Thermodynamics and Introductory Statistical Mechanics / Edition 1

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Overview

"Thermodynamics is concerned with the macroscopic properties of matter. Statistical mechanics, on the other hand, relates and interprets the properties of a macroscopic system in terms of its microscopic units. Thermodynamics and Introductory Statistical Mechanics covers the necessary mathematical tools and computational techniques for understanding both, first providing a separate overview of each and then illustrating and exploring the connections between the two." Subtleties and conceptual difficulties are addressed head-on, while ten problem sets and solutions reflect and illuminate the content covered. For advanced undergraduate and graduate students as well as professionals, Thermodynamics and Introductory Statistical Mechanics provides an introduction and review that is both concise and comprehensive.
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Editorial Reviews

From the Publisher
"…a thorough treatment of thermodynamics at a level somewhat higher level than that in a typical undergraduate physical chemistry work." (CHOICE, February 2005)
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Product Details

  • ISBN-13: 9780471474593
  • Publisher: Wiley, John & Sons, Incorporated
  • Publication date: 9/28/2004
  • Edition description: New Edition
  • Edition number: 1
  • Pages: 209
  • Product dimensions: 6.40 (w) x 9.45 (h) x 0.84 (d)

Meet the Author

BRUNO LINDER is Professor Emeritus of Chemistry at Florida State University. Founder of the Southeastern Theoretical Chemistry Association, he was formerly a John Simon Guggenheim Fellow at the Theoretical Physics Institute of the University of Amsterdam.
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Table of Contents

1 Introductory remarks 1
Pt. I Thermodynamics 5
2 Basic concepts and definitions 7
3 The laws of thermodynamics I 14
4 The laws of thermodynamics II 32
5 Useful function : the free energy functions 52
6 The third law of thermodynamics 65
7 General conditions for equilibrium and stability 70
8 Application of thermodynamics to gases, liquids, and solids 83
9 Phase and chemical equilibria 94
10 Solutions - nonelectrolytes 102
11 Processes involving work other than pressure-volume work 114
12 Phase transitions and critical phenomena 119
Pt. II Introductory statistical mechanics 127
13 Principles of statistical mechanics 129
14 Thermodynamic connection 143
15 Molecular partition function 150
16 Statistical mechanical applications 158
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First Chapter

Thermodynamics and Introductory Statistical Mechanics


By Bruno Linder

John Wiley & Sons

Copyright © 2004 John Wiley & Sons, Inc.
All right reserved.

ISBN: 0-471-47459-2


Chapter One

INTRODUCTORY REMARKS

Thermodynamics, as developed in this course, deals with the macroscopic properties of matter or, more precisely, with processes on a macroscopic level. Mechanics (especially quantum mechanics) is concerned with molecular behavior. In principle, and in some limited cases, the molecular properties can be calculated directly from quantum mechanics. In the majority of cases, however, such properties are obtained from experimental studies such as spectral behavior or other devices, but the interpretation is based on quantum mechanics. Statistical mechanics is the branch of science that interconnects these seemingly unrelated disciplines: statistical mechanics interprets and, as far as possible, predicts the macroscopic properties in terms of the microscopic constituents.

For the purposes of the course presented in this book, thermodynamics and statistical mechanics are developed as separate disciplines. Only after the introduction of the fundamentals of statistical mechanics will the connection be made between statistical mechanics and thermodynamics. As noted, the laws of (macroscopic) thermodynamics deal with processes not structures. Therefore, no theory of matter is contained in theselaws. Traditional thermodynamics is based on common everyday experiences. For example, if two objects are brought in contact with each other, and one feels hotter than the other, the hotter object will cool while the colder one will heat up. Because thermodynamics is based on the common experience of macroscopic observations it has a generality unequaled in science. "Classical Thermodynamics," Einstein remarked, "... is the only physical theory of universal content ... which ... will never be overthrown" (Schilpp, 1949).

1.1 SCOPE AND OBJECTIVES

Class make-up varies greatly. Some students take this course as part of one-year course, in preparation for a comprehensive or preliminary exam, required for a Master's or Ph.D. degree. Others sign up because they heard it was a "snap" course. Still others take it because they think, or their major professor thinks, that it may help them in their research. A course designed to satisfy all students' aspirations is difficult, if not impossible. A suitable compromise is one, which provides a reasonable balance between fundamentals and applications, which is the aim of this book.

1.2 LEVEL OF COURSE

Most students are likely to have had previous exposure to thermodynamics in some undergraduate course, such as physical chemistry, physics, or engineering. The present course is intended to be more advanced from the standpoints of both principles and applications. The emphasis is on the logical structure and generality of the subject. All topics of interest cannot possibly be covered in a semester course; therefore, topics that are likely to have been adequately treated in undergraduate courses are skipped.

1.3 COURSE OUTLINE

The idea is to proceed from the general to the particular. The following outline suggests itself.

Part I: Thermodynamics

A. Fundamentals

1. Basic concepts and definitions

2. The laws of thermodynamics

2.1 Traditional approach 2.2 Axiomatic approach

3. General conditions for equilibrium and stability

B. Applications

1. Thermodynamics of (Real) gases, condensed systems

2. Chemical equilibrium

2.1 Homogeneous and heterogeneous systems 2.2 Chemical reactions

3. Phase transitions and critical phenomena

4. Thermodynamics of one- and two-dimensional systems

4.1 Film enlarging 4.2 Rubber stretching

Part II: Introductory Statistical Mechanics

A. Fundamentals

1. Preliminary discussion 2. Maxwell-Boltzmann, Corrected Maxwell-Boltzmann Statistics

3. Partition Functions

4. Thermodynamic connection

B. Applications 1. Ideal gases

2. Ideal solids 3. Equilibrium constant

4. The bases of chemical thermodynamics

In addition, mathematical techniques are introduced at appropriate times, highlighting such use as:

1) Exact and inexact differentials (Section 3.3)

2) Partial Derivatives (Section 3.6)

3) Pfaffian Differential Forms (Section 4.6)

4) Legendre Transformation (Section 5.1)

5) Euler's Theorem (Section 5.7)

6) Combinatory Analysis (Section 13.5)

1.4 BOOKS

Because of the universality of the subject, books on Thermodynamics run into the thousands. Not all are textbooks, and not all are aimed at a particular discipline, such as chemistry, physics, or engineering. Most elementary chemical texts rely heavily on applications but treat the fundamentals lightly. Real systems (real gases, condensed systems, etc) are often not treated in any detail. Some books are strong on fundamentals but ignore applications. Other books are authoritative but highly opinionated, pressing for a particular point of view.

Two chemical thermodynamics books, which discuss the fundamentals in depth, are listed below.

1. J. de Heer, Phenomenological Thermodynamics, Prentice-Hall, 1986.

2. J. G. Kirkwood and I. Oppenheim, Chemical Thermodynamics, McGraw-Hill, 1961.

Other books that may provide additional insight into various topics are listed in the Annotated Bibliography on page....

(Continues...)



Excerpted from Thermodynamics and Introductory Statistical Mechanics by Bruno Linder Copyright © 2004 by John Wiley & Sons, Inc. . Excerpted by permission.
All rights reserved. No part of this excerpt may be reproduced or reprinted without permission in writing from the publisher.
Excerpts are provided by Dial-A-Book Inc. solely for the personal use of visitors to this web site.

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