Chemical Engineering
Thermodynamics II
(CHE 303 Course Notes)
,
,Contents
Chapter 1: Introduction
1.1 Basic Definitions 1-1
1.2 Property 1-2
1.3 Units 1-3
1.4 Pressure 1-4
1.5 Temperature 1-6
1.6 Energy Balance 1-7
Example 1.6-1: Gas in a piston-cylinder system 1-8
Example 1.6-2: Heat Transfer through a tube 1-10
Chapter 2: Thermodynamic Property Relationships
2.1 Type of Thermodynamic Properties 2-1
Example 2.1-1: Electrolysis of water 2-3
Example 2.1-2: Voltage of a hydrogen fuel cell 2-4
2.2 Fundamental Property Relations 2-5
Example 2.2-1: Finding the saturation pressure 2-8
2.3 Equations of State 2-11
2.3-1 The Virial Equation of State 2-11
Example 2.3-1: Estimate the tank pressure 2-12
2.3-2 The Van de Walls Equation of State 2-13
Example 2.3-2: Expansion work with Van de Walls EOS 2-15
2.3-3 Soave-Redlick-Kwong (SRK) Equation 2-17
Example 2.3-3: Gas Pressure with SRK equation 2-17
Example 2.3-4: Volume calculation with SRK equation 2-18
2.4 Properties Evaluations 2-21
Example 2.4-1: Exhaust temperature of a turbine 2-21
Example 2.4-2: Change in temperature with respect to pressure 2-24
Example 2.4-3: Estimation of thermodynamic property 2-26
Example 2.4-4: Heat required to heat a gas 2-27
Chapter 3: Phase Equilibria
3.1 Phase and Pure Substance 3-1
3.2 Phase Behavior 3-4
Example 3.2-1: Specific volume from data 3-7
3.3 Introduction to Phase Equilibrium 3-11
3.4 Pure Species Phase Equilibrium 3-12
3.4-1 Gibbs Free Energy as a Criterion for Chemical Equilibrium 3-12
3.4-2 The Chemical Potential 3-13
3.4-3 Vapor Liquid Phase Equilibrium 3-16
Example 3.4-1: Horsepower of a compressor 3-18
Example 3.4-2: Two-level refrigeration system 3-19
3.4-4 The Clapeyron Equation 3-23
Example 3.4-3: Triple point estimation 3-27
3.5 Refrigeration 3-30
i
, Example 3.5-1: A vapor compression refrigeration cycle 3-31
Example 3.5-2: A refrigeration cycle using refrigerant 134a 3-32
Example 3.5-3: A refrigeration cycle using refrigerant 134a 3-34
Example 3.5-4: A refrigeration cycle with nonideal compressor 3-35
3.6 Partial Molar Properties 3-36
Example 3.6-1: Partial molar volume 3-37
Example 3.6-2: Enthalpy of mixing 3-38
Example 3.6-3: Enthalpy-concentration chart 3-39
Chapter 4: Principle of Phase Equilibrium II
4.1 The Phase Rule 4-1
Example 4.1-1: The degree of freedom 4-1
Example 4.1-2: Degree of freedom for vapor-liquid equilibrium 4-2
4.2 The Fugacity 4-3
Example 4.2-1: Fugacity of liquid water 4-5
Example 4.2-2: Fugacity using Van der Waals EOS 4-6
Example 4.2-3: Fugacity of steam 4-10
Example 4.2-4: Change in Gibbs energy 4-11
4.3 Fugacity of Species i in a Gas Mixture 4-15
Example 4.3-1: Fugacity using Peng-Robinson EOS 4-17
4.4 Fugacity in the Liquid Phase 4-19:20
Chapter 5: Applied Phase Equilibrium
5.1 Vapor-Liquid Equilibrium for Ideal Systems 5-1
Example 5.1-1: Bubble point temperature calculation 5-3
Example 5.1-2: Bubble point pressure calculation 5-5
Example 5.1-3: Dew point temperature calculation 5-6
Example 5.1-4: Dew point pressure calculation 5-8
Example 5.1-5: Txy diagram for benzene-toluene mixture 5-9
Example 5.1-6: Dew point pressure using K-values 5-11
5.2 Isothermal Flash Calculation Using K-values 5-15
Example 5.2-1: Isothermal flash with V/F specified 5-18
Example 5.2-2: Isothermal flash with T specified 5-20
5.3 Vapor-Liquid Equilibrium with Non-ideal Liquid 5-23
Example 5.3-1: Bubble point pressure with Van Laar model 5-25
Example 5.3-2: Bubble point temperature with Wilson model 5-26
Example 5.3-3: Dew point temperature with Wilson model 5-28
Example 5.3-4: Txy diagram with Wilson model 5-31
5.4 Fitting Activity Coefficient Models with VLE Data 5-35
Example 5.4-1: Evaluation of Margules and Van Laar parameters 5-37
Example 5.4-2: Evaluation of Wilson parameters 5-43
5.5 Azeotropes 5-45
Example 5.5-1: Evaluation of Wilson parameters 5-50
5.6 Estimation of Activity Coefficients 5-52
Example 5.6-1: Acetone mole fraction in a system with air 5-52
Example 5.6-2: Solubility of ethane in n-heptanol 5-54
5.7 Phase Behavior in Partially Miscible Systems 5-55
ii
Thermodynamics II
(CHE 303 Course Notes)
,
,Contents
Chapter 1: Introduction
1.1 Basic Definitions 1-1
1.2 Property 1-2
1.3 Units 1-3
1.4 Pressure 1-4
1.5 Temperature 1-6
1.6 Energy Balance 1-7
Example 1.6-1: Gas in a piston-cylinder system 1-8
Example 1.6-2: Heat Transfer through a tube 1-10
Chapter 2: Thermodynamic Property Relationships
2.1 Type of Thermodynamic Properties 2-1
Example 2.1-1: Electrolysis of water 2-3
Example 2.1-2: Voltage of a hydrogen fuel cell 2-4
2.2 Fundamental Property Relations 2-5
Example 2.2-1: Finding the saturation pressure 2-8
2.3 Equations of State 2-11
2.3-1 The Virial Equation of State 2-11
Example 2.3-1: Estimate the tank pressure 2-12
2.3-2 The Van de Walls Equation of State 2-13
Example 2.3-2: Expansion work with Van de Walls EOS 2-15
2.3-3 Soave-Redlick-Kwong (SRK) Equation 2-17
Example 2.3-3: Gas Pressure with SRK equation 2-17
Example 2.3-4: Volume calculation with SRK equation 2-18
2.4 Properties Evaluations 2-21
Example 2.4-1: Exhaust temperature of a turbine 2-21
Example 2.4-2: Change in temperature with respect to pressure 2-24
Example 2.4-3: Estimation of thermodynamic property 2-26
Example 2.4-4: Heat required to heat a gas 2-27
Chapter 3: Phase Equilibria
3.1 Phase and Pure Substance 3-1
3.2 Phase Behavior 3-4
Example 3.2-1: Specific volume from data 3-7
3.3 Introduction to Phase Equilibrium 3-11
3.4 Pure Species Phase Equilibrium 3-12
3.4-1 Gibbs Free Energy as a Criterion for Chemical Equilibrium 3-12
3.4-2 The Chemical Potential 3-13
3.4-3 Vapor Liquid Phase Equilibrium 3-16
Example 3.4-1: Horsepower of a compressor 3-18
Example 3.4-2: Two-level refrigeration system 3-19
3.4-4 The Clapeyron Equation 3-23
Example 3.4-3: Triple point estimation 3-27
3.5 Refrigeration 3-30
i
, Example 3.5-1: A vapor compression refrigeration cycle 3-31
Example 3.5-2: A refrigeration cycle using refrigerant 134a 3-32
Example 3.5-3: A refrigeration cycle using refrigerant 134a 3-34
Example 3.5-4: A refrigeration cycle with nonideal compressor 3-35
3.6 Partial Molar Properties 3-36
Example 3.6-1: Partial molar volume 3-37
Example 3.6-2: Enthalpy of mixing 3-38
Example 3.6-3: Enthalpy-concentration chart 3-39
Chapter 4: Principle of Phase Equilibrium II
4.1 The Phase Rule 4-1
Example 4.1-1: The degree of freedom 4-1
Example 4.1-2: Degree of freedom for vapor-liquid equilibrium 4-2
4.2 The Fugacity 4-3
Example 4.2-1: Fugacity of liquid water 4-5
Example 4.2-2: Fugacity using Van der Waals EOS 4-6
Example 4.2-3: Fugacity of steam 4-10
Example 4.2-4: Change in Gibbs energy 4-11
4.3 Fugacity of Species i in a Gas Mixture 4-15
Example 4.3-1: Fugacity using Peng-Robinson EOS 4-17
4.4 Fugacity in the Liquid Phase 4-19:20
Chapter 5: Applied Phase Equilibrium
5.1 Vapor-Liquid Equilibrium for Ideal Systems 5-1
Example 5.1-1: Bubble point temperature calculation 5-3
Example 5.1-2: Bubble point pressure calculation 5-5
Example 5.1-3: Dew point temperature calculation 5-6
Example 5.1-4: Dew point pressure calculation 5-8
Example 5.1-5: Txy diagram for benzene-toluene mixture 5-9
Example 5.1-6: Dew point pressure using K-values 5-11
5.2 Isothermal Flash Calculation Using K-values 5-15
Example 5.2-1: Isothermal flash with V/F specified 5-18
Example 5.2-2: Isothermal flash with T specified 5-20
5.3 Vapor-Liquid Equilibrium with Non-ideal Liquid 5-23
Example 5.3-1: Bubble point pressure with Van Laar model 5-25
Example 5.3-2: Bubble point temperature with Wilson model 5-26
Example 5.3-3: Dew point temperature with Wilson model 5-28
Example 5.3-4: Txy diagram with Wilson model 5-31
5.4 Fitting Activity Coefficient Models with VLE Data 5-35
Example 5.4-1: Evaluation of Margules and Van Laar parameters 5-37
Example 5.4-2: Evaluation of Wilson parameters 5-43
5.5 Azeotropes 5-45
Example 5.5-1: Evaluation of Wilson parameters 5-50
5.6 Estimation of Activity Coefficients 5-52
Example 5.6-1: Acetone mole fraction in a system with air 5-52
Example 5.6-2: Solubility of ethane in n-heptanol 5-54
5.7 Phase Behavior in Partially Miscible Systems 5-55
ii
