Chem 3010-Exam 3

Summer 2021 key

Name:_____________________________
Dr. N. Stessman
.

Instructions: This exam has 9 questions and is administered on Canvas on Monday,

June 28. The exam will start at 8:45 am and end at 10:00 am which allows you 75
minutes total to answer, scan or take pictures and submit in Canvas. Be sure to
organize all the pages and each of them is in focus and readable before you
submit. If I can’t read your answer you will not receive credits. You don’t have
to print out the quiz. You may write your answers on separate sheets of paper
clearly label each answer and organize them in chronological order. Late
submission will be penalized for each minute late it is one-point deduction. For
example, if you submit your quiz at 10:15 am, 15 points will be taken off your
quiz total score so please time yourself. This quiz is open notes and an open book
quiz. This quiz is solely based on individual student’s efforts thus seeking help
from another human being either by email, phone or internet, etc. is prohibited.
Posting and, or sharing exam questions or any intellectual property on the
internet is strictly prohibited. Those found violating this policy will earn a failing
grade for the course.
After the quiz, please sign and Print your name below.
I, myself, have worked on this quiz and I have not received any help from another
human being either by phone, email, internet or any form of communications.

____________________________ ______________________________
Print your name Your signature
 1. (12 pts) Draw curved arrows for each step of the following mechanism. Add atoms
and electrons where appropriate to show bond breaking and bond forming.

IN A Ed ?
H

OH
it
O H OH2
H ⇐ H 2O<

2. (12 pts) For each of the following cases use the information given to determine
whether or not the equilibrium will favor products over reactants:
(Each answer should be either “favor products” or “favor reactants”.)
Favor products
A. A reaction with Keq = 1.2 __________________________________

Favor Reactants
B. A reaction with Keq = 0.2 ___________________________________

Favor Reactants
C. A reaction with a positive ΔG _______________________________

Favor
D. An exothermic reaction with a positive ΔS _____________________ product .

3. (8 pts). Draw and label two different carbocation structures, a primary carbocation
and a tertiary carbocation. Explain clearly why one is more stable than the other.
H
Gt3
*


H TECH }

p it
} go
and each additional
3° carbonation has more alkyl groups ,
a
substituent
than hydrogen
as

group is
has more electron density
alkyl
electron deficient species thus
the alkyl group
A carbocation donate
can its electron density
4. (12 pts) Look at the following energy diagram: induction to
through carbocation

stabilize the
.

E
N
E is Ts
R
G
Ts
Y - -

Reaction Progress

C-I
A. Is ΔG° for the reaction positive or negative? Label it on the diagram. __________
4
Steph
B. How many steps are involved in the reaction?_____________________
y Ts
C. How many transition states are there? Label them on the diagram _____________
 D. Label the intermediates on the diagram.
E. Which step is most exergonic? Circle it.
F. Which step is the rate determining step? Draw a rectangle around it.

5. (16 pts) From among the isomeric compounds of molecular formula C4H9Cl, Choose
the one having a 1H NMR spectrum that
(a) Contains only a single peak

fee
-

Ee
(b) has several peaks including a doublet at δ 3.4
.

(c) has several peaks including triplet at δ 3.5

F- a

(d) has several peaks including two distinct three-proton signals, one of them a triplet at δ
-

1.0 and the other a doublet at δ 1.5

e
-

6. (10 pts) Use the two IR templates below and draw IR signals that discussed in class to
distinguish between the organic reactant and the organic product for the reaction below.
O

OH Na2Cr2O7
H2SO4, H2O OH

Thr
i

/0
"
c
;¥
aint
f¥p3
É

wavenumber wavenumber
reactant product
 7. (10 pts) A compound with molecular formula C7H7Br displays the following 13C
NMR along with the DEPT-90 and DEPT-135 13CNMR spectrum. What is the structure
for this compound?

⇐¥+3
CA
DEPT-90 CH
only
DEPT-135 CH cutlets → positive cetg
a+u negative ÉBR
Broadband decoupled C C
city

170
B. Calculate the molecular ion [M+] for the formula, C7H7Br,___________

171
C. Does C7H7Br have a [M+1]+ signal? What is the value?________

172
D. Does C7H7Br have a [M+2]+ signal? What is the value?____________

8. (10 pts). A compound with molecular formula C7H14O2 displays the following IR,
1
HNMR and 13CNMR spectrum. Propose a structure for this compound. Clearly show
your work and label signals all spectra. For carbon and proton NMRs, label each signal
with the corresponding carbons and protons of the structure, respectively.

i
I
o
I
1
I

:
i:}
I .ge# city
6 -
cha
-
CH
city
c
]
-

,c ¥É%
b
"
c" }

egg CH CH,
( Hz 3
•

d
1 c 2 2e
 µ

cio -4+-4+3
Fitz carat
-

e
C
,
-

b '

city

% or
et c
d
et
b

180 160 140 120 100 80 60 40 20 0

PPM

9. (10 pts) Use the following mass spectrum to answer each of the following questions

mass
A. What does m/z stand for? _____________________________ / charge
72
B. What is the m/z for the base peak?______________________

⑨*
C. What is the m/z for the molecular ion peak?________________

D. From looking at the mass spectrum, this compound contains (bromine, chlorine,
nitrogen or phosphorus) _______________.
Nitrogen
E. What type of species does not appear in a mass spectrum?

i. a cation ii. an anion

iii. a radical cation 0iv. a radical