EXPERIMENT 4

EXPERIMENT 4:
Quantitative determination of calcium in powdered
milk
I.

INTRODUCTION:
1.

PURPOSE
Measuring the calcium concentration contains in powdered milk samples to determine how much

of the calcium in milk or knowing the amount of calcium that contain in milk

Understanding the practical steps of doing the experiment

2.
GENERAL PRINCIPLE
Oxalate ammonium will precipitate all calcium ion in any solution when the experimenter set up
all following conditions severely:

pH of solution environment is greater than 4

The hot, saturated (COONH4)2 solution is filled only one time into the sample containing calcium
ion.

Freeze the solution immediately after the solution has heated up for 1 minute
This method can be used for calcium quantification in milk, blood sample, urine, food, etc. and
the reactions are performed as following:
Ca2+ + (COONH4)2

2NH4+ + Ca(COO)2 (1)

Ca(COO)2 + H2SO4

CaSO4 + (COOH)2 (2)

5(COOH)2 + 2KMnO4 + 3H2SO4

3.

K SO + 2MnSO + 10CO
2
4
4
2

MATERIAL:
Equipment
Racemic crucibles
Muffle furnace
Desiccator
Burette
Erlenmeyer flasks
Beakers
Filter paper
pH meters

Categorize

250 mL
100 mL
11 mL

EXPERIMENT 4
Chemicals
Powdered milk
Saturated (COONH4)2
Concentrated HCl
Methyl red
0.1M NH4OH
Acetic acid
Saturated Calcium chloride
1N H2SO4
0.02N KMnO4
4.

Locations
Assigned area
Assigned area
Assigned area
Assigned area
Assigned area
Assigned area
Assigned area
Assigned area
Assigned area

METHOD:
Preparation of sample
Step 1: Pretreat milk sample of 0.5g by burning them with absolute ethanol or dehydrate them
with concentrated sulfuric acid.
Step 2: After the milk sample is almost completely burned, it turns into black color.
Step 3: Put the pretreated milk samples contained in racemic crucibles into the muffle furnace to
heat with temperature of 500oC for 15 minutes, counted from the time that temperature of the muffle
furnace reach 500oC.
Step 4: Let the milk ash sample cool down and put them into desiccator over night before
performing experiment.
Calcium quantification
Step 1: Take three milk ash samples contained in three separated racemic crucibles out of the
desiccator and add 5mL of distilled water, and then 5 drops of concentrated chlohydric acid.
Step 2: Mix well and transfer these solutions separately into 3 different beakers of 250mL to
adjust pH.
Step 3: Add 10-15 drops of methyl red and carry out the neutralization by 0.1 ammonium
solution.
Step 4: Adjust the pH of the solution to from 5 to 5.2 by acetic acid of weak concentration. At
that point, the solution color is orange-pink. Due to the instrumental error, each pH meter will give a
different value of pH. Therefore, observe the color of solution is also very important. Do not over-rely
on any type of machine.
Step 5: While heating theses beakers by water bath, stirring these solutions and fill 2-3mL of
saturated (COONH4)2 solution.

EXPERIMENT 4
Step 6: Continue to provide heat to these beakers and then mix these solution well for 30
seconds.
Step 7: Put these beakers in cool basin of water immediately.
Step 8: Keep the beaker in the basin of water for about 30 minutes.
Step 9: Use filter paper to collect all the precipitate.
Step 10: Use distilled water to wash the filter paper to know whether (COO)22- ions are all
eliminated or not. To check it, we use saturated calcium chloride solution.
Step 11: Collect precipitate retained by filter paper and put them into Erlenmeyer flask
Step 12: Add 20mL of 1N sulfuric acid solution into each Erlenmeyer flask and heat them in
water bath with temperature of 70oC for 1 minute.
Step 13: Titrate the solution with 0.02 N potassium permanganate solution to determine the
concentration of (COO)22- ion in the solution.
Step 14: Use the rule of three to calculate the amount of calcium ion in the solution and in
the sample.

II.

RESULTS AND DATA ANALYSIS:

1.

Result table:
The amount of KMnO4 (mL) is used to titrate the unknown calcium in each flask:

Flask number
Flask 1
Flask 2
Flask 3

2.

Data analysis:

KMnO4
12.7
13.8
11.9

EXPERIMENT 4
Base on the reaction (3): Mn7++ 5e Mn2+
The relation between the concentration (M) and the concentration (N) is:
N 0.02
M= =
=4 103
ne
5
It is also the moles of 0.02N KMnO4 that contains in 1 liter of solution.
The moles of 0.02 N KMnO4 that contains in V liter of solution is:

n = V410-3(mol)
Base on the reactions (1), (2), (3), we have:
5
5
Ca2+= n KMnO 4= V 4 103=0.01 V (mol)
2
2
n
The gram of Calcium that contains in (m) g of milk powder:

mCa2+ = 0.01V40 = 0.4V (g)

The gram of Calcium that contains in 100g of milk powder:

0.4 V 100
Ca2+=
=80 V (g)
0.5
m

Where:
V: the volume (L) of 0.02 N KMnO4 that is used to determine the quantitative measurement
m: the weight of the powdered milk (m=0.5g)
ne: is quantity of electron(s) that is/are used to transfer from reductive substance to
oxidative substance in the reaction.
Apply the below equation, the the grams of Calsium in 100g of milk powdered are

Calsium(g)/ 100g

Flask 1
1.016

Flask 2
1.104

milk
Average (g)

1.024

Flask 3
0.952

EXPERIMENT 4

III.

DISCUSSION:
The result show the average amount of calcium in 100g powderd milk is 1.024g. The number we

got is quitte close in compare with the one that the company powdered on milk packaging (1.1/100g).
The result of this experiment can be affected by:
The equipment are contaminated
The chemicals added are excessive or deficiency.
In the theory, after heat the beaker, we have to put these beakers in cool water container
immediately. However, when doing the experiment, the beaker may not put in cool water quick

IV.

enough.
The ammonium solution was added too much or not enough in the sample.
CONCLUSION
In the experiment, it proves that the Oxalate Ammonium is played an important role in
quantitative Calcium in milk powder, which means the calcium ions content in milk was precipitate
and filtered to determine the mass.