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Chemistry 303b

fall, 1999
FIRST EXAMINATION
7:30 PM, OCTOBER 18TH, 1999

KEY
(if you do not know his/her name, give day of lab section)
This is an "open book" examination; you may use anything which is not alive.
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.
WRITE SOMETHING
Write only in the space provided for each question.
Score:
1___________/15
2___________/20
3___________/18
4___________/18
5___________/09
6___________/20

Total:

/ 100

There are 7 pages in this exam; please check now to be sure you have a complete set.
Please be aware that a small number of students will be taking the exam at different times up until the afternoon on
Tuesday. It would be well not to discuss the exam until after that time.

Pledge:_________________________________________________________________________________
1

1. (15 pts). Circle the most acidic molecule in each pair and explain the single most important reason for your
choice in terms of differential resonance, inductive (electronegativity), or hybridization effects. Draw the
conjugate base of the most acidic molecule.
For each part: +2 for the right circle, +1 for the conj base; +1 for naming the right reason; +1 for
explaining how the reason works.
CH3 H
C C
C
CH

A.

CH3
C C C H
CH3

or

CH3
C C C
CH3

The conjugate base is stabilized by hybridization factors,


having the non-bonding electron pair in an sp orbital, more s character, more stable anion

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B.

or

4 other resonance structure. Resonance stabilization is greater here than for


the corresponding anion from the other molecule (only three resonance
structures total in that case.

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C.

NH3

NH3

Resonance stabilization is available to the


conjugate base (aniline) which is not available
to the starting acid (nor to the other acid or its
conj base). More stabilized conj base means
more acidic starting acid.

vs

NH2

NH2

NH2

NH2

2. (20) pts). Consider the molecule, formamide, written here in its "best" resonance structure.
O

H
N

formamide

H
A. Draw on the structure above all non-bonding electron pairs and formal charges. 2 pts
B. Re-draw formamide here and then use the arrow formalism to generate the second-best resonance structure
for
formamide, and show all non-bonding electrons and formal charges.
O

H
N
H

H
N

arrows: +1
charges: +1
lone pairs: +1

C. The C-H bond involves overlap between what types of atomic orbitals? : __sp2-s
[specify combination of two from the list: p, s, sp, sp2, or sp3]
D. Would you expect the C-N bond to be: Shorter
Longer About the same as the C-N bond in methylamine? Explain in one sentence. 2 pts
Shorter, because the contribution of the dipolar structure shows a C=N double bond. More double bond
character, depending on the importance of this structure. At least there is some double bond character, and
therefore there is some shortening of the C-N distance.
F. Should formamide be classified as an aprotic or protic solvent? Explain. 2 pts
Protic. The presence of any N-H (or OH) is sufficient to make it "protic". This is particularly "protic"
because of the contribution from the dipolar resonance structure, suggesting an electron-poor H attached to
N+
G. Evaluate formamide as a solvent, by considering its ability to dissolve methyl alcohol.
a. Is it a good H-bond donor? Explain by analyzing what is necessary in a good H-bond donor and
illustrate with the interaction of formamide with methyl alcohol.
It is a good H.bond donor (see above). Good H-bond donors have polarized H capable of associating with the
negative end of a dipole or non-bonding electron pair.

CH3
H

H-bond

O
H

N
H

O
H

b. Is it a good H-bond acceptor? Explain by analyzing what is necessary in a good H-bond acceptor and
illustrate with the interaction of formamide with methyl alcohol.
It is a good H-bond acceptor. Good H-bond acceptors have strong (-) polarized atoms with non-bonding
electron pairs. The carbonyl O is particular highly polarized (-).

N
H

O
H

H
O

CH3

H-bond
3

3. (18 pts). Compound A is a weak acid and can be converted to its conjugate base when treated with a very
strong base. When the conjugate base is neutralized with acid, two isomers are formed, the original A and a
new species, B.
1 2
(CH3)2 CH C

3 4
C C(CH3) 3
A

base
Conjugate Base

A + B

-H

A. Which is the shortest bond between carbon atoms in A? Circle the single correct answer.
2 pts

C1-C2

C2-C3

C3-C4

B. What is the bond angle C1-C2-C3 in the ideal structure?

2 pts

90o

109o

120o

180o

none of the above (explain)

C. Draw carefully the two best resonance structures for the conjugate base. 2 pts each
Show clearly the location of the anion (non-bonding electron pair) in each structure. 1 pt each
Pick ONE of the structures and label it carefully with the hybridization at carbon atoms C1 to C4. 2 pt
On both structures, write the hybridization (s,p,sp,sp2,sp3)of the orbital which contains the anion (nonbonding electron pair) 2 pt (both right)
sp

3
sp sp sp

C
p
D. Draw the structure for B. The carbon atoms in B use which hybridizations? Circle all correct answers.
sp3
1 pt

C
H

3 pt

sp2

sp

4. (18 pts). Consider the molecules X and Y. Each has two important resonance structures, the one shown and
one other.
H

H 3C
B

C
X

For calibration:

CH3

H 3C

H 3C
H 3C C
H 3C

H
C
Y

CH3

sp
A. What is the hybridization of the N in trimethylamine?
1 pr

CH3

C
N

CH3

sp2

sp3

cannot tell

(circle single best answer)

B. What is the hybridization of the B in trimethylboron, (CH3)3B?


1 pt

sp

sp2

sp3

cannot tell

(circle single best answer)

C. Re-draw X here and use the arrow formalism (1 pt) to show the formation of the other important resonance
structure
for X. (a) Show carefully any new bonds, electron pairs, and/or charges. 2 pt
(b) Compare the structures in terms of "importance" (stability). What are the two most
important differences between them?. 2 pt
(c) What is the hybridization of the N in X? 1 pt
(d) What is the hybridization of the B in X? 1 pt
H

H 3C
B

H 3C
X

H 3C

CH3

C N
H

H 3C

(B)

CH3

CH2
N
CH3

Structure B has separation of charge, but it also has one more bond compared to X. Not necessarily clear
which is more stable, although probably should go with B since an extra bond is a large difference.
N is sp2 hybridized
D. Re-draw Y here and use the arrow formalism (1 pt) to show the formation of the other important resonance
structure
forY. (a) Show carefully any new bonds, electron pairs, and/or charges. 2 pt
(b) Compare the structures in terms of "importance" (stability). What is the most
important difference between them?. 2 pt
H
H 3C
CH3
H 3C C C
C
N
H 3C
Y H
CH3

H
H 3C
CH2
H 3C C C
C N
H 3C
CH3
H

(B)

structure B has separation of charge, with (-) localized on C (not great) and (+) on N (not great). It has the
same number of bonds. Therefore, B is much less favorable than Y.

E. Which is more basic, X or Y? Explain carefully, with reference to your resonance structures.
The resonance structure for X shows the non-bonding electron pair from N involved in a new bond, very tightly
held. The resonance structure for Y suggests a little delocalization of the non-bonding electron pair, but nothing
like the situation in X. Therefore, the electron pair in Y is less tightly held and Y is more basic.
2 pt for choosing the more basic one correctly
2 pt for the reason.

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5. (9 pts). Consider how to distinguish the following pairs of molecules by mass spectrometry. For each pair,
explain which of the following features you could use for each case and how it would solve the problem.
You may use each feature only once. 3 pts each [1 pt for the feature and 2 pt for the reason]
1. fragmentation pattern?
2. integer molecular weight?
3. exact mass measurement?
4. pattern of isotope peaks?
_______________________________________________________
A. CH3 CH2 CHCl2 vs CH 3CH2Br
The pattern of isotope peaks around the parent ion. The first compound should have significant P+2 and P+4
due to the abundant Cl-37 isotope. the second compound should have a P+2 just as intense as the Parent, due to
the abundance of Br-81.
[fragmenation and exact mass measurement would also be OK]

CH3

B.

CH3

H
C

CH3

vs

C C H

CH3

Same molecular formula. Only by fragmentation. Hard to predict exact difference, but the assumption is that two
different structures will give different patterns.

C.

OH

vs

H 2N

NH2

Could use fragmentation, exact mass, or a careful analysis of the pattern of isotope peaks. Exact Mass is the
choice. While the integer MW are the same, the different composition means that the exact MWs will be a little
different and distinguishable at high resolution.

6. (20 pts) Consider the three molecules, M, N, and K. Respond to the following questions. If you are using
resonance delocalization in your answer, please draw the relevant structures carefully.
O

NH

C
H 2N

CH2

C
NH2

H 2N

C
NH2

H 2N

NH2

A. Which molecule is most acidic? Re-draw it here and show the conjugate base. Explain your choice briefly.
O

H 2N

NH2

H 2N

O
C
NH

H 2N

NH

Strong resonance delocalization;


Excess charge delocalized on the
highly electroneg atom, O

conj base
1 pt for correct choice of molecule; 1 pt for drawing conj base; 3 pt for explaination
B. Which molecule has the most electron-rich carbon atom? Re-draw it here, indicate that carbon clearly and
explain your choice.
most
electon
CH2
CH2
CH2
rich
C
H 2N

C
NH2

H 2N

NH2

H 2N

NH2
K
Two acceptable answers: best is based on the two resonance structures which show (-) pushed out onto the
carbon CH2 group. However, one can simply saw that this carbon (CH2) is more electron rich since it is the
only one without an electronegative atom directly attached [inductive effect]

1 pt for correct choice; 1 pt for indicating correct carbon; 3 pts for reason (either resonance or inductive)
C. Which molecule has the most electron-deficient carbon atom? Re-draw it here, indicate that carbon clearly
and
explain your choice.
O

most electron poor


C
H 2N

The carbon has the largest number of and strongest electron


withdrawing groups attached

NH2

M
1 pt for correct molecule; 1 pt for correct carbon; 3 pt for correct explanation
D. Which molecule is most basic? Re-draw it here and show the conjugate acid. Explain your choice briefly.

NH

NH2

C
H 2N

H
NH2

NH2

C
H 2N

NH2

NH2

H 2N

C
NH2

H 2N

NH2
N
Protonation at the sp2 hybridized N leads to a highly resonance stabilized cation [three equivalent
resonance structures]. Protonation at the -NH2 group is favored by hybridization (sp3 vs sp2), but such
strong resonance is dominant.

1 pt for correct molecule; 1 pt for correct conj acid; 3 pt for reason.