CHE4804/001/0/2023

Tutorial Letter 001/0/2023

Analytical Chemistry IV

CHE4804

Year Module

Department of Chemistry

IMPORTANT INFORMATION
Please register on myUnisa, activate your myLife e-mail account and
make sure that you have regular access to the myUnisa module
website, CHE4803-2023-0, as well as your group website.

Note: This is a fully online module. It is, therefore, only available on myUnisa.

BARCODE
Dear Student,

Due to the unforeseen reasons, assignment due dates were extended as follows:

Assignment Number Initial due date New due date

1 24 April 2023 15 May 2023
2 29 May 2023 19 June 2023
3 28 June 2023 17 July 2023
.
EXTENSIONS of the due date for the submission of an assignment will be considered ONLY in
the case of ILLNESS, supported by an original DOCTORS CERTIFICATE attached to the
assignment, and then for a maximum of SEVEN DAYS.

NO EXTENSIONS WILL BE GRANTED BY TELEPHONE

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1. ASSIGNMENTS
1.2 ASSIGNMENT #1 (Due date: 15 May 2023)

When preparing for this assignment, you must review sample preparation and/or pre-
concentration methods from suitable sources. Moreover, read Chapters 1,5-9, spectroscopic
methods of analysis of the prescribed textbook. This assignment is COMPULSORY. Completing
and submitting this assignment will contribute to 40%-year mark subminimum required to have
examination admission to CHE4804 module.

QUESTION 1
Find the IUPAC website to locate the Compendium of Chemical Technology by using the
search engine.

a) What is the definition of detection limit as recommended by Compendium? Compare this

definition in the Compendium and that given in the textbook. Comment on the symbology
used. (2)

b) Briefly, explain the importance of internal standards in instrumental methods of

determination in analytical chemistry. (2)

c) Briefly, but informatively, discuss the standards addition approach methods in analytical
instrumental analysis. {Be sure to include the advantages and challenges of each
method}. (4)

d) In analytical chemistry we develop and validate methods of analysis. Discuss the

importance of figure of merits in analytical instrumental analysis. Briefly, but informatively,
what are the key fundamental criteria used to achieve the objective according to your
textbook. (6)

e) In analytical chemistry we develop and validate methods of analysis. Discuss the

importance of figure of merits in analytical instrumental analysis. Briefly, but informatively,
what are the key fundamental criteria used to achieve the objective according to your
textbook. (6)

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QUESTION 2
a) The following atomic absorption results were obtained for the determination of cadmium
content in blood samples: 0.752, 0.756, 0.753, 0.755, 0.754 and 0.760 ppm Cd.
Calculate the mean, the standard deviation, and the coefficient of variation for the data.
(6)
b) Differentiate between calibration sensitivity and analytical sensitivity. (2)

c) Briefly, discuss the concept used by classical methods of analysis in comparison with
instrumental methods. Give examples where possible. (6)

d) Noise reduction is very important in analytical instrumental analysis. Briefly, discuss the
methods that are commonly used for noise reduction. (6)

QUESTION 3

a) With the aid of diagrams, briefly differentiate between atomic absorption and molecular
absorption spectra. (5)

b) With the aid of diagrams, briefly differentiate between atomic absorption and molecular
absorption spectra. (5)

c) Calculate the frequency in Hertz, the energy in joules, and the energy in electron volts of
an X-ray photon with wavelength of 5.275 Å. (4)

d) Briefly, but informatively, discuss gratings used in modern spectroscopic measurement.

What are the advantages and limitations of these gratings? (6)

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QUESTION 4

Knowledge of construction materials, wavelength selectors, sources and detectors are of

paramount importance in analytical spectroscopic instruments. Please review the section on
sources, wavelength selectors and radiation transducers.

a) What is the function of a monochromator in an analytical spectroscopic instrumentation?

Give examples of monochromators used in spectroscopy. Briefly, but informatively,
discuss the major components of one of the monochromators and how it achieves its
function. (10)

b) Detection for the spectroscopic instrumentation has developed since its early models.
Give examples of detectors used in spectroscopy. Briefly, but informatively, discuss
major components one of the detectors commonly used and how it achieves its function.
(10)

QUESTION 5

Knowledge of types of atomizers and sample introduction is important in analytical atomic

spectroscopy (AAS) instruments. Please review this section (CHAPTER 8).

a) Briefly, but informatively, discuss the methods of atomisation for atomic absorption
spectroscopy instrument. (10)

b) Briefly, discuss the important of hydride generation techniques in atomic absorption

spectroscopy. What is/are the advantages of using hydride generation technique?
(3)

c) Flames play an essential role in atomic absorption spectroscopy. Briefly, but

informatively, discuss types of flames and their temperatures in flame emission and
atomic absorption spectroscopy. (3)

d) Atomic absorption spectroscopy is not known to be a good instrument for the

determination of group 1 metals, i.e. Na. Briefly justify this statement and how is this
limitation resolved? (4)

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2. ASSIGNMENTS
2.2 ASSIGNMENT #2 (Due date: 19 June 2023)

Before doing this assignment, study Chapters 9-10 (pp 210-252); Chapter 11 on Mass
spectrometry (pp 253 - 302), Chapter 12. Atomic X-ray spectrometry (pp 274-302), Chapter 15;
Molecular Luminescence spectrometry (pp 361-388), Chapter 18; Raman spectrometry,
Chapter 19 (pp 437-452); Nuclear magnetic resonance spectroscopy (pp 453-500) and Chapter
20; Molecular mass spectrometry (pp 501-536).

QUESTION 1

a) Hollow cathode lamp (HCL) is fundamentally key to the successfully development of

atomic absorption spectroscopy (AAS). Who developed the HCL and what was the
nationality of the developer? (3)

b) With the aid of a well labelled diagram, briefly, but informatively describe the functions of
hollow cathode lamp used in AAS. (5)

c) Discuss the processes involved during atomisation of sample in the flame atomic
absorption spectroscopy (FAAS). (5)

d) What are the reasons for lower sensitivity of the flame atomisation in comparison to the
other atomisation methods? (2)

e) Briefly discuss the importance of burners in atomic absorption spectroscopy. What is the
main function of burners in AAS? Give examples of types of burners in AAS if any.
(5)

QUESTION 2

a) Briefly, but informatively, discuss electrodeless discharge lamps for AAS. What are the
advantages and disadvantages of this type of AAS source? (5)

b) With the aid of a diagram describe a double-beam flame atomic absorption spectroscopy.
(5)

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c) Chemical interferences are known to exist due to various chemical processes occurring
during atomisation leading altered absorption characteristic of the analyte. Discuss the
methods used for the background correction in atomic absorption spectroscopy. (10)

QUESTION 3

a) What are the advantages and disadvantages of flame and electrothermal atomic
procedures in comparison with high energy sources in atomic spectroscopy?
(3)

b) With the aid of a diagram describe the function of an inductively coupled plasma source
used for plasma emission spectroscopy. (10)

c) List desirable properties for the emission spectroscopy. (5)

d) Why are ionisation interferences less severe in ICP than in flame emission
spectroscopy? (2)

QUESTION 4

a) What mass analysers are used for the ICPMS? Briefly state how they differ from one
another. (6)

b) Briefly state why ICPMS has increased in its importance as an analytical instrumental
technique. (2)

c) Briefly, but informatively, describe how laser ablation could be used for solid sample in
ICPMS. (4)

d) Briefly, but informatively, discuss how high resolution in ToF has been achieved. How
does high resolution impact on ICPMS? (6)

e) Differentiate between isobaric and a polyatomic ion interferences in ICPMS? (2)

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QUESTION 5

a) List methods of generating X-rays in spectroscopy. (2)

b) With the aid of a well labelled diagram, discuss the function of commonly used radiation
sources in X-rays in spectroscopy. (6)

c) List detector used to detect X-rays in X-rays in spectroscopy. (5)

d) Use a well labelled diagram to discuss an X-ray detector, that is similar to a detector
used in UV/Visible and mass spectrometry. Indicate what modifications have been made
for the X-rays in spectroscopy detector. (7)

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3. ASSIGNMENTS
3.2 ASSIGNMENT #3 (Due date: 17 July 2023)

Before attempting this assignment, review Chapter 20, 26, study the Chapter 28-30 on Liquid
Chromatography (pp 816-890), of the prescribed textbook and answer the review questions
below. This will assist you to revise the chromatographic terms that you learnt in CHE3704
and/or level 3.

REVIEW QUESTIONS:

a) Define the following terms in chromatography;

i. Distribution constant
ii. Retention time
iii. Retention factor
iv. Selectivity factor
v. Plate height
vi. Longitudinal diffusion
vii. Column resolution
viii. Support
ix. Stationary phase
x. Elution

b) By using Van Deemter equation, discuss how each term contribute to the value of H.
i. Describe as many elution problems as possible.
ii. What variables are likely to affect α values for a pair of solutes?

QUESTION 1

Review molecular spectrometry (Chapter 20). Study the ionisation sources and their
applications.

a) Use well labelled diagrams for electron ionisation (EI) and chemical ionisation sources.
Briefly describe how ions are formed in each of the sources. Indicate the difference
between the spectra formed if any. (10)

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b) Mass spectrometry is probably one of the greatest analytical tools in the 21st centaury
that has seen great stride in its evolution and has become key to molecular biology, i.e.
proteomics, geonomics, etc. The human geonomics was completed because of the use
atmospheric pressure ionisation sources such as electrospray ionisation (ESI) used as
ESI-MS. Discuss the three sources (compare these sources) to each other. (10)

QUESTION 2

a) Briefly, but informative, describe the principle of X-ray spectroscopy using a Ni atom as
an example. (5)

b) What is the origin of the Kα X-Ray line? (3)

c) Why does a 109Cd radioactive source emit Ag Kα X-rays? (3)

d) Can X-ray radiation from a tungsten target be used to excite copper atoms? Also can X-
ray radiation from a copper target be used to excite tungsten atoms? (3)

e) The mass absorption coefficient for Ni, measured with Cu Kα line is 51.25 cm2/g.
Calculate the thickness of a nickel foil that was found to transmit 47.25 % of the incident
power of a beam of Cu Kα radiation. Assume that the density of Ni is 8.93 cm2/g. (6)

QUESTION 3

a) Define the following terms commonly used in chromatography and in each case indicate
the importance of the parameter in separation and give its symbol.

i. Retention time
ii. Retention factor
iii. Distribution factor
iv. Selectivity factor
v. Eddy diffusion (5)
a) Briefly describe how selectivity factor, can be manipulated for a pair of solutes. (2)

b) Describe how the retention factor for a solute can be manipulated. (2)

c) Briefly explain why the minimum in a plot of plate height versus flow rate occurs at lower
flow rate with liquid chromatography than with gas chromatography? (5)

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d) What is gradient elution? In what type of chromatography uses gradient elution? What is
its equivalent known as? (3)

e) List the variable in chromatography that lead to zone separation. (3)

QUESTION 4

a) The following data apply to a column for liquid chromatography:

Length of packing: 250.0 mm

Flow rate: 0.450 mL/min
VM: 1.45 mL
VS: 0.165 Ml

A chromatogram of a mixture of species X, Y, Z, and K provided the following data, in Table

below.

Analyte Retention time, min Width of Peak Base (W), min

Non-retained 1.9 -
X 3.3 0.19
Y 4.7 0.28
Z 6.2 0.32
K 7.7 0.54

Calculate the following:

i. The number of plates from each peak and the average number of plates (5)
ii. The plate height for the column (2)
iii. The retention factor for X and Z (2)
iv. The distribution constant for Y and K (2)
v. The resolution for species Y and Z (2)
vi. The selectivity factor for Y and Z (2)
vii. The length of column necessary to give a resolution 1.5 for species Y and Z (3)
viii. The time required to separate Y and Z with a resolution of 1.5 (2)

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QUESTION 5

a) What are the fundamental differences between adsorption mode and partition mode in
chromatography? (3)

b) The terms sample preparation and sample pre-treatment are commonly used in
analytical chemistry. Differentiate between the two terms. (4)

c) Briefly, but informatively, demonstrate or show the similarities between normal-phase

partition and adsorption chromatography. (3)

d) What is the order in which the following compounds would be eluted from a reverse
phase HPLC column?
i. Benzene, diethyl ether & n-hexane (3)
ii. Acetone, dichloroethane & acetamide (3)

e) Briefly explain what types of compounds can be separated by HPLC but not by GC?
What is the requirement for compounds to be separated by gas chromatography?
(4)

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4. ASSIGNMENTS
4.2 ASSIGNMENT #4 (Due date: 21 August 2023)

These are scenario-based questions, do not contribute to year mark, but will be assessed
during the final exam. These questions cover the whole syllabus of CHE4804 module.

QUESTION 1

You are an environmental scientist and tasked to conduct quantitative analysis of chlorinated
organic compounds at ppb concentration levels in a river. Which sampling strategy, sample
preparation method and quantification technique would you choose and why {Kindly emphasis
on the best detectors as well. (25)

QUESTION 2

How would you approach this analysis (question 1 above) if your target analyte was ppb levels
of Hg within the same river? (25)

QUESTION 3

You are working in an energy sector and your main responsibility as an Analytical Chemist is to
recover Rare Earth Elements (REEs) form electronic waste. What would be your daily routine
for this role? Elaborate more on sampling strategies, sample preparation methods, detection
techniques, validation methods, precipitation methods and on how you would calculate your
final yield. (25)

QUESTION 4

You are an independent consultant and one of the toothpaste companies approaches you to
assist with issues of inconsistence fluoride ions concentration levels. How would you go about
assisting your client based on verified scientific report? (25)

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