CH306: Special Topics in Chemistry

FSTE
School of Biological & Chemical Sciences

Final Examination

Semester 2 2018

Face to Face Mode

Duration of Exam: 3 hours + 10 minutes

Reading Time: 10 minutes
Writing Time: 3 hours

Instructions:
1. There are six questions but only answer FIVE questions.
2. Each question is worth 20 marks.
3. This exam is worth 50% of your overall mark. The minimum final exam
pass mark is 40/100.
4. This is a close book exam and there are eight (8) pages altogether.
5. The use of non-programmable scientific calculator is permitted during
the exam.
ANSWER ONLY FIVE QUESTIONS

Question 1 (20 marks)

A. During the drinking water treatment process, adsorption techniques could be used
to remove contaminants from water. It is a physical process whereby dissolved
contaminants adhere to the porous surface of the solid particles. Discuss three
adsorbents used in the treatment of drinking water with relevance to its benefits
and limitations.
(6 marks)

B. There are two sources of drinking water, that is, groundwater and surface water.

i. Compare and contrast the treatment process for groundwater and surface
water. Explain the reason for any differences in the treatment process.
(4 marks)

ii. In Wailoku treatment plant in Suva, what is the main source of drinking
water?
(1 mark)

C. Two water samples were analysed for Total Dissolved Solids (TDS). The bottled Fiji
water had higher concentration of TDS than the tap water. Explain your answer.
(3 marks)

D. Climate change will impact water resources and therefore alternative sources of
drinking water need to be investigated. For tropical Pacific island countries, it is
suggested that seawater could be desalinized for drinking. This can be achieved
through electrodialysis and reverse osmosis treatment techniques. Explain how both
the techniques can desalinize sea water for drinking. For clarity please use diagrams
to explain your answer.
(6 marks)

Question 2 (20 marks)

A. In sewage wastewater treatment there are two types of biological systems (fixed
film system and suspended film system) used to reduce BOD. Explain these two
systems and state which system does the Sequence Batch Reactor (SBR) belong to?
(3 marks)

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 B. Explain the difference between the activated sludge system and SBR and comment
on the efficiency and carbon footprint of the two techniques.
(4 marks)

C. Nitrogen and phosphorus are two key nutrients for causing eutrophication in
receiving waters. Discuss techniques used in wastewater treatment to remove
nitrogen and phosphorus. Discuss two removal techniques for both nitrogen and
phosphorus with appropriate equations.
(6 marks)

D. Accidentally a large amount of lime was dumped at Naboro landfill and as a result
the pH of the leachate was very alkaline (pH = 13.1). It was noted that the
concentration of ammonia, nitrates and nitrites was very low in the discharged
effluent. Explain what happened at the landfill leachate treatment process to reduce
the levels of inorganic nitrogen forms.
(3 marks)

E. The final step for Naboro landfill leachate treatment is leachate flow through a
constructed wetland. There are reed plants to enhance phytoremediation in uptake
of heavy metals. Discuss two other heavy metal removal mechanisms in the wetland.

(4 marks)

Question 3 (20 marks)

A. The metabolite xanthoxylin has been isolated from the fungus Zanthoxyli fructus.
Xanthoxylin is derived from the polyketide pathway.

HO

0
'-....,CH3
xanthoxylin

i. Identify one feature of xanthoxylin that indicates its derivation from the
polyketide pathway.

2
 (1 mark)

ii. Draw the structure of the poly-β-keto chain that is the immediate
precursor of xanthoxylin.
(2 marks)

B. Outline the steps in the biosynthesis of xanthoxylin from this poly-β-keto chain. In
your answer, give each intermediate structure and identify the conversion that
occurs at each biosynthetic step.
(5 marks)

C. Show which carbon atoms in xanthoxylin would be labeled if, in a feeding

experiment, [1-13C]-acetate was employed.
(2 marks)

D. Stearidonic acid is a fatty acid and is given the structural designation of 18:4 ω3.
Describe the meaning of this designation and draw a structure of the fatty acid to
support your answer (including the configuration of the double(s)).
(4 marks)

E. Fatty acids are biosynthesised from acetyl CoA as a starter unit and subsequently
involved several reduction reactions. State the reducing agent for the in vivo
formation of fatty acids.
(1 mark)

F. Name one alkaloid and its chemical medicinal application.

(1 mark)

G. Psilocin was first isolated from the fungus Psilocybe mexicana. Outline the
biosynthetic sequence in the derivation of psilocin from tryptophan.
(4 marks)

psilocin

3
Question 4 (20 marks)

A. Tetrahydroyangonin is kavalactone of mixed origin, derived predominantly from the

shikimic acid pathway and polyketide pathways.

OH

HO
tetrahydroyangonin 4-hydroxycinnamic acid

i. Draw the structure of tetrahydroyangonin and mark clearly the carbon

atoms that are derived from the polyketide pathway.
(2 marks)

ii. Outline the biosynthesis of tetrahydroyangonin starting from 4-

hydroxycinnamic acid
(5 marks)

B. Prephenic acid and chorismic acid are important intermediates in the shikimic acid
pathway. Chorismic acid undergoes a simple rearrangement to prephenic acid.

COOH

OH OH
chorismic acid prephenic acid

i. Use curly arrows to show the mechanism for the rearrangement that
occurs in the above reaction.
(2 marks)

ii. Name the amino acid(s) that is derived from prephenic acid.
(1 mark)

4
C. Identify the isoprene units in these structures and classify each as monoterpenes,
sesquiterpenes or diterpenes, etc.

OH

(4 marks)
D. Alpha (α)-pinene is a terpene found in a number of coniferous trees.

alpha-pinene

linaloyl pyrophosphate (LPP)

i. Using curly arrows, give a detailed mechanism of the steps in the

derivation of α-pinene from linaloyl pyrophosphate (LPP).

(5 marks)

ii. There are two structural isomers of pinene found in nature. Draw the
other isomer based on your answer in (i).

(1 mark)

5
Question 5 (20 marks)

A. The DSC thermogram of Coke PET bottle is given below. The scan was done at 10
oC/min. Using the information answer the questions.

5 147.40•C

3
--
NOTE SMALL START-UP 1100K

~ 1
-
E
~ -1
74 .95°<-· 78.89"C (I)
232.32°C
40 l3Jlg
LL 137.l6'C
36.36)/g
~ -3
Cl)
::c
-5 Fl RST IIEAT OF QUENCIIED SAMPLE

-7
247.8 i"C
-9
-50 0 50 100 150 200 250 300
Temoerature (°C)
i. Label all the transitions that are seen in the thermogram.
(3 marks)

ii. What is the percentage crystallinity of the original sample (sample

before subjected to heating) if the enthalpy of fusion of the pure
crystal is 141 J/g?
(3 marks)

iii. Depending on your answer in (ii) above, indicate why the bottle
appears transparent.
(2 marks)
iv. Explain if this material can be used for hot beverage (hot drinks).
(2 marks)

B. When polymers are designed for different applications, most undergo pressure
treatment during molding. Below is the GPC analysis of the samples exposed to
different pressures. Explain what can be interpreted from the results in terms of
stability of the sample.

6
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\

' !
I ,'
Il
!
.\
'·
~
\
I I
- -un.,.,-d • ,!
-200 ~11>. 1
·-- $00 MP.a ' i
_ _ _,l'.,1/..
. .;

18 20 22 24 28 28
Rentention time (min)

(5 marks)

C. The micrograph below is of poly(butylene succinate) when crystallized isothermally

at 78 oC. Of the several reasons learnt in the class, explain using the best reason for
the formation of the rings.

(5 marks)

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Question 6 (20 marks)

A. What is the difference in the chain structure of atactic, isotactic and syndiotactic
polystyrene. Which one will not crystallize? Explain.
(5 marks)

B. Over the last two decades, mothers of new babies have been given relief by the
diapers, thanks to the polymer chemists. Diapers contain water absorbing materials
called hydrogels.
i. What are “hydrogels”?
ii. What types of polymers are normally used in hydrogels?
iii. How do you determine the degree of swelling?
(3 marks)

C. Explain the difference between cold and melt crystallization.

(2 marks)

D. Equilibrium melting temperature (𝑇𝑚𝑜 ) is generally used to explain the melting of

pure polymer crystals with extended chain. One method to determine the 𝑇𝑚𝑜 is
using the linear Hoffman Weeks method. Explain this method.
(5 marks)

E. Miscibility in amorphous polymer blends is generally determined by the glass

transition temperature (Tg). For the blend system of Poly(butylene succinate) (Tg of -
35 oC) and the pine gum (no Tg), explain how the miscibility can be determined.
(5 marks)