THERMODYNAMICS AND INTRODUCTORY STATISTICAL MECHANICS

This book is based on a set of lecture notes for a one-semester first-year
chemistry graduate course in Thermodynamics and Introductory Statistical
Mechanics, which I taught at Florida State University in the Fall of 2001 and
2002 and at various times in prior years. Years ago, when the University was
on the quarter system, one quarter was devoted to Thermodynamics, one
quarter to Introductory Statistical Mechanics, and one quarter to Advanced
Statistical Mechanics. In the present semester system, roughly two-thirds of
the first-semester course is devoted to Thermodynamics and one-third to
Introductory Statistical Mechanics. Advanced Statistical Mechanics is
taught in the second semester.
Thermodynamics is concerned with the macroscopic behavior of matter,
or rather with processes on a macroscopic level. Statistical Mechanics
relates and interprets the properties of a macroscopic system in terms of
its microscopic units. In this book, Thermodynamics was developed strictly
from a macroscopic point of view without recourse to Statistical-Mechanical
interpretation, except for some passing references to fluctuations in the discussion of critical phenomena. Both Thermodynamics and Statistical
Mechanics entail abstract ideas, and, in my opinion, it is best not to introduce them simultaneously. Accordingly, the first 12 chapters (Part I) deal
exclusively with Thermodynamics; Statistical Mechanics is only then introduced.
Thermodynamics, unlike some other advanced subjects in Physical
Chemistry, does not require complicated mathematics, and for this reason
the subject is often thought to be ‘‘easy.’’ But if it is easy, it is deceptively
easy. There are subtleties and conceptual difficulties, often ignored in
elementary treatments, which tend to obscure the logical consistency of
the subject. In this book, conceptual difficulties are not ‘‘swept under the
rug’’ but brought to the fore and discussed critically. Both traditional and
axiomatic approaches are developed, and reasons are given for presenting
alternative points of view. The emphasis is on the logical structure and
generality of the approach, but several chapters on applications are included.
The aim of the book is to achieve a balance between fundamentals and
applications.
In the last four chapters of the book, which are devoted to Statistical
Mechanics, not much more can be hoped to be accomplished than to cover,
from an elementary point of view, the basics. Nonetheless, for some students, especially those who are not physical-chemistry majors, it is essential
that simple statistical-mechanical applications be included, thus acquainting
students with some working knowledge of the practical aspects of the subject. Among the applied statistical-mechanical topics are numerical calculations of entropy and other thermodynamic functions, determination of
equilibrium constants of gases, and determination of heat capacity of solids.
Although all fundamental equations are developed from first principle,
my treatment is more advanced than what some students are likely to
have been exposed to in elementary discussions of thermodynamics. This
book is designed as a one-semester course, useful both to students who
plan to take more advanced courses in statistical mechanics and students
who study this as a terminal course.
An essential feature of this book is the periodic assignment of homework
problems, reflecting more or less the content of the topics covered. Ten
typical problem sets are included in Appendix I and their solutions in
Appendix II.
I am grateful to Kea Herron for her help in formatting the manuscript, and
to members of the Wiley Editorial staff, especially Amy Romano and
Christine Punzo, for their advice, patience, and encouragement