Schieber_and_Depablo_Chapter_1

Schieber_and_Depablo_Chapter_1 - Chemical, Biological and...

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Unformatted text preview: Chemical, Biological and Materials Engineering Thermodynamics by Prof. Jay D. Schieber Department of Chemical Engineering Illinois Institute of Technology 10 W. 33rd Street Chicago, Illinois 60616 schieber@iit.edu and Prof. Juan J. de Pablo Department of Chemical Engineering University of WisconsinMadison 1415 Johnson Drive Madison, Wisconsin 53706 depablo@engr.wisc.edu All rights reserved c circlecopyrt 1997-2005 ii Contents Table of Contents viii 1 Introduction 1 1.1 Relevant Questions for Thermodynamics . . . . . . . . . . . . . . . . 3 1.2 Work and Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 1.3 Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2 The Postulates of Thermodynamics 9 2.1 The Postulational Approach . . . . . . . . . . . . . . . . . . . . . . . 10 2.2 The First Law: Energy Conservation . . . . . . . . . . . . . . . . . . 11 2.3 Definition of Heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 2.4 Equilibrium States . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 2.5 Entropy, the Second Law, and the Fundamental Relation . . . . . . 19 2.6 Definitions of T , P , and . . . . . . . . . . . . . . . . . . . . . . . . 27 2.7 Temperature Differences and Heat Flow . . . . . . . . . . . . . . . . 39 2.8 Pressure Differences and Volume Changes . . . . . . . . . . . . . . . 42 2.9 Thermodynamics in One Dimension . . . . . . . . . . . . . . . . . . 43 2.10 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 2.11 Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 3 Generalized Thermodynamic Potentials 61 3.1 Legendre Transforms . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3.2 Extrema Principles for the Potentials . . . . . . . . . . . . . . . . . . 69 3.3 Maxwell Relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 3.4 The Thermodynamic Square . . . . . . . . . . . . . . . . . . . . . . 80 3.5 Second-Order Coefficients . . . . . . . . . . . . . . . . . . . . . . . . 82 3.6 Thermodynamic Manipulations . . . . . . . . . . . . . . . . . . . . . 91 3.7 One- and Two-Dimensional Systems . . . . . . . . . . . . . . . . . . 96 3.7.1 Nonideal Rubber Band . . . . . . . . . . . . . . . . . . . . . 97 iii iv CONTENTS 3.7.2 Unzipping DNA . . . . . . . . . . . . . . . . . . . . . . . . . 99 3.7.3 Langmuir Adsorption . . . . . . . . . . . . . . . . . . . . . . 104 3.8 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 3.9 Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114 4 First Applications of Thermodynamics 127 4.1 Stability Criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128 4.1.1 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128 4.1.2 Internal Energy . . . . . . . . . . . . . . . . . . . . . . . . . . 132 4.1.3 Generalized Potentials . . . . . . . . . . . . . . . . . . . . . . 133 4.2 Single Component Vapor-Liquid Equilibrium . . . . . . . . . . . . . 1344....
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This note was uploaded on 01/31/2010 for the course CHEM 2106 taught by Professor Liz during the Spring '08 term at University of Minnesota Crookston.

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Schieber_and_Depablo_Chapter_1 - Chemical, Biological and...

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