Experimental Thermodynamics: Non-equilibrium Thermodynamics With Applications (10) - Hardcover

Hardcover

ISBN 10: 1782620249 ISBN 13: 9781782620242

Verlag: Royal Society of Chemistry, 2015

Inhaltsangabe

The book covers recent developments in the theory of non-equilibrium thermodynamics and its applications. Four chapters are devoted to the foundations; an overview chapter is followed by recent results addressing the underlying principles of the theory. The applications are concerned with bulk systems, with heterogeneous systems where interfaces are central and with process units in industry where entropy production minimization is useful. There is also a collection of chapters under the heading mesoscopic non-equilibrium thermodynamics, giving in the end an overview of extensions of the theory into the non-linear regime. Bringing the literature up to date and detailing new approaches in this area of research, it is aimed at a predominantly, but not exclusively, academic audience of practitioners of thermodynamics and energy conversion.

Über diesen Titel

Von der hinteren Coverseite

The book covers recent developments in the theory of non-equilibrium thermodynamics and its applications. Four chapters are devoted to the foundations; an overview chapter is followed by recent results addressing the underlying principles of the theory. The applications are concerned with bulk systems, with heterogeneous systems where interfaces are central and with process units in industry where entropy production minimization is useful. There is also a collection of chapters under the heading mesoscopic non-equilibrium thermodynamics, giving in the end an overview of extensions of the theory into the non-linear regime. Bringing the literature up to date and detailing new approaches in this area of research, it is aimed at a predominantly, but not exclusively, academic audience of practitioners of thermodynamics and energy conversion.

Auszug. © Genehmigter Nachdruck. Alle Rechte vorbehalten.

Experimental Thermodynamics Volume X

Non-equilibrium Thermodynamics with Applications

By Dick Bedeaux, Signe Kjelstrup, Jan V. Sengers

The Royal Society of Chemistry

Copyright © 2016 International Union of Pure and Applied Chemistry
All rights reserved.

ISBN: 978-1-78262-024-2

Contents

Chapter 1 Basis and Scope Dick Bedeaux, Signe Kjelstrup and Jan V. Sengers, 1, 
Chapter 2 Fluctuating Hydrodynamics and Fluctuation–Dissipation Theorem in Equilibrium Systems José M. Ortiz de Zárate and Jan V. Sengers, 21, 
Chapter 3 Thermal Fluctuations in Non-equilibrium Steady States Jan V. Sengers, José M. Ortiz de Zárate and Theodore R. Kirkpatrick, 39, 
Chapter 4 Local Equilibrium in Non-equilibrium Thermodynamics Signe Kjelstrup and Dick Bedeaux, 61, 
Chapter 5 Diffusion in Liquids: Experiments, Molecular Dynamics, and Engineering Models Christine Peters, Ludger Wolff, Thijs J. H. Vlugt and André Bardow, 78, 
Chapter 6 Non-equilibrium Molecular Dynamics Fernando Bresme, Anders Lervik and Jeff Armstrong, 105, 
Chapter 7 Non-equilibrium Molecular Self-assembly Ger Koper and Wouter Hendriksen, 134, 
Chapter 8 Non-equilibrium Thermodynamics for Evaporation and Condensation Dick Bedeaux and Signe Kjelstrup, 154, 
Chapter 9 Non-equilibrium Thermodynamics Applied to Adsorption Jean-Marc Simon, 178, 
Chapter 10 Non-equilibrium Thermodynamics of Aqueous Solution–Crystal Interfaces F. Elif Genceli Güner, 204, 
Chapter 11 Membrane Transport Juan P. G. Villaluenga and V. María Barragán, 221, 
Chapter 12 Electrochemical Energy Conversion Signe Kjelstrup and Dick Bedeaux, 244, 
Chapter 13 Entropy Production Minimization with Optimal Control Theory Øivind Wilhelmsen, Eivind Johannessen and Signe Kjelstrup, 271, 
Chapter 14 Mesoscopic Non-equilibrium Thermodynamics Ignacio Pagonabarraga and J. Miguel Rubí, 290, 
Chapter 15 Non-equilibrium Thermodynamics for Nucleation Kinetics David Reguera and J. Miguel Rubí, 314, 
Chapter 16 Mesoscopic Non-equilibrium Thermodynamics in Biology Anders Lervik and J. Miguel Rubí, 338, 
Chapter 17 Dynamics of Complex Fluid–Fluid Interfaces Leonard M. C. Sagis, 356, 
Subject Index, 382, 

CHAPTER 1

Basis and Scope

DICK BEDEAUX, SIGNE KJELSTRUP AND JAN V. SENGERS

1.1 Short Historic Overview

Non-equilibrium thermodynamics describes transport processes in systems that are not in global equilibrium. The now classical field, which we briefly review here, resulted from efforts of many scientists to find a more explicit formulation of the second law of thermodynamics. This had started already in 1856 with Thomson's studies of thermoelectricity. Onsager is, however, counted as the founder of the field with his papers published in 1931, because these put earlier research by Thomson, Boltzmann, Nernst, Duhem, Jauman and Einstein into a systematic framework. Onsager was given the Nobel prize in chemistry in 1968 for this work.

The second law is reformulated in terms of the entropy production, σ. In Onsager's formulation, the entropy production is given by the product sum of so-called conjugate fluxes, Ji, and forces, Xi, in the system. The second law then becomes

[MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (1.1)

The entropy production is per unit of volume. Each flux is taken to be a linear combination of all forces,

[MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (1.2)

Onsager showed that the reciprocal relations

Lji = Lij, (1.3)

apply. They now bear his name. In order to use the theory, one first has to identify a complete set of extensive independent variables, αi, like, for instance, the internal energy and the mass densities per unit of volume. The resulting conjugate fluxes and forces are Ji = dαi/dt and Xi = [partial derivative]S/[partial derivative]αi respectively. Here t is the time and S is the entropy of the system. The three equations above contain then all information on the non-equilibrium behaviour of the system. For cases where dαi/dt is equal to minus the divergence of a flux density, this flux density replaces Ji and the gradient of [partial derivative]S/[partial derivative]αi. For surfaces and contact lines the densities are per unit of surface area or length, respectively.

Following Onsager, a consistent theory of non-equilibrium processes in continuous systems was set up in the forties by Meixner and Prigogine. They calculated the entropy production for a number of physical problems. Prigogine received the Nobel prize for his work on dissipative structures in systems that are out of equilibrium in 1977, and Mitchell the year after for his application of the (driving) force concept to transport processes in biology.

The most general description of classical non-equilibrium thermo-dynamics is still the 1962 monograph of de Groot and Mazur reprinted in 1985. Haase's book, also reprinted, contains many results for electro-chemical systems and systems with temperature gradients. Katchalsky and Curran developed the theory for biophysical systems. Their analysis was carried further by Caplan and Essig. Førland and co-workers gave various applications in electrochemistry and biology, and they treated frost heave. Their book presented the theory in a way suitable for chemists. Newer books on equilibrium thermodynamics or statistical thermodynamics often include chapters on non-equilibrium thermodynamics, see, e.g., Carey. Kondepudi and Prigogine presented a textbook which integrated texts on basic equilibrium and non-equilibrium thermodynamics. Jou et al. published a book on extended non-equilibrium thermodynamics. Öttinger gave a non-equilibrium description which also extends to the nonlinear regime.

Non-equilibrium thermodynamics is constantly being applied in new contexts. Fitts gave an early presentation of viscous phenomena. In 1994 Kuiken wrote the most general treatment of multicomponent diffusion and rheology of colloidal systems. Rubí and co-workers used internal (molecular) degrees of freedom to explore the development towards equilibrium within a system. This allows us to deal with chemical reactions within the framework of non-equilibrium thermodynamics. Bedeaux and Mazur extended the theory to quantum mechanical systems. Kjelstrup and Bedeaux wrote a book dealing with transport into and across surfaces, presenting non-equilibrium thermodynamics for heterogeneous systems. Doi used the variational principle of Onsager at constant temperature to derive equations of motion for colloids.

A fundamental assumption in non-equilibrium thermodynamics is that of local equilibrium. In recent years the nature and conditions of local equilibrium have been investigated with computer simulations. Kjelstrup et al. pointed out that there can be local equilibrium in volume elements exposed to large fields, with as few as 10 particles. We have reasons to expect that the same holds true in surfaces and in systems at the mesoscale (see Chapter 4). Non-equilibrium thermodynamics has also been extended to include thermal non-equilibrium fluctuations as reviewed by Ortiz de Zárate and Sengers. Local equilibrium is no longer valid for hydrodynamic fluctuations, however. Correlations of the densities and temperature are much larger and longer-ranged in a system exposed,...

Details zur Ausgabe

• Verlag: Royal Society of Chemistry
• Erscheinungsdatum: 2015
• Sprache: Englisch
• ISBN 10: 1782620249
• ISBN 13: 9781782620242
• Einband: Gebundene Ausgabe
• Anzahl der Seiten: 405
• Herausgeber: Bedeaux Dick, Kjelstrup Signe, Sengers Jan V.
• Kontakt zum Hersteller: Nicht verfügbar
• Verantwortliche Person: preigu; mail@preigu.de; ; Lengericher Landstr. 19; Osnabrück; 49078; Deutschland