Physical Chemistry for the Chemical and Biological Sciences

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 (ÆfG°)
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
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
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
16.6 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