Physical Chemistry
for the Chemical and Biological Sciences

Raymond Chang
Williams College


Table of Contents

Chapter 1 Introduction

1.1 Nature of Physical Chemistry

1.2 Units

1.3 Atomic Mass, Molecular Mass, and the Chemical Mole

Chapter 2 The Gas Laws

2.1 Some Basic Definitions

2.2 An Operational Definition of Temperature

2.3 Boyle's Law

2.4 Charles' and Gay-Lussac's Law

2.5 Avogadro's Law

2.6 The Ideal Gas Equation

2.7 Dalton's Law of Partial Pressures

2.8 Real Gases

2.9 Condensation of Gases and the Critical State

Chapter 3 Kinetic Theory of Gases

3.1 The Model

3.2 Pressure of a Gas

3.3 Kinetic Energy and Temperature

3.4 The Maxwell Distribution Laws

3.5 Molecular Collisions and the Mean Free Path

3.6 Gas Viscosity

3.7 Graham's Laws of Diffusion and Effusion

3.8 Equipartition of Energy

Appendix 3.1 Derivation of Equation (3.24)

Appendix 3.2 Total and Partial Differentiation

Chapter 4 The First Law of Thermodynamics

4.1 Work and Heat

4.2 The First Law of Thermodynamics

4.3 Enthalpy

4.4 A Closer Look at Heat Capacities

4.5 Gas Expansion

4.6 Thermochemistry

4.7 Bond Energies and Bond Enthalpies

Appendix 4.1 Exact and Inexact Differentials

Chapter 5 The Second Law of Thermodynamics

5.1 Spontaneous Processes

5.2 Entropy

5.3 The Carnot Heat Engine

5.4 The Second Law of Thermodynamics

5.5 Entropy Changes

5.6 The Third Law of Thermodynamics

5.7 Residual Entropy

Appendix 5.1 Statements of the Second Law of Thermodynamics

Chapter 6 Gibbs and Helmholtz Energies and Their Applications

6.1 Gibbs and Helmholtz Energies

6.2 Meaning of Helmholtz and Gibbs Energies

6.3 Standard Molar Gibbs Energy of Formation (fG)

6.4 Dependence of Gibbs Energy on Temperature and Pressure

6.5 Gibbs Energy and Phase Equilibria

6.6 Thermodynamics of Rubber Elasticity

Appendix 6.1 Some Thermodynamic Relationships

Appendix 6.2 Derivation of the Phase Rule

Chapter 7 Nonelectrolyte Solutions

7.1 Concentration Units

7.2 Partial Molar Quantities

7.3 The Thermodynamics of Mixing

7.4 Binary Mixtures of Volatile Liquids

7.5 Real Solutions

7.6 Phase Equilibria of Two-Component Systems

7.7 Colligative Properties

Chapter 8 Electrolyte Solutions

8.1 Electrical Conduction in Solution

8.2 A Molecular View of the Solution Process

8.3 Thermodynamics of Ions in Solution

8.4 Ionic Activity

8.5 Debye-Huckel Theory of Electrolytes

8.6 Colligative Properties of Electrolyte Solutions

8.7 Biological Membranes

Appendix 8.1 Notes on Electrostatics

Appendix 8.2 The Donnan Effect Involving Proteins Bearing Multiple Charges

Chapter 9 Chemical Equilibrium

9.1 Chemical Equilibrium in Gaseous Systems

9.2 Reactions in Solution

9.3 Heterogeneous Equilibria

9.4 The Influence of Temperature, Pressure, and Catalysts on the Equilibrium Constant

9.5 Binding of Ligands and Metal Ions to Macromolecules

9.6 Bioenergetics

Appendix 9.1 The Relationship Between Fugacity and Pressure

Appendix 9.2 The Relationships Between K1 and K2 and the Intrinsic Dissociation Constant K

Chapter 10 Electrochemistry

10.1 Electrochemical Cells

10.2 Single-Electrode Potential

10.3 Thermodynamics of Electrochemical Cells

10.4 Types of Electrodes

10.5 Types of Electrochemical Cells

10.6 Applications of EMF Measurements

10.7 Potentiometric Titration of Redox Reactions

10.8 Biological Oxidation

10.9 Membrane Potential

Chapter 11 Acids and Bases

11.1 Definitions of Acids and Bases

11.2 Dissociation of Acids and Bases

11.3 Salt Hydrolysis

11.4 Acid-Base Titrations

11.5 Diprotic and Polyprotic Acids

11.6 Amino Acids

11.7 Buffer Solutions

11.8 Maintaining the pH of Blood

Appendix 11.1 A More Exact Treatment of Acid-Base Equilibria

Chapter 12 Chemical Kinetics

12.1 Reaction Rate

12.2 Reaction Order

12.3 Molecularity of a Reaction

12.4 More Complex Reactions

12.5 Effect of Temperature on Reaction Rates

12.6 Potential-Energy Surfaces

12.7 Theories of Reaction Rates

12.8 Isotope Effects in Chemical Reactions

12.9 Reactions in Solution

12.10 Fast Reactions in Solution

12.10 Oscillating Reactions

Appendix 12.1 Derivation of Equation (12.9)

Appendix 12.2 Derivation of Equation (12.38)

Chapter 13 Enzyme Kinetics

13.1 General Principles of Catalysis

13.2 The Equations of Enzyme Kinetics

13.3 Chymotrypsin: A Case Study

13.4 Multisubstrate Systems

13.5 Enzyme Inhibition

13.6 Allosteric Interactions

13.7 pH Effects on Enzyme Kinetics

Appendix 13.1 Kinetic Analysis of the Hydrolysis of p-Nitrophenyl Trimethylacetate Catalyzed by Chymotrypsin

Appendix 13.2 Derivations of Equations (13.17) and (13.19)

Appendix 13.3 Derivation of Equation (13.32)

Chapter 14 Quantum Mechanics

14.1 The Wave Theory of Light

14.2 Planck's Quantum Theory

14.3 The Photoelectric Effect

14.4 Bohr's Theory of Hydrogen Emission Spectra

14.5 de Broglie's Postulate

14.6 The Heisenberg Uncertainty Principle

14.7 The Schrodinger Wave Equation

14.8 Particle in a One Dimensional Box

14.9 Quantum-Mechanical Tunneling

14.10 The Schrodinger Wave Equation for the Hydrogen Atom

14.11 Many-Electron Atoms and the Periodic Table

Chapter 15 The Chemical Bond

15.1 Lewis Structures

15.2 Valence Bond Theory

15.3 Hybridization of Atomic Orbitals

15.4 Electronegativity and Dipole Moments

15.5 Molecular Orbital Theory

15.6 Diatomic Molecules

15.7 Resonance and Electron Delocalization

15.8 Coordination Compounds

15.9 Coordination Compounds in Biological Systems

Chapter 16 Intermolecular Forces

16.1 Intermolecular Interactions

16.2 The Ionic Bond

16.3 Types of Intermolecular Forces

16.4 The Hydrogen Bond

16.5 Structure and Properties of Water

16.4 The Hydrophobic Interaction

Chapter 17 Spectroscopy

17.1 Vocabulary

17.2 Microwave Spectroscopy

17.3 Infrared Spectroscopy

17.4 Electronic Spectroscopy

17.5 Nuclear Magnetic Resonance Spectroscopy

17.6 Electron Spin Resonance Spectroscopy

17.7 Fluorescence and Phosphorescence

17.8 Lasers

Appendix 17.1 Fourier-Transform Spectroscopy

Chapter 18 Molecular Symmetry and Optical Activity

18.1 Symmetry of Molecules

18.2 Polarized Light and Optical Rotation

18.3 Optical Rotatory Dispersion and Circular Dichroism

Chapter 19 Photochemistry and Photobiology

19.1 Introduction

19.2 Earth's Atmosphere

19.3 The Greenhouse Effect

19.4 Photochemical Smog

19.5 The Essential Role of Ozone in the Stratosphere

19.6 Photosynthesis

19.7 Vision

19.8 Biological Effects of Radiation

Chapter 20 The Solid State

20.1 Classification of Crystal Systems

20.2 The Bragg Equation

20.3 Structural Determination by X-ray Diffraction

20.4 Types of Crystals

Appendix 20.1 Derivation of Equation (20.3)

Chapter 21 The Liquid State

21.1 Structure of Liquids

21.2 Viscosity

21.3 Surface Tension

21.4 Diffusion

21.5 Liquid Crystals

Appendix 21.1 Derivation of Equation (21.13)

Chapter 22 Macromolecules

22.1 Methods for Determining the Size, Shape, and Molar Mass of Macromolecules

22.2 Structure of Synthetic Polymers

22.3 Structure of Proteins and DNA

22.4 Protein Stability

Appendix 22.1 DNA Fingerprinting

Chapter 23 Statistical Thermodynamics

23.1 Macrostates and Microstates

23.2 The Boltzmann Distribution Law

23.3 The Partition Function

23.4 Molecular Partition Function

23.5 Thermodynamic Quantities from Partition Functions

23.6 Chemical Equilibrium

23.7 Transition-State Theory

Appendix 23.1 Justification of Q = qN/N! for Indistinguishable Particles

Appendices

A. Review of Mathematics and Physics

B. Thermodynamic Data

Glossary

Answers to Even-Numbered Numerical Problems

Index