10.40 | Fall 2003 | Graduate
Chemical Engineering Thermodynamics


Part I - Fundamental Principles
1 Course Outline; Motivation to Connect Classical Concepts and Laws to Physical Properties from Macroscopic to Molecular; Definitions; Nomenclature; Exams Plus Homework Policy; Approach to Solving Problems; Constitutive Property Models and the Ideal Gas State; Postulatory Approach; 1st Law Concepts

2 Postulatory Approach
1st Law Concepts (Work, Heat, and Energy); Closed and Open System Treatments, Including PE Plus KE Effects; Tank Blowdown [Demo - CO2 Fire Extinguisher]

3 1st Law Open Systems; Tank Blowdown and Filling - Class Examples; Problem 3.9 Assignment 1 due
4 2nd Law Concepts; Reversible Heat Engines; Carnot Efficiency; Entropy; Clausius Theorem; Reversibility [Demo - Drinking Bird]

5 Entropy Balance; 1st and 2nd Laws Combined [Demo - Hilsch Vortex Tube]

6 2nd Law Concepts and Applications; Steady State and Transient Flow Work

7 Availability and Exergy Concepts; Heat Integration and Pinch Analysis; Power Cycle Analysis [Demo - Stirling Engine] Assignment 2 due
8 Calculus of Thermodynamics; Gibbs Fundamental Equation; Graphical Interpretation of Fundamental Surface

9 Derivative Transformation and Manipulation; Maxwell Relations; Jacobian Transformations

10 Legendre Transformations; Equivalent Forms of the Fundamental Equation; Examples

11 Legendre Transforms Continued; Connections to the Gibbs Surface and Other Derived Properties Assignment 3 due
12 Equilibrium Criteria Concepts and Applications - Phase, Chemical, and Membrane; Phase Rule; Examples of Simple Phase Diagrams

13 Stability Criteria, Concepts and Applications; Critical States

14 Pure Component Properties; Fundundamental Equation; Theorem of Corresponding States; Constitutive Property Models - Stress Connections to Molecular Level Interactions and Effects

15 Real Fluid Properties; PVTN Equations of State; Ideal Gas Heat Capacity Cp*

16 Departure Functions; Concepts and Applications; Standard Δ_G°_ and Δ_H°_ of Formation

17 Mixtures; PVTN EOSs; Partial Molar Properties; Gibbs-Duhem Relation; Mixing Functions; Discuss Problem 9.2; Ideal Gas Mixtures and Ideal Solutions; Fugacity and Fugacity Coefficients; Standard States Assignment 4 due
18 Ideal Solution Conditions; Excess Properties; Activity and Activity Coefficients; ΔGEX-γi Models (See Table 11.1); Standard States; Thermodynamic Consistency using the Gibbs-Duhem Relation

19 Mixture Equations of State, Continued and Needs Assignment 5 due
20 Review for Exam 1

Exam I: 2 hours

Part II - Introduction to Statistical Mechanics for the Interpretation of Thermodynamic Functions and the Computation of Thermodynamic Properties
21 Fundamental Principles of Quantum and Classical Statistical Mechanics - N-body Problem; Phase Space; Statistics and Distribution Functions and Averaging Methods; Boltzmann Distribution

22 Postulates of Statistical Mechanics; Gibbs Ensembles - Micro-canonical and Canonical; States of System; Probabilities

23 Computation of Ideal Gas Properties from Intramolecular Effects - Translation, Rotation, Vibration using Statistical Mechanics I

24 Computation of Ideal Gas Properties from Intramolecular Effects - Translation, Rotation, Vibration using Statistical Mechanics II

25 Classical Statistical Mechanics; Hamiltonian and Ideal Gases; Factoring the Partition Function with the Semi-classical Approximation; PVTN Properties via Configuration Integral from Intermolecular Effects; Grand Canonical Ensemble I

26 Semi-classical Approximation; PVTN Properties via Configuration Integral from Intermolecular Effects; Grand Canonical Ensemble II - Examples

27 Gibbs Ensembles Continued: Micro-canonical Ensemble Revisited, Grand Canonical, NPT, etc., Including Equivalence of Ensembles; Time Averaging and Ergodicity, and Fluctuations; Macroscopic Connection Assignment 6 due
28 Intermolecular Forces and Potentials; Role of Quantum Mechanics; Commonly used Potential Functions; Pairwise Additivity

29 Virial Equation of State and Molecular Corresponding States from Statistical Mechanics; Connection of PVTN Equations of State to Statistical Mechanics and Molecular Simulations

30 Mean Field Theory; Connecting the van der Waals EOS Model to Statistical Mechanics; Hard Sphere Fluids; Perturbed Hard Sphere Fluids; Lattice Models

31 Statistical Mechanical Models of Fluids I - Expanding the Virial EOS to Mixtures; Radial Distribution Functions; Structure of Fluid and Solid Phases; Critical Phenomena (Fluctuations, Critical Opalescence) Assignment 7 due
32 Statistical Mechanical Models of Fluids II - Biological Materials and Protein Applications

33 Foundations of Molecular Simulations - Monte Carlo and Molecular Dynamics

34 Application of Molecular Simulations to Estimating Pure Component and Mixture Properties

Part III - Multi-scale Thermodynamics of Pure Fluids and Mixtures - Physical Properties and Phase and Chemical Equilibria
35 Calculation of Pure Component Properties (Vapor Pressure, Δ Hvap, … etc.) Using Equation of State and Other Models - Departure Functions Assignment 8 due
36 Review of Mixture Thermodynamics; Fugacity; Fugacity Coefficient; Activity; Activity Coefficient; Standard States and Constitutive Models for Capturing Non-Ideal Effects

37 Phase Equilibrium and Stability - Gibbs Phase Rule; Phase Diagrams; Using Constitutive Property Models for Capturing Non-Ideal Effects Assignment 9 due
38 Applications of Mixture Thermodynamics to VLE Phase Equilibria; Minimum Work of Separation, etc.

39-40 _Review for Exam II

_Review of Statistical Mechanics Principles and Applications, and Pure Fluid and Mixture Properties

Exam II: 2 hours

41 Phase Equilibria; Differential Approach; Constitutive Property Models Continued; P-T Relationships

42 Phase Equilibria; Integral Approach; Applications; Solubility - Gas - Liquid, Liquid - Liquid, and Solid - Liquid Systems

43 Phase Equilibria Applications - Examples Colligative Properties; Ternary Diagrams; S-L-V Three Phase Monovariant Binary Equilibria; Biological Examples

44 Phase Stability Applications; Spinodal Decomposition; Critical Points; Uses of Equations of State and Gibbs Free Energy Models; Polymer and Materials Examples; Pictures of Crystalization

45 Chemical Equilibrium - General Approach; Nonstoichiometric and Stoichiometric Formulation; Statistical Mechanical Approach Assignment 10 due
46 Equilibrium Constants and Standard States; Gibbs Phase Rule Applications

47 Chemical Equilibria Applications and Example Problems; Combined Phase and Chemical Equilbria Assignment 11 due
48 Review Session

Final Exam: 3 hours

Course Info
As Taught In
Fall 2003