WALTER SISULU UNIVERSITY

DEGREE EXAMINATIONS: NOVEMBER/ DECEMBER 2019

FACULTY OF SCIENCE AND ENGINEERING

CHEMISTRY LEVEL ‘3’- CHE 31M5

Project and Seminars

Due Date: 20 Dec 2019

Submission Method: email on ankaule@wsu.ac.za or 2968236@myuwc.ac.za

Project Instructions 2019 - A.Nkaule

Choose any of the projects from below, emphasising on the following structure:

1. Summary or Abstract
2. Introduction
3. Theory
4. Labelled figures
5. Analysis of the projected spectrums/spectroscopy (if any)
6. Conclusion and proposed future work (what can be improved for future
work)
7. You can also include your own images and discussions
8. Creativity is absolutely accepted such as: further synthesis and
characterization methods with proper description and reasons.

Plagiarism should be avoided when writing up. Therefore, include

references (in text and at the end of the project)
 Project 1
Synthesis, properties and performance of organic polymers used in
flocculation applications
Flocculation is a usual method that is extensively used in many industrial applications to
promote solid-liquid separation processes. The addition of a polymeric flocculant allows for
destabilization of suspended colloidal particles, and thus significantly promotes their
sedimentation rate. Polymeric flocculants are generally divided into four categories, which
include non-ionic, cationic, anionic, and amphoteric polymers (Saito, 2015).
Discuss and summarise important information in the form of a mini-project, recent design and
synthesis of polymeric materials from these four categories. In addition, their properties and
flocculation efficiency should be presented and discussed by including the terms below:

Scheme 1: Schematic representation of colloidal suspension flocculation by: (a) charge

neutralization, (b) polymer adsorption and bridging, and (c) electrostatic patch.
1.1 Type of flocculants and chemical structures
1.2 Mechanisms of flocculation Numerous mechanisms for flocculation
1.3 Aim and scope of the review
1.4 Future challenges for flocculation

Scheme 2: Example mechanistic pathway for the synthesis of starch graft copolymer via:
(i) formation of free radical on the polysaccharide backbone, (ii) propagation of monomer
M, and (iii) termination of graft copolymerization.
 Project 2
Technology for polymer characterization
Characterization of a polymer is a vital part of polymer technology. Once the
polymers are designed and synthesized, we need to characterize them chemically
to confirm their chemical structures and to evaluate their properties for physical
behaviours and actual usages (Bikales, 1971).
Mention and discuss Instruments and Testing Methods for Polymer
Characterization, including their chemical structures. Furthermore, Analyse,
describe and account for the following spectroscopic results. Finally, describe
how these spectroscopic instruments function.

Figure 1: Infrared spectrum (KBr pellets) of polyimide (—) and model compound (- - - -).

Figure 2: Fourier transform infrared spectra of isotactic polystyrene in the 640–840 cm-1 region: (A)
semicrystalline; (B) amorphous; and (C) the difference spectrum obtained by subtracting B from A.
Figure 3: Comparison between IR and Raman of trans-poly pentenamer.

Figure 4: The absorption spectrum of 4-methyl-3- penten-2-one.

Figure 5: Thermogravimetric analysis of polythiazoles.

 Project 3
Analysis for polymer characterization
3.1. A copolymer of propylene and vinyl chloride contains 35wt. % chlorine. What is the molar
ratio of vinyl chloride to propylene in the copolymer?
3.2. What kind of polymer can you deduce from the following IR spectrum?

3.4. One stereoregular form of polystyrene (A) has a 1 H NMR spectrum containing a triplet
centered at about 1.4 ppm and a quintet at about 1.9 ppm. Another stereoregular form (B) has
an octet at about 1.6 ppm. Interpret the spectra and determine which corresponds to isotactic
and which to syndiotactic.
3.5. How would you distinguish between the following two polymers by IR and NMR?

What changes would be observed in the XRD patterns of rubber that has been stretched?
3.6. Please use a spectroscopic method to determine the following and explain your answer. (a)
The amount of styrene in a styrene-butadiene copolymer. (b) The amount of 1,2- polymer in
poly(1,3-butadiene). (c) The stereochemistry of double bonds in 1,4-poly(1,3-butadiene). (d)
Unreacted polyacrylonitrile (PAN) is present in a sample of carbon fiber prepared by pyrolysis
of PAN. (e) Poly(vinyl acetate) has undergone hydrolysis on exposure to moisture. (f) A
polyester surgical implant has been coated with polyterafluoroethylene completely to improve
its chemical resistance.
3.7. Which technique would you use to solve the following problems, (a) locate a crystalline
melting temperature, (b) determine the degree of orientation, (c) determine the arrangement of
molecular chains in a polymer crystal, (d) locate the glass transition temperature, (e)
characterize the double bond in the diene polymer, (f) measure the enthalpy of fusion, (g)
investigate the mechanism of oxidation of a polymer, (h) study the molecular motion of
polymer chains, (i) estimate the degree of crystallinity, (j) measure the amide content of an
esteramide copolymer.
3.8. Show how NMR can be used to (a) distinguish between head-to-head and head-to-tail
polymerization in polymer, (b) distinguish between a random copolymer and a mixture of
homopolymers.
3.9. Draw typical DSC and DTA thermograms for a crystalline polymer, showing the glass
transition, crystallization, crystalline melting and thermal degradation.
3.10. Please answer the following questions: (a) Which of the following aromatic compounds
do you expect to absorb at the longer wavelength?

(b) Naphthalene is colorless, but its isomer azulene is blue. Which compound has the lower-
energy pi electronic transition?
 Project 4
Synthesis, optical and morphological characterization of CdSe/ZnSe quantum dots for
cytotoxicity studies.
Colon cancer (CC) ranks high in morbidity and mortality amongst the most frequent occurring cancers worldwide.
Mortality rates are mostly caused by mis-diagnosis and the poor efficacy of treatment. The aim of this study was
to enhance our insights of quantum dots, for early detection and targeted drug delivery, thereby reducing toxicity
to normal cells and reducing side effects that are caused by previous colon cancer medicine. The synthesis,
characterization and cytotoxicity studies of CdSe/ZnSe quantum dots (QDs), nanocrystals are reported.
Toxicological properties of the Cd2+ core are reduced by capping quantum dots with ZnSe, varying chain length
and functional group ligands. Fluorescence wavelength and their size is improved by varying Cd 2+ source and
varying nanocrystal synthesis growth temperature. CdSe/ZnSe quantum dots are characterized with FT-IR to
elucidate their structure. High-resolution transmission electron microscopy (HRTEM), X-Ray Diffraction (EDX),
Photoluminescence spectroscopy (PL) and Ultraviolet-visible spectroscopy (UV-Vis) are used to measure their
size and composition. Ligand exchange reactions are conducted with the use of 3-Mercaptopropanoic acid (3-
MPA) to facilitate bio-compatibility and stability of CdSe/ZnSe QDs. Temperature stability of various ligand
capped and stabilized CdSe/ZnSe QDs are measured by using thermogravimetric analysis (TGA). Caco-2 cell line
is cultured from colon cancer, and cytotoxic studies are conducted to test for cell viability of various capped 3-
Mercaptopropanoic acid (3-MPA) CdSe/ZnSe quantum dots at various concentrations. Myristic acid capped
CdSe/ZnSe quantum dots produce high fluorescing mono-disperse quantum dots. The capping material, synthesis
temperature and Cd2+ source of CdSe/ZnSe QDs affect fluorescence wavelength and thermal stability of quantum
dots. Fluorescence wavelength is improved by using CdCl2.7H2O source of Cd2+ . Cytotoxicity was found to be
dependent on the concentration and the capping material of quantum dots. CdSe/ZnSe quantum dots toxicity is 3
adjusted and reduced by varying the length, size and type of the capping ligand on the surface of quantum dots
(Nkaule, 2014).

Figure 1.1: Shows (a) the structure of the colon with colon cancer, (b) stages of polyp development, (c) before
removal, removal and after removal of polyp, and (d) post colon cancer surgical removal treatment (Nkaule,
2014).

Furthermore, Quantum dots (QDs) show extra-ordinary unique properties than conventional imaging and
therapeutic tools, such as unique optical and electrical properties of different character than those of the
corresponding bulk material due to their nano-scale dimensions (Wise, 2000). The apparent curiosity in its
properties is stimulated by the ability of photons to be emitted under excitation which is visible to the human
eye. The wavelength of photon emission is dependent on both the type of material which the core is made up
of and the size of the quantum dots (Parak, Ellegrino & Plank, 2005). Quantum dots are able to be tuned during
the synthesis process by changing various parameters to give nanoparticles that emit the desired colour of light
(Bera et al., 2010).

4.1. Discuss discovery, challenges and limitations with quantum dots.

4.2. Discuss how QDs function and their various applications.

4.3. Importance of researching quantum dots (QDs) and their advantages over fluorescent dyes How do
quantum dots (QDS) function?

4.4. Discuss properties of quantum dots and of it’s Composition materials for quantum dots.
4.5. Describe the process/method of adding capping agents and conjugation of quantum dots (QDs).
4.6. Describe any synthesis and characterization techniques for QDs.
4.7. The following FT-IR spectra for Oleic acid-capped CdSe/ZnSe QDS and 3-MPA-capped CdSe/ZnSe QDS were
obtained from analyses (Figure 1 & 2). Account for the peaks in relation with the capped QDs and describe
how the FTIR spectroscopy functions.

Figure 1: FT-IR spectra for Oleic acid-capped CdSe/ZnSe QDS

Figure 2: FT-IR spectra for 3-MPA-capped CdSe/ZnSe QDS

4.8. The following photoluminescent spectrum of oleyamine capped CdSe/ZnSe QDs samples was obtained by
analysis of the sample which was collected within vials after 10, 15, 30, and 65 mins (Figure 3, below).
Describe the result which is obtained from the spectra in relation with the QDs and describe how the
photoluminescent spectrum spectroscopy functions.

Figure 3: The photoluminescent spectrum of oleyamine capped CdSe/ZnSe QDs.

4.9. Describe how the HRTEM and Surface area diffraction spectra functions. What is your observation for the
Figure 4, below for the same sample of oleyamine capped QDs in correlation with the Figure 3, above?
Explain.

Figure 4: (a) HRTEM micrograph and (b) Surface area diffraction (SAD) micrograph for oleyamine capped QDs.

Figure 5: FT-IR spectra of oleyamine capped CdSe/ZnSe QDs.