2.43 Advanced Thermodynamics
Spring 2024
Room 3-442
Tuesday 2:30pm - 4:30pm
Friday 11:00am - 1:00pm
Self-contained concise review of general thermodynamics concepts, multicomponent equilibrium properties, chemical equilibrium, electrochemical potentials, and chemical kinetics, as needed to introduce the methods of nonequilibrium thermodynamics and to provide a unified understanding of phase equilibria, transport and nonequilibrium phenomena useful for future energy and climate engineering technologies. Applications include: second-law efficiencies and methods to allocate primary energy consumptions and CO2 emissions in cogeneration and hybrid power systems, minimum work of separation, maximum work of mixing, osmotic pressure and membrane equilibria, metastable states, spinodal decomposition, Onsager’s near-equilibrium reciprocity in thermodiffusive, thermoelectric, and electrokinetic cross effects.
Prereq: 2.42 or permission of instructor
Midterm assignment on allocation: 15%
Four midterm quizzes: 10% each
Final oral exam: 45%
Grading type: Letter grades (A-F) with ±
Final grade: weighted average (rounded upwards) based on A=5, B=4, C=3, D=2, F=0, ±=±0.33
Grading characteristics: Can repeat for credit
The first part of the course provides a brief and concise review of: (1) general thermodynamics concepts needed for the third part of the course, with emphasis on the definitions of entropy for nonequilibrium states and of energy and entropy transfer in a heat interaction, and (2) their use in energy and materials processing applications to evaluate exergies and second-law efficiencies, and in hybrid power facilities to allocate primary energy consumption and greenhouse gas emissions. This part will end with a pass/fail midterm examination before drop date.
The second part of the course focuses on chemical potentials and the equilibrium properties of multicomponent systems, ideal and nonideal gas mixtures and solutions, liquid-vapor, liquid-liquid and membrane equilibria for binary systems. Applications to minimum work of separation, maximum work of mixing, osmotic pressure, metastable states, and spinodal decomposition. It ends with a brief review of chemical equilibrium, electrochemical potentials, and chemical kinetics concepts, as needed for the third part of the course.
The third part is an introduction to concepts and methods of non-equilibrium thermodynamics: the local and constrained equilibrium assumptions that underlie the description of multicomponent flows, the simultaneous diffusion of energy, mass, charge, and entropy modeled by extending the concept of heat interaction, the near-equilibrium Onsager reciprocal relations derived from Ziegler’s principle of maximum entropy production, Curie's symmetry principle. Applications to heat transfer in anisotropic composite materials (Righi-Leduc effect), thermodiffusive cross effects (Soret, Dufour, membrane thermo-osmosis), thermoelectric effects (Seebeck, Peltier) electrokinetic phenomena (electro-osmosis, streaming potential, electrophoresis, sedimentation potential). This part will end with a brief overview of how recent research efforts attempt to extend thermodynamics to the realm of far-nonequilibrium phenomena.
A set of instructor's viewgraphs will be made available to the students after each lecture. A book writing project specific for this course is under way, but will not be available for the 2024 course. Until then, additional reading on nonequilibrium thermodynamics and the connections with advanced fluid mechanics, heat transfer, and transport phenomena can be done on: Kjelstrup, Bedeaux, Johannessen, and Gross, Non-Equilibrium Thermodynamics for Engineers, World Scientific 2010. Proofs and examples to complement the first two parts of the course can be found in the reference text: Gyftopoulos and Beretta, Thermodynamics. Foundations and Applications, Dover 2005.
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