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Name_____KEY______________________________

Inorganic Chemistry 411

Midterm Exam # 1

60 minutes
Partial credit is given, please show all your work. A periodic table is on the last page if needed.

1. For both of the following: [8 pts each]

(i) write a Lewis structure, (ii) draw the species showing the geometry and (iii) indicate if
the structure has the ideal VSEPR coordination angles, or what deviation is expected.

1a. SO32- (sulfite anion)

Trigonal pyramidal geometry, all S-O are equivalent due to resonance,

Expect <Oax-S-Oeq less than 109.5° since lone pair is more repulsive than oxo ligand
(OSO angle is actually ≈106°)

1b. I3¯ (triiodide anion)

This has 5 e prs around the central I, so based on trigonal bipyramidal angles with 3 lone
pairs in equatorial positions and the two I in axial positions. This means it’s a
linear anion. No deviations from linear.

2a. Construct a molecular orbital diagram for the linear molecule BeH2. Show atomic
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orbitals and molecular orbital levels with appropriate energies and symmetry labels, and
indicate the electron filling. [14 pts]

See Fig in CH 2 of notes or below

2b. Draw a picture of one non-bonding π molecular orbital in BeH2. [6 pts]

No change from a px or py -orbital on Be. No participation from H ligand orbitals

2c. Explain how the energy of just ONE of the σ symmetry molecular orbitals in BeH2
changes as the H-Be-H bond angle decreases. [6 pts]

See the correlation (Walsh) diagram presented in CH 2. For example, the σg orbitals will
decrease when the angle decreases due to added in-phase, constructive overlap of the H
ligand orbitals. The σu orbitals will increase when the angle decreasesdue to destructive
overlap of H ligand orbitals. One of the π orbitals will decrease in energy (the one in the
bent molecular plane), one will remain unchanged.

3a. Give a Born-Haber analysis of ΔHf for TiO2(s). Do not provide any numeric values, just
write all the reaction steps, and label each with an energy term such as ionization energy
(I), or electron affinity (Ea) , or bond enthalpy (D0) , etc. Clearly indicate the sign (+ or -)
of each term. Equations and energy terms should combine correctly to give the full
reaction. [15 pts]

Ti(s) → Ti(g) ΔHat (Ti)

Ti(g) → Ti(g)4+ + 4e- I1(Ti)+ I2(Ti)+I3(Ti)+ I4(Ti)
O2(g) → 2 O(g) D0(O2)
2O(g) + 4e- → 2O2-(g) - 2Ea1(O) - 2Ea2(O)
Ti(g)4+ + 2O2-(g)→ TiO2(s) -ΔHL(TiO2)
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Ti(s) + O2(g) → TiO2(s) ΔHf(TiO2)

3b. MgF2 adopts the same structure, rutile, as one common form of TiO2. The lattice enthalpy
of rutile TiO2 is 12,500 kJ/mol. Using just the Kapustinskii relation, below, estimate ΔHL
for MgF2. Explain your answer. [8 pts]

ΔHL = (1.21 kJ pm / mol) (Nion │zAzB │/ d) (1 – 34.5 pm / d)

ΔHL is proportional to Nion │zAzB │. For both lattices Nion is 3. For TiO2, │zAzB │is 8 and
for MgF2 it’s 2. So, we can estimate that ΔHL (MgF2 ) ≈ (¼ )(12,500 kJ/mol) = 3100
kJ/mol. The reported value is actually 2910 kJ/mol.

4. The ionization energy of ground-state He is greater than that for ground-state H. Using
the concept of effective nuclear charge, explain why this is true. [8 pts]

He involves adding 1 proton and 1 e to H. Electron shielding means that the two 1s
electrons will not see a charge of +2, but a lower Zeff of ≈ +1.35. Still, this is greater
than the Z=+1 for H atoms, so IE, which is prop to Z2/n2 or Zeff2/n2, will be greater for
He.

5. Sketch (draw a picture) and also describe in writing the unit cell for the fluorite (CaF2)
structure. [13 pts]

or
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It’s a close packed anion array with cations in all the Td sites.

6. Circle ONE choice for all the questions below. [4 pts each]

i. A salt crystallizes where anions (Y) are in a hexagonal close-packed array and cations
(X) occupy all of the octahedral and tetrahedral sites in the Y anion array. What is the
composition of this salt?
(a) X3Y (b) X2Y (c) XY (d) XY2 (e) XY3 (f) X3Y2

ii. How many unpaired electrons are in the ground state of Fe2+(g)?
(a) 1 (b) 2 (c) 3 (d) 4 (e) 5 (f) 6

iii. Which of the following salts has the largest lattice enthalpy?
(a) LiF (b) LiBr (c) NaCl (d) NH4I (e) RbCl (f) CsI

iv. Which is an example of fluxional behavior?

(a) the dissolution of salts with low lattice enthalpies into polar solvents
(b) the similar atomic radii of second and third row transition metals
(c) the different kinetic energies of electrons emitted when metals are ionized
(d) the appearance of only one 19F NMR peak for PF5 measured at room
temperature
(e) the multiple structural isomers known of the composition C2H4O2
(f) the “flexing” of C-C bonds when carbon bonds to a more electronegative element
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