Chem126 Lab Instrumental Analysis

EXPERIMENT 3
Analysis of Permanganate Dichromate Mixture
Vanessa Olga J. Dagondon and Ken M. Menez
Department of Chemistry, College of Arts and Sciences,
University of the Philippines Visayas, Miag-ao Iloilo

ABSTRACT
Spectrophotometry
can
used
to
determine
the
concentration of the components of a binary system. The sample
that was analyzed was a mixture of KMnO 4 (permanganate) and
K2Cr2O7 (dichromate) solutions. Both of these components
absorbs at different wavelengths. Therefore, a simple
spectrophotometric method and calculations cannot be used to
determine the concentration of these components. In this
experiment, two sets of standards were prepared: KMnO4
(permanganate) and K2Cr2O7 (dichromate) standards; two
wavelengths were selected at maximum absorbance; four
calibration curves were plotted; and, four molar Absorptivities
were calculated to simultaneously determine the concentration
of the permanganate and dichromate ion. The concentration of
the dichromate and permanganate ion was determined to be
227.64 ppm and 12.6 ppm, respectively. Percentage errors of
0.18% and 1.50% resulted from the analysis. This implies good
accuracy in the analysis and therefore yields no significant
difference between the spectrophotometric and theoretical
measurements.
INTRODUCTION
Several methods have been developed over the years to determine the
individual compositions of mixtures under a binary system. The
concentrations of the isolated substances are usually also measured as to
obtain complete reference of the substances. This experiment used
spectrophotometry to separate the two very different components of a
binary system by their concentration and absorbance.
Typically, as with this experiment, the substances of
(permanganate) and K2Cr2O7 (dichromate) were chosen as
Page 1 of 16

KMnO 4
binary

Chem126 Lab Instrumental Analysis

components for having different properties, most especially on maximum
absorbance difference. Since the absorbances are considered additive and
must never react with each other in any way as shown in this formula:
A 1 = 1 A 1 + 1 A 2

(1)

A 2 = 2 A 1 + 2 A 2

(2)

where A = the measured absorbance and = wavelength

The maximum absorbances of each component should correspond to a
unique wavelength to prevent each resulting absorptivity curve from
overlapping and creating constant and identical results. The permanganate
solution absorbs at a maximum wavelength around 650 nanometers (nm),
while dichromate absorbs at a maximum wavelength of 350 nm.
The molar absorptivity coefficient, denoted by

, which is the only

constant value between measurements, is calculated from the linear

regression function obtained from the graph of concentration versus the
absorbance of the substances. Substituting this formula to (1) and (2) will
provide the concentration of each component:
A= C b

(3)

where C is the concentration of the sample and b is the path length of the
cuvette.
The molar absorptivity coefficient that was taken from the
standardization process of the permanganate and dichromate solutions is
used to determine the individual absorbances of each component of the
mixture or binary system. The formula is:
350

A total=

350

b Mn [ Mn ] +

350

b Cr [ Cr ]

350
A 350
b M n [ Mn ] + 350 b Cr [ Cr ]
total =

(4)
(5)

where [Mn] and [Cr] are the concentrations of each component at the
specific wavelength

Page 2 of 16

Chem126 Lab Instrumental Analysis

The determination of the concentrations of each component at
different wavelengths should show a significant difference in the two
components, as long their maximum and minimum absorbance refrain from
overlapping.
METHODOLOGY
A stock solution of about 0.01 M solution of KMnO 4 was prepared and
standardized; while a solution of 1.5 liters of 0.25 M H2SO4 was also prepared.
Separate volumes of 0.5, 1.0, 3.00, and 4.00 milliliter (mL) portions were
then pipetted from the standard KMnO4 solution and placed into separate
100 mL volumetric flasks. Another empty flask was added to the set and
each flask was labeled respectively from 1 to 5. Each solution was then
diluted to mark with the 0.25 M solution of H2SO4.
About 0.55 to 0.60 grams of dried K2Cr2O7 reagent was weighed on an
analytical balance. This dry reagent was then transferred into a 100 mL
volumetric flask and diluted to the mark with distilled water. Using a pipette,
2.00, 4.00, 8.00, and 10.00 mL portions of the diluted K 2Cr2O7 were placed
separately into 100 mL volumetric flasks. An empty flask was added to the
set and the flasks were numbered from 1 to 5, respectively. Each flask was
then diluted to the mark with the 0.25 M H2SO4.
The middle permanganate solution, the third one with intermediate
concentration, had its absorbance measured against a blank of pure 0.25
H2SO4. The wavelength interval used was between 350 to 650 nanometers.
The absorbance was recorded at 20 nm intervals; at the maximum and
minimum reach of the spectrum the intervals were reduced to every 5 nm.
The absorbance and wavelengths obtained from each permanganate solution
were plotted in a single graph. The process was repeated for the dichromate
solutions.
Two wavelengths for the determination of the molar absorptivity were
selected from the data. The absorbances of each standard solution were
measured from each wavelength, and were plotted against the concentration
of each primary ion present in each solution. The molar absorptivity was then
calculated from these two wavelengths.
The absorbances of each standard solution were derived from the
maximum absorption wavelengths of each. The absorbances were then
plotted against the concentration of each primary ion at the two chosen
wavelengths. This formed a calibration curve where the molar absorptivity
Page 3 of 16

Chem126 Lab Instrumental Analysis

was calculated for each ion. The path length was calculated from the b
values for each wavelength.
A known amount of KMnO4 and K2Cr2O7 solution was prepared in a 100
mL volumetric flask. The absorbance was measured for each of the two
previously chosen wavelengths. The concentration of each of the primary
ions present in the solution was then calculated from the absorbances. The
calculated concentrations were then compared with the standard
concentrations obtained from the previous processes.
RESULTS

AND

DISCUSSION

Beer Lamberts law is only valid for a binary system in a set of

conditions. One of these conditions includes the independence of the
components of the sample analyzed from each other such that they are noninterfering; are homogenous; and, the incident radiation must be
monochromatic (R. Sanjeev, 2013). Thus, an instrument cannot differentiate
two species present in the sample absorbing specific wavelengths. It can
only determine the total absorbance as shown in equations 1 and 2. In this
experiment, an unknown mixture of K2Cr2O7 and MnO4 are analyzed by
measuring the absorbances of the solution at two determined wavelengths.
Four calibration curves were constructed each of which contains the ions
present in the sample.
The wavelengths which correspond to the highest absorbances of each
standard solution, K2Cr2O7 and KMnO4 were determined by the Absorption
spectrum shown in Figure 1. The highest absorbance in the KMnO4 standard
solution corresponds to a wavelength of 437.5 nm. The K2Cr2O7 standard
corresponds to a wavelength of 526 nm. These were used to record the
absorbances of the series of standards containing both of the components of
the sample.

Page 4 of 16

Chem126 Lab Instrumental Analysis

0.35
0.3
0.25
0.2

Wavelength (nm)

0.15
Potassium permanganate

Potassium dichromate

0.1
0.05
0
400

450

500

550

600

650

700

750

Absorbance

Fi
gure 1. Absorption Spectrum: Wavelength vs. Absorbance for maximum
absorbance determination
Figure 2 and 3 shows the calibration curves obtained from measuring
the absorbances at 437.5 nm. Figure 2 is the plot of the absorbance against
the concentration of the permanganate ion. Figure 3 is the plot of the
absorbance against the concentration of the dichromate ion. Consequently,
Figure 4 and 5 are the calibration curves obtained from measuring the
absorbances at the 526 nm of the permanganate and dichromate ion,
respectively. The information needed from these calibration curves is the
molar absorptivity which is the slope of the calibration curves. According to
equation 3, if the path length is 1 cm (such that in this experiment), the
absorbance is linearly related to the concentration with the molar
absorptivity as its slope.

Page 5 of 16

Chem126 Lab Instrumental Analysis

Absorbance vs. ppm MnO4

at 437.5
0.04
0.04

f(x) = 0x + 0.01
R = 1

0.03
0.03
Absorbance

0.02
0.02
0.01
0.01
0
0

10

15

20

25

30

35

40

45

ppm MnO4

Figure 2. Calibration Curve: Absorbance vs. ppm MnO4 at 437.5

Page 6 of 16

50

Chem126 Lab Instrumental Analysis

Absorbance vs. ppm Cr2O7

at 437.5

Absorbance

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

f(x) = 0x + 0
R = 1

100

200

300

400

500

600

ppm Cr2O7

Figure 3. Calibration Curve: Absorbance vs. ppm Cr2O7 at 437.5

Page 7 of 16

Chem126 Lab Instrumental Analysis

Absorbance vs. ppm MnO4

at 526
1.2
1
f(x) = 0.02x + 0.01
R = 1

0.8
Absorbance

0.6
0.4
0.2
0
0

10

15

20

25

30

35

40

45

50

ppm MnO4

Figure 2. Calibration Curve: Absorbance vs. ppm MnO4 at 526

Absorbance vs. ppm Cr2O7

at 526
0.06
0.05

f(x) = 0x + 0.01
R = 0.99

0.04
Absorbance

0.03
0.02
0.01
0
0

100

200

300

400

500

600

ppm Cr2O7

Figure 5. Calibration Curve: Absorbance vs. ppm Cr2O7 at 526

Page 8 of 16

Chem126 Lab Instrumental Analysis

Table 1 summarizes the molar Absorptivities in each calibration curves.
These were obtained by using the least square methods in determining the
slope of a regression line (Seep Appendix: Calculations).
Molar Absorptivities (Lmg-1 cm-1)

4
437.5

Mn O

0.00068112 7

Mn O4 526

0.02013437 8

Cr 2 O7 437.5

0.00145308 9

Cr 2 O2
7 526

7.56909 105

Table 1. Summary of the Molar Absorptivities obtained in each calibration

curve.
These molar Absorptivities are used to determine the concentration of
each ion present in the solution. As mentioned, only the total absorbance in
each specific wavelength can be detected in the instrument. Incorporating
this concept to equation 3 and by measuring the absorbances of the sample
at the two selected wavelengths, we may be able to get the concentration of
each ion in the sample as shown in equations 4 and 5. Manipulating this
system of equation, the concentration of the dichromate ion and
permanganate ion can be calculated as follows:

Page 9 of 16

Chem126 Lab Instrumental Analysis

526
Mn O
Cr 2 O

2
7

437.5

Mn O 437.5

Cr2 O2
7 526

b
Mn O

Mn O

4
437.5 A 440

A 545
[ C r 2 O7 ]=

(6)

4
526

MnO4

Cr 2 O7

Mn O

Cr 2 O2
7 545

A545

(7)

4
545

The sample that was analyzed in the experiment consists of 4ml

K2Cr2O7 and 1ml KMnO4. Table 2 shows the summary of the concentrations
obtained experimentally and theoretically. The percentage errors in each
determination were calculated. Minimal error resulted in the analysis. This
suggests an accurate laboratory handling and experimentation and also, a
successful experiment.

Experimental

Theoretical

Page 10 of 16

Percentage Error

Chem126 Lab Instrumental Analysis

Mn O 4

12.06 ppm

11.88 p pm

1.50

2
Cr 2 O7

227.64 ppm

227.24 ppm

0.18

Table 2. Summary of the analysis of the unknown sample.

CONCLUSION
Simultaneous determination of the concentration of a sample
composed of two or more components can be done using spectroscopic
measurements. By using a series of standards of solution present in the
sample, four calibration curves were obtained. The slope of these calibration
curves were calculated to the molar absorptivity. These values were used to
calculate for the concentration of the two ions present in the sample. The
sample composed of 4ml K2Cr2O7 and 1ml KMnO4 was analyzed. The
spectroscopic measurements determined the concentration of the
dichromate and permanganate ion to be 227.64 ppm and 12.6 ppm,
respectively. The theoretical values for these concentrations were calculated
in order to compare the accuracy of the results of the analysis. A percentage
error of 1.50% and 0.18% resulted from the determination of the
permanganate and dichromate concentrations. These minimal values
indicate accuracy in the analysis and therefore yield no significant difference
between the experimental and theoretical values.
LITERATURE CITED
Harvey, D. Modern Analytical Chemistry. United State of America: The
McGraw-Hill Companies, Inc.; 2000 [cited 2016 February]. Available
from: http://elibrary.bsu.az/
Skoog D. A., West D. M., Holler F. J., Crouch S. R. 2014. Fundamentals of
Analytical Chemistry Ninth Edition. Canada: Nelson Education, Ltd.
1026p.

SIMULTANEOUS DETERMINATION OF COMPOSITION OF BINARY MIXTURES

(SPECTROPHOTOMETRIC ANALYSIS). C241 Exp8.pdf. School of
Chemical Sciences,
National Institute of Science Education and Research
(NISER), IOP Campus, Sachivalaya Marg,
Sainink
School
(P.
O.),
Bhubaneswar

751
005,
Orissa,
India.
Retrieved
from:

Page 11 of 16

Chem126 Lab Instrumental Analysis

chemistry.niser.ac.in/labhandouts/C241-Exp8.pdf.
March 19, 2016.

Date

Accessed:

Experiment 8: Simultaneous Spectrophotometric Determination. Department

of Chemistry,
College of Science, Sultan Qaboos University, Sulatanat of
Oman. April 30, 2011. Retrieved
from:
www.eoman.almdares.net/up/33576/1306406816.doc. Date Accessed:
March 19, 2016.
Harris, D. C. Chapter 20. Quantitative Chemical Analysis, 6th Ed. Julet, M. R.
Freeman and Co.,
New York, 1982.

APPENDICES
TABLES
mL K2Cr2O7
standard
added

ppm Cr2O7-

Absorbance at
437.5

Absorbance at
526

113.62

0.161

0.019

227.24

0.338

0.029

454.48

0.671

0.047

10

568.1

0.82

0.053

Table 3. Summary of Data using the Potassium Dichromate Standards

mL KMnO4
standard
added

ppm MnO4-

Absorbance at
437.5

Absorbance at
526

0.5

5.939861543

0.009

0.14

11.87972309

0.014

0.243

35.63916926

0.029

0.732

Page 12 of 16

Chem126 Lab Instrumental Analysis

4

47.51889234

0.038

0.97

Table 4. Summary of Data using the Potassium Manganese Standards

Final Volume
Initial Volume
Used Volume
Trial
(mL)
(mL)
(mL)
1
37.79
0.0
37.79
2

31.19

1.0

30.19

42.00

11.90

30.1

Table 5. Data for the standardization of Potassium Manganese stock solution

CALCULATIONS
Least Squares Method (To determine molar absorptivity)
Absorbance vs. ppm MnO4 at 437.5 (Fig. 2)

( x )2
( 100.9776462)2
S xx = x
=3704.60529
=1155.484031
n
4
2

( xy )
[ ( 100.9776462) ( 0.09 ) ] =0.787031654
S xy =xy
=3.059028695
n
4

Mn O
4 437.5 =m=

S xy 0.787031654
=
=0.00068112 7
S xx 1155.484031

Absorbance vs. ppm MnO4 at 526 (Fig. 3)

S xx = x 2

( x )2
( 100.9776462)2
=3704.60529
=1155.484031
n
4

Page 13 of 16

Chem126 Lab Instrumental Analysis

( xy )
[ ( 100.9776462) ( 2.085 ) ] =23.2649527
S xy =xy
=75.89955079
n
4

Mn O
4 526 =m=

S xy 23.2649527
=
=0.02013437 8
S xx 1155.484031

Absorbance vs. ppm Cr2O7 at 437.5 (Fig. 4)

( x )2
( 1363.44 )2
S xx = x
=593837.2024
=129095.044
n
4
2

( xy )
[ ( 1363.44 ) ( 1.99 ) ] =187.58662
S xy =xy
=865.89802
n
4

Cr 2 O2
7 437.5 =m=

S xy 187.58662
=
=0.00145308 9
S xx 129095.044

Absorbance vs. ppm Cr2O7 at 526 (Fig. 5)

( xy )
[ ( 1363.44 ) ( 0.148 ) ] =9.77132
S xy =xy
=60.2186
n
4

Cr 2 O2
7 526 =m=

Molarity of

Trial 1:

S xy
9.77132
=
=7.56909 105
S xx 129095.044

KMnO 4

0.1264 g Na2 C2 O4
1 mol Na 2 C 2 O 4
2 mol KMn O4

=0.00998746 M KMn O4
0.03779 L KMn O4 133.96 g Na2 C2 O4 5 mol Na 2 C2 O4

Page 14 of 16

Chem126 Lab Instrumental Analysis

Trial 2:

0.1011 g Na2 C 2 O 4
1 mol Na2 C 2 O4
2 mol KMn O4

=0.009999376 M KMn O4
0.03019 L KMnO 4 133.96 g Na 2 C2 O 4 5 mol Na 2 C 2 O 4

Trial 3:

0.1006 g Na2 C 2 O 4
1 mol Na 2 C 2 O4
2 mol KMnO 4

=0.009979674 M KMn O4
0.03010 L KMn O4 133.96 g Na2 C2 O4 5 mol Na 2 C 2 O 4

M KMnO (average )=
4

0.00998746 M +0.009999376 M +0.009979674 M

=0.009988836 M
3

Concentration of Standards

ppm Mn O 4=

0.009988836 mol KMn O4 1mol Mn O 4 118.93 g Mn O4 1000 mg

=1187.972309 ppm 1188

1L
1 mol KMn O 4
1 mol Mn O4
1g

ppm Cr2 O7=

0.5681 g K 2 Cr 2 O7 1000 mg

=5681 ppm Cr 2 O7
0.1 L
1g

Composition of unknown using the calibration curves

526
Mn O

Cr 2 O

2
7

437.5

Mn O
4 437.5

Cr2 O2
7 526

b
Mn O

Mn O

4
437.5 A 440

A 545
[ C r 2 O7 ]=

4
526

[ C r2 O7 ]=

0.260 ( 0.00068113 )0.339 ( 0.020134378 )

=227.64 ppm
( 7.56909 105 ) ( 0.00068113 )( 0.00145309 )( 0.020134378 )

Page 15 of 16

Chem126 Lab Instrumental Analysis

Mn O

4
545

Mn O 4

2
Cr 2 O 7

0.260( 7.56909 105 ) ( 227.64 ppm )

=
=12.06 ppm
0.020134378

Cr2 O 2
7 545

A 545

Theoretical composition of unknown

4 ml

[ C r 2 O7 ]=5681 ppmCr 2 O7 100 ml =227.24 pp m

Mn O4

Percentage Error
For

[ C r 2 O7 ]

For

Mn O4

%Error=

%Error=

227.64 ppm227.24 pp m
=0.18
227.24 pp m

12.06 ppm11.88 pp m
=1.50
11.88 pp m

Page 16 of 16