10.40
Chemical Engineering Thermodynamics
Basic postulates of classical thermodynamics. Application to transient open and closed systems. Criteria of stability and equilibria. Constitutive property models of pure materials and mixtures emphasizing molecular-level effects using the formalism of statistical mechanics. Phase and chemical equilibria of multicomponent systems. Applications emphasized through extensive problem work relating to practical cases.
Fall 2003
Topics
- Postulatory Approach 1st Law Concepts (Work, Heat, and Energy); Closed and Open System Treatments, Including PE Plus KE Effects; Tank Blowdown [Demo - CO 2 Fire Extinguisher]
- 1st Law Open Systems; Tank Blowdown and Filling - Class Examples; Problem 3.9
- 2nd Law Concepts; Reversible Heat Engines; Carnot Efficiency; Entropy; Clausius Theorem; Reversibility [Demo - Drinking Bird]
- Entropy Balance; 1st and 2nd Laws Combined [Demo - Hilsch Vortex Tube]
- 2nd Law Concepts and Applications; Steady State and Transient Flow Work
- Availability and Exergy Concepts; Heat Integration and Pinch Analysis; Power Cycle Analysis [Demo - Stirling Engine]
- Calculus of Thermodynamics; Gibbs Fundamental Equation; Graphical Interpretation of Fundamental Surface
- Derivative Transformation and Manipulation; Maxwell Relations; Jacobian Transformations
- Legendre Transformations; Equivalent Forms of the Fundamental Equation; Examples
- Legendre Transforms Continued; Connections to the Gibbs Surface and Other Derived Properties
- Equilibrium Criteria Concepts and Applications - Phase, Chemical, and Membrane; Phase Rule; Examples of Simple Phase Diagrams
- Stability Criteria, Concepts and Applications; Critical States
- Pure Component Properties; Fundundamental Equation; Theorem of Corresponding States; Constitutive Property Models - Stress Connections to Molecular Level Interactions and Effects
- Real Fluid Properties; PVTN Equations of State; Ideal Gas Heat Capacity C p *
- Departure Functions; Concepts and Applications; Standard Δ_G°_ and Δ_H°_ of Formation
- 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
- Ideal Solution Conditions; Excess Properties; Activity and Activity Coefficients; ΔG EX -γi Models (See Table 11.1); Standard States; Thermodynamic Consistency using the Gibbs-Duhem Relation
- Mixture Equations of State, Continued and Needs
- Fundamental Principles of Quantum and Classical Statistical Mechanics - N-body Problem; Phase Space; Statistics and Distribution Functions and Averaging Methods; Boltzmann Distribution
- Postulates of Statistical Mechanics; Gibbs Ensembles - Micro-canonical and Canonical; States of System; Probabilities
- Computation of Ideal Gas Properties from Intramolecular Effects - Translation, Rotation, Vibration using Statistical Mechanics I
- Computation of Ideal Gas Properties from Intramolecular Effects - Translation, Rotation, Vibration using Statistical Mechanics II
- 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
- Semi-classical Approximation; PVTN Properties via Configuration Integral from Intermolecular Effects; Grand Canonical Ensemble II - Examples
- Gibbs Ensembles Continued: Micro-canonical Ensemble Revisited, Grand Canonical, NPT, etc., Including Equivalence of Ensembles; Time Averaging and Ergodicity, and Fluctuations; Macroscopic Connection
- Intermolecular Forces and Potentials; Role of Quantum Mechanics; Commonly used Potential Functions; Pairwise Additivity
- Virial Equation of State and Molecular Corresponding States from Statistical Mechanics; Connection of PVTN Equations of State to Statistical Mechanics and Molecular Simulations
- Mean Field Theory; Connecting the van der Waals EOS Model to Statistical Mechanics; Hard Sphere Fluids; Perturbed Hard Sphere Fluids; Lattice Models
- 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)
- Statistical Mechanical Models of Fluids II - Biological Materials and Protein Applications
- Foundations of Molecular Simulations - Monte Carlo and Molecular Dynamics
- Application of Molecular Simulations to Estimating Pure Component and Mixture Properties
- Calculation of Pure Component Properties (Vapor Pressure, Δ Hvap , … etc.) Using Equation of State and Other Models - Departure Functions
- Review of Mixture Thermodynamics; Fugacity; Fugacity Coefficient; Activity; Activity Coefficient; Standard States and Constitutive Models for Capturing Non-Ideal Effects
- Phase Equilibrium and Stability - Gibbs Phase Rule; Phase Diagrams; Using Constitutive Property Models for Capturing Non-Ideal Effects
- Applications of Mixture Thermodynamics to VLE Phase Equilibria; Minimum Work of Separation, etc.
- Phase Equilibria; Differential Approach; Constitutive Property Models Continued; P-T Relationships
- Phase Equilibria; Integral Approach; Applications; Solubility - Gas - Liquid, Liquid - Liquid, and Solid - Liquid Systems
- Phase Equilibria Applications - Examples Colligative Properties; Ternary Diagrams; S-L-V Three Phase Monovariant Binary Equilibria; Biological Examples
- Phase Stability Applications; Spinodal Decomposition; Critical Points; Uses of Equations of State and Gibbs Free Energy Models; Polymer and Materials Examples; Pictures of Crystalization
- Chemical Equilibrium - General Approach; Nonstoichiometric and Stoichiometric Formulation; Statistical Mechanical Approach
- Equilibrium Constants and Standard States; Gibbs Phase Rule Applications
- Chemical Equilibria Applications and Example Problems; Combined Phase and Chemical Equilbria
- Review Session
Readings
- Tester, Jefferson W., and Michael Modell. Thermodynamics and its Applications. Upper Saddle River, NJ: Prentice Hall, 1996. ISBN: 9780139153563.
- Chapter readings in the table are from the course text, Tester, J. W., and Modell, Michael. Thermodynamics and Its Applications . Upper Saddle River, NJ: Prentice Hall PTR, 1996. ISBN: 9780139153563.
- SES #: 1 · TOPICS: 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 · READINGS: Handouts
- SES #: 2 · TOPICS: Postulatory Approach 1st Law Concepts (Work, Heat, and Energy); Closed and Open System Treatments, Including PE Plus KE Effects; Tank Blowdown [Demo - CO 2 Fire Extinguisher] · READINGS: 1 (all sections), 2 (all sections), 3.1-3.8
- SES #: 3 · TOPICS: 1st Law Open Systems; Tank Blowdown and Filling - Class Examples; Problem 3.9 · READINGS: 3.7-3.9
- SES #: 4 · TOPICS: 2nd Law Concepts; Reversible Heat Engines; Carnot Efficiency; Entropy; Clausius Theorem; Reversibility [Demo - Drinking Bird] · READINGS: 4.1-4.5
- SES #: 5 · TOPICS: Entropy Balance; 1st and 2nd Laws Combined [Demo - Hilsch Vortex Tube] · READINGS: 4.6-4.7
- SES #: 6 · TOPICS: 2nd Law Concepts and Applications; Steady State and Transient Flow Work · READINGS: 4.8-4.9
- SES #: 7 · TOPICS: Availability and Exergy Concepts; Heat Integration and Pinch Analysis; Power Cycle Analysis [Demo - Stirling Engine] · READINGS: 14.1-14.3, 14.5-14.6
- SES #: 8 · TOPICS: Calculus of Thermodynamics; Gibbs Fundamental Equation; Graphical Interpretation of Fundamental Surface · READINGS: 5.1-5.4
- SES #: 9 · TOPICS: Derivative Transformation and Manipulation; Maxwell Relations; Jacobian Transformations · READINGS: 5.1-5.4
- SES #: 10 · TOPICS: Legendre Transformations; Equivalent Forms of the Fundamental Equation; Examples · READINGS: 5.5-5.7
- SES #: 11 · TOPICS: Legendre Transforms Continued; Connections to the Gibbs Surface and Other Derived Properties · READINGS: 5.5-5.7
- SES #: 12 · TOPICS: Equilibrium Criteria Concepts and Applications - Phase, Chemical, and Membrane; Phase Rule; Examples of Simple Phase Diagrams · READINGS: 6.1-6.7
- SES #: 13 · TOPICS: Stability Criteria, Concepts and Applications; Critical States · READINGS: 7.1-7.2
- SES #: 14 · TOPICS: Pure Component Properties; Fundundamental Equation; Theorem of Corresponding States; Constitutive Property Models - Stress Connections to Molecular Level Interactions and Effects · READINGS: 8.1-8.2
- SES #: 15 · TOPICS: Real Fluid Properties; PVTN Equations of State; Ideal Gas Heat Capacity C p * · READINGS: 8.3-8.4
- SES #: 16 · TOPICS: Departure Functions; Concepts and Applications; Standard Δ_G°_ and Δ_H°_ of Formation · READINGS: 8.5, 8.7-8.9
- SES #: 17 · TOPICS: 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 · READINGS: 9.1-9.7
- SES #: 18 · TOPICS: Ideal Solution Conditions; Excess Properties; Activity and Activity Coefficients; Δ_G EX _-γi Models (See Table 11.1); Standard States; Thermodynamic Consistency using the Gibbs-Duhem Relation · READINGS: 9.8, 11.2, 11.4, 11.7, 11.9
- SES #: 19 · TOPICS: Mixture Equations of State, Continued and Needs · READINGS: 11.7, 11.9
- SES #: 21 · TOPICS: Fundamental Principles of Quantum and Classical Statistical Mechanics - N-body Problem; Phase Space; Statistics and Distribution Functions and Averaging Methods; Boltzmann Distribution · READINGS: 10.1, handouts
- SES #: 22 · TOPICS: Postulates of Statistical Mechanics; Gibbs Ensembles - Micro-canonical and Canonical; States of System; Probabilities · READINGS: 10.1, handouts
- SES #: 23 · TOPICS: Computation of Ideal Gas Properties from Intramolecular Effects - Translation, Rotation, Vibration using Statistical Mechanics I · READINGS: 10.1, handouts
- SES #: 24 · TOPICS: Computation of Ideal Gas Properties from Intramolecular Effects - Translation, Rotation, Vibration using Statistical Mechanics II · READINGS: 10.1, handouts
- SES #: 25 · TOPICS: 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 · READINGS: 10.1, handouts
- SES #: 26 · TOPICS: Semi-classical Approximation; PVTN Properties via Configuration Integral from Intermolecular Effects; Grand Canonical Ensemble II - Examples · READINGS: 10.1, handouts
- SES #: 27 · TOPICS: Gibbs Ensembles Continued: Micro-canonical Ensemble Revisited, Grand Canonical, NPT, etc., Including Equivalence of Ensembles; Time Averaging and Ergodicity, and Fluctuations; Macroscopic Connection · READINGS: 10.1, handouts
- SES #: 28 · TOPICS: Intermolecular Forces and Potentials; Role of Quantum Mechanics; Commonly used Potential Functions; Pairwise Additivity · READINGS: 10.2-10.3
- SES #: 29 · TOPICS: Virial Equation of State and Molecular Corresponding States from Statistical Mechanics; Connection of PVTN Equations of State to Statistical Mechanics and Molecular Simulations · READINGS: 10.4-10.6
- SES #: 30 · TOPICS: Mean Field Theory; Connecting the van der Waals EOS Model to Statistical Mechanics; Hard Sphere Fluids; Perturbed Hard Sphere Fluids; Lattice Models · READINGS: 10.6, 10.8
- SES #: 31 · TOPICS: 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) · READINGS: 10.7
- SES #: 32 · TOPICS: Statistical Mechanical Models of Fluids II - Biological Materials and Protein Applications · READINGS: 10.7
- SES #: 33 · TOPICS: Foundations of Molecular Simulations - Monte Carlo and Molecular Dynamics · READINGS: 10.9
- SES #: 34 · TOPICS: Application of Molecular Simulations to Estimating Pure Component and Mixture Properties · READINGS: 10.9
- SES #: 35 · TOPICS: Calculation of Pure Component Properties (Vapor Pressure, Δ Hvap , … etc.) Using Equation of State and Other Models - Departure Functions · READINGS: 8.5, 8.7, 8.9
- SES #: 36 · TOPICS: Review of Mixture Thermodynamics; Fugacity; Fugacity Coefficient; Activity; Activity Coefficient; Standard States and Constitutive Models for Capturing Non-Ideal Effects · READINGS: 9.1-9.8
- SES #: 37 · TOPICS: Phase Equilibrium and Stability - Gibbs Phase Rule; Phase Diagrams; Using Constitutive Property Models for Capturing Non-Ideal Effects · READINGS: 15.1-15.2, 15.8
- SES #: 38 · TOPICS: Applications of Mixture Thermodynamics to VLE Phase Equilibria; Minimum Work of Separation, etc. · READINGS: 9.7-9.9, 11.4, 11.7, 11.9
- SES #: 41 · TOPICS: Phase Equilibria; Differential Approach; Constitutive Property Models Continued; P-T Relationships · READINGS: 15.3-15.4, 11.1-11.7
- SES #: 42 · TOPICS: Phase Equilibria; Integral Approach; Applications; Solubility - Gas - Liquid, Liquid - Liquid, and Solid - Liquid Systems · READINGS: 15.5
- SES #: 44 · TOPICS: Phase Stability Applications; Spinodal Decomposition; Critical Points; Uses of Equations of State and Gibbs Free Energy Models; Polymer and Materials Examples; Pictures of Crystalization · READINGS: 7.1-7.2, 15.6-15.7
- SES #: 45 · TOPICS: Chemical Equilibrium - General Approach; Nonstoichiometric and Stoichiometric Formulation; Statistical Mechanical Approach · READINGS: 16.1-16.4, 16.9
- SES #: 46 · TOPICS: Equilibrium Constants and Standard States; Gibbs Phase Rule Applications · READINGS: 16.5-16.6
- SES #: 47 · TOPICS: Chemical Equilibria Applications and Example Problems; Combined Phase and Chemical Equilbria · READINGS: 17.1-17.3
- Bejan, Adrian. Advanced Engineering Thermodynamics. New York: Wiley, 1988. ISBN: 9780471830436. [Graduate Level, mechanical engineering emphasis, generalized exergy/availability analysis].*
- Callen, Herbert B. Thermodynamics: An Introduction to the Physical Theories of Equilibrium Thermostatistics and Irreversible Thermodynamics. New York: Wiley, 1960. Reprint available: Temecula, CA: Textbook Publishers, 2003. ISBN: 0758103360. [Physics approach, recommended section on Legendre transformations].*
- Denbigh, Kenneth. Principles of Chemical Equilibrium. 4th ed. London: Cambridge University Press, 1981. ISBN: 9780521281508. [Well-written, alternative intermediate text from a Chemistry perspective].*
- Gibbs, J. W. The Collected Works of J. Willard Gibbs, I: Thermodynamics. Edited by W. R. Logley and R. G. Van Name. New York: Longmans, Green, and Company, 1928. [Historical reference].*
- Gyftopoulos, Elias P. and Beretta, Gian Paolo. Thermodynamics: Foundations and Applications. Mineola, NY: Dover, 2005. ISBN: 9780486439327. [Comprehensive mechanical engineering approach, power cycles, availability/exergy analysis].
- Hatsopoulous, George N. and Keenan, Joseph H. Principles of General Thermodynamics. New York: Wiley, 1964. Replrint available: Melbourne, FL: Krieger, 1982. ISBN: 9780898743036. [Detailed theoretical, postulatory approach].
- Hougen, O. A. and Watson, K. M. Chemical Process Principles, I: Thermodynamics. 2nd ed. Wiley, 1959. [Corresponding-states principle, a classic Chemical Engineering Thermodynamics text].
- Keenan, Joseph H. et al . “International System of Units.” In Steam Tables: Thermodynamic Properties of Water Including Vapor, Liquid, and Solid Phases. New York: Wiley, 1969. Reprint available: Melbourne, FL: Krieger, 1992. ISBN: 9780894646850.[Good reference].
- Pitzer, Kenneth S. Thermodynamics. 3rd ed. New York: McGraw-Hill, 1995. ISBN: 9780070502215. [Well-written, revision of classic 1923 text by G.N. Lewis and M. Randall, treats electrolytes].
- Prausnitz, John M., de Azevedo, Edmundo Gomez, and Lichtenthaler, Rudiger N. Molecular Thermodynamics of Fluid-Phase Equilibria. 3rd ed. East Rutherford, NJ: Prentice-Hall, 1998. ISBN: 9780139777455. [Intermolecular forces, bridges the gap between Classical and Statistical Thermodynamics, presents many practical models for non-ideal behavior].
- Prigogine, Ilya and Defay, Raymond. Chemical Thermodynamics. London: Longmans, 1954. ISBN: 0598248242. [Detailed, theoretical, good on mixtures and phase equilibria].
- Reid, Robert C., Prausnitz, John M., and Poling, Bruce E. The Properties of Gases and Liquids. 4th ed. New York: McGraw-Hill, 1987. ISBN: 9780070517998. [Essential for estimating thermodynamic properties].
- Sandler, Stanley I. Chemical and Engineering Thermodynamics. New York: Wiley, 1998. ISBN: 9780471182108.[Introductory, well-organized].
- Smith, J. M. (ed.), van Ness, H. C., and Abbott, M. Introduction to Chemical Engineering Thermodynamics. 5th ed. New York: McGraw-Hill, 1996. ISBN: 9780070592391. [Introductory, classic chemical engineering undergrad text, well-organized].
- Walas, Stanley M. Phase Equilibria in Chemical Engineering. New York: Buttersworth, 1985. ISBN: 9780750693134. [Excellent, practical treatment of VLE and LLE].
- Weber, Harold C. Thermodynamics for Chemical Engineers. 2nd ed. New York: Wiley, 1957. [Well-written, introductory text].
- Chandler, David G. Introduction to Modern Statistical Mechanics. New York: Oxford University Press: 1987. ISBN: 9780195042771. [Concepts and modern theory, particularly helpful for phase transitions.]
- Callen, Herbert B. Thermodynamics: An Introduction to the Physical Theories of Equilibrium Thermostatistics and Irreversible Thermodynamics. New York: Wiley, 1960. Reprint available: Temecula, CA: Textbook Publishers, 2003. ISBN: 0758103360. [Critical-point scaling theories.]
- Debenedetti, Pablo G. Metastable Liquids: Concepts and Principles. Princeton, NJ: Princeton University Press, 1996. ISBN: 9780691085951. [Modern treatment of experimental data and theories regarding stability and criticality.]
- Hill, Terrell L. Statistical Mechanics: Principles and Selected Applications. Mineola, NY: Dover, 1987. ISBN: 9780486653907. [Advanced text covering basic aspects of liquid state theory.]
- Hirschfelder, Joseph L., Bird, R. Byron, and Curtiss, Charles F. Molecular Theory of Gases and Liquids. New York: Wiley, 1964. ISBN: 0471400653. Reprint available: Textbook Publishers, 2003. ISBN: 075810443X. [Excellent comprehensive treatment of theory and early work.]
- Huang, Kerson. Statistical Mechanics. New York: Wiley, 1987. ISBN: 9780471815181. [Advanced text with extensive discussion of Ising models.]
- McQuarrie, Donald A. Statistical Mechanics. New York: Harper and Row, 1973. ISBN: 9780060443658. Reprint available: Sausalito, CA: University Science Books, 2000. ISBN: 9781891389153. [Good detailed treatment of classical statistical mechanics.]*
- Pathria, R. K. Statistical Mechanics. 2nd ed. San Diego, CA: Elsevier Science and Technology Books, 1996. ISBN: 9780750624695. [Intermediate text, with a thorough coverage of phase transitions and condensed matter theory.]
- Reed, T. M. and Gubbins, K. E. Applied Statistical Mechanics. New York: McGraw-Hill, 1973. ISBN: 9780070514959. Reprint available: San Diego, CA: Elsevier Science and Technology Books, 1991. ISBN: 9780750691369. [Intermediate level text with a solid treatment of intermolecular potentials and some liquid state theory.]
- Reif, Frederick. Fundamentals of Statistical and Thermal Physics. New York: McGraw-Hill, 1965. ISBN: 9780070518001. [Introductory text with clear explanations of basic concepts of statistical mechanics, motivated from probability theory.]
- Rowley, Richard L. Statistical Mechanics for Thermophysical Property Calculations. Upper Saddle River, NJ: Prentice-Hall, 1994. ISBN: 9780130308184. [Clear basic treatment, including simulation methods, written by a Chemical Engineer.]
- Stanley, H. Eugene. Introduction to Phase Transitions and Critical Phenomena. Oxford: Oxford University Press, 1971. ISBN: 01995014588. [A classic text in its field, with clear discussions of scaling relations and critical exponents.]
- Yeomans, J. M. Statistical Mechanics of Phase Transitions. Oxford: Oxford University Press, 1992. ISBN: 9780198517306. [An introductory text, simpler than Stanley, with discussions of a number of techniques commonly used in studying the behavior of many-body systems.]
- Allen, M. P. and Tildesley, D. J. Computer Simulation of Liquids. Oxford: Oxford University Press, 1988. ISBN: 9780198553755. Reprint available: Oxford: Oxford University Press, 1989. ISBN: 0198556454. [Classic treatment.]
- Frenkel, Daan and Smit, Berend. Understanding Molecular Simulation. San Diego, CA: Elsevier Science and Technology Books, 1996. ISBN: 9780122673702. Reprint available: San Diego, CA: Elsevier Science and Technology Books, 2001. ISBN: 9780122673511. [Good overview with more recent advances than Allen and Tildesley.]
Prerequisites & course information
Prereq: 10.213 G (Fall) 4-0-8 units
Sources
- Course catalogue ↗2026–2027
- MIT OpenCourseWare ↗Fall 2003
- MIT OCW calendar ↗
- MIT OCW syllabus ↗
- MIT OCW readings ↗
- Historical MIT OpenCourseWare offering. Named reading entries and schedule topics are automatically extracted from the linked source pages.