Thermodynamics, Statistical Thermodynamics, & Kinetics: United States Edition

This full-color, modern physical chemistry text offers arresting illustrations that set it apart from others of its kind. The authors focus on core topics of physical chemistry, presented within a modern framework of applications. Extensive math derivations are provided, yet the book retains the significant chemical rigor needed in physical chemistry.

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