Lectures / Pittsburgh: University of Pittsburgh, Department of chemical and petroleum engineering, 2013. — 911 p.: ill.A working knowledge of thermodynamics and statistical mechanics is critical for solving many classes of problems that occur in both academic and industrial settings. Statistical thermodynamics is important in solving problems in areas as diverse as reaction kinetics, catalysis, biochemical engineering, polymer engineering, drug design, and separations. This class will provide the student with basic thermodynamic tools for solving many classes of problems. It will also help the student gain a working knowledge of classical and statistical thermodynamics specifically as it relates to the calculation of thermophysical properties, phase equilibria, and chemical equilibria.Contents
Fundamentals of Thermodynamics
Overview
Basics of Thermodynamics
The Four Laws of Thermodynamics
Work
Heat, work and the first law
The second law
Generalized equations
Ideal Gas State Properties
Open system example
The first and second law fundamental equation for a closed pure system
Auxiliary energy functions
Mixtures and open systems
Legendre Transforms
Example of using Legendre transforms
Process Evaluation
Partial derivative game
Example: Evaluate the Joule-Thompson coefficient
Residual Functions
Pressure Explicit Residual Functions
Introduction to Statistical Mechanics
What is Statistical Mechanics?
Classical Mechanics
Quantum Mechanics
Example: Particle in a box
The Harmonic Oscillator
The Rigid Rotor
Electronic Excitations in Molecules
Statistics
Ensembles
Ensemble Averages
Thermodynamic Properties
Classical and Semi-Classical Partition Functions
Statistical Mechanics of Ideal Gases
Populations of ground and excited states
Heat Capacities
Notation of chemical reactions
General Equilibrium Formulation
Reactions in ideal gases
Example: Association in sodium vapor
Nonideal mixture behavior in fluid phase reactions
Gas phase nonidealities
Evaluation of U
Model Potentials
Equations of State in Intermolecular Potentials
Virial Equation of State
Cubic Equations of State
Higher-order Equations of State
Van der Waals partition function
Phase behavior of pure fluids
Conformal Solutions, corresponding states and pure fluids
The generalized Cubic EOS
Van der Waals EOS
Redlich-Kwong EOS
Soave EOS
Peng-Robinson EOS
The Hard Sphere Equation of State
Conformal Solution Theory Example Calculations
Conformal Solution Theory for Mixtures
Property changes of mixing
Ideal Solutions: The Lewis-Randall Rule
Partial Properties (Molar and Mass)
Computing partial molar properties
Example of computing partial molar properties
Gibbs-Duhem Equation
Fugacity and fugacity coefficients
Relation to partial properties
Computing fugacity from an equation of state
Computing fugacity from an equation of state
Define activity coefficients
Define activity
The van der Waals partition function and mixture models
Example: Derive ideal mixing from assumption for the free volume
Example: Derive the Flory-Huggins equation
There are many empirical activity coefficient models
Example calculations with the Wilson Equation
Homework
Thermodynamics and Statistical Mechanics
Equilibrium and entropy
Energy and how the microscopic world works
Entropy and how the macroscopic world works
The fundamental equation
The first law and reversibility
Legendre transforms and other potentials
Maxwell relations and measurable properties
Gases
Phase equilibrium
Stability
Solutions
Solids
The third law
The canonical partition function
Fluctuations
Statistical mechanics of classical systems
Ensembles
Chemical reaction equilibrium
Reaction coordinates and rates
Problems
