Fall 2006 Cumulative Outline

(This will slide around abit as the semester proceeds to accommodate shifts in emphasis. After each lecture, the "Lecture X" hyperlink will connect to that lecture's slide collection. The numbers in green refer to chapter/sections in the textbook where there is some discussion on the topic indicated.) Previews may be found via the "Main Index" under "Preview".

Lecture 1. History

• The first 2000 years
• Stoichiometry Laws [1.3]

• • Conservation of Mass
  • Law of Definite Proportions
  • Law of Multiple Proportions

• Law of Multiple Proportions illustrated

Lecture 2. History [1.3]

• Dalton's Postulates and Atomic Theory [1.3]
• Dalton's "Postulate of Simplicity"
• Law of Combining Volumes
• Avogadro's Law
• Cannizzaro's Stoichiometric Analyses
• Early recognition of "Periodicity" [3.1]

Energies [1.7]

• Kinetic energy
• Potential energy (and forces)
• Internal energies (rotation and vibration)
• Light [15.1]

Lecture 3. H-atom line spectra (emission and absorbtion) [15.3]

Bohr/Rutherford's atomic model [15.4]

• Core nucleus with Z protons
• Electrons [1.4]

Mass Spectroscopy [1.4]

• Ions
• Mass spectrometer
• Isotopes

Problems with some results of physical measurements [15.2]

• Line spectra
• Photoelectric Effect
• Blackbody Radiation (and the ultraviolet catastrophe)

Physics puzzles "solved" by quantization

• Blackbody radiation, Planck, E=hv, energy jumps [15.2]
• Photoelectric Effect, Einstein, the photon [15.2]
• Line spectra, Bohr's Planetary Model, quantized angular momentum [15.4]

Lecture 4. (Old Quantum Theory)

Physics puzzles "solved" by quantization

• Blackbody radiation, Planck, E=hv, energy jumps [15.2]
• Photoelectric Effect, Einstein, the photon [15.2]
• Line spectra, Bohr's Planetary Model, quantized angular momentum [15.4]

• • discrete orbit radii
  • quantized energy states
  • absorbtion and emission photons between states

(New Quantum Theory) [15.5]

• deBroglie and wave-particle duality of matter
• Schrodinger wave equation (concept), amplitude squared = local probability densities

Particle-in-a-box model [15.6]

Lecture 5. Wave Nature of Matter

Particle-in-a-box [15.6]

• one dimension
• two dimenstions
• three dimensions

Schrodinger's Wave Equation applied to the hydrogen atom, orbitals [15.7]

• n, principal quantum number
• l, angular momentum or shape quantum number
• m_l, magnetic or orientation quantum number

Electron "spin"

m_s, spin quantum number

Energies and geometries

Lecture 6. More outcomes of wave-particle duality

• (Heisenberg's) Uncertainty Principle [15.5]

• • simultaneous precise measurements restrictions
  • paths or orbits of particles are not legitimate topics of discussion

• Radial density distributions and electron density plots [15.7]

• • screening and penetration of electrons in the same shell

Lecture 7. Many-electron systems

• (Pauli) Exclusion Principle
• Effective nuclear charge
• Photoelectron spectra of atoms
• Electron configuration

Lecture 8. Many-electron systems

• Electron configuration
• Hund's rules for most stable configurations
• paramagnetism
• Configuration sequences

The Periodic Table demystified

• Effective nuclear charge and electron configurations
• Valence electrons
• Chemical "groups"

Lecture 9. The Periodic Table demystified

• (Exceptions in configurations)
• Atomic size trends
• Isoelectronic species

Electron Configurations and Ionization Energies

• First ionization energies
• Ionization energy and effective nuclear charges

Lecture 10. Electron Configurations and Ionization Energies

• Trends across a row
• Detailed comparisons
• Periodicity in trends
• Second and third ionization energies
• Electron Affinity

Lewis Electron Dot Structures

• Valence electrons (Main groups)

Lecture 11. Review for Exam I

Lecture 12. Electronegativity

Molecular Structure

Lewis Structures

• Valence electrons (Main groups)
• Octet Rule

• • Multiple Bonds
  • Bond energies
  • Bond lengths
  • Lone pairs

• Skeletal framework
• Structural isomers (constitutional isomers)
• Formal charge and preferred structures

Lecture 13. Lewis structures (continued)

Exceptions to the Octet Rule

• Incomplete octets
• Odd electron numbers
• Expanded octets (hypervalency)

Resonance (Benzene puzzles)

Lecture 14. Lewis structures (continued)

Resonance

• Equivalent preferred contributors

• Bond order

Lecture 15. Lewis structures (continued)

Examples

Reaction heats

Lecture 16.

Molecular structure and acid strength (continued)

Polar bonds

• Dipole moments
• Partial ionic character

Molecular structure and acid strength

• (Binary Acids)
• pK values
• Oxoacids

• Electronegativity of central atom
• Adding oxygens

Lecture 17. Molecular structure and acid strength

• Oxoacids (continued)

• Adding oxygens
• Resonance stabilization
• Importance of Lewis structure
• Carboxylic acids

Molecular Geometries

VSEPR Model

• Steric number (and coordination number)
• Electronic geometries
• (Ideal) Molecular geometries

Lecture 18. Molecular Geometries

VSEPR Model

• (Ideal) Molecular geometries
• Distortions from ideal geometries

  effect of lone pairs vs bonding pairs
  effect of multiple bonds
  effect of lone single electrons
  effect of electronegativity differences

Lecture 19. Molecular Geometries

• Examples
• Free and restricted rotations about bonds
• Rigidity about double bond
• Molecular dipoles from "bond" dipoles
• Geometrical isomers

Lecture 20. Quantum Theory of the Chemical Bond

Molecular orbitals (in "homonuclear diatomic molecules")

• Approximated by combinations of atomic orbitals
• Constructive and destructive interference effectsCombining 1s atomic orbitals
• "Sigma" bonding molecular orbital
• "Sigma" antibonding molecular orbital
• Bond order and properties

Lecture 21. Quantum Theory of the Chemical Bond

Molecular orbitals (in "homonuclear diatomic molecules")

• Combining 1s atomic orbitals
  • "Sigma" bonding molecular orbital
  • "Sigma" antibonding molecular orbital
• Bond order and properties
• Combining 2s atomic orbitals

• • "Sigma" bonding molecular orbital
  • "Sigma" antibonding molecular orbital

• Combining 2p atomic orbitals

• • "Sigma" bonding molecular orbital
  • "Sigma" antibonding molecular orbital
  • "Pi" bonding molecular orbitals
  • "Pi" antibonding molecular orbitals

• Building up electron configurations

Lecture 22. Review for Exam II

Lecture 23. Quantum Theory of the Chemical Bond

• Molecular Orbitals

  • Importance of energy match vs mismatch
  • Importance of net overlap
  • Heteronuclear diatomic molecules
  • Pure atomic orbitals don't work
  • Hybrid atomic orbitals

Lecture 24. Molecular Orbitals in Polyatomic Molecules

• Pure atomic orbitals don't work
• Hybrid atomic orbitals
• Molecular orbitals from combinations of hybrid atomic orbitals
• The rigid double bond
• The freely rotating single sigma bond
• Pi --> Pi* light absorption

Lecture 25. Molecular orbitals (localized, continued)

• Strained bonds in small rings

Molecular orbitals (delocalized)

1,3 butadiene example

• Orbitals delocalized over more than two atoms
• Bond order determination from electron configuration
• Partial bond order per electron
• Comparison to Lewis structure resonance

Lecture 26. Molecular Orbitals (delocalized)

• Continuing with excited states and bond orders
• Benzene
• Ozone
• Carbon dioxide
• Energies via particle-in-a-box
• Light-induced transitions

Lecture 27. Molecular Orbitals (delocalized, continued)

• Energies via particle-in-a-box
• Light-induced transitions
• Metallic bonds

Lecture 28. Intermolecular Interactions

Gases

• Ideal Gases
  • Ideal Gas Law
  • Dalton's Law of Partial Pressures
• Real Gases
  • Excluded volume
  • Intermolecular attractions
  • Van der Waals equation

Induced dipoles

• Polarizability

Lecture 29. Intermolecular Interactions (condensed phases)

• Induced dipoles

• Van der Waals interactions

• Permanent dipoles
• Temporary (induced) dipoles
• Boiling points, melting points, densities

• Effects of size
• Effects of shape

• Liquids and Solids

• Hydrogen Bonding

Lecture 30. Intermolecular Interactions

• Liquids and Solids

• Hydrogen Bonding

• Molecular Basis of Solubility

Lecture 31. Intermolecular Interactions

• Viscosity
• Examples

Lecture 32. Review for Exam III

Lecture 33. Oxidation numbers

Transition Metal Chemistry

• Tramsition metal ion electron configurations
• Coordination complexes

Lecture 34. Transition Metal Complexes

• Coordination complexes

• • Isomers

  Square planar geometries
  Octahedral geometries
  Optical isomers

• Observations to explain

  • Colors
  • Stability
  • Magnetic behavior

  Crystal Field theory

Lecture 35. Transition metals

Crystal Field theory

• Weak field vs strong field
• Spectrochemical series

• • Octahedral geometry
  • Distorting the octahedral geometry
  • Square Planar geometry
  • Tetrahedral geometry

Lecture 36. Transition metals

• Tetrahedral geometry

• Ligand Bonding to central ion's hybrid orbitals

Lecture 37.

Hemoglobin

Lecture 38. Review for Exam IV