Physical Chemistry

Concepts and Theory

1st Edition - November 11, 2016
Author: Kenneth S Schmitz
Language: English
Hardback ISBN:
9 7 8 - 0 - 1 2 - 8 0 0 5 1 4 - 9
eBook ISBN:
9 7 8 - 0 - 1 2 - 8 0 0 6 0 0 - 9

Physical Chemistry: Concepts and Theory provides a comprehensive overview of physical and theoretical chemistry while focusing on the basic principles that unite the sub-disci… Read more

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Physical Chemistry: Concepts and Theory provides a comprehensive overview of physical and theoretical chemistry while focusing on the basic principles that unite the sub-disciplines of the field. With an emphasis on multidisciplinary, as well as interdisciplinary applications, the book extensively reviews fundamental principles and presents recent research to help the reader make logical connections between the theory and application of physical chemistry concepts.

Also available from the author: Physical Chemistry: Multidisciplinary Applications (ISBN 9780128005132).

Preface
Acknowledgments
Prologue
Chapter 1. Overview
- 1.0. Introduction
- 1.1. Three Levels of Mathematics in the Characterization of Nature
- 1.2. Nature Has Patterns
- 1.2.1. Nature Is Golden
- 1.2.2. Nature Is Numbers
- 1.2.2.1. Geometry and Calculus
- 1.2.2.2. Arithmetization of Analysis
- 1.2.2.3. God Made the Integers, All Else Is the Work of Man
- 1.2.2.4. Classification of Real and Imaginary Numbers
- 1.2.3. Nature Is Recursion Relationships
- 1.3. Nature Has Reasons
- 1.4. Nature Has Surprises
- 1.5. A Prime Example of the Application of Mathematics to the Underlying Reality of Nature
- 1.5.1. Prime Numbers
- 1.5.2. The Distribution of Prime Numbers
- 1.6. Parallels in the Mathematical Descriptions of Prime Numbers and Nature
- 1.7. Mathematics and Truth
Chapter 2. Five Important Equations in Thermodynamics
- 2.0. Introduction
- 2.1. Heat and Work
- 2.2. The Experimental Form of the First Law of Thermodynamics
- 2.3. The Calculus Form of the First Law of Thermodynamics
- 2.4. Steam Power and the Industrial Revolution
- 2.5. The Carnot Cycle and Heat, Work, and Entropy
- 2.5.1. Entropy: The Quantification of the Carnot Cycle by Application of the First Law of Thermodynamics
- 2.5.2. Entropy Is a State Function
- 2.6. The Carnot Cycle and the Second Law of Thermodynamics
- 2.7. The Second Law of Thermodynamics and the Arrow of Time
- 2.8. What Is Entropy?
- 2.8.1. Thermodynamic Interpretation of Entropy
- 2.8.2. Molecular Interpretation of Entropy
- 2.9. Entropy of Mixing
- 2.9.1. Entropy of Mixing in the Gas Phase
- 2.9.2. Entropy of Mixing Two Liquids
- 2.9.2.1. Particles of Unequal Size
- 2.9.2.2. Particles of Equal Size
- 2.10. Ambiguity of “Randomness” and “Order” as a Description of Entropy
- 2.10.1. The Mixing of Two Liquids and the Chess Board
- 2.10.2. The Transferring of Information and the Chess Board
- 2.10.3. The Degeneracy of States and the Chess Board
- 2.10.4. “Order” and “Disorder” Are Generations Apart
- 2.11. Enthalpy From the First Law of Thermodynamics: The Joule–Thomson Expansion Experiment
- 2.12. Combined First and Second Laws of Thermodynamics: Work and the Free Energies
- 2.12.1. Helmholtz Free Energy
- 2.12.2. Gibbs Free Energy
- 2.13. Latent Heat
- 2.14. Maxwell Relationships
- 2.14.1. Internal Energy
- 2.14.2. Enthalpy
- 2.14.3. Helmholtz Free Energy
- 2.14.4. Gibbs Free Energy
- 2.15. Thermodynamic Equation of State
- 2.16. Isothermal Compressibility and Isobaric Thermal Expansion and the Difference in Heat Capacities C_p−C_V
- 2.17. The Joule–Thomson Coefficient
- 2.18. Expansion of the Thermodynamic Functions
Chapter 3. Gibbs Free Energy, Work, and Equilibrium
- 3.0. Introduction
- 3.1. Criteria for Stability of a System—Clausius Inequality
- 3.2. The Gibbs Free Energy and the Chemical Potential
- 3.3. The Clausius Equation for a Phase Transition
- 3.4. Phase Diagrams and the Gibbs Phase Rule
- 3.5. The Gibbs Free Energy and the Concentration Potential
- 3.6. The Gibbs Free Energy and Reference States
- 3.7. The Gibbs Free Energy and Equilibrium
- 3.8. State Functions, Standard States, and Thermodynamic Calculations
- 3.9. Temperature Dependence of the Equilibrium Constant
- 3.10. The Osmotic Pressure—Ideal Solutions
- 3.11. The Osmotic Pressure and Work
- 3.12. Bond Energy/Enthalpy and Work
- 3.13. Burning of Fossil Fuels—Heterogeneous Phases
- 3.13.1. Coal Versus Natural Gas
- 3.13.2. Group Energies of Alkanes
- 3.13.3. Energy Density of Mixed Alcohol–Gasoline Fuels: The E-fuels
- 3.13.4. Fossil Fuels, Oxidation States, and Energy Content
- 3.14. The Chemical Potential With an External Potential
- 3.14.1. Centrifugal Force
- 3.14.2. Gravitational Force
- 3.15. The Anatomy of an Oxidation–Reduction Reaction
- 3.16. The Gibbs Free Energy and Electric Work
- 3.16.1. The Hydrogen Electrode
- 3.16.2. The Nernst Equation
- 3.16.3. The pE Scale
- 3.17. The Thermodynamic Functions from the Temperature Dependence of ^o
- 3.18. The Heat Change of a Redox Reaction During the Reaction
- 3.19. Oxidation–Reduction Reactions and Anaerobic Decomposition
- 3.19.1. Biochemical Oxygen Demand
- 3.19.2. Chemical Oxygen Demand
Chapter 4. Thermodynamics of the Gas State
- 4.0. Introduction
- 4.1. Ideal Gas Law
- 4.1.1. Empirical Expression of the Ideal Gas Law
- 4.1.2. The Ideal Gas Law and the Kinetic Theory of Gases
- 4.2. Real Gases and the Ideal Gas Law
- 4.3. From Generalized Differential Equations to Practical Integrated Expressions
- 4.3.1. Choice of a Theoretical Expression
- 4.3.2. Choice of Experimental Conditions
- 4.3.3. Final Step—The Integral Form
- 4.4. Ideal Gas Law and Dalton's Law of Partial Pressures
- 4.5. Dalton's Law of Partial Pressures and Gas Phase Chemical Reactions: Dimerization
- 4.6. Dalton's Law of Partial Pressures and Gas Phase Chemical Reactions: Extent of Reaction
- 4.7. Adiabatic Expansion/Contraction of an Ideal Gas
- 4.8. Entropy Change of the Ideal Gas: Reversible and Irreversible Processes
- 4.9. The Thermodynamic Representation of a Real Gas: Fugacity
- 4.10. Reference State for a Real Gas
- 4.11. Determination of the Activity Coefficient for Real Gases
- 4.11.1. Approximate Method
- 4.11.2. Graphics Method
- 4.12. Virial Expansion Representation of Real Gases
- 4.13. Analytical Expressions for Real Gases—The van der Waals Equation
- 4.14. Internal Pressure and Second Virial Coefficient for the van der Waals Gas
- 4.15. Activity Coefficient and the van der Waals Gas
- 4.16. Work, Heat, and the van der Waals Gas for an Isothermal Reversible Process
- 4.17. The Physics Behind the van der Waals Gas for an Isothermal Reversible Process
- 4.18. Generalized Relationship Between C_P and C_V With Application to Ideal and van der Waals Gases
- 4.19. The Stability of the van der Waals Gas
- 4.20. Anatomy of the P–V Plot for Real Gases
- 4.21. The van der Waals Gas and the Critical Point
- 4.22. The van der Waals Gas and Phase Transitions
- 4.23. Reduced van der Waals Equation of State
- 4.24. Relationship Between the Boyle Temperature and the Critical Temperature for a van der Waals Gas
- 4.25. The Joule–Thomson Inversion Temperature and the van der Waals Gas
- 4.26. Other Expressions for Real Gas Systems
Chapter 5. Thermodynamics of the Liquid State
- 5.0. Introduction
- 5.1. The Pressure–Temperature Dependence of the Phase Transition: The Clapeyron and Clausius–Clapeyron Equations
- 5.1.1. The Clapeyron Equation—Incompressible Phases
- 5.1.2. Clausius–Clapeyron Equation—Compressible Phases
- 5.2. Gibbs Free Energy of Mixing for Ideal and Real Solutions
- 5.2.1. Gibbs Free Energy of Mixing: Ideal Solutions
- 5.2.2. Gibbs Free Energy of Mixing: Real Solutions
- 5.3. The Gibbs–Duhem and Duhem–Margules Equations
- 5.4. Duhem–Margules Equation for Ideal and Real Solutions
- 5.4.1. Real Solution at the Infinite Dilution Limit
- 5.4.2. Ideal Solution—Raoult's Law and Henry's Law
- 5.4.2.1. Different Forms of Henry's Law
- 5.4.2.2. Gas Solubility and Henry's Law
- 5.5. Real Solutions and Raoult's and Henry's Laws: A Molecular Interpretation
- 5.5.1. Molecular Interpretation of Raoult's Law
- 5.5.2. Molecular Interpretation of Henry's Law
- 5.5.3. Temperature Dependence of Henry's Law Constant
- 5.6. Colligative Properties of Solutions Using General Thermodynamic Principles
- 5.6.1. Changes in the Solvent Upon Introduction of a Solute—Raoult's Law
- 5.6.2. Solute Effects on the Transition Temperature
- 5.7. Colligative Properties and Number Average Molecular Weight
- 5.8. Nonideal Solutions: The Practical Osmotic Coefficient
- 5.8.1. Thermodynamic Representation of Nonideality
- 5.8.2. Statistical Mechanics Representation of Nonideality
- 5.9. Solubilities of Gases, Liquids, and Solids
- 5.10. The Solubility Product
- 5.10.1. Common Ion Effect
- 5.10.2. Complex Formation and Solubility
- 5.11. The Partition Coefficient
- 5.12. Acid–Base Equilibrium
- 5.13. Ionic Solutions and Nonideality: The Debye–Hückel Limiting Law
Chapter 6. Solid State
- 6.0. Introduction
- 6.1. Categories of Solids
- 6.2. The Lattice Constants and Unit Cell of Crystalline Solids
- 6.3. The Bravais Lattices
- 6.4. Miller Indices (hkℓ)
- 6.5. Lattice Energy for Ionic Crystals
- 6.6. Covalent Solids
- 6.7. Metallic Solids
- 6.8. Molecular Solids
- 6.9. Amorphous Solids
- 6.10. Heat Capacity of Solids
- 6.11. Adsorption on Lattice Surfaces
Chapter 7. Quantum Principles
- 7.0. Introduction
- 7.1. The Sign of Four
- 7.1.1. Black Body Radiation Spectrum
- 7.1.2. Photoelectric Effect
- 7.1.3. Heat Capacity of Solids (ca1860s)
- 7.1.4. Atomic Spectra
- 7.2. Enter the Quantum
- 7.2.1. Black Body Radiation Spectrum
- 7.2.2. Photoelectric Effect
- 7.2.3. Heat Capacity of Solids
- 7.2.4. Atomic Spectra
- 7.3. The Light Quantum hυ
- 7.4. The Wave–Particle Duality of Light from Planck's Radiation Law
- 7.5. Symmetrization of Nature—the Wave–Particle Duality of Matter
- 7.5.1. Ad Hoc Derivation of the de Broglie Wavelength
- 7.5.2. de Broglie Derivation—1924 Doctoral Thesis
- 7.5.3. Experimental Verification of the de Broglie Wavelength
- 7.5.4. Why Can Rory McIlroy Hit a Golf Ball on a Tee?
- 7.5.5. The de Broglie Wavelength and the Stability of the Bohr Orbits
- 7.6. The Schrödinger Wave Equation
- 7.7. Quantum Mechanics and Linear Operators
- 7.8. Postulates of Quantum Mechanics
- 7.9. Heisenberg Matrix Mechanics
- 7.10. The Heisenberg Indeterminacy Principle (Tolerance Principle)
- 7.11. The Hamiltonian, the Wave Function, the Probability and Graphics
- 7.12. The Spin Quantum Number
- 7.13. Superposition of Wave Functions
- 7.14. Bra-Ket Notation
- 7.15. What Is the Wave Function?
- 7.15.1. The 1927 Solvay Conference
- 7.15.2. The Copenhagen Interpretation
- 7.15.3. Beyond the Copenhagen Interpretation
- 7.16. Indeterminacy in Measurement
- 7.17. Indeterminacy in Nature
Chapter 8. Quantum Systems With Constant Potential
- 8.0. Introduction
- 8.1. The Free Particle in Three Dimensions
- 8.2. The One-Dimensional Schrödinger Equation With a Step Constant Potential
- 8.2.1. E < V
- 8.2.2. E > V
- 8.3. The One-Dimensional Schrödinger Equation With a Square Barrier
- 8.3.1. E < V: Tunneling Through a Square Barrier
- 8.3.2. E > V: Transmission Over a Square Barrier
- 8.4. The One-Dimensional Schrödinger Equation With a Finite Symmetric Square Well
- 8.4.1. E > 0: Transmission Over a Square Well
- 8.4.2. E < 0 Bound Particles
- 8.5. The One-Dimensional Schrödinger Equation for a Particle-in-a-Symmetric Box
- 8.6. Orthonormal Property of the Particle-in-a-Box Wave Functions
- 8.7. Spatial Degeneracy in an Arbitrary Three-Dimensional Rectangular Box
- 8.7.1. Cubic Box
- 8.7.2. Rectangular Box
- 8.8. Expectation Values and Probability
- 8.9. Degeneracy Due to Exchange of Indistinguishable Particles
- 8.10. Degeneracy Due to Spin of the Particles
- 8.11. Product Wave Functions in the Bra-Ket Notation
- 8.12. Real Systems and Perturbation Theory
- 8.13. First-Order Correction to the Wave Function With the Bra-Ket Notation
- 8.14. Shapes of Perturbation Potential and the Perturbed Wave Function
- 8.15. Slater Determinants and Particle Symmetry
Chapter 9. Quantum Energies for Central Potentials
- 9.0. Introduction
- 9.1. Central Potential Defined
- 9.2. Polar Coordinate System
- 9.3. The Hamiltonian Operator in Polar Coordinates
- 9.4. Solutions to the ϕ-Equation and θ-Equation: Spherical Harmonics
- 9.4.1. Generating Equation for Legendre and Associated Legendre Polynomials
- 9.4.2. Recursion Relationship for Legendre Polynomials
- 9.5. Rotation Energies of a Rigid Rotor
- 9.6. Solution to the r-Equation: Inverse Distance Central Potential
- 9.6.1. Outer Solution: Asymptotic Limit ρ → ∞
- 9.6.2. Inner Solution: Generating Functions for Laguerre and Associated Laguerre Polynomials
- 9.6.3. Recursion Relationship for Laguerre Polynomials
- 9.6.4. Normalized Radial Wave Function
- 9.7. The Energy for the Coulomb Potential From the Recursion Relationship of Coefficients
- 9.8. Vibrational States and the Harmonic Oscillator
- 9.8.1. Harmonic Oscillator in Reduced Coordinates
- 9.8.2. Harmonic Oscillator in the Asymptotic Limit ξ → ∞
- 9.8.3. Harmonic Oscillator: Inner Solution to the Wave Function
- 9.8.4. Recursion Relationships of Expansion Coefficients and the Energy
- 9.8.5. Generating Function for the Hermite Polynomials
- 9.8.6. Recursion Relationship for the Hermite Polynomials
- 9.9. Transitions Between Rotation–Vibration States: Selection Rules
- 9.10. Spectral Regions for Pure Rotation Transitions and Pure Vibration Transitions
- 9.10.1. Pure Rotation
- 9.10.2. Pure Vibration
- 9.11. The Indeterminacy Principle and the Harmonic Oscillator
- 9.12. Particles in a Spherical Box
- 9.12.1. Impenetrable Spherical Shell
- 9.12.2. Penetrable Spherical Shell
- 9.13. The Shell Model of Electrons and Nucleons
- 9.14. Characterization of Nuclei
- 9.14.1. Atomic Mass Units
- 9.14.2. Atomic Mass Unit Expressed as Energy
- 9.15. The Stability of the Nucleus
- 9.16. The Instability of the Nucleus
- 9.16.1. Radioactive Decay
- 9.16.1.1. Beta Decay
- 9.16.1.2. Alpha Decay
- 9.16.1.3. Gamma Decay
- 9.16.2. Nuclear Reaction
- 9.17. Carbon-14
- 9.17.1. Carbon-14 Dating
- 9.17.2. Carbon-14 and Fossil Fuels
Chapter 10. Electronic and Nuclear States
- 10.0. Introduction
- 10.1. Quantum Mechanics, Special Relativity, and Description of the Electron
- 10.1.1. Dirac's Approach to Solve the Relativistic Schrödinger Equation
- 10.1.2. The Electron “Spin”
- 10.1.3. Prediction of Antimatter
- 10.1.4. Sea of Electrons
- 10.1.5. Time-Dependent Dirac Equation for a Free Particle in One Dimension
- 10.1.6. The Nodes and Bound Particles
- 10.1.7. The Electron in an Electric Field—The Beginning of Quantum Electrodynamics
- 10.1.8. The Relativistic de Broglie Wavelength
- 10.1.9. Beauty in the Equations
- 10.2. Paul Dirac—A Concise Picture
- 10.3. The Schrödinger Atoms and the Periodic Table of the Elements
- 10.4. Multielectron Atoms
- 10.5. Electron Spin: Singlet and Triplet States of Excited Helium
- 10.6. Spatially Directed Atomic Orbitals: 2p_x, 2p_y, and 2p_z
- 10.7. Spatially Directed Bonding Orbitals—Hybridization
- 10.7.1. The sp hybrid orbital
- 10.7.2. The sp² Hybrid Orbitals
- 10.7.3. The sp³ Hybrid
- 10.7.4. The Geometry of the Hybrid Orbitals
- 10.8. The Chemical Bond: Valence Bond and Molecular Orbital Approaches
- 10.8.1. The Valence Bond Approach
- 10.8.2. The Molecular Orbital Approach
- 10.8.3. Comparison of the VB and LCAO–MO Approaches
- 10.9. LCAO–MO Description of Double and Triple Bonds
- 10.10. LCAO–MO for Benzene
- 10.11. Hückel Molecular Orbital Description of Benzene
- 10.12. Other Effects That Alter the Electronic Energy States of Atoms and Molecules
- 10.13. Einstein Model for Steady-State Electronic Transitions
- 10.14. Nuclear Structure
- 10.14.1. The Particles: Hadrons and Leptons
- 10.14.2. The Force Carrying Particles: Quarks and Bosons
- 10.14.3. The Standard Model
- 10.15. Energy From the Sun: Fusion
- 10.16. The Liquid Drop Model of the Nucleus and Fission
- 10.16.1. A Wafer Thin Mint
- 10.16.2. The Liquid Drop Nucleus and Nuclear Fission
- 10.17. Nuclear Power Unleashed
- 10.18. Fossil Fuels and Nuclear Fuels: A Comparison
- 10.19. Energy for the Future
Chapter 11. Rotation–Vibration Spectra
- 11.0. Introduction
- 11.1. The Total Hamiltonian for a Diatomic Molecule
- 11.2. The Interaction of a Molecule With Light—Absorption, Emission, and Scattering
- 11.2.1. Infrared Spectroscopy—Absorption and Emission of Light
- 11.2.2. Raman Spectroscopy—Scattering of Light
- 11.2.3. Complementary Tools—Infrared and Raman Spectroscopy
- 11.3. General Construct for Transitions to a New Molecular State
- 11.4. Selection Rules for a Diatomic Molecule in the Presence of Light
- 11.4.1. Translation Motion of Molecules and Light Absorption
- 11.4.2. Rotation Motion of Molecules and Light Absorption
- 11.4.3. Vibration Motion of Molecules and Light Absorption
- 11.5. Spectral Regions for Rotation and Vibration Transitions
- 11.6. Interpretation of the Infrared Spectrum: The Diatomic as an Example
- 11.7. Vibration–Rotation Modes of Real Diatomic Molecules
- 11.8. Vibration–Rotation Modes of Multiatom Molecules
Chapter 12. Classical Statistical Mechanics
- 12.0. Introduction
- 12.1. Gambling—The Origin of Statistical Analysis
- 12.1.1. Pennies and Particles
- 12.1.2. Conditional Probabilities
- 12.1.3. Knowledge and Probabilities
- 12.2. Casino Games of Chance and the Principles of Statistical Mechanics
- 12.2.1. “True” Odds and Probabilities
- 12.2.2. The Lore of Large Numbers
- 12.2.3. “Perfect” and “Imperfect” and True Probabilities and Odds
- 12.2.4. The Unusual Luck of Joseph Hobson Jagger
- 12.2.5. Independent Probabilities for Nonuniform Distributions: Craps
- 12.2.6. “Or” and “And” Probabilities: Craps
- 12.2.7. Changing Probabilities: Blackjack and Texas Hold'em
- 12.2.8. Time and Ensemble Averages: The Slot Machines
- 12.3. Distributions, Fluctuations, and Averages
- 12.4. Laplace's Demon and Phase Space
- 12.4.1. Phase Space
- 12.4.2. μ-Space, the Dynamics of Individual Bees
- 12.4.3. γ-Space, the Dynamics of the Swarm of Bees
- 12.5. The Liouville Theorem
- 12.6. The Poincaré Recurrence Theorem
- 12.7. Ergodic Hypothesis
- 12.8. Types of Ensembles
- 12.9. The Microcanonical Ensemble
- 12.9.1. The Maximum Number of Configurations
- 12.9.2. Moving Arrays
- 12.9.3. Randomness: You Walk Into a Bar……
- 12.10. The Canonical Ensemble and the Probability
- 12.11. The Canonical Partition Function and Thermodynamic Functions
- 12.12. The Canonical Partition Function and the Hamiltonian for the System
- 12.12.1. The Configuration Integral and the Ursell–Mayer Cluster Diagrams
- 12.12.2. Validity of Expressions: Check With the Particle in a Box
- 12.13. The Canonical Partition Function for a System of Particles
- 12.14. The Canonical Partition Function and the Characteristic Temperature
- 12.14.1. Translational States
- 12.14.2. Rotational States
- 12.14.3. Vibrational States
- 12.14.4. Electronic States
- 12.15. The Canonical Ensemble and the Equilibrium Constant
- 12.16. The Grand Canonical Partition Function
- 12.17. Coarse Grain, Fine Grain, and Averages
- 12.18. The Boltzmann H Theorem
- 12.18.1. The Boltzmann H Function
- 12.18.2. Collisions: The Mechanism of Change
- 12.19. The Kac Ring Model
Chapter 13. Quantum Statistical Mechanics
- 13.0. Introduction
- 13.1. The Framing of the Problem of Degeneracy
- 13.1.1. A Tale of Two Electrons
- 13.1.2. A Tale of Two Die
- 13.2. Fermi–Dirac and Bose–Einstein Statistics and Playing Cards
- 13.2.1. Bose–Einstein Degeneracy
- 13.2.2. Fermi–Dirac Degeneracy
- 13.3. The Grand Partition Function: Maxwell–Boltzmann, Boltzmann, Fermi–Dirac, and Bose–Einstein Statistics
- 13.4. Occupation Numbers and Fermi–Dirac and Bose–Einstein Statistics
- 13.5. Comparison of Maxwell–Boltzmann, Fermi–Dirac, and Bose–Einstein Statistics
- 13.6. Relationships Between Classical Statistical Mechanics and Quantum Statistical Mechanics
- 13.7. The Quantum Behavior of Helium-4
- 13.7.1. Bose–Einstein Condensation
- 13.7.2. Lambda Transition for Helium-4
- 13.8. Pairwise Interactions Between Bound Polymer Sites: Random and Exact
- 13.8.1. The Scatchard Model for Binding Isotherms
- 13.8.2. The Exact Nearest-Neighbor Model for Binding Isotherms
Chapter 14. Nonequilibrium Thermodynamics
- 14.0. Introduction
- 14.1. Fluxes and Flows
- 14.2. Nonequilibrium and Entropy Change: The Dissipation Function
- 14.3. Diffusion and Dissipation
- 14.4. Hydrodynamic Flow and the Reynolds Number
- 14.5. The Friction Factor for Particles at Low Reynolds Numbers
- 14.6. Mutual, Self, and Tracer Friction Factors
- 14.7. Fick's Laws of Diffusion—The Mutual Diffusion Coefficient
- 14.8. The Motion of a Particle in a Solvent: The Langevin Equation
- 14.9. Heat Transport
- 14.10. Principle of Minimum Entropy Production
- 14.11. Onsager Reciprocity Relationships
Chapter 15. Reaction Rates and Mechanisms
- 15.0. Introduction
- 15.1. Determination of the Order of the Chemical Reaction
- 15.2. Time Course of the Zeroth-, First-, and Second-Order Reactions
- 15.2.1. Second-Order Reactions
- 15.2.2. First-Order Reactions
- 15.2.3. Zeroth-Order Reactions
- 15.2.4. Reaction Order and Stoichiometry of the Reaction
- 15.3. Reaction Mechanisms and Microscopic Reversibility
- 15.4. Reaction Mechanisms With Decision-Making Steps: Parallel Reactions
- 15.5. Reaction Mechanisms With Continuing Steps: Consecutive Reactions
- 15.6. Reaction Mechanisms With Regretful Steps: Reversible Reactions
- 15.7. Reaction Mechanisms With Consecutive and Reversible Steps
- 15.8. The Michaelis–Menten Mechanism for Enzyme Kinetics
- 15.8.1. The Michaelis–Menten Mechanism: Inhibition
- 15.8.2. The Michaelis–Menten Mechanism: Activation
- 15.8.3. The Michaelis–Menten Mechanism: Activator Plus Component X
- 15.9. Collisions and Reaction Kinetics
- 15.9.1. Pseudo First-Order Reactions: The Lindemann–Christiansen Mechanism
- 15.9.2. Chain Reactions: Hydrogen Bromide
- 15.10. Photodissociation Reactions
- 15.11. The Chapman Cycle
- 15.11.1. Catalytic Destruction of Ozone—The Hole Story
- 15.11.2. The Chapman Cycle Revisited—Microscopic Reversibility
- 15.12. Hard Sphere Collisions in the Gas Phase: Theory
- 15.12.1. Generalized Form of Bimolecular Collision Number
- 15.13. Hard Sphere Collision Model for Gas Phase Reaction Kinetics
- 15.14. Ad Hoc Modifications to the Hard Sphere Collision Model
- 15.15. Potential Energy Surface of a Chemical Reaction
- 15.16. Transition State Theory
- 15.17. Solution Kinetics—General Considerations
- 15.18. Diffusion-Controlled Reactions: The Smoluchowski Limit
- 15.19. Bimolecular Solution Kinetics: The Schurr Model
- 15.19.1. The Degree of Activation and Diffusion Contributions to Bimolecular Rate Constants
- 15.19.2. Effect of Rotation on the Forward Reaction Rate Constant
- 15.20. Temperature and Pressure Dependence of the Rate Constants
- 15.21. Caldin-Hasinoff: Reaction of Ferroprotoporphyrin IX With Carbon Monoxide
- 15.22. Nuclear Radiation and Dosage Rates
Mathematics Supplement
Appendices
Author Index
Subject Index

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Kenneth S Schmitz