# A Textbook of Physical Chemistry

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A Textbook of Physical Chemistry: Second Edition provides both a traditional and theoretical approach in the study of physical chemistry. The book covers subjects usually covered in chemistry textbooks such as ideal and non-ideal gases, the kinetic molecular theory of gases and the distribution laws, and the additive physical properties of matter. Also covered are the three laws of thermodynamics, thermochemistry, chemical equilibrium, liquids and their simple phase equilibria, the solutions of nonelectrolytes, and heterogenous equilibrium. The text is recommended for college-level chemistry students, especially those who are in need of a textbook for the subject.

## Table of Contents

Preface

Preface to the First Edition

1 Ideal and Nonideal Gases

1-1 Introduction

1-2 Equations of State

1-3 Development of the Concept of an Ideal Gas; The Absolute Temperature Scale

1-4 The Ideal Gas Law and Related Equations

1-5 Mixtures of Ideal Gases; Partial Pressures

1-6 Partial Volumes; Amagat's Law

1-7 The Barometric Equation

1-8 Deviations from Ideality—Critical Behavior

1-9 Semiempirical Equations of State. The van der Waals Equation

1-10 The van der Waals Equation, Critical Phenomena, and the Principle of Corresponding States

Commentary and Notes

Special Topics

General References

Cited References

Exercises and Problems

Exercises

Problems

Special Topics Problems

2 Kinetic Molecular Theory of Gases

2-1 Introduction

2-2 The Boltzmann Distribution Law

2-3 The Distribution of Molecular Velocities

2-4 Average Quantities from the Distribution Laws

2-5 Some Applications of Simple Kinetic Molecular Theory. Collision Frequency on a Plane Surface and Graham's Law

2-6 A Rederivation of the Ideal Gas Law

2-7 Bimolecular Collision Frequency and Mean Free Path

2-8 Transport Phenomena; Viscosity, Diffusion, and Thermal Conductivity

2-9 Summary of Kinetic Molecular Theory Quantities

Commentary and Notes

2-CN-1 Some Further Comments on the Various Distribution Laws

2-CN-2 Verification of the Distribution Laws

2-CN-3 Molecular Diameters; Avogadro's Number

2-CN-4 Transport Phenomena; Phenomenological Equations

2-CN-5 Verification of the Kinetic Molecular Theory

Special Topics

2-ST-1 Use of a Lennard-Jones Potential Function

2-ST-2 Collision Frequencies and Mean Free Paths for Mixtures

General References

Cited References

Exercises

Problems

Special Topics Problems

3 Some Additive Physical Properties of Matter

3-1 Introduction

3-2 Absorption of Light

3-3 Molar Refraction

3-4 Molar Polarization; Dipole Moments

3-5 Dipole Moments and Molecular Properties

Commentary and Notes

3-CN-1 Systems of Units

Special Topics

3-ST-1 The Charge Distribution of a Molecule

3-ST-2 Magnetic Properties of Matter

General References

Cited References

Exercises

Problems

Special Topics Problems

4 Chemical Thermodynamics. The First Law of Thermodynamics

4-1 Introduction

4-2 The Story of a Man

4-3 Energy and the First Law of Thermodynamics

4-4 Mathematical Properties of State Functions. Exact and Path-Dependent Differentials

4-5 Heat and Work for Various Processes

4-6 Enthalpy. An Alternative Form of the First Law

4-7 Applications of the First Law to Ideal Gases

4-8 Molecular Basis for Heat Capacities. The Equipartition Principle

4-9 Statistical Mechanical Treatment of First Law Quantities

4-10 Translational Partition Function for an Ideal Gas

4-11 The Rotational Partition Function

4-12 The Vibrational Partition Function

Commentary and Notes

4-CN-1 Internal Pressure

4-CN-2 Additional Aspects of Statistical Mechanical Treatments

Special Topics

4-ST-1 The Joule-Thomson Effect

4-ST-2 The Heat Capacity of a Solid

General References

Exercises

Problems

Special Topics Problems

5 Thermochemistry

5-1 Introduction

5-2 Measurement of Heats of Reaction: Relationship between ΔE and ΔH

5-3 Some Enthalpies of Combustion, Hydrogenation, and Solution

5-4 Combining ΔH or ΔΕ Quantities

5-5 Enthalpies of Formation

5-6 Dependence of ΔH and ΔE on Temperature

Commentary and Notes

5-CN-1 Explosions, Flames, and Rockets

5-CN-2 The Thermochemistry of Nutrition

Special Topics

5-ST-1 Chemical Bond Strengths

5-ST-2 Internal Energy and Enthalpy Functions

General References

Cited References

Exercises

Problems

Special Topics Problems

6 The Second and Third Laws of Thermodynamics

6-1 Introduction

6-2 The Carnot Cycle—Heat Machines

6-3 Generalization of the Carnot Cycle—The Entropy Function

6-4 Calculations of ΔS for Various Reversible Processes

6-5 Calculation of ΔS for Various Irreversible Processes

6-6 Free Energy. Criteria for Equilibrium

6-7 Second Law Relationships

6-8 The Third Law of Thermodynamics

6-9 Statistical Mechanical Treatment of Second Law Quantities

Commentary and Notes

6-CN-1 Summary of the Statements of the Laws of Thermodynamics

6-CN-2 Statistical Thermodynamics—Ensembles—and J. Willard Gibbs

6-CN-3 Additional Comments on the Third Law of Thermodynamics and on the Attainment of 0 Κ

Special Topics

6-ST-1 Thermodynamic Relationships

6-ST-2 Thermodynamic Treatment of a Nonideal Gas—Fugacity

6-ST-3 The Free Energy Function

General References

Cited References

Exercises

Problems

Special Topics Problems

7 Chemical Equilibrium

7-1 Introduction

7-2 The Thermodynamic Equilibrium Constant

7-3 The Determination of Experimental Equilibrium Constants

7-4 The Variation of KP with Temperature

7-5 Gas-Solid Equilibria

7-6 Le Châtelier's Principle

7-7 Free Energy and Entropy of Formation

Commentary and Notes

7-CN-1 Chemical Equilibrium and the Second Law of Thermodynamics

Special Topics

7-ST-1 Effect of Pressure on Chemical Equilibria Involving Gases

7-ST-2 Application of Statistical Thermodynamics to Chemical Equilibrium

General References

Cited References

Exercises

Problems

Special Topics Problems

8 Liquids and Their Simple Phase Equilibria

8-1 Introduction

8-2 The Vapor Pressure of Liquids (and Solids)

8-3 Enthalpy and Entropy of Vaporization; Trouton's Rule

8-4 Liquid-Solid and Solid-Solid Equilibria. Phase Maps

8-5 The Free Energy of a Liquid and Its Vapor

8-6 The Surface Tension of Liquids. Surface Tension as a Thermodynamic Quantity

8-7 Measurement of Surface Tension

8-8 Results of Surface Tension Measurements

8-9 The Kelvin Equation. Nucleation

8-10 Viscosity of Liquids

Commentary and Notes

8-CN-1 Additional Thermodynamic Properties of Liquids

8-CN-2 The Structure of Water

8-CN-3 Anomalous Water

Special Topics

8-ST-1 Intermodular Forces

8-ST-2 The Viscosity of Liquids

General References

Cited References

Exercises

Problems

Special Topics Problems

9 Solutions of Nonelectrolytes

9-1 Introduction

9-2 The Vapor Pressure of Solutions. Raoult's and Henry's Laws

9-3 The Thermodynamics of Multicomponent Systems

9-4 Ideal Gas Mixtures

9-5 Ideal and Nonideal Solutions. Activities and Activity Coefficients

9-6 The Temperature Dependence of Vapor Pressures

9-7 Boiling Point Diagrams

9-8 Partial Miscibility

Commentary and Notes

9-CN-1 Other Properties of Solutions

9-CN-2 Ideal, Regular, and Athermal Solutions

9-CN-3 Statistical Thermodynamics of Solutions

Special Topics

9-ST-1 Partial Molal Quantities

9-ST-2 The Surface Tension of Solutions. The Gibbs Equation

General References

Cited References

Exercises

Problems

Special Topics Problems

10 Dilute Solutions of Nonelectrolytes. Colligative Properties

10-1 Vapor Pressure Lowering

10-2 Boiling Point Elevation

10-3 Freezing Point Depression

10-4 Summary of the First Three Colligative Properties

10-5 Osmotic Equilibrium

10-6 Activities and Activity Coefficients for Dilute Solutions

10-7 Other Methods of Molecular Weight Determination

Commentary and Notes

10-CN-1 Colligative Properties and Deviations from Ideality

10-CN-2 Relationship between Freezing Point Depression and Solubility

10-CN-3 Osmotic Pressure

10-CN-4 Water Desalination

Special Topics

10-ST-1 Dilute Solution Conventions for Activities and Activity Coefficients

10-ST-2 Theoretical Treatment of Diffusion

General References

Cited References

Exercises

Problems

Special Topics Problems

11 Heterogeneous Equilibrium

11-1 The Gibbs Phase Rule

11-2 One-Component Systems

11-3 Two-Component Systems

11-4 Sodium Sulfate-Water and Other Systems

11-5 Three-Component Systems

11-6 Three-Component Solubility Diagrams

Commentary and Notes

11-CN-1 Definitions of the Terms Component and Phase

Special Topics

11-ST-1 Two-Component Freezing Point Diagrams. Partial Miscibility

11-ST-2 Partial Miscibility in Three-Component Systems

General References

Cited References

Exercises

Problems

Special Topics Problems

12 Solutions of Electrolytes

12-1 Introduction

12-2 Conductivity—Experimental Definitions and Procedures

12-3 Results of Conductance Measurements

12-4 Some Sample Calculations

12-5 Ionic Mobilities

12-6 Transference Numbers—Ionic Equivalent Conductivities

12-7 Activities and Activity Coefficients of Electrolytes

12-8 The Debye-Hückel Theory

12-9 Ionic Equilibria

Commentary and Notes

12-CN-1 Electrolytic Dissociation

12-CN-2 Activity Coefficients for Other than Dilute Aqueous Solutions

12-CN-3 Acids and Bases

Special Topics

12-ST-1 Ionic Diffusion Coefficients

12-ST-2 The Hittorf Method

12-ST-3 Treatment of Complex Ionic Equilibria

General References

Cited References

Exercises

Problems

Special Topics Problems

13 Electrochemical Cells

13-1 Definitions and Fundamental Relationships

13-2 Experimental Procedures

13-3 Determination of E0 Values and Activity Coefficients

13-4 Additivity Rules for Emf's. Standard Oxidation Potentials

13-5 Emf and Chemical Equilibria

13-6 Concentration Cells

13-7 Oxidation-Reduction Reactions

13-8 Determination of pH

13-9 Irreversible Electrode Processes

Commentary and Notes

13-CN-1 Standard Oxidation Potential E0 and Standard Electrode Potential V0

13-CN-2 Storage Batteries

13-CN-3 Thermodynamic Quantities for Aqueous Ions

13-CN-4 Electrocapillarity. Absolute Electrode Potentials

Special Topics

13-ST-1 Liquid Junctions

13-ST-2 Polarization at Electrodes. Polarography

General References

Cited References

Exercises

Problems

Special Topics Problems

14 Kinetics of Gas-Phase Reactions

14-1 Introduction

14-2 Rate Laws and Simple Mechanisms

14-3 Experimental Methods and Rate Law Calculations

14-4 Rate Laws and Reaction Mechanisms

14-5 Temperature Dependence of Rate Constants

14-6 Collision Theory of Gas Reactions

14-7 Unimolecular Reactions

14-8 Absolute Rate Theory. The Activated Complex

Commentary and Notes

14-CN-1 Termolecular Reactions

14-CN-2 Collision versus Transition-State Theory

14-CN-3 Radicals, Molecular Beams, and Reaction Trajectories

14-CN-4 Explosions

Special Topics

14-ST-1 Heterogeneous Catalysis. Chemisorption of Gases

14-ST-2 Statistical Thermodynamic Treatment of Transition-State Theory

General References

Cited References

Exercises

Problems

Special Topics Problems

15 Kinetics of Reactions in Solution

15-1 Additional Comments on Rate Laws. Reversible Reactions

15-2 Experimental Methods

15-3 Kinetic-Molecular Picture of Reactions in Solution

15-4 Diffusion-Controlled Reactions

15-5 Transition-State Theory

15-6 Linear Free Energy Relationships. Reactions Involving an Acid or a Base

15-7 Ionic Reactions. Role of Activity Coefficients

Commentary and Notes

15-CN-1 Comparison of Collision-Encounter and Transition-State Theories

15-CN-2 Relationship between the Equilibrium Constant for a Reaction and Its Rate Constants

15-CN-3 Entropy Production during a Chemical Reaction

Special Topics

15-ST-1 Enzyme Catalysis

15-ST-2 Integrated Forms for Some Additional Rate Laws

15-ST-3 Effect of Mechanical Pressure on Reaction Rates

General References

Cited References

Exercises

Problems

Special Topics Problems

16 Wave Mechanics

16-1 Introduction

16-2 Energy Units

16-3 Hydrogen and Hydrogen-Like Atoms

16-4 The Schrödinger Wave Equation

16-5 Some Simple Choices for the Potential Function V

16-6 The Harmonic Oscillator

16-7 Solutions of the Wave Equation for the Hydrogen Atom

16-8 The Graphical Appearance of Hydrogen-Like Orbitals

16-9 Graphical Appearance of the Electron Density around a Hydrogen-Like Atom

16-10 Hybrid Orbitals

16-11 The Variation Method. Polarizability of the Hydrogen Atom

Commentary and Notes

16-CN-1 Albert Einstein

16-CN-2 An Alternative Interpretation of the Uncertainty Principle

16-CN-3 Steps beyond Hydrogen-Like Wave Functions

Special Topics

16-ST-1 Atomic Energy States

16-ST-2 The Rigid Rotator

16-ST-3 First-Order Perturbation Theory

16-ST-4 Quantum Theory of Blackbody Radiation

General References

Cited References

Exercises

Problems

Special Topics Problems

17 Molecular Symmetry and Bonding

17-1 Introduction

17-2 Symmetry and Symmetry Operations

17-3 A Set of Symmetry Operations as Constituting a Group

17-4 Representations of Groups

17-5 Atomic Orbitals as Bases for Representations

17-6 Character Tables

17-7 Bonds as Bases for Reducible Representations

Commentary and Notes

17-CN-1 Crystal Field Theory

Special Topics

17-ST-1 The Direct Product

General References

Cited References

Exercises

Problems

Special Topics Problems

18 Wave Mechanics and Bonding

18-1 Introduction

18-2 The Valence Bond Method for the Hydrogen Molecule

18-3 Molecular Orbitals. The Hydrogen Molecule Ion, H2+

18-4 Variation Method for Obtaining Molecular Orbitals

18-5 Molecular Orbital Energy Levels for Diatomic Molecules

18-6 Triatomic Molecules. Walsh Diagrams

18-7 Polyatomic Molecules. The Hückel Method

Commentary and Notes

18-CN-1 Comparison of the Valence Bond and Molecular Orbital Methods

Special Topics

18-ST-1 Ligand Field Molecular Orbital Diagrams

General References

Cited References

Exercises

Problems

Special Topics Problems

19 Molecular Spectroscopy and Photochemistry

19-1 Introduction

19-2 Excited States of Diatomic Molecules

19-3 Electronic, Vibrational, and Rotational Transitions

19-4 Electronic Excited States of Polyatomic Molecules

19-5 Vibrational Spectra

Commentary and Notes

19-CN-1 Geometric and Electronic Nature of Ground-State Molecules

19-CN-2 Structure and Chemistry of Excited States

19-CN-3 Conversion of Light to Chemical Energy

Special Topics

19-ST-1 Emission and Absorption of Radiation. Transition Probability

19-ST-2 Optical Activity

19-ST-3 Vibrational-Rotational Spectra

19-ST-4 Glossary of Abbreviations

General References

Cited References

Exercises

Problems

Special Topics Problems

20 The Solid State

20-1 Space-Filling Lattices

20-2 Crystal Planes; Miller Indices

20-3 Some Simple Crystal Structures

20-4 Some Geometric Calculations

20-5 Diffraction by Crystals

Commentary and Notes

20-CN-1 Modern Crystal Structure Determination

20-CN-2 Some Structures of Biological Importance

20-CN-3 The Band Model for Solids. Semiconductors

20-CN-4 Crystal Defects

Special Topics

20-ST-1 Symmetry Notation for Crystals

20-ST-2 X-Ray Diffraction Intensities

20-ST-3 Lattice Energies

20-ST-4 Ionic Radii

General References

Cited References

Exercises

Problems

Special Topics Problems

21 Colloids and Macromolecules

21-1 Lyophobic Colloids

21-2 Association Colloids. Colloidal Electrolytes

21-3 Gels

21-4 Rheology

21-5 Liquid Crystals. Mesophases of Matter

21-6 Polymers

Special Topics

21-ST-1 Electrokinetic Effects

General References

Cited References

Exercises

Problems

Special Topics Problems

22 Nuclear Chemistry and Radiochemistry

22-1 Introduction

22-2 Nuclear Energetics and Existence Rules

22-3 Nuclear Reactions

22-4 Absorption of Radiation

22-5 Kinetics of Radioactive Decay

Commentary and Notes

22-CN-1 Theories of Radioactive Decay

22-CN-2 Nuclear Reactors and "Atomic" Bombs

22-CN-3 Nuclear Chemistry

22-CN-4 Quantum Statistics

22-CN-5 Experimental Detection Methods

22-CN-6 The Mossbauer Effect

Special Topics

22-ST-1 The Natural Decay Series. Age Dating

22-ST-2 Statistical Fluctuations in Radioactive Decay

General References

Cited References

Exercises

Problems

Special Topics Problems

Subject Index

## Product details

- No. of pages: 996
- Language: English
- Copyright: © Academic Press 1979
- Published: September 15, 1970
- Imprint: Academic Press
- eBook ISBN: 9780323161282

## About the Author

### Arther Adamson

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**Aamir R.**Wed Sep 12 2018**good work**dear sir I'm very happy to say that the book is very good after i studied some topics gone very well keeping my interest in. thank you so much for your service