Chemistry 331 Spring 2008 Chapter 1 Notes.
Homework: none.
General appreciation of scope of inorganic chemistry.
Chapter 2 Notes.
Homework: 2.1, 3, 10, 12, 13, 14, 15, 16, 18, 22, and 25.
General understanding of history of atomic structure and periodic table development. (cheat sheet)
Know what
contributions were made by Democritus, Epicurus, Aristotle,
The role of atomic spectra in history of atomic structure.
Schrodinger's wave mechanics equation - what does it tell us?
Significance and meaning of quantum numbers n, l, m1, and ms.
How did Bohr's Model of the atom differ from Schrodinger's?
How does a0 relate to both models?
Orbitals are probabilities. Explain.
Be able to draw simple versions of s, px, py, pz, dxy, dxz, dyz, dx2-y2, and dz2 orbitals.
Nice orbital web site -> http://winter.group.shef.ac.uk/orbitron/MOs/H2/1s1s-sigma/index.html
Electron configurations.
Aufbau principle.
Shielding, nuclear charge, and effective nuclear charge (s, Z, and Zeff).
Difficulties in predicting relative energies or orbitals beginning with n = 3.
Periodic trends relationship to Zeff and electron configurations. Atomic size, ionization energy, electron affinity.
Chapter 3 Notes.
Homework: 3.1, 2, 3, 4, 6, 7, 10, 13, 16, 17, 20, 21, and 22.
Lewis Structures.
Resonance.
Formal charge and its relationship to structure and reactivity.
VSEPR models. Geometry of molecules. Good site with examples.
Predicting relative bond angles.
Naming shapes like "trigonal planar", "T-shaped", etc.
Electronegativity's impact on polarity of bonds and molecules.
Chapter 5 Notes.
Homework: 5.1, 2, 5, and 6.
Orbital interactions. Be able to draw s, p, and d atomic orbitals and their interactions (s, p, and d) to form molecular orbitals (e. g. a p orbital can interact with an s orbital to make a s bond or s* antibond). Which are ungerade or gerade ?
Qualitative understanding of LCAO method. Mathematically, how are MO's formed from AO's ?
Be able to construct
a MO diagram using AO diagrams for diatomic molecules or ions made from
elements from H through Ne. You will be given a "
From the MO diagram be able to write the electron configuration for a molecule. For example, the electron configuration for He2 is sg2su*2 .
Calculate bond order.
Predict magnetic properties (diamagnetic or paramagnetic)
When bonding with transition metals, why does carbon monoxide bond through C? (see page 126 and figure 5-12)
Photoelectron Spectroscopy.
What is it ? What is it used for?
Be able to use a photoelectron spectrum to predict or explain a MO diagram.
Be able to predict a photoelectron spectrum from a MO diagram.
Frontier Orbitals.
What is the HOMO and LUMO ?
Why are these MO's important to reactivity?
Appreciate that Group Theory, mathematics of shape and symmetry from chapter 4, is needed to predict/explain bonding in molecules with more than 2 atoms.
Chapter 7 Notes.
Homework: 7.2, 3, 5, 8, 10, 11, 14, 20, and 21.
Unit cell
- What is it?
- What fraction of an atom contributes to a unit cell if it is . . .
- in the body of the cell? 1
- on the face of the cell? 1/2
- on the edge of the cell? 1/4
- on the corner of the cell?1/8
What determines type of lattices a given solid will form? Stoichiometry, ion size, ion radii, ion charge as well as some experimental factors like temperature.
Be able to write and use a Born-Haber process for solid formation.
What is lattice energy (U)?
What is the Madelung constant (M)?
How are M and U related?
Calculate a few terms of M give a simple 1D, 2D or 3D array of ions? Practice Pythagorean theorem.
How does ion charge affect lattice energy?
Conductors, insulators, semiconductors, and superconductors.
- What is a band, a valence band, a conduction band and band gap? Draw diagram.
- How is band gap related to conductivity of a solid?
- List some metals that are semiconductors - Si, Ge.
- What is doping? If Si or Ge is doped with Al or P, what type of semiconductor is formed? Draw diagram.
- What is a Fermi level (EF)? Draw diagram.
- Appreciate that semiconductors can be arranged to create diodes, transistors, chips, and computers.
- What is a superconductor? The major goal of superconductor research is to develop high temperature (room temperature or greater) superconductor especially if it is ductile.
- What are Cooper pairs?
X-ray crystallography.
- What is it?
- What can we learn from it?
Chapter 6 Notes.
Homework: 6.1, 2, 3, 10, 12, 23, 26, and 31(use computer).
Appreciate historical development of acid-base chemistry. Know these definitions . . .
- Arrhenius - Acids form H+ (H3O+) in water.
- Brønsted-Lowry - Acids are H+ donors. Bases are H+ acceptors.
- Lewis - Acids are electron pair acceptors. Bases are electron pair donors.
- Frontier Orbital Theory.
Conjugate acid and base.
Appreciate various ways that are used to measure acid-base interactions. For example . . .
- Thermodynamic
- directly: HA + H2O 
H3O+ +
A‑. DHº
- indirectly using Hess's Law.
- UV/Vis, NMR, IR methods can also be used to detect acid-base interactions.
Acidity and bacisity trends
- What are pKa, pKb, Ka, and Kb?
- As acid strength increases base strength of the conjugate base decreases. Explain, give some examples.
- In a series of compounds that vary by atom directly attached to the leaving proton - acidity increases moving from left to right in a period because of increasing electronegativity. This could be call inductive effect.
- In a series of compounds that vary by atom directly attached to the leaving proton - acidity decreases moving from bottom to top in a period inspite of increasing electronegativity. This appears to be opposite of the inductive effect and can be explained in terms of anion stability.
- Inductive effects - electronic effects, acidity increases when the electron withdrawing ability of groups nearby, but not directly attached to leaving proton increase.
- Steric effects - some interactions are controlled by the size of interacting groups.
- Strength of oxyacids
- Use 8-5n or 9-7n to estimate pKa's . n is the number of oxygen atoms that are not bonded to H.
- Successive removal of H+ from an oxyacid increases the negative charge by 1 and increases the pKa by about 5.
- Solvent effects.
- What does amphoteric mean?
- Acid-base equilibrium can be affected by degree of solvation. How?
- Leveling Effect - The strongest acid that can exist in any solvent is the conjugate acid of the solvent. The strongest base that can exist in any solvent is the conjugate base of the solvent.
-Superacids
- How are superacids defined?
- What is Hammett acidity function (H0)? How is H0 determined?
Qualitative aspects of Hard and Soft Acid-Base Theory (HSAB)
Chapter 9 Notes.
Homework: 9.1, 2, 4, 5, 8 a b c h, 14, and 17.
Nomenclature of coordination compounds. A list of ligands will be given.
Isomerism - be able to recognize and give examples of the following types isomers
- constitutional
- configurational
- enantiomers
- diastereomers
- conformational
- geometric
Chirallity
- Be able to determine if a complex is chiral.
- How are enantiomers separated (resolved)?
Qualitative understanding of ORD and CD
- What can we learn from these techniques?
- Why is CD favored over ORD for transition metal complexes?
Chapter 10 Notes.
Homework: 10.1, 2, 14, 15 a, 17, and 19.
Crystal Field Theory (CFT) and Ligand Field Theory (LFT)
- How are the energies of the d orbitals affected by point charges (or ligands) approaching from a specified geometry (along z axis for example)?
- High spin and low spin complexes
- Strong field and weak field ligands. Spectrochemical sereies will be given.
- Magnetic properties
- Do and Dt
- What are they?
- Relationship to magnetic properties and electronic (UV/Vis) spectra.
- What is ligand field stabilization energy (LFSE)?
- Jahn-Teller Distortion
- When?
- Why?
- How?
Chapter 11 Notes.
Homework: 11.5, 6, 12, 15, and 22.
Qualitative understanding of relationship among
- color of complex
- peaks in UV/Vis spectrum
- Do
and Dt
- What is CTTM and CTTL
|
|
|
complementary |
|
l (nm) |
color |
color |
|
< 400 |
UV |
|
|
425 |
violet |
yellow |
|
470 |
blue |
orange |
|
520 |
green |
red |
|
570 |
yellow |
violet |
|
620 |
orange |
blue |
|
680 |
red |
green |
|
>700 |
IR |
|
Be able to estimate Do and Dt (energies) when the wavelength of the absorbance that corresponds to that transition is known.
Useful Equations that will be given:
E = hn = hc/l
n = 1/l
E(kcal/mol) = 2.86 x 10-10 /l (nm)
E(kcal/mol) = 2.86 x 10-17 *n (cm-1)
h = 6.626 x 10 -34 J•s
c = 3.00 x 108 m/s = ln
Chapter 12 Notes.
Homework: 12.1, 2, 3, 12, and 15 .
Inert and Labile compounds.
- memorize and rationalize that d3, and ls d4, ls d5, and ls d6 are inert. Consider LFSE for these. Also square planar d8 compounds are inert.
- labile and inert are kinetic terms
- definition
involving t1 /2
- stable and unstable are thermodynamic terms
Substitution
- mechanisms associative (A), dissociative (D), and interchange (I).
- rough kinetics: A is second order and depends on [complex] and [incoming ligand] while D is first order and depends on [complex]
- substitution in octahedral complexes typically occurs by a D mechanism, while substitution in square planar complexes typically occurs by an A mechanism. Why ?
- Stereochemistry of octahedral substitution. difficult to predict.
- Trans-effect in substitution of square planar complexes and reaction sequence.
- Explanation of trans-effect (consider s ligands only)
Redox (electron transfer) reactions
- what role does molecular geometry/molecular vibrations play in electron transfer.
- inner sphere
- know the mechanism. key player: bridged intermediate.
- outer sphere
- know the mechanism. key player: encounter complex.