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2.43 Advanced Thermodynamics

2.43 Advanced Thermodynamics (Spring 2024, MIT OCW). Instructor: Prof. Gian Paolo Beretta. This course is a 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, and Onsager's near-equilibrium reciprocity in thermodiffusive, thermoelectric, and electrokinetic cross effects. (from ocw.mit.edu)

Lecture 20 - Chemical Kinetics; The Arrhenius Law; Degree of Disequilibrium; Principle of Detailed Balance

Chemical kinetics. Collisions and Arrhenius activation energy. Principle of detailed balance. Affinity as degree of disequilibrium. Entropy production as product of affinity and reaction rate. DoD build-up in supersonic nozzle expansion. CO2 power laser.


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Lecture 01 - Definitions of System, Property, State, and Weight Process; First Law and Energy
Lecture 02 - Second Law and Entropy; Adiabatic Availability; Maximum Entropy Principle
Lecture 03 - Energy vs Entropy Diagrams to Represent Equilibrium and Nonequilibrium States
Lecture 04 - Temperature, Pressure, Chemical Potentials; the Clausius Statement of the Second Law
Lecture 05 - Definition of Heat Interaction; First and Second Law Efficiencies
Lecture 06 - Free Energies, Available Energies, and Stability Conditions
Lecture 07 - Availability Functions and the LeChatelier-Braun Principle
Lecture 08 - Few versus Many Principles: The Euler Relation; Review of Various Forms of Energy (Part I)
Lecture 09 - Minimum Work of Partitioning Small Systems; The Gibbs Phase Rule; The Van der Waals Model
Lecture 10 - Review of Various Forms of Energy (Part II); Allocation of Consumptions in Cogeneration
Lecture 11 - Allocation in Hybrid Power Production; Chemical Potentials and Partial Pressures
Lecture 12 - Ideal Mixture Behavior; Work from Reversible Mixing; Entropy of Irreversible Mixing
Lecture 13 - The Gibbs Paradox; Shannon Information Entropy; Single Quantum Particle in a Box
Lecture 14 - Ideal Solution Model; Osmotic Pressure; Blue Energy; Minimum Work of Separation
Lecture 15 - Stratification in Gas and Liquid Mixtures; Liquid-Vapor Spinodal Decomposition
Lecture 16 - Liquid-Vapor Equilibria in Mixtures; Ideal and Excess Chemical Potentials
Lecture 17 - Liquid-Liquid Spinodal Decomposition; Introduction to Systems with Chemical Reactions
Lecture 18 - Properties of Reaction; Heating Values and Energy of Fuels; Adiabatic Flame Temperature
Lecture 19 - Affinity and Nonequilibrium Law of Mass Action; Potential Energy Surface
Lecture 20 - Chemical Kinetics; The Arrhenius Law; Degree of Disequilibrium; Principle of Detailed Balance
Lecture 21 - Introduction to Nonequilibrium Theory; Onsager Reciprocity and Maximum Entropy Reduction
Lecture 22 - Definition of "Heat&Diffusion" Interaction; Diffusive and Convective Fluxes
Lecture 23 - Direct and Cross Effects; General Principles of Entropy Production; The Fourth Law
Lecture 24 - Relative Diffusion Fluxes; Thermoelectric Effects
Lecture 25 - Thermoelectric Effects; Multicomponent Transport