UN~

TEKNOLOGI
PETRONAS

COURSE CDB3093 -ANALYTICAL CHEMISTRY

DATE 6 APRIL 2019 (SATURDAY)
TIME 9.00 AM - 12.00 NOON (3 HOURS)

INSTRUCTIONS TO CANDIDATES

1. Answer ALL questions in the Answer Booklet.

2. Begin EACH answer on a new page in the Answer Booklet.
3. Indicate clearly answers that are cancelled, if any.

4. Where applicable, show clearly steps taken in arriving at the solutions and
indicate ALL assumptions, if any.
5. DO NOT open this Question Booklet until instructed.

Note
1. There are THIRTEEN (13) pages in this Question Booklet including the
cover page and Appendix.
ii. DOUBLE-SIDED Question Booklet.
iii. Graph paper(s) will be provided
Universiti Teknologi PETRONAS
 COB 3093
...
1. a. Define the precipitation gravimetry and explain how relative
supersaturation can affect the precipitation.
[5 marks]

b. A 0.6113 g sample of Alpha metal, containing aluminum, magnesium

and other metals, was dissolved and treated to prevent interferences
by the other metals. The aluminum and magnesium were precipitated
with a-hydroxyquinoline. After filtering and drying, the mixture of
AI(CgH5N0)3 and Mg(CgHsNO)z 'Nas found to weigh 7.8154 g. The
mixture of dried precipitates then was ignite, converting the
precipitate to a mixture of AI203 and MgO. The weight of this mixed
solid was found to be 1.0022 g. Molar mass of the compound is given
in the TABLE 1b. Calculate AI and Mg in w/w %.

TABLE1b
Compound Molar mass I g.mol- 1
AI203 101.96
AI(CgH5N0)3 459.45
MgO 40.304
Mg(CgH5N0)2 312.61
Note: Atomic weight of elements is given in the Appendix.
[12 marks]

..
_

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 COB 3093

c. The efficiency of a particular catalyst is highly dependent on its

zirconium content. The starting material for this preparation is
received in batches with purity between 68% and 84% ZrCI4. Routine
analysis is based on precipitation to form AgCI and considering there
are no sources of chloride ion other than the ZrCI4 in the sample.
Given that molar mass of AgCI and ZrCI4 are 143.32 g.mol- 1 and
233.03 g.mol- 1, respectively.

i. Determine the sample mass should be taken to ensure at

least 0.400 g AgCI is precipitated.
[4 marks]

ii. If this sample mass is used, determine the maximum mass of

AgCI that can be expected in this analysis?
[4 marks]

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 COB 3093

2. a. Define the absorption of radiation and outline the difference between

atomic spectroscopy and molecular spectroscopy.

[4 marks]

b. Potassium, K concentration can be determined by flame emission

spectrometry (flame photometry) using a lithium internal standard.
The data in TABLE 2b were obtained for standard solutions of KCI
and a sample containing a known concentration of UCI as the internal
standard. Calculate the concentration of Kin the sample and propose
potential systematic error that may occur during the process.

TABLE 2b
Concentration of K Intensity of K Intensity of K
/ppm Emission Emission
1.0 10.0 10.0
2.0 15.3 7.5
5.0 34.7 6.8
7.5 65.2 8.5
10.0 95.8 10.0
20.0 110.2 5.8
sample 47.3 9.1

[8 marks]

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 COB 3093

c. Coloured complexes EDTA in a variety of metal ions can serve as

the basis for a quantitative spectrophotometric method of analysis.

The molar absorptivity, E of the EDTA complexes of Cu 2+, Co2+, and

Ni 2+ at three wavelengths are summarized in the TABLE 2c.

TABLE 2c

E37a.7 E4s2.9 €732.o

Metal I M-1 cm- 1 I M- 1 cm- 1 I M- 1 cm- 1

Cu 2+ 3.11 15.8 2.11

Co2+ 7.73 2.32 95.2
Ni2+ 13.5 1.79 3.03

Using this information and the path length, b of the cell for all
measurements is 1.00 em. Determine:

i. The concentration of Cu 2+ in a solution with absorbance of

0.338 at a wavelength of 732.0 nm.

[2 marks]

ii. The concentrations of Cu 2+ and Co2+ in a solution having

absorbance of 0.453 and 0.107 at wavelength of 732.0 nm
and 462.9 nm, respectively.

[3 marks]

iii. The concentrations of Cu 2+, Co 2+, and Ni 2+ in a sample that

having absorbance of 0.423, 0.184 and 0.291 at the
wavelengths. of 732.0 nm, 462.9 nm and 378.7 nm,
respective!~ .

[3 marks]

·"'
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 COB 3093

d. The spectrum in FIGURE 2d was obtained from Fourier transform

infrared (FTIR) spectrometer for a compound A. The spectrum and
propose FOUR (4) main bondings present in compound A. If the
sample, empirical formula is given as CH4N20, justify your selection
for peak at wavenumber of 3448 cm-1.

[5 marks]

100
90

60
70

60

~
t-
;# ~

40

30
I
20

10

0.0
v
4000 3000 '2000 1500 1000 400

Wavenumber cm·1

FIGURE 2d: FTIR spectrum for compound A

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 COB 3093

3. a. Three types of sample from different sources were received for

chromatography analysis. The samples contain a mixture of solutes
and the information of samples is shown in TABLE 3a. Propose the
type of chromatography to be used for analysis of each samples.
Justify your answer by providing the mechanism of solute separation
as the samples in the mobile phase passing through the stationary
phase.
TABLE 3a
Sample Nature of sample Physical
properties
A Non Polar Volatile Boiling point:
hydrocarbon 40-60t

B Polar and Non volatile of Melting point:

Polyol and Carboxylic acids >120t

c Polymer with molecular Melting point:

weight ranging from 20,000 >140t
to 100,000 g/mol.

[9 marks]

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 COB 3093

b. The gas chromatography data obtained for two compounds

separated on a 2 m pack column are shown in TABLE 3b.

TABLE 3b
Compound Retention time, tr Width at the base, w
Is Is
A 350 19.8
B 370 20.3

i. Calculate the number of theoretical plates (N) for each

compound and discuss why it is possible for each compound
to have a different number of theoretical plates.
[5 marks]

ii. Determine the resolution and selectivity factors for the above
compounds and suggest method to improve the resolution.
The retention time for an unretained solute is 50 s.
[6 marks]

iii. Estimate the height of theoretical plates to achieve resolution

(Rs) of 1.5 without increasing the length of the column.
[5 marks)

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 COB 3093

4. a TLC is fast method for quantitative analysis. Illustrate a typical TLC

plate with the sample spot and show how the response factor, R1 is
determined.
[3 marks]

b. The concentration of pesticide in vegetables can be determined by

high performance liquid chromatography (HPLC). A 5.0 g sample of
tomato was extracted with 20.00 ml of ethanol. After filtering to
remove insoluble material, 1 ml portion of the extract was diluted to
10 ml with acetone and 5 ml of the diluted extract was injected into
a HPLC giving a signal of 0.217 (arbitrary units) for the malathion.
When 5 ml of a 20.0 ppm malathion standard is analyzed using the
same conditions, a signal of 0.258 was measured.

i. Suggest ONE (1) method to increase the resolution of the

above analysis. Explain your answer.
[4 marks]

ii. Determine the concentration of malathion in the tomato in

ppm.
[6 marks]

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 COB 3093

c. Vitamin 8 complex (81, B6 etc) tablet is crushed and placed in a

beaker with 20.00 ml of a 50% v/v methanol solution and contains
o-ethoxybenzamide as internal standard. An approximately 4 !JL
sample is loaded into a capillary column. When a solution of 100.0
ppm B1 and 100.0 ppm o-ethoxybenzamide was analyzed, the peak
area for vitamin B1 was 71% of that for the internal standard. The
analysis of a 0.125 g vitamin 8 complex tablet gave a peak area for
vitamin 81 that was 1.82 times as great as that for the internal
standard. Estimate the content of vitamin 81 in the tablet
(mg B1/tablet).
[6 marks]

d. A water sample is analysed for trace of benzene using Gas

Chromatography (GC). Samples and standards are spiked with a
fixed amount of toluene as internal standard. The GC data are shown
in TABLE 4d. Estimate the concentration of benzene in the sample.

TABLE 4d

Benzene Benzene Peak Area Toluene Peak Area

/ppm

10 252 376

15.0 373 370

25.0 636 371

Sample 533 368

[6 marks]

-END OF PAPER-

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APPENDIX A

FTIR Group Frequencies for Organic Functional Groups

Bond Type of Compound Frequency Intensity

Range, cm- 1
C-H Alkanes 2850-2970 Strong

C-H Alkenes 3010-3095 Medium

675-995 strong
C-H Alkynes 3300 Strong
C-H Aromatic rings 3010-3100 Medium
690-900 strong
0-H Monomeric alcohols, phenols 3590-3650 Variable
Hydrogen-bonded alcohols, phenols 3200-3600 Variable,
Monomeric carboxylic acids 3500-3650 sometimes
Hydrogen-bonded carboxylic acids 2500-2700 broad
Medium
broad
N-H Amines, amides 3300-3500 medium

C=C Alkenes 1610-1680 Variable

C=C Aromatic rings 1500-1600 Variable
Alkynes 2100-2260 Variable
C-N Amines, amides 1180-1360 Strong
Nitriles 2210-2280 Strong
C-0 Alcohols, ethers,carboxylic acids, esters 1050-1300 Strong

C=O Aldehydes, ketones, carboxylic acids, 1690-1760 Strong

esters
N02 Nitro compounds 1500-1570 Strong
1300-1370

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TABLE: Simple correlations of group vibrations to regions of infrared absorption

5000 4000 3000 2500 2000

f r 1 ~ I!! q I I I I 1!!
lo-H
= Wavenumbers in em-'
150014001300 1200 1100 1000 900
1 1 1 p1111111 : ~ : : 1 : :11 ::!llljl 1! t 1! :::

aodN-HstretchmgC;::Ostretctung.
!
C-Ostrolching.
800 700
!: r 1111 : 1! 1 I l 1 ! r l ! : ! ! ! 1 'I
'I
'
I

I
C-H- strotch~ng

- - C=N -slretchsng

c=c and c=N s.tretching C=C stretching

C-N stretching

c-c stretchmg
I
I
-
i
1 -
N-H beoding N-H bending •

C-H beoding C-H oonding

I
! 'j
2 3 4 7 8 9 10 11 12 13 15

Wavelength in micrometers

List of Formula

Beer's Law

Axs = Exb[X]s
Avs = Eyb[Y]s
Azs = Ezh[Z]s
Am= Exb[X] + Eyb[Y] + Ezh[Z]

%Analyte, A

%A= weight of ppt x gravimetric factor (G.F.) x 100

weight of sample
Area of Gaussian peak
= 1.064 X h X W112

= 1.064 X h X 2.35 a

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 CDS 3093

Adjusted retention time, t'r =~- tm

Relative retention, a= t'rit'r 1 = k' 2/k' 1

Capacity factor, k'=(lr-lm)ltm = t'/tm

Plate height, H =UN

Resolution =f).t/wav
=
0 1
f ( ~ )(1:~?av)
Response factor:

PtF(~)
Atomic weight of element

AI = 26.982 g/mol

Cl = 35.45 g/mol

Mg = 24.305 g/mol

N = 14 g/mol

0 = 16 g/mol

S = 32.07 g/ mol

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