Chem 156 Syllabus

Chem 156 Physical Chemistry I (Chemical Thermodynamics) Number of units: 3 Pre-requisites: Chem 18, Chem 18.1, Math 73, Physics 72 Co-requisite: Chemistry 156.1 (Physical Chemistry I Laboratory) I.

S Y L LA B U S The Gas System 1. Ideal gases. State Variables: p, V, n and T 1.1. Ideal gas equations: Boyle’s Law, Charles’ Law, Avogadro’s Law, Combined gas equation Generalized gas equation of state. Universal gas constant, R Dalton’s Law of partial pressures Amagat’s Law of combining volumes Graham’s Law 1.2. Kinetic Molecular Theory Postulates Particle in a box, u, v and α Average kinetic energy 2. Real gases equations: Van der Waals gas, Berthelot, Deiterici, Redlich Kwong, Virial equations Unifying equation: Reduced equation of state and Hougen and Watson chart (The compressibility factor, z) 3. Fluids: Gases and liquids 3.1. System property: Viscosity, η Poiseuille equation and Stokes’ Law 3.2. Application: Viscosity average molecular weight (Mv) of straight-chain polymers PROBLEM SET 1 LONG EXAMINATION 1

II.

Chemical Thermodynamics 1. Formalism 2. Types of system: Open, Closed, Isolated 3. System properties 3.1. Homogeneous functions: Test for homogeneity (λ and k) 3.2. Partial derivatives and their properties: Inverter, Permuter, the Cyclic rule 3.3. Intensive and Extensive 3.4. State and Non-state function: Exact and Inexact differentials 3.5. Second order derivatives (System properties: α, β and C) 4. Energy state of the system: The Internal Energy (U) problem 4.1. U = U(S, V, N1, N2, … NJ) Evaluation of ∆U 4.1.1.Gibb’s-Duhem equation (The Euler’s theorem) 4.1.2.Law of Conservation of energy: The First Law of Thermodynamics Evaluation of non-state functions: q and w Isobaric, Isochoric, Isothermal and Adiabatic processes Reversible and irreversible process PROBLEM SET 2 LONG EXAMINATION 2 5. Equivalent (U) Energy representations: The Legendre Transform, H, A, G

5.1. Evaluation of H, A, G and 3 other L.T.’s of U 5.2. Second-order derivatives: The 21 Maxwell’s equations. The Thermodynamic Square 6. Thermodynamic equations of state: U = U(T, V) and H = H(T, p) 6.1. Ideal system 6.2. Real system 6.3. ∆H of isothermal process for ideal and real gases 7. The Carnot Cycle: Engine, Heat Pump, Refrigerator 8. Isenthalpic process: The Joule Thomson coefficient, μ

JT

9. Thermochemical equations: Evaluation of ∆H 9.1. Calorimetry 9.2. Other ways of evaluating ∆H for specific processes 9.3. Adiabatic Flame temperature 9.4. Dependence of ∆Hreaction (and ∆Ureaction) on temperature: The Kirchoff’s equation ∆H = f(T) and ∆U = f(T) PROBLEM SET 3 LONG EXAMINATION 3 10. The Second Law of Thermodynamics: Evaluation of ∆S of the system: S = S(T,V) and S = S(T, p)  Liquid, solid and mixtures of solid and liquid  Phase changes  Ideal gas mixture  Chemical reactions 11. Third Law of Thermodynamics: Evaluation of absolute entropy, S 12. The Free Energy functions: A and G and evaluation of ∆G (and ∆A)  Solid and liquid state  Ideal gases  Real gases: V = V(p)T and G. N. Lewis’ fugacity concept  Chemical reactions: ∆G = f(T)P and ∆A = f(T)V III.

Equilibrium  Clapeyron equation  Claussius-Clapeyron equation

IV.

Other Topics  Introduction to Statistical Thermodynamics  The solid state PROBLEM SET 4 LONG EXAMINATION 4 FINAL

E XAM I NAT I O N