Exercise 12

Permanganimetric Determination of Calcium

Determination of the calcium content of a sample may be determined through many methods
such as gravimetry, and direct or indirect titrations. It is commonly determined by a method
involving the combination of precipitation and titration. In this method, the sample was initially
added with hot hydrochloric acid to liberate calcium ions in the solution. These liberated calcium
ions are precipitated as calcium oxalate monohydrate by employing certain conditions.
12.1

CaCO3 + 2H3O+ Ca2+ + CO2 + H2O

Reaction

Ca2+ + C2O42- + H2O CaC2O4H2 O

Reaction

12.2
After precipitation of calcium oxalate, it is then separated from the mother liquor and washed
free of excess oxalate with cold distilled water. Then it is dissolved in sulphuric acid to convert
the oxalate ions to oxalic acid, which is titrated with a strong oxidizing agent such as standard
potassium permanganate solution.
2MnO4- + 5H2C2O4 + 6H3O+ 2Mn2+ + 10CO2 + 14H2O
Reaction 12.3
Coprecipitation of other ions in the solution as oxalates can occur due to excess oxalate in the
solution; this may lead to a positive error. To minimize these kinds of errors, conditions and
precautions for the determination are designed. A technique called reprecipitation may be
employed to be sure that all other contaminants in the precipitate are eliminated. Addition of
ammonia in the acidic solution with calcium and oxalate ions can also be employed to minimize
coprecipitation.
At equivalence point, the following relationships are obtained:
eq H2C2O4 = eq KMnO4
(m/EW) H2C2O4 = (NVL) KMnO4
m H2C2O4 = (NVL) KMnO4 [EW H2C2O4]
Then the mass of oxalic acid is related to the mass of calcium and calcium oxide in the
sample.
m Ca = (NVL) KMnO4 (EW Ca)

Equation

12.1
m CaO = [m Ca (FM CaO/FM Ca)]

Equation

% Ca = [m Ca/m sample] (100)

Equation

% CaO = [m CaO/m sample] (100)

Equation

12.2
12.3
12.4

References:
CHEM 32 Lecturers and Lab Instructors. (2008). Quantitative Inorganic Analysis Laboratory
Instruction Manual.
Laguna: UPLB.

Jeffery G.H., Bassett, J., Mendham, J. & Denney, R.C. (1989). Vogels Textbook of Quantitative
Chemical Analysis. 5th edition. New York: Longman Group UK Limited.
Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2004). Fundamentals of Analytical Chemistry.
8th edition.
Belmont: Brooks/Cole-Thomson Learning, Inc.