Experiment 7

Determination of Calcium by KMnO4 Titration

Objective:
To determine calcium using redox titration method.

Introduction
The objective of this analysis is to determine the amount of Ca in a limestone sample (reported
as the mass percentage of CaO) by a redox titration with a standard solution of the oxidizing
agent, KMnO4. Like most analytical procedures based on redox chemistry, this experiment
involves a lot of steps and some complex reactions that must be fully understood ahead of
time. The limestone sample is first dissolved in strong acid and then Ca 2+ is quantitatively
precipitated and isolated as calcium oxalate, CaC2O4. The precipitate is re-dissolved in acid and
the oxalate is titrated with a standard solution of KMnO 4. Note the stoichiometry here in which 2
moles of MnO4- react with 5 moles of oxalate and, thus, 5 moles of Ca.

5 H2C2O4 + 2 MnO4- + 6 H+  2 Mn2+ + 10 CO2 + 8 H2O

Since aqueous MnO4- has an intense violet colour, the end-point in the titration is the first
permanent appearance of pink colour due to the slight excess of MnO 4-. The same titration
procedure is first used to standardize the KMnO4 solution against a primary standard, i.e., solid
Na2C2O4 (FM = 134.00).

Unknown
The "limestone" unknown provided will be a powdery solid containing CaO along with other
oxides, mainly MgO and SiO2, that do not interfere in the Ca analysis.

Materials and Methods

Glassware and Apparatus

 Burette; 50 mL and stand
 Measuring (Graduated) cylinders; 10 mL and 100 mL
 Beaker; 400 mL
 Hot Plate

Chemicals
 Potassium Permanganate (KMnO4)
 Sodium oxalate (Na2C2O4)
 Ammonium oxalate (NH4C2O4)
 Concentrated H2SO4 (~18 M)
 Concentrated NH3 (~15 M)
 Concentrated HCl
 Deionized water
Procedure

A. Reagents and standard solutions preparation

KMnO4 stock solution (~0.02 M): In a large beaker, dissolve ~1.6 g of KMnO4 (FM = 158.03) in
about 500 mL of deionized water. After mixing well, boil the solution gently for about 30
minutes, then let it stand and cool to room temperature. (To use lab time efficiently, prepare the
following three solutions and weigh out your Na2C2O4 samples while the KMnO4 solution is
being heated and cooled). If you observe any brown precipitate of MnO 2, filter the solution
through a clean fritted glass crucible to remove the solid prior to standardizing the solution.
Avoid contact of the strongly-oxidizing KMnO4 solution with organic matter including paper.
Store the solution in the dark in a clean brown bottle. If necessary, clean the fritted crucible (i.e.,
remove MnO2 that collected on the frit) with 1 M H2SO4 containing a few mL of 3% H2O2 and
discard this cleaning solution after use.

H2SO4 Dilution (~1 M): Measure ~55 mL of concentrated H2SO4 (about 18 M) with a graduated
cylinder and pour it slowly into ~1 L of deionized water in a large beaker or bottle. Mix well
and store in a glass or plastic bottle. You will also need to make another 500 mL of 1 M H2SO4
(using ~28 mL of conc. H2SO4) for the second part of this experiment. Caution: Concentrated
acids must be handled with care in the fume hood. Always prepare dilute acid solutions by
adding acid to water!

Ammonium oxalate solution (~3 %): Dissolve ~15 g of solid (NH4)2C2O4 in ~500 mL of
deionized water and mix well. Store it in a glass bottle or flask.

Ammonia solution (6 M): Measure ~60 mL of concentrated NH3 (15 M) with a graduated
cylinder and slowly pour it into ~90 mL of deionized water. Caution: Handle concentrated
ammonia with care in the fume hood.

B. Standardization of 0.02 M potassium permanganate solution (KMnO4)

1. Dry ~1.5 g of pure Na2C2O4 at 110 ºC for ~30 minutes.

2. Weigh (to ±0.1 mg) three 0.25-g samples of Na2C2 O4 in clean dry weighing bottles.
3. Transfer the samples quantitatively to three 400 mL beakers (use a few mL of deionized
water to rinse the weighing bottles).
4. Dissolve each sample in ~200 mL of 1 M H2SO4. Heat each solution to 80-90ºC and titrate
with KMnO4 while stirring. Note that at the very beginning of the titration there may be a
slight pink colour in the solution. This should dissipate after a few drops of MnO4 - are added.
5. Reheat the solution if the temperature falls below ~60 ºC. The first persistent pink colour
(i.e., lasting ~30 seconds) of MnO4 - is the end-point.
6. Determine the concentration of KMnO4, keeping in mind the 2:5 stoichiometry of the
reaction, to 4 significant figures.
C. Analysis of Limestone (CaO) Unknown

1. Dry about 1.0 g of unknown for at least one hour at 110ºC. Cool in a desiccator.
2. Precisely weigh three 0.25-g samples of the unknown and transfer each to 250 mL beakers.
3. Slowly add ~10 mL of concentrated HCl to each to dissolve the sample. Be careful to avoid
losses due to spattering and, if necessary, rinse the weighing bottles with an additional 1-2
mL of HCl to ensure complete transfer of the sample.

The next step is to quantitatively precipitate and collect CaC2O4 while avoiding co-precipitation
of Ca2+ with either HC2O4- (at low pH’s) or OH- (at high pH’s). Moreover, crystallization of
CaC2O4 must occur slowly and the precipitate should be digested.

4. Dilute each sample to ~50 mL with deionized water and bring it to a boil.
5. Then add 100 mL of hot 3% (NH4)2C2O4.
6. Add ~6-8 drops of methyl red indicator.
7. Precipitate CaC2O4 by slowly adding 6 M NH3 in ~1 mL increments. When the indicator
starts to change colour, slow the rate to 1 drop of 6 M NH3 every few seconds while swirling
or stirring the mixture. At the yellow-orange intermediate colour of the indicator, stop
adding NH3.
8. Filter the mixture promptly through a fritted-glass crucible, being careful to collect all of the
precipitate. Wash the precipitate with three 10-mL portions of cold water. Rinse off the
outside of the filter with deionized water, discarding the washings, to remove any traces of
(NH4)2C2O4.
9. Place each crucible, containing CaC2O4, into a separate 400 mL beaker. To each, add 100
mL of deionized water and 150 mL of 1 M H2SO4.
10. Heat the solution to 80-90oC and then titrate with standard KMnO4 in the same manner used
in the standardization procedure.

Results and Discussion

For each trial, calculate the mass percent of CaO in the sample, paying careful attention to the
stoichiometry. Report for all three values, the mean, standard deviation and relative standard
deviation using manual and Microsoft Excel. Discuss the relative standard deviation obtained.