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Name: Chalmer M.

Belaro Date: 11 March 2010

Section: 2ChE-C Schedule: Tuesday & Thursday, 2-5 pm

Student No.: 2008-007430

OPTICAL METHOD OF ANALYSIS


Use of Beer’s Law on a KMnO4 Solution

Abstract:

Potassium permanganate (KMnO4) solution was analyzed using the basic aspects of
spectrophotometry. An approximately 0.050 M of solution was prepared and was standardized
using sodium oxalate (Na2C2O4) as the primary standard. Sodium oxalate was dissolved in 0.75 M
sulfuric acid (H2SO4), heated to 90℃ and was titrated against KMnO4 solution. The molarity of the
standard solution was calculated using their molar relationship in the volume of the solution used to
reach the endpoint. From the standard KMnO4 solution, a spectral transmittance curve was made
by measuring its absorbance using a spectrophotometer in a range of wavelength. The measured
absorbance was plotted against the corresponding wavelength and the maximum wavelength (max)
of 540 nm was determined. From this max is to which the analysis of different concentrations of the
solution was made. Five different concentrations of the solution were prepared by diluting a number
of drops into a 250-mL volumetric flask. Their corresponding absorbances were measured in the
spectrophotometer and was plotted to make the standard curve checked by Beer’s Law. The
unknown molarity of a KMnO4 sample solution was determined by measuring its absorbance and
projecting it to the standard curve or using linear regression of the same curve. From the measured
absorbance of 0.071, the projected and calculated molarities were 4.0617× 10−4 𝑀 and 4.10×
10−4 𝑀, respectively, which shows no difference as expected.

I. Introduction:

All substances providing absorption spectra in the ultraviolet and/or visible regions
absorb radiation in the wavelength of 200-800 nm (Nemcová, Cermáková, & Gaspari, 1996).
This visible region—the kind that our eyes detect— represents only a small fraction of the
magnetic spectra (see appendix 2: figure 1). Absorption and emission of electromagnetic
radiation are molecular characteristics used in quantitative and qualitative analysis (Harris,
2009).

A spectrophotometer measures transmission of light. If a substance absorbs light, the


radiant power of a light beam decreases as it passes through the substance. Transmittance, T,
is the fraction of incident light that passes through a sample that ranges from 0 to. And the most
useful quantity for the chemical analysis is absorbance, A, defined as the -log 𝑇. It is
proportional to the concentration of light-absorbing molecules in the sample (Mendham,
Denney, Barnes, & Thomas, 2000). Absorbance is also proportional to the pathlength of
substance through which light has to travel. These relations are expressed in Bouguer-Lambert-
Beer Law, or simply Beer’s law; where A is dimensionless, b is the path length, c is the
concentration in moles per liter (M) and  is called the molar absorptivity (units M-1 cm-1):
(Harris, 2009)

A=εbc (2)

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Although KMnO4 can undergo several different reductions, it is most commonly used in
acid solution under conditions that give the reduction to manganese (II) ion, Mn2+. In neutral
solutions, it slowly decomposes, and is also reduced by dust, organic matter, etc., in the water.
The manganese dioxide (MnO2) formed in these reactions, catalyzes the further decomposition
of the MnO4- (Kolthoff, 1942).

Generally, Na2C2O4 was considered as the best primary standard for MnO4- . Another
that could be used as a primary standard is arsenic (III) oxide (As2O3). Iron wire, ferrous
ammonium sulphate hexahydrate [Fe(NH4) 2(SO4) 2 6H2O] and oxalic acid hydrate (C2H2O4
H2O) were considered secondary standard. (Welcher, 1962)

II. Methodology

6.4 g of KMnO4 was measured using a tap load balance and was gradually dissolved in
distilled water in portions before transferred and diluted to make a 1.0 L of the solution. It was
heated just below its boiling point for an hour. It was then allowed to cool and stored in an
amber bottle that prevented the solution to decompose.

From the instructed weight range of 0.2000 g – 0.2500 g of Na2C2O4, 0.2406 g and
0.2383 g were measured using weighing by difference in analytical balance for two trials in a
250-mL beaker/flask. Each was dissolved in 75.0 mL of of 0.75 M H2SO4 heated to about 90℃
and was titrated while it’s hot against the prepared approximately 0.05 M of KMnO4 until the
solution had turned to faint pink. The reaction was hastened by the elevated temperature and by
the autocatalytic effect of the product, Mn2+, produced by the redox reaction:

2MnO4- + 16H+ + 5C2O4- 2Mn2+ + 8H2O + 10CO2 (1)

The molarity of the standardized KMnO4 solution was computed through the molar
relationship of the KMnO4 and Na2C2O4, and the volume of the titrant (appendix 1: A). As the
result, 0.04225 M and 0.04209 M were calculated for trials 1 and 2, respectively; and 0.04217 M
as the arithmetic mean.

Optical method of analysis of the KMnO4 was started by making a spectral transmittance
curve using a pre-powered spectrophotometer. The absorbance of a sample of the KMnO4
solution was measured from the range of 440 nm to 770nm using the interval of 10 nm and
smaller in the region of maximum absorbance. The absorbance was plotted against the
wavelength making the spectral curve of the solution and identifying 540 nm as the max . The
identified max was expected to be on the same range as some written academic texts have
cited based on analytical experiments, that is 525 nm – 545 nm (see appendix 2: fig 2) (Lieu &
Kalbus, v. 81 no. 1 January 2004).

Five different concentrations; 3.00× 10−5 , 5.00× 10−5 , 7.00× 10−5 , 9.00× 10−5 ,
1.00× 10−4 ; were prepared using a number of drops of the standardized KMnO4 of groups 1-5,
respectively, by diluting it with distilled water. For each solution, the absorbance was measured
and plotted against its molar concentration making up the standard curve to which the analysis
of the test solution was based (see appendix 2: C) and is checked by the Beer’s Law. The

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unknown concentration of the test solution was determined by using the standard curve made
and/or by using the equation of the trend line of the absorbance. The absorbance of the test
solution read 0.071.Using its value and projecting it to the mentioned curve, 4.10 × 10−5 M was
determined. And using the equation of the trendline, 4.0618× 10−5 M was calculated which is
significantly equal to 4.10 × 10−5 𝑀.

III. Discussion of Results


Following are the obtained molarities of the standard KMnO4 of groups 1 to 5.

Table 1. Standardization of KMnO4 solution


GROUP AVERAGE
NUMBER MOLARITY

1 0.0422

2 0.0400

3 0.0435

4 0.0445

5 0.0470

AVERAGE: 0.04344

As of the table 1, no significant difference can be observed among others even if


many factors may have contributed in the standardization of the KMnO4 solution. One is
the concentration of the H2SO4 that the rate of and the equilibrium reaction (1) directly
increases with each other. Thus, having equilibrium favoring backwards when the
concentration of the H2SO4 is relatively small making the product Mn2+ not acidic enough
and that reacts to the remaining MnO4- ion to produce MnO2. Another is the autocatalytic
effect of the Mn2+, which dictates how fast the reaction would be that is directly relational
with the molar concentration of the KMnO4. (Lieu & Kalbus, v. 81 no. 1 January 2004).
But as far as the procedure done was concern, the molarity of the acid used is strong
enough to avoid the fast decomposition of Mn2+.

Other influences in spectrophotometric reactions are the solvent used,


temperature, spectrophotometric reagent concentration, ionic strength of a solution,
interfering substances, and surfactants ( (Haeberli & Gilbert, 75 (4) April 2007).

With the determination of the concentration of the test solution, it could already
be estimated even when you’re not yet given the curve but you have measured the
absorbance different known concentrations. Following is the table of the measured
absorbance for each known concentration.

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Table 2. Absorbance of the Known Concentration
GROUP
MOLARITY ABSORBANCE
NUMBER

1 3.00× 10−5 , 0.055

2 5.00× 10−5 , 0.084

3 7.00× 10−5 , 0.140*

4 9.00× 10−5 , 0.154

5 1.00× 10−4 0.138*

Evaluating this table would show that the molarity of the solution that has an
absorbance of 0.071 would be from 3.00× 10−5 to 5.00× 10−5 , which makes the
obtained value of concentration reasonably acceptable.

All the data marked with asterisk (*) were not considered in making the standard
curve (see appendix 2: C). Absorbance at 1.00× 10−4 was not considered because it is
obviously an outlier. And the same for the other that does not satisfy the Beer’s law that
it should be linear, thus deleting it from data. According to equation (2), there is a linear
dependence between the absorbance and the analyte concentration in solution.
However, the validity this rule has certain limitations, and in practice, deviations from this
linear relationship have been observed. These deviations can arise from instrumental
effects, and or from a change of chemical acid-base reactions, polymerization reaction,
the effect of solvent molecules and inert salts. (Lieu & Kalbus, v. 81 no. 1 January 2004)

IV. Conclusion / Recommendations

The absorbance of a certain solution can include the absorbance of excess of


spectrophotometric reagent and/or the absorbance of solvent, if they absorb the
wavelength selected for the measurement. To get the calibration curve to pass through
the origin, the measurement should be performed against pure solvent or against a
reagent blank. Moreover, to obtain the correct value of concentration, it is necessary that
the value of  should not be taken from the literature, but determined prior to the
calculation under the same experiment conditions and using the same instruments that
were used to measure absorbance value, because these factors affect its value.

A closer analysis reveals the rate-limiting step of a typical procedure is often the
time spent filling and washing the cuvette alternatively with blank and sample and
performing the two-point calibration (Thompson, 83 (6) June 2006). In connection, make
the determination of max be more precise by using a better spectrophotometer. By using
such, wavelength and absorbance reading will be more accurate. Wavelength

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reproducibility is more important than absolute accuracy, especially if the measurement
is being made on the side of the peak which is very crucial in the determination of max
into which the analysis of an unknown will be based on (Nollet, 2000).

Basic instruments do not correct for source and detector spectral distributions.
Consequently, recalibration is necessary every time the wavelength is changed. That is
tedious and slow. Therefore, a computer generated plotting program is recommended to
hasten the process of determining the max. (Mattison & Mattson, 72 (6) June 1995)

References:
Haeberli, W., & Gilbert, P. (75 (4) April 2007). Experiments on Subtractive Color Mixing with
Spectrophotometer. American Journal of Physics , 313-319.

Harris, D. C. (2009). Exploring Chemical Anslysis. New York: W. H. Freeman and Company.

Kolthoff, I. (1942). Volumetric Analysis 2nd ed. Vol I: Theoretical Fundamentals. New York:
Interscience Publishers Inc.

Lieu, V. T., & Kalbus, G. E. (v. 81 no. 1 January 2004). A Spectrophotometric Study of the
Permanganate-Oxalate Reaction. Journal of Chemical Education , 100-102.

Mattison, M. E., & Mattson, W. A. (72 (6) June 1995). Obtaining Spectrum Easily: Using a
Single-Beam Spectrophotometer. Journal of Chemical Education , 569-571.

Mendham, J., Denney, R., Barnes, J. D., & Thomas, M. J. (2000). Vogel's Quantitative Chemical
Analysis (6th ed). New York: Prentice Hall.

Nemcová, I., Cermáková, L., & Gaspari, J. (1996). Spectrophotometric Reactions. New York:
Marcel Dekker, Inc.

Nollet, L. (2000). Handbook of Water Analysis. New York: Marcel Dekker, Inc.

Thompson, J. E. (83 (6) June 2006). A Simple Method for Rapidly Obtaining Absorption
Spectronic-20D+ Spectrophotometer. Journal of Chemical Education , 913-914.

Welcher, F. J. (1962). Standard Methods of Chemical Analysis 6ed Vol II Part A. Princeton, New
Jersey: D. Van Nostrand Comany.

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Appendices:

APPENDIX 1: Computations

A. Standardization of KMnO4 solution

TRIAL 1 TRIAL 2

Mass of Na2C2O4 0.2406 g 0.2383 g

Volume of KMnO4 used 17.0 mL 16.9 mL

Molarity of KMnO4 0.04225 0.04209

AVERAGE Molarity: 0.04217 M

Computation:

Trial 1:
0.2406 𝑔 2 𝑚𝑜𝑙𝑒 KMnO 4 1000𝑚𝐿 /1𝐿
MKMnO4= x x
134 𝑔/𝑚𝑜𝑙 5 𝑚𝑜𝑙𝑒 Na 2C2O4 17.0 𝑚𝐿

MNaOH= 0.04225M

Trial 2:
0.2383 𝑔 2 𝑚𝑜𝑙𝑒 KMnO 4 1000𝑚𝐿 /1𝐿
MKMnO4= x x
134 𝑔/𝑚𝑜𝑙 5 𝑚𝑜𝑙𝑒 Na 2C2O4 16.9 𝑚𝐿

MNaOH= 0.04209M

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APPENDIX 2: Reference Figures

Figure 1. The Electromagnetic Spectrum (Harris, 2009)

Figure 2. Absorption Spectrum of KMnO4 Solution at


Different Concentration (Harris, 2009)

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Absorbance
0.18

0.16 y = 1664.3x + 0.0034


R² = 0.998
0.14

0.12

0.1
Absorbance
0.08
Linear (Absorbance)

0.06 Unknown

0.04

0.02

0
0 0.00002 0.00004 0.00006 0.00008 0.0001

Figure 3. Standard Curve of KMnO4 Solution

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