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Experiment No.4
Estimation of total manganese content in manganese ore (pyrolusite)

Materials Required Na2C2O4 H2SO4 KMnO4 Pyrolusite

Equipments and glasswares Burette Pipette 500 ml conical flask 250 ml conical flask Time required: 4 hours

Purpose A method for the analysis of metal ores

Theory: Pyrolusite is the ore of manganese containing Mn as MnO2 with some MnO and Fe2O3. For its higher standard reduction potential it oxidizes C2O42- or Fe2+ of Mohrs salt in acid medium quantitatively.
MnO2 + 4H+ + 2e 2 CO2 + 2e Fe3+ + e Mn2+ + 2H2O C2O42Fe2+ E0 E0 E0 1.23 V -0.49V 0.77 V

Work to be done:
1. 2. Preparation of 100 ml f (N/10) standard Na2C2O4 solution (1.675 g for 250 ml). Preparation of 100 ml approximately (N/10) standard KMnO4 solution and its standardization against Na2C2O4 solution.

Titration Procedure: 25 ml aliquot of standard Na2C2O4 solution is pipetted out

into a 500 ml conical flask. 150 ml of 2(N) H2SO4 is added; the mixture is heated on an asbestos board to about 70-80C and titrated in the hot condition with KMnO4 solution dropwise, running from a burette. Disappearance of the pink

2 color is slow at the beginning, then becomes rapid as the Mn2+ formed auto catalyses the reaction. The end point is marked by the appearance of a pale pink color by the addition of a drop of KMnO4. Burette reading is noted. The experiment is repeated to get two concordant readings.
MnO4- + 8H+ + 5e 2CO2 + 2e Mn2+ + 4H2O C2O42E0 E0 1.51 V -0.49V

Results:
Serial no. Initial burette reading (ml) Final burette reading(ml) Vol. of KMnO4 used (ml)

Calculation:
S KMnO4

Na2C2O4 X V

1 (N)

KMnO4

Titration Procedure:
About 0.2 g finely ground dry Pyrolusite is weighed out accurately by a chemical balance and transferred into a 250 ml conical flask. 50 ml 4(N) H2SO4 is added, followed by the addition of 50 ml of standard f (N/10) Na2C2O4 solution. The mouth of the flask is covered with short stem funnel, and the flask is heated on an asbestos board until all black particles have dissolved. The solution is cooled to 70-80C and excess Na2C2O4 in the mixture is back titrated with standard KMnO4 solution until the appearance of a faint pink color.

Results:
50 ml of f (N/10) Na2C2O4 (added) 50 f ml of (N/10) Na2C2O4 Vol. of f1(N/10) KMnO4 (required for back titration) Vf1 ml of (N/10) KMnO4

Vf1 ml of (N/10) Na2C2O4

Calculation:
Weight of Pyrolusite taken = W g Vol. of N/10) Na2C2O4 reacted with W g Pyrolusite = (50 f) (Vf1) ml 1ml of (N/10) Na2C2O4 0.004347 g of MnO2 [(50 f) (Vf1)] ml of (N/10) Na2C2O4 [(50 f) (Vf1)] 0.004347 g of MnO2 MnO2 = {[(50 f) (Vf1)] 0.004347 100} / W %