4.7 The Chemistry of Acid Rain

1622 Pages·2012·44.96 MB·English

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About the Authors
Acknowledgments
Dedication
Preface
Introduction to Chemistry
Chemistry in the Modern World
The Scientific Method
A Description of Matter
A Brief History of Chemistry
The Atom
Isotopes and Atomic Masses
Introduction to the Periodic Table
Essential Elements for Life
Essential Skills 1
End-of-Chapter Material
Molecules, Ions, and Chemical Formulas
Chemical Compounds
Chemical Formulas
Naming Ionic Compounds
Naming Covalent Compounds
Acids and Bases
Industrially Important Chemicals
End-of-Chapter Material
Chemical Reactions
The Mole and Molar Masses
Determining Empirical and Molecular Formulas
Chemical Equations
Mass Relationships in Chemical Equations
Classifying Chemical Reactions
Chemical Reactions in the Atmosphere
Essential Skills 2
End-of-Chapter Material
Reactions in Aqueous Solution
Aqueous Solutions
Solution Concentrations
Stoichiometry of Reactions in Solution
Ionic Equations
Precipitation Reactions
Acid-Base Reactions
The Chemistry of Acid Rain
Oxidation-Reduction Reactions in Solution
Quantitative Analysis Using Titrations
Essential Skills 3
End-of-Chapter Material
Energy Changes in Chemical Reactions
Energy and Work
Enthalpy
Calorimetry
Thermochemistry and Nutrition
Energy Sources and the Environment
Essential Skills 4
End-of-Chapter Material
The Structure of Atoms
Waves and Electromagnetic Radiation
The Quantization of Energy
Atomic Spectra and Models of the Atom
The Relationship between Energy and Mass
Atomic Orbitals and Their Energies
Building Up the Periodic Table
End-of-Chapter Material
The Periodic Table and Periodic Trends
The History of the Periodic Table
Sizes of Atoms and Ions
Energetics of Ion Formation
The Chemical Families
Trace Elements in Biological Systems
End-of-Chapter Material
Ionic versus Covalent Bonding
An Overview of Chemical Bonding
Ionic Bonding
Lattice Energies in Ionic Solids
Lewis Electron Dot Symbols
Lewis Structures and Covalent Bonding
Exceptions to the Octet Rule
Lewis Acids and Bases
Properties of Covalent Bonds
Polar Covalent Bonds
End-of-Chapter Material
Molecular Geometry and Covalent Bonding Models
Predicting the Geometry of Molecules and Polyatomic Ions
Localized Bonding and Hybrid Atomic Orbitals
Delocalized Bonding and Molecular Orbitals
Polyatomic Systems with Multiple Bonds
End-of-Chapter Material
Gases
Gaseous Elements and Compounds
Gas Pressure
Relationships among Pressure, Temperature, Volume, and Amount
The Ideal Gas Law
Mixtures of Gases
Gas Volumes and Stoichiometry
The Kinetic Molecular Theory of Gases
The Behavior of Real Gases
Essential Skills 5
End-of-Chapter Material
Liquids
The Kinetic Molecular Description of Liquids
Intermolecular Forces
Unique Properties of Liquids
Vapor Pressure
Changes of State
Critical Temperature and Pressure
Phase Diagrams
Liquid Crystals
Essential Skills 6
End-of-Chapter Material
Solids
Crystalline and Amorphous Solids
The Arrangement of Atoms in Crystalline Solids
Structures of Simple Binary Compounds
Defects in Crystals
Correlation between Bonding and the Properties of Solids
Bonding in Metals and Semiconductors
Superconductors
Polymeric Solids
Contemporary Materials
End-of-Chapter Material
Solutions
Factors Affecting Solution Formation
Solubility and Molecular Structure
Units of Concentration
Effects of Temperature and Pressure on Solubility
Colligative Properties of Solutions
Aggregate Particles in Aqueous Solution
End-of-Chapter Material
Chemical Kinetics
Factors That Affect Reaction Rates
Reaction Rates and Rate Laws
Methods of Determining Reaction Order
Using Graphs to Determine Rate Laws, Rate Constants, and Reaction Orders
Half-Lives and Radioactive Decay Kinetics
Reaction Rates--A Microscopic View
The Collision Model of Chemical Kinetics
Catalysis
End-of-Chapter Material
Chemical Equilibrium
The Concept of Chemical Equilibrium
The Equilibrium Constant
Solving Equilibrium Problems
Nonequilibrium Conditions
Factors That Affect Equilibrium
Controlling the Products of Reactions
Essential Skills
End-of-Chapter Material
Aqueous Acid-Base Equilibriums
The Autoionization of Water
A Qualitative Description of Acid-Base Equilibriums
Molecular Structure and Acid-Base Strength
Quantitative Aspects of Acid-Base Equilibriums
Acid-Base Titrations
Buffers
End-of-Chapter Material
Solubility and Complexation Equilibriums
Determining the Solubility of Ionic Compounds
Factors That Affect Solubility
The Formation of Complex Ions
Solubility and pH
Qualitative Analysis Using Selective Precipitation
End-of-Chapter Material
Chemical Thermodynamics
Thermodynamics and Work
The First Law of Thermodynamics
The Second Law of Thermodynamics
Entropy Changes and the Third Law of Thermodynamics
Free Energy
Spontaneity and Equilibrium
Comparing Thermodynamics and Kinetics
Thermodynamics and Life
End-of-Chapter Material
Electrochemistry
Describing Electrochemical Cells
Standard Potentials
Comparing Strengths of Oxidants and Reductants
Electrochemical Cells and Thermodynamics
Commercial Galvanic Cells
Corrosion
Electrolysis
End-of-Chapter Material
Nuclear Chemistry
The Components of the Nucleus
Nuclear Reactions
The Interaction of Nuclear Radiation with Matter
Thermodynamic Stability of the Atomic Nucleus
Applied Nuclear Chemistry
The Origin of the Elements
End-of-Chapter Material
Periodic Trends and the s-Block Elements
Overview of Periodic Trends
The Chemistry of Hydrogen
The Alkali Metals (Group 1)
The Alkaline Earth Metals (Group 2)
The s-Block Elements in Biology
End-of-Chapter Material
The p-Block Elements
The Elements of Group 13
The Elements of Group 14
The Elements of Group 15 (The Pnicogens)
The Elements of Group 16 (The Chalcogens)
The Elements of Group 17 (The Halogens)
The Elements of Group 18 (The Noble Gases)
End-of-Chapter Material
The d-Block Elements
General Trends among the Transition Metals
A Brief Survey of Transition-Metal Chemistry
Metallurgy
Coordination Compounds
Crystal Field Theory
Transition Metals in Biology
End-of-Chapter Material
Organic Compounds
Functional Groups and Classes of Organic Compounds
Isomers of Organic Compounds
Reactivity of Organic Molecules
Common Classes of Organic Reactions
Common Classes of Organic Compounds
The Molecules of Life
End-of-Chapter Material
Appendix A: Standard Thermodynamic Quantities for Chemical Substances at 25°C
Appendix B: Solubility-Product Constants (Ksp) for Compounds at 25°C
Appendix C: Dissociation Constants and pKa Values for Acids at 25°C
Appendix D: Dissociation Constants and pKb Values for Bases at 25°C
Appendix E: Standard Reduction Potentials at 25°C
Appendix F: Properties of Water
Appendix G: Physical Constants and Conversion Factors
Appendix H: Periodic Table of Elements
Appendix I: Experimentally Measured Masses of Selected Isotopes
Art and Photo Credits
Molecular Models
Photo Credits
About the Authors
Bruce A. Averill
Bruce A. Averill grew up in New England. He then received his B.S. with high honors in chemistry at Michigan State University in 1969, and his Ph.D.
in inorganic chemistry at MIT in 1973. After three years as an NIH and NSF Postdoctoral Fellow at Brandeis University and the University of
Wisconsin, he began his independent academic career at Michigan State University in 1976.
He was promoted in 1982, after which he moved to the University of Virginia, where he was promoted to Professor in 1988. In 1994, Dr. Averill
moved to the University of Amsterdam in the Netherlands as Professor of Biochemistry. He then returned to the United States to the University of
Toledo in 2001, where he was a Distinguished University Professor. He was then named a Jefferson Science Policy Fellow at the U.S. State
Department, where he remained for several years as a senior energy consultant. He is currently the founder and senior partner of Stategic Energy
Security Solutions, which creates public/private partnerships to ensure global energy security. Dr. Averill’s academic research interests are centered
on the role of metal ions in biology. He is also an expert on cyber-security.
In his European position, Dr. Averill headed a European Union research network comprised of seven research groups from seven different European
countries and a staff of approximately fifty research personnel. In addition, he was responsible for the research theme on Biocatalysis within the E. C.
Slater Institute of the University of Amsterdam, which consisted of himself as head and a team of 21 professionals, ranging from associate professors
to masters students at any given time.
Dr. Averill’s research has attracted a great deal of attention in the scientific community. His published work is frequently cited by other researchers,
and he has been invited to give more than 100 presentations at educational and research institutions and at national and international scientific
meetings. Among his numerous awards, Dr. Averill has been an Honorary Woodrow Wilson Fellow, an NSF Predoctoral Fellow, an NIH and NSF
Postdoctoral Fellow, and an Alfred P. Sloan Foundation Fellow; he has also received an NSF Special Creativity Award.
Over the years, Dr. Averill has published more than 135 articles dealing with chemical, physical, and biological subjects in refereed journals, and he
has also published 15 chapters in books and more than 80 abstracts from national and international meetings. In addition, he has co-edited a graduate
text on catalysis, and he has taught courses at all levels, including general chemistry, biochemistry, advanced inorganic, and physical methods.
Aside from his research program, Dr. Averill is an enthusiastic sailor and an avid reader. He also enjoys traveling with his family, and at some point in
the future he would like to sail around the world in a classic wooden boat.
Patricia Eldredge
Patricia Eldredge was raised in the U.S. diplomatic service, and has traveled and lived around the world. She has degrees from the Ohio State
University, the University of Central Florida, the University of Virginia, and the University of North Carolina, Chapel Hill, where she obtained her
Ph.D. in inorganic chemistry following several years as an analytical research chemist in industry. In addition, she has advanced offshore sailing
qualifications from both the Royal Yachting Association in Britain and the American Sailing Association.
In 1989, Dr. Eldredge was named the Science Policy Fellow for the American Chemical Society. While in Washington, D.C., she examined the impact of
changes in federal funding priorities on academic research funding. She was awarded a Postdoctoral Research Fellowship with Oak Ridge Associated
Universities, working with the U.S. Department of Energy on heterogeneous catalysis and coal liquefaction. Subsequently, she returned to the
University of Virginia as a Research Scientist and a member of the General Faculty.
In 1992, Dr. Eldredge relocated to Europe for several years. While there, she studied advanced Maritime Engineering, Materials, and Oceanography at
the University of Southampton in England, arising from her keen interest in naval architecture.
Upon her return to the United States in 2002, she was a Visiting Assistant Professor and a Senior Research Scientist at the University of Toledo. Her
research interests included the use of protein scaffolds to synthesize biologically relevant clusters. Dr. Eldredge has published more than a dozen
articles dealing with synthetic inorganic chemistry and catalysis, including several seminal studies describing new synthetic approaches to metal-
sulfur clusters. She has also been awarded a patent for her work on catalytic coal liquefaction.
Her diverse teaching experience includes courses on chemistry for the life sciences, introductory chemistry, general, organic, and analytical
chemistry. When not authoring textbooks, Dr. Eldredge enjoys traveling, offshore sailing, political activism, and caring for her Havanese dogs.
Acknowledgments
The authors would like to thank the following individuals who reviewed the text and whose contributions were invaluable in shaping the product:
Rebecca Barlag, Ohio University
Greg Baxley, Cuesta College
Karen Borgsmiller, Hood College
Simon Bott, University of Houston
David Burgess, Rivier College
William Bushey, St. Marks High School and Delaware Technical Junior College
Li-Heng Chen, Aquinas College
Jose Conceicao, Metropolitan Community College
Rajeev Dabke, Columbus State University
Michael Denniston, Georgia Perimeter College
Nathanael Fackler, Nebraska Wesleyan University
James Fisher, Imperial Valley College
Brian Gilbert, Linfield College
Boyd Goodson, Southern Illinois University, Carbondale
Karin Hassenrueck, California State University, Northridge
James Hill, California State University, Sacramento
Robert Holdar, North Lake College
Roy Kennedy, Massachusetts Bay Community College
Kristina Knutson, Georgia Perimeter College
Chunmei Li, University of California, Berkeley
Eric Malina, University of Nebraska
Laura McCunn-Jordan, Marshall University
Giovanni Meloni, University of San Francisco
Mark Ott, Jackson Community College
Robert Pike, The College of William & Mary
Dedication
To Harvey, who opened the door
and to the Virginia Tech community for its resilience and strength. We Remember.
Preface
In this new millenium, as the world faces new and extreme challenges, the importance of acquiring a solid foundation in chemical principles has
become increasingly important to understand the challenges that lie ahead. Moreover, as the world becomes more integrated and interdependent, so
too do the scientific disciplines. The divisions between fields such as chemistry, physics, biology, environmental sciences, geology, and materials
science, among others, have become less clearly defined. The goal of this text is to address the increasing close relationship among various disciplines
and to show the relevance of chemistry to contemporary issues in a pedagogically approachable manner.
Because of the enthusiasm of the majority of first-year chemistry students for biologically and medically relevant topics, this text uses an integrated
approach that includes explicit discussions of biological and environmental applications of chemistry. Topics relevant to materials science are also
introduced to meet the more specific needs of engineering students. To facilitate integration of such material, simple organic structures,
nomenclature, and reactions are introduced very early in the text, and both organic and inorganic examples are used wherever possible. This
approach emphasizes the distinctions between ionic and covalent bonding, thus enhancing the students’ chance of success in the organic chemistry
course that traditionally follows general chemistry.
The overall goal is to produce a text that introduces the students to the relevance and excitement of chemistry. Although much of first-year chemistry
is taught as a service course, there is no reason that the intrinsic excitement and potential of chemistry cannot be the focal point of the text and the
course. We emphasize the positive aspects of chemistry and its relationship to students’ lives, which requires bringing in applications early and often.
Unfortunately, one cannot assume that students in such courses today are highly motivated to study chemistry for its own sake. The explicit
discussion of biological, environmental, and materials issues from a chemical perspective is intended to motivate the students and help them
appreciate the relevance of chemistry to their lives. Material that has traditionally been relegated to boxes, and thus perhaps perceived as peripheral
by the students, has been incorporated into the text to serve as a learning tool.
To begin the discussion of chemistry rapidly, the traditional first chapter introducing units, significant figures, conversion factors, dimensional
analysis, and so on, has been reorganized. The material has been placed in the chapters where the relevant concepts are first introduced, thus
providing three advantages: it eliminates the tedium of the traditional approach, which introduces mathematical operations at the outset, and thus
avoids the perception that chemistry is a mathematics course; it avoids the early introduction of operations such as logarithms and exponents, which
are typically not encountered again for several chapters and may easily be forgotten when they are needed; and third, it provides a review for those
students who have already had relatively sophisticated high school chemistry and math courses, although the sections are designed primarily for
students unfamiliar with the topic.
Our specific objectives include the following:
1. To write the text at a level suitable for science majors, but using a less formal writing style that will appeal to modern students.
2. To produce a truly integrated text that gives the student who takes only a single year of chemistry an overview of the most important
subdisciplines of chemistry, including organic, inorganic, biological, materials, environmental, and nuclear chemistry, thus emphasizing unifying
concepts.
3. To introduce fundamental concepts in the first two-thirds of the chapter, then applications relevant to the health sciences or engineers. This
provides a flexible text that can be tailored to the specific needs and interests of the audience.
4. To ensure the accuracy of the material presented, which is enhanced by the author’s breadth of professional experience and experience as active
chemical researchers.
5. To produce a spare, clean, uncluttered text that is less distracting to the student, where each piece of art serves as a pedagogical device.
6. To introduce the distinction between ionic and covalent bonding and reactions early in the text, and to continue to build on this foundation in the
subsequent discussion, while emphasizing the relationship between structure and reactivity.
7. To utilize established pedagogical devices to maximize students’ ability to learn directly from the text. These include copious worked examples in
the text, problem-solving strategies, and similar unworked exercises with solutions. End-of-chapter problems are designed to ensure that students
have grasped major concepts in addition to testing their ability to solve numerical, problems. Problems emphasizing applications are drawn from
many disciplines.
8. To emphasize an intuitive and predictive approach to problem solving that relies on a thorough understanding of key concepts and recognition of
important patterns rather than on memorization. Many patterns are indicated throughout the text as notes in the margin.
The text is organized by units that discuss introductory concepts, atomic and molecular structure, the states of matter, kinetics and equilibria, and
descriptive inorganic chemistry. The text breaks the traditional chapter on liquids and solids into two to expand the coverage of important and topics
such as semiconductors and superconductors, polymers, and engineering materials.
In summary, this text represents a step in the evolution of the general chemistry text toward one that reflects the increasing overlap between
chemistry and other disciplines. Most importantly, the text discusses exciting and relevant aspects of biological, environmental, and materials science
that are usually relegated to the last few chapters, and it provides a format that allows the instructor to tailor the emphasis to the needs of the class. By
the end of , the student will have already been introduced to environmental topics such as acid rain, the ozone layer, and periodic extinctions, and to
biological topics such as antibiotics and the caloric content of foods. Nonetheless, the new material is presented in such a way as to minimally perturb
the traditional sequence of topics in a first-year course, making the adaptation easier for instructors.
Chapter 1
Introduction to Chemistry
As you begin your study of college chemistry, those of you who do not intend to become professional chemists may well wonder why you need to
study chemistry. You will soon discover that a basic understanding of chemistry is useful in a wide range of disciplines and career paths. You will also
discover that an understanding of chemistry helps you make informed decisions about many issues that affect you, your community, and your world.
A major goal of this text is to demonstrate the importance of chemistry in your daily life and in our collective understanding of both the physical world
we occupy and the biological realm of which we are a part. The objectives of this chapter are twofold: (1) to introduce the breadth, the importance, and
some of the challenges of modern chemistry and (2) to present some of the fundamental concepts and definitions you will need to understand how
chemists think and work.
An atomic corral for electrons. A corral of 48 iron atoms (yellow-orange) on a smooth copper surface (cyan-purple) confines the electrons on
the surface of the copper, producing a pattern of “ripples” in the distribution of the electrons. Scientists assembled the 713-picometer-diameter corral
by individually positioning iron atoms with the tip of a scanning tunneling microscope. (Note that 1 picometer is equivalent to 1 × 10-12 meters.)
1.1 Chemistry in the Modern World
LEARNING OBJECTIVE
1. To recognize the breadth, depth, and scope of chemistry.
Chemistry is the study of matter and the changes that material substances undergo. Of all the scientific disciplines, it is perhaps the most extensively
connected to other fields of study. Geologists who want to locate new mineral or oil deposits use chemical techniques to analyze and identify rock
samples. Oceanographers use chemistry to track ocean currents, determine the flux of nutrients into the sea, and measure the rate of exchange of
nutrients between ocean layers. Engineers consider the relationships between the structures and the properties of substances when they specify
materials for various uses. Physicists take advantage of the properties of substances to detect new subatomic particles. Astronomers use chemical
signatures to determine the age and distance of stars and thus answer questions about how stars form and how old the universe is. The entire subject of
environmental science depends on chemistry to explain the origin and impacts of phenomena such as air pollution, ozone layer depletion, and global
warming.
The disciplines that focus on living organisms and their interactions with the physical world rely heavily on biochemistry, the application of chemistry
to the study of biological processes. A living cell contains a large collection of complex molecules that carry out thousands of chemical reactions,
including those that are necessary for the cell to reproduce. Biological phenomena such as vision, taste, smell, and movement result from numerous
chemical reactions. Fields such as medicine, pharmacology, nutrition, and toxicology focus specifically on how the chemical substances that enter our
bodies interact with the chemical components of the body to maintain our health and well-being. For example, in the specialized area of sports
medicine, a knowledge of chemistry is needed to understand why muscles get sore after exercise as well as how prolonged exercise produces the
euphoric feeling known as “runner’s high.”
Examples of the practical applications of chemistry are everywhere (). Engineers need to understand the chemical properties of the substances when
designing biologically compatible implants for joint replacements or designing roads, bridges, buildings, and nuclear reactors that do not collapse
because of weakened structural materials such as steel and cement. Archaeology and paleontology rely on chemical techniques to date bones and
artifacts and identify their origins. Although law is not normally considered a field related to chemistry, forensic scientists use chemical methods to
analyze blood, fibers, and other evidence as they investigate crimes. In particular, DNA matching—comparing biological samples of genetic material to
see whether they could have come from the same person—has been used to solve many high-profile criminal cases as well as clear innocent people who
have been wrongly accused or convicted. Forensics is a rapidly growing area of applied chemistry. In addition, the proliferation of chemical and
biochemical innovations in industry is producing rapid growth in the area of patent law. Ultimately, the dispersal of information in all the fields in
biochemical innovations in industry is producing rapid growth in the area of patent law. Ultimately, the dispersal of information in all the fields in
which chemistry plays a part requires experts who are able to explain complex chemical issues to the public through television, print journalism, the
Internet, and popular books.
Figure 1.1 Chemistry in Everyday Life
Although most people do not recognize it, chemistry and chemical compounds are crucial ingredients in almost everything we eat, wear, and use.
By this point, it shouldn’t surprise you to learn that chemistry was essential in explaining a pivotal event in the history of Earth: the disappearance of
the dinosaurs. Although dinosaurs ruled Earth for more than 150 million years, fossil evidence suggests that they became extinct rather abruptly
approximately 66 million years ago. Proposed explanations for their extinction have ranged from an epidemic caused by some deadly microbe or
virus to more gradual phenomena such as massive climate changes. In 1978 Luis Alvarez (a Nobel Prize–winning physicist), the geologist Walter
Alvarez (Luis’s son), and their coworkers discovered a thin layer of sedimentary rock formed 66 million years ago that contained unusually high
concentrations of iridium, a rather rare metal (part (a) in ). This layer was deposited at about the time dinosaurs disappeared from the fossil record.
Although iridium is very rare in most rocks, accounting for only 0.0000001% of Earth’s crust, it is much more abundant in comets and asteroids.
Because corresponding samples of rocks at sites in Italy and Denmark contained high iridium concentrations, the Alvarezes suggested that the impact
of a large asteroid with Earth led to the extinction of the dinosaurs. When chemists analyzed additional samples of 66-million-year-old sediments from
sites around the world, all were found to contain high levels of iridium. In addition, small grains of quartz in most of the iridium-containing layers
exhibit microscopic cracks characteristic of high-intensity shock waves (part (b) in ). These grains apparently originated from terrestrial rocks at the
impact site, which were pulverized on impact and blasted into the upper atmosphere before they settled out all over the world.