FACULTY OF SCIENCE

DEPARTMENT OF CHEMICAL SCIENCES

DIPLOMA IN ANALYTICAL CHEMISTRY (4 YEARS)

MODULE CETATB1
ANALYTICAL CHEMISTRY 2 (THEORY)

CAMPUS DFC

SUPPLEMENTARY EXAMINATION

DATE:10 /01/2020 SESSION: 8:00 – 11:00

ASSESSORS: DR LN DLAMINI & DR N MABUBA

INTERNAL MODERATOR: MS H DU PLESSIS

DURATION: 3 HOURS MARKS 125

NUMBER OF PAGES: 5 PAGES

INSTRUCTIONS: CALCULATORS ARE PERMITTED (ONLY ONE PER STUDENT).

THE QUESTION PAPER MUST BE HANDED IN WITH THE ANSWER SHEET.

REQUIREMENTS: TWO ANSWER SCRIPT.

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INSTRUCTIONS TO STUDENTS:

1. Answer all the questions. Questions may be answered in any order as long as each
answer is clearly numbered.

2. Report all numerical answers to the correct number of significant figures and
with the appropriate units. Marks will be deducted for incorrect significant figures
and answers without units.

3. Report p–values to 3 decimal digits.

QUESTION 1: PRECIPITATION TITRATIONS

1.1 Consider the titration of 25.00 mL of a 0.04500 M BaI2 solution with a

0.1125 M AgNO3 solution. Calculate pAg after the addition of 22.00 mL
of the AgNO3 solution.
[For AgI: Ksp = 8.3 x 10−17] (8)

1.2 Analysis of a 1.5562 g feldspar sample produced a mixed precipitate of

NaCl and KCl weighing 0.3663 g. The precipitate was dissolved and
diluted to a final volume of 100 mL in a volumetric flask. A 20.00 mL
aliquot of the solution was treated with 25.00 mL of a 0.09932 M
AgNO3 solution. After the silver chloride solid was removed by filtration,
the excess silver nitrate required 17.63 mL of 0.08056 M KSCN to
reach the endpoint in a titration using Volhard’s method.
[Molar masses (g mol−1): NaCl = 58.443; KCl = 74.551; K2O = 94.196;
Na2O = 61.979]

1.2.1 Calculate the weight percentage of potassium oxide in the feldspar

sample. (14)
1.2.2 Give reaction equation(s) to show how the endpoint is detected in the
Volhard method. (3)
1.2.3 Briefly explain why it is necessary to remove the sparingly soluble
silver chloride before the excess silver ions are back-titrated with
thiocyanate. You may use reaction equation(s) in your explanation. (4)
1.2.4 Explain why the sample is acidified before precipitation using Volhard’s
method. (1)

1.3 Name three types of endpoints for argentometric titrations

(silver nitrate titrations). (3)

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QUESTION 2: COMPLEXOMETRIC TITRATIONS

2.1 A 25.00 mL aliquot of a dissolved coin sample, containing Fe3+ and

Cu2+ required 16.86 mL of 0.04983 M EDTA for complete titration of
both cations. Another 50.00 mL aliquot of the same sample was
treated with NH4F to complex the Fe3+. The Cu2+ was then reduced and
masked by addition of thiourea. Upon the addition of 25.00 mL of
0.04983 M EDTA, the Fe3+ was liberated from the fluoride complex and
formed an EDTA complex. The excess EDTA required 17.84 mL of
0.01852 M Pb2+ to reach the endpoint using xylenol orange as an
indicator.

2.1.1 State three circumstances in which an EDTA back-titration might be

necessary. (3)
2.1.2 Calculate the molar concentrations of Fe3+ and Cu2+. (10)

2.2 Discuss the influence of the following parameters on the shape of an

EDTA titration curve:

2.2.1 Nature of the analyte cation (3)

2.2.2 pH (3)

2.3 Read the following paragraph from Quantitative Analysis by R.A Day,
A.L. Underwood, 6th edition, Prentice Hall, New Jersey, 1991, p. 211:

‘Water-soluble chelating agents such as EDTA provide titrimetric

methods for metal ions in aqueous media and may have other uses as
well, e.g. “masking agents”, i.e., agents that “hide” metal ions from
other reagents with which their interaction is undesired. EDTA is added
to mayonnaise, for example, to chelate trace metals such as Fe3+
which otherwise catalyze the air oxidation of fatty acids or esters to the
odorous products associated with rancidity. Other, less water-soluble,
chelating agents are used as precipitants for metal ions or to extract
metals into organic solvents. Chelation, however, is not confined to
analytical chemistry. Many interesting metal chelate compounds are
found in biological systems.’

This is a comprehension question. Answer the questions by using your

own words. Marks will be deducted for incorrect spelling and grammar.

2.3.1 Explain what is meant by the terms “odorous” and “rancidity”. (2)
2.3.2 Chelating agents are used in complexometric titrations. List two other
uses of chelating agents. (4)

2.4 Briefly describe the displacement method used in EDTA titrations and
mention when it is necessary to use this method. (5)

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QUESTION 3: SEPARATION METHODS

3.1 A solute has a distribution coefficient of 8.0 between water and carbon
tetrachloride. In an experiment you want to extract the solute from
100 mL of water. Do a calculation to prove that it is more efficient to do
two consecutive extractions with 50 mL of carbon tetrachloride than
one extraction with 100 mL of carbon tetrachloride. (6)

3.2 The following retention times and base line peak widths were obtained
from a chromatographic column with a length of 90 cm:

Mobile phase Retention time (s) Peak width (s)

Air 15 –
Acetylsalicylic acid 130 15
Codeine 160 18

3.2.1 Calculate the resolution obtained between the acetylsalicylic acid and
codeine peaks. Comment on the separation. (3)
3.2.2 Calculate the average number of theoretical plates for the column. (4)
3.2.3 Calculate the plate height of the column using the average number of
theoretical plates. Comment on the efficiency of the column. (3)

3.3 Explain the principles on which column chromatography is based. (4)

3.4 Define the following terms, “resolution” and “retention time”. (2)

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QUESTION 4: GRAVIMETRY

4.1 Explain the difference between a specific precipitating agent and a

selective precipitating agent. Give an example of each. (4)

4.2 Discuss two experimental ways by which coagulation of colloidal

precipitate can be achieved. Mention in your discussion what effect
these actions will have on the electric double layer around the colloidal
particles. (6)

4.3 Colloidal precipitates are prone to coprecipitation due to surface

adsorption. Give two experimental ways to minimize coprecipitation
due to surface adsorption. (2)

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QUESTION 4 (CONTINUED)

4.4 A 0.6615 g sample containing only a mixture of KCl and NH4Cl, was
treated with an excess of chloroplatanic acid (H2PtCl6) and a mixed
precipitate of (NH4)2PtCl6 and K2PtCl6 was obtained. Upon heating the
mixed precipitate, the following reactions resulted:

(NH4)2PtCl6 (s) → Pt (s)

K2PtCl6(s) → Pt (s) + 2KCl(s)

The solid residue obtained after heating the mixed precipitate was
washed with deionized water to dissolve potassium chloride. The
remaining precipitate was dried and the mass was determined as
1.0880 g. Calculate the weight percentage of KCl and NH4Cl in the
sample.
[Molar masses (g mol−1): NH4Cl = 53.491; KCl = 74.551; Pt = 195.078] (12)

4.5 A 1.6253 g sample of oven dried clay, collected from a river contained
1.552 ppm Ca. Calculate the parts per million of calcium in the sample
on an ‘as received’ basis, if it is known that the clay sample contained
23.58 % moisture. (6)

4.6 List five desirable properties of an ideal precipitate. (5)

4.7 Ni(II) can be precipitated as nickel dimethylglyoximate Ni(DMG)2 by

addition of dimethylglyoxime (DMG). The balanced equation is as
follows:

Ni2+ + 2DMG → 2H+ + Ni(DMG)2 (s)

Nickel dimethylglyoximate is a bulky precipitate that is inconvenient to

manipulate in amounts greater than 175 mg. The amount of nickel in
coins ranges between 55 and 63 % (m/m). Calculate the sample size
that should not be exceeded when analysing these coins for nickel.
[Molar masses (g mol−1): Ni(DMG)2 = 288.917; Ni = 58.6934] (5)

4.8 Give three reasons why gravimetric analysis is preferred above other
analytical methods. (3)

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TOTAL MARKS: 128

FULL MARKS: 125

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