Nonequilibrium Thermodynamics

Natural phenomena consist of simultaneously occurring transport processes and chemical reactions. These processes may interact with each other and may lead to self-organized structures, fluctuations, instabilities, and evolutionary systems. Nonequilibrium Thermodynamics, Third Edition emphasizes the unifying role of thermodynamics in analyzing the natural phenomena. This third edition updates and expands on the first and second editions by focusing on the general balance equations for coupled processes of physical, chemical, and biological systems. The new edition contains a new chapter on stochastic approaches to include the statistical thermodynamics, mesoscopic nonequilibrium thermodynamics, fluctuation theory, information theory, and modeling the coupled biochemical systems in thermodynamic analysis. This new addition also comes with more examples and practice problems. Informs and updates on all the latest developments in the field Contributions from leading authorities and industry experts A useful text for seniors and graduate students from diverse engineering and science programs to analyze some nonequilibrium, coupled, evolutionary, stochastic, and dissipative processes Highlights fundamentals of equilibrium thermodynamics, transport processes and chemical reactions Expands the theory of nonequilibrium thermodynamics and its use in coupled transport processes and chemical reactions in physical, chemical, and biological systems Presents a unified analysis for transport and rate processes in various time and space scales Discusses stochastic approaches in thermodynamic analysis including fluctuation and information theories Has 198 fully solved examples and 287 practice problems An Instructor Resource containing the Solution Manual can be obtained from the author: [email protected]

This book gives the first detailed coherent treatment of a relatively young branch of statistical physics - nonlinear nonequilibrium and fluctuation-dissipative thermo dynamics. This area of research has taken shape fairly recently: its development began in 1959. The earlier theory -linear nonequilibrium thermodynamics - is in principle a simple special case of the new theory. Despite the fact that the title of this book includes the word "nonlinear", it also covers the results of linear nonequilibrium thermodynamics. The presentation of the linear and nonlinear theories is done within a common theoretical framework that is not subject to the linearity condition. The author hopes that the reader will perceive the intrinsic unity of this discipline, and the uniformity and generality of its constituent parts. This theory has a wide variety of applications in various domains of physics and physical chemistry, enabling one to calculate thermal fluctuations in various nonlinear systems. The book is divided into two volumes. Fluctuation-dissipation theorems (or relations) of various types (linear, quadratic and cubic, classical and quantum) are considered in the first volume. Here one encounters the Markov and non-Markov fluctuation-dissipation theorems (FDTs), theorems of the first, second and third kinds. Nonlinear FDTs are less well known than their linear counterparts.

This two-volume work gives the first detailed coherent treatment of a relatively young branch of statistical physics - nonlinear nonequilibrium and fluctuational dissipative thermodynamics. This area of research has taken shape rather recently: its de~elopment began in 1959. The earlier theory - linear nonequilibrium ther modynamics - is in principle a simple special case of the new theory. Despite the fact that the title of the book includes the word 'nonlinear', it also covers the results of linear nonequilibrium thermodynamics. The presentation of the linear and nonlinear theories is done within a common theoretical framework that is not subject to the linearity condition. The author hopes that the reader will perceive the intrinsic unjty of this dis cipline, the uniformity and generality of its constituent parts. This theory has a wide variety of applications in various domains of physics and physical chemistry, enabling one to calculate thermal fluctuations in various nonlinear systems. The book is divided into two volumes. Fluctuation-dissipation theorems (or relations) of various types (linear, quadratic and cubic, classical and quantum) are considered in the first volume. There one encounters the Markov and non-Markov fluctuation-dissipation theorems (FDTs), theorems of the first, second and third kinds. Nonlinear FDTs are less known than their linear counterparts. The present second volume of the book deals with the advanced theory. It consists of four chapters. The connection and interdependence of the material in the various chapters of both volumes are illustrated in the accompanying diagram.

This book addresses research challenges in the rapidly developing area of nonequilibrium thermodynamics and fluctuation kinetics. This cross-disciplinary field comprises various topics, ranging from fundamental problems of nonequilibrium statistical mechanics and thermodynamics to multiple applications in plasma, fluid mechanics, nonlinear science, systems of dissipative particles, and high-Q resonators. The purpose of this book is to bring together world-leading experts in the above fields to initiate a cross-fertilization among these active research areas. The book is dedicated to and honours the memory of Professor Slava Belyi who passed away unexpectedly on May 20, 2020. He was pioneering the theory of nonequilibrium fluctuations, in particular the application of the Callen-Welton fluctuation-dissipation theorem to nonequilibrium systems and its generalization. This and related problems also feature in the book.

Discover the many facets of non-equilibrium thermodynamics. The first part of this book describes the current thermodynamic formalism recognized as the classical theory. The second part focuses on different approaches. Throughout the presentation, the emphasis is on problem-solving applications. To help build your understanding, some problems have been analyzed using several formalisms to underscore their differences and their similarities.

The structure of the theory ofthermodynamics has changed enormously since its inception in the middle of the nineteenth century. Shortly after Thomson and Clausius enunciated their versions of the Second Law, Clausius, Maxwell, and Boltzmann began actively pursuing the molecular basis of thermo dynamics, work that culminated in the Boltzmann equation and the theory of transport processes in dilute gases. Much later, Onsager undertook the elucidation of the symmetry oftransport coefficients and, thereby, established himself as the father of the theory of nonequilibrium thermodynamics. Com bining the statistical ideas of Gibbs and Langevin with the phenomenological transport equations, Onsager and others went on to develop a consistent statistical theory of irreversible processes. The power of that theory is in its ability to relate measurable quantities, such as transport coefficients and thermodynamic derivatives, to the results of experimental measurements. As powerful as that theory is, it is linear and limited in validity to a neighborhood of equilibrium. In recent years it has been possible to extend the statistical theory of nonequilibrium processes to include nonlinear effects. The modern theory, as expounded in this book, is applicable to a wide variety of systems both close to and far from equilibrium. The theory is based on the notion of elementary molecular processes, which manifest themselves as random changes in the extensive variables characterizing a system. The theory has a hierarchical character and, thus, can be applied at various levels of molecular detail.

The importance of thermodynamics, particularly its Second Principle, to all branches of science in which systems with very large numbers of particles are involved cannot be overstated. This book offers a panoramic view of non-equilibrium thermodynamics. Perhaps the two most attractive aspects of thermodynamic equilibrium are its stability and its independence from the specifics of the particular system involved. Does an equivalent exist for non-equilibrium thermodynamics? Many researchers have tried to describe such stability in the same way that the Second Principle describes the stability of thermodynamic equilibrium - and failed. Most of them invoked either entropy, or its production rate, or some modified version of it. In their efforts, however, those researchers have found a lot of useful stability criteria for far-from-equilibrium states. These criteria usually take the form of variational principles, in terms of the minimization or maximization of some quantity. The aim of this book is to discuss these variational principles by highlighting the role of macroscopic quantities. This book is aimed at a wider audience than those most often exposed to the criteria described, i.e., undergraduates in STEM, as well as the usual interested and invested professionals.

The purpose of this book is to encourage the use of non-equilibrium thermodynamics to describe transport in complex, heterogeneous media. With large coupling effects between the transport of heat, mass, charge and chemical reactions at surfaces, it is important to know how one should properly integrate across systems where different phases are in contact. No other book gives a prescription of how to set up flux equations for transports across heterogeneous systems.The authors apply the thermodynamic description in terms of excess densities, developed by Gibbs for equilibrium, to non-equilibrium systems. The treatment is restricted to transport into and through the surface. Using local equilibrium together with the balance equations for the surface, expressions for the excess entropy production of the surface and of the contact line are derived. Many examples are given to illustrate how the theory can be applied to coupled transport of mass, heat, charge and chemical reactions; in phase transitions, at electrode surfaces and in fuel cells. Molecular simulations and analytical studies are used to add insight.