MIT 5.60: Thermodynamics & Kinetics
Spring 2008 - 36 comprehensive lectures on classical thermodynamics and chemical kinetics
About MIT 5.60
MIT's first-year graduate course in thermodynamics and kinetics. This course provides rigorous training in classical thermodynamics, phase equilibria, chemical thermodynamics, and reaction kinetics. Essential for physical chemistry, materials science, and chemical engineering.
The course develops thermodynamics from its fundamental postulates (the four laws) through applications to phase transitions, chemical equilibria, and reaction dynamics. Emphasizes mathematical rigor while maintaining connection to experimental reality.
Why study this before statistical mechanics: Thermodynamics provides the phenomenological framework and experimental grounding. Once you understand thermodynamics deeply, statistical mechanics reveals the microscopic origin of these laws and extends them to quantum systems. The macro → micro progression builds solid intuition.
Note: The 36 lectures cover both thermodynamics (Lectures 1-24) and chemical kinetics (Lectures 25-36). Each lecture builds on previous material, so watching in order is recommended.
Lectures 1-12: Classical Thermodynamics
Foundation of thermodynamics: the four laws, state functions, thermodynamic potentials, and Maxwell relations.
Introduction and Course Overview
Introduction to thermodynamics, scope of the course, state functions vs path functions, equilibrium.
Video Lecture
Lecture 1: Introduction and Course Overview
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Zeroth and First Laws
Zeroth law: temperature and thermal equilibrium. First law: energy conservation, internal energy U, heat Q, work W.
Video Lecture
Lecture 2: Zeroth and First Laws
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First Law Applications
Applications of dU = δQ - δW. Reversible vs irreversible processes. Exact and inexact differentials.
Video Lecture
Lecture 3: First Law Applications
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Heat Capacity
C_V and C_P, relationship between heat capacities. Enthalpy H = U + PV. Constant pressure processes.
Video Lecture
Lecture 4: Heat Capacity
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Adiabatic Processes
Adiabatic expansion/compression. Ideal gas adiabatic relations. γ = C_P/C_V.
Video Lecture
Lecture 5: Adiabatic Processes
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Second Law Introduction
Need for second law. Carnot cycle. Efficiency of heat engines. Refrigerators and heat pumps.
Video Lecture
Lecture 6: Second Law Introduction
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Entropy
Definition of entropy: dS = δQ_rev/T. Clausius inequality. Entropy as state function.
Video Lecture
Lecture 7: Entropy
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Entropy Calculations
Calculating entropy changes. T-S diagrams. Entropy of ideal gas. Third law of thermodynamics.
Video Lecture
Lecture 8: Entropy Calculations
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Helmholtz Free Energy
Helmholtz free energy F = U - TS. Criterion for equilibrium at constant T and V. Work and free energy.
Video Lecture
Lecture 9: Helmholtz Free Energy
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Gibbs Free Energy
Gibbs free energy G = H - TS = U + PV - TS. Equilibrium at constant T and P. Chemical potential.
Video Lecture
Lecture 10: Gibbs Free Energy
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Maxwell Relations
Deriving Maxwell relations from exact differentials. Applications to connect measurable quantities.
Video Lecture
Lecture 11: Maxwell Relations
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Review and Problem Solving
Review of classical thermodynamics. Problem-solving techniques. Preparing for applications.
Video Lecture
Lecture 12: Review and Problem Solving
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Lectures 13-24: Phase Equilibria & Chemical Thermodynamics
Applications to phase transitions, mixtures, solutions, and chemical reactions. Chemical potential and equilibrium.
Phase Diagrams
Phase diagrams: P-T, P-V. Coexistence curves. Critical point. Triple point. Phase rule F = C - P + 2.
Video Lecture
Lecture 13: Phase Diagrams
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Clausius-Clapeyron
Clausius-Clapeyron equation: dP/dT = ΔH/(TΔV). Applications to phase transitions. Latent heat.
Video Lecture
Lecture 14: Clausius-Clapeyron
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Phase Equilibria Applications
Applications of phase equilibria. Water, CO₂. Supercritical fluids. Phase separation.
Video Lecture
Lecture 15: Phase Equilibria Applications
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Chemical Potential
Chemical potential μ = (∂G/∂N)_{T,P}. Meaning and significance. μ determines direction of mass transfer.
Video Lecture
Lecture 16: Chemical Potential
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Ideal Solutions
Ideal solutions and mixtures. Raoult's law. Colligative properties. Freezing point depression, boiling point elevation.
Video Lecture
Lecture 17: Ideal Solutions
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Non-Ideal Solutions
Deviations from ideality. Activity coefficients. Phase separation in mixtures. Gibbs-Duhem relation.
Video Lecture
Lecture 18: Non-Ideal Solutions
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Chemical Reactions
Thermodynamics of chemical reactions. Reaction coordinate. Gibbs energy change ΔG_rxn.
Video Lecture
Lecture 19: Chemical Reactions
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Chemical Equilibrium
Equilibrium condition: ΔG_rxn = 0. Law of mass action. Equilibrium constant K_eq = e^(-ΔG°/RT).
Video Lecture
Lecture 20: Chemical Equilibrium
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Temperature Dependence
Van't Hoff equation: d(ln K)/dT = ΔH°/RT². Temperature dependence of equilibrium.
Video Lecture
Lecture 21: Temperature Dependence
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Electrochemistry
Electrochemical cells. Nernst equation. Relationship between ΔG and cell potential: ΔG = -nFE.
Video Lecture
Lecture 22: Electrochemistry
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Applications to Reactions
Applications of chemical thermodynamics. Industrial processes. Biological systems.
Video Lecture
Lecture 23: Applications to Reactions
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Review: Thermodynamics
Comprehensive review of classical and chemical thermodynamics. Preparation for kinetics.
Video Lecture
Lecture 24: Review: Thermodynamics
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Lectures 25-36: Chemical Kinetics
Reaction rates, mechanisms, and dynamics. Transition state theory, catalysis, and advanced kinetics topics.
Introduction to Kinetics
Chemical kinetics: study of reaction rates. Rate laws. Zeroth, first, second order reactions.
Video Lecture
Lecture 25: Introduction to Kinetics
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Integrated Rate Laws
Integrated rate laws for different orders. Half-life. Determining reaction order from data.
Video Lecture
Lecture 26: Integrated Rate Laws
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Temperature Dependence
Arrhenius equation: k = Ae^(-E_a/RT). Activation energy E_a. Temperature dependence of rates.
Video Lecture
Lecture 27: Temperature Dependence
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Reaction Mechanisms
Elementary reactions. Reaction mechanisms. Rate-determining step. Intermediates vs transition states.
Video Lecture
Lecture 28: Reaction Mechanisms
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Steady-State Approximation
Steady-state approximation for intermediates. Pre-equilibrium approximation. Applications to mechanisms.
Video Lecture
Lecture 29: Steady-State Approximation
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Chain Reactions
Chain reactions: initiation, propagation, termination. Branching chains. Explosions.
Video Lecture
Lecture 30: Chain Reactions
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Catalysis
Homogeneous and heterogeneous catalysis. How catalysts work: lowering E_a without changing ΔG.
Video Lecture
Lecture 31: Catalysis
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Enzyme Kinetics
Michaelis-Menten kinetics. Enzyme-substrate complex. K_M and V_max. Biological catalysis.
Video Lecture
Lecture 32: Enzyme Kinetics
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Transition State Theory
Transition state theory (TST). Activated complex. Eyring equation. Connection to thermodynamics.
Video Lecture
Lecture 33: Transition State Theory
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Collision Theory
Collision theory of gas-phase reactions. Steric factors. Comparison with transition state theory.
Video Lecture
Lecture 34: Collision Theory
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Advanced Topics in Kinetics
Advanced kinetics: diffusion-limited reactions, photochemistry, relaxation methods.
Video Lecture
Lecture 35: Advanced Topics in Kinetics
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Course Review and Summary
Comprehensive course review. Thermodynamics and kinetics connections. Looking forward to statistical mechanics.
Video Lecture
Lecture 36: Course Review and Summary
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Study Guide
Recommended Approach:
- • Lectures 1-12: Master the four laws and thermodynamic potentials. Work through derivations of Maxwell relations yourself.
- • Lectures 13-24: Focus on phase diagrams and chemical equilibrium. These concepts apply broadly (plasma ionization, chemical reactions).
- • Lectures 25-36: Chemical kinetics is essential for non-equilibrium processes. Transition state theory bridges thermodynamics and kinetics.
Key Mathematical Skills:
- • Exact vs inexact differentials (dU is exact, δQ and δW are inexact)
- • Legendre transforms (converting between thermodynamic potentials)
- • Maxwell relations from mixed partial derivatives
- • Integration of rate laws (kinetics)
- • Equilibrium calculations using ΔG° and K_eq
After Thermodynamics:
- • Statistical Mechanics: See the microscopic origin of S, T, and thermodynamic laws
- • Plasma Physics: Apply equilibrium concepts to ionization, recombination, Saha equation
- • Quantum Mechanics: Extend to quantum statistics (Fermi-Dirac, Bose-Einstein)
- • Condensed Matter: Phase transitions, critical phenomena, symmetry breaking
Most Important Concepts: (1) Entropy S as measure of disorder and arrow of time, (2) Gibbs free energy G as criterion for equilibrium at constant T,P (most common experimental conditions), (3) Chemical potential μ determining mass/particle flow. Master these and you have the essence of thermodynamics.
Recommended Textbooks
The classic graduate text. Postulational approach. Rigorous and elegant. Perfect companion to MIT 5.60.
Concise and clear. Fermi's legendary clarity. Short but complete coverage.
For chemical applications and kinetics. Standard chemistry text with excellent problems.