H = -(EAEB + CACB)

1. (15 pts) (a) Define the term lattice energy.

Energy needed to vaporize a crystal into a gas of its ions (per mole)
NaCl (s) Na+ (g) + Cl- (g) , Hlattice U
(b) The Born-Land equation is a sum of two terms. Explain these two terms in 1-2 sentences.

Term 1: electrostatic (Coulomb) attraction/repulsion of ions

Term 2: Born or Pauli repulsion term (repulsion of electron clouds)
(c) Which of the following compounds has the largest lattice energy: NaCl, CsF, MgO, SrO? Explain.

MgO (highest charges, smallest ions)

(d) For which of the following compounds is the Born-Land lattice energy likely to be in worst
agreement with the experimental lattice energy: SrS, SrO, SrTe, SrSe? Explain.

SrTe (least ionic of the three compounds)

2. (10 pts) Draw a simplified molecular orbital diagram for the reaction of BF3 with NH3. Label
the HOMOs and LUMOs of the reactants and product as well as the driving force for adduct
formation. What is the point group of the adduct in the staggered and eclipsed conformations?

H3N-BF3 is C3v in both the staggered

and eclipsed conformations.

3. (10 pts) We discussed how Li and Mg are used to prepare reagents that are very strong Lewis
bases (nucleophiles). Write down two balanced chemical reactions in which these reagents are
employed to make new carbon-carbon bonds (use a Li reagent in the first reaction and a Mg
reagent in the second).

Many possible answers to this question. Two examples:

solvent

nBuLi + CH3Cl C5H12 + LiCl(s)

HX
MgX2
RMgX
solvent

4. (10 pts) Predict whether the equilibrium constants for the following reactions are greater than
1 or less than 1 at room temperature (298 K). Explain.
(a)

CdI2(s) + CaF2(s)

CdF2(s) + CaI2(s)

Use hard-soft acid-base principles. Cd2+ and I- are soft, while Ca2+ and F- are hard.
CdI2 is a soft-soft interaction and CaF2 is a hard-hard interaction, which are
favorable compared to the soft-hard combinations of both products. Therefore, we
expect the equilibrium to lie strongly toward reactants and Keq << 1.
(b)

SO2(g) + (C2H5)2S(g)

SO2(C2H5)2S(g)

(For this one, assume that So = -0.035 kcal / mol K)

Use Drago-Wayland parameters to estimate Ho of adduct formation. From the provided D-W
equation and table of D-W values, we have:
-Ho = (0.920*0.399 + 0.808*7.4) = -6.35 kcal/mol
which gives, G = H - TS = -6.35 (298)*(-0.035) = +4.08 kcal/mol
since Go = -RTlnK, a positive Go means that Keq < 1.

5. (15 pts) (a) Define the term Bravais lattice. How many such lattices exist? Name three of them.

An infinite array of points with an arrangement and orientation that is exactly the
same at every lattice point. 14 Bravais lattices, including FCC, BCC, hexagonal,
simple monoclinic, base-centered orthorhombic, etc.
(b) Name the crystal structures expected for cubic AB compounds with the following radius
ratios: 0.25, 0.5, and 0.75. Draw the plan view diagram for the unit cell of the crystal with a radius
ratio of 0.75.

0.25: CN = 4; zinc blende

0.5: CN = 6: NaCl
0.75: CN = 8: CsCl

Cesium chloride
1/2

=
Cesium chloride
6. (10 pts) (a) Which is the strongest base to H+ in the gas phase: NH3, CH3NH2, (CH3)2NH, (CH3)3N?
Explain your answer in one sentence.

(CH3)3N is the strongest base because it has the highest

electron density on N (largest inductive effect from electrondonating alkyl groups).
(b) Which is the strongest base to B(t-Bu)3 in the gas phase: NH3, CH3NH2, (CH3)2NH, (CH3)3N?
Explain.

Now the acid is very bulky, so steric effects become as

important as inductive effects. CH3NH2 is the best base.
(c) Which is the strongest Brnsted acid in the gas phase: AsH3, PH3, H2Se, H2S? Explain.

The best acid is the one with the smallest proton affinity. Acidity
increases across a row (due to electronegativity) and down a
column (due to anion size). H2Se is therefore the strongest acid.

7. (15 pts) Consider the interhalogen compound IF7.

(a) Explain the formation of this compound in acid-base terms.

Iodine acts as Lewis acid, fluorines Lewis bases

(b) What is the point group of this molecule?

D5h
(c) What is the oxidation state of iodine in this compound?

All fluorines are -1, so the oxidation state of iodine is +7

(d) Predict the products of the reaction between IF7 and Fe2O3.

Interhalogens are oxidizing agents that evolve O2 from metal oxides:

IF7 + Fe2O3 FeF3 + I2 + O2 (unbalanced)
8. EXTRA CREDIT (10 pts) Draw the energy level diagram for a p-n junction at zero applied
bias. Include the conduction and valence band positions and the Fermi levels, indicate the
direction of the diffusion and drift motion of electrons and holes, and label the p and n sides of
the junction.

9. EXTRA CREDIT (10 pts). Derive the packing fraction (i.e., the percentage of filled space) for a
simple cubic lattice. Show your work (as always!).

Packing fraction =

volume occupied by spheres

total volume of unit cell

1 sphere per unit cell for SC lattice

Volume of unit cell = a3
Volume of sphere =
packing fraction =

0.524, or 52.4%

10. EXTRA CREDIT (10 pts). List the sequence of four (possibly five) chemical reactions used to
produce nitric acid on an industrial scale from N2, CH4, H2O, and O2. Dont bother balancing the
reactions.

Make H2 :
CH4 + H2O H2 + CO
CO + H2O H2 + CO2 (this is the possible extra reaction)
Fix N2 :
N2 + 3H2 2NH3
Oxidize NH3 :
NH3 + O2 NO2 + H2O
Make HNO3 :
NO2 + H2O HNO3 + NO