## Table of Contents

CHAPTER 1: FUNDAMENTAL CONCEPTS OF THERMODYNAMICS

1.1 What Is Thermodynamics and Why Is It Useful?

1.2 Basic Definitions Needed to Describe Thermodynamic Systems

1.3 Thermometry

1.4 Equations of State and the Ideal Gas Law

1.5 A Brief Introduction to Real Gases

CHAPTER 2: HEAT, WORK, INTERNAL ENERGY, ENTHALPY, AND THE FIRST LAW OF THERMODYNAMICS

2.1 The Internal Energy and the First Law of Thermodynamics

2.2 Work

2.3 Heat

2.4 Heat Capacity

2.5 State Functions and Path Functions

2.6 Equilibrium, Change, and Reversibility

2.7 Comparing Work for Reversible and Irreversible Processes

2.8 Determining and Introducing Enthalpy, a New State Function

2.9 Calculating q, w, , and for Processes Involving Ideal Gases

2.10 The Reversible Adiabatic Expansion and Compression of an Ideal Gas

CHAPTER 3: THE IMPORTANCE OF STATE FUNCTIONS: INTERNAL ENERGY AND ENTHALPY

3.1 The Mathematical Properties of State Functions

3.2 The Dependence of U on V and T

3.3 Does the Internal Energy Depend More Strongly on V or T?

3.4 The Variation of Enthalpy with Temperature at Constant Pressure

3.5 How Are CP and CV Related?

3.6 The Variation of Enthalpy with Pressure at Constant Temperature

3.7 The Joule-Thomson Experiment

3.8 Liquefying Gases Using an Isenthalpic Expansion

CHAPTER 4: THERMOCHEMISTRY

4.1 Energy Stored in Chemical Bonds Is Released or Taken Up in Chemical Reactions

4.2 Internal Energy and Enthalpy Changes Associated with Chemical Reactions

4.3 Hess’s Law Is Based on Enthalpy Being a State Function

4.4 The Temperature Dependence of Reaction Enthalpies

4.5 The Experimental Determination of and for Chemical Reactions

4.6 Differential Scanning Calorimetry

CHAPTER 5: ENTROPY AND THE SECOND AND THIRD LAWS OF THERMODYNAMICS

5.1 The Universe Has a Natural Direction of Change

5.2 Heat Engines and the Second Law of Thermodynamics

5.3 Introducing Entropy

5.4 Calculating Changes in Entropy

5.5 Using Entropy to Calculate the Natural Direction of a Process in an Isolated System

5.6 The Clausius Inequality

5.7 The Change of Entropy in the Surroundings and = +

5.8 Absolute Entropies and the Third Law of Thermodynamics

5.9 Standard States in Entropy Calculations

5.10 Entropy Changes in Chemical Reactions

5.11 Refrigerators, Heat Pumps, and Real Engines

5.12 (Supplemental) Using the Fact that S Is a State Function to Determine the Dependence of S on V and T

5.13 (Supplemental) The Dependence of S on T and P

5.14 (Supplemental) The Thermodynamic Temperature Scale

CHAPTER 6: CHEMICAL EQUILIBRIUM

6.1 The Gibbs Energy and the Helmholtz Energy

6.2 The Differential Forms of U, H, A, and G

6.3 The Dependence of the Gibbs and Helmholtz Energies on P, V, and T

6.4 The Gibbs Energy of a Reaction Mixture

6.5 The Gibbs Energy of a Gas in a Mixture

6.6 Calculating the Gibbs Energy of Mixing for Ideal Gases

6.7 Expressing Chemical Equilibrium in an Ideal Gas Mixture in Terms of the

6.8 Calculating and Introducing the Equilibrium Constant for a Mixture of Ideal Gases

6.9 Calculating the Equilibrium Partial Pressures in a Mixture of Ideal Gases

6.10 The Variation of KP with Temperature

6.11 Equilibria Involving Ideal Gases and Solid or Liquid Phases

6.12 Expressing the Equilibrium Constant in Terms of Mole Fraction or Molarity

6.13 The Dependence of on T and P

6.14 (Supplemental) A Case Study: The Synthesis of Ammonia

6.15 (Supplemental) Expressing U and H and Heat Capacities Solely in Terms of Measurable Quantities

CHAPTER 7: THE PROPERTIES OF REAL GASES

7.1 Real Gases and Ideal Gases

7.2 Equations of State for Real Gases and Their Range of Applicability

7.3 The Compression Factor

7.4 The Law of Corresponding States

7.5 Fugacity and the Equilibrium Constant for Real Gases

CHAPTER 8: PHASE DIAGRAMS AND THE RELATIVE STABILITY OF SOLIDS, LIQUIDS, AND GASES

8.1 What Determines the Relative Stability of the Solid, Liquid, and Gas Phases?

8.2 The Pressure–Temperature Phase Diagram

8.3 The Phase Rule

8.4 The Pressure–Volume and Pressure–Volume–Temperature Phase Diagrams

8.5 Providing a Theoretical Basis for the P–T Phase Diagram

8.6 Using the Clapeyron Equation to Calculate Vapor Pressure as a Function of T

8.7 The Vapor Pressure of a Pure Substance Depends on the Applied Pressure

8.8 Surface Tension

8.9 Chemistry in Supercritical Fluids

8.10 Liquid Crystals and LCD Displays

CHAPTER 9: IDEAL AND REAL SOLUTIONS

9.1 Defining the Ideal Solution

9.2 The Chemical Potential of a Component in the Gas and Solution Phases

9.3 Applying the Ideal Solution Model to Binary Solutions

9.4 The Temperature– Composition Diagram and Fractional Distillation

9.5 The Gibbs–Duhem Equation

9.6 Colligative Properties

9.7 The Freezing Point Depression and Boiling Point Elevation

9.8 The Osmotic Pressure

9.9 Real Solutions Exhibit Deviations from Raoult’s Law

9.10 The Ideal Dilute Solution

9.11 Activities Are Defined with Respect to Standard States

9.12 Henry’s Law and the Solubility of Gases in a Solvent

9.13 Chemical Equilibrium in Solutions

9.14 Solutions Formed From Partially miscible Liquids

9.15 The Solid-Solution Equilibrium

CHAPTER 10: ELECTROLYTE SOLUTIONS

10.1 The Enthalpy, Entropy, and Gibbs Energy of Ion Formation in Solutions

10.2 Understanding the Thermodynamics of Ion Formation and Solvation

10.3 Activities and Activity Coefficients for Electrolyte Solutions

10.4 Calculating Using the Debye–Hückel Theory

10.5 Chemical Equilibrium in Electrolyte Solutions

CHAPTER 11: ELECTROCHEMICAL CELLS, BATTERIES, AND FUEL CELLS

11.1 The Effect of an Electrical Potential on the Chemical Potential of Charged Species

11.2 Conventions and Standard States in Electrochemistry

11.3 Measurement of the Reversible Cell Potential

11.4 Chemical Reactions in Electrochemical Cells and the Nernst Equation

11.5 Combining Standard Electrode Potentials to Determine the Cell Potential

11.6 Obtaining Reaction Gibbs Energies and Reaction Entropies from Cell Potentials

11.7 The Relationship between the Cell EMF and the Equilibrium Constant

11.8 Determination of E° and Activity Coefficients Using an Electrochemical Cell

11.9 Cell Nomenclature and Types of Electrochemical Cells

11.10 The Electrochemical Series

11.11 Thermodynamics of Batteries and Fuel Cells

11.12 The Electrochemistry of Commonly Used Batteries

11.13 Fuel Cells

11.14 (Supplemental) Electrochemistry at the Atomic Scale

11.15 (Supplemental) Using Electrochemistry for Nanoscale Machining

11.16 (Supplemental) Absolute Half-Cell Potentials

CHAPTER 12: PROBABILITY

12.1 Why Probability?

12.2 Basic Probability Theory

12.3 Stirling’s Approximation

12.4 Probability Distribution Functions

12.5 Probability Distributions Involving Discrete and Continuous Variables

12.6 Characterizing Distribution Functions

CHAPTER 13: THE BOLTZMANN DISTRIBUTION

13.1 Microstates and Configurations

13.2 Derivation of the Boltzmann Distribution

13.3 Dominance of the Boltzmann Distribution

13.4 Physical Meaning of the Boltzmann Distribution Law

13.5 The Definition of

CHAPTER 14: ENSEMBLE AND MOLECULAR PARTITION FUNCTIONS

14.1 The Canonical Ensemble

14.2 Relating Q to q for an Ideal Gas

14.3 Molecular Energy Levels

14.4 Translational Partition Function

14.5 Rotational Partition Function: Diatomics

14.6 Rotational Partition Function: Polyatomics

14.7 Vibrational Partition Function

14.8 The Equipartition Theorem

14.9 Electronic Partition Function

14.10 Review

CHAPTER 15: STATISTICAL THERMODYNAMICS

15.1 Energy

15.2 Energy and Molecular Energetic Degrees of Freedom

15.3 Heat Capacity

15.4 Entropy

15.5 Residual Entropy

15.6 Other Thermodynamic Functions

15.7 Chemical Equilibrium

CHAPTER 16: KINETIC THEORY OF GASES

16.1 Kinetic Theory of Gas Motion and Pressure

16.2 Velocity Distribution in One Dimension

16.3 The Maxwell Distribution of Molecular Speeds

16.4 Comparative Values for Speed Distributions:

16.5 Gas Effusion

16.6 Molecular Collisions

16.7 The Mean Free Path

CHAPTER 17: TRANSPORT PHENOMENA

17.1 What Is Transport?

17.2 Mass Transport: Diffusion

17.3 The Time Evolution of a Concentration Gradient

17.4 (Supplemental) Statistical View of Diffusion

17.5 Thermal Conduction

17.6 Viscosity of Gases

17.7 Measuring Viscosity

17.8 Diffusion in Liquids and Viscosity of Liquids

17.9 (Supplemental) Sedimentation and Centrifugation

17.10 Ionic Conduction

CHAPTER 18: ELEMENTARY CHEMICAL KINETICS

18.1 Introduction to Kinetics

18.2 Reaction Rates

18.3 Rate Laws

18.4 Reaction Mechanisms

18.5 Integrated Rate Law Expressions

18.6 (Supplemental) Numerical Approaches

18.7 Sequential First-Order Reactions

18.8 Parallel Reactions

18.9 Temperature Dependence of Rate Constants

18.10 Reversible Reactions and Equilibrium

18.11 (Supplemental) Perturbation-Relaxation Methods

18.12 (Supplemental) The Autoionization of Water: A T-Jump Example

18.13 Potential Energy Surfaces

18.14 Activated Complex Theory

CHAPTER 19: COMPLEX REACTION MECHANISMS

19.1 Reaction Mechanisms and Rate Laws

19.2 The Preequilibrium Approximation

19.3 The Lindemann Mechanism

19.4 Catalysis

19.5 Radical-Chain Reactions

19.6 Radical-Chain Polymerization

19.7 Explosions

19.8 Photochemistry

APPENDIX A Data Tables

APPENDIX B Math Supplement

APPENDIX C Answers to Selected End-of-Chapter Problems

INDEX