RHODES UNIVERSITY

Department of Chemistry

November 2021

Chemistry 201 Paper B

Time: 3.5 hours Marks: 90

Attachments: Chemical shift tables

Periodic Table and Physical Constants

Instructions: Attempt ALL questions.

Internal Examiners: Dr T. Geswindt Course coordinator

Dr X. Siwe Noundou
Dr A. May

Notes: Please (1) start each new question on a NEW PAGE.

(2) do NOT use red ink anywhere in your script.
(3) fill in the question numbers on the front cover of your answer
book in the order answered.
(4) Scan your pages in order and submit them as ONE document.
(5) Write your student number on each page.

This question paper consists of 7 pages including this cover sheet.

Please make sure that you have them all.
 Page 2 of 7 Chemistry 201B
November 2021

QUESTION 1
a) Briefly describe anodic stripping voltammetry (ASV). (3)
b) For the electrochemical cell represented below, the potential can be measured without drawing
substantial current:
reference electrode ∣ salt bridge ∣ analyte solution ∣ indicator electrode
Draw and label a typical cell of this type. Briefly describe each component. (13)
c) There are generally two types of interfacial electrochemical methods, namely potentiometric
methods and dynamic methods. What are the two types of electrochemical processes at the
electrode-solution interface that produce current? How do they differ? (4)
[20]

QUESTION 2
a) Discuss four limitations associated with pH measurement using the glass electrode. (8)
b) Which voltammetric technique is more sensitive between cyclic voltammetry and differential
pulse voltammetry? Why? (2)
[10]

QUESTION 3
Z A Name Spin Abund. Magnetogyric Recept rel Larmor Frequency
13
Ratio C 9.39798T
% [107rad s-1T-1] MHz
1 1 H Hydrogen ½ 99.9885 26.7522205 5.87E+3 400.13
1 2 D Deuterium 1 0.0115 4.10662914 6.52E-3 61.422
6 12 C Carbon 0 98.93 - - -
6 13 C Carbon ½ 1.07 6.728286 1.00E+0
7 14 N Nitrogen 1 99.636 1.9337798 5.90E+0 28.915
7 15 N Nitrogen ½ 0.364 -2.7126188 2.23E-2
8 16 O Oxygen 0 99.96 - -

a) With reference to the above table, answer the following questions:

(i) At what frequency will 13C resonate in a 9.39798T magnet? (2)

13 1
(ii) Why is C NMR a less sensitive spectroscopic technique than H NMR? (2)
(iii) Explain why the signal from Ha in [5]paracyclophane A appears at 6.54ppm while
that of Hb appears at 0.01ppm, in the 1H NMR spectrum. (3)

H2
C H2
H C
C
H2C Hb
CH2

a
H
A Question 3 continues over the page
 Page 3 of 7 Chemistry 201B
November 2021

b) Use the mass spectrum of 5-chloro-2-pentanone (below) to answer the following questions:

(i) What is the mass of the molecular ion? (1)

(ii) What is the mass of the base peak? (1)
(iii) The base peak represents an ion formed by an -cleavage reaction. Give the structure of
this ion and the mechanism that led to its formation. (3)
(iv) The peak at m/z 58 results from a McLafferty type rearrangement. Give the structure of
the ion and the mechanism that led to its formation. (3)

c) The 1H NMR spectrum of ethanol (dissolved in DMSO) is unusual in that the OH signal
appears as a triplet (when dissolved in CDCl3 the OH signal is broad and signal splitting
is not evident).

b a
H H
HO C C H
H H 5.3 ppm

3.7 3.6 ppm

5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
1.00

2.00

3.00

Explain why the signal assigned to the OH (δ=5.28) appears as a triplet, and why the
multiplet assigned to Hb (δ=3.62) appears as eight signals on the NMR spectrum.(Jb-
OH=5.1Hz and Jb-CH3=7.3Hz) (5)
[20]

Question 4 continues over the page

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QUESTION 4
Use the IR, 1H and 13C NMR spectrum of the aromatic compound Y (C7H14O2) given below and
the tables of 1H and 13C chemical shift data provided on page * to propose a structure for compound
Y. You must explain how you arrived at the structure you have proposed for compound Y.
(20)
Compound Y C7H14O2 1H Spectrum

ppm

4.0 ppm ppm 1.65 ppm

ppm

4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

2.024

1.000

2.029

6.103

3.015
Compound Y C7H14O2 13C Spectrum
177.148

65.861

34.182

22.203
19.073

10.411
d q
t
s t
q

200 180 160 140 120 100 80 60 40 20 ppm

Compound Y C7H14O2 IR Spectrum

[20]
 Page 5 of 7 Chemistry 201B
November 2021

QUESTION 5

5(a) List all variables/parameters which influence column efficiency. (6)

5(b) List 4 methods used to reduce band broadening. (4)
5(c) Draw and label the components of a gas-liquid chromatography instrument and describe the
general operation conditions. (10)
[20]
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END OF PAPER
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APPENDIX 1: CHEMICAL SHIFT TABLES

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