Contents

Cover

Half Title page

Title page

Copyright page

Dedication

Preface

Part I: Introduction

Chapter 1: Basic Calculations

Introduction

Units and Dimensions

Conversion of Units

The Gravitational Constant, gc

Significant Figures and Scientific Notation

References

Chapter 2: Process Variables

Introduction

Temperature

Pressure

Moles and Molecular Weights

Mass and Volume

Viscosity

Heat Capacity

Thermal Conductivity

Reynolds Number

pH

Vapor Pressure

Property Estimation

References

Chapter 3: Gas Laws

Introduction

Boyle’s and Charles’ Laws

The Ideal Gas Law

Standard Conditions

Partial Pressure and Partial Volume

Critical and Reduced Properties

Non-Ideal Gas Behavior

Non-Ideal Mixtures

References

Chapter 4: Conservation Laws

Introduction

The Conservation Laws

The Conservation Law for Momentum

The Conservation Law for Mass

The Conservation Law for Energy

References

Chapter 5: Stoichiometry

Introduction

Combustion of Methane

Excess and Limiting Reactant(s)

Combustion of Ethane

Combustion of Chlorobenzene

References

Chapter 6: The Second Law of Thermodynamics

Introduction

Qualitative Review of the Second Law

Quantitative Review of the Second Law

Ideal Work and Lost Work

The Heat Exchanger Dilemma

Chemical Plant and Process Applications

The Third Law of Thermodynamics

References

Part II: Enthalpy Effects

Chapter 7: Sensible Enthalpy Effects

Introduction

The Gibbs Phase Rule (GPR)

Enthalpy Values

Heat Capacity Values

Predictive Methods for Heat Capacity

References

Chapter 8: Latent Enthalpy Effects

Introduction

The Clausius–Clapeyron (C–C) Equation

Predictive Methods: Normal Boiling Point

Predictive Methods: Other Temperatures

Industrial Applications

References

Chapter 9: Enthalpy of Mixing Effects

Introduction

Enthalpy-Concentration Diagrams

H2SO4–H2O Diagram

NaOH–H2O Diagram

Enthalpy of Mixing at Infinite Dilution

Evaporator Design

References

Chapter 10: Chemical Reaction Enthalpy Effects

Introduction

Standard Enthalpy of Formation

Standard Enthalpy of Reaction

Effect of Temperature on Enthalpy of Reaction

Gross and Net Heating Values

References

Part III: Equilibrium Thermodynamics

Chapter 11: Phase Equilibrium Principles

Introduction

Psychometric Chart

Raoult’s Law

Henry’s Law

Raoult’s Law vs Henry’s Law

Vapor–Solid Equilibrium

Liquid–Solid Equilibrium

References

Chapter 12: Vapor–Liquid Equilibrium Calculations

Introduction

The DePriester Charts

Raoult’s Law Diagrams

Vapor–Liquid Equilibrium in Nonideal Solutions

NRTL Diagrams

Wilson Diagrams

Relative Volatility

References

Chapter 13: Chemical Reaction Equilibrium Principles

Introduction

Standard Free Energy of Formation, ΔGfo

Standard Free Energy of Reaction, ΔG0

The Chemical Reaction Equilibrium Constant, K

Effect of Temperature on ΔG0 and K: Simplified Approach

Effect of Temperature on ΔG0 and K: α, β, and γ Data

Effect of Temperature on ΔG0 and K: a, b, and c Data

Procedures to Determine K

References

Chapter 14: Chemical Reaction Equilibrium Applications

Introduction

Rate vs Equilibrium Considerations

Extent of Reaction

The Reaction Coordinate

Gas Phase Reactions

Equilibrium Conversion Calculations: Simplified Approach

Equilibrium Conversion Calculations: Rigorous Approach

Other Reactions

References

Part IV: Other Topics

Chapter 15: Economic Considerations

Introduction

Capital Costs

Operating Costs

Project Evaluation

Perturbation Studies in Optimization

References

Chapter 16: Open-Ended Problems

Introduction

Developing Students’ Power of Critical Thinking

Creativity

Brainstorming

Inquiring Minds

References

Chapter 17: Other ABET Topics

Introduction

Environmental Management

Health, Safety, and Accident Management

Numerical Methods

Ethics

References

Chapter 18: Fuel Options

Introduction

Fuel Properties

Natural Gas

Liquid Fuels

Coal

Fuel Selection

Stoichiometric Calculations

References

Chapter 19: Exergy: The Concept of “Quality Energy”

Introduction

The Quality of Heat vs Work

Exergy

Quantitative Exergy Analysis

Environmental Impact

Exergy Efficiency

References

Appendix

I. Steam Tables

II. SI Units

III. Conversion Constants

IV. Selected Common Abbreviations

References

Index

Thermodynamics for the Practicing Engineer

Copyright © 2009 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey
Published simultaneously in Canada

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley.com/go/permission.

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Library of Congress Cataloging-in-Publication Data:

Theodore, Louis.
Thermodynamics for the practicing engineer / Louis Theodore.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-470-44468-9 (cloth)
1.  Thermodynamics.   2.  Energy conversion.   I.  Title.
TJ265.T455 2009
621.402′1—dc22

2009016146

Thermodynamics for the Practicing Engineer

A. Edward Newton [1863–1940]

I wish that some one would give a course in how to live. It can’t be taught in the colleges: that’s perfectly obvious, for college professors don’t know any better than the rest of us.

—This Book-Collecting Game

Louis Theodore
Francesco Ricci
Timothy Van Vliet

Agnes Repplier [1858–1950]

That little band of authors who, unknown to the wide careless world, remain from generation to generation the friends of a few fortunate readers.

—Preface to James Howell

André Gide [1869–1951]

A unanimous chorus of praise is not an assurance of survival; authors who please everyone at once are quickly exhausted. I would prefer to think that a hundred years hence people will say we did not properly understand him.

—Pretexts

To my family and friends for their love and support, and to the Manhattan College Chemical Engineering Department for its commitment to greatness—without either of which, my dreams could never be realized (FR)

To George Scott, my high school technology teacher, for introducing me to this wonderful profession (TVV)

To Cecil K. Walkins, a friend who has contributed mightily to basketball and the youth of America (LT)

Plato [427–347 b.c.]

The beginning is the most important part of the work.

—The Republic, Book II

Preface

Sir Walter Scott [1771–1832]

Good wine needs neither bush nor preface to make it welcome.

—Peveril of the Peak

This project was a rather unique undertaking. Rather than prepare a textbook on thermodynamics in the usual and traditional format, the authors considered writing a book that highlighted applications rather then theory. The book would hopefully serve as a training tool for those individuals in academia and industry involved directly, or indirectly, with this topic. Despite the significant reduction in theoretical matter, it addresses both technical and pragmatic problems in this field. While this book can be viewed as a text in thermodynamics, it also stands alone as a self-teaching aid.

The book is divided into four parts:

The first part of the book serves as an introduction to the subject of thermodynamics and reviews such topics as units and dimensions, the conservation laws, gas laws, and the second law of thermodynamics. The second part of the book is concerned with enthalpy effects and reviews such topics as sensible, latent, mixing, and chemical enthalpy effects. The third part of the book examines equilibrium thermodynamics. Topics here include both phase and chemical reaction equilibrium. The fourth section of the book addresses the general all purpose title of other topics. Subjects reviewed here include economics, open-ended problems, environmental concerns, health and safety management, numerical methods, ethics, and exergy analysis.

The authors cannot claim sole authorship to all the problems and material in this book. The present text has evolved from a host of sources, including: notes, homework problems and exam problems prepared by L. Theodore for a required one-semester, three-credit “Chemical Engineering Thermodynamics” undergraduate course offered at Manhattan College; Introduction to Hazardous Waste Incineration, 2nd Edition, J. Santoleri, J. Reynolds, and L. Theodore, John Wiley & Sons; Chemical Reaction Kinetics, L. Theodore, a Theodore Tutorial; and, Introduction to Chemical Engineering Thermodynamics, 3rd Edition, J.M. Smith and H.C. Van Ness, McGraw-Hill. Although the bulk of the problems are original and/or taken from the sources that the authors have been directly involved with, every effort has been made to acknowledge material drawn from other sources.

The policy of most technical societies and publications is to use SI (metric) units or to list both the common British engineering unit and its SI equivalent. However, British units are primarily used in this book for the convenience of the majority of the reading audience. Readers who are more familiar and at ease with SI units are advised to refer to the Appendix of this book.

It is hoped that this writing will place in the hands of academic and industrial individuals a book covering the principles and applications of thermodynamics in a thorough and clear manner. Upon completion of the text, the reader should have acquired not only a working knowledge of the principles of thermodynamics but also experience in their application; and, the reader should find himself/herself approaching advanced texts, engineering literature, and industrial applications (even unique ones) with more confidence.

Sincere thanks are extended to Shannon O’Brien at Manhattan College for her invaluable help in solving some of the problems in the text, preparing part of the initial draft of the solutions manual, and proofing the manuscript. Special thanks are due Eric Huang and Pat Abulencia for their technical assistance in preparing parts of the manuscript.

L. THEODORE
F. RICCI
T. VAN VLIET

February 2009

Part I

Introduction

Nicolò Machiavelli [1469–1527]

There is nothing more difficult to take in hand, more perilous to conduct, or more uncertain in its success, than to take the lead in the introduction of a new order of things.

—The Prince. Chap. 6

Part I serves as the introductory section to this book. It reviews engineering and science fundamentals that are an integral part of the field of thermodynamics. It consists of six chapters, as noted below:

Those individuals with a strong background in the above area(s) may choose to bypass this Part.

Chapter 1

Basic Calculations

Johann Wolfgang Von Goethe [1749–1832]

The sum which two married people owe to one another defies calculation. It is an infinite debt, which can only be discharged through all eternity.

—Elective Affinities [1808]. Book I, Chap. 9

INTRODUCTION

This first chapter provides a review of basic calculations and the fundamentals of measurement. Four topics receive treatment:

The reader is directed to the literature in the reference section of this chapter if additional information on these four topics is deemed necessary.(1–3)

UNITS AND DIMENSIONS

The units used in this text are consistent with those adopted by the engineering profession in the United States. For engineering work, SI (Système International) and English units are most often employed; in the United States, the English engineering units are generally used, although efforts are still underway to obtain universal adoption of SI units for all engineering and science applications. The SI units have the advantage of being based on the decimal system, which allows for more convenient conversion of units within the system.

There are other systems of units. Some of the more common of these are shown in Table 1.1; however, English engineering units are primarily used in this text. Tables 1.2 and 1.3 present units for both the English and SI systems, respectively.

Table 1.1 Common Systems of Units

Table 1.2 English Engineering Units

Physical quantity	Name of unit	Symbol for unit
Length	foot	ft
Time	second	s
Mass	pound (mass)	lb
Temperature	degree Rankine	°R
Temperature (alternative)	degree Fahrenheit	°F
Moles	pound · mole	lbmol
Energy	British thermal unit	Btu
Energy (alternative)	horsepower · hour	hp · h
Force	pound (force)	lbf
Acceleration	foot per second square	ft/s2
Velocity	foot per second	ft/s
Volume	cubic foot	ft3
Area	square foot	ft2
Frequency	cycles per second, hertz	cycles/s, Hz
Power	horsepower, Btu per second	hp, Btu/s
Heat capacity	British thermal unit per (pound mass · degree Rankine)	Btu/lb · °R
Density	pound (mass) per cubic foot	lb/ft3
Pressure	pound (force) per square inch	psi
	pound (force) per square foot	psf
	atmospheres	atm
	bar	bar

Table 1.3 SI Units

Physical unit	Name of unit	Symbol for unit
Length	meter	m
Mass	kilogram, gram	kg, g
Time	second	s
Temperature	Kelvin	K
Temperature (alternative)	Celsius	°C
Moles	gram · mole	gmol
Energy	Joule	J, kg · m2/s2
Force	Newton	N, kg · m/s2, J/m
Acceleration	meters per square second	m/s2
Pressure	Pascal, Newton per square meter	Pa, N/m2
Pressure (alternative)	bar	bar
Velocity	meters per second	m/s
Volume	cubic meter, liters	m3, L
Area	square meter	m2
Frequency	Hertz	Hz, cycles/s
Power	Watt	W, kg · m2 · s3, J/s
Heat capacity	Joule per kilogram · Kelvin	J/kg · K
Density	kilogram per cubic meter	kg/m3
Angular velocity	radians per second	rad/s

Some of the more common prefixes for SI units are given in Table 1.4, and decimal equivalents are provided in Table 1.5. Conversion factors between SI and English units and additional details on the SI system are provided in the Appendix III.

Table 1.4 Prefixes for SI Units

Table 1.5 Decimal Equivalents

Inch in fractions	Decimal equivalent	Millimeter equivalent
	A. 4ths and 8ths
1/8	0.125	3.175
1/4	0.250	6.350
3/8	0.375	9.525
1/2	0.500	12.700
5/8	0.625	15.875
3/4	0.750	19.050
7/8	0.875	22.225
	B. 16ths
1/16	0.0625	1.588
3/16	0.1875	4.763
5/16	0.3125	7.938
7/16	0.4375	11.113
9/16	0.5625	14.288
11/16	0.6875	17.463
13/16	0.8125	20.638
15/16	0.9375	23.813
	C. 32nds
1/32	0.03125	0.794
3/32	0.09375	2.381
5/32	0.15625	3.969
7/32	0.21875	5.556
9/32	0.28125	7.144
11/32	0.34375	8.731
13/32	0.40625	10.319
15/32	0.46875	11.906
17/32	0.53125	13.494
19/32	0.59375	15.081
21/32	0.65625	16.669
23/32	0.71875	18.256
25/32	0.78125	19.844
27/32	0.84375	21.431
29/32	0.90625	23.019
31/32	0.96875	24.606

Two units that appear in dated literature are the poundal and slug. By definition, one poundal force will give a one pound mass an acceleration of one ft/s2. Alternatively, one slug can be defined as the mass that will accelerate one ft/s2 when acted upon by a one pound force; thus, a slug is equal to 32.2 pounds mass.

CONVERSION OF UNITS

Converting a measurement from one unit to another can be conveniently accomplished by using unit conversion factors; these factors are obtained from simple equations that relate the two units numerically. For example, from

(1.1)

the following conversion factor can be obtained:

(1.2)

Since this factor is equal to unity, multiplying some quantity (e.g., 18 ft) by this factor cannot alter its value. Hence

(1.3)

Note that in Equation (1.3), the old units of feet on the left-hand side cancel out leaving only the desired units of inches.

Physical equations must be dimensionally consistent. For the equality to hold, each term in the equation must have the same dimensions. This condition can be and should be checked when solving engineering problems. Throughout the text, great care is exercised in maintaining the dimensional formulas of all terms and the dimensional homogeneity of each equation. Equations will generally be developed in terms of specific units rather than general dimensions (e.g., feet rather than length). This approach should help the reader to more easily attach physical significance to the equations presented in these chapters.

ILLUSTRATIVE EXAMPLE 1.1

Convert units of acceleration in cm/s2 to miles/yr2.

SOLUTION: The procedure outlined above is applied to the units of cm/s2:

Thus, 1.0 cm/s2 is equal to 6.18 × 109 miles/yr2.

THE GRAVITATIONAL CONSTANT, gc

The momentum of a system is defined as the product of the mass and velocity of the system:

(1.4)

One set of units for momentum are therefore lb · ft/s. The units of the time rate of change of momentum (hereafter referred to as rate of momentum) are simply the units of momentum divided by time, i.e.,

The above units can be converted to lbf if multiplied by an appropriate constant. As noted earlier, a conversion constant is a term that is used to obtain units in a more convenient form; all conversion constants have magnitude and units in the term, but can also be shown to be equal to 1.0 (unity) with no units.

A defining equation is

(1.5)

If this equation is divided by lbf, one obtains

(1.6)

This serves to define the conversion constant gc. If the rate of momentum is divided by gc as 32.2 lb · ft/lbf · s2—this operation being equivalent to dividing by 1.0—the following units result:

(1.7)

It can be concluded from the above dimensional analysis that a force is equivalent to a rate of momentum.

SIGNIFICANT FIGURES AND SCIENTIFIC NOTATION(3)

Significant figures provide an indication of the precision with which a quantity is measured or known. The last digit represents, in a qualitative sense, some degree of doubt. For example, a measurement of 8.32 inches implies that the actual quantity is somewhere between 8.315 and 8.325 inches. This applies to calculated and measured quantities; quantities that are known exactly (e.g., pure integers) have an infinite number of significant figures.

The significant digits of a number are the digits from the first nonzero digit on the left to either (a) the last digit (whether it is nonzero or zero) on the right if there is a decimal point, or (b) the last nonzero digit of the number if there is no decimal point. For example:

370	has 2 significant figures
370.	has 3 significant figures
370.0	has 4 significant figures
28,070	has 4 significant figures
0.037	has 2 significant figures
0.0370	has 3 significant figures
0.02807	has 4 significant figures

Whenever quantities are combined by multiplication and/or division, the number of significant figures in the result should equal the lowest number of significant figures of any of the quantities. In long calculations, the final result should be rounded off to the correct number of significant figures. When quantities are combined by addition and/or subtraction, the final result cannot be more precise than any of the quantities added or subtracted. Therefore, the position (relative to the decimal point) of the last significant digit in the number that has the lowest degree of precision is the position of the last permissible significant digit in the result. For example, the sum of 3702., 370, 0.037, 4, and 37. should be reported as 4110 (without a decimal). The least precise of the five numbers is 370, which has its last significant digit in the tens position. The answer should also have its last significant digit in the tens position.

Unfortunately, engineers and scientists rarely concern themselves with significant figures in their calculations. However, it is recommended that—at least for this chapter—the reader attempt to follow the calculational procedure set forth in this subsection.

In the process of performing engineering calculations, very large and very small numbers are often encountered. A convenient way to represent these numbers is to use scientific notation. Generally, a number represented in scientific notation is the product of a number (< 10 but > or = 1) and 10 raised to an integer power. For example,

A positive feature of using scientific notation is that only the significant figures need appear in the number.

REFERENCES

1. R. Perry and D. Green (editors), “Perry’s Chemical Engineers’ Handbook,” 8th edition, McGraw-Hill, New York, 2008.

2. J. REYNOLDS, J. JERIS, and L. THEODORE, “Handbook of Chemical and Environmental Engineering Calculations,” John Wiley & Sons, Hoboken, NJ, 2004.

3. J. SANTOLERI, J. REYNOLDS, and L. THEODORE, “Introduction to Hazardous Waste Incineration,” 2nd edition, John Wiley & Sons, Hoboken, NJ, 2000.

NOTE: Additional problems for each chapter are available for all readers at www. These problems may be used for additional review or homework purposes.