University Chemistry

Frontiers and Foundations from a Global and Molecular Perspective

by Anderson

ISBN: 9780262365932 | Copyright 2021

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Contents (pg. v)
Preface (pg. xiii)
Acknowledgments (pg. xvi)
About the Author (pg. xvi)
1 Energy: Conceptual Foundation and the Laws That Govern Its Transformation (pg. 1)
Framework: Setting the Context (pg. 2)
Road Map (pg. 9)
Emergence of Energy as a Scientific Concept (pg. 9)
Energy, Work, and Newton’s Laws (pg. 12)
Conservation of Energy: Tracking the Flow of Energy (pg. 15)
Energy at the Molecular Level: Microscopic and Macroscopic Forms of Energy (pg. 18)
Exchange of Kinetic and Potential Energy on a Surface (pg. 20)
The Mechanical Equivalent of Heat (pg. 22)
Heat and Temperature at the Molecular Level (pg. 26)
Energy Transformations: The Central Role of Electromagnetic Radiation (pg. 30)
Energy and Power: A Very Important Distinction (pg. 38)
Summary of the Core Concepts (pg. 38)
Case Studies (pg. 43)
2 Atomic and Molecular Structure: Energy from Chemical Bonds (pg. 63)
Framework: Setting the Context (pg. 63)
Road Map (pg. 71)
Atomic View of Matter (pg. 71)
Discovery of the Electron (pg. 73)
Discovery of the Atomic Nucleus (pg. 75)
Atomic Number, Mass Number, and Atomic Symbol (pg. 78)
Isotopes (pg. 79)
Molecular Structure (pg. 79)
Chemical Formulas (pg. 83)
Chemical Formulas and Molecular Models (pg. 83)
Stoichiometry (pg. 86)
Avogadro’s Number (pg. 88)
Molar Mass (pg. 88)
Balancing Chemical Equations (pg. 89)
Oxidation-Reduction Reactions (pg. 93)
Oxidation and Reduction in Combustion Reactions (pg. 95)
Redox Reactions where Oxygen Is Not Involved (pg. 96)
Summary Concepts (pg. 97)
Case Studies (pg. 101)
3 Thermochemistry: Development of the First Law of Thermodynamics (pg. 129)
Framework: Setting the Context (pg. 129)
Road Map (pg. 133)
Development of the First Law of Thermodynamics (pg. 134)
The Concept of Internal Energy (pg. 138)
State Variables in Thermodynamics (pg. 139)
Heat and Heat Capacity: How Thermal Energy Transfer (Heat) Is Calculated from Temperature Change (pg. 146)
Enthalpy (pg. 150)
Standard Enthalpies of Formation (pg. 152)
Hess’s Law (pg. 154)
Pressure-Volume Work and the First Law (pg. 156)
Isochoric, Isobaric, and Isothermal Processes (pg. 160)
Adiabatic Processes (pg. 167)
Phase Changes and the Thermodynamics of Melting, Vaporization, and Sublimation (pg. 173)
Summary Concepts (pg. 178)
Case Studies (pg. 183)
4 Entropy and the Second Law of Thermodynamics (pg. 203)
Framework: Setting the Context (pg. 203)
Road Map (pg. 211)
Determination of Probability at the Molecular Level (pg. 212)
Entropy (pg. 216)
Boltzmann and the Microscopic Formulation of Entropy (pg. 217)
Qualitative Prediction of Entropy Change: Establishing the Sign of ΔS (pg. 221)
Quantitative Treatment of Entropy: Calculating ΔS for a System (pg. 225)
Joining the Macroscopic and Microscopic: Calculation of Entropy Change, ΔS (pg. 230)
The Second Law of Thermodynamics (pg. 231)
Gibbs Free Energy (pg. 232)
Gibbs Free Energy and Spontaneous Change (pg. 233)
Absolute Value for Entropy: The Third Law of Thermodynamics (pg. 236)
Calculation of Entropy Change for a Chemical Reaction (pg. 237)
Calculation of Gibbs Free Energy for a Reaction (pg. 239)
Summary Concepts (pg. 242)
Case Studies (pg. 247)
5 Equilibria and Free Energy (pg. 257)
Framework: Setting the Context (pg. 257)
Road Map (pg. 263)
The Concept of Chemical Equilibrium (pg. 264)
The Equilibrium Constant (pg. 265)
Determination of a Generalized Expression for Kc from the Specific to the General (pg. 269)
Manipulation of the Equilibrium Constant (pg. 270)
Converting between Concentration Units and Pressure Units (pg. 273)
Stressed Equilibria (pg. 275)
The Principle of Le Chatelier (pg. 281)
Quantitative Determination of Concentrations Following an Impressed Stress on a System at Equilibrium (pg. 282)
Equilibrium Problems Involving Multiple Steps (pg. 284)
Equilibrium Constants, Spontaneous Processes, and Gibbs Free Energy (pg. 286)
Gibbs Free Energy Under Non-standard Conditions (pg. 289)
ΔGo at Temperatures Other than 298 K (pg. 292)
Thermodynamic Equilibrium Constant: Activities (pg. 295)
Assessing Spontaneity for Non-standard Conditions (pg. 295)
ΔGo and Keq as Functions of Temperature (pg. 296)
Gibbs Free Energy: The Maximum Amount of Work That Can Be Extracted from a Chemical Process (pg. 298)
Summary Concepts (pg. 299)
Case Studies (pg. 305)
6 Equilibria in Solution: Acid–Base Control of Life Systems (pg. 315)
Framework: Setting the Context (pg. 315)
Road Map (pg. 323)
Introduction (pg. 324)
The Bonding Structure of Water (pg. 324)
Theory of Acid-Base Reactions (pg. 326)
Equilibria and Free Energy in Acidic Solution (pg. 330)
Solutions That Are Basic: Manipulation of pOH and pKa (pg. 333)
Neutralization Reactions: The Addition of an Acid to a Base (pg. 335)
Strong Acid Reacting with a Strong Base (pg. 336)
Strong Base Reacting with a Weak Acid (pg. 338)
Buffer Solutions (pg. 344)
Titration Reactions (pg. 347)
Titration of a Weak Acid by a Strong Base (pg. 349)
Titration of a Weak Base by a Strong Acid (pg. 351)
Summary Concepts (pg. 353)
Case Studies (pg. 359)
7 Electrochemistry: The Union of Gibbs Free Energy, Electron Flow, and Chemical Transformation (pg. 379)
Framework: Setting the Context (pg. 379)
Road Map (pg. 386)
Free Energy, Electron Flow, and Electrochemistry (pg. 387)
The Galvanic or Voltaic Cell (pg. 392)
The Half-Cell Reactions (pg. 395)
The Standard Hydrogen Electrode (pg. 396)
Calculation of the Cell Potential (pg. 399)
Active vs. Inactive Electrodes (pg. 405)
Notation for an Electrochemical Cell: A Shorthand Technique (pg. 407)
Maximum Work from a Cell: Gibbs Free Energy (pg. 408)
Link between Keq, G°, and E°cell (pg. 411)
Death of an Electrochemical Cell: The Nernst Equation (pg. 414)
The Master Diagram (pg. 416)
Non-spontaneous Reactions: Driving the Electrochemical Cell Uphill (pg. 418)
Corrosion: A Redox Reaction That Causes Problems (pg. 422)
Summary Concepts (pg. 425)
Case Studies (pg. 427)
8 Quantum Mechanics, Wave-Particle Duality, and the Single Electron Atom (pg. 453)
Framework: Setting the Context (pg. 453)
Road Map (pg. 459)
Waves and Particles: From Separation to Union (pg. 460)
Einstein, the Photon, and the Union of Planck and the Photoelectric Effect (pg. 460)
Momentum of the Photon (pg. 466)
Spectroscopy and the Study of Light Emission from Atoms (pg. 468)
Bohr Model of the Hydrogen Atom (pg. 469)
The de Broglie Wavelength of the Electron (pg. 477)
Nature of Waves and the Wave Equation (pg. 479)
Particle-in-a-Box: An Important Example (pg. 483)
Uncertainty in the Position of the Electron in the Square Well Potential (pg. 488)
The Schrödinger Equation (pg. 490)
The Hydrogen Atom (pg. 493)
Energy Levels of the Hydrogen Atom (pg. 495)
Quantum Numbers That Define the Radial and Angular Solutions to the Schrödinger Equation (pg. 497)
Physical Interpretation of the Schrödinger Wavefunction ψn,ℓ,mℓ(r,θ,ϕ) (pg. 506)
Summary Concepts (pg. 509)
Case Studies (pg. 515)
9 Quantum Mechanics of Multielectron Systems and the Link Between Orbital Structure and Chemical Reactivity (pg. 527)
Framework: Setting the Context (pg. 528)
Road Map (pg. 533)
Multielectron Atoms (pg. 534)
Penetration, Shielding, and Effective Nuclear Charge, Zeff (pg. 537)
Building Up the Periodic Table (pg. 540)
Building Up Period 3 (pg. 542)
Building Up Period 4 (pg. 544)
Organization of the Periodic Table (pg. 546)
Joining Periodic Behavior to Chemical Reactivity (pg. 548)
Electron Shielding and Penetration (pg. 549)
Periodic Trends in Atomic Size (pg. 551)
Periodic Trends in Ionization Energy (pg. 554)
Periodic Trends in Electron Affinity (pg. 557)
Linking Periodic Trends in IE and EA (pg. 559)
Electronegativity: Unify the Concepts of Ionization Energy and Electron Affinity (pg. 559)
Trends in the Chemical Behavior of Metals (pg. 560)
Summary Concepts (pg. 561)
Case Studies (pg. 565)
10 Theories of Molecular Bonding I: Valence Electron Configuration, Electron Sharing, and Prediction of Molecular Shape (pg. 585)
Framework: Setting the Context (pg. 586)
Road Map (pg. 592)
The Structure of the Molecular Bond (pg. 593)
Types of Chemical Bonds (pg. 599)
Representation of Valence Electrons in a Chemical Bond (pg. 602)
Lewis Structures for Ionic Bonds (pg. 604)
Lattice Energy and the Formation of Ionic Crystals (pg. 606)
Lewis Structures and Covalent Bonding (pg. 607)
Lewis Structures for Covalent Bonds (pg. 607)
Lewis Structures for Single Covalent Bonds: Diatomics (pg. 608)
Lewis Structures for Single Covalent Bonds: Polyatomic Molecules (pg. 609)
Lewis Structures and Bonding Character (pg. 611)
Constructing Lewis Structures For Polyatomic Molecular Compounds (pg. 612)
Method of Formal Charge (pg. 617)
Limitation to the Lewis Theory (pg. 618)
Determination of Molecular Shapes: Valence Shell Electron Pair Repulsion Theory (pg. 620)
Shapes of Molecules: Bond Lengths and Bond Energies (pg. 627)
Summary Concepts (pg. 630)
Case Studies (pg. 635)
11 Theories of Molecular Bonding II: Quantum Mechanical Based Theories of Covalent Bonding (pg. 661)
Framework: Setting the Context (pg. 661)
Road Map (pg. 669)
Valence Bond Theory: Orbital Overlap and the Name of the Chemical Bond (pg. 670)
Molecular Shape and the Concept of Bond Hybridization (pg. 678)
sp3 Hybridization and the Structure of Methane (pg. 680)
sp2 Hybridization and the Formation of σ and π Double Bonds (pg. 682)
sp Hybridization and the Formation of Triple Bonds (pg. 684)
sp3d and sp3d2 Hybrid Orbitals: Trigonal Bipyramidal and Octahedral Geometry (pg. 688)
Molecular Orbital Theory and Electron Delocalization (pg. 691)
Bonding and Antibonding Orbitals (pg. 695)
Molecular Orbital Structure of Molecular Oxygen (pg. 699)
Molecular Orbital Structure and the Potential Energy Structure (pg. 701)
Molecular Orbital Structure of Homonuclear Diatomics (pg. 705)
Molecular Orbital Structure of Heteronuclear Molecules (pg. 707)
Molecular Orbital Theory Applied to Benzene: The Central Role of Delocalization (pg. 710)
Summary Concepts (pg. 715)
Case Studies (pg. 719)
12 Kinetics: The Principles That Govern the Rate at Which Chemical Reac tions Occur (pg. 743)
Framework: Setting the Context (pg. 743)
Road Map (pg. 755)
Kinetics (pg. 756)
Chemical Reactions and Molecular Collisions (pg. 757)
The Overall Reaction vs. the “Elementary Reaction” (pg. 760)
Determination of the Rate of a Chemical Reaction (pg. 761)
Determination of the Reaction Rate Constant (pg. 763)
Reaction Rate Order: Determination of the Effect of Concentration on Reaction Rate (pg. 765)
The Behavior of Zero-Order, First-Order, Second-Order, and Third-Order Kinetics (pg. 768)
Integration of the Rate Law: Defining the Concentration as a Function of Time (pg. 772)
Steady State Approximation (pg. 780)
Arrhenius Expression for Temperature Dependence (pg. 784)
Relating Molecular Motion to the Arrhenius Expression (pg. 785)
Manipulation of the Arrhenius Expression (pg. 788)
Summary Concepts (pg. 789)
Case Studies (pg. 795)
13 Nuclear Chemistry: Energy, Reactors, Imaging, and Radiocarbon Dating (pg. 807)
Framework: Setting the Context (pg. 807)
Road Map (pg. 821)
Elementary Nuclear Particles and Reactions (pg. 822)
Nuclear Reactions: Fusion (pg. 823)
Nuclear Stability: Binding Energy (pg. 824)
Nuclear Reactions: Fission (pg. 826)
Radioactive Dating (pg. 828)
Appendixes (pg. 831)
Appendix A: Standard Thermodynamic Values for Selected Substances (pg. 831)
Appendix B: Equilibrium Constants for Selected Substances (pg. 835)
Appendix C: Standard Electrode (Half-Cell) Potentials (pg. 841)
Appendix D: Fundamental Physical Constants, SI Unit Prefixes, Conversions, and Relationships (pg. 842)
Appendix E: The Elements (Atomic Numbers and Atomic Masses) (pg. 843)
Appendix F: Periodic Table (pg. 845)
Index (pg. 847)

James G. Anderson

James G. Anderson, recipient of the 2021 Dreyfus Prize in Environmental Chemistry, is Philip Weld Professor in the Departments of Chemistry and Chemical Biology, Earth and Planetary Sciences, and the School of Engineering and Applied Sciences at Harvard University.

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