Table of Contents Chapter 1 Introduction 1.1 Nature of Physical Chemistry 1.2 Units Force Pressure Energy 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 The van der Waals Equation The Virial Equation of State 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 Work Heat 4.2 The First Law of Thermodynamics 4.3 Enthalpy 4.4 A Closer Look at Heat Capacities 4.5 Gas Expansion Isothermal Expansion Adiabatic Expansion 4.6 Thermochemistry Standard Enthalpy of Formation Dependence of Enthalpy of Reaction on Temperature 4.7 Bond Energies and Bond Enthalpies Bond Enthalpy and Bond Dissociation Enthalpy Appendix 4.1 Exact and Inexact Differentials Chapter 5 The Second Law of Thermodynamics 5.1 Spontaneous Processes 5.2 Entropy Statistical Definition of Entropy Thermodynamic Definition of Entropy 5.3 The Carnot Heat Engine Thermodynamic Efficiency The Entropy Function Refrigerators, Air Conditioners, and Heat Pumps 5.4 The Second Law of Thermodynamics 5.5 Entropy Changes Entropy Change due to Mixing of Ideal Gases Entropy Change due to Phase Transitions Entropy Change due to Heating 5.6 The Third Law of Thermodynamics Third-Law or Absolute Entropies Entropy of Chemical Reactions 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 Helmholtz Energy Gibbs Energy 6.3 Standard Molar Gibbs Energy of Formation (AEfG Degrees) 6.4 Dependence of Gibbs Energy on Temperature and Pressure Dependence of G on Temperature Dependence of G on Pressure 6.5 Gibbs Energy and Phase Equilibria The Clapeyron and Clausius-Clapeyron Equations Phase Diagrams The Phase Rule 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 Percent by Weight Mole fraction (x) Molarity (M) Molality (m) 7.2 Partial Molar Quantities Partial Molar Volume Partial Molar Gibbs Energy 7.3 The Thermodynamics of Mixing 7.4 Binary Mixtures of Volatile Liquids 7.5 Real Solutions The Solvent Component The Solute Component 7.6 Phase Equilibria of Two-Component Systems Distillation Solid-Liquid Equilibria 7.7 Colligative Properties Vapor-Pressure Lowering Boiling-Point Elevation Freezing-Point Depression Osmotic Pressure Chapter 8 Electrolyte Solutions 8.1 Electrical Conduction in Solution Some Basic Definitions Degree of Dissociation Ionic Mobility Applications of Conductance Measurements 8.2 A Molecular View of the Solution Process 8.3 Thermodynamics of Ions in Solution Enthalpy, Entropy, and Gibbs Energy of Formation of Ions in Solution 8.4 Ionic Activity 8.5 Debye-Huckel Theory of Electrolytes The Salting-In and Salting-Out Effects 8.6 Colligative Properties of Electrolyte Solutions The Donnan Effect 8.7 Biological Membranes Membrane Transport 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 Ideal Gases Real Gases 9.2 Reactions in Solution 9.3 Heterogeneous Equilibria 9.4 The Influence of Temperature, Pressure, and Catalysts on the Equilibrium Constant The Effect of Temperature The Effect of Pressure The Effect of a Catalyst 9.5 Binding of Ligands and Metal Ions to Macromolecules One Binding Site per Macromolecule n Equivalent Binding Sites per Macromolecule Equilibrium Dialysis 9.6 Bioenergetics The Standard State in Biochemistry ATP - The Currency of Energy Principles of Coupled Reactions Glycolysis Some Limitations of Thermodynamics 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 The Nernst Equation Temperature Dependence of EMF 10.4 Types of Electrodes Metal Electrodes Gas Electrodes Metal-Insoluble Salt Electrodes Gas Electrodes The Glass Electrode Ion-Selective Electrodes 10.5 Types of Electrochemical Cells Concentration Cells Fuel Cells 10.6 Applications of EMF Measurements Determination of Activity Coefficients Determination of pH 10.7 Potentiometric Titration of Redox Reactions 10.8 Biological Oxidation The Chemiosmotic Theory of Oxidative Phosphorylation 10.9 Membrane Potential The Goldman Equation The Action Potential Chapter 11 Acids and Bases 11.1 Definitions of Acids and Bases 11.2 Dissociation of Acids and Bases The Ion Product of Water and the pH scale The Relationship Between the Dissociation Constant of An Acid and Its Conjugate Base 11.3 Salt Hydrolysis 11.4 Acid-Base Titrations Acid-Base Indicators 11.5 Diprotic and Polyprotic Acids 11.6 Amino Acids Dissociation of Amino Acids Isoelectric Point 11.7 Buffer Solutions Effect of Ionic Strength and Temperature on Buffer Solutions Preparing a Buffer Solution With a Specific pH Buffer Capacity 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 Zero-Order Reactions First-Order Reactions Second-Order Reactions Determination of Reaction Order 12.3 Molecularity of a Reaction Unimolecular Reactions Bimolecular Reactions Termolecular Reactions 12.4 More Complex Reactions Reversible Reactions Consecutive Reactions Chain Reactions 12.5 Effect of Temperature on Reaction Rates The Arrhenius Equation 12.6 Potential-Energy Surfaces 12.7 Theories of Reaction Rates Collision Theory Transition-State Theory Thermodynamic Formulation of the Transition-State Theory 12.8 Isotope Effects in Chemical Reactions 12.9 Reactions in Solution 12.10 Fast Reactions in Solution The Flow Method The Relaxation Method 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 Enzyme Catalysis 13.2 The Equations of Enzyme Kinetics Michaelis-Menten Kinetics Steady-State Kinetics The Significance of KM and Vmax 13.3 Chymotrypsin: A Case Study 13.4 Multisubstrate Systems The Sequential Mechanism The Nonsequential or "Ping-Pong" Mechanism 13.5 Enzyme Inhibition Reversible Inhibition Irreversible Inhibitions 13.6 Allosteric Interactions Oxygen Binding to Myoglobin and Hemoglobin The Hill Equation The Concerted Model The Sequential Model Conformational Changes in Hemoglobin Induced by Oxygen Binding 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 Electronic Spectra of Polyenes 14.9 Quantum-Mechanical Tunneling 14.10 The Schrodinger Wave Equation for the Hydrogen Atom Atomic Orbitals 14.11 Many-Electron Atoms and the Periodic Table Electron Configurations Variations in Periodic Properties Chapter 15 The Chemical Bond 15.1 Lewis Structures 15.2 Valence Bond Theory 15.3 Hybridization of Atomic Orbitals Methane (CH4) Ethylene (C2H4) Acetylene (C2H2) 15.4 Electronegativity and Dipole Moments Electronegativity Dipole Moment 15.5 Molecular Orbital Theory 15.6 Diatomic Molecules Homonuclear Diatomic Molecules of the Second-Period Elements Heteronuclear Diatomic Molecules of the First and Second-Period Elements 15.7 Resonance and Electron Delocalization The Peptide Bond 15.8 Coordination Compounds Crystal Field Theory Molecular Orbital Theory Valence Bond Theory 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 Dipole-Dipole Interaction Ion-Dipole Interaction Ion-Induced Dipole and Dipole-Induced Dipole Interactions Dispersion or London Interactions Repulsive and Total Interactions The Role of Dispersion Forces in Sickle-Cell Anemia 16.4 The Hydrogen Bond 16.5 Structure and Properties of Water Structure of Ice Structure of Water Some Physiochemical Properties of Water 16.4 The Hydrophobic Interaction Chapter 17 Spectroscopy 17.1 Vocabulary Absorption and Emission Units Regions of the Spectrum Line Width Resolution Intensity Selection Rules Signal-to-Noise Ratio The Beer-Lambert Law 17.2 Microwave Spectroscopy 17.3 Infrared Spectroscopy Simultaneous Vibrational and Rotational Transitions 17.4 Electronic Spectroscopy Organic Molecules Transition Metal Complexes Molecules that Undergo Charge-Transfer Interactions Application of the Beer-Lambert Law 17.5 Nuclear Magnetic Resonance Spectroscopy The Boltzmann Distribution Chemical Shifts Spin-Spin Coupling NMR and Rate Processes NMR of Nuclei Other Than 1H 17.6 Electron Spin Resonance Spectroscopy 17.7 Fluorescence and Phosphorescence Fluorescence Phosphorescence 17.8 Lasers Properties and Applications of Laser Light Appendix 17.1 Fourier-Transform Spectroscopy Chapter 18 Molecular Symmetry and Optical Activity 18.1 Symmetry of Molecules Proper Rotation Axis Plane of Symmetry Center of Symmetry Improper Rotation Axis Molecular Symmetry and Dipole Moment Molecular Symmetry and Optical Activity 18.2 Polarized Light and Optical Rotation 18.3 Optical Rotatory Dispersion and Circular Dichroism Chapter 19 Photochemistry and Photobiology 19.1 Introduction Thermal versus Photochemical Reactions Primary versus Secondary Processes Quantum Yields Measurement of Light Intensity Action Spectrum 19.2 Earth's Atmosphere Composition of the Atmosphere Regions of the Atmosphere Residence Time 19.3 The Greenhouse Effect 19.4 Photochemical Smog Formation of Nitrogen Oxides Formation of O3 * Formation of Hydroxyl Radical Formation of Other Secondary Pollutants Harmful Effects and Prevention of Photochemical Smog 19.5 The Essential Role of Ozone in the Stratosphere Formation of the Ozone Layer Destruction of Ozone Polar Ozone Holes Ways to Curb Ozone Depletion 19.6 Photosynthesis The Chloroplast Chlorophyll and Other Pigment Molecules The Reaction Center Photosystems I and II Dark Reactions 19.7 Vision Structure of Rhodopsin Mechanism of Vision Rotation About the C=C Bond 19.8 Biological Effects of Radiation Sunlight and Skin Cancer Light-Activated Drugs Chapter 20 The Solid State 20.1 Classification of Crystal Systems 20.2 The Bragg Equation 20.3 Structural Determination by X-ray Diffraction The Powder Method Determination of the Crystal Structure of NaCl The Structure Factor Neutron Diffraction 20.4 Types of Crystals Metallic Crystals Ionic Crystals Covalent Crystals Molecular 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 The Capillary-Rise Method Surface Tension in the Lungs 21.4 Diffusion Fick's Laws of Diffusion 21.5 Liquid Crystals Thermotropic Liquid Crystals Lyotropic 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 Molar Mass of Macromolecules Sedimentation in the Ultracentrifuge Viscosity Electrophoresis 22.2 Structure of Synthetic Polymers Configuration and Conformation The Random-Walk Model 22.3 Structure of Proteins and DNA Proteins DNA 22.4 Protein Stability The Hydrophobic Interaction Denaturation Protein Folding 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 Translational Partition Function Rotational Partition Function Vibrational Partition Function Electronic Partition Function 23.5 Thermodynamic Quantities from Partition Functions Internal Energy and Heat Capacity Entropy 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

'I have found Ray Chang's P. Chem book to be the ideal textbook for students from the life sciences. Whereas so many other textbooks seem to be written for the instructor, this text works well with students who have traditionally struggled with this course.' - George Bodner, Purdue University, USA 'I adopted the P Chem text by Raymond Chang here at McGill two years ago, for a course populated with ~180 biochemistry and biology students, many of them 'pre-med.' I had formerly used a well-known text by a different author, but I (and the students) found it a little short on good explanations, and there were many errors in the end-of-chapter problems and answers. I am very pleased with how the Chang text approaches thermodynamics, especially applications, such as in the chapter on macromolecules. Similarly, I very much appreciate the biological emphasis in this text, and especially the relevance of the problems. Overall, I consider this to be an excellent text.' - Christopher J. Barrett, McGill University, USA 'This book offers an alternative approach to physical chemistry that is particularly well suited for those who want to pursue a course of study more focused on the biological sciences.' - Journal of Chemical Education 'A distinct and excellent publication worth recommending to biological chemists...I have learnt something new about biology, [the book] is very refreshing in its aims and clarity.' - Times Higher Education