Oxidation-Reduction Titrations

Reactions in which electrons are transferred from one species to another

are called oxidation-reduction (redox) reactions. When one species loses
electrons by an oxidation process another species simultaneously gains
electrons by a reduction process in a chemical reaction. The balanced
chemical reaction can be written as the combination of two half-reactions
representing the oxidation reaction and the reduction reaction , respectively.
For example, if solid iron is placed in a solution of gold (III) ions, the gold
(III) ions are reduced to solid gold and the iron is oxidized to iron(III) ions ,
according to the following half-reactions:
Fe3+(aq) + 3 e-

Fe(s)

Oxidation Half-Reaction

Au3+(aq) + 1e-

Au(s)

Fe(s) + Au3+(aq)

Au(s) + Fe3+(aq)

Reduction Half-Reaction
Oxidation-Reduction reaction

Standardization of potassium permanganate with oxalic acid

The permanganate ion is strong oxidizing reagent. The half-reaction
is:
MnO4- + 8H+ + 5e- Mn2+ + 4H2O

E0 = 1.51 V

Potassium permanganate is not primary standard substance because it

contains reduced products like manganese oxide MnO2 where the
concentration of KMnO4 changed after preparation because it dissociated
via reducing agents such as ammonia and organic substances in water
;therefore, potassium permanganate must be standardized before use it and
keep it at least 7-10 days after preparation at dark place and dark bottle
Oxalate compounds have importance in many chemical and biological
reactions. They are used in the photographic sciences, and are the main
component of kidney stones. Excess vitamin C is converted into oxalate and
excreted in the gut and urine, therefore, kidney stone patients must limit
their intake of vitamin C to control the formation of calcium oxalate stones,
as well as foods high in oxalate, such as spinach, beets, and beans.

Sodium oxalate is commonly used as a primary standard for

determining the concentration of many strong oxidizers used in
oxidation/reduction analyses.
Sodium oxalate, Na2C2O4, is a strong electrolyte that dissociates
completely in water according to the following equation:
Na2C2O4 2 Na+ (aq) + C2O42- (aq)

Oxidation process of potassium permanganate conducted in acidic, neutral

and basic and its as follows:
At acidic medium,
MnO4 + 8H+ + 5e

Mn

eq.wt, ofKMnO 4

2+

+ 4H2 O

Mo.wt.
5

At neutral or basic medium like, Sodium or potassium carbonate

MnO4- + 8H2O + 3 e-

MnO2 + 4OH-

eq.wt ofKMnO 4

Mo.wt.
3

At strong basic medium,

MnO4- + 1e

MnO3

eq.wt ofKMnO 4

Mo.wt.
1

Aqueous solutions of permanganate are not entirely stable because the

permanganate ion tend to oxidize water forming manganese dioxide.
4 MnO4- + 2 H2O 4 MnO2 (s) + 3 O2(g) + 4 OH-

In this experiment, The oxalate ion, C2O42-, will react quantitatively with
permanganate ion, MnO4-, in the presence of strong acid according to the
following equation:

2 MnO4- (aq) + 5 C2O42- (aq) + 16 H+ (aq)

2Mn2+ (aq) + 10 CO2 (g) + 8 H2O

The numerical value of Keq for the equilibrium is very large. When
reaction conditions are anywhere near optimum (in terms of pH and
temperature) the reaction can be considered to be quantitative.
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.
C2O42- 2 CO2 + 2 eReduction is shown by the permanganate ion as it gains electrons and Mn decreases in
oxidation state from +7 to +2.
8 H+ + MnO4- + 5 e- Mn2+ + 4 H2O

No indicators are necessary in permanganate titrations because the

end point is easily observed. The permanganate ion is intensely purple,
whereas the manganese (II) ion is nearly colorless. The first slight excess of
permanganate imparts a pink color to the solution, signaling that all of the
oxalate has been consumed.
Apparatus

burette
250-mL Erlenmeyer flasks
10-mL pipette
250-mL volumetric flask

Chemicals

Potassium Permanganate
Sodium Oxalate (AR grade) (0.1 N)
Sulfuric acid ( 6 N)

Procedure
1. Transfer 10.0 mL of sodium oxalate (0.1 N) to 250 mL conical flask.
2. Add 5.0mL of 6.0 N sulfuric acid.
3. shake the solution well and warm it ( 75-80 oC)

4. Titrate the hot solution against potassium Permanganate solution.

5. Continue with titration drop by drop till the color is changed from

colorless to pink ( permanganate dye)

6. Repeat the titration for three times and record the mean.

Calculations
The average volume

V1 V2 V3
3

From reaction equation:

2 moles of KMnO4 5 moles of oxalic acid
1000mL of 2M KMnO4 1000mL of 5M Oxalic acid
VmL of ? M KMnO4 10mL of 0.1M Oxalic acid
Molarity of KMnO 4

10 0.1
VmL of KMnO 4

Normality of KMnO 4 5 Molarity

Conc(g/L)of permenganate N eq.wt.

Volume End Start No.

of
point point
KmnO4
V1
1
V2
2
V3
3