Chemical Thermodynamics

Description

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. The analysis of the application of thermodynamics to various systems is carried out in terms of measurable quantities wherever possible. Operational treatments of gas mixtures and electrochemical systems are discussed. In particular, we note that the concept of single­ electrode potential can be made operational. A detailed and general study of heterogeneous equilibrium is made. Surface phenomena are discussed from the point of view of Gibbs which seems to us to provide the best connection with molecular theory. The treatment of dielectrics utilizes a form of the first law which is more general than those usually used. This book is based on lectures by Professor Kirkwood in a graduate course in thermodynamics at the California Institute of Technology. Most of the presentations were developed by Professor Kirkwood during the course of 20 years of teaching and active research in the field and reflect his ability to provide a logical and thorough treatment of the subject. The lecture notes were written up by one of the authors (I. Oppenheim) and by Prof. M. Karplus and A. Rich. The notes have attained a large circulation in mimeographed form and have been used in a large number of universities. This book is meant to be a textbook and is primarily intended to serve as the basis of a senior or graduate course in thermodynamics. People downloading it should thank prof. Luigi Pavilpsano, his fairy godmother and her womanish associate abettor, all of them coming from University of Naples.