EXPERIMENT 3

COMPLEXOMETRIC TITRATION OF METAL ION

Name : Nisha Rata Karusan

Lecturer : Dr Tay Kheng Soo

Matrics Number : 17202843/1

TTILE:

Spectrophotometric Determination of Manganese in Steel

Objectives:

1. To understand and apply Beer’s Law in Spectrochemical analysis 2. To

determine spectrophotometrically manganese as permanganate ion, MnO4- in
steel

INTRODUCTION:

Carbon, silicon, sulphur, phosphorus, and manganese are all found in pure carbon
steel. Other elements such as chromium, vanadium, molybdenum, tungsten,
titanium, nickel, cobalt, zirconium, and copper are added in varying amounts for
special purposes. The content of these elements has a direct influence on the
physical properties of steel. Stainless steel, for example, contains a high amount of
chromium, which forms an invisible coating on the steel to avoid corrosion and
staining (Figure 1). As a consequence, quantitative analysis of these components is
highly useful.

Manganese (Mn) in carbon steel will be measured spectrophotometrically as the

purple color permanganate ion, MnO4 in this experiment. This is a standard and
effective method for measuring manganese concentrations in steel. A solution of
manganese (II) ions is obtained by dissolving the steel sample in nitric acid.
Manganese (II) is readily oxidized to permanganate by the periodate ion, which is
added as the potassium salt, KIO4. The equation is as following:

2Mn2+ + 5IO4-+ 3H2O --> 2MnO4- + 5IO3- + 6H+

The concentration of MnO4-, which reflects Mn2+, will be determined using a UV-Vis
spectrophotometer in this experiment. The UV-Vis spectrophotometric method for
determining the concentration of an analyte in solution is fast, simple, and
inexpensive. It can be used to conduct a quantitative analysis to assess the
concentration of analytes when the type of compound to be analyzed (‘analyte') is
known. A beam with a wavelength ranging from 180 to 1100 nm passes through a
solution in a cuvette in UV-Vis. This UV (400 nm) or visible radiation (> 400 nm) is
absorbed by the sample in the cuvette. The amount of light absorbed by the solution
is determined by the concentration, the light's path duration through the cuvette, and
how well the light absorbs at a certain wavelength by the analyte. The concentration
of analyte can be measured using a UV-Vis spectrophotometer using the Beer
Lambert law. Figure 3 indicates that I0 is always greater than I. The value of I
decreases as the concentration of the solution increases (darker solution), resulting
in an increase in the value of absorbance (A). The absorbance (A) is proportional to
the concentration of analyte, according to the Beer-Lambert law (c).

The calibration curve is used to assess the concentration of analyte in a sample for
quantitative analysis. A calibration plot can be made by making a series of standard
solutions with a variety of concentrations and using a UV-Vis spectrophotometer to
calculate the absorbance (A) of each standard solution. The permanganate solution
can be standardized first using a primary standard, sodium oxalate, to improve
measurement accuracy. In acid solution at 60-70°C, the oxalate anion, C2O42-,
reduces permanganate to manganese (II) according to the equation:

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

EXPERIMENTAL PROCEDURES:

(A)Standardization of Permanganate with Oxalate (conduct in fume hood)

An approximately 1.000 g Mn dm-3 solution was supplied. The solution was

standardized with oxalate solution as follows:

i. About 1.6 g of sodium oxalate was weighed out and made up to 250 cm3
in a standard flask.
ii. In a fume hood, a 25 cm3 aliquot was acidified with 5 cm3 of 5 mol dm-3
sulphuric acid. The mixture was warmed up to 60-70℃ and titrated with
potassium permanganate until a faint pink coloration persists for at least
30 seconds.

From the mean of three concordant titrations, the concentration of the potassium
permanganate solution was calculated.

(B)Determination of the Calibration Curve

The standard potassium permanganate solution was diluted accurately and a series
of five standards was prepared which give an absorbance range between 0.1 to 0.9.
The absorbance of these five solutions were measured using a spectrophotometer
set at 525 nm. Water was used as the reference solution.

(C) Determination of manganese in steel

i. Duplicate (i.e. x 2) sample was accurately weighed out (approx. 0.2 g) of the
steel sample into 150 cm3 beakers.

ii. The beaker was covered with watch glass and 30 cm3 of 1:1 nitric acid was
added.
iii. The solution was warmed to dissolve the alloy (add further nitric acid if
necessary) and then heated to gentle boiling for a few minutes to expel oxides
of nitrogen.
iv. About 1 g ammonium peroxydisulphate was added cautiously and boiled for
 10-15minutes. When the solution is pink or contains brown oxide of
manganese
(as a deposit of MnO2) about 0.1g sodium bisulphate was added and heated
for 5 minutes.
v. The watch glass was cooled, rinsed down and the solution was transferred
quantitatively to a 100 cm3 volumetric flask and diluted to the mark with
distilled water.
vi. Two 25 cm3 aliquots of the sample solution was pipetted into small beakers and
5 cm3 of phosphoric acid was added.
vii. 0.5 g KIO4 was added to one of the two aliquots and the solution was boiled for
5 minutes.
viii. The second aliquot is not treated with periodate and served as the blank. ix. The
solution was cooled to room temperature. Each aliquot was transferred quantitatively
to a 50 cm3 volumetric flask and diluted to the mark with distilled water.

The absorbance of the solution and the blank was measured using distilled water as
the reference solution.

RESULTS AND CALCULATIONS:

Table 2: Results from the analysis of standard solution for calibration
Concentrati Absorbance(A)
on of
Mn(mgdm 3)

2.022 0.1404

4.044 0.2163

6.066 0.3087

8.088 0.3824

10.11 0.4874
 R² = 0.9968
0.4

0.3

0.2

Absorbance 0.1
Graph Of Absorbance against
0
Concentration0.6 0 2 4 6 8 10 12 Concentration of
Mn(mgdm-3)
0.5

y = 0.0425x + 0.049
Questions:

1. After going through the experiment, explain what is calibration plot. What is
the role of the calibration plot in the chemical analysis?

One of the most important procedures for maintaining instrument accuracy is

instrument calibration. Calibration is the process of setting up an instrument so that it
can produce a result for a sample that is within a reasonable range. Calibration
curves are often used to determine the instrumental response to an analyte and to
predict the analyte concentration in a sample. Preparing a set of standard solutions
with known analyte concentrations is the first step in creating a calibration curve.
 2. Explain in brief, what is colorimetric analysis.
As a wavelength is passed through a sample, some of the light is absorbed and
some passes through, and colorimeters are used to detect colour and determine the
concentration of the solution. The wavelengths of light passing through are the ones
that are observed. The detector will determine which coloured wavelengths were
absorbed by knowing which wavelengths passed through. If the solution to be tested
is colourless, introducing a reagent that interacts with the solution to create a
coloured solution is a normal practice. The results are compared to existing
standards. The wavelength absorbance is detected by the colorimeter using the
Beer-Lambert law. The rule of Beer-Lambert is generally written as:

A= Ɛcl

Where A is the absorbance, (epsilon) is the molar absorptivity, c is the solution

concentration, and l is the duration through which the light passes (also known as
the mean free path). Aside from that, if the solution is constantly changing, such as
during a reaction, percent of transmittance against time is commonly used. The
amount of light absorbed to determine concentrations is proportional to the amount
of solute (also known as the analyte because it is the species being measured) in the
solution: a higher concentration of dissolved solute means more light would be
absorbed, and vice versa; thus, the concentration can be backed out from the
absorption of specific wavelengths.

3. Define spectrophotometry.
Spectrophotometry is a technique for determining how much light a chemical
material absorbs by calculating the strength of light moving through a sample
solution. Each compound absorbs or transmits light over a specific wavelength
spectrum, according to the basic principle. This calculation can also be used to
determine how much of a known chemical material is present. In fields such as
chemistry, physics, biochemistry, material and chemical engineering, and clinical
applications, spectrophotometry is one of the most useful methods of quantitative
research.
4. What is the purpose of measuring blank?
As a reference point, the blank solution is used. It has no analyte of interest. It was
not injected with KIO4 in this experiment. It prevents the solution from containing the
periodate ion, resulting in the manganese(II) remaining unchanged. Manganese(II) is
converted to manganese(VII) in the form of permanganate in the presence of
periodate ion. It also means that it is oxidized. As a result, the blank solution is only
used to compare absorbance and colour.
5. Describe in brief, what is sample preparation in analytical chemistry. Sample
preparation is a process of extracting larger amount of representative piece of
material into small amount that is needed and making it ready for the analysis

Conclusion

The concentration of MnO4 from the calibration curve in sample A and sample B is
3.54 gdm-3 and 3.64 gdm-3respectively. And the average percentage of the Mn in
steel is 36%.

References

Stone, J. O. (2021, January 29). Spectroscopy. Retrieved March 23, 2021, from
https://www.britannica.com/science/spectroscopy

Calibration curves. (n.d.). Retrieved March 23, 2021, from

https://www.jove.com/v/10188/calibration-curves
Blank (solution). (2021, March 14). Retrieved March 23, 2021, from
https://en.wikipedia.org/wiki/Blank_(solution)#:~:text=A%20blank%20solution
% 20is%20a,instruments%20such%20as%20a%20colorimeter