Matter in Equilibrium Statistical Mechanics and Thermodynamics includes CD-ROM

by Berry, R. Stephen; Rice, Stuart A.; Ross, John

• ISBN13: 9780195147490
• ISBN10: 0195147499
• Edition: 2nd
• Format: Hardcover
• Copyright: 2001-08-30
• Publisher: Oxford University Press

Summary

Originally Part II of Physical Chemistry, Second Edition , and now published as its own volume, Matter in Equilibrium: Statistical Mechanics and Thermodynamics simultaneously develops the statistical molecular theory and the classical thermodynamic theory of the bulk properties of matter in a mutually reinforcing fashion. Despite presenting both a microscopic and macroscopic approach, this sophisticated text offers a rigorous treatment of classical thermodynamics and allows professors to separate the two theories if desired. Packed with tables, graphs, and figures, it describes the equilibrium properties of bulk matter and develops the tools needed to study gases, solids, liquids, phase transformations, solutions of nonelectrolytes, and solutions of electrolytes. The book makes extensive use of computer simulations of molecular behavior and, where appropriate, uses experimental data to illustrate concepts and principles. Ideal for advanced undergraduate and beginning graduate level courses, Matter in Equilibrium broadens and challenges student perspectives while offering valuable information to researchers.

Table of Contents

Preface	xi
Suggested Topic Selections	xv
Glossary of Symbols	xvii
PART II: MATTER IN EQUILIBRIUM: STATISTICAL MECHANICS AND THERMODYNAMICS	351	(696)
The Perfect Gas at Equilibrium and the Concept of Temperature	353	(16)
The Perfect Gas: Definition and Elementary Model	353	(2)
The Perfect Gas: A General Relation between Pressure and Energy	355	(2)
Some Comments about Thermodynamics	357	(2)
Temperature and the Zero-th Law of Thermodynamics	359	(2)
Empirical Temperature: The Perfect Gas Temperature Scale	361	(3)
Comparison of the Microscopic and Macroscopic Approaches	364	(5)
The First Law of Thermodynamics	369	(19)
Microscopic and Macroscopic Energy in a Perfect Gas	369	(2)
Description of Thermodynamic States	371	(2)
The Concept of Work in Thermodynamics	373	(2)
Intensive and Extensive Variables	375	(1)
Quasi-static and Reversible Processes	376	(3)
The First Law: Internal Energy and Heat	379	(2)
Some Historical Notes	381	(1)
Microscopic Interpretation of Internal Energy and Heat	382	(1)
Constraints, Work, and Equilibrium	383	(5)
Thermochemistry and Its Applications	388	(32)
Heat Capacity and Enthalpy	388	(4)
Energy and Enthalpy Changes in Chemical Reactions	392	(2)
Thermochemistry of Physical Processes	394	(3)
Introduction to Phase Changes	397	(1)
Standard States	398	(2)
Thermochemistry of Solutions	400	(4)
Molecular Interpretation of Physical Processes	404	(1)
Bond Energies	405	(4)
Some Energy Effects in Molecular Structures	409	(2)
Lattice Energies of Ionic Crystals	411	(9)
The Concept of Entropy: Relationship to the Energy-Level Spectrum of a System	420	(34)
The Relationship between Average Properties and Molecular Motion in an N-Molecule System: Time Averages and Ensemble Averages	421	(4)
Ensembles and Probability Distributions	425	(3)
Some Properties of a System with Many Degrees of Freedom: Elements of the Statistical Theory of Matter at Equilibrium	428	(3)
The Influence of Constraints on the Density of States	431	(4)
The Entropy: A Potential Function for the Equilibrium State	435	(19)
Appendix 15A: Comments on Ensemble Theory	443	(5)
Appendix 15B: Ω (E) as a System Descriptor	448	(2)
Appendix 15C: The Master Equation	450	(4)
The Second Law of Thermodynamics: The Macroscopic Concept of Entropy	454	(22)
The Second Law of Thermodynamics	454	(2)
The Existence of an Entropy Function for Reversible Processes	456	(3)
Irreversible Processes: The Second-Law Interpretation	459	(4)
The Clausius and Kelvin Statement Revisited	463	(2)
The Second Law as an Inequality	465	(1)
Some Relationships between the Microscopic and Macroscopic Theories	466	(10)
Appendix 16A: Poincare Recurence Times and Inversibility	468	(8)
Some Applications of the Second Law of Thermodynamics	476	(12)
Choice of Independent Variables	476	(2)
The Available Work Concept	478	(1)
Entropy Changes in Reversible Processes	479	(3)
Entropy Changes in Ireversible Processes	482	(2)
Entropy Changes in Phase Transitions	484	(4)
The Third Law of Thermodynamics	488	(11)
The Magnitude of the Entropy at T = 0	489	(5)
The Unattainability of Absolute Zero	494	(1)
Experimental Verification of the Third Law	495	(4)
The Nature of the Equilibrium State	499	(25)
Properties of the Equilibrium State of a Pure Substance	499	(4)
Alternative Descriptions of the Equilibrium State for Different External Constraints	503	(3)
The Stability of the Equilibrium State of a One-Component System	506	(2)
The Equilibrium State in a Multicomponent System	508	(4)
Chemical Equilibrium	512	(1)
Thermodynamic Weight: Further Connections between Thermodynamics and Microscopic Structure	513	(5)
An Application of the Canonical Ensemble: The Distribution of Molecular Speeds in a Perfect Gas	518	(6)
An Extension of Thermodynamics to the Description of Nonequilibrium Processes	524	(22)
General Form of the Equations of Continuity	525	(1)
Conservation of Mass and the Diffusion Equation	526	(1)
Conservation of Momentum and the Navier-Stokes Equation	527	(3)
Conservation of Energy and the Second Law of Thermodynamics	530	(3)
Linear Transport Processes	533	(2)
Negative Temperature	535	(2)
Thermodynamics of Systems at Negative Absolute Temperature	537	(9)
Appendix 20A: Symmetry of the Momentum Flux Tensor	543	(3)
The Properties of Pure Gases and Gas Mixtures	546	(51)
Thermodynamic Description of a Pure Gas	546	(8)
Thermodynamic Description of a Gas Mixture	554	(5)
Thermodynamic Description of Gaseous Reactions	559	(2)
An Example: The Haber Synthesis of NH3	561	(4)
Statistical Molecular Theory of Gases and Gas Reactions	565	(10)
The Partition Function	565	(5)
The Heat Capacity of a Perfect Gas of Diatomic Molecules	570	(5)
The Statistical Molecular Theory of the Equilibrium Constant	575	(2)
The Statistical Molecular Theory of the Real Gas	577	(20)
Appendix 21A: Influence of Symmetry of the Wave Function on the Distribution over States: Fermi-D and Bose-Einstein Statistics	585	(4)
Appendix 21B: Symmetry Properties of the Molecular Wave Function: Influence of Nuclear Spin on the Rotational Partition Function	589	(2)
Appendix 21C: The Semiclassical Partition Function; Equation of State of an Imperfect Gas	591	(6)
Thermodynamic Properties of Solids	597	(22)
Differences between Gases and Condensec Phases	597	(1)
The Influence of Crystal Symmetry on Macroscopic Properties	597	(4)
Microscopic Theory of the Thermal Property of Crystalline Solids	601	(7)
The Contribution of Anharmonicity to the Properties of a Crystal	608	(2)
Some Properties of Complex Solids and of Imperfect Solids	610	(2)
Electronic Heat Capacity of Metals	612	(7)
Appendix 22A: Evaluation of Fermi-Dirac Integrals
Thermodynamic Properties of Liquids	619	(36)
Bulk Properties of Liquids	619	(4)
The Structure of Liquids	623	(6)
Relationships between the Structure and the Thermodynamic Properties of a Simple Liquid	629	(2)
The Molecular Theory of Monoatomic Liquid General Remarks	631	(5)
The Molecular Theory of Monoatomic Liquid Approximate Analyses	636	(6)
The Molecular Theory of Polyatomic Liquids	642	(13)
Appendix 23A: X-ray Scattering from Liquids: Determination of the Structure of a Liquid	647	(2)
Appendix 23B: Functional Differentiation	649	(6)
Phase Equilibria in One-Component Systems	655	(39)
General Survey of Phase Equilibria	655	(4)
Thermodynamics of Phase Equilibria in One-Component Systems	659	(7)
The Clausius-Clapeyron Equations	659	(4)
The Critical Point	663	(3)
Phase Transitions Viewed as Responses to Thermodynamic Instabilities	666	(8)
The Statistical Molecular Description of Phase Transitions	674	(20)
Appendix 24A: The Scaling Hypothesis for Thermodynamic Functions	687	(2)
Appendix 24B: Aspects of Density Functional Theory	689	(5)
Solutions of Nonelectrolytes	694	(51)
The Chemical Potential of a Component in an Ideal Solution	694	(2)
The Chemical Potential of a Component in a Real Solution	696	(3)
Partial Molar Quantities	699	(1)
Liquid-Vapor Equilibrium	700	(6)
Liquid-Solid Equilibrium	706	(2)
The Collegative Properties of Solutions: Boiling-Point Elevation, Freezing-Point Depression, and Osmotic Pressure	708	(3)
Chemical Reactions in Nonelectrolyte Solutions	711	(1)
More about Phase Equilibrium in Mixtures	712	(9)
Critical Phenomena in Mixtures	721	(2)
The Molecular Theory of Solutions of Nonelectrolytes	723	(22)
The Statistical Mechanics of Mixtures	723	(2)
Molecular Theory of Crystalline Mixtures	725	(8)
Molecular Theory of Liquid Mixtures	733	(12)
Equilibrium Properties of Solutions of Electrolytes	745	(302)
The Chemical Potential	745	(2)
Cells, Chemical Reactions, and Activity Coefficients	747	(5)
Determination of Solute Activities	750	(1)
Determination of an Equilibrium Constant	750	(2)
Comments on the Structure of Water	752	(4)
The Influence of Solutes on the Structure of Water	756	(16)
The Statistical Mechanics of Electrolyte Solutions	772	(11)
Debye-Huckel Theory	772	(4)
An Alternative View of the Debye-Huckel Approximation	776	(1)
Beyond the Debye-Huckel Approximation	777	(5)
Semiempirical Representation of the Properties of Electrolyte Solutions	782	(1)
Molten Salts and Molten Salt Mixtures	783	(7)
The Structure of an Electrolyte Solution Near an Electrode	790	(229)
The Structure of Water Near a Surface	790	(5)
The Electrolyte Solution-Electrode Interface	795	(224)
Appendices
Appendix I: Systems of Units	1019	(3)
Appendix II: Partial Derivatives	1022	(3)
Appendix III: Searching the Scientific Literature	1025	(22)
Index	1047