Physical Chemistry
Series: Topics in Physical Chemistry;
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Product details:
- Edition number 2
- Publisher OUP USA
- Date of Publication 11 May 2000
- ISBN 9780195105896
- Binding Hardback
- No. of pages1080 pages
- Size 218x279x55 mm
- Weight 2517 g
- Language English
- Illustrations 7 halftones, numerous line illustrations 0
Categories
Short description:
Physical Chemistry is a textbook for courses in physical chemistry taught to chemistry students at both the undergraduate and graduate level. It develops the fundamentals of physical chemistry in a logical sequence from the simple to the more complex, from atomic and molecular structure to properties of condensed matter, then to statistical and thermodynamic properties of systems in equilibrium and then to transport phenomena and chemical reaction processes. The conceptual structure of physical chemistry is emphasized throughout the presentation. the text assumes no prior knowledge of physical chemistry, but carries the reader to a level appropriate for graduate study.
MoreLong description:
The authors' goal is the presentation of the three major areas of physical chemistry: molecular structure, the equilibrium properties of systems, and the kinetics of transformations of systems. The theoretical foundations of these subjects are, respectively, quantum mechanics, thermodynamics and equilibrium statistical mechanics, and chemical kinetics and kinetic theory. These theories, firmly based on experimental findings, constitute the structure required for the understanding of past accomplishments and the basis for recognition and development of significant new areas in physical chemistry.
The presentation of the theories of physical chemistry requires careful discussions at several levels of exposition. The authors' approach aims toward depth of understanding of fundamentals more than toward breadth of recognition of the multitude of activities that go on under the name of physical chemistry. The organization of the book, with its three principal sections, should make this clear. The mathematical level begins with elementary calculus, and rises to the use of simple properties of partial differential equations and the special functions that enter into their solutions. The authors' intention is to keep the reader's mind on the scienc rather than on the mathematics, especially at the beginning. This procedure also corresponds to the pattern, followed by many students, of taking physical chemistry and advanced calculus concurrently. Appendices develop the details of the mathematical tools as they are needed.
The text discussion contains more material than can be covered in the traditional one-year physical chemistry sequence; it is designed to fulfill the dual purpose of providing a clear and incisive treatment of fundamental principles at a level accessible to all students while broadening the perspectives and challenging the minds of the best students. Individual instructors will wish to make their own selections of material for inclusion and exclusion, respectively.
"The authors have taken great care to present the material in a clear and concise way and have made links, where appropriate, between chapters. Throughout the book, diagrams and illustrations are clear and informative ... There is much to commend in this book and I would suggest that all chemistry libraries stock at least one copy ... The range and depth of topics covered will serve undergraduates on any physical chemistry or chemical physics course well, even to an advanced level, making this book good value for money." Dudley Shallcross in Education in Chemistry, May 2001
Table of Contents:
Preface
PART ONE: THE STRUCTURE OF MATTER
1. The Microscopic World: Atoms and Molecules
Development of the Atomic Theory: Relative Atomic Weights
Atomic Magnitudes
The Charge-to-Mass Ratio of the Electron: Thomson's Method
The Charge of the Electron: Millikan's Method
Mass Spectrometry
The Atomic Mass Scale and the Mole
The Periodic Table
2. Origins of the Quantum Theory of Matter
The Franck-Hertz Experiment
The Photoelectric Effect
x Rays and Matter
The Emission Spectra of Atoms
The Nuclear Atom
The Problem of Black-Body Radiation
The Concept of Action
The Harmonic Oscillator
Action Quantized: The Heat Capacity of Solids
Some Orders of Magnitude
Bohr's Model of the Atom
Appendix 2A: Rutherford Scattering
3. Matter Waves in Simple Systems
The de Broglie Hypothesis
The Nature of Waves
Dispersion Relations and Wave Equations: The Free Particle
Operators
Eigenfunctions and Eigenvalues
The Particle in a One-Dimensional Box
The Interdeterminacy or Uncertainty Principle
Expectation Values; Summary of Postulates
Particles in Two- and Three-Dimensional Boxes
Particles in Circular Boxes
Particles in Spherical Boxes
The Rigid Rotor
Appendix 3A: More on Circular Cooridnates and the Circular Box
4. Particles in Varying Potential Fields; Transitions
Finite Potential Barriers
The Quantum Mechanical Harmonic Oscillator
The Hydrogen Atom
The Shapes of Orbitals
Transitions Between Energy Levels
5. The Structure of Atoms
Electron Spin; Magnetic Phenomena
The Pauli Exclusion Principle; the Aufbau Principle
Electronic Configuration of Atoms
Calculation of Atomic Structures
Atomic Structure and Periodic Behavior
Term Splitting and the Vector Model
Fine Structure and Spin--Orbit Interactions
Appendix 5A: The Stern--Gerlach Experiment
6. The Chemical Bond in the Simplest Molecules: H2+ and H2
Bonding Forces Between Atoms
The Simplest Molecule: The Hydrogen Molecule-Ion, H2+
H2+: Molecular Orbitals and the LCAO Approximation
H2+: Obtaining the Energy Curve
H2+: Correlation of Orbitals; Excited States
The H2 Molecule: Simple MO Description
Symmetry Properties of Identical Particles
H2: The Valence BOnd Representation
H2: Beyond the Simple MO and VB Approximations
H2: Excited Electronic States
Appendix 6A: Orthogonality
Appendix 6B: Hermitian Operators
7. More About Diatomic Molecules
Vibrations of Diatomic Molecules
Rotations of Diatomic Molecules
Spectra of Diatomic Molecules
The Ionic Bond
Homonuclear Diatomic Molecules: Molecular Orbitals and Orbital Correlation
Homonuclear Diatomic Molecules: Aufbau Principle and the Structure of First-Row Molecules
Introduction to Heteronuclear Diatomic Molecules: Electronegativity
Bonding in LiH: Crossing and Noncrossing Potential Curves
Other First-Row Diatomic Hydrides
Isoelectronic and Other Series
Appendix 7A: Perturbation Theory
8. Triatomic Molecules
Electronic Structure and Geometry in the Simplest Cases: H3 and H3+
Dihydrides: Introduction to the Water Molecule
Hybrid Orbitals
Delocalized Orbitals in H2O: The General MO Method
Bonding in More Complex Triatomic Molecules
Normal Coordinates and Modes of Vibration
A Solvable Example: The Vibrational Modes of CO2
Transition and Spectra of Polyatomic Molecules
9. Larger Polyatomic Molecules
Small Molecules
Catenated Carbon Compounds; Transferability
Other Extended Structures
Some Steric Effects
Complex Ions and Other Coordination Compounds: Simple Polyhedra
Chirality and Optical Rotation
Chiral and Other Complex Ions
Magnetic Properties of Complexes
Electronic Structure of Complexes
Appendix 9A: Schmidt Orthogonalization
10. Intermolecular Forces
Long-Range Forces: Interactions Between Charge Distributions
Empirical Intermolecular Potentials
Weakly Associated Molecules
11. The Structure of Solids
Some General Properties of Solids
Space Lattices and Crystal Symmetry
x Ray Diffraction from Crystals: The Bragg Model
The Laue Model
Determination of Crystal Structures
Techniques of Diffraction
Molecular Crystals
Structures of Ionic Crystals
Binding Energy of Ionic Crystals
Covalent Solids
The Free-Electron Theory of Metals
The Band Theory of Solids
Conductors, Insulators, and Semicondutors
Other Forms of Condensed Matter
PART TWO: MATTER IN EQUILIBRIUM: STATISTICAL MECHANICS AND THERMODYNAMICS
12. The Perfect Gas at Equilibrium and the Concept of Temperature
The Perfect Gas: Definition and Elementary Model
The Perfect Gas: A General Relation Between Pressure and Energy
Some Comments About Thermodynamics
Temperature and the Zeroth Law of Thermodynamics
Empirical Temperature: The Perfect Gas Temperature Scale
Comparison of the Microscopic and Macroscopic Approaches
13. The First Law of Thermodynamics
Microscopic and Macroscopic Energy in a Perfect Gas
Description of Thermodynamic States
The Concept of Work in Thermodynamics
Intensive and Extensive Variables
Quasi-static and Reversible Processes
The First Law: Energy and Heat
Some Historical Notes
Microscopic Interpretation of Internal Heat and Energy
Constraints, Work, and Equilibrium
14. Thermochemistry and Its Applications
Heat Capacity and Enthalpy
Energy and Enthalpy Changes in Chemical Reactions
Thermochemistry of Physical Processes
Introduction to Phase Changes
Standard States
Thermochemistry of Solutions
Molecular Interpretation of Physical Processes
Bond Energies
Some Energy Effects in Molecular Structures
Lattice Energies of Ionic Crystals
15. The Concept of Entropy: Relationship to the Energy Level Spectrum of a System
The Relationship Between Average Propertis and Molecular Motion in an N-Molecule System: Time Averages and Ensemble Averages
Ensembles and Probability Distributions
Some Properties of a System with Many Degrees of Freedom: Elements of the Statistical Theory of Matter at Equilibrium
The Influences of Constraints on the Density of States
The Entropy: A Potential Function for the Equilibrium State
Appendix 15A: Comments on Ensemble Theory
Appendix 15B: (E) as a System Descriptor
Appendix 15C: The Master Equation
16. The Second Law of Thermodynamics: The Macroscopic Concept of Entropy
The Second Law of Thermodynamics
The Existence of an Engropy Function for Reversible Processes
Irreversible Processes: The Second Law Interpretation
The Clausius and Kelvin Statements Revisited
The Second Law as an Inequality
Some Relationships Between the Microscopic and Macroscopic Theories
Appendix 16A Poincare-- Recurrence Times and Irreversibility
17. Some Applications of the Second Law of Thermodynamics
Choice of Independent Variables
The Available Work Concept
Entropy Changes in Reversible Processes
Entropy Changes in Irreversible Processes
Entropy Changes in Phase Transitions
18. The Third Law of Thermodynamics
The Magnitude of the Entropy at T=0
The Unattainability of Absolute Zero
Experimental Verification of the Third Law
19. The Nature of the Equilibrium State
Properties of the Equilibrium State of a Pure Substance
Alternative Descriptions of the Equilibrium State for Different External Constraints
The Stability of the Equilibrium State of a One-Component System
The Equilibrium State in a Multicomponent System
Chemical Equilibrium
Thermodynamic Weight: Further Connections Between Thermodynamics and Microscopic Structure
An Application of the Canonical Ensemble: The Distribution of Molecular Speeds in a Perfect Gas
20. An Extension of Thermodynamics to the Description of Non-equilibrium Processes
General Form of the Equation of Continuity
Conservation of Mass and the Diffusion Equation
Conservation of Momentum and the Navier-Stokes Equation
Conservation of Energy and the Second Law of Thermodynamics
Linear Transport Processes
Negative Temperature
Thermodynamics of Systems at Negative Absolute Temperature
Appendix 20A: Symmetry of the Momentum Flux Tensor
21. The Properties of Pure Gases and Gas Mixtures
Thermodynamic Description of a Pure Gas
Thermodynamic Description of a Gas Mixture
Thermodynamic Description of Gaseous Reactions
An Example: The Haber Synthesis of NH3
Statistical Molecular Theory of Gases and Gas Reactions
The Statistical Molecular Theory of the Equilibrium Constant
The Statistical Molecular Theory of the Real Gas
Appendix 21A: Influence of Symmetry of the Wave Function on the Distribution over States: Fermi-Dirac and Bose-Einstein Statistics
Appendix 21B: Symmetry Properties of the Molecular Wave Function: Influence of Nuclear Spin on the Rotational Partition Function
Appendix 21C: The Semiclassical Partition Function: The Equation of State of an Imperfect Gas
22. Thermodynamic Properties of Solids
Differences Between Gases and Condensed Phases
The Influence of Crystal Symmetry on Macroscopic Properties
Microscopic Theory of the Thermal Properties of Crystalline Solids
The Contribution of Anharmonicity to the Properties of a Crystal
Some Properties of Complex Solids and of Imperfect Solids
Electronic Heat Capacity of Metals
Appendix 22A: Evaluation of Fermi-Dirac Integrals
23. Thermodynamic Properties of Liquids
Bulk Properties of Liquids
The Structure of Liquids
Relationships Between the Structure and the Thermodynamic Properties of a Simple Liquid
The Molecular Theory of Monoatomic Liquids: General Remarks
The Molecular Theory of Monoatomic Liquids: Approximate Analyses
The Molecular Theory of Polyatomic Liquids
Appendix 23A: x Ray Scattering from Liquids: Determination of the Structure of a Liquid
Appendix 23B: Functional Differentiation
24. Phase Equilibria in One-Component Systems
General Survey of Phase Equilibria
Thermodynamics of Phase Equilibria in One-Component Systems
Phase Transitions Viewed as Responses to Thermodynamic Instabilities
The Statistical Molecular Description of Phase Transitions
Appendix 24A: The Scaling Hypothesis for Thermodynamic Functions
Appendix 24B: Aspects of Density Functional Theory
25. Solutions of Nonelectrolytes
The Chemical Potential of a Component in an Ideal Solution
The Chemical Potential of a Component in a Real Solution
Partial Molar Quantities
Liquid-Vapor Equilibrium
Liquid-Solid Equilibrium
The Colligative Properties of Solutions: Boiling-Point Elevation, Freezing-Point Depression, and Osmotic Pressure
Chemical Reactions in Nonelectrolyte Solutions
More About Phas Equilibrium in Mixtures
Critical Phenomena in Mixtures
The Statistical Molecular Theory of Solutions of Nonelectrolytes
26. Equilibrium Properties of Solutions of Electrolytes
The Chemical Potential
Cells, Chemical Reactions, and Activity Coefficients
Comments on the Structure of Water
The Influence of Solutes on the Structure of Water
The Statistical Molecular Theory of Electrolyte Solutions
Molten Salts and Molten Salt Mixtures
The Structure of an Electrolyte Solution Near an Electrode
PART THREE: PHYSICAL AND CHEMICAL KINETICS
Molecular Motion and Collisions
Kinematics
Forces and Potentials
Collision Dynamics
Types of Collisions
Scattering Cross Sections
Elastic Scattering of Hard Spheres
Elastic Scattering of Atoms
Quantum Mechanical Scattering
28. The Kinetic Theory of Gases
Distribution Functions
Collision Frequency in a Dilute Gas
The Evolution of Velocity Distributions in Time
The Maxwell-Boltzmann Distribution
Collision Frequency for Hard-Sphere Molecules
Molecular Fluxes of Density, Momentum Density, and Energy Density
Effusion
Transport Properties of Gases
Energy Exchange Processes
Sound Propagation and Absorption
29. The Kinetic Theory of Dense Phases
Transport Properties in Dense Fluids
Some Basic Aspects of Brownian Motion
Stochastic Approach to Transport
Autocorrelation Functions and Transport Coefficients
Transport in Solids
Electrical Conductivity in Electrolyte Solutions
Vignette: Transport of Ions Through Membranes, by R. Eisenberg
30. Chemical Kinetics
General Concepts of Kinetics
Interactions Between Reactive Molecules
Collisions Between Reactive Molecules
Hard-Sphere Collision Theory: Reactive Cross Sections
Hard-Sphere Collision Theory: The Rate Coefficient
Activated-Complex Theory
Vignette: Present Day View of Transistion State Theory, by D.G. Truhlar
Activated-Complex Theory: Thermodynamic Interpretation
Theory of Reaction Kinetics in Solution
Vignette: Chemical Reactions in Condensed Phases, by P.G. Wolynes
Linear Free-Energy Relationships
Experimental Methods in Kinetics
Analysis of Data for Complex Reactions
Mechanisms of Chemical Reactions
Bimolecular Reactions
Unimolecular Reactions
Termolecular Reactions
31. Some Advanced Topics in Chemical Kinetics
More About Unimolecular Reactions
Kinetics of Photochemically Induced Reactions
Chain Reactions
Non-linear Phenomena
Fluctuations in Chemical Kinetics
Symmetry Rules for Chemical Reactions
Introduction to Catalysis
Enzyme Catalysis
Acid-Base Catalysis
Metal-Ion, COmplex, and Other Types of Homogeneous Catalysis
Heterogeneous Reactions: Adsorption of Gas on a Surface
Heterogeneous Catalysis
Kinetics of Electrode Reactions (by C. Chidsey)
Appendices
Systems of Units
Partial Derivatives
Glossary of Symbols
Searching the Scientific Literature
Index
