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