Introduction to CHEMICAL ENGINEERING THERMODYNAMICS

Front Cover
PHI Learning Pvt. Ltd., Sep 2, 2014 - Technology & Engineering - 304 pages
This book, now in its second edition, continues to provide a comprehensive introduction to the principles of chemical engineering thermodynamics and also introduces the student to the application of principles to various practical areas. The book emphasizes the role of the fundamental principles of thermodynamics in the derivation of significant relationships between the various thermodynamic properties. The initial chapter provides an overview of the basic concepts and processes, and discusses the important units and dimensions involved. The ensuing chapters, in a logical presentation, thoroughly cover the first and second laws of thermodynamics, the heat effects, the thermodynamic properties and their relations, refrigeration and liquefaction processes, and the equilibria between phases and in chemical reactions. The book is suitably illustrated with a large number of visuals. In the second edition, new sections on Quasi-Static Process and Entropy Change in Reversible and Irreversible Processes are included. Besides, new Solved Model Question Paper and several new Multiple Choice Questions are also added that help develop the students’ ability and confidence in the application of the underlying concepts. Primarily intended for the undergraduate students of chemical engineering and other related engineering disciplines such as polymer, petroleum and pharmaceutical engineering, the book will also be useful for the postgraduate students of the subject as well as professionals in the relevant fields.
 

Contents

683 Residual Enthalpy Relation from Cubic Equation of State
246
69 Fugacity and Fugacity Coefficient
247
691 Effect of Temperature and Pressure on Fugacity
249
692 Fugacity Coefficient from Compressibility Factor
250
694 Fugacity Coefficient by Equation of State
252
Summary
253
Important Equations
254
Exercises
256

14 Terminology and Fundamental Concepts
14
142 State of a System
17
143 Thermodynamic Equilibrium
18
144 Boundary Wall of a System
19
146 Properties of a System
20
15 Zeroth Law of Thermodynamics
21
18 Temperature and Ideal Gas Temperature Scale
22
19 Reversible Process
24
110 Irreversible Process
26
1111 Quasistatic Work for Various Processes
28
Summary
32
Important Equations
35
Exercises
36
2 First Law ofThermodynamics
39
Mechanical Equivalence of Heat
40
22 Statement of First Law of Thermodynamics
41
24 Concept of Internal Energy
42
25 Sign Convention for Heat and Work Interactions
43
27 Internal Energy of an Ideal Gas
47
28 Thermodynamic State
48
210 Enthalpy
49
211 Heat Capacity
51
2111 Relation between CP and CV
52
212 Adiabatic Process or Isocaloric Process
54
213 Reversible Adiabatic Expansion of Ideal Gas
55
2133 Enthalpy H
56
2135 Relation between Pressure and Volume
57
214 ConstantVolume Isochoric Process
60
216 ConstantTemperature Isothermal Process
61
217 Mass Balance for Open System
71
218 Energy Balance for Open System or First Law of Thermodynamics to Flow Processes
72
Summary
75
Key Terms
76
Exercises
78
3 Properties of PureSubstances
83
31 Pure Substance
84
34 PVT Behaviour of Pure Substance
88
342 PV Diagram
89
343 PT Diagram
90
35 Equation of StateMathematical Representation of PVT Behaviour
91
36 Ideal Gas Equation of State
92
37 Equation of State for Real Gases
96
372 RedlichKwong Equation of State
100
373 RedlichKwongSoave Equation of State
102
374 PengRobinson Equation of State
103
377 Virial Equation of State
104
38 Compressibility Factor
109
39 Law of Corresponding State
110
310 Acentric Factor
111
Summary
113
Important Equations
115
Exercises
117
4 Heat Effects
121
41 Exothermic and Endothermic Reactions
122
43 Hesss Law of Constant Heat Summation
123
431 Thermodynamic Explanation of Hesss Law
124
45 Standard Heat of Formation
125
46 Standard Heat of Combustion
128
47 Adiabatic Flame Temperature
130
Kirchhoff s Equation
132
Summary
136
Important Equations
137
Exercises
138
5 Second Law of Thermodynamics
141
51 Limitations of First Law of Thermodynamics
142
52 Basic Concepts of Heat Engines Heat Pumps and Refrigerators
143
522 Heat Pumps
145
523 Refrigerators
146
53 Statements of Second Law of Thermodynamics
147
531 KelvinPlanck Statement
148
533 Equivalence of KelvinPlanck and Clausius Statements
149
54 Carnot Cycle
150
541 Efficiency of Carnot Cycle
154
55 Carnot Theorem
158
56 Thermodynamic Temperature Scale
160
57 Concept of Entropy
163
571 EntropyA Thermodynamic State Function
164
572 EntropyAt a glance
165
573 Relation between Entropy and Internal Energy
166
581 Entropy Change in Reversible Process
167
582 Entropy Change in Irreversible Process
168
583 Entropy at Phase Change
169
584 Entropy Changes of Ideal Gas
170
585 Entropy Changes in Mixture of Nonidentical Ideal Gases
172
586 Entropy Changes with Temperature
174
59 Mathematical Statement of Second Law of Thermodynamics
178
510 Entropy Balances for Open Systems
183
511 The Third Law of Thermodynamics
184
Microscopic Point of View
185
513 Criterion of Irreversibility
187
515 Irreversibility and Lost Work
189
Summary
191
Key Terms
193
Important Equations
194
Exercises
197
6 THERMODYNAMIC PROPERTY RELATIONS
200
61 Thermodynamic Properties
201
63 Free Energy Functions
204
631 Helmholtz Free Energy Work Function A
205
632 Gibbs Free Energy Gibbs Function G
206
633 Variation of Free Energy with Pressure at Constant Temperature
207
641 Fundamental Property Relations
208
642 Maxwells Relations
209
643 Clapeyron Equation
210
644 GibbsHelmholtz Equation
214
645 General Equations for Differential Changes in Internal Energy
216
646 General Equations for Differential Changes in Enthalpy
217
647 General Equations for Differential Changes in Entropy
218
648 TdS Equations
219
6410 Isothermal Compressibility and Volume Expansivity
223
6411 JouleThomson Coefficient
230
65 Residual Property
236
662 Residual Enthalpy Relation from Equation of State
238
663 Residual Entropy Relation from Equation of State
240
664 Residual Gibbs Function Relation from Equation of State
241
67 Residual Properties from Virial Equation of State
242
68 Residual Properties from Cubic Equation of State
245
7 THERMODYNAMICS TO FLOW PROCESSES
261
711 Continuity Equation and Mass Analysis of Control Volume
262
712 Energy Analysis of Control Volume and Bernoullis Equation
265
713 Throttling Device
269
714 Compressor
271
715 Ejectors or Jet Pumps
277
716 Heat Exchangers
278
717 Nozzles and Diffusers
281
72 Unsteadyflow Processes and Devices
289
Summary
291
Important Equations
292
Exercises
294
8 REFRIGERATION AND LIQUEFACTION PROCESSES
296
81 Refrigeration
297
812 Coefficient of Performance
299
813 Capacity of Refrigerator
300
814 Carnot Refrigeration Cycle
301
815 VapourCompression Refrigeration Cycle
306
816 Absorption Refrigeration Cycle
313
817 Air Refrigeration Cycle
316
818 Comparative Study of Carnot VapourCompression Absorption and Air Refrigeration Systems
322
819 Selection of Right Refrigerant
323
82 Liquefaction Process
328
822 JouleThomson Expansion Isenthalpic Expansion
331
823 Exchanging Heat at Constant Pressure
333
Key Terms
334
Important Equations
335
Exercises
336
PROPERTIES
340
91 Partial Molar Properties
341
911 Evaluation of Partial Molar Properties
343
92 Chemical Potential
350
921 Influence of Pressure on Chemical Potential
352
93 Activity and Activity Coefficient
354
931 Temperature Dependence of Activity Coefficient
355
94 GibbsDuhem Equation
356
95 Fugacity of Component in Mixture
360
96 Fugacity of Liquids and Solids
362
Gibbs Theorem
367
972 Gibbs Free Energy Change of Mixing
369
973 Enthalpy Change of Mixing
370
974 Volume Change of Mixing
372
98 Excess Property of Mixture
373
LewisRandall Rule
376
910 Raoults Law and Ideal Solution
378
911 Henrys Law and Dilute Solution
379
Summary
381
Key Terms
382
Exercises
384
10 VAPOURLIQUID EQUILIBRIUM
390
101 Criteria of Equilibrium
391
102 Criterion for Phase Equilibrium
393
103 Phase Rule for Nonreacting Systems and Duhems Theorem
394
104 Phase Equilibrium for Singlecomponent System
396
105 Phase Equilibrium for Multicomponent System
398
106 VapourLiquid Equilibrium Diagram for Binary Mixture
399
1061 TemperatureComposition Txy Diagram
400
1062 PressureComposition Pxy Diagram
401
Raoults Law
403
108 Modified Raoults Law for VapourLiquid Equilibrium
405
Nonideal Solutions
411
1010 Azeotrope Formation
413
Excess Gibbs Free Energy Model
415
10111 Wohls Equation
416
10112 Margules Equation
417
10113 van Laar Equation
418
Wilson and NRTL Equations
422
10115 Universal QuasiChemical Equation UNIQUAC
426
10116 Universal Functional Activity Coefficient UNIFAC Method
428
1012 VapourLiquid Equilibrium at High Pressure
429
10121 Methodology for Bubble Point Calculations
431
10122 Methodology for Dew Point Calculations
434
10123 Flash Calculations
437
1013 Thermodynamic Consistency Test of VLE Data
441
Summary
445
Key Terms
447
Important Equations
448
Exercises
450
11 ADDITIONAL TOPICS IN PHASE EQUILIBRIUM
456
1111 Effect of Temperature on LiquidLiquid Equilibrium
457
112 Ternary LiquidLiquid Equilibrium
460
113 SolidLiquid Equilibrium
461
114 Depression of Freezing Point of Solution
463
115 Elevation of Boiling Point of Solution
466
116 SolidVapour Equilibrium
469
117 Osmotic Pressure and Equilibrium
470
Key Terms
473
Exercises
474
12 CHEMICAL REACTION EQUILIBRIA
476
121 Reaction Coordinate
477
122 Multireaction Stoichiometry
479
123 Equilibrium Criterion of Chemical Reaction
481
124 Equilibrium Constant
482
125 Standard Gibbs Free Energy Change
484
126 Feasibility of Chemical Reaction
485
127 Relation between Equilibrium Constant and Standard Gibbs Free Energy Change
487
Vant Hoff Equation
489
129 Homogeneous Gasphase Reaction Equilibrium
494
1210 Effect of Pressure on Chemical Equilibrium
498
1211 Effect of Other Factors on Equilibrium Conversion
500
12112 Effect of Presence of Excess Reactants
502
1212 Homogeneous LiquidPhase Reaction Equilibrium
503
1213 Heterogeneous Reaction Equilibria
506
12132 LiquidGas Reaction Equilibrium
510
1214 Phase Rule For Reacting Systems
511
1215 Chemical Equilibrium for Simultaneous Reactions
513
1216 Fuel Cell
517
Summary
519
Key Terms
520
Important Equations
521
Exercises
523
Property Tables
531
Solved Model Question Papers
561
Multiple Choice Questions
614
Bibliography
657
Index
659
Copyright

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About the author (2014)

Gopinath Halder, Ph.D., is Associate Professor, Department of Chemical Engineering, National Institute of Technology, Durgapur, West Bengal. Earlier, he served as Assistant Professor in the Department of Petroleum Engineering, Indian School of Mines University, Dhanbad. Prof. Halder has more than two decades of teaching and research experience. A member of various professional societies such as Indian Institute of Chemical Engineers (IIChE) and Indian Society for Technical Education (ISTE), Dr. Halder has authored several research papers published in reputed national and international journals. His areas of research interest include Chemical Engineering Thermodynamics and Environmental Engineering.

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