligand. trio." and so forth are used to indicate the number of ligands. G. Fe(H. the suffix" -ium" is used.3+. 2nd ed. G. Pearson for a more complete discussion of nomenclature.2+ the coordination number is 6.

Nomenclature and Definition of Terms


Ligahds that attach to a central metal ion at only one point, such as H,O, OH-, CI-, and CN-, are called monodentate ligands. Ligands that attach at two or more sites are multidentate ligands or chelating agents. The complex formed by a chelating agent and a central metal ion is known as a chelate. Chloride, for example, forms a monodentate complex with mercuric ion, while carbonate and sulfate can occasionally be bidentate-attaching to a central metal ion at two sites:

o o











The chelating agent EDTA'- can attach at six sites, since each of the acetate groups and the two nitrogen atoms have free electron pairs necessary for coordinate bond formation. For example, the EDTA complex with Ca2+ that forms during the titrimetric determination of water hardness is

Each mole of the chelating agent 1,IO-phenanthroline, which is used as an indicator for Fe'+ in the titrimetric finish of the COD test, can satisfy two coordination sites with the electron pairs on the two nitrogen atoms in each molecule. With Fe'+ a red-colored complex is formed with three molecules of 1,IO-phenanthroline satisfying the coordination number of 6 for the Fe'+ ion:


- - -Fe'+--N
/\ / /








Complexes containing one central ion are called mononuclear complexes; when there is more than one central ion or molecule the complexes


Coordination Chemistry

are 1?0lynucJear complexes. When aluminum ions are added to water buffered at about a neutral pH, there· is evidence that polynuclear hydroxoaluminum(III} complexes form from the condensation (dehydration) of mononuclear hydroxoaluminum(lII) complexes:
AI(H,O}.'+ + H,O "" AI(H,O},OH'+ + H,O
hexaquoaluminum(III) ion monohydroxopentaaquoaluminum(IIl) ion

(H,O},-A( [

OH] 2+ H,O







hydroxoaquoaluminumQII} complexes

polynuclear hydroxoaquoaluminumQII} complex

or 2AI(H,O}50H'+ "" AI,(H,o},(OH},4+ + 2H,O The bond strength of metal ion complexes varies considerably. Weakly associated complexes that have one or more layers of water between the ligand and the central ion are known as ion pairs, for example, CaC03 ', CaHC03 +, CaSO,', CaOH+, MgC03', and MgSO,o. In these compounds, the degree of interaction is only slightly greater than the electrostatic interactions accounted for by the DeBye-Hiickel theory.


The rates of coordination reactions are characterized by the terms labile (very fast reactions) and inert (very slow reactions). It is important to understand that these terms do not, in any way, indicate the stability of a complex. They describe the kinetics of the interaction of ligands and a central ion; complex stability is described by the magnitude of the equilibrium constant of the reaction by which a complex dissociates into its component central ion and ligands. An inert complex is not necessarily stable. that is, it does not necessarily have little tendency to dissociate. For example, the tetracyanomercurate(II} complex, Hg(CN}f-, is labile but very stable; while the reverse is true for the tetracyanonickelate(II) complex, Ni(CN}f-, which is inert and unstable.' The substitution reaction in which a ligand replaces a coordinated water molecule to form a complex in aqueous solution, M(H,O}n + L "" ML(H,O}n-l + H,O

R. G. Wilkins, The Study of Kinetics and Mechanism or Reactions of Transition Metal Complexes, Allyn and Bacon, Boston, 1974.

Complex Stability and Equilibrium Calculations


is virtually complete within seconds to minutes at typical natural water concentrations (!O~' M) for the following coinbinations of central metal ion (M) and ligand (L): METAL ION NiH
Mn2+, FeN, C02+,


Cu2 +, Zn2+, Cd2+ Mn2+, CON, CuN , Zn2+, Cd2+ CON, NF+, CuN , Zn2+

H,O, NH,



Substances that are not complexes, for example, methylmercury, HgCH,+, will not undergo ligand replacement reactions. For the same reaction, if Fe'+ is the metal and CI~ is the ligand several hours are required, but if Fe'+ has an OH~ attached to it, that is, FeOH'+, only minutes are required. The reaction between Fe3+ and SO.'~ or SCN~, on the other hand, requires only minutes. Notable exceptions to the statement that coordination reactions occur rapidly are the reactions involving replacement of H,O from Cr(H,O),3+ by ligands such as SO.'~, which take days to years. Changes in the structure of polymeric metal hydroxide species may take weeks. 5.4. COMPLEX STABILITY AND EQUILIBRIUM CALCULATIONS

Equilibrium constants for- complexes are usually stated for reactions written in the direction of complex formation, that is, Ligand

+ central

metal ion"" complex

For example, for the am mine copper complex, NH3(,q, + Cu'+ "" Cu(NH,)'+ and {Cu(NH,)"} _ +4 _ _ .. {Cu'+ }{NH3(,q,} - 10 - K - stabIlity constant When stated for a complex formation reaction, the equilibrium constant is called a formation or a stability constant. Conversely, if the equilibrium constant is stated for the dissociation of the complex it is called a dissociation or an instability constant. Large values of stability constants indicate stable complexes. It is difficult to formulate general rules, or scales of strength, for complex stability because so many exceptions to the rules exist. However, some general statements can be made that aid in predicting what will take place in aqueous solution. A·metal cations, including the alkali metals, Na+ and K+; alkaline earth metals, Mg'+ and Ca"; and other ions such as AI'+ and Si4+ preferentially coordinate with ligands containing oxygen as the electron donor, such as carbonate, hydroxide, borate, and so forth. Other metal ions, of the so·called B-metals, which include Ag+,



Coordination Chemistry

Zn'+, Hg'+, Pb'+, and Sn'+, show a stronger tendency to form complexes with'ligands containing S, P, or N as donor atoms, such as ammonia, sulfide, and phosphite, rather than with oxygen-containing electron donors. Within these groups of metal ions, complex stability is proportional to the charge of the metal ion. Alkali metals form the least stable complexes and indeed rarely complex with any ligand except H,O, while the transition metal ions, for example, CrN , Cr'+, Fe'+, Fe'+, and Ni'+ have a strong tendency to form complexes with a wide variety of ligands. Ligands also differ in their ability to form stable complexes. The ligands phosphate, hydroxide, carbonate, and so forth, are potent complex formers while the perchlorate, CIO,-, and nitrate, NO,-, ions show very little tendency to form complexes. It is for this reason that nitrate or perchlorate salts are used as swamping electrolytes in experiments where it is desirable to have a constant ionic strength.' ' We can also make some general statements about the stability of chelates. Coordination compounds containing five- and six-membered rings are the most stable. For example, EDTA'- and I.IO-phenanthroline complexes with five-membered rings are more stable than some carbonate and sulfate complexes that have four-membered rings. The stability of a chelate generally increases with an increase in the number of points of attachment between the chelating agent and the central metal ion. For example, the complexes formed between Cu'+ and the compounds ethylenediamine.


NH /,,,-





, '





and Iriethylenetetramine,
NH CH/' 'cH



2 ........

CH, ' CH, / , '-H,N- - - -- -Cu2+__ - - - --NH



For a more extensive discussion of the complexing ability of metal ions and ligands, see the following references: S. Arhland, S. J, Clatt, and W. R. Davies, Quart. Rev. (London) 12: 165 (1958); and W. Stumm and J. J. Morgan, Aquatic Chemistry, Wiley-Interscience, New York, 1970.

Complex Stability and Equilibrium Calculations

203 ,

have stability constants, respectively, of -10", -1016 , and _10 20 . The phenomenon of increasing complex stability 'with the increasing number of attachments is called the chelate effect. If we introduce a ligand that forms complexes with two metal ions into a solution containing equal concentrations of the two metal ions, the ligand will form complexes preferentially with the metal ion that produces the complex with the larger stability constant. The titration of hardness with EDTA illustrates this point. The chelating agent, EDTA'-, is gradually added (by titration) to a solution containing Ca2+ and Mg2+. The following complex-forming reactions can occur: Ca2+ + EDTA'- "" (EDTA-Ca)'Mg2+ + EDTA'- "" (EDTA-Mg)'-

K = 10+10•7


Because the stability constant of the (EDTA-Ca)2- complex is two orders of magnitude greater than the stability constant of the (EDTA-Mg)2complex, the reaction between EDTA'- and Ca2+ is virtually complete (i.e" all Ca2+ is complexed) prior to any reaction between EDTA'- and Mg2+. Another aspect of complex equilibria that can be understood using a knowledge of stability constant values is the converse of the previous situation, that is, the competition of a number of ligands for a single metal ion rather than the competition of a number of metal ions for a single ligand. The complex with the largest stability constant again forms preferentially. When a ligand that forms a v,,"ry stable complex with a metal ion is added to a solution of the metal ion complexed with another ligand in a less stable complex, the stronger complexing agent (ligand) will tend to decompose the existing complex and withdraw the metal ion into a complex with itself. The weaker complex must be sufficiently labile for this to occur. This fact is used in the titration of hardness with EDTA. The solution to be titrated (containing Ca2+ and Mg2+) is dosed with the complexing agent Eriochrome Black T (EBT), or comparable substance, which forms a complex with Mg2+ as follows:






0 N-N~ + Mg2+ ","S03Hg-J \N~O





+ 2W

EBT (blue)

EBT-Mg (red)

[EBT-Mg][Wl' [EBT] [Mg 2+] We can note two things from the above equations:


Coordination Chemistry

I., The EBT-Mg complex (K = 10+7) is weaker than the EDTA-Mg complex (K = 10+8 .,),


The color of the EBT ,Mg complex is red and the color of uncomplexed EBT is blue, Thus when the EBT-Mg complex is destroyed by, for example, adding EDTA, the color of the solution will change from red to blue. It should be possible to detect the endpoint when all of the EBT -Mg complex has been destroyed.

In the total hardness analysis, EDTA is added from a buret into the solution containing Ca2+ and the EBT-Mg complex, We have seen previously that EDTA forms a stronger complex with Ca2+ than with Mg2+ so that the EDTA will first react to form an EDTA-Ca(II) complex. Only when virtually all the Ca2+ has been complexed will the EDTA start to decompose the EBT -Mg(II) complex. The completion of the reaction with EBT -Mg is heralded by the color change from the red of the EBT-Mg complex to the blue of free EBT. It signifies the endpoint of the titration at which all of both the Ca2+ and Mg2+ (total hardness) have reacted with the EDTA titrant. For complexes that contain more than one ligand or central metal ion, there are two ways of writing stability constants. Stepwise formation constants are equilibrium constants for the reactions in which the central metal ion consecutively adds one ligand. An overall formation constant is the equilibrium constant for the reaction in which the central metal ion combines with all of the ligands necessary to form a specific complex. We can illustrate these two types of constants using the formation constants of the chloromercury(II) complexes as an example. For stepwise formation we have Hg'+ + CI-:o= HgCI+; HgCI+ + CI-:o= HgCI,'; HgCl,' + Cl-:o= HgCJ,-; HgCI 3- + CI-:o= HgCll-; logK,=7,15 log K, = 6.9 logK3 = 2.0

(5-1) (5-2) (5-3) (5-4)

and for the overall formation reactions we can write

Hg'++CI-:o=HgCI+; Hg'+ + 2CI-:o= HgCI,'; Hg'+ + 3CI-:o= HgCI3-; Hg'+ + 4CI-:o= HgCt.'-;

log{3,=7.15 log {3, = 14.05 log {33 = 16.05 log {34 = 16.75

(5-5) (5-6) (5-7)

whereK, is the equilibrium constant for the reaction in which the complex containing "i" ligands is formed from the complex containing "i -I" ligands and {3, is the equilibrium constant for the reaction in which the complex

Complex Stability and Equilibrium Calculations


containing i ligands is formed from the metal ion and i ligands. Although either type of constant (but not both) may be used to determine the concentrations of the various complexes in solution, it is somewhat safer to use the stepwise formation constants. The inexperienced User may not remember all of the complex species that can be formed when using the overall formation constants. Such an omission is not possible when the stepwise formation constants are used. When one or more of the intermediate species is unknown (or their stability constant value is not defined), we are forced to use the overall formation constan!. For example, for the series of complexes formed between the hydrated ferric ion, Fe(H,O).'+, and the hydroxide ion we have Fe(H,O).'+ + OH- "" Fe(H,O),OH'+ + H,O; Fe(H,O).(OH)2+ + OH- "" Fe(H 20).(OH), + + H2 0; Fe(H 2 0).(OH), + + OH- "" Fe(H 2 0),(OH),o,,,,; Fe(H 2 0),(OH)30"Q' + OH- "" Fe(H,O),(OH), - + H20; K1 K, K, K,

The concentration of the species Fe(H,O)3(OH),O"Q) which exists in solution is unknown so that while K, and K, are defined, K3 and K, are not. K = [Fe(H,O).(OH)2+] = 10+1184 1 [Fe(H,O).'+][OH] [Fe(H,O),(OH)2 +] K2 = [Fe(H 2 0),(OH)'+][OH] 10+
9 42 •

K = [Fe(H,O),(OH),o"qt] = ? , [Fe(H,O),(OH), +][OH] . K, = [Fe(H20),(OH),-] [Fe(H 20)3(OH),o"Q,][OH ]


However, for the overall formation constants, we have a defined relationship involving the species Fe(H 2 0)'(OH),-. [Fe(H,O),(OH)2+] f31 = [Fe(H 20).'+][OH ] [Fe(H 20).(OH), +] f32 = [Fe(H 20).'+][OH l' [Fe(H 20)3(OH),O"Q,j
10 11 ,84

f3, = [Fe(H,O).'+][OH],
_ [Fe(H 2 0)'(OH), -] _


f3, - [Fe(H 20).'+][OH ]' - 10


Coordination Chemistry

Note that it is common to omit the H,O ligands when writing equations such as those give" here. For example. Fe(H,O),(OH)2+ is usually written as Fe(OH)'+. We generally follow this practice throughout the remainder of this text. The procedures for calculating species concentration in a solution containing metal ions and ligands are similar to that used for acid·base problems in Chapter 4; these procedures are illustrated in the following example. Example 5-1
The COD analysis employs mercuric sulfate, HgS04 , as a source of Hg 2+ to complex CI- ion and so prevent its oxidation to CI2(aQ) by K2Cr207 during the

analysis. Typically. 0.4 g HgSO, is added to 20 ml of sample along with 40 ml of
other reagents. If a sample contains 1000 mg CI-/liter, what will be the concen· tration of each chloromercury(Il) complex and of the free Cl- ion in the solution? Recall that in the COD analysis the sulfuric acid concentration is 50 percent so that the pH is very low « 1) and hydroxomercury(II) complexes are not important. Neglect ionic strength effects and assume a temperature of 25°C.

Solution The unknowns are [Hg2+J. [CI-J. [HgCI+J.

[HgCI 3-J. and [HgCl/-J.

[H+] and [OH-] are not of importance because they do not enter into reactions with Hg 2+ or CI- under the conditions of the COD test, Six equations are needed. These are the mass balances on Hg and Cl and the four equilibrium equations.

0) C


OAgHgSO, x I 60 ml total volume/IOOO mlfliter 297 g HgSOJmoie 2.24 x



[Hg2+J + [HgCJ+J + [HgCI,'J + [HgCI,-j + [HgCIl-J

(2) C

_ 1000 mg/liter X (20·ml sample/IOOO mlfliter) I ,." (60 ml total volume/1000 mlfliter) x 35.500 mg CI /mole

9.39 x 10- 3 M ( ~ 10 -'.02 M) [Cl-J + [HgCI+J + 2[HgCI,'J + 3 [HgCI 3 -J + 4[HgCIl-J [HgCI+J - [Hg2+][CI J [Hg2+][CI J'
[HgC1 2°(aQ)]



f3 - 10"" ,-


= 1014.05 =



f3 ~


[HgCI, -J [Hg2+][Cl l'


f3, -

- 10 .s,,, _ [HgCl.'-J - [Hg2+][Cl J'

We will use a trial and error approach to solve this problem. We will make certain assumptions, find a solution, and then check the assumptions against the results. If the assumptions do not check out, we will make new assumptions and try again.

Complex Stability and Equilibrium Calculations


Assume that the concentrations of all complexes are insignificant in the mass )::>alance equations so that . [Cl-]





Then, from Eqs. (3) to (6), [HgCl+]



IHgCI 2 0(aQ)]
[HgCI 3-] [HgCl;-]

~ ~

(10+14.05)(l0-1.6S){1O ':"'2.02) 2 = 10 +8.3& (10+ 16''')(10-1.'')(10 -'''')' (10+ 16 "5)(10-'-")(10-"")'

10 +8.3<


We can see immediately that the assumption is not valid, since the concentration of each complex for exceeds the values of both C T,H9 and CT,CI' Even though the calculated concen~rations of the chloromercury complexes are for too high, we can glean some useful information from this otherwise disappointing result. We see that the concentration of theHgCI0 21aG ) complex is larger than the concentrations of the other complex species and that CI- is much less than the concentrations of all the complexes. Using this information, let us assume that the HgCI02laG ) complex is the sole important Cl.containing species. The CI mass balance now becomes or (HgCI20IaQI]

10 -2.32

Since Cr,Hg > ~CT.CJ' we must assume that some free [Hg 2+] is present~there is just not enough Cl- to complex it all. We therefore assume that the important Hg. containing species are Hg2+ and HgCI0 2laQ). The Hg mass balance becomes C T ,H9 = 10-1.65 = [Hg2+] + [HgC1 2\'G}] Then [Hg2+1 From Eq. (4) _ ,_ [HgCl,'] [Cl ] - 10"'" [H\lH]

10-1.65 _ 10- 2 •32 = 10,1.75

10-2.32 10 '4 .05 10 1.75

10- 14 .62

From Eqs. (3), (5), and (6), [HgCl+] [HgCl+] [HgCI 3-] [HgC1 3-] [HgCIl-} [HgCll-]

1O"'''[HgH][CI-] 10-""


10"'''10-''''10- 7 ."


1O+16'''[HgH][Cl-P 10- 7•63 1O+16.75[Hg2+][Cl-]4 10-,,·2+


10+16.7510 -1.75(10-7.31 )4

O.'-] ~ 6 X 10-' ~ ~ ~ 1. we find [CI-] ~ 3 X 10-' M.Cr.-> Cl.. (4). (3') (4') 10-'-" ~ [Hg'+](1 + 1O""[CI-] + 1O".-> 2Cr'+ + 7H. This example shows that the majority of the chloride is tied up as HgCl+ and HgCl..e obtain [HgCI+] [HgCI.3 x 10-' 6 x 10-16 Checking our assumptions in Eqs.'. (4') and (6') to eliminate [HgH] and solve for [CI-]. will not oxidize any of the chloromercury(II) complexes. since K. ~ [HgCI+] + 2 [HgCI.. it should not be neglected. (1 '). (3). and (6). If we were to conduct a COD analysis on the 1000 mg Cl-/liter solution in the absence of HgSO.+ l4H+ + 6Cl.-] [HgCI. with minor amounts present as other chloromercury(Ii) complexes and a very small amount (3 x 10-8 M) as the free Cl.208 Coordination Chemistry Substituting this set of values into the mass balance equations for Cl. we see that the values obtained satisfy these equations to within 3 percent accuracy. + 2e-) x 3 Cr.-> 2Cr'+ + 3CI.42 X 10-' M. (2'). (5') and solving for [Hg'+] yields [Hg'+] ~ 1.'. .'] (2') C u . (3').05[CI ]' From Eqs. The implication of this calculation for the COD analysis is that the oxidation of chloride can be almost completely excluded. the following redox reaction would proceed:' 6e.O 6 See Chapter 7 for an extensive discussion of oxidation-reduction reactions. (3)...65 [Hg'+] ~ I + 1O""[CI ] + 1O". .'".05[CI ]' Combining Eqs. and (4).)-Ig and Cl.. Using these values for [CI-] and [HgH] in Eqs. (5). ~ [Hg'+] + [HgCI+] + [HgCI.O.'"". 0) and (2).59 x 10-' 4.'] ~ ~ 10-"" 10-"" From Eqs. Examination of the new values shows [HgCl +] to have a value close to that of [HgCI 2°1<lQ)}' Therefore.O.. the mass balances become (1') CT. (2').05[C!l-]~ 10-1.+ l4H+ + Cr.. Taking this into account.CI shows again that the calculated concentrations are still too high. and (4') (5') 10-"" ~ [Hg H](10""[CI-] + 2 X IO"'''[CI-]') and (6') [H '+] g 10-"" ~ 1O""[CI ] + 2 X IO"..ion.H.] [HgCI.. + 7H. Substituting this value in Eq.O (2CI.

O)4(OH). free metal ions are complexed with water.11) (5·12) J. The metal ions are said to be hydrated.:= Hg'+ + 2ClCripps and Jenkins' found that the extent of this oxidation was a function of the duration of the COD digestion.0). 36: 1240-1246 (1964).oxidation. the stepwise hydrolysis of the aquoaluminum(III) ion can be represented by the following series of equations: Al(H. HYDROLYSIS OF METAL IONS-H.from solution and forc'.5 (= 142) mg of CI-.Hydrolysis of Metal Ions-H. If we assume that the entire 1000 mg Cl-/liter is oxidized..oxidation was 0. the greater the extent of chloromercury(Il) complex dissociation and the greater was the COD due to CI. This oxidation removes CI. --7 2CI.(OH)3(" + H. will oxidize 4 x 35.O). Control Fed . The longer that the oxidation was allowed to proceed.+ H30+ 7 (5·9) (5·10) (5.O.O.O and OH..:= Al(H.OW+ + Ligands 209 Since we express the COD result in terms of the equivalent amount of oxygen to complete the oxidation.O)." it is productive to write the redox reaction in terms of oxygen: 4CI. The interaction of these hydrated metal ions with acids and bases is a ligand exchange reaction that is commonly called hydrolysis. and express the result as "mg O.+ 0. a COD of 32 x 1000/142 = 225 mg/ liter will result.O). For example. + + H.00041 X mg Cl-/liter X time of digestion in hours. because there is some oxidation of the Cl.O+ Al(H.:= Al(H. These terms describe the general reaction in which a proton is transferred from an acid to water.present in equilibrium with chloromercury(II) complexes. Formulated as an empirical "chloride correction factor. For example.--7 2CI".O+ Al(H. or from water to a base.OW+ + H. Water Pollut.3+ + H. "A COD Method Suitable for the Analysis of Highly Saline Waters.AS LIGANDS In aqueous solution. Jenkins. + 4e4e.q." they found that the COD due to Cl./liter.O.(OH)3(" + H. or protolysis.+ 4H+ + 0. M.O).:= Al(H. . HgCl.donors or acids occurs readily and is of extreme importance in natural waters. + 2H.O AND OH. This type of reaction involving hydrated metal cations as the proton.0 4H+ + 4CI.·"q.O).--7 2H.(OH)4.O+ Al(H. Cripps and D.s further dissociation of the complexes.0 Thus 32 mg of 0.(OH).5. In the presence of sufficient HgS04 the COD of 1000 mg Cl-/liter is very small. but not zero." J.O.:= Al(H.O). 5. + + H.

' Fe3+ AP+ log Jl.4 4. 33.O)s'+] and [AI(H. as was done for the hydrolysis reactions of Fe'+ in Section 5-4.2) (9.l) -38 -33 -19. The hydrolYSiS reactions depicted in Eqs. In general. In Eqs.6 (15.O). The alkaline earth metals hydrolyze Significantly only at high pH TABLE 5-1 Equilibrium Constants for Mononuclear Hydroxo Complexes log i3. The two ways of writing the reaction are essentially the same because they can be interconverted by using the reaction for ionization of water.OH'+] as a function of pH.15 4. . just as the concentration of a conjugate base would increase if the pH of a solution containing its conjugate acid were raised. K. Equilibrium constants of the hydroxocomplexes of some metal ions of importance in water chemistry are presented in Table the pH of natural waters.6 ~ f3.O "" AI(H. Mn+ + iOHM(OH)'n-1J+ .0 5. 5-9 to 5-12 are acid-base (proton transfer) reactions.5 -12. is the equilibrium constant for the reaction.84 9 8. Because of this. b nOH-.5) (8.8 -17.8) (10. All trivalent and most divalent metal ions are complexed to some extent with OH. the pH of the solution will influence the distribution of the various species. 5-9 to 5-12 this replacement occurs by the transfer of protons from waters of hydration to free water molecules to form an hydronium ion.O)s'+ = 10' 10-' + H.26 log Jl.2) 8. K.8) log l<so b CuH Fe2+ Mn2+ Zn2+ Cd2+ a 11.4 !O 7. The hydrolysis reaction can also be written as the replacement of a water of hydration by a hydroxyl ion.1.O+. log Jl. This table shows that Fe(ll!) and many other multivalent ions behave similarly to the aquoaluminum(III) ion. = Note that the equilibrium constants are different but that each defines the relationship between [AI(H.210 Coordination Chemistry From these equations it is easy to visualize that the hydrolysis of metal ions is a stepwise replacement of coordinated molecules of "water of hydration" by hydroxyl ions.(OH)2+ + H. the percentage of the hydrolyzed species increases as the pH increases.8 (14.1)' (6.3 16.O).3 -14.2 (9.7 3.16 15.2 -13. ~ Mn+ + . e ( ) Kso is the equilibrium constant for the reaction M(OH)n(s) indicates an estimated value. 21. AI(H.0 34.1 9.

Charge Balance (4) 2[Hg2+] + [H+] ~ [CIO. [OH-]. (6). The pH of a solution to which metal ion is added can be calculated just as it was for acids in Chapter 4.-] + [OH-] Dissociation of Water (5) Kw ~ 10-" ~ [W][OH-] There are five unknowns. ~ ([H+]' + 10 '. [H+]. We will combine these equations to arrive at one equation in (H+]. First let us set a2 = [Hg(OH).5 [CIO.'] Cr. perchloratomercury(1I) complexes can be neglected.-].'] from Eq.CIO. The procedure is demonstrated by the following example. Neglect ionic strength effects. [Hg(OH).'] ~ ~ 10.). [Hg'+].Hydrolysis of Metal Ions-H. Solution Because CI0 4.Hg Combining Eqs. If this species had not been neglected. The equilibrium of concern is (I) Hg2+ + 2H.'] + [OH-] and substituting for [Hg(OH). Mass Balances (2) C r . Example 5·2 Calculate the pH of a 10-5 M Hg(CIO. (I) and (2) yields 10.-] ~ 2C r . solution at 25'. (2).is a very poor complex former. ~ 10.'] and [CIO. which we will solve by trial and error.O and OH.H. and for [OH-] from Eq. combining Eqs. log K ~ -6.6.3 The species HgOH+ can also form in solution by the following reaction log K ~ -3.3 (6) cx.O '" 2H+ Hg(OH). [W] - [~:] - 2cx.H.5 Cr. and (4) to eliminate [C10. we neglected HgOH+. our approach would have been similar to that used to determine the pH of a diprotic acid Ligands 211 (pH> 9 to 10). we obtain (7) [H+] ~ 2[Hg(OH). (5).3) Then. (3).Cr.-]. to simplify this example.7 but the Hg(OH)2° complex generally predominates.'. (3) ~ [Hg2+] 2 X + [Hg(OH). and we have stated five equations.Ho ~0 .

252 mM 40 mg NaOH 10 I N 0H!1' x mM = .0 and a total alkalinity of 80 mg/liter as CaCO.(SO. requires a dose of 25 mglliter aluminum sulfate (AI2(S04)3 .5". the pH of equimolar H. ~ 0 10.7. it does not . and Fe3+ solutions are similar. What is the dose of sodium hydroxide (NaOH) in mg/ liter required to maintain the alkalinity of the water at 80 mg/liter as CaC03 during coagulation/flocculation? Make the simplifying assumption that the only hydroxoaluminum(III) species to form is Al{OH)3{s). showing that the mercuric ion has the property of a weak acid of approximately the same strength as acetic acid.212 or (8) Coordination Chemistry [W] .[W] . 14H 20) for effective coagulation/flocculation. Solution We can treat this problem as a stoichiometric acid/base reaction.0 + 6NaOH "" 2Al(OH)"" + 6Na+ + 3S0. or the amount of hydroxide that must be added to restore that which reacted with the alum. (6) and (8) by trial and error yields a solution pH of 4.252 mM NaOH!1iter We assumed in Example 5·3 that when alum was added to water. Example 5·3 A raw water with a pH of 8. just as the addition of an equal amount of strong mineral acid would. The metal ion "titrates" (or reacts with) a stoichiometric amount of alkalinity.). this assumption is valid at many surface water treatment plants. The pH found in Example 5·2 is quite low. For example. The strong acid properties of hydrated metal ions become evident in processes such as coagulation/flocculation. mg a Iter liter 0.14 Solving Eqs. The acid strength of some metal ions is quite considerable. Since the alkalinity for the reaction will come entirely from the NaOH to be added. 14H. we use it as the base in the reaction. or 0. Thus 25 mg/liter x 6 mM NaOH 594mgalumlmM mMalum is required. where hydrated aluminum sulfate (alum) or ferric chloride is added to a natural water that is buffered with bicarbonate. Although this assumption is good enough for estimating the amount of natural alkalinity that reacts. . Al.2 X 10.PO. there was a stoichiometric reaction with the hydroxide to form aluminum hydroxide.'The molecular weight of alum is 594 and that of NaOH is 40.

pp. As we have seen . 25&--258. W. already.. Morgan. coagulation/flocculation takes place in the "sweep floc" range because it is very difficult to vary the 8 J. Wiley-Interscience. J. a variety of mononuclear hydroxoaluminum(III) complexes form.(OH). 67. Fig. to They argue that the polynuclear species act as short-chain polymers that adsorb to specific sites on particles. J. At low alum doses there is no reduction in turbidity. 5-1. 1967.C.4+ and AI.' such as AI2(OH)24+. Morgan. illustrates how alum functions as a coagulant for a water of moderate alkalinity. At these low doses there is insufficient hydroxoaluminum(III) species to provide effective destabilization. Series No. The polynuclear complexes generally have higher OH. thereby destabilizing them so aggregation can take place.{OH)3:+' It is thought that such species are formed by the condensation of mononuclear hydrolysis products (see Section 5-2). 9 We shall indeed see (Chapter 6) that when we consider the presence of the stable polynuclear aluminum hydrolysis species in the representation of heterogeneous equilibria. American Chemical Soc . D. The further addition of alum to the point at which complete destabilization occurs causes a reduction in turbidity to a minimum value. 1970. 1970. Some workers suggest that the higher OH. AI.. W. Wiley. Aquatic Chemistry. This bulky precipitate enmeshes particles in it and settles rapidly to form the so-called "sweep floc" region of coagulation-flocculation. Aquatic Chemistry. The further addition of alum to very high doses results in the formation of a precipitate of AI(OH)"" because the solubility product of Al(OH)"" is exceeded (see Chapter 6). other polynuclear hydroxoaluminum(III) complexes are thought to exist as short~lived intermediates between the hydrated aluminum ion and aluminum hydroxide precipitate (AI(OH)". 246..Hydrolysis of Metal Ions-H20 and OH.and less H2 0 content per mole of aluminum than the mononuclear hydroxoaluminum complexes. in Chern. Although adsorption can take place even if the polymer and particle are of the same charge. New York.content of these species makes "hydrolyzed aluminum ion" a more effective coagulant in water treatment than the mononuclear hydrolysis species. Washington. chapter in "Equilibrium Concepts in Natural Water Systems. Aqueous solutions of aluminum ions at neutral pH values have also been reported to contain polynuclear hydroxoaluminum(III) complexes. New York. Ligands 213 accurcitely represent the detailed equilibrium picture. p. 9 10 . At most water treatment plants. The classical "residual turbidity" versus "alum dose" plot. the stability region of the aluminum hydroxide solid is more confined than when their presence is disregarded.) in supersaturated solution. Stumm and J. The further increase in alum dose will result in restabilization of the particles because of a near complete coverage of the particle with aluminum hydrolysis product.. J. destabilization appears more efficient if they have opposite charges. Although the above species have been proposed as stable species." Adv. Stumm and J.

.e.04 M. Fe(I1I). Reprinted by permission of Svensk Kim. After mixing to simulate that which occurs in a water treatment plant. the sample is allowed to settle for 30 min before turbidity is measured. 5-1. For example.7'---'-' [Pbs (OHls4 +11 CT..[P-=b~3~(O~H:"14'-"-'-1 CT.0 r--"-'.. Pb'+ 1. These complexes tend to predominate at high metal concentrations and intermediate to high pH values. 73: 482 (l961). Wiley-Interscience." Trivalent iron. J.25l_--1. Alum dose versus residual turbidity for water coagulation/flocculation. form polynuclear hydroxocomplexes.75 (j 0. for a complete review and discussion of coagulation/flocculation. After Olin A . Fig.c~_I..0 6. as well as other multivalent metal cations (e.. The residual turbidity is that which remains in a test solution to which alum was added." ~ 0.Pb 0. 5-2 is a distribution diagram of the hydroxocomplexes of Pb2+ in aqueous solution. Below pH 6.. 5-2.O Fig. .g . lead). coagulant dose to correspond to changing influent conditions as required to operate in the range of complete particle destabilization. Weber..214 Coordination Chemistry log alum dose --... chapter in "Physiochemical Processes. .0 B. Svensk Kim Tidskr . Tidskr. New York.. Q'Melia. Fig. Species distribution of lead in an aqueous Pb(lI) solution CT.. R.:~::~J-. 1971.---:~-:-::-:'::'7'. which like aluminum(III) is used in water and wastewater treatment as a coagulating agent. Jr..0 pH 7.-~~~).50 0.Pb o 5. 11 See C." by W.

The equilibria on which the diagram is based are + 4H.4+ + 2H+. Also illustrated in Fig. Aquatic Chemistry. 5-3 is the effect of total iron{I1I) concentration on the predominance of polymeric hydroxocomplexes of Fe{I1I). virtually no Fe. Stumm and J.(I!D solution. the fraction of the total iron{III) present as hydroxo complexes.4+ + 8H+.'+ + 4H+.(OH)r + 4H+.'+.'+ is 2Fe'+ + 2H. In general. such as clays or organic solution whereas a significant amount exists in the 10-' M CT.2 10gK = -42. for example.9 10gK = -23. Species distribution in an aqueous Fe(III) solution. Pb.{OH).{OH). The previously discussed interaction of hydroxoaluminum{III) polymers with particle surfaces is but one example of the ways in which the types of species of metals.4+ is present in the 10-' M CT. Reprinted by permission of John Wiley & Sons. 4Pb H CT.(OH). 6Pb2+ + 8H.predominate.Fe!ITIl=1O. 5-3.{OH). The bulk of the total metal content of natural waters and wastewaters is usually associated with particulates either as precipitates (solids) or adsorbed on particle surfaces.lf " • • ~ • 0 1 3 4 Fe(OHb(l) 0 1 pH 3 4 Fig. at higher pH values the polymeric hydroxocomplexes Pb.4+. The equilibrium constant for the dimeric Fe. 5-3. Wiley-Inter science.O "" Pb.91.{OH). including the dimeric Fe. At pH 2. 3Pb'+ + 4H. influence the distribution of metals in the natural water environment.O "" Pb. carbonato.F.'+. New York.O "" Fe. J. 1970.'+. hydroxo. increases as the pH increases..OIO 10gK = -19.{OH). log K = -2.Hydrolysis of Metal Ions-H.O "" Pb.F. The diagrams are based on equilibrium constants of mononuclear hydroxo complexes (see Table 5-0.7 Similar distribution diagrams for concentrations of total iron{III) of '= 10-' M and C T• F'(1I11 = 10-' M are presented in Ligands 215 is the major lead-containing species. and 100 50 Fe(OHh hl Fe3+ CT. Like lead.{OH). and Pb.O and OH.Fe!m) =: \0 " 2 pH 10--4M " 100 " 50 Fe 3 t2 CT . . Morgan.{OH). After W.F. especially the complexes.{OH).

2 C{Co(OH)~ 0 0 2 4 6 pH 8 10 12 14 Fig. 40: 42 (1972).:.O From 1. Healy.. Healy.."" Co(OH)"" Co(OH)+ + H+ "" Coo. 17 (1964).. + H.8 80 .' + H+ "" Co(OH)+ + H.::..4 20 0 0. James and T.--T--. 15 glliter SiO.O Co(OH). James and T. W. TABLE 5-2 Cobalt Equilibria Equilibria log K 14. Colloid Interfac. 40: 42-52 (1972) by permission of Academic Press. Computed hydrolysis data for this concentration are also shown as the percentage of each aquo complex as a function of pH. 5-4). + 20H. where the cobalt is present entirely as Co". James and Healy" have shown that the adsorption of cobalt on silica surfaces is a function of the ionic state of the cobalt (see Table 5-2 and Fig. Chemical Society of London.2 x 10-' M on silica at 25'C. as Model Systems. Sillen and A..... W. Sci . .:::. l. 0.:or--.0 o 0.---r--'(-.' + H.7 Coo.. At pH values below 6. 5·4. Colloid and Interface Sci.. Co(lI) Adsorption on SiO. For example. Martell. Experimental adsorption isotherm for Co(II).6 9.6 • ~ E • "eo" 40 0.O Co(OH). Adsorption at 1. 100 . and TiO. E.+ H+ "" Co(OH). there is very little adsorption. J. No. Reprinted from R. Special Bull .' "" Co(OH)"" Co(OH).g E' g ~ c 60 0. "Adsorption of Hydrolyzable Metal Ions at the Oxide-Water Interface. G..9 9.2 5.:O::lB=.1. "R." J.7 12. O.216 Coordination Chemistry sulfato complexes of metals tend to sorb more strongly at clay surfaces than do the free metal ions.

CaH .CO. Walnut Creek. Montgomery as AI" and Fe'+. In the pH range from 6 to 8. ion decreases from 100 percent of the total cobalt to zero. HCO. and SO/-. H+.c. 5.'. For complicated systems such as natural waters it is necessary to use a computer to determine the degree of complexation of the various cations with the ligands available. the removal of cobalt from solution by adsorption on the silica particle's increases dramatically.5.Complexes with Other Inorganic Ligands 217 As the pH increases to between 6 to 8.2 9. CO. CI-.8 3.5.'-. CoOH+ and Co(OHl.2 1.+. CaOH+. The next section of this chapter will deal with organic ligands. and KSO. CaHCO. COMPLEXES WITH OTHER INORGANIC LIGANDS Natural waters contain significant concentrations of inorganic and organic iigands in addition to H. NaOH'.13 Assume the following compositions for ocean and river water at 25'C: Ocean C r .N• (M) Cr. Reference to Table 1-5 shows that the predominant metal cations in typical fresh and ocean waters are Na+. Calif.o.O and OH-. At the typical natural water pH values of between 6. NaSO.S04 (M) Average River Water Total alkalinity 0.(M) C T.6.. CaCO.9 We neglect interactions with the atmosphere and consider the following species: K+. In this section we will look at some examples of the effects of inorganic ligands on the speciation and properties of metals in natural waters.'. we determine the degree of complexation of the various cations present in the ocean and in average river water. HSO. MgHCO.9 2.-.7 5.-. Mg'+.'. . the major ligands are HCO.5 to 8.'.-.M. MgOH+.5 the free Co'+.(M) Cr. MgSO.(M) Cr.47 10-' 10-' 5.+. To illustrate this technique.-.4 2. SO/-. CaSOt. these metals are not strong complex formers in comparison with metals s!. H. NaHCO.-. OH-.4 10-' 10-' (eq/liter) pH (units) 7.13 These calculations were made by Dr. L. CI-. L.6 X X X X X X X 10-' 10-' 10-' 10-' 10. NaCO.55 3. Na+.(M) Cr. and MgH.3 X 10-' 7.4 X 10-' 0.c. RusselL James M. MgCO.9 3. Ca'+.. and the predominant cobalt species become the adsorbable hydroxocobalt(IIl complexes.8 X 10-' 2.

NaOH"" Na+ + OH-.4 0• K 10-.'-. . = [SO.O "" H+ + OH-. K K K = 10-'" K = 10-1. HSO.218 Coordination Chemistry The equations that describe the system are the mass balances: C TK = [K+) + [KSO.O) C TMo = [MgH) + [MgOH+) + [MgHCO. H.CO.O "" Mg2+ + CO. +) + 2[Mg H) + [MgOH+) + [MgHCO.'-) + [CaHCO. -.'-) + [OH-) .-) + [ + [CaSO.O "" Mg'+ + SO.."" Ca'+ + OH-. MgCO. CT.'-. + "" Mg'+ + HCO.16 K = 10-.10.O) . K = 10-1.'-. 96 . 26 CaSO.o "" Ca H + CO."" Na+ + SO.O) + [MgSO. "" H+ + HCO.' CaHCO.-J [Cl-) CT.O) + [NaSO."" H+ + SO.'-) + [HSO. . MgSO."" H+ + CO..CI = = [Na+) + [NaOHO) + [NaHCO.27 10-0 •72 K = 10."" Ca'+ + HCO. -) + 2[CO.-) Charge Balance [K+) + 2[Ca'+) + [CaOW) + [CaHCO.o "" Ca H + SO. = [Ca'+) + [CaOH+) + [CaHCO. . MgOH+ "" Mg'+ + OH-. +) + [CaCO.0 . -.-) + [HCO..-.'-.+) + [H+) + [Na+) = [KSO.-) + [NaSO. K= NaHCO."" K+ + SO..+) + [CaCO.+) + [MgCO. .-) + [NaSO.o "" Na+ + HCO.-) .'-.O) C TSC.·31 CaCO.1 = K.") + [MgSO. NaCO.. K = 10-.c. KSO. CT.'-.'-.-) + [CaSO.·58 MgHCO. CaOH. HCO.) + [HCO.CO. . = 10-6 . Kw = 10-14 K.-) + [NaCO. -) + [CO. .O) + [NaCO'.'-.'-) + [Cl-) + [OW) Alkalinity Equation Total alkalinity (eq/liter) = [HCO. -.[W) and the equilibrium relationships: H. = [H.-) + 2[CO. K = 10-1. C TN . = 10-' K'. K = = 10-'. NaS04.'-. 10.·36 10+ 7 K = = = 10+0 •25 10-1.."" Na+ + CO.

2 1.4 X 10 4 1.4 3.7 X 10.5 0.3 4.9 X 10-3 3.5 x 10-3 1.4 1.7 X 102. Complexed with Cation Calcium Magnesium Sodium Potassium Uncomplexed OH~ HC03~ CO.4 5. Calion Calcium Magnesium Sodium Potassium Hydrogen Uncomplexed Concentrations of Various Species in Ocean Water (moles! Complexed with Uncomplexed 7.1 8.4 x x 10.3 X 10-2 X 10-3 X 10-2 TABLE 5-4 Percentage Distribution 01 Complex Species in Ocean Water.8 x 4.5 x 10-1 9.6 x 10-6 4.6 X 10-4 7.2 9.7 5.1 X 10-2 4.1 1.5 5.4 x 10-8 X 10-8 X 10-6 HC0 3- COl5 S04~- Total 10-2 5.1 X X X X x X 1010-6 10-7 10-7 10-10 10-4 6 Total 3.4 x 10.9 OH- HeO l 5.4 X 10-3 2.4 x 10.0 x 10-6 1.4 X 10-2 4.21 22 78 76 96 96 0.2 80. TABLE 5-3 liter).'0.4 x 10-5 2.8 x 10.7 X 10-4 5.3 2 4 TABLE 5-5 Concentration of Various Species in Average River Water (moleslliter).3 5.9 X 10.5 X 10.2 5.8 X 10-5 X 10-5 1. Complexed with Cation Calcium Magnesium Sodium Potassium Hydrogen Uncomplexed Uncomplexed 3. Percentage Distribution 01 Complex Species in Average River Complexed with Cation Calcium Magnesium Sodium Potassium Uncomplexed OH~ HC03~ 97 97 100 100 .4 10.8 1.7 0.4 x 10.6 x 10-3 10-3 OW 5.3 X 10.3 X 10-7 6 CO/1.6 6 SO/5.1 X 10-10 X 10-9 9.8 X 10-4 2.8 1.6 TABLE 5-6 Water.8 X 102.2 X 103.4 4.B X 10.7 3.Complexes with Other Inorganic Ligands 219 Tables 5-3 to 5-6 are the results of the solution 01 these equations.5 1.2 X 10.1 1O-~ 6.7 X 10---5 1.3 2.4 3.

MgH. and the alkalinity ions (HC03 . since the alkalinity usually increases together with the water hardness." To determine the relative amounts of complexed and uncomplexed metal ion in a solution.. the species distribution would not be quite the same. Specific ion electrodes only respond to the free metal ion for which they are "specific. especially sulfate. The distribution of copper species in a natural water buffered by the carbonate system is presented in Fig. We can provide an explanation of this result in terms of complex formation between the heavy metal copper. and spectroscopy not only can differentiate between "free" and "complexed" metal ion species but in some instances can be used to identify the nature and determine the concentrations of individual complex species. SO/-. Increasing the pH value or ligand concentration. Therefore. CuO". when dealing with fresh waters of neutral pH values. polarographic. 14th ed . we can use a "wet chemical" method to measure the total concentration of "free + complexed" ions. Inorganic ligands that complex metal ions can alter the effects that metal ions exert in natural waters. polarography.. Several analytical methods will differentiate the "free" (hydrated) metal ions from dissolved complexed metal ions.. The general observation made is that heavy metals are much less toxic to fish in hard water than they are in soft water. 5-5.and COj-).14 free and complexed calcium and magnesium ion's are measured. radical changes would not occur. 1975. the literature on fish toxicity contains references to the effects of water hardness on the toxicity of heavy metals. CI-. HC03 -. Health Assoc . In addition only sulfate is a significant complexing agent and only calcium and magnesium complexes are important. Care must be taken to eliminate interferences that may affect these measurements. New York. Na+. The diagram is based on the presence of the copper precipitate jenorite. and COj-. This type of calculation gives us confidence in ignoring the complexes of CaH . may require that complexes of these metals be taken into consideration. These methods include specific ion electrodes. From Fig. however. For example.220 Coordination Chemistry The results show that only in ocean water are any of the metals in this model complexed to any significant extent by the inorganic ligands examined. Am. and then an ion-specific electrode to determine the free metal ion concentration (activity). in the EDTA titration method for hardness. and other amperometric and voltammetric methods and various types of spectroscopy (see Section 7-10).5 is free 14 Standard Methods for AnalysiS" of Water and Wastewater. . the diagram can be used to determine regions where certain species are important. If the solution were not in equilibrium with this solid. For example. and K+ with OH-. Methods such as anodic stripping voltammetry. Pub!. We deduce the concentration of the "complexed ions" by the difference between these two measurements. 5-5 it can be seen that only at below pH 6.

. at pH 7 increasing the alkalinity from 50 to 250 mg/liter as CaCO.'.8 controls the concentration of Cu'+ in this pH range.and Cu(OH). decreases the Cu2+ ion level from 25 to 9 percent of the total copper present. the predominant copper-containing species..C~' = 1O~3 M. Cu2+. Cu(OH). Other Inorganic Ligands 221 0 . CT. Copper species distribution in a water containing total inor· ganic carbon.-. . Making the assumption that the complex formation reaction 10gK = -6. copper ion... the Cu'+ concentration at various alkalinities can be calculated for a variety of pH values (rable 5-7)..Complexes with... At higher pH values the carbonatocopper(II) complex. are the major coppercontaining species. / 10 5 pH 10 14 Fig. 5·5. The diagram predicts that in the pH range 6. For example. and the hydroxocopper(II) complexes. Returning to our original observation that .5 (a range that covers the pH span of most natural waters) the major coppercontaining species is CuCO. CuCO.'. .5 to 9.'-. It is apparent that alkalinity has a profound effect on the free copper ion concentration...

the following equilibria are applicable to the addition of nickel to a cyanide solution.1 mglliter). in hard water a greater fraction of the total copper is complexed than in soft water.complex.'ing both heavy metals and cyanide.5 M. since metal cyanide solutions are used in a variety of metal finishing processes. we need only consider the Ni(CN).= W + CN-. that is.will be displaced in the direction of CN. Knowing that the component toxic to fish . 100 mglliter as CaC03 14 6 250 mg/liter as CaC03 7 25 II 9 3 7.5 8 For CT. we should note that high hardness is usually accompanied by high alkalinity. K. therefore.forming metal ion is added to a cyanide solution. At pH 7.222 Coordination Chemistry TABLE 5·7 Effect of Alkalinity and pH on Cu'+ Levels [Cu'+] x 100(%) at Alkalinity of C T.17 X 10-10 (34 = 10" There is no evidence for the existence of the mono·.. then increasing the fraction of the carbonatocopper(II) complex by increasing the carbonate concentration will decrease the toxicity. all of the cyanide present is HCN. Most heavy metals form cyano complexes. and tricyanonickel(II) complexes. An important example of this relates to the toxicity of "cyanide" to fish. It is not uncommon to encounter waste discharges contai. HCN.7 M to 1.6 X 10.'.5. Most toxicity researchers agree that the toxic component of a "cyanide" solution is undissociated hydrocyanic acid. 0.from solution.because the metal ion will remove free CN.9 copper is more toxic to fish in soft water than in hard 2 values from 8 x 10. If we assume that the only copper species toxic to fish is the Cu'+ ion.08 mglliter) while in the cyanide solution containing no nickel the HCN level is 4 X 10-5 (-1. Therefore. for example. the equilibrium between HCN and CN. For example..Cu pH SO mg/liter as CoCO. = 6. When a complex. incorporating it into a cyano metal complex. Complex formation influences the concentration of ligands (and their effects) as well as metal ions. the solution containing nickel has an HCN level of about 3 x 10-6 M (-0. Figure 5·6 shows the profound effect that this complex has on the HCN concentration. HCN. di.

5. with no correction for ionic ~ 6. Doudoroff et al. no sensible relationship could be obtained. i34 for Ni(CN)/. Doudoroff.7. we can guess that the addition of Ni'+ to a cyanide solution would have a dramatic effect on its toxicity. when the same plot was made against the concentration of molecular HCN in the complex cyanide solutions there was a linear relationship between HCN concentration and median resistance time (see Fig. Leduc. copper. organic compounds are used as complexing agents. CT." Progr. However. Schneider. COMPLEXES WITH ORGANIC LIGANDS Complex formation involving organic ligands is important in two general areas of water chemistry. First. When the median resistanc<. and (b) 4 x 10-5 M totaL cyanide. . G. strength.~ 10+". Free HCN in equilibrium at 25'C with (a) 10-5 M nickel. 95: &-22 (1966). C." Trans. zinc. and silver cyanide complexes. 5-7). in the analysis of various constituents of water. Montgomery. "Acute Toxicity to Fish of Solutions Containing Complex Metal Cyanides. K. R.Complexes with Organic Ligands 223 3 x 10 -5 pH value Fig. For example.15 have provided a striking illustration of this effect using the toxicity to fish of solutions of nickel.! (or immobilization) time of the fish is plotted against the total cyanide concentration of these solutions (log/log plot). cadmium. Reprinted from H. A. for HCN 3: 73 (1973) by permission of Pergamon Press. Fish Soc .. 5·6. is HCN. "Some Analytical Aspects of the Behavior of Certain Pollutants in Aqueous Systems.CN. and C.. EDTA is used to determine water hardness by forming 15 P. Amer. in Relation to Concentrations of Molecular Hydrocyanic Acid.17 X 10-". Water Technol.

95: 6-22 (J966).050. forming a complex with Fe'+. HO-N=C-CH.~ ~ c clOD " '" 1: 50 • II A " 20 + NaCN NaCN NaCN NaCN NaCN + NiS04 + CUS04 + ZnS04 + CdS04 • NaCN + AgN0 3 0. Bluegill median resistance (immobilization) times plotted against free.0 10 50 100 500 HCN(aq) concentration..1'0 2 CHJ-CNOH) ( CHJ---CNOH CHJTN I + Ni2+-+ ~N'/ /''---.5 1. I + 2H+ CH. and dimethylglyoxime. Trans. Soc. The nature and extent of metal ion complexation by natural water organics is not welldefined. 1. probably because of the poorly defined nature of these organic compounds and also because of the staggering complexity of these . Adapted from P_ Doudoroff.E '~ B . HCN concentration in various simple and complex cyanide solutions.224 Coordination Chemistry 1000 • 500 c 'E 200 .-C=N-OH ~=C-CH. Amer.. complexes with Ca2+ and Mg'+.1O-phenanthroline is used as an indicator in the COD test. 5·7. CHJ-CNOH CHJ-CNOH I can be used for the colorimetric determination of nickel by forming the red complex . a wide variety of organic compounds in natural waters and wastewater can act as complexing agents for metal ions. mg/liter Fig.1 0.0 5.01 0. O':? red complex Second..0 2. et ai. Fish. Reprinted by permission of the American Fisheries Society.

".9 202 3.7. Reprinted by permission of Pergamon Press.00 . Stilf. in the categories of "amino acid complex" and "inert humic complex. Several examples will be given here to illustrate the importance of complexation by various organic compounds in determining free metal ion concentration in natural waters and wastewaters and to illustrate the complexity of the systems. /3. 5. "The Chemical States of Copper in Polluted Fresh Water and a Scheme of Analysis to Differentiate Them.51 5. both inorganic and organic that are present in water and wastewater. multiligand systems. M. the river waters contained significant amounts of copper complexed by organic ligands. "M. The Nature of Copper in Water and Wastewater Copper forms complexes with numerous ligands. R-GH-GOO- 2 ~H. Water Research. S.ff7 7. Amino Inert HCO l mgniter Humic He:lanol Acid mmoleJJiter as CaCO l Cu" CuCOlo Complex Complex Extractable Cyanide complex. J---l) R-GH-GO ~+ . J. 5B5-S99 (1971).' 0.62 B.00 7.1 5. TABLE 5-8 Distribution of Soluble Copper in Natural and Treated Water and Wastewater Coppar Concentration.1.Y. 5: 585-599 (1971). 11 0. etc. Elmsford.5 435 148 32 126 .. in the form of Copper added pgnUer pH Hardness." Water Research. J. I + eu" "" ( .7 320 5. Sample Tap water Stevenage Settled sewage Stevenage River Anow River Lee 01 Edmonton 200 200 7. pglliter. Beside complexes with inorganic ligands (Le.19 2SO 400 340 40 24 480 " 100 200 170 Source.Complexes with Organic Ligands 225 multimetal." Amino acid complexes of copper are formed according to the following general equation:' R-GH-GOO- NH.6 9 5. Table 5-8 gives some examples of the types of soluble complexes detected by Stiff" in natural and treated waters and sewage. that is. Stiff. .. carbonate and cyanide). N.


Coordination Chemistry

For the amino acids leucine, valine, alanine, serine, glutamic acid, aspartic acid. and tyrosine. the values of log 13, range from 7 to -9; values of log 13, are in the approximate range of 14 to 16. The amino acid cysteine. which contains the -SH group forms an extremely strong complex with cuprous ion (Cu+) with a log 13, value of 19.5. As we will see later. "humic acids" are an extremely complex group of compounds. Because of this no one compound can act as a true model for this group. However. phenolic and carboxylic acid groups are common functional groups in humic acids. The substance 3.4.dihydroxybenzoic acid serves to illustrate one type of complexing group that may bind metals such as copper to humic acids:

o ¢:







= 12.8


3,4 dihydroxybenzoic acid From the values of the stability constants of these organic complexes of copper, it is evident that they must play a significant role in the complexation of copper in natural waters. Indeed. il is significant to note that in none of the waters listed in Table 5·8, is Cu'+-the uncomplexed cupric ion---a major copper-containing species. The picture becomes even more complex when the distribution of copper between solution and particulate phases is considered. Beside the copper·containing precipi. tates (e.g .. tenorile. CuO",) we must also realize that the types of organic and inorganic ligand groups which complex with copper in solution also can exist on the surfaces of particulate solids such as organic detrital material; there they serve to bind the copper to a solid particle and transfer it from the "soluble copper" category to the "particulate copper" category. Stiff17 analyzed some polluted river waters in England and found that between 43 to 88 percent (average 69 percent) of the total copper present was in the particulate phase. 5.7.2. Complexation by NTA Nitrilotriacetic acid (NTA) is a triprotic acid with the struclure:

nitrilotriacetic acid, NTA


J. Stiff. Water Research. 5: 585--599 (1971).

Complexes with Organic Ligands


Its sodium salt. N(CH,COONa),. can be used as a component of commercial laundry detergents. In these products the NTA is a so-called "builder." Its function is to complex the components of water hardness (Ca2+ + Mg2+) and prevent them from reacting with the detergent molecule itself. thereby reducing the effectiveness of the detergent. This type of deliberate complexation is often called "sequestration." and compounds such as NTA are known as "sequestering agents." Commercial laundry detergents containing NTA were developed because some regions of the United States and Canada prohibited the use of detergents containing the usual sequestering agents for Ca2+ and Mg2+-the polyphosphates-because of their suspected contribution to causing accelerated eutrophication of surface waters. The introduction of NTA caused concern in some segments of the scientific community on several counts. It was thought that NTA introduced into detergents would find its way into domestic sewage. Being a strong complexing agent. it will keep toxic heavy metals in solution. thereby preventing their precipitation as hydroxides. carbonates. phosphates. sulfides. and so forth. and their subsequent removal by incorporation into wastewater-derived ·sludges. If the NTA itself and the NTA heavy metal complexes are not readily biodegradable. they will pass through the wastewater treatment processes, carrying into the receiving waters both their complexing ability and any heavy metals complexed by them. Once in the receiving water. free NTA will have the ability to transport heavy metals from sediments into solution by complexing them. In the course of time the NTA heavy metal complexes will be biodegraded. releasing the complexed heavy metal that will cause toxicity in the receiving water. Some aspects of these concerns. such as the question of biodegradability of NTA and its heavy metal complexes. are beyond the scope of this text. However. NTA appears to be biodegradable in secondary. biological. waste treatment processes. The concerns dealing with complexation will be examined here. Because NTA forms many metal complexes with a wide range of stabilities. it is important to examine a model or conduct experiments on systems where the concentrations of the metals and the amount of NTA available for complexing closely resemble that found in the natural water system of interest. In addition. the presence of other ligands. both inorganic and organic. should be considered. Because pH influences the speciation of NTA and the concentrations of other ligands such as CO,'-. OH-. and so forth. the pH of the system under study should be carefully controlled in experimental and model systems. Equilibrium models that consider many metals and many ligands are constructed using the same set of equations used for simple acid-base and complexation calculations. First. total concentrations of all components are stated; then all possible species are identified; and mass balances. a charge balance. and equilibrium equations are written. It is.


Coordination Chemistry

however, tedious and virtually impossible to solve these equations manually so that a computer solution is needed. The reader is referred to published articles for descriptions of computer programs suitable for the solution of multimetal, multiligand systems." Here we will examine the results of such a solution. Consider the system shown in Table 5-9 which represents the composition of a lake water at pH 8. The model does not consider the presence of organic ligands other than NTA. However, it is estimated that the stability constants of NTA metal complexes are
significantly greater than other organic-matter metal complexes. Because

of this the result should approximate what might be found in a water containing a low organic-matter concentration. The acid base equilibria of NTA, carbonic acid, and phosphoric acid and the complex formation of all metals with OH-, HCO,-, CO?-, PO,'-, SO.'-, and CI- as well as with NTA'- were considered. The results of the calculations will be discussed here; for details of the equations used see Childs." The results of the computations are presented in Table 5-10, which shows that at pH 8, NTA, just like any other complexing agent, complexes metals in order of the values of the stability constants of the NTA metal complex. At an NTA concentration of 10-7 M, there is only sufficient NTA to result in minor complexation of only the metals with the largest NTA metal complex stability constants. Thus 4 percent of the total Cu(lI) (log K = 13, where K is for the reaction Cu'+ + NTA'- -,> CuNTA-), 2 percent of the total Pb(II) TABLE 5-9
Major Components
Cr,Ca Cr,Mg Cr,Na C r ,eo 3 Cr,so" Cr,er


Minor Components
Cr,euao Cr,Feam Cr,sdm Cr,MnUO Cr,ZnUO Cr,Pb(JO Cr,BaaO Cr,Nrao Cr,po" Cr,NrA


10-' 2.5 X 10- 4 5 x 10-' 10-'
3 x 10-' 7.5 X 10-4




2 x 10-< 2 X 10-6 2 X 10-6 1.5 X 10- 6 3 X 10-7 1.5 X 10-7

10- 6 10- 8 to 2 X 10- 4


J. N. DeBoice and J. F. Thomas. "Chemical Treatment for Phosphate Contro!,"

J. Water Pollut. Control Fed., 47: 2246 (IS75); F. Morel and J. J. Morgan, "A
Numerical Method for Computing Equilibria in Aqueous Chemical System." Env. Sci. Technol., 6: 58 (1972); and D. D. Perrin and I. G. Sayee, "Computer Calculation of Equilibrium Concentrations in Mixtures of Metal Ions and Complexing Species," Talanta, 14: 833-S42 (lS67). C. W. Childs. "Chemical Equilibrium Models for Lake Water which Contains Nitrilotriacetate and for 'Normal' Lake Water," Proe. 14th Can!. Great Lakes Res., ISB-210 (lS7!), IntI. Assoc. Great Lakes Res.


Complexes with Organic Ligands


TABLE 5-10 Variation of Metal Complexation by NTA with NTA Concentration at pH 8
Total Concentration

M Cu(II) ~ 2 x 10-' Pb(II) ~ 3 x 10-' Ni(II) ~ 10-' Fe(IID

Complex Species

Log Formation Constant of 13 11.8 11.3 10.9 } 3.1 10.4 10.3 7.4 6.4 5.4 5.0 4.8 2.2

Percentage of Total Metal Present as Indicated Complex at Stated NTA Concentration

NTA ~ 10-7 M


x lO--6M
82 80 60 34 20 0 0 <0.1 0 0 0 0



NTA 100 100 100 100 100 9 100 17 2 0 0 0


2 x 1O- 4 M

2 x 10-'

Zn(ll) ~ 1.5 x 10-' H+ = 10- 6 Mn(ll) ~ 2 x 10-' Ca(ll) ~ 10-' Mg(lD ~ 2.5 x 10-' Sr(ll) ~ 2 x 10-' Ba(ll) ~ I.S x 10-' Na(l) ~ 5 x 10-'


2 0.4 0.2 0 0 0 0 0 0 0

Source: C, W. Childs, Proc. 14th Coni. Great Lakes Res" 198-210 (1971). Inti. Assoc. Great Lakes Res. (Reprinted by permission of the International Association for Great Lakes Research.)

(log K = 11.8), and I percent of the total Ni(II) (log K = 11.3) as well as fractional percentages of Fe (III) (log K = 10.9) and Zn(II) (log K = 10.4) are complexed with NTA. As the NTA supply increases to 3 X 10-' M, significant complexing of the above metals takes place; for example Cu(Il), 82 percent; Pb(II). 80 percent; Ni(II), 60 percent; Fe(III), 34 percent; and Zn(II), 20 percent. Again, since the NTA is not present in a quantity in excess of the combined concentration of all the heavy metals, there is incomplete complexing of each of them. Moreover, the completeness of complexation is in strict order of values of the stability constants of the heavy metal NTA complexes. At a total NTA level of 2 x 10-4 all of the heavy metals are completely complexed oy NTA. In addition, some of the major cations, Ca(ll) and Mg(II), which form weaker NTA complexes than the heavy metals, are bound to NTA at levels of 17 and 2 percent, respectively. It is interesting to note that although the log (11K,,,) value for NTA is 10.3, (an equilibrium constant value that is comparable to the log K of the Zn-NTA complex (10.4», only 9 percent of the H+ is bound to NTA at total NTA levels of 2 x 10- 4 M, while the Zn(Il) is completely complexed by NTA. The difference in degree of complexation lies in the relative concentrations of Zn(II) and H+. C T•znM is two orders of magnitude greater than [H+] at pH 8, that is, 1.5 x 10-' M versus 10-8 M. Comparison of the equilibria


Coordination Chemistry

[Zn-NTA-] _ 10.4 [Zn2+][NTA' ] - 10 and [HNTA'-] _ 010.,
[W][NTN-] - 1

shows that for the same [NT N-] concentration, for [H+] = 10- 6 ,


10-' and [Zn'+]

(10-') Therefore,

[ZnNTA-] 6)[NTA' ] [HNTA'-] (10 ')[NTA' ] [ZnNTA-]

10'0•4 10'0 ., = 0.1

[HNTA'-](1O- 6)(0.1)

That is, higher concentrations of metal ions as well as large complex formation constant values tend to favor the formation of NTA-metal
complexes. If we examine the other side of the coin, we can see the way in which

the concentration of NTA and the relative values of the stability constanls of metal ion-NTA complexes determine the distribution of added NTA between the various metal ion NTA complexes. Figure 5-8 shows that at very low levels of added NTA the NTA is primarily present as the CuNTAcomplex with minor amounts present as PbNTA- and CaNTA- complexes in descending order of importance. As the quantity of added NTA increases to levels such as those typically encountered (Le., -10- 6 M) in waters receiving secondary sewage effluent from communities using NTA based detergents, the Fe(OH),NTA'-, Fe(OH)NTA-, and ZnNTA- complexes start to be more important but, although decreasing in percentage, the CuNTA complex is still by far the most significant repository of added NTA. At added NTA levels of 10- 4 M, CaNTA accounts for close to 85 percent of the NTA in solution, HNT A'- for close to 8 percent, and MgNTA - for about 2 percent. The heavy metal complexes of NTA account cumulatively for less than 5 percent of the added NTA. It should be kept in mind, however, that while these heavy metal NTA complexes only account for a minor fraction of the added NTA, the heavy metals are completely complexed by NTA. Table 5-10 and Fig. 5-8 emphasize the importance of conducting model studies and experiments on complex multi-metal, multi-ligand systems at concentrations of metals and ligands that closely resemble the environment being studied.


Complexes with Organic Ligands
c T,



0.0019 80 70 60 50







~ 40 ~
30 20


"0 10

• 0 • ~ •


8 6 4 2 1a-"







Fig. 5·8. Distribution of nitrilotriacetate in model lake water at pH 8. After C. W. Childs. Proe. 14th Coni. Great Lakes Res .. 198-210. 1971. Reprinted by permission of the International Association for Great Lakes Research.

The influence of NTA as a complexing agent on the distribution of metal species can be assessed by comparing the concentrations of various metal species both in the presence and absence of NTA. Table 5-11 shows the calculated distribution of some selected metals in a water in the absence of NTA. but otherwise of the same composition as that used to compute the distribution of NTA complexes given in Table 5-10. NTA at 3 X 10-6 M effectively draws the metals that are complexed by the inorganic ligands present from these complexes into NTA complexes. The metals that are poorly complexed by inorganic ligands are not significantly affected by the addition of this amount of NTA. 5.7.3. Metal Ion Association with Humic Substances CHARACTERISTICS OF HUMIC SUBSTANCES Humic substances are an extremely complex and diverse group of organic materials


Coordination Chemistry

TABLE 5-11

Complexation of Metal Ions by Inorganic Ligands
Percent CQmplexed with Indicated Ligand Percent CQm. plexed by NTA3Percent alter addition Complexed of byedl 3 x 10-5 M Ligands NTA

Metal Ion
Cu(IO = 2 x 10~ Pb[ID "" 3 X 10-1 MI(IO "" 10-1 Fe{l1O "" 2 X 10--11 Zn(ID = 1.5 X 10-5



Mn(1O = 2




2 2

" " ,.


72 2 100



811 60

0 <0.1 0 0 0

Ca{ID = 10-3

Mg(1O "" 2.5 x

5 5

Sr(II)=2xlO-5 Ba(ll) = 1.5 x 10-1 Na{Q = 5 x 10'"

5 5 5 5 5

Source: C. W. Childs, Proc. 14th Coni. Great Lakes Res .. 198-210 (1971). Inti. Assoc. Great Lakes Res. (Reprinted by permission of the International Association lor Great Lakes Research.)

whose structure is not well-defined. They are a mixture of poorly biodegradable decomposition products and by-products of natural organic matter produced by both plants and animals. Humic substances have poorly defined physical and chemical characteristics (e.g .• melting point. refractive index. and molecular weight) and have been characterized by Schnitzer and Khan" as "amorphous. brown or black. hydrophilic. acidic, polydisperse substances of molecular weights ranging from several hundreds to tens of thousands." Humic substances account for the bulk of the organic material in natural waters and soils. In dilute aqueous solution their "brown or black" color becomes the "yellow-brown" typical of natural water color and of the color of biologically treated sewage effluents. Humic substances have been arbitrarily divided into three diverse groups of compounds on the basis of their solubility in dilute acid and dilute base. Fulvic acids are soluble in both dilute acid (pH I) and dilute base. Humic acids are soluble in dilute base but are precipitated by dilute acid (pH I). Humin is insoluble in both dilute acid and dilute base. Some authorities divide humic substances into only two groups: the humic acids and the fulvic acids. stating that the humins have the same characteristics as humic acids but that their solubility in base is hindered because they are associated with clay minerals in natural waters.21 The gross chemical and physical properties of humic acids and fulvic acids are presented in Table 5-12. It is the fulvic acid fraction that appears to

M. Schnitzer and S. U. Khan. Humic Substances in the Environment. Dekker.

York. 1972.


R. F. Packham, "Studies on Organic Color in Natural Water," Proc. Soc. Water

Treat. Exam. 13: 316-329 (1964).

Complexes with Organic Ligands


be the" predominant group of humic substances in natural waters. Fulvic " acids appear to have lower molecular weights than humic acids; they contain a higher percentage of oxygen and the oxygen appears to be located in a greater percentage of carboxyl groups. Although the chemical structure of both the humic acid and fulvic acid fractions of the humic substances is not precisely known, the nature of the major functional groups present is fairly well defined. The following types of functional groups have been reported:

-e "OH


Carbonyl Ether



Phenolic Alcohol Methoxyl



-c-o-e/ /



.f0 --?o-e-R


-G-GH -O-eH,

TABLE 5-12 Physical and Chemical Properties of Humic and Fulvic Acids
Elemental Composition (% by weight) C H Humic Acids

Fulvic Acids

5!l-B0 4-S

N S Solubility in strong acid (pH I)
Molecular weight range Functional group distribution


40-50 4-S 44--50 <1--3

1-2 Not soluble
Few 100 -4 se:~ral


mllhon Percent of oxygen in indicated functional group



-eOOH -<Q>-OH
[ 4-O H -G==O

14-45 10-38 1:>--15

11-16 4-11

phenol alcohol



methoxyl -O-eH,



Source: M. Schnitzer and S. U. Khan, Humic Substances in the Environment, Dekker, New York, 1972.


Coordination Chemistry



HO-~¥o:0- -O~*LOH-O~J¢rC:;~






o II








OH- -0=<; C-OH OH



C ~O




9 I
0 0








~H /O-~*~--OH'"
I 0 OH 1-



'0 OH










Fig. 5·9. Suggested chemical structure of fulvic acid. Reprinted from M. Schnitzer and S. U. Khan, Humic Substances in the Environment. p. 196, Marcel Dekker, New

York, 1972, by courtesy of Marcel Dekker, Inc. Schnitzer" has proposed that the structure in Fig, 5-9 represents a significant portion of the fulvic acid group. The various aromatic ring structures are bonded together by hydrogen bonds between the functional groups on adjacent rings, This structure does not account for the nitrogen and sulfur content of humic substances. It has been suggested that these elements are derived from parts of other types of molecule, for example, proteins, which are associated with the humic substances. Indeed it has been proposed" that humic substances consist of an -aromatic core to which pep tides, carbohydrates, metals, and phenolic acids are chemically or physically attached. It can be seen that the structure in Fig. 5-9 is an "open" network, In fact, there have been suggestions that organic and inorganic materials associated with humic substances are trapped inside these "holes" in the humic substance structure. 24
5.7,3.2, INTERACTION OF HUMIC SUBSTANCES WITH METALS A discussion of this topic must always start with a statement of the difficulties

" M. Schnitzer, "Agron. Abstracts," Am. Soc. Agron, 197L p. 71.
M. Schnitzer and S. U. Khan, Humic Substances in the Environment. Dekker,

New York, 1972.

M. Schnitzer and S. U. Khan, Humic Substances in the Environment, Dekker,

New York, 1972.

Am. eds. For this reason there is no question about the ability of humic materials to combine with metals. Christman. "Metal.4 mg Fe(II1) and 4. stabilized. 28 M. eds . Hunter. Pub!. Hood. New York. S. Two modes of binding appear to be significant. . Schnitzer suggests that humic sub· 2S R. D. and (2) an association between the humic substances and a colloidal particle of metal hydroxide (possibly through sorption on the surface of the particle) whereby the colloidal particles are peptized. Faust. 27 M. Alaska. New York. and J.Organic Matter Interactions in Soils and Waters. University of Alaska. 1968. many metals can be enriched into peat (which is a type of soil organic matter of a humic nature) from soil waters so that the concentration of the metal in the peat is up to 10. The formation of one or another of these associations between humic material and metals may depend on the initial states of humic matter and metal and their absolute and relative concentrations. since the exact chemical structure of humic substances is not well defined and this structure can change from one water to another." in Organic Compounds in Aquatic Environments.. 1975. Symposium on Organic Matter in Natural Waters.r. "Metal-Organic Matter Interactions in Soils and Waters. Schnitzer. Humic substances undoubtedly have the ability to combine with (or bind) considerable quantities of metal ions.000 times that of its concentration in the water. Schnitzer. It has also been observed that in many natural waters. For example. Fe(II1) is associated with the color causing organics. These are (I) the formation of complexes or chelates between the functional groups of the humic substance and the metal." in Organic Compounds in Aquatic Environments. 26 Standard Methods for the Examination of Water and Wastewater 14th ed. Indeed Schnitzer" proposes that the transport and deposition of metals such as Fe(II1) in soils is regulated by humic substance·iron compounds of various solubilities. D. 64. Schnitzer" has estimated that a solution containing 100 mg of fulvic acid/liter can maintain in solution 8. Dekker. F. High concentrations of metal (exceeding the solubility limits of the metal hydroxide) and high metal to humic substance ratios would seem to favor the formation of peptized particles over soluble complexes. V. 297. 197L p. V. 297. it is the nature of the association that is open to question. For example. S. ed. College.association between humic substances and metals. We are faced with this situation here.Complexes with Organic Ligands 235 involved with determining the nature of the . New York. Christman" has found that several waters each with the same color intensity (measured as 100 cobalt· platinum units)26 contained dissolved organic carbon concentrations of anywhere from 10 to 30 mg Clliter. The concentration of Fe(II1) is more than two orders of magnitude greater than that expected in solution in a water at -pH 7 in equilibrium with ferric hydroxide. It is difficult to define the nature of the product of a chemical reaction when the nature of the reactants is not known. 197L p. in suspension and prevented from coagulating or settling. W. p. Hunter. D.0 mg AI(II1)/lite. Dekker. Faust and 1. that is. Health Assoc.

As the soil water percolates down through the soil. and uranium in highly organic soils and deposits (such as peat and coal) are thought to arise also from the association of metals with natural organics in these materials. By blocking various functional groups on the humic substances and then exposing the modified humic material to metals in solution. 2':1 To determine mole ratios. . Schnitzer and Khan'· report that at pH 3. it is possible to obtain an idea of which functional groups are important in the complexation of metals. Al(III).humic substance gradually becomes more and more enriched with Fe(lII) (mole ratios of up to 6: 1 have been found) and concomitantly more and more insoluble. Dekker. 30 M.5. From these results we can account for in excess of 80 percent of the complexed Fe(III).humic substance complexes. and 50 percent of the Cu(II) reacted simultaneously with strongly acidic carboxyl groups and with phenolic groups. 66 percent of the Al(III). the complexes precipitate out to form iron·rich layers in the soil horizon. 1972. 75 percent of the complexed Fe(III). At the surface of the soil these complexes contain a mole ratio" of Fe(III):humic substance of I: I. For the fulvic acid studied by Schnitzer the average molecular weight was 670. Humic Substances in the Environment. New York. Khan. the Fe(III). it is necessary to know the average molecular weight of fulvic acid. The nature of the complexes formed between humic substances and metals are not known unequivocally. and Cu(I1) by complexes such as + Cu (lJ) <= or The experiments also indicated that the alcoholic OH groups were not involved in forming metal complexes.236 Coordination Chemistry stances dissolve Fe(lII) from iron·containing solids in the soil to form Fe(III). The high concentrations of metals such as iron. U. copper. Schnitzer and S. 20 percent of the Al(IIl). At very high Fe(III)-humic substance mole ratios. and 32 percent of the Cu(II) reacted with the more weakly acidic carboxyl groups alone. A further 8 percent of the Fe(III).

p. the K values would be lower because the protonation reaction would have to be accounted for.4). Indeed some of the values of the constants for metal-fulvic acid complexes approach the values for the very weak inorganic ion pairs (e. Morgan. . Hood.Complexes with Organic Ligands 237 Although it is impossible to write an exact complexation reaction for metal ions and humic substances. Discussion of paper by R. Schnitzer and E. L. that is.3 31 32 . 479.NTA -] and [H.3. but at 3 < pH < 10./ CH. totally deprotonated species. it is possible to derive stability constants on an operational basis.O.. University of Alaska.COO- 7 is predominant (e. of Marine Science.= 10'·" I (5-14) M. A comparison of the formation constants for metal-fulvic acid complexes shown in Table 5-13 with those values for the complexes of the same metals with NTA (Table 5-10) would seem to indicate that the metal-fulvic acid complexes are much weaker than the metal-NTA complexes. 1970. CH. D. If the K values were measured where the species COOH " . The stability constants for NTA complexes reported in Table 5-10 are for th. the predominant NTA species is HNTA . -noc" /COO- C~N/CH. Malcolm. and P.. W. The formation constant values in Table 5-13 were obtained by Schnitzer and Hansen" for a particular fulvic acid.. "CH. Jenne. log K = 3.3 K = 10" (5-13) (neglecting [HNTA'-J. "Conditional Stability Constants of a North Carolina Soil Fulvic Acid with Co2+ and Fe 3 +" in Organic Matter in Natural Waters. A. McKinley. [H. ed.3. Inst. E.COO- CH.g. Thus at pH > 10. J. H. MgCO. log K = 2. Morgan" has pointed out that the values for the metal-fulvic acid complexes were measured at much lower pH values than the K values for other complexing agents such as NTA and EDTA. W. Soil Science.NTA]).g" at pH 7). J.. for individual preparations of humic acids and fulvic acids from specific sources. CaSO.9.". Hansen. 109: 333 (1970).and the reaction Ka .-COO- a species that is only predominant in solutions with pH of greater than 10.

Malcolm. Metal complexes of humic substances are important in natural waters because as we have already seen. 3 = 10'" (5-15) The measured values of the formation constant for Cu-NTA . . we should divide the equilibrium constant values presented in Table 5-13 by the dissociation constant of the -COOH group. Hood ed. Discussion of paper by R.3 = 10 13 X 10-10. Morgan.. when the carboxyl groups are ionized. Subtracting Eq.tto" values for metal ion-fulvic acid <:omplexes would be in the range 10' to 10". "Conditional Stability Constants of a North Carolina Soil Fulvic Acid with C02+ and Fe 3+" in Organic Matfer in Natural Waters D. The same is true for the humic substance-metal ion complex equilibrium constants measured at low pH values. E.f0 + Cu'+ "" R-CH-C"" 6 H Kinto pH = K. that is.- "0-CU2 + If we estimate the value of K. then the true K'o<m.. + Cu'+ "" R-CH-C"" I I "OH "0 0 0 ""Cu2+ H H #0 R-CH2 I "00 H . and particulate states. the presence of complexing agents such as the humic substances may 33 J. . weaker than the corresponding NTA and EDTA complexes. and P. Morgan 33 estimates that at pH 2 to 3 the -COO.f0 R-CH-e + H+-. they strongly influence the distribution of metals between the dissolved .f0 . p. W. A. They are.238 Coordination Chemistry must be taken into account.ow pH K. 5-13 yields Cu'+ + HNTA'-"" Cu-NTA. of Marine Sciences. which makes them moderately strong to strong complexes. which accounts for the observed ability of EDTA to extract metals from humic materials. L. McKenley.groups. to be -I X 10-'. Jenne. J. 1970. W. 5-14 from Eq. 479. . Thus to obtain the value of the formation constant at intermediate pH for metal ion fulvic acid complexes. lnst. which are important in forming fulvic acid-metal ion complexes.f0 R-CH-C"" "0- " + H+ "" R-CH-Cf' 6 H _1_ "OH K. University of Alaska. Because of this. are virtually all in the -COOH or protonated form. in intermediate pH will then be 10'" which is significantly less than the value of 1013 measured at high pH.+ H+ K = 1013 X K.

1971.0 3.1 3.0 3. Therefore. Let us also assume that the Fe{III)-humic substance complexes are labile-that is. we have in solution the Fe(IlI)-humic substance complexes.7 3. they will dissociate rapidly to release Fe{III). the maximum possible Fe(I1I) concentration is 10-11 M.9 2. "Metal-Organic Matter Interactions in Soils and Waters. influence the biological productivity or the amount of organisms such as algae and higher plants and animals that a natural water can support.3 3. Let us assume that there are no humic substances in the lake water and that the Fe{III) concentration is controlled by its equilibrium with ferric hydroxide.7 2. For example.0 3. V. Thus the water will contain only a minute amount of Fe{II1) and as the growth of algae consumes the Fe (III). . D. In this situation we have not only seen an increase in the total dissolved iron but also an increase in the pool of readily available Fe{III).1 2.6 2." in Organic Compounds in the Environment. Schnitzer.I I Complexes with Organic Ligands 239 I TABLE 5-13 Formation Constants of Various Metal Ion Fulvic Acid Complexes (Ionic Strength = 0_1 M) Metal Ion Fe3 + pH of Measurement log K for Metal Ion-Fulvic Acid complex a 6. in addition to the Fe (III) in equilibrium with Fe(OH)"". the dissolution of Fe{OH)"" to replace the depleted Fe{III) may be quite slow. Fe{OH)"".1 1.. Fe{III). Observations made by Schnitzer" discussed previously have indicated 34 M. Now consider the situation in the presence of humic substances that can complex Fe{I1I). We shall see from calculations made in Chapter 6 that at pH 8. fulvic acid.4 mglliter. let us suppose that the growth-limiting nutrient for algae in a lake is iron. Dekker.9 AI" Cu2+ NiH Cp2+ Pb2 + Zn2 + Mn2 + Mg2+ M 1. Hunter. We also will learn in Chapter 6 that some precipitates like Fe{OH)"" are notoriously slow to reach equilibrium because they form slowly and dissolve slowly.0 3. are for the reaction + fulvic acid M . S.0 3.0 ~ a Formation constants. The total amount of dissolved Fe{III) must be greater than in the absence of humic substances because. eds. we might expect very little and very slow growth of algae under these circumstances. Faust and J.4 2. or 6 X 10. K.0 3.35 3.

if the complexing agent (I) forms a stable and or inert complex with the metal of interest. the productivity of the water was reduced below the level of the control containing no added complexing agents. However. When the concentration of the weakest complexing agent was increased to 10-5 M. 265. it stimulated productivity more than did cysteine. S. DPTA is such a strong complexing agent that 10-5 M of it will reduce the metals level to a value below that required for as much growth as the control. and NTA.240 Coordination Chemistry that the increase in total dissolved iron in the presence of humic 'substances can indeed be significant. when the strongest complexing agent (DPTA) concentration was increased to 10-5 M.'. Siegel35 quotes unpublished work of Barber on the effect of several complexing agents on the productivity of water from the Gulf of Mexico. EDTA. it may have the effect of reducing the level andlor availability of metal ions below that found in the absence of any complexing agent. they might even increase the Fe(III) concentration to such a level that it would no longer be the nutrient in shortest supply that limits growth. K = 1028 . eds. increased levels of the weakest complexing agent. cysteine. and the weakest complexing agent (NTA) stimulated the productivity the least. In our example their presence would increase the amount and rate of algal growth. V. K = 10'. At concentrations of 10-' M the four complexing agents stimulated the productivity of the water in the order expected. that is. These are DPTA. In such a situation we would expect a decrease in the productivity of the water over that of a water in which there was no complexing agent. The presence of complexing agents in a water may not always have this effect. "Metal-Organic Reactions in the Marine Environment. p. Dekker. Hunter." in Organic Compounds in Aquatic Environments. The productivity of the solutions was therefore in the following order: IO-'M EDTA 10-5 M EDTA > 10-5 M NTA > 10-' M cysteine> 10-' M DPTA 10-' M NTA > control> 10-5 M DPTA Apparently. K = 10" and NTA. EDTA.. As an example of this type of effect. NT A. . Siegel. The complexing agents studied were DPTA (diethylenetriaminepentaacetic acid). D. the strongest complexing agent (DPTA) stimulated the productivity the most. increase productivity while a tenfold difference in concentration of a 35 A. Faust and J. cysteine. K = 10". We can judge the relative "complexing ability" of these complexing agents by comparing the formation constant values of their complexes with Fe(III). or (2) is present at a sufficiently high concentration. 1971. For example. Increasing the concentration of the next strongest complexing agent (EDTA) did not produce the same reduction in productivity. In this hypothetical example the presence of the complexing ability of humic substances was seen to result in an increase in dissolved iron species.

and Pb(II). solution? Check your answer to be certain that CU(OH)2(S) will not precipitate.after the addition of 2 x 10-' moles EDTA'-/liter of sample.S. a small amount of Eriochrome 2. 8. CT.'-.S. What is the pH of a 10-' M Cu(CIO.). CT•Mg = 5 X 10. the color of the solution changes from red to blue.(H. Given the formation constants for CaEDTA2.H.01 M EDTA solution. 6. as well as 5 mgnlter of fulvic acid.and MgEDTA2.2 ml of 0. Hg(CN). does not change its effect on productivity.6 and lOS·7. PROBLEMS Name the following complexes: PtCJ. what is the fraction of CT •N1 in the form of Ni(CN}l-? A solution contains 2 X 10-3 moles Ca2+/liter and 3 X 10. . Arrange 9. Co(NH. calculate (I) The concentration of MgEDTA'.). Does the presence of Mg2+ significantly interfere with the determination of Ca2+ by the EDTA titration procedure? S. In order to determine the hardness of a solution. 7.4 moles Mg2+/liter. What is the hardness concentration in moleslliter and mglliter as CaCOa? 3.4 M and a very high sulfate concentration. (b) The concentration of MgEDTA'.4. Given a CT.'-. and a pH of 8. is dosed with 80 mglliter of alum.) A natural water contains equal concentrations in the micromolar range of Fe(lll).of 1010 . EDTA.co3 = 1 xlO. A wateT.+.). (Noie: You may wish to use Fig. how much of the Co and Mg is complexed with sulfate? Given the conditions listed for development of Fig. Ni(NH.after the addition of 1.5 after coagulation? The calculation in Section 5-6 showed that the only complexes of significance in a typical natural water are the sulfate calcium and magnesium complexes. After addition of 11. Mg(IIl.Problems 241 complexing agent of intermediate strength.-. Black T is added to 100 ml of sample.5. 4. respectively. = 1 X 10-3 M.CT. 5·6.3 M. 5-2. 5·2 to obtain a good initial estimate of the species concentrations of interest.O)3+. I. Cu(lI). pH 5. 10.5 x 10-' moles EDTA'-nlter of sample. Show that [HgOH+] is negligible in Example 5·2. CaHCO. Fe(PO).S04 = 2 x' 10. Calculate the Pb4(OH)44+ concentration at pH 6 for the conditions given in Fig. Ca(OH)" is needed so that the pH does not change during coagulation? (b) How much hydrated lime must be added to produce a water with a pH of 7. (a) How much hydrated lime.

HUMIC SUBSTANCES Chapters by R. ADDITIONAL READING COMPLEX FORMATION Basolo. Beck.. Stumm. Hunter. Christman and R.. Faust and J.. Gjessing. London. and S. Complex Formation. 36 Note: Additional problems on the effect of complexation on solubility appear at the end of Chapter 6. Benson. Boston. G. Reinhold.9.242 Coordination Chemistry the metals in order of the extent of complexation with fulvic acid and give your reason for this order. Pearson. 1967. The Study of Kinetics and Mechanisms of Reactions of Transition Metal Complexes. 1972. S. How can one explain the ability of EDTA in solution to extract metals from dissolved metal-humic acid complexes? Under what conditions will the addition of a trace metal chelating agEl'nt aid the biological productivity of a water? Under what conditions will it decrease biological productivity?3& 12. and M. .. 2nd ed. Hunter. Dekker. W. Schnitzer in Organic Compounds in Aquatic Environments. 1970. Stumm.. John Wiley. Mich .. Dekker. 11. 1967. M. R. A. eds. John Wiley. V. New York. Allyn & Bacon.. Wilkens. Mass . 1971. E. U. and J. New York.. S. T.. New York. Humic Substances in the Environment. McGraw-Hill." in Principles and Applications of Water Chemistry. D. 1968. M. Ann Arbor. 1970. New York. Physical and Chemical Characteristics of Aquatic Humus. Mechanisms of Inorganic Reactions. D. Ann Arbor Science. and R. G.. W. Morgan. Minear. New York. Wiley-Interscience.. Schnitzer. F . Faust and J. A. Siegel. 5. 1974. eds. A Study of Metal Complexes in Solution. V. F. New York. J. 1975. Mechanisms of Inorganic Reactions in Solution. "Metal Ions in Aqueous Solutions. D. Khan. Aquatic Chemistry.

PRECIPITATION AND DISSOLUTION 6.1. Knowledge of equilibrium relationships permits the calculation of concentrations at equilibrium and thus the amount of precipitate or amount of the material that dissolves can be calculated. Dissolution of minerals is a prime factor in determining the chemical composition of natural waters. 6. I. INTRODUCTION Precipitation and dissolution phenomena are extremely important in both natural waters and water treatment processes. coagulation with hydrolyzing metal salts. 3. 2. 4. In many instances rate controls the extent of reaction because insufficient time is available for equilibrium to be achieved. We must be aware that equilibrium calculations and log-concentration diagrams of systems involving heterogeneous equilibria may only provide us with the boundary conditions of the system rather than the situation that truly exists. The ions produced by the dissolution of solids may undergo further reaction in solution. iron removal. Both equilibrium considerations and the rates of reactions are important. There is a wide variation in the reported values of heterogeneous equilibrium constants. and phosphate precipitation are based on precipitation phenomena. Supersaturation may exist. . Solubility depends both on the degree of crystallinity and the particle size of the solids (which may vary from case to case). that is. Thus equilibrium calculations involving solids in waters and wastewaters are generally less representative of the true situation than acid-base equilibrium calculations for the following reasons. solution concentrations in excess of those predicted by equilibrium calculations may prevail. Some heterogeneous equilibria are slowly established. The thermodynamically predicted stable solid phase for a given set of conditions may not indeed be the phase that is formed. Water and wastewater treatment processes such as lime-soda softening. Natural water chemical composition can be altered by precipitption of minerals and the subsequent sedimentation of these solids from supersaturated solutions. 5.

' It is possible for a solution that is only slightly supersaturated with respect to a solid phase to be stable indefinitely. In this chapter we will deal with the kinetics and equilibrium calculations of heterogeneous systems. 6. (2) crystal growth.244 Precipitation and Dissolution Because of the last reason it is imperative that one be sure of the conditions under which equilibrium constants were measured prior to using a particular value. the nucleation is said to be heterogeneous.) precipitate." Macmillan. Wiley-Interscience.. Thesis. New York. 1964. PRECIPITATION AND DISSOLUTION KINETICS Precipitation has generally been observed to occur in three steps: (1) nucleation.D. J. Nuclei can be formed from clusters of a few molecules or ion pairs of component ions of the precipitate. If the nuclei are formed from the component ions of the precipitate. and A. When the degree of supersaturation is increased or when fine particles of a substance are mixed with this solution. Trussell.1. should be consulted in addition to references given in this section. G. The Formation and Properties of Precipitates. . 1972. Nucleation A nucleus is a fine particle on which the spontaneous formation or precipitation of a solid phase can take place. Stumm and J. or they may be fine particles unrelated chemically to the precipitate but with some similarity of crystal lattice structure. Precipitation from homogeneous solution (Le. "Kinetics of Precipitation. 6. California. The precipitation of calcium carbonate will be discussed in some detail. most nucleation is heterogeneous. and (3) agglomeration and the ripening of the solids. University of California. Because virtually all aqueous solutions contain fine particles of various types. E. Aquatic Chemistry. 1 2 References such as A. the initial phase of precipitation is referred to as homogeneous nucleation. For example. Walton. Morgan. Wiley-Interscience. The turbidity of the solution was monitored after various increments of NaOH addition to detect the formation of a CaCO".) had been exceeded by 40 to 50 times that evidence of precipitate formation was shown. "Systematic Aqueous Chemistry for Engineers.2. Nielson. a solution with no solid phase present) requires that nuclei be formed from ions in solution. R. if the foreign particles are the nuclei. R. Trussell' reports a simple experiment in which three solutions containing Ca'+ and carbonate species were titrated with NaOH." Ph.2. 1970. and the chemistry of phosphorus will be used as a detailed example of several heterogeneous equilibria that are of relevance to natural waters and treatment processes. 1967: W. Figure 6·1 shows that it was not until the value of the equilibrium constant for the precipitation of CaCO". Berkeley. precipitation occurs. Graphical and computational methods for solving equilibrium problems will be presented.

The influence of the saturation ratio (= the initiation of crystal formation for CaC0 3.Precipitation and Dissolution Kinetics 245 · 5 0 ' .cac~) on The formation of nuclei from precipitate ions is an energy-consuming process because one creates an organized structure with defined surfaces from a random arrangement of solution constituents. H. Acta Chern. Christiansen and A.. tends to be larger for homogeneous nucleation than for heterogeneous nucleation because the precipitate ions can collect on the surface of the foreign particle.1 .d r 1 I -0--1 - Solution ' _ --0 1 o 10 20 30 40 Saturation ratio 50 60 70 80 Fig.' .' 1 .' . E. Crystal growth rate can be expressed as de ~ -kS(e . Because of this energy requirement it is necessary for solutions to be supersaturated..1 .' 1 .e'j" dt 3 (6·1) J. [Ca2+]{COl-]/Kso.' '- 40 ISolution 2 - ~ 30 r-'0 - i :0 ~ 20 rSolution 3 l( J. Scand... the rate of crystal growth is of critical importance. 5: 673 (195!)..' 6. or have concentrations greater than that predicted by equilibrium with the precipitate. the only requirement is that the foreign surface be somewhat similar to the precipitate in lattice structure and distance between adjacent ions.. .2. and because the free energy to form a crystallite on a similar surface is less.. or necessary degree of supersaturation.' . before the precipitate will form from a homogeneous solution..1 . 6-1. Crystal Growth Crystals form by the deposition of the precipitate constituent ions onto nuclei..-1 .. This driving force. Nielsen.1 ..' .. Since water and wastewater treatment processes involving precipitation often do not reach equilibrium. In essence the foreign surface serves the same function as the surface of the precipitate particles.2.

Agglomeration and Ripening The initial solid formed by precipitation may not be the most stable solid (the thermodynamically stable phase) for the reaction conditions. mole(1-n) = surface area available for precipitation. Equilibrium constants 4 G. (6-2) 6. mole/liter rate constant.1 . Nancollas and M. The value of k depends on solution conditions and the nature of the solid being precipitated. molelliter actual concentration of limiting ion. a different rate equation is expected for solutions with other properties. a reduced solution concentration because the more stable phase usually has a lower solubility than the initially formed phase. . M. the solution concentration in equilibrium with small particles is higher than that in -equilibrium with larger particles. in a mixture of particle sizes. Chapter in Aqueous Environmental Chemistry of Metals. then over a period of time the crystal structure of the precipitate may change to that of the stable phase. The changes in crystal structure that take place over time are often called aging.1 min-to Of course. Reddy. Since very small particles have a higher surface energy than larger particles. Consequently. A.246 Precipitation and Dissolution where C' C k S saturation concentration. J. Nancollas and Reddy' found that the precipitation of calcium carbonate from a particular solution corresponded to the rate law: d[Ca2+] = kS ([Ca'+] _ [Ca2+]')' dt where k = 5. mg/liter of a given particle size n = constant = = = For example.3. the smaller particles dissolve because the solution concentration is now below their saturation value. ed" Ann Arbor·Science. This change may be accompanied by additional precipitation and. If this is the situation. consequently. the exponent may have a value other than unity. A phenomenon called ripening may also take place whereby the crystal size of the precipitate increases.2.t mole. When the diffusion rate of ions to the surface of the crystal controls the crystal growth rate.76 liter' mg. Rubin. litem time. 1975. the exponent n has a value of unity. This discussion should indicate that selection of an equilibrium constant for a precipitating solution is extremely difficult. when other processes such as the reaction rate at the crystal surface are rate limiting. As the concentration in the solution is lowered through the growth of the larger particles.1 mg. Conversion of small particles into larger particles is also enhanced by the agglomeration of particles to form larger particles. H. the large particles will continue to grow because the solution is still supersaturated with respect to them.

6. Walton.3. Solids such as CaF". etc. adsorption of impurities at the crystal interface.4. Examples are CaC03(. If solid is absent. This situation results in the so·called common ion effect in which the presence of a common ion modifies the solubility of the solid. G. complex formation.e) dt (6·3) is followed.2. . Very few examples of this situation exist in water chemistry. Precipitates that dissolve to produce reactive solutes.) in solution at moderate concen· trations and at an approximately neutral pH. 3. 5 A. Accordingly. New York.) and BaSO". A solid phase or precipitate in a water containing no other constit· uents than those derived from the dissolution of the precipitate. It may be further complicated by the production or presence of solutes that react further with solution constituents. or complex formation. and formation of solid mixtures. Wiley. one must account for factors such as . Dissolution According to Walton. 1967.) generally fit into this category under natural water condi· tions. the rate law. The reaction may be hydrolysis (protolysis). 6. On occasion the rate of dissolution of the substance may be affected by the formation of surface complexes.Equilibrium Calculations 247 reported for individual solids may vary widely because beside the effects of the particle size and aging.lnterscience. they may only be used to test whether saturation with a particular solid exists. EQUILIBRIUM CALCULATIONS At the outset of any qiscussion on heterogeneous equilibria it is important to realize that heterogeneous equilibrium calculations only apply when there is an excess of the solid of interest present.) and AI(OH)3(') dissolving in water. hydrolyze. The solutes produced by the dissolution of the precipitate do not react (form complexes. The situations commonly encountered are 1. the equilibrium calculations are not valid for predicting solution composition. 2. The Formatlon and Properties of Precipitates. de =kS (e' . Solids that dissolve in a solution containing a species that is the same as one of the species that results from dissolution of the precipitate.5 dissolution is nearly always controlled by the rate of diffusion of the species away from the solids.

Strong acid addition occurs from N. COl~. 6·2.issolution of CaCO"" and the reaction of CO.'. a typical one is the dissolution of CaCO"" from the soil during the passage of sewage effluent in groundwater recharge. More complex systems where a variety of processes such as gas transfer and redox reactions are superimposed on the dissolution reactions and reactions of the dissolved solute. These four situations are influenced by solution ionic strength. oxidation of NH. Gas exchange of CO. 4. the solubility of salts increases with increasing ionic strength. The magnitude of this effect can be assessed at most ionic strengths of interest to us using the DeBye-Hiickel. These are the types of situation usually encountered in nature and in water and wastewater treatment processes. and reduction of NO. or related. Fig. strong acid removal takes place with denitrification.'.. 6. . 6-2). + to NO. In general.after CaCO"" dissolution in the soil water (Fig. and CO 2{g} add. CaC0 3is ) equilibria in the presence of alkalinity.!.3.(nitrification). HC03 ~ H2 CO. H+ from nitrification foe i::Ienitrification C~(aq) ea2 +.248 Precipitation and Dissolution Examples are CaF2 (s) dissolving in water containing ea2+ ion and CaCO"" dissolving in a solution containing CO. with the soil atmosphere.(" (denitrification) are superimposed on the d. laws.ition and removal occurs through gas transfer. The Solubility Product Solubility product is the name given to the equilibrium constant that describes the reaction by which a precipitate dissolves in pure water to form its constituent ions. .ion.

0 12.0 10. .3 26. Accordingly.. Zn(OH).} (6-4) The activity of the solid pliase can be taken as unity (see Section 3-3). PbCI. ZnS pKso AI(OH). Ag. It is important to differentiate between the terms solubility product and solubility. Table 6-1 gives many K. cK. Generally stated. Ca(OH)..9 33 14.2 21. Mn(OH). fe. Solubility is the amount of a substance in moleslliter or mglliter that can dissolve in a solution under a given set of conditions.(PO.3 4.8 14.7 10 19.PO. (amorph) AIPO.5 17. fe(OH).Equilibrium Calculations 249 TABLE 6-1 'Solubility Product Constants at 25°C' Solid fe(OH).7 12. SiO. but the two quantities are interrelated. values of interest to us.o. (6-5) Assuming that the solution components have activity coeffici~nts of unity and that the solid has an activity of one.8 10.59 2. AgCI Ag. •. (amorph) a 38 17. cKso f KSQ and cKso is a function of ionic strength.0 4.8 27. (dolomite) Caf.0 8.6 5. PbSO. cK so ' has the same form as the equilibrium constant except that the concentrations of the species in solution are used instead of their activities. CaSO.34 8. CaCO.7 10. Solubility product is the colloquial term for the equilibrium constant. (amorph) fePO.3 7.0 11. the equilibrium constant.3 88 33 21. feS Fe2S 3 pK~ Solid EaSO. CaiPO.22 16. (calcite) CaCO.).8 17. Solubility does not equal the solubility product. K.= zAY+ + yBz-..3 5. Mg(OH). is Kso = {N+}' {B'-P {A.). The concentration product. Cu(OH). PbS MgNH.).SO. MgCO. (aragonite) CaMg(CO..5 Equilibrium constants for the reaction Al'By{s) . Pb(OH). If the activity coefficients are not equal to unity.B y{. = K.6 4.CrO.

does not hydrolyze. is about 8 times more soluble than AgCl and [Ag+] is about 17 times greater in the Ag.CrO. S = X 10-12 8. and (S)(S) = K" = 10-10 Therefore. although the solubility product of Ag. Ag+. therefore. [CrO.'-] = Sand [Ag+] = 2S. AgCl.5 X 10-12 • Which silver salt will allow the greater solution concentration of silver ion. which salt has the greater solubility? For AgCl at 25'C. silver chloride. S = "10-5 molelliter For Ag.o = 2.6 X 10-5 moleslliter Thus.CrO. The molecular weight of CaF2 is 78. we have S = [Ag+] and S = [Cl-]. Solution (I) K" = 5 x 10-" = 'K" = [CaH][F-l' Each mole of CaF2 that dissolves in pure water produces I mole of Ca2+ and 2 moles of F-..CrO. and (3) S(2S)' Therefore. solution. For example.CrO. neglecting ionic strength effects.32 x 10-' molesiliter x 10' mg/g = 18. S = 78 g/mole x 2. Therefore. it happens that Ag. we can write (2) [CaH) = S and (3) [F-) = 2S From (I).1 mglliter.5 Therefore. is more than 2 orders of magnitude smaller than the solubility product of AgCI. neglecting ionic strength. It can be difficult to judge the solubility of a substance from its solubility product.250 Precipitation and Dissolution Example 6·1 Calculate the solubility in mg/liter of CaF 2 in pure water qt 25°C. This fact is used in the argentimetric .'. under conditions where CrO. (2). S = = 4S' = 5 x 10-" 2. if we set S = solubility in moles/liter. (S)(2S)' = K" = 2. has a K" = 1 X 10-10 • and silver chromate has a K.4 molesiliter. at equilibrium? This is equivalent to asking the question.32 X 10.

In general. FeP04 (s) :::.C~[ K". 6.".Equilibrium CalCulations 251 method for determining chloride.19 Thus the FeP04{s) solubility decreases with increasing temperature. 6 In this method a solution containing an unknown amount of chloride is titrated with silver nitrate solution in the presence of a small amount of the yellow·colored potassium chromate {used as an indicator}.7 [_I__ 1. ~ K.!. 1976.444 K $0..] T. since AgCl is less soluble than Ag. In K.!J] ~ -2. 303.CrO..G' ~ .4 kcal !l.G' Solution Knowing !l. we find ~ 1. p..03 10. 14th ed. solubility increases with increasing temperature with a few notable exceptions such as CaCO" Ca3{PO.7 kcal 24. When sufficient Ag+ has been added to lower the Cl.!. starts to precipitate.:= Fe3 + + POltill' ~ ~ -18.CrO. and and (3·27) Setting Then InK"..'c -18. Silver chloride {white} precipitates first. The effect of temperature on equilibrium is presented in Section 3·4 and the following example illustrates the effect on a typical precipitation reaction. Amer. Effect of Temperature on Solubility Temperature affects both the equilibrium position of the precipitation reaction and the reaction rate. Health Assoc.19 X 10. Publ..5'OoC = 1..}" CaSO" and FePO" which are of importance in water chemistry. indicating the endpoint of the titration.18 We can then use the relationship derived by Van't Hoff from Chapter 3..987 x 10 3 298 323J X .3. R till'[. T. _. . the red Ag. 6 Standard Methods for the Examination of Water and Wastewater.concentration to less than 10-5 moleslliter.RT In K.....2. Example 6-2 Find Kso for FeP04 at 50°C given the following information at 25°C for the reaction.

When a solution contains an ion that is the same as one of the ions which result from the dissolution of the solid.7 . The Common Ion Effect .8 X 10-9 (0.012 g/100 ml. What is the solubility of SnF2{sl in a 0.08)' 2.8 x 1O-7mol es lliter = \ 5.7 x 10-')(7. we need to remember that the solubility is based on ions or species lhat come only from the dissolution of the solid.7 x 10-' x 2)' ~ 1.8 x 10-9 1. which will dissolve.8 x 10. 'K~ ~ 10 -4 moleslliter / (7. is reduced from 7. The modification of solubility is called the common ion effect.6 g 1000 ml I mole S ~ 0.3. The assumption is valid. 10-7 « We see from this example that the solubility of SnF. When calculating the solubility of the solid in such a solution.3. Example 6-3 The solubility of stannous fluoride.6 -g- = 7. the solubility of the solid will be less than that when the solid dissolves in pure water.012 100 ml x Iliter x IS6.9 Now let S' = moleslliter of SnF2 . SnF2 {s) ~ SnH + 2F~ K~ ~ 'K~ ~ [Sn'+][F-]' The molecular weight of SnF2 is 156.8 X 10-9 For this example let us assume that 2S' is negligible compared to 8 x 10.7 x Therefore. we see that 2S' 8 x 10-2 .08]' ~ 1. SnF2{s). in water at 20°C is 0.2• Then 'K~ ~ [S'][O. [F-] [Sn'+] ~ (8 x 10-' + 2S') ~S' and 'K~ ~ (8 x 10-' + 2S')'(S') ~ 1.6 X S' Checking OUI assumption that 8 x 10-2 > 2S'.252 Precipitation and Dissolution 6. If 8 x 10-2 mole of F-/liter is originally present.08 M NaP solution neglecting ionic strength effects? Solution Let us first calculate the concentration product for the reaction.

1.6 X 10-4 molelliter.5 x 10.2 X 10-4 » 10. Then S' ~ 9.5 x 10.4 mole/liter to 2.4. we find 2S' = 19. Solution From Example 6·3. We will therefore proceed as we did in the solution of acid-base equilibrium problems and make the opposite assumption.4 so that the assumption is acceptable and the solubility is 9. The assumption is not valid.9 S'.35 « 10- 4 . Then and 'K "" Assuming that 2 S' ~ (S ')(10-4 + 28 'J' 0.4 Checking the assumption. 'K"" Let [Sn2+] ~ ~ 3. This type of behavior is indeed the rule rather than the exception for the systems encountered in natural waters and treatment processes.:. A similar calculation shown in Example 6·4 for a solution containing 10-4 mole NaFlliter . which is not « 10.4. Example 6-4 What is the solubility of SnF2 in a 10-4 molelliter NaP solution? Neglect ionic strength effects. The conditional solubility product has the form (6-6) . assume that 2S I » 10.r Equilibrium Galculations X 253 10. Also.9 (10 ~' Checking the assumption that 2S' « X 10-7 molelliter by the presence of 0. we obtain S' ~ 3.08 M F-.6 X 10. 6. a conditional solubility product is one whose value depends on solution conditions other than the presence of a common ion. in many analytical measurements the total concentration of species is determined rather than the free ion concentration.3. Conditional solubility products are useful when determining the solubility of precipitates whose ions interact with solution constituents through reactions such as complexation or hydrolysis. Conditional Solubility Product As the name implies. we find 2S' = 7 X 10.hows essentially no decrease in solubility caused by the common ion. that is.

.3 M? The ionic strength is 10-2 and P s = 10.Ca = 10-2 M..1.COl = Will CaC03{s) precipitate at pH 9. Solution (C T. if aM = fraction of C T •M present as the free metal ion.5.C. consider Ca(OH)"" and sparingly soluble Mg(OH)"". Ca(OH)"" or hydrated (slaked) lime is commonly used to bring about the precipitation of Ca2+ as CaCO"" and Mg2+ as Mg(OH)"".')' Then or Therefore.74 . < 10. For ariy set of conditions. [M+] = aM (C T •M).M and CT. 7 at pH 9. 10. the solubility product.5 . may change as a function of solution properties such as pH and concentration of complex-forming species because the fractions of CT. The equilibrium relationships at 25'C are Ca(OH)"" Mg(OH)"" ¢ ¢ Ca2+ + 20H-. [A -] = aA (CT.A present as the free cation and anion may vary as a function of these properties. Mg 2+ + 20H-.254 Precipitation and Dissolution where P.3 10gK50= -10. are related.1 from a solution containing CT.6. For example. Log Concentration Diagrams The presentation of precipitation equilibria on log concentration diagrams greatly aids the solution of problems and the understanding of these equilibria. logK50 = -5.)(C T. the solution is supersaturated and CaC03(S) will 6. 6 7 .CO) = 10 -2 X 10 -3 = 10 -. Example 6-5 CT. Since Ps = 10precipitate.3. The conditional solubility product and K. C LM CT.A = = = conditional solubility product total concentration of the metal ion M in all of its complex forms and total concentration of the anion A in all of its forms The value of P. both of which are important in water treatment. and if aA = fraction of C T•A present as free anion.

74 (6-8) Equations 6-7 and 6-8 can be plotted as a log concentration diagram (Fig. 12'L-____ ~ ______ ~ ____ ~~ _____L______L__ _ _ __L______" Fig. we would use cKso ('Yea2+)('YOH-)2 instead of KSO' = Ksol . This diagram can be used handily to solve a variety of problems. for Mg(OH)"".3 Similarly. 7 If the activity coefficients were not equal to unity. activity coefficients are unity: 7 or log [CaH or -log [CaH ] + 2pOH = 5. 6-3. The pC-pH diagram for Ca'+ in eqsilibrium with Ca(OH)2(. that is.3 (6-7) 10.) and Mg2+ in equilibrium with Mg(OH)2{S) at 25°C. -log [Mg 2+] + 2pOH = ] + 2 log [OH-] -5. 6-3).Equilibrium Calculations 255 Assuming that the activity effects are negligible.

8 s Example 6-7 ~ 1. -log [Mg2+] ~ 3. we find that the 10.5.7. when [Mg2+1 = 10-6 M and the solution is in equilibrium with Mg(OH)". which are presented in Fig.0. At this pH. Solution (I) Ca(OH)". the pH is 11.5.) Again from the diagram in Fig.6 x 10-' M Sodium hydroxide is added to a groundwater containing 10.3 + log [CaH ] ~ log [OW] or pOH ~ -log [CaH ] . that is. 6-3.3 M CaH • At what pH will Mg(OH)". Solution From Fig.) will precipitate when the pH exceeds 10. 6·3 we find -log [Ca2+] = 2. and Kw for water. 6·3.4 M Mg2+ and 10.) and (2) Mg(OH)". we find this equation is satisfied at point A in Fig. Since S ~ [Ca2+]. When pOH ~ s or ~ [Mg2+] ~ 10-3 . At this point.7).) precipitate at this pH? At what pH will [Mg2+] be reduced to 10-8 M? The temperature is 25°C.65 (point D). When pOH ~ 1.) ~ 1O. 6·3. pOH 3. 6·7.8. 2[CaH ] ~ [OH-] 0.4 M Mg2+ solution is in equilibrium with Mg(OH)". from Fig.) only at pH 10.65. .3 Plotting the line (-log [Ca H ] .65 (point C). Thus 3.) begin to precipitate? Will Ca(OH)".) In addition to the equilibrium relationship for Ca(OH)2(s)' Eq. Thus Mg(OH)". the solution is very much undersaturated with Ca(OH)2(s)' (From the diagram we see that more than 1 M Ca2 + is required for a saturated solution.) in distilled water. 6·3. The assumption that [H+] « 2[Ca H] is valid at this point.3).2 M Similarly. the charge balance for dissolution of Mg(OH}2(s) in distilled water is 2[MgH] + [H+] ~ [OW] ~ which is satisfied at point B in Fig. 6-3 (pOH ~ 1.256 Precipitation and Dissolution Example 6-6 Find the solubility of (I) Ca(OH)". the charge balance equation must be satisfied. 2[CaH ] + [H+] ~ [OH-] Assuming that [H+] « 2[Ca H ].0.). S (2) Mg(OH)".

L______ ~ ____ ~ ______ ~ ____--' Fig. 6-4.(. -log K" = 8. 12 '-' 0. 6-4).34 (6-9) where pCO. = -log [CO. Since the carbonate species is common to each of the precipitates.34 -logK. The pC-pH diagram for Mg2+ in equilibrium with MgCO". which can be used to solve problems such as those in Examples 6-8 and 6-9.34 = 8.log [CO. MgC03(. Equations 6-9 and 6-10 are plotted in a log concentration diagram (Fig. As an example consider the carbonate salts of Ca2+ and Mg2+: CaCO.o = 5 These equilibria can be represented in linear form as follows: -log [Ca'+] .) ¢ Ca2+ + 'CO. and -log [Mg'+] + pCO. Diagrams using the negative logarithm of concentrations of other ions are often useful in the solution of solubility problems.Equilibrium Calculations 257 Master variables other than pH and pOH can be used in log concentration diagrams.~ co § c T 8 8 8' 10~-- __. it is useful as a master variable.'-] or -log [Ca2+] + pCO. = 5 (6-10) = 8.) ¢ Mg'+ + CO.'-.) and Ca2+ in equilibrium with CaC03 (s)' .'-j.'-.L______ ~ ____.

Example 6-9 The pH of the initial solution in Example 6-8 is 8..5. CN. or if the anion is a weak base.. if [Mg'+) = 5 x 10-' at equilibrium. 6·4. = 1. 6. such as CN.3 and the total alkalinity is 3 x 10-' eqiliter.'. SOLUBILITY OF SALTS OF WEAK ACIDS AND BASES Precipitation and dissolution phenomena become more complicated if the cation of the salt is a weak acid.3) and pCO.'-) = 10-"') M.15 (6-12) Example 6-10 illustrates the effect of protonation of CN.present to begin to precipitate the Ca2 + and the Mg"? Solution After conversion of 3 x 10.will (I) [Ca2+).85.7. 6·4). that is. When pCO. From Fig.3 M Ca2 + is in equilibrium with CaC03iS ) when pC03 = 5.'-.ion reacts with water log Kb = -4. the solution is supersaturated with CaCOJ and it will precipitate. = 0.on the solubility of AgCN. All of the alkalinity is converted to CO. Fig.'.+ W .=: Ag+ + CN-. is there sufficient COl. or alternatively.258 Precipitation and Dissolution Example 6-8 . A surface water contains [Ca2+) = 10-' M and [Mg2+) = 5 10-' M. Fig. 6·4). (point C. When [Mg") = 5 x 10-' (-log [Mg'+) = 3. 6-4). = -log (3 x 10-') = 2. = 2. Similarly for Mg'+. the solution is undersaturated with MgC03 and thus it will not precipitate. point E. [Mg'+] = 5 x 10-'.by adding OH-. After this conversion.concentration must be increased to 10-4 .3. when [Ca") = 10-' and pCO. 10. such as NH. = 9. point D.8 (6-11) and the CN.4 • pC03 must be reduced to 4.. 10gK" = -13. Fig.' . = 2. the C032. At what concentration of CO.=: HCN.or CO. AgCN"" for example.4.+. and (2) [Mg'+) be reduced by one order of magnitude at equilibrium? A Solution 1.3 (point A.3 eq/liter of alkalinity (all present as HC03 -) to C032 -. . I log K.5. To reduce the Ca2+ concentration to 10. pCO. 2.5.3 M at equilibrium (point B. pCO. dissolves as follows: AgCN .7 ([CO.

Kw ~ 10-" ~ [H+][OH-] [CN-] + [OW] (S-15) and the electroneutrality equation. ~ ~ [Ag+][CN-] (S)(".8) ~ ". say [H+J. or from Appendix 1. 6-12 and 6-14 to yield (S·17) and (S-18) Also. 6-1S yields [WI +S ~ ". and then to solve it by trial and error. First. The equilibrium constants for Eqs. we then determine if Eq. Using these values. Six independent equations are thus required. [W]. Solution The unknowns are S. S-13 and S-18 in Eq. [CN-]. 6·19 is satisfied. 6-17.. [OW ] ~ [H+] Kw and Kw K" Therefore. ~ (S-13) C UN [HCN] + [CN-] (S-14) the equilibrium constant.S + ~:] (S·19) or For an assumed pH. neglecting ionic strength effects and Ag+ complexes. a new value of pH . [Ag+].8' Substituting Eqs. we can determine U1 from Eq. and [OW]. [HCN].Solubility of Salts of Weak Acids and Bases Example 6-10 259 Find the solubility of AgCN{s) in distilled water'in a closed system (volatile HeN can not escape). S·ll and 6-12 can be used together with the mass balances. I~ not. [WI + [Ag+] ~ (S·IS) The most straightforward way to solve these equations is to substitute in the electroneutrality equation to'obtain an equation with one unknown.. combine Eqs. S ~ ~ [Ag+] ~ CT.

6·19 (see Fig. we plot the value of Eq. 6-19 has a value of zero at approximately pH 7.9 x 10-' 1.7 and pH 7.9 X 10-8 7. 6·19 versus the assumed pH and extrapolating will enable good successive estimates of pH to be obtained. the electroneutrality equation is eliminated making it unnecessary to determine or know the amount of strong acid or strong base added. 77 x 10-' -2. 6·5b) determine that the left-hand side of Eq.1 x 1O-7M \ TABLE 6-2 pH 7 8 Solution to Eq. Value of Eq. It is interesting to examine the solubility of salts such as AgCN as a function of pH.54 X 10-2 3.39 4. one less equation is needed than when the solubility of AgCN was determined in distilled water (Example 6-10). 8 We first plot the value of Eq. Usually.24 X X 7. .7. that is. Plotting the value of Eq. 6-19 1. For the purposes of this example let us assume that the solution pH is controlled by the addition of a strong acid or a strong base.8. Solution to Eq. Rounding off to the nearest tenth of a pH unit.7 7.08 x 10-3 6. Further narrowing it down.2 <0 . 6-19 at pH 7.6 -4. 6-19 a.2 10.8. 6-19. and from the graph (Fig. pH 7. The value changes from positive to negative at approximately pH 7.8 10. 6·5.78.260 Precipitation and Dissolution is assumed and the process is repeated.58 X 10. Example 6-11 Determine the solubility of AgCN as a function of pH in a closed system. The results of this process are given in Table 6·2. '" 0 . Because we wish to obtain S as a function of pH. '" <0 cr w ~ '0 0 8 pH w 0 cr • '0 > " (b) • Fig. we find that S = (~~o) 1J2 = 6. 8 The use of a digital computer would further facilitate the solution. 6·5a) at pH 7 and pH 8.

1). AgCN -= Ag+ + CN-. [Ag+]." and log S = . we obtain Sa 1 =KS{) S Therefore. [HCN]....15 the solubility is constant at 10-6 . S When [H+] «K" = (~r' =[ (~:) S = ([W]+K. S = [HCN] + [CN-] + [CN-] = [CW]([W] + K.r [K. and [OW]. or (6) [CN-] = Sa.. (I) (2) (3) (4) -= W + CW. HCN S log K. = -9. K" [CN-] = [Ag+][CN-] = K" =K" [Ag+] S Substituting for [CW] from (6).) Ka S = [WHCW] Ka or = [CN-] a.15 log K" = -13. From (2) and (3). When [H+] »K" S = [K"IrT' and .]. [CN-] .:..log K" = k-13. [H+]. molelliter..Solubility of Salts of Weak Acids and Bases 261 The six unknowns are S.9 Thus at pH > 9. The required number of equations is 5 (number of unknowns .8 = [Ag+] = C Uo [HCN] + [CN-] = CT.CN S = (5) Kw = [W][OH-] Solution From (4) and (I).8) = -6.

=: HCdO.IS) -pH] log S = 1:[ .O.65 log K" = -9. C T•Cd .= -12. can . Solubility of AgCN as a function of pH.}:. 6·6. Consider the dissolution of cadmium hydroxide.=: CdOH+ + OH-.O.1S the solubility is a function of pH.(. -pH] logS =>[-13. increasing as pH decreases.} in the atmosphere above the liquid the equilibrium concentration in solution would be zero.0 using strong acid or base.'.O.42 log K. there will be an increase in the solubility of the solid. The following reactions are important. in an open system with no HCN.} + OH-:.49 (2) (3) log K" = -9.+ H. " -I o ~ c· • § I 6.=: Cd'+ + 20H-. Cd(OH). 6. Cd(OH)". 6·6. the pH of which is controlled at 9. log K '0 = -13. (I) Cd(OH)".(. Both of the preceding examples were solved for closed systems so that HCN could not leave the liqUid.} + 20H.}:.+ 2H.=: Cd(OH).pH] Thus at pH < 9.8 -(-S.5. Since the solution is equilibrated at pH 9. (5) Cd(OH).):.:.97 log K" = -13. Cadmium is of particular importance because of the adverse health effects that it can cause if it is consumed in sufficient quantities. Cd(OH)". in water.}.. EFFECT OF COMPLEXATION ON SOLUBILITY When any of the constituent ions of a solid participate in complex formation following dissolution.(.97 (4) Cd(OH).65 .=: CdO. the concentration at equilibrium would be a function of the HCN partial pressure.. If the system were open so that HCN could escape.15 pH ~~ ~ Fig.262 Precipitation and Dissolution logS =l:~ogK" -logK. the solubility. The solubility variation is shown graphically in Fig.4..9 --------f'?"----I I 9.

65 or 2.[OH-]. CdCl+ + Cl.24 X 10-'.o + Cl. = 10-13 . .[OH-] = 10-12 •97 From (5). [HCdO. the concentration of Cd2+ in equilibrium with Cd(OH). [Cd(OH).'-] = K .9 .Cd=' 2.09 = -0.Cd X = K" = 10-9 . log K.45 The concentrations of the chlorocadmium(II) complexes are .Cd and CT. Let us now assume that in addition to the hydroxide ion.CI the following reactions are important as well as those for the hydroxo complexes.(. Thus for cadmium hydroxide the formation of hydroxocadmium(II) complexes increases the solubility by approximately 14 percent. Since [OH-] from (1) we find I _ '0_ [Cd2+] .Effect of Complexation on Solubility 263 10-'. CT.90 = 0.-] = 10-3.97 + 10-23 •97 + [CdO.-.o. 97 From the mass balance on cadmium. CdCI 3 . As the pH is increased..O] + [HCdO. Cd'+ + Cl.32 = 0.'" solution so that the free Cl. readily be calculated from the equilibrium equations. 97 (10-5)' 10-23 •97 = [Cd'+] + [CdOH+] + [Cd(OH). log K3 log K. log K. 42 X 10-5 = = 10-17 . that would result if there were no complexes. = 1. [CdO. To calculate CT. at lower pH values they are not present in significant concentrations.'-] CT.65 + 10-4·49 + 10-9. -] = K .. there is sufficient Cl.'" CdC!.49 10-' From (3).56 X 10-' M = S This value can be compared to a solubility of 10-3 .[OH-].13 •65 = = 10-3 . [CdOW] = [O~'-] = = 10-.'" CdCl+.·49 K 10.concentration is 10-3 M.42 + 10-17. 65 From (2). CdCl.O] From (4).(10-')' K 10.+ Cl.). the various complex forms become more dominant.'" CdCl.

In seawater of pH 8 the solubility of cadmium hydroxide (including all hydroxo and chlorocomplexes) is approximately 10+0.32 [CdCl+][Cl-]K.concentration selected.Cd = [Cd'+] + [CdOW] + [Cd(OH).O] + [HCdO.(OH). The solubilization of metals such.4+ + 2H+.+ 4H+.O] + [CdC1 3-] + [Cd(Cl)l-] = 2.43 X 10-3 X 10°·09 = 10. 10gK Fe(OH)3(".has increased the total dissolved cadmium concentration even further.43 M [CdC13-] [CdCll-] [CdCl. of the trivalent metal ions and many other divalent metal ions have a dramatic effect on the solubility of these ions.65 M if no Cd(II) complexes were formed. 10gK 2Fe'+ + 2H. Although the increase is approximately 2 percent in this example because of the CI.O.o Fe3+ + 4H.45 = 10. 10-5.= Fe(OH)4 .= Fe(OH).56 M.34 M = = [CdC13-][Cl-]K4 = 10. as cadmium and mercury by the formation of soluble chloro complexes has significance in relation to marine waste disposal.= FeOH'+ + H+.O.O.-] + [CdO.o.10.10. 10gK. 10gK = = = = = -2. 10gK.= Fe.+ + 2H+. To plot these equations on a pCpH diagram requires that they be expressed in terms of soluble Fe (Ill) . Consider the following equilibria that relate to the behavior of Fe'+ in pure water: Fe3+ + H.concentration is approximately 20 glliter or 0.61 X 10-4M Thus the presence of 10-3 M Cl.16 -6.65 X 10-3 X 101. where the CI. This is an increase of 110 times in cadmium solubility.O][Cl-]K3 = 10-7 .33 M [CdCl.O] = = = 10-7. The hydroxo complexes. Fe3+ + 2H.'-] + [CdCl+] + [CdCl. In seawater the major dissolved species is CdCI.34 X 10-3 X 10-0.= Fe'+ + 30H-. quite significant increases in solubility are observed in solutions such as seawater.79 The total dissolved cadmium concentration is CT.13.O. The discharge of freshwater streams containing these metals in suspension to a saline environment could well result in increased dissolved metal levels because of the formation of dissolved chloride complexes.3' M compared with 10-1.85 The effect of these hydroxo complexes on solubility is most conveniently illustrated by using a pC-pH diagram.33 X 10-3 X 10"-' = 10-5.264 Precipitation and Dissolution [CdCl+] = = [Cd2+][Cl-]K 1 10-3.74 -38 -23 -2. or hydrolysis products.

Fe(OH).16 14 = log [Fe(OH)'+] 1.{. +] or log [Fe(OH).=: Fe(OH). 10gK.4+ + 40H-.).74 .16 log K.).-] we obtain log [Fe(OH). adding the equations.16 = log [Fe(OH)2+] + 2 log [OH-] or log [Fe(OH)2+] and since pH + pOH = = 2pOH . which describes the behavior of the species Fe(OH)2+ with pH in a solution in equilibrium with Fe(OH)3(.2pH This equation plots as line 1 in Fig. + + OH-. we obtain (l) log( L) Fe(OH). we obtain log K" = -26. (4) 2Fe(OH)3(. H+ and Fe(OH).Effect of Complexation on Solubility 265 species. Similarly.=: Fe(OH)2+ + H+. log K" = -16.) is unity so that the equilibrium constant is then in terms of soluble Fe(III) and H+..{. we can derive equations for [Fe(OH)2+]' [Fe(OH).-] = pH -19 . 6-7.(OH).74 + 14 .=: Fe(OH)2+ + 20H-.26. K" = [Fe(OH)2+][OH-l' Taking logarithms. describing the behavior of Fe(OH). Fe'+ + H20..=: Fe(OH).pH -2.).pH This is line 2 in Fig. 6·7..).)...).+ species. = -2.-]. For [Fe(OH).8 Equations (l) through (4) can be plotted on a pC-pH diagram. log K" = -26..74 log K" = -5 log K = -50. We can rearrange these equations so that each Fe(I1I) species is in equilibrium with Fe(OH).84 .{. For example. and [Fe.=: Fe.=: Fe'+ + 30H-.) and then assume that the activity of the solid Fe(OH). +] log [Fe(OH). for equation (1). (3) Fe(OH).(OH).o = -38 = 14 W + OR-.(.-..'+] (2) Fe(OH)3(.) + OH. For example.+] = = = log K" + pOH -16. we have log [Fe(OH).{.{..16 Similarly.=: H2 0. for equation (2).

3pH and is drawn as line 5 in Fig.(OH).4+] = 5. For [Fe. From an inspection of this diagram we can sketch in the region where Fe(OH)". 6-7.j will precipitate. 6-7. we can reason that any concentration of a particular species . 6-7. 6·7. This completes the pC-pH diagram for the species considered.j.~ o " c- 6 • u c 0 u E ~ 10 Fig. Equilibrium concentrations of hydroxo iron(III) complexes in a solution in contact with freshly precipitated Fe{OHh(s) at 25°C.4pH which is line 4 in Fig. which is line 3 in Fig.2 .4+] we find log [Fe. The line for Fe3+ is obtained from the K" equation as log [Fe3+] = 4 .266 Precipitation and Dissolution pH '-' . Since all of the lines represent the concentrations that may exist at various pH values when in equilibrium with solid Fe(OH)".(OH).

First.(OH).4+ does not predominate at any pH value. . we can sketch in the Fe(OH)"" boundary. at typically encountered natural water pH values in the presence of Fe(OH)"". From Fig. Conversely stated. we must assure ourselves that the solid of interest is present and that a heterogeneous equilibrium truly does exist.-]. 6-7. but it is a significant species at pH values below about 2.+] + 2[Fe.5 to 8 (which covers virtually all natural waters).+ line at 10-6 •74 M and last the FeOH'+ line at 10-6 . C T "'IlIIl =.Effect of Complexation on Solubility 267 above the line in the diagram will be supersaturated with respect· to Fe(OH)"" for that species.4+] + [Fe(OH). next we encounter the line for [Fe. for diagrams that involve solids containing an anion other than hydroxide. Fe(OH). controls the solubility of Fe(OH)"" only below about pH 2. It is important to note that Fe'+. Moreover we can reason that the Fe(OH)"" boundary will be somewhere above the line that is at the highest concentration of iron species at any point in the diagram. we first encounter the line for [Fe(OH). we must always realize that these diagrams are equilibrium diagrams.6 •74 + 2 10-6.+ is the predominant species and likewise it forms the solution boundary for Fe(OH)"". as an example later) there is a unique pC -pH diagram for each concentration of the anion.-] at 10. A word of caution in the use of pC-pH diagrams that include heterogeneous equilibria is in order at this point. The polymer (dimer) Fe. We can use pC-pH diagrams that include heterogeneous equilibria for the rapid evaluation of both the total concentration of all species present as well as to provide a graphic representation of the concentrations of individual species present at various pH values.(OH). Fe(OH).5. 16 + 10. 6-7. For them to be validly applied to the solution of natural water problems. we must stipulate a certain solution concentration for that anion. for example.5. Fe'+ is a minor component of the ferric iron species.predominates and its concentration line is the Fe(OH)"" boundary in this region. . As we move vertically up the diagram. 16 M.4+] at 10-10.6. Second. AlPO"". CT. We can see this happening in a couple of places in Fig. The boundary of Fe(OH)"" at this pH is at the point represented by the sum of these concentrations.15 M. we can deduce that in the pH range from 4.• M. For example. Between pH 5-7 Fe(OH). = 10-' + 10. For such precipitates (and we shall consider aluminum phosphate. Thus at pH values higher than 9. ferric ion. Intuition tells us that if one species predominates at a particular pH.Fo(ll1) = [Fe'+] + [FeOH2+] + [Fe(OH). let us examine the situation at' pH 4. next is the [Fe'+] line at 10-' M. then its concentration will coincide closely with the Fe(OH)"" boundary. that is. + is the predominant soluble ferric iron species.05 X 10-10 •• + 10-15 By performing such an exercise at various pH values throughout the diagram. then the Fe(OH).(OH).

r + 34H+.4+ + 2H+.(OH)174+ control AI(OH)3(5) solubility below a pH value of approxi.·14H.4 (4) AI(OH)3(. behaves very much like Fe'+ in solution except that it has a greater tendency to form polynuclear species. For the equilibria that exist in the presence of freshly precipitated aluminum hydroxide.Fe(lm is the sum of all the concentrations of species present at a given pH.3 These equations can be rearranged so that the concentration of each complex is expressed as an equilibrium with solid AI(OH)3(.268 Precipitation and Dissolution ~xample 6-12 An acid industrial waste discharge containing a high ferrous iron concentration is discharged into an oxygenated receiving water that has a neutral pH and is well buffered.3 ~ (6) 2AI'+ + 2H. we have (I) AI'+ + H.(OH).5+ and AI.006 p.O) is used to coagulate a water (I) at pH 6. (The major problem may well be caused by the Fe(OHh{s) that precipitates and either settles to the stream bottom or is carried in suspension.(OH)174+ + l7H+. since the water is well buffered and we are adding an acid waste. or 0. highly charged polymeric species such as AI. ferrous iron will be rather rapidly oxidized to ferric iron at neutral pH in oxygenated water. a minute amount. AI(OH)3(').). or 10-'·30 M.) Solution First.(OH). The pC-pH diagram plotted from these equations (Fig. thus only Fe(lll) species are of interest.).-.g Fe/liter..5 and (2) at pH 9.·14H. log K -6.8 ~ log K -33 ~ -97."" Al(OH).5. What problems (if any) can be expected in the stream from increased dissolved iron? (Assume that only hydroxo complexes are of importance.(SO.{SOJ. log K" 1.{SOJ.) as was done for Fe(OH)3(.O is 594.O "" AI.O (l50/594) x 2 ~ 5. Thus 150 mg/liter Al.10 M. mately 6.06 to 0. Second.O "" AI.. .) Aluminum ion. Solution ~ The molecular weight of AI.O "" AI. we find that total soluble Fe(III) concentration is 10-9 to 10.. ~ -5 ~ (2) 7AI'+ + 17H. Example 6-13 Compare the concentration of AI(lIl) in solution with the amount that precipitates [as AI(OH)". Using Fig.) "" AI'+ + 30H-.·14H.] per liter if 150 mglliter filter alum (AI. (3) l3AI'+ + 34H.(OH).05 X 10-' mmoles AI/liter. (fresh precipitate) (5) AI(OH)". log K" ~ log K -48.) + OH. we should be interested in pH values below but near neutrality. 6.O "" AI(OH)2+ + W. AI'+.. log K.8a) shows that the large. 6-7 and knowing that Cr.

.O).. (a) Freshly precipitated Al(OHl". -l 2 41- \ . . pH 4 6 8 10 2i .: (h) aged Al(OH)"".. . 4 '-' 0. 3H. 6~8.villi ~. §' 6 "' b • 0 0 0 0 0 " • " 0 0 0 0 T ~ 0 8 [AI 13 (OH)345+] ::: 8 T 10 'T 12f(a) t-V [A17 (OH)174 +j ~\\\ \~ --I 12 (b) Fig.O.!lllll)). Equilibrium concentrations of hydroxo aluminum(IIT) complexes in a solution in contact with Al(OH)3(S) at 2Sc C. $ ."IIIII~ . 1\ '" ill/HI 01 .~"'~ \\ \\'1 '\} AI(OHI". gibbsite (Al. §' 6 AI(OHh(sl '-' 0. 2 .pH 2 4 6 8 10 0.

(3).62 percent of the aluminum added [(3.A!{III)' At pH 6. Water Works Assoc . Stumm and J. which corresponds to CT.') the solution concentration of aluminum species is about two orders of magnitude less than at pH 9.05 x 10-')(100)] does not precipitate.6 . 6-Sb." However.5 (which is close to the pH of minimum solubility of AI(OH)3{. and (6) and plotting yields the pC-pH diagram shown in Fig. J.' shows that gibbsite predominates over a much larger region than does freshly precipitated AI(OH)3{'" Also. at pH 6. COMPETITIVE EFFECTS OF SEVERAL LIGANDS In the preceding discussions we examined only the equilibrium of solids with pure water or with solutions containing an ion common to o1. 10. at pH 9. AI'+ rather than the polymeric AI-species tends to predominate below pH values of about 5. This observation is consistent with the proposition that polymeric aluminum species are formed as intermediates between Al'+ and the precipitation of Al(OH)3{'" Other species can compete with OH.. Combining equation (7) with equations (1).5 CT. (5).6.3 . when filter alum is added to water in the water treatment process of coagulation. for example. 6·8a at pH 6.1e 9 W." J. 54: 971 (1962).At(IIn = 10-3 . Competitive effects probably cause a difference in coagulation phenomena based on a difference in the ligand concentrations in the water being treated.1 M '.AtUIO = 10.16 x 10-'/5.270 Precipitation and Dissolution From Fig. The solubility product for gibbsite is log K" = -36.5 and 9 the values of the total aluminum species in solution can be derived from the boundary of the Al(OHbsl region.S.3 .3 - 10.5 = 10.3 - 10-3. Aluminum hydroxide precipitated freshly. Am.0 CT.for coordination sites on Al(III). more well-defined crystal structure. gibbsite. 5 M " 10. At both pH values the filter alum precipitates as Al(OH)3{.3 .7 ppts. This material has the same composition but a different.0. S. At pH 9. it can be shown' that the amount of OH. Further.3 ppts. in equilibrium with gibbsite. Morgan. "Chemical Aspects of Coagulation. . is more soluble than the thermodynamically-stable Al(OH)"" phase. (2). . As evidence that such competition takes place. A comparison of the pC-pH diagram for gibbsite with the diagram for freshly precipitated Al(OH)3{.3. 1 = 10..which must be' added to a solution to bring about the formation of Al(OH)"" is less when phosphates are present in solution than when they are not.3 which is slightly smaller than the value of 10-" for the freshly precipitated solid.

6-20 through 6-25.) Sketch a diagram showing all soluble Fe(II) species in equilibrium with FeCO. log K = -5. -.'-].1 log K" = ."'" Fe(OH). AI(OH)"".(s) for a constant total soluble carbonate concentration. Using Eqs. and ferrous carbonate. FeCO"" + 30H. We approach this problem by determining which soluble Fe(II) species exist in our system which might influence the solubility of the two solids.5 log K" = -9. the second type is a predominance area diagram. indeed. Fe(OH)"" "'" FeOH+ + OH-. it is possible to construct two types diagrams to show the region of pH and total Fe(II) concentration over which each solid phase can exist.-pC-pH and Predominance Area Diagrams 1.'.6.. Fe(OH)"" + OH. govern the type of solid that forms..CO. and aluminum phosphate.. The first diagram is the pC -pH diagram as previously constructed for AI(OH)".10. Fe(OH)""."'" FeOH+ + CO. .-] + [CO. log K" = -14.7 FeCO"" + OH. The pC-pH diagram is constructed as follows: I. as may occur during the lime-soda softening of an iron-bearing groundwater."'" Fe(OH). pC-pH Diagrams.] + [ Note that a different diagram results if we use a different concentration of C r . as may occur when alum is added to wastewater to remove phosphate. FeCO"".cc.4 log K" = -5. Combine the above two diagrams to show 0) the variation of soluble Fe(II) concentration with pH and (ii) the regions where the FeCO"" and Fe(OH)"" precipitates predominate.'-. Precipitation of Fe(OH)"" and FeCO".'-. = [H. AIP04{. In the example we will use C T •CC . constant C T •CC.3 (6-20) (6-21) (6-22) (6-23) (6-24) (6-25) 6. The following equilibria are pertinent to this case: Fe(OH)"" "'" Fe'+ + 20H-. Two examples of this type of situation will be presented: the precipitation of ferrous hydroxide. = IO-'M and assume that we are dealing with a closed. . Sketch a diagram for a solution containing all soluble Fe(II) species in equilibrium with Fe(OH)"". 2. C r . This type of situation is rare in natural waters and wastewaters where there are a wide variety of ligands that can influence both the solubility of a solid and.6 10gK = -1. system. (If carbonato complexes were of importance.. 3.+ CO.Competitive Effects of Several Ligands 271 of the constituent ions of the solid. and the precipitation of aluminum hydroxide. they would be included.1.

4-17.) and Al(OH)3(') diagrams constructed previously (Figs. 6-7 and 6-8). -] = = = 13. therefore. 6-21.'-] with pH. The equations plotted in Fig.6 . Fig. .. 6-10. 6-9 and defines the cross-hatched area of predominance of Fe(OH)2(. line 2 pH .) solubility product equation.. T = 25°C. and 6-22 can be used to construct pC-pH diagrams 'in the same manner as for the Fe(OH)3(.). The FeCO". The pC-pH diagram for soluble Fe(II) in equilibrium with Fe(OH)"". To do this.5 . we must first determine the variation of [CO. From Chapter 4.7 Knowing the variation of [CO. in a pC -pH diagram it will be a mirror image of the [C0 3'-] line such that log [Fe'+] + log [C03'-] = -10.19. we can plot the log [Fe'+] line in Fig. = 10-3.2pH.)' The next step in construction of the diagram is to draw the area of predominance for FeC03. 6-23 must be satisfied and. 6-10 (line 2).1. the variation of [C03'-] with pH is as plotted in Fig. If we had a hypothetical system with no other ligands pH o 8 10L_____ ~ ____-L____ ~ ______ L_~~~ __ ~~ ____ ~ Fig. line 1. line 3 The boundary line of C U "))) = [Fe2+] + [F\"OH+] + [Fe(OH)3-] is shown in Fig. line 1 4.272 Precipitation and Dissolution Equations 6-20. 6-9.'-] with pH for CT. 6-9 and their corresponding line numbers are log [Fe'+] log [FeOW] log [Fe(OH).pH.

co.. using Eqs. 6-24 and 6-25. CT..F. the ligand OH. the additional hydroxo complexes that need to be considered are Fe(OH)+ and Fe(OH).'-.'-] and log [Fe(OH).) and FeCO"" is therefore the solid phase that is stable. line 2 would represent the boundary of the predominance region for FeCO"".system in which either FeCO"" or Fe(OH)"" predominates. Below pH 10. Solid Fe(OH). From it we can determine the regions for a Fe(II) . save CO. 6-10). and the condition under which both solid phases are stable. 6-10.OH-. Thus. log [Fe(OH)+] + log [CO.5.. 6-9 and 6-10. ~ g> 8 11 T 10L-____ ~ ____ ~_L _ __ L_ _ _ __L_ _ _ __ J_ _ _ _~L___~ in equilibrium with Fe(OH)". -] = -19. this figure shows that FeCO"" is less soluble than Fe(OH)"" (i. respectively. 6-ll. However.Competitive Effects of Several Ligands 273 o.'-] = -43.'-] at each pH from Fig. ~ 10-3 M.) C r . Assuming for now that Fe(OH)"" is not present. we obtain the equations for [Fe(OH)+] and [Fe(OH).CO.6 + pH + log [CO.5 is FeCO"" and that Fe(OH)"" is the only solid at pH above 10. 6-10.-.------'i---i--. 2 4 6 8 10 12 14 2 <.is present in any system in equilibrium with solid FeCO"".> c . T ~ 25°C.'.3 + 3pH Obtaining [CO. we can plot the [Fe(OH)+] and [Fe(OH). -] in the presence of FeCO"".5.e. The pC-pH diagram for soluble Fe(1I) in equilibrium with FeC03(. From this diagram it can be seen that the only solid below pH 10. Fig. in .~ 00.-] lines (lines 3 and 4.'U) in equilibrium with FeCO"" is less than CT"."{fl" Combining the predominance regions developed in Figs. we obtain Fig. The boundary of the FeCO"" predominance region (cross-hatched) is the line for Cr.

5 is the dividing line between the two predominance areas.5. 6-20 to 6-25 on a pC-pH diagram.f.'.-----.274 Precipitation and Dissolution pH Or------. 6-21 and 6-24. it is necessary to fix the maximum total . we can show that this equation represents a vertical line at pH 10.=<= Fe(OH)". [OH-]' log K = 3. The pC. Above pH 10. it was necessary to fix the total carbonate concentration. and that both phases are stable at pH 10.5 (see Fig.6 FeCO"" + 20H.) or Fe(OH)".5 can be shown by combining Eqs.'-.=<= Fe(OH)"" + CO. To sketch such a diagram. Thus only at one point [pH = 10.'-..5. 6-10).'-) " log K = -5.5. 2.8 = [CO.on = 5. and pH on the predominant Fe(II) species. M..). This diagram only shows the predominant species at any particular pH.). the CO. 6·11. however-not the concentration of each soluble species. pCT.=<= Fe(OH)+ + CO. I log--K = 9. Fe(OH)".8] is the solution in equilibrium with both solid phases.pH diagram for soluble Fe(ll) in equilibrium with FeCO".~ 2 4 6 8 10 12 14 2 6 Fig.. thus FeOH+ + OH. K = 10.) becomes the least soluble phase so that here Fe(lI) is precipitated as Fe(OH)"".concentration at pH 10..'-] = 10-3 .8 Taking logarithms and setting [CO. contact with solutions in this pH range will dissolve and be reprecipitated as FeCO".4 + OH. FeC03 ". Predominance Area Diagrams. That pH 10. To present the equilibria in Eqs. In the second type of diagram-the predominance area diagram-we can show the effect of C T•CO .

There are 5 different species.Fe(OH). Selection of the first relationship to plot is arbitrary.pH predominance area diagram.We will state these equations and draw the lines they represent on a pCT. in this case we begin with Fe(OH)"" .Fe(OH)"" and FeCO"" FeCO"" and Fe(OH).co.. -] log {Fe(OH)". .-..} + pOH -5. The task of deciding where to draw the lines that describe boundaries between hydroxo species and FeCO"" will then be made easier. We will assume that the maximum [Fe(II)] is 10-5 M.Fe2+ and FeCO"" FeOH+ and Fe(OH)"" FeOH+ and Fe(OH). 10-5•1 = [Fe(OH). Fe(OH)"" and Fe(OH). 6·22.-.1 = L .-] {Fe(OH)". and it is necessary to develop equations for the boundaries between the regions where each of these species predom· inate. and will allow the establishment of pH regions of the predominance of the various hydroxo species. There will be 10 possible equations interrelating all these species as follows: Fe2+ and FeOH+ Fe2+ and Fe(OH)"" Fe'+ and Fe(OH).Competitive Effects of Several Ligands 275 concentration of Fe(ll). Our approach will be to first examine the equilibria between Fe'+ and the various hydroxo complexes. since these are independent of CT. then by deduction we will select the areas of predominance for each species.FeOH+ and FeCO"" Fe(OH)"" and Fe(OH). From Eq. I.CO. this concentration will only be reached 'if all precipitate dissolves.}[OH-] [Fe(OH).

10-9 . 6·12. It is independent of CT. pOH = -5. From Eq.1.1 because they represent relationships with minor or insignificant quantities relative to Fe(OH)"".5 M.276 Precipitation and Dissolution When precipitate is present in very small amounts and when [Fe(OH). 6·12 (line I). FeOH+ and Fe(OH)"".co. and therefore plots as a vertical line at pH 14..4 = [Fe(OH)+][OH-] {Fe(OH)".} pH + 9.0 = less than 10-5 M... CT.} [Fe(OH)+] pOH = log {Fe(OH)".. Fe(OH).5' precipitate predominates with respect to Fe(OH).1 equations containing Fe(OH)"" are not significant. We can therefore disregard any equilibrium relationships with Fe(OH).1.below pH 14. Predominance area diagram for FeC0 31s /Fe(OH)2!s/H 20 system at 25°C.4 = log [OH ] + log {Fe(OH)".Fe(lD = 10.1 This line is plotted in Fig.-] = 10-5 M (the maximum soluble concentration).. 2.} _ [Fe(OH)+] -9. When the pH is below 14.1 and pH = 14. . We must keep these facts in mind because it will allow us to greatly simplify construction of the diagram. Likewise above pH 14.4 8 ill ~ M 16 Or----r----T---rT----T---~~--~--~rr_--_l 2 4 6' u CD <f ~ 6 Fe{OHbB 10 Fig. 6·21.and the concentration of Fe(OH)3 .1 + 5.

the diagram would be complete and we would not have gained much more useful information from it than would be obtainable from the simpler-to-construct pC -pH diagram. Fig. However. we recall that Cr.'-] and Ka . C T. also can form when carbonates are present the boundaries between FeCO"" and Fe2+ and the various hydroxo iron(II) species must be determined.10 . Fe'+ since FeC0 3". The boundary between Fe2+ and Fe(OH)"s' would fall within the FeOH+ predominance region. pOH = 5. This is drawn as a vertical line (line 2) at pH 9. . and because we are interested in only the predominant species. FeOH+ predominates.Fe(OH)3.6 in Fig.4 and the pH = 9.co3K a. 3 so that when pH > 10. = [H. for example. 6·20 and 6-21 yields 10gK = 5.Competitive Effects of Several Ligands 277 When the precipitate is present and [Fe(OH)+] = lO-s M.9 (line 3.1 and pH = 8. Similar reasoning can be applied to the other two pairs of species.1 = 10-6 . (6-26) When 6. 6·12. this boundary is not of interest to us.9. The region of Fe(OH)"s' predominance can be deduced to be between pH 9. we must express the variation of [CO.1 [FeOW] 5.'-] in terms of Cr. equilibria involve carbonate.6.] K.CO. Combining Eqs. 3 + [HC03-] + [CO. The region of predominance for FeOH+ is defined between pH 8. pOH = 4. At pH values below 9.6. At pH < 8.Fe(OH)"". If no carbonates were present. From Chapter 4.3.2 [H+] + K. (6-27) .Fe(OH)3-.and FeOH+ . 6-12). There is now no reason to determine equations relating the species Fe'+ .. Since the FeC03". This is a vertical line at pH 8.3.2 = 10. Fe2+ and and 14.3 < pH < 10.. and pH.9 and 9. 3. Fe2+ predominates..1.1 = log [Fe2+] + pOH When [Fe2+] = [Fe(OH)+].

I og [ [CO. 6-21 and 6-24 yields CO. For 6.K". Combining Eqs. .3 = When [Fe(OH).K". = 3. 6-27.aD = 10-5 M and when FeCO"" is present.'-] [Fe(OH).+ Fe(OH)"" "" FeCO"" + 20Hlog K = -3. 5. We only plot this line as far as the intersection with the boundary line between Fe(OH)"5' and FeOH+.'-] For pH > 10.} + log CT. [CO '-]_ Cr.-.8 = log {FeCO".. . and the equation plots as line 4.[H+]'+ [H+]K.K. concentrations and very high pH FeCO"" and Fe(OH)"".'-] ='-] ..log [CO. FeCO"" and Fe(OH).3 [Fe(OH). (6-28) Let us now determine the relationship between FeCO"" and each of the Fe'+ and hydroxo Fe(II) species. . The region it defines is beyond the limits of consideration for natural aquatic systems.. -1. [CO.'-] When both solids are present at eqUilibrium.3 = log K = -1. from Eq.} {Fe(OH)2(.. From Eq. 2p OH .278 Precipitation and Dissolution And when pH < 6.3 8 predominant.3log [OH-] = At pH > 14.'. Therefore.. log CT.-. starting with Fe(OH).K". where Fe(OH).at very high pH values and working our way down to lower pH values. . [CO. 6-25 we obtain FeCO"" + 30H.3 < pH < 10.3.} + log [" -1.8 .+ Fe(OH).. It is not within the limits of our diagram so we cannot plot it. + 3pOH = CT."" CO.. +K". 4.'.) J which plots as shown-line . = 3.3.-] log {FeCO".7 -3pOH This boundary exists only at extremely high CT.3.F. . ([H+] +K". -] CT. -] log {FeCO".'} 2pOH 2pOH .

6 to 8. . [FeOH+] -5.10.7 . ] og ([H+]'+ [H+]K. we obtain ..] This plots as line 7 in Fig.) This expression plots as line 6 in Fig... 6-12 completing the diagram.] og ([W] + K . Aluminum Phosphate Precipitation Aluminum ion interacts with water to form hydroxo-complexes and solid Al(OH)"". From Eq.6 ~ log {Fe CO".'. 6.(OH)"" will precipitate.K". 6-23.and OH-.} + log [CO.log [OH-] When FeCO"" is present. 7. - I [CT.3 and 10.3. we see that we must seek a boundary between FeCO"" and FeOH+ for the pH range from 9. 6-12.. ~I C T•CO jC.- - 06 . 6-27.5 . 6-27).9.3. Below pH 6.. of course. [Fe2+] . using Eq.F.J I [CT.7 ~ + og ([W] +K. FeCO"" and Fe'+.) [ which plots as line 8 in Fig. ] When [Fe'+] ~ 10-5.Competitive Effects of Several Ligands 279 Beyond this point Fe(OH)"" is not a malor species so that boundaries with it are not considered for this diagram. and with orthophosphate to form the solid aluminum phosphate. and pH regions in which FeCO"" and Fe. 6-12.. [FeOH+] ~ 10-5 M. and for pH in the region between 6. The concentrations of PO. From Eq.. Examining Fig. FeCO"" and FeOH+.} + log [CO. AIPO"".co.'-] . 6-12..' but the approach to developing diagrams for other this equation becomes -5 7 . Below pH 8..F'IIO values is identical to that used here.9 the significant boundary will be between FeCO"" and Fe'+.l K •.l +K.log {FeCO".l K.6. are .2. p OH . 6-12 shows the pC TCO . FeCO"" is present and the solution is between pH 6..3 and 10.._ .. 6-24. 6.. and the regions in which Fe(ll) is soluble.K. The diagram is a function of CT. The diagram in Fig.3 (from Eqs. .

'-. 6-8 to obtain a diagram that will give us much useful information about the nature of AIPO"" precipitation.. = -2.3 + [H. PO.'-][W).'-: H.'-.O.] C T• PO. and (3) the only aluminum phosphate solid formed is AIPO..3 + [PO. Defining C uo. (6-30) log K. Our approach to this problem now will be to develop a pC-pH diagram for AIPO"" precipitation assuming no AI(OH)31" precipitates.. we obtain + [pO. 10gK. that no hydroxoaluminum phosphate will form).. K a.-: + H..AI' [H+] and constants as follows: CT.= H+ + H.'-][W).=AI(OH). HPO... with the only important species in solution being AP+. We will greatly simplify the problem by assuming that (I) we need be concerned only wIth freshly precipitated AI(OH)3(.PO. K.2K a. This knowledge is of importance in certain phosphate removal processes.-] + [HPOl-] + [pO.AI = [AP+] + [~:] [AP+] + [::]' [AP+] = [AP+] ( I + [~:] + I::]') K.. \ -. = -7.2K a.O.+ 4W. 7 Defining C T •AI = [AP+] + [AIOW+] + [AI(OH). We have already examined the precipitation of AI(OH)3(" from solutions that do not contain phosphate (see Fig. We would like to examine the amount of total phosphate -that could be present in a solution in equilibrium with AIPO"" at various pH values.-].2 (6-32) (6-33) (6-34) logK.3-][W] K a.3 = -12. where aluminum sulfate (AI. let us consider the interaction of aluminum ion with water. K a." (2) there are no polymeric hydroxo-aluminum(III) complexes formed..'-].= H+ + HPO.0 (6-29) AP+ + 4H. = [H.PO. we can express [AP+] in AP+ terms of CT. and AI(OH). (Le.. = -21. = log K.PO.3 + [pO. -.. H.-... 6-8). ] (6-35) 3- . = -5.1 log K. (6-31) 3+ _ ( [AI ] .=AIOW+ + W.C T•AI I + [W] + [W]'J We will now proceed in an identical fashion for the second component ion of the AIPO"" precipitate.(SO')3) is added to wastewater to remove phosphate as AIPO"". First.'-.3 [pO.PO. AIOH2+. and then to combine this diagram with Fig. 1K a.PO. We will examine the importance of these assumptions later.280 Precipitation and Dissolution a function of pH.=H+ + PO.

This information is useful to us because it indicates that it would be inappropriate to attempt AIPO 4". It shows that AlP04{.3 + [H+]' K a. precipitation for phosphate removal from solutions containing in the range of 10-' to 10-3 mole.AI I + [H+] + [H+]' x C T PO ( • 4 [H+j' Ka.PO.Competitive Effects of Several Ligands 281 The solubility product equation AIP04{.3 +I )-' (6-37) Using Eq. 6·36. and substituting from Eqs.A< is controlled by Al(OH)s(s) solubility.. .2K a .3 +- [H+] K a . K.4C.4. Concentration of phosphate and aluminum that can exist at various pH values when AIP0 4 (s) is precipitated from or dissolved in pure water.1Ka. we can determineC T.PO" that is. )-' T.' has a minimum solubility in the neighborhood of pH 5.Al' . Above pH 5. PO. 6-37.2Ka.6-371 Fig. (= CUI) as a function of pH. and thus C T'P04 concentrations in this range are greater than Cr. we obtain K _C '0 - ( K. This relationship is plotted in Fig.AI =Cr.5. Concentrations of phosphate and aluminum are controlled by AIP04(.' solubility below pH 5. po4 (Eq.' ~ Al'+ + PO?-. Assuming for this case tpat CUI =C T.fliter (which is typical of wastewaters) at pH 2 3 4 5 6 7 8 9 10 Cr. 6-13. 6-31 and 6-35 into Eq. (6-36) must also be used because the solution is either saturated or supersaturated. 6-13. that a stoichiometric amount of aluminum salt is added to the phosphate solution.

CaCO"". thus the solid phase was a hydroxoaluminum = 1O~3 to 1O~4 M. 0 such as CaOH+ as well as forming the sparingly soluble solid.' (fresh precipitate) controls aluminum solubility. there were also polymeric forms of hydroxoaluminum complexes present. 6. . CALCIUM CARBONATE SOLUBILITY AND WATER STABILITY 6. Also. and it did contain some phosphate.S. U. Calcium ion forms weak soluble complexes with carbonates. The Al(OH)"" may have been aged somewhat. CaCO"". L. freshly precipitated A1P0 4(" to be the only solid phase present was incorrect. we do not expect Al(OH)3(" to form at pH 5 when CT.5.1. We might deduce from Fig. Results of A1P0 4\" precipitation from wastewater agree in general with the above observations. Recht and Ghassemi 'o observed Al(OH)3(" precipitate at pH above 5. and with hydroxides. before equilibrium is achieved. 6·8h). A1PO. the Al(OH)"" was of importance because it aided the removal of the fine. 10 An optimum pH of about 6 was observed and it was necessary to use twice as much aluminum salt as required for phosphate precipitation because Al(OH)3(. This pH is just above the pH (= SA) at which we can expect Al(OH)3('( to precipitate if the solid phase is a fresh precipitate.(". Figure 6·13 shows the curve for CT. If Al(OH)3(. Dept. but in spite of these differences. such as CaC0 3 and CaHC0 3+.' also precipitated. but it is somewhat above the pH at which Al(OH)3(. "Kinetics and Mechanism of Precipitation and Nature of the Precipitate Obtained in Phosphate Removal from Wastewater Using Aluminum(III) and Iron(III) Salts:' Report No.cipitate phosphate. Federal Water Quality Adm. This curve is calculated from Eq. Also. of Interior. 6·13 that the best place to remove phosphate from wastewater by A1PO"" precipitation would be at pH 5. all conclusions made should be verified experimentally because of the limiting assumptions that must be made. indicating that our assumption of only pure. 170lOEKI 04170. removal by phosphate adsorption onto or incorporation into the Al(OH)3(. Calcium Carbonate Solubility in Open and Closed Systems Many of the concepts presented in Chapter 5 and in the previous sections of this chapter can be incorporated into calculations concerning calcium carbonate.13. rather difficult to settie. our calculations allowed us to make a reasonable assessment of what to expect when aluminum is used to pre.' precipitates in addition to A1PO"". 1970. 6. According to Fig. Ghassemi. however. 6·13.' will precipitate if the solid phase is aged Al(OH)3('( (see Fig.. 10 H. po. 6·37.' precipitate is possible. in equilibrium with Al'+ in the region where Al(OH)3(. When making similar calculations. Undoubtedly. Cincinnati.282 Precipitation and Dissolution pH values below 3 to 4 or above 6 to 7. Recht and M. for example.\such removals are not accounted for in Fig.7. additional aluminum salt will have to be added to achieve good phosphate removal.

and M. E. precipitation takes place from solutions containing high magnesium concentrations. K. of 10-8 .34 and the orthorhombic solid. as shown in the following figure.5 a tm) in a spring. P. Chave. aragonite.". 3 as the magnesium carbonate content of the solid increased from 3 to 20 percent. H2 CO. When CaC0 3 ". These are the trigonal solid calcite which in its pure forms has a solubility product K".9 or from the supernatants of some anaerobic sludge digesters. "Observation on the Solubility of Skeletal Carbonates in Aqueous Solutions. In this section we will consider various situations that involve equilibria with CaC03 ". E. CaC0 3 (S) may precipitate in the form of the mineral travertine. In nature this might apply to CaC0 3 (S) dissolving in the high P cOz atmosphere of the soil air. for example. both at 25'C. Garrels.co3 2 - ~ 11 K. CASE I CaC03 {sl is dissolving in pure water that is closed to the atmosphere. When the water rises to the surface (FeO:! = 1O-3. Thompson. M. seawater with a [Ca 2+]/[Mg2+] ratio of = 0. a more soluble solid-a so-called magnesium calcium carbonate-is formed. K. CASE 2 CaC0 3 dissolving or precipitating in water open to the atmosphere. R. Weyl." Science. . The following three cases can serve as models for the behavior of natural systems in which CaCO"" participates. which in pure state has K" = 10-8 . ~ HC03 ea 2 +. Chave et al.. 11 found that the solubility product of calcium carbonate solid increased from 10-8 to 10-6 . S. Deffeyes.Calcium Carbonate Solubility and Water Stability 283 Pure calcium carbonate exists in two distinct crystalline forms. 137: 33 (1962). An example in nature of this model system is CaC03 (S) dissolvi!l-S from a sediment into the bottom of a stratified lake. as shown in the following figure.

-]. open to the atmosphere and to which various quantities of strong acid or base have been added.. = 10-"" (4) K" = [H+][CO... F:quilibrkt (I) Kw = 10-14 = [W][OH-] (2) K.CO. a groundwater recharge operation. as shown in the following figure..]..CO. ] = 10-'" = [CaH][CO. Neglect ionic strength effects and calcium complexation. [CaH ]. [W].'-] .'-] [HCO. Example 6-14 Case I Find the concentrations of all species. for example. the alkalinity and the hardness of the solution that resu~ts when CaC0 3 (s) is equilibrated with distilled water closed to the atmosphere. (strong acid) produced by the oxidation of ammonia present in sewage spread on the soil in. [" S. Thus eight equations are required to define the system.284 Precipitation and Dissolution CASE 3 . = 10-6. Solution The unknowns are Cr. This could model the dissolution of CaC03{s) from soil by H+. and [OH-].-] [H. HCOi We will consider each of these cases further in the following three examples. the temperature is 25°C.] (3) K.'-]. CaC0 3 (s) is in equilibrium with water. [CO.= [W][HCO. [H.

Calcium Carbonate Solubility and Water Stability


Mass Balances
(5) S
(6) S

[Ca'+] [H,cO;] + [HCO,-] + [CO,'-]


S ~ C T,CO,

Charge Balance
(8) 2[Ca H

+ [W]


[OW] + [HCO, -] + 2[CO,'-]

Our approach to solving these problems will be to express the concentration of each constituent appearing in the electroneutrality equation in terms of [H+] and constants and then substitute into this equation. The resulting expression can then be solved for [H+] by trial-and-error. Then using the determined value for [H+], the values of each component can be determined. In making these manipulations, the a values given in Appendix I are helpful.



Substituting equations (I), (5), and the c< values into (8), we obtain
2S + [H+1

[~:] +

ale T,COl

+ 20'2C T,C03

From equations (4), (5), and (7),

K'" ~ (S)(c<,S)
s= ( K ) ~




equations (5) and (7), and since CaC0 3 (S) is dissolving in pure water, [Ca 2+]


Substituting these values in (8), we find

(9) 2(K,")" + [H+] ~ IH+] + c<,(K"),, + 2c<,(K,")" Kw
0:2 0'2 0'2

The only unknown in this equation is [H+J. A trial-and-error solution yields: pH

9.95. [Ca H ] ~ 1.27 x Hl-', [HCO, -] ~ 8.9 x 10-', [CO,'-] ~ 3.8 x 10-', [H,CO;] 2.5 x 10-', total alkalinity ~ 2.5 x 10- 4 eqlliter, total hardness ~ 1.27 x 10- 4 moleniter, S ~ 1.27 X 10-' mole/liter.


Example 6-15 Case 2
Find the solubility of CaC0 3 (sl in a distilled water system open to an atmosphere with, Pc~ = 10- 3 . 5 atm. Determine the concentration of each. species, the alkalinity,


Precipitation and Dissolution

and the hardness. Neglect calcium complexation and ionic strength effects; the temperature is 25°C.

The unknowns are S, C T •CO" [H+], [OH-], [H,CO;], [HCO, -I, [CO,'-], and [CaH]. Thus eight equations are required.






[W][OH-] [H,CO;]

(2) K

~ 10-6., ~ [W][HCO,-]
•• 1

(3) K

•. ,

~ 10-10., ~ [H+][CO,'-]


K~ ~






K HP co, ~ (10 -1.5 mo!elliter·alm)(l0 -,.5a l m)



Mass Balances
(6) S ~




C T•CO, ~ [H,CO;]

+ [HCO,-] + [CO,'-I

Note that S :I CT,eo3 because [H2COiJ is controlled not by the dissolution of CaCOS(s) but rather by equilibration with the atmospheric Peo2 •

Charge Balance

2[CaH ] + [WI


[OW] + [HCO,-] + 2[CO,'-]

We will use the same technique as in Example 6-14, namely, finding concentrations in terms of [H+] and constants and then substituting them in the charge balance equation. From (5) and using aO we obtain

[H,CO;]. ~ 10-5 or


aOC T •CO,

CT,eCl;) = - ao




and a" [CO,' ]


Substituting 1O- 5 for C T.eo3 /ao
[C 2+1



K 50a O (a,1O 5)

Calcium Carbonate Solubility and Water Stability
and supstituting into (8) yields


~~~~: + [H+] = [~:] + ", (I~J '+ 2",( l~~~
The only unknown in this equation is [H+]; accordingly, it can be solved by trial

and error yielding pH = B,3, [H,CO;] ~ [CO,'-] = 10-' M, [HCO, -] = 10-' M, [Ca H ] = 5 X 10- 4 M, total alkalinity = 10-' eqliiter, total hardness = 5 X 10- 4 M, and S = 5 X 10-4 M. Note the effect of exposing the solution equilibrated with CaCO",) to an atmosphere containing only 10-'" atmospheres of CO,. The pH of the solution has been depressed from 9.95 to 8.3 while the CaCO",) solubility has increased from 1.27 X 10- 4 M to 5 X 10-4 M (or from 12.7 mglliter as CaCO, to 50 mg/liter as CaCO,)-an almost fourfold increase. This solubility increase is reflected in increases in alkalinity and total hardness. Comparing these two examples illustrates the solvent effect of CO, on carbonate minerals and provides an explanation for the way in which groundwaters pick up hardness and alkalinity. Consider the situation in a limestone strata that is ip contact with an atmosphere containing 10-' atm of CO,--{I reasonable amount of CO, for soil air. The water will have a pH of approximately 7.3, and a total hardness and alkalinity of approximately 125 to 150 mglliter as CaCO, at equilibrium. Example 6-16 Case 3
This case is identical to the second case, except that strong acid or strong base is added to the system. We must determine the same concentrations. In this example we will add 10-3 mole of the strong acid H2S04 per liter of solution although a similar approach to the problem could be taken if a strong base were

Equations 1-7 in Example 6-15 are applicable, together with








and a modified charge balance,

2[Ca'+] + [H+] = [OH-] + [HCO,-] + 2[CO,'-] + 2[SO;-]
Substituting in the same way as in Example 6·15, we obtain 2,,$'0 [H+] 10 -'a2 +

[H+] +











Solving by trial and error yields pH = B.O, [H,CO;] = 10-', [HCO,-] = 5 X 10- 4 , [CO,'-] = 3.6 X 10-', [Ca'+] = 2.5 X 10-', total alkalinity = 5 X 10- 4 eqlliter, and total hardness = 2.5 X 10-' moleliiter. Two types of problems that often arise in conjunction with water treatment processes such as softening and water co,:,ditioning are: Is this


Precipitation and Dissolution

solution saturated with respect to CaCO",,? If not, is it undersaturated or oversaturated and what doses of which chemicals must be added to a water to produce a treated water of specified composition (alkalinity, pH, hardness, and degree of saturation with respect to CaCO",)? The latler question is only addressed in an introductory fashion in this text, and the reader is referred to books on water treatment for a more detailed discussion of water conditioning. The use of diagrams such as the Arbatsky" and Caldwell-Lawrence" diagrams is common. More modern approaches utilize the computer to solve the equilibria involved in these problems. In water conditioning the water is treated as a closed system with CaCO"" present, but the calculations may be somewhat in error because the system does not entirely behave as a closed system. The composition of the system is computed prior to chemical dosing, chemicals (e.g., acid, base, CO" and alkalinity) are added, and the composition of the system is computed following chemical additionagain assuming a closed system. The determination of whether a solution is in equilibrium with CaCO"" can be accomplished by calculating the free energy of the solution as described in Chapter 3. Example 6-17
Water of the following composition is obtained following a softeninglrecarbon. alion process: [CaH ] = I X 10-', [HCO,-] = 2 x 10-', pH = 8.7, temperature = lOoC, J.1. = 5 X 10-3 • Is the water at equilibrium with CaC03{S)?

Combine the equations 14 using Table 4·7, Chapter 4 to obtain the necessary constants.

CaCO"" "" Ca H + CO,'-;

log K"



(2) H+ + CO,'- "" HCO,-;

log - = 10.49 Ka ,2 log K

(3) CaCO"" + W "" Cao. + HCO,-; From Eqs. 3-20 and 3-22,

= 2.34

tJ.G = tJ.Go+RTlnQ tJ.G o = -RT InK


J. W. Arbatsky, "Zeichnerische ErmiUlung der Enhartungs Verhaltnisse von

Wassem. Nach dem Nomogramm von F. W. Staffeldt und dem Kalk-SodaWasserbild" Gas und Wasselfach, 83: 9()"92 (1940). 13 D. H. Caldwell and W. B. Lawrence, "Water Softening and Conditioning Problems," Ind. Eng. Chem., 45: 535 (1953). 14 Equation (1) could have been used, but the combination equation (3), is more appropriate, since HC0 3 - is the major carbonate species at the pH values typically encountered and it can be more accurately determined.

Calcium Carbonate Solubility and Water Stability
Let us first calculate AGo and then Q.


AGo ~ -(1.987 x 1O-')(283)ln 10,·34

-3.02kcal {Ca'+}{HC0 3 -} {H+}

so that

-log {H+}



Also, {Ca'+}
From Fig. 3.4 15 for
J.I.- =


(Yc,H)[Ca2+}; {HC0 3 -}


(YHco,-)[HC0 3-}




= 0.75,

Q ~ (0.75)(1 x 10-3)(0.93)(2





and using the values of AGO and Q we obtain

AG ~ -3.02 + (1.987 ~ 0.66 kcal


10-')(283) In 6.99 x 10 '

Because .6.G > 0, the reverse of reaction (3) as written is proceeding spontaneously and precipitation of CaC031sl is taking place.

The Langelier Index The problem of determining whether or not a water is in equilibrium with CaC03 {,) can be approached by determining whether the so·called Langelier Index (L.I.) (or Saturation Index, S.I.) is positive or negative. The L.1. is defined as the difference between the actual (or measured) pH of a water and the hypothetical pH the water would have if it were in equilibrium with CaCO,{,)."

where pH, pH,


pH, - pH,




actual pH of water pH of water if it were in equilibrium with CaCO",) at the existing solution concentrations 17 of HCO, - and Ca2+



Note that the DeBye-Hiickellimiting law could also have been used to calculate the activity coefficients. W. F. Langelier. "The Analytical Control of Anticorrosion Water Treatment," J. Am. Water Works Assoc .. 28: 1500 (1939). Some determine pH, by using the total alkalinity in place of the [HCO,-} concentration in the existing water. However, this leads to a reversal in sign for L.r. at pH > pKa .2 • i.e .. precipitation occurs if the L.!. < 0. instead of precipitation occurring if pH > 0 as is true at pH < pKa•2 • (See R. E. Lowenthal and C. V. R. Marais, Carbonate Chemistry of Aquatic Systems: Theory and Application, Ann Arbor Science Publishers, 1976.) Defining pHs as presented above avoids this problem. In the pH range normally encountered. the two approaches are essentially the same, since total alkalinity (eqlliter) ~ [HC03-}.


Precipitation and Dissolution

If a water has a L.I. of zero, it is in equilibrium with CaCO",,; if the L.I. i,s a positive value, the water is oversaturated with respect to CaC03 (S) and will tend to precipitate CaCO",); and if the L.I. is a negative value, the water is undersaturated with respect to CaCO",) and will tend to dissolve CaCO",). The expression for the value of pH, is derived from the equilibrium constant of the equation,
K = Kso K a ,2

K'0 K,.2 log {H+) or pH,
= =

{Ca 2+}{HCO,-) {H+)

'Ye,H[Ca2+] 'YHeo,-[HCO, -]


log K,.2 - log K,o + log [Ca 2+] + log [HCO,-] + log 'Ye,H + log 'YHeo,pK'.2 - pK,o + p[Ca2+] + p[HCO,-] - log 'Ye,H - log 'YHeo,-


The total alkalinity in eq/liter can be used interchangeably with [HCO,-] for waters with pH < 9. When calcium complexes make up a significant portion of the total calcium concentration, the concentration of these complexes must be substracted from the total calcium to yield [Ca2+]. Also, if species such as aqueous silica contribute to the total alkalinity (see Section 4.13.5) the portion of the total alkalinity attributable to these species must be subtracted from the total alkalinity; the difference is then used to calculate the HCO,- concentration. Using the constants, the measured values of [Ca2+] and [HCO, -] and the values of the activity coefficients as given in Example 6-17, we can solve for pH, thus: pH, Therefore,

10.49 - 8.15 + 3 + 2.7 + 0.12 + 0.03





pH, - pH,


8.7 - 8.09



The L.I. is positive, so the water is "encrustive" and will tend to precipitate CaCO"". The two procedures for assessing the state of a water with respect to CaCO",) are identical. This is shown as follows: Consider the reaction CaCO",) + H+ :0= Ca2+ + HCO,{Ca 2+}{HCO,-) 'Ye,H'YHeo, _[Ca2+] [HCO,-]




Calcium Carbonate Solubility and Water Stability


where l ] and { } denote equilibrium concentration and activity and [ ], and { }, denote actual or measured concentrations or activity. Now

Q _ 'Yc,H'YHco,-[Ca 2 +],[HC0 3-],{H+}
K - 'Yc,H'YHco,-[Ca H ][HC0 3 j{H+}.

From the definition of pH, given above, [CaH and [HC0 3oj, then





Since pH, pH, We have log K From Eq. 3·23,
Q tJ.G = 2.3RT log K = 2.3RT (L.I.)

-log {W}

= -log {W},


= pH, - pH, = L.r.

Thus a positive tJ.G corresponds to a positive L.r. The question of whether a water is oversaturated, undersaturated, or in equilibrium with calcium carbonate is important in the water industry, where processes called water conditioning are used to adjust the state of CaCO"" saturation. The importance of the CaCO"" saturation condition of a water relates to its behavior during transport, for example, in distribution systems and conduits and to some extent to its behavior during granular media filtration. Waters grossly oversaturated with CaC0 3 will tend to lay down precipitates of CaCO"" on the interior of the pipe, reducing its carrying capacity and in extreme cases blocking the pipe altogether (Fig. 6-14). Waters grossly undersaturated with respect to CaC0 3 tend to dissolve the protective CaC0 3(" coatings of transmission lines and are often classified as being "corrosive." Generally, an attempt is made in practice to maintain the L.r. slightly positive, although in some areas of the United States and Europe a slightly negative or zero value is used. If the water is supersaturated, it is desirable to know how


Precipitation and Dissolution

Fig. 6-14. Water distribution conduit virtually blocked with precipitated GaC0 3 . Courtesy of R. R. TrusselL J. M. Montgomery Engineers. Pasadena, Calif.

much CaCO"" will precipitate or dissolve. The L.r. has limited application because it tells us only whether precipitation or dissolution, if any, will tend to take place. Indeed, a water with a L.r. of 0.3 and a high buffer intensity may precipitate more CaCO",) than one that has L.r. of 0.5 and a low buffer intensity. Precipitation Potential We can calculate the amount of CaCO"" that will precipitate or dissolve as the water equilibrates by applying the two following principles to calculate equilibrium concentrations: I. 2. Total acidity does not change as CaCO"" precipitates or dissolves. Total alkalinity (eqiliter) - calcium (eqiliter) itation or dissolution takes place.

constant, as precip.

The total acidity does not change because CO,'- does not enter into the equation for it, that is, Total acidity


+ [HC03 -] + [H+]

- [OH-]

Calcium Carbonate Solubility and Water Stability


This is analogous to the lact that the addition or elimination 01 CO, does not alter the total alkalinity if it does not cause CaCO"" to precipitate or dissolve. The total alkalinity, defined as Total alkalinity


+ [HCO, -] + [OH-] -


changes as CaCO"" precipitates or dissolves but total alkalinity (eq/liter) - Ca'+ (eqlliter) does not change because the number 01 eq/liter 01 Ca2+ removed or added via CaCO"" precipitation or dissolution is equal to the eqlliter 01 total alkalinity removed or added. The calculation procedure is illustrated in the lollowing example. Example 6-18
Calculate the amount of CaC03{S1' in eq/liter and mg/liter as eaC03 , which will precipitate as the solution in Example 6-17 is equilibrated. Neglect ionic strength effects in this calculation.

The system is assumed to 'be closed so no CO 2 can enter or leave. The unknown concentrations after equilibration are [H,CO;], [HCO,-], [CO,'-], [H+), [OH-]. [ea H ], ande r,co3 ' Thus seven equations are needed to determine the equilibrium concentrations. From Example 6-17, before precipitation, we know [Ca2+]ori9 = 1 X 10-3, pH = 8.7, and [HCO,-] = 2 x 10-'. At 10°C, K,.l = 10- 6 .", K,., = 10-10.", K,o = 10-•. 15 (from Table 4-7) and Kw = 10-14 . 5 (interpolating from Table 4-2), Using K a•1 and K a,2, we calculate [H,CO;] = 1.1 x 10-' and [CO,'-] = 3.2 x 10-'. Using these values in the equation for total acidity given above, we find total acidity = 2.02 x 10-3 eqlliter. Also. total alkalinity (= 2.07 x 10-' eqlliter) - Cao. (= 2 x 10-3 eqlliter) = 0.07 x 10-' eqlliter. After the solution equilibrates we can calculate the equilibrium concentrations knowing that total acidity and [total alkalinity - Ca" (eqlliter)] does not change. The equations we need are

Total acidity

= 2[H,CO;] +

[HCO, -] + [W] - [OW]

= 2.02

x 10-' eqlliter

(2) Total alkalinity - Cao. (eqlliter) 2[Ca 2 +] = 7 x 10-'
(3) K,.l

= 2[CO,'-] +

[HCO,-] + [OW] - [W] -


[W][HCO,-] [H,CO;] [H+][CO,'-] [HCO,]

(4) K,., =

(5) C,.co,= [H,CO;] + [HCO,-] + [CO,'-]
(6) Kw = [W][OW]

(7) K ~


To solve, substitute into equation (2) to obtain one equation with one unknown, [H+], and solve by trial and error, just as was done in Examples 6-14, 6-15, and

Merrill and R. we find [H+] ~ 10-•. 08• From equation (7). Waters that have a low calcium concentration and a low alkalinity.VC T. calculatingC T. Remembering ao = [H 2CO. and prevents corrosion by preventing low pH values from occurring (see Section 7-6 for a discussion of the effect of pH on corrosion).02 X 10-'. as well as calculation of the precipitation potential.C ( ) Kw _ . and thus the CaC03 (s)' which precipitates per liter of solution.04 x 10-' eqlliter x 50. Water Works Assoc . and 34: 133 (1978). use of these diagrams is discussed by Merrill and Sanks. L. L. and thus a low buffer 18 19 D. 9. Am.. C. Water with the desired precipitation potential is thought to provide a thin protective coating of CaCO"" on the inside of distribution lines and so aid in preventing their deterioration by corrosion.COl ' 2. Subtracting the [Ca'+] at equilibrium from the [Ca H ] originally present yields the Ca 2 +.52 x IO-'molelliter X 2 eqimole ~ 1. Yahalom.2 mg/liter.04 x 10 -'eqlliter 1. 2". and then determining if equation (8) is satisfied./eq ~ 5.T.' The result from combining equations (3). obtaining a values from Appendix 1. [Ca H ] ~ 9.2 mglliter as CaCO. The' most effective CaC03{. are facilitated by the use of diagrams such as the Caldwell-Lawrence diagrams. . 19 A slight supersaturation with CaC03{" and high alkalinity also provides the water with pH buffering capacity against CO.' layers appear to be those associated with iron hydroxide and iron carbonate precipitates. "Corrosion Control by Deposition of CaC03 Films.[Ca2+]eQuH ~ = 1 X 10-3 - The theoretical precipitation potential of CaC03{. Sanks. Such calculations.[W] 2ao + a1 + (Kw/[W]) We can solve equations (8) and (9) by assuming [H+]. 69: 592 (1977). [Ca 2 +1orlg .CO. 69: 634 (1977).COJ' and a2 = iCO.co3 from equation (9). and J. by slime growths for example. Feigenbaum. (4) and (5) and using equation (7) to obtain [ea2+] =Kso/(a2CT. a new value of [H+] is assumed. Using this approach.52 X IO-'molelliter 0. and 70: 12 (1978).+ "" + [H+] a'2 2K" C [H+] T.294 Precipitation and Dissolution 6-16.CO.48 X 1O~4 0. Corrosion.000 mg CaCO." J. Gal·or. which is within the range of 4 to 10 mglliter suggested for a well-conditioned water by Merrill and Sanks.. If not. 34: 65 (1978).. T. We can simplify the procedure somewhat in this case by assuming [H+1 and K w/[H+] to be small relative to the other terms in equations (8) and (9).C0 3 and from equation (1) (9) C ~ T." A similar approach to that given in Example 6-18 can be used to determine the concentrations of conditioning chemicals to add if they are needed.'-]lC T. generated in the distribution systems.C03' al = [HC03~]/CT.COJ) and substituting into equation (2) is (8) 7 X I0 _.48 X 10-' M.' found in Example 618 was 5.

6·15 together with the equation C T •C. Stumm found that when a high pH was necessary to create a positive L. We can combine these equilibria with the equation for CaCO"" precipitation and then plot the resulting equations to determine the effect of these complexes on total soluble calcium. CaOH+ . Ill" 1975. good protective films' usually do not form under these conditions. = [Ca2+] + [GaOW] + [CaHC03 +] + [CaC0 3' ] and the equation for [Ca'+] determined from K" for CaCO""..=..2." Illinois State Water Survey Bulletin 59.3 1 log Kd = 3.) is in equilibrium with solution." Am. Larson. "Corrosion by Domestic Waters.26 log Kd = -1.1 (0.=' Ca2+ + OH-.26 or [CaHC0 3 +] = 1.) The following carbonato and hydroxo complexes and their dissociation constants at 25'C have been reported for Ca'+: CaC0 3'. The values used here are representative. Soc.2 CaCO". For CaC03 ' . Sanit. Ca'+ + HC0 3 -.49 (6·4]) (6·42) (6·43) It should be noted that the reported values of constants for these equilibria vary widely. 20 However. log K = 3.3 10-6 M whenever CaCO". Urbana. values as high as 1.22 log Kd = -1.=.7.45) 21 T. may require the use of L.. Civil Engls" J. 21 6. 20 (6. . The procedure used to develop the plot is illustrated in the following example.. For CaHC03 +. W. "Investigations on the Corrosive Behavior of Water. 1 = [CaC03 '] = 8. Stumm. The Effect of Complex Formation on the Solubility of CaCO". E.l.=' CaC03' . scale formation was not uniform. CaHC03 +.. Eng. Div" 86: 27 (1960).I. log K" = -8. X log K = -5. log Kd = -3. Ca2+ + C03' .) Thus .Calcium Carbonate Solubility and Water Stability 295 intensity.8 x 103 [H+] and for CaOH+ (6·46) Equations 6·44 to 6·46 are plotted in Fig..0 to prevent _corrosion.8 mglliter as CaC03 ) (6·44) 10-5 .

eo.'-]. What is the concentration of dissolved calcium? The unknowns are CT. 6-15.'].co3 is measured and found to be 10-3 M. -]. [HCO. = [Ca2+] + [CaHCO.CO. Example 6-19 The pH of a 25°C solution in equilibrium with CaC03{s) is 12. -] + [CaHC0 3 +] + [CaCO.296 Precipitation and Dissolution 1. There are eight equations.+].'-] (2) Cr. +] + [CaC03'] + [CaOW] (3) Kw = 10-6 •3 . and [CO.e.0 2. [CaHCO.CO. [CaOH+]. = 10-' = [H.'] + [CO. [CaCO.].0 7 pH 12 Fig. The Cr.0 § i 8 ~ .] + [HCO. Concentration of calcium species in equilibrium with CaC0 3 {S) at 25'C. (I) C T. Assume a closed system and that activities are equal to concentrations.Q J 9. [H. [Ca2+]..e.

1 = Hl'·26 [CaHCO.'-J Obtain [Ca'+J from equation (3).4. 3 (6) (7) [CaCO. = 10-10 .• 10.-[CO.+J 10-' = 10.e. neglect [HCO. [CO. [CaOWJ = " . == [CO.'-J [CaHJ = -.3 + 10-•. 74 [CaCO.'J [CaOWJ = 10-5 . 1 = 10-•.5. [Ca'+J + [CaHCO. K [CO.'J Therefore.' J 10-3 J = 10-5 .Calcium Carbonate Solubility and Water Stability 297 (5) Ie. equation (2). 74 + 10-5 .J = 10'·26 X = Therefore.12 10-5 . = = = From the calcium mass balance.• = 31 C T •e.3 X 10-' = 10.+J = [WJ (8) 31 [Ca'+][OH-J Determine [CO.74 + 10-5 •1 + 10-5. [CO.5. C T. - ..84 = 1.' J = C T •eo .. From equation (7) [CaHCO.[C '+J _ a K" . we would have underestimated the dissolved calcium by 1.4 X 10-5 If the complexes had been neglected.CO. 3 31[Ca H ][OH-J X 10.'-J + 10-•.[CO.4 X 10-5 - 5 X 10-6 = 9 X 10-6 M .. +J + [CaC03'J + [CaOWJ 10-5 . 3 10-3 10.-J and [H. 1 10-' 10-'" = [c a HJ [CaH From equation (8).CO. At pH 12.'-J from equation (I).'-J » [HCO.J.= 10-3 X 10-•.5 •3 = 5 10-6 M From this calculation it can be deduced that if we had neglected the calcium complexes in our computation.-J » [H.1 = 10-0·3 (5) K.

'-. and water treatment. that is. EDTA can break these complexes. wastewater. For example. MgHCO.'-. MgOW ¢ Mg'+ + OH-. HC03 -. Phosphorus. the concentrations of calcium complexes should be subtracted from the total calcium concentration to yield the Ca'+ concentration.complex. When calculating the L. MgSO. equation.9 mg/liter as CaCO.S. Reactions of Phosphates The chemistry of phosphates as relevant to aquatic systems is discussed as an example of the importance of heterogeneous equilibria in waters. 6. CO.4 -2. is of central concern to a wide variety of biological and chemical processes in natural at pH 9. assuming that the concentrations of complexes are not taken into account when the L.complex formation: CaSO.. Phosphate is a nutrient required for the growth of all living protoplasm that. the presence of 200 mg SOl-fliter will increase the solubility of CaCO"" from I X 10-' M to 1.31 log K d log K d = = -3. phosphorus can be the . The presence of complexes may require that a higher value of L.I . = I X 10-3 M. and SO. 6-15 show that the consideration of calcium complexes becomes significant in determining calcium solubility at pH values above 9. This value can then be used directly in the L. MgCO. be used to produce a noncorrosive water.I.1.6 logKd= -1.36 The consideration of complex formation by both Ca2+ and Mg'+ is of significance in determining the lowest achievable residual hardness by the lime-soda water-softening process.'-. PHOSPHATE CHEMISTRY 6. The solubility of calcium is affected by the SO. Eq. 6·39. The curves in Fig.'.I. complexometric. This example provides a further illustration of the way in which complexation increases the solubility of sparingly soluble solids. log Kd = -2.4 X 10-' M when Cr. contains approximately 2 percent phosphorus on a dry weight basis. titration analytical procedure and so will register as residual hardness. Complexes of Ca2+ and Mg'+ are weak enough to be titrated by EDTA.' ¢ Mg'+ + CO. and magnesium solubility is affected by OH-.'¢Mg2++S0. ·As such.I. is calculated. in the commonly used.' ¢ Ca'+ + SO.S. present as various forms of phosphate.-¢ Mg'+ + HC03 -.298 Precipitation and Dissolution or 9 X 10-6 X 10' mg/mole = 0.'-.'.2 logK d =-2.

the P atom is centrally bonded to the oxygen atoms. pyrophosphate. the metaphosphates are cyclic. ensures the hydrolysis. as "threshold treatment agents" (e. and indeed prolonged coniact with the microorganisms in raw sewage. While polyphosphates are .+ 2H+ Hydrolysis is catalyzed by H+. Examination of Fig.. at pH 7 is many years and at pH 10 is over a century! Of course. Phosphate is used as a nutrient by organisms in biological waste treatment processes. In the orthophosphate anion. Secondary biological treatment.. Tripolyphosphate. The calcium phosphate system by itself is very complex. Also.O . In fresh raw domestic wastewater the phosphate is distributed approximately as follows: orthophosphate. tripolyphosphate. and complexes Ca2+ and Mg2+ to prevent them from combining with the detergent molecule).linear molecules. hydrolyzes as follows: HP3 0 1O' .=: 3HPOj.g . some estimates of the phosphate content of natural waters assign between 30 to 60 percent of the total phosphate to the organically bound category.+ 2H. Wastewater effluent and natural waters contain significant amounts of organically bound phosphate. Phosphate solubility equilibrium constants and complexation equilibrium constants are given in Table 6-5. From Table 6-5 it can be learned that . which are located at the corners of a tetrahedron. catalysis of the hydrolysis reaction by enzymes is important in nonsterile natural waters. I mg/liter as phosphorus and organic phosphates < I mglliter as phosphorus. 5 mglliter as phosphorus. Phosphates are used in industrial water-softening processes. The behavior of calcium phosphate precipitates in dilute aqueous solutions serves to illustrate some of the difficulties that one may face when attempting to apply equilibrium calculations to predict solution concentrations of ions in contact with a solid.) precipitation) and as builders in synthetic detergent formulations (where tripolyphosphate stabilizes dirt particles. ("reversion") of condensed phosphates to orthophosphate. 2-8 shows that at 10°C the time for 5 percent hydrolysis of a pyrophosphate solution at pH 4 is about I year. condensed phosphates are employed as agents for complexing CaN and Fe'+ in boiler waters. Typical concentrations of phosphates found in various waters are given in Table 6-4. the use of sodium tripolyphosphate which adsorbs on the surface of calcite crystallites and thus prevents CaCO". where their ability to form sparingly soluble calcium salts is capitalized upon. The condensed phosphates-the polyphosphates and metaphosphates-are formed by the condensation of two or more orthophosphate groups and have the characteristic P-O-P linkage. Several of the more common classes of phosphorus-containing compounds are presented in Table 6-3. Indeed.Phosphate Chemistry 299 element'in short supply that limits the growth~ of photosynthetic aquatic plants. for example. 3 mglliter as phosphorus.

~ ~ complexes 7. 12. including phospholipids. HPOl-.PO" H. P30 105-. there are the acid-base equilibria of phosphoric acid to consider as well as complex formation of species such as CaHPO. pK •." ~ 6." ~ 2. ~ 9." ~ 2. pK •.'-.2. phosphoamides. HP20l-." ~ 1.6. pK.• ~ 9.1.4. . etc. there are a variety of solids that may form (and many more than listed may form). PO.2 Metaphosphates pK. = 2. ~ 6.P0 4-. HP20l~ complexes pK.3 II II II -O-P--Q-P--Q-P-OI I I 000tripolyphosphate o 0 0 H3P30102-. HP 30 104 .300 Precipitation and Dissolution TABLE 6-3 Classes of Phosphorus-Containing Compounds of Importance in Aquatic Systems Structural Representation Group Acid Ionization Constants (25°C) (Typical) Species of Importance Orthophosphate o I -O-P-OI 0II II -O-P--Q-P-OI I 00pyrophosphate H. sugar phosphates.1 trimetaphosphate OH CH. pK •.complexes pK.." pK •.' and . nucleotides. P2 0/-." ~ 2.5.1 pK. HP30104-. pK. HPOl~ pK a .O-IT--QH Organic I phosphates ~H OH glucose 6-phosphate L--~ Very many types.3. H 2P30 103-.52. .3 o 0 Polyphosphates H4P207' H 3P20 7-' H 2 P20 l-.

'.PO.66 6.~ Ca2+ + HP 20 7S- + 5.0 phosphate Hydroxyapatite /3.6 CaH. and temperature.5.o.).'" Na+ + HPO/MgHPO<. ¢ 5Ca2+ + 3PO.5 + 2. K".75 .)"" '" 3Cao. 9 . let us consider the magnitude 6f the phosphate concentration that we would predict to be in equilibrium with hydroxy.+ OH-. However.'With tripolyphosphate CaP SO t03~ Ca2+ + PsO tOS- + 8. . + HPO.9 +24.1 CaH.+ H+ With pyrophosphate CaP 20 72. = 10-55 •9 [Ca'+]' [pO.3.0 +21. r Phosphate Chemistry TABLE 6·4 Typical Concentrations of Total Phosphorus in Water 3-15 mglliter as P 0.6 + 9.+ '" Cao. '" Mg'+ + HPO/CaHP0 4° ~ Ca 2 + + HPO/MnHP0 4° ¢ Mn2+ + HPOlFeHP0 4+ ~ Fe3+ + HPO/- With orthophosphate + 0.14 Ca.0 +22 Fe(HP.6 M 301 Domestic waste water Agricultural drainage Lake surface water 3-13 x 10-' M TABLE 6·5 Representative Heterogeneous and Complexation Equilibria of Phosphates (25°C) Heterogeneous Equilibria Calcium hydrogen + + 6.(PO')30H". apatite-the thermodynamically stable solid under typical natural water conditions of solution concentration. From Table 6·5.'" FeH + 2HP. + 2PO. Ca.PO. pH.Ca3(PO.4 M 2-30 X 10.+.01-0.6 + 2.6 + 2.l.9 +21.04 mglliter as P 1--5 X 10.2 + 2.66 phosphate Calcium hydrogen phosphate Calcium dihydrogen + 1.a-p [OH-] = 10-55 .'+55.05-1 mglliter as P 0.(PO. + 3PO. '" 5Cao.3.: .. Tricalcium phosphate Ferric phosphate Aluminum phosphate Complexation Equilibria FeP0 4(s) ~ Fe s+ + P0 4sAWO 4(s) ~ AP+ + PO l- pK NaHPO.a.+ OHj3.~ Ca 2+ + P20 74 CaHP207 .(OH)".O.

7 X = 1. F. B. phase transformation." we would not be much concerned with problems of algal growth associated with phosphorus. We would also encounter remarkable success if we were to precipitate phosphate from wastewater by adding calcium salts such as lime. This so-called induction period represents the time for nuclei to form. D. 5: 369-381 (I97l). "Chemical Processes for Phosphate Removal.~ &. we might deduce that if natural waters were in equilibrium with hydroxyapatite. 6~16. A general picture of the nature of calcium phosphate precipitation is provided by Fig.5 = X 10-' M (150 mg/liter as 10-')' [PO..5 X 1. 10 J. treated with calcium salts and in natural waters far exceed the calculated equilibrium value. .1O showed Induction t ] c Nucleation. precipitation of amorphous phase Phase transformation . and crystal growth. What then is happening? While the entire answer to this question is beyond the scope of this text.. Ferguson. Jenkins. Because we know that phosphate levels in wastewater. we might deduce that hydroxyapatite does not control the orthophosphate level. or stated another way "if the orthophosphate concentration of natural waters was controlled by hydroxyapatite. and A.2 as . [PO.2 x 10. In a supersaturated solution there is at first a period of time before any decrease in dissolved phosphate takes place.'-l' (10-') 10-55 .5 '28 > c Crystal growth of stable crystalline solid ~ Time Fig. Ferguson et al.g ~ o. Idealized scheme for calcium phosphate precipita- tion kinetics.'-] or 3.) (1.12 M 10-' f.'302 Precipitation and Dissolution For typical conditions of pH 8 and [Ca'+] CaCO.'g/liter as phosphorus Therefore." Water Research. some facets of the system can be explored to illustrate the practical consequences of the previous discussion in this chapter on precipitate formation by nucleation. 6-16. Menar.

Reprinted by permission of Pergamon Press. that if a crystal seed of precipitated calcium phosphate were added to a solution supersaturated with respect to hydroxyapatite. "Calcium Phosphate Precipitation in Wastewater Treatment. albeit slowly. .25 ~ 2 ~ E 0. The amorphous nature of calcium phosphate precipitates may indeed be an important reason why phosphate solution concentrations are present in natural waters at higher levels than predicted by equilibrium with the crystalline solid. Water Research.10 ~ ~ S 0.. University of California. B. to the stable solid phase. 6-17. Jenkins. Ferguson et aI. in the presence of magnesium ion. Menar and D. For the example of calcium phosphate precipitation given.20 c' 'g • u c 0 u ~ 0 c 0.3 M pH X = 7. Sanitary Engineering Research Laboratory. Effect of crystal seeding on rate of calcium phosphate precipi- tation. 5: 369-381 (l971). there was a virtual elimination of the induction period as the precipitate acted as a nucleus for further precipitation as shown in Fig." who found that. original composition I Crystals added to solution 0. hr 300 450 Fig. C~= 5 303 CT . 1972.05 o 150 200 250 Time. we can see that precipitation not only results in an amorphous solid but also a precipitate whose solubility is greater than the thermodynamically stable phase. Such a solid is not stable and will transform.3 M Temperature'" 25 ± 1°C t of approx. Following nucleation the formation of an amorphous precipitate occurs. An example of such a system is provided by the work of Menar and Jenkins. L F. The term amorphous refers to a solid that does not have a well-organized crystal structure and is almost always more soluble than the corresponding crystalline solid. the first-formed solid may be stable enough to control solution phosphate concentrations in a pseudo-equilibrium or steady state situation. However." SERL Report 72-6. the residual phosphate concentration in wastewater after treatment with calcium salts 11 A. Ca "" 2 X 10. 6·17.15 ~ 0. Berkeley.6 10.Phosphate Chemistry CT.

Thus dC =K'cn dt where K' is a constant.'- = 0. A further factor important in the control of phosphate levels by calcium phosphate precipitation is the rate of crystal growth.6 x 10. Jenkins.M 8 PO.304 Precipitation and Dissolution could be described by an equilibrium between it and the solid phase (3tricalcium phosphate.5 X 10-' M. Control fed" 45. 12 showed that a rate law of the form dC dt = -kS(C .'-] or = ( (1.24 • Let us compare two systems at pH 8 and [Ca2+] = 1. we can assume it to be zero. (3-Caj. Water Pollut.POJ" with a solubility product of 10. or where an induction period was absent. Eastman. "Calcium Phosphate Precipitation at Slightly Alkaline pH values. for phosphate in equilibrium with hydroxyapatite.5 x 10-')' 1. [Ca2+J'[POt-]' 10-24 = 10-24 = ) 1/' [PO." J. the limiting reactant equilibrium concentration time from the end of the induction period a constant Since for hydroxyapatite.C)" was applicable for post induction periods. D. Also. and J. one in equilibrium with hydroxyapatite and the second with (3-tricalcium phosphate. where n = order of reaction S C C* = = = t = k = available crystal surface area concentration of phosphate. F. C· is very low. Ferguson et al. POt= 3. we can assume that S is a constant if a constqnt amount (excess) of seed particles of hydroxyapatite are present. .5 ILgiliter as phosphorus This shows that the system in equillbrium with the less soluble solid can contain four orders of magnitude less orthophosphate than the water in equilibrium with (3-tricalcium phosphate. Ferguson.7 X 10-5 ILgiliter as phosphorus For (3-tricalcium phosphate. 12 J. From previously. 620-631 (1973).

recycle flow/throughput flow. Ferguson et mM. temperature = 25°C. 45: 620-631 (1973). Water Pollution Control Fed . are mixed throughout.. C r.Phosphate Chemistry 305 By carrying out calcium phosphate precipitation in solutions containing various levels of carbonate.7 tells us that the rate is extremely sensitive to concentration. @ 1973 Water Pollution Control Federation.3 1.2. C r'P04 = 0.1 0. From J. Assumed conditions includeC r. and n = 2. 80 to 100 percent removal.1. Thus reactors that have regions of high concentration will have precipitation rates greater than equivalent reactors that. hr 100 ~ Fig. The concentration exponent of 2. J. These features are illustrated by Fig.co3 = 1. are in units of millimoleslliter and t is in' which was shown to affect precipitation.3 mM.. Predicted phosphate removal versus hydraulic detention time for four reactor types. which shows the predicled phosphate removal by flow types of reaclors at various average hydraulic detention = 2. reprinted with permission. C T . The dashed line indicates the limits of practical application. 100 90 Tubular with solids recycle l' ~ 0 ~ ~ • ~ E ~ 80 70 60 50 40 ~ • "- ~ 8 30 20 10 0 0.0. 6-18. pH = 8. 6-18. In addition to being an inverse function of the alkalinity (CT. F. .7. OjO = 3.0. solid residence time/liquid residence time.0 mM.0 3 10 Hydraulic detention time. 2 hI ~ (J ~ 8 hr. Plug-flow reactors are therefore more efficient than CSTR (completely stirred tank reactors). an empirical rate expression was determined as follows: where C and CT. qlQ = 0. the rate and extent of calcium phosphate precipitation are strongly dependent on reactor configuration. The form of this rate equation has important practical implications for phosphate removal by calcium phosphate precipitation at slightly alkaline pH values. Reaclors that feature a recycle stream are far more efficient than equivalent reactors that do not because of the presence of much larger surface area of preformed precipitate contributed by the recycled stream. K' = 4.

that is. Thus log K.+ = [NH. is plotted as a function of pH in Fig. it follows that there should be a pH value where the solubility of MgNH. struvite (MgNH. aNH. is a function of pH and its minimum value will occur when the product (aMgH) x (aNH. ammonia nitrogen.+) and the phosphate ion (PO. NH4+ and P0 43.3 (Kl '.1 log (_1_) 2.'-).2.1 = Kd •M9 Defining the ionization fractions for Mg 2+.. C TNH" and CT. Activity coefficients were obtained from Fig.7.'-j is a minimum.PO".+}{PO.+j[pO. assuming in one case that I-' = 0 and in the other that I-' = 0. Because an increase in pH will decrease the ammonium ion concentration and increase the phosphate ion concentration.8.'-]lCT.' as K" = {Mg'+}{NH.NH. 6-19.2 log (_1_) 2.P04[.306 Precipitation and Dissolution 6. magnesium. We can see from this figure that the minimum solubility occurs at about pH 10.dependent reactions involving each of the species in the aMgH = [Mg2+j/C T.are the total analytical concentrations of . These species are the ammonium ion (NH.1 K = a .PQ.+) x (apo. respectively.'.' ) = 12. Magnesium Ammonium Phosphate Precipitation The conditional solubility product of magnesium ammonium phosphate.'-)is a maximum.+j/CT. log = -9.3 = 10g(K:J 7.1. the pH where the product [Mg2+][NH.PO" we can write the solubility product of MgNH.M9 .= [PO.) illustrates a situation where more than one of the dissolving species is affected by solution pH.M9 . and orthophosphate. P. 3-4.P04[" is a minimum. and apo.'-} where C T. The values of these ionization fractions are presented in Appendix I. We can define the conditional solubility product as Then P. Where is this point? We can attack this problem by writing equations for the pH. .

g is exceeded. digested sludge. Let us examine the basis for this solution to the problem.NH. For raw sludge. X CT.M9CT. Similar accumulation of struvite blocked the screens through which digested sludge was passed prior to discharge to the ocean.NH3 C T . With the concentrations indicated in Table 6-6 we can compute the product CT. Magnesium ammonium phosphate precipitation is a recognized problem in anaerobic sludge digesters. and if this significantly exceeds the conditional solubility product. P" then struvite should precipitate.M9 x CT.cT. orthophosphate. Table 6-6 presents the concentrations of ammonia.'-] to values where K. especially at elbows and on the suction side of pumps. by struvite precipitation. Conditional solubility product. +][PO.PQ. This happens at these locations because they are regions of reduced pressure and CO.. = (5 x 10-')(5 x 10-')(4 ~ 10-') = 10-6 . CT. and magnesium and the pH of the raw sludge. pipe has been reduced to less than 4 in. where it precipitates in digester supernatant recycle lines. This causes a rise in pH of the digester supernatant with an accompanying increase in the product [Mg2+][NH.M9 C T .P0 4' for magne· sium ammonium phosphate at 25°C.1 \ '\ 8 / " '_. and diluted digested sludge.NH. the solution to this problem was to dilute the digested sludge with effluent in a volume ratio of about 3: I.Phosphate Chemistry 307 2\ \ 6 \ \ \ "~0. 6-19. is released from solution. Figure 6-20 is an illustration of a severe case of magnesium ammonium phosphate (struvite) deposition.PQ. Because the Hyperion plant discharges both digested sludge and sewage effluent to the ocean. Figure 6-21 shows the flow sheet of the wastewater treatment plant. This photograph was taken from a digestor recycle line at the City of Los Angeles Hyperion plant and shows that the cross section of a 14-in. P s = C T ./ I pH 10 6 8 Fig.

6·20.= 0.5 and f1. If P. Because 10-6 •3 > 10-7•5. From Fig. P. From Fig. at pH = 7. For diluted digested sludge.·5» 10-7 . Magnesium ammonium phosphate deposition in digester pipeline. CT.5 X 10-2 . is corrected for activity. 6-19.5 and f1.PO. = = 10-3 X 2.NH. the digested sludge is highly oversaturated with respect to struvite and should tend to precipitate.= 0. P. at pH = 5. 3 X 10-2 From Fig.7 = 10-6 . Because 10-'» 10-6. = 10-7•5. = 10-'. at pH = 7. the raw sludge is highly undersaturated with respect to struvite and it will not tend to precipitate.5 X 10-5 = 10-4 .MgCT. the diluted digested sludge is supersaturated with respect to struvite but not the same degree as the digested sludge. = 5 X 10-3 X 10-1 X 7 = 3.CT.1gCT. = 10-7 •5 Because 10-. 6-19.cT. For digested sludge.308 Precipitation and Dissolution Fig. 5 .5 and f1.NH.PO. P. .= 0.5 X 10-2 X 2 5 X 10. 6-19. CU.

American Cyanamid Corporation) at doses of 10 to 20 mglliter).5 5 x 10-3 5 x 10-3 4 200 -1400 2000 7. they must be used when that TABLE 6·6 Values of Constituents in Hyperion Sludges Diluted Digested Raw Sludge Constituent CT.Mg Digested Sludge mglliter moies/liter Sludge mglliter moleslliter _10.5 x 10-2 -2 X 10. in solution (and therefore keep pH depressed) was not practicable.3 mgmter moleslliter 250 75 1200 5. handling digester supernatant to keep CO.. assuming /L = O. California. Flowsheet for digested sludge treatment at the Hyperion plant.5 5 X 10-3 Ammonia Nitrogen (total) Phosphate Phosphorus (total) pH 10-1 7 X -2.1 Screened digested Digested sludge Screen sludge Fig. treatment plant of the East Bay Municipal Utility District. however. One such example is the Oakland. At this plant a MgNH4 PO"" scaling problem developed. 1 so that the solution is actually undersatur· ated.5 .Phosphate Chemistry Primary Raw sewage sedimentation ~-L_~ 309 Activated sludge. The solution to the scaling problem was to add a material that inhibited crystal formation (a polyacrylamide crystal inhib· itor (Cyanamer P-70. Thus the dilution provided appears to be adequate to prevent struvite precipitation. 6-21. The solution to the problem is soundly based. Secondary sedimentation ISecondary Ieffluent Raw sludge/ Ocean _ _ _ _ _ _ _ .2 x 10-2 10-2 7. The solution to this problem at the Hyperion plant represents something of a luxury because there are not many plants that have the ability to dilute digester supernatant with secondary effluent and then discharge the mixture. Such solutions to scaling problems are not as "safe and sure" as reducing the value of an ion product to below the solubility product of a scale·forming precipitate.L P. Dilution to below P. = 10-6 .. was not feasible.

and NaH. was formed under the conditions of anaer· obic sludge digestion.).{P04)".2) or iron salts to wastewater for phosphate removal results in the precipitation of alu· minum hydroxyphosphate (Alx{OH). The pH of individual bottles was then adjusted with Na.310 Precipitation and Dissolution alternative does not exist.3. 6. to several values in the pH range 4 to 8. for example. Singer" proposed that the reason for this was that the sparingly soluble ferrous phosphate. These solids are incorporated into the sludge or underflow solids streams that in a typical municipal treatment plant are treated by anaerobic digestion (see Fig. After sealing.P04 were added to water through which nitrogen gas was bubbled to remove all traces of dissolved oxygen and so to produce reducing conditions. FeCI.. vivianite. "Anaerobic Control of Phosphate by Ferrous Iron. the bottles were stored for I month during which time a blue·white precipitate 2S P.8..). Ferrous perchlorate Fe{CI0 4). after metal salt addition phosphate levels in digester supernatants decreased.{S04)" are used as phosphate precipitants with the objective of removing phosphate." J. rather.o value of Fe. A constant ionic strength medium (a.6. It is useful to remember that thermodynamics is more reliable than kinetics in the solution of precipitation/scaling problems. Water Pollut.{PO. 6·22.) The method used by Singer to determine the K. I M NaCI04) was prepared to eliminate the need for activity corrections. 2POl~ 3Fe{I1I) -> 3Fe{II) ----> Fe. 44: 663 (1972). respectively. and Fe. Singer. The experimental system is illustrated in Fig.{P04). . C.) and ferric hydroxyphosphate (Fex{OH). When Fe{I1I) salts.CO. a question arises concerning the fate of this precipitate in the highly reducing conditions of the anaerobic digestion process. Control Fed. 6·21). Under such conditions Fe{I1I) will be reduced to Fe{II)what then is the fate of the phosphate that has been precipitated with the Fe{I1I)? Does it remain in the solid phase or is it released to solution to be recycled back through the treatment plant in the digester supernatant stream? The early literature on the effect of iron and aluminum salt addition on phosphate concentrations in digester supernatant seemed to indicate that phosphate release was not occurring during digestion.{P0 4 )". Iron Phosphate Precipitation from Wastewater The addition of aluminum salts (see Section 6.) is a useful illustration of typical meihods employed for equilibrium constant measurement.

.) or .. 6-22. . Sample precipita· tion technique used to deter.cT.P04 were measured. 6-47. Water Pollution Control Fed.P0 4 -] + 410g [H+] p'K.-]'[Fe'+j' [H+]' (6-47) where cK a. 44: 663 (1972).PO. N'H.------N. .2 log [H.(PO.3 = -3 log [Fe2+] . Now 1-'=0.PO.PO.[H. © 1972 Water Pollution Control Federation.. p'K" ..J2(S)' From P.2p'K.2p'K. and Fe2 + and C T.2p'K".3 are the second and third dissociation constants of phosphoric acid. mine K so for Fe~PO.2p'K •. A final pH measurement was made.Phosphate Chemistry 311 . 3. 6-48 are either known (P'K •. J. the samples were filtered. Fe(CI0 4 )2 ( NaC10 4 Fig.1 We can write the reaction as a dissolution of Fe.PO)'] (6-48) All quantities in Eq. reprinted with" permission. Thus Fe. 3 + 4pH = -log [[Fe'+j'(a2.)"" + 4H+ '" 3Fe'+ + 2H. C..o . From Eq. -Singer. a.(PO.2 and cK a.PO.)"" by acid.PO. formed." p'K •.

analytically measured. 3-4 yields a value of 8 X 10-34 • Examination of the solid by X-ray crystallography provided evidence that it was indeed vivianite.2p'K'.. The intercept at pH = 0 is p'K...2 .2 = 6. 6-23.3 = -7. J.."2.1 M NaCl04 4 5 6 pH 8 9 Fig.3 when pH = O..7 p'K. A plot of -log ([Fe 2+j'(Cr. From P.9. © 1972 Water Pollution Control Federation.. Figure 6-23 shows Singer's data plotted in this fashion. (Fe2+. Singer.312 Precipitation and Dissolution 25 15 T = 25°C 11 = 0.2p'K... Experimental data on solubility product of ferrous phosphate.2p'K. . C T • PO" [H+]) except p'K".78 and p'K .1 since p'K . Water Pollution Control Fed" 44: 663 (1972). using the activity coefficients in Fig. Similar study of solids from digesters that had received sludges from plants employing iron addition for phosphate removal also revealed the presence of vivianite.po.po.2 . re~ printed with permission. = 29. C.3 = 11. atfL= 0.1 The determination of K.l'l versus pH should give a line with a slope of +4 and an intercept of p'K" . .2p'K'.

?w much 80/. at 25°C. Ka for HCr04. at 25°C.) 4. (Le. Sketch the pC .? (b) How many moles of OH~ must be added to reach the pH for precipitation of Mg(OH). 5.) in distilled water at 25°C. What concentration of COl.affects the calculations.4 M Mg 2+? Sketch the pC.4 molelliter of SOi. and MgCO.). .4 moielliter of Mg2+ is raised to pH 12. C T•SUIl ~ [H. and that no other ions are present which will precipitate. 5 • Sketch a pC. determine the [COl-1 in equilibrium with 5 x 10-5 M CaH .pCOs'~ diagram for necessary to begin precipitating Mg 2+ as the carbonate in a solution containing 3 x 10. No further base is added.pOH diagram for Mg(OH).pH diagram showing the concentration of Fe2+ versus pH in a 25°C solution that is in equilibrium with solid FeS. PROBLEMS 1. what factors should be studied experimentally to determine the feasibility of the process? A 25°C water sample has the following species present in addition. OH. 3. Show how the formation of HCr04.. Sr2+. Make the simplifying assumption that the total sulfide concentration is 10. Given that 10-4 molel liter of 8rH and 10. 7.? (Assume negligible Ca2+ in the solution and that any other ions or molecules that are present will not react with H+. Using this diagram.Problems 313 6.9.6 .Cr04(. to other ions: [H+] ~ 1O~··' molelliter [HCO.S] + [HS~] + [S'~] ~ 1O~' at each pH).is 10.~] ~ 1O~'moleliiter 2. and that there are no Fe(ll) complexes present at significant concentrations.or the carbonates).are originally present and that pKso ~ 7. (o) How much Sr 2+ will precipitate (moleslliter) if 1 x 10-3 mole Na2S04 is added per liter of solution? (b) H.and 8rH remain after precipitation? (c) Assuming that the residuals calculated in part (b) are satisfactory. Strontium. What will the equilibrium pH and Mg'+ concentration be? (Assume that the concentration is equal to the activity. [~gH] ~ 1O~4 molelliter (a) To what pH must the water be adjusted to precipitate Mg(OH).3 M at each pH.8 for SrSO~. 6. Some preliminary calculations are necessary to determine whether it is feasible to precipitate 8rH as the sulfate. The pH of a 25°C groundwater containing 10. is a heavy metal that frequently causes concern when it is present in water. and Ca(OH). To what level must the pH be raised to precipitate Mg2+ from a 3 X 10-3 M Mg 2+ solution? To what level must the pH be raised to reduce [Mg2+] to 5 X 1O~' M at equilibrium? At what pH will Ca2+ just begin to precipitate if [ea H ] = 1 x 1O~' M? Find the solubility of Ag.

the temperature = 25°C. pH = 9. Note: Consider that each addition is independent of the other additions.4.co3)' where CT. Calculate the precipitation potential for the water described in Example 6· 18. [Ca"].are important. Note that the calculated concentrations change very much with small changes in ll'2' Therefore an accurate value of ll'2 should be used.col represent the total concentrations of these species in a solution with p. 14. Include ionic strength effects. 5 atm.-. Q g. = 10. total alkalinity. HPO.6. and total hardness (assume no MgH is present)? A sample of this water is equilibrated with a P C02 = 10-3 . 5 atm (atmospheric conditions) and CaC0 3 (SO)' How much CaCO l precipitate (dissolves)? What is the new pH.co3 = 10. Precipitation and Dissolution Calculate the conditional solubility product for CaC0 3IS )' P s = (Cr. -. Water is in contact with solid CaC03. the temperature = 2S C. and [HCO. 2C r . IS.Ci! andCr. H. Indicate only whether the concentrations will increase or decrease. (e) CO. (c) KCl.PO. Q 10. ° Q 12. Discuss the implications of this change with respect to water treatment and the pumping of What is its pH. Assume that FeJPO. Ca5(P04hOHcs).PO" H.-]. When C r ..7. [CaH ] = 3 X 10-' M. Set up the equations necessary to calculate the solubility of calcium hydroxyapatite. and total dissolved solids = 250 mglliter.J2Is1 is the only solid phase present and that Fe'+. Assume that the only soluble calcium species is Ca 2+. FeOH+.Fe{W = 3C T •P04 ' Compare the diagram obtained with Fig.) Calculate the Langelier Index of a water with the following characteristics: total alkalinity = 8 X 10-' eqiliter. Equilibrium conditions exist. Q 13.J2{SI can be precipitated alone or whether Fe(OHh{SI andlor FeC0 3(sl are also likely to precipitate. (a) KOH. 11. .2. pH = 8.. The complexes that are of importance are CaHP04 and CaOH+. total alkalinity. Groundwater 25°C equilibrates with calcareous (CaCOJ rock in an atmosphere that has a CO 2 partial pressure of 10-1. in aqueous solution at 2S C. (b) Ca(NO. 6·11 to determine for the applicable conditions whether FeJPO. Include ionic strength effects. Fe(OH). Calculate the solubility of Fe3(P04)2{slas a function of pH and plot the diagram of pCT. at what pH will FeC0 3Is ) begin to precipitate as pH is increased? At what pH will Fe(OHhlsl begin to precipitate? The temperature = 2S C. What is the effect of small additions of the following on the calcium concentration and the total alkalinity of the solution? Neglect ionic strength effects. taking ionic strength effects into account.4 M and Fe2+ = 2 X 10. [Ca H). (d) Na.314 8. and PO+.fe{IO versus pH at 2S C. (Neglect ionic strength effects. [HC0 3-J. For this problem.). -..

1964. Addison-Wesley.Additional Readings 315 16.Interscience. Mass. Butler. Walton. Wiley-Interscience. A. List (but do not calculate) the equations required to determine the amount of Ca(OH)2 required to produce a saturated water from one that has a negative Langelier Index. The Formation and Properties of Precipitates. Macmillan. New York. Morgan. Stumm and J. E. 17. 1967. N. ADDITIONAL READING J. G. Ionic Equilibrium. W. New York. Kinetics of Precipitation.. 1970. List the equations required to de:termine the amount of Ca(OH)2 required to produce a water with a theoretical precipitation potential of 5 mg/liter as CaC03 from one which has a negative Langelier Index. New York. Reading.10. Wiley. . 1. A. 6. 1964. Nielson. Aquatic Chemistry.

and sulfur dioxide. metals. Redox reactions are encountered in many of the analyses conducted on water and wastewater. and manganese in natural waters and treatment processes is largely influenced by redox reactions.2. Many of the chemicals employed in water and wastewater treatment processes are used to alter the chemical nature of water and wastewater constituents by oxidation-reduction processes. oxygen. and anaerobic digestion. for example. nitrogen. Oxidation-reduction reactions catalyzed by enzymes (microorganisms) form the basis for waste treatment processes like activated sludge. the application of redox reactions to various measurement methods will be discussed using electrochemical instruments as examples. Such microbially mediated redox reactions are also significant in transformations of nutrients.1. In this chapter we will examine oxidation-reduction stoichiometry. The applications of redox reactions to natural waters will be presented in the context of a discussion of iron chemistry. ozone. equilibria. and the graphical representation of simple and complex equilibria.OXIDATION-REDUCTION REACTIONS 7. The behavior of compounds containing carbon. permanganate. biological filtration. INTRODUCTION Oxidation-reduction or "redox" reactions playa central role in many of the reactions occurring in natural waters and in water and wastewater treatment processes. the biochemical oxygen demand (BOD) and the chemical oxygen demand (COD) tests and the analysis of dissolved oxygen are based on them. chlorine dioxide. hydrogen peroxide. and other chemical species in natural waters. such as chlorine. finally. a presentation of chlorine chemistry will include a discussion of the kinetics of redox reactions and the reactions of chlorine with organic matter. sulfur. REDOX STOICHIOMETRY The first step in solving any equilibrium problem is to determine the identity of the reactants and products and then to present them in a . iron. the subject of corrosion will provide a vehicle for a discussion of the application of electrochemical processes. and the rate of oxidation-reduction reactions. 7.

5. and heterogimeous equilibria using the principles of stoichiometry. Example 7-1 Balance the reaction in which ferrous iron (Fe 2 +) is oxidized to ferric iron (Fe 3 +) by permanganate (Mn04-)' which itself is reduced to manganese dioxide (Mn02(S)' The reaction takes place in alkaline solution. Identify the principal reactants and products. We will use this fact in our technique for balancing redox reactions. 7. Balance the charge with electrons. A redox reaction consists of two parts or half·reactions. . complex. 8. If it is known that the reaction takes place in alkaline solution. species other than H+. Working with each half-reaction. The coupling between the two half-reactions is by the electrons that are either generated (by oxidation) or consumed (by reduction). In this section we will learn how to write a balanced chemical equation for an oxidation-reduction reaction. which basically is a stepwise stoichiometric (mass) balancing of each constituent followed by a balancing of charge (electroneutrality). 4. Then to obtain balanced half-reactions. balance the atoms other than hydrogen and oxygen by multiplying the reactants or products by appropriate integers. An oxidation reaction and a reduction reaction must always be coupled because "free" electrons cannot exist in solution and electrons must be conserved. add the reaction for dissociation of water to the balanced equation to eliminate H+ and form H 20. in the oxidation half-reaction and the reduction half-reaction and write each half-reaction in crude form. . that is. 2. OH-.Redox Stoichiometry 317 balanced chemical equation. I. 3. we use the following procedure for balancing. At the beginning we will not inquire whether such a reaction is possible (this question will be answered later in our discussion of the thermodynamics of redox systems). Balance the oxygen using H2 0. Add the two balanced half-reactions. and H2 0. 6. Steps I to 7 will sometimes produce an equation that has H+ as a reactant or a product. In previous chapters we have seen how to do this for acid·base. Multiply each half-reaction by an appropriate integer so that both contain the same number of electrons. These are the oxidation reaction in which a substance loses or donates electrons and the reduction reaction in which a substance gains or accepts electrons. Balance the hydrogen with H+.

3.3Fe'+ + MnO"" +40H8. thus eliminating electrons 3 X (Fe H :.O + 3Fe'+ + MnO..O "" 4H+ + 40H+ MnO.::":Fe3+ Mn04.::": MnO 2(s) (reduction) 2. Fe 2 +:. .::...O + 3Fe H From this example we can see how a redox reaction is composed of the reduction half-reaction and the oxidation half-reaction.::":3Fe3+ + Mn0 2 (s) +2HP 4H. Fe 2 + ¢Fe 3 + 4H+ + Mn0 4-:.""Fe(OH)".)0 3Fe3+ + Mn02(S) + 2H:tJ The equation is now balanced.will combine to form Fe(OH)3(s)' Adding this reaction. Fe 2+ :. Fe 3+ and OH. we obtain the final equation.---.+ 4H+ + Mn0 4. 4H+ + 3Fe2+ + Mn04..::":Mn0 2 (s)+2H 20 5.. Multiply the Fe half·reaction by 3. 2H.::": Fe 3 + (oxidation) MnO 4.O + 3Fe" + MnO.-". In some instances it may be desirable to modify it to take into account other reactions and to make it more useful. We note that ferrous iron is oxidized (it loses electrons) and permanganate is reduced . The reaction takes place in alkaline solution. The reactants and products are Fe H :.+ 50H-""3Fe(OH)". as shown in steps (7) and (8). The atoms oHier than Hand 0 are already balanced.J 2H.+ 4H+ + MnO. e-. then add the two half·reactions..::."" MnO"" + 2H..: Fe 3+ + e3e.::":Mn0 2 (s) + 2H20 4. Further.:. Balance the charge with electrons.. + MnO"" This last step would not have been necessary if in step (1) we had taken Fe(OHhiS) as the product rather than Fe3+.:.:...:. Add the water dissociation equation to eliminate H+ as a reactant....::":Mn02{S) + 2H 20 6."" 3Fe3+ + MnO"" + 40H3 x (Fe'+ + 30H. we know that in alkaline solution..O 4H+ + 3Fe2+ + Mn04. Balance the oxygen with water.318 Oxidation·Reduction Reactions Solution 1. 7. 2H.: Fe 3+ + e-) 3e . Balance the hydrogen with H+.

" "D.Cr.O.+ 14H+ + Cr. remembering that we are dealing with an acid the half-reaction. Since the ferrous iron is donating electrons for the reduction of permanganate to MnO.250 N potassium dichromate. Conversely. " "Ozone.. of the organic matter . tlle equivalent weight of K2Cr 207 is its formula weight divided by 6... and for the oxidation of reduced iron or manganese salts to insoluble oxides .. We encounter these terms widely in water chemistry. that is. we balance the half-reaction. . charge.0315 6 .'- 0= 2C r J+ + 7H.O.. using the previously described technique.. . or precipitation standpoint bears no relationship to its equivalent weight in a redox system. which accepts the electrons from the oxidation of ferrous iron.. One equivalent weight of an oxidizing or reducing agent is the formula weight divided by the number of electrons taking part in the half-reaction. (dissolved oxygen) rapidly oxidizes an equivalent amount of the dispersed divalent manganese solution . also is used as an oxidizing agent for the destruction of organic compounds . 00. a knowledge of the specific half-reaction in which an oxidant or a reductant participates is needed to determine its equivalent weight and to make up a solution of desired normality. if you thumb quickly through Standard Methods for the Examination of Water and Wastewater.189. a potent germicide. you will discover statements such as "The chemical oxygen demand (COD) determination is a measure . is called an oxidizing agent.07 must be added to 2 liters of water to prepare this solution? The product of oxidation is chromic ion (Cr 3 +) and the reaction takes place in acid solution.. susceptible to oxidation by a strong chemical oxidant. The formula weight of K. " Before we proceed further we should address one more aspect of stoichiometry and the balancing of reactions. we state the relevant reactant and product: CraOi~ Cr3+ Next. This is especially important for some oxidants and reductants that participate in different half-reactions depending on solution conditions such as pH. is 294.. it is called a reducing agent. Example 7-2 A COD analysis is to be performed using 0. For this reason. .O Since there are 6e.Cr.. the question of equivalent weight (and normality) for oxidizing and reducing agents. For example.(".O. It should also be pointed out that the equivalent weight of a substance from an acid-base. Solution First. the permanganate. . Thus Equivalent weight = 294 189 = 49. How many grams of K..Redox Stoichiometry 319 (it gains electrons).

125 N potassium permanganate.250 N K. London. Using the result of this computation. the instructions only call for 4 glliter. Thus.O in which Mn04. What is the rationale behind the recipe for this solution? Solution We must find what fraction of the formula weight of KMn0 4 corresponds to the situation that 4 glliter KMnO. if there were one electron involved in the half~reaction.e .07 to I liter of water is stipulated.' + 4W + 39' "" MnO".125 N). KMn04' The instructions for preparing this reagent call for the addition of 4. However.75 g (or approximately 20 g KMnO. It is therefore poor 1 Analysis of Raw.259 g of K.Cr. If we let x be the number of electrons involved in the half-reaction. MnO.M.O This fits the bill.has an equivalent weight of!.O.250 eqlliter x 2 liter x 49. 0.O. Formula weight of KMnO.) to I liter to make a 0.516 g This checks nicely with the instructions given in Standard Methods for preparing 0. then and x = 5.. of the formula weight. The reagents for this test include 0.320 Oxidation~Reduction Reactions For 2 liters of a 0. we would obtain a solution with an entirely different composition. Dept. MnO.) + 2H. This raises the question of expressing concentrations of standard solutions (especially those used in oxidation-reduction reactions) in terms of normality.S. p. H.' + 8H+ + Sa' "" Mn1+ + 4H. had been used to compute the normality of the permanganate solution. = 19.0 9 KMn04 to I liter distilled wqter.75.125 N solution. of the Environment. Potable and Wastewater. '" 158 One eighth of the formula weight of KMnO. we would need to add 19. .and it takes place in acid solution.Cr. unless he made it up himself and can remember how much KMn04 he put in the bottle or unless he knows for what reaction the KMn04 is intended.0315 g/eq = 24. since it has Se. Imagine the mental anguish experienced by the chemist confronted with a bottle labeled I N KMn04' How does he know which reaction the normality is based upon? He does not.. we can see that if the reaction from Example 7-1. = 0. 125. 1972.250 N solution we require 0.-the addition of 12. Example 7-3 The United Kingdom Department of the Environment' proposes a test method for "permanganate value" in which a diluted waste is oxidized for 4 hours at 27°C by a dilute acidic solution of potassium permanganate. instead of!.125 eqlliter (i. Searching the literature we find the reaction where permanganate forms manganous ion.

.+ 2H+ + NaOCI .+ NH: Equivalent weight = formula weight of NH.5/2 = 25. on an "electrons consumed per unit weight" basis..Redox Stoichiometry 321 practice to label bottles with "normality. For CI"g.+ Na+ + H.CI.O In this reaction.. NH. The derivation of "percent available chlorine" is based on the half-reaction 2e.. (35. The strength of chlorine·con· taining disinfectants is often expressed in terms of "percent available chlorine.75 x 100 = 138 pergent. NH2Cl Half-reaction 2e. The half-reaction for NaOCI is 2e.5/2 = 35. Stated another way. .C]f2 = 51.5/37.5/25. and that the N in NH2 Cl is converted to NH4+? Solution 1.+ 2H+ + NH.5 g.5 g oxidizing agent to accept I mole of electrons.=! CI. Monochloramine." and incredible though it may seem.=! 2CI- in which chlorine gas is reduced to chlorine ions with the consumption of two electrons. each mole 'of electrons is associated with the formula weight of NaOCII2 = 37. In this equation the equivalent weight of chlorine is 2 X 35. NaOCI. we needed 35.5 g of CI.75 Percent available chlorine = 35.Cl and HTH is converted to CI-. there will be no confusion." If you lise molar concentrations or weight concentrations. for NaOCI we need 37..CI "" Cl. . on a weight-to-weight basis. we can say that each unit of oxidizing power (Le. each mole of electrons consumed) is associated with 35.25) X 100 = 95 percent as good as CI"g). We say that NaOCI has "95 percent available chlorine" meaning. NaOCI has 95 percent of the oxidizing power of C12{g)' Example 7-4 What is the percent available chlorine in (I) monochloramine. NaOCI is worse at consuming electrons than CI"g)' It is precisely. Ca(OCI)" given that the Cl in the NH. Now let us consider another chlorine-containing oxidizing agent. Therefore. HTH. sodium hypochlorite. for example. which is 70 percent by weight calcium hypochlorite. and (2) high test hypochlorite.25 g of CI.25 g to do the job.+ CI"g. some of these agents have more than 100 percent available chlorine. The equivalent weights of oxidizing agents play an important practical role in water chemistry in the computation of the relative oxidizing capacity of various chlorine compounds.

for 2 hours during which time some of the K. An indicator called orthophenanthroline is added.'. The balanced half·reaction for NHCl 2 shows that it can accept 4 moles of electrons.. to mass concentration as C12 • One mole each of HOCI. the excess dichromate must be measured. Half·reaction 4e.O 6 x (Fe'+ -> Fe'+ + e-) (7 -I) The dichromate is reduced to chromic ion while the ferrous ion is oxidized to ferric ion.322 2.O. Fe'+. When all of the Cr. The reaction products for the NH 2CI and NHCl 2 reactions are NH. OCI-.5 percent. just as Cl 2 can. However. To illustrate the situation.O. which forms a red complex with Fe'+ and thereby detects the presence of . NHCl2 .75 x 100 ~ 99.. Oxidation·Reduction Reactions 70 percent Ca(OC!).ng this digestion. The unit mglliter as Cl2 is commonly used in the water treatment field.O.3.'" 2Cr'+ + 7H. once we had balanced the half-reactions and written a complete redox reaction we still did not know whether the reaction could proceed as written.1. while NHCI. This reaction is utilized in the titrimetric finish of the chemical oxygen demand (COD) test. Followi. oxidizes the organic matter to CO. and water. OCI-.3 percent. OCI-. In this section we will explore methods for making such a determination and in doing so will use many of the concepts and techniques developed in Chapter 3.O" and ferrous iron. Thus I mole of HOC!. ~ 99.+ 4W + Ca(OC!). we will examine the redox reaction between potassium dichromate.'.3. Thus knowing the balanced half·reaction for a species allows us to convert to "mg/liter as C1 2• II 7.!4 143/4 ~ 35. K. Equivalent weight ~ ~ 2CI.has been reduced. REDOX EQUILIBRIA 7.O ~ formula weight of Ca(OC!). ~ 35. is equivalent to 2 moles (142 g) of CI. and NH2 Cl can accept 2 moles of electrons. For 70 percent Ca(OC!). or NH.75 Percent available chlorine for Ca(OC!).O. Direction of Reaction In the previous section we learned how to balance redox reactions.5/35. We use the concept of equivalents to convert from molar or mass concentration of a given chlorine species. and CI-. NH2 Cl. it is possible for Fe2+ to exist in solution. such as HOCI.3 percent x 701100 ~ 69.+ Ca" + 2H. The test consists of boiling a sample with a known amount of K.Cr.Cr.Cr.CI is equivalent to I mole (71 g) of CI. This is done by titrating with a standardized solution of ferrous ammonium sulfate (a source of ferrous ions) upon which the following reactions take place: 6e - + l4H+ + Cr.

From Table 3-1.O. the green turns to the red of the orthophenanthroline.8 and since tlGo = -RTlnK K = 10"" K is certainly large and the reaction should be displaced far to the right at equilibrium.6G(.H+ tlGo = 7(-56.. [Fe'+] = 10-4.-J+ . 7-1? The first approach would be to determine the standard free energy change. just like a stoplight changing.(-315. kcallmole o -315. The orange color of Cr.'Fe 2+ tlGt.52) + 2(-51.30) . as follows. K.O..14(0) tlGo = -77. to use Fe2+ as a reducing agent to determine the amount of Cr.52 -56.changes through an olive intermediate hue to the deep green color of the chromic ion and then suddenly. how could we be sure that the reaction would proceed as written in Eq.Fe3+ + 2AG'f. [Cr'+] = a solution.O. Q = [Fe2+]6[Cr. . aGO = 7 aG~. Neglecting ionic strength effects.6(-20. 3-13.AG'f.O.69) + 6(-2.69 Cr 3 + Fe3+ H.) If we were proposing.4 -20.Cr2o/.) Calculating the reaction quotient.6AG"Fe2+ .H2o + S. the larger the equilibrium constant.·4. Remember that the more negative the tlGo value.. [Cr..5) . (These are realistic concentrations for the situation that exists in an actual COD titration. Species H+ Cr.'.30 -51. we assume that the titration has proceeded a little way and that the reactant concentrations are [Fe'+] = 10-'.14. for purely aesthetic reasons this is one of the more delightful titrations to observe.'-][H+]" (10-')'( I 0-'.'.O(t) From Eq. Q.c.4) . for the first time.5 -2.Redox Equilibria 323 free Fe2+.O. tlGo of the reaction as written and determine if it was negative.'-] = 10-'" and [H+] = 10+1 .4)' (I 0-4)6( I 0-" ')( I 0" ')" 10.14AG'f.Fe2+ complex. (Incidentally.

we can see that t.'.Gl..Gl. 3·10 to calculate t. aGo = (7-3) 2AG'. in which direction a reaction could proceed spontaneously if they were combined.. it is often useful to consider e. 7-2 and 7-3 to produce overall redox equation..~ 8. do not exist in solution for a significant period of time.. 7.'-. 8.has. The reaction takes place in acid solution..2.0.G' + RT lnQ t.+ I~.Gl..G' values for each half-reaction and then add them to determine the value of t.AG'. 2 2 With e.8 + RT In 10-14 .. Free Energy and Potential 01 Hall-Reactions Our calculation has involved the overall redox reaction and thus far we have done nothing different from our previous thermodynamic treatment of other types of equilibria.ilG'. . For the sake of convenience it would be profitable to be able to examine any two half-reactions and judge from them independently.I.'.+ 2eFor Eq. Thinking one step ahead to the addition o~Eqs. 7-2.2.-.will cancel out so that it does not really matter what value a separate entity such as in a half·reaction just as we did for the proton in acid·base equilibria.'-.S2032- In both of these equations we need to know the value of the free energy of formation of the electron t.12(aQ) . 8. By convention. similarly to free protons. H+. Free electrons. However. which is itself oxidized to tetrathionate.ilG'.2 Thus the reaction is spontaneous to the right.3. Let us examine one of the steps of the Winkler method for determining dissolved oxygen (DO) as an example of this technique. t.we have a situation quite similar to the proton.324 Oxidation·Reduction Reactions we can use Eq.Gl.G = -77.e-.0. however.S40&2-+ 26. t.G at 25'C.0.G' for the complete redox reaction.) ~ 21(7 -2) 28. The two half-reactions are 2e. The proton is always attached to some molecule or ion in solution as is the electron.0. One way to do this is to determine the t.G'.G = t. The last step of the Winkler method is the titration of iodine ( assigned a value of zero and this assignment permits us to examine half-reactions independent of the overall reaction.e- - - and for Eq.qJ to iodide (1-) using thiosulfate. aGO = . 7-3.. 3 = -97.2AG'.

ies are at unit activity.3 + 2(0) .2(-127.0 3 ' 8 4 0. tlGo = -28. kcallmole o +3.93) . a transfer of e. We then introduce a piece of platinum wire into both containers and connect the platinum wires externally from the solutions through a high.1 Therefore. if we were able to isolate the oxidation half·reaction and the reduction half·reaction into two separate containers.through the platinum wire could be accompanied by a buildup of negative charges in one compartment and positive charge in the other. Without ion movement between the compartments.2) = +8. when Q I. assuming that the reactions in question can take place on the platinum surface.resistance voltmeter.2 -246. I".'.63 + 8.' the reduction of 12(aq) to 2I-. We have formed a galvanic cell .0. that is.0.'Thus for Eq.Redox Equilibria From Table 3·1.0. tlGo = 2( -12.q) + 28.'. We also ensure that there is connection between the two solutions so that ions formed in one container can eventually move to the other container and so maintain electroneutrality in the solutions.(+3. The electron transfer takes place between species in intimate contact all throughout the solution.1 -20. for the overall reaction. the voltmeter will register a voltage reading showing (I) that a difference in potential exists between the two electrodes. 8pecies e 12 (aq) 325 tlG . 7·2. 7·3.63 and for Eq.53 kcal Thus the reaction. Imagine. Because this would violate the electroneu· trality requirements. all of the participating species are in close contact with each other.3 18.35) . however.2(0) = -28. The electrons generated in the oxidation of 2S.93 8 40. As soon as we connect the platinum wires. tlGo = -246. the reaction would not proceed. In a well·mixed solution such as exists during the titration of I". The system is illustrated in Fig.0. 7·1.'.'. and (2) that electrons are flowing in the external circuit between the two compartments.35 -127."" 8 40.q) with 8.+ 21is spontaneous when all spec.

This reaction is the reduction of hydrogen ion to hydrogen gas: E' H+. Like ~G'.. Since it is not necesary for the reaction to take place in a cell... and E:. respectively. 7-1.. The cell emf for these conditions is the electrochemical version of ~G' for the reaction.= O. The E' values for various half-cells. cannot be determined absolutely. if all species are present at unit activity. This convention is consistent with the assignment of ~Gf.. E' is related to -nFE' . Like ~G.d are. in which the chemical energy of the redox reaction is converted into electrical energy.326 Oxidation·Reduction Reactions Voltmeter Ion 'ftransport I I Fig.. and the pressure is I atm. the symbol E' is often used in place of E.' values they are measured with reference to a particular half-reaction that is assigned an E' value of zero at 25'C and I atm. like the ~Gf' values for various species. the half-reaction potentials for the oxidation half-reaction and the reduction half-reaction. and is identical to it. we assign it a symbol of Eg. the redox potential can be split up into two parts. the temperature is 25'C. one for the oxidation half-reaction and one for the reduction half-reaction: E~ell = E~x + E~ed where E~. We call the potential that develops the electromotive force (emf) of the cell.. Iodine-thiosulfate cell. since we have previously stated that and E is related to ~G.. by ~G' = = 0 ~Gf = (7-4) 0 for H2(g) and ~G'.

e~ t. 25°. or per equivalent.500 coulombs/equivalent) For Eq.AGf. In this equation... or Faraday's constant. is (7-6) Voltmeter Ion "*"-' transport ---. 7·2. 3 The Faraday.H2(g) .Go = 0. The cell reaction for standard conditions. see Fig.. AGO = ~AGf... I I (r)~ 1 e~ 1/2 H2 !g1 -)- H+ + e~ 1/2 h!aq) + .Go = 0 .AG'f. is the charge per mole of electrons. Cell for definition of EO for a half-readion. The physical setup that defines EO for a half-reaction is a hydrogen gas electrode (Standard Hydrogen Electrode) connected to an electrode where the half-reaction of interest takes place (let us say the I"". and 1 atm H'2(9) pressure. 7-4.Redox Equilibria or 327 t. r Standard hydrogen electrode Fig. . EO = O.Ht.. 7-2).G = -nFE where n = number of electrons involved in the reaction (7-5) F = the Faraday" = 23.=: 21half-reaction.0 .0 Since t. nf represents the quantity of charge which is transported through a potential difference of E volts. unit activities.q) .06 kcal/volt-equivalent (or 96. + 2e. from Eq. 7-5.

Under these conditions the value ofEJ.72 -2...9 +2....:::-: Fe(s) Fe(OH)31" + 3H+ + e .:::-: NatS) Mg2+ + 2e..¢ 2Cr 3 + + 7H 2O Cr 3 + + e-..:::-: Cr 2 + Mn0 4 . and we will use it throughout this text. If EO is negative. the reaction will proceed spontaneously as written because AGO.44 +1.16 p€o( ~~IOgK) 0 -46. 2nd ed.0 +25.51 +1. and the EO value has a sign opposite to the standard reduction potential.:::-: Cu+ Volt 0 -2.23 +0. the half·reaction is written as an oxidation rather than a reduction..0 -7.~ Fe'+ + 3H. accepts electrons1 and that the reaction at the hydrogen electrode is an oxidation reaction. the EO value for the reduction half-reaction has a sign opposite to the standard electrode potential so that AG ~ nFE.5 +27.O + 3e..:= !H2(g) Na+ + e.~ Mn2+ + 4H.4 +17..59 +1. If EO for the reaction in Eq.O Cu2+ + e-. by W. the reverse reaction will occur spontaneously.41 +0. Note that the half-reaction of interest is written as a reduction reaction [I"".. Englewood Cliffs..J" 1952) employs a convention that is exactly opposite to that used here.S +13. 7-6 is positive and all activities are unity.. N. Latimer (Prentice-Hall.0 -40.0 +22.7 4 Not all texts use the IUPAC convention so that caution must be exercised in using values of EO taken from tables. M. .:::-: Mn 3 + Mn02tS) + 4H+ + 2e-..+ 14H+ +6e. TABLE 7-1 Standard Electrode Potentials at 25°C EO Reaction H+ + e-'.~ MnO"" + 40HMnO.e.+ 2H.33 -0.65 +1. The convention for defining the standard electrode potential value as EO for the reduction half-reaction was adopted by the International Union of Pure and Applied Chemistry (IUPAC) in 1953.77 -0.5 -6. for the reaction is negative.+ SH+ + 5e.:::-: Mn 2+ + 2H 2O Fe3+ + e. In other textbooks.9 +10.¢ Mg(s) Cr20/. Inc. the extensive presentation of half-reaction potentials in Oxidation Potentials.O Mn H + e-.06 +0.r is called the standard electrode potential and has the same sign as the emf of the cell of which it is a component. i..328 Oxidation-Reduction Reactions a_nd Therefore.' Table 7-1 presents a compilation of some EO values relevant to water chemistry.:::-: Fe2+ Fe2+ + 2e .37 + 1.9 +20. and thus AG. Notably.


O.O.-i> S.18) -2F(+0. = 0.3./I.44) 121aq ) + 2e . and that 12(aq) has a greater affinity for electrons than H+.+ 2e- -28.q. 7-2 and 7-3) and determine the value of nfE~. we added the EO values for the halfreactions to obtain the E~.Go would change..Go values for the half-reactions.. for the cell in Fig. This will always be the case when two half-reactions are added to give an overall reaction because the equations must be added so that the electrons cancel. This is only possible because the nf component of the term -nfEo was identical for both half-reactions.'. values. however.63 + 8. is more "noble" than H+. We can make a similar series of statements labout 1-. it is a weaker reducing agent than H 2{911 or it is less noble than H 2(g)' The standard electrode potential for the S. The positive EO value tells us that 1. when we compose a new half-reaction by adding two half-reactions.03'. This is exactly equivalent to adding ".Go previously determined. E~. This means that the reaction in Eq.::'!: 2S20:la~) + H~q) can proceed spontaneously as written when all reactants and products are at unit activity..3. that is. the overall reaction S40da~) + !H 2(9).Go = -nfEO and n = 1 rather than n = 2. the number of electrons involved in the reaction.44.q.o.. using the values of ".62) -2F( -0. is -+0. + S. For example. Note that the value of EO is independent of reaction stoichiometry.has less tendency to donate electrons than H""..---? 212S. However.62 volts..44).53 Since -2fE~. that is. The addition of EO values for half-reactions is not always correct.O. Combination of Half-Reactions We can now combine the two -half-reactions (Eqs..G°(kcal) -nfEO -2f(+0. the same number of electrons were involved in each half-reaction.q.18 volts. = -2f(0.. 12{aq) is a better oxidizing agent than H+.+ ts. In this example and in the previous computations with the cell involving the standard hydrogen electrode. the value of EO would still be +0. EO. Thus if the reaction had been written H". the value of ".half-reaction is EO = +0.half-reaction the standard electrode potential. In the terminology of the corrosion chemist we would say that I". 7. since ". 7 -6 will proceed spontaneously as written if all reactants and products are at unit activity.1 -20. that is.'-.330 Oxidation-Reduction Reactions For the I". Because EO is positive. For example. the EO value of the new half-reaction may only .03'. that is. ". 7-1 from the two nfEo values for the half-reactions.44 volts.'c -i> 1.'-/S..

77 volt (2) ~ Solution Adding (l) and (2).""Fe". The Nernst Equation Thus for we have confined 'our discussion to cells and half-reactions at standard state. To determine the effect of reactant and product concentrqtion. In simplified form it is.Fel. Fe" + e .F( +0. that is. 7-5 we see that E has the opposite sign to t.H..037 volt 7..". Example 7-5 Find EO for the half-reaction. From Eq.Feul + (-nfE'Fe 3i.3 RTIF has the value of 0.. thus if t.G ~ t. and unit activity for all species. since the term 2. (~ 331 -nFE") values.G is negative.3. Q. Using the free energy equation as developed in Chapter 3.0.G.Fe 2-J - 3FE~. we obtain -nFE}eJ+.059 Iog Q n (7-8) at 25"C. t.I:<} = -2F( -0. knowing that (1) Fe H + 2e. E is the cell potential and is a function of the reaction quotient. I atm pressure.44) .44 volt +0.G" + RT InQ -nF -nF -nF Substituting from Eq.77) ."" Fe". In all instances . we need to draw further on our analogy between free energy change and electrode potential or cell emf.E" -0.4. = -nFE'Fe2+.F. we obtain t.G" -nFEo values are additive.. -E . E is positive .G ~ t. 7-5 yields E~E"_RTlnQ nF which is the Nernst equation. EO EO ~ -0. 25"C. ~ E'Fe3+.G" +RTlnQ (7-7) and dividing each term in the equation by -nF.059.Redox Equilibria be computed by the summation of t.

at equilibrium.76 volt andE clJ 2+. INote that if we had assumed that CUtS) was oxidized and Zn 2 + was reduced. the cell reaction is Zn(s) 2e~ ~ Zn2+ + 2e~ + Cu 2 + ~ Cu(s) -2F(+0. Example 7·6 A Daniell cell consists of a zinc electrode in a zinc chloride solution connected to a copper electrode in a cupric chloride solution. E = 0.znl~\ = What is the equilibrium constant.10 volts.9) because. Q = K. E~ell would have the same absolute -magnitude but the . Conversely.Zn 2+ CI- Cu 2 + CI- + 2e Anode (negative) Cu2+ + 2e.10) Thus E~(!lI = + 1.-+ Cu cathode (positive) E~n2+.34 volt. and from Eq.34) -2F( +1.76) -2F(+0. Solution Assuming that Zn is oxidized and Cu 2+ is reduced in the cell. The application of the Nernst equation to the reactions that take place in an electrochemical cell and in solution is illustrated in Examples 7·6 and 7·7. 7·8 we obtain Eo=RT 1nK nF (7.332 Oxidation.Reduction Reactions and the reaction will proceed spontaneously to the right. If tlG = 0.clJlS> = +0. -0. of the cell reaction at 25°C? From Table 7·1. respectively. if LlG is positive. E is negative and the reaction will proceed spontaneously to the left.- \ Cu ~ Zn ~ K+ CI Salt Bridge Zn 2 + Zn . fr' Voltmeter .

5 X 10. After reduction of half of the Mn02(s) to Mn 2+ with 1-.yields 2I-~I21a'Il+2e­ 0 Mn02(S) + 4H+ + 2e. M .~Mn2+ + 2H 2 Then E~ell = Ef-'{21~Q) + E~ln02>Mn2+ = -0. when no current flows through the circuit.o:MnO.14 moleslliter) = 1. The following reagent concentrations and quantities Qre used in the determination: I.40 x IO-'M The reaction of Mn02(s) with 1.Mn' 400 giliter MnSO. MnSO.62 + 1.90 moleiliter (2 ml/300 ml sample)(0.2H..+4H++2e-) 4e.O x 10 -4 M) = 1.S(S.l = K (0.s) +4H+ Thus 8 mgiliter DO [= (8 mgiliter)/(32.Mn .23 = +0. The H+ concentration is approximately 1 M.61 .000 mg/mole) = 2. E q:nd from Eq.90 moleiliter) = 6 x 10-3 M Manganous ion reacts with DO to form manganese dioxide. 2 x (Mn" + 2H. KI: 2 ml of a ISO giliter solution per 300-ml sample volume.O: 2 ml of a 400 glliter solution per 300-ml sample volume.aQ)+2HP ~2Mn02l.+ 4H+ + 02(aq)~2H20 2Mn 2+ + 02l. The Mn02(S) is then reacted with I~ to form 12(aq)' Determine the E value of a solution that contained 8 mg DOlliter at a point when half of the Mn02ts) formed by reaction with DO has been reduced to Mn2+ by 1.43 x 10-' M ISO glliter KI = 0. 2.'2H.number 01 moles of MnO 2{S)niter = 1.O..{which itself is oxidized to 12(aqJ.4 = 5..O .O = 2.S x 10-' molesiliter] will produce 2 X 2.0 X 10-4 mole Mn02(S/liter.2 log K Example 7-7 The Winkler determination of dissolved oxygen involves the formation of Mn0 2 <sl by the Qxidq:tion of Mn 2 + with oxygen. CT.] At equilibrium. 7·8 we have 333 = 0 EO = + l. [Mn H ] = C T.43 x 10 -.~S9) = l'O+37.i I Redox Equilibria opposite ·sign. Solution Neglect the volume changes caused by the addition of MnS0 4 and KI solutions.14 molesiliter (2 ml/300 ml sample)(2.

for the reduction of cupric copper (Cu'+) to cuprous copper (Cu+).059 +0. to the overall reaction.][Mn '+J .-2-1og0.5 X 10-')(1. 2. We can make Eq.334 Oxidation·Reduction Reactions 1 mole of Mn02(s) produces I mole of I2(aQ)' Therefore.61 {Cu'+} and when activity effects are negligible. 2.2[1"".64 volt Thus the remaining Mn02(S) will continue to oxidize the 1-.5 X 10-4 M Mn02(S) produces .. we find that = ~ {Cu'+}(P H.16 = RT {W}{Cu+} 0.5 5.16 . For example. 7-8.I .16 .. Eq. we obtain = 0.4 M I2(aQ)' WJ ~ CT.. i EO Applying Eq.5 X 1O-3 M X lIT') and iJ i Q_ [I..4 X 10-') (1)(5.)[1 ]'[H+J' (2.116 +0. RT {Cu+} E = 0.5 X 10 3)'(1)' 0.16 . ) ' " Because {H+} and p" • "«g) are unity in the standard hydrogen electrode. 7-8 applicable to a half-reaction by writing the halfreaction in combination with the standard hydrogen electrode reaction. E = (7 -10) RT [Cu+] 0.116 Applying the Nernst equation.5 X 10.J = = 6 X 10-3 .{MnO". iCu'+] .2(2.

we will follow the common practice of referring to the potential E as E H (the redox potential) when the half-reaction is written as a reduction reaction.O What is the redox potential of this half-reaction.059 [ 10-3 ] -0.yin {Cu'+} RT {Cu+} Example 7-8 The half-reaction for reduction of sulfate to sulfite is (I) 80. The subscript H is used to emphasize that the potential only has meaning in reference to the standard hydrogen electrode reaction. we obtain EH =Eo . The value of EH for a halfreaction simply tells us the potential relative to the H+/H"g) half-reaction.059 1ogQ n = 0. is a function of the activities of the reactants and products of the half-reaction other than e-_ In the following sections of this book.04 for the reduction half-reaction. We must be careful not to use E H values for half-reactions in the same way as the E values for overall reactions.rnst equation for the halfreaction and the potentiaL E.+ H. . Eq.4 moles SO/-/liter at a pH of 81 Neglect ionic strength effects. 7-8. EO = -0.059 ( [80.16 .1og (10 8)'(10 4) -0.-2. the laUer reaction must be written as a reduction reaction.'] 0. we will follow the practice of writing the Nernst equation for half-reactions without explicit reference to the standard hydrogen electrode. 7-10 is written as EH ~ 0.04 . Using this nomenclature. E HI at 25°C if it takes place in the presence of 10-3 moles S032-/liter and 10.50 vol! = = Note that determining the potential of a half·reaction is the same as determining the emf of a cell in which one electrode is the standard hydrogen electrode and at the other electrode the half-reaction in question proceeds. Solution From Table 7-1. If the potential is to be called a redox potential.'- + 2H+ + 2e.-2. Eq.1og [H+]'[80.Redox Equilibria 335 Thus the Nernst equation for an overall reaction involving the standard hydrogen electrode is the same as the N'.~ 80 3' . Furthermore.'-] ) -0.0.04 . Applying the Nernst equation.

ionic interactions. + 2H. 7·8. H 2S0 4 = I M solution.6. For example. The equation is analogous to the proton balance and is based on the principle that electrons are conserved. Formal potentials. is whereas the Nernst equation using formal potentials is EH' = EOI _ RT In C T. and so forth.336 Oxidation-Reduction Reactions whereas the value of E for an overall reaction tells us whether or not that reaction is at equilibrium. For example. Eq. we obtain the electron balance by establishing an electron reference level (ERL) as the species that are either oxidized or reduced and with which the solution was prepared. In many solutions. the value of EO' changes as the solution composition changes. and acid-base reactions must be taken into account. for the half·reaction Fe 3 + + e.68 volts in a C u .:. Remembering this will eliminate much con· fusion in the use of E H values."mD represent the analytical concentrations of Fe(I!) and Fe(II!). regardless of the degree of complexation.::. was added. = 0. For example.3. however. The Electron Balance and Equilibrium Calculations In making equilibrium calculations for redox reactions it is often necessary to make use of the electron balance. In this example. Whereas EO has a value of +0. concentration can be used in place of activity and there is no need to account for the portion of the total concentration of a species that might be complexed. Fe 2 + the Nernst equation. In very dilute solutions in which there is no formation of complexes. E' and EO' are often used for this purpose and apply only to a given set of solution conditions.Fe(ID F CT.77 volts.3. ionic interactions. + 2e-->2CICl. respectively. Formal Potentials The E and EO values as used in the Nernst equation are defined in terms of the activities of individual species. when CI.. complex formation. EO' = +0.5. 7. is added to a solution.or HOCI was present before the CI. the following half·reactions take place: Cl.O and .O -> 2HOCI + 2H+ + 2eGiven that these half·reactions are the only ones of importance and that no CI. the solution was prepared with H. 7.1 M.Fe(JID where CT.h(II) and CT.

equations are needed. Since there are no other sources or sinks of electrons and given that no Fe 3 + or Cr 3 + was in the solution prior to adding Cr.1 M Fe'+ (in the form of ferrous ammonium sulfate).1 moleiliter)(0.Fe(lll) - (0.'6Fe2+ -> 6Fe3+ + 6e+ 14H+ + 6e . For this problem we can write the following equations.Fe(U)' Cr.02liter) T.'-.-> 2Cr 3 + + 7H.O.Cr. [H+J can be considered constant and it is thus not an unknown. Mass Balances number of moles of Cr liter (2)(0.01 moleiliter)(O.lliter) (0.'.O.02)liter = 0.O. each CI in HOCI has one electron less than the ERL.C T. Cr.O.>-< . Cr.68 volts P' = 1. Calculate formal potentials are Cr. Because 1M H2 S0 4 is used.1 + O."""" .0167 M (2) C .CrOin.Fe{lll).33 volts Solution There are five unknowns (E H Cr.and Fe'+' the electron balance yields Example 7-9 To 100 ml of 0. Thus the electron balance is [HOCI] = [CI-] In the oxidation of Fe'+ by Cr.CrOID' The EO.Fe - Than + C _ (0.FecrO' CT. in 1M H. CT. is oxidized or reduced so it alone is the ERL..01 M K.O The ERL is Fe'+ and Cr.02)liter = 0.0167 M Equilibrium Relationships E"=EO' _RT InQ nF .SO" add 20 ml of 0.'-.cr201' and Cr. Each CIformed has one electron more than the CI at the ERL.1 + 0.O.Redox Equilibria 337 CI" but only CI. = + 0. and C r.:.Fe(lm.cr2o) and thus five . One electron is produced for each Fe 3 + formed and three electrons are used in the formation of each Cr 3 +.

06) n CT.338 Oxidation~Reduction Reactions (3) (4) E' .05 X 10.68 _ 0.33 .Cr(IIO Because Cr20/.987 x 10-')(298) I CT.[H+]14 Electron Balance (5) CT.Feom -28 and when CT.2 C T.F. complexation.• (6)(23.(IO In C T.Fe= MO.06) n C T•C. The approach is extremely useful when working with redox equilibria in natural waters.56 x 10 ') ~ 1. Thus from (3) E' . 7. Thus CT. Cr20 7 = 5. and so forth.39 ~ 0.57 x 10-')' ] EH ~ 1.Fe(1l1 CT. CT. or C T. In addition.00427 In (2)14(5.39 volts At equilibrium.56 X 1O. ELECTRON ACTIVITY AND p.Feom = 0.I 33 _ (1.FeOrn = C r.987 X 10-')(298) I (CT.3 M Then from (I).0257 In C T.3 M and combining these values with equations (1) and (4) yields .0.Femn CT.. we see that our assumption of complete reaction was satisfactory. The concept of electron activity is used in the description of oxidation· reduction equilibria and especially in the solution of problems that involve both redox and other equilibria such as acid·base.FeOJlJ = a very strong oxidizing agent. [ (5. we can assume that the Fe 2+ which is added reacts completely.F. this concept provides a useful basis for the graphical representation of complicated redox equilibria.Feon = 10-12. EH for the Cr20/-/Cr3+ couple is equal to that for the Fe3+IFe 2+ couple.14 Substituting these val ues into the mass balances.crllllJ)' H. .o.0167 M.0l67) = 5."n H • (1)(23.57 X 10.0 68 _ (1.CdlIll = -iCT.Fe(In ~ 1.4.

K2 HA + H20"" H30+ + A-. M2+ + !H"" "" M+ + H+. and K. is for the acid dissociation half-reaction (with the proton on" the right-hand side of the. The negative logarithm of electron activity. pE (I) (2) (3) M2+ + e. Thus K3 = K. pH (I) (2) HA""W+A-. is analogous to pH. = {H+}{A -}/{HA} or where pH = -log {H+}. when problems are concerned with topics such as analytical methods and corrosion that involve electrochemical cells. It provides the datum to which all other acid base reactions are referenced. K2 K3 By convention. Thus K3 = K. pE is a measure of the availability of electrons in solution (even though no free electrons exist in solution). Whereas pH is a measure of the availability of protons in solution (even though no free protons exist in solution).K2 = K. it is often more convenient to work with potentials and the Nernst equation because this can be related directly to voltage measurements. For redox equilibria. and or pE = {M+} pEa -log {M2+} where pE = -log {e -} and pEa = log K " where K 1 is for the reduction halfreaction (with the electron on the left-hand side of the equation)."" M+.K2 = K. H+ + H2 0"" H30+. pE = -log {e-}. = -log K where K. !H"" "" H+ + e -. the ." We will instruct the reader how to readily use both methods interchangeably. K. Whatever the system or situation it is beneficial to know how to "do it both ways. The equations for the development of pH and pE can be compared. + log {HA} (3) K3 By convention. K2 = I. the negative logarithm of the hydrogen ion activity. For acid-base equilibria the proton exchange reaction between H30+ and H20 at standard conditions is assigned a free energy change of zero and an equilibrium constant of unity. {A-} pH = pK.Electron Activity and p€ 339 However. K. K2 = I. equation). and pK.

Taking the reduction of ferric ion. = log {Fe3+} .340 Oxidation-Reduction Reactions reduction of H+ to tH 2(g) at standard conditions is assigned a free energy change of zero and an equilibrium constant of unity.77 K. we can write for reaction (3) {Fe'+}) il.3RT) 16. we can write EO.9E H (7 -14) FEo PEo (2.Go + RT In ( {Fe3+} and (7-12) EH=EO~(:. as an example. we find that pE = (2.log {e } Setting pE = -log {e-} and PEo = log K" we find that {Fe2+} pE = PEo .:RT) EH=C.} = I. Fe2+.log {Fe3+} (7·11) pE = PEo = log K. to ferrous ion.:RT) EO-log ~~:::~ Comparing this equation with Eq.3RT) FEH = 16. Fe 3 +. we obtain {Fe'+} _ log K.) InU~:::D Rearranging this equation and substituting n = I yields (7 -13) C.~ Fe2+ ~H2(9J ---7 H+ + eFe 3 + + ~H2(9) ~ +0. 7-11 for 25°C.= 1013 K. we have {Fe2+} K.77 0 +0. For comparison. volts (I) (2) (3) K =exp ( nFEO) RT Fe 3 + + e.G= il. knowing that {H+} = {H2(g. = {Fe3+}{e } Taking logarithms. It provides the reference point for defining pE.9EO (7 -IS) .= I K3= 1013 H+ + FeN Writing the equilibrium constant for (I).

Several useful pE relationships are summarized in Table 7-2. However.9E H at 25°C) (7 -18) and . thus its value cannot be used to indicate position of that half-reaction with respect to equilibrium.9 EO at 25°C) (7-19) where EH and EO apply to the reduction half-reaction.3RT) (= 16. contrary to the value of E for an overall reaction. Example 7-10 The pH of a stabilization pond effluent is measured in the field and found to be 7.3nRT (7 -21) = -tl. Also. pE and -tl. Again FEH pE = (2.GO PEo = 2. pE = PEo where n ! log ({red}) {ox} (7 -16) I p€°=-logK n (7 -17) where K is the equilibrium constant for the reduction half-reaction. The application of pE is illustrated in the following example.3RT) (= 16. Several pE relationships for use when more than one electron is exchanged are also summarized in Table 7-2. if two halfreactions in the same solution have equal values of pE. a similar development shows. For any half-reaction.Electron Activity and p€ 341 where 'Eo is the standard potential for the reduction half-reaction. A sample of the effluent is taken back to the laboratory by an . Note that pE only applies to a half-reaction. those halfreactions are in equilibrium. since tl.8 at 25°C. FEo PEo = (2.G -nFE.G 2.3nRT (7-20) From these interrelationships we can deduce that PEo is proportional to the free energy change accompanying the transfer of I mole of electrons from a reducing agent at unit activity to H+ at unit activity.

pE ~ PE° .3nRT -I1Go PEo ~ 2. From Eq.3RT ~ 16.pE . Photosynthesis occurred in the sample. and the sample? Solution We will solve this problem first using the equation.3RT ~16.-Iog K'~ 2.+ 4H+ + (2) redox potential (E H.2. ro _ ° {W} pE . from Table 7·1. what was the change in (1) p€.3RT Also Also FEH pE ~ 2.9EHat25°c ~ 16.O governed the redox conditions in the sample.3RT PE~ FEH 2.342 Oxidation·Reduction Reactions TABLE 7-2 p< Relationships For a multiple electron exchange reaction written as a reduction reaction ox + ne~ For a one electron exchange reaction written as a reduction reaction red.log .9EOat25'C ~ I FEo PEo ~ 2.3nRT inexperienced graduate student who had the misfortune to place the sample container in full sunlight in the back of a pick.8. (7·16). volts) of O~g) "'" 2H. Assuming that the oxygen reduction half-reaction 4e.up truck. the atmosphere above the sample was found to contain 40 percent oxygen and the temperature was 25°C.n {ox} where PE peo and ~ ~ where -log {e-} 10gK and -log {e-} I peo~-logK n PE~ FEo log K ~ 2.9E Hat25'C FEo PEo ~ 2. On arrival at the laboratory the sample pH was found to be 10. p€ method and then the Nemst The oxygen reduction half-reaction governs the redox conditions.3RT -I1G -I1G PE ~ 2.9Eo at 25°C pE ~ 2.3RT 16..3RT I " FEo . PEo ~ +20.log {M"} pE ~ ° I {red} pE .. 1.-I Iog P n ~(g) [R+I' .3RT -I1Go PEo ~ 2.

14 volt. ~ 10. we obtain E H~E.[H+]' ~ 20..).059) 1og { Po. not necessarily of the existing or imminent situation. like the graphical treatment of acid-base.8 ~ Hog 0.76 volt ~ For the sample in the laboratory.5 ~ The decrease in pE 2..8 -tlog [(O. 1 0.( -4. 1 \ EH ~ 1. 0.8 . ~ +0. In many cases.5.2 and Po.21)(~0 7.).059) 10. applying Eq.] ~ 12. 0.)'} ~ +0. The graphical presentations of redox equilibria are seldom simple because redox reactions usually involve .4 x (:o 10.33. we find that PE ~ 20.23 . For the oxygen reduction half·reaction. 7.76 . 7-8.log 0.23 volts.83 .1 1 pE ~ 20.21 x'{lO ~ 7.21 atm.83 P02 = When the sample is brought back to the laboratory.8.Graphical Representation of Redox Equilibria 343 Let" us asume that the stabilization pond effluent is in equilibrium with the normal atmosphere that contains 21 percent bxygen. natural systems are not at equilibrium from a redox standpoint.. and precipitation equilibria is helpful in understanding complicated problems and in obtaining approximate solutions to equilibrium questions. Knowing that the pH is 7.(0.62 ~ The decrease in E H ~ 0.4 atm and pH .5 2.[H+]'} 1 -40 From Table 7-1. ~ 12. og Po. For the field sample. The diagrams usually present an idea of what is possible.2.log 0. complexation..4 atm EH~ 1.8 and Po. EO ~ +1...62volt 0.059) ( ~ 0. pH ~ 7.10. For redox systems in natural waters the equilibrium condition is truly a boundary condition. pH 0. GRAPHICAL REPRESENTATION OF REDOX EQUILIBRIA Graphical presentation of redox equilibria.4 x 0010.23 .( -4.0. 10.).

which in logarithmic form is -logC T • F. we can show EHversus pC too. and the formation of hydrolysis products is negligible.- base equilibria. We proceed with the construction of this diagram using methods similar to those employed for preparing acid-base equilibrium diagrams. 7-19). for example.log [Fe3+] (7-22) = Mass Balance (7 -23) Like the pC-pH diagrams. The solution is maintained at pH 2 so that Fe3 + and FeH are the major ferric and ferrous iron species. 7-3). Although we use pE in our development of the diagram (Fig.pH predominance area diagram. PEo = 13.344 Oxidation-Reduction Reactions changes in solution composition other than electron transfer.log [Fe3 +] [Fe'+] 13 . The PE-PC Diagrams Let us first examine an aqueous solution at 25°C in which the halfreaction between Fe3 + and Fe2+ governs the redox conditions. Equilibrium Relationship (from Table 7-1) EO = +0. at 25°C. In this section we will first present the development of a simple diagram (the so·called PE'PC or EH"PC diagram) for a reaction that involves only electron transfer in a homogeneous system. neglecting ionic strength effects. " . 7.77 volt. Usually.1. Next we will consider the predominance area diagrams for presenting combined redox and aci9. pE pE = [Fe'+] pEa . Fig. . Finally. since pE has a fixed relationship toE. pE = 16:9 EH (Eq. respectively.0 From Eq. 7-3). There is a total analytical concentration of iron of C T •F.5. 7-16. the first equation we plot is the mass balance. = 4 (7 -24) Equation 7-24 is not a function of pE so it plots as a horizontal line at pC = 4 (line 1. = 10-' M. we will add a third dimension and consider systems with multiple phases using the pE. pH changes must be considered and often complexation and solubility equilibria must be superimposed on redox equilibrium diagrams to obtain a realistic picture of the situation.

Graphical Representation of Redox Equilibria 345 0 -5 0 +5 "" .0 Fig. = [Fe'+] = 10.2 E.2 I I 0 +0.4 I 0. For example.log [FeN] = 2 Thus at pE = + 15. 7-3.8 +1. Eq. 7-25 becomes 15 .pC diagram for a Fe2+/Fe 3+ system at 25°C.4 -log [Fe'+] = 4 (7-26) . C u . when pE = +15. Now we will develop the -log concentration versus pE lines for Fe'+ and FeH .2 I m '£ c • 0 c 0 0 o c- 15 . +10 +13 +15 [Fe 2 + J ~ 0 " 5 CT. From the mass balance equation. The pe. 7-22 becomes (7-25) When pE» PE' (= 13). [Fe3+] = 100[Fe'+] and therefore [Fe2+] is negligible compared to [Fe3+].fe .13 = log [Fe3+] . +0.2 I m 20 0. = [FeN] + [Fe3+] [Fe'+] with [Fe'+] » C u . pH = 2.2 I ~ m I " 10 . Eq.4 volts +0.6 +0. In logarithmic form Eq. 7-25 indicates that log [Fe'+] »Iog [FeN].

Equation 7-27 has a slope of + I and passes through the point (-log [Fe2+] = 4. 7-25 yields pE = -log [Fe2+] + 9 (7-27) which again is valid for the region pE » pEo.+ 4H+ + Knowing PEo = 02(91 ' " 2H. EO = + 1. I! is interesting to plot on the Same diagram two equations that show the redox stability limits of water. This line is plotted as line 3 in Fig. 7-3.3 I I.pH (7 -28) 2. I og Po. we can complete the diagram in the vicinity of pE = PEo as shown.23 volts 16. The straight line portions of each line are connected with the curved lines in the region approximately one pE unit from PEo. pE = I pE ° -. the -log {Fe'+] line is a horizontal line at pC = 4 (line 2. 7-26 in Eq.[H+]4 yields pE For pH I = = 20. . 7-3 as lines 4 and 5.8 + t log Po.O can be converted to oxygen. H.. 4e . (7 -29) 1- . These are plotted in Fig. pE = 13). 7-3).346 Oxidation~Reduction Reactions Thus in the region of the PE-PC diagram where pE » PEo.8 + t log Po. Eq. . By a similar type of reasoning. pE = 18. At high pE. However. log [Fe'+] = log [Fe'+]' and when we find or -log [Fe'+] = -log [Fe'+] = 4. I! is dashed in the region where pE is close to PEo because here the assumption that pE » PEo does not hold. Since the reactions of solutes we wish to examine take place in aqueous solution. respectively. this latter step depends on the slopes of the concentration lines. or under highly oxidizing conditions. Equation 7-25 shows that when pE = PEo = + 13. 7-16. is stable. Substituting Eq. we should know whether the redox reactions we are describing are possible while the solvent.9 EO at 25°C.action. a line for -log [Fe'+] versus pE and -log [Fe'+] versus pE can be developed in the region where pE « pEo. The half-r!. water. Fig.O. just as was done for the pC-pH diagrams for acid base systems. After plotting these points.

and pE ~ -2 . if FeH is to predominate and be in equilibrium with the O.O couple. line 7. 2H. pE Since PE' ~ + 2e-¢ ~ H2(g) + 20H-. 3. Solution 1.83 volt PE' . at pE values of less than 13.iH./H.O From Eq. this line shows that a solution in equilibrium with 0.21 atm has p€ = +18.: a solution containing 1O~4 M total iron? Does p€ change significantly when the pH is changed to 6? At pH 2 what partial pressure of oxygen would be in equilibrium with a solution containing lOS times as much Fe'2+ as Fe3 +? 2.Hog PH. the pE calculated using one half-reaction will differ from the pE calculated from the other half-reaction..9E' ~ -14 at 25'C. = 0.6. From Fig. The PE-PC diagram conveys the idea that both Fe H and Fe3+ have regions where they can be the predominant species in water at pH 2. 4. a solution in equilibrium with Po: At this pE..O half-reaction. 7-3 with -log Po.Fe complexes.. What are the predicted equilibrium concentrations of Fe2 + and Fe3+ under these conditions foI. Fe'+ will predominate whep. Neglect solids and hydroxo. on the -log concentration scale. (7 -31) which plots as shown. the oxygen partial pressure in equilibrium with the water couple is less than 10. Fe 3+ predominates.21 atm of oxygen at pH 2 has a pE ~ + 18. 7-16. For example. + pOH 16. If the pE is controlled Jjy the O.) Next the reduction of water to hydrogen gas must be considered as the lower bound of the stability field of water. the solution must essentially be stripped of dissolved oxygen. (Note: Two half-reactions taking place in the same solution may not be in equilibrium with each other. Fig. pOH ~ 12. . Example 7-11 1. 3.6. II not. 7·3.! log PH. What is the predominant iron species in oxygenated water at pH 2 and 25°C? Assume a" normal earth atmosphere and that the iron species are in equilibrium with the OiH 2 0 couple. pE ~ (7 -30) When pH ~ 2.Graphical Representation of Redox Equilibria 347 This equation plots as line 6 in Fig. However. X [OH-]' -14 -Hog PH. E' ~ -0.22 atm..

0.2.4 and [Fe"] = 10-'-'. We will illustrate the construction of a pE-pH diagram for the aqueous chlorine system. Ferric iron is still the major species and the equilibrium concentrations have not changed significantly from the standpoint of the iron couple. precipitation.6 From Fig. Since we assume that the oxygen couple is in equilibrium with the iron.6. at pE ~ +14. as we shall see later in our discussion of iron chemistry. the pE value of the 02/H20 couple will change because [H+] is involved in this equilibrium. [Fe'+] ~ 10. 7-3. 7-3.348 Oxidation-Reduction Reactions 2. The pE-pH Predominance Area Diagram The construction of a pE-pH or E IrpH diagram is the next step in complexity in the graphical representation of redox equilibria. There are two basic rules: I. Because the graph for P02 versus pE does not extend to pE = 7. 7. For the construction of such diagrams we must first state the ground rules for drawing boundaries between any two species. based on equilibrium calculations. we use Eq. 2. experiments show that. 7-29 to calculate P02 pE ~ +7 ~ +18. A boundary will be drawn between two species at the place where the concentration of the two species is equal. this will also be the pE value for the 021H20 couple. At pE ~ + 18. Boundaries will only be drawn between the two major species under a given set of conditions. From Fig. From Eq. on one side of the boundary. we ccrn state that although the equilibrium calculations show Fe3+ as the predomipant species at both pH 2 and pH 6. As the pH is changed to 6. at pH 2. 3. the kinetics of ferrous iron oxidation by oxygen plays a highly significant role in determining the form of iron found in oxygenated solutions of different pH values.6.17 .0. However. In such diagrams we establish areas of predominance in a pE-pH coordinate system for various species involved in redox. Just to whet the reader's appetite. one of the species predominates in concentration I- . 4. [Fe3+] ~ 10-' M and [Fe H ] ~ 10-'" M. [Fe"] ~ 10' [Fe3+] when pE ~ +7. P02 = 10-41 atm Thus Fe 2 + is only stable at minutely small partial pressures of oxygen and. 7-28 pE = pe" + ±log Po 2 -pH ~ 20.6 ~ + 14. Fe 2+ is essentially not oxidized in oxygenated solutions while at pH 6 its oxidation to Fe 3 + is rapid.8 . acid-base. Thus. and complexation equilibria.8 + ilog Po.5. should be oxidized to Fe 3 + when there is any measurable quantity of dissolved oxygen in water.

The necessary equilibria can either be obtained from Table 7-1. 7-4. For the aqueous chlorine system these are CI". if pE is above this line H. H 20 is converted to O"g)' If pE lies below the line. We have four basic equations to work with. we must remember to follow the golden rule -of always writing the reactions as reductions. At a given pH. on the other side. H2 0 is reduced to H"g). 7-4). At a given pH and a H"g) pressure of I atm. Fig. H20 is stable. In writing the redox equilibria. HOC!. . Combining these ground rules allows us to state 'that boundaries in apE-pH diagram are drawn at places of significant equality. 7-30.pH 0. The first thing to consider is the stability domain of water. For the reduction of water. the second species predominates. OCI-. ~ log PH.pH (7-32) In the pE-pH diagram this plots as a straight line. 7-28 pE At Po. + pOH pE = -14 + pOH (7 -33) This plots as a straight line in the pE-pH diagram (line 2.6 . and CIThen we set up equations in terms of pH and pE relating each species to each of the other species.21 atm pE = 20.. pE = -14 and when PH. decreases.4n the reactions of interest.O is stable.. = I. Next we must list all the species invoIved. = = +20.Graphical Representation of Redox Equilibria 349 and. the H2 0!H 2 line is raised thereby making smaller the area of H2 0 stability.q). As PH.8 + t log Po. or from combining the equilibria in this table. we have from Eq. 2H 20 + 2e . For the halfreaction.= H"g) + 20HFrom Eq. while if it is below this line. . if pE lies above line I. line I in Fig.

pKa = 7.+ H+ + HOCI "'" !Cl"aq. 7-4.6 "0 > w " i 0---10 -20~__~____L-__~____~__~~__~__~~__~ 0. 25°C. + H 20.8 1.+ Cl"aq. PE' = + 27..4 M = 2[CI"aq. C T•C . and ClHOCI and OCI- .2 14 Fig. CT.CI = 10.' in this example: (4) CT. "'" 2CI-.0 -0.6 -2 0 2 4 6 pH 8 10 12 -1.2 0. .4 M.Reduction Reactions 40~---r----~---'----'---.4 5 30 HOCI OCI- 1. PE' = +23. The formation of aqueous chlorine from hypochlorous acid: (I) e.350 Oxidation.0 The formation of chloride ion by the reduction of aqueous chlorine: (2) 2e.5 The value for the total concentration of chlorine-containing species. and HOCI Cl"". (3) HOCI "'" H+ + OCI-.CI = 1 x 1O.] + [HOCI] + [OCI-] + [Cl-] With these equations we must find relationships in terms of only pE and pH between Cl"".----'-----~---' 2.5 The dissociation of hypochlorous acid: I. The pe-pH diagram for aqueous chlorine.

pH -log 174 pE=24.log [HOCI] At the boundary.3 x 10 5 174 Substituting this value in the pE equation.pH .]I/[HOCI] is a function of CT.].]t pE = +27. 2[CI".] = 3. the ratio [CI""... [HOC I] = [CI"". therefore. in this region. arid HOCI From equation (J) we find o [CI"".0 .CI = 2[CI"".] + [HOCI] » [OCI-] + [CI-] Substituting in the mass balance. .( and OCILet us first work with the species in the higher oxidation state (i..CI .CI' Now.3 x 10-5 Evaluating the logarithmic term.]i pE = pE . CI 2(".4 Now at the boundary.4 and [CI"".log [HOCI][H+] or [CI" ..] = 10.0 .3 X 10-.q.. we find pE = +27.e . 3[CI"". we find [CI" . equation (4). J (3.]l [HOC I] [CI"". yields CT.]i CT.7-pH This equation plots as line 3 in Fig.2[CI" ...] + [HOCI] = 10..and CICI2(.pE --log[CI n 2(aq)] _ 0 (7 -34) .)1 3. when [HOCI] = [CI"". CI 2(. 7-4.Graphical Representation of Redox Equilibria 351 HOCland CIOCI. and CIFrom equation (2) we obtain I [CI-]2 pE. the belter oxidants) and thus develop the portion of the diagram at high pE.].

3 X 10-5 23.+ ~12{. 2[Cl""..-> CI. HOCI and ClAdding equations (I) and (2). when [HOCI] = [OCI-]. Thus pE pE When [HOCI] = = = ° )I [CI-] pE .4. we obtain (I) (2) HOCI + H+ + e .5 This line (line 5 in Fig. og [HOCI][W] +25.4 == 2[Cl.5.3 25.60 = + 1.SEo = +25.7 X 10-5 (7-35) This equation plots as a horizontal line (line 4) in Fig. = 10.4 - ~pH - ~ log ([CI-]/[HOClj) [CI-].O -F( + 1.and CITo relate OCI.39) (5) HOCI + W + 2e.q.-> e .q.and Cl-.O -2FEO EO = -F( + 1.q. = [OCI-] log [HOCI] 0 (7-36) pH= 7.50 and from Eq. 7-4.4 .CI [HOC1] + [OC1-]. we subtract equation (3) from equation (5).39) +1.] + [Cl-]. 7-15.+ H.! 352 Oxidation·Reduction Reactions In this region of the diagram. we find that CT. + H.60) -F(+ 1.5 -~ log 3. PEo = 16. and since [Cl". pE = +25.] [Cl".) -> CI- ~I".] + [Cl-] » Substituting in equation (4).tpH (7-37) This equation is plotted as line 6 in Fig.] pE pE = = = = [Cl-] 3. . 7-4.. OC1. HOCI and OCIFrom equation (3). To find the other chlorine species relationships we must use combinations of equations (I) through (3). 7-4) is a vertical line at pH = 7.

72 pe' = 16. . This line will fall somewhere between the OCI. 7-4. However. -RT In 107 .4 M Cr. We can now use reasoning to finalize the drawing of the diagram. -(3) OCI. and below line 4. Chloride ion is the stable chlorine-containing species in-the pe-pH range of natural waters.log [OCI ] pe = 29. 3. we have already shown that to the right of line 3. I.Graphical Representation of Redox Equilibria 353 L\.2 -79. C]..pH (7 -38) This equation appears as line 7 in Fig.q) disproportionates into HOCI and CI-. we have not yet dealt with the OCI-/CI2(") solution.+ H20.50) = -69.. Stumm and J.+ H 20. -2f (+1. [CI-] 29. (6) OCI. regions in Fig.1.4 E' =79.predominates over HOC!. since we are only interested in boundaries between predominant species.4/2f = + 1. Other advanced texts in this area (e. 1970) illustrate procedures whereby such diagrams can be drawn.¢ CI. 2. As G r. Below line 7.and Cl. CI.2 = -10. 5 Systems much more complex than aqueous chlorine are time-consuming to draw. log [OCI ][H+l' = . CI2(.' From the diagram we can draw the following conclusions for a 10. Again we are only interested in boundaries between predominant species and we must therefore terminate line 5 as shown..G' = -nfE' (5) HOCI + H+ + 2e. W. similar calculations show the pH value at which C12{aq) predominates increases.pH . J. CI2(. Thus we can save ourselves the time of establishing this line. below line 6.predominates over OCI-.. At higher pH values.¢ CI.q) as a predominant species only exists at low pH values (below pH 0). Aquatic Chemistry. Morgan. For example. 7-4. We can also ask why line 5 terminates at the intersection of lines 6 and 7. Wiley.lnterscience.1.+ H+ ¢ HOCI.+ 2H+ + 2e.cI increases. CI2{aq} is not a predominant species.9E' = +29.1 For equation (6) we have " [CI-] pe = pe .g.

OBe .9. which itself is reduced to chloride ion. For example. 2HOCI "" 2Cl- + 2H+ + 02(. -.5.the two axes of the diagram. 2. or E: H .+ 2H 20 This reaction is basically the oxidation of water to oxygen by chlorine."" 2Cl.CI' Thus the diagram in Fig. CI2(.+ 02{'Q) 2HOCI + 2H+ + 4e.CI = 10.4 was used in these calculations. The reaction proceeds only when catalyzed. Lines representing equality of concentration between significant species are sought in the form of equations containing [Be] and pH . the concentration of one species of a system can significantly affect the concentrations of other species that are present.3. To develop such a diagram. Only Cr. The overall reactions relating the species of interest are 1. It is the reaction that accounts for the "decay" of chlorine solutions that are exposed to sunlight.354 Oxidation-Reduction Reactions 4. HOC!.are stronger oxidants than O 2 in accordance with the reaction. as a variable. K = 15.4. it is necessary to combine half-reactions to form overall reactions. by ultraviolet light. S. 2H2 0 "" 4H+ + 4e . for example. can be most useful. Frequently. let us consider such a predominance area diagram for aqueous bromine species at 25" in which the diagram axes are pH and the negative log of the bromide concentration. HOBr "" OBe + H+. Other Predominance Area Diagrams In the previous section we used pH and pE as the coordinates of the diagram. 7-4 vary little with CT. 7-4 is generally applicable at other total concentrations as well. in this case a diagram with the concentration of that species as one variable.q) which is the sum of the two half-reactions. 7. Br2('Q) + H20 ¢ HOBr + H+ + Be.CI shows that the boundaries in Fig. The species are Br2{'Q)' Br. = 8. and OC1. together with pH as the other variable. HOBr. We will use a similar approach to that used for constructing pE-pH diagrams. but the use of other values of CT. thus eliminating pE.q). pK.

. 7-5. -4.4 = [W][OBcJ [HOBrJ . When [OBcJ = [HOBrJ.-J. 7-5. K = 10-8.4 which plots as line I in is necessary to combine equations (I) and (3).OBc and Br.4 When [HOBrJ = = . this equation simplifies to pH = 8. 7-5. To derive the relationship for HOBr and Br.. Or---r---~--. In logarithmic form we have -9. Predominance area diagram for aqueous bromine species at 25°C.Graphical Representation of Redox Equilibria 355 Possible relationships are HOBr and OBc HOBr and Br". log [BcJ = (7 -39) This is plotted as line 2 in Fig.7 + ~pH [Br.aBc and Br 2 (aq) Br2{aq) Br3- and HOBr and OBc are related by the Ka equation.----r---r---r---r--7T---' 2 '" 0 ~ T 3 4 5 0 2 3 4 5 pH 6 7 8 9 10 Fig. [HOBrJ 2 log [BeJ .pH + log J [Br. HOBr and Br.q.

4 _] [ r3 log [Be] '" pH -8. log (6 x 10-') When [HOBr] = = [HOBr] log [H+] + log [Be] + log O. 7-5.2pH + log-B = -17.2 pH + log [ ] = -16.22 + pH which plots as line 4 in Fig. Therefore.. 7-6) used as water disinfectants.16 .6 (7.] log [Be] = -8. we obtain [OBe] 210g [Be] . 7-5. we . 7-5 with those developed for the other halogens (Fig.3 M).q. From equation (3) we obtain the relationship between Br".2 = [Br 3 -] -log [Be] + log [B I2(aq)] log [Be] = -1.41) This equation plots in the region where [HOBr] predominates over [OBr-] so that it does not represent a significant equality and is therefore not shown in Fig.6 Br2(aq) (7-40) log [Be] = 2 pH . Using the same type of reasoning that was employed in the construction of the pE-pH diagram in Fig. 7-5).q. Combining equations (I) and (2). Seawater contains about 70 mg Belliter (~1O.2 (line 5 in Fig. 7-5. The bromide concentration of most fresh natural waters is oSl mgJliter.9 This plots as line 3 in Fig.356 Oxidation~Reduction Reactions Combining the relationship derived above for [HOBr] and [Br 3-] with equation (2). we obtain [OBe] log [Br-] . from this diagram we can conclude that in most natural waters bromine will be present as the undissociated HOBr. 7-4.[BO------:I 2(aq)] [Br". relationship. 7-5. From equation (I) we obtain the HOBr/Br.2 (7 ·42) This plots as a horizontal line at -log [Be] = 1. chlorine and iodine. 1. and Br3-. we can map out the significant boundaries in Fig. Comparing the diagram in Fig.

J. G. Johnson. and (3) the relative predominance of the undissociated hypohalous acid (HOX).1 M and pH below about 7. Mich. ed ..]. Predominance area diagrams for aqueous chlorine and aqueous iodine at 25°C. HOC! and HOBr are the . After D. Rubin.. 7·6. D. and I". progressively extend over a greater range of halide and pH values. see that bromine occupies an intermediate position as far as (I) the relative predominance of the trihalide anion (Xa-). Inc. 1974.. A. Treatment and Distribution.a M) and up to higher pH levels. la-is important at lower [1-] levels (> approximately IO. and (b) aqueous iodine. The Cia-species does not exist· as a predominant species within the bounds of the coordinates given. (2) the relative predom. (a) Aqueous chlorine.levels above 10-2 M) while Br". Bra-is important at Be concentrations of greater than approximately 10. inance of the diatomic aqueous halogen molecule [X""...Graphical Representation of Redox Equilibria 357 2 2 T 0 ~ I 3 HOCI OCI- 4 5 6 2 3 4 5 pH (a) 6 7 8 9 2 ~ ~ 0 3 T 4 5 5 6 7 8 pH (h) 9 10 11 Fig. Reprinted by permission of Ann Arbor Science Publishers. CI2 (". chapter in Chemistry 01 Water Supply. is only important in a limited pH range (below pH 3 and for Cl.• Ann Arbor Sci· ence. Taylor and J.

For our example we will use a Fe concentration of 10-7 M (5.' FeOH2+ Fe(OH)2+ Fe2 + I ! ! FeOH+ The task of diagram construction is broken down into four stages.and possibly OBc.6 p. HOI may be a major species. The pE·pH Diagrams Incorporating Solids The last step in complexity that we will explore in detail for the construction of diagrams to illustrate redox equilibria involves the ad· dition of heterogeneous equilibria to redox and acid·base equilibrium diagrams. We will illustrate this system with a pE. For an unknown system we would achieve this by searching' the literature for relevant reactions and equilibrium data. We will expand on this diagram later in this chapter during the discussion of iron chemistry. can be important species under natural water conditions-:. .5. 2. A concentration of dissolved component is selected and the stipulation is made that the solid/solution boundary is valid for the selected concentration of the indicated solution component.) Fe(OH)". Boundaries are construoted between the solids of interest if more than one solid exists. The complete solids·solution boundary (with various solution com· 3. .g Fel liter) although in the later discussion of iron chemistry several solid·solution boundaries are entered on a single diagram to represent different solution concentrations of Fe species at the boundary. but I". For example.358 Oxidation-Reduction Reactions major halogen species in oxygenated water at natural water pH values .) SOLUTION COMPONENTS Fe3+ I I I. ) I 7. SOLIDS Fe(OH)".q) can also be present in significant quantities.These species distributions are extremely important from the standpoint of disinfection efficiency. the ability of "chlorine" to kill coliform organisms is 80 to 100 times greater when the chlorine is present as HOCI than when it is present as OCI-. In this example the following components are of interest.4. Boundaries are constructed between solids and individual solution components. I.pH diagram for iron species in aqueous solution containing no anions other than hydroxide. First we must identify which solids and solution components are important. but never 01-. OCl.

We will not present many of the detailed considerations required for deciding significant boundaries between the various solids and species because this would needlessly complicate the presentation. To the left of and below these lines.+ predominance region does not appear. . Fe". 7-4. Of these 10 equations. For the region of the diagram that describes solution (away from solids predominance areas). 7-7. We next proceed to the solution equilibria. a third solid. we first enter in Fig. dissolved components predominate. 7-7. see Stumm and Morgan.. Wiley. These lines describe the boundaries of the two solids. Morgan.g. Next we refer to Table 7-3 that presents equations that interrelate all species and solids. 7·7 the stability limits of water that were established for Fig. only 4 are employed in the diagram construction. from a detailed study of the diagram construction. The region to the right of and above these lines is the area of predominance of the solids. 1970. below pE = -7. The rest describe insignificant boundaries. Along this line Fe(OH)"" and Fe(OH)2{. We now develop the diagram for the equilibria of the solids Fe(OH)"" and Fe(OH)"" with soluble species. Aquatic Chemistry. For a full description of the procedure for developing a diagram such as this using other types of diagrams as aids.' and Fe(OH)"".4 in the pH range 0-8). J. If we examine Fig. these equations apply only in specific regions of the diagram. 4. (metallic iron) may be formed (e. We would find. 6 W. the equilibria between solution components are plotted for all combinations of solution components.F' . At very low pE values.' To develop the diagram. + does exist but because of the selection of a solidslsolution equilibrium concentration. Significant boundaries are deduced as lines of equal concentration of solution components.ponents in different parts of the diagram) is constructed. When significant boundaries are in doubt. Stumm and J. CT. that only a few of these equations describe significant boundaries: moreover. we find that a Fe(OH). Line I is the boundary between the two solids Fe(OH)2{.lnterscience.Graphical Representation of Redox Equilibria 359 . (equations 12 through 21 in Table 7·3).' are in equilibrium with each other. The dividing line between solids and solution is based on a maximum soluble iron concentration of 10-7 M. they can be established by testing various pE-pH coordinates in the equations in Table 7-3 to determine the species of significance. However an area occupied by Fe(OH). of 10-7 and because of our rounding off of equilibrium constants. New York.S describe significant boundaries and are plotted in Fig. Of the 10 equations in Table 7-3 relating solids to soluble Fe-species. We will not consider this solid as part of the diagram.

/Fe(OHb+ Fe(OHhs.--+ Fe(OHhl'.2 +2.+] pc: "'" +17.log [Fe3+] p< ~ +9_25 .9 .4 -2_3 +17_9 +9. =-.2 .log [FeOHH ] pH ~ +2.3 . For Boundaries between Two Solids Fe(OHhs) + H+ + eFe(OH)2(S/Fe(OHhs) Reaction LogK +4_62 -15.=~cc./ Fe(OH)2IS/FeOH+ Fe(OH)z(siFe3+ Fe(OH)2(S/FeOH2+ Fe(OH)21".3pH .-~ '0" . For Boundaries between Solids and Solution Components Fe(OHbs) -7 Fe 2 + + 20HFe(OH)21&) + H+ ..-1-1og [FeN] pH ~ +4.--=--..log [FeOW] 5 6 7 8 9' lO' II' .::-.2pH .6 .log [FeOW] p< ~ +0_2 + 2 pH + log [Fe"] pc: "'" +2.1 +4..i) + 2H+ + e.--+ Fe 3 + + 30HFeOH2+ + Fe(OH):/ + H 20 FeN + 3H 20 FeOH+ + 2H 20 pH "'" +6./Fe(OH)2+ + e2H zO Fe(OHb(5)/Fe3+ Fe(OH)3(S.-:.-./FeOH2+ Fe(OH)31r.FeOH+ + 2H 20 Fe(OH)2Is1 -I> FeJ + + 20H.+ eFe(OH)2(S) + H+ .Fe(OH):..log [FeOH2+] p< ~ +6_9 + log [Fe(OH)'+] pH ~ + 1.2 + pH ..I log [Fe"] pH ~ + 1.5 .log [Fe(OH).2 -6_9 -37.6 -28_2 -2.6 .FeDHN + H20 + eFe(OH)2(SI. + H 20 pH + p< ~ 4_62 1" 2 3' 4 Fe(OH)21&)iFe2+ 2.lFe2+ Fe(OH)3(S/FeOH+ Fe(OHhs) _ Fe(OHhs) + 2H+ ---+ Fe{OHhsl + H+ --+ Fe(OHhs) + 3H+ + e.25 Equilibrium Statement (Figure 7-7) ~ Fe(OHh("..::-::--:------ ------- ----~~~-- '" '" C> TABLE 7-3 Equilibria and Equations for Construction of Aqueous Fe(II)-Fe(III) p€-pH Diagram (Figure 7-7) Line Number Boundary 1.

0 = = [FeN] .6 + log {FeN] pE 16' 17' IS Fe 2 +/FeOH2+ Fe 2 +/Fe(OH)2+ FeOH2-I- + H+ + e+ e- = + 15.7 .4 +4.7 pH pE +2.pH + log [FeOW] [FeOH'+] pH ~ +4.Fe(OH)z+ + H+ + e- Pe(OH)z + + H+ . Fe(OH)z + + 2H+ --.'] p€ ~ +l1..S +4.S + Uog [Fe(OH).TABLE 7-3 (continued) Line Number (Figure 7-7) Boundary Reaction LogK Equilibrium Statement 3.9 .4 -7.log [FeOW] [Fe(OH).log [Fe(OH).4 + pH ..log [Fe3+J [FeOH2+] [Fe3+J 12' 13' Fe3 +lFeOH2+ Fe 3 +lFeOH+ Fe 3 +/Fe(OH)2+ + H 20 + H+ -2. For Boundaries between Solution Components Pe3+/Fe 2 + Fe 3 + Fe 3 + Fe 3 + + e...5 -20.'] [Fe H ] Fe2+lFeOH+ Fe2 + FeN Fe 2+ + H+ [FeOW] pH = +8.5 .ZpH + log [FeN] [FeOH"] p€ ~ +S.pH + log [Fe 2+] [FeOH"] + 2H zO .9 -ll.'] pE = +20...2 -S._ Fe 3 + FeOH+ + H+ [FeOW] +4..S .1 -S. [Fe(OH).'] 7~7. FeOH+/FeOH2+ FeOH+ FeOH+ FeOHN + e- 19 20 21' FeOH+/Fe{OHh + FeOH2+/Fe{OH)2+ + H 20 -). '" ..4 + log + H 20 + e._Fe 2 + --'" FeOHN +13.S -15.1 pE = + 13... FeOHN + H 2O a Only these lines describe significant equalities and thus appear in some region of Figure ::..2 .log [Fe3+J 14 15 + 2H zO ---10 Fe(OH)2 + + H+ + H 20 + H 20 -> FeOH+ -)0 pH ~ +3.I..

Equation 21 (Table 7 ·3) states: [FeOH'+] while equation 8 is pH = = [Fe(OH). A small region would exist for Fe(OH). the area becomes so small it is difficult to draw in on the scale used.6 8 10 12 14 Fig.362 Oxidation-Reduction Reactions 22 20 18 16 14 12 10 8 Fe 3 + + 1.+ had our choice of solution Cu .+].3 Fe(OHhls) ~ .+] at pH 4.6 • ~ 6 Fe2+ ~ +0. when [FeOH2+] = 10-7 M. The pE.7.7 1. been smaller than 10-7 M. .3 -6 -8 -10 0 2 4 6 pH -0.t log [FeOH'+] which.pH diagram for a Fe(II)·Fe(III) system at 25"C. 7·7.2 +0.2 .9 +0. Thus the solid phase boundary with FeOH'+ is superimposed on the equality line between [FeOH'+] and [Fe(OH). reduces to pH = 4.j 4 2 o -2 -4 -0. One striking feature of the diagram is the large area occupied by Fe'+.

10-'. CORROSION Corrosion is the deterioration of metallic structures. When this is done the diagram is more complex but the rules of the game are the same. Fe'+. A further useful presentation is to draw more than one boundary between solid phases and solution species. Each boundary represents a different selected total solution concentration of iron (e. usually with the loss of metal to solution. the presence of all the components of an electrochemical cell is required.1. . in the absence of oxygen. Thus one of the corrosion products of iron is iron oxide (Fe. total carbonate carbon or total sulfur) must be specified. 7.6. However. It manifests itself in many ways including rusting. 10-'. The Corrosion Cell For corrosion to occur. February 1964. we will continue to present diagrams (some of greater complexity). 7-7 only considers the soluble species Fe'+.O"." presented at the 39th Annual Rural Electric Conference. Such diagrams help us to judge the solution concentration of species at various p€ and pH values. knowing that the reader will understand them and appreciate the time that it takes to construct them. An additional constraint is introduced in that the total concentration of anion (e.. cracking (or embrittlement) etc. 7. for this reason we will consider corrosion as an example of the application of redox chemistry or electrochemistry to a practical situation. This is as far as we will go in the details of diagram construction. The diagram for the iron system in Fig. species.g .6. Almost all types of corrosion can be explained in terms of electrochemistry (oxidation-reduction reactions). Dean "Corrosion in Irrigation Systems. O.g . 10-5 M. University of California. etc). In the later section on iron chemistry we will follow up on this observation. We will not present a detailed quantitative analysis of corrosion and the design of corrosioncontrol systems. it has been estimated that some 25 percent of the annual production of steel in the United States is for the replacement of material lost to corrosion'? All refined metals have a tendency to revert to a thermodynamically more stable form such as those in which they occur naturally on earth..) which is one form of iron ore. Davis. a 7 R.. There is an individual diagram for each specified anion level. and hydroxo iron . Other texts should be consulted for this type of information_ . Such diagrams become more useful (as we shall see in the section on iron chemistry) when other iron-containing solids and species such as carbonates and sulfides are introduced.Corrosion 363 From this observation we might suspect that. Corrosion is a costly and wasteful process. pitting. tuberculation. iron in solution has a very good chance of being present as ferrous ion. These components are an anode.

If anyone of these components is absent. An anode and cathode are sites on a metal that have a difference in potential between them. .I'' . yet both are electrochemical cells-<:md both will be subject to the reactions that go to make up corrosion.%~ DC charge) + H+ + 1402 -+Y2H2O Fig. Reduction (consumption of electrons) or deposition of metal occurs at the cathode. and an internal circuit or conducting solution (electrolyte). Features of a galvanic cell.+ H+ -). We have previously discussed a galvanic cell of this kind in Example 76. copper was the cathode and copper ions in the copper chloride solution surrounding the cathode plated out as copper metal.+ Cathode (positive charge) M2 + -+ M2 {sl DC /" e- '-Anode (negative '-e- e. a corrosion cell does not exist and no corrosion will occur. It is difficult to make the translation between this situation and that of a water pipe running through alternate marshy and sandy patches of soil. between the anode and cathode. Figure 7-8 illustrates the general features of a galvanic cell indicating the direction of current and electron flow. 364 Oxidation-Reduction Reactions I I I j. which consequently is negatively charged. or a connection between the anode and cathode. 7-8. an external circuit. i cathode. where zinc metal was the anode and corroded to form zinc ions. 7-9). The electrolyte is the water flowing .. The galvanized pipe is the anode and the copper pipe is the cathode.t+ Jf e. Persons accustomed to the laboratory will visualize an electrochemical cell as a beaker containing electrolyte in which to pieces of metal are immersed and joined externally with a wire. The oxidation (removal of electrons) or dissolution of metal occurs at the anode. - Volt- meter n Ml(S)~ M. That mystery often surrounds the process of corrosion is probably because of the hard·to·recognize forms that the electrochemical cell takes. which consequently is positively charged. We can visualize a similar situation existing when a copper water pipe is connected to a galvanized (zinc-coated steel) pipe (Fig.

local. Small variations in composition. 7-10. .Galvanized pipe (anode) Corrosion - • Current Soil (by ion transport) Copper pipe (cathode) Fig. These so· called "local·action cells" form because the surface of a piece of metal is not uniform. The moist soil surrounding the pipes is the electrolyte. through the pipe. we have the makings of a corrosion cell (Fig. adjacent anodes and cathodes on the same piece of metal. 7·10). If it is connected to a galvanized pipe in one residence and a copper pipe in a neighboring dwelling.Corrosion Galvanized (zinc) pipe (anode. The external circuit is the pipe materiaL and contact between the zinc and copper is required. the copper pipe is the cathode. local environment. Corrosion cells can be far more subtle. The common neutral wire is the external circuit. ::::=A. Corrosion cell between galvanized and copper pipes joined together. Corrosion cells can be produced by the interaction of small. electrical code states that a neutral wire must be bonded to a water pipe. corrodes) 365 Water Fig. and differences in the amount of stress and surface imperfections all may contribute to the creation of tiny areas of . The galvanized pipe is the anode. 7·9. Corrosion cell between galvanized pipe and copper pipe in separate residences. . orientation of the grain structure. For example.

The gas that bubbles from the surface of the iron is hydrogen being produced at the small local cathodes (Fig. (less subject to corrosion} when they are in an environment with oxygen present (the lower listing)..6.366 Oxidation-Reduction Reactions metal with different potentials. In general. but not exactly so. The anodic. Corrosion of iron in acid solution. the farther apart the metals. 7. and the metals within these groups can generally be used together safely (Le" without either one corroding significantly). If metals from separate groups are connected in a situation where a corrosion cell forms. differences in the external environment (such as the amount of moisture.) + 2H+ --> Fe'+ + H"g) (net) As we shall see later. 7-11. This is because the behavior of some metals from a corrosion standpoint is not solely dictated by differences in the electrode potential.2. For example. the metal that is highest on the list will corrode. The metals are listed in groups. The reader can prove this by immersing a piece of iron into a dilute solution of Hel. a piece of iron is covered with many tiny corrosion cells. At the higher position where they occur they are listed as "active". this list is in the order of decreasing oxidation potentials. and dissolved oxygen concentration) also can produce corrosion cells on the same piece of metal. cathodic. Therefore. and net reactions that are taking place are (anode) (cathode) Fe. . Basically." These metals become "active" (more subject to corrosion) when they are present in an oxygen-starved environment (the higher listing). 7-1I). the greater will be the potential for corrosion because the potential difference between them will be greater. at the lower position they carry the designation "passive. they are passive. chromium and stainless steel each appear at two widely separated places in the list. Fig. temperature. The Galvanic (or Electromotive) Series The galvanic series (Table 7 -4) is a listing of metals presented in the order of their tendency to corrode (or go into solution).

74 +0. ohms and 1=R E .5 -1. E=IR where E = potential difference. October 1963. Dean.345 +0. volts I = current. Orton and R.44 -0.Corrosion 367 TABLE 7-4 The Galvanic Series Anode Reaction MgH + 2eAP+ + 3eZ1"1(S) ---?o ZnH + 2eCcI.44 +0.Fe(s) ---?o CuH + 2eCr3+ FeH Gold Platinum + 3e+ 2eAg(s) ---?o Ag+ + eAu.44 +0.8 -1.136 +0." --> Cd2+ + 2eMg(s) A~s) ~ ---?o Anode Magnesium Aluminum Zinc Cadmium Steel or iron Cast iron Chromium (active) Stainless steel (active) Potential E' (volts) +2.25 -0. for direct current.76 +0.126 +0. "Swimming Pool Corrosion". J.68 +0.37 + 1. amperes R = resistance. The rate of corrosion (loss of metal) is proportional to the amount of current that flows in the corrosion cell.s) ---?o Au3+ + 3ePt(s) ---?o Pt 2 + + 2e---?o ---?o Source: M.44 +0.S) Cr(S) . O.42 Fe(s) Fe(s) Cr(s) Fe(s) S1"1(S) Pb(s) N~s) ---?o ---?o ---?o ---?o FeH + FeH + Cr3+ + Fe2 + + 2e2e- 3e2e- Soft solder Tin Lead Nickel Brass Bronze ---?o ---?o Sn2+ + 2ePb2+ + 2eNi2+ ---?o + 2e- Copper Silver solder Chromium (passive) Stainless steel (passive) Silver CU.40 +0. paper to San Francisco Bay Section of the National Association of Corrosion Engineers.74 +0. From Ohm's law we know that.

year I . Corrosion Reactions Reactions occurring during corrosion are conveniently divided into those taking place at the anode and those taking place at the cathode. The basic galvanic cell is illustrated in Fig.·5 Corrosion Loss by Various Metals I.'/ . '·12. leaves electrons behind in the metal.3.500 coulombs. Faraday's law states that the amount of a material that can be produced electrochemically is proportional to the amount of charge in COUlombs. and produces a negative charge on the metal. One equivalent of a material on a charge basis (Avagadro's number of positive or negative charges) is produced by 1 Faraday or 96.368 Oxidation·Reduction Reactions Thus the greater the potential difference (Le" the greater the separation in the galvanic series) and the lower the resistance.• 75 46 43 23 20 9 Carbon 6 2 .500 coulombs/equivalent) It F where F = the Faraday constant. r: I Metal Lead Copper Tin Zinc Iron Magnesium Aluminum lb Lost/amp. At anodic areas an oxidation reaction releases Fe2+ ions into solution. '.=: Fe'+ + 2eTABLE . The reactions may be (and usually are) more extensive and complex than the primary oxidation reduction half-reactions. That is. A coulomb is the amount of charge transferred when I ampere flows for 1 second.S. Fe .. . the greater will be the amount of current carried in the corrosion cell. Let us consider the corrosion of a piece of iron pipe. Number of equivalents reacted = current (amp) X time (sec)/(96. and t = time in seconds Table 7·5 translates Faraday's law into practical terms by indicating the pounds of various metals that would be lost from an anode of the metal in a corrosion cell with a current of 1 amp flowing for 1 year..

The electrons travel in the external circuit from the anode to the cathode.. the cathode reaction may produce water thus: 4e - + 4H+ + O"aq) :0= 2H.-8 Fe 2 + f r t . if no oxygen is present and pH becomes sufficiently high. These ions migrate through the electrolyte toward the anode. ferrous hydroxide will precipitate. Fe2+ + 20H. It is referred to as "hydrogen evolution corrosion.) In oxygenated water Fe'+ is converted to Fe3+ 4Fe2+ + 4H+ + O"aq) :0= 4Fe3 + + 2H.-• 2H+ + 2eCurrent Corrosion 369 et r- f _. which bubbles out of solution.ions appear. at the cathode they may react with H+ ions in solution to form hydrogen gas.t .O In both of these cathodic reactions. At the anode. 2H+ + 2e.:0= H"g) This is the reaction we mentioned previously in our discussion of the corrosion of iron in dilute He!. Galvanic cell for corrosion of iron. if there is oxygen in the solution surrounding the cathode.~ -.K' H (g) 2 Fe2 + Electrolyte rMetal less noble than Fe ~ Fig.- f Current .:0= Fe(OH)".O . " Alternatively. thus conducting current through the solution. 7·12. H+ is consumed so that the pH rises and significant amounts of OH.

).. Fig.. may form a thin protective coating over the metal surface. and possibly iron precipitates.. depending on the COl. FeN + C032- -> FeCO. both FeC03(') and calcium carbonate may precipitate HCO. red water results. Formation of pits and tubercules in the corrosion of iron pipe..) (siderite) Corrosion of an iron pipe under certain conditions can also manifest itself in the formation of "pits" and "tubercules" (Fig. under other conditions CaCO". + OW"" H20 + COlCaN + CO."" CaCO".'.) The iron and calcium precipitates together form the familiar knarled tubercules that surround the anodic areas where FeN dissolves to form pits. Also. 7-13). The OHproduced by the cathodic reaction not only may precipitate Fe(OH). [or Fe(OH)..) Fe(OH)". 2Fe(OH)".) and Fe(OH). ferric oxide. 7·13. The precipitate Fe(OH)"..) is much more soluble.) which is then oxidized to Fe(OH)3].) is sparingly soluble in waters with pH values above 5 to 6 while Fe(OH). . FeN may'precipitate as a carbonate solid.. sloughs of! the pipe into the water.."" Fe(OH)". which has the familiar red color of rust.) + 3H20 If the precipitate of Fe(OH).370 Oxidation-Reduction Reactions which in turn may precipitate as ferric hydroxide at the anode: Fe3+ + 30H.. In the locally high pH region around the cathode.) dehydrates to form Fe203.)..) "" Fe20.) but can also react with bicarbonate ion (alkalinity) in the water to produce carbonate ion. However.. Fe 2 + + 2 OH~ -> Fe{OHhlsl I " Pit F.concentration and whether oxygen is absent....

Concentration Cells If adjacent portions of a surface are in contact with a solution having metal ions of different concentration. In the anaerobic soiL At the interface between the pipe and the soil.) + H+ 7. a potential will develop that can result in corrosion. The black ferrous sulfide is produced by reactions. 7·14). we can deduce that the portion of metal in contact with the dilute solution will become the anode-it will corrode and cbntribute metal ions to solution. . The part of the metal in the more concehtrated metal ion solution will become the cathode and either metal ions will plate out on it or some oxidizing agent such as 0. To illustrate such a concentration cell let us consider the galvanic cell made up of a piece of zinc metal with two sites A and B (Fig. At the anode..4.6."'" FeS. Fe'+ + HS. 7-14. The ferrous ions produced at the anode react with sulfide present in the anaerobic soil (bacteria may reduce sulfate to sulfide in the absence of oxygen). will be reduced at its surface. Therefore.Corrosion 371 The exterior of iron pipes in marshy (anaerobic) soils are often coated with a black film of material that results from a mode of iron corrosion. Zinc concentration cell. Site Zn --->' Zn 2 + + 2eBarrier that permits passage of some ions (current flow) but maintains Zn 2 + ion gradient Fig. The corrosion process in such a situation will always tend to equalize the concentrations of metal ion by dissolving metal from the metal surface.

t>G is negative and the reaction is spontaneous as written. or in crevices.3RT log Q nF _ 0. Since oxygen is not produced by either the anode or cathode reaction. at Site B: ZnB'+ + 2e.0 From Eq. Oxygen participates in the cathodic reaction 0. a bacterial slime.2. which may be things such as a barnacle. E = E' . this is often referred to as "differential oxygenation corrosion. washers.-22 = +0. in contact with the lower metal ion concentration. we will write the reaction assuming site A to be the anode and site B to be the cathode.-> ZnB. for example. E' (volts) at Site A: ZnA -> Zn."" 2H. Site A. Common areas for differential oxygenation corrosion are between two metal surfaces. and then examine the resulting potential to determine if the reaction will be spontaneous as written.059 [Zn. and site B is in contact with a 10-3 M zinc ion solution.059 10. Also common is the area beneath various types of surface adhesion. the reaction in a differential aeration cell will proceed in a manner that tends to equalize the oxygen concentrations.76 -0. To prove this.'+] _ -0.1 ':1 l' 372 Oxidation-Reduction Reactions A is in contact with a solution containing 10. One of the more common causes of corrosion due to concentration galvanic cells is the presence of different concentrations of dissolved oxygen or hydrogen ion at different sites on a metal surface. 7-15. From the Nernst equation we can show that site A is the anode and site B is the cathode. When caused by dissolved oxygen. is the cathode.O Thus the part of metal in contact with the higher oxygen concentration . As with the concentration cell formed by two metal ion solutions of differing concentrations. is the anode and site B.'+ + 2e-. under rivets. neglecting ionic strength effects." Some examples of these situations are illustrated in Fig. or a piece of mill scale.0 .1.76 0.03 Since t>G = -nFE. 7-8.4 M zinc ion. in contact with the higher metal ion concentration.4 log [ZnB2+] 10g 10-3 . the corrosion will proceed in such a way that the higher oxygen concentration is reduced. + 4H+ + 4e. +0.

71 + 4H. /3. EO (volts) 2Fe --> 2FeB'+ + 4<>4<>- +0. Because 0.27 + 1. This is consistent with the observation that corrosion takes place underneath adhesions on metal surfaces. Underneath the barnacle the oxygen concentration is lower than outside the confines of the barnacle shell. Examples of differential oxygenation corrosion.O From Eq. Waters that have a high buffer intensity. 7·15. 7-15). also will have less tendency to develop regions of different pH. differences in pH have the same effect as 0.44 +1. 0059 [FeB2+]. concentration differences. A .+ + O"'O'A --> 2H. If we assume that the cathode is at A and the anode is at B. reduction depends on H+ concentration. E A =E A --'--log [0 ][H +)' 4 2(aqlp. Let us consider the example of a piece of iron with a barnacle growing on it (Fig. We will examine the tendency of the corrosion reaction to proceed at both locations (A under the barnacle and B outside the barnacle).Corrosion Bo[t low 00 Metal plate low DO Heta[ plate High 00 373 ~lOW / Barnacle DO / High DO Metal plate High DO::::~: ~£ Piece of mill scale Iron plate Fig. 7-8. and thus will not be as corrosive. will be the cathode and the metal in contact with the lower oxygen concentration will be the anode and will corrode. The ferrous iron and pH levels in solution at both places are assumed to be identical.

S.'+ + 4e2H 20 02(aQ)B~ +0.. E R = 0 and no corrosion would take place. Because there is oxygen at both sites. is the anode rather than vice versa. and [Fe..log [0 2(aQ1a ][H S +]' For the concentration cell. the potential is E R.71 From Eq.44 +1.374 Oxidation. Calculation of E Aand E Bfor this problem using typical concentrations such as [Fe'+] = 10-5 M. and if [O".+ 4Hs + + --'> 2Fe. Corrosion control functions by eliminating or reducing the effectiveness of one or more of these com· ponents. 7·8...'+].].. If E R has been negative.q)] = 10.].'+]' EB=EB --4. Corrosion Control We have previously mentioned that all of the components of a galvanic cell must be present for corrosion to occur. B would have been the anode.1og [0 2(aq)a ][H B+]'[Fes '+]' Given that the pH and Fe'+ concentration are the same at both sites..059 [Fe B '+].log [0 ][H +]' 2(aQ1A A 2(aQ1a S _ 0.'+] = [Fe B'+] .-4. by eliminating or reducing differences in potential between metallic sites.4 M and pH = 7 show that both potentials are positive.. it is necessary to examine the value of the relative potential.059 [0"..1 = [O". where ER = EB ~ EA = +0.q). .S. [HA +] = [HB +]. and by breaking internal or external circuits. Since tlG = -nFE.059 [Fe. Thus we can control corrosion by eliminating anodes and cathodes. Some of these objectives are achieved by subtle methods but the secret in corrosion .'+]' 4 log [0 ][H +]' . E R rather than • the individual values of E Aand E B' 7. [O"..1 [HA+]'[Fe. and since [0". o 0. 0..q). the free energy change is negative and there is a greater tendency for the corrosion reaction to take place when B is the cathode and A. the area of low oxygen concentration.Reduction Reactions Assuming the cathode is at B and the anode is at A.1 <[0".-4. EO (volts) 2Fe 4e.059 [Fe.27 + 1.

When aluminum is immersed in a dilute mineral acid. cannot be based solely upon the position of a metal in the galvanic series. however. accompanied by hydrogen evolution. The CI. The choice. The presence of chromates in the electrolyte will encourage the formation of 'Y-Fe. metal oxides. Some ions such as CI. Paints. They effectively protect the base metal beneath an oxide layer and render it "passive. and also aid in the pas. The City of San Francisco does not use aluminum light poles to the west of Twin Peaks because of the chloride content of the atmosphere close to the Pacific Ocean. next follows a heavily pigmented undercoat for the purpose of reducing the permeation of water to the metal surface (elimination of the internal circuit-the electrolyte). wrappings. Selection of Materials. Aluminum saucepans are dull and greyish after use because of the accumulation of the protective oxide film. finally a third decorative coat that is resistant to the atmosphere. that cling tenaciously to the metallic surface and block further corrosive attack or significantly reduce the rate of corrosion. cements. isolating the surfaces from corrosion. The most obvious corrosion-combating measure in this category is to select nonmetallic materials or materials low in the galvanic series so that they are more likely to become cathodic rather than anodic. can all act to combat corrosion by isolating either or both the anode or the cathode.Corrosion 375 control. occurs. bituminous materials." For example the presence of 12 percent chromium in steel renders the steel passive in an oxygenated environment because it promotes the formation of a thin but tightly-bound oxide layer. Painting for corrosion protection usually involves a thorough cleaning of the metal surface to remove any corrosion products followed by application of a primer containing a corrosion inhibitor such as zinc chromate or calcium plumbate.can penetrate the aluminum oxide film and promote corrosion of the underlying metal." A good example of this type of behavior is aluminum whose oxide is always present at an aluminum surface.ion can apparently aid in the release of aluminum ions. Under certain conditions some metals high in the galvanic series form corrosion products.age of the electrical current necessary to maintain corrosion. .03 on iron surfaces. ' I.· as in assessing a corrosion problem. Coatings. and precipitates. is to reduce the situation to basic principles. such as calcium carbonate. Corrosion is very slow beneath the film. 2. the oxide film is dissolved away and rapid corrosion of the aluminum. for example. possibly through the formation of soluble chloroaluminum complexes. Other metals also can be "passivated. For this reason aluminum is a poor choice of metal to be in contact with saline water.

) can lead to corrosion problems if the scale accumulation is excessive or uneven. if the same small hole were to develop in a protective coating on an anode there would be a tiny anode area and a huge cathode.. may not actually precipitate on the metal surface because of localized conditions in the immediate vicinity of the surface. 7-16). It should be kept in mind. Uneven deposition and poor adhesion of scale is a problem. when alkalinity and calcium concentrations Coated cathode with hole in coating Slow corrosion rate Coated anode with hole in coating Rapid corrosion rate Fig. The protection of metal surfaces with a thin layer of CaCO. However. a positive Langelier Index. corrosion will proceed at a very low rate from a large anode to a small cathode (Fig. . Coating metallic structures to isolate them from the corrosive environment is often practiced. or hole in a pipe develops rapidly (Fig. 376 Oxidation~Reduction Reactions I..) containing iron salts) is one of the objectives underlying the conditioning of municipal water supplies to have a slightly positive Langelier Index prior to distribution (see Sec 6-7). especially along buried pipelines that have anodic and cathodic regions. however. 7-16). Thus a water that has a tendency to precipitate. The electrons generated at the small anode could be rapidly discharged. The cathodic areas are wrapped. All the current is generated from a small area and a pit. for example. The coating of metal pipes with scales such as CaCO". that the pH immediately adjacent to a metal surface may be different from that in the bulk solution.) (or CaCO". 7-16. Corrosion control by coating cathodes.: I . that is. The rationale is that if a small hole develops in the coating on a cathode. The electrons generated over the large anodic area must be discharged to an oxidizing agent such as oxygen over a very small area.

Zinc sulfate can be used as a cathodic inhibitor. for example. "Investigations on the Corrosive Behavior of Water" Am. Div. I 4. 7-9) can be eliminated by inserting a dielectric coupling between the galvanized pipe and the copper pipe which effectively breaks the external circuit and eliminates the corrosion cell. The Zn'+ ions in solution will react with OH. silicates. Engr. The elimination of dissolved oxygen from the electrolyte will prevent these reactions from occurring. The presence of these chemicals in the electrolyte allows any faults in the metal surface or its oxide film to be repaired. Insulation. Steam degasilication is among the more common physical methods. 8 W.produced by the cathodic reactions or with carbonates to form sparingly soluble zinc precipitates that coat the cathode. 3. We have seen that the presence of dissolved oxygen is important in several corrosion reactions such as differential aeration corrosion and the cathodic reaction with H+ to produce H. Cathodic protection is the technique of con· 5. J. A wide variety of chemicals and water treat· ments are used for corrosion control. and nitrites promote the formation of a stable surface oxide on metals.O. Corrosion inhibitors usually act by forming some type of impervious layer on the metallic surface of either the anode or cathode that impedes the reaction at the electrode and thereby slows or inhibits the corrosion reaction. However this is not common practice because brass fixtures are used in nearly all systems instead of galvanized material. The corrosion cell that would develop in this case (Fig. hydrazine (N.). chromates. they may promote intense local allack because they can leave a small unprotected area on the anode where the current density will be very high. It is common industrial water treatment practice to deoxygenate waters for circulating heating and cooling systems and boilers.) or ~odium bisulfite (NaHS03 ) with cobalt as a catalyst. galvanized water service pipes to a hot water heater from which copper hot water lines emerge. Typical methods are to use sulfur dioxide (SO. Soc. Cathodic Protection. . If they are used in too small a quantity as anodic inhibitors. borates.H. or to use a degasilier. Stumm.' Thus scale may be washed off by the flowing water in the pipe and leave exposed metal areas where corrosion can proceed. various alkali metal hydroxides. It is often necessary to connect two types of metal. carbonates. 86: 27 (1965).r Corrosion 377 are low and pH is high. Chemical Treatment. For example. phosphates. Civil Engrs. Sanit.. This is particularly true of chromates and polyphosphates.

7-17.1. Good electrical connections (by soldering or brazing) must be made between the sacrificial electrode and the structure to be protected. adhere to the galvanized surface and render it passive. the carbonates and hydroxides. The oxidation of reduced iron minerals. the corrosion products of zinc.all of the structural components of interest into cathodes. the oxidation of metallic iron is an important corrosion reaction. The reaction kinetics of redox reactions will be discussed using ferrous iron oxidation as an example. Iron in Groundwaters Iron equilibria in groundwaters can be nicely modeled with a p€-pH diagram that includes the interaction of iron species with sulfide and . which from Table 7-4 one can see is the least noble (most anodic) of all the metals listed. 2. A galvanized pipe is a steel pipe coated with a thin layer of zinc. IRON CHEMISTRY The redox reactions of iron are involved in several important phenomena occurring in natural waters and water treatment systems. 7.. produces acidic waters and the problem of acid mine drainage. thereby increasing resistance to the current flow. Galvanizing is another form of cathodic protection. by using a so-called sacrificial anode electrically connected to the material to be protected. but it has a lower oxidation potential. By impressing upon the system a doc current of a magnitude that opposes the current generated by the galvanic corrosion cell.. scrap iron or graphite) is used as the anode. Moreover. Sacrificial anodes for galvanic cathodic protection are commonly made from magnesium. the zinc will corrode preferentially to the iron and so protect it. The oxidationlreduction of iron in soil and ground waters determines the iron content of these waters. The purpose of this section is to expand the discussion on the chemistry of iron and to use it as an example of redox reactions in natural waters. These two methods are illustrated in Fig. I! can be achieved in two ways: I. The anode material is anodic to the entire system (less noble than the material to be protected) and will therefore convert it into a cathode. To minimize the rate of degradation of the sacrificial anode.['I 378 Oxidation-Reduction Reactions verting. In this case a piece of metal (e. Since zinc is anodic to steel (Table 7-4).7. such as pyrite (FeS". 7. the external surface of the metal being protected is usually coated with a substance such as bitumin. As we have already seen in Section 7-6. Zinc is also utilized.7.g.). Redox reactions are intimately involved in the removal of iron from waters.

) has been reduced in size by FeS"" and FeCO"". 7-7).flow Fe2+ Original ~ is made cathodic relative to the scrap iron Original anodic (Original corrosionl area raj Original cathodic area Entire pipe is the cathode when connected to magnesium Original anodic area (corrosion) Original Original flow of e- - -- cathodic area H.O Ion transport Iron pipe through moist roil l (bJ Sacrificial magnesium anodes Fig.e.S = 10-' M). bicarbonate. = 10-3 M) and of total inorganic sulfur (C T.O ~ Entire pipe --+.CO.).Iron Chemistry 379 Sacrificial anode ~ ~ {moist soil) Electrolyte H.. Another feature of this particular po-pH diagram is the presentation of several boundaries between solid and solution phases. Two more solids are evident: ferrous carbonate (FeCO". The stability region of ferrous hydroxide (Fe(OH). 7-18 has been drawn for a specified level of total inorganic carbon (C T. It is important to note that the diagram in Fig. each repre- . 7-18 bears some resemblance to the p€-pH diagram for iron species in pure water presented earlier (Fig. 7-17.J and ferrous disulfide (FeS". Cathodic protection with (a) impressed current and (b) mag· nesium sacrificial anodes. The diagram presented in Fig.

0 15 0. "Some Ferrous Iron. Solubility of iron in relation to pH and pE at 25°C and Chemical Relationships Among Sulfur Species and Dissolved I atm. .C" 1960. and the predominant iron·containing mineral is Fe(OH)". Hem. D. and 3.0 -5 -0.6 5 p' 0. Geological Service Water Supply Paper. Washington.8 10 Intake I would be for a shallow well that has its source of water in aerated (unsaturated) soil." U. These bound· aries range all the way from 10 M (570 g Felliter) to 10-' M (0.4 -10 -0. has been drawn on Fig. constant pH with depth will be assumed. Well K = I()3 20 1.6 -0.O. Such a "well.2 1. = 10-' M. D. CT " = 10-4 M.2 0 w I 0.S. one may visualize it as passing vertically down through the pE·pH diagram in Fig. The iron here is near equilibrium with atmos· pheric oxygen (oxygenated water). For our purposes. 7·18. 7·18.). When a well is drilled into the ground.57 mg Fel liter).8 0 2 4 6 pH 8 10 12 14 Fig. 7·18.2 -0.4 E 0 > 0. The iron content of the water is therefore governed by the equilibrium: Fe(OH)"5J + 3H+ "" Fe3+ + 3H." with three inlets labeled L 2. After J. CT.380 Oxidation·Reduction Reactions senting a different allowable solution concentration of iron.

+ 4W + 0. The iron concentration shown is more than predicted. no hydrogen sulfide determination was made.J. 7-lS) is in an intermediate zone between the Fe(OH)"" and FeS"" regions. Well intake 2 (Fig. In this region the mineral that controls the solution concentration 01 iron is ferrous carbonate (FeCO". but this may be due to iron contained in organic complexes.g Fe'+llitei is in solution at equilibrium (see Fig. The iron content of the well water will be controlled by the reaction K = 10-26 This reaction will allow the solution 01 less than I p. shows a partial analysis for this type of well water (Fe(OH)3(. they are potentially corrosive. This arises because we can treat the formation of an FeCO". 6. production takes place. only a fraction of a p.O) 2H. Table 7-6. but Cr.-. for example.giliter 01 iron assuming that S. the predicted iron concentration is approximately 20 mglliter. FeS"". K = 10-4 •4 At pH 6 and [HCO. -] = 10-' M.O + FeS"" 7 x (4e.' Zon". usually the mineral siderite. Well inlet 3 (Fig. content and a low pH value. Unfortunately.'. They produce waters with a low pH because they are often in the biologically active zone 01 the soil where considerable CO.+ 4H+ This equilibrium picture can be used to teach several lessons in well placement relative to water quality. ..7).Fe will not be greatly affecteq. FeCO"" + H+ ~ Fe'+ + HCO.'. ~ 2Fe'+ + 4S0.O + 2FeS"" + the only sulfide species. In this soil zone the iron is in the form of lerrous iron and the sulfur in the form 01 sulfide. Note also the increase in sulfate concentration in the well water lrom the FeCO"" zone. Thus waters in this region can have significantly higher dissolved iron contents than waters in equilibrium with Fe(OH)"" and FeS"" at a comparable pH. ~ ~ Fe'+ + 2S0. and they often contain traces 01 hydrogen sulfide. iron disulfide has precipitated. thus: 2 x (SH. 7-lS) would be for a deep well that draws water from soil that is in equilibrium with pyrite. The analysis lor this type 01 water shown in Table 7-6 shows only slightly more iron than predicted. Wells in the Fe(OH)"" zone have a high CO.'. In Table 7-6 is shown a partial analysis for this type 01 water.I I Iron Chemistry 381 The iron content of waters from this region is very low because at pH 6.. For wells drilled into the FeS"" zone one must make certain that the surface 9 Other polysulfide and sulfide species will exist in the same solution under certain conditions.). 9 Waters 01 this type have low iron contents and low sulfate levels.+ 16H+ + 14e-) 2H.-zone water as the oxidation of FeS"" to ferrous sulfate.

) zone. This will also prevent oxidizing water from the Fe(OH)".) zone so that oxygen-containing water cannot enter this zone.9 121 2. Chern. I: : I:. 53: 143 (1961). City of Pittsburgh.) zone." Ind.I· 7.2 62 213 378 7. Menlo Park.7. 700 ft. 23 ft.. Stumm and G.3 6 4. . (7-43) W. casing extends down to the FeS". the surface of the casing should be cemented to prevent corrosion of the casing in the Fe(OH).) Zonea FeC03 (sl Zone b FeS2{S) Zonee TDS (calculated). John D. Eng.' . b Lloyd justice.umho at 25°C ! II 0. Calif. Lee. Route 2. june I. . 1963.) zone. Na+ K+ Fe (total) HC03 SOlCISiO.3.6 24 \02 162 31 18 585 329 7. Dangerfield. 1961.5 0. july 16. pH units Ca2+ M g 2+ 163 4. and pumping is at a rate that keeps water above the screens from being drawn down into the FeS".S. At pH values of greater than 5. Screens for such wells are set only in the FeS". 641 ft.5 mi Southeast of Pittsburgh.0 0.18 55 22 0. "Oxygenation of Ferrous Iron.) a Center Point Community Center.3 3. since they will produce a water that is unacceptably high in iron.382 Oxidation-Reduction Reactions TABLE 7-6 Typical Waters from the Three Iron-Mineral Zones .5 the rate law for the oxygenation of ferrous iron is10 -d[Fe(II)] dt 10 k[Fe(II)][OH-]' Po. Acid Mine Drainage Reaction kinetics are an interesting aspect of iron chemistry in addition to the redox and precipitation reactions discussed in the previous section.2.).06 248 48 18 13 534 I i I' I Source: (Data provided by Dr. Specific conductance.9 ! I I i I I. In addition. Hem. Tex . 8. 1960. U. Well No. . '. The consideration of kinetics is very important in problems of waterquality significance such as acid mine drainage and the removal of iron from water. Geological Service.{. i Constituent as mglliter of Indicated Species Except Where Noted Fe(OH)". mglliter pH.) zone that it passes through. July 27. Wells should not be located in the zone where iron solubility is governed by FeCO".) zone from running down the well casing into the FeS". F.4 42 17 50 7.

= 1 X 10-25 (lfatm-min) at 25°C. Figure 7·19 shows that this is indeed true for experimental data at pH 5. This conclusion is at odds with the known phenomenon of acid mine drainage in which pyrite (FeS". when p~ is not a constant. At pH values below this the rate law appears to approach the form _ --=dc. (7·46) where k.mole') at 20°C" partial pressure of oxygen. 1970.min. at this pH.) in mine waters is oxidized very rapidly to Fe 3 + at pH values of 2 to 3. Fe2+ is stable in oxygenated solutions.5 or above. The rate equation can be transformed to -d([Fe(II)J) = k[OH 'P = -d In [Fe'+] ] 0. Indeed. This is an extremely slow rate of iron oxidation.Iron Chemistry where. below pH 5.[F:. Stumm and J. 534. Aquatic Chemistry. . dt OI. high iron. rate constant 8 (± 2.:l. 383 k = = = Po. so on this basis we conclude that. high TDS and with a brown-yellow color (Table 7-7). Morgan.5 the rate is negligible (half-life of many years). 11 W. Wiley~Interscience.5) X 10 13 liter'f(atm. atm From this equation we can see that the rate of ferrous iron oxidation is first order with respect to oxygen and Fe2+ and second order with respect to OH-. dt [Fe(II)] dt For a constant partial pressure of oxygen we have -d In [Fe2+] dt (7·44) k' [OH-]' = rate Taking logarithms of both sides and substituting Kwf[H+] for [OH-] we have log (rate) = log k" + 2pH (7 ·45) A plot of log (rate) versus pH should give a straight line with a slope of 2. New York. J.:'--.::n". high hardness.-+] =k. p.:e:. Such acid mine drainage gives rise to waters of low pH..

..___---'---. After P. Res. 7-19. k" ~ -d In [Fe(II)Jldt. ~ 0..----. and temperature ~ 25°C. + 12H+ (7 -47) (7-48) (7-49) 1.0 ~ /I -1. 14010·06169.0 1.O 4Fe'+ + 12H.---. Water Quality Adm" Water PoUn.:.---. Singer and W. Cont. Dept..0 -3.0 o / Extrapolation of Eq..O:.0 0.0 ~~ -2. Po. C.----.O:.0 L -_ _~_ _'-:-_ _.--. exposed to light. Stumm.=: 4Fe(OHh".. " i' i I· -6. Experimental points obtained in this study: 0.0.S.1 . + 4H.L_ _ pH ---:. 2. Fed.20 atm.0 o -4. of Interior.. The classical stoichiometric picture of acid mine drainage is 4FeS"" I' I + 140.'4Fe2+ + 8H+ + O. "Oxygenation of Ferrous Iron.=: 4Fe2+ + 8H+ + 8S0.J 1 2 3 4 5 6 7 i Fig. 7-44 -5.----. June 1970.0 / / / / . Rate of oxidation of ferrous iron by oxygen. 0 in darkness." U.384 Oxidation-Reduction Reactions 3. Series Rept.=: 4Fe3+ + 2H.

Iron Chemistry 385 TABLE 7-7 Water Quality from Roaring Creek-Grassy Run Watershed of Elkins. 7-20. "Autotrophic Bacteria and the Formation of Acid in Bituminous Coal Mines. I: 255 (1953).. are able to catalyze the oxygenation of ferrous iron. mglliter as CaC0 3 2. 12 K. .+ ISH+ (7-50) These classical stoichiometric statements do not give a true picture of what is happening in acid mine drainage. 12 moles of H+ (strong acid) are produced which then react with calcareous minerals in the soil to give rise to waters that have a high hardness and high total dissolved solids content. Delchamps. Parameter Concentration Range pH Mineral acidity. it has been shown that various microorganisms such as Thiobacillus thiooxidans. Thiobacillus ferrooxidans. Another reaction of importance in acid mine drainage is the oxidation of FeS"" by ferric iron (Fe3+)..o: 15Fe2+ + 2S0. Some pyrite is oxidized by oxygen to produce Fe2+ and this in turn is oxidized by oxygen to Fe'+. mglliter as GaC03 Fe. mg/liter Total hardness.3 204-980 3f>--260 34!l--1650 19!1--740 The net result of these reactions is that 4 moles of pyrite are oxidized to produce 4 moles of Fe(OH)3('" which causes the yellow-brown discoloration of the water. and Ferrobacillus ferrooxidans." Appl.. W_Va. The ferric ion may either precipitate as Fe(OH)3(" or be available to oxidize more FeS"" to Fe2+ by the reaction in Eq. Microbiol.+ SH+ + 8e- while Ferrobacillus ferroxidans mediates the couple.4-3.0: SO 1. W. Temple and E. A more accurate picture" is given by the scheme shown in Fig. this reaction is FeS"" + 14Fe3+ + SH2 0. From our previous discussion it would appear that the rate-limiting step in this cyclical oxidation of pyrite would be the slow oxidation of Fe2 + at low pH. Stoichiometrically. Thiobacillus ferrooxidans catalyzes or mediates the redox reactions of Fe2+ Fe2+ ~ Fe3+ + e- as well as 4H 20 + Sf" . 7-50. L. However. mg/liter SO. .

7-50. Stumm." From Fig." U. Res. June 1970. Water Pollution Cont. . that is. 7-49 will be present right at the site of iron oxidation. sulfide oxidation. 14010-06/69. 7.e .386 Oxidation~Reduction Reactions Fe82 {s) -4 Fe2+ + 8 2 2 ~--- +~ 0. they need only low levels of oxygen to survive. i.' precipitates generated by the reaction in Eq. As an oxidizing agent it is used for taste and odor control and color removal in municipal water treatment (oxidation of organics). Fig. Oxygen is only needed initially for FeS"" oxidation and the microorganisms that catalyze Fe'+ oxidation are microaerophiles. Chlorine is employed for slime or biofouling 13 I P. it is used for oxidation of Fe(I1) and Mn(lI) in groundwater supplies. As a disinfectant it is used in municipal drinking water treatment and for wastewater disinfection. C. Singer and W. . " ' The importance of microbial catalysis can be demonstrated by comparing the rate of Fe2 + oxidation in waters from a mine where acid mine drainage occurs with the rate in the same water that has been sterilized. 0. I . in domestic waste treatment its uses include odor control. "Oxygenation of Ferrous Iron. CHLORINE CHEMISTRY i'l . 7-20 we can deduce that once the pyrite oxidation cycle has started [i. The rate in the un sterilized water was shown to be about 10' times greater than in the sterilized water. 7~20.8. Mechanism of pyrite oxidation. in industrial waste treatment it is employed for cyanide oxidation. and disinfection.J further oxygen is only needed for the microbially catalyzed oxidation of Fe'+ to Fe3 +. An ample supply of Fe3+ for this reaction is guaranteed because Fe(OH)3{. ammonia removal. Series Rept. The observations made above have an important bearing on the methods for controlling acid mine drainage. Further FeS"" is oxidized by Fe3 + according to Eq.• once a small amount of FeS"" has been oxidized by O. Chlorine is used widely in water and waste treatment both as an oxidizing agent and a disinfectant.S. Department of Interior Federal Water Quality Administration. Sealing mines to keep out oxygen will not necessarily be successful for two reasons.

. 1974." chapter in Chemistry of Water Supply. ed. . are used for swimming pool disinfection.. and J. The chlorinated cyanuric acid will hydrolyze in solution to yield free chlorine.4'C. It can be compressed at room temperatures to a yellow-green liquid. 14 J. NaOCl. Butler. 1. HOC!. E. Chlorine is also widel y used as a disinfectant in swimming pools. J. Also in a role that may be regarded as selective disinfection.I I Chlorine Chemistry 387 control in industrial water treatment applications such as cooling towers and condensers. NHCI. Treatment and Distribution." At room temperature and atmospheric pressure. 7. Both the gaseous and liquid chlorine react with water to become hydrated. but also to a variety of other species including hypochlorous acid. "chlorine ice. Some undesirable compounds may be formed under certain conditions when chlorine reacts with organic matter as we will see in Section 7. NH. OCI-. Ann Arbor. CI"g).. At the present time it is most often used as a gas. hypochlorite ion. Morris. and dichloramine. A typical use is disinfection of potable water and wastewater. "Equilibria in Aqueous Solutions of Chlorinated Isocyanurate. CI =c! "c=o CI-N h ~ I N-CI I "C/ which is stable in the presence of sunlight.O. All these types of "chlorine" find use in swimming pool disinfection."below 9.!. N. organic chlorine~c. Forms of Aqueous Chlorine The term aqueous chlorine as it is used in water and wastewater treatment refers not only to the elemental chlorine species CI. and calcium hypochlorite or HTH (high-test hypochlorite).'8H. is a pale-green gas. Rubin. Ann Arbor Science Publishers. O'Brien.CI. C. Liquid chlorine forms the compound CI. Salts of HOCI such as sodium hypochlorite or bleach. chlorine is utilized for the control of filamentous microorganisms (bulking) in the activated sludge treatment of wastewater. A. or selective killing. generated from the vaporization of liquid chlorine stored under pressure..8. In addition. Ca(OCI)" are also used. CI.4. Mich .8. and several chloramine species such as monochloramine. Chlorine is used (or applied) in several forms.::ontaining compounds such as chlorinated cyanuric acid.

5.q.2 X 10-2 (7-51) . At pH values below 7. HOCI is about 80 to 100 times more effective at killing E.= HOCI + H+ + CIThe HCI formed is completely dissociated under usual dilute aqueous solution conditions.concentration.5 the activities {HOCI} and {OCI-} are equal.8.= CI~. This is of more than academic interest because the disinfecting ability of HOCI is generally regarded to be far greater than that of OCI-. CI".4 (7-52) Equation 7-52 is a combination of the two half-reaelions. I.q) + H 20... on the other hand. e . Distribution diagram for chlorine species. value it can be deduced that at pH 7. This is often referred to as disproportionation. I:i f KH = 6.I Ii I I 388 Oxidation·Reduction Reactions Chlorine gas dissolves in water thus CI~g).= HOCI + H+ + CI-.... 7-52 and 7-53 it is evident that the relative amount of the various oxidized chlorine species is a function of pH.] + [HOClj + [OCI-j. I I' I . HOCI.= HOCI + H+ + eCI".is the predominant species.". or OCI-) is plotted versus pH for a fixed CI. [CI-j C w = [CI. i' pH Fig. 7. reaels with water.5 From Eqs..q) + H20. Chlorine Equilibria As we have seen previously in the development of pE-pH diagrams. 7·21.q). with one atom being oxidized to CI( + I). Kh = 4 X 10.+ ~C12(aQ) ~ ClH2 0 + ~CI". I f'. OCI. CI". the other being reduced to Cl( . .q). coli than is OCI-. . Figure 7 -21 is such a diagram for i I I' .I). 25°C. = 7. = 10-' M.q). Hypochlorous acid.2. is a relatively weak acid: (7-53) pK. We can illustrate the distribution of the various chlorine species with pH using a distribution diagram in which the fraction of the total aqueous chlorine that is a particular species (CI". From the 25°C pK.5. HOCI predominates while above pH 7.

Distribution diagrams for (a) aqueous bromine and (b) iodine at 2S'C. Fig. HOCI and OCI.Chlorine Chemistry 1. 6 pH CT.J 0.L____ 8 pH ~~~~-L ____ ~ 2 4 (b) 6 10 12 14 [r] ~ 10-' M. For comparison.0 r------~ 389 . For bromine all three species (Br". With iodine only I"". HOCI and OCI.Br= 8 10 12 [8r2 1 + [HOBr] + [08r-1 1..--------_ a H Q I[HOI] =-Cu C\':OI - =-- 0.aOE~'. The diagram for chlorine shows that in the pH range of natural waters (pH 6 to 9). CT. As we have previously mentioned. and HOI are important.are the major chlorine species. 7-22.q" HOBr and aBc) could conceivably be important species under natural water conditions.5 mg CI-/Iiter). . CI"M' is unimportant above pH 2. The diagram shows what previous diagrams in Figs."'" [08(.r~·[I.] + [HOI] + [01-] Fig.5 CT •Br o 2 (0) 4 [Br-} = 10.0.differ greatly in their disinfecting ability so that pH control can be a critical factor in determining the degree of disinfection achieved by a certain level of chlorine.4M.. 7-4 and 7-6 (pE-pH and predominance area) have hinted: under typical natural water conditions. the relative amounts of HOCI and OCI.are very sensitive to pH.5 [On Cu O~ ____ ~ ______ ~~ __. 7-22 shows distribution diagrams for the other two halogens used as disinfectants (bromine and iodine). a fixed [CI-] of 10-3 M (35.

and OCI~ ~ Since CT. if chlorine is dosed as a salt of hypochlorous acid: NaOCI--> Na+ + OCland OCl. What dose of chlorine would be required to achieve the same disinfection efficiency if the pH of the water was 8. Disinfection effectiveness = concentration x relative disinfection effectiveness ~ 0..3.91 X 1.09 X 100 + 0.reacts with H.+ H.O ~ 2HOCI + 20W 1 . OCI- ~ 1.S.5.+ 2H.0.0 = 9.O ~ HOCI + OW there will be an increase in alkalinity to the extent that OCl.24 0.CI liter.76 = 0.7 times the dose applied at pH 7.5? Assume that HOCl is 100 times more effective as a disinfectant than OCl~ and that the temperature is 25°C. Solution From Fig.O.0.9 units per mg/liter of chlorine need 76/9.76 x 100 + 0. lXCI 2 lXHOCI = lXOCI- =O 0. HOCI ~ 0.B. ~ 1 mglliter as Cl. I· I 7. we would therefore ~ 7.09 t:¥OCI. The addition of chlorine gas to a water will lower its alkalinity because of the production of the strong acid and HOCI by the reaction in Eq. .0 = 76 units per mg/liter of chlorine From Fig. 7-21 at pH 7. Q'e1 2 = 0 = 0.24 mgl The relative disinfection effectiveness.= 0.76 mglliter as CI. The use of calcium hypochlorite (HTH) increases both the alkalinity and the total hardness (Ca'+) of a water Ca(OC!). 7-52: However.9 To achieve the same effectiveness of disinfection at pH B. Chlorine Reactions with Inorganic Species The form in which chlorine is added to a water affects some of the chemical properties of the water.390 Oxidation-Reduction Reactions Example 7-12 A chlorine dose of 1 mglliter as C12 satisfactorily disinfects a water at pH 7.. --> CaH + 20CI20Cl. 7-21 at pH 8. HOCI 100.24 x 1.91 (¥HOCI The disinfection effectiveness is ~ 0.

We say that the water has a "chlorine demand. for example. The reactions between chlorine and reduced inorganic compounds (e.chlorine residual The chlorine demand is the result of a va~iety of reactions in which chlorine is consumed by various constituents of the water and by decomposition. in groundwater treatment. I! we were to add (or dose) a water with a known amount of one or another of the forms of chlorine. Mn(Il). + 2Fe2+ ~ 2Fe3+ + 2Clor HOCI + H+ + 2Fe'+ ~ 2Fe3+ + Cl.+ 2H. Fe(l!). and then after a time interval (contact time) were to analyze the water for chlorine (the chlorine residual). Radiation in the ultraviolet region provides energy for the reaction of chlorine with water. we would find less chlorine present than we added. Cl"". precipitation) problems. and (4) those with organic compounds. The use of HTH as a disinfectant in swimming pools is not to be recommended because the increase in hardness and alkalinity that accompanies its addition can aggravate scale (CaCO. .~ 2Cl.Chlorine Chemistry 391 These consic.+ H.O proceed almost instantaneously at pH values near aI).lerations are important because they show that the form in which chlorine is added can affect the water chemistry in different ways. Sunlight. Reactions with Inorganics. chlorine demand = chlorine dose . We will consider each of these types of reaction in this section as an illustration of the importance of kinetics and reaction mechanisms of redox reactions. (2) those with inorganic compounds.+ 0. Bleach addition would' not cause such a pH depression. Thus when chlorine is used to oxidize ferrous iron to ferric iron.g. S(-II)) are usually rapid. The reactions of chlorine with water constituents can be conveniently grouped into (I) those promoted by sunlight. (3) those with ammonia. 1. 2HOCI + 2W + 4e.O ~ 4H+ + 0.O 2H.d above neutrality. NO. to a low alkalinity water could depress pH to an unacceptably low value." where after a certain contact time. + 4e2HOCI ~ 2W + 2Cl. unless you are interested in purchasing a bottle of salt solution.. that is. 2. the reactions. The addition of significant amounts of Cl"g. Aqueous chlorine solutions are not stable when exposed to sunlight.-. This reaction accounts for a major part of the chlorine consumption in outdoor swimming pools. It is the reaSOn why bleach is sold in opaque plastic bottles and it should be the reason that you should never buy bleach in a clear bottle "on sale" from your neighborhood supermarket. .

chlorine oxidation of sulfide tends to form polysulfides. The reactions of chlorine with ammonia and organic nitrogen are quite different from those of chlorine with other inorganic and organic compounds. No residual chlorine appears until all the Fe2+ has been oxidized to Fe'+. . Chlorine dose.. NO.+ 2H+ + 2e- + W + HOCI "" Cl. NO. When this has taken place.--Niliter will consume approximately 5 mglliter of HOCI as CI. and NO. chlorine reacts with ammonia to produce a series of chlorinated ammonia compounds called chloramines (Table 7·8) and eventually oxidizes the ammonia to nitrogen gas (N .)..-. It is a common complaint of operators of activated sludge plants that encounter partial nitrification that "It is impossible for me to maintain a chlorine residual.O HOCI + NO..392 Oxidation~Reduction Reactions 1'1 I " j.+ Cl. H.11).-."" NO.5 g as HOCI or 71 g as CI.(gJ or a variety of nitrogen·containing chlorine·free products (Table 7. When present at high pH values.5. we would obtain a plot of dosed chlorine versus residual chlorine like that in Fig. .+ H. Let us illustrate the situation with the most studied of these reactions-that between chlorine and ammonia. Simply stated. .+ W Each mole of NO. Reactions of chlorine with S( .or 14 g as N) oxidized requires I mole HOCI (52.(46 g as NO. chlorine residuals appear and the further dosing of chlorine results in the appearance of chlorine equal to the additional dose. 7·23. 7·23. in the effluent that chlorine will oxidize to nitrate. 3. Chlorine dose-residual curve for Fe2+ oxidation. Reactions with Ammonia."" NO.O 2e- + NO.all follow this pattern except that the reaction with Mn(II) only occurs at pH > 8."I' If we were to conduct an experiment in which a ferrous iron solution Was dosed with increasing amounts of chlorine. .. Mn(II). mg/liter Fig." Almost without fail this is because of the presence of nitrite. .9).. Thus each mg NO.

2 17. may be used instead. These "Cl. the two most common end products of TABLE 7·9 Possible Products of Oxidation of Ammonia by Chlorine Oxidation Products R r f Cl.I I I I Chlorine Chemistry 393 TABLE 7-8 Chlorinated AmmOJ.7 20. and the products vary with conditions such as the pH.O "" HOCI + H+ + CIa mole of HOCI (or OCI-) can be used interchangeably on a mole-formole basis with CI.O NHCl.5 N. + H. in ordeLto determine the required dosage to achieve the reaction.- 2.1 12.Cl NHC1. + H.0 J. + HOCI "" NCl. The oxidation of ammonia to the various end products listed in Table 7-9 requires different amounts of chlorine per unit amount of ammonianitrogen oxidized. These ratios are calculated from the pertinent redox reaction stoichiometry.0 2.O These reactions are written here in terms of HOC!. ratio of Cl.Cl + HOCI "" NHCl. Formation of the chloramines can be depicted as a stepwise process: NH". NH.O NH.7 15. NC1.0 3.3 N. For example.q) + HOCI "" NH.54 5. Since Cl. reduced alOO NH'N OXl'd'lze d 3Mole Basis Name Hydrazine Hydroxylamine Nitrogen Formula Weight Basis 2.5 3. + H. reduced to NH.Cl + H. and contact time. but CI. add_ed to ammonia present.O NO NO.0 .S1 10.lia Compounds Name Formula Monochloramine Dichloramine Trichloramine or nitrogen trichloride NH.OH 0. N.H.07 7.5 1.5 4. not completely understood. The reaction mechanism is complex.N2 0 4 Nitrous oxide Nitric oxide Nitrite Nitrogen tetroxide Nitrate NO.-N oxidized" ratios are given in Table 7-9 for each possible end product on both a molar and a weight basis.

I . and it occurs at a molar ratio of 1. Dose-demand curve for chlorine-ammonia reaction after approximately 1 hr at pH 7 to 8. + NH".+ 9H+ (2e - The chlorine reduced to ammonia·oxidized mole ratio is 4. the chlorine residual falls to a value close to zero. "" N0 3.CI + HOCI "" N2(g. which can be represented as 2NH.] dose to [NH3] molar ratio of about 1.O "" 8CI.0. 7·24).containing solutions (Fig. + 2NH 3"" N 2(g' + SHCI The chlorine reduced to ammonia oxidized ratio. The chlorine dose corresponding to this minimum is called the "breakpoint" dose.+ N0 3. mg/liter Fig.q.5 on a mole basis or 1. (7·55) Largely "free" chlorine Chlorine dose. depending upon solution conditions.q. + 3H.+ 9H+ + 8ei i i + CI.O or as (7 ·54) 3HOCI + 2NH3(. As the chlorine dose is increased further.5: I to 2: I. + 3H+ + 3CI.q. For oxidation to N0 3.+ 3H.3. 7-24. Chloramine formation and oxidation of ammonia by chlorine combine to create a unique dose·residual curve for the addition of chlorine to ammonia. [CI.we have 3H. As the chlorine dose increases. "" 3H+ + 3CI.+ H.O + NH~.Imole)/(J4 g NH 3 -N/mole) = 7. while on a weight basis the ratio is 4 X ft = 20. is t = 1.I[ I :: :1 ( i 394 Oxidation·Reduction Reactions ~mmonia oxidation are nitrogen gas and nitrate.5 X (71 g CI. for nitrogen gas we have 3CI.]/[NH 3 ].O + N"g. The primary reaction that causes the residual chlorine concentration to decrease and thus to form the breakpoint is the breakpoint reaction.S on a weight basis. "" 2CI-) x 4 4CI. the chlorine residual at first rises to a maximum at a [CI.

. monochloramine and dichloramine are produced (I.0 and that nitrogen is not eliminated until the ratio is equal to or greater than 1. Chlorine residual as a function of chlorine dose/initial ammonia ratio at near-neutral pH. and the formation of the known common oxidation products." As the chlorine dose is increased in excess of that required to produce the breakpoint. Il we were to examine the nature of the chlorine residual after the breakpoint. we would find that it is largely free chlorine with some combined chlorine. ' l .. the increase in dose can generally be attributed to the formation of some NO.e.r Chlorine Chemistry 395 These tIre not mechanistic representations but they do account for the observed stoichiometry of 3 moles chlorine' per 2 moles of NH" If the observed stoichiometry is greater than 3:2 (or 1. Following the breakpoint. free chlorine (HOCI and OCI-) predominate but some dichloramine and trichloramine may be in evidence. A similar plot for nitrogen-containing species (Fig.0 and thereafter decrease. A reaction mechanism must therefore describe the formation of chloramines and their subsequent disappearance. Prior to the breakpoint.and/or NCl" An examination of the nature of the chlorine residual present prior to the breakpoint will reveal that it is composed almost entirely of chloramines. A more detailed examination of the types of chlorine residual would produce the picture presented in Fig. the increase in residual chlorine will be approximately equal to the excess.5). -).0. 7-26) shows that there is no free ammonia present at CI. Prior to examination of such a mechanistic model for the breakpoint chlorination of ammonia. molar ratios of greater than 1. Free chlorine HOCI & ocr- Trace of NHCI 2 & Nel3 Fig. let us look at the rates of some of the important constituent reactions. 7·25. dose to initial NH.) and nitrate (NO. The figures further indicate that the chloramines increase in concentration up to a ratio of 1. 7 -25. nitrogen gas (N 2(g. and HOCI which are known as "free chlorine residuals. under the "hump" of chlorine residual). In the jargon of water chemistry these are referred to as "combined chlorine residual" as opposed to Cl" OCI-.

q)' From the rate law. Because of this influence of pH on the speciation of reactants.3).1 x 10' liter/mole-sec. 7-26. the reaction rate can be written in terms of the dissociation constants of HOCI and NH3(.CI(+I) = ' d[NH. Lowering the pH from 9 to 8 will increase [HOC1]. John Wiley. V. [NH3(.q. = 9..NH. and decrease [NH". Faust and J.q)]. 1967. C.NH.Cl] dt k. 15 HOCI + NH".CI(+1) where aHOCI = [HOCl]/CT. (pK. pH can be expected to exert a dramatic effect on the reaction rate..' d[NH. = 7. [NH3] where a. D. Since the reaction occurs between HOCI and NH". [HOCl][NH3 ] [HOCl] + [OCl-]. The reaction is first order with respect to both HOCI and NH3 and second order overall.Cl + H.5 1. [NH3 ]/C TN Then .NH. New York. (pK. "Kinetics of Reactions Between Aqueous Chlorine and Nitrogenous Compounds.cT. S.Cl] dt 15 J.q).j.q)] + [NH4+]' Then . eds.. = total ammonia concentration.0 [C1 2lOOse I[NH3-N]lnitial 2." in Principles and Applications of Water Chemistry. I The formation of monochloramine has been shown to be an elementary reaction as follows. Hunter. we find d[HOC1] dt Let CT.q) ~ NH.396 Oxidation-Reduction Reactions NH3-N plus chloramine-N NCh-N o 0. raising pH from the range for optimum reaction rate will decrease [HOC1] and increase [NH3(.' Let C TNH . . = = a.O (7-56) i.' :: ·1 ' with a rate constant of 5. H.0 Fig. Nitrogen residual as a function of the chlorine dose/initial ammonia ratio at near-neutral pH.5). Then [HOCI] = aHOCICT..

7 x 10". John Wiley..0 is 1.. New York.5 pH 9. C.4 397 - - - -:.1 X 10. "The Chemistry of Aqueous Nitrogen Trichloride. C. Hunter. L. Rate of monochloramine formation as a function of pH. The formation of dichloramine.r Chlorine Chemistry 6.6 liter/mole-sec.0-. Figure 7-27 shows the variation of the rate of monochloramine formation as a function of pH." chapter in Disinfection.. The rate constant has the general form: k2 The formation of NCI" = 3. V. D.16 Th. Eq. Saguinsin and J. eds . It is an elementary reaction with a rate constant of 3 x 10-5 sec. Faust and J. S.5 Fig. 17 The rate constant for formation at pH 4.1 .e ratio of forward to back reaction rate constants yields an equilibrium constant for monochloramine formation of 1. and HOCI-is considerably slower than the forward reaction. The back reaction in Eq .CI + HOCI '" NHCI.4 4.. The a values at a particular pH can be determined from the mass balances and equilibrium constants. Johnson.6 X 10. 17 J. 7-56.3 10. S... Morris..3 I I I I 7. Ann Arbor Science. + H20 (7-57) is also elementary and thus is first order with respect to each reactant and second order overall. Ann Arbor. The reaction is catalyzed by H+. 7-56--decomposition of monochloramine to NH.. Morris." in Principles and Applications of Water Chemistry. 1975. + H26 (7-58) is first order with respect to each reactant and second order overall. J.4 X 102(1 + 5 X 10' [WJJ NH2 Cl + HOCI '" NCI. a value that is 16 J._ -r-: I I -+--+-~-I I I I I I 6. ed. "Kinetics of Reactions Between Aqueous Chlorine and Nitrogenous Compounds. Mich. D. . NH. 1967.. 7·27.

+ HOCI with a rate law of -d[ NCI31 dt k[NC1 31 where k ~ 3. Ann Arbor Science. The mechanism of the breakpoint reaction is. NOH. They also found that NCI 3 would react with NH3 and thereby be removed from solution. NCI 3 decomposes by hydrolysis to NHCI. than is HOC!. with the decomposition rate increasing rapidly as pH increases in the range 7 to 9." in Chemistry of Water Supply. Palin. which is about 10 4 times more reactive toward NHCI. J. while below 7. NCl 3 will not appear in significant quantities under the "hump" unless the pH is of the order of 4 or lower.2 X 10-5(1 + 5.C!. essentially only NH. 20 B. at pH values greater than 7.. C. significant amounts of NHCI. "Water Disinfection~Chemical Aspects and Analytical Control.. Selleck. A. NHCI. "Dynamics of Breakpoint Chlorination. Wei and J.OH) and possibly hydrazine (N. particularly at mole ratios between I: I and the breakpoint.. are found.398 Oxidation. Berkeley. but did not prove. Ann Arbor Science.. They concluded that the model fits "breakpoint chlorination results. Saunier and Selleck" examined this model and experimentally deter· mined the rate constants for each of the reactions in Table 7·10.or reaction of the NCI 3 with OH-.. and NH." Sanitary Engineering Research Laboratory Report 76·2.. Ann Arbor..1. A.(Table 7·10). Ann Arbor.CI is present. ed. pH has a profound effect on the species of combined chlorine that make up the "hump" of the breakpoint curve. at mole ratios less than I: I is favored only below a pH of approximately 5. The most comprehensive model is that of Wei and Morris" who proposed a scheme consisting of reactions that formed chloramines. They suggested. J. 18 . 19 I. The rate of NCI 3 formation increases significantly as the pH decreases below pH 3 because of the presence of CI2taQ ). Sanguinsin and Morris 17 found that the decomposition reaction could be given as NCI 3 + H. T. and reo actions by which NOH decomposed to form N. 1975. W. reactions that converted chloramines into a hypothetical intermediate. At pH 7 and above. Johnson. unresolved. that hydroxylamine (NH. D." in Disinfection. thus indicating catalysis by OH. E." NHCI. May 1976.Reduction Reactions about two orders of magnitude less than for NHCI. 1974. Saunier and R.. "Kinetics of Breakpoint Chlorination and of Disinfection. University of California. Treatment and Distribution. Mich. Rubin ed.88 X 10-5 [OH-j)sec. Because of the effect of pH on the formation of chloramine.) could be intermediates in the breakpoint reactionperhaps the hypothetical NOH of Wei and Morris. Morris.O . and N03.H. Mich. as yet.

NHCI. NH. + H. . eds . New York.. NHCI.. -NH-. In some reactions.. CH3 NH" is typical HOCI + CH3 NH..O . S.. C. Amides. compounds in which the group -oCNH.. + H. are very common.CI .O HOCI + NHCI.Chlorine Chemistry TABLE 7·10 Model Reactions for Breakpoint Chlorination HOCI + NH..o HOCI + NH. Although some of the chlorinated organics that form during the chlorination of natural and wastewaters are known... which have the group -NH.. Hunter. + HOCI + H+ + CI NOH + 2HOCI . "Kinetics of.Reactions Between Aqueous Chlorine and Nitrogen Compounds" in Principles and Applications of Water Chemistry. NO...8. Analysis of other similar reactions showed that as the base strength of the amine (indicated by the basicity constant K b) increased.O .. incorporated..O + H+ + CINOH + NHCI. + H. NOH + 2H+ + 2CINOH + NH.. is higher than that found for formation of NH.. N.4..CI. Cl is substituted for a hydrogen atom. + H. H.+ 3W + 2CI(I) 399 + (2) (3) (4) (5) (6) (7) (8) 7. V.. 21 J.. --> CH3 NHCl + H.. Morris.. Reactions with Organic Nitrogen. the formation of dichlorometh· ylamine. + HOCI NHCI.O The rate constant for this reaction. ...CI .. such as those with organic nitrogen compounds and phenols. behave in a similar fashion to the amines but do not react as rapidly because they are not as basic. Chlorine can also be incorporated into a molecule by addition reactions. 1. John Wiley. . k = 108 ·S6 liter/mole·sec. The elementary reaction with methylamine. The organic amines.. many still remain to be identified. CH3 NCl. Chlorine reacts readily with many organic nitrogen compounds just as it does with ammonia.O NCI. D.. or it may react with a compound to oxidize it without chlori· nating it. Faust and J. HOCI + CH3 NHCl .. the rate of the reaction with HOCI increased. or -N= as part of their molecule.. NCI.. Chlorine Reactions with Organic Substances Chlorine at concentrations used for water and wastewater treatment readily reacts with organic compounds in the water. or -oCNH. N." Also.CI + H. .O is acid catalyzed just as is the formation of dichloramine from mono· chloramine.. + H. thus producing the chlorinated com· pound.

B. Ettinger. in the various analytical procedures for residual chlorine. Water Works Assoc. OCI-. 1967. The chlorine attached to the nitrogen has not in all cases lost its capacity to oxidize." J. Hunter. A. "'" I Low molecular Oxidation .1 i : i Fig. V. H. The amount of any species present at a given time depends upon pH. but it is generally not as potent an oxidant as HOCI or NH. "Kinetics of Reactions Between Chlorine and Phenolic Compounds:' in Principles and Applications of Water Chemistry. The curves give an indication of the parameters which can be changed to control a chlorophenol odor problem. . "'" '0 I [3] 0" OH CIOCI 0" . and M. Reaction scheme for the chlorination of phenol. A. 2. along with HOC\. "Chlorine Derivatives of Phenol Causing Taste and Odor. phenol concentration..CI. A typical reaction between HOCI and phenol is shown in Fig. 22 G.. and because several of the chlorinated phenols are very odorous. Burttschell. S.1 i The reaction of chlorine with organic nitrogen is important because it exerts a demand. their formation has long been a concern of water treatment plant operators. D. eds . John Wiley. © 1959.CI. Reactions with Phenols. weight products "ZoC)- '\(0 HOCI . Reprinted by permission of the Ameri· can Water Works Association. F. Middleton. 7·28. Chlorine readily substitutes on to phenol. Because these compounds can be present in water supplies resulting from industrial discharges or natural decay processes. @-OH. and temperature. 22 Predicted threshold odor versus time curves that show the effect of reactant concentration and pH are presented in Fig. 7-28. it requires that more chlorine be added to achieve a given level of disinfection. 7-29. and so forth. Some chlorinated organic nitrogen compounds react as residual chlorine. chlorine dose. 51: 205-214 (1959).400 Oxidation·Reduction Reactions OH Do/ [2J O [>1000] "'" I OH)Y" YO OI ""'" OH CI [250J CI OH CIOCI HOCI. NH. Faust and J. New York.s. Rosen. that is. and compounds containing the phenolic group. Lee. Am. [1 indicates odor thresh· old concentration (p. The threshold odor numbers of each chlorinated species indicating the concentrations that will just produce a detectable odor are also shown. From R. . 07 OH CI CI [2J ~dY"[> 1OOOJ " CI . M.g/liter). F.

401 . 1967.2 ppm. (a) Initial chlorine 0. chapter in Principles and Applications of Water ~ " r. Threshold odor from chlorination of phenol. All were 25°C. From G. (b) initial chlorine 1.6 ~ ~ ~ ~ OL-~~2~3-L4~5~6~7~8~9~10~11~12~13~14~'~5~ Time. initial phenol 5. and (c) initial chIa· rine 0.• John Wiley. Faust and J. D.36 32 " ~ ~ v v 5 0 28 24 20 16 12 8 4 0 4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 Time. eds .0 ppb.0 ppm. initial phenol SO (h) v v 5 28 0 24 5 6 8 3. Hunter. V.4 3. initial phenol 50 rc) Fig.0 v pH 9 5 0 2. & Sons. Lee.2 ppm.) 36 32 " 20 11 ~ 16 12 8 4 0 3 4 Time. 7·29. Reprinted by permission of John Wiley. F. Inc. S.

Hamilton. A series of reactions demonstrating the basic steps by which chloroform may be produced during water treatment is as follows: OttI R---G---GH. . 2. or I. Jr . Ann Arbor Science. is of particular interest because it is a suspected carcinogen. Mich . "" R---G ~ CH. C." For example. 23 J. H. eds . Trihalomethanes have the general form CHX3 where X can be Ct Br. R.. + H+ 0 R---G ~ CCI. + H. the reaction proceeds much more rapidly at high pH than at low pH. its formation o I o II i I . "Precursors and Mechanisms of Haloform Formation in the Chlorination of Water Supplies. because these are favored in the presence of OH-. "" R---G ~ CCI. the reaction with acetone. Ann Arbor. chloroform. .CI + OH" R---G I ~ o (3) 0- " OHI R-C---GH. Jolley. However. L. + H+ (1) o II O- 0(2) 0 CH. and D. Not all compounds that have the acetyl group. + HOCI --> R---G---GH. + OH" (4) (5) R---G I ~ o 0(6) 0- " OHI R-C---GHCI. The health effects of the other species are unknown. and (5). + HOCI--> R-C-CCI3 + OH- I I o (7) 0 " OH" R-C---GCI.CI "" R-C ~ CHCI + H+ 0- 0 CHCI + HOCI--> R---G---GHCI. Vol. Gorchev.402 Oxidation-Reduction Reactions 3. 1978." chapter in Water Chlorination. Bourn.. Trihalomethane Formation. H. Morris and B.. -C-CH3' react rapidly enough to pose a problem during water treatment. CH3-C-CH3' at concentrations found in polluted water supplies is too slow for it to be of concern. since there is organic matter in natural water and wastewater with functional groups that undergo attack by chlorine to form chloroform rapidly.O--> R-C-QH + CHCI3 The slow steps in the reaction are (I). (3). CHCI3.

24 If 1.. Ann Arbor. The major source of these groups appears to be in the so-called humic substances. Chlorine can undergo an addition reaction if the organic compound has a double bond. CHCIBr. which were discussed in Section 5-7.O. this reaction is too slow to be of importance in water treatment.• Ann Arbor Science. o 0 such as oxalic acid. ed ." However.. and H. Addition and Oxidation Reactions. The dose· residual curves presented in Fig." in Water Cblorination-Environmentallmpact and Health Effects. . ed . and CHBr. Many treated waters contain not only chloroform but other chlorinated and brominated trihalomethanes such as CHCl.• Ann Arbor Science. Mich ..Chlorine Chemistry 403 is of concern during water treatment. Vol. 7-28) will break the aromatic ring of the phenol forming 2-carbon residues. 7-30 represent the slow progress of the 24 1\ II J. 4. and H. continued reaction of 2. L.g .• 1978. Vol. lactose) or with a fat or fatty acid such as oleic acid is generally quite slow. The bromine compounds then react with the organic matter in the same way as HOCI. Dichloroiodomethane is one of the species commonly observed. These brominated species form because aqueous chlorine converts Br. 1.4. R-C-DH + W + CI- a I For example.-' ion in the water to HOBr. Jolley. C. presumably HOCI will also oxidize it and the product will react similarly to HOCI.. producing additional trihalomethanes species. and continued reaction with chlorine results in conversion of the 2-carbon residues to CO. Ann Arbor. . "The Chemistry of Aqueous Chlorine in Relation to Water Chlorination.. 25 J.6-trichlorophenol (see Fig.. Morris. 1. R../ CP=C + HOCI ..Br... L. HQ-C-C-OH. The oxidation reaction with a carbohydrate (e." in Water Cblorination---Environmental Impact and Health Effects. and Cl-. C. The reactions are generally far too slow to be considered significant in the context of the reaction times involved in various chlorination practices.• 1978. The organic compound is eventually converted to CO.O. Mich . Jolley. "The Chemistry of Aqueous Chlorine in Relation to Water Chlorination. R. Chlorine can also oxidize· organic compounds as follows: R--cHO + HOCI .is also present in the water.. --c--cOH CI I I /" I I For many compounds with double bonds. more must be learned of the characteristics of some of the substances that are found in water before we can be certain that this will always be the case. Morris.

mg/liter Fig. must obey the laws of thermodynamics. algae.Ol1 ¢ l2CO..O + C. Because photosynthetic organisms are active in most natural waters and in some waste treatment systems we must be careful in some calculations. It is important to realize that microorganisms. to treat them as steady. state open systems with an energy input from a source external to the system.404 Oxidation-Reduction Reactions CJ 2 residual after 1 hr CJ 2 residual after 24 hr Chlorine dose. However.9. for example. and other microorganisll!s. Microorganisms (or any other organisms) do not perform chemical reactions.O + 24Cl. + llH.+ 24H+ + 24HOCI ¢ 24Cl. + 48H++ 48e48e . it must be realized that photosynthetic organisms must have an input of energy (sunlight) to drive the reaction. and Hp-a reaction that is not thermodynamically spontaneous.O C"H"Ol1 + 24HOCI ¢ 12CO. They are able to mediate a reaction that goes in the opposite direction to thermodynamic predictions only because they have devised a means of capturing energy from an external source and using it to reverse the internal energy gradient of the system.+ 24H+ 7. Chlorine dose-residual curves for lactose oxidation. One might wonder about this statement in view of the well·known observation that photosynthetic organisms have the ability to synthesize organic matter frpm CO. bacteria. The pertinent half·reactions and the net reaction for lactose (C"H"Ol1) are l3H. rather than as closed systems. like inanimate objects. they catalyze them and use them for purposes such as deriving . BIOLOGICALLY IMPORTANT REDOX REACTIONS Many of the phenomena encountered in natural waters and many of the processes that make up wastewater treatment are due to redox reactions that are catalyzed (or mediated) by biological systems. 7-30.H. reaction.+ 24H..

Many of the reactions in the nitrogen cycle are microbially catalyzed redox reactions. the reduction of N0 3 .Biologically Important Redox Reactions 405 energy for metabolic processes or source materials for biosynthesis. We have already seen that the production of acid mine drainage is made possible by the microbial catalysis of an oxidation that in the absence of microorganisms would proceed very slowly if at all. In this section we will examine the reactions of the nitrogen cycle. the sequence of the use of various electron acceptors in biological systems. + into nitrogencontaining organic matter (ami nation) or its release (deamination or ammonification) is the only nonreclox reaction involving a nitrogen transformation in the entire nitrogen cycle. 7. L The Nitrogen Cycle The way in whiCh nitrogen circulates on the earth's surface and in its atmosphere is usually depicted as the nitrogen-cycle (Fig. . + to NO. . Nevertheless the importance of the microbial catalysis of redox reactions cannot be stressed enough. redox reactions by microorganisms and the amount of cell material (yield) that they can produce. and the relationship between the amount of energy obtained from. to NH. + (nitrogen fixation). and the reduction of N" N"" (denitrification).. the reduction of N0 3·. 7·31. The nitrogen NO.and then to N0 3 (nitrification). The various redox reactions of inorganic nitrogen containing species are presented in Table 7·1.+ (nitrate reduction). These are the oxidation of NH. The incorporation of NH. 7-31).and then to NH. These reactions Can be used to construct a pC- Fig.

7·32.5. predominates. CT. T 30 40~____~____~__~~7-__~~____oh. +] + [NO.-the typical N"g. NH. one would predict from Fig. estimated from the pE of the reaction in which CO.5 <J 0. -] + [NO. or N"g" the very strong N=N bond must be broken. -. -.q.--L~o-__~ -8 0 P' +20 . then the earth's atmosphere would be virtually devoid of N"g. -J).0 to -7. We know that neither of these predictions are accurate. all dissolved nitrogen gas should be converted to NO.77 atm of N"g. at pH 8 (pE = + 12. and NO. Marked on the pE axis is the pE value of water in equilibrium with an atmosphere containing 0. since the earth's atmosphere contains PN. 7·32). Since all of the major nitrogen·containing species.21 atm of 0.g c' g 20 • u e 0 u ~ 0 Ii I . to form NO.77 atm and nitrate is a very minor component of natural water. content of the normal surface earth's atmosphere (Fig.+ from N". If this were indeed the case.I . Because of .21 atm PE::: +12. it would be expected that their interconversion would be rapid. equilibrium with PN2 = 0..q. The disparity between prediction and observation stems from the slowness and complexity of reactions involving N"g" Nitrogen gas consists of two atoms of nitrogen joined by a triple bond (N N). In the pE range where N".would be a major aqueous species. and NO. .406 Oxidation~Reduction Reactions Oxygenated water at pH8.] + [NH.77 atm. is converted to glucose). N".q. The other nitrogen-containing species in the nitrogen cycle all contain one nitrogen atom. the solution is approximately in equilibrium with an atmosphere containing a partial pressure of 0. or NH. Moreover.have regions of predominance within the pE range over which microbially catalyzed reactions can occur.N = 10-' = 2[N"".N 10-3 .5) and the PE value estimated for the interior of a photosynthetic cell (pE = -7.5 Interiorl)f photosynthetic cell. in pE diagram for a model system at pH 8 containing a total dissolved nitrogen concentration of 10-' M (CT. -. The pC-pe diagram for nitrogen system. in oxygenated water at pH 8. = 0. pe:::~7. P0:2 =0. 7-32 that. +. Therefore. NO. \ : Fig.

it is necessary for the microorganisms to generate a highly reducing locaL environment (such as that produced by photosynthesis) to drive the nitrogen fixation reaction. Electron Acceptors in Microbial Systems It is common in waste treatment practice and in water pollution control to classify environments or processes as either "aerobic" or "anaerobic. it is a the predominant species is extremely narrow. . It is observed that the chemical reactions that take place and the types of organisms that predominate are different in aerobic and anaerobic systems. Such environments exist in the interior of photosynthetic cells including the blue. It shows that N2{aq)] is a common reaction catalyzed by many bacteria and proceeds rapidly. A closer examination of natural waters and waste treatment processes r!Oveals that the dividing .5 to +6.2. and anaerobic environments are those in which oxygen is absent. is only spontaneous below pE "" -6.q. -> algae that fix nitrogen (e.-). This is tantamount to converting the system from an open system in contact with an atmosphere containing N2(y) to a closed system in which N 2{y) and therefore N2(aq) is absent.are all major species in the very narrow pE range from +4.. Also note that the pE region over which NO.g" Microcystis. at pH 8. Anabaena.2. and N". Denitrification [the conversion of N0 3 . Such a presentation is consistent with the observation that these species are easily and rapidly interconvertible (by nitrification and nitrate reduction).+ does take place in organisms that fix N". Because of these observations it is profitable to redraw the pC'PE diagram for CT.q. .+. 7 ·33. Aerobic systems are those in which oxygen is present..: pE" = +4. it appears that microbial catalysts are unable to catalyze the reverse of the denitri· fication reaction (N"....proceed slowly. This is consistent with the observation that N0 2 ~ is a transitory species in natural waters and waste treatment processes-it only exists in significant quantities over a very narrow pE range and it is readily interconverted to NO. to NH." These gross classifications are usually made on the basis of whether or not dissolved oxygen is present in the water or wastewater.+. omitting N".supported observation that the i:n:terconversion of the other nitrogen. 7. However. NO. However.Biologically Important Redox ReQ(~tions 407 this the rate of these reactions is quite slow. Such a diagram is drawn in Fig.9.+ or NO.and NO. However. the conversion of N. Aphanizomenon) and in the symbiotic association in root nodules between bacteria of the genus Rhizobium and certain leguminous plants. From this discussion it is evident that reactions involving the conversion of N".68 Since this reaction.N = 10-' and pH 8.containing species of the nitrogen cycle proceeds relatively easily and quite rapidly. to NH.and NH.

From the t1Go values of these coupled reactions it can be deduced that the amount of free energy that a microorganism can obtain from the coupled redox reactions listed in Table 7-11 is in direct proportion to its PEo value. and H.O.--> 2H. + 4H+ + 4e.O.----. I 2 Very narrow pc range I .20 This reaction can be coupled with anyone of the electron accepting (reduction) reactions listed in Table 7-11.-----.1 . To say that a water or process was aerobic would be tantamount to stating that in the aerobic system the redox conditions are controlled by the reaction O"g. When we examine which "other" reactions are likely candidates for controlling the redox environment of anaerobic processes. .408 Oxidation·Reduction Reactions 0. Microorganisms use these reduction reactions to consume the electrons generated by the oxidation of their energy-yielding substrate.11 . let us take for an example the oxidation of formaldehyde (CH. line between aerobic and anaerobic environments is not sharply drawn.----.-----. Table 7-11 lists these reactions in the order of descending PEo values.~ CH. pH 8) omitting nitrogen gas and aqueous N2 .-----. PEO = 20. PE = O -1. The pC-Pf diagram for nitrogen species (Cr. 8 r 10~----~-L--~~--~~----~----~~----~----J o +8 +10 +12 +14 P' Fig.N = 1O~3 M.----. + 4H+ + 4e.O) to CO. r. we find that there are many.-----.8 whereas in the anaerobic environment (oxygen absent) the redox conditions are controlled by another reaction.O + H. Although this substrate can be any of a variety of substances.O by the reaction: CO"g. 7·33.

H.Biologically Important Redox Reactioris 409 TABLE 7-11 Electron Acceptance Reactions (Reduction Reactions) (Energy-Producing Reactions) in Aerobic a'.3 percent 0. Caldwell. for the simple reason that they do not get as much energy per mole out of doing so. the concentration of dissolved oxygen in contact with the bacteria must fall to about 4 X 10-6 M (corresponding to an atmosphere containing 0..+ lOW + 8e.+ 12W + lOe.'. the reaction to produce N"" (denitrification) is favored over the reduction of NO. It is generally supported by the observation that "anaerobic" communities cannot develop in oxic (or oxygen-containing) environments. Greenwood" has found that.O 2W + 2e.+ + 3H. The effect is not always as dramatic as indicated. . Niles. 17: 365-378 (1962).to NH. For example. Some anaerobes.--> HS.0 +14.O Name of Reaction Aerobic respiration +20. "Full Scale Testing of a Water Reclamation System.87 NO.~ 2H 2O Anaerobic 2NO. Horstkotte et a!. . A. "Nitrification and Nitrate Dissimilation in Soil. they cannot grow as fast as the aerobes and they become overgrown. 27 found that dentrification of nitrate ion in a secondary effluent would proceed in a biofilm when the solution concentration of dissolved oxygen was approximately I mg/liter (-3.99 +4." Plant and Soil. D. Part 2. J. for soil bacteria. 46: 181-197 (1974).--> CIL. In' this general sense. Parker.O Aerobic 02lg} + 4H+ + 4e.O + Denitrification Nitrate reduction Fermentation Sulfate reduction Methane fermentation This trend is supported by many observations in natural waters and '1 waste treatment systems. since many organismsthe so-called facultative aerobes-have the ability to use both oxygen and nitrate as electron acceptors.--> NH. Control Fed. . Effect 27 of Oxygen Concentration. . Therefore.) before the use of nitrate as an electron accepter starts. the redox conditions of a water determine the type of biological community that develops.+ 4H.8 +21. G. G. in a nitrifying activated sludge plant. When nitrate is utilized. there is 26 D. Horstkotte. Using' the same substrate.through NO. and D. D.13 +2. Greenwood. Water Pollut.d Anaerobic Systems p.OH (Formaldehyde) (Methanol) SO.5 x 10-5 M). such as the methane fermenters. I are poisoned by oxygen.O CH.O CO"" + 8W + 8e.--> CH. They only use nitrate when the concentration of dissolved oxygen is very low." J. S. the anaerobic organisms cannot get as much energy per mole by its oxidation as can the aerobic organism.." + 2H. + (nitrate reduction) for the same reason: it yields more usable energy to the organism that catalyzes it.9 +3.--> N"" + 6H.+ 9H+ + 8e.

There are other such examples. especially if the sulfides 18 Eutrophication of Surface Water-Lake Tahoe's Indian Creek microorganisms growing within the carbon column on biodegradable adsorbed organic matter. When the . nitrification then denitrification). a sludge blanket forms in which high concentrations of activated sludge continue to respire. Many unsaturated soils are known to convert NH.(Le. nitrification may occur in the oxygenated epilimnion (upper layer) and denitrification in the hypolimnion (bottom water) and in the sediment pore water where dissolved oxygen concentrations fall to zero. Denitrification (not nitrate reduction) will occur with the accompanying production of the sparingly soluble N2(g)' Small bubbles of N"g) are produced within the activated sludge blanket (possibly within the activated sludge floc itself).-Nlliter. The effluent has at times contained 15 to 20 mg NH. one of the problems encountered is that the carbon columns become highly odorous. They achieve this because there are local oxic and anoxic environments in the soil waters that. unmixed and unaerated. Levels of ammonia of this magnitude are toxic to fish. allow nitrification and denitrification to proceed. 660/3·75·003. respectively. This reservoir is fed by the tertiary effluent from the City of South Lake Tahoe sewage treatment plant. This is achieved because the top waters of the lake nitrify the ammonia to nitrate and this is reduced to N2(g) by the anoxic bottom waters. This is the sulfatereduction reaction. If the sludge is maintained in this quiescent. yet in the reservoir there is a thriving fishery.. and they rise to the surface of the secondary sedimentation basin. February 1975. blanket for an extended period of HS. Then some of the microorganisms in the activated sludge (those that have the enzyme. using electron acceptors. .410 Oxidation-Reduction Reactions usually dissolved oxygen and nitrate present in the aeration basin. EPA Report No. The summer concentrations of nitrogen species of the reservoir 28 are approximately 4 mg N0 3 --Nlliter and 4 mg NH.+ to N2(g) via N03 . In stratified lakes. all of the dissolved oxygen will be consumed. The odor derives from the reduction of SO/. Attempts to alleviate the situation by injecting air into the columns have met with little success because the oxidation of sulfide by oxygen is not always a rapid process. When domestic wastewater is treated by chemical precipitation followed by carbon adsorption. This is the vexing problem of "blanket rising" or "sludge rising.activated sludge settles in the secondary sedimentation basin." In this example the oxidation of ammonia to nitrate (nitrification) and denitrification occur in the same process with the only difference being environments where dissolved oxygen is present or absent. nitrate reductase) will turn to the nitrate for an electron acceptor. The nitrification and denitrification process is important in preserving the fishery in Indian Creek Reservoir in the Sierra Nevada mountains. carrying with them particles of activated sludge which are more often than not carried over into the secondary effluent.+-Nlliter.

Control Fed. The series of redox. Water Pollut.9 1. HS-.4 mg N0 3 -Nlliter o Source: L." in which both oxygen and chlorine were unsuccessfully used to eliminate sulfides from carbon column effluents.) in the digester gas. With a normal (nontoxic level of metals in the digesting sludge. 37: 392 (1965). Directo. "Pilot-Plant Study of PhysicalChemical Treatment.-. Control Fed. 7-34 control the atmospheric H. Kugelman. "The Role of Sulfide in Preventing Heavy Metal Toxicity in Anaerobic Digesters. 49: 2081 (I977). 49: 2081 (977). In the presence of NO.. "Pilot·PIant Study of PhysicaIChemical Treatment. L.. Water Pollut. Using this observation and the knowledge that many toxic heavy metals form insoluble sulfides. we can predict from Table 7 -Il that SO. The successful use' of nitrate for preventing sulfide 'production in the columns is clearly evident.3 mg N0 3-Nlliter (1) plus 5. 30 A. C. W. the PH. Control Fed. S..using the reaction grow N"..) than SO. heterogeneous.S concentration (PH". In Table 7-Il' the electron ac_ceptpnce reaction with the lowest energy yield for microorganisms is the reduction of CO'{g) to methane.Biologically Important Redox Reactions 411 TABLE 7 -12 Control Methods for Sulfide in Carbon Adsorption Columns Mean Total Sulfide Content in Carbon Column Effluent.9 1. since they get far more energy out of it (Table 7-12).s value will be constant and can be "L. fed to anaerobic sl)ldge digestion units at waste treatment plants. and I. Lawrence and McCart). ." J. and acidbase equilibria shown in Fig. McCarty. When the methane fermentation reaction occurs. L. J. Sulfide Control Method (1) Surface and backwash mg S/liter 2. Chen and 1. Directo.02 (2) Surface and backwash plus increase of column influent to 2-6 mglliter DO (2) plus 40 mg Cblliter to column influent (1) plus 5. One successful method of preventing the sulfide odor has been to feed sodium nitrate to the carbon column influent.ry slowly compared with aerobic heterotrophic bacteria because they obtain so little energy per mole of substrate reduced. the socalled methane fermentation reaction." J.'will be absent having been completely reduced to sulfide. Lawrence and P. are present in a particulate form." J.· derived an ingenious technique for detecting the presence of potentially harmful concentrations of toxic metals in the sludge. The data in Table 7 -12 are from work conducted by Directo et aJ.1 0. S.'. sulfide generation ceases because the microorganisms would rath~r reduce NO. C. Kugelman. J. The reaction occurs only under strictly anaerobic conditions and the organisms . Water Pollut. L.

The amount of energy available to a microorganism is. Organisms that oxidize organic matter (CH 20) all the way to CO 2 and H20 (respiration) obtain more energy per mole than do organisms that only take "CH 2 0" as far as.j. therefore. formic acid (an example of a fermentation reaction).and H2 S"q.3.":ever.. The pE values for the following equations illustrate this: CO 2 + 4H+ + 4e.82 Organisms that use substrates with lower energy content for energy generation produce even less energy per mole of substrate oxidized. By determining the acceptable range of P". Microbial Yields In the previous section we saw how microorganisms use or become established to use electron-acceptance reactions strictly in the order of the amount of energy per mole of electrons consumed that they can derive from them.--> CH 2 + H20. Expressed in microbial terms. 7.412 Oxidation·Reduction Reactions Sludge "'" Sludge H2 S(aq) H HS(~ql H HeavY metal + ~ ~ Heavy metal sulfide Fig. for example.20 o PE = +2. ho. will decrease. a function of both the electron-generating (oxidation) halfreaction and the electron-acceptance (reduction) reaction.S' since its concentration is determined by [H2S"q. HCOO. 7·34. If a high concentration of heavy metals is fed to the digester. we say that the yield (g cell material per g substrate . is that the amount of energy available per mole of substrate for processes such as the biosynthesis of new cell material varies widely from organism to organism. PH2S in an anaer· measured and recorded. The result of the various combinations of redox couples used by different microorganisms for energy generation. more metal sulfide solids will form and the concentrations of S2-.s levels in the digester gas.+ 3W + 2e.--> CH 2 + H 2 0 0. Schematic of controls on ohic sewage sludge digester. HS. 0 PEO = -1.9. an early warning system for toxic levels of heavy metals is available. These will be accompanied by a fall in PH.

McCarty" has related cell yield for various microorganisms to the amount of free energy produced by coupled SUDstrate oxidation and electron-accepting reduction reactions. S. eds. Hunter. + ® 181 • ®+ <> NH4 + 0. Some of his data are plotted in Fig. 1: 157 (1975). Progress in Water Technology. The plot shows that nitrifying organisms have cell yields on the order of 0.2 <.. 7.3 . 0. "Energetics and Bacterial Growth. McCarty. L.r Biologically Important Redox Reactions 413 I i consumed) varies widely. .. N03 - 6 A . D. Dekker.. 7·35. 7·35. and P. 0" Benzoate S 2 S2 0 3 - ·0 -0 o. 0. chapter in Organic Compounds in Aquatic En· vironments.7 Acetate Ethanol 0. After P. D. ] 0. CO. 1971. These microorganisms oxidize ammonia to nitrite and reduce carbon dioxide to their cell material.G. 0.5 00 "~ 0." in Organic Compounds in Aquatic Environments. 1971. P.'> . kcal per electron mole transferred Fig. c0 0 . .> 0. L. Faust and J.6 • '" ~ cr 0 0 Fe 2 + 0. New York.4 kcal! 0. "'~ cr 0 0. V. 0. 0. L. The free energy change for this reaction is -13. New York.. McCarty.1 cell equivalents/equivalent of electrons transferred in the substrate oxidation/electron acceptance reaction. V. Faust and 31 1.8 Electron Electron Symbol DOllor Acceptor 0. Hunter. S. X H. Glucose Fructose 0 E_ 0. N03 - ~ 0 0 • • 0 c 0 ] Acetate CO.~~ o c ~ ~ " " Alanine 0.4 =c ~ E:. Dekker. Relationship of microbial cell yield to free energy available from substrate oxidation. eds. McCarty.1 0 0 5 10 15 20 25 30 -t:J.

respectively. First. The free energy change for this redox couple is -28. but also the maximum rate at which various microorganisms can grow is related to the available energy. and then using the potential/activity relationship to determine the activities in unknown solutions from potential measurements of these solutions.10. Potentiometric Measurements 1. If we wish to achieve this objective for the measurement of a single species or a single ion activity.1. rather we will select examples to illustrate the use of electrochemical techniques in water chemistry. and the measurement of activity (concentration) by electrolytic cells using techniques such as polarography and amperometric titration.7 kcal per electron mole. The maximum growth rates are quite clearly related to tlie amount of energy available to the microorganisms from substrate oxidation. . as an electron acceptor. Table 7-13 shows typical growth rates of microorganisms growing under various redox conditions. the measuring instrument.O and using 0. or indicator electrode. we have several hurdles to overcome. Not only does the amount of cell material that a microorganism can produce per unit amount of substrate processed vary with the energy available from the redox reaction that the microorganism catalyzes. We will not deal with all types a'f electrochemical measurements here.10. 7. ELECTROCHEMICAL MEASUREMENTS ii! The properties of electrochemical cells allow us tQ use them in a variety of ways for determining the concentrations of individual ions on physicalchemical properties. This equation indicates that the activities of the oxidized and reduced species are factors in determining the potential of an electrode. We can turn this fact to use by measuring the potential of an electrode at several known activities of reacting species. Our examples will include the measurement of activity (concentration) by potentiometric methods using galvanic cells and specific ion electrodes. This cell yield can be compared with the value of 0. 7. Electrode Systems. The general form of the Nernst equation is E =E' _ RT In {red} nP {ox} (7-59) for the reaction ox + ne~ ¢ red where "ox" and "red" indicate "oxidized" and "reduced" species. and H. this means that the other components of the reaction must . must only respond to the activity of one component of the reaction taking place at the electrode.414 Oxidation-Reduction Reactions mole of electrons.74 foI'a heterotrophic aerobic microorganism oxidizing fructose to CO.

"A Practical Approach to Activated Sludge Kinetics. and A. Painter. D. L. the response of the electrode must be specific to the activity of the ion or species being measured. L. The internal contact between the indicator and reference electrodes is through a salt bridge or liquid junction that allows the passage of ions but does not permit significant mixing of solutions. Because there is little current the reaction at the indicator electrode does not shift perceptibly from equilibrium and there is no significant consumption of the species of interest at the electrode. Loehr. "Biological Kinetics of Suspended-Growth Denitrification. The potential of the cell is Ecell = Ereference electrode + Elndicator electrode- + EJunction whereEJunction is the potential across the liquid junction. Water Poll"t. Purif" Part 2: 130 (1964)."on are designed to be virtually constant so that ideally E"" = constant + E ..Go/n. Downing. lnst. Second. L. the so-called indicator electrode must be made part of an electrochemical cell with another electrode-the reference electrode-whose potential remains constant over the range of conditions in which the cell is used. Electrochemical Measurements 415 TABLE 7 -13 Relationship of Maximum Microorganism Growth Rate Under Various." J. Sew. Knowles. be kept constant.7 1. "Determination of Kinetic Constants for Nitrifying Bacteria in Mixed Culture with the Aid of an Electrdnic Computer. Lawrence. R. Stensel. "Nitrification in the Activated Sludge Process. "Kinetics of Methane Fermentation in Anaerobic Treatment."". kcallelectron mole Aerobic treatment of domestic sewag~ Denitrification using methanol b Nitrite oxidation in estuary water Ammonia oxidation in activated sludged Methane fermentation of acetic acide a 3. A.r I . Lawrence and P. 45: 249 (1973). Control Fed. W. that is. The indicator electrode and the reference electrode are joined externally through a voltmeter (potentiometer) that is of the type which draws very little current because it has near-infinite internal resistance.nF In {ox} o RT {red} (7 -60) ." J. W. Barnett. Horath. Microbio1" 38: 263 (1965).65 0. eA. Gen. the electrode must be highly selective." J_ Water Pollut. and G. C G.33 0. The Ereference electrode and E. Control Fed" 41: HI (]969). Knowles. Practically Defined Redox Conditions Typical Free Energy Redox Condition Maximum Growth Rate. Downing. Third. McCarty.8 0. Benedek and 1. day-1 Change of Redox Reaction 6. d A. A. H.13 -28 -25 -18 -10 <-I P. J. C. ." Water Res" 1: 663 (1963)_ b H." J. and M.

at I atm pressure bubbling through it] was used to define the standard electrode potential scale (see Section 7.." = constant + 0.. The normal hydrogen electrode [a platinum wire in 1.. then E"" = constant + 0. Calomel Electrode.. 2.. the potential will change 0.2M) The salt bridge or liquid junction between the saturated KCliHg. KCI".').2).CI. that is. {Ag(. 2Hg (f) + 2CI'! ' .059 log [Ag+] and the potential of the cell is a logarithmic function of [Ag+]. consider the electrode reaction EO = 0.416 Oxidation-Reduction Reactions where constant = Ereference electrode + EjunCllon and Elndlcatorelectrode =E . and potassium chloride (KC!). Substituting into Eq..288 N HCI solution ({H+} = 1) with H2(g...059 volt (V) or 59 millivolts (m V).CI"". 7·36). For example. we find E . This electrode is not convenient to use on an everyday basis. For every tenfold change (decade) in [Ag+] concentration.3.799 + 0. One of the most commonly used laboratory reference electrodes is the saturated calomel electrode... 7·36) consists of a platinum wire set in a paste that is a mixture of mercury (Hg(f))' mercurous chloride (calomel. This type of response. The electrode can be represented as HgiHg. 7·60.. the change in m V reading per concentration decade can be used to judge whether an indicator electrode is behaving in an ideal or a "Nernstian" fashion. The electrode (Fig.nF ln {ox} o HT {red} If we can keep one of the reaction component activities constant at the indicator electrode..799 volt With a silver metal electrode. so a series of secondary reference electrodes has been developed for this purpose. The potential of the saturated calomel electrode is determined by the reaction Hg .CI2(. The paste is in contact with a solution that is saturated with KCI and Hg .CI.CI"" + 2e . solution and the solution being measured can be made through a capillary tube filled with asbestos fibers (Fig.(4.799 + nF In {Ag+} HT If the activity is approximately equal to the concentration. we can use the cell to measure the activity of the other component.} is virtually constant and is taken as unity. Hg.

E = E' . the potential of the electrode should be constant at a given temperature. 7-36. Since both Hg.Electrochemical Measurements 417 Platinum wire -4+'i Saturated KCI_~. Courtesy of the Corning Glass Works. and since {CI-} is constant (the KCI solution is saturated).constant = +0.CI"" and Hg'fI have unit activity the potential of the electrode can be written E = E' -~ In {CI-}. that is.244 volt at 25'C .I r .iH solution ""~_ Asbestos fiber Fig.Y. N.. Corning. The calomel reference electrode. and is +0.244 volt at 25°C.

the CuSO. see Fig. Therefore. saturated copper sulfate (CuSO . Its variation over a wide range of {H+} is minimized by "standardizing" the electrode system at {H+} levels that are close to those which are anticipated in the test solutions to be measured. constant {H+} solution from the test solution of variable {H+}. Ion exchange only takes place satisfactorily when the glass electrode surface is hydrated. glass electrodes must be "conditioned" by soaking in dilute acid prior to use. 4. The potential between D and E is approximately constant. The copper (Cu".1 M HCl solution into which is immersed an internal reference electrode (usually Ag/AgCl). The potential of interest is between C and D.) reference electrode represented as Cu".. This process of standardization leads to the operational definition of pH. the measured potential of the cell is as indicated in Fig. The potentials between A and B and between Band C are constant because the internal reference solution concentration is constant. 7-37) consists of a bulb of thin glass (a glass membrane) that is sensitive to changes in H+ activity./CuSO . The electrode is sturdily constructed with a wood outer case and a screw connection for a liquid junction made from a porous plug. solution will be saturated.).. When the glass electrode is made part of a galvanic cell with a reference electrode. The glass electrode (Fig. usually a 0. allowing charges to be transported through the glass. To satisfy yourself that the electrode is in working order you merely shake it to hear if you can detect the rattle of the CuSO"" crystals in the internal CuS0 4 solution. 7-38 between A and E. It is not possible to measure this or any other single ion activity absolutely because single ions cannot be isolated in solution nor can potential measurements be obtained from one electrode in isolation. Glass Electrode.. Three indicator electrodes are discussed to illustrate the various types of construction and modes of operation of these electrodes.418 Oxidation~Reduction Reactions 3. The inside of the glass membrane contains a reference solution of fixed [H+] . The glass membrane separates the internal. If they are present. Hydrogen ions selectively exchange at the glass surface.34 finds use in the field measurement of potential in applications such as corrosion control.' and with an electrode reaction of E' = +0. such as the saturated calomel electrode. thereby determining the potential difference between the constant internal {H+} and the variable external {H+}. 737. The potential of the glass electrode appears to develop because of an ion exchange reaction that takes place at the glass surface. We recall that pH is defined !llathematicallyas pH c= -log {W} where {H+} is the activity of the H+ ion. This . Copper/Copper Sulfate Electrode.

0.Y.Electrochemical Measurements 419 Ag/AgCI coat on a platinum wire --.059 pH The potential of the glass electrode/saturated calomel electrode cell is Ecell = Ecatomel + Eg'ass + Ejunctfon .3RT log {W} nF and since pH = -log {H+}. Courtesy of Coming Olass Works. Coming. 7-37. N. The glass electrode.-->-1 H+ sensitive glass Internal Solution: 0. leads to the need for an operational definition of activity and concentration as determined from electrochemical measurements. For the glass electrode.1 M HC! Fig. E =E' + 2. E = E' .

glass Internal reference electrode ptf Ag/ Agel!» Internal reference solution constant {H+J (e.. The dial of the pH meter (which is basically a high. .0. Hydrated (layers of --.g. Instead of developing a potential across a glass membrane. The technique is repeated until the meter reads the indicated pH of both buffers.1 AI Hen B Glass membrane Test solution Reference electrode (e. 0. it develops a potential over an inert porous disc that is saturated with a water· immiscible.OS9 will be directly proportional to the pH. Divalent Cation Electrode.059 pH where "constant" = E~lass + Ecalome' + Ejunctlon' Therefore. The divalent cation electrode for hard· ness is a selective ion electrode that detects Ca2+ and Mg2+ and other divalent ions in much the same way that the glass electrode detects H+./0.. saturated calomel electrode) E A c D Potential of glass electrode Measured potential on pH meter Fig. resistance voltmeter with a scale that has been converted to read in pH units instead of millivolts) is set to read the indicated pH of the buffer. In the process of standardization one selects a buffer of known {H+} and immerses the electrode system in it. The process is repeated with another buffer solution with a different pH. Potentials in a glass electrode·calomel electrode system commonly used for pH measurement. liquid ion exchanger which is selective for divalent ions.OS9 for the pH range of interest so that the value of Eoe . The first buffer is reread and the meter readjusted.059 E cell 0. pH=-~c- constant 0. By this technique we have "dialed in" the value of constantlO.g.420 Oxidation-Reduction Reactions or Eoe " = constant .059 (7 ·61) Equation 7·61 is the operational definition of pH.. 7·38. 5.

Inc._ sensitive Ion _ area Fig. There is an internal Ag/AgCl reference electrode.5 for [FeuJ.54 for [S1'+J. Because the dodecyl phosphoric acid-Ca2+ salt is sparingly soluble.. Cambridge. 3. for example.059 EO + -2-log ([Ca2+J + [Mg2+J + KxlX2+j) . the sparingly soluble calcium salt of dodecyl phosphoric acid dissolved in a di-n-octyl phenyl phosphonate and immobilized in a cellulose membrane. ions that... as the relative response produced by I mole of [xuJ to that produced by I mole of either [Ca2+J or [Mg2+J. The calcium dodecyl phosphoric acid transports Ca2+ ions across the membrane and is responsible for establishing the potential of the electrode.. The liquid ion exchanger is. some Ca2+ ion is in solution in equilibrium with it so that the electrode potential reaches a plateau value at [CaHJ = 10-'.1. Mass. The degree of interference is expressed by the selectivity constant Kx.1 for [Cu2+J. 7-39. Divalent cation electrode. For the div<.Electrochemical Measurements 421 espeCially Ca2+ and Mg2+ (Figure 7-39)_ Theinternal solution is a calcium chloride solution saturated with the ion exchanger.. The pH affects the operating region of the electrode. and 0.Ilent cation electrode some selectivity constants are 3. Courtesy of Orion Research. The lower bound Module housing Electrical contact Internal reference element IAg/AgCI) Internal aqueous reference solution Spring _~_ Internal sensing assembly Porous organophilic membrane Porous plastic ion exchange reservoir -=~~::::. where Kx is defined by the equation E = 0. . This particular electrode responds to ions other than Ca2+ and Mgu.... may be regarded as interferences.

g. and Mn(IV) ¢ Mn2+ + 2e- All the important redox reactions involved in the nitrogen cycle. The only potentials that will register in the ORP cell are those from species that can react at the indicator electrode surface-we call these electroactive species. they can be of qualitative use. At best. The measurement of ORP has found use in nonbiological situations such as the control of chlorination and dechlorination of sewage effluents.. The oxidation-reduction potential is measured in a galvanic cell consisting of a reference electrode (e. extent of biological oxidation of organics in wastewater). Moreover. which is not detected by the electrode. ioo.. and the carbon cycle are not completed at the indicator electrode in an ORP cell.e. The anode is made of a highly noble metal so that the potential for its oxidation is less than that of any oxidizable solution components. aerobic or anaerobic) or the degree of treatment (i.5 at 10-5 M divalent cation to about 5 at 10-1 M. 6. The calomel electrode is the cathode and the inert platinum or gold electrode is the anode. This behavior is due to the general process of polarization and of "poisoning" of the indicator electrode surface by the accumulation of oxidation products on the surface of the electrode. Oxidation-Reduction Potential. " . for example. wastewaters. 7.10. The upper bound is about pH 10 and is set by the presence of the MgOH+ ion. The term polarography derives from the fact that the electrode at which the reaction of interest occurs is in a polarized I:'I I. The measurement of the so-called "oxidation reduction potential" (ORP) of natural waters. the voltage reading produced by an ORP cell is a reflection of many reactions-it is a "mixed potential" and its value is difficult if not impossible to interpret in any fundamental chemical terms. Oxidation-reduction potential measurements in natural waters and wastewaters are difficult to interpret.e . Despite all of these limitations ORP measurements have been used widely in biological systems where. platinum or gold).. usually falling from the initial reading obtained. when an ORP electrode combination is immersed in a water the voltage reading will vary with time. The anode thus is a site of the oxidation of solution constituents but ideally is not affected itself. In natural waters only a few reactions proceed at the electrode surface.g. and waste treatment systems has been advanced by some wor)<ers as a useful index of the state of the system (i. if they are treated as indices or "black box measurements" rather than fundamental indicators of a specific chemical environment. amperometric techniques involve the measurement of current. calomel) and an indicating electrode of a highly noble metal (e.422 Oxidation-Reduction Reactions of pH depends on the [Ca'+] + [Mg2+] concentrations and varies from about 6. Amperometric (polarographic) Measurements As the name implies. the sulfur cycle..2.

high close to the electrode surface. area of electrode surface diffusion coefficient of reactant thickness of layer around electrode through which diffusion takes place bulk concentration of reactant electrode surface concentration of reactant = For a polarized electrode Co O. When the rate at which the reactant is supplied by diffusion is just balanced by the rate at which it is consumed by reaction at the electrode. in the electrolyte solution). Therefore. In turn.Electrochemical Measurements 423 condition.. the current generated in a cell with a polarized electrode can be made a function of the bulk solution concentration of reactant. dM' = Ad (C _ C ) dt 8 0 (7 ·62) M' = t = time A= D= 8= C Co = = mass of reactant . for a completely polarized electrode we can safely assume that at the electrode surface the reactant concentration is zero. Conversely. When an electrode is in such a polarized condition. dM' -ADC -. In such a condition the amount of current that the electrode will pass is directly related to the mass flux of reactant from the bulk of the electrolyte solution to the electrode surface across the concentration gradient established by polarization. In fact. The polarization of an electrode occurs when the products of a reaction that occurs at it accumulate to such an extent that they limit the rate of reaction at the electrode.-dt 8 (7 ·63) Since the reactants at the electrode are the current·carrying vehicles in the internal circuit (Le. the concentration of the reactants at the electrode surface will be very low. we can visualize that the concentration of the product of the electrode reaction is very . the rate of mass flux or diffusion of reactant is (by Fick's law) a function of the bulk concentration of reactant. we can write Rate of supply of reactant by diffusion = rate of reaction at electrode (7·64) ADC 8 where i = current n = number of electrons in reaction nF F = the Faraday constant .

sometimes enclosed in a membrane that selectively passes the reactant of interest. if they are involved in unique electrode reactions. Sci. H. all isolated from solution by an oxygen-permeable polyethylene membrane (Fig. This oxidation drives the cathodic reaction in which oxygen is reduced to OH-. "An Improved Galvanic Cell for Determination of Oxygen Concentrations in Fluids." J.. but the emergence of atomic absorption spectrometry (AAS) has largely replaced polarography of this type for metals analysis. is a galvanic cell employing a lead anode and a silver cathode in an aqueous KHC03 electrolyte. 1nstrum. 1. One of the current wide applications of polarographic techniques in water chemistry is using solid inert electrodes.D. An example of this type of cell is provided by the "dissolved oxygen probe" or "dissolved oxygen electrode." This electrode may be either of the electrolytic or galvanic type discussed above. the other electrode is usually a reference electrode (e. However. Makereth. 7·40). that is.:Ac:. a calomel electrode). Atomic absorption spectrometry measures the total metal content.-=-C 8 (7 -65) For a particular electrode system.g. all species containing a specific metal. it should be realized that the two techniques are capable of measuring different things. 41: 38 (1964). Dissolved Oxygen Electrode. unless some effort is made to separate one species from another prior to AAS analysis. The indicating or polarized electrode is usually an inert metal (such as platinum) or a mercury droplet.Reduction Reactions Then i = =nF:. Polarography and other electrochemical methods are capable of measuring individual species.424 Oxidation. With galvanic cells the potential required to drive the reaction at the polarizing electrode is generated by making the polarized electrode part of a galvanic celL With an electrolytic cell the potential is supplied by an external voltage source such as a battery. 1. Some ~ I 32 F. the term nFADI8 is a constant and therefore i =KC (7·66) The measurement of the current in a cell with a polarized electrode can therefore be used to measure the concentration of the reactant-producing polarization. Lead ions (Pb2+) are produced at the anode. Polarographic measurements can be conducted with either galvanic or electrolytic cells.. Polarographic methods using the dropping mercury electrode found wide acclaim for measuring metal concentrations in waters. for example. .. excluding complex forms. the same temperature and physical conditions such as the stirring rate and the same electrode reaction. The Makereth "oxygen electrode"" for example.

+ 2H. the diffusion rate is a function of the oxygen concentration outside the membrane in the bulk solution.. This supply depends on the diffusion rate of oxygen across the membrane.HsAsO(OH). Free chlorine (HOCI and OCI-) can be determined by amperometric titration with the reductant phenylarsine oxide (C. In these instruments the polarization current is read out on a dial. Amperometric Titration of Chlorine.. The dial reading decreases. 7 -41).. Schematic of the Mackereth dissolved oxygen electrode. Since the oxygen concentration inside the membrane is kept low (virtually zero). l . Therefore.HsAsO). The reaction is HOCI + C. A reagent is added that reacts with the polarizing reactant so that its bulk concentration is decreased.O ~ HCI + C. 2..Electrochemical Measurements Ammeter )--_-. Therefore. OH. When using these electrodes. The second wide application of amperometric methods in water chemistry is the use of amperometric titration devices. This indicates that all of the reacting species has been consumed because the current flowing in the cell no longer is influenced by a reagent that reacts with it. 7·40. therefore. + 2Pb". The current is. 0"".ions migr~te to the anode and react with Pb2+ to produce Pb(OH)".O "'" 2Pb(OH)"" and its rate is controlled by the rate of supply of oxygen to the silver cathode. The overall cell reaction is .+ O2 + 2H 20 --->- Ag cathode (polarized) Pb2++20~ --->- 40H- Pb(OHhls) KHC0 3 electrolyte Solution Oxygen permeable membrane Fig. proportional to the bulk solution oxygen concentration. the current in the external circuit is controlled by the rate of the oxygen supply to the cathode.::'_-~ 425 Pb anode Pb ls )-+Pb 2 ++2e- 4e. it is important that the bulk oxygen concentration close to the membrane does not become depleted. Reagent is added until there no longer is a decrease in current upon the addition of further reagent (Fig.HsAsO + H. it is essential to stir the bulk solution to ensure that the layer close to the membrane surface is constantly renewed with water of a composition representative of the bulk solution.

A typical aperometric titrator is shown in Fig. 1976. TOC. 3.Cl. PROBLEMS Write balanced equations for oxidation of NH3 with HOCI assuming the following major end products. 10-' M NH.426 OXidation-Reduction Reactions '?-----I Endpoint Volume of reagent added Fig. 7-42. Combined chlorine can also be measured by this technique if the proper solution conditions are used. Publ. Health Assoc . H20. (c) 6 mglliter of NH3 (BOD only). and Cl-.H.? 33 Standard Methods of the Examination of Water and Wastewater.B M Cl" 10-' M HOCl. Assume that NO.. C..6 moles HOC1I2 moles of NH" which of the three cases is likely to predominate? 2. and 10-5 M NHC12 . Amperometric titration endpoint. and ultimate BOD of the following solutions? (a) 100 mglliter of phenol. 33 7.OH (b) 50 mglliter of ethane.and Cl-. Theoretical COD and ultimate BOD are the amounts of oxygen required to oxidize the compounds in question to CO2 . (b) NO". ." and the nitrogen end product. For the three cases. (c) N03. 1. A solution contains IO. required per mg NH 3-Nlliter. 10-7 M 0(. (a) N. If the stoichiometry observed in the laboratory is 3.:1-.H.. What is the total concentration of chlorine residual in mglliter as Cl. What is the theoretical COD. Assume that Fe(OH)"" is the end product. determine the moles of HOCI required per mole of NH3 and the HOCI in mglliter as Cl. and other end products as stated. 7-41. Am. (d) 10 mglliter of FeH (COD only). Note: TOC is the mass of carbon in the organic{s) under consideration. 14th ed .11. C.

Courtesy of the Fischer & Porter Co .Problems 427 Fig. Assume that it is completely oxidized by dichromate in the COD test. Warminster. Amperometric titratar.CH.. (a) Write the balanced reaction for CH 3CH2 CN with Cr20l~. The nitrogen product of the reaction is NHa . Pa. Propionitrile has the general formula CH3 CH2 CN. (b) What is the COD of a 50 mgiliter solution of CH. 4. 7-42.CN? .

-+8H++5e-:. CNO-.=2CI-.15 volts (a) Write the stoichiometric equation for the reaction that occurs when 0 3 is mixed with NaCI02 in aqueous solution.. + H. and [Fe H ] = 10-'.. CT.-. . + 2H+ + 2e. Also add 10.25 N Cr2 0/.to N.36 volts CI.for each step? :.= 2e.. When CT. cyanides are frequently eliminated from waste discharges by treatment with chlorine at high pH (alkaline chlorination process).Q:. (b) What is the value of the equilibrium constant for this reaction? Is ozone a stronger or weaker oxidizing agent than chlorine dioxide? (c) What is the standard free energy change for this reaction? 7. is required per mglliter of CN.23 volts What is EO for the half-reaction representing the reduction of Mn0 4. Given: MnO.428 Oxidation-Reduction Reactions (c) Add 10. + e-:.0 ml of 0. = solution in the COD flask after the reaction is completed? (Assume 100 percent oxidation of CH. the Cr 20/.) 5. and (2) oxidation of CNO. CN-. E' = 1. and CO. E'= +1.21) and pH = 7. (a) Find the balanced reaction and the corresponding EO for the oxidation of Fe 2+ by dissolved oxygen. Dilute to 50 ml total volume. (b) How much chlorine.CH.4.= the oxidizing chlorine species and that CI.:.51 volts E' = -1. E' =2. K h = 3. 2e-+ CI.solution plus the necessary reagents.07 volts CIO. In the metal plating industry. [Fe"] = 10-'. in mglliter as C12 . Mn H + 2H..0 ml of a 500 mgiliter solution of propionitrile to a COD formed as the reduced chlorine species in each step. Two steps are involved: (1) the oxidation of cyanide.Q. = 0. + H.Cr{IIl) = 10-4. Ozone (03) and chlorine dioxide (CI02) are both strong oxidizing Mn02{S)? 10.e. is the reaction at equilibrium? Given: 8. What is the molarity of the Cr20/.+ 4H+ + MnO".= HOCI + H + + CI-. In the COD test.=Mn H + 4H.8 x 10 -. Po. Given the half-cell reactions for these species as follows: 0. (a) Write balanced reactions for each of the two steps given that OCl.CN. E'= +1. calculate EO for the reaction andK w = 10 -14 9.remaining after oxidation of the organic matter is determined by titration with Fe 2+. to cyanate. 02(aQ)' (b) If the water is in equilibrium with the atmosphere with respect to O 2 (i.

the total alkalinity = ISO mglliter as CaCOl . and [H+] = 1 M. (a) The p€ of a solution can be controlled by controlling the solution composition. The resulting pH is 7. To show this. and HS. (a) Draw the pC-p.4.has been added until [HS-JI [SO.exist in solution.05 mglliter) are present? 16.FeUlJ 429 = 10. What is the p€ of each of these solutions? 14. HOBr. Thus the following reaction can be used. CT. As water is transported through an iron distribution main.originally present in the sample. at equilibrium. diagram for the sulfur system at pH ~ 10.4 M and 25°C. 15. (b) What is the value of the Langelier index? (c) Give three specific actions that could reasonably be expected to eliminate or significantly reduce the problem.and SO. (2) The p< of a pH 10 solution to which HS.'-].+ 4H. What is the pH of the solution and the HOCI concentra~ion? (Neglect ionic strength effects. is the reaction for the reduction of the Cr2072.9 10. it develops a reddish color. and the temperature = 25°C. and OBc? 13.are in equilibrium with each other. ~ 10. Note that SIS) is not a stable species under these conditions. calcium hardness = 100 mglliter as CaCOl • Na+ = 30 mglliter. dissolved oxygen = 5 mglliter. [HS-J ~ [SO. Indicate the important elements of the cell and give the chemical reactions that are taking place as well as the point in the corrosion cell where they are occurring.Problems CT. assuming that irqn species are present in solution. Br2 • is added to a liter of water.5.=H++OBr-..) 12.0.+ 9W + 8e~ HS. pH ~ 10.8. SO. calculate ' (I) The p< of a pH 10 solution in equilibrium with the atmosphere at 25°C. .0 (b) Assume that 02(9) is in equilibrium with an aqueous system in which [HS-J + [SO. EC'r£J1~-JCrH = 1.7 Kh X ~6 x 10.} ratio in the solution in part (a.~3.. What is the partial pressure of oxygen under these conditions? Can significant concentrations of HS. HOBr. what are the molar concentrations of Br2.68 volt. (a) Diagram the "corrosion cell" that is probably causing the red water. one at pH 9 and the other at pH 6. Br.) II.'-J ~ 10-4 .O . if measurable concentrations of dissolved oxygen (>0. The (02(9) in the atmosphere is in equilibrium with two aqueous solutions.FeUID = 10.'. Given that the following reactions are at equilibrium? (E'~~mI)JFean = 0. (Note: This solution is not in equilibrium with the atmosphere.2). Analysis of the water shows that pH = 7.=H+ + Br.33 volts. including the fjr.'. + H.l X 10.5.+ HOBr.) (b) Also. K. Cr.'-J ~ 10 at equilibrium. 10-4 mole of bromine. 10-4 mole of C1 2 is added to 1 liter of water at 25°. calculate the [FeHJ/{Fe(OH)".9 and that [Br-) = !.

CORROSION Evans. Elmsford. Johnson. I and II. J. H. A. Aquatic Chemistry. 1. Atlas of Electrochemical Equilibria in Aqueous Solution. U. C. and Equilibria. Vols. 2nd ed" Pergamon.. Pergamon.r-N. W. Pourbaix. given the dose in part (a) and given that the reaction with NH3 is complete? (Assume that C1 2{g) is the source of chlorine. A. N. R. Morris. 1965. including those by J. 1970. J. and J. L.12. Jolley et al. ed. Garrels.. . Mass" 1964. New York. M. 1960. J.. R. Dean. H. Elmsford. D. Christ. and others are of interest. W. 1. (a) What chlorine dose (in mglliter as C12 ) is required to insure a free residual of 1.Y" 1966. Assume that the oxidation oI-NH 3 to N 2{g) is the only reaction which takes place in the effluent. . L. Solutions. Morgan. 1974. M. (Several chapters. H. Coo The Fundamentals of Corrosion..430 17. L. New York. Glaze et aI. how much hydrated lime (Ca(OH)J in moleslliter will have to be added so that no pH change results from chlorination with the dose in part (a)? 7. Reading. R. The Corrosion and Oxidation of Metals. and C. Merritt... ADDITIONAL READING OXIDATION-REDUCTION REACTIONS Butler. CHLORINE CHEMISTRY Jolley. Stumm. 5th ed" Van Nostrand. R.) ELECTROCHEMICAL MEASUREMENTS Willard.0 mglliter as Cl. and J. Instrumental Methods of Analysis. Oxidation-Reduction Reactions A secondary effluent contains 15 mgniter of NH. New York. Minerals. N..) (c) Assuming that the ammonia was initially present as NH4+ and taking into account the hydrogen ion resulting from the addition of Cl2(g). F.Y" 1975. R. Ann Arbor. Christman et aI. J. Scully. Wiley-Interscience. Jr. A. New York. Martins.. Harper.? (b) How much chloride ion (in mglliter) will be added to the effluent. St.. N" Ionic Equilibrium-A Mathematical Approach. Ann Arbor Science.. Water Chlorination-Environmental Impact and Health Effects. Mich" 1978. Addison-Wesley. Stevens et aI..

and 'K... in which case the formula for cK.. 'K. AI-S to AI-9 can be used. for example. = ([H+]".)/ "0.434 Ionization Fractions The accuracy of the non-zero a values for pH between the p'K values is as given above for diprotic acids.. .... = ([H+]"')/. can be used. Eqs... = ([H+]a. and if more accuracy is required. 'K.. An intermediate level of accuracy is often acceptable for the value that cannot be determined from the table.)/".

0306 0.7993 0.6131 0.1.9901 0.1367 0.8633 0.2401 0.9407 0.0 peKa + 4.7 peKa + 0.9091 0.0 pCKa + S.1 peKa + 0.2401 0.4 .A 0.0909 0.2007 0.IONIZATION.S peKa + 0.0010 0.0099 0.0 . - "'0 = [HAl/CT.O 1.I IONIZATION FRACTIONS FOR A MONOPROTIC ACID peR (or pH peKa ± . pCKa pCKa pCKa pCKa p'K.6 p'K.9407 0.0.pcH ± npH when p.0477 0.3869 0. = 0) = = pK.0.7153 0.7599 0.0477 0.5000 0.9901 0.4427 0.5 .3 pCKa + 1.9755 0.1 p'K.4427 0.9999 1.7153 0.3337 0.3 . + 1.6 .3 5 4 3 2 .7 .2847 0.6663 0.8337 0.0001 0.8337 0.7993 0.2 .1663 0.0.4 pCKa + O.0.5 pCKa + 1.6663 0.2847 0. FRACTIONS Al.0099 0.1.3337 0.1.0000 0.5000 0.0593 0.9999 0.0306 0.8 .0 pCKa + 1.2 peKa + 1.+O.000Q pCKa pCKa pCKa pCKa p'K.0001 0.7599 0.1.2 pCKa + 0.0000 0.6131 0.5 .9523 0.5573 0.0593 0.9990 0.1.0000 .9694 0.6.8 p'K.2007 0.5573 0.0. pCKa pCKa peKa pCKa peKi! pCKa + 0. pCKa pCKa p'K.8633 0.3 .9694 0.0 peKa + 3. + 2.0.0245 0.0.2 .9523 0.3869 0.+0.0245 0.6 .1367 0.0.6 p'K.0909 0.9990 0.0010 0.9091 0.9755 0.1663 0.

7.T.5 liter/mole-sec (a) k ~ In2 ~ 0./RT.25 X 10. .1 X 10.6 keaUmole 10. E. k ~ 4.IRT. (c) E. exp [(E.T2) (a) k.1 hr 10. 3. (a) 2.4 see-'.7 x 10-' sec (E.9 days) (b) Total time required ~ 3(12) + l.0279 hr-' 1 ~ 165 hr (or 6. Analysis of the plot in accordance with Eq.5 liter/mole-sec (b) k" ~ 3.\ ANSWERS TO PROBLEMS CHAPTER 2 1.89 X 10.8 mglliter. and La ~2. [A]-' versus t is linear whereas 1n [AJ versus t is curvelinear. (a) 1 ~ 3. t1 (b) I" ~ 3. 2·45 yields k k ~ ~ 0.4 sec (b) E.693 t.8 keallmole 11.11 (base 10).T.5 x 10-' mole/ee-min 1.Tl1 where 8 = exp (b) E.192 liter/mmole·see 6. Thus the rate is second order. Plot (I/y)'" versus 1 (days) and fit this plot with a straight line.322 I.)(T.70 X 2.l ~ 37. 1 ~ 157 min (a) k ~ 1. ~ ~ ~ 7. .7 keallmole (a) k ~ 0. 9. ~ 20.5 x 10-' molelliter·see (b) 2. 10. ~ k.5 x 10. 0.8 keaUmole 7.25 (base e) 0. 8.)] = k 1 O(T2. 1 ~ 7.10 mole/ee·see (c) 1. S.

reaction is endothermic. :.·68 0.32) ~ + 13.4 kcallmole Temperature rise = 35. 5. the maximum amount of energy available. :..0"" -> CH. K25 -1lH'(..- 9. . 10. ~ 10-. assuming pH ~ 8.. llG > 0.8 kcallmole CH. till' ~ -46. 7.15 x lO.. K = 10 1 1. Percent as HN0 3 = 8.7 kcal :.. (a) p.!.8% 8.6 x 10-' M llG' ~ -37. CH.436 Answers to Problems CHAPTER 3 I. (a) llG < 0. till.35 kg or 4.5 (b) llG < 0. -212. 3.(-56.) R - T40 T25 (a) K 40 ~ 2. Reaction goes to left.35 liter of H 20 at standard conditions will be vaporized.5 and po. (b) At equilibrium.95 x I{)-H (b) llHO is positive. ~ 0.1 till' ~ -54.9 kcal = ~208.COCOOH + H. :.(-68. _.Ow.07 [MgH] ~ 8. -26.7°C 4.. (a) K ~ 10-' moles liter·atm II.83 X 10. (a) K ~ 1.CHOHCOOH + tlGo .21 atm [Mn H ] ~ 2.26 kcallg CH..7) ~ +19. Mn2+ is still being oxidized after 10 days. 4. ~ 2. -13.!.n M ~ 12. 6. (b) pH ~ 7. (a) llG ~ -15.17 13.51 14.. Reaction goes to right. ~ 0.36 llG' ~ -RT In K K 2 5' = 1O~14 InK.13 (b) 'K (c) k. :..96 ..6 . Reaction goes to right.2 kcaI.

0 ~ ~ 6. Y±.N. Po.18 [O".'-J + [pO.5 X 10-23.-J + [HPO.. pH 10."J ~ 0 (d) Since 9.95 kcalfmole (b) K. pH ~ 9.66 (from Fig.35 At 25'C.pK.50 and pH ~ 5.4 mglliter) at 50'C.J + [H.0 (b) pH ~ 6.5 (a) C T.5 atm the reaction tends to go to the left.'-J When fL ~ 0. 437 uGo ~ +31.'-J + 3[PO.'-J + [OH-J (c) [Na+J + [WJ ~ [OWJ + [H. 3. ~ 0. (a) pH ~ 3.8% 5. [SO.6 When fL ~ 10-'.5 (c) pKb ~ pK" ." ~ 3.39 X 10-4 (4.-J ~ [pO.-J + 2[HPO.-J At WC.45 Proton condition: [WJ + 2[H.1 (a) pH ~ 7. ~ 6. ~ 0 [O". whenever the sludge is exposed to an atmosphere with a Pc~ of IO~3.o. \ 16. (a) uG1. Y±. (a) pH ~ 9. ~ 2 x 10-' M ~ [Na+J CT. pH ~ 5.'-J (b) [WJ + 2[H.5 mglliter) at 100'C.J + [HCO.62 x 10-' M (8.o2 p'H ~ 5.PO.5 > 8.00 Proton condition: [H+J pH ~ 3.'-J Approximate proton condition: [H+J ~ [HPO.25 (b) pH ~ 7. 3·4) and cK a. ~ 0."J ~ 1.PO.PO.Answers to Problems 15.o."J ~ 2.PO. [OH-J 9. 8. ~ 0.PO.J + [H. ~ I x 10-' M ~ [H.0 2.CO. Po.9.20 [O". P 0. pH ~ 9.12 Since Pc~ = K = 1.98 (a) pH ~ 10 (b) pH ~ 8. ~ 7.74 X 10-' (c) At 25'C. 4.'-J + [OH-J .. CHAPTER 4 I.2 = 1O~7. 7. ~ 0.4 (from part c) the solution is not at equilibrium.95 (b) 99.

. pK"..3..11 (b) (c) = 0.. = 0 (approx.21.85 X 10-' moles of phosphate salt added to I liter of solution. "..) + [NH.CO.). pCK a . p'K. 4.9. = 0.6859.12.. At pH = 6. = 0.3) (a) p'H <>0 = II. pK. ".-) = [H.8954.. = 0.3) (c) "0 = 0 (approx. pK".1.. = an acceptable buffer. ".'2 X 10-' moles Na.12 <>0 = 0. ".85 = 14. = 12.. = 7. Dilution ratio = 0.1 liter wastell liter stream.21. <>0 = 1. {3 17..3 x 10-' (exact) (pK. H. = 0 (approx.-) =2 X 10-' M.'-) + [OH-) 15.1367.+) pH = 7.). 1 moleslliter (b) {3 = 9. = 0 (approx...[HAc) pH = 10.8633. = 10. = 7. will give the desired result.8 X 10-' (exact) 12..9091 (pK. p'K".3 I-4+ p'H = 9.CO. p'K = 3.+ 4Na+ + SO.0909. Assuming complete reaction of the H+ added with HC0 3 -.8 x 10-' (exact) p'H = 7.00013 (exact) (pK. <>. or "0 = 1.9152 p'H = 6.01.15. [CO.iliter H. I X 10. = 0 (approx.CO. ".2 = 10.0. = 6.).01... + H'S04 .6 x 10-' 2Na.3 moles H+ can be addedlliter.3337. = 0. = 5. ".3. = 10.55. (a) Moles Na 2C0 3 required = moles H+/liter = 10-2 .) or ". = 2. or ".CO.7 = [OH-) where 13. = 0.438 10.1046. ".0848. the solution is supersaturated if no CO 2 escapes. = 4.P04. ". followed by adjustment of the pH to 8. = 1. pCKa .) + [NH. ". [HCO. = 0. = 0. (b) pHco. = 0.l5 x 10-' molesfliter 19.+ H+ . = 2.3141. p'K".. (a) At pH 8. = 4. ".+) + [W) + [Na+) = [Ac-) + [OH-) where [Na+) = 10-' and [Ac) = 10-' .6663. p'K. Charg'e balance: [Na+) + [H+) + [NH. [HCO.8. 2HCO.95. +) + [W) pCK a . p'K". (b) {3 = l.).). ". 1. N = 9.) = I x 10-' HCO.. (a) As the pH is lowered below 8. <>. = 0.+) [Na+) = [NH"". <>. = 12. Charge balance: [NH.2 x 10-' (exact).6 Proton condition: [H. = 7. pH = 9.7 X 10-' (exact).01 <>0 = 0 (approx.35 (c) pHco.5 ..1 = 6.2) (b) "0 = 0. 16.CO. = 3.. Answers to Problems (a) "0 = 0.2.. = 4.3.12 X 10-' molesfliter 18.

[HCO. M [HC0 3-] = !. [CO.] .000 mgCaC03/eq as CaC0 3 0.SO.CO.2 x 10-' M JL = 0.' 10 6 ft3 = 0.. [H." M.' - [H.8 x 10-' M Exact procedure: pH = 10. (b) 0. (a) Carbonate alkalinity = 2.'-] 9.-] = 4.0008 eqlliter Total acidity = 8 x 10-' eq/liter (c) C T.6)(0. [CO.6 meqlliter Caustic alkalinity = a (b) (Vmo .] = 6. 439 (a) (b) (c) (d) (e) Total Alkalinity Decrease Decrease No effect No effect Increase Total Acidity Increase Increase No effect Increase No effect 21. = 4. [H.'-] = 2.4 pHco.C~ = total alkalinity . [HCO.-] = 0.C03 = 3.] .H".8.= 10. must be added. [CO. .02 N H. [CO.02) 50 0.)(0.-] = 4.86 x 10-' M = H+ added per liter of lake water Thus 17. (a) Total alkalinity = 3 X 10-' eqlliter = 3 X 10-' eqlliter x 50.2 x of rain are required.'-] = 9.Answers to Problems 20.'.H".4 meq/liter Total alkalinity = 5.8 (e) Approximate procedure: pH = 10. M.55. (a) [CO.'-] = 3.3 moleslliter (d) pHco.1 x 10-' M. acidity = 10-' eq/liter Total acidity = 4 X 10-' eqlliter (d) pH = 7. Predominant reaction: H+ + HC0 3 - ~ H2CO.0 23.3 M = JL = 0: [H+] = 10-9.3 x 10-' M 25.CO.CO.4 x 10-' M.02) 50 (8 . CT.9 . [HCO.carbonate alkalinity = 5 X 10.5 x 10-' M 24.04 liter can be added per liter of natural water.Ql5 liter of 0.'-] = 2.1 x 10-' M.V.99 x 10-' M = 150 mglliter (b) Caustic and carbonate alkalinity = a Total alkalinity = 100 mglliter as CaC03 (c) Mineral acidity is zero CO.05 x 10-'.2 X 10. 22.IS x 10-3 M.01: [H+] = 10.

less EDTA than calculated above will be associated with the Mg2+ and more will be associated with the calcium.5 moles of Sr80". Thus. ~ [HgOW] I x 10-' M « [Hg(OHl. 6-4.5 (or [CO. Note that in the standard procedure for calcium titration. (b) OH. 1. Assume 4[NHCN). Using Fig. 5. CT. 9.99 x 10. 3.5 moles Mg 2+/liter will precipitate. 112 mgiliter as CaCO.(OH).93 x 10-' M :. ~ 1. pCO. 10. ~ 4 (or [CO. the pH is such that OH.440 Answers to Problems CHAPTER 5 2.) will precipitateiliter.Ca and 2SOio of CT. C T •Pb ~ 0.40 X 10-' moles Ca(OH).added: 7. pH ~ 5.1 x 10-5 M (b) [MgEDTA'-] ~ 7..'-] ~ 10-"'). 5% of C T.3. 3.will complex some of the Mg2+. Using the equilibrium constants for the complexes as given in Section 5·6.'-] When -log [MgH] ~ 3. (a) 8.6 (The concentrations of the Cu(OH). pCO.5.) From Fig.'. pH ~ 10.N! 7.02 x 10-5 moles Ca(OH).65. when -log [Ca H ] ~ 4. 4.Mg are in the form of sulfato complexes. (b) [8r H ] ~ 1. 6.0 . 10-').4 x 10-' [Ni(CN).5 M [CaEDTA'-] ~ 1.12 X 10-' molesiliter.4+] [Pb.36 X 10-' M 9.004 M 8.'+] ~ 0.'-] ~ 1.'+] ~ 1.and Cu(OHl.iliter to raise the pH.(OH).complexes are negligible. CHAPTER 6 I. 6-3.4 X 10.04 M ~ [Pb H ] + 4[Pb. (a) [MgEDTA'-] ~ 1.'-] » [HCN] + [CN-] Knowing [HCN] + [CN-] ~ 4[NiH] Calculate [N.o] ~ 9. the trimer and hexamer complexes are negligible.« is not complexed at the equivalence point for calcium.4 x 10.98 X 2. ~ 4.6 M) (a) 0. 5-2. .6 x 10-5 M [80.iliter (b) The amount in part (a) for coagulation plus 4..'-] '" 1.02 x 10-' M (a) From Fig. 25% of CT.

0 (K w /4a. [CO. pH ~ 8. and thus total alkalinity. Then."0) + [H+f .'-]o + X .-] ~ 4.-[H+] + U1KHPco22 -:. total alkalinity ~ 4. ([CaH]o . :.+ HCO.16 x 10-' Draw a diagram following the procedure given for Fig.5 atm. some will dissolve. (a) Neglecting [HCrO. Increase Decrease No effect Increase Increase Reason for (a): OH.)'" (2 . FeC0 3(s) will precipitate at pH 7.'-]o.Y)([CO.2a. X 6.O".61 X 10-'..'-]o + X . thus increasing [Ca 2+1 and total alkalinity. +.55 x 10-' M.55 (b) Taking HCrO.'-±b by this step solution is now supersaturated. Knowing [CaH]oX [CO.Kw/[H+] ~ 0 S ~ 8.into account. P.'-. 10.CO. using Appendix 1. Total Alkalinity (a) (b) (c) (d) (e) KOH Ca(NO~. that X > Y.8.'-]o ~ K". Then. [Ca H ] decreases [Ca [CO. Using Fig.Answers to Problems 5.. 10-'.'-]. 10-' and pH ~ 7. pH'~ 9. whenPc~ = 1O~1. 13 2aoKso .25 x 10-' moles/liter . 8. when [MgH] when [MgH] ~ ~ 441 3 4 X X 10-' M.'-]oY [CaH] ° and. Addition of CO 2 will have no effect on total alkalinity if CaC0 3 is not {s) present. moles CaC0 3is /liter that ppt K" Y.2 so solubility is increased by 6 X 1O~7 moleslliter. KHPC02U2 Kw + [H+] -. Reason for (e). increase in [CO. [Ca H ] ~ 2. we find that X _ Y ~ [CO. CO.25 X 10-' M. but the = CO/.no Uo (a) Using constants from Table 6-1. ~ 3.3.Y.55 x 10-' eq/liter.+ Ca2+ ~ CaC0 3(S). thus.Y) ~ X. 6. by expanding. Since CaC0 3{S) is present.:a""K=HP:. S ~ 8.-> CO.-]. However.3 whereas Fe(OH)2(s) will precipitate at 8. H ] ~ [CaH]o .C". 6·11. [HCO. simplifying and assum· ing both X and Yare much less than [CaH]o and [CO. we find that pH ~ 6. :.98. 9. it will cause the solution to become undersaturated with CaC0 3{S) because the solution pH is lowered.7. [Ca H ] Decrease Increase No effect Decrease Increase ~ KCl Na. total hardness ~ 2. pH ~ 10. increases.Y.'-] ~ [CO.9. .

INH"N) (a) (b) (c) 3:2 5:2 4: 1 7.6:1 12. probably accounts for the amount of the ratio in excess of 3:2. This precipitation will tend to occur as CO 2 is released during treatment or pumping. 2. (a) COD ~ 238 mglliter TOC ~ 76. = = (CT.18.5 M Ca(OH). 3.75 x 10-3 moles CaC0 3 /liter will precipitate.5 M 2.). [Ca'+] ~ 5 X 10-+ Thus 1. BOD ~ 187 mg/liter (c) Ult. ~ 0. BOD ~ 238 mglliter (b) COD ~ 187 mglliter TOC ~ 40 mglliter Ult.3 . moleslliter ~ (Ca(OH).442 Answers to Problems (b) When Pea. reaction (0) likely predominates. First determine (Ca(OH)2. CO 2 release should he controlled.4 mg/liter 2. Formation of a small amount of product such as N0 3 [Ca 2+] [Ca2+1initia.] wt ratio (Cl. BOD ~ 22. use equations 3 to 7 in Example 6·18 plus (Total alkalinitY}final = (Total alkalinity) Initial +2 (Ca(OH) 2' moleslliter) 2 [Ca 2+]'inal = [Ca2+1sa\ + 5 x 10. solution yields (see Example 6·15): ~ 8. const..5:1 20:1 Since the stoichiometry is just greater than 3:2. which requires a larger ratio. + Ca(OH)2added. to saturate the water as in Problem G16.CO)Unal = (CT.5 X 10-' x 10' ~ 2.75 X 10-+ M at equilibrium.5 X 10. thus. . 1.1.3. p'H ~ 8.7 15. Precipitation potential = I x 10. (see Example 6·18).).J/[NH.CO/initial CHAPTER 7 1.6 mglliter (d) COD ~ 1. the precipitation potential is 5. (C T .7 mglliter Ult. pH ~ ~ 10-'" atm.CO)!nllia! ~ 16. mole ratio req'd [HOCl]/[NH. -] ~ 10-'.85 mg/liter as Cl. Equations 3 to 7 in Example 6·18 plus Total acidity -2 [Ca"] (CT.75 X 10.21 [Ca"] ~ 9.5 mg/liter as CaCO. total alkalinity (eq/liter) [HCO. If ionic strength effects are not accounted for. moleslliter 17.9. pH ~ 8. added.4 = 2.] ~ [Cl. moles/liter).2 mgll as CaCO. 14. Then. + (Ca(OH).

S If pH ~ S. (b) COD ~ 102 mg/liter (c) Concentration of Cr20/.4 kcal 7.51 volt Since E' > 0. II.14 mmoles Ca(OH).1 mg/liter as CI.S mg/liter (c) 2.S (a) (I) P€ ~ continuing. Po.O + 2CIO. (b) 1. (a) 4Fe 2+ + 02!i1Q} + 4H+ :. 13.7 x 10-' M.2 x 10-5 M ~ -7.S 3. 8. P€ ~ 14. 5. the reaction is tending to proceed to the left.+ OCI. 12.CH. For step 2: 4.~ ll4.3 x 10" --> 0.68 ~ O. par mg CN-/litar.2 1.+ CI2CNO.46 From the Nernst equation.83 x 10-7 M 14.:::::: 4Fe 3 + + 2H 20.0.--> CNO.0. 10-" atm Since Po~ decreases as p€ decreases (and as the ratio [HS-]/[SO/-] increases).33 . + 3lH. (a) 0.O (b) For step I: 2. ~ 0 (a) llS.0 " 4. [Br. + H.1 mg/liter as C1 2 per mg CN-niter.Answers to Problems 443 4. EO EO ~ ~ + 1. E = . EO = + 0. + 3CI. (a) CN. [OBc] pH ~ 9.92 volt (b) K ~ 1. [HOCI] ~ 10-' ~ [HOBr] '" I x 10-'. 6.+ S6W -> l4Cil+' + 9CO. + H. 9.70 volt E' ~ EO' -(0.remaining = + 3NH. the stable form of S is 80/.. + 2CIO.73 mg/liter as CI.'. (2) P€ (b) [Fe H ] 15. (a) 3CH. the reduction of Cr2 0/. 0 (c) "'Go ~ -nFEo ~ -42.+ 2CO. EO ~ +0.+ 2H+ EO ~ 0." + 4H+ "" 4Fe'+ + 2H. P€ ~ ll.05 volt + 1.+ 2W -> N. 10. Because 0 3 will oxidize CI0 2-. . (b) P€ ~ ~ ~ -7.0.when measurable O 2 is present.14 volt Since E < 0. pH ~ 4.+ 30CI.50 +0.CN + 7Cr.1.] ~ 1.2 mmolesniter. (b) 4Fe H 3 is the stronger oxidizing agent.-0.OS9/n) log Q EO' ~ 1. (b) Total CI. 17. IS.Iliter .SS volt E' ~ 0.

69 -17.1 C{s) graphite C0219) I C02(aQ) CH.22 -89.0 -11.0 -165.05 -98.77 -288.0 -53.78 -144. acetate ~~q) H2(g) Fe~~) Fe[iq) Fe(OH)~.889 -167.30 -2. because a critical review of the research on which they are based has not been made.63 -116.0 -54.3 -124.31 -12.aQ) HCQiaq) CO&~q) CH3COO~.84 0 0 -21. TABLE 3·[ Thermodynamic Constants for Species of Importance in Water Chemistry" Species C~2at) kcaUmole -129.Ug ) H2 CO.) M~~"Jq) Mn02(S) .4 -197. The tables of constants should not be used for general reference.26 -92.140 -149.18 -269.4 0 -94.USEFUL DATA The tables and figure that follow are collected here for the convenience of students working on the problems in the text.31 -126.G" keal/mole CaC03 {S) calcite CaO(s) I -132.4 -111.45 -151.52 -166.9 0 -94. however.0 0 0 -20.00 -140.2 Illi" 6.18 -161.

Solutions..4 6.6357 -56. Species kcaVrnole -110.37 -19. Christ. Harper & Row.99 -199.G.892 -6.00 -49.976 Mg(OH)"" . Minerals. Cleveland. Chemical Rubber Publishing Company.93 0 -37.7979 -68.41 3.04 -19.9 0 -54. Garrels and C. R. .74 -49.34 3. which is approximately equal to that of unit mo- larity. L.815 -9. New York.372 -11.90 -4. M. Ohio.Useful Data 445 " TABLE 3-1 continued till.690 -177.54 NOiaQj NH3(g) NH3(aq) NHtaq) HN03(aq) 02(aQ) 02(g) ORt~q) H2O(g) H 20 W Sot~q) HS~q) H2 S(g) H2SCaq ) Source.957 -57. and Equilibria.27 -26.372 -3.22 -4.43 -3.\08. a For a hypothetical ideal state of unit molality.595 -54.01 -7.41 -221. and Handbook of Chemistry and Physics..32 -31.00 -26. 1965. kcallmole Mgt.3174 -216.

NO.OH'+ FNO. FINO..H.9 6.sO.8 9..7 Ferric ion Hydrofluoric acid Nitrous acid Acetic acid Aluminum ion Carbon dioxide and ccrrbonie acid Hydroxo iron (lID complex Fluoride ion Nitrite ion Acetate ion FINO.CO.3 9.OH'+ HCO."'" "'" '" [ '" '" Q c:: ~ TABLE 4-1 Acid HCIO.5 9.PO. HCI H.COOAl(H.1 7.7 4.3+ HF Acidity and Basicity Constants for Substances in Aqueous Solution at 25°C -log K.2 3.- Bisulfate ion Nitrate ion Water Iodate ion Sulfate ion Dihydrogen phosphate ion 21 17 17 14 14 13_2 12 11.CH.2 4.3 CIO. = pK. HSO.8 10. Fe(H.O).O 10.H.O).COOH Al(R.5 4.9 11.PO. H30 + HIO.1 2.Fe(H.SOlR. CH. Hydroxo aluminum (lID complex Bicarbonate ion . Perchloric acid Conjugate Base -log Kb = pKb Perchlorate ion Chloride ion Hydrochloric acid Sulfuric acid Nitric acid Hydronium ion lodie acid Bisulfate ion Phosphoric acid -7 --3 --3 a a 0_8 2 2.O).CIHSO.O)t+ H.

NH. .9 10..H.7 4.O NH 3(aql OH- Hydrogen sulfide Dihydrogen phosphate Hypochlorous acid Hydrocyanic acid Boric acid Ammonium ion Orthosilicic acid Phenol Bicarbonate ion Monohydrogen phos~ phate Trihydrogen silicate Bisulfide ion Water Ammonia Hydroxide ion 7.2 7.1 3.9 6.5 9. C.7 1.7 4.HSH.0'- Bisulfide ion Monohydrogen phosphate ion Hypochlorite ion Cyanide ion Borate ion Ammonia Trihydrogen silicate ion Phenolate ion Carbonate ion Phosphate ion Dihydrogen silicate ion Sulfide ion Hydroxide ion Amide ion Oxide ion 6.5 4...OH HCO. -9 -10 c: " is Q ~ 0 i'i / '" .7 4.H.3 9.8 6.5 9.SiO.HP042H.3 12.7 1.OC032P043H2 SiQlS'OHNH.3 9.C.H:$(aq) H.+ H.SiO.4 4.4 0 o.BO.SiO.PO. .1 7..3 12.3 9.6 14 14 -23 -24 HSHPOlOCICNB(OH).NH3I01Ql H.HOCI HCN(aQ) H.

"Calcium Carbonate Saturation Index and Alkalinity lnterpretations. 2. S.38 6.28 8.+ W. Ed . 3rd.68 x 10-" I.O "" CO~.47 1.'.53 pH of a "neutral" solution ({W) ~ (OW}) 0 15 20 25 30 40 7.. E.12 X IO-H 0.CO. °c 25 40 60 Reaction 5 10 15 20 I. Owen.35 6. Reinhold.83 13. 3.'-.27 1.18 7.17 14.47 7.20 1.OC Kw 0. Amer.74 CaCO"" + H+ "" Ca'+ + HCO.51 8.21 -2.30 6." J. Water Works Assoc . Larson and A.47 -2. pK •.76 Source. .46 6. 5.40 p(K"IK •.71 -1.-.30 HCO.43 10.34 1.41 1.OI x 10-" 1.08 7. T. pK" 8. . 1958.) Source. "" HCO. 1664 (1942).93 14.22 10.448 Useful Data TABLE 4-2 Ion Product of Water Temperature. pK H 1..35 14. 34.00 6. The Physical Chemistry of Electrolyte Solutions. 10. pK •. Buswell. Harned and B.09 8. TABLE 4-7 Temperature Dependence of Some Important Carbonate Equilibrium Constants Temperature.45 x 10-" 0.34 -2.42 6. -2.99 -1. CO~" + H.15 8. New York.64 1.49 10.22 8.8 H. B. .. 6.10 -1.47 X 10-" 2... H.+ W.56 10.52 '6.95 X 10-" pKw 14.14 CaCO"" "" Ca2+ + CO.38 10. 4. .33 10.34 8. M...00 13.92 6."" CO.

).8) (10.0 12. (calcite) CaCO.5 17.2) (9.11' (S.~ M(OHyn-/H.22 IS.7 10.9 33 14.84 9 8. Fe(OH).2 10 7. .8 14.0 8.0 ll.S 5.34 8.4 4. (dolomite) CaF. PbSO.8 -17.2 21.y{s) ~ zAY+ + yBZ-. SiO.S /31 is the equilibrium constant for the reaction. log f3.CrO. PbS MgNH. Mg(OH).7 10 19. 21. Pb(OH).PO.3 7.8 17.(pO. Zn(OH).5) (8.SO. Ag. PbCI. CaSO.2S log f3. c ( ) TABLE 6-1 Solubility Product Constants at 25°C' pKso Solid Fe(OH).0 34. AgCI Ag.59 2.). (amorph) a Solid EaSO.5 Equilibrium constants for the reaction AzE.2 -13. CaCO. Mn(OH).1 9.4 15. Ca. Mn+ + i OH.' Fe3 + AP+ log f3. FeS Fe2S3 A!(OH). log Ksob Cu2 + Fe2+ MnH ZnH CdH a b 11.1S (9. Ca(OH). ZnS pKso 38 17. .0 4.3 IS.3 4.8 (14.2) 8.8 27. (amorph) FePO. Fe.8) . Kso is the equilibrium constant for the reaction M(OH)(1(s) ~ Mn+ + nOH-. (amorph) AIPO.!) -38 -33 -19. 33. indicates an estimated value.(PO.3 88 33 21.7 3.S (15. MgCO.3 26.3 -14.3 5.6 4.74 12. Cu(OH).5 -12.8 10. (aragonite) CaMg(CO.Useful Data TABLE 5-1 449 "Equilibrium Constants for Mononuclear Hydroxo Complexes log f3.0 5.0 10.).15 4.

'" Ag".4 -28.33 -0.+ 2H+ + 2e.75 +4.0 2NO.8 +13.'" 2Cr H + 7H. + 2e.:::: 2S2:0lS{S) + 2H+ + 2e .:::: Sn(s) Hg.O S40l.0 02(aQ) + 4H+ + 4e.0 +22.+ H.13 +0.9 +6.~ Mg{s) Cr.7 +33.0 +35.0 +20.9 .72 -2.9 +4.41 +0.'.59 0 -46.88 +0.+ 2H.'.44 +1.59 +1.'" Na " + 6H.S.68 -0.O NO.0 SO.8 +21..39 +1.27 -0..68 +15.06 +0.:::= Zn(SJ Cd 2 + + 2e-:::= Cd(s) 2Hg 2+ + 2e.0 -7.10gK) H+ + e~ ~ -tH2(g) Na+ + e.5 -6.'.+ 12H+ + 10e.'" NH. + e.~ Cr 2 + MnO.:::= 2H2:0 SO.0 N 2 (g) + 8H+ + 6e.O..28 +0.5 +27..35 +0.'" H..0 SO.450 Useful Data TABLE 7·1 Standard Electrode Potentials at 25°C E' Reaction Volt PE' (=.:::= Fe{s) Cu 2 + + e. + 2H.'" HS.0 +2.13 +27.2 +14.'" 2Hg«() + 2CI- PhO"" + 4H+ + SO.g.+ IOH+ + 00.'" NO.'" SO.34 +0.5 +26.:::= Mn3+ Mn02{s) + 4H+ + 2e.5 -0.'.2 +14.'" MnO"" + 40HMnO.51 +1.76 -0.:::= Fe2+ + 2e .'" Br'll) + 2H..'" S".0 +21. + 2e.8 +0.8 +4.¢ 02(9) + H2O 0"" + 4H+ + 49. . + CIAu 3 + + 3e-:::= AU(sJ Zn H + 2e.0 0 -2.'.:::= Hg 22+ AP+ + 3e .8 +13.16 +0.'" Mn N + 4H.CI"" + 2e.24 +1.0 AgCI".= Ag+ Ag+ + e .68 -0.34 +2..0 +0.+ 9H+ + Be.'" 2H.9 +10.72 +25.:::= Ag (5) Fe(OH)"" + 3H+ + e.9 +20.0 -40.18 +0.'.+ 8H+ + 00.37 + 1.+ + 2H.0 +23.'" 2CI2HOBr + 2H+ + 2e.:::= AI(s) Sn2+ + 2e .17 +0.40 +0.+ 14H+ + 00.24 +2.84 +0.65 +1.07 +1.+ H.'" FeN + 3H.4 -2.23 +1.91 -1.22 +1..4 -2.8 -6..60 +1.68 +3.'" 2CICI".+ 8H+ + Sa.0 +5.23 +0.0 CI"g.+ 8H+ + 00.36 +1.:::= H2 S(g) SO.3 -12..:::= Cu+ Cu2+ + 2e-:::= eu(S) AgH + e-.56 +15.27 +0.0 +23.0 Cr 3 + + e.0 Mn4+ + e. NO.¢ 2NH 4+ NO.0 +25.'" NH.04 +0.+ 2H+ + 2e.4 +17...7 +5.::::: Na{s) Mg2+ + 2e.0 2HOCI + 2H+ + 2e.37 +28.89 +1.+ 2e.+ IOH+ + Be.+ 2e .14 +1.'" Ph".0 + 3e.77 -0.0 Ph N + 2e.:::= Mn H + 2H 2O Fe3+ Fe H + e .'" PhSO"" + 2H..5 -0.9 +2.+ 4H.0 03{g) + 2H+ + 2e. + 4H.'" CI"".'.+ + 3H... + 4H.5 +3.

. New York. continued EO Reaction Volt PEo ( ~~ log K ) Br. L. . Aquatic Chemistry.01 -0. E.09 +1. The Chemical Society.31 + 18. + 2e.(glucose) + 6H.H 12 0. + e ..Interscience. J. Special Publication No.54 +1. London.4 +24.12 + 19."" I"" + 2H. Morgan.44 +2.::::: CH~g) + 2H 2O 6CO"" + 24H+ + 24e . Martell."" C. Stability Constants of Metal Ion Complexes...:.48 +9. W.5 + 10.::::: 211.62 +0. G.+ 2e. Sillen and A."" 31CIO.45 +0.15 +0..20 -5."" HCOO-(formate) +1.C02(g) + 8H+ + Be .O 12(aq) + 2e ."" CIO.87 -0. 16.Useful Data 451 Table 7-\.23 Source.17 -0."" 2Bc 2HOI + 2H+ + 2e . 1970. Wiley.O CO"" + H+ + 2e. Stumm and J.:. 1964.


Y" 155 Childs. W" 54 Elving. G. 399. 196.t 202 Dean.H. 401 . R. 357. D. D.A. Hill. R. 409 Hunter. H..M" 157. 9.. R. C.R. 196..G.A" 430 Dean. 232. 1.F . 64. 157. T. 229. H.S.s. 23 Davies. G. e..445 Ghassemi. C. K. K.W.... P" 415 Benson. A. 38. I. R. 23. 57 Hansen...I" 415 Basolo. 237. J. 385 Deflino.D" 3 Gorchev..430. F" 198.S" 187.0.. K. 402.I" 83 Deffeyes.. 196 Kugelman.. 202 Cripps. M" 242 Benedek. R.430 Bywaters. S. C. 430 Kern.0" 380 Hembree.I" 60.. 238 Horath. L.S" 93.J. 411 Doudoroff.401. 237. K.F" 235.M" 209 Davies. I.. 409 Campbell.401. 26. 399. 294. T.N" 98. 400 Evans. 430. 411 Kuhn. I. 400. 305 Feth. E. 400.. 430 Kolthoff. 382. M. 238 lohnson.... 57 J. 1. 224 Downing. 76.. C. 242 Brewer. 9. 1.. H. A. W.B. W...L . 409 Grove.L . 398.F . W" 228. 57 Laitinen...M. 413 loms. 195. 234. 161 Khan. W. 94. 39 Laidler.D" 235. S. 448 Butler. 83. D. Jr" 47 Buswell.283 Deweist. 237 Hamed.H" 288. 445 Christiansen. 415 Eckhoff. 397. 93.A. p" 223.. I. 235..N.F" 80 Faust. 228 Delchamps. 302. H. A" 12 Caldwell. A. 402 Hammes. W" 235.. L. R..413 Feigenbaum.. G.A .L" 411 Chen... 242 Bourn. I.W" 288 Arhland... 5 Frost. 430 lolley. C. 1. M. 304 Knowles.. E. 396. 448 Healy. S" 202 Barduhn. 239. A. 367 Deboice. 47 Barnett.S" 39 Hamilt<~m. 294 Ferguson. E. R. 240. 411.. 231 Christ.. 240.K.W. A. E.D" 23 Hood. H" 402 Granat. 198 Ettinger. I. 242. 242.. 11 Christman. A..M . E. 282 Gjessing. 60.V. W... J. 57 Chave. 242.. 43.387. LA" 26. I. 54. LN. 415 Lawrence. 57 Langelier. M.H. 328 Lawrence.. 396. 304. 415 Eastman. 294 Gambell. 448 Latimer. 23 Directo.J.I. B.F" 302. 64. 242 Beck. G . W. T. 403. G.U . D . D. 304 lenne.M . L. 0 . S.A.283. 223 Lee.H" 430 Goldberg.H.. 245 Haldane. 289 Larson. E. 397. W" 216 Hem.B" 288 Leduc... 27.L" 23.O.B .I . 303. W. LV" 235. 239... 397.. 402 Gal·or.M" 7. 233. 236 Khandelwal.E. C. D. K. U.M" 3 Holland. 47 King..1 AUTHOR INDEX Arbatsky. 11 James. 400. 415 Horstkotte.. S. P.M" 5 Garrels.M..H . 430 Clatt.C. 209. DJ. Jr. 303.H" 5 Fisher. L..L .R. 196 Failey. W. 5 Greenwood.O" 363. 85 Glaze. 216 lenkins.315.E" 283 Chen. I. D.

387. 213. D.G . H.. A... I. 430 Scheraga. D. 75..C .E. 413.. 85 Morel. I.A.L ... C.451 Singer. G. 228 Morgan. 0. W. 398 Russel.. 216..T. A. K. 238 Makereth. ISS Taylor.G . 25.. 1 Schnitzer. M . 12 Palin.270.. 384..F .1. 76. R. I .1.. I. Ir . M. 315 Wei. R..K .. SO Thomas.. M.G. M. 283 Trussell.L. I.C . 448 Packham.L . 245. 430 Yahalom... W . 23.Z ...329. 77 Loehr. 424 Malcolm.M . R.S. A.B . 246 Ricci. J. B.. 85 Lind. 237. H. 10 Nemethy. C.. A. L. 12. 302. H.S. 196. A . 232 Painter..C.• 294 Saunier. 23. 236.. 237. 398 Parker.238. 310.E. 246 Neal. 242 Willard..N. 415 Lowenthan. 312. 415 Stevens. 386 Skinner.. 383.I .. 399. 233.. 289 Rubin. 228 Scully.N.I.. 28.. 24 Pearson.R .H.. 8... 294 Pye. 415 Mackenzie. 5 Rosen. A. 242 Siever. L. 225.. 242 Selleck. 240.. A. 153. 398.R.A. 396. M.A. 213. 57 Stensel.353.315. 2 Nielson.V...359.I..295. 223 Monod.L .. G. 242. 4 Sayee.. 303 Merrill. P. E.M . 292 Viney. 397.382. 202..S . R. M.. 60 Lewis. 386. 215...L .C . D. 234.A. H.S.A... 196. W.. 246.. P. 93. 215. 289 McCarty.... 398 Sanks. 430. R. I.I. 387. F. P.. 11 O'Brien. 223 Moore. R.430 Monis. 2 Schneider. 85 Pourbaix. 244..E. 5 Rogers.... C. R... 235. 367 Owen.D .329.E . W.. 247. 47 . G. 80. 85 Recht. a Sillen. 1. 75.. T.E.. 357 Temple. H. 57. 282 Reddy. Ir. 451 Sycip. R. 202. 5 Wilkins.:76. G . F . 198. M .. W.242. R. 24 Nancollas. 409 Pearson.J. I. 451 Marais.. 430 Stiff.H . W. A. 228 Pitzer. 409 Oakland.E . 196.R . 357.W" 398 Weber. L...L .. 228 Thompson.I. 214 Orton.. B. F.T . 387 Okey.. R.. 0.H . Jr. 200. 294 Merritt..216.. 430 Middleton. 400 Lee. 214 O'Melia. 402.H . 232. 237. K. 397. 415 Stumm. F... C. 25.B. 329..315.E .. C.383. 283 Whitehead. 242 Mirtoy.. 196 Roberson. P. 385 Thomas.. W.T . 53 Montgomery. I.L.244.329. I. 226 Stcdfeldt. G.377.I .L .F . 270.B .L . 238 Martell. 403. I. 398 Menar. R. 315 Niles. 430. 411. 288 Storrs..H. 237. M.242 Perrin. P . ISS Olin.G .. 244.G ..M.. F. 384.R. A.. 214 Wayl. 228. 400 Minear.. D. 239.E..0 . 217 Saguinsin.G ..C..G . A. B.A..A. 430 Walton. 24. 7 McKinley.353. 244. 398 Siegel.. H.454 Author Index Randall..A..C . A. R. H. 244. G.359... 451 Morris.

88 table of values. 183-184 calculation of carbonate species.> pC-pH diagram. 403 Acid and base: ampholyte. 87 rate of ionization. 246-247 Agriculture effect on natural water. 41-42. 78 of nonelectrolytes. 173-174 methyl orange. 139-145 weak acid-strong base. 100-191 calculation of carbonate species. pC-pH diagram. 405 Ammonia: pC-pH diagram. 190-192. 139-145 Acidity: analytical definition.SUBJECT INDEX Acetic Acid: buffer. 177. 89 equilibrium calculations. 136-139 strong acid-weak base. 302-303 Amperometric measurements. 215-217 Aerobic processes.74-82 Activity coefficient.59. 41-44 Active metals. . 9 Alkalinity. 114-133 ionic strength effect. 101-102 graphical solutions. 268-270. 88-89. 307-310. 409 Agglomeration of precipitates. 268. 174 contribution of noncarbonate species. 136-145 strong acid-strong base. 249 Adsorption: cobalt on silica. 88-89. 87 relationship of ionization constants. 422-427 Amperometric titration. 382-386 Acid rain. 179-180. 411-413 . 310 Amination. 17. 16-17. 52-54 Activation energy. 95-98 carbonate system. 108-114 free energy change of ionization. 407 Anaerobic digestion. 177 methyl orange acidity. 173-174 operational definition. 446-447 metal ions as acids. 92 . 97-98. 212. 183-190 carbonate. 175-177. 112-114 mass balances. 270. 97 . 173-192. 74-82 mean activity coefficient. 92 Activated complex. 86-87 conjugate acid. 284-287. 90-91.66. see Acid and base. 178-179 silicate contribution. strong acid and strong base. 101-101 proton reference level. 180-183 tota1. 213-214. 407-412 Aerobic respiration. 177 mineral acidity.base pairs. 44 Activated sludge. 290 analytical definition. 95-96 proton condition. 178-179 titration endpoint. 159. 173 phenol phthalein. 279-282 Aluminum phosphate solubility. 87 Bronsted and Lowry definition. 376. 180-183 Acid mine drainage. 280 Aluminum corrosion. 95-192 analytical concentration. 220-222. 366 Activity. 271. 98-97 general solution method. 173 relation Ie. 98-101 equilibrium relationships. 212. 108-110 titraJ:ion curve. 177 operational definition. 132-133 Amorphous solid. 93-95 titrations. 98-101 electroneutrality equation. 66. 143-145 Ammonium acetate. 174 relationship to pC-pH diagram. 183-190 carbon dioxide acidity. 179-180.173-174 Alum. 146. 174 caustic. 153-155 calculation of species. 8 Acid solution.93 ionization constants: definition. 425-427 'Amphoteric substance. 146. 279-282. ampholyte Anabaena. 392-399 titration curve. 156-192 charge balance. see Hydroxoaluminum complexes solubility. 79-82 of solids. 148 buffer intensity. 183-184. 121-123 reactions with chlorine. 409-410 kinetics.290 titration endpoint. 102-108 weak acid and weak base. 212 proton transfer. 375 Aluminum hydrOXide: complexes. 107-108. 140-143 Acetone. 190-192 measurement.

73-74 conditional solubility product. 79 open homogenous system: closed system comparison. 156 ionic strength effects.224. 197 oxidation in COD. 254-256. 162-164 Carbon dioxide hydration. 154 Central atom. 422 Carbon adsorption. 58-60 thermodynamic basis. 21. see pH buffers Cadmium hydroxide solubility. 173-192 carbon dioxide hydration. 156.206-209. magnesium ammonium phosphate precipitation. 25. 36-40 reaction order. 160-162 closed homogenous system: species calculation. inside back cover Bromine: distribution diagram. 2$4 Calomel electrode. inside front cover *Atomic Weights. 63-68. 208-209 Chlorine.448 importance. 24-54 catalysts.319-320.Lawrence diagram. 424 *Atomic Numbers. 92 Biochemical oxygen demand (BOD). 416-417. 36 monomolecular reaction. 254 effect on corrosion. 99 sodium dihydrogen phosphate. 174 Caustic sOda. 48-52 Thomas slope method. 60-82 Chemical kinetics. 256-258. 202-204 Chemical equilibrium: dynamic nature. 283 Arbatsky diagram. 227 Biological redox reactions. 147. 156-192 . 44-48 heterogenous. 98-101 use in water analysis. 45 elementary reaction. 388-404 aqueous chlorine. 99-100 Anode. 407 ~Boltzmann Constant. 321-322 Basic solution. 40-44 Chemical oxygen demand (COD). 220 Aphanizomenon. 53-54. 164-165 strong acid and base effect. SO-52 Biodegradation. 404-414 Biosynthesis. 27-36. 307-310 Anaerobic processes. 262-264 Cage effect. 389 predominance area diagram. 228. 368 Available chlorine. 45 Cathode. 251. 44-48 heterogenous. 251 thermodynamics. 254. 21. 199. 100 Chelates. 382-388 reactant orientation effect. 392-399 Chloride: argentometric determination.373 Buffers. 165-166 species concentration calculation. 157-159 equilibrium constants.404-405 Blanket rising. 363 Anodic stripping Yoltammetry. 26-27 temperature effect. 45 homogenous. 199 chelate effect. 161 Buffer intensity. 99 use in acid. 59-60 reaction mechanism. base calculations. 93-95 carhon dioxide hydration. 70-72. inside front cover Avogadro's Number. 407-412 Anion-cation balance. 387 Calcium phosphate precipitation. 387-388 Anaerobic digest~rs.456 Subject Index alkalinity and acidity. 254-256 Calcium hypochlorite. 250-251 mercurimetric determination. composition. 299-305 Calcium sulfate. 149-156. 322-324 Chloramines. 292-295 solubility. 197-198 Central ion. see Calcium carbonate Calcium carbonate: calcite precipitation and dissolution. 4-44 Atmosphere. 4. 202-203 stability. 161-162 empirical rate laws. 410-411 Carbonate alkalinity. 375-377 precipitation potential. 53 kinetics. 25 Atomic absorption spectrophotometry. 288 Arrhenius Law. 251 Caldwell. 354~357 Bromothymol blue. 147 solubility. 160-162 Catalysts. 410 blue-green algae. 407 Aragonite. 197-198 Charge balance: acid. 48-54 iron oxidation. 321-322. 99 salt. base reactions. 250 Calcium hydroXide. 244-247 temperature effect. 282-298 Calcium fluoride solubility. 28-38 reaction rate: acid. 197. 299 kinetics. 364 Cathodic protection. 283. 167-173 definition of systems. 36 rate laws. 45 homogenous. 156-157. 377-379 Caustic aHc:alinity. 26 Calcite. 174 Carbonate system.

386-387 measurement. 321-322 breakpoint reaction. demand. 237-238. 204-205. 363-366 concentration cell. IS-17 normal solution. 201 ion pairs. 391-392 equilibria. 11 Combined chlorine residual. 17-21 equivalents per million. 377 coatings. 220-222 effect on cyanide toxicity. 363 . 247. 22-23 equivalents. 201-204 stability constant: definition. 217-223 metal ion organic ligand. 47-48 Cobalt-platinum units. 392-399 chemistry. 378 impressed current. see Complexes Coordination number. 388-390 forms. 388 dose.211-212 Hydroxometal. 212 central atom. 216 hydroxoiron(llI). 204-205. 223-241 nomenclature. 403-404 humic substances. 366 cell. table of stability constants. 399-404 addition. 217-220. 204-206 rate of formation. 375 definition. 14-23 CaC03 system. 200. 243. 252-253 Complexes. 200-201 stability. 200 ligands. 253-254 Conductivity. 375-377 deoxygenation.227-231. 215 Hydroxolead(Il). 235 Colorado River. 403-404 phenols: 400-401 trihalomethane formation. 402-403 chloramines. 200 instability constant. 197-198 chelating agents. 222-224 effect on metal sorption. 232. 45-47. 220-222. 371-374 coptro!. 205-206. 299 Conditional solubility product. 391 Chloroform. 371-374 Concentration expression. 213-214. 197-200 metal ion hydrolYSis. 386-404 reactions with ammonia. 14-16 mass/volume. 363-378 active metals. 76-77 "Conversion factors. 339. 394-395 Common ion effect. 22 mass/mass. 198-199 Copper/copper sulfate electrode. 378-379 inhibitors. 201 EDTA. 225-226. 391-392 disinfectant. 418 cathodic protection.Subject Index available ·chlorine. 213-214 hydroxocobalt(IO. 210. 387-388 residual. 449 stepwise formation constant. 399-400 oxidation. 388-390 distribution diagram. 14-16 Mass/volume as 02. 210. 222-225 definition of terms. 225-226 cyanide. 418 Copper solubility. 425-427 pE-pH diagram. 225-226 Copper toxicity. 206-208 Coagulation. see Chemical oxygen demand Color of natural water. 378-379 selection of materials. 146. 377-379 chemical treatment. 226-231. 377 galvanizing. 215-217 COD. 377 insulation. 9. 167. 377 sacrificial anode. 392-399 reactions with inorganics. 402-403 Chloromercury(IO comph~xes.202-204 effect on copper toxicity.215-217 table of equilibrium constants. 403 organic nitrogen. 215-217 effect on natural water composition. 17-21 Condensed phosphates. 197-241 acid properties of metal cations. 391-392 nitrite. 199. 375. 387 importance in waters.214-215 Hydroxomercury(In. 392-399 . 201 table of values. 197 inert.238-241 effect on solubility. 354. 270 Coal carbonization waste.21 molar. 391-392 sunlight effect. 209-210 457 in coagulation/flocculation. 262-282 humic substances. 230-241 hydroxoaluminum. 349-354 properties. 212. 220-222 Corrosion. 206-208 coordination number. 209-217 metal ion inorganic ligand. 200 labile. 188. 390-392 iron.202-204 chloromercury(Il). 197-198 central ion. 240-241 overall formation constant. 204-208 Concentration cell. 198-200 NTA. 220-221.. 392 reactions with organics. 294-295. 198-199 copper. 197-200 dissociation constant. 235 Cobalt sorption on silica. 387-388 ice. 374-378. inside back cover Coordination compounds.449 importance in water chemistry.

333-338 Elementary reaction. 423 Fish toxicity. 247 lissolved oxygen. 410 Equilibrium constant. 388 EDTA. 370 rate. 36 :!ysteine. 146 Ferric hydrOXide. 424 Dry ice.70. 332-333 )eamination. 364~366 local action cell. 326 Electromotive series. 333-334 >istribution diagrams. 319-322 Eriochrome black T. 25. 82. 71 Enthalpy. 363 embrittlement. 388-390 )issolution kinetics. 157. 36 Embrittlement. 324-326. -197. 199. 363 tubercula formation. 389 phosphoric acid. 249. 409 activity. 25 East Bay Municipal Utility District. 264-268 Ferric phosphate. 71-74 table of values. 210. 226 )imethylglyoxime. 388 iodine. 319. 449 solubility product. 107. 336-338 Electroneutrality. 385 Ferrous ammonium sulfate. 47-48 Cyanide: complexes. 202 )iethyienetriamine pentaacetic acid (DPTA). 59-82 acid and base. 10. 409 Ferric chloride. 222-225 oxidation. 71 Facultative aerobe. 215. 422-427 polarographic measurements. 45-46. see Electromotive force Encrustive water. 222-223 ::. 93. 271-279 Ferrous phosphate sol'lbility. 393-399 )ichloromethylamine. 202-204. 387. 47-48 toxicity. 227. 203-204 Ethylenediaminetetraacetic acid (EDTA). 309 Cyanate. 327 Faraday's Law. coli. 223-224. 69. 409 Faraday. 414-427 amperometric measurements. 220. 248. 290 Endothermic reaction. 405-407. 375 pit formation. 368 passive metals. redox reactions. 370 rust.yanuric acid.289 Guntelberg approximation. 248. 363. 161 Earth atmosphere composition. 363. 309 Cyanamer P. 366-368 Electron activity. 4. 82. 12 . 422-424 Electromotive force (EMF). 220~224. 372-374 effects. 363 EMF. 368-371 red water. 414-422 Electrode poisoning. 44. (DO). 61 Enzyme kinetics. 38-40 Epilimnion. 448 mononuclear hydroxocomplexes. 389 hydrogen sulfide. 64 Entropy. 299 Eutrophication. 399 )iethylenetriamine. 367-368 reactions. 363 metal loss. 325-330 Electrochemical measurements.yclopropane. 310-312 Fick's Law. 205-206. 410 )aniell cell. 186-189 )enitrification. 309 Corrosion (Continued) differential oxygenation corrosion. 449 standard electrode potentials. 240 E. 78. 299 )ichloramine. 448 ion product of water. 338-339 Electron balance. see Ethylenediaminetetraacetic acid EH-pH diagrams. 366. 446-447 carbonate equilibria. 224 )isinfection. 363. 333-334 Winkler method. 227 Exothermic reaction. 90-91. 422-427 potentiometric measurements. 191-192. 409-411 letergents. 240-241 lihydroxybenzoic acid. 302-304 Crystal inhibitor.200. 450-451 Equivalent weight. 363 galvanic cell. 387 :::. see Dissolved oxygen )omestic sewage composition. 135. see pE-pH diagrams Electrochemical cell. 268. 135 >ivalent cation electrode. 424-425 redox reactions. 324-325.458 Subject Index Dropping mercury electrode. 61. 365-366 mechanism. 76-79. 251 Ferrobacillus ferrooxidans. 368 Fermentation. 134-135 bromine. 322 Ferrous hydroxide solubility. 245-246. 291 Crystal growth. 405 )eBye·Hiickellirniting law. 135 hypochlorous acid. 407. 422 Electrode polarization. 324-326. 107 )effeyes diagram. 240-241. 420-422 >0. 80-82 electrode. 18 Electron reference level. 370 Corrosive water. 328-329.

76 Ionization fractions. 283 Magnesium carbonate solubility. 284-287. 76-77 relationship to total dissolved solids. 123-125 Hypolimnion. 302-303 Inert complexes. 410 Indicator electrode. 107-108. 212. 432-434 Ion pairs. 364-366 Galvanic series. 415-416 Local action cell. 415-416 Kaolinite. 393. 215-217 Hydroxoiron(UD complexes. 43-44 distribution diagram. 328 Junction potential. 71-74 Henry's law. 211-212 Hydroxyapatite. 215 Hydroxolead(lD complexes. 136-139 Hydrocyanic acid. 205-206. 122-125 effect on activity coefficients. 199. 407 Ligand. 391-392 kinetics. 256-258 Magnesium hydroxide solubility. 344-348. 162. 158. 135 rate of dissociation. 200 Instability constant. 378-386. 301-304 Hydroxylamine. 75-82 relationship to specific conductiVity. 75 effect on acid and base. 88. 382 importance in waters. inside back cover Geochemical cycle. 298. 424-425 Maxwell-Boltzmann theory. 365-366 Magnesium ammonium phosphate solubility. 213-214 Formaldehyde. 327-330 Hydrogen iodide. 205-206. 382-386 removal from water. 330-332 table of values. 408 Formal potential. 306-310 Magnesium calcium carbonate. 165 HTH. 398 Hydrochloric acid: species concentration. 87 Hydroxoaluminum complexes. 94-95 Hydronium ion. 368-371. 92-93 of formation. 147. 403 Humin. 393. 366-368 Galvanized pipe. 254-256 Makereth electrode. 107 Hardness. 24-25. 135. 307-308 Hypochlorous Acid: distribution diagram. pC-pH diagram. 37. 325-326. 220. 44. 37 Hydrogen peroxide. 254-256 Liquid junction. 389 predominance area diagram. 410 459 Indian Creek reservoir. 270 Glass electrode. 43-44 Hydrogen sulfide: distribution diagram. 232-240 Galvanic cell. 209-210. 114-119 Hydrogen bromide. 378 'Gas constant. 225-226. 248. 38 Fulvic acid. 322-328. 201 Insulation. 138 Ionic strength: calculation. 215 corrosion. 298 Heat of reaction. 200. 134-135. base reactions. 377 Iodine. 134-135 monoprotic acids. 107 titration curve. 414-416 Induction period. 119-121. 418-420 Glucose. 336 Free chlorine residual. 394 -395 Free energy. 215. 213-214 Hydroxocoba1t(Il) complexes. 159. 214-215 Legumes. 7-8 Gibbs free energy. 344-348 pE. 37-38 Hydrogen electrode. 231-234 complexes with metals. 34-36. 378 IUPAC convention. 373-374. 357 Ion exchange. 232 Hydrazine. 364-366. 42 . 64. 251. 6-7. 264-268. 60-74 acid. 203-204. 321-322. 135. 444-445 Fructose. see Free energy Gibbsite. 431 multiprotic tlCids. 388 pC-pH diagram. 269. 22. 61-71 redox reactions. 271-279 pE·pC diagrams. 102-104. 289-292. 146. 223-224. 232-233 Humic substances. 197-200 Lime. 378 in ground waters.pH diagrams. 197. 200 Iron: carbonate solubility.Subject Index Flocculation. 403 characteristics. 271-279 complexes. 75-76 definition. 310-312 redox reactions. 398 Hyperion. 287 Growth rate. see Chemical kinetics Labile complexes. 403-404 Langelier index. 146 Kinetics. 376 Lead hydrOXide complexes. 230-241 reactions with chlorine. 414-415 Guntelberg approximation. 61. 378 hydrOXide solubility. 25. 200 Lactose. 227. 387 Humic acid. 358-363 phosphate solubility.431-432 table of values. 38 Groundwater composition. 78. 214-215 Hydroxomercury(I1} complexes. 64. 231-241. 295. 69.

392. 339-340 definition. see Oxidation reduction potential )rthophenanthroline. 349-354 iodine. 173 Michaelis. 338-339 relationship to equilibrium constant. 378-382 Percent available chlorine. 358-363. 411-413 Methylamine. 405-411. 300 Methane fermentation. 319 Partial pressure. 344-348 method of construction. 26-27 )RP. Microorganisms: catalysis by. 244-245 )cean. 419-420 pH buffers. 237-238.Menten constant. 46-47 Ozone. 204-205. 132-133 hydrocyanic acid. 399 Monad equation. 244-245 homogenous. 122 pE and pE": analogy to pH. 149-156. 39-40. 331-338. 146. 367-368 )rganic carbon determination. 373 acetic acid. 338-342 electron activity. 125-132 phosphoric acid. sodium hydroxide mixture. 235 pE·pC diagrams. 415 Nitrate reduction. inside front cover Permanganate value. see Seawater )hm's Law. 339-343 table of values. 339-343 relationship to free energy. 264-267. 37 Nitrogen fixation. 393-399 Nucleation. 146-156 buffer intensity. 414-415 yield. 123-125 ionic strength effect. 244 -245. 46. 104-106 Nitrification. 25-26 Mole fraction. 357 iron. 405-408 pE. 412-414 Mineral acidity. 217-220. 240-241 Nitrite oxidation. see Redox reactions Oxidizing agent. 13-14 effect of photosynthesis. 403 Oxidation reduction potential (ORP): measurement. 153-155 calculation of pH. 319 Oxygen electrode. 405-407 Nitrogen system. 404-405 effect on natural waters. 45. 227-231. 271-279 multiprotic acid. 177 Methyl orange alkalinity. 28-30. 48 )rganic phosphates. 13 effect of wastes. 422 table of values. 114-119 hypochlorous acid. 248. 342-343. 121-123 ammonium acetate. 13-14 growth rate. 66 Monochloramine. 413. pE. 146~ 147 pH calculation: qcetic acid. 92-93. 224 Nitrate. 322 . 66 Passivation. see Activity coefficient Mercuric chloride complexes. 450-451 Peat. 343-363 iron. 410 Nitrilotriacetic acid (NTA). 147-148 Metaphosphates. 25. 372. 405-407 Nitrogen dioxide decomposition. 92 Nickel determination. 348-363 bromine. 419-421 Neutral solution. 354-357 chlorine. 147-149 in natural waters. 129-130 temperature effects. 9 effect of complexes. 159. 366 pC. 238-241 effect of man. 119-121. 414-417.pH p·redominance area diagrams. 405. 339. 114-133 acid and base mixtures. 53-54 Microcystis. 302-304 pH. 375 Passive metals. 140-143 Mean activity coefficient.pC diagram. 211-212 Metal plating waste. 328-329. 320-321 Phase transformation. 8-9 effect of microorganisms. 122-125 iron system. 299-300 )rientation effect. 399 Methyl orange acidity.460 Subject Index Orthophosphates. 226-231. 300 Orthophosphoric acid. 405-407 Nitric acid. 405-408 Nitrogen trichloride. 146-147 Nernst equation. 424-425 Oxygen transfer. 409. 387. 393-399 Monochloremethylamine. 139. 132-133 ammonia system. 344-347 nitrogen system. 302-303 heterogenous.base systems. 328-329 Oxidation reduction reactions.pH diagrams. operational definition. 300 Oxalic acid. 130-132 succinic -acid. 321-322 ·Periodic table. 10-13 pH buffers. 177 Molecular collision. 392 Nitrogen cycle. 70. 53-54 Monomolecular reaction. 206-206 Mercuric hydroxide complexes. 321. 339-343 relationship to standard electrode potential. 36 Natural water composition: effect of agriculture. 407 .

302-305 effect of particle size. 300 Phosphoric acid: buffer. 301 condensed phosphates. 174. 300 organic phosphates. 310-312 magnesium ammonium phosphate precipitation. 392 Potassium chromate indicator. 73. 217-220 Rust. 342-343. 404-414 equivalent weight. 136-139 strong acid aTld weak base mixture. ammonia mixture. 418-420. 450-451 Redox reactions: balancing half·reactions. 174. 407 River water composition. 143-145 strong acid and strong base mixture. 415-418 Respiration. 299 equilibrium constants. 97 from mass and charge balances. 306 -310 metaphosphates. 46 Pyrophosphoric acid. 404 pH scale basis. 1. 378-379 Salt bridge. 97 -101 acid. reaction rate Recarbonation. 45. 281-282. 75. 331-332 Reaction rate. 46. 130-132 Photosynthesis. 251. 45-47. 316-318 biological electron acceptors. 139-145 strong base and weak acid mixture. 135 pC-pH diagram. 328-329. 8 composition. 87 Proton reference level. FfJ. 354-357 chlorine system. I. 322-338 Nemst equation. 298-299 iron phosphate precipitation. 418-420 phosphates. 151 Potentiometer. 1. 246-247 ripening. 97 sodium bicarbonate. 299. 79-82 . 244-247 Precipitation kinetics. 92 Poisoned electrode. 299-301 Polysulfides. 174 Phenyl arsine oxide. see Chemical kinetics. 300-301 hydroxyapatite. 246-247 aging. 36 Rain: acid raid. 372. 336 relationship to free energy.414-417.Subject Index acid and base mixtures.pC diagrams. 10. 316-322 Reducing agent. 349-354 iodine system. pH meter. 400-401 Pheriol phthalein acidity: 177 Phenol phthalein alkalinity.419-421 oxidation half. 415 Salting out coefficient. 363 Saccharase. 27-36.' 139-145 Phenanthroline. 147. 330-332 table of values. 414-422 Precipitation. 324-328. 148-149 distribution diagram. 319-322 importance in waters. 323. 422-424 Polyphosphates. 425-426 pH measurement. 357 Propylene. 375 Proton condition.409. 100-101 phosphoric acid. 343-363 reduction haH. 10. 67-70. 292-295 461 Predominance area diagram: bromine system. 246 calcium carbonate. 25. 422 Polarization. 38-40 Sacrificial anode. 407-412 biological redox reactions. 415 Potentiometric measurements. 45-47. PAO. 298-312 aluminum phosphate precipitation. 28-36 Reaction quotient. 10. 98 salt. 98 Proton hydration. 36 Protective oxides. 59-60 Reaction mechanism. 316 stoichiometry. 279-282 calcium phosphate precipitation. 136-145 hydrochloric acid. 317 Redox potential: formal potential. 156. 299 removal from wastewater.412 Rhizobium.reactions. 339. 299-301 hydrolysis. 299-300 orthophosphates. 300 structure. 97 Proton transfer. 299. 370 Reference electrode. 319 Red water. 378-386 Pyrophosphate phosphohydrolase. 244-247 agglomeration. 5-6 Rate laws. 25. 227. 89. 244-247 calcium phosphates. 13. 300 polyphosphates. 299-305 classification. 86-88 Pyrite. 331-338. 79-82 Salting out effect. 299-300 concentration in water. 288 Redox equilibria. 317 pE. 300 Radioactive decay. 36-40 Reaction order.reactions. 199 Phenol. 156. 301-304 importance in waters. 302-305 sodium tripolyphosphate. 246-247 Precipitation potential.

328 table of values. 125 enthalpy of formation. 250 calcium phosphates. 2 Saturated calomel electrode. 254-256. 80-82 Sequestering agent. 247-298 importance in waters. 220-221 Thermodynamics. 138-139 Surface water composition. 310-312 Voltmeter. 450-451 Standard free energy of formation. 251 Vivianite. 10-13 phosphate remova1.)odium thiosulfate. 279-282. 385 Thiobacillus thiooxidans. 7. adsorption of cobalt on. 252-253 Stoichiometric coefficient. 282-298 closed system. 227 Siderite. 45. 271-279 ferrous phosphate. 299. 217-220 Swamping electrolyte. 213-214 Synthetic detergents. 27 Sodium hydroxide solution: species calculation. 159.298. 410 Snow composition. 310-312 magnesium ammonium phosphate. 254-256 Jilver chloride. 254. 62-63.462 Subject Index stannous fluoride. 303-305 Trichloramine. 330-331 )odium trlpolyphosphate. 248-249 measurement. 251 ferrous carbonate. 324-328. 46-47 . 202 Sweep floc. 328. 268. 258-262 Solubility product. 306-310 Succinic acid. 174. 243-312 characteristics. 252-253 weak acid salts.291-292_ hydrogen bonding. 258-262 weak base salts. 227. 24. 254-258 ferric hydroxide. 287-295. 26-27. 250-251 Silver cyanide solubility. 299-305 common ion effect. 416 Sludge rising. 136-139 30dium hypochlorite. 306-310 equilibria. 217-220. 301. 249-251 table of values. 264-268 ferric phosphate. 41-42 f3-tricalcium phosphate. 300 Tubercules. 262-264 calcium carbonate. 295-298 open system. 88-89 Specific conductivity. 108 titration curve. 285-287 calcium fluoride. 247. 215-217 Silicates. 299 Ti tration curve: carbonate system. 248-251 definition. 147. 166-183 strong acid. 306-310 magnesium carbonate. 410-411 Sulfide oxidation. 450-451 IUPAC convention. 6-7. 262-282 conditional solubility product. 76-77 Specific ion electrodes. 122.6. 72-73.I . 190-192. 159 Sodium acetate. 385 Threshold odor number. 154. see Langelier index Scaling. strong base. 5-6 Soda ash.243. 215. 402-403 Tripolyphosphoric acid.287-289. 220 Spectroscopy. 70 Sulfuric acid. 290 Silver chloride. TrichlorophenoL 403 Trihalomethanes. 271-279 ferrous hydroxide. see Free energy of formation Stannous fluoride solubility. 321. 65 Struvite. 129-130 Sucrose hydrolysis. 136-139 weak acid. 310-312 relationship to solubility. 284-285 complex effect. 256-258 nagnesium hydroxide. 110-114 :. 449 Solvent levelling effect. 307-310. 409.299 )olubility: aluminum hydroxide. contribution to alkalinity. 74 titration curve. 139-143 Total dissolved solids. 243 log concentration diagrams. 264 oxygen activity coefficient in. 302-305 Water: conditioning. 3. 167.4. 370 V'ant Hoff equation. 268-270 aluminum phosphate. 310 cadmium hydroxide. 92. 264 composition. 252-253 competing ligand effect. 376-377 Seawater: cadmium solubility in. 300 )o!tening. 45-46. 270-282 complexation effect. 76 Transition" complex. 400-401 Threshold treatment. 249. 250-251 iilver cyanide. 60-82 Thiobacillus ferrooxidans. 220 Standard electrode potential. 287-289. 250-251 Silver chromate. 379-382 Silica. ISS. 38 SuHate reduction.271. 258-262 . 258-262 Silver electrode. 253-254. 9. 106-107. strong base. 387 species calculation. 328-329. 301. 415 Wastewater: effect on natural water. 363. 281-282. 393-399 2.odium sulfite. 299 Tenorite. 256-258. 243-244 equilibrium calculations. 415-417 Saturation index.

)56. 299 stabilization.Subject Index ionization.271. 324-325. 298. 349 463 softening. 448 effect of temperature. 333-334 X-Ray crystallography. 92-93 properties. 312 . 88. 87 rate of reaction. 147. 287 -289. 174. 93-94 ion prOduct. 1-3 redox stability. 159. 82. 167 Winkler method.243.

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