Preface to the Fourth Edition

Preface to the Fourth Edition This book introduces the theory of nonequilibrium thermodynamics and its use in simultaneously occurring transport processes and chemical reactions of physical, chemical, and biological systems. Thus, it provides a unified approach in describing natural phenomena and should be used in senior and graduate education in chemical, mechanical, system, biomedical, tissue, biological, and biological systems engineering, as well as physical, biophysical, biological, chemical, and biochemical sciences. This edition updates and revises most of the chapters of the third edition. It incorporates some of the new descriptions of the nonequilibrium thermodynamics of physical, chemical, and biological systems. In the vicinity of equilibrium, linear nonequilibrium thermodynamics provides a linear relation between forces and flows (fluxes). The laws of conventional thermodynamics involve averages of the physical properties of macroscopic systems but ignore their fluctuations. The second law for irreversible processes states that the average entropy produced internally in an irreversible process has to be positive. Introduction of the concept of internal degrees of freedom allows for the description of a wider class of irreversible processes and scales such as biomolecules. For such systems, the probabilistic approach formulates the first law and entropy valid along single fluctuation trajectories. One of the main advantages of the probabilistic approach compared to the macroscopic phenomenological theory is that a thermodynamically consistent kinetics valid beyond the linear region can be imposed. The collection of the degrees of freedom makes up the state. The change of the state, either due to the driving force or due to the fluctuations, leads to a trajectory of the system. The thermodynamic quantities like work and heat follow a distribution defined along the trajectory. The Crooks fluctuation theorem compares probability distributions for the work spent in the original process with the time-reversed one. This theorem describes how the probability of violations of the second law of thermodynamics becomes exponentially small as time or the system size increases and refines the laws of thermodynamics by taking into account the fluctuations. Every chapter contains example problems and practice problems to be solved. Chapter 1 was expanded in its description of basic elements of classical thermodynamics, such as irreversibility, equilibrium state, thermodynamic principles, kinetic theory, the Gibbs equation, and the phase equilibria. Chapter 2 briefly introduces transport processes, chemical reactions, thermodynamic branch, and some well-known examples of coupled phenomena. It emphasizes the unifying power of thermodynamics in describing the transport and rate processes. Chapter 3 discusses the general balance equations of mass, momentum, energy, and entropy, which are used in the Gibbs equation to derive the local rate of entropy production based on local equilibrium in terms of fluxes and forces. Chapter 4 focuses on thermodynamic analysis of transport processes, power-generating systems, and chemical reactions. It also introduces the concept of exergy, the equipartition principle, and pinch analysis with various example problems to underline the contribution of thermodynamic analysis towards creating optimum designs and assessing the performance of existing designs. Chapter 5 introduces the thermodynamic optimum approach in the design and optimization of various processes. Here, the concept of thermoeconomics is emphasized. Chapter 6 summarizes the diffusion in nonelectrolyte and electrolyte systems and explores some related applications. Chapter 7 describes coupled heat and mass transfer and the level of coupling without chemical reaction. Chapter 8 briefly summarizes chemical reactions and coupled phenomena. Chapter 9 describes coupled transport processes and chemical reactions; it focuses on the dynamic balance equations consisting of coupled flows as well as the coupling between

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chemical reactions and the flows of heat and mass. Chapter 10 briefly describes the nonequilibrium formulations of the transport through membranes. Chapter 11 introduces various applications of thermodynamics in biological systems as well as energy conversion and coupling phenomena in bioenergetics. It also discusses the facilitated and active transport in biological systems. Based on the nonequilibrium thermodynamic approach, the stability aspects of various transport processes and chemical reactions are covered in Chapter 12. Chapter 13 briefly describes some organized structures maintained with the outside supply of energy and matter. It also discusses self-organized criticality and ecosystems and their implication with entropy production and constructal law. Some biological systems are good examples of maintaining dissipative organized structures. Chapter 14 summarizes some of the other thermodynamic approaches, such as extended nonequilibrium thermodynamics, mesoscopic thermodynamics, and quantum thermodynamics. Chapter 15 introduces statistical thermodynamics, stochastic thermodynamics approach, fluctuation theorems, and information theory. This chapter emphasizes various applications of nonequilibrium thermodynamics in design of small systems, process intensification, and information processing. The probabilistic approach reached the broader appeal due to advances in experimental techniques for tracking and manipulating of single particles and molecules. Future research in the field may focus on specific applications, most likely for molecular motors, biomolecular networks, and information processing. The appendix supplies some data needed in the example and practice problems. All through the editions, the work of many people who contributed to both the theory and applications of thermodynamics for transport and rate processes in physical, chemical, and biological systems has been visited and revisited. We acknowledge and greatly appreciate the contributions of all these people. We are also thankful to colleagues, students, and reviewers who have contributed with their comments and suggestions over the past 20 years of evolution of this edition. Ya¸sar Demirel and Vincent Gerbaud, April 2018