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Preface | |

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Introduction | |

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Nature of Physical Chemistry | |

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Units | |

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Force | |

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Pressure | |

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Energy | |

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Atomic Mass, Molecular Mass, and the Chemical Mole | |

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The Gas Laws | |

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Some Basic Definitions | |

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An Operational Definition of Temperature | |

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Boyle's Law | |

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Charles' and Gay-Lussac's Law | |

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Avogadro's Law | |

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The Ideal Gas Equation | |

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Dalton's Law of Partial Pressures | |

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Real Gases | |

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The van der Waals Equation | |

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The Virial Equation of State | |

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Condensation of Gases and the Critical State | |

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Problems | |

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Kinetic Theory of Gases | |

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The Model | |

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Pressure of a Gas | |

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Kinetic Energy and Temperature | |

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The Maxwell Distribution Laws | |

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Molecular Collisions and the Mean Free Path | |

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Gas Viscosity | |

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Graham's Laws of Diffusion and Effusion | |

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Equipartition of Energy | |

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Derivation of Equation 3.24 | |

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Total and Partial Differentiation | |

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Problems | |

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The First Law of Thermodynamics | |

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Work and Heat | |

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Work | |

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Heat | |

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The First Law of Thermodynamics | |

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Enthalpy | |

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A Closer Look at Heat Capacities | |

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Gas Expansion | |

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Isothermal Expansion | |

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Adiabatic Expansion | |

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Thermochemistry | |

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Standard Enthalpy of Formation | |

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Dependence of Enthalpy of Reaction on Temperature | |

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Bond Energies and Bond Enthalpies | |

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Bond Enthalpy and Bond Dissociation Enthalpy | |

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Exact and Inexact Differentials | |

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Problems | |

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The Second Law of Thermodynamics | |

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Spontaneous Process | |

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Entropy | |

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Statistical Definition of Entropy | |

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Thermodynamic Definition of Entropy | |

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The Carnot Heat Engine | |

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Thermodynamic Efficiency | |

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The Entropy Function | |

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Refrigerators, Air Conditioners, and Heat Pumps | |

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The Second Law of Thermodynamics | |

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Entropy Changes | |

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Entropy Change due to Mixing of Ideal Gases | |

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Entropy Change due to Phase Transitions | |

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Entropy Change due to Heating | |

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The Third Law of Thermodynamics | |

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Third-Law or Absolute Entropies | |

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Entropy of Chemical Reactions | |

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Residual Entropy | |

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Statements of the Second Law of Thermodynamics | |

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Problems | |

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Gibbs and Helmholtz Energies and Their Applications | |

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Gibbs and Helmholtz Energies | |

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Meaning of Helmholtz and Gibbs Energies | |

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Helmholtz Energy | |

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Gibbs Energy | |

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Standard Molar Gibbs Energy of Formation ([Delta][subscript f]G[degree]) | |

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Dependence of Gibbs Energy on Temperature and Pressure | |

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Dependence of G on Temperature | |

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Dependence of G on Pressure | |

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Gibbs Energy and Phase Equilibria | |

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The Clapeyron and Clausius-Clapeyron Equations | |

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Phase Diagrams | |

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The Phase Rule | |

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Thermodynamics of Rubber Elasticity | |

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Some Thermodynamic Relationships | |

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Derivation of the Phase Rule | |

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Problems | |

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Nonelectrolyte Solutions | |

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Concentration Units | |

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Percent by Weight | |

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Mole Fraction (x) | |

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Molarity (M) | |

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Molality (m) | |

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Partial Molar Quantities | |

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Partial Molar Volume | |

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Partial Molar Gibbs Energy | |

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The Thermodynamics of Mixing | |

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Binary Mixtures of Volatile Liquids | |

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Real Solutions | |

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The Solvent Component | |

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The Solute Component | |

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Phase Equilibria of Two-Component Systems | |

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Distillation | |

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Solid-Liquid Equilibria | |

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Colligative Properties | |

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Vapor-Pressure Lowering | |

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Boiling-Point Elevation | |

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Freezing-Point Depression | |

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Osmotic Pressure | |

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Problems | |

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Electrolyte Solutions | |

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Electrical Conduction in Solution | |

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Some Basic Definitions | |

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Degree of Dissociation | |

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Ionic Mobility | |

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Applications of Conductance Measurements | |

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A Molecular View of the Solution Process | |

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Thermodynamics of Ions in Solution | |

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Enthalpy, Entropy, and Gibbs Energy of Formation of Ions in Solution | |

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Ionic Activity | |

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Debye-Huckel Theory of Electrolytes | |

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The Salting-In and Salting-Out Effects | |

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Colligative Properties of Electrolyte Solutions | |

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The Donnan Effect | |

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Biological Membranes | |

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Membrane Transport | |

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Notes on Electrostatics | |

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The Donnan Effect Involving Proteins Bearing Multiple Charges | |

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Problems | |

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Chemical Equilibrium | |

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Chemical Equilibrium in Gaseous Systems | |

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Ideal Gases | |

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Real Gases | |

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Reactions in Solution | |

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Heterogeneous Equilibria | |

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

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The Effect of Temperature | |

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The Effect of Pressure | |

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The Effect of a Catalyst | |

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Binding of Ligands and Metal Ions to Macromolecules | |

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One Binding Site per Macromolecule | |

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n Equivalent Binding Sites per Macromolecule | |

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Equilibrium Dialysis | |

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Bioenergetics | |

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The Standard State in Biochemistry | |

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ATP--The Currency of Energy | |

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Principles of Coupled Reactions | |

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Glycolysis | |

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Some Limitations of Thermodynamics | |

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The Relationship Between Fugacity and Pressure | |

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The Relationships Between K[subscript 1] and K[subscript 2] and the Intrinsic Dissociation Constant K | |

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Problems | |

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Electrochemistry | |

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Electrochemical Cells | |

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Single-Electrode Potential | |

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Thermodynamics of Electrochemical Cells | |

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The Nernst Equation | |

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Temperature Dependence of EMF | |

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Types of Electrodes | |

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Metal Electrodes | |

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Gas Electrodes | |

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Metal-Insoluble Salt Electrodes | |

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The Glass Electrode | |

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Ion-Selective Electrodes | |

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Types of Electrochemical Cells | |

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Concentration Cells | |

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Fuel Cells | |

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Applications of EMF Measurements | |

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Determination of Activity Coefficients | |

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Determination of pH | |

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Potentiometric Titration of Redox Reactions | |

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Biological Oxidation | |

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The Chemiosmotic Theory of Oxidative Phosphorylation | |

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Membrane Potential | |

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The Goldman Equation | |

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The Action Potential | |

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Problems | |

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Acids and Bases | |

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Definitions of Acids and Bases | |

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Dissociation of Acids and Bases | |

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The Ion Product of Water and the pH Scale | |

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The Relationship Between the Dissociation Constant of an Acid and Its Conjugate Base | |

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Salt Hydrolysis | |

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Acid-Base Titrations | |

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Acid-Base Indicators | |

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Diprotic and Polyprotic Acids | |

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Amino Acids | |

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Dissociation of Amino Acids | |

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The Isoelectric Point (pI) | |

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Buffer Solutions | |

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The Effect of Ionic Strength and Temperature on Buffer Solutions | |

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Preparing a Buffer Solution With a Specific pH | |

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Buffer Capacity | |

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Maintaining the pH of Blood | |

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A More Exact Treatment of Acid-Base Equilibria | |

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Problems | |

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Chemical Kinetics | |

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Reaction Rate | |

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Reaction Order | |

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Zero-Order Reactions | |

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First-Order Reactions | |

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Second-Order Reactions | |

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Determination of Reaction Order | |

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Molecularity of a Reaction | |

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Unimolecular Reactions | |

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Bimolecular Reactions | |

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Termolecular Reactions | |

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More Complex Reactions | |

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Reversible Reactions | |

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Consecutive Reactions | |

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Chain Reactions | |

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The Effect of Temperature on Reaction Rates | |

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The Arrhenius Equation | |

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Potential-Energy Surfaces | |

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Theories of Reaction Rates | |

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Collision Theory | |

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Transition-State Theory | |

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Thermodynamic Formulation of Transition-State Theory | |

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Isotope Effects in Chemical Reactions | |

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Reactions in Solution | |

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Fast Reactions in Solution | |

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The Flow Method | |

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The Relaxation Method | |

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Oscillating Reactions | |

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Derivation of Equation 12.9 | |

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Derivation of Equation 12.38 | |

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Problems | |

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Enzyme Kinetics | |

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General Principles of Catalysis | |

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Enzyme Catalysis | |

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The Equations of Enzyme Kinetics | |

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Michaelis-Menten Kinetics | |

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Steady-State Kinetics | |

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The Significance of K[subscript M] and V[subscript max] | |

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Chymotrypsin: A Case Study | |

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Multisubstrate Systems | |

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The Sequential Mechanism | |

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The Nonsequential or "Ping-Pong" Mechanism | |

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Enzyme Inhibition | |

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Reversible Inhibition | |

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Irreversible Inhibition | |

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Allosteric Interactions | |

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Oxygen Binding to Myoglobin and Hemoglobin | |

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The Hill Equation | |

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The Concerted Model | |

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The Sequential Model | |

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Conformational Changes in Hemoglobin Induced by Oxygen Binding | |

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pH Effects on Enzyme Kinetics | |

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

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Derivations of Equations 13.17 and 13.19 | |

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Derivation of Equation 13.32 | |

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Problems | |

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Quantum Mechanics and Atomic Structure | |

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The Wave Theory of Light | |

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Planck's Quantum Theory | |

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The Photoelectric Effect | |

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Bohr's Theory of the Hydrogen Emission Spectrum | |

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de Broglie's Postulate | |

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The Heisenberg Uncertainty Principle | |

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The Schrodinger Wave Equation | |

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Particle in a One-Dimensional Box | |

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Electronic Spectra of Polyenes | |

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Quantum-Mechanical Tunneling | |

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The Schrodinger Wave Equation for the Hydrogen Atom | |

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Atomic Orbitals | |

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Many-Electron Atoms and the Periodic Table | |

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Electron Configurations | |

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Variations in Periodic Properties | |

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Problems | |

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The Chemical Bond | |

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Lewis Structures | |

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Valence Bond Theory | |

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Hybridization of Atomic Orbitals | |

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Methane (CH[subscript 4]) | |

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Ethylene (C[subscript 2]H[subscript 4]) | |

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Acetylene (C[subscript 2]H[subscript 2]) | |

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Electronegativity and Dipole Moment | |

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Electronegativity | |

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Dipole Moment | |

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Molecular Orbital Theory | |

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Diatomic Molecules | |

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Homonuclear Diatomic Molecules of the Second-Period Elements | |

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Heteronuclear Diatomic Molecules of the First-and Second-Period Elements | |

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Resonance and Electron Delocalization | |

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The Peptide Bond | |

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Coordination Compounds | |

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Crystal Field Theory | |

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Molecular Orbital Theory | |

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Valence Bond Theory | |

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Coordination Compounds in Biological Systems | |

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Problems | |

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Intermolecular Forces | |

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Intermolecular Interactions | |

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The Ionic Bond | |

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Types of Intermolecular Forces | |

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Dipole-Dipole Interaction | |

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Ion-Dipole Interaction | |

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Ion-Induced Dipole and Dipole-Induced Dipole Interactions | |

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Dispersion, or London, Interactions | |

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Repulsive and Total Interactions | |

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The Role of Dispersion Forces in Sickle-Cell Anemia | |

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The Hydrogen Bond | |

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The Structure and Properties of Water | |

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The Structure of Ice | |

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The Structure of Water | |

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Some Physiochemical Properties of Water | |

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Hydrophobic Interaction | |

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Problems | |

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Spectroscopy | |

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Vocabulary | |

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Absorption and Emission | |

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Units | |

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Regions of the Spectrum | |

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Line Width | |

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Resolution | |

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Intensity | |

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Selection Rules | |

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Signal-to-Noise Ratio | |

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The Beer-Lambert Law | |

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Microwave Spectroscopy | |

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Infrared Spectroscopy | |

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Simultaneous Vibrational and Rotational Transitions | |

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Electronic Spectroscopy | |

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Organic Molecules | |

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Transition Metal Complexes | |

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Molecules that Undergo Charge-Transfer Interactions | |

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Application of the Beer-Lambert Law | |

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Nuclear Magnetic Resonance Spectroscopy | |

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The Boltzmann Distribution | |

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Chemical Shifts | |

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Spin-Spin Coupling | |

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NMR and Rate Processes | |

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NMR of Nuclei Other Than [superscript 1]H | |

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Electron Spin Resonance Spectroscopy | |

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Fluorescence and Phosphorescence | |

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Fluorescence | |

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Phosphorescence | |

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Lasers | |

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Properties and Applications of Laser Light | |

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Fourier-Transform Spectroscopy | |

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Problems | |

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Molecular Symmetry and Optical Activity | |

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Symmetry of Molecules | |

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Proper Rotation Axis | |

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Plane of Symmetry | |

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Center of Symmetry | |

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Improper Rotation Axis | |

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Molecular Symmetry and Dipole Moment | |

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Molecular Symmetry and Optical Activity | |

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Polarized Light and Optical Rotation | |

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Optical Rotatory Dispersion and Circular Dichroism | |

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Problems | |

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Photochemistry and Photobiology | |

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Introduction | |

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Thermal Versus Photochemical Reactions | |

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Primary Versus Secondary Processes | |

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Quantum Yields | |

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Measurement of Light Intensity | |

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Action Spectrum | |

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Earth's Atmosphere | |

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Composition of the Atmosphere | |

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Regions of the Atmosphere | |

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Residence Time | |

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The Greenhouse Effect | |

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Photochemical Smog | |

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Formation of Nitrogen Oxides | |

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Formation of O[subscript 3] | |

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Formation of Hydroxyl Radical | |

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Formation of Other Secondary Pollutants | |

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Harmful Effects and Prevention of Photochemical Smog | |

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The Essential Role of Ozone in the Stratosphere | |

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Formation of the Ozone Layer | |

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Destruction of Ozone | |

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Polar Ozone Holes | |

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Ways to Curb Ozone Depletion | |

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Photosynthesis | |

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The Chloroplast | |

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Chlorophyll and Other Pigment Molecules | |

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The Reaction Center | |

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Photosystems I and II | |

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Dark Reactions | |

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Vision | |

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Structure of Rhodopsin | |

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Mechanism of Vision | |

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Rotation About the C=C Bond | |

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Biological Effects of Radiation | |

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Sunlight and Skin Cancer | |

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Photomedicine | |

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Light-Activated Drugs | |

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Problems | |

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The Solid State | |

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Classification of Crystal Systems | |

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The Bragg Equation | |

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Structural Determination by X-ray Diffraction | |

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The Powder Method | |

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Determination of the Crystal Structure of NaCl | |

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The Structure Factor | |

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Neutron Diffraction | |

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Types of Crystals | |

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Metallic Crystals | |

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Ionic Crystals | |

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Covalent Crystals | |

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Molecular Crystals | |

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Derivation of Equation 20.3 | |

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Problems | |

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The Liquid State | |

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Structure of Liquids | |

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Viscosity | |

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Surface Tension | |

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The Capillary-Rise Method | |

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Surface Tension in the Lungs | |

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Diffusion | |

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Fick's Laws of Diffusion | |

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Liquid Crystals | |

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Thermotropic Liquid Crystals | |

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Lyotropic Liquid Crystals | |

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Derivation of Equation 21.13 | |

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Problems | |

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Macromolecules | |

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Methods for Determining Size, Shape, and Molar Mass of Macromolecules | |

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Molar Mass of Macromolecules | |

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Sedimentation in the Ultracentrifuge | |

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Viscosity | |

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Electrophoresis | |

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Structure of Synthetic Polymers | |

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Configuration and Conformation | |

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The Random-Walk Model | |

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Structure of Proteins and DNA | |

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Proteins | |

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DNA | |

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Protein Stability | |

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Hydrophobic Interaction | |

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Denaturation | |

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Protein Folding | |

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DNA Fingerprinting | |

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Problems | |

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Statistical Thermodynamics | |

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Macrostates and Microstates | |

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The Boltzmann Distribution Law | |

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The Partition Function | |

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Molecular Partition Function | |

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Translational Partition Function | |

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Rotational Partition Function | |

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Vibrational Partition Function | |

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Electronic Partition Function | |

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Thermodynamic Quantities from Partition Functions | |

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Internal Energy and Heat Capacity | |

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Entropy | |

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Chemical Equilibrium | |

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Transition-State Theory | |

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Justification of Q = q[superscript N]/N! for Indistinguishable Molecules | |

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Problems | |

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Review of Mathematics and Physics | |

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Thermodynamic Data | |

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Glossary | |

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Answers to Even-Numbered Computational Problems | |

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Index | |