CHEMISTRY 209

PRELIM II

November 8, 2007

Your Name:
(P lease print)

Last

F irst

CORN ELL N etID

Day and Time of Your

Lab-Recitation Section:
Lab-Recitation TA:
Complete academic integrity is expected of all students of Cornell University at all
times, whether in the presence or absence of members of the faculty or teaching sta.
Understanding this, I declare that I shall not give, use, or receive unauthorized aid
in this examination.
Your Signature:
There are 5 (some of them multipart) questions and a total of 11 pages (including this cover
sheet, a blank page after all the questions and a periodic table at the end). Make sure that your
examination booklet is complete. The prelim is not designed with the idea that all, or necessarily
any of you, will complete each and every question; rather, it provides a menu covering many dierent
areas of relevance to the course, and I expect that each of you should have something substantial
to say about most of those areas.
Write your answers directly on these sheets. Use the blank page, or if necessary the backs of
pages, but clearly indicate on the problem page where work can be found. If you need to include
additional pages, please attach them securely to the rest of the test book. Be brief, concise, and
neat. Include only material pertinent to the question asked. Proctors are not allowed to interpret
questions for you. In case of doubt, indicate the assumptions on which your answer is based. Pay
attention that the signicant gures reported in your answers are not unreasonable.
You may leave when you are nished, but please do so quietly after turning your paper.
Question 1.

(15)

Question 2.

(20)

Question 3.

(20)

Question 4.

(20)

Question 5.

(25)

Total

(100)

Show your work! (Unless you dont care to receive partial credit).

1. (a) For the molecule tetracyanoethylene, with molecular formula (NC)2 CC(CN)2 (indicating
that each of the 4 N atoms is an end of the molecule) determine:

i. (2 points) The total number of valence electrons:

ii. (2 points) The number of electrons in bonds:
iii. (2 points) The number of electrons in bonds:
iv. (2 points) The number of lone pair electrons:
(b) Consider the chemical reaction
BF3 + NH3 F3 BNH3
i. (4 points) Draw Lewis dot structures incorporating all valence electrons representing
the molecules BF3 and NH3 , and describe the hybridization you expect at B and N
atoms and the
FBF and
HNH bond angles in the two structures.

ii. (3 points) Describe the changes if any, which take place at B and N in the reaction
which creates a bond between B and N.

2. (a) (10 points) Predict the geometry about the central I atom in the IF+
4 ion.

(b) (10 points) Consider the anion nitroamide, HNNO

2 . Draw Lewis structures which you
expect to contribute signicantly to the properties of the anion, assess formal charges
and suggest which of your structures should be considered the most relevant.

3. Radioactive decay is characterized by a decay rate which is always proportional to the amount
of sample left, so the N (t) = N0 et for N0 the amount of sample at zero time, and N (t) is the
0.693
,
amount at time t. The decay constant is often presented instead as a half-life, t1/2 =

where t1/2 is the time required for half the sample to undergo a decay event.
(a) (10 points) A 0.0100 g sample of a radioactive isotope with a half life t1/2 = 1.3 109
yr decays at a rate A = 2.9 104 decay events per minute. What is the mass of the
isotope?

(b) (10 points) 14 C is produced in the atmosphere by cosmic rays from the sun interacting
with nitrogen; the radioactive C atoms can then be incorporated into plants via the
processes of photosynthesis, and may be, for example, found in the wood from trees. Once
the tree dies, however, no further incorporation of 14 C takes place, and the concentration
of 14 C decays with its half-life t1/2 = 5730 yr. An allegedly ancient relic is tested, and
demonstrates a 14 C to 12 C ratio which is 95% of that found in a sample of newly harvested
wood. What does this test suggest the age of the wood to be?

4. (a) (10 points) Explain why the electron anities of both Si and S are larger than that of P.

(b) (10 points) Moseleys work on the x-ray spectra of atoms provided the nal information
required to organize the periodic table. He observed that the x-ray emission lines came
grouped in energy as families of lines, and assigned the families with one-letter names
as indicated in the drawing below at left; at right is shown the spectrum of Germanium
(Z = 32) where lines are found at 10.3 and 11.0 keV.

For the K and L lines he found a set of particularly simple relationships, such that
3
K = (Z 1)2 
4

and

L =

5
(Z 7.4)2 
36

where  is the Rydberg constant associated with the H-atom spectrum.

Below is shown the spectrum observed for an unknown element; lines are found at 6.95,
7.87, 48.0 and 55.7 keV.

Identify Z of the unknown element based on its spectrum.

5. (a) An MO diagram describing the molecule BO is shown below. Only the electron orbitals
associated with the n = 2 valence shell are shown.

i. (2 points) Identify which atom (B or O) corresponds to atom A.

ii. (2 points) Label according to the conventional labeling scheme each of the atomic
orbitals (AOs) and molecular orbitals (MOs) by entering the label names into the
diagram.
iii. (2 points) Assign electrons to the ground state of the molecule BO by lling the
appropriate MOs in the slots provided in the MO diagram. Indicate spin state with
and symbols.
iv. (4 points) Consider the isoelectronic species C
2 . Describe how the MO diagram for

C2 would dier from that shown for the BO molecule, above.

(b) (5 points) Below is shown the complete photoelectron spectrum of an atom, X containing
no d or f electrons in its ground state; peak intensities can be assumed to represent
the numbers of electrons per energy state. X is known to form a diatomic gas phase
molecule. Identify the atom shown, assuming that the entire spectrum is shown; and
in the graph below sketch the spectrum you would expect to observe for the molecule
X2 in the energy region provided. Your sketch should show intensities corresponding
to the numbers of electrons found in the energies you determine; the energies need not
be determined with precision, but energy relationships will be important. Ignore the
possibility that vibrational structure in the molecule may be important.

Atomic X

8.0

7.2

6.4

5.6

4.8

4.0

3.2

2.4

1.6

0.8

0.0

Energy to ionization (MJ/mole)

Molecular
X2

8.0

7.2

6.4

5.6

4.8

4.0

3.2

2.4

1.6

0.8

0.0

Energy to ionization (MJ/mole)

8

(c) (5 points) O2 is paramagnetica result not predicted from its Lewis structure, but instead
obvious from its MO diagram. Identify the highest energy occupied molecular orbital(s)
for O2 , state their occupancy, and sketch both the atomic orbitals which come together
to form the highest energy MOs and the shape of the molecular orbital(s).

(d) (5 points) Some evidence exists for a weakly bound compound joining two O2 molecules
together into the form O4 . An MO diagram for O4 can be easily composed if we treat
each O2 molecule as if it were a pseudo-atom, and its MOs, as if they were pseudoatomic orbitals. Based on this model, and assuming that only the highest energy
pseudo-atomic orbitals contribute to the bonding in the O4 species, predict which O2 based orbitals might be expected to contribute to the bonding observed in O4 . Comment
on whether or not the new bonding orbitals are localized, sketch their spatial extent and
describe the magnetic state you would expect in the ground state of the O4 molecule.
Your description should incorporate as much of the language of MO theory as possible.

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