Chemistry 303 Fall, 2009

Exam 1
October 21, 2009
Exam starting time: 7:30 pm
Exam duration: 2.0 hr
Name: __________________KEY_________________
Lab TAs name____________________________
NOTE: this is an open book exam. You may consult anything that is not alive nor connected to the
internet. No computers nor cell phones are allowed to be used in the examination room.
NOTE: if you do not know the complete or specific answer, give a partial or general answer
We love to give partial credit.
If there seems to be more than one good answer, explain your thinking.
If you invoke resonance delocalization as part of your answer, draw the relevant resonance
structures.
WRITE SOMETHING
BUT: write legibly! We will not work too hard to decipher sloppy writing.
READ each problem carefully!
Chemistry is communicated with words and pictures. In some cases, pictures are necessary.
Use them liberally in your answers.
NOTE: The last page of the exam contains:
1. The table of common isotopes
2. The table of electro-negativities
3. The mass spectrum for problem V

Score:
p2______/22

p3______/10

p4______/08

p7______/11

p8______/10 p9_______/08

Lecture Total_________/100

p5_____15
LAB:

p6______/16
p10______/10

p11______/04

Lab Total__________/14

Pledge:_________________________________________________________________________

I. (22 pts). Nitrilimines belong to an important class of organic compounds known as 1,3dipoles. The Lewis structure of a nitrilimine shown below (1) gives the correct connectivity between
atoms, although no particular geometry is implied by this structure.
A. (04 pts).
i. Draw all appropriate formal charges
on the Lewis structure depicted here
ii. Identify on the structure whether
each of the bonds drawn is or .

H3 C

B. (06 pts). Draw three better resonance

structures (2, 3, 4) for the nitrilimine.

H3C

CH3

H3 C

CH3

"

(1)H C
3

CH3

(3)

(2)

Bad alternative: H3C

CH3

(4)

CH3

C. (06 pts). Give the hybridization of the atoms

labeled 2, 3, and 4, and indicate bond
angles labeled as (a) (b) (c).

a
H3 C

Hybridization at: 2_sp_

3__sp__
4_sp2___
Bond angle at: (a) 1800__ (b)_1800_ (c)_1200_

CH3
5

D. (04 pts). Of the four resonance structures 1-4, circle the one that contributes most to the resonance
hybrid, and draw a box around the resonance form that is the second most important. Explain your
choices.
Structures 3 and 4 have one more bond than the others. In structure 3, the negative charge
is on the nitrogen, while in 4 it is on a carbon. Since N is more electronegative than C,
structure 3 has the negative charge in the more favorable position. The plus charge is the
same in both.
E. (02 pts). Which is the shortest bond in the actual molecule (not a particular resonance structure)?
Explain.
Circle single best answer: C1-C2

C2-N3

N3-N4

N4-C5

A triple bond would be shorter than any of the single or double bonds. Only one resonance
structure shows a triple bond, between C2 and N3. This is the more stable structure and will
contribute strongly to the overall structure; the molecule will have the shortest bond at this
position.

II. (18 pts). Two structures with the formula C2H5N

are provided here.

A. (03 pts). Draw the other three possible isomers, showing

H3C
all bonds and lone pairs. Label them 1, 2, and 3.
Consider only those three isomers in the following questions.
N-H
1

NH2
2

H
N

N
H

H3C

N
3

B. (03 pts). Which isomer (1,2,3) would be most soluble in cyclohexane? Give the single most
important reason for your choice and compare it with the second most soluble.
Cyclohexane is not able to provide H-bonding or dipole interactions. (2) can engage in two
H-bonds to itself, and therefore cannot be broken up by cyclohexane, not very soluble. Cpn 1
can have one H-bond, not quite so difficult to dissolve in the non-polar solvent. Cpn 3 has no
H-bond donor capability and should be most soluble in the non-polar solvent, cyclohexane.
Cpn 1, with one H-bond per molecule should be second most soluble.

C. (04 pts). Which isomer is most soluble in water? Provide the single most important reason and
draw a picture of the solvent interactions.
The dominant factor with water is H-bonding interaction. Each molecule of (2) can enter into
H-bonding with the water solvent using two N-H bonds, leading to good solvation. The effect
is less with (1) and absent with (3). (3), along with the other two, has a nitrogen which can
serve as H-bond acceptor. (2) is most water soluble due to effective H-bonding
H

N
2

H
O

D. (02 pts). Which isomer has the lowest boiling point? Explain your choice compared to the
other two isomers you drew.
H-bonding provides the strongest self-association and raises the bp. Since (3) cannot
participate in H-bonding to itself, it will have the weakest self-association and therefore the
lowest bp. (1) has less opportunity for H-bonding to itself compared to (2) and will have the
second lowest bp.

E. (03 pts). Which isomer has the longest C-N bond? Explain your choice.
Single bonds are longer than double bonds. The possibilities are shown with arrows. More
(s) character leads to a shorter bond. Poorer orbital overlap leads to a longer (weaker) bond.
Therefore, the ring bond in the 3-membered ring, with minimal (s) character and poor overlap
will be the longer.
spx-spx (x>3)

sp2-sp2
sp2-sp3

N-H

NH2
2

N
3

(nitrogen involved
in resonance wtih pi bond

F. (03 pts). One isomer contains an amino (NH2) group. Protonation of this compound occurs most
favorably at a carbon instead of nitrogen. Use the arrow formalism to show the formation of
the conjugate acid, and explain why protonation at carbon is favored.
NH2

+ H+

NH2 + H+

NH2
H

NH2

+ H+

NH2

NH2

none possible

H
NH2

none possible
one fewer bonds

Protonation at carbon leads to a conj acid cation which has minor resonance stabilization.
Protonation at nitrogen leads to an ammonium ion with no special stabilization.
Therefore, protonation at carbon is favored.
4

III. (15 pts). Vitamin C (also known as ascorbic acid) can be representated by structure X
and has a pKa of 4.2 in water. This means that vitamin C is more acidic than acetic acid (pKa = 4.8)
despite the fact that it does not contain the carboxylic acid functional group. There are related
compounds (Y, Z) with higher pKa.
H

HO Y OCH3
pKa 6.8

HO

X OH
pKa 4.2

H3CO Z OH
pKa 13.2

__________________________________________________________________________________
A. (04 pts). Which proton in X is the most acidic? Draw the corresponding conjugate base.
H
R

most
acidic

HO

OH

OH

B. (04 pts). From among our general parameters (electronegativity, resonance, inductive,
hybridization), which are the most important two in stabilizing the conjugate base? Explain your
choice.
Resonance and electronegativity (inductive could be allowed, if explained properly).
H
R

OH

OH

OH

negative charge on
very electronegative atom

One other really good resonance structure (like a carboxylic acid). Minus charge delocalized
onto oxygen.
C. (03 pts). Consider the data for Y and Z. They suggest that the two general parameters from part B
may not be sufficient to rationalize the low pKa for X. Please describe a special feature of the
structure of the conjugate base for X that helps to account for the low pKa relative to Y and Z.
Cpn Y would have the same resonance and electronegativity
stabilization as for X. But it is less acidic. Must be some other factor. There can be very
favorable internal hydrogen bonding
H
H
O
O
in two of the resonance structures
O
R
O
R
(only one applies; one cannot change
H
the atom locations in various resonance
O
structures). This H-bonding gives
O
O
O
strong stabilization for the conj. base.
H
D. (04 pts). If the pKa of vitamin C were measured in methylene chloride (CH2Cl2) instead of water,
would you expect it to be higher or lower than 4.2? Explain with words and pictures.
No H-bonding in methylene chloride. Therefore
H
the anionic conj. base is poorly solvated
O
O
R
compared to the process in water, less
strong stabilization by H-bonding to water.
favorable, less acidic acid. Higher pKa.
H
O H O
O
H
O H

Nothing comparable in CH2Cl2;

only dipole/dipole

IV. (27 pts). Consider the two isomeric ketones, G or H.

A. (06 pts). Which is more stable? Use a resonance analysis to

rationalize your choice.
O

G has one more "good" resonance structure compared to H; G is more stable.

B. (05 pts). Circle the most acidic proton in G, draw all significant resonance structures for the
conjugate base for G. Circle the best structure.

Hb

H
e

Ha
Ha
Hc

H
e

G
Ha

H
e

Hd

Hd

C. (05 pts). Circle the most acidic proton in H, draw all significant resonance structures for the
conjugate base for H. Circle the best structure.
H

H
H

most acidic

Continued

D. (08 pts). Which is more acidic, G or H? Explain. As part of your answer, express
the two reactions on the free energy diagram here. Show an energy level for each reactant, and an
energy level for each conjugate base. Indicate on the diagram the energy change (G) for each.
The conjugate base is the same from each (exactly the same resonance structures). So this
is a special case where the acidity is dominated by the stability of the acids. Since G is more
stable than H, it is less acidic than H
conjugate base of
conjugate base
G
of H

energy

!G G

!G H

H
G

reactants

products

E. (03 pts). Circle the least acidic proton in G.? Explain by discussing the factors which make the
other protons more acidic.

Ha

Ha

Hb

Ha

He H

G
Hc Hd Hd

He

Ha

Ha

Hb

Ha

He H

Hc Hd Hd

No special stabilization
of this anion. Slight inductive
stabilization by the carbonyl group,
but that also applies to other conj. bases
such as that from removal of Hb. But
Hb is on an sp2 bond, and is already more
acidic.

Hc is also slightly acidified by being attached to an sp2carbon, and has the C=O nearby to stabilize the anion somewhat by
the inductive effect.

V. (10 pts). The following is a list of mass spec data for compound Q (m/z position
followed by % intensity compared to the base peak as 100%). The actual spectrum is also available at
the end of the exam.
m/z 115(2.2%), 114(31.8), 113(6.8), 112(100), 78(3.5), 77(52), 76(4.3), 75(5.2), 74(5.2), 73(2.3),
57(1.0), 51(16), 50(12).
A. (06 pts). Circle the molecular formula from this list that is most consistent with the data. Explain
by first detailing how three key features of the parent ion region the spectrum are consistent with
your choice.
1. C3H3F2Cl
2. C8H16
3. C6H5Cl
4. C6H12N2
5. C5H5Cl
1. For the isotope distribution 12C61H535Cl, the molecular ion should be 112; consistent
with the base peak in the spectrum.
2. The M+1 is 6.8%, consistent with a molecule having 6 carbons (would give 6.6%)
3. The M+2 is 31.8% of the M peak. This is almost exactly correct for the natural
isotope distribution for one Cl atom (35Cl/37C = 75/25, or 100:33).

B. (04 pts). For each of the other choices, describe briefly one element of the mass spectral data that
is inconsistent with that choice
For C3H3F2Cl: correct molecular ion, OK for Cl isotope distribution, but M+1 should be 4.4%
For C8H16 : correct molecular ion, but inconsistent with the Cl isotope distribution
For C6H12N2: correct molecular ion, but inconsistent with the Cl isotope distribution
For C5H5Cl: wrong parent ion

VI. (08 pts) Anthracene, tetracene, and pentacene belong to a class of organic
molecules known as polycyclic aromatic hydrocarbons. Anthracene is a major component of coal tar,
and both tetracene and pentacene are used as organic semiconductors.

anthracene

tetracene

!max 374 nm

!max 472 nm

colorless

orange

pentacene
!max 585 nm

A. (02 pts). What type of electronic transition results in the observed max for this series of
compounds? Circle single best answer.
a. n to *

b. to *

c. to *

d. to *

B. (02 pts). Explain in general terms why max increases as one moves from anthracene to
tetracene to pentacene.
More pi orbitals in conjugation means smaller energy gap between highest filled orbital and
lowest empty orbital, longer wavelength.

C. (02 pts). Explain in general terms why anthracene is colorless and tetracene is orange.
Anthracene is colorless because its absorption is not in the visible region, to low wavelength.
Tetracene absorbs at wavelengths in the visible region, allowing the orange light to be
reflected (or transmitted, if in solution). Looking at 472 on the color wheel shows orange
across the wheel.

D. (02 pts). What is the color of pentacene? Explain how you chose it.
Using the color wheel, absorption at 585 nm means that blue light is reflected (or transmitted,
if in solution).

VII. (14 pts). Lab Related Question.

While performing the Method A separation of aspirin and

9

caffeine in the Analgesic Experiment, Joe L. Sapphire inadvertently extracted the methylene chloride
solution, containing the aspirin and caffeine, with 4 mL of 0.1 M aqueous NaOH solution (left over
from the Startup Experiment), instead of the recommended 4 mL of 10% (~2.8 M) aqueous NaOH
solution. As a result of this error, Joe L. obtained a negligible amount of aspirin/salicylic acid upon
acidification of his alkaline aqueous extract. On a brighter note, he did manage to isolate a whopping
500 mg of crude caffeine from his dried methylene chloride solution.
A. (07 pts). Explain why Joe L. obtained a negligible amount of aspirin/salicylic acid upon
acidification of his alkaline aqueous extract.
The basis for the separation of aspirin and caffeine in Method A is that aspirin, a
carboxylic acid, will be converted into a water-soluble salt upon treatment with aqueous
NaOH solution, while the caffeine will remain in the methylene chloride layer. The
problem here is that Joe L. has used only 0.4 mmoles (4 mL x 0.1 M) of NaOH
solution, rather than the recommended 11.2 mmoles (4 x 2.8 M) of NaOH solution.
There is not enough NaOH present to convert the aspirin (520 mg, 2.9 mmoles) into its
water-soluble salt.

B. (03 pts). Where is the rest of Joe L.s aspirin/salicylic acid? Explain.

Thus, most of Joe L.s aspirin remained in the methylene chloride layer along with the
caffeine, explaining Joe L. prodigious yield of crude caffeine. (According to the
manufacturer, there should only be 32.5 mg of caffeine in each powder.)

10

C. (04 pts)

What should Joe L. do to recover the rest of his aspirin/salicylic acid? Explain.

The solution to Joe L.s problem is to simply redissolve his crude caffeine in
methylene chloride and re-extract with 4 mL of 10 % aqueous NaOH solution. Then
follow the normal Method A separation protocol.

____________________________________end exam____________________________________
Possibly Useful Information
1. Table of common isotopes:

11

2. Partial table of electronegativities: (text fig 2.2)

3. The mass spectrum for problem V:

12