Laboratory Report

Full Laboratory Report

SIC2022 Basic Analytical Chemistry

Experiment No: 5
Title: Spectrophotometric Determination of Manganese in Steel
Name: Sharvani A/P Karthigesu
Matric number: U2103660/1
Name of Partners: 1. Low Ru Yi
2. Nur Eillia Shuhada Binti Ab Rahman
Date: 1/11/2022
Objective

1. To determine the calibration curve of permanganate ion in steel sample by

spectrophotometric method.
2. To quantitatively determine the percentage of manganese in steel sample
from the permanganate ion, MnO4-.

Introduction

Steel is an alloy mainly composed of iron, with a carbon content between 0.02 % and
1.7 % by weight, depending on grade. Plain carbon steel contains a certain amount of
carbon, silicon, sulphur, phosphorus and manganese. There are also other alloying
elements such as chromium, vanadium, molybdenum, tungsten, titanium, nickel,
cobalt, zirconium and copper which are added to achieve specific properties. The
physical properties of steel depend highly on the content of these elements. Varying
the amount of alloying elements and their distribution in the steel controls qualities
such as the hardness, elasticity, ductility, and tensile strength of the resulting steel.
For instance, all commercial steels have manganese as an alloy, which greatly
enhances steel's strength and hardness in a similar way to carbon but to a lower extent.
Typically, the concentration of manganese in steel ranges from 0.20 to 2.00% (Mar,
2017). Thus, the quantitative analysis of these elements is of great practical
importance in order to study the physical properties of steel.

In this experiment, the composition of manganese in steel is determined by

spectrophotometric method. Spectrophotometry is a method to measure how much a
chemical substance absorbs light by measuring the intensity of light as a beam of light
passes through sample solution. Every chemical compound absorbs, transmits, or
reflects light (electromagnetic radiation) over a certain range of wavelength. A
spectrophotometer can determine the concentration of a sample solution by
measuring the amount of photons (the intensity of light) absorbed after it passes
through sample solution.

In this experiment, UV spectrophotometer is used to determine the concentration of

purple coloured permanganate ion, MnO4- in steel sample. The UV spectrophotometer
is also used to determine the calibration curve by measuring the absorbance of a
series of standardised permanganate solution prepared.

Experimental Procedure

Part A Standardization of Permanganate with Oxalate

Potassium permanganate solution was standardized with sodium oxalate solution as

follows:

1. 1.6071g of sodium oxalate was weighed and diluted in a 250cm3

volumetric flask.
2. In a fume hood, 5cm3 of 5 mol dm-3 sulphuric acid was added to 25 cm3 of
the aliquot in a beaker to acidify it.
3. The mixture was warmed to 60°C and titrated with potassium
permanganate solution until a faint pink colouration persist for at least 30
seconds as shown in Figure 1.

Figure 1: Potassium permanganate solution after standardized with

sodium oxalate solution.

4. Step 2 and 3 were repeated two more times to obtain the mean reading for
three concordant titrations. Then, the concentration of potassium
permanganate solution was calculated.
Part B Determination of the Calibration Curve

1. 0.1ml of standard potassium permanganate solution was pipetted using a

1cm3 pipette into a 50 cm3 volumetric flask to obtain a solution with
concentration of approximately 2ppm.
2. The same step was then repeated to prepare standard solutions of 4ppm,
6ppm, 8ppm and 10ppm with 0.2ml, 0.3ml, 0.4ml and 0.5ml potassium
permanganate solutions respectively as shown in Figure 2.

Figure 2: Standard solutions of potassium permanganate of concentrations

2ppm, 4ppm, 6ppm, 8ppm and 10ppm (right to left).

3. The absorbance of these 5 solutions was measured with a spectrophotometer

with the wavelength set at 525 nm by using distilled water as the blank.

Part C Determination of manganese in steel

*This part of the experiment was carried out fully in the fume hood.

1. Two steel samples(sample A and sample B) of mass 0.2046 g and 0.2010 g

were weighed in 150 cm3 beakers.

2. 30 cm3 of 1:1 nitric acid was added into both beakers; beakers were covered
with watch glass.

3. The samples were heated to dissolve the alloy and then were let to boil gently
for a few minutes to expel oxides of nitrogen.
 4. 1g of ammonium peroxydisulphate was added to both sample solutions and
they were let to boil for 15 minutes.

5. The solutions were cooled down and diluted in 100 cm3 volumetric flasks.

6. Two 25 cm3 of each aliquots were pipetted into small beakers and 5 cm3 of
phosphoric acid was added into each beaker.

7. In one of the beakers containing aliquot A, 0.5014 g of KIO4 was added

whereas the second aliquot was not treated with periodate as it served as blank.
Similar action was done for one of the beakers containing aliquot B with 0.5043 g
of KIO4.

8. The aliquots were boiled for 5 minutes and cooled to room temperature. Each
aliquot was diluted in 50 cm3 volumetric flask with distilled water.

9. The absorbance of the solutions and the blanks were measured using a
spectrophotometer with wavelength set at 525 nm by using distilled water as the
reference solution.

Results and Discussion

Part A Standardization of Permanganate with Oxalate

Molarity of Sodium Oxalate solution:

Mass of Na2C2O4 = 1.6071 g

Relative molecular mass of Na2C2O4

= 22.99(2) + 12.01(2) + 16.00(4)

= 133.98 g mol-1

Mass of Na2C2O4
No. of mole of Na2C2O4 =
RMM of Na2C2O4

1.6071 g
= 133.98 g mol-1

= 0.011995 mol

No. of mole of Na2C2O4

Molarity of Na2C2O4 = Volume of Na C O
2 2 4 Solution
 0.011995 mol
= 0.250 𝑑𝑚3

= 0.04798 mol dm-3

Table 1: Burette reading for the standardization of KMnO4 solution with Na2C2O4
solution.

Volume
No. of Titration Initial reading/cm3 Final reading/cm3
used/cm3
1 3.60 27.95 24.35
2 0.85 25.70 24.85
3 16.18 41.20 25.02

Concentration of manganese in potassium permanganate solution:

24.35 + 24.85 + 25.02

Average volume of KMnO4 used = cm3
3

=24.74 cm3

Based on the reaction equation,

5C2O42- + 2MnO4- + 16H+ → 2Mn2+ + 10CO2 + 8H2O

It is noted that:

M1 = molarity of C2O42- solution.

M2 = molarity of MnO4- solution.
V1 = volume of C2O42- solution.
V2 = volume of MnO4- solution.
𝑀1 𝑉1 5
=2
𝑀2 𝑉2

0.04798 ×25.00 5
=2
𝑀2 ×24.74

M2 = 0.01939 mol dm-3

Thus, the concentration of MnO4- solution is 0.01939 mol dm-3.

The concentration of Mn in MnO4- solution

= 0.01936 mol dm-3 x 54.94 gmol-1

= 1.065 g dm-3

= 1065 mg dm-3

Thus, the concentration of Mn in MnO4- solution is 1065 mg dm-3.

Part B Determination of the Calibration Curve

Table 2: Concentration of MnO4- and absorbance.

Standard Volume of std. Concentration of Mn /

Absorbance /A
No. KMnO4 /dm-3 mg dm-3
1 0.10 2.13 0.08689
2 0.20 4.26 0.16523
3 0.30 6.39 0.27437
4 0.40 8.52 0.3582
5 0.50 10.65 0.46205

It is noted that,

M1 = molarity of Mn in MnO4- solution before standardization.

M2 = molarity of Mn in MnO4- solution after standardization.
V1 = volume of MnO4- solution before standardization.
V2 = volume of MnO4- solution after standardization.

M1V1=M2V2

For standard 1,

1.065 𝑔 𝑑𝑚−3 ×0.10 𝑑𝑚−3

M2 = 50 𝑑𝑚−3

= 0.00213 g dm-3

= 2.13 mg dm-3
*The formula above is assigned to calculate the concentration of Mn in the other four
standard solutions of MnO4-.

Absorbance against concentration of Mn y = 0.0443x - 0.0136

R² = 0.9977
0.50
0.45
0.40
0.35
Absorbance/A

0.30
0.25
0.20
0.15
0.10
0.05
0.00
0 2 4 6 8 10 12
Concentration of Mn (mg/dm-3 )

Figure 1: Graph of absorbance against concentration of Mn

Part C Determination of Concentration and Percentage of Manganese in Steel

Mass of steel sample A = 0.2046 g

Mass of steel sample B = 0.2010 g

Mass of KIO4 for sample A = 0.5014 g

Mass of KIO4 for sample B = 0.5043 g

Table 3: Concentration of Mn in steel sample and its absorbance.

Type of solution Concentration of Mn / mg/dm3 Absorbance/A

Sample A 4.5549 0.1881

Sample B 4.4531 0.1837

 A BSO RBA NCE AG A I NST CO NCE NT RAT I O N O F MNO 4 -
0.50
0.45
0.40
0.35
ABSORBANCE

0.30 y = 0.0443x - 0.0136

R² = 0.9977
0.25
0.20
Std. sol
0.15
Steel
0.10
Linear (Std. sol)
0.05
0.00
0 2 4 6 8 10 12
CONCENTRATION OF MNO4- (MG/L)

Figure 2: Graph above shows absorbance against concentration of Mn in steel

sample relative to the absorbance of standard solutions.

The graph above shows a direct relationship between absorbance and concentration
which is the calibration plot. The linearity of calibration plot roots from the Beer’s Law
which states that absorbance of light by a compound is directly proportional to its
solution concentration. Therefore, the concentration of manganese can be calculated
by using Beer’s law.

A = 𝜀lc

By substituting in general form y=mx + c, we can see that slope m = 𝜀l.

From the graph plotted we know that y = 0.0443x - 0.0136 whereby x is the
concentration of MnO4- while y is the absorbance.

For sample solution A,

0.18812 = 0.0443x -0.0136

x = 4.55485

The sample solution is being diluted from 25cm3 to 50cm3.

Therefore, the concentration of Mn in 25cm3 , M2 is calculated as:

 M1V1=M2V2

M1 = molarity of MnO4- solution before dilution.

M2 = molarity of MnO4- solution after dilution.
V1 = volume of MnO4- before dilution.
V2 = volume of MnO4- solution after dilution.

4.55485 𝑚𝑔 𝑑𝑚−3 ×50.00 𝑐𝑚

M2 = 25.00 𝑐𝑚

= 9.1097 mg/dm3

= 0.0091097 g/dm3

= 0.01 g/dm3

In 100 cm3 of solution contain 0.2046 g of steel, steel in 25 cm 3 sample solution A is

0.2046 𝑔 ×25 𝑐𝑚3

= 100 𝑐𝑚3

= 0.0512 g

Then the steel is being diluted from 25 cm3 to 50 cm3, the concentration of steel in 50
cm3 solution is

1000
= 0.0512 g × dm-3
50

= 1.023 g/ dm-3

Percentage of manganese in steel for sample A is

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑀𝑛
= 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑡𝑒𝑒𝑙 × 100%

0.01
= 1.023 × 100%

= 0.9775 %

=0.98%
For sample solution B,

0.18367 = 0.0443x -0.0136

x = 4.45305

Therefore, the concentration of Mn in 25cm3 , M2 is calculated as:

M1V1=M2V2

M1 = molarity of Mn in MnO4- solution before dilution.

M2 = molarity of Mn in MnO4- solution after dilution.
V1 = volume of MnO4- before dilution.
V2 = volume of MnO4- solution after dilution.
M2 =
4.45305 𝑚𝑔 𝑑𝑚−3 ×50.00 𝑐𝑚
25.00 𝑐𝑚

= 8.9061 mg/ dm-3

= 0.0089061 g/ dm-3

= 0.0089 g/ dm-3

In 100 cm3 of solution contain 0.2010 g of steel, steel in 25 cm3 sample solution B is

0.2010 𝑔 ×25 𝑐𝑚3

= 100 𝑐𝑚3

= 0.05025 g

Then the steel is being diluted from 25 cm3 to 50 cm3, the concentration of steel in 50
cm3 solution is

1000
= 0.0503 g × dm-3
50

= 1.01 g/ dm-3

Percentage of manganese in steel for sample B is

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑀𝑛
= 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑡𝑒𝑒𝑙 × 100%

0.0089
= × 100%
1.01
 = 0.8811%

0.9775%+0.8811%
Average percentage of manganese in steel = 2

= 0.9293%

= 0.93%

In part A of the experiment, potassium permanganate solution was standardized with

sodium oxalate solution in order to find out the concentration of Mn from MnO4-. The
oxalate anion reduces permanganate to manganese(II). The sodium oxalate solution
was acidified with sulphuric acid because dilute sulphuric acid prevents hydrolysis and
provides surplus H+ ions in the solution to keep the reaction active. It is also neither
an oxidizing agent nor an reducing agent. Meanwhile, sodium oxalate is weak acid
and as a result it is not able to provide the required acidic medium and enough H+
ions to keep reaction going. The reaction equation is shown below:-

2MnO4- + 16H+ + 5C2O42- -> 2Mn2+ + 8H2O + 10CO2

Other acids like nitric acid or hydrochloric acid are not used for this acidification
process because they are strong oxidizing agents which may interfere with the result
of titration as KMnO4 is an oxidizing agent as well. Meanwhile, dilute sulphuric acid
would not interrupt the titration result by causing a decline in the value of KMnO4 used
(McBride, 1913). The acidification was followed by heating up the sodium oxalate to
60°C to speed up the rate of decolourization during titration as temperature increases
the rate of reaction.

As for the determination of manganese in steel, 1:1 nitric acid was added to steel
samples to dissolve the steel and to oxidize Mn to Mn2+ ions. The chemical equation
is shown below:-

3Mn + 2NO3- +8H+ ⇌ 3Mn2++ 2NO + 4H2O

However, a greenish brown nitrogen oxide gas is released. It may interfere with
periodic acid to reduce it later in the experiment. So, in order to eliminate the nitrogen
oxide formed, a strong oxidising agent, ammonium peroxydisulphate is added. The
chemical equation is as follows:
 2𝑁𝑂2(𝑔) + 𝑆2𝑂 82− (𝑎𝑞) + 2𝐻2𝑂(𝑙) → 2𝑁𝑂3− (𝑎𝑞) + 2𝑆𝑂42− (𝑎𝑞) + 4𝐻 + (𝑎𝑞)

Ammonium peroxydisulphate oxidises oxides of nitrogen and any other organic matter
present such as carbon (Vedantu, 2022). Then, the sample solution is boiled for 15
minutes to decompose the ammonium peroxydisulphate that is unreacted.

2𝑆2𝑂 82− (𝑎𝑞) + 2𝐻2𝑂(𝑙) → 4𝑆𝑂42− (𝑎𝑞) + 𝑂2(𝑔)) + 4𝐻 + (𝑎𝑞)

During the heating process, there were some brown precipitate observed which were
deposits of manganese oxides. To remove it, sodium bisulphate was added. Sodium
bisulphate reduces manganese oxides into manganese ions.

𝑀𝑛𝑂2 + 𝐻𝑆𝑂3 − + 𝐻 + → 𝑀𝑛2+ + 𝑆𝑂4 2− + 𝐻2 𝑂

The sample solution was boiled for another 5 minutes till no residue seen at the bottom
of beaker. A clear solution was obtained. Then potassium periodate was added to one
of the two aliquots of the sample and then boiled to oxidise manganese (II) ions into
permanganate ion which then turned the colourless solution to pink. This reaction was
carried out at the boiling point to increase the solubility of potassium periodate. The
reaction equation is shown below:

2𝑀𝑛2+ + 5𝐼𝑂4 − + 3𝐻2 𝑂 → 2𝑀𝑛𝑂4 − + 5𝐼𝑂3 − + 6𝐻 +

The other aliquot was set as the blank as it contains all the other compounds in it
except for the compound of interest which is manganese ion.

From graph 2, we can see it is proven that as concentration increases (darker solution),
more light is absorbed by the sample resulting in a linear graph. The concentration of
manganese in sample A and B falls within 4-6 mg dm—3 range in the calibration plot
of standard solution. We can see in figure 1 that, R2 = 0.9977 which is close to the
ideal calibration curve. There might have been some errors that could have occurred
while conducting this experiment. So, necessary safety precautions shall be taken to
obtain accurate measurements. We need to ensure that all the instruments are
calibrated with the solution to be filled in prior to measurement to avoid dilution of
chemicals. Titration must be repeated several more times to obtain a more accurate
reading. Next, we need to be cautious when handling the chemicals to avoid any
spillage or contamination. Mainly, when heating the sample solution, nitrogen dioxide
gas which is harmful to our respiratory system is released. So, it is a must to handle
reactions involving nitric acid in fume chamber. While handling spectrophotometer, the
cuvette must be calibrated each time the absorbance is measured. The cuvette must
be wiped with tissue to remove any fingerprint or dirt adhered to the surface of it prior
to measurement. We must also make sure that there are no air bubble in the sample
in cuvette.

Conclusions

A linear calibration curve is obtained and concentration of manganese in steel falls

within the range of calibration curve. The percentage of manganese in steel obtained
is 0.93%. It was determined quantitatively by spectrophotometric method by finding
the average percentage of manganese in two similar samples.

Question and Answer

1. After going through the experiment, explain what is calibration plot.

What is the role of the calibration plot in the chemical analysis?
Calibration plot is a linear plot with x axis as the Concentration /mg L-1 and y
axis as the Instrument response. A linear regression is established to describe
the linear relationship between instrument response and concentration which is
best shown as the equation y=mx+c. y-coefficient of determination(R2)
quantifies a good fit if R2 is 1.00. (Azadeh et al., 2017)

In chemical analysis, calibration plot is a method used to determine the

concentration of a substance in an unknown sample by comparing the unknown
to a set of standard samples which are within a range of known concentration.
The data are then fit with a function to enable the prediction of unknown
concentrations.

2. Explain in brief, what is colorimetric analysis.

Colorimetric analysis is a method of determining the concentration of a
chemical compound in a solution with the aid of coloured reagent. The
absorbance between set of standards within a range of known concentration is
compared to the sample using a calibration curve to determine the sample
 concentration with the aid of a colouring reagent added to the samples. The
higher the concentration the darker the colour(high absorbance).

3. Define spectrophotometry.
Spectrophotometry is a method that uses both quantitative and qualitative
analysis to measure light absorption or the amount of particular compound of
interest in a solution. When light beam is passed through a sample solution,
each compound in the solution absorbs or transmits light over a certain
wavelength. Spectrophotometry is measured by a spectrophotometer which
consist of two main instruments which are the spectrometer and a photometer.
The spectrometer produces light beam while the photometer measures the
intensity of light by measuring the amount of light that passes through the
sample solution. It also consist of other main components such as light source,
monochromator, sample cuvette detector and recorder.

4. What is the purpose of measuring blank?

Blank is a solution containing all the compound in the sample to be analyzed
except for the sample of interest to allow the instrument to zero the
background readings and only report the values for the compound of our
interest.

5. Describe in brief, what is sample preparation in analytical chemistry.

Sample preparation refers to the way a sample is treated before being
analysed whereby a small part is extracted from a larger amount of a material.
Some of the sample preparation techniques involve dissolution, extraction,
filtering and dilution. These preparations are necessary to prepare the sample
into a form that is ready to be analysed by specified analyte equipments.

References

Mar, E. (2017). Chemical Composition of Steel. TECH MATTERS BAILEY METAL

PROCESSING LIMITED - PRODUCTS. Retrieved November 3, 2022, from
 http://www.baileymetalprocessing.com/techmatters/blog-category-
1/2017/09/28/chemical-composition-of-steel

McBride, R. S. (1913). Standardization of potassium permanganate solution by

sodium oxalate. Bulletin of the Bureau of Standards, 8(4), 611.
https://doi.org/10.6028/bulletin.198

Azadeh, M., Gorovits, B., Kamerud, J., MacMannis, S., Safavi, A., Sailstad, J., &
Sondag, P. (2017). Calibration curves in quantitative ligand binding assays:
Recommendations and best practices for preparation, design, and editing of
Calibration Curves. The AAPS Journal, 20(1). https://doi.org/10.1208/s12248-
017-0159-4

Colorimetric Analysis (3). 4. Hitachi High-Tech GLOBAL. (n.d.). Retrieved November

5, 2022, from https://www.hitachi-
hightech.com/global/products/science/tech/ana/uv/basic/course4.html

Vedantu. (2022). Ammonium persulfate. VEDANTU. Retrieved November 5, 2022,

from https://www.vedantu.com/chemistry/ammonium-persulfa