CHE - 620 and MT-603: Chemical Thermodynamics

CHE - 620 and MT-603

Chemical and Materials Engineering Thermodynamics

Lecture Notes and Homework

     The course expands and deepens the understanding of Chemical Engineering Thermodynamics obtained in undergraduate studies. The course provides a more consistent and detailed description of:

▪ Laws of thermodynamics;

▪ Mathematics of fundamental thermodynamic relationships;

▪ Description of equilibria and stability conditions;

▪ Properties of pure materials and thermodynamics of mixtures;

▪ Treatment of gas-liquid, liquid-liquid, gas-solid, and solid-solid equilibria;

▪ Chemical reaction equilibria.

    The course also provides an introduction to the statistical thermodynamics and transition state theory. In addition, the course introduces software tools for estimating thermodynamics of pure materials, solid surfaces and chemical reactions.

    The general objective of the course is to establish a strong understanding of the thermodynamic fundamentals of materials and both physical and chemical processes and to ensure the ability to apply these thermodynamic principles to various chemical engineering applications in process development, equipment design and process control.

Specific objectives include:

      -          Establish detailed knowledge in the field of thermodynamics of materials and chemical processes.

-          Establish the ability to perform thermodynamic analysis of materials syntheses, processes involving mixing and physical separation and also processes involving chemical transformations, including catalytic reactions.

-          Provide an opportunity for students to work in teams and facilitate problem-solving skills with case studies and class projects.

Schedule for Fall 2016: Monday at 6:15 - 8:45 pm in Burchard-430

Textbook: H.W. Tester and M. Modell, Thermodynamics and Its Applications, 3rd Edition, Prentice Hall, ISBN: 978-80139153563.

Recommended: Terrell L. Hill, An Introduction to Statistical Thermodynamics, Dover Publications, ISBN: 978-0486652429.

Grading:

Homework

24

Class participation

5

Project and presentation

15

Midterm test

23

Final exam
33

Class tests and the final exam will be open book, open notes. You do not have to memorize lengthy formulas or definitions. You do, however, need to understand the material and know how to apply it for solving problems. If you do not know the materials, you will run out time on the tests.

Homework is due in class. No late homework will be accepted, for any reason. If you unable to attended the class and still want to submit your homework, please scan and send it as an Adobe pdf file. You can miss 1 homework assignment and still receive full credit for it. If you submit all homework assignments, your lowest homework score will be adjusted to 100%.

Course outline:

1. The Scope of Classical Thermodynamics

2. Basic Concepts and Definitions
    2.1. System and Boundaries
    2.2. Primitive Properties
    2.3. Classification of Boundaries
        2.3.1. The Adiabatic Wall
        2.3.2. Simple and Composite Systems
    2.4. State of a System
    2.5. Stable Equilibrium States
        Postulate I
        Postulate II
    2.6. Thermodynamic Processes
    2.7. Derived Properties
    2.8. Nomenclature and Units

3. First Law
    3.1. Work Interactions
    3.2. Adiabatic Work Interactions
    3.3. Energy
    3.4. Heat Interactions
    3.5. The First Law for Closed Systems
        3.5.1. Specific Heats
        3.5.2. Standard States
        3.5.3. Heats of Reactions
        3.5.4. Heats of Formation
        3.5.5. Process Calculations for the Ideal gas
    3.6. The First Law for Open Systems
        3.6.1. Applications of the First Law for Open Systems

4. Second Law
    4.1. Heat Engines
    4.2. Reversible Processes
    4.3. Thermodynamic Temperature
    4.4. The Theorem of Clausius
    4.5. Entropy
    4.6. Internal Reversibility
    4.7. Combined Statement of First and Second Law for Closed Systems
    4.8. Reversible Work of Expansion or Compression in Flow Systems
    4.9. The Chemical Potential
        4.9.1. Introduction of the Chemical Potential
        4.9.2. Extensive Properties
        4.9.3. Partial Molar Properties
        4.9.3.1. Definition and Relationships
        4.9.3.2. Graphical Representation: The Method of Intercepts
        4.9.3.3. Independent Variables

5. The Calculus of Thermodynamics
    5.1. Fundamental Equations
    5.2. Intensive and Extensive Properties
    5.3. Methods for Transforming Derivatives
    5.4. Legendre Transformations
    5.5. Non-Simple Systems

6. Equilibrium Criteria
    6.1. Classification of Equilibrium States
    6.2. Derivations of the Conditions of Equilibrium in a Heterogeneous System
        6.2.1. Membrane Equilibrium
        6.2.2. Phase Equilibria
        6.2.3. Chemical Reaction Equilibria
    6.3. Applications of the Conditions of Equilibrium in a Heterogeneous System
        6.3.1. Examples
        6.3.2. Common Tangent Construction
        6.3.3. Phase Rule

7. Stability
    7.1. Stable and Unstable Equilibria
    7.2. One-Component System
        7.2.1. Gibbs Free Energy Function
        7.2.2. Clausius-Clapeyron Equation
        7.2.3. Triple Points
        7.2.4. Critical Points
    7.3. General Discussion of Stability Conditions with Respect to Infinitesimal Fluctuations
    7.4. Stability Criteria for Infinitesimal Fluctuations
    7.5. Spinodal Line and Critical Point
    7.6. Thermodynamic Calculations Associated with the Nucleation and Growth of Precipitates
        7.6.1. Free energy Changes
        7.6.2. Selection of the Displacement Variable
        7.6.3. Driving Forces

8. Properties of Pure Materials
    8.1. Fundamental Equations
    8.2. PVT Behavior of Pure Fluids and the Theorem of Corresponding States
    8.3. PVTN Equations of State
        8.3.1. Cubic Equation of State
        8.3.2. Volume Translated Cubic Equation of State
        8.3.3. Hard-Sphere Equation of State
        8.3.4. Virial Expansions
    8.4. Specific Heat of Ideal Gases
    8.5. Evaluating Changes in Properties Using Departure Functions
    8.6. Specific Heat and Other Properties of Solids
    8.7. Derived Property Representations
    8.8. Standard Enthalpy and Gibbs Free Energy of Formation

9. Property Relationships for Mixtures, Fugacities, Activities
    9.1. General Approach and Conventions
    9.2. PVTN Relations for Mixtures
    9.3. Partial Molar Properties
    9.4. Generalized Gibbs-Duhem Relation for Mixtures
    9.5. Functions of Mixing
    9.6. Chemical Potential of a Single Component
        9.6.1. Perfect Gas
        9.6.2. Real Gases: the Fugacity Function
        9.6.3. Solids and Liquids
        9.7. Mixture of Ideal Gases
    9.8. Fugacities in a Mixture of Real Gases
        9.8.1. Fugacity Coefficient
    9.9. Solid and Liquid Solutions: The Activity Function
        9.9.1. Ideal Solution
        9.9.2. Excess Properties
        9.9.3. Raoult’s and Henry’s Laws
    9.10. Partial Vapor Pressure of a Solute
    9.11. Reversible Work of Mixing and Separation

10. Phase Equilibrium and Stability: Phase Diagrams
    10.1. The Phase Rule
    10.2. Phase Diagrams
        10.2.1. Pure Component
    10.3. Binary Solid-Liquid Systems
        10.3.1. General Features
        10.3.2. Ideal and Nearly Ideal Systems
        10.3.3. Maxima and Minima
        10.3.4. Eutectic Points
        10.3.5. Peritectic Points
        10.3.6. Complex Phase Diagrams
        10.3.7. Calculations of Phase Diagrams
    10.4. Binary Liquid-Vapor Systems
        10.4.1. General Features
        10.4.2. Calculations of Liquid-Vapor Phase Diagrams
            10.4.2.1. The Differential Approach
            10.4.2.2. Pressure-Temperature Relations
            10.4.2.3. The Integral Approach
    10.5. Equilibrium in Systems with Supercritical Components

11. Chemical Equilibria
    11.1. Problem Formulation and General Approach
    11.2. Conservation of Atoms
    11.3. Non-Stoichiometric Formulation
    11.4. Stoichiometric Formulation
    11.5. Equilibrium Constants
    11.6. The Phase Rule for Reacting Systems
    11.7. Effect of Chemical Equilibrium on Thermodynamic Properties
    11.8. Le Chatelier Principle

12. Introduction to Statistical Thermodynamics
    12.1. Statistical-Mechanical Ensembles and Postulates
    12.2. Ideal Monoatomic Gas
    12.3. Ideal Monoatomic Crystals
    12.4. Lattice Statistics
    12.5. Chemical Equilibrium
    12.6. Chemical Reaction Rates

13. Thermodynamics of Solid Surfaces
    13.1. Crystal Planes, Surface Reconstruction And Relaxation
    13.2. Energetics Of Adsorption, Gas Adsorption Isotherms
    13.3. Reactions On Solid Surfaces
    13.4. Rate Laws For Surface Reactions And Chemical Kinetics
    13.5. Rates And Mechanisms Of Surface Reactions

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Lecture notes and Homework

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