Physical Chemistry (3rd Edition)
The third edition of this book builds on user and reviewer comments on the previous editions. Our goal remains to provide students with an accessible overview of the whole field of physical chemistry while focusing on basic principles that unite the subdisciplines of the field. We continue to present new research developments in the field to emphasize the vibrancy of physical chemistry. Many chapters have been extensively revised as described below. We include additional end-of-chapter concept problems and most of the numerical problems have been revised. The target audience remains undergraduate students majoring in chemistry, biochemistry, and chemical engineering, as well as many students majoring in the atmospheric sciences and the biological sciences. The following objectives, illustrated with brief examples, outline our approach to teaching physical chemistry.
• Focus on teaching core concepts. The central principles of physical chemistry are explored by focusing on core ideas, and then extending these ideas to a variety of problems. The goal is to build a solid foundation of student understanding rather than cover a wide variety of topics in modest detail. • Illustrate the relevance of physical chemistry to the world around us. Many students struggle to connect physical chemistry concepts to the world around them. To address this issue, example problems and specific topics are tied together to help the student develop this connection. Fuel cells, refrigerators, heat pumps, and real engines are discussed in connection with the second law of thermodynamics. The particle in the box model is used to explain why metals conduct electricity and why valence electrons rather than core electrons are important in chemical bond formation. Examples are used to show the applications of chemical spectroscopies. Every attempt is made to connect fundamental ideas to applications that are familiar to the student. Art is used to convey complex information in an accessible manner as in the images here of U.S. carbon dioxide emissions.
• Present exciting new science in the field of physical chemistry. Physical chemistry lies at the forefront of many emerging areas of modern chemical research. Recent applications of quantum behavior include band-gap engineering, quantum dots, quantum wells, teleportation, and quantum computing. Single-molecule spectroscopy has led to a deeper understanding of chemical kinetics, and heterogeneous catalysis has benefited greatly from mechanistic studies carried out using the techniques of modern surface science. Atomic scale electrochemistry has become possible through scanning tunneling microscopy. The role of physical chemistry in these and other emerging areas is highlighted throughout the text. The following figure shows direct imaging of the arrangement of the atoms in pentacene as well as imaging of a delocalized molecular orbital using scanning tunneling and atomic force miscroscopies.
• Web-based simulations illustrate the concepts being explored and avoid math overload. Mathematics is central to physical chemistry; however, the mathematics can distract the student from “seeing” the underlying concepts. To circumvent this problem, web-based simulations have been incorporated as end-of-chapter problems throughout the book so that the student can focus on the science and avoid a math overload. These web-based simulations can also be used by instructors during lecture. An important feature of the simulations is that each problem has been designed as an assignable exercise with a printable answer sheet that the student can submit to the instructor. The Study Area in MasteringChemistry® also includes a graphing routine with a curve-fitting capability, which allows students to print and submit graphical data. The 50 web-based simulations listed in the end-of-chapter problems are available in the Study Area of MasteringChemistry® for Physical Chemistry. MasteringChemistry® also includes a broad selection of end-of-chapter problems with answer-specific feedback. • Show that learning problem-solving skills is an essential part of physical chemistry. Many example problems are worked through in each chapter. They introduce the student to a useful method to solve physical chemistry problems.
1 Fundamental Concepts of Thermodynamics 1 2 Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics 17 3 The Importance of State Functions: Internal Energy and Enthalpy 45 4 Thermochemistry 67 5 Entropy and the Second and Third Laws of Thermodynamics 85 6 Chemical Equilibrium 125 7 The Properties of Real Gases 165 8 Phase Diagrams and the Relative Stability of Solids, Liquids, and Gases 181 9 Ideal and Real Solutions 209 10 Electrolyte Solutions 243 11 Electrochemical Cells, Batteries, and Fuel Cells 259 12 From Classical to Quantum Mechanics 293 13 The Schrödinger Equation 309 14 The Quantum Mechanical Postulates 331 15 Using Quantum Mechanics on Simple Systems 343 16 The Particle in the Box and the Real World 361 17 Commuting and Noncommuting Operators and the Surprising Consequences of Entanglement 383 18 A Quantum Mechanical Model for the Vibration and Rotation of Molecules 405 19 The Vibrational and Rotational Spectroscopy of Diatomic Molecules 431 20 The Hydrogen Atom 465
21 Many-Electron Atoms 483 22 Quantum States for Many-Electron Atoms and Atomic Spectroscopy 507 23 The Chemical Bond in Diatomic Molecules 537 24 Molecular Structure and Energy Levels for Polyatomic Molecules 567 25 Electronic Spectroscopy 601 26 Computational Chemistry 631 27 Molecular Symmetry 687 28 Nuclear Magnetic Resonance Spectroscopy 715 29 Probability 747 30 The Boltzmann Distribution 771 31 Ensemble and Molecular Partition Functions 793 32 Statistical Thermodynamics 825 33 Kinetic Theory of Gases 857 34 Transport Phenomena 877 35 Elementary Chemical Kinetics 909 36 Complex Reaction Mechanisms 955 APPENDIX A Math Supplement 1007 APPENDIX B Data Tables 1029 APPENDIX C Point Group Character Tables 1047 APPENDIXD Answers to Selected End-of-Chapter Problems 1055
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