5.

112 Name (Print):

Fall 2016
Final Exam Review Worksheet
Suggested Time: 180 Minutes TA:

This worksheet contains 19 pages (including this cover page) and 15 problems, for a total of
300 points. Before you begin, please check to see if any pages are missing. A suggested time
limit and point values have been provided for the purposes of self-evaluation.

Show and organize your work in a reason-

Problem Points Score
ably neat and coherent way. Orderly, intelligi-
ble calculations are the difference between par-
1 15
tial credit and no credit.

Use appropriate significant figures. An 2 15

otherwise-correct answer with the incorrect
number of significant figures may not receive 3 15
full credit.
4 15
The use of programmable calculators is
prohibited on exams. Familiarize yourself 5 16
with the usage of simple four-function or sci-
entific calculators. 6 24

7 25

8 25

9 30

10 35

11 21

12 19

13 15

14 10

15 20

Total: 300

By Jo Melville (5.112R5) Page 1 of 19

5.112 Fall 2016

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5.112 Fall 2016

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5.112 Fall 2016

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5.112 Fall 2016

1. An antinoise system is set up to cancel a sound wave with a frequency =261.63 Hz by (15)
emitting the same tone in such a manner to create destructive interference. If the speed
of sound is 340.29 m/s, what is the minimum distance between the sound source and
the antinoise source?

2. X-rays with a wavelength of 3.1 nm strike an atom of boron, photoinducing the emission
of several electrons of various speeds.
(a) Which orbitals are electrons being excited from? (2)

(a)
(b) How many unique electron velocities will be observed? (3)

(b)
(c) What is the velocity of the slowest electron released from the atom? (10)

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5.112 Fall 2016

3. The next three questions relate to the following homoatomic molecular orbital diagram.

(a) Fill in the correct number of electrons for the AOs and MOs for O2 . (5)
(b) Calculate the bond orders for the following species: O2 , O2 + , O2 - , O2 2- . (4)

(c) Which of the species from part (b) would you expect to have the shortest bond (3)
length? The longest?

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(d) Which of the following best describes the highest-occupied MO in the hypothetical (3)
He2 molecule?
A. -bonding, full B. -antibonding, full C. -bonding, full
D. -antibonding, full E. -bonding, half-full F. -antibonding, half-full

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4. 10 mL of a solution of benzoic acid (ka =6.31105 ) with unknown concentration is

titrated with 0.10 M NaOH.
(a) After 10 mL of NaOH is added, the pH is measured to be 4.00. Calculate the ratio (7)
of protonated benzoic acid to its conjugate benzoate ion.

(b) To a first approximation, the amount of conjugate base in a buffered solution near (8)
the half-equivalence point will be equal to the amount of neutralizing titrant added.
Calculate the initial concentration of benzoic acid.

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5. Mark each of the following statements as true or false, and explain your reasoning.
(a) As you move down the periodic table to heavier transition metals, the octahedral (4)
ligand-field splitting O increases.

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(b) Fluoride (F- ) is a strong-field ligand, meaning it increases O . (4)

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(c) [Fe(CN)6 ]3- is a high-spin d5 complex. (4)

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(d) -accepting ligands like CO or CN- will lower the t2g energy level, raising O . (4)

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6. Draw each of the following metal complexes, then calculate the oxidation state and the
number of d-electrons at the metal center.
(a) cis-[PtCl2 (NH3 )2 ] (6)

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(b) [Ni(CO)4 ] (6)

(c) [WCl5 (5 -C5 H5 )] (6)

(d) mer -[CoF3 (PMe3 )] (6)

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7. The vibrational zero-point energy of an unknown hydrogen halide (HX) is 13.28 kJ/mol.
(a) Calculate the fundamental frequency of the HX bond. (6)

(b) Given that the HX bond has a force constant k = 291 N/m, calculate the reduced (7)
mass of the HX system.

(c) A photon with frequency = 2234.5 cm-1 excites the HX system from the ground (12)
vibrational and rotational state (v = 0, J = 0) to the first excited vibrational and
rotational states (v = 1, J = 1). Calculate the moment of inertia I of the system.

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8. The following question relates to the metal complexes [Fe(CN)5 (CO)]3- and [CrCl3 (H2 O)3 ]3- .
(a) Draw and fill a pair of octahedral d-orbital splitting diagrams for the d6 high- and (7)
low-spin cases.

(b) Which of these cases corresponds to [Fe(CN)5 (CO)]3- and [CrCl3 (H2 O)3 ]3- , respec- (4)
tively?

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..................................................................................
(c) If the pairing energy is P and the splitting energy is O , what is the total crystal- (7)
field stabilization energy (CFSE) for the two complexes?

(d) Calculate the magnetic moment of the two complexes to three significant figures, (7)
in units of Bohr magnetons.

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9. The following questions pertain to different types of metal-ligand interaction.

(a) For each of the following ligand binding diagrams, list the type of bonding in-
teraction that is being depicted (-donation, -acceptance, -donation, and/or -
acceptance), and give an example of a ligand which would bind to a metal center
in such a fashion.

i.

.............................................................................

.............................................................................

ii.

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iii.

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(b) In 30 words or less, explain you would expect binding of CO to a metal center like (8)
Fe2+ to affect the properties of the CO bond.

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(c) Order the following MOs for the cyclopentadienyl ligand (cp- ) from lowest to highest (6)
energy.

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(d) 2 is capable of -bonding with the dz2 orbital of a metal oriented above the (7)
cyclopentadienyl ring. Which combinations of metal d orbitals and cp- would be
capable of bonding in a -type fashion? Draw one such interaction.

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10. Transition metals play a small but vital role in a number of biological processes.
(a) For each of the following bioinorganic molecules, list the active transition metal
center(s) and briefly describe their biological function (<15 words).
i. Chlorophyll A/B (4)

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ii. Nitrogenase (4)

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iii. Hemoglobin (4)

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iv. Myoglobin (4)

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v. Vitamin B12 (cobalamin) (4)

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(b) Ferredoxins are crucial electron-transfer proteins that contain cubical iron-sulfur
clusters, like so:

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i. What are the range of possible total charges for the cluster? (Hint: consider (3)
the charges of the RS and bridging S ligands, and the possible oxidation states
of Fe.)

.............................................................................
ii. Fill out the following table with the number of FeII and FeIII centers per cluster (10)
in terms of the overall charge of the cluster.

charge #FeII atoms #FeIII atoms

iii. Under the range of biological redox potentials, which of these charge states are (2)
accessible?

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11. When individual molecular orbital states are extended out to create a solid material, the
result is the creation of continuous electronic bands.
(a) Sketch the band structure of each of the following materials and, if applicable,
identify the valence band, conduction band, and band gap.
i. glass (5)

ii. pure Ge (5)

iii. Ag metal (5)

(b) Identify all of the following materials that are p-type semiconductors. (6)
A. pure Ge B. Ga-doped Ge C. As-doped Si D. In-doped Si E. Sn-doped Ge
F. Te-doped Sn

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12. Many metal complexes are capable of catalyzing complex organic reactions that are
otherwise inaccessible.
(a) Fill in the following incomplete mechanism for the Schrock olefin metathesis reac- (10)
tion.

(b) Match each of the following fundamental organometallic reactions to their descrip-
tion.

oxidative addition reductive elimination migration

i. The introduction of a new ligand to a metal center (3)

with open coordination sites, causing an increase in the
charge of the metal center.

ii. The insertion of one ligand into another, producing a (3)

new ligand still bound to the metal center.

iii. The extrusion of two ligands into a molecular species (3)

that is then ejected, returning electrons to the metal in
the process.

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13. For each of the following molecules, fill in the number of valence electrons, the best Lewis (15)
dot structure, the molecular geometry, and the VSEPR type (e.g. AXn Em ).

Formula # e s Lewis Structure Geometry VSEPR

ICl3

XeF2

PCl3

O3

SF4

14. Fill in the blanks by identifying whether each of the following elements have a higher or (10)
lower first ionization energy than their neighbors.

Na Mg Al Si P S Cl Ar

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15. Consider the harpoon mechanism as it relates to the formation of sodium bromide.
(a) On the following graph, plot the overall energetic favorability of the harpoon (6)
mechanism as a function of the distance between the two atoms.

(b) Using the following table of ionization energies and electron affinities, calculate the (6)
energetic favorability (in kJ/mol) of the harpoon mechanism at a distance r = .

IE1 (kJ/mol) EA (kJ/mol)

Na 495.8 52.8
Br 1139.9 324.6

(c) What is the cost of the mechanism at the equilibrium bond length of re = 2.50
A? (8)

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