Thermodynamics, Statistical Thermodynamics, & Kinetics

Thomas Engel has taught chemistry for more than 20 years at the University of Washington, where he is currently Professor of Chemistry and Associate Chair for the Undergraduate Program. Professor Engel received his bachelor's and master's degrees in chemistry from the Johns Hopkins University, and his Ph.D. in chemistry from the University of Chicago. He then spent 11 years as a researcher in Germany and Switzerland, in which time he received the Dr. rer. nat. habil. degree from the Ludwig Maximilians University in Munich. In 1980, he left the IBM research laboratory in Zurich to become a faculty member at the University of Washington.   Professor Engel's research interests are in the area of surface chemistry, and he has published more than 80 articles and book chapters in this field. He has received the Surface Chemistry or Colloids Award from the American Chemical Society and a Senior Humboldt Research Award from the Alexander von Humboldt Foundation, which has allowed him to establish collaborations with researchers in Germany. He is currently working together with European manufacturers of catalytic converters to improve their performance for diesel engines. Philip Reid has taught chemistry at the University of Washington since he joined the chemistry faculty in 1995. Professor Reid received his bachelor's degree from the University of Puget Sound in 1986, and his Ph.D. in chemistry from the University of California at Berkeley in 1992. He performed postdoctoral research at the University of Minnesota, Twin Cities, campus before moving to Washington.   Professor Reid's research interests are in the areas of atmosphere chemistry, condensed-phase reaction dynamics, and nonlinear optical materials. He has published more than 70 articles in these fields. Professor Reid is the recipient of a CAREER award from the National Science Foundation, is a Cottrell Scholar of the Research Corporation, and is a Sloan fellow.

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