Tài liệu Chemistry and Chemical Reactivity, Sixth Edition - John C. Kotz, Paul M. Treichel, Gabriela C. Weaver

Tutorials Active Figures Additional Resources 1 Matter and Measurement • Screen 1.5: Mixtures and Pure Substances • Screen 1.12: Chemical Changes • • • • • 1.1: Classifying Matter • 1.2: States of Matter–Solid, Liquid, and Gas • 1.3: Levels of Matter • 1.15: Comparison of Farenheit, Celsius, and Kelvin Scales • Screen 1.6: Separation of Mixtures • Screen 1.7: Elements and Atoms • Screen 1.13: Chemical Change on the Molecular Scale 2 Atoms and Elements • Screen 2.6: Electrons • Screen 2.8: Protons • Screen 2.10: The Nucleus of the Atom • Screen 2.16: The Periodic Table • Screen 2.11: Summary of Atomic Composition • Screen 2.14: The Mole • Screen 2.15: Moles and Molar Mass of the Elements • 2.3: Measuring the Electron’s Charge to Mass Ratio • 2.6: Rutherford’s Experiment to Determine the Structure of the Atom • 2.8: Mass Spectrometer • 2.10: Some of the 113 Known Elements • • • • • 3.1: Reaction of the Elements Aluminum and Bromine • 3.4: Ways of Depicting the Methane (CH4) Molecule • 3.6: Ions • 3.8: Common Ionic Compounds Based on Polyatomic Ions • 3.10: Coulomb’s Law and Electrostatic Forces • 3.17: Dehydrating Hydrating Cobalt(II) Chloride, CoCl2 · 6H2O • Screen 3.13: Alkanes 3 Molecules, • Screen 3.19: Hydrated Ions, and Their Compounds Compounds • • • • • • 4 Chemical Equations and Stoichiometry Screen 1.10: Density Screen 1.15: Temperature Screen 1.16: The Metric System Screen 1.17: Using Numerical Information Screen 3.5: Ions Screen 3.6: Polyatomic Ions Screen 3.10: Naming Ionic Compounds Screen 3.12: Binary Compounds of the Nonmetals Screen 3.14: Compounds, Molecules, and the Mole Screen 3.15: Using Molar Mass Screen 3.16: Percent Composition Screen 3.17: Determining Empirical Formulas Screen 3.18: Determining Molecular Formulas Screen 3.19: Hydrated Compounds • Screen 4.3: The Law of • Screen 4.4: Balancing Chemical Conservation of Mass Equations • Screen 4.5: Weight • Screen 4.6: Calculations in Relations in Chemical Stoichiometry Reactions • Screen 4.9: Percent Yield • Screen 4.8: Limiting Reactants • Screen 3.8: Ionic Compounds • Screen 3.13: Alkanes • Screen 3.14: Compounds, Molecules, and the Mole • 4.2: The Reaction of Iron and Chlorine • Screen 4.5 Weight Relations in Chemical Reactions • 4.4: Oxidation of Ammonia • 4.8: Analysis for the Sulfate Content of a • Screen 4.7: Reactions Controlled by the Supply of Sample One Reactant • 4.9: Combustion Analysis of a • Screen 4.8: Limiting Reactants Hydrocarbon http://chemistry.brookscole.com/kotz6e Exercises The Media Integration Guide on the next several pages provides you with a grid that links each chapter to the wealth of interactive media resources you will find at General ChemistryNow, a unique web-based, assessmentcentered personalized learning system for chemistry students. i Media Integration Guide Chapter ii Media Integration Guide Chapter Exercises Tutorials Active Figures Additional Resources 5 Reactions in Aqueous Solution • Screen 5.13: Oxidation Numbers • Screen 5.14: Recognizing Oxidation–Reduction Reactions • Screen 5.16: Preparing Solutions of Known Concentrations • Screen 5.18: Stoichiometry of Reactions in Solution • Screen 5.4: Solubility of Ionic Compounds • Screen 5.7: Net Ionic Equations • Screen 5.11: Gas Forming Reactions • Screen 5.13: Oxidation Numbers • Screen 5.15: Solution Concentrations • Screen 5.16: Preparing Solutions of Known Concentrations • Screen 5.17: The pH Scale • Screen 5.19: Titration • 5.2: Classifying Solutions by Their Ability to Conduct Electricity • 5.3: Guidelines to Predict the Solubility of Ionic Compounds • 5.8: An Acid–Base Reaction, HCl and NaOH • 5.14: The Reaction of Copper with Nitric Acid • 5.18: Making a Solution • 5.20: pH Values of Some Common Substances • 5.23: Titration of an Acid in Aqueous Solution with a Base • Screen 5.2: Solutions • Screen 5.3: Compounds in Aqueous Solution • Screen 5.4: Solubility of Ionic Compounds • Screen 5.5: Types of Aqueous Solutions • Screen 5.8: Acids • Screen 5.9: Bases • Screen 5.11: Gas Forming Reactions 6 Principles of Reactivity: Energy and Chemical Reactions • Screen 6.3: Forms of Energy • Screen 6.7: Heat Capacity of Pure Substances • Screen 6.10: Calculating Heat Transfer • Screen 6.15: Hess’s Law • Screen 6.17: ProductFavored Systems • Screen 6.5: Energy Units • Screen 6.10: Calculating Heat Transfer • Screen 6.13: Enthalpy Changes for Chemical Reactions • Screen 6.14: Measuring Heats of Reactions • Screen 6.16: Standard Enthalpy of Formation • 6.3: Energy and its Conversion • 6.8: Exothermic and Endothermic Processes • 6.10: Heat Transfer • 6.11: Heat Transfer and the Temperature Change for Water • 6.12: Changes of State • 6.13: Energy Changes in a Physical Process • 6.15: The Exothermic Combustion of Hydrogen in Air • 6.17: Constant Volume Calorimeter • 6.18: Energy Level Diagrams • Screen 6.4: Directionality of Heat Transfer • Screen 6.7: Heat Capacity of Pure Substances • Screen 6.10: Calculating Heat Transfer • Screen 6.11: The First Law of Thermodynamics • Screen 6.14: Measuring Heats of Reactions • Screen 6.15: Hess’s Law 7 Atomic Structure • Screen 7.5: Planck’s Equation • Screen 7.6: Atomic Line Spectrum • Screen 7.13: Shapes of Atomic Orbitals • Screen 7.3: Electromagnetic Radiation • Screen 7.6: Atomic Line Spectrum • Screen 7.8: Wave Properties of the Electron • Screen 7.12: Quantum Numbers and Orbitals • 7.1: Electromagnetic Radiation • 7.3: The Electromagnetic Spectrum • 7.8: The Line Emission Spectrum of Hydrogen • 7.10: H Atom in the Bohr Model • 7.11: Absorption of Energy • 7.12: Electronic Transitions That Can Occur in an Excited H Atom • 7.13: Magnesium Oxide • 7.14: Different Views of a 1s (n = 1 and  = 0) Orbital • 7.15: Atomic Orbitals • • • • Screen 7.4: Electromagnetic Spectrum Screen 7.5: Planck’s Equation Screen 7.6: Atomic Line Spectrum Screen 7.9: Heisenberg’s Uncertainty Principle iii Media Integration Guide Chapter Exercises Tutorials Active Figures Additional Resources 8 Atomic Electron Configurations and Chemical Periodicity • Screen 8.6: Effective Nuclear Charge, Z* • Screen 8.7: Atomic Electron Configurations • Screen 8.8: Electron Configuration in Ions • 8.2: Observing and Measuring Paramagnetism • 8.4: Experimentally Determined Order of Subshell Energies • 8.7: Electron Configurations and the Periodic Table • 8.9: Examples of the Periodicity of Group 1A and Group 7A Elements • 8.11: Atomic Radii in Picometers for Main Group Elements • 8.13: First Ionization Energies of the Main Group Elements of the First Four Periods • 8.14: Electron Affinity • 8.15: Relative Sizes of Some Common Ions • Screen 8.3: Spinning Electrons and Magnetism • Screen 8.6: Effective Nuclear Charge, Z* • Screen 8.7: Atomic Electron Configurations • Screen 8.8: Electron Configuration in Ions • Screen 8.9: Atomic Properties and Periodic Trends • Screen 8.10: Atomic Sizes • Screen 8.11: Ionization Energy • Screen 8.12: Electron Affinity • Screen 8.14: Ion Size • Screen 8.15: Chemical Reactions and Periodic Properties 9 Bonding and Molecular Structure: Fundamental Concepts • Screen 9.8: Drawing Lewis Structures • Screen 9.14: Determining Molecular Shape • • • • • • 9.3: Lattice Energy • 9.8: Various Geometries Predicted by VSEPR • 9.14: Electronegativity Values for the Elements According to Pauling • 9.16: Polarity of Triatomic Molecules, AB2 • 9.17: Polar and Nonpolar Molecules of the Type AB3 • Screen 9.2: Valence Electrons • Screen 9.4: Lattice Energy • Screen 9.5: Chemical Reactions and Periodic Properties • Screen 9.6: Chemical Bond Formation— Covalent Bonding • Screen 9.13: Ideal Electron Repulsion Shapes • Screen 9.16: Formal Charge • Screen 9.17: Bond Polarity and Electronegativity • Screen 9.18: Molecular Polarity • Screen 9.19: Bond Properties • Screen 9.20: Bond Energy and 䉭Hrxn 10 Bonding and Molecular Structure: Orbital Hybridization and Molecular Orbitals • Screen 10.8: Molecular Fluxionality • Screen 10.9: Molecular Orbital Theory • Screen 10.11: Homonuclear Diatomic Molecules • 10.1: Potential Energy Change During • Screen 10.5: Sigma Bonding H¬H Bond Formation • Screen 10.6: Determining Hybrid Orbitals • Screen 10.7: Multiple Bonding • 10.5: Hybrid Orbitals for Two to Six Electron Pairs • 10.6: Bonding in the Methane (CH4) Molecule • 10.10: The Valence Bond Model of Bonding in Ethylene, C2H4 • 10.13: Rotation Around Bonds • 10.22: Molecular Orbital Energy Level Diagram Screen 9.7: Lewis Electron Dot Structures Screen 9.8: Drawing Lewis Structures Screen 9.9: Resonance Structures Screen 9.10: Exceptions to the Octet Rule Screen 9.13: Ideal Electron Repulsion Shapes • Screen 9.14: Determining Molecular Shape • Screen 10.3: Valence Bond Theory • Screen 10.4: Hybrid Orbitals • Screen 10.10: Molecular Orbital Configurations Chapter Exercises Tutorials Active Figures Additional Resources • Screen 11.3: Hydrocarbons • Screen 11.4: Hydrocarbons and Addition Reactions • Screen 11.6: Functional Groups • Screens 11.9, 11.10: Synthetic Organic Polymers • Screen 11.6: Functional Groups (1): Reactions of Alcohols • Screen 11.4: Hydrocarbons and Addition Reactions • Screen 11.6: Functional Groups • • • • • 12 Gases & Their Properties • Screen 12.5: Gas Density • Screen 12.12: Application of the Kinetic-Molecular Theory: Diffusion • Screen 12.6: Using Gas Laws: Determining Molar Mass • Screen 12.7: Gas Laws and Chemical Reactions: Stoichiometry • Screen 12.8: Gas Mixtures and Partial Pressures • 12.4: An Experiment to Demonstrate Boyle’s Law • 12.6: Charles’s Law • 12.18: Gaseous Diffusion • • • • 13 • Screen 13.5: Intermolecular Intermolecular Forces (3) Forces, • Screen 13.17: Phase Changes Liquids, and Solids • Screen 13.5: Intermolecular Forces (3) • Screen 13.9: Properties of Liquids • 13.2: Ion–Dipole Interactions • 13.8: The Boiling Points of Some Simple Hydrogen Compounds • 13.11: The Temperature Dependence of the Densities of Ice and Water • 13.17: Vapor Pressure • 13.18: Vapor Pressure Curves for Diethyl Ether [(C2H5)2O], Ethanol (C2H5OH), and Water • 13.39: Phase Diagram for Water • Screen 13.2: Phases of Matter • Screens 13.3, 13.4, 13.5: Intermolecular Forces • Screen 13.6: Hydrogen Bonding • Screen 13.7: The Weird Properties of Water • Screens 13.8, 13.9, 13.10, 13.11: Properties of Liquids • Screens 13.12, 13.13, 13.14, 13.15: Solid Structures • Screens 13.17: Phase Changes 14 • Screen 14.2: Solubility • Screens 14.5, 14.6: Factors Affecting Solutions and • Screen 14.5: Factors Solubility Their Behavior Affecting Solubility (1)— • Screens 14.7, 14.8, 14.9: Colligative Henry’s Law and Gas Pressure Properties • Screens 14.7, 14.8: Colligative Properties • 14.6: Solubility of Nonpolar Iodine in Polar Water and Nonpolar Carbon Tetrachloride • 14.9: Dissolving an Ionic Solid in Water • Screen 14.3: The Solution Process: Intermolecular Forces • Screen 14.4: Energetics of Solution Formation—Dissolving Ionic Compounds • Screen 14.9: Colligative Properties 15 Principles of Reactivity: Chemical Kinetics • 15.2: A Plot of Reactant Concentration Versus Time for the Decomposition of N2O5 • 15.7: The Decomposition of H2O2 • 15.9: Half-Life of a First-Order Reaction • 15.13: Activation Energy • 15.14: Arrhenius Plot 11.2: Optical Isomers 11.4: Alkanes 11.7: Bacon Fat and Addition Reactions 11.13: Polyethylene 11.18: Nylon-6,6 iv Media Integration Guide 11 Carbon: More Than Just Another Element • Screen: 15.4 Concentration Dependence • Screen: 15.5 Determination of the Rate Equation (1) • Screen 15.12: Reaction Mechanisms • Screen 15.13: Reaction Mechanisms and Rate Equations • Screen 15.14: Catalysis and Reaction Rate • Screen 15.4: Concentration Dependence • Screen 15.5: Determination of the Rate Equation (1) • Screen 15.6: Concentration–Time Relationships • Screen 15.7: Determination of Rate Equation (2) • Screen 15.8: Half-Life • Screen 15.10: Control of Reaction Rates (3) Screen 12.3: Gas Laws Screen 12.4: The Ideal Gas Law Screen 12.5: Gas Density Screen 12.9: The Kinetic-Molecular Theory of Gases: Gases on the Molecular Scale • Screen 12.10: Gas Laws and KineticMolecular Theory • Screen 12.11: Distribution of Molecular Speeds: Maxwell-Boltzmann Curves • Screen 12.12: Application of the KineticMolecular Theory: Diffusion • Screen 15.2: Rates of Chemical Reactions • Screens 15.3, 15.4, 15.10: Control of Reaction Rates • Screen 15.4: Concentration Dependence • Screen 15.5: Determination of the Rate Equation (1) • Screens 15.9, 15.10: Microscopic View of Reactions • Screen 15.14: Catalysis and Reaction Rate Chapter Exercises Active Figures Additional Resources • • • • Screen 16.6: Writing Equilibrium Expressions Screen 16.8: Determining an Equilibrium Constant Screen 16.9: Systems at Equilibrium Screen 16.10: Estimating Equilibrium Concentrations • Screens 16.12, 16.13: Disturbing a Chemical Equilibrium • 16.3: The Reaction of H2 and I2 Reaches Equilibrium • 16.9: Changing Concentrations • • • • • • • Screen 16.2: The Principle of Microscopic Reversibility Screen 16.3: Equilibrium State Screen 16.4: Equilibrium Constant Screen 16.5: The Meaning of the Equilibrium Constant Screen 16.6: Writing Equilibrium Expressions Screen 16.9: Systems at Equilibrium Screens 16.11, 16.13, 16.14: Disturbing a Chemical Equilibrium • • • • • Screen 17.2: BrØnsted Acids and Bases Screen 17.4: The pH Scale Screen 17.5: Strong Acids and Bases Screen 17.8: Determining K a and Kb Values Screen 17.9: Estimating the pH of Weak Acid Solutions • Screen 17.11: Estimating the pH Following an Acid-Base Reaction • Screen 17.13: Lewis Acids and Bases • Screen 17.15: Neutral Lewis Acids • 17.2: pH and pOH • • • • • • • Screen 17.3: The Acid–Base Properties of Water Screen 17.4: The pH Scale Screen 17.6: Weak Acids and Bases Screen 17.7: Acid–Base Reactions Screen 17.12: Acid–Base Properties of Salts Screen 17.14: Cationic Lewis Acids Screen 17.16: Molecular Interpretation of Acid–Base Behavior 18 Principles of Reactivity: Other Aspects of Aqueous Equilibria • • • • • • • • • • • • Screen 18.3: Buffer Solutions Screen 18.4: pH of Buffer Solutions Screen 18.5: Preparing Buffer Solutions Screen 18.6: Adding Reagents to a Buffer Solution Screen 18.7: Titration Curves Screen 18.12: Solubility Product Constant Screen 18.13: Determining Ksp, Experimentally Screen 18.14: Estimating Salt Solubility: Using Ksp Screen 18.15: Common Ion Effect Screen 18.16: Solubility and pH Screen 18.17: Can a Precipitation Reaction Occur? Screen 18.19: Complex Ion Formation and Solubility • 18.2: Buffer Solutions • 18.5: The Change in pH During the Titration of a Weak Acid with a Strong Base • • • • • • • • • • • • • • • Screen 18.2: Common Ion Effect Screen 18.3: Buffer Solutions Screen 18.4: pH of Buffer Solutions Screen 18.5: Preparing Buffer Solutions Screen 18.7: Titration Curves Screen 18.8: Titration of a Weak Polyprotic Acid Screen 18.9: Titration of a Weak Base with a Strong Acid Screen 18.10: Acid-Base Indicators Screen 18.11: Precipitation Reactions Screen 18.12: Solubility Product Constant Screen 18.15: Common Ion Effect Screen 18.16: Solubility and pH Screen 18.17: Can a Precipitation Reaction Occur? Screen 18.18: Simultaneous Equilibria Screen 18.20: Using Solubility 19 Principles of Reactivity: Entropy and Free Energy • Screen 19.5: Calculating 䉭S for a Chemical Reaction • Screen 19.6: The Second Law of Thermodynamics • Screen 19.7: Gibbs Free Energy • Screen 19.8: Free Energy and Temperature • Screen 19.9: Thermodynamics and the Equilibrium Constant • 19.12: Spontaneity 䉭G º with Temperature • 19.13: Free Energy Changes as a Reaction Approaches Equilibrium • • • • • • Screen 19.2: Reaction Spontaneity Screen 19.3: Directionality of Reactions Screen 19.4: Entropy: Matter Dispersal and Disorder Screen 19.6: The Second Law of Thermodynamics Screen 19.8: Free Energy and Temperature Screen 19.9: Thermodynamics and the Equilibrium Constant 16 Principles of Reactivity: Chemical Equilibria 17 Principles of Reactivity: The Chemistry of Acids and Bases v Media Integration Guide Tutorials • Screen 17.2: BrØnsted Acids and Bases Chapter Exercises Tutorials • Screen 20.6: Standard Potentials • Screen 20.8: Cells at Nonstandard Conditions • Screen 20.12: Coulometry: Counting Electrons 20 Principles of Reactivity: Electron Transfer Reactions Media Integration Guide vi 21 The Chemistry of the Main Group Elements • Screen 21.4: Boron Hydrides Structures • Screen 21.5: Aluminum Compounds • Screen 21.6: Silicon-Oxygen Compounds: Formulas and Structures • Screen 21.8: Sulfur Allotropes • Screen 21.9: Structures of Sulfur Compounds 22 The Chemistry of the Transition Elements • Screen 22.2: Formulas and Oxidation Numbers in Transition Metal Complexes • Screen 22.5: Geometry of Coordination Compounds • Screen 22.6: Geometric Isomerism in Coordination Compounds 23 Nuclear Chemistry • Screen 23.5: Kinetics of Nuclear Decay • Screen 21.2: Formation of Ionic Compounds by Main Group Elements Active Figures • 20.13: A Voltaic Cell Using Zn 0 Zn (aq, 1.0 M) and H2 0H+(aq, 1.0 M) Half-Cells • Screen 20.2: Redox Reactions: Electron Transfer • Screen 20.3: Balancing Equations for Redox Reactions • Screen 20.4: Electrochemical Cells • Screen 20.5: Batteries • Screen 20.5: Electrochemical Cells and Potentials • Screen 20.6: Standard Potentials • Screen 20.11: Electrolysis: Chemical Change from Electrical Energy • 21.15: Industrial Production of Aluminum • 21.22: Compounds and Oxidation Numbers for Nitrogen • 21.32: A Membrane Cell for the Production of NaOH and Cl2 Gas from a Saturated, Aqueous Solution of NaCl (Brine) • 22.8: A Blast Furnace • Screen 23.2: Radioactive Decay • Screen 23.3: Balancing Nuclear Reaction Equations • Screen 23.4: Stability of Atomic Nuclei • Screen 23.5: Kinetics of Nuclear Decay Additional Resources 2+ • Screen 21.7: Electronic Structure in Transition Metal Complexes • Screen 21.8: Spectroscopy of Transition Metal Complexes • Screen 22.3: Periodic Trends for Transition Elements • Screen 23.4: Stability of Atomic Nuclei • Screen 23.6: Nuclear Fission Chemistry & CHEMICAL REACTIVITY SIXTH EDITION John C. Kotz SUNY Distinguished Teaching Professor State University of New York College at Oneonta Paul M. Treichel Professor of Chemistry University of Wisconsin–Madison Gabriela C. Weaver Associate Professor of Chemistry Purdue University Australia • Canada • Mexico • Singapore • Spain • United Kingdom • United States Publisher/Executive Editor: David Harris Development Editor: Peter McGahey Assistant Editor: Annie Mac Editorial Assistant: Candace Lum Technology Project Manager: Donna Kelley Executive Marketing Manager: Julie Conover Senior Marketing Manager: Amee Mosley Marketing Communications Manager: Nathaniel Bergson-Michelson Project Manager, Editorial Production: Lisa Weber Creative Director: Rob Hugel Print Buyers: Rebecca Cross and Judy Inouye Permissions Editor: Kiely Sexton Production Service: Thompson Steele, Inc. Text Designers: Rob Hugel and John Walker Design Photo Researcher: Jane Sanders Miller Copy Editor: Thompson Steele, Inc. Developmental Artist: Patrick A. Harman Illustrators: Rolin Graphics and Thompson Steele, Inc. Cover Designer: John Walker Design Cover Images: Motohiko Murakami Cover Printer: Transcontinental Printing/Interglobe Compositor: Thompson Steele, Inc. Printer: Transcontinental Printing/Interglobe COPYRIGHT © 2006 Brooks/Cole, a division of Thomson Learning, Inc. Thomson LearningTM is a trademark used herein under license. Thomson Brooks/Cole 10 Davis Drive Belmont, CA 94002-3098 USA ALL RIGHTS RESERVED. No part of this work covered by the copyright hereon may be reproduced or used in any form or by any means—graphic, electronic, or mechanical, including but not limited to photocopying, recording, taping, Web distribution, information networks, or information storage and retrieval systems— without the written permission of the publisher. 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Library of Congress Control Number: 2004109955 Student Edition: ISBN 0-534-99766-X Volume 1: ISBN 0-495-01013-8 Volume 2: ISBN 0-495-01014-6 Two-volume set: ISBN 0-534-40800-1 Instructor’s Edition: ISBN 0-534-99848-8 International Student Edition: ISBN 0-495-01035-9 (Not for sale in the United States) Asia Thomson Learning 5 Shenton Way #01-01 UIC Building Singapore 068808 Canada Nelson 1120 Birchmount Road Toronto, Ontario M1K 5G4 Canada Australia/New Zealand Thomson Learning 102 Dodds Street Southbank, Victoria 3006 Australia Europe/Middle East/Africa Thomson Learning High Holborn House 50/51 Bedford Row London WC1R 4LR United Kingdom About the Cover What lies beneath the Earth’s surface? The mantle of the Earth consists largely of silicon-oxygen based minerals. But about 2900 km below the surface the solid silicate rock of the mantle gives way to the liquid iron alloy core of the planet. To explore the nature of the rocks at the core-mantle boundary, scientists in Japan examined magnesium silicate (MgSiO3) at a high pressure (125 gigapascals) and high temperature (2500 K). The cover image is what they saw. The solid consists of SiO6 octahedra (blue) and magnesium ions (Mg2+; yellow spheres). Each SiO6 octahedron shares the four O atoms in opposite edges with two neighboring octahedra, thus forming a chain of octahedra. These chains are interlinked by sharing the O atoms at the “top” and “bottom” of SiO6 octahedra in neighboring chains. The magnesium ions lie between the layers of interlinked SiO6 chains. For more information see M. Murakami, K. Hirose, K. Kawamura, N. Sata, and Y. Ohishi, Science, Volume 304, page 855, May 7, 2004. ix Chapter 1 Matter and Measurement ix Preface Brief Contents Part 1 18 Principles of Reactivity: Other Aspects of Aqueous Equilibria 848 The Basic Tools of Chemistry 1 Matter and Measurement 10 19 Principles of Reactivity: Entropy and Free Energy 2 Atoms and Elements 20 Principles of Reactivity: Electron Transfer Reactions 58 INTERCHAPTER: The Chemistry of the Environment 3 Molecules, Ions, and Their Compounds 96 4 Chemical Equations and Stoichiometry 140 5 Reactions in Aqueous Solution 902 942 998 Part 5 174 The Chemistry of the Elements 6 Principles of Reactivity: Energy and Chemical Reactions 232 21 The Chemistry of the Main Group Elements INTERCHAPTER: The Chemistry of Fuels and Energy Sources 282 22 The Chemistry of the Transition Elements Part 2 Appendices 23 Nuclear Chemistry The Structure of Atoms and Molecules 1012 1068 1108 A Using Logarithms and the Quadratic Equation A-2 294 B Some Important Physical Concepts A-7 8 Atomic Electron Configurations and Chemical Periodicity 332 C Abbreviations and Useful Conversion Factors A-10 D Physical Constants A-14 E Naming Organic Compounds A-16 10 Bonding and Molecular Structure: Orbital Hybridization and Molecular Orbitals 436 F Values for the Ionization Energies and Electron Affinities of the Elements A-19 11 Carbon: More than Just Another Element G Vapor Pressure of Water at Various Temperatures A-20 H Ionization Constants for Weak Acids at 25 °C A-21 I Ionization Constants for Weak Bases at 25 °C A-23 J Solubility Product Constants for Some Inorganic Compounds at 25 °C A-24 K Formation Constants for Some Complex Ions in Aqueous Solution A-26 L Selected Thermodynamic Values A-27 M Standard Reduction Potentials in Aqueous Solution at 25 °C A-33 N Answers to Exercises A-36 O Answers to Selected Study Questions A-56 P Answers to Selected Interchapter Study Questions A-107 7 Atomic Structure 9 Bonding and Molecular Structure: Fundamental Concepts 372 474 INTERCHAPTER: The Chemistry of Life: Biochemistry 530 Part 3 States of Matter 12 Gases and Their Properties 546 13 Intermolecular Forces, Liquids, and Solids 588 INTERCHAPTER: The Chemistry of Modern Materials 14 Solutions and Their Behavior 656 642 Part 4 The Control of Chemical Reactions 15 Principles of Reactivity: Chemical Kinetics 16 Principles of Reactivity: Chemical Equilibria 17 Principles of Reactivity: Chemistry of Acids and Bases 796 698 756 ix This page intentionally left blank xi Chapter 1 Matter and Measurement xi Preface Contents This text is available in these student versions: • Complete text ISBN 0-534-99766-X • Volume 1 (Chapters 1–12) ISBN 0-495-01013-8 • Volume 2 (Chapters 12–23) ISBN 0-495-01014-6 • Two-volume set ISBN 0-534-40800-1 Preface 1.8 xxiii A Preface to Students Mathematics of Chemistry Exponential or Scientific Notation 2 Significant Figures Graphing The Basic Tools of Chemistry Matter and Measurement How Hot Is It? Key Equations 10 Study Questions Classifying Matter 12 States of Matter and Kinetic-Molecular Theory 13 Matter at the Macroscopic and Particulate Levels 14 Pure Substances 14 Mixtures: Homogeneous and Heterogeneous 15 Elements and Atoms 1.3 Compounds and Molecules 1.4 Physical Properties 20 Density 20 Temperature Dependence of Physical Properties Extensive and Intensive Properties 23 2 1.6 Units of Measurement 25 Temperature Scales 26 Length 28 Volume 30 Chemical Perspectives: It’s a Nanoworld! Mass 32 58 58 2.2 Atomic Number and Atomic Mass 67 Atomic Number 67 Relative Atomic Mass and the Atomic Mass Unit Mass Number 67 22 23 31 2.3 Charles D. Winters 48 Protons, Electrons, and Neutrons: Development of Atomic Structure 60 Electricity 60 Radioactivity 60 Cathode-Ray Tubes and the Characterization of Electrons 61 Protons 64 Neutrons 64 Historical Perspectives: Uncovering Atomic Structure 65 The Nucleus of the Atom 65 Making Measurements: Precision, Accuracy, and Experimental Error 32 A Closer Look: Standard Deviation 33 page 19 46 2.1 18 Physical and Chemical Changes 44 47 Atoms and Elements Stardust 17 1.5 41 43 Chapter Goals Revisited 10 1.2 1.7 38 Problem Solving and Chemical Arithmetic Charles D. Winters 1.1 35 Problem Solving by Dimensional Analysis Part 1 1 35 Isotopes 69 Isotope Abundance 69 Determining Atomic Mass and Isotope Abundance 70 A Closer Look: Atomic Mass and the Mass Defect 2.4 Atomic Weight 2.5 Atoms and the Mole 73 Historical Perspectives: Amedeo Avogadro and His Number 74 Molar Mass 74 67 71 72 page 25 xi xii Contents 3.4 Molecular Compounds: Formulas, Names, and Properties 114 3.5 Formulas, Compounds, and the Mole 3.6 Describing Compound Formulas 119 Percent Composition 119 Empirical and Molecular Formulas from Percent Composition 121 A Closer Look: Mass Spectrometry, Molar Mass, and Isotopes 127 3.7 Hydrated Compounds Charles D. Winters Chapter Goals Revisited Key Equations 116 128 130 131 Study Questions 132 page 82 2.6 2.7 2.8 4 The Periodic Table 77 Features of the Periodic Table 77 Developing the Periodic Table 80 Historical Perspectives: Periodic Table 81 Black Smokers and the Origin of Life An Overview of the Elements, Their Chemistry, and the Periodic Table 82 Group 1A, Alkali Metals: Li, Na, K, Rb, Cs, Fr 82 Group 2A, Alkaline Earth Metals: Be, Mg, Ca, Sr, Ba, Ra 82 Group 3A: B, Al, Ga, In, Tl 82 Group 4A: C, Si, Ge, Sn, Pb 83 Group 5A: N, P, As, Sb, Bi 85 Group 6A: O, S, Se, Te, Po 85 Group 7A, Halogens: F, Cl, Br, I, At 86 Group 8A, Noble Gases: He, Ne, Ar, Kr, Xe, Rn 86 The Transition Elements 87 Essential Elements Key Equations Study Questions Chemical Equations 142 Historical Perspectives: Antoine Laurent Lavoisier (1743–1794) 143 4.2 Balancing Chemical Equations 4.3 Mass Relationships in Chemical Reactions: Stoichiometry 148 4.4 Reactions in Which One Reactant Is Present in Limited Supply 152 A Stoichiometry Calculation with a Limiting Reactant 153 4.5 Percent Yield 4.6 Chemical Equations and Chemical Analysis Quantitative Analysis of a Mixture 158 Determining the Formula of a Compound by Combustion 162 89 Key Equation 90 Molecules, Ions, and Their Compounds DNA: The Most Important Molecule 3.1 Molecules, Compounds, and Formulas Formulas 99 96 Molecular Models 100 A Closer Look: Computer Resources for Molecular Modeling 102 3.3 Ionic Compounds: Formulas, Names, and Properties 103 Ions 104 Formulas of Ionic Compounds 107 Names of Ions 109 Names of Ionic Compounds 111 Properties of Ionic Compounds 111 165 166 96 5 Reactions in Aqueous Solution Salt 98 3.2 158 165 Study Questions 3 145 157 Chapter Goals Revisited 89 140 140 4.1 88 Chapter Goals Revisited Chemical Equations and Stoichiometry 174 174 5.1 Properties of Compounds in Aqueous Solution Ions in Aqueous Solution: Electrolytes 176 Types of Electrolytes 177 Solubility of Ionic Compounds in Water 179 5.2 Precipitation Reactions 181 Net Ionic Equations 183 5.3 Acids and Bases 185 Acids 185 Chemical Perspectives: Sulfuric Acid 187 A Closer Look: The H + Ion in Water 188 176 xiii Contents Bases 188 Oxides of Nonmetals and Metals 189 Chemical Perspectives: Limelight and Metal Oxides 190 5.4 Reactions of Acids and Bases 5.5 Gas-Forming Reactions 5.6 Classifying Reactions in Aqueous Solution 195 A Summary of Common Reaction Types in Aqueous Solution 196 A Closer Look: Product-Favored and Reactant-Favored Reactions 197 5.7 5.8 Temperature and Heat 237 Systems and Surroundings 238 Directionality of Heat Transfer: Thermal Equilibrium 238 A Closer Look: Why Doesn’t the Heat in a Room Cause Your Cup of Coffee to Boil? 239 Energy Units 240 Chemical Perspectives: Food and Calories 241 191 194 Oxidation–Reduction Reactions 197 Redox Reactions and Electron Transfer 198 Oxidation Numbers 200 A Closer Look: Are Oxidation Numbers “Real”? 201 Recognizing Oxidation–Reduction Reactions 202 Measuring Concentrations of Compounds in Solution 205 Solution Concentration: Molarity 205 Preparing Solutions of Known Concentration 209 5.9 pH, a Concentration Scale for Acids and Bases 5.10 Stoichiometry of Reactions in Aqueous Solution General Solution Stoichiometry 214 Titration: A Method of Chemical Analysis 216 Chapter Goals Revisited Key Equations Study Questions 212 6.2 Specific Heat Capacity and Heat Transfer 241 A Closer Look: Sign Conventions 243 Quantitative Aspects of Heat Transfer 244 6.3 Energy and Changes of State 6.4 The First Law of Thermodynamics 250 Historical Perspectives: Work, Heat, Cannons, Soup, and Beer 251 A Closer Look: P-V Work 252 Enthalpy 253 State Functions 254 6.5 Enthalpy Changes for Chemical Reactions 6.6 Calorimetry 257 Constant Pressure Calorimetry: Measuring ΔH 257 Constant Volume Calorimetry: Measuring ΔE 259 6.7 Hess’s Law 261 Energy Level Diagrams 214 221 223 223 Principles of Reactivity: Energy and Chemical Reactions 232 Energy: Some Basic Principles Conservation of Energy 236 Study Questions 236 270 271 272 INTERCHAPTER The Chemistry of Fuels and Energy Sources 282 Supply and Demand: The Balance Sheet on Energy Energy Consumption 283 Energy Resources 284 Fossil Fuels 284 Coal 285 Natural Gas 286 Petroleum 286 Other Fossil Fuel Sources Charles D. Winters 6.1 Key Equations 232 268 Product- or Reactant-Favored Reactions and Thermochemistry 269 Chapter Goals Revisited page 145 Charles D. Winters Abba’s Refrigerator 254 262 6.8 Standard Enthalpies of Formation 265 Enthalpy Change for a Reaction 267 A Closer Look: Hess’s Law and Equation 6.6 6.9 6 246 page 214 287 Energy in the Future: Choices and Alternatives Fuel Cells 288 A Hydrogen Economy 289 Biosources of Energy 291 Solar Energy 292 288 283 xiv Contents What Does the Future Hold for Energy? Suggested Readings Study Questions 8 292 292 293 Everything in Its Place 8.1 Part 2 The Structure of Atoms and Molecules 7 Atomic Structure Colors in the Sky 7.1 7.2 7.3 294 Electromagnetic Radiation 296 Wave Properties 296 Standing Waves 298 The Visible Spectrum of Light 299 Atomic Line Spectra and Niels Bohr 305 Atomic Line Spectra 305 The Bohr Model of the Hydrogen Atom 307 The Bohr Theory and the Spectra of Excited Atoms 309 A Closer Look: Experimental Evidence for Bohr’s Theory 304 Quantum Mechanical View of the Atom 314 Historical Perspectives: 20th-Century Giants of Science 315 The Uncertainty Principle 315 Schrödinger’s Model of the Hydrogen Atom and Wave Functions 316 Quantum Numbers 316 Useful Information from Quantum Numbers 318 320 Atomic Orbitals and Chemistry 323 Chapter Goals Revisited Key Equations Study Questions 8.3 Atomic Subshell Energies and Electron Assignments 339 Order of Subshell Energies and Assignments Effective Nuclear Charge, Z* 341 325 326 324 Atomic Electron Configurations 343 Electron Configurations of the Main Group Elements 343 Electron Configurations of the Transition Elements 349 8.5 Electron Configurations of Ions 8.6 Atomic Properties and Periodic Trends Atomic Size 353 Ionization Energy 357 Electron Affinity 359 Ion Sizes 361 8.7 Periodic Trends and Chemical Properties Study Questions 353 363 365 366 Bonding and Molecular Structure: Fundamental Concepts 372 Molecules in Space 9.1 372 Valence Electrons 374 Lewis Symbols for Atoms 339 351 313 9 336 337 338 8.4 313 7.5 7.7 The Pauli Exclusion Principle Chapter Goals Revisited The Wave Properties of the Electron The Shapes of Atomic Orbitals s Orbitals 320 p Orbitals 321 d Orbitals 323 f Orbitals 323 Electron Spin 334 Magnetism 334 Paramagnetism and Unpaired Electrons 335 A Closer Look: Paramagnetism and Ferromagnetism 8.2 294 Planck, Einstein, Energy, and Photons 300 Planck’s Equation 300 Einstein and the Photoelectric Effect 302 Energy and Chemistry: Using Planck’s Equation Chemical Perspectives: UV Radiation, Skin Damage, and Sunscreens 305 332 Chemical Perspectives: Quantized Spins and MRI 7.4 7.6 Atomic Electron Configurations and Chemical Periodicity 332 375 9.2 Chemical Bond Formation 376 9.3 Bonding in Ionic Compounds 377 Ion Attraction and Lattice Energy 378 Why Don’t Compounds Such as NaCl2 and NaNe Exist? 381 9.4 Covalent Bonding and Lewis Structures Lewis Electron Dot Structures 382 The Octet Rule 383 Predicting Lewis Structures 386 382 xv Contents 9.5 9.6 Resonance 390 A Closer Look: Resonance Structures, Lewis Structures, and Molecular Models 391 Key Equations Study Questions Exceptions to the Octet Rule 392 Compounds in Which an Atom Has Fewer Than Eight Valence Electrons 393 Compounds in Which an Atom Has More Than Eight Valence Electrons 393 Chemical Perspectives: The Importance of Odd-Electron Molecules 396 9.7 Molecular Shapes 397 Central Atoms Surrounded Only by Single-Bond Pairs 398 Central Atoms with Single-Bond Pairs and Lone Pairs 399 Central Atoms with More Than Four Valence Electron Pairs 401 Multiple Bonds and Molecular Geometry 403 9.8 Charge Distribution in Covalent Bonds and Molecules 405 Formal Charges on Atoms 405 A Closer Look: Formal Charge and Oxidation Number 407 Bond Polarity and Electronegativity 408 A Closer Look: Electronegativity 410 Combining Formal Charge and Bond Polarity Molecular Polarity 413 Historical Perspectives: Developing Concepts of Bonding and Structure 415 Chemical Perspectives: Cooking with Microwaves 416 9.10 Bond Properties: Order, Length, and Energy Bond Order 419 Bond Length 419 Bond Energy 421 The DNA Story—Revisited 10 427 Bonding and Molecular Structure: Orbital Hybridization and Molecular Orbitals 436 Orbitals and Bonding Theories 10.2 Valence Bond Theory 439 Orbital Overlap Model of Bonding 439 Hybridization of Atomic Orbitals 441 Multiple Bonds 450 Cis-Trans Isomerism: A Consequence of p Bonding 454 Benzene: A Special Case of p Bonding 455 10.3 Molecular Orbital Theory 457 Principles of Molecular Orbital Theory 457 Bond Order 459 Molecular Orbitals of Li2 and Be2 460 Molecular Orbitals from Atomic p Orbitals 461 Electron Configurations for Homonuclear Molecules for Boron Through Fluorine 462 A Closer Look: Molecular Orbitals for Compounds Formed from p-Block Elements 464 Electron Configurations for Heteronuclear Diatomic Molecules 465 Resonance and MO Theory 465 Chapter Goals Revisited 419 Key Equations Study Questions 424 11 J. Hester and P. Scowan, of Arizona State University, and NASA. Scott Camazine & Sue Trainor/Photo Researchers, Inc. page 373 436 10.1 438 467 467 468 Carbon: More Than Just Another Element A Colorful Beginning page 339 425 427 Linus Pauling: A Life of Chemical Thought 411 9.9 9.11 Chapter Goals Revisited 474 11.1 Why Carbon? 476 Structural Diversity 476 Isomers 477 A Closer Look: Writing Formulas and Drawing Structures 478 A Closer Look: Optical Isomers and Chirality 480 Stability of Carbon Compounds 480 11.2 Hydrocarbons 481 Alkanes 481 A Closer Look: Flexible Molecules 487 Alkenes and Alkynes 487 Aromatic Compounds 492 A Closer Look: Petroleum Chemistry 495 474 xvi Alcohols, Ethers, and Amines 496 Alcohols and Ethers 497 Properties of Alcohols and Ethers 499 Amines 500 11.4 Compounds with a Carbonyl Group 502 Aldehydes and Ketones 503 Carboxylic Acids 504 A Closer Look: Glucose and Sugars 506 Chemical Perspectives: Aspirin Is More Than 100 Years Old! 507 Esters 507 Amides 509 A Closer Look: Fats and Oils 510 11.5 Polymers 512 Classifying Polymers 512 Addition Polymers 513 Condensation Polymers 517 Chemical Perspectives: Super Diapers Chapter Goals Revisited Study Questions 520 Nucleic Acids 537 Nucleic Acid Structure 537 Protein Synthesis 538 The RNA World and the Origin of Life The Ideal Gas Law 557 The Density of Gases 559 Calculating the Molar Mass of a Gas from P, V, and T Data 560 12.4 Gas Laws and Chemical Reactions 12.5 Gas Mixtures and Partial Pressures 564 Historical Perspectives: Studies on Gases 567 12.6 The Kinetic-Molecular Theory of Gases 567 Molecular Speed and Kinetic Energy 567 Kinetic-Molecular Theory and the Gas Laws 570 12.7 Diffusion and Effusion 12.8 Some Applications of the Gas Laws and Kinetic-Molecular Theory 573 Separating Isotopes 573 Deep Sea Diving 574 Concluding Remarks Suggested Readings 544 12.9 Nonideal Behavior: Real Gases 575 Chemical Perspectives: The Earth’s Atmosphere 531 542 544 544 Chapter Goals Revisited Key Equations Study Questions Part 3 States of Matter 12 Gases and Their Properties 550 12.3 540 Metabolism 541 Energy and ATP 541 Chemical Perspectives: AIDS and Reverse Transcriptase Oxidation–Reduction and NADH 543 Respiration and Photosynthesis 543 The Properties of Gases 548 Gas Pressure 548 A Closer Look: Measuring Gas Pressure Gas Laws: The Experimental Basis 550 The Compressibility of Gases: Boyle’s Law 550 The Effect of Temperature on Gas Volume: Charles’s Law 552 Combining Boyle’s and Charles’s Laws: The General Gas Law 554 Avogadro’s Hypothesis 556 522 530 page 568 12.2 520 Proteins 531 Amino Acids Are the Building Blocks of Proteins Protein Structure and Hemoglobin 533 Sickle Cell Anemia 533 Enzymes, Active Sites, and Lysozyme 535 Study Questions page 515 12.1 INTERCHAPTER The Chemistry of Life: Biochemistry Charles D. Winters 11.3 Christopher Springmann/Corbisstockmarket.com Contents 13 546 561 571 577 578 579 580 Intermolecular Forces, Liquids, and Solids 588 The Mystery of the Disappearing Fingerprints Up, Up, and Away! 546 13.1 588 States of Matter and the Kinetic-Molecular Theory 590 xvii Intermolecular Forces 591 Interactions Between Ions and Molecules with a Permanent Dipole 592 Interactions Between Molecules with Permanent Dipoles 594 A Closer Look: Hydrated Salts 595 Interactions Involving Nonpolar Molecules 596 13.3 Hydrogen Bonding 599 Hydrogen Bonding and the Unusual Properties of Water 602 13.4 Summary of Intermolecular Forces 13.5 Properties of Liquids 606 Vaporization 606 Vapor Pressure 609 Boiling Point 613 Critical Temperature and Pressure 613 Surface Tension, Capillary Action, and Viscosity 13.6 13.7 13.8 13.9 Charles D. Winters 13.2 Charles D. Winters Contents 604 page 646 Fired Ceramics for Special Purposes: Cements, Clays, and Refractories 651 Modern Ceramics with Exceptional Properties 652 614 The Solid State: Metals 616 Crystal Lattices and Unit Cells 617 A Closer Look: Packing Oranges 621 Biomaterials: Learning from Nature The Future of Materials Suggested Readings The Solid State: Structures and Formulas of Ionic Solids 622 Other Kinds of Solid Materials Molecular Solids 625 Network Solids 625 Amorphous Solids 626 Study Questions 14 Key Equation 633 634 INTERCHAPTER The Chemistry of Modern Materials The Solution Process 662 Liquids Dissolving in Liquids 662 A Closer Look: Supersaturated Solutions Solids Dissolving in Water 664 Heat of Solution 666 659 663 14.3 Factors Affecting Solubility: Pressure and Temperature 669 Dissolving Gases in Liquids: Henry’s Law 14.4 Colligative Properties 672 Changes in Vapor Pressure: Raoult’s Law 672 Boiling Point Elevation 674 Freezing Point Depression 677 Colligative Properties and Molar Mass Determination 678 Colligative Properties of Solutions Containing Ions 679 Osmosis 681 A Closer Look: Reverse Osmosis in Tampa Bay 685 14.5 Colloids 686 Types of Colloids 687 Surfactants 688 644 Chapter Goals Revisited Key Equations 650 656 656 Units of Concentration 642 Semiconductors 645 Bonding in Semiconductors: The Band Gap 646 Applications of Semiconductors: Diodes, LEDs, and Transistors 647 Microfabrication Techniques Using Semiconductor Materials 648 Ceramics 649 Glass: A Disordered Ceramic Solutions and Their Behavior 14.2 631 Metals 643 Bonding in Metals 643 Alloys: Mixtures of Metals 655 14.1 634 Study Questions 654 655 The Killer Lakes of Cameroon 630 Chapter Goals Revisited 653 625 The Physical Properties of Solids 627 Melting: Conversion of Solid to Liquid 627 Sublimation: Conversion of Solid to Vapor 628 13.10 Phase Diagrams Water 630 Carbon Dioxide page 651 Study Questions 691 692 690 669 xviii Contents Part 4 The Control of Chemical Reactions Faster and Faster 698 15.1 Rates of Chemical Reactions 15.2 Reaction Conditions and Rate 15.3 Effect of Concentration on Reaction Rate Rate Equations 707 The Order of a Reaction 707 The Rate Constant, k 709 Determining a Rate Equation 709 15.4 15.5 15.6 700 704 page 686 706 Concentration—Time Relationships: Integrated Rate Laws 712 First-Order Reactions 713 Second-Order Reactions 715 Zero-Order Reactions 716 Graphical Methods for Determining Reaction Order and the Rate Constant 716 Half-Life and First-Order Reactions 719 A Microscopic View of Reaction Rates 722 Concentration, Reaction Rate, and Collision Theory 722 Temperature, Reaction Rate, and Activation Energy 723 A Closer Look: Reaction Coordinate Diagrams 726 Effect of Molecular Orientation on Reaction Rate The Arrhenius Equation 727 Effect of Catalysts on Reaction Rate 729 A Closer Look: Enzymes: Nature’s Catalysts 732 726 Key Equations 16.3 Determining an Equilibrium Constant 16.4 Using Equilibrium Constants in Calculations 772 Calculations Where the Solution Involves a Quadratic Expression 774 16.5 More About Balanced Equations and Equilibrium Constants 777 16.6 Disturbing a Chemical Equilibrium 781 Effect of Temperature Changes on Equilibrium Composition 781 Effect of the Addition or Removal of a Reactant or Product 783 Effect of Volume Changes on Gas-Phase Equilibria 16.7 Applying the Principles of Chemical Equilibrium The Haber-Bosch Process 787 Key Equations Study Questions 17 741 770 788 789 789 796 17.1 Acids, Bases, and the Equilibrium Concept 744 17.2 The Brønsted-Lowry Concept of Acids and Bases Conjugate Acid–Base Pairs 802 16 Principles of Reactivity: Chemical Equilibria 756 17.3 16.1 The Nature of the Equilibrium State Water and the pH Scale 802 Water Autoionization and the Water Ionization Constant, K w 803 The pH Scale 805 Determining and Calculating pH 806 16.2 The Equilibrium Constant and Reaction Quotient Writing Equilibrium Constant Expressions 763 17.4 Equilibrium Constants for Acids and Bases Aqueous Solutions of Salts 810 Study Questions Fertilizer and Poison Gas 756 758 760 785 787 Principles of Reactivity: The Chemistry of Acids and Bases 796 Nature’s Acids 743 page 763 A Closer Look: Equilibrium Constant Expressions for Gases–Kc and Kp 764 The Meaning of the Equilibrium Constant, K 765 The Reaction Quotient, Q 767 Chapter Goals Revisited Reaction Mechanisms 732 Molecularity of Elementary Steps 733 Rate Equations for Elementary Steps 734 Molecularity and Reaction Order 734 Reaction Mechanisms and Rate Equations 736 Chapter Goals Revisited Charles D. Winters Principles of Reactivity: Chemical Kinetics 698 Charles D. Winters 15 798 806 799 xix Contents A Logarithmic Scale of Relative Acid Strength, pK a 812 Relating the Ionization Constants for an Acid and Its Conjugate Base 813 17.5 Equilibrium Constants and Acid–Base Reactions Predicting the Direction of Acid–Base Reactions 17.6 Types of Acid–Base Reactions 816 The Reaction of a Strong Acid with a Strong Base 816 The Reaction of a Weak Acid with a Strong Base 817 The Reaction of Strong Acid with a Weak Base 817 The Reaction of a Weak Acid with a Weak Base 818 18 Principles of Reactivity: Other Aspects of Aqueous Equilibria 848 Roses Are Red, Violets Are Blue, and Hydrangeas Are Red or Blue 848 814 814 18.1 The Common Ion Effect 850 18.2 Controlling pH: Buffer Solutions 854 General Expressions for Buffer Solutions Preparing Buffer Solutions 857 How Does a Buffer Maintain pH? 860 856 17.7 Calculations with Equilibrium Constants 818 Determining K from Initial Concentrations and Measured pH 818 What Is the pH of an Aqueous Solution of a Weak Acid or Base? 820 What Is the pH of a Solution After an Acid–Base Reaction? 824 18.3 Acid–Base Titrations 861 Current Perspectives: Buffers in Biochemistry 862 Titration of a Strong Acid with a Strong Base 862 Titration of a Weak Acid with a Strong Base 864 Titration of Weak Polyprotic Acids 867 Titration of a Weak Base with a Strong Acid 868 pH Indicators 870 17.8 Polyprotic Acids and Bases 18.4 17.9 The Lewis Concept of Acids and Bases Cationic Lewis Acids 829 Molecular Lewis Acids 830 Solubility of Salts 873 The Solubility Product Constant, K sp 873 Relating Solubility and K sp 875 A Closer Look: Solubility Calculations 877 Solubility and the Common Ion Effect 879 The Effect of Basic Anions on Salt Solubility 882 18.5 Precipitation Reactions 884 K sp and the Reaction Quotient, Q 884 K sp, the Reaction Quotient, and Precipitation Reactions 885 18.6 Solubility and Complex Ions 18.7 Solubility, Ion Separations, and Qualitative Analysis 890 826 828 17.10 Molecular Structure, Bonding, and Acid–Base Behavior 832 Why Is HF a Weak Acid Whereas HCl Is a Strong Acid? 832 Chemical Perspectives: Lewis and Brønsted Bases: Adrenaline and Serotonin 833 Why Is HNO2 a Weak Acid Whereas HNO3 Is a Strong Acid? 833 Why Are Carboxylic Acids Brønsted Acids? 835 Why Are Hydrated Metal Cations Brønsted Acids? 836 Why Are Anions Brønsted Bases? 836 Why Are Organic Amines Brønsted and Lewis Bases? 836 Chapter Goals Revisited Study Questions 838 19 839 892 893 894 Principles of Reactivity: Entropy and Free Energy 902 Perpetual Motion Machines page 882 page 921 902 19.1 Spontaneous Change and Equilibrium 19.2 Heat and Spontaneity 19.3 Dispersal of Energy and Matter 906 Dispersal of Energy 906 Dispersal of Matter 907 Applications of the Dispersal of Matter 909 The Boltzmann Equation for Entropy 911 A Summary: Matter and Energy Dispersal 911 19.4 Entropy and the Second Law of Thermodynamics 912 A Closer Look: Reversible and Irreversible Processes 914 Entropy Changes in Physical and Chemical Processes 915 Charles D. Winters Study Questions Key Equations 837 Charles D. Winters Key Equations Chapter Goals Revisited 887 904 904