Learn the basics of thermodynamics in this complete and practice-oriented introduction for students of chemical engineering

Thermodynamics is a vital branch of physics that focuses upon the interaction of heat, work, and temperature with energy, radiation, and matter. Thermodynamics can apply to a wide range of sciences, but is particularly important in chemical engineering, where the interconnection of heat and work with chemical reactions or physical changes of state are studied according to the laws of thermodynamics. Moreover, thermodynamics in chemical engineering focuses upon pure fluid and mixture properties, phase equilibrium, and chemical reactions within the confines of the laws of thermodynamics.

Given that thermodynamics is an essential course of study in chemical and petroleum engineering, Thermodynamics for Chemical Engineers provides an important introduction to the subject that comprehensively covers the topic in an easily-digestible manner. Suitable for undergraduate and graduate students, the text introduces the basic concepts of thermodynamics thoroughly and concisely while providing practice-oriented examples and illustrations. Thus, the book helps students bridge the gap between theoretical knowledge and basic experiments and measurement characteristics.

Thermodynamics for Chemical Engineers readers will also find:

• Practice-oriented examples to help students connect the learned concepts to actual laboratory instruments and experiments
• A broad suite of illustrations throughout the text to help illuminate the information presented
• Authors with decades working in chemical engineering and teaching thermodynamics

Thermodynamics for Chemical Engineers is the ideal resource not just for undergraduate and graduate students in chemical and petroleum engineering, but also for anyone looking for a basic guide to thermodynamics.

Preface xi

1 Introduction 1

1.1 Definition 1

1.2 Dimensions, Fundamental Quantities, and Units 2

1.3 Secondary or Derived Physical Quantities 4

1.4 SI Usage of Units and Symbols 13

1.5 Thermodynamic Systems and Variables 14

1.6 Zeroth Law 16

Problems for Chapter 1 16

2 Energy and the First Law 21

2.1 Introduction 21

2.2 Energy 22

2.3 First Law of Thermodynamics 24

2.4 Application of Solution Procedure to Simple Cases 30

2.5 Practical Application Examples 34

2.5.1 Compressors/Pumps 34

2.5.2 Turbines/Expanders 35

2.5.3 Condensers/Vaporizers/Reboilers 36

2.5.4 Heat Exchanger 36

2.5.5 Sample Cylinder 38

2.6 Differential Form 39

2.7 Inserting Time: Unsteady-State Flow Process 39

2.8 Recap 40

Problems for Chapter 2 40

Reference 45

3 PVT Relations and Equations of State 47

3.1 Introduction 47

3.2 Graphical Representations 47

3.3 Critical Region 53

3.4 Tabular Representations 54

3.5 Mathematical Representations 56

3.5.1 Perfect and Ideal Gas EOS 57

3.5.2 Reversible Processes Involving Ideal Gases in Closed Systems 58

3.5.2.1 Constant Volume (Isochoric) Process 59

3.5.2.2 Constant Pressure (Isobaric) Process 59

3.5.2.3 Constant Temperature (Isothermal) Process 60

3.5.2.4 Adiabatic Process 60

3.5.2.5 Polytropic Processes 62

3.5.3 Virial Equation of State 65

3.5.3.1 Correlations for the Second and Third Virial Coefficient 69

3.5.4 Other Special Equations 75

3.5.4.1 Tait Equation 75

3.5.4.2 Rackett Equation 75

3.5.4.3 Riedel Equation 75

3.5.4.4 Yen and Woods Equation 76

3.5.4.5 Chueh and Prausnitz Equation 76

3.5.4.6 Generalized Lee-Kesler Correlation 76

3.5.5 Cubic Equations of State 77

3.5.5.1 van der Waals (vdW) Equation of State 77

3.5.5.2 Other Cubic EOS 79

3.5.5.3 Redlich-Kwong (RK) EOS 80

3.5.5.4 Soave-Redlich-Kwong (SRK) Equation of State 82

3.5.5.5 Peng-Robinson (PR) Equation of State 82

3.5.6 Multiparameter Equations of State 83

3.5.6.1 Benedict-Webb-Rubin (BWR) Equation of State 83

3.5.6.2 Boublik-Alder-Chen-Kreglewski 83

3.5.7 Reference Equation of State 85

3.6 Calculation of Volumes from EOS 86

3.7 Vapor Pressure and Enthalpy of Vaporization Correlations 89

3.8 Ideal Gas Enthalpy Changes: Applications 91

3.8.1 Heat of Reaction 91

3.8.1.1 Standard Heat of Reaction 91

3.8.1.2 Standard Heat of Formation 92

3.8.1.3 Standard Heat of Combustion 92

3.8.2 Temperature Dependence of the Heat of Reaction 92

3.8.3 Practical Calculations 94

3.8.3.1 Adiabatic Flame Temperature 95

3.8.3.2 Reaction with Heat Transfer 95

Problems for Chapter 3 99

References 109

4 Second Law of Thermodynamics 113

4.1 Introduction 113

4.2 General and Classical Statements of the Second Law 114

4.3 Heat Engines, Refrigerators, and Cycles 116

4.4 Implications of the Second Law 117

4.5 Efficiency 127

4.6 Specific Heat/Heat Capacity 128

4.6.1 Entropy Changes for Ideal Gases 130

4.7 Entropy Balance Equation for Open Systems 133

4.8 Availability and Maximum/Minimum Work 137

Problems for Chapter 4 139

5 Thermodynamic Relations 145

5.1 Introduction 145

5.2 Mathematics Review 145

5.2.1 Exact Differentials 145

5.2.2 Inexact Differentials and Line Integration 146

5.2.3 Properties of Functions of Several Variables 147

5.3 Fundamental Thermodynamics Equation 148

5.4 Legendre Transforms 149

5.5 Maxwell Relations 151

5.6 Derivation of Thermodynamic Relationships 153

5.7 Open Systems: Chemical Potential 155