Sample Problem - Thermodynamics
Sample Problem - Thermodynamics
Sample Problem - Thermodynamics
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2 authors:
Jarrell Richard Elliott
Carl T. Lira
University of Akron
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Introductory chemical
engineering
Thermodynamics
J. Richard Elliott
Carl T. Lira
What's New? Why another thermodynamics textbook? Read our Preface.
To learn more, read our short overview of the textbook.
View the Table of Contents.
View selected examples using computer programs.
View the subject index.
Visit our website to download programs or view the errata.
ISBN (0-13-011386-7), Solution Manual ISBN (0-13-011387-5)
Prentice Hall website: www.phptr.com
Authors email addresses: [email protected], [email protected].
Authors websites: Elliott, Lira
1998 J. Richard Elliott, Carl T. Lira. All rights reserved.
modern engineering disciplines. The computer tools that students can use on exams as well as in homework reinforce the application of the derived models in a way that has not been possible previously.
To support this unit, we furnish calculator and spreadsheet programs for calculating entropy and
enthalpy changes of ideal and real gases. We end Unit II by coverage of fugacity and phase equilibria in
pure fluids calculated by equations of state.
Unit III (Phase equilibria in mixtures)
We introduce phase equilibria using ideal solutions and ideal gases. We then return to equations of
state to apply them to phase equilibrium in mixtures, and closely parallel the development for pure fluids
covered at the end of Unit II. We stress the relationship between the fugacity coefficient and departure
functions developed in Unit II. In this way, Unit III builds on the conceptual foundation and methodology
of Unit II. By keeping the conceptual framework tightly in step with that of Unit II, students can focus on
the relatively large number of practical issues that arise from the fundamental extension of thermodynamic
principles to binary and multicomponent systems. Our approach focuses on the equation of state approach
more than previous undergraduate texts, but other model equations are shown to be simplified, approximate deductions from the equation of state, rather than a smorgasbord of models with little basis for distinguishing between them. In this way, our presentation maintains conciseness without sacrificing depth of
understanding. We provide calculator, spreadsheet and compiled FORTRAN programs for calculations of
phase equilibria.
In discussion of non-ideal mixtures, we introduce activity coefficients, and discuss azeotropes. We
provide a comprehensive treatment of solution models, and provide discussion as to their relationships to
each other. Practical illustrations include water contamination with hydrocarbons, polymer blending/recycling, oxygenated fuels, and the traditional issues related to distillation. We provide spreadsheets for calculation of phase equilibria, and for fitting of activity coefficient parameters. Our discussion of high
pressure phase behavior is more complete than any other undergraduate text.
Unit IV (Reacting Systems)
Our book differs from other texts by providing integration of spreadsheets for the calculation of
chemical reaction equilibria. We also introduce equations of state for hydrogen bonding systems, a topic
that would probably not be covered in most undergraduate courses today, but will become important in the
future.
Level
The text is directed to sophomore or junior chemical engineering students. It also is comprehensive
enough that it could be used for self study, but the majority of purchases are expected to be for class usage.
The textbook level is at an introductory/intermediate level with a mixture of drill-oriented problems and
advanced concepts. We have used it for part of our graduate courses as well as the introductory sophomore/
junior course. Most students will have completed an introductory material and energy balance course
before using the text but review of linear interpolation is included . Students should have also completed
multivariable calculus to permit integration and partial differentiation.
PREFACE
No happy phrase of ours is ever quite original with us; there is nothing of our
own in it except some slight change born of our temperament, character, environment, teachings and associations.
Mark Twain
Thank you for your interest in our book. We have developed this book to address ongoing evolutions in applied thermodynamics and computer technology. Molecular perspective is becoming
more important in the refinement of thermodynamic models for fluid properties and phase behavior. Molecular simulation is increasingly used for exploring and improving fluid models. While
many of these techniques are still outside the scope of this text, these new technologies will be
important to practicing engineers in the near future, and an introduction to the molecular perspective is important for this reason. We expect our text to continue to evolve with the chemical engineering field.
Computer technology has made process simulators commonplace in most undergraduate curriculums and professional work environments. This increase in computational flexibility has moved
many of the process calculations from mainframe computers and thermodynamic property experts
to the desktop and practicing engineers and students. This increase in computational ability also
increases the responsibility of the individuals developing process simulations to choose meaningful
models for the components in the system because most simulators provide even more options for
thermodynamic models than we can cover in this text. We have included background and comparison on many of the popular thermodynamic models to address this issue.
Computational advances are also affecting education. Thus we have significant usage of equations of state throughout the text. We find these computational tools remove much of the drudgery
of repetitive calculations, which permits more class time to be spent on the development of theories, molecular perspective, and comparisons of alternative models. We have included FORTRAN,
Excel spreadsheets, TI85, and HP48 calculator programs to complement the text. The programs are
summarized in the appendices.
xv
xvi Preface
(a) Solutions to cubic equations of state are no longer tedious with the handheld calculators
available today for about $100. We provide programs for calculation of thermodynamic
properties via the Peng-Robinson equation, vapor pressure programs, Peng-Robinson K-ratios
and bubble pressures of mixtures, and van Laar and UNIFAC activity coefficients as well
as several other utility programs. Our choice of the HP48 calculator is due to its being
one of the first to provide a computer interface for downloading programs from a PC and
provide calculator-to-calculator communication, which facilitates distribution of the programs. If all students in the class have access to these engineering calculators, as practiced at the University of Akron, questions on exams can be designed to apply to these
programs directly. This obviates the need for traditional methods of reading charts for
departure functions and K-ratios and enables treatment of modern methods like equations
of state and UNIFAC.
(b) Spreadsheets have also improved to the point that they are powerful tools for solving
engineering problems. We have chosen to develop spreadsheets for Microsoft Excel
because of the widespread availability. Certainly Mathcad, Mathematica, and other
software could be used, but none has the widespread availability of spreadsheets. We
have found the solver within Excel to provide a good tool for solving a wide variety of
problems. We provide spreadsheets for thermodynamic properties, phase and reaction
equilibria.
(c) High-level programming is still necessary for more advanced topics. For these applications, we provide compiled programs for thermodynamic properties and phase behavior.
For an associating system, such as an alcohol, we provide the ESD equation of state.
These programs are menu-driven and do not require knowledge of a computer language.
In a limited number of instances, we provide FORTRAN source code. We provide
FORTRAN code because of our own abilities to program faster in FORTRAN, although
other languages are finding increasing popularity in the engineering community. We have
tried to avoid customization of the code for a specific FORTRAN compiler, which
improves portability to other operating platforms but also limits the bells and whistles
that a specific interface could provide. These programs provide a framework for students
and practicing engineers to customize for their own applications.
Energy and entropy balances are at the heart of process engineering calculations. We develop
these approaches first using the ideal gas law or thermodynamic tables, then revisit the topics after
developing equation-of-state techniques for thermodynamic properties. We are well aware of the
concern that students often apply the ideal gas law inappropriately. Therefore we clearly mark
equations using the ideal gas law or assuming a temperature-independent heat capacity. From a
pedagogical standpoint, we are faced with the issues of developing first and second law balances,
equations of state (and their departure functions) for fluid properties, and then combining the principles. We have found it best that students quickly develop ability and confidence in application of
the balances with simple calculational procedures before introducing the equation of state. The balance concepts are typically more easily grasped and are essential for extension to later courses in
the curriculum. Another benefit of this approach is that the later development of the equation of
state can be directly followed by departure functions, and the reasons for needing properties such as
enthalpy and entropy are well understood from the earlier emphasis on the balances. This enables
students to focus on the development of the departure functions without being distracted by not
completely understanding how these properties will be used.
Fugacity is another property which is difficult to understand. We have tried to focus on the need
for a property which is a natural function of T and P, and also stress how it is related to departure
Preface
xvii
functions. There are many ways to calculate fugacities (which provides many trees to block the
view of the forest), and we have tried to provide tables and diagrams to show the inter-relations
between fugacity coefficients, activity coefficients, ideal gases, ideal solutions, and real solutions.
A distinct feature of this text is its emphasis on molecular physics at the introductory level. Our
perspective is that this background must be made available to students in an integrated manner, but
it is up to instructors to decide the level of emphasis for the entire spectrum of their students. We
have organized this material such that it may be covered as a supplementary reading assignment or
as a homework and test assignment. With the latter emphasis, it is possible to formulate a graduate
course based on this text.
Throughout the text, we have used text boxes to highlight important statements and equations.
Boxed equations are not always final results of derivations. In some cases, the boxes highlight mathematical definitions of important intermediate results that might be useful for homework problems.
We consider the examples to be an integral part of the text, and we use them to illustrate important points. In some cases, derivations and important equations are within an example because the
equations are model-specific (e.g., ideal gas). Examples are often cross-referenced and are therefore listed in the table of contents.
There are many marginal notes throughout the text. Where you find a ! , it means that an
important point is made, or a useful equation has been introduced. Where you find a HP or TI , it
means that a calculator program is available to assist in calculations. The calculator programs are
sometimes not necessary, but extremely helpful. Where you find a
, it means that an Excel
spreadsheet or a compiled program is available. In some cases, the program is simply convenient,
but typically you will find that these calculations are tedious without the program. For calculator or
PC icons, the program names are given by the icons. See the computer appendix or the readme files
for specific program instructions.
We periodically update computer software and the computer appendix. The latest software is
available from our website http://www.egr.msu.edu/~lira/thermtxt.htm. We hope you find our
approaches helpful in your learning and educational endeavors. We welcome your suggestions for
further improvements and enhancements. You may contact us easily at the email addresses below.
Unfortunately, we will be unable to personally respond to all comments, although we will try.
NOTES TO STUDENTS
Computer programs facilitate the solution to homework problems, but should not be used to replace
an understanding of the material. Always understand exactly which formulas are required before
turning to the computer. Before using the computer, we recommend that you know how to solve the
problem by hand calculations. If you do not understand the formulas in the spreadsheets it is a good
indication that you need to do more studying before using the program so that the structure of the
spreadsheet will make sense. When you understand the procedures, it should be obvious which
spreadsheet cells will help you to the answer, and which cells are intermediate calculations. It is
also helpful to rework example problems from the text using the software.
ACKNOWLEDGMENTS
We would like to thank the many people who helped this work find its way to the classroom. We
express appreciation to Professors Joan Brennecke, Mike Matthews, Bruce Poling, Ross Taylor,
xviii Preface
and Mark Thies, who worked with early versions of the text and provided suggestions for improvement. We are also greatly indebted to Dave Hart for proofreading an early version. There are many
students who suffered through error-prone preliminary versions, and we thank them all for their
patience and vision of the common goal of an error-free book. CTL would like to thank Ryoko
Yamasaki for her work in typing many parts of the manuscript and problem solutions. CTL also
thanks family members Gail, Nicolas, and Adrienne for their patience while the text was prepared,
as many family sacrifices helped make this book possible. JRE thanks family members Guliz,
Serra, and Eileen for their similar forbearance. We acknowledge Dan Friend and NIST, Boulder for
contributions to the steam tables and thermodynamic charts. Lastly, we acknowledge the influences
of the many authors of previous thermodynamics texts. We hope we have done justice to this distinguished tradition, while simultaneously bringing deeper insight to a broader audience.
Carl T. Lira, Michigan State University, [email protected]
J.Richard Elliott, University of Akron, [email protected]
CONTENTS
PREFACE
NOTATION
xv
xix
CHAPTER 1
1.1
1.2
1.3
1.4
1.5
1.6
CHAPTER 2
2.1
2.2
2.3
2.4
2.5
2.6
INTRODUCTION
EXPANSION/CONTRACTION WORK
SHAFT WORK
WORK ASSOCIATED WITH FLOW
LOST WORK VS. REVERSIBILITY
Example 2.1 Isothermal compression of an ideal gas
PATH PROPERTIES AND STATE PROPERTIES
Example 2.2 Work as a path function
HEAT FLOW
5
10
10
11
15
22
23
24
25
26
28
29
30
31
35
35
36
37
38
41
41
42
43
vi Contents
2.7
2.8
2.9
2.10
2.11
2.12
2.13
2.14
2.15
2.16
2.17
2.18
2.19
CHAPTER 3
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
ENTROPY
43
45
47
49
51
53
56
57
58
58
59
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65
66
66
68
69
70
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72
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80
87
87
89
93
94
96
100
102
102
103
104
105
107
109
110
112
113
114
116
117
Contents
3.11
3.12
3.13
3.14
3.15
3.16
3.17
3.18
3.19
3.20
TURBINE CALCULATIONS
Example 3.10 Turbine efficiency
MULTISTAGE TURBINES
PUMPS AND COMPRESSORS
STRATEGIES FOR APPLYING THE ENTROPY BALANCE
ADDITIONAL STEADY-STATE EXAMPLES
Example 3.11 Heat pump analysis
Example 3.12 Entropy in a heat exchanger
UNSTEADY-STATE OPEN SYSTEMS (Optional)
Example 3.13 Entropy change in a leaky tank
Example 3.14 An ideal gas leaking through a turbine (unsteady-state)
THE ENTROPY BALANCE IN BRIEF
SUMMARY
PRACTICE PROBLEMS
HOMEWORK PROBLEMS
CHAPTER 4
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
THERMODYNAMICS OF PROCESSES
vii
119
120
121
122
123
124
124
125
127
127
128
129
129
130
131
141
141
143
144
145
146
146
148
149
151
154
155
156
157
158
160
161
164
165
165
171
CLASSICAL THERMODYNAMICS
GENERALIZATION TO ANY FLUID
173
174
180
176
181
182
viii Contents
Example 5.4
Example 5.5
Example 5.6
5.3
5.4
5.5
CHAPTER 6
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
6.10
6.11
6.12
EXPERIMENTAL MEASUREMENTS
THREE-PARAMETER CORRESPONDING STATES
GENERALIZED COMPRESSIBILITY FACTOR CHARTS
Example 6.1 Application of the generalized charts
THE VIRIAL EQUATION OF STATE
Example 6.2 Application of the virial equation
CUBIC EQUATIONS OF STATE
SOLVING THE EQUATION OF STATE FOR Z
Example 6.3 Solution of the Peng-Robinson equation for molar volume
Example 6.4 Application of the Peng-Robinson equation
IMPLICATIONS OF REAL FLUID BEHAVIOR
Example 6.5 Derivatives of the Peng-Robinson equation
THE MOLECULAR THEORY BEHIND EQUATIONS OF STATE
Example 6.6 Deriving your own equation of state
MATCHING THE CRITICAL POINT
Example 6.7 Critical parameters for the van der Waals equation
SUMMARY AND CONCLUDING REMARKS
PRACTICE PROBLEMS
HOMEWORK PROBLEMS
CHAPTER 7
7.1
7.2
7.3
7.4
7.5
7.6
DEPARTURE FUNCTIONS
183
183
184
184
185
185
186
186
189
190
193
194
195
198
198
200
201
202
205
207
208
210
210
210
217
220
220
220
221
222
229
230
231
234
234
235
236
238
240
241
241
242
Contents
7.7
7.8
7.9
7.10
7.11
REFERENCE STATES
Example 7.6 Enthalpy and entropy from the Peng-Robinson equation
Example 7.7 Liquefaction revisited
Example 7.8 Adiabatically filling a tank with propane (optional)
GENERALIZED CHARTS FOR THE ENTHALPY DEPARTURE
SUMMARY
PRACTICE PROBLEMS
HOMEWORK PROBLEMS
CHAPTER 8
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
8.10
8.11
8.12
8.13
8.14
9.5
9.6
9.7
9.8
9.9
9.10
INTRODUCTION TO MULTICOMPONENT
SYSTEMS
PHASE DIAGRAMS
CONCEPTS
IDEAL SOLUTIONS
VAPOR-LIQUID EQUILIBRIUM (VLE) CALCULATIONS
Example 9.1 Bubble and dew temperatures and isothermal flash of
ideal solutions
EMISSION MODELING
NON-IDEAL SYSTEMS
ADVANCED TOPICS (Optional)
SUMMARY AND CONCLUDING REMARKS
PRACTICE PROBLEMS
HOMEWORK PROBLEMS
ix
243
245
245
247
247
247
249
250
257
258
258
260
260
261
262
263
264
266
368
268
271
273
274
274
275
277
278
278
279
283
285
285
288
296
301
305
307
310
313
314
315
315
x Contents
CHAPTER 10
10.1
10.2
10.3
10.4
10.5
10.6
10.7
10.8
CHAPTER 11
11.1
11.2
11.3
11.4
11.5
11.6
11.7
ACTIVITY MODELS
EXCESS PROPERTIES
MODIFIED RAOULTS LAW AND EXCESS GIBBS ENERGY
Example 11.1 Activity coefficients and the Gibbs-Duhem
relation (optional)
Example 11.2 VLE prediction using UNIFAC activity coefficients
DETERMINATION OF GE FROM EXPERIMENTAL DATA
Example 11.3 Gibbs excess energy for system 2-propanol + water
Example 11.4 Activity coefficients by the one-parameter Margules equation
Example 11.5 VLE predictions from the Margules one-parameter equation
THE VAN DER WAALS PERSPECTIVE
Example 11.6 Application of the van Laar equation
Example 11.7 Infinite dilution activity coefficients from van Laar theory
Example 11.8 VLE predictions using regular-solution theory
Example 11.9 Scatchard-Hildebrand versus van Laar theory for
methanol + benzene
Example 11.10 Combinatorial contribution to the activity coefficient
Example 11.11 Polymer mixing
FLORY-HUGGINS & VAN DER WAALS THEORIES (Optional)
LOCAL COMPOSITION THEORY
Example 11.12 Local compositions in a 2-dimensional lattice
Example 11.13 Application of Wilson's equation to VLE
Example 11.14 Calculation of group mole fractions
Example 11.15 Detailed calculations of activity coefficients via UNIFAC
FITTING ACTIVITY MODELS TO DATA (Optional)
Example 11.16 Using Excel for fitting model parameters
319
321
321
324
328
329
331
332
334
335
336
337
339
340
342
344
345
345
346
355
356
357
359
360
363
363
365
365
367
370
371
373
375
378
378
379
381
383
388
397
397
400
401
Contents
11.8
11.9
11.10
11.11
11.12
CHAPTER 12
12.1
12.2
12.3
12.4
12.5
12.6
12.7
12.8
12.9
CHAPTER 13
13.1
13.2
13.3
13.4
SPECIAL TOPICS
PHASE BEHAVIOR
SOLID-LIQUID EQUILIBRIA
Example 13.1 Eutectic behavior of chloronitrobenzenes
Example 13.2 Eutectic behavior of benzene + phenol
Example 13.3 Wax precipitation
RESIDUE CURVES
HOMEWORK PROBLEMS
xi
403
404
410
411
412
423
423
424
424
426
427
430
432
432
433
434
435
436
438
439
439
445
445
459
463
464
465
470
475
481
CHAPTER 14
483
14.1
14.2
14.3
14.4
14.5
14.6
REACTING SYSTEMS
REACTION COORDINATE
Example 14.1 Stoichiometry and the reaction coordinate
EQUILIBRIUM CONSTRAINT
Example 14.2 Calculation of standard state Gibbs energy of reaction
REACTION EQUILIBRIA FOR IDEAL SOLUTIONS
Example 14.3 Computing the reaction coordinate
Example 14.4 Butadiene revisited
TEMPERATURE EFFECTS
Example 14.5 Equilibrium constant as a function of temperature
SHORTCUT ESTIMATION OF TEMPERATURE EFFECTS
Example 14.6 Application of the shortcut vant Hoff equation
ENERGY BALANCES FOR REACTIONS
Example 14.7 Adiabatic reaction in an ammonia reactor
483
485
486
487
489
489
490
492
493
494
495
496
498
xii Contents
14.7
14.8
14.9
14.10
14.11
14.12
14.13
14.14
CHAPTER 15
502
503
503
505
507
509
510
511
514
516
517
520
521
521
522
524
529
15.1
15.2
15.3
15.4
529
534
536
537
538
539
540
541
542
547
551
555
565
569
571
573
GLOSSARY
579
583
A.1
A.2
A.3
A.4
A.5
A.6
A.7
A.8
A.9
A.10
A.11
583
587
587
587
588
589
589
589
590
595
597
Contents
Appendix B
B.1
B.2
B.3
MATHEMATICS
IMPORTANT RELATIONS
SOLUTIONS TO CUBIC EQUATIONS
THE DIRAC DELTA FUNCTION
Example B.1 The Hard Sphere Equation of State
Example B.2 The Square-Well Equation of State
EOS METHODS
ACTIVITY COEFFICIENT (GAMMA-PHI) METHOD
OVERVIEW
EQUATIONS OF STATE
SOLUTIONS MODELS
HYBRID MODELS
RECOMMENDED DECISION TREE
THERMAL PROPERTIES OF MIXTURES
Example D.1 Contamination from a reactor leak
LITERATURE CITED
Appendix E
E.1
E.2
E.3
E.4
E.5
E.6
E.7
E.8
E.9
E.10
INDEX
xiii
599
599
603
606
608
610
613
613
618
623
623
623
624
624
625
626
627
628
631
631
634
634
635
636
637
640
651
652
653
655
xiv Contents
1.1
EXAMPLE PROBLEMS
The following examples have been taken from the book to demonstrate the use of spreadsheets and
fortran programs. Note that no effort has been taken to include cross references to original pages
that are not included in these extracted examples. .
150.86
Current State
T (K)
P (MPa)
4.898
-0.004
8.314
V
3
cm /gmol
fugacity
MPa
Roots
105.6
0.498
Solution to Cubic
Intermediate Calculations
Tr
Pr
Z + a2Z + a1Z + a0 =0
2
a2
a1
a0
p
-0.9887 0.083661 -0.00108 -0.24218
Method 1 - For region with one real root
P
Q
Root to equation in x
#NUM!
#NUM!
#NUM!
R = q /4 + p /27 =
-1.8E-05
q
If Negative, three unequal real roots,
-0.0451 If Positive, one real root
2 Examples
PREOS.xls,
PRPURE.
Reevaluate the liquefaction of methane considered in Example 4.6 on page 155 utilizing the
Peng-Robinson equation. Previously the methane chart was used. Natural gas, assumed here to
be pure methane, is liquefied in a simple Linde process. Compression is to 60 bar, and precooling is to 300 K. The separator is maintained at a pressure of 1.013 bar and unliquefied gas at this
pressure leaves the heat exchanger at 295 K. What fraction of the methane entering the heat
exchanger is liquefied in the process?
2
Precooler
Compressor
3 (6 MPa, 300 K)
8
Heat Exchanger
1
4
Throttle valve
5
Flash Drum
Solution: The solution is easily obtained by using PREOS.xls. When running PREOS, we must
specify the temperature of the flash drum which is operating at the saturation temperature at
1.013 bar. This is specified as the boiling temperature for now (111 K).1
Before we calculate the enthalpies of the streams, a reference state must be chosen. A convenient
choice is the enthalpy of the inlet stream (Stream 3, 6 MPa and 300 K). The results of the calculations from PREOS are summarized in Fig. 1.3.
State 8
Current State
Roots
T (K)
295
Z
V
fugacity
H
3
cm /gmol
P (MPa)
0.1013
MPa
J/mol
& for 1 root region
0.9976741 24156.108 0.101064 883.5669
State 6
Current State
Roots
U
S
J/mol
J/molK
-1563.45 35.86805
T (K)
111
Z
V
fugacity
3
cm /gmol
MPa
P (MPa)
0.1013
answers for three
0.9666276 8806.4005 0.09802
root region
0.0267407 243.61908
0.0036925 33.640222 0.093712
H
J/mol
-4736.62
-6972.95
-12954.3
U
S
J/mol
J/molK
-5628.7 6.758321
-6997.63 -26.6614
-12957.7 -66.9014
Figure 1.3 Summary of enthalpy calculations for methane as taken from the file PREOS.xls.
xm
0.000
ym
0.000
T(K)
353.25
0.026
0.050
0.088
0.164
0.333
0.549
0.699
0.782
0.898
0.973 1.000
0.267
0.371
0.457
0.526
0.559
0.595
0.633
0.665
0.760
0.907 1.000
343.82 339.59 336.02 333.35 331.79 331.17 331.25 331.62 333.05 335.85 337.85
Solution: Solving this problem is computationally intensive enough to write a general program
for solving for bubble-point pressure. Fortunately, computer and calculator programs are readily
available. We will discuss the solution using the PC program PRMIX.EXE. Select the option KI
for adjusting the interaction parameter. This routine will perform a bubble calculation for a
guessed value of kij. When prompted, enter the temperature (331.15 K) and liquid composition
xm = 0.614. The program will give a calculated pressure and vapor phase composition. The vaporphase composition will not match the liquid-phase composition because the azeotrope is not perfectly predicted; however, we continue to change kij until we match the pressure of 1.013 bar. The
following values are obtained for the bubble pressure at the experimental azeotropic composition
and temperature with various values of kij.
kij
0.0 0.1 0.076 0.084
P(bars) 0.75 1.06 0.9869 1.011
HP
PRMIX offers
bubble pressure.
PRMIX offers
option KI for iterating on a single
point.
4 Examples
355
350
T(K)
345
k ij =0
340
k ij =0.084
335
330
325
0
0.2
0.4
0.6
0.8
x,y methanol
Figure 1.4 T-x,y diagram for the azeotropic system methanol + benzene. Curves show the
predictions of the Peng-Robinson equation (kij = 0) and correlation (kij = 0.084)
based on fitting a single data point at the azeotrope. xs and triangles represent
liquid and vapor phases, respectively.
PRMIX offers
bubble pressure.
PRMIX offers
other routines as
well.
Use the Peng-Robinson equation (kij = 0) to determine the phase diagram of nitrogen + methane at
150 K. Plot P versus x, y and compare the results to the results from the shortcut K-ratio
equations.
P(bars)
90
80
70
The shortcut
K-ratio method
provides an initial
estimate when a
supercritical component is at low liquidphase compositions, but incorrectly predicts VLE
at high liquid-phase
concentrations of
the supercritical
component.
Shortcut
K-ratio
Ideal solution
60
50
40
30
20
10
0
PR - EOS
kij=0
0.2
0.4
0.6
0.8
xN2,yN2
Figure 1.5 High pressure P-x-y diagram for the nitrogen + methane system
comparing the shortcut K-ratio approximation and the Peng-Robinson
equation at 150 K. The data points represent experimental results.
Both theories are entirely predictive since the Peng-Robinson equation
assumes that kij = 0.
6 Examples
INDEX
A
acentric factor, 197
activity, 293
coefficient, 293, 358
temperature dependence, 404
adiabatic, 41, 66, 99, 579
reaction temperature, 497, 588
adiabatic compressibility, 188, 190
Antoine equation, 55, 264, 584, 635
See also vapor pressure
approach temperature, 124
association, 529, 579
athermal, 376, 377
Avogadros number, xix
azeotrope, 310, 370, 373, 447, 579
B
barotropy, 579
binary vapor cycle, 154
binodal, 579
boiler, 60, 143
boundaries, 66, 76
Boyle temperature, 223
Brayton cycle, 156
bubble line, 19, 286, 310
bubble point, 301
pressure, 302, 327, 336, 361, 366, 614, 618
temperature, 303, 305, 360, 433, 614, 619
C
carboxylic acid, 455, 529
Carnot cycle, 110, 141
Carnot heat pump, 112
cascade refrigeration, 154
655
656 Index
critical locus, 342, 447
critical point, 21, 195, 203, 204, 220, 341, 343, 447,
552, 604
critical pressure, 21
critical temperature, 21
cubic equation, 202
solutions, 205, 603
cubic equation
stable roots, 208
D
dead state, 579
degrees of superheat, 21
density, 12, 163
departure functions, 229
deviations from ideal solutions, 295
dew line, 19, 286, 310
dew point, 301, 588
pressure, 302, 615, 620
temperature, 303, 305, 616, 621
diathermal, 43, 579
diesel engine, 159
thermal efficiency, 160
differentiation, 601
diffusion, 4, 123
coefficient, 4
E
economizer, 153
efficiency, 164, 579
thermal, 110
turbine and compressor, 115, 141
electrolytes, 516, 588
endothermic, 492, 502
energy, 5
See also potential energy, kinetic energy, internal
energy
of fusion, 55
of vaporization, 21, 54
energy balance, 35, 496
closed-system, 43
complete, 49
hints, 65
steady-state, 47
energy equation, 211
enthalpy, 27, 31, 48, 175
of formation, 492, 637
of fusion, 55, 100
of mixing, 296, 496
of vaporization, 21, 54, 83
See also latent heat
entropy, 5, 27, 87
and heat capacity, 101
combinatorial, 378
configurational, 89
generation, 97, 115
macroscopic, 96
microscopic, 89
of fusion, 99, 462
of vaporization, 21, 99
thermal, 89
entropy balance, 104
hints, 129
Environmental Protection Agency, 307
EOS, 579
EPA, 307
equal area rule, 276
equation of state, 66, 193, 268, 272, 274, 319
Benedict-Webb-Rubin, 202
ESD, 555, 587
Lee-Kesler, 202
Peng-Robinson, 203, 207, 236, 240, 245, 269,
274, 584, 585, 587, 588
Redlich-Kwong, 249
SAFT, 615
Soave-Redlich-Kwong, 225, 250
van der Waals, 202, 218, 220, 275, 322,
332, 547
virial, 200, 217, 242, 268, 320, 331,
588
equilibrium, 5
criteria
chemical reaction, 486
liquid-vapor, 258, 289, 291
reaction, 588
solid-liquid, 459
liquid-liquid, 423, 445, 453, 564
liquid-liquid-vapor, 424, 447
liquid-vapor, 564
solid-liquid-vapor, 453
Eulers Law, 180
eutectic, 455, 463, 464
eutectic composition, 463
eutectic temperature, 463
exact differential, 179
Excel, 590, 591
excess enthalpy, 403
excess entropy, 403
excess Gibbs energy, 357, 403
excess properties, 356
excess volume, 403
exothermic, 492, 495, 501
expander, 62, 164
See also turbine
expansion, 76
expansion rule, 178
extensive properties, 16, 288
Index
F
first law of thermodynamics, 35
flash
drum, 303
isothermal, 301, 305, 337, 428, 588, 617,
622
flash point, 316, 417
Flory, 375, 386, 389
Flory-Huggins theory, 379, 426
force
frictional, 77
free energies, 176
free volume, 376
friction factor, 58, 162
fugacity, 208, 266, 290, 571, 579
coefficient, 267, 293, 324, 326, 548, 554, 557,
562
fundamental property relation, 174
fusion, 55, 459
G
gas turbine, 156
generalized correlation, 198, 247
Gibbs energy, 176, 208
of a mixture, 356
of formation, 486, 637
of fusion, 461
of mixing, 297, 358
Gibbs phase rule, 16, 176, 450
Gibbs-Duhem equation, 313, 404
Goal Seek, 591
H
hard-sphere fluid, 213
head space, 308
heat, 5, 43
heat capacity, 51, 182, 183, 186, 210, 631
and entropy, 101
heat conduction, 15, 123
heat convection, 15
heat engine, 107
heat exchanger, 60, 116
heat of fusion
See latent heat, enthalpy of fusion
heat of reaction
standard, 492
heat of vaporization
See latent heat, enthalpy of vaporization
heat radiation, 15
Helmholtz energy, 175, 235, 325, 554, 562
Henrys law, 295, 351, 418
heteroazeotrope, 447, 473, 579
hydrogen bonding, 7, 529
657
I
ideal chemical theory, 537, 588
ideal gas law, xvi, 17, 213, 583
ideal solutions, 296, 489
ignition temperature, 159
incompressible flow, 163
incompressible fluid, 20
infinite dilution, 371, 579
instability, 423
See also cubic equation (stable roots), unstable
integration, 601
intensive, 16
internal combustion engine, 156
internal energy, 11, 174
interpolation, 22, 583
interstage cooling, 122, 153
irreversible, 66, 77, 97, 579
isenthalpic, 579
isentropic, 99, 579
isentropic efficiency, 579
isobaric, 41, 98, 579
isobaric coefficient of thermal expansion, 182
isochore, 41, 98, 580
isolated, 66, 580
isopiestic, 580
isopleth, 342
isopycnic, 580
isosteric, 580
isotherm, 208
isothermal flash, 41, 99, 580
isothermal compressibility, 182, 195, 604
J
Jacobian, 183, 187
jet engines, 157
Joule/Thomson expansion, 59
Joule-Thomson coefficient, 155, 187
K
Kamlet-Taft acidity/basicity, 531
kinetic energy, 5, 17, 59
K-ratio, 298, 301, 327, 357
L
laws
See first law, second law, third law
latent heat, 636
LeChateliers principle, 502
Legendre transformation, 175, 186
Lewis fugacity rule, 295, 324
Lewis/Randall rule, 295
liquefaction, 154, 245
LLE, 423, 580
local composition, 381
lost work, 10, 38, 97, 103, 115, 162
658 Index
M
Macros for Excel, 593
Margules, 365, 400, 587
mass balance, 15
master equation, 580
matrix, 594, 599
Maxwells relations, 179, 180
measurable properties, 176, 580
metastable, 209, 580
See also unstable, cubic equation
(stable roots)
microstate, 89
mixing rule, 320, 546, 624
differentiation, 329
molecular basis, 322
modified Raoults law, 357
molecular asymmetry, 450
monomer, 533
multistage compressors, 122
multistage turbines, 121
N
Newton-Raphson, 206
noncondensable, 308
normal boiling temperature, 54
normalization of mole fractions, 337
nozzle, 59, 66, 116, 157, 580
O
open system, 47
ordinary vapor compression cycle, 150
Otto cycle, 158
thermal efficiency, 158
P
partial condensation, 304
partial molar
Gibbs energy, 288, 290
properties, 288
volume, 289
partial pressure, 293, 294
path properties, 41
permutations, 92
phase behavior
classes, 448
phase envelope, 19, 286
Pitzer correlation, 198, 247
Plait point, 431
polytropic, 580
potential
Lennard-Jones, 9
square-well, 9, 610
Sutherland, 9, 219
potential energy, 6
intermolecular, 6
Poynting correction, 272, 273, 358
pressure, 12
equation, 211
gradient, 39
probability, 322
conditional, 322
process simulators, 623
properties
convenience, 175
measurable, 176
pump, 63, 116, 122, 164
purge gas, 308
Q
quadratic equations
solution, 599
quality, 26, 119, 258, 580
R
radial distribution function, 212, 608
Rankine cycle, 143
Raoults law, 299
deviations, 370
modified, 357
negative deviations, 310, 542
positive deviations, 310, 542
rdf
See radial distribution function
reaction coordinate, 484, 489
reduced pressure, 196
reduced temperature, 52, 195, 196
reference state, 5, 55, 233, 236, 243, 580
refrigeration, 149
regular solution theory, 368
See also van Laar, Scatchard-Hildebrand
theory
relative volatility, 413
reservoir, 15
residual contribution, 378, 386
residue curve, 470, 588
retrograde condensation, 343
reversible, 38, 66, 97
internally, 113
Reynolds number, 163
roots
See quadratic, cubic
S
saturated steam, 20
Index
saturation, 19
saturation pressure, 20
saturation temperature, 19
Scatchard-Hildebrand theory, 371, 587
second law of thermodynamics, 97
sensible heat, 580
separation of variables, 67, 69
simple system, 87, 174
sink, 15
SLE, 459, 580
solubility, 458
parameter, 371
solvation, 529, 580
Solver, 591, 595
specific heat, 580
specific property, 580
spinodal, 580
stable, 208
standard conditions, 580
standard heat of reaction, 492
standard state, 486, 488, 580
Gibbs energy of reaction, 487
state of aggregation, 21, 53, 56,
243, 492, 580
state properties, 16, 41
states, 16
reference, 243
statistical thermodynamics, 96
steady-state, 17, 65, 581
energy balance, 47
steam properties, 587
steam trap, 83
Stirling's approximation, 93
stoichiometric
coefficient, 483
number, 483
stoichiometry, 483
STP, 581
strategy
problem solving, 65
subcooled, 21, 581
successive substitution, 593
supercritical, 301
superficial molar density, 545
superficial mole fraction, 533
superficial moles, 544, 551
superheated, 21, 581
superheater, 61, 143
surface fraction, 390
sweep gas, 308
system, 15
closed, 15
open, 15
simple, 174
T
temperature, 16
reference, 496
thermal efficiency, 141, 581
thermodynamic efficiency, 581
third law of thermodynamics, 55
throttle, 59, 66, 116, 581
tie lines, 19, 430
ton of refrigeration capacity, 151
triple product rule, 178, 188
true molar density, 545
true mole fraction, 533
true moles, 544, 551
turbine, 62, 116, 119, 164
turbofan, 157
two-fluid theory, 384
U
UNIFAC, 360, 393, 407, 427, 428, 464, 586,
588
UNIQUAC, 388, 407, 588
unstable, 208, 581
unsteady-state, 65
V
valve, 116
See also throttle
van der Waals, 194
van der Waals loop, 273
van Laar, 368, 369, 374, 400, 585, 587
vant Hoff equation, 492, 550
shortcut, 495
vapor pressure, 20, 54, 197, 264, 274, 276,
290, 301
See also Antoine equation
shortcut, 260
velocity gradients, 39
virial coefficient
See equation of state, virial
viscosity, 163
viscous dissipation, 39
VLE, 581
VOC, 308
volatile organic compounds, 308
volume
saturated liquid, 272
volume fraction, 371, 390
volume of mixing, 297
W
wax, 465, 588
wet steam, 20, 581
659
660 Index
Wilson equation, 386, 392, 407
work, 15, 497
expansion/contraction, 35
flow, 37
maximum, 114
minimum, 114
shaft, 36
Z
Z
compressibility factor, 196
zeroth law of thermodynamics, 14