Fundamentals of Thermodynamics

Modern inorganic chemistry is a quantitative science. Consequently, when performing experimental work, students must determine the yield of the substances obtained and certain constants such as the boiling points, solubility, and cryohydrate points, and also perform the required calculations with the use of the fundamentals of thermodynamics. 

This chapter deals with the thermodynamics of one-phase systems, and it is understood that the phase is homogeneous and at uniform temperature. The basic structure of thermodynamics provides the tools for the treatment of more complicated systems in later chapters. This book starts with the fundamentals of thermodynamics, but the reader really needs some prior experience with thermodynamics at the level of undergraduate thermodynamics (Silbey and Alberty, 2001). Legendre transforms play an important role in this chapter, and the best single reference on Legendre transforms is Callen (1960, 1985). Other useful references for basic thermodynamics are Tisza (1966), Beattie and Oppenheim (1979), Bailyn (1994), and Greiner, Neise, and Stocker (1995). 

In either case, it becomes important to understand the structure of the databases involved, because the modeling program expects to find the data in a certain format.1 To understand and conform to this format, we must read the program documentation, and in doing this it helps to understand the fundamentals of thermodynamics as given in Chapter 3. In this book we cannot discuss the structure of all databases that may be encountered, but it may be helpful to go through one example in detail. 

Fundamentals of thermodynamics. Applications to phase transitions. Primarily directed at physicists rather than chemists. Reid C E 1990 Chemical Thermodynamics (New York. McGraw-Hill)... 

Since we do not use absolute values of U or U, we cannot use absolute values of any quantities having U in their equations of definition. This may become a point of some regret if you find yourself puzzling over some unfamiliar standard states later on. Somewhat paradoxically, in spite of being possibly the most fundamental of thermodynamic quantities. Internal Energy or even changes in U are little use d in geochemical applications. It is never listed in tables of thermodynamic values. 

The main purpose of this book is to present a rigorous and logical discussion of the fundamentals of thermodynamics and to develop in a coherent fashion the application of the basic principles to a number of systems of interest to chemists. The concept of temperature is carefully discussed, and special emphasis is placed on the appropriate method for the introduction of molecular weights into thermodynamics. A new treatment of the second law of thermodynamics is presented which demonstrates that Caratheodory s principle is a necessary and sufficient consequence of the physical statements of Clausius and Kelvin. 

Kern, R., Weisbrod, A. (1966). Fundamentals of thermodynamics for mineralogists, petrographers and geologists. Trcuisl. from French and foreword K.M. Fedotyev. Moscow, Mir, 277 p. (in Russicui). 

Chapters 4 and 5 are dedicated to the thermodynamic and kinetic fundamentals of RD processes. In Chapter 4, Hasse reviews the fundamentals of thermodynamic modeling of simultaneous phase and reaction equilibria. The author emphasizes the importance of consistency of phase equilibrium models. Thermodynamic consistency provides a sound basis for developing predictive reaction models for RDs, which are valid over a wide range of concentrations. To develop phase equilibrium models, reliable experimental data of phase equilibria in reactive systems have to be available. For successful measurements, suitable experimental techniques are needed, which are briefly summarized in this chapter. Criteria for their selection are also given. 

We also want to mention the contribution to modem thermodynamics made by Muller [10, 16, 29] which lies somewhere between the extended irreversible and rational approaches as indicated in the title of one of corresponding books, coauthored by Ruggeri [30]. Particularly, the reference [ 16] can be recommended even for the very beginners in modern approaches to fundaments of thermodynamics. Although the substantial part of this book deals with the equilibrium theory Mullers reintroduce time into consideration and thermodynamics equations and treat both the equilibrium and (and least some) nonequilibrium processes within a natural, common framework. Their book contains a lot of real application examples and explains and illustrates the common basis of probably all rigorous thermodynamic approaches— the equations of balance of mass, momenrnm, and energy and equations describing the specific behavior of different material bodies (systems) which were traditionally called the equations of state and in modern terms the constitutive equations. 

MUUer, I., MUUer, W.H. Fundamentals of Thermodynamics and Apphcations. Springer, Berlin (2009)... 

In contrast to the large achievements in investigations of kinetic stability, modest attention has been paid to the fundamentals of thermodynamic stability in emulsions, especially regarding the surfactant adsorption layer s influence on the coalescence time. There are several investigations devoted to the surface chemistry of adsorption related to emulsification and demulsification. However, the link between the chemical nature of an adsorption layer, its structure, and the coalescence time is not yet quantified. 

The models of electrolyte solutions and the fundamentals of thermodynamics and statistical thermodynamics are given in Electrolyte Solutions, Thermodynamics. 

This book deals with the thermodynamic properties of seawater as a multicomponent electrolyte solution. Each chapter covers a thermodynamic property of seawater and its constituents. There are chapters on the fundamentals of thermodynamics, the entropy, the volume, the expansibility, and the compressibility. Included in each chapter is a discussion of the methods for calculating or estimating the desired property with tables of values of experimental and calculated properties. There are extensive references to the primary... 

Mtiller, I. Muller, W.H. (2009). Fundamentals of Thermodynamics and Applications, Springer, ISBN 978-3-540-74645-4, Berlin Heidelberg. 

Three types of information will be mentioned only briefly. First, little attempt will be made to relate free energy to other thermodynamic quantities. Many excellent books and articles on thermodynamics, some especially for biochemists, have appeared and may be recommended to those who are not familiar with the fundamentals of thermodynamics. Second, certain subjects such as applications of free energy in carbohydrate metabolism and protein synthesis are discussed in other chapters of this book, and therefore they will not be discussed at length in this chapter. Third, the eventual utilization of energy for work is outside the scope of this treatise and will not be discussed here. 

In the hrst section this handbook provides the fundamentals of thermodynamics and kinetics of reference electrodes, and then liquid junction potentials and salt bridges are discussed, as they are involved in almost ah reference systems. The following chapters present the various reference electrodes and systems as they are presently used. A hnal chapter is devoted to the Kelvin probe and discusses this instmment as a reference electrode for contact potential measurements. 

---