©Ylayron, Tono

University of the Philippines Visayas-Miagao campus

BS Fisheries

Name Ma. Novem Grace Ylayron Date Performed: 04/07/2017

:
Jan Linzelle Tono Group No. 8

Experiment No. 6
Oxidation-Reduction Titration: Determination of Oxalate in the Sample

I. Background

The objective of this experiment is to improve skills of students with quantitative titrimetric
determinations, to be familiar with oxidation reduction titrations for determinations of oxalate in
the sample, and to be able to correctly balance a redox reaction chemical equation. The students
aim to determine the amount of oxalate in an impure sample through the use of a titration with
potassium permanganate, after standardization with pure sodium oxalate.
In this experiment, the oxalate in the sample is determined by oxidation- reduction titration.
Oxidation-Reduction titration involves the transfer of electron in a substrate. Oxidizing agent is
when there is a gain of electrons and it is reduced, while the reducing agent is when there is a
loss of electron and it is oxidized (Wasserman, 2015).

Oxidation is defined as the loss of electrons or increase in oxidation state (each C changes
from +3 to +4) as shown below by the half-reaction involving oxalate ion (Harris, 1982):

C O 2- → 2 CO2 + 2 e-
2 4

Reduction is shown by the permanganate ion as it gains electrons and Mn decreases in

oxidation state from +7 to +2 (Harris, 1982):
8 H+ + MnO4- + 5 e- → Mn2+ + 4 H2O

According to Hargis, oxidation and reduction must occur together and are often designated as
redox processes. To emphasize this; the number of electrons lost by one substance must be equal
the number of electrons gained by the other substance. If we combine the two half-reactions
above, we would end with a balanced net ionic equation if we have a total of 10 electrons
exchanged:

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

Because the materials that were weighed and measured occur as compounds, it is often
useful to have the balanced molecular equation (sometimes called the balanced total equation):
©Ylayron, Tono
University of the Philippines Visayas-Miagao campus
BS Fisheries

8 H2SO4 + 2 KMnO4 + 5 Na2C2O4→2 MnSO4 +10 CO2 + K2SO4 + 5 Na2SO4 + 8 H2O

The balancing of oxidation-reduction reactions generally involves breaking down the

reaction into two separate so-called half-reactions, one for the oxidation reaction and one for the
reduction reaction.

In the titration, two solutions are mixed which contains reactants for specific chemical
reactions under conditions that: (a) the equivalence point can be detected though occurrence of
color change and (b) the concentration of the reactant in a standard solution shall be used to
calculate the amount of the other (Cervantes, et al. 2014).

II. Results

Table 1. Standardization of Potassium Permanganate Solution

Primary Standard used: Na2C2O4
Formula mass of 1O standard: 133.9986 g/mol
% Purity of 1O standard: 99.8

Trials 1 2 3
Weight of NaC2O4 (g) 0.1058 0.1040 0.1050

Final Reading KMnO4 (ml) 19.8 39.2 19.8

Initial Reading KMnO4 (ml) 0 19.8 0
Volume KMnO4 used (ml) 19.8 19.4 19.8

Corrected Vol. of KMnO4, mL 9.9 9.5 10

Molarity of KMnO4 0.03190 0.03268 0.03134

Ave. Molarity of KMnO4 0.03197
Normality of KMnO4 0.1595 0.1634 0.1567
Ave Normality of KMnO4 0.1599

Table 2. Indicator Blank

Trials 1 2 3
Final volume KMnO4 (ml) 31.3 41.2 9.8
Initial volume KMnO4 (ml) 21.4 31.3 0
Net Volume KMnO4 (ml) 9.9 9.9 9.8
Ave. volume of KMnO4 (ml) 9.867

Table 3. Sample Analysis

Trials 1 2 3
Weight of the sample (g) 0.1083 0.1170 0.1007
Final volume KMnO4 (ml) 10.3 21.4 30.8
Initial volume KMnO4 (ml) 0 11.1 9.4
Net Volume KMnO4 (ml) 10.3 1.2 0.4
Corrected volume of KMnO4, ml 0.4 1.2 0.4
mg Na2C2O4 of unknown 4.275 13.14 4.200
% Na2C2O4 of unknown 3.947 11.23 4.171
©Ylayron, Tono
University of the Philippines Visayas-Miagao campus
BS Fisheries
Average % Na2C2O4 of unknown 6.449

Figure 1. Titration of Blank indicator

Figure 2. Titration for the Standardization of Potassium Permanganate

©Ylayron, Tono
University of the Philippines Visayas-Miagao campus
BS Fisheries

III. Discussion
Figure 3. Titration for the Determination of Oxalate
Sodium oxalate (Na2C2O4) served as the primary standard because of its high purity,
stability and nonhygroscopicity. It was dissolved in Sulfuric acid before titrated with
potassium permanganate (KMnO4). Sulfuric acid is added to sodium oxalate to produce
H2C2O4 and sodium chloride. H2C2O4 dissociates into C2O4 plus two H+ ions in acidic
environment. Potassium permanganate dissociates into potassium and permanganate ions.
(Harris, 1982). This reaction is shown below.

Na2C2O4 + H2SO4  H2C2O4 + Na2SO4

H2C2O4  C2O4 2- + 2H+

KMnO4  MnO4- + K+

Oxidation-reduction titration endpoint is reached when there is a physical change of analyte

observed. In this experiment, the Potassium Permanganate (KMnO4) itself served as the indicator
when used as a titrant in strongly acidic solution. The permanganate ion is very highly colored
(purple), while its reduction product, Mn2+, is almost colorless (pale pink) in dilute solutions. So,
the small excess of potassium permanganate titrant that occurs just past the equivalence point
produces the purple color that signals the end of titration (Hargis, 1988). Potassium
permanganate is reduced because it contains permanganate ion; we can also say that it behaves
as an oxidizing agent that causes something else to become oxidized (the oxalate). Sodium
oxalate is oxidized because it has the oxalate ion and acts as the reducing agent that causes the
permanganate to become reduced. It can also be seen from both net ionic equation and
molecular equation where acid is required for this reaction to occur ( i.e., H + or H2SO4 show up
in the balanced equations). We also know from the previous experience that a temperature
higher than room temperature makes a reaction more rapid (Luza, et al. 2016).

In the oxidation-reduction titration, sodium oxalate (Na2C2O4) is titrated with potassium

permanganate. Before it was titrated, it was heated to 60°C to 90°C. Heating is necessary since
the analyte and titrant react slowly in room temperature. Moreover, when solutions of sodium
oxalate are titrated to 60°C to 90°C, the consumption of permanganate is from 0.1 to 0.4% less
than the theoretical result, it is probably due to the air oxidation of a fraction of the oxalic acid
(Skoog et al, 2014). The solution of sodium oxalate dissolved in sulfuric acid served as analyte
while potassium permanganate served as the titrant. Sodium oxalate is oxidized since the carbon
©Ylayron, Tono
University of the Philippines Visayas-Miagao campus
BS Fisheries
from the oxalate anion loses electrons while the potassium permanganate is reduced since the
manganese atoms gain electrons (Wasserman,2015).

As for this study, the general chemical reactions that will be involved in the redox processes
are the following:

(1) Na2C2O4 → 2Na+ + C2O2−¿¿

4 C2O 2−¿→
4
CO¿
2

C2O42- → 2CO2 + 2e-

(2) KMnO4 → K+ + MnO4 MnO4- → Mn2-

10e- + 16H+ + 2MnO4- → 2Mn2+ + 8H2O

(3) C2O42- + MnO4- → CO2 + Mn2+

5C2O42- → 10CO2 + 10H+ + 10e-

10e- + 16H+ + 2MnO4- → 2Mn2+ + 8H2O

Overall balanced equation: 5C2O42- + 6H+ + 2MnO4- → 10CO2 + 2Mn2+ + 8H2O

From this equation, we can calculate the molar ratio of permanganate to oxalate which will
allow us to determine the number of moles of oxalate in the unknown.

Table 1 show that the average molarity of KMnO4 is 0.03197. Calculating the molar
concentration of KMnO4 is vital in order to determine the weight of the Na 2C2O4 of unknown.
The average normality was calculated by adding the results obtained each trial and dividing it by
three. The average normality is 0.1599. Determining the concentration of the solution by reacting
material of known purity to a material of unknown purity is called standardization reaction. The
standardized volume of KMnO4 was 0.9 mL. The calculated molarity of KMnO4 in each trial
were lower than the standardized molarity of the said compound. The highest was 0.0327 M and
the lowest was 0.0313 M thus, its effect does not exceed the 100% of Na 2C2O4 percentage value.
In this case the titrant prepared was dilute because it needed higher volume for the reaction to
occur and to end. The calculated molarity of KMnO4, however, may be affected by human errors
such as spilling while weighing it into analytical balance, pipet that has not been rinsed with the
standard sodium oxalate solution or the Erlenmeyer flask was rinsed with sodium oxalate instead
of deionized water.

Table 2 shows the volume used in performing a blank titration. This titration is carried
out by titrating a fixed and known concentration of titrant into a solvent containing none of the
analyte. The only difference from the regular titration is the absence of analyte (Skoog, et al.,
2009). This allows the amount of reactive substance within the plain solvent to be determined
and hence allows a determination of the error in future titration experiments using this solvent.
©Ylayron, Tono
University of the Philippines Visayas-Miagao campus
BS Fisheries
In this experiment the blank sample was the oxalate. It was prepared by adding 20 mL
concentrated H2SO4 to 400 mL diluted water and was titrated with permanganate solution.

The corrected volume of KMnO4 was obtained by subtracting the volume of blank sample
which is 0.3 mL to the original volume of KMnO 4 in each trial. First trial’s corrected volume
was 9.9 mL, second trial’s corrected volume was 9.5 mL and third trial’s corrected volume was
10 mL. It can be observed that the third trial had the highest volume needed to reach the end
point.

Table 3 shows the unknown weight in mg of Na 2C2O4 that was obtained by multiplying
the volume required in mL of the unknown to the calculated molarity of KMnO 4 in mmol/mL and
stoichiometrical ratio of KMnO4 and Na2C2O4. The % Na2C2O4 was calculated by dividing the
obtained weight in mg of the Na2C2O4 by the original weight of the sample in mg. The answers
vary and depend on the given volume and weight of the unknown Na 2C2O4 per trial. For trial 1, it
resulted to 3.947 %; 11.2 % for trial 2; and 4. 17 % for trial 3. As observed, trial 2 had the
farthest result among the three trials. This is because of the error done while weighing the sample
(refer to table 3). The decimal differences while weighing was not put into consideration,
resulting to an error.

Errors while titrating in the determination of Oxalate were observed. Trials 1 and 3 resulted
to overrun (refer to Fig. 3). These errors may be due to human errors: lack of control of the
student in handling the buret, absence of mind of the student during titration, or contamination
since the equipments was not washed and cleaned properly.

IV. Calculation

Table 1. Standardization of KMnO4 Solution

A. Corrected Volume KMn O 4= Net vol. – vol. of Blank indicator

Trial 1: 19.8-9.9 = 9.9 mL

Trial 2: 19.4- 9.9 = 9.5 mL

Trial 3: 19.8-9.8 = 10 mL

W corr Na2 C 2 O 4
B. Molarity of KMnO4: x Equivalent factor
V corr KMn O 4 × FW Na 2 C 2 O 4
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University of the Philippines Visayas-Miagao campus
BS Fisheries
0.1058 g 2
×
Trial 1: 0.0099 L ×133.9986 g 5 = 0.031901M
mol

0.1040 g 2
×
Trial 2: g 5 = 0.0326791M
0.0095 L ×133.9986
mol

0.1050 g 2
×
Trial 3: g 5 = 0.0313436M
0.01 L ×133.9986
mol

5 molar equivalence
C. Normality : Normality of KMnO4: M KMn O × 4
mol

5 molar eq .
Trial 1: 0.031901 × =¿ 0.159505
mol

5 molar eq .
Trial 2: 0.0326791× =¿ 0.163395
mol

5 molar eq .
Trial 3: 0.0313436× =¿ 0.15672
mol

Table 3. Sample Analysis

5
A. mg of Na2C2O4 of unknown ¿ M KMn O ×V corr . KMnO × FW Na C 2O 4 ×
4 4 2
2

mmol mg 5
Trial 1: 0.031901 × 0.4 mL ×133.9986 × =4.27469mg
mL mmol 2
©Ylayron, Tono
University of the Philippines Visayas-Miagao campus
BS Fisheries
mmol mg 5
Trial 2: : 0.0326791 ×1.2 mL× 133.9986 × =13.1369 mg
mL mmol 2

mmol mg 5
Trial 3: : 0.0313436 × 0.4 mL ×133.9986 × =4.1999985mg
mL mmol 2

weight of Na2 C 2 O 4
B. %Na2C2O4 of unknown = ×100 %
weight of sample

4.27469 mg
Trial 1: ×100 %=3. 95 %
108.3 mg

13.1369mg
Trial 2: × 100 %=11.2 %
117 mg

4.1999985 mg
Trial 3: ×100 %=4.17 %
100.7 mg

V. Conclusion

In this experiment, the oxalate in the sample was determined by oxidation- reduction
titration. Oxidation-reduction titration endpoint is reached when there is a physical change of
analyte observed. Three trials were made for the standardization of KMnO4 Solution and used to
solve for the Corrected Volume KMn O 4, Molarity of KMnO4 and its Normality. In sample
analysis, mg of Na2C2O4 of unknown is solved same with the %Na 2C2O4 of unknown. The results
revealed that there is a difference in the concentration of oxalate in a sample depending on the
amount that was weighed. Based on the gathered data, as the weight of the unknown sample
increased, the concentration or the observed amount of oxalate in the sample decreased.
Therefore, there is a little amount of oxalate in the unknown sample but enough for it to be
notable in the analyzation or experiment.

VI. References
©Ylayron, Tono
University of the Philippines Visayas-Miagao campus
BS Fisheries
Cervantes, C.K.V., Borja, K., Tadifa, G. (05 December 2014). OXIDATION – REDUCTION
TITRATION: Determination of the Oxalate in the Sample. University of the Philippines Visayas;
Miag-ao, Iloilo, Philippines
Hargis, L.G. (1988). Analytical Chemistry: Principles and Techniques; Prentice Hall Inc.:
Unites States of America

Harris, D.C. (1982). Quantitative Chemical Analysis; W.H. Freeman and Company; Unites
States of America

Luza, J.C., Galor, J.Y., Castillo, K.A. (22 November 2016). Determination of Oxalate in the
sample. Retrieved April 9, 2017 from: http:// academia.edu.ph

Skoog, D. A.; West, D. M.; Holler F. J., Crouch, S. R. (2004). Fundamentals of Analytical
Chemistry, 8th ed.; Brooks/Cole: Belmont, CA.

Wasserman, R. (2015). Does Sodium Oxalate react with Potassium Permanganate?.

Retrieved on April 8, 2017 from http://www.livestrong.com/article/286203-does-sodium-
oxalate-react-with-potassium-permanganate/