(A) ABSTRACT

The aim of experiment was to analyse the pyrolusite ore (MnO2) by determining the
amount of Manganese (Mn2+) present in the ore. This was achieved by using Volumetric
analysis method where the ore was reacted with a known excess oxalic acid and then followed
by titration against standard solution of 0.0193M KMnO4 in acidic medium of diluted 6M
H2SO4.
The amount of oxalic acid obtained after titration was 0.005911moles in a total of 0.009525
moles oxalic in the sample and the mass of Manganese (Mn2+) found in 0.4112g of the ore
was 0.1988g and its percentage was 48.35%.
(B) THEORY
Pyrolusite is a chief ore of manganese. In the ore manganese is found in form of
manganese dioxide from which the manganese content in the ore is analysed. The
manganese (Mn2+) is determined from the ore by using a strong reducing agent (C2O42).
Volumetric titration enables the determination of excess oxalic acid and hence the oxalic
acid used to dissolve the ore.
The Ore (MnO2) which is black in color that contain a tetravalent manganese is
boiled with the excess of oxalic acid (H2C2O4) and diluted sulphuric acid (H2SO4) so as to
facilitate the reaction.
MnO2 + H2C2O4 + H2SO4 ―>MnSO4 + 2H2O + 2CO2
All manganese (ore) present will react with the excess oxalic acid to give
carbondioxide, water and manganese sulphate.
Where manganese dioxide (MnO2) is reduced to manganese two
MnO2 + 4H+ + 2e- ―> Mn2+ + 2H2O
While the oxalic acid was oxidized to carbon dioxide
C2O42- ―> 2CO2 + 2e-
Overall is
MnO2 + C2O42- + 4H+ ———> Mn2+ + 2H2O + 2CO2
The amount of oxalic acid unreacted (excess) is determined through titration of the
mixture against a standard solution of Potassium permanganate, KMnO4. Potassium
permanganate is widely used as an oxidizing agent in volumetric analysis. This is due to
its oxidizing ability. The balanced net ionic equation for the reaction of permanganate ion
with oxalate ion is as follows:
16 H+(aq) + 2 MnO4-(aq) + 5 C2O42-(aq) ―> 10 CO2(g) + 2 Mn2+(aq) + 8 H2O(l)
Since permanganate ion is violet in color and manganese (II) ion is nearly
colorless, the endpoint in titrations using permanganate as the titrant can be taken as the
first permanent pink color that appears in the solution. The obtained titre volume in
relation to the volumetric analysis, the oxalic acid left out and that consumed is obtained
as well as the amount of MnO2 present in a sample.
(C) EXPERIMENTAL PROCEDURES
In this analysis of Pyrolusite ore (MnO2) where the amount and percentage of Mn2+ was
obtained, the following chemicals and apparatus were used.
Chemicals.
➢ Standard solution of 0.0193M KMnO4
➢ Diluted sulphuric acid 6M H2SO4
➢ 1.2001g Oxalic acid H2C2O4
➢ Distilled water
➢ 0.4112g Pyrolusite ore (MnO2)
Apparatus
- 250ml conical flask, - 20ml pipette, - Spatula, - Analytical
balance
- Funnel, - Beaker, - Burette,
- Measuring flask, - Retort stand, - Filter paper.
Procedures taken during an experiment
1.2001g of oxalic acid was accurately weighed on analytical balance and dissolved
in 50ml of distilled water. 0.4112g of the ore (MnO2) was accurately measured on
analytical balance and transferred into a 250ml conical flask, then the prepared oxalic
acid solution and 25ml diluted sulphuric acid (H2SO4) was poured into a conical flask
containing the ore. This solution had a black colour. A small funnel was placed in the
mouth of the flask and boiled gently until no black particles remained undissolved and
finally the solution was cooled and filtered in a 100ml measuring cylinder by using filter
paper.
Then by using pipette, three portions of 20ml aliquots were taken, mixed with
30ml dilute sulphuric acid (6M) and boiled to a temperature of 70 - 800C. These solutions
were then titrated against a standardized 0.0193M ,KMnO4 changed from colourless to
pink.
.
(E) EXPERIMENTAL RESULTS AND CALCULATIONS:
Experimental data:
Mass of the ore = 0.4112g
Mass of oxalic acid=1.2001g
Volume of pipette used=20ml

Titration readings:
Burette Pilot 1 2 3
reading(ml)
Final volume 24.5 48.3 25.2 49.7
Initial volume 0.00 24.5 0.00 25.2
Titre volume 24.5 23.8 25.2 24.5

Average volume of KMnO4 used:

= 23.8+25.2+24.5 = 24.5cm3
3
The color change observed was from colorless to pink.
Calculations:
Reaction equations:
Ore and oxalic acid:
MnO2 + C2O42- + 4H3O+ Mn2+ + 6H2O + 2CO2 --------- (1)
Titration equation:
5C2O42- + 2MnO4- + 16H+ 2Mn2+ + 10 CO2 + 8H2O ---------(2)
Volume of oxidant (KMnO4) = V1 = 24.5cm3
Volume of reductant (H2C2O4) = V2= 20.00 cm3
Morality of oxidant (permanganate) = M1 = 0.0193M
 Moles of Permanganate (N1) = 2, Mole of oxalic acid (N2) = 5

From the relation;

N1 = M1V1
N2 M2V2
M2 = M1V1N2 = 0.0193x24.5x5 = 0.05911M
N1 V2 2x20
But the total volume of oxalic acid (reductant) used was 100cm3, Hence
0.05911M of oxalic acid ――> 1000 cm3
? ――> 100 cm3
= 0.005911 moles of oxalic acid.
The amount of oxalic acid used in titration against potassium permanganate (KMnO4)
is 0.005911 moles.

The amount of oxalic acid consumed in dissolving ore ;

Mass of oxalate acid (H2C2O4.2H2O) = 1.2001g

Molar mass of oxalate acid (H2C2O4.2H2O) = 126g
Number of moles of Oxalic = Mass of oxalate acid
Molar mass of oxalate acid
= 1.2001g = 0.009525moles
126gmol
Oxalic acid consumed = 0.009525 - 0.005911= 0.003614 moles
Therefore the amount of oxalic consumed in dissolving the ore was 0.003614 moles

Also, the amount of MnO2 & its percentage in the sample was;

From the redox reaction;

MnO2 + H2C2O4 + H2SO4 ―>MnSO4 + 2H2O + 2CO2
Molar mass of MnO2 = 55 + 32 = 87g/mol
1 mole of MnO2 ―> 1 mole of H2C2O4
Then, the amount of (MnO2) present in the sample (ore) is also 0.003614 moles
Thus mass of MnO2 present in a sample = 0.003614x87 = 0.3144g
 Hence; Percent of manganese dioxide (MnO2) in the ore is
= 0.3144x100 % = 75.73%
0.4112
Therefore the amount (mass) MnO2 present in the sample was 0.3144g and its
percentage in the sample was found to be 75.73%

Also the percentage of Mn in the ore was;

87g/mol of MnO2 55g (Mn)
0.3144g of MnO2 ?
Mass of Mn = 0.3144x 55 = 0.1988g
87
Percentage of Mn in the ore:
= Mass of Mn in the ore x100%
Mass of the ore used
= 0.1988 x100%
0.4112

= 48.35%

Therefore the percentage of Mn in the ore was 48.35%

(F) DISCUSSION
Potassium permanganate is a strong oxidizing agent and it oxidizes carbon in the oxalic acid
from trivalent state to tetravalent state. Oxalic acid is a reducing agent and it reduces manganese
from the oxidation state of +7 to the oxidation state of +2.
During the titration process the potassium permanganate was used both as an oxidizing agent and
indicator where as the excess oxalic acid was used as a reducing agent.

Titration done at higher temperature helps to speed-up the rate of reaction.

The obtained mass percentage of manganese in the pyrolusite ore is large enough to allow the
extraction of manganese from the pyrolusite ore. Thus pyrolusite is seen to be dominant/chief
manganese ore.

Sources of errors:

There are various factors that led to errors in the results obtained in this experiment. These
include;
-Failure to exactly observe/notice the colour change during titration. This could lead into
incorrect titre value thereby introducing errors in the calculations to determine the amount of
manganese.
-Insufficient boiling of the mixture/solution containing oxalic acid and dilute sulphuric acid. This
could interfere the titration process and give wrong volume of KMnO4
Contamination of the equipments used in the analysis process.
-Decomposition of oxalic acid during the heating Period

(G) CONLUSION:
Percentage of mass Manganese (Mn2+) obtained in the pyrolusite ore was 53.69%
The obtained a mass percentage of manganese in the pyrolusite ore is large enough to
allow the extraction of manganese from the pyrolusite ore. Thus pyrolusite is seen to be
dominant/chief manganese ore.

(H) REFERENCES
➢ Internet (Google):Ask.com
➢ ANAND S.DAS S.C.,DAS R.P.,JENA P.K.,1980,Leaching of manganese nodules at
elevated temperature and pressure in the presence of oxygen
pressure,Hydrometallurgy,20,155-168.
 ANSWERS TO THE GIVEN QUESTIONS
Problem 1.
A 0.2250g sample of a mixture contain only of iron and ferric oxide (Fe2O3) was
brought into solution and the iron was reduced to divalent state with permanganate. If
37.50ml of 0.02M permanganate was required, calculate the percentage of iron and Fe2O3
in the sample.

Solution
Redox reaction is
5Fe2+ + MnO4- + 8H+ ―> 5Fe3+ + Mn2+ + 4H2O
Mass of the ore = 0.2250g
Volume of KMnO4 = 37.50ml
Morality of KMnO4 = 0.02M
From the relation
Number of moles = Mass of the sample
Molar mass of the sample
Molar mass of Fe2O3 = 56x2 + 16x3 = 160g/mol
Then, number of moles of Fe2O3 = 0.2250g = 1.40625 10-3 moles
160gmol
0.02 moles of KMnO4 ―> 1 litre
―> 37.50 10-3 litres
= 7.5x10-4 moles of KMnO4 used
From the redox reaction above
5 moles of Fe2+ ―> 1 mole of KMnO4
? ―> 7.5x10-4 moles of KMnO4
= 5x 7.5x10-4 = 3.75x10-3 moles of Fe2+ was used
Mass of Fe2+ = 3.75x10-3 x 56 = 0.21 g
Percentage of Iron
= Mass of Iron in a sample x 100% = 0.21 x 100% = 93.33%
Mass of the sample 0.225
Percentage of iron ore is 100% - 93.33% = 6.67%
Therefore the percentage of Iron in the sample is 93.33% and the percentage of iron
ore in the sample is 6.67%
 Solution Qn. 2
Method for estimation of iron and iron ore:
Small amount of the sample that contains iron and iron ore is mixed with water to
form a solution. Then a known volume of the solution is taken into a volumetric flask and
mixed with a dilute hydrochloric acid HCL. This solution is then titrated against the
standard solution of Potassium permanganate KMnO4 in the presence of Zimmerman
Rein hard solution while noticing the colour change. Finally the volume of KMnO4 used
is taken. Since the morality of KMnO4 and its volume and the volume of the sample used
are known, then the amount of iron and iron ore in the sample can be estimated.

For proposal

J. P. Speirs, A. Anderton, and J. G. Anderson, “A study of the microbial content of the domestic kitchen,”
International Journal of Environmental Health Research, vol. 5, no. 2, pp. 109–122, 1995. View at Publisher · View
at Google Scholar · View at Scopus
J. E. Finch, J. Prince, and M. Hawksworth, “A bacteriological survey of the domestic environment,” Journal of
Applied Bacteriology, vol. 45, no. 3, pp. 357–364, 1978. View at Publisher · View at Google Scholar · View at
Scopus
J. T. Holah and R. H. Thorpe, “Cleanability in relation to bacterial retention on unused and abraded domestic sink
materials,” Journal of Applied Bacteriology, vol. 69, no. 4, pp. 599–608, 1990. View at Publisher · View at Google
Scholar · View at Scopus
J. Dufrenne, W. Ritmeester, E. Deffgou-van Asch, F. Van Leuden, and R. de Jonge, “Quantification of the
contamination of chicken and chicken products in the netherlands with Salmonella and Campylobacter,” Journal of
Food Protection, vol. 64, no. 4, pp. 538–541, 2001. View at Google Scholar
H. D. Kusumaningrum, G. Riboldi, W. C. Hazeleger, and R. R. Beumer, “Survival of foodborne pathogens on
stainless steel surfaces and cross-contamination to foods,” International Journal of Food Microbiology, vol. 85, no.
3, pp. 227–236, 2003. View at Publisher · View at Google Scholar · View at Scopus
T. Regnath, M. Kreutzberger, S. Illing, R. Oehme, and O. Liesenfeld, “Prevalence of Pseudomonas aeruginosa in
households of patients with cystic fibrosis,” International Journal of Hygiene and Environmental Health, vol. 207,
no. 6, pp. 585–588, 2004. View at Publisher · View at Google Scholar · View at Scopus
W. Tesfaye, B. Ketema, A. Melese, and S. Henok, “Prevalence and antibiotics resistance patterns of S. aureus from
kitchen sponge's,” International Journal of Research Studies in Biosciences, vol. 3, pp. 63–71, 2015. View at Google
Sch