instructor: Prof. Sharon Burgmayer, sburgmay@brynmawr.edu
   

Key Concepts for Topics Covered

    symmetry
    bonding
    acids and bases
    cordination chemistry: structure, bonding and spectroscopy
    cordination chemistry: reactivity
    ideal solids: structure and properties
    non-ideal solids: structure and properties
    materials
   
 
     
  Symmetry Concepts

Be able to define and recognize:

  • an n-rotation axis and improper axis
  • a mirror plane
  • an inversion center
  • a screw axis
  • a glide plane
  • a point group symbol
  • a unit cell
  • a primitive cell
  • a centered cell
  • the asymmetric unit of a cell
  • Be able to assign a point group label

Know :

  • Bragg's Law
  • the experimental configuration for both film and diffractometer methods in single crystal and in powder diffraction analyses
     
 

Bonding

VSEPR

  1. Lewis structures
  2. resonance
  3. formal charge vs. oxidation number
  4. molecular shapes
  5. distortions from ideal shapes
  6. localized bonding

Terms used in both MOT & VBT

  1. linear combination of atomic orbitals (LCAO)
  2. basis set
  3. normalization
  4. conservation of orbitals
  5. bond order and bond length

Terms used in MOT

  1. bonding orbital and antibonding orbital
  2. non-bonding orbitals
  3. MO energy level diagrams for homodiatomic molecules
  4. molecular electronic configurations
  5. HOMO, LUMO and frontier orbitals
  6. polar covalent bonding
  7. orbital nodes and orbital energies
  8. delocalized bonding

Terms used in VBT

  1. hybridization
  2. resonance
     
  Acids & Bases

definitions:
1. Arrhenius vs Bronsted acid & base definitions
2. Lewis acid & base
3. solvent system
4. hard-soft acid-base 'theory'
5. MOT

concepts:
1. solvent leveling and implications for reactivity
2. metal ions as acids
3. metal ion hydrolysis
4. superacids
5. molecular orbital view of donor/acceptor reactions
6. periodic trends of acid/base strength

     
 

Coordination Chemistry: Structure, Bonding and Spectroscopy

definitions:
1. field strength
2. spinstate, high spin vs low spin
3. CFT
4. LFT
5. MOT

concepts:
1. bonding theories - CFT
2. CFSE
3. role of pairing energies
4. role of symmetry
5. spectrochemical series

6. magentic susceptibility- calculation, variation between experiment and theory, use in determining structure
7. spectrochemical series

8. pi-acids, pi-bases and pi-innocent ligands

9. Jahn-Teller distortion: why and what happens

 

     
 

Coordination Chemistry: Reactivity adn Mechanisms

definitions:
1. stable vs unstable
2. inert vs. labile
3. thermodynamic vs kinetic terms
4. formation constants and stepwise formation constants

concepts
1. LS mechanisms: D, I, A

2. ligand substitution related issues for octahedral and square planar complexes

3. conjugate base (kinetic) effect

4. sterochemical outcomes of reaction mechanisms

5. isomerizations
6. redox reaction mechanisms: inner vs outer sphere
7. Irving- Williams series/plot as HSAB example
6. CFT implications for thermodynamic and kinetic reactivities

     
 

Ideal Solids

Be able to recognize and define the characteristics of Prototype lattices:

  1. NaCl
  2. sphalerite
  3. wurzite
  4. fluorite
  5. cesium chloride
  6. perovskite
  7. rutile

Be able calculate lattice enthalpies and determine the relative stabilities of ionic materials

Know :

  • Born-Lande/Mayer Equation
  • Born-Haber cycle
  • Reasons for deviations from experimental values
  • Radius Ratio Rule
     
 

Non-ideal Solids

layered structures

polarizability and covalency

types of defects

where to expect defects

band theory

density of states

ionic conductivity

electronic (metallic) conductivity

band gap

semi-conductors

photoconduction and thermal conduction

     
 

Materials