University Chemistry: Frontiers and Foundations from a Global and Molecular Perspective

by James G. Anderson

Overview

A new approach to teaching university-level chemistry that links core concepts of chemistry and physical science to current global challenges.

Introductory chemistry and physics are generally taught at the university level as isolated subjects, divorced from any compelling context. Moreover, the “formalism first” teaching approach presents students with disembodied knowledge, abstract and learned by rote. By contrast, this textbook presents a new approach to teaching university-level chemistry that links core concepts of chemistry and physical science to current global challenges. It provides the rigorous development of the principles of chemistry but places these core concepts in a global context to engage developments in technology, energy production and distribution, the irreversible nature of climate change, and national security.

Each chapter opens with a “Framework” section that establishes the topic’s connection to emerging challenges. Next, the “Core” section addresses concepts including the first and second law of thermodynamics, entropy, Gibbs free energy, equilibria, acid-base reactions, electrochemistry, quantum mechanics, molecular bonding, kinetics, and nuclear. Finally, the “Case Studies” section explicitly links the scientific principles to an array of global issues. These case studies are designed to build quantitative reasoning skills, supply the technology background, and illustrate the critical global need for the infusion of technology into energy generation. The text’s rigorous development of both context and scientific principles equips students for advanced classes as well as future involvement in scientific and societal arenas. University Chemistry was written for a widely adopted course created and taught by the author at Harvard.

Product Details

ISBN-13:	9780262542654
Publisher:	MIT Press
Publication date:	05/10/2022
Pages:	872
Product dimensions:	8.50(w) x 10.87(h) x 1.12(d)

About the Author

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.

Table of Contents

Preface xiii

Acknowledgments and About the Author xvi

Chapter 1 Energy: Conceptual Foundation and the Laws That Govern Its Transformation 1

Framework: Setting the Context 2

Road Map 9

Emergence of Energy as a Scientific Concept 9

Energy, Work, and Newton's Laws 12

Conservation of Energy: Tracking the Flow of Energy 15

Energy at the Molecular Level: Microscopic and Macroscopic Forms of Energy 18

Exchange of Kinetic and Potential Energy on a Surface 20

The Mechanical Equivalent of Heat 22

Heat and Temperature at the Molecular Level 26

Energy Transformations: The Central Role of Electromagnetic Radiation 30

Energy and Power: A Very Important Distinction 38

Summary of the Core Concepts 38

Case Studies 43

Chapter 2 Atomic and Molecular Structure: Energy from Chemical Bonds 63

Framework: Setting the Context 63

Road Map 71

Atomic View of Matter 71

Discovery of the Electron 73

Discovery of the Atomic Nucleus 75

Atomic Number, Mass Number, and Atomic Symbol 78

Isotopes 79

Molecular Structure 79

Chemical Formulas 83

Chemical Formulas and Molecular Models 83

Stoichiometry 86

Avogadro's Number 88

Molar Mass 88

Balancing Chemical Equations 89

Oxidation-Reduction Reactions 93

Oxidation and Reduction in Combustion Reactions 95

Redox Reactions where Oxygen Is Not Involved 96

Summary Concepts 97

Case Studies 101

Chapter 3 Thermochemistry: Development of the First Law of Thermodynamics 129

Framework: Setting the Context 129

Road Map 133

Development of the First Law of Thermodynamics 134

The Concept of Internal Energy 138

State Variables in Thermodynamics 139

Heat and Heat Capacity: How Thermal Energy Transfer (Heat) Is Calculated from Temperature Change 146

Enthalpy 150

Standard Enthalpies of Formation 152

Hess's Law 154

Pressure-Volume Work and the First Law 156

Isochoric, Isobaric, and Isothermal Processes 160

Adiabatic Processes 167

Phase Changes and the Thermodynamics of Melting, Vaporization, and Sublimation 173

Summary Concepts 178

Case Studies 183

Chapter 4 Entropy and the Second Law of Thermodynamics 203

Framework: Setting the Context 203

Road Map 211

Determination of Probability at the Molecular Level 212

Entropy 216

Boltzmann and the Microscopic Formulation of Entropy 217

Qualitative Prediction of Entropy Change: Establishing the Sign of ΔS 221

Quantitative Treatment of Entropy: Calculating ΔS for a System 225

Joining the Macroscopic and Microscopic: Calculation of Entropy Change, ΔS 230

The Second Law of Thermodynamics 231

Gibbs Free Energy 232

Gibbs Free Energy and Spontaneous Change 233

Absolute Value for Entropy: The Third Law of Thermodynamics 236

Calculation of Entropy Change for a Chemical Reaction 237

Calculation of Gibbs Free Energy for a Reaction 239

Summary Concepts 242

Case Studies 247

Chapter 5 Equilibria and Free Energy 257

Framework: Setting the Context 257

Road Map 263

The Concept of Chemical Equilibrium 264

The Equilibrium Constant 265

Determination of a Generalized Expression for K_c from the Specific to the General 269

Manipulation of the Equilibrium Constant 270

Converting between Concentration Units and Pressure Units 273

Stressed Equilibria 275

The Principle of Le Chatelier 281

Quantitative Determination of Concentrations Following an Impressed Stress on a System at Equilibrium 282

Equilibrium Problems Involving Multiple Steps 284

Equilibrium Constants, Spontaneous Processes, and Gibbs Free Energy 286

Gibbs Free Energy Under Non-standard Conditions 289

ΔG⁰ at Temperatures Other than 298 K 292

Thermodynamic Equilibrium Constant: Activities 295

Assessing Spontaneity for Non-standard Conditions 295

ΔG⁰ and K_eq as Functions of Temperature 296

Gibbs Free Energy: The Maximum Amount of Work That Can Be Extracted from a Chemical Process 298

Summary Concepts 299

Case Studies 305

Chapter 6 Equilibria in Solution: Acid-Base Control of Life Systems 315

Framework: Setting the Context 315

Road Map 323

Introduction 324

The Bonding Structure of Water 324

Theory of Acid-Base Reactions 326

Equilibria and Free Energy in Acidic Solution 330

Solutions That Are Basic: Manipulation of pOH and pK_a 333

Neutralization Reactions: The Addition of an Acid to a Base 335

Strong Acid Reacting with a Strong Base 336

Strong Base Reacting with a Weak Acid 338

Buffer Solutions 344

Titration Reactions 347

Titration of a Weak Acid by a Strong Base 349

Titration of a Weak Base by a Strong Acid 351

Summary Concepts 353

Case Studies 359

Chapter 7 Electrochemistry: The Union of Gibbs Free Energy, Electron Flow, and Chemical Transformation 379

Framework: Setting the Context 379

Road Map 386

Free Energy, Electron Flow, and Electrochemistry 387

The Galvanic or Voltaic Cell 392

The Half-Cell Reactions 395

The Standard Hydrogen Electrode 396

Calculation of the Cell Potential 399

Active vs. Inactive Electrodes 405

Notation for an Electrochemical Cell: A Shorthand Technique 407

Maximum Work from a Cell: Gibbs Free Energy 408

Link between K_eq, G^o, and E^o_Cell 411

Death of an Electrochemical Cell: The Nernst Equation 414

The Master Diagram 416

Non-spontaneous Reactions: Driving the Electrochemical Cell Uphill 418

Corrosion: A Redox Reaction That Causes Problems 422

Summary Concepts 425

Case Studies 427

Chapter 8 Quantum Mechanics, Wave-Particle Duality, and the Single Electron Atom 453

Framework: Setting the Context 453

Road Map 459

Waves and Particles: From Separation to Union 460

Einstein, the Photon, and the Union of Planck and the Photoelectric Effect 460

Momentum of the Photon 466

Spectroscopy and the Study of Light Emission from Atoms 468

Bohr Model of the Hydrogen Atom 469

The de Broglie Wavelength of the Electron 477

Nature of Waves and the Wave Equation 479

Particle-in-a-Box: An Important Example 483

Uncertainty in the Position of the Electron in the Square Well Potential 488

The Schrödinger Equation 490

The Hydrogen Atom 493

Energy Levels of the Hydrogen Atom 495

Quantum Numbers That Define the Radial and Angular Solutions to the Schrödinger Equation 497

Physical Interpretation of the Schrödinger Wavefunction ψ_n,l,ml(r,θ,φ) 506

Summary Concepts 509

Case Studies 515

Chapter 9 Quantum Mechanics of Multielectron Systems and the Link Between Orbital Structure and Chemical Reactivity 527

Framework: Setting the Context 528

Road Map 533

Multielectron Atoms 534

Penetration, Shielding, and Effective Nuclear Charge, Z_eff 537

Building Up the Periodic Table 540

Building Up Period 3 542

Building Up Period 4 544

Organization of the Periodic Table 546

Joining Periodic Behavior to Chemical Reactivity 548

Electron Shielding and Penetration 549

Periodic Trends in Atomic Size 551

Periodic Trends in Ionization Energy 554

Periodic Trends in Electron Affinity 557

Linking Periodic Trends in IE and EA 559

Electronegativity: Unify the Concepts of Ionization Energy and Electron Affinity 559

Trends in the Chemical Behavior of Metals 560

Summary Concepts 561

Case Studies 565

Chapter 10 Theories of Molecular Bonding I: Valence Electron Configuration, Electron Sharing, and Prediction of Molecular Shape 585

Framework: Setting the Context 586

Road Map 592

The Structure of the Molecular Bond 593

Types of Chemical Bonds 599

Representation of Valence Electrons in a Chemical Bond 602

Lewis Structures for Ionic Bonds 604

Lattice Energy and the Formation of Ionic Crystals 606

Lewis Structures and Covalent Bonding 607

Lewis Structures for Covalent Bonds 607

Lewis Structures for Single Covalent Bonds: Diatomics 608

Lewis Structures for Single Covalent Bonds: Polyatomic Molecules 609

Lewis Structures and Bonding Character 611

Constructing Lewis Structures For Polyatomic Molecular Compounds 612

Method of Formal Charge 617

Limitation to the Lewis Theory 618

Determination of Molecular Shapes: Valence Shell Electron Pair Repulsion Theory 620

Shapes of Molecules: Bond Lengths and Bond Energies 627

Summary Concepts 630

Case Studies 635

Chapter 11 Theories of Molecular Bonding II: Quantum Mechanical Based Theories of Covalent Bonding 661

Framework: Setting the Context 661

Road Map 669

Valence Bond Theory: Orbital Overlap and the Name of the Chemical Bond 670

Molecular Shape and the Concept of Bond Hybridization 678

sp³ Hybridization and the Structure of Methane 680

sp² Hybridization and the Formation of a and n Double Bonds 682

sp Hybridization and the Formation of Triple Bonds 684

sp³d and sp³d² Hybrid Orbitals: Trigonal Bipyramidal and Octahedral Geometry 688

Molecular Orbital Theory and Electron Delocalization 691

Bonding and Antibonding Orbitals 695

Molecular Orbital Structure of Molecular Oxygen 699

Molecular Orbital Structure and the Potential Energy Structure 701

Molecular Orbital Structure of Homonuclear Diatomics 705

Molecular Orbital Structure of Heteronuclear Molecules 707

Molecular Orbital Theory Applied to Benzene: The Central Role of Delocalization 710

Summary Concepts 715

Case Studies 719

Chapter 12 Kinetics: The Principles That Govern the Rate at Which Chemical Reactions Occur 743

Framework: Setting the Context 743

Road Map 755

Kinetics 756

Chemical Reactions and Molecular Collisions 757

The Overall Reaction vs. the "Elementary Reaction" 760

Determination of the Rate of a Chemical Reaction 761

Determination of the Reaction Rate Constant 763

Reaction Rate Order: Determination of the Effect of Concentration on Reaction Rate 765

The Behavior of Zero-Order, First-Order, Second-Order, and Third-Order Kinetics 768

Integration of the Rate Law: Defining the Concentration as a Function of Time 772

Steady State Approximation 780

Arrhenius Expression for Temperature Dependence 784

Relating Molecular Motion to the Arrhenius Expression 785

Manipulation of the Arrhenius Expression 788

Summary Concepts 789

Case Studies 795

Chapter 13 Nuclear Chemistry: Energy, Reactors, Imaging, and Radiocarbon Dating 807

Framework: Setting the Context 807

Road Map 821

Elementary Nuclear Particles and Reactions 822

Nuclear Reactions: Fusion 823

Nuclear Stability: Binding Energy 824

Nuclear Reactions: Fission 826

Radioactive Dating 828

Appendixes 831

Appendix A Standard Thermodynamic Values for Selected Substances 831

Appendix B Equilibrium Constants for Selected Substances 835

Appendix C Standard Electrode (Half-Cell) Potentials 841

Appendix D Fundamental Physical Constants, SI Unit Prefixes, Conversions, and Relationships 842

Appendix E The Elements (Atomic Numbers and Atomic Masses) 843

Appendix F Periodic Table 845

Index 847

What People are Saying About This

From the Publisher

“This well-written textbook from a leader in the field highlights the role of chemistry in addressing some of the most important challenges of the twenty-first century, in particular those dealing with energy and the environment. A must-read for chemistry students."
—Harry B. Gray, Arnold O. Beckman Professor of Chemistry, California Institute of Technology; coeditor of Biological Inorganic Chemistry

“Jim Anderson has produced an audaciously original general chemistry book. He succeeds brilliantly in expressing deep insight into chemical principles and an evident zeal to demonstrate what chemistry is good for.”
—Matthew Tirrell, Dean, Pritzker School of Molecular Engineering, University of Chicago
 
“This outstanding text connects chemistry to societal challenges of climate and energy. Introductory courses can be dry as desiccant, but this rigorous work has the zing of real-world relevance to draw students into our discipline.”
—Neil M. Donahue, Thomas Lord University Professor of Chemistry, Carnegie Mellon University