Physical Chemistry

Physical Chemistry

2nd Edition - March 21, 2000

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  • Author: Robert Mortimer
  • eBook ISBN: 9780080538938

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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.

Key Features

@bul:* Emphasizes clarity; every aspect of the first edition has been examined and revised as needed to make the principles and applications of physical chemistry as clear as possible.
* Proceeds from fundamental principles or postulates and shows how the consequences
of these principles and postulates apply to the chemical and physical phenomena being studied.
* Encourages the student not only to know
the applications in physical chemistry but to understand where they come from.
* Treats all topics relevant to undergraduate physical chemistry.


Undergraduate and graduate students of Physical Chemistry, professional chemists, students of Physics, Biology, and Engineering.

Table of 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

    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

    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

    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

    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

    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

    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

    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.

    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

    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

    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

    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

    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

    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 Schrödinger Equation.
    14.5 The Particle in a Box. The Free Particle.
    14.6 The Harmonic Oscillator

    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

    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

    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

    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

    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

    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

    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

    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

    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

    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 Hückel Method
    I. Symbols Used in this Book

Product details

  • No. of pages: 1136
  • Language: English
  • Copyright: © Academic Press 2000
  • Published: March 21, 2000
  • Imprint: Academic Press
  • eBook ISBN: 9780080538938

About the Author

Robert Mortimer

Robert Mortimer
Robert G. Mortimer is a Professor Emeritus of Chemistry at Rhodes College in Memphis, Tennessee. He has taught physical chemistry at Indiana University and Rhodes College for over 40 years. He has carried out both experimental and theoretical research in the area of nonequilibrium processes in fluid systems.

Affiliations and Expertise

Professor Emeritus of Chemistry, Rhodes College, Memphis, TN, USA

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