Introduction/Theory:

Numerous techniques can be employed to determine the quantitative amount of a metal present in
an alloy, e.g. Colorimetric determination or Spectroscopic techniques, based on the different
oxidation state of the metal. For this experiment Visible Spectroscopy (see Figure 1) and the
standard addition method (i.e. a technique that compensates for the effect of the presence of other
metals other than the analyte) will be used to find out the manganese in steel.
Steel is an alloy that is made up of mainly of carbon where a metal like manganese can be added to
the steel’s matrix to increase the alloys hardness, strength and stiffness. The steel is first dissolved
in Aqua Regia, C + 2H2O + 2HS2O81- = 4HSO41- + CO2 + 2H1+ then ammonium peroxydisulfate

is added to the solution for the oxidation of carbon to CO2 . 2S2O8= + C + 2H2O ⃗
Δ

CO2 + 4HSO4- .This is done because in the steel sample there exist fine particles of carbon or iron

carbide whose existence when the MnO4- is formed, will as they reduce the MnO4- and scatter
some of the light, an effect which will be interpreted as light absorption. Following this oxidation
of the colourless Mn2+ ions to form the purple permanganate ion (MnO4 - ions), using KI04 5IO4- +

2Mn++ + 3H20 ⃗Δ 2MnO4- + 5IO3- + 6H+. The formation of this coloration allows the
spectroscopic method to be used to show the relationship the concentration of a species in solution
has to the amount of light it absorbs, i.e. the more intense the colour, the higher the concentration.
Beer-Lambert’s Law (A= εCl ) is then applied to determine the concentration of Mn in steel, where
A = absorbance; ε = molar absorptivity in L/ (mole cm); l = cell path length in cm; c =
concentration in mole/L. As a result absorbance of an absorbing species is related to its
concentration. But at high concentration this relationship moves from a linear relationship to a
curve. In this experiment Beer’s law expands to: As= (ϵVxCx /Vt)+ (ϵVsCs/Vt)
A plot of As as a function of Vs produces a straight line:
As =mVs + b, where slope (m) =(ϵbcs) and intercept (b) = (ϵVxCx)/Vt
equating to Cx=bCs/ mVx
Another method is where two samples can be used where the addition of Vs mL of Standard Mn is
added to one of the two samples increments prior to the colour forming reagent is added to both
sample increments and the solutions made up to volume. Where;
A1 = (ϵVxCx)/Vt and A2 = (ϵVxCx/Vt) + (ϵVsCs/Vt)
Resulting in: Cx =( A1csVs)/ (A2-A1)Vx Where: A1: absorbance of dilute sample 1; A2:absorbance of
dilute sample 2; Cs: known solution of standard Mn solution; Cx:Mn concentration ; Vs:variable
volume of standard Mn solution; Vt: volumetric flask volume; Vx: identical aliquots
 Figure 1: Schematic Diagram of a typical UV- Vis Spectrometer

Image taken from: Scribd- webpage: http://www.scribd.com/doc/10514205/Measuring-Manganese-

Concentration-Using-Spectrophotometry [accessed 28/03/10]

Experimental:

Carried out as stated in lab manual with the following modifications (solutions used from Expt: 6 -
Determination of Manganese in Steel by Visible Spectroscopy) where:

(i) Rinsing of steel turnings to clean oils off with acetone and dry briefly in an oven at >
50ᵒC was NOT done, as this was carried out by lab technicians

(ii) Masses of steel replicates where between 0.05-0.1g instead of the 1.0-2.0g stated

(iii) 5ml of Aqua Regia was used instead of 10ml, also NO overnight pre-digestion was
done.

Results:
Table#1: (Taken from Experiment:6 Determination of Manganese in Steel by Visble Spectroscopy)
Showing masses of the watch glasses and the steel turnings used in experimentation, with numbered
boiling tubes and their respective steel turning masses

Boiling tube number

1 2 3 4

Mass of empty watch 47.9284g 48.2174g 47.9284g 48.2174g

glass

Mass of watch glass + 48.0280g 48.3108g 48.0241g 48.2174g

steel turnings

Mass of steel turnings 0.0998g 0.0934g 0.0957g 0.0000g

Table#2: Showing the Absorbance’s of Sample’s 1,2 & 3

Wavelength of Spectrophotomer = 525nm

Absorbance
Aliquot
Sample 3 (Blank) Sample 1 Sample 2

A 0.00 0.010 0.069

B 0.00 0.077 0.128

C 0.00 0.026 0.121

0.1124g/L of steel was used as the sample to be analysed.

Treatment of Results:
Using the equation: Cx =( A1csVs)/ (A2-A1)Vx
For Sample A
Cx =( 0.010 ×0.1124×2.5×10-3)/ (0.069-0.010) 25×10-3
= 2.8100×10-6/2.360
=1.2 ×10-6 μgL-1

For Sample B
Cx =( 0.077×0.1124×2.5×10-3)/ (0.128-0.077) 25×10-3
= 2.1637×10-5/2.04
=1. 1×10-5μgL-1

For Sample C
Cx =( 0.026×0.1124×2.5×10-3)/ (0.121-0.026) 25×10-3
= 7.3060×10-6/3.80
= 1. 9×10-6 μgL-1

Table#3: Showing values for calculation of Cx for Samples A, B & C

A B C

A1 0.010 0.077 0.026

A2 0.069 0.128 0.121

Cs (gL-1) 0.1124 0.1124 0.1124

Vs (L) 2.5×10-3 2.5×10-3 2.5×10-3

Vx (L) 25×10-3 25×10-3 25×10-3

Cx (μgL-1) 1.2 ×10-6 1. 1×10-5 1. 9×10-6

Determination of the Mn concentration for replicates A, B & C

For Sample A
1.2 ×10-6 μg is contained in 25×10-3 L
Therefore 250 ×10-3will contain 1.2 ×10-6× 10 = 1.2 ×10-5μg
Concentration in Sample A replicate =1.2 ×10-5μg /0.0998g
= 1.2×10-4μg /g
For Sample B
1. 1×10-5μg is contained in 25×10-3 L
Therefore 250 ×10-3will contain 1. 1×10-5μg × 10 = 1. 1×10-4μg
Concentration in Sample A replicate =1. 1×10-4μg /0.0934g
= 1.1×10-3μg /g

For Sample C
1. 9×10-6 μg is contained in 25×10-3 L
Therefore 250 ×10-3will contain 1. 9×10-6 μg × 10 = 1. 9×10-5 μg
Concentration in Sample A replicate =1. 9×10-5 μg/0.0957g
= 1. 9×10-4 μg/g

Mean concentration, x̄ =Ʃxi /n

Mean concentration, x̄ = (1.2×10-4μg /g + 1.1×10-3μg /g + 1. 9×10-4 μg/g)/3
Mean concentration, x̄ = 4.7×10-4μg /g

xi (xi- x̄) (xi- x̄)2

1.2×10-4 -3.5×10-4 1.22×10-7
1.1×10-3 6.3×10-4 3.96×10-7
1. 9×10-4 -2.8×10-4 7.8×10-8
Totals 1.41×10-3 0 5.96×10-7

Std dev.(s) Of Mn Concentrations

s = ❑√ Ʃ ¿ ¿
s = 5.467×10-4

Mn Concentration=4.7×10-4± 5.467×10-4
Correlation of variance = (s/ x̄)×100
=(5.467×10-4/4.7×10-4)×100
=116%
Conclusion/Discussion :
This lab has shown how spectroscopy techniques can be used to determine the concentration on Mn
in Steel, of which was found to be 4.7×10-4± 5.467×10-4. The manganese content of most steels is
quite low (<1%). It is therefore difficult quantitatively to analyze for Mn in the presence of small
amounts of steel by purely chemical techniques. Looking at the figures attained, one can safely say
that the used of two weeks old solutions definitely affect the final result as the CV was found to be
116%, when a 5% value would have been tolerable. Another factor that may have added to such an
outcome was the fact that not overnight predigesting was preformed. During the reaction it was
noticed heating of the solution produced a colour change of light green to pink. This occurred since
the phosphoric acid reducing Fe(III)to an iron phosphate complex releasing the pink colour of the
permanganate. Overall this experiment is not without its fair share of errors, these source of error
can all be minimised/ eliminated by the following (i) Measurement errors: can be minimized and
some types eliminated on the whole by careful experimental design and control, (ii) experimenter /
lab tech/ Forgetting to include indicator/ setting the spectrometer at an incorrect wavelength value
error: can be reduced by careful observation and record keeping, equipment maintenance and
training of laboratory personnel (iii) fluctuations in measured quantities- random error can also be
minimized by careful experimental design and control.

Answers to Questions:
a) Linearity of response will affect the accuracy of the determination of the Mn present in the
 sample as a straight line assumes that the plot is linear and there is no curvature, i.e. only an
average is taken. This causes the gradient of the line to differ from what it actually might be.
In the case a polynomial line should be applied and its gradient use as I will give the best for
such a case

b) In this experiment a blank solution was not needed as Sample 3(reference solution) acted as
a blank as no colour producing reagent was added to allow for the purple colour formation
of the manganese ion. Also because Sample 3 contained only the “impurities”, when placed
in the instrument an absorbance is taken, the instrument is then adjusted to zero absorbance
with the Sample 3, thereby using the instrument to subtract the absorbance of the impurity.
Then the absorbance indicated for the Samples 1 & 2 will be only the absorbance of the
species

c) Matrix effects due to extraneous species in the sample that are not present in the standards
or blank can cause the same analyte concentrations in the sample and standards to give
different responses. Differences in experimental variables at the times at which blank,
sample, and standard are measured can also invalidate the established calibration function.
Even when the basic assumption is valid, errors can still occur owing to contamination
during the sampling or sample preparation steps. The method i.e. the standard addition
method is often helpful in counteracting matrix effects.

References:
1. CHEM 2460 Principles of Chemical Analysis Laboratory Manual.pg 17-21
2. James N Miller & Jane C Miller, “Statistics and Chemometrics for Analytical” Chemistry,
5th Ed(2005) Publ. Pearson Education Limited pg 114
3. Absorption Spectroscopy and Mn Analysis- Webpage: http://www.kzoo.edu/pfolio
/archive/example/weigandt/ChemLabReport.html [Accessed 28/03/10]

4. Experiment 8: Determination Of Manganese In Steel By Absorption Spectrophotometry –

Webpage: http://www.chem.utk.edu/~chem319/Experiments/Exp8.pdf[Accessed 28/03/10]