This comprehensive text, suitable for introductory as well as advanced courses on thermodynamics, has been widely used by chemists, physicists, engineers and geologists. Fully revised and expanded, this new edition includes the following updates and features:
- Includes a completely new chapter on Principles of Statistical Thermodynamics.
- Presents new material on solar and wind energy flows and energy flows of interest to engineering.
- Covers new material on self-organization in non-equilibrium systems and the thermodynamics of small systems.
- Highlights a wide range of applications relevant to students across physical sciences and engineering courses.
- Introduces students to computational methods using updated Mathematica codes.
- Includes problem sets to help the reader understand and apply the principles introduced throughout the text.
- Solutions to exercises and supplementary lecture material provided online at is an essential resource for undergraduate and graduate students taking a course in thermodynamics.
Preface to the First Edition
Since half a century ago, our view of Nature has changed drastically. Classical science emphasized equilibrium and stability. Now we see fluctuations, instability, evolutionary processes on all levels from chemistry and biology to cosmology. Everywhere we observe irreversible processes in which time symmetry is broken. The distinction between reversible and irreversible processes was first introduced in thermodynamics through the concept of 'entropy', the arrow of time, as Arthur Eddington called it. Therefore our new view of Nature leads to an increased interest in thermodynamics. Unfortunately, most introductory texts are limited to the study of equilibrium states, restricting thermodynamics to idealized, infinitely slow reversible processes. The student does not see the relationship between irreversible processes that naturally occur, such as chemical reactions and heat conduction, and the rate of increase of entropy. In this text, we present a modern formulation of thermodynamics in which the relation between the rate of increase of entropy and irreversible processes is made clear from the very outset. Equilibrium remains an interesting field of inquiry but in the present state of science, it appears essential to include irreversible processes as well.
It is the aim of this book to give a readable introduction to present-day thermodynamics, starting with its historical roots as associated with heat engines but including also the thermodynamic description of far-from-equilibrium situations. As is well known today, far-from-equilibrium situations lead to new space-time structures. For this reason the restriction to equilibrium situations hides, in our opinion, some essential features of the behavior of matter and energy. An example is the role of fluctuations. The atomic structure of matter leads to fluctuations. However, at equilibrium or near equilibrium, these fluctuations are inconsequential.
Indeed a characteristic feature of equilibrium thermodynamics is the existence of extremum principles. For isolated systems entropy increases and is therefore maximum at equilibrium. In other situations (such as constant temperature) there exist functions called thermodynamic potentials which are also extrema (that is maximum or minimum) at equilibrium. This has important consequences. A fluctuation that leads to a temporal deviation from equilibrium is followed by a response that brings back the system to the extremum of the thermodynamic potential. The equilibrium world is also a stable world. This is no longer so in far-from-equilibrium situations. Here fluctuations may be amplified by irreversible dissipative processes and lead to new space-time structures which one of us (I. Prigogine) has called 'dissipative structures' to distinguish them from 'equilibrium' structures such as crystals. Therefore distance from equilibrium becomes a parameter somewhat similar to temperature. When we lower the temperature, we go from the gaseous state to a liquid and then a solid. As we shall see, here the variety is even greater. Take the example of chemical reactions. Increasing the distance from equilibrium we may obtain in succession oscillatory reactions, new spatial periodic structures and chaotic situations in which the time behavior becomes so irregular that initially close trajectories diverge exponentially.
One aspect is common to all these nonequilibrium situations, the appearance of long-range coherence. Macroscopically distinct parts become correlated. This is in contrast to equilibrium situations where the range of correlations is determined by short-range intermolecular forces. As a result, situations that are impossible to realize at equilibrium become possible in far-from-equilibrium situations. This leads to important applications in a variety of fields. We can produce new materials in nonequi