Nonequilibrium Nondissipative Thermodynamics

by Wang, Ji-Tao

• ISBN13: 9783540428022
• ISBN10: 354042802X
• Format: Hardcover
• Copyright: 2002-07-01
• Publisher: Springer Verlag

Summary

This book provides a framework for analysing complex systems for which classical thermodynamics is often not applicable. Since the success of the activated process in 1970, diamond growth with simultaneous graphite etching under low pressure has often been regarded as a violation of the second law of thermodynamics. A series of nonequilibrium phase diagrams, which agree excellently with the activated diamond experiments, have been calculated by the author and his coworkers on the basis of reaction coupling. The book goes on to demonstrate how these lead to a complete new systematization of modern thermodynamics.

Table of Contents

Classical Thermodynamics	1	(22)
Basic Laws of Classical Thermodynamics	1	(1)
Classical Equilibrium Thermodynamics	1	(7)
Nonequilibrium Thermodynamics in Classical Thermodynamics	8	(2)
Criteria of Change Direction and Limitation	10	(1)
Relationship Between Gibbs Free Energy and Temperature or Pressure	11	(2)
Chemical Potential and Its Relationship with Temperature and Pressure	13	(4)
Change of Gibbs, Free Energy in Chemical Reactions	17	(4)
Limitation to the Applicability of Classical Thermodynamics	21	(2)
Fundamentals of Modern Thermodynamics	23	(30)
Modern Formulation of Basic Thermodynamic Laws	24	(2)
Some Basic Concepts in Nonequilibrium Thermodynamics	26	(3)
Irreversibility of Change with Time	27	(1)
Equilibrium State, Stationary State and Nonequilibrium State	27	(1)
Reversible and Irreversible Processes	28	(1)
Assumption of local Equilibrium	29	(2)
Calculation of Entropy	31	(4)
Systematization of Modern Thermodynamics	35	(5)
Onsager's Reciprocity Relation	40	(5)
Entropy Production Minimization Principle	45	(2)
Prigogine's Dissipative Structures	47	(6)
Benard's Pattern	47	(1)
Laser Emission	48	(3)
Chemical Oscillation	51	(2)
High-Pressure Synthesis and Low-Pressure Vapor Growth of Diamond Seeds	53	(22)
Early History of Diamond Synthesis	53	(2)
Thermodynamic Predictions	55	(2)
Success of the High-Pressure Process	57	(7)
Early Exploration of Low-Pressure Vapor Growth of Diamond Seeds	64	(1)
Thermodynamic Conditions for Crystal Growth from the Vapor Phase	65	(6)
Supersaturation Degree	65	(1)
Nucleation Barrier	66	(5)
Diamond Seed Growth from the Vapor Phase	71	(4)
Activated Low-Pressure Diamond Growth from the Vapor Phase	75	(24)
Success of Activated Low-Pressure Vapor Growth Process	75	(4)
Setup of Activated Low-Pressure Growth from the Vapor Phase	79	(6)
Preferential Etching Kinetic Model of SAH	85	(1)
Kinetic Control Model	86	(3)
Some Thermodynamic Theoretical Models of the 1980s	89	(10)
Quasiequilibrium Model	90	(4)
Surface Reaction Thermodynamic Model	94	(2)
Defect-Induced Stabilization Model	96	(3)
Reaction Coupling Model	99	(40)
Chemical Pump Mode	99	(5)
Mechanism of the Chemical Pump	100	(3)
Chemical Pump Reaction	103	(1)
Calculation of the Chemical Pump Effect	104	(5)
Reaction Coupling Model	109	(3)
Thermodynamic Data for Activated Graphite	112	(4)
New Concept of Nonequilibrium (Stationary) Phase Diagrams	116	(3)
Nonequilibrium Nondissipation Principle	119	(3)
Calculation of Nonequilibrium Phase Diagrams	122	(3)
Some Results and Discussions	125	(7)
Morphology of Diamond Crystals and Orientation of Diamond Films	132	(7)
Nonequilibrium Phase Diagrams of C-H, C-O and Other Binary Systems	139	(14)
T-X Nonequilibrium Phase Diagrams C-H Binary Systems	139	(7)
T-p-X Nonequilibrium Phase Diagrams for C-H and C-O Binary Systems	146	(4)
Nonequilibrium Phase Diagrams for Other Binary Systems	150	(3)
Nonequilibrium Phase Diagrams of C-H-O and Other Ternary Systems	153	(20)
Bachmann's Empirical Phase Diagram for the C-H-O System	154	(3)
Projective Nonequilibrium Phase Diagrams for C-H-O Systems	157	(4)
Influences of T and p Ranges on C-H-O Ternary Phase Diagrams	161	(4)
Cross-Sectional Nonequilibrium Phase Diagrams for C-H-O Ternary Systems	165	(4)
Nonequilibrium Phase Diagrams for C-H-X Ternary Systems	169	(4)
Further Discussions on Some Debates	173	(40)
Coupled Reaction in Biochemistry	174	(4)
The Seventy-Year Controversy About Reaction Coupling in Chemistry	178	(7)
Quantitative Verification of Reaction Coupling in Inanimate Systems	185	(10)
Reaction Barrier in Synthetic Diamond Processes	195	(14)
``Unified Barrier'' Model	195	(1)
Thermodynamic Coupling Effect and Catalytic Effect	196	(7)
Analysis of Calculated Results and Conclusions	203	(6)
Other Thermodynamic Discussions on Activated CVD Diamond	209	(4)
Charged Cluster Model	209	(2)
Other Thermodynamic Discussions	211	(2)
Other Applications and Summary	213	(24)
Nonequilibrium Phase Diagrams for the Activated CVD cBN Process	213	(4)
Modern Thermodynamics for Belousov-Zhabotinsky Reactions	217	(2)
A Characteristic of Life: Drawing Negative Entropy from its Environment	219	(5)
Some Similarities of Reaction Coupling in Biological and Inanimate Systems	224	(4)
Some Conclusions, Further Development and Prospects	228	(9)
References	237	(14)
Index	251