Lecture Outlines

Introduction to the Course

  1. 1887: New Discipline of Physical Chemistry is Announced
    1. van't Hoff
    2. Ostwald
    3. Arrhenius
  2. Overview of the History of Physics and Physical Chemistry
    1. Newtonian Mechanics
    2. Start of Modern Chemistry
    3. Confusion about Atoms/Debates about Atomic Weights
    4. Electricity, Magnetism, and Light
    5. Thermodynamics
    6. Kinetic Theory and Statistical Thermodynamics
    7. Early 20th Century Physics
  3. Approaches to Teaching Thermodynamics

Ch 1: The Properties of Gases

  1. Temperature and Thermal Equilibrium
    1. Temperature vs. Heat
    2. Zeroth Law of Thermodynamics
    3. Diathermal vs. Adiabatic Walls
    4. Temperature Scales
  2. Perfect Gas Law
    1. Equation of State
    2. Physical Model
    3. Pressure and Partial Pressure (Dalton's Law)
  3. Introduction to Real Gases
    1. Physical Expectations
    2. The Virial Equation
    3. Van der Waals Model
  4. PVT Surfaces and Critical Phenomena
    1. One Component Systems
    2. Critical Points
Only a small part of section 1B will be used for this course: (b) "The Maxwell-Boltzman distribution of Speeds".

Ch 2: The First Law of Thermodynamics

  1. System vs. Surroundings
    1. Isolated Systems
    2. Closed Systems
    3. Open Systems
    4. System Properties
  2. Statement of the First Law
    1. Conservation of Energy
    2. Formal Statement
  3. Exact vs. Inexact Differentials
    1. Partial Deriviatives
    2. Exact Differentials
  4. Work and Heat
    1. PV Work Examples
    2. Other Work Examples
    3. Heat and Internal Energy
    4. Heat Capacity
  5. Enthalpy
    1. Another State Function
    2. Heat Capacity Revisited
  6. Adiabatic Changes
  7. U & H: More Connections to Experiments
    1. General Considerations
    2. Expansion Coefficient & Isothermal Compressibility
    3. Joule-Thomson Expansion
  8. Thermochemistry
    1. Standard Enthalpy Changes
    2. Hess's Law
    3. Calorimetry

Ch 3: Second and Third Laws of Thermodynamics

  1. Energy vs. Entropy
    1. The Second Law
    2. Thermodynamic Definition of Entropy
  2. The Carnot Cycle
    1. Steps in the Cycle
    2. P-V Diagram
    3. Identify a New State Function: Entropy
  3. The Clausius Inequality: A Criterion for Spontaneity
  4. Sample Problems involving Entropy
    1. Gas Expansion/Compression
    2. Phase Changes
  5. Entropy and Statistical Probablity
  6. Absolute Entropies and the Third Law
  7. Free Energy: Two Additional Thermodynamic Potentials
    1. Helmholtz Energy
    2. Gibbs Energy
  8. Foundation for More Thermodynamic Relationships
    1. Fundamental Equation for Internal Energy
    2. Maxwell Relations
  9. Properties of the Gibbs Energy
  10. Fugacity

Ch 4: Physical Transformations of Pure Substances

  1. Examples of Phases and Phase Transitions
    1. Common Examples
    2. Other Examples
  2. Chemical Potential and Phase Equilibria
    1. T-Dependence of Phase Equilibria
    2. P-Dependence of Phase Equilibria
  3. The Gibbs Phase Rule
  4. Location of Phase Boundaries
    1. Liquid-Solid Boundary
    2. Gas-Liquid or Gas-Solid Boundaries
Skip sections 4B.1(c) "The vapor pressure of a liquid subjected to pressure".

Ch 5: Simple Mixtures

  1. Partial Molar Quantities
    1. Partial Molar Volume
    2. Partial Molar Gibbs Energy
    3. The Gibbs-Duhem Equation
  2. Thermodynamics of Mixing
    1. Gibbs Energy of Mixing
    2. Entropy of Mixing
    3. Enthalpy of Mixing
  3. Chemical Potentials for Liquids
    1. Vapor Pressure Above a Liquid
    2. Solution-Vapor Equilibria with Two Components
    3. Ideal Solutions
    4. Ideal Dilute Solutions
  4. The Properties of Solutions
    1. Liquid Mixtures
    2. Colligative Properties
  5. Phase Diagrams of Binary Systems
    1. Liquid-Vapor Diagrams
    2. Liquid-Liquid Diagrams
  6. Solution Activities
    1. Solvents
    2. Solutes
    3. Electrolytes
      1. Mean Activity Coefficients
      2. Use of Molality
      3. Debye-Hückel Theory
Skip 5B 1(b) "Excess Functions and Regular Solutions", 5D "Phase Diagrams of Binary Systems: Solids", and 5E "Phase Diagrams of Ternary Systems".

Ch 6: Chemical Equilibrium

  1. Reaction Gibbs Energy
    1. Essential Equations
    2. Revisit Connections to Gibbs Energies of Formation
  2. Chemical Equilibrium: General Considerations
    1. Expressions for Equilibrium Constants
    2. Deriving Equilibrium Expressions for Perfect Gasses
    3. Response of Equilibria to Conditions
  3. Electrochemical Reactions
    1. Example of an Electrochemical Cell
    2. Classification of Cell Types
    3. Electrochemical Cell Notation
  4. Thermodynamics of Electrochemical Reactions
    1. Electrostatic Essentials
    2. The Nernst Equation
    3. Electrode Potentials

Ch 20: Chemical Kinetics

  1. Introduction: Thermodynamics vs. Kinetics
  2. Reaction Rates and Rate Constants
  3. Rate Laws and Reaction Order
    1. Definitions and Examples
    2. Integration of Simple Rate Laws
    3. Approach to Equilibrium
  4. Common Experiments
    1. Pseudo First-Order Kinetics (Isolation Method)
    2. Initial Velocity Kinetics
    3. Determining Reaction Order
  5. Reaction Mechanisms and Chemical Kinetics
    1. Derivation of Rate Laws for Mechanisms
    2. Steady-State Approximation
    3. Rapid-Equilibrium Approximation
  6. Arrhenius Equation
Cover only sections 20A,B,C,D,E. Skip 20C.2 (Relaxation Methods).