Experiment No.

6: Spectroscopy
Arianne May Balaoing
Jana Beatriz Erlano
Raissa Athena Ortiz
Group#1 Chem 27.1 WEJ3 Maam Fatima Joy Cruz
Date Submitted: Saptember 28, 2011

I. Abstract
Spectroscopy is the study of the interaction of matter and radiation. There are many types of
spectrochemical methods, but the one that is applied in the experiment is absorption spectroscopy,
because it measures light as a function of wavelength. A spectrophotometer was used to determine the
absorbency at certain wavelength of the potassium permanganate and potassium dichromate solutions,
which in this experiment, are 545 and 440 nm. Using absorption spectroscopy, the concentrations of
Manganate and Chromium ions in the mixture were known and they were founded to be 13.63 ppm with
3.34% error, and 34.44ppm with 10.26% error, respectively.

II. Keywords: Spectroscopy, Beers Law, Absorbance, Wavelength, Spectrophotometer, Molar Absorptivity
III. Introduction permanganate ions at these wavelengths would
be the sum of the absorbances of the two species
Spectroscopy pertains to the interactions of provided there is no rection between the solutes.
radiation and matter. It basically aims to measure Hence:
the amount of radiation emitted or absorbed by a (2)
molecular or anatomic species. It is particularly [ ] [ ] (3)
useful in the determination of concentration of [ ] [ ] (4)
elements in alloy steel so as to predict its
mechanical properties and resistance to corrosion. It is desirable that the wavelengths are such that
This experiment used simultaneous the ratio of molar absorptivities is largest. The
spectrophotometric determination of two solutes in concentrations follow:
a solution, chromium and manganese, in
accordance to Beer-Lamberts Law [ ]
(1)
(6)
[ ]
where , absorption measured at wavelength ;
, molar abrsoptivities at wavelength ; b, amount
[ ]
of em radiation impinging on surface
(rad/area/time) or cell path length (cm); and C, (7)
[ ]
concentration.

Upon dissolution of steel containing chromium and OR

manganese, we get these elements as their ions, [ ]
3+ 2+ [ ] (8)
Cr and Mn ions, respectively. Hence in
laboratory determinations, these are oxidised
respectively to such ions. The orange red coloured Since is constant, Beer-Lamberts is rewritten
dichromate shows maximum absorption ( ) at as . Beer-Lamberts plot of Concentration
440 nm while for the pink coloured permanganate (C) vs. Absorbance ( evaluates the values of
is at 545 nm. However, permanganate also molar absorption coefficients 1 and 2 as a co
absorbs at 440 nm to a smaller extent similarly as
dichromate ions also absorbs at 545 nm. Direct Absorbances derived from Beers Law or simply
determination of both species in the presence of measured by spectrometers are also useful in
the other is made difficult since their spectra deriving the transmittance (T) or the fraction of
overlap to some extent and there are no radiant energy transmitted when light has been
wavelength at which either of the ions do not made to pass through the sample at certain
absorb significantly. Thus, the absorption of the wavelength:
solution containing a mixture of dichromate and (9)

Chem27.1 Spectroscopy Page 1 of 6

 (10) V. Results and Sample Computations

(11)
(12)

wherein I is emergent or transmitted radiation and

Io is the incident radiation assumed to be 100%.

Spectroscopy is a complex art - but it can be very

useful in helping scientists understand how an
object like a black hole, neutron star, or
active galaxy is producing light, how fast it is
moving, and even what elements it is made of.

IV. Experimental Table 1 KCr2O7 at 440nm

A. Determination of Concentration Range for

Analysis of Potassium Permanganate in
Solution

One-tenth of a liter each of 0.001M KMnO4 and

0.001M K2Cr2O7 were prepared for the
experiment. This was done by weighing 0.01580g
of KMnO4 and 0.02942g of K2Cr2O7 and diluting
them to 100ml.

Ten solutions of each were prepared with varying

dilutions with water: 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, Figure 1 1 ppm Cr vs A at 440nm
6:4, 7:3, 8:2 and 9:1 proportions. r= 0.9980 m= 0.004370 y-int= 0.01498
The spectrophotometer was warmed up for 20
minutes. A reference blank with distilled water was
prepared and placed inside the instrument and the
absorbance was set to 0 and the transmission to
100%. Permanganate and dichromate absorbance
were measured under 545nm and 440nm. The
cuvette containing the sample was placed inside
the spectrophotometer and the absorbance of
each sample was measured.

B. Spectophotometric Determination of Mn and

Cr in a Mixture
Figure 1 2 ppm Cr vs T at 440nm

The absorbance of a 2:8 dilution of KMnO4 was

measured at 440nm and the 2:8 dilution of
K2Cr2O7 at 545 nm. The absorbance of an
unknown solution was measured at both 545 and
440 nm wavelengths.

Chem27.1 Spectroscopy Page 2 of 6

Table 2 KCr2O7 at 545nm Table 3 KMnO4 at 440nm

Figure 2 1 ppm Cr vs A at 545nm Figure 3 1 ppm Mn vs A at 440nm

r= 0.6324 m= 0.0001521 y-int=0.008182 r= 0.9445 m= 0.002249 y-int= 0.01149

Figure 2 2 ppm Cr vs T at 545nm Figure 3 2 ppm Mn vs T at 440nm

Table 4 MnO4 at 545nm

Chem27.1 Spectroscopy Page 3 of 6

 ppm Cr:

% T of Cr at 545:

% T of Cr at 440:
Figure 4 1 ppm Mn vs A at 545nm
r= 0.9991 m=0.04033 y-int=-0.02946
%T of Mn at 545:

%T of Mn at 440:

VI. Discussion

A. Determination of Concentration Range for

Analysis of Potassium Permanganate (and
Potassium Dichromate) in Solution
Figure 4 2 ppm Mn vs T at 545nm
For the determination of Concentration Range for
maximum, the absorbances at 545nm and 440nm
Weight KMnO4:
of different dilutions of pure solutions of Mn and Cr
=
were measured. Yet, only the absorbance of
potassium permangate at 545 and potassium
dichromate at 440 was much noted since greatest
Weight K2Cr2O7: absorbance of Mn and Cr is at 545nm and 440nm,
respectively.

From the Beer-Lamberts plot of Absorbance of

Mn at 545nm vs. Concentration (ppm) the slope is
2:8 Dilution of KMnO4: 0.040324982 and the y-intercept is -0.029454545
translating to:

ppm Mn: (-0.029454545)

Solving for the concentration x,

Absorbance of Mn at 545 therefore

3:7 Dilution of K2Cr2O7:

From the Beer-Lamberts plot of Absorbance of Cr

at 440nm vs. Concentration (ppm), the slope is
0.004370382 and the y-intercept is 0.014981818
translating to:

0.014981818
Chem27.1 Spectroscopy Page 4 of 6
Solving for the concentration x,
B. Spectophotometric Determination of Mn and
Cr in a Mixture
Beers Law requires the use of monochromatic
radiation and it is under the restraint that the linear
dependence of absorption and concentration
occurs. If 2 or more species in a sample absorb at
a specific wavelength, the instrument cannot
distinguish between the individual species; it can
only determine the total absorbance of the sample
as shown by equations 2, 3 and 4. In a
spectrophotometric analysis, these equations can
be developed from the equation 1.
The main concern of this experiment is the
determination of concentrations of manganese
and chromate in a sample. By measuring the
absorbance at two different wavelengths of a
solution containing both ions, it is possible to
simultaneously determine the concentration of
each ion in the solution. In simultaneous
determination of 2 species it is necessary to
generate 2 equations in order to determine the 2
unknown concentrations.
The 2 equations derived from the Beer-Lambert
Law which will allow the simultaneous
determination of potassium dichromate and
potassium permanganate are equations 3 and 4:
[ ] [ ] (3)
[ ] [ ] (4)
These equations require that the 4 molar
absorptivities, the length of pathway, and the total
absorbance be known to calculate the
concentrations. Since has been known to be
known to be constant, they can be treated as a
single entity, k, which can be derived from four
Beer-Lambert plot of Absorbance versus
Concentration, ppm. These plots evaluate KMnO4b,
and K2Cr2O7b for wavelength 1, and KMnO4b, and
K2Cr2O7b for wavelength 2 as follows:
at 440:
at 545:
Given the measured absorbance of the mixture at
different wavelengths and the evaluated molar
Chem27.1 Spectroscopy
absorptivities, the concentration of both Cr and Mn
in mixture may be determined based from
equations 6 and 7:
[ ]
[ ]
(6)
[ ]
[ ]
[ ]
[ ]
(7)
[ ]
The concentrations therefore in the mixture of Mn
is 13.19 ppm with 3.34% error and Cr is 31.2 ppm
with 10.26 % error.
VII. Conclusion and Recommendation
Spectroscopy is an easy method to use in
determining the concentration of an unknown
species since it only needs the molar absorptivity
of the sample, the absorbance, and the cell path
length to calculate the concentration of the
analyte. An absorption law called the Beers Law
governs the overall process of spectroscopy since
it gives the relationship of the quantities obtained
from spectophotometric data in order to know the
quantity of unknown in the sample. The
absorptivites directly measured form the
spectrometer or derived from the Beers Law can
be used to derive the transmittance of the
substance at certain wavelengths. The Beer-
Lamberts plot of Absorbance vs. Concentration
(ppm) shows positive trend of the graph. The
positive trend of the graph is obvious in the
positive value of the slope which is actually k
which is in turn equal to . On the other hand, the
plot of Absorbance vs. Transmittance shows the
inverse relationship of the two quantities. This is
obvious in the equation which evaluates
Page 5 of 6
Absorbance as a function of the negative _______________________
logarithm of Transmittance. In simulataneous
determination of the concentration of two species Erlano, Jana Beatriz
within a mixture, a direct Beers Law cannot be
applied but instead a combined Beers Law must _______________________
be used since the absorbance measured is the
total absorbance of both ions. Ortiz, Raissa Athena

It is highly advised to keep the cuvettes clean, and

wipe them before placing them inside the
spectrometer so as not to make discrepancies in
the results. Cuvettes made of quartz are also
preferred since cuvettes made of plastic has been
known to contribute to the absorbance measured.
Sulfuric acid is also preferred to be used as blank
reference and for dilution over water. Water is only
preferred since it is deionized hence it gives a
100% transmittance. But since blank reference will
always be set as a zero mark with 100%
transmittance regardless of the substance used, it
is more ideal to use sulfuric acid since it ensures
that the chromium and manganate ions are in their
3+ 2+ 3+
oxidized form which is Cr and Mn . The Cr and
2+
Mn are the species actually absorbed. Also, work
on the dark places or use foil to cover the
containers or amber bottles to store the sample
solutions to avoid light exposure as it may
absorbance or reflect the light and decompose
that sample.

VIII. Reference

http://www.britannica.com/EBchecked/topic/55890
1/spectroscopy

http://chemistry.niser.ac.in/labhandouts/CL301-
exp6.pdf

http://imagine.gsfc.nasa.gov/docs/teachers/lesson
s/xray_spectra/background-spectroscopy.html

Skoog, D.A., West, D.M., Holler, F.J. and Crouch,

S.R. (2004). Fundamentals of analytical
th
chemistry. 8 Ed. Toronto, Ontario:
Brooks/Cole Thomas Learning Inc.

I hereby certify that I have given substantial

contribution to this report

_______________________

Balaoing, Arianne May

Chem27.1 Spectroscopy Page 6 of 6