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By Robert Mortimer, Rhodes College, Memphis, TN, USA
Description This new edition of Robert G. Mortimer's Physical Chemistry has been thoroughly revised for use in a full year course in modern physical
chemistry. In this edition, Mortimer has included recent developments in the theories of chemical reaction kinetics and molecular quantum
mechanics, as well as in the experimental study of extremely rapid chemical reactions. While Mortimer has made substantial improvements
in the selection and updating of topics, he has retained the clarity of presentation, the integration of description and theory, and
the level of rigor that made the first edition so successful.
Audience
Undergraduate and graduate students of Physical Chemistry, professional chemists, students of Physics, Biology, and Engineering.
Contents Preface
Chapter 1 Systems, States, and Processes
1.1 Scientific Inquiry
1.2 Systems and States
1.3 Units of Measurement.
SI Units
1.4 State Functions
1.5 The Relationship Between Macrostates and Microstates
1.6 Processes
Problems
Chapter 2 The
Equilibrium Macroscopic States of Gases and Liquids
2.1 Mathematical Functions and the Equilibrium Macroscopic State of a Simple System
2.2 Real Liquids and Solids
2.3 Real Gases
2.4 The Coexistence of Phases and the Critical Point
Problems
Chapter 3 Work,
Heat, and Energy: The First Law of Thermodynamics
3.1 Work and the State of a System
3.2 Heat
3.3 Internal Energy; The First Law.
3.4 Calculation of Amounts of Heat and Energy Changes
3.5 Enthalpy - A Convenience Variable
3.6 Calculation of Enthalpy Changes for
Non-chemical Processes
3.7 Calculation of Enthalpy Changes for a Class of Chemical Reactions
3.8 Energy Changes of Chemical Reactions
Problems
Chapter 4 The Second and Third Laws of Thermodynamics: Entropy
4.1 The Second Law of Thermodynamics and the Carnot
Heat Engine
4.2 The Mathematical Statement of the Second Law. Entropy.
4.3 The Calculation of Entropy Changes
4.4 Statistical Entropy
4.5 The Third Law of Thermodynamics and Absolute Entropies
Problems
Chapter 5 The Thermodynamics of Real Systems
5.1 Criteria
for Spontaneous Processes and for Equilibrium.
The Gibbs and Helmholtz Energies.
5.2 Fundamental Relations for Closed Simple Systems
5.3 Gibbs Energy Calculations
5.4 The Description of Multicomponent and Open Systems
5.5 Additional Useful Thermodynamic Identities
5.6 Euler's Theorem and the Gibbs-Duhem Relation
Problems
Chapter 6 Phase Equilibrium
6.1 The Fundamental Fact of Phase
Equilibrium.
6.2 The Gibbs Phase Rule
6.3 Phase Equilibria in a One-Component System
6.4 The Gibbs Energy and Phase Transitions.
6.5 Surface Structure and Thermodynamics
6.6 Surfaces in Multicomponent Systems
Problems
Chapter7 Multicomponent Systems
7.1 Ideal Solutions
7.2 Henry's Law and Ideally Dilute Nonelectrolyte Solutions
7.3 The Activity and the Description of General Systems
7.4 Activity Coefficients in Electrolyte Solutions
7.5 Phase Diagrams for Nonideal Mixtures
7.6 Colligative Properties
Problems
Chapter 8 Chemical Equilibrium
8.1 Gibbs Energy Changes and Equilibria of Chemical Reactions: The Equilibrium Constant.
8.2
Reactions involving Gases and Pure Substances.
8.3 Chemical Equilibrium in Solution
8.4 Equilibria in Solutions of Strong Electrolytes.
8.5 Acid-Base Equilibrium Calculations.
8.6 Temperature and Pressure Dependence of Equilibrium Constants: The Principle of le Chatelier.
8.7 Chemical Reactions and Biological Systems.
Problems
Chapter 9 The Thermodynamics of Electrochemical Systems
9.1 The Chemical
Potential and the Electric Potential
9.2 Electrochemical Cells at Equilibrium
9.3 Half-Cell Potentials and Cell Potentials
9.4 The
Determination of Activity Coefficients of Electrolytes
9.5 Thermodynamic Information from Electrochemistry
Problems
Chapter
10 Gas Kinetic Theory. The Molecular Theory of Dilute Gases at Equilibrium
10.1 The Model System for a Dilute Gas
10.2 The Velocity
Probability Distribution
10.3 The Distribution of Molecular Speeds
10.4 The Pressure of an Ideal Gas
10.5 Wall Collisions and Effusion
10.6 The Model System with Potential Energy
10.7 The Hard Sphere Gas
10.9 The Molecular Structure of Liquids
Problems
Chapter
11 Transport Processes
11.1 The Macroscopic Description of Nonequilibrium States
11.2 Transport Processes
11.3 Transport Processes
in the Hard Sphere Gas
11.4 The Structure of Liquids and Transport Processes in Liquids
11.5 Transport in Electrolyte Solutions
Problems
Chapter 12 The Rates of Chemical Reactions
12.1 The Macroscopic Description of Chemically Reacting Systems
12.2 Forward
Reactions with one Reactant.
12.3 Forward Reactions With More than One Reactant
12.4 Inclusion of a Reverse Reaction. Chemical Equilibrium
12.5 Consecutive Reactions
12.6 The Experimental Study of Fast Reactions
Problems
Chapter 13 The Molecular Nature of Chemical
Reactions
13.1 Elementary Processes in Gases
13.2 Elementary Reactions in Liquid Solutions
13.3 Reaction Mechanisms and Rate Laws
13.4 Some Additional Mechanisms, Including Chain and Photochemical Mechanisms. Competing Mechanisms
13.5 Catalysis
13.6 The Temperature
Dependence of Rate Constants. The Collision Theory of Gaseous Reactions
13.7 Experimental Molecular Study of Chemical Reactions
Problems
Chapter 14 The Principles of Quantum Mechanics I: The Schrodinger Equation
14.1 Classical Mechanics
14.2 Properties of Waves
in Classical Mechanics.
14.2 The Old Quantum Theory
14.4 DeBroglie Waves and the Schrodinger Equation.
14.5 The Particle in a Box.
The Free Particle.
14.6 The Harmonic Oscillator
Problems
Chapter 15 The Principles of Quantum Mechanics II: The Postulates
of Quantum Mechanics
15.1 The First Two Postulates of Quantum Mechanics.
15.2 Mathematical Operators
15.3 Postulate III. Mathematical
Operators in Quantum Mechanics
15.4 Postulate IV. Expectation Values
15.5 Postulate V. The Determination of the State of a System
Problems
Chapter 16 The Electronic States of Atoms I: The Hydrogen Atom and the Simple Orbital Approximation for Multi-electron
Atoms
16.1 The Central Force Problem and the Hydrogen Atom. Angular Momentum
16.2 The Hydrogen-like Atom
16.3 The Helium Atom in
the "Zero-order" Orbital Approximation
16.4 Atoms with More than Two Electrons
Problems
Chapter 17 The Electronic States of
Atoms II: Higher-Order Approximations for Multi-electron Atoms
17.1 The Variation Method and its Application to the Helium Atom
17.2
The Perturbation Method and its Application to the Helium Atom
17.3 The Self-Consistent Field Method
17.4 Excited States of the Helium
Atom
17.5 Atoms with More than Two Electrons
Problems
Chapter 18 The Electronic States of Molecules
18.1 The Born-Oppenheimer
Approximation. The Hydrogen Molecule Ion.
18.2 LCAO-MO's - Molecular Orbitals That Are Linear Combinations of Atomic Orbitals
18.3
Homonuclear Diatomic Molecules
18.4 Heteronuclear Diatomic Molecules
18.5 Symmetry in Polyatomic Molecules. Groups of Symmetry Operators
18.6 Matrix Representations of Groups
18.7 Electronic Structure of Polyatomic Molecules
18.8 More Advanced Treatments of Molecular
Electronic Structure
Problems
Chapter 19 Translational, Rotational, and Vibrational States of Atoms and Molecules
19.1 Translational
Motions of Atoms
19.2 The Nonelectronic States of Diatomic Molecules
19.3 Rotation and Vibration in Polyatomic Molecules
19.4 The
Equilibrium Populations of Molecular States
Problems
Chapter 20 Spectroscopy and Photochemistry
20.1 Spectroscopic Study of
Energy Levels
20.2 Spectra of Atoms
20.3 Rotational and Vibrational Spectra of Diatomic Molecules
20.4 Electronic Spectra of Diatomic
Molecules
20.5 Spectra of Polyatomic Molecules
20.6 Fluorescence, Phosphorescence, and Photochemistry
20.7 Other Types of Spectroscopy
20.8 Magnetic Resonance Spectroscopy
20.9 Fourier Transform Spectroscopy
Problems
Chapter 21 Equilibrium Statistical Mechanics
21.1 The Quantum Statistical Mechanics of a Sample System of Four Molecules
21.2 The Probability Distribution for a Dilute Gas
21.3
The Probability Distribution and the Molecular Partition Function
21.4 The Calculation of Molecular Partition Functions
21.5 Calculations
of Thermodynamic Functions of Dilute Gases
21.6 Chemical Equilibrium in Dilute Gases
21.7 The Activated Complex Theory of Bimolecular
Chemical Reactions in Dilute Gases
21.8 The Canonical Ensemble
Problems
Chapter 22 The Structure of Condensed Phases
22.1
General Features of Solids and Liquids
22.2 Crystals
22.3 Crystal Vibrations
22.4 The Electronic Structure of Solids
22.5 Classical
Statistical Mechanics
22.6 The Structure of Liquids
22.7 Polymer Formation and Conformation
22.8 Rubber Elasticity
22.9 Polymers
in Solution
Problems.
Chapter 23 Theories of Nonequilibrium Processes
23.1 Theories of Chemical Reactions
23.2 The Molecular
Case History of a Chemical Reaction
23.3 Theories of Transport Processes in Fluid Systems
23.4 Nonequilibrium Electrochemistry
23.5
Electrical Conductivity in Solids
23.6 Oscillatory Chemical Reactions and Chemical Chaos
Problems
Appendixes
A. Tables
of Numerical Data
B. Some Useful Mathematics
C. A Short Table of Integrals
D. Classical Mechanics
E. Some Derivations
of Thermodynamic Formulas and Methods
F. Some Mathematics in Quantum Mechanics
G. The Perturbation Method
H. The Huckel Method
I. Symbols Used in this Book
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