Oxidation – Reduction Titration

Determination of the Oxalate in the Sample

I. Background

The technique of titration has been used previously in acid-base reactions to detect
the amount of acid using a known base (or the reverse). It can also be used in situations
in which the reaction involves oxidation and reduction. Oxidation is defined as the loss
of electrons (on right of arrow) or increase in oxidation state (each C changes from +3
to +4) as shown below by the half-reaction involving oxalate ion (Rosenberg, 2004).

C2O42- → 2 CO2 + 2 e-

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

in oxidation state from +7 to +2. 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 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 (Cain, 2002).

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

Potassium permanganate is reduced because it contains the permanganate ion; we

can also say that it behaves as an oxidizing agent because it causes something else to
become oxidized (the oxalate). Sodium oxalate is oxidized because it has the oxalate
ion and we could also specify it as the reducing agent because it causes the
permanganate to become reduced. It can also be seen from both the net ionic equation
or molecular equation that acid is required for this reaction to occur; i.e., H+ or H2SO4
show up in the balanced equations.

This experiment aims 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. The titration is based on oxidation-reduction properties of the
reactants.
II. Results
Standardization of Potassium Permanganate Solution
Primary Standard used: Na2C2O4
O
Formula mass of 1 standard: 133.9986g/mol
O
% Purity of 1 standard: 99.9 %
 Trials 1 2 3
Weight of NaC2O4 (g) 0.1056 0.1118 0.1046
Final Reading KMnO4 (ml) 17.50 35.29 49.70
Initial Reading KMnO4 (ml) 00.01 17.49 35.29
Volume KMnO4 used (ml) 17.49 17.80 14.41
Molarity of KMnO4 0.01802 0.01875 0.02167
Ave. Molarity of KMnO4 0.01948
Ave Normality of KMnO4 0.09740
Indicator Blank
Trials 1
Final volume KMnO4 (ml) 0.20
Initial volume KMnO4 (ml) 0.01
Net Volume KMnO4 (ml) 0.19

Figure 1. Results on Standardization of Potassium Permanganate Solution with the

Indicator Blank

Sample Analysis
Trials 1 2 3
Weight of the sample (g) 0.1009 0.1019 0.1041
Final volume KMnO4 (ml) 26.50 33.80 41.60
 Initial volume KMnO4 (ml) 18.70 26.50 33.80
Net Volume KMnO4 (ml) 07.80 07.30 07.80
mg Na2C2O4 of unknown 0.2636 0.2492 0.2720
% Na2C2O4 of unknown 31.03 34.37 32.16
Average % Na2C2O4 of unknown 32.52

Figure 2. Results on Determination of Oxalate in the Sample

III. Discussion

Potassium permanganate (KMnO4) is a common chemical found in most

laboratories. It can be used for a variety of purposes and although hazardous in
concentrated solutions it is relatively safe in small concentrations. It is best known for
its deep purple color that can be seen with the naked eye at low concentrations (James
Madison University and JMU Board of Visitors, 2016). It dissolves in water as a strong
electrolyte to give K+ and MnO4 - ions. Manganese is in the +7 oxidation state (the
highest) in KMnO4. Therefore it can only be reduced (gain electrons) to lower
oxidation states in redox reactions. Although it is possible to make +4, +3, 0 and other
oxidation states, the most common reaction is a five electron reduction to +2; that is
Mn2+ which occurs as a hydrated ion in water.

Sodium oxalate has weak base properties, and in strong acid it is immediately
converted to oxalic acid (H2C2O4). The sodium form dissolves to give 2 Na+ and one
oxalate (C2O4 2- ): a trio of ions ( Boundless, 2016). The two half reactions have
 different numbers of electrons, five for the reduction and two for the oxidation. The
rules for balancing redox reactions include that electron must be canceled out when
adding and stoichiometry are done. If the first reaction is multiplied by 2 and the second
by 5, then the two are added together we get the balanced, overall redox reaction:
5C2O4 2- + 2MnO4 - + 16H+ 10CO2 + 2Mn2+ + 8H2O

This reaction tells us that five oxalate (C2O4 2- ) and two permanganate (MnO4 -)
on a mole basis go together to make products in the presence of a lot of acid (H+). A
titration is a process of combining two liquids – a titrant and an analyte – in a manner
so that stoichiometric equivalence is achieved. When that occurs the following equation
must be true for the above overall redox reaction:
2 mol permanganate = 5 mol oxalate

This equation tells us that if you want to convert moles of permanganate into moles
of oxalate (stoichiometry) you must multiply by 5/2.

As KMnO4 is not a primary standard substance so determination of the strength of

it will be erroneous. The solution must be strongly acidic in order to avoid other side
reactions. Sulfuric acid is used. The main reason for using acid in the titration is that it
transforms oxalate to oxalic acid and this acid solution reduces the KMnO4. Any side
reaction may hamper the result. In the KMnO4 solution, there remains some impurities
mainly MnO2. Some Mn+2 are produced from MnO2 which reacts with KMnO4 and
forms more MnO2. This is known as auto decomposition. This will manipulate the
result. 2 MnO4 -1 + 2 H2O + 3 Mn+2 5 MnO2 + 4 H+ ix) Even in the distilled water
there remains some reducing agent which reacts with MnO2 and produces more MnO2
and more auto decomposition occurs. This is also responsible for erroneous result. To
safeguard this re-distilled water from alkaline permanganate should be used. 4 MnO4
-1 + 2 H2O (containing reducing agent) 4 MnO2 + 3 O2 + 4OH-1 x) Even in the
distilled water there remain some reducing agents which react with MnO2 and produce
more MnO2 and more auto decomposition occurs. This is also responsible for
erroneous result. 4 MnO4 -1 + 2 H2O (containing reducing agent) 4 MnO2 + 3 O2 +
4OH-1 XI) Permanganate solution should be added moderately and at the same time it
has to be stirred to clear the solution constantly. But nonreactor permanganate should
no way be allowed to accumulate in the solution because this may result in auto
decomposition which will definitely manipulate the result.

IV. Calculations

𝑊𝑁𝑎2 𝐶2 𝑂4
Molarity of KMnO4:
𝑉𝐾𝑀𝑛𝑂4 ×𝐹𝑊𝑁𝑎2 𝐶2 𝑂4
 0.1056𝑔 2
Trial 1: 1𝐿 𝑔 × = 0.01802M
17.49𝑚𝐿× ×133.9986 ⁄𝑚𝑜𝑙 5
1000𝑚𝐿

0.1118𝑔 2
Trial 2: 1𝐿 𝑔 × = 0.01875M
17.80𝑚𝐿× ×133.9986 ⁄𝑚𝑜𝑙 5
1000𝑚𝐿

0.1046𝑔 2
Trial 3: 1𝐿 𝑔 × = 0.02167M
14.41𝑚𝐿× ×133.9986 ⁄𝑚𝑜𝑙 5
1000𝑚𝐿

5 𝑚𝑜𝑙𝑎𝑟 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑐𝑒
Normality of KMnO4: 𝑀𝐾𝑀𝑛𝑂4 × 𝑚𝑜𝑙

5 𝑚𝑜𝑙𝑎𝑟 𝑒𝑞.
Trial 1: 0.01802 × = 0.09010
𝑚𝑜𝑙

5 𝑚𝑜𝑙𝑎𝑟 𝑒𝑞.
Trial 2: 0.01875× = 0.09375
𝑚𝑜𝑙

5 𝑚𝑜𝑙𝑎𝑟 𝑒𝑞.
Trial 3: 0.02167× = 0.10835
𝑚𝑜𝑙

Sample Analysis

5
mg of Na2C2O4 of unknown = 𝑀𝐾𝑀𝑛𝑂4 × 𝑉.𝐾𝑀𝑛𝑂4 × 𝐹𝑊𝑁𝑎2 𝐶2 𝑂4 × 2

1𝐿 5
Trial 1: 0.1009 × 7.80𝑚𝐿 × 1000𝑚𝐿 × 133.9986 × 2 = 0.2636𝑚𝑔

1𝐿 5
Trial 2: 0.1019 × 7.30𝑚𝐿 × 1000𝑚𝐿 × 133.9986 × 2 = 0.2492𝑚𝑔

1𝐿 5
Trial 3: 0.1041 × 7.80𝑚𝐿 × 1000𝑚𝐿 × 133.9986 × 2 = 0.2720𝑚𝑔

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓𝑁𝑎2 𝐶2 𝑂4
%Na2C2O4 of unknown = × 100%
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒

100.9 𝑚𝑔
Trial 1: × 100% = 31.03%
325.2𝑚𝑔

111.8 𝑚𝑔
Trial 2: × 100% = 34.37%
325.2𝑚𝑔

104.6 𝑚𝑔
Trial 3: × 100% = 32.16%
325.2𝑚𝑔

V. Conclusion

Potassium permanganate, KMnO4, is probably the most widely used of all

volumetric oxidizing agents. It is a powerful oxidant and readily available at modest
 cost. The intense color of the permanganate ion, MnO4 - , is sufficient to detect the end
point in most titrations.

In conclusion as observed, the amount of an oxalate in an unknown given sample

decreases as the obtained unknown sample weight increases. Therefore, there is little
amount of oxalate in the unknown sample but enough for it to be notable in the
analyzation or experiment.

VI. References

Boundless. (2016, August 9). Redox Titrations. Retrieved from Chemistry Boundless:
https://www.boundless.com/chemistry/textbooks/boundless-chemistry-
textbook/aqueous-reactions-4/oxidation-reduction-reactions-48/redox-
titrations-248-1533/
Cain, J. (2002, December 9). Reduction. Retrieved from http://hyperphysics.phy-
astr.gsu.edu/hbase/chemical/electrode.html
James Madison University and JMU Board of Visitors. (2016). Oxidation-Reduction
Titration. Retrieved from
https://www.jmu.edu/chemistry/132%20Lab/Exp%208--
Oxidation%20Reduction%20Titration.pdf
Rosenberg, J. (2004, March 3). Oxidation-Reduction Titration. Retrieved from
http://www.lahc.edu/classes/chemistry/arias/exp%208%20-%20redox.pdf