NAMIBIA UNIVERSITY
OF SCIENCE AND TECHNOLOGY
FACULTY OF HEALTH AND APPLIED SCIENCES
DEPARTMENT OF NATURAL AND APPLIED SCIENCES
QUALIFICATION: BACHELOR OF SCIENCE HONOURS
QUALIFICATION CODE: O8BOSH LEVEL: 8
COURSE NAME: ADVANCED ANALYTICAL METHOD
COURSE CODE: AAC811S
AND CHEMOMETRICS
SESSION: JULY 2019 PAPER: THEORY
DURATION: 3 HOURS MARKS: 100
SUPPLEMENTARY/SECOND OPPORTUNITY EXAMINATION QUESTION PAPER
EXAMINER(S) | DRJULIEN LUSILAO
MoperRATOR: | DR JAMES ABAH
INSTRUCTIONS
1. Answer ALL the questions in the answer book provided.
2. Write and number your answers clearly.
3. All written works MUST be done in blue or black ink.
PERMISSIBLE MATERIALS
Non-programmable Calculators
ATTACHMENTS
List of Useful Tables and formulas
THIS QUESTION PAPER CONSISTS OF 8 PAGES (Including this front page and attachments)
Question 1 [20]
1.1 (a) What is quality analysis? (3)
(b) What does it mean to say that a laboratory worker has good analytical skills? (3)
1.2 Briefly discuss the impact of wrong analytical results in
(a) trade (2)
(b) environmental monitoring (2)
1.3 When would you choose an instrumental analysis procedure over a wet chemical
analysis procedure? (3)
1.4 What does it mean to carry out an analytical method? Avoid the word “analyse” in
your answer. (3)
1.5 What is method validation and what are the results of this validation used for in
analytical chemistry? (4)
Question 2 [20]
2.1 Why are sampling and sample preparation procedures as crucial to the success of
an analysis as the analytical method chosen? (3)
2.2 What is a representative sample? Do not use the words “represent” or
“representative” in your answer. (2)
2.3 Briefly explain the concept of random sampling and give its advantages as well as
its disadvantages. (5)
2.4 (a) The constituents of an ink sample can be quantified either by HPLC (Method A)
or by acarefully designed method based on TLC separation and UV-Vis
quantification (Method B). Which of the two methods will likely lead to greater
error and why? (3)
(b) If you want to determine the level of cadmium in drinking water, what reagent
grade would you use for that purpose and why? (2)
2.5 (a) Differentiate between solid—liquid extraction (SLE), liquid-liquid extraction (LLE),
and solid phase extraction (SPE). (3)
(b) Why are solvents such as aliphatic hydrocarbons, methylene chloride, toluene,
diethyl ether and chloroform useful in the extraction of organic analytes
from water samples? (2)
Question 3 [20]
3.1 One method for the analysis of Fe**, which can be used with a variety of sample
matrices, is to form the highly coloured Fe?*—thioglycolic acid complex. The
complex absorbs strongly at 535 nm. Standardizing the method is accomplished
using external standards. A 10.00 ppm Fe** working standard is prepared by
transferring a 10-mL aliquot of a 100.0 ppm stock solution of Fe** to a 100-mL
volumetric flask and diluting to volume. Calibration standards of 1.00, 2.00, 3.00,
4.00, and 5.00 ppm are prepared by transferring appropriate amounts of the
10.0 ppm working solution into separate 50-mL volumetric flasks, each containing
5 mL of thioglycolic acid, 2 mL of 20% w/v ammonium citrate, and 5 mL of 0.22 M
NH3. After diluting to volume and mixing, the absorbances of the external standards
are measured against an appropriate blank. Samples are prepared for analysis by
taking a portion known to contain approximately 0.1 g of Fe**, dissolving ina
minimum amount of HNO3 and diluting to volume in a 1-L volumetric flask.
A 1.00-mL aliquot of this solution is transferred to a S5O-mL volumetric flask, along
with 5 mL of thioglycolic acid, 2 mL of 20% w/v ammonium citrate, and 5 mL of
0.22 M NH3 and diluted to volume. The absorbance of this solution is used to
determine the concentration of Fe?* in the sample.
(a) What is an appropriate blank for this procedure?
(b) Ammonium citrate is added to prevent the precipitation of Al?*. What is the
effect on the reported concentration of iron in the sample if there is a trace
impurity of Fe3* in the ammonium citrate? (2)
(c) Why does the procedure specify that the sample contains about 0.1 g of Fe?*? (3)
3.2 For each of the pair of calibration curves shown in the figure below, select the
calibration curve using the most appropriate set of standards. Briefly explain the
reasons for your selections. The scales for the x-axis and y-axis are the same for
each pair. (6)
(a)
1 2
€ 2
a e
Ca Ca
b)
1 2
Ca Ca
(9
Signal
Signal
Ca Ca
3.3 Many of the analytical methods used to determine the concentration of fibrinogen
in plasma are based on light scattering following its precipitation. Light scattering
is measured nephelometrically at a wavelength of 340 nm. Analysis of a set of
external calibration standards gives the following calibration equation
Ils = -4.66 + 9907.63 x C
where Is is the intensity of scattered light and C is the concentration of fibrinogen in
g/L. A9.0-mL sample of plasma was collected from a patient and mixed with 1.0 mL
of an anticoagulating agent. A 1.0-mL aliquot of this solution was then diluted to
250 mL in a volumetric flask. Analysis of the resulting solution gave a scattering
intensity of 44.70. What is the concentration of fibrinogen, in gram per liter, in the
plasma sample? (4)
3.4 Give three disadvantages of the isotope dilution method. (3)
Question 4 [20]
4.1 (a) What is quenching in Atomic Fluorescence Spectroscopy (AFS) and why is this
phenomenon considered to have a negative effect in quantitative AFS analysis? (4)
(b) It has been reported that an Atomic Absorption Spectrometer (AAS) can easily
be converted into an AFS if a fluorescence lamp (or a continuous source with the
right wavelength selector) is used instead of a hollow cathode lamp. What other
critical change would you make to the AAS design if you were to convert it into
an AFS instrument? Explain your choice. (3)
4.2 (a) Name the components labelled as A to E for the Mass Spectrometer (MS)
represented in the figure below.
i
A B _ ¢ p E
Sample Vacuum Count ions f
. ; System
introduction fb reeset mre alec result. |
lonization . ,
Minimize collisions, interferences
(5)
(b) Differentiate between the following MS techniques:
(i) EIMS and TIMS (2)
(ii) ICP-QMS and ICP-SFMS. (2)
4.4 List the different classes of chemical speciation. (4)
Question 5 [20]
5.1 Researchers have developed an analytical method for determining trace levels of
atmospheric gases. An analysis of a sample containing 40.0 parts per thousand
(ppt) 2-chloroethylsulfide yielded the following results
43.3 34.8 31.9
37.8 34.4 31.9
42.1 33.6 35.3
(a) Determine whether there is a significant difference between the experimental
mean and the expected value at a = 0.05. (5)
(b) As part of this study a reagent blank was analyzed 12 times, giving a mean of
0.16 ppt and a standard deviation of 1.20 ppt. What are the IUPAC detection
limit and limit of quantitation for this method? (2)
5.2 Lord Rayleigh, J.W. was one of the most well-known scientists of the late 19" and
early 20' centuries, receiving the Nobel Prize in 1904 for the discovery of argon.
An important turning point in his discovery of Argon (Ar) was the experimental
measurements of the density of N2. Rayleigh approached this experiment in two
ways: 1° by taking atmospheric air and removing all O2 and Hz (at the time, air was
thought to be only made of O2, H2 and No); and 2"4, by chemically producing N2 by
decomposing nitrogen containing compounds (NO, N20, and NH4NOs) and again
removing all O2 and Ho. Following are his results for the density of Nz, published in
Proc. Roy. Soc. 1894, LV, 340 (all values are for grams of gas at an equivalent
volume, pressure, and temperature).
Atmospheric Chemical
origin origin
2.31017 2.30143
2.30986 2.2989
2.3101 2.29818
2.31001 2.30182
2.31024 2.29869
2.3101 2.2994
2.31028 2.29849
2.29889
(a) Use the appropriate statistics (a = 0.05) to explain why these results led Rayleigh
to look for, and discover Ar. Assume that there is no significant difference in the
precision of both set of measurements. (8)
(b) In the measurement of the density of Nz in air from atmospheric origin, the
value of 2.30986 seems to be an outlier, use the Q test to assess whether this
value should be rejected (a = 0.05). (5)
END
Data sheet
Value of t for a confidence interval of 90% 95% 98% 99%
Critical value of Itl for P values of 0.10 0.05 0.02 0.01
number of degrees of freedom
6.31 12.71 31.82 63.66
OMPONANAAWHN
2.92 4.30 6.96 9.92
2.35 3.18 4.54 5.84
2.13 2.78 3.75 4.60
2.02 2.57 3.36 4.03
1.94 2.45 3.14 3.71
1.89 2.36 3.00 3.50
1.86 2.31 2.90 3.36
2.26 2.82 3.25
1.81 2.23 2.76 3.17
2.18 2.68 3.05
ool soi
DONWON ©
weed’ seme: commie)
2.14 2.62 2.98
taodasa
2.12 2.58 2.92
2.10 2.59 2.88
2.09 2.53 2.85
2.04 2.46 2.75
ees
2.01 2.40 2.68
cock: cece
1.96 2.33 2.58
Critical values of F for a one-tailed test (P = 0.05)
YM
7 T{
1 2 3 |4 5 6 17
} 8 9 10 12 15 20
161.4 199.5 215.7 224.6 230.2 234.0 236.8 238.9 240.5 241.9) 243.9 245.9 248.0
19.40) 19.41
HNhWN—
18.51 19.00 19.16 19.25 19.30 19.33 19.35 19.37 19.38 19.43 19.45
10.13 9.552 9.277 9.117 9.013 8.941 8.887 8.845 8.812 8.786 | 8.745 8.703 8.660
7.709 6.944 6.591 6.388 6.256 6.163 6.094 6.041 5.999 5.964} 5.912 5.858 5.803
6.608 5.786 5.409 5.192 5.050 4.950 4.876 4.818 4.772 4.735 | 4.678 4.619 4.558
5.987 5.143 4.757 4.534 4.387 4.284 4.207 4.147 4.099 4.060} 4.000 3.938 3.874
SOONAHA
5.591 4.737 4.347 4.120 3.972 3.866 3.787 3.726 3.677 3.637 | 3.575 3.511 3.445
5.318 4.459 4.066 3.838 3.687 3.581 3.500 3.438 3.388 3.347) 3.284 3.218 3.150
5.117 4.256 3.863 3.633 3.482 3.374 3.293 3.230 3.179 3.137, 3.073 3.006 2.936
4.965 4.103 3.708 3.478 3.326 3.217 3.135 3.072 3.020 2.978 2.913 2.845 2.774
4.844 3.982 3.587 3.357 3.204 3.095 3.012 2.948 2.896 2.854 2.788 2.719 2.646
4.747 3.885 3.490 3.259 3.106 2.996 2.913 2.849 2.796 2.753, 2.687 2.617 2.544
4.667 3.806 3.411 3.179 3.025 2.915 2.832 2.767 2.714 2.671 2.604 2.533 2.459
4.600 3.739 3.344 3.112 2.958 2.848 2.764 2.699 2.646 2.602 2.534 2.463 2.388
4.543 3.682 3.287 3.056 2.901 2.790 2.707 2.641 2.588 2.544| 2.475 2.403 2.328
4.494 3.634 3.239 3.007 2.852 2.741 2.657 2.591 2.538 2.494| 2.425 2.352 2.276
4.451 3.592 3.197 2.965 2.810 2.699 2.614 2.548 2.494 2.450| 2.381 2.308 2.230
4.414 3.555 3.160 2.928 2.773 2.661 2.577 2.510 2.456 2.412) 2.342 2.269 2.191
4.381 3.522 3.127 2.895 2.740 2.628 2.544 2.477 2.423 2.378) 2.308 2.234 2.155
4.351 3.493 3.098 2.866 2.711 2.599 2.514 2.447 2.393 2.348) 2.278 2.203 2.124
v, = number of degrees of freedom of the numerator; v. = number of degrees of freedom of the denominator.
-_ a Ke—%o|
ae
[acxne
[Ma My
t calculated = pa# VN t caituiated = tt (calculated
Ss d S pooled na +n,
s?(N, —1)+s¢(N, —1) tess
s pooled = |
N, +Ny +... — Nsets of data
Critical Values for the Rejection Quotient
Qerit (Reject if Qexp > Qerit)
N 90% 95% 99%
Confidence | Confidence | Confidence
3 0.941 0.970 0.994
4 0.765 0.829 0.926
5 0.642 0.710 0.821
6 0.560 0.625 0.740
7 0.507 0.568 0.680
8 0.468 0.526 0.634
9 0.437 0.493 0.598
10 0.412 0.466 0.568
N = number of observations
