Chemistry 102 Midterm Examination Answer Key

Name:__________________________________

Due Thursday, May 10, 2012 Before Class (1:00 pm, 151 Crellin) Rules: Closed Notes, Closed Book. Time limit: 4 hours. Only six out of the seven problems worth points will count toward your grade. Select the problem you would like to drop by crossing out the problem number (1-6) below. If no problem is crossed, problem 7 will not be counted.

Periodic and character tables are provided at the end of the exam. The use of molecular model kits is allowed. Question Points Available Points Earned Problem 1 120 120 Problem 2 120 120 Problem 3 120 120 Problem 4 120 120 Problem 5 120 120 Problem 6 120 120 Problem 7 120 120 Total 720 Problem 8 For fun! (NO CREDIT) 0

Problem 1 (120 points) a) Draw Lewis dot structures for N 2 O 3 , N 2 O 4 , and N 5 + (none of these are cyclic) including resonance structures where appropriate. Limit your answer to the three most important resonance structures. Include all valence electrons in your drawings. Predict which N-O bond will be shortest in the first two molecules above; label the N-O bonds expected to have length.

b) For each of the molecules from part (a), assign VSEPR geometries to every unique center, assign angles (>90, <120, etc), and assign oxidation states to all atoms.

c) Draw Lewis dot structures (in the VSEPR geometries) and important resonance forms for NO 2 , NO 2 , and NO 2 +, and assign their point groups. Assign oxidation states to all atoms. Compare, explaining your answer, the O-N-O angles in the three species.

d) The molecule P 4 O 6 is in the T d point group. Draw a Lewis dot structure of this molecule and assign oxidation states. Hint: think of adamantane.

e) The oxoacids of chlorine and iodine in which each halogen is in its highest oxidation state were discussed in class. Draw the structures of these two acids and provide an explanation for the different structures.

f) The geometry of Cl 2 O resembles that of water, would you expect the Cl-O-Cl angle to be greater than, less that, or equal to that of water (104.5)? Explain your reasoning.

Problem 2 (120 points) Part A a) Which of the following molecules are paramagnetic? B 2 , C 2 , N 2 , O 2 , F 2 .

Only B2 and O2 are paramagnetic. A complete discussion of this topic is found on pages 38 and 39 of the textbook.

b)

Indicate the bond order for the following molecules: B 2 , C 2 , N 2 , O 2 , F 2 . B2: C2: N2: O2: F2: 1 2 3 2 1

Part B In Problem Set #3 you were asked to analyze the molecular orbitals of trans-SF 4 Cl 2 , shown below.

Cl F S F Cl F F

a) Without deriving an MO diagram, what is the maximum number of bonds, overall, that the sulfur atom can make with its ligands? (remember that d orbitals are too high in energy to be involved in bonding) Explain. The sulfur atom can make 4 bonds overall with its ligands. As stated the d orbitals are too high in energy to be involved in bonding leaving only the s and p orbitals for binding.

b) Describe the molecular orbitals depicted below as bonding, antibonding, or non-bonding. For the bonding and antibonding interactions, identify them as or relative to the appropriate S-F and S-Cl vectors (the chlorides are in the axial positions as drawn). Two examples: -bonding interactions S-Cl -bonding interactions S-F

non-bonding (based primarily on the chlorides)

non-bonding on F

antibonding on S-Cl and S-F

bonding on S-Cl antibonding on S-F

 bonding on S-Cl

non-bonding on F atoms

bonding on S-F

antibonding on S-Cl antibonding on S-F

bonding on S-F bonding on S-F

Problem 3 (120 points) In order to calibrate his polarimeter, Paul needs to identify some chiral molecules. He has access to the following compounds (assume frozen conformations). For each molecule or ion: i. Assign the point group. ii. Indicate if the molecule is chiral or not. iii. If the molecule is achiral, indicate a symmetry element present that precludes chirality.

Problem 4 (120 points) Cubane (1) is a highly strained hydrocarbon that is kinetically stable despite the large amount of strain energy it contains. Many substituted cubanes have been studied, especially as new explosive materials.

A researcher in your lab has been working on fluorine-substituted cubanes. He has been able to isolate a compound with the formula C 8 H 4 F 4 , but is uncertain on how to determine the specific isomer(s) he obtained. Your labmate has already thought of one possible structure, one in which the four fluorines occupy the vertices of one face of the cube, but he needs help with the other possibilities. Knowing of your expertise in symmetry and spectroscopic predictions he has asked you to compile a list of predicted 19F-NMR, IR, and Raman signals for all the possible isomers of C 8 H4 F4 . a) Draw all the isomers of C 8 H 4 F 4 cubanes; the structure proposed by your labmate is already drawn in for you. Assign a point group to every proposed structure.

b) For each of the isomers proposed, derive the reducible representation for the C-F stretches, then reduce it to sums of irreducible representations and fill in the table below.

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c) Fill in the table below with the predicted total number of 19F-NMR signals, total number of C-F stretches, IR- and Raman-active C-F stretches, and polarimetric behavior for each isomer. Note: An achiral molecule will not affect polarized light (0), while enantiopure chiral molecules will; enantiomers rotate polarized light by the same angle, in opposite directions (x, -x).

d) Using a combination of 19F-NMR, IR, and Raman spectroscopies and polarimetry, can you help your labmate discern all possible C 8 H 4 F 4 isomers?

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Problem 5 (120 points) In Problem Set #3 you were asked to derive a molecular orbital diagram for a hypothetical SeH 6 species in the trigonal prismatic geometry. Shown below is a different geometry for a similar neutral molecule with the general formula AH 6 , where A is a group 16 element (d orbitals are not involved in bonding). The angles between the AH bonds and the z-axis are all the same (as shown) and the A-H bonds are all the same length.

a) Assign the point group to AH 6 in the geometry shown above.

b) Determine the reducible representation of the 6 H 1s orbitals, 6H , in the AH 6 analog. Reduce the reducible representation to a sum of irreducible representations using the appropriate character table.

c) Draw the symmetry-adapted linear combinations (SALCs) of orbitals that correspond to these irreducible representations, and label them with their Mulliken symbols. Then draw the valence orbitals of A and assign their irreducible representations.

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d) Construct a molecular orbital (MO) diagram for AH 6 . Label each MO with its Mulliken symbol and determine whether it has bonding, nonbonding, or antibonding character. Fill in the appropriate number of electrons (assume that A has 6 valence electrons), identify the HOMO and LUMO, and determine the overall bond order. Draw all MOs. Predict whether this molecule is diamagnetic or paramagnetic.

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e) Consider what happens when the angle a is increased (this could be caused, for example, by an increase in the steric bulk of the six ligands). Draw a Walsh diagram for the distortion that increases the angle a from 35 to 55.

f) Draw a Lewis structure for AH 6 that obeys the octet rule. What is the average A-H bond order? How does this compare with the MO theory prediction?

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Problem 6 (120 points) Carbon dioxide, CO 2 , is a molecule that acts as a greenhouse gas and therefore has been receiving a lot of attention lately. a) Draw the most favorable Lewis structure of CO 2 . Use this structure and VSEPR theory to predict its geometry.

b)

While CO 2 has higher symmetry, it is easier and an interesting exercise to start by considering it of lower symmetry, such as the D 4h point group. Draw a coordinate system for the molecule. The z axis should be along C n . The x axis should lie in the mirror plane perpendicular to C n .

c)

For the complete molecular orbital picture of CO 2 it is necessary to consider all the valence orbitals. Using the symmetry operations of the molecule determine which oxygen orbitals transform together. For each set of orbitals that transform together, determine the reducible representation, , for that basis set.

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d)

Reduce the reducible representations of the oxygen orbitals to a sum of irreducible representations in the point group D 4h .

e)

Sketch out the 8 SALCs for the oxygen atoms and label them clearly with the corresponding Mulliken symbols (D 4h ).

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f)

Determine the irreducible representations of the valence orbitals on the central carbon (in D 4h ).

g)

Generate a molecular orbital (MO) diagram for CO 2 by combining oxygen SALCs and carbon atomic orbitals of appropriate symmetry. Note that the oxygen s orbitals are significantly lower in energy compared to the other valence orbitals involved and will mix less. Label each molecular orbital with the corresponding Mulliken symbol (D 4h ). Fill with the correct number of electrons. Indicate the HOMO and the LUMO.

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h)

Clearly draw the HOMO and the molecular orbitals corresponding to the p bonds in CO 2 . Label with Mulliken symbols. By inspection of the appropriate character table, assign Mulliken labels to these orbitals in the correct point group of CO 2 .

i)

Pictured below is the photoelectron spectrum of CO 2 . The energy of each excitation increases from left to right. Each peak corresponds to an excitation from a different molecular orbital. Label each peak with the corresponding molecular orbital Mulliken symbol (in D4h).

Note that the peak to the far right corresponds to two overlapping peaks. Why are the energies of these two orbitals so close? Those two peaks correspond to the largely non-bonding oxygen 2s orbitals. The two oxygen orbitals do not have much physical overlap so they do not efficiently split each other and their energies are too far from the energy of the carbon valence orbitals to mix efficiently. The tiny bit of interaction they have with the carbon orbitals gives the tiny bit of splitting seen in the photoelectron spectrum. j) How many peaks would you expect in the photoelectron spectrum of XeF 2 ? Since XeF2 has the same type of valence orbitals as CO2 the same MO diagram can be used. If 6 more electrons are filled in, two more energy levels are occupied, and two more peaks would be expected for a total of 8 peaks.

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Problem 7 (120 points) Part A Walsh diagrams provide a convenient method to track how angular distortions to a molecule affect orbital energies. Molecules with the general formula AH 4 can adopt a number of different geometries. The orbital energies and SALCs of such a generic molecule with T d symmetry have been derived for you below.

a) Draw a Walsh diagram for the distortion of such a T d symmetric AH 4 molecule to one with D 4h symmetry. Keep the coordinate system the same. This diagram should include the full MO diagram of such a molecule including MO drawings (Mulliken labels are not required). Clearly correlate the molecular orbitals.

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b) Based on this diagram, determine which geometry is favored for CH 4 and XeH 4 (model compound for XeF 4 ). Explain. T d is favored for CH 4 because if you fill the MO diagrams in with 8 electrons, for T d geometry only bonding MOs are filled, while for D 4h geometry, a non-bonding orbital is populated. D 4h is favored for XeH 4 because if you fill in the MO diagrams in with 12 electrons, for T d geometry two anti-bonding orbitals are populated, but for D 4h geometry, one anti-bonding orbital is populated.

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Part B a) The irreducible representations for the degrees of freedom of a square planar AH 4 are provided below: A 1g + A 2g + B 1g + B 2g + E g + 2 A 2u + B 2u + 3 E u Determine the irreducible representations corresponding to translations, rotations, stretching modes and bending modes. For the purpose of this vibrational analysis, consider a coordinate system in which the z-axis corresponds to the principal axis of rotation and the x and y axes are along the A-H bonds.

b) How many peaks do you expect in the 19F-NMR, IR, and Raman spectra for this molecule?

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c) Draw and label with Mulliken symbols the vibrations for square planar AH 4 .

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Problem 8 (sorry, no credit) What is the point group of the object in the stereogram below? Neglect texture.

D2

END OF EXAM

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