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Classical Thermodynamics of Fluid Systems
Principles and Applications
This text explores the connections between different thermodynamic subjects related to fluid systems. Emphasis is placed on the clarification of concepts by returning to the conceptual foundation of thermodynamics and special effort is directed to the use of a simple nomenclature and algebra. The book presents the structural elements of classical thermodynamics of fluid systems, covers the treatment of mixtures, and shows via examples and references both the usefulness and the limitations of classical thermodynamics for the treatment of practical problems related to fluid systems. It also includes diverse selected topics of interest to researchers and advanced students and four practical appendices, including an introduction to material balances and stepbystep procedures for using the Virial EOS and the PRSV EOS for fugacities and the ASOGKT group method for activity coefficients. The OliveraFuentes table of PRSV parameters for more than 800 chemical compounds and the GmehlingTochigi tables of ASOG interaction parameters for 43 groups are included.
less451 pages; ISBN 9781315399058
Read online, or download in secure PDF format
Title: Classical Thermodynamics of Fluid Systems
Author: Juan H. Vera; Grazyna WilczekVera
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 Contents
PART I. FUNDAMENTALS
Chapter 1. Basic Concepts and Definitions
The Concepts of System and Surroundings
The Thermodynamic Process, State and Path Functions
The Concept of a Reversible Process
Compressible and Incompressible Fluids
Chapter 2. The First and Second Laws of Thermodynamics
Principle of Conservation of Energy in a Closed System
Reversible or Quasistatic Processes
The Concept of Entropy, the Extremum Principle and Clausius Inequality
Confirmation of agreement with the directional nature of heat flow.
Refrigerators, AirConditioners and Heat Pumps
Heat Engines
Chapter 3. Conservation of Energy in an Open Flow System. Definition of enthalpy
Closed System Moving in Space
Open Flow System at Unsteady State
Definition of Enthalpy
Open Flow System at Steady State
Mechanical Energy Balance
Use of the Enthalpy Function in Closed Systems
Chapter 4. The Algebra of State Functions. The Helmholtz and Gibbs Functions
Thermodynamic Functions in Open Systems
The Chemical Potential
Maxwell’s Relations
Other Useful Mathematical Relations
Chapter 5. Calculation of Changes in the Value of Thermodynamic Properties
Measurable Properties
Calculation of Property Changes for Solid and Liquid Phases
Calculation of Property Changes for Phase Change of a Pure Compound
Use of Equations of State (EOS) for a Pure Compound or for a Mixture of Constant Composition
Case of Independent Variables v and T, :
Case of Independent Variables P and T, :
Changes in the Values of the Thermodynamic Properties of the Ideal Gas
Adiabatic Reversible Compression or Expansion of the Ideal Gas
Deviations from the Ideal Gas Behavior
Preparation of Tables and Plots of Thermodynamic Properties
PART II. MIXTURES
Chapter 6. Partial Molar Properties and Property Changes by Mixing
Partial Molar Properties and the GibbsDuhem Equation
Maxwell Relations Applied to Partial Molar Properties
Generality of the Relations between Thermodynamic Properties
Limiting Values of the Partial Molar Properties
Partial Molar Properties as a Function of Mole Fractions
Equations and Plots for Binary Mixtures
Property Changes by Mixing
Ideal Mixtures
Chapter 7. The Chemical Potential and the GibbsHelmholtz Equation
The Chemical Potential as Partial Molar Property
Chemical Potential Dependence on Temperature and Pressure
The GibbsHelmholtz Equation
The GibbsDuhem Equation in Terms of Chemical Potentials
Maxwell Relation in Terms of the Chemical Potential
Chapter 8. The Principles of Physical and Chemical Equilibrium
Extremum Principle for Functions Other than Entropy
Phase Equilibrium without Chemical Reactions
Chemical Equilibrium in a Single Phase Closed System
Phase and Chemical Equilibrium in a Closed System
Chapter 9. The Phase Rule and Duhem Theorem
The Phase Rule for Non Reacting Systems
The Phase Rule for Reacting Systems
Common Cases of Application of the Phase Rule
The Duhem Theorem
The Phase Rule with Additional Constraints
Chapter 10. Generality of the Thermodynamic Treatment
Equilibrium Involving Ions
Adsorption of Chemical Species on a Surface
Chapter 11. The Ideal Gas and Ideal Gas Mixtures
Chemical Potential of a Compound in an Ideal Gas Mixture
Property Changes in the Mixing of Ideal Gases
Chapter 12. The Use of Fugacity and Activity in Equilibrium Studies
Definition of Fugacity and Fugacity Coefficient
Phase Equilibrium in Terms of Fugacities
Definition of Activity
Chemical Equilibrium in Terms of Activity
Property Changes of Reaction
Chapter 13. Calculation of Fugacities from Equations of State (EOS)
Use of Volume Explicit EOS:
Use of Pressure Explicit EOS:
Chapter 14. Fugacity of a Mixture and of Its Components
Fugacity and Fugacity Coefficient of a Mixture
Fugacity Coefficients as Partial Properties
The GibbsDuhem Equation in Term of Fugacity Coefficients
The GibbsDuhem Equation in Terms of Fugacities
Chapter 15. Fugacities and Activities in Liquid Mixtures of Non Electrolytes
Lewis’ Convention for Activity Coefficients
Henry’s Convention for the Activity Coefficient of a Solute
Generalized Definition of Activity
Relations between the Activity Coefficients in Lewis’ and Henry’s Conventions
Generalized Equations for an Ideal Mixture
Properties of Ideal Mixtures in Lewis’ Convention
Use of Molality as a Measure of Concentration
Chapter 16. Activity Coefficients and Excess Properties
Evaluation of the Fugacity of a Pure Compound Liquid at P and T of the system
Evaluation of Activity Coefficients from Phase Equilibrium Studies
The GibbsDuhem Equation in Terms of Activity Coefficients in Lewis’ Convention
The Excess Gibbs Energy and Other Excess Functions in Any Convention
Activity Coefficients and their Relation to Excess Functions and in Any Convention
Thermodynamic Consistency of Activity Coefficients in Lewis’ Convention
Excess Gibbs Energy in Lewis’ Convention in Terms of Fugacity Coefficients
Chapter 17. Mixture Behavior, Stability and Azeotropy
Basic Relations
Positive and Negative Deviations from ideal Behavior in Lewis’ Sense.
Berg Classification of Liquids and Mixture Behavior
Partial Miscibility
Condition for Stability of Liquid Mixtures
Phase Equilibrium Diagrams
Chapter 18. The Thermodynamics of Aqueous Electrolyte Solutions
Basic Relations
Mean Ionic Activity Coefficient.
Osmotic Coefficient
The Need for Considering the Existence of Individual Ions
The Behavior of the Activity of Individual Ions
DebyeHückel Theory for Dilute Aqueous Electrolyte Solutions
Limiting Values of the Mean Ionic Activity Coefficient and the Osmotic Coefficient at High Dilution
Indirect Measurement of the Mean Ionic Activity Coefficient
Direct Electrochemical Measurement of the Mean Ionic Activity Coefficient
Electrochemical Measurement of the Mean Ionic Activity Coefficient with Independent Measurements for the Cation and the Anion
The Activity of a Second Solute in an Aqueous Electrolyte Solution
Aqueous Solutions of Weak Electrolytes
Charged Organic Molecules
Experiment to Determine the Charge of a Protein
Conclusions
PART III. APPLICATIONS
Chapter 19. The Thermodynamics of Chemical Reactions
Statement of the Problem and Basic Definitions
Determination of the Number of Independent Reactions
Example 1. Catalytic Oxidation of Ammonia
Example 2. Production of 1,3 Butadiene
Example 3. Isomerization of 1,3 Butadiene
The Thermodynamic Equilibrium Constant in Terms of the Equilibrium Compositions
The Solvay Process
Reactions in the Gas Phase
Reactions in the Liquid Phase
Reactions with Compounds in the Solid Phase
Calculation of the Thermodynamic Equilibrium Constant
Examples of Evaluation of the Thermodynamic Equilibrium Constant
Example of a Heterogeneous Reaction
Example of a Reaction in the Gas Phase
Example of a Reaction in Liquid Phase
Expression of K_{x} as a Function of the Conversion of One of the Reactants
Chemical Equilibrium with More than One Independent Reaction
Chapter 20. The Thermodynamics of Equilibrium Based Separation Processes
Distribution Coefficient and Selectivity
Azeotropic and Solvent Distillation
VaporLiquid Equilibrium
Bubble and Dew Point Calculations
Flash Calculations
LiquidLiquid Equilibrium
SolidLiquid Equilibrium
Phase Equilibrium through Membranes
Recapitulation of Concepts
Chapter 21. Heat Effects in Pure Compounds and Mixtures
Heat Effects in Pure Compounds
Example 1. Determination of Steam Quality
Heat Effects in Mixtures
Heat of Mixing,
EnthalpyConcentration Diagrams
Example 2. Calculation of a Heat of Dilution from Heats of Formation
Example 3. Calculation of the Enthalpy of a Solution
Use of Enthalpy Concentration Information
Mixing of Two Solutions
Example 4. Mixing of Diluted and Concentrated H_{2}SO_{4}
Concentration of a Solution of a Nonvolatile Solute by Evaporation of Solvent
Example 5. Dilution of a Concentrated NaCl solution
Heat Effects in Reactive Systems
Example 6. Calculation of the Heat of Formation
Example 7. Calculation of Standard Heats of Reaction
Example 8. Heat Effects in Reacting Mixtures
Example 9. Production of Allyl chloride in an Adiabatic Continuous Stirred Tank Reactor
Chapter 22. Adsorption of Gases in Solids
A Twodimensional Thermodynamic Approach
The Gibbs Treatment for the Isothermal Adsorption of a Pure Compound Gas at a Solid Surface
Isothermal Adsorption of a Gas Mixture
Example of the Gibbs Treatment for the Adsorption of a Gas Mixture
Thermal Effects on Adsorption
Heat Effects in "Ideal" Adsorption of a Mixture of Gases
PART IV. SELECTED TOPICS
Chapter 23. The Thermodynamics of Flow of Compressible Fluids
Subsonic, Sonic and Supersonic Flow
A Thermodynamic Understanding of the Limiting Speed
Enthalpy and Entropy Changes in Compressible Flow
Relation of Fluid Properties to Mach Number at Entrance Condition
Determination of Critical Length
Chapter 24. Elements of Statistical Thermodynamics
The Canonical Ensemble and Probability
The Internal Energy and the Partition Function
Entropy and Probability
Equation of State, Chemical Potential and Partition Function
Chapter 25. Statistical Thermodynamics Basis of Equations of State
Equation of State for the Ideal Gas
Virial Equations of State
Cubic Equations of State
Relation of Intermolecular Potentials to the Second Virial Coefficient
Second Virial Coefficients of Binary Mixtures
Mixing Rule for Cubic Equations of State
Noncubic Equations of State of Theoretical Interest
Chapter 26. Statistical Thermodynamics Basis of Excess Gibbs Functions
The van Laar Model
The Regular Solution Theory
The TwoSuffix Margules Equation and the RedlichKister Polynomial
The Flory Huggins and the GuggenheimStaverman’s Models for Athermal Mixtures
The Complete Regular Solutions and FloryHuggins Expressions
Modern Times
The Quasi Chemical Theory
The Wilson Equation for the Excess Gibbs Energy
The Birth of the Solution of Groups Method to Calculate Activity Coefficients in Liquid Mixtures
The Analytical Solution of Groups, ASOG
The NonRandomTwoLiquid Equation (NRTL) for the Excess Gibbs Energy
The UNIQUAC Equation
UNIFAC
Wang’s Renormalization of Guggenheim’s Partition Function
SAFT
Conclusions
Summary of Some Useful Equations for the Correlation of Activity Coefficients
Chapter 27. The Activity Coefficients of Individual Ions. Measurements and Modeling
The Crux of the Problem
Methods Used to Reduce the Experimental Data
Indirect Electrochemical Approach
Direct Electrochemical Approach
Effect of an Error in the Sign of the Junction Potential
Additional Experimental Studies
Henderson’s Approximation
New Equation to Calculate Liquid Junction Potentials
Use of the Activity of Individual Ions in Multiions Aqueous Solutions
Comparison of Experimental Results for the Activity of Individual Ions Obtained by Different Researchers
Emerging Theories of Electrolyte Solutions
Fraenkel’s Smallerion Shell (SiS) Theory.
Liu and Eisenberg PoissonFermi (PF) Theory.
PART V. APPENDICES
Appendix A. Material Balances in Open Flow Systems
Material Balances for Systems without Chemical Reactions
Material Balances for Systems with Chemical Reactions
Appendix B. Working with the Virial EOS
The Virial EOS Truncated After the Third Term
Fugacity Coefficient of a Pure Compound
The Virial EOS for Mixtures
Fugacity Coefficient of a Compound in a Mixture
Appendix C. Working with the PRSV EOS
The PRSV EOS
Exact Solution of a Cubic Equation
Volume roots for PRSV EOS at given T and P
How to Calculate the Saturation Pressure of a Pure Compound with PRSV EOS
How to Calculate Saturated Liquid Molar Volumes with the PRSV EOS
How to Calculate Enthalpies and Heats of Vaporization with the PRSV EOS
How to Calculate Fugacity Coefficients in Mixtures with PRSV
A ‘TwoBinaryParameter’ Mixing Rule and its Extension to Multicomponent Mixtures
A Consistent Method to Combine the PRSV EOS with Excess Gibbs Energy Models
Tables of Parameters
Additional Table of PRSV Parameters Contributed by Professor Claudio Olivera Fuentes.
Appendix D. Working with ASOGKT
Basic Equations
How to Read Parameters in Table D.2
The System HexaneMethanol
GmehlingTochigi Complete Tables of Parameters
Abbreviations
Index

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