Thermodynamics of Materials, Volume 2

by Ragone, David V.

• ISBN13: 9780471308867
• ISBN10: 0471308862
• Edition: 1st
• Format: Paperback
• Copyright: 1994-12-13
• Publisher: Wiley

Summary

Clear explanation of reaction kinetics for liquids, gases, and solids

Thermodynamics of Materials provides a comprehensive reference for chemical engineers and others whose work involves materials science. Volume 2 reviews macroscopic thermodynamics before moving on to the more complex behavior of defects and interfaces. The kinetics of liquids and gases are explored through discussion of evaporation, diffusion, and molecular movement, while solids are explored through in-depth explanations of nucleation, spinodal decomposition, and reaction kinetics. Concise, with clearly-defined equations and constants, this guide is an invaluable reference for both theoretical and practical applications.

Author Biography

About the Author David V. Ragone received his S. B., S. M., and Sc.D. degrees in metallurgical engineering from MIT. He taught undergraduate and graduate courses in thermodynamics at the University of Michigan in Ann Arbor from 1953 to 1962. From 1962 to 1967, as chairman of the materials department and assistant director of the Hopkins laboratory at the General Atomic Division of General Dynamics, he directed research on materials for advanced, high-temperature, gas-cooled nuclear reactors. He then served as Alcoa Professor of Metallurgy at the Carnegie- Mellon University, where he was also Associate Dean of Urban and Public Affairs. In 1970, he was named dean of the Thayer School at Dartmouth, and returned to the University of Michigan as Dean of Engineering in 1972. In 1980, he was named President of the Case Western University, where he served until 1987. He returned to teaching undergraduate courses in thermodynamics and the physical chemistry of materials at MIT in 1988, and began writing texts shortly thereafter. In addition to his appointment at MIT, David Ragone is a partner in Ampersand Ventures, a firm whose focus is on ventures in specialty materials and chemicals. He has also served as a member of the National Science Board and as a director of more than a dozen public and private companies. His professional society memberships include ASM, AIME, and ACS.

Table of Contents

Thermodynamics: Review	1	(26)
The First Law	1	(4)
System and Surroundings	1	(1)
Heat and Work	2	(1)
Reversibility	2	(1)
Internal Energy	2	(1)
State Functions	2	(1)
The First Law	2	(1)
Enthalpy	3	(1)
Intensive and Extensive Properties and Notation	3	(1)
Heat Capacities	3	(1)
Ideal Gas	4	(1)
Enthalpy of Formation	4	(1)
Entropy, and the Second Law	5	(2)
Entropy Not Conserved	5	(1)
Entropy Changes	5	(1)
Entropy Changes in Chemical Reactions and the Third Law	6	(1)
Property Relations	7	(2)
Free Energies	7	(1)
Maxwell Relations	7	(1)
Chemical Potentials	8	(1)
Partial Molar Quantities	9	(1)
Other Definitions	9	(1)
Equilibrium	9	(1)
Thermodynamics Activity	10	(1)
Chemical Equilibrium	11	(1)
Electrochemical Cells	11	(1)
Solutions	12	(5)
Ideal Solutions	12	(1)
Immiscibility	12	(2)
Regular Solutions	14	(2)
Spinodal Points	16	(1)
Gibbs--Duhem Equation	17	(1)
Phase Rule	17	(10)
Problems	18	(9)
Statistical Thermodynamics	27	(40)
Macrostates and Microstates	29	(2)
The Boltzmann Hypothesis	31	(1)
Entropy of Mixing	31	(1)
Systems at Constant Temperature and the Canonical Ensemble	32	(1)
Boltzmann Distribution	32	(1)
Partition Function	33	(1)
Degeneracy	33	(2)
Distinguishability of Particles	35	(1)
Ideal Gas	36	(1)
Maxwell--Boltmann Distribution: Ideal Gas	36	(1)
Fermi--Dirac Distribution	37	(2)
Effusion: Langmuir Equation	39	(4)
Mean Free Path	43	(2)
Diffusion in Gases	45	(5)
Elasticity of Rubber	50	(17)
References	61	(1)
Appendix 2A	61	(1)
Appendix 2B Evaluation of K	62	(1)
Appendix 2C Calculation of x2	63	(1)
Problems	64	(3)
Defects in Solids	67	(30)
Structural Point Defects in Elemental Crystals	68	(3)
Vacancies: Experimental Verification	71	(2)
Interactions Between Vacancies and Impurities	73	(2)
Interaction Between Imperfections and Impurities	75	(2)
Electronic Defects	77	(3)
Defects in Ionic Compounds	80	(1)
Frenkel Defects	81	(2)
Schottky--Wagner Defects	83	(1)
Interactions Among Defects	84	(2)
Intrinsic and Extrinsic Defects in Ionic Crystals	86	(3)
Experimental Determination of Defect Type	89	(2)
Nonstoichiometry	91	(6)
References	92	(1)
Problems	93	(4)
Surfaces and Interfaces	97	(30)
Surface Energy-Surface Tension	98	(1)
Approximate Calculation of Solid Surface Energy	99	(2)
Effect of Surface Curvature	101	(4)
Vapor Pressure	105	(1)
Solubility of Small Particles	106	(3)
Melting Temperature of Small Particles	109	(2)
Measurement of Surface Energy	111	(1)
Surface Energy of Solids	112	(2)
Relative Surface Energies	114	(1)
Wetting of Surfaces	115	(1)
Surface Energy and Impurity Segregation at Interfaces (Gibbs Absorption Isotherm)	116	(3)
Adsorption on Solids (Adsorption Isotherms)	119	(2)
Equilibrium Shape of a Crystal	121	(2)
Effect of Temperature on Surface Energy	123	(4)
References	123	(1)
Problems	123	(4)
Diffusion	127	(38)
Fick's First Law	127	(6)
Fick's Second Law	133	(5)
Kirkendall Effect	138	(3)
Mobility	141	(4)
Diffusion in Ionic Solids	145	(1)
Temperature Dependence of Diffusion	146	(2)
High Diffusivity Paths	148	(4)
Formation of Compounds	152	(2)
Boltzmann--Matano Analysis	154	(11)
References	156	(1)
Appendix 5A: The Error Function	156	(2)
Problems	158	(7)
Transformations	165	(26)
Types of Diffusional Transformation	166	(2)
Homogeneous Nucleation	168	(2)
Size Distribution of Nuclei	170	(2)
Supercooling	172	(2)
Heterogeneous Nucleation	174	(4)
Rate of Nucleation	178	(2)
Growth of Transformed Phase	180	(2)
Spinodal Transformations	182	(9)
References	186	(1)
Appendix 6A	186	(1)
Problems	187	(4)
Reaction Kinetics	191	(30)
Rate of Reaction	192	(1)
Order of Reactions	193	(2)
Equilibrium Constants: Relation to Reaction Rate Constants	195	(1)
First-Order Reactions	196	(2)
First-Order Reactions with Forward Reverse Rates	198	(4)
Higher Order Reactions	202	(2)
Reactions in Series	204	(1)
Temperature Dependence of Reaction Rate	205	(3)
Heterogeneous Reactions	208	(5)
Solid State Transformation Kinetics	213	(8)
References	216	(1)
Problems	216	(5)
Nonequilibrium Thermodynamics	221	(2)
Entropy Generation	223	(2)
Forces and Fluxes	225	(1)
Onsager Reciprocity Relationship	226	(1)
Thermal Diffusion	227	(3)
Electromigration	230	(2)
Thermal--Electrical Effects	232	(6)
References	238	(1)
Appendix 8A	239	(2)
Index	241