Experiment No.

12
The Amount of Calcium in Hard Water Sample

Introduction:
Water containing calcium and magnesium ions to a certain amount is called
hard water. Hard water has some detriment effects to industries and
household living. The extent of hard water is represented by the total amount
of calcium carbonate (ppm) in water sample. The determination of hard water
is by titration with EDTA, since EDTA can form complex with calcium and
magnesium ions in a 1:1 ratio the following equation established when the
end point is reached:

M
W
V
W
M
E
V
E

where V
W
and V
E
is the volume of water and EDTA, respectively, M
W
and M
E

is the concentration of calcium ion in water and of EDTA, respectively.
The formula of EDTA (H
4
Y) is:
HOOCCH
2
NCH
2
CH
2
N
HOOCCH
2
CH
2
COOH
CH
2
COOH

It can become the form of H
2
Y
2
in solution of pH = 10 and generate stable
complexes with calcium and magnesium ions.
The indicator of this titration is Eriochrome Black T (EBT), it is required to use
Mg
2+
to aid the color change by forming crimson MgIn

, at the end point of

titration the solution turns blue color HIn
2

:
Major reaction: H
2
Y
2
(aq)
Ca
2+
(aq)
CaY
2
(aq)
2H
+
(aq)
At the end point: H
2
Y
2
(aq)
MgIn

(aq)
MgY
2
(aq)
HIn
2
(aq)
H
+
(aq)
Procedure:
A.
1. Weigh 2 g of EDTA in a 250-mL beaker and add 250 mL of deionized water
into it. Stir it with a glass rod to dissolve the solid.
2. Wash a burette with a small amount of EDTA solution in step 1. Fill the
solution to the 0 scale of the burette.
3. Weigh 0.16 g of CaCO
3
in a 100-mL beaker, add 10 mL of deionized water
and 12 drops of concentrate HCl into the beaker.
4. Stir the solution carefully to dissolve the solid.
5. Pour the solution in step 4 to a 100-mL volumetric flask, wash the residue
solution of the beaker with deionized water into the volumetric flask, then fill
deionized water to the scale of the flask and mix well.
6. Pipette 25 mL of deionized water into an Erlenmeyer flask, add 5 mL of
buffer solution, 2 drops of indicator and 15 drops of MgCl
2
. Titrate the flask
with EDTA solution from purple to blue. This is called the blank titration.
7. Pipette 25 mL of solution in step 5 into an Erlenmeyer flask, add 5 mL of
buffer solution, 2 drops of indicator and 15 drops of MgCl
2
. Titrate the flask
with EDTA solution from purple to blue.
8. Repeat step 7 twice.
B.
1. Pipette 25 mL of solution provided by teacher into an Erlenmeyer flask, add
5 mL of buffer solution, 2 drops of indicator and 15 drops of MgCl
2
. Titrate
the flask with EDTA solution from purple to blue.
2. Repeat step 1 and let the difference of these two titrations within 3%.
Results:
(I)
Volume of CaCO
3
: 100 mL
Weight of CaCO
3
g
Ca
2+
M
Ca
2+
m mol
Blank titration mL
I II III
Volume of EDTA added
Subtract volume of blank titration
Average volume
EDTA M

(II) volume of sample analyzed mL
I II III
Volume of EDTA added
Subtract volume of blank titration
Average volume
Ca
2+
M
Hardness of water ppm CaCO
3











Questions:
1. Describe why EDTA is a hexadentate-ligand when it complexes with a
metal ion.
2. If we dissolve 0.4505 g of CaCO
3
in HCl and dilute to 250 mL, measure out
25 mL of this solution and titrate it with EDTA solution. It takes 24.25 mL of
EDTA solution to the titration end point. (a) How many moles of CaCO
3

present in its solution? (b) What is the [Ca
2+
] in its solution? (c) How many
moles of EDTA present in 24.25 mL of its solution? (d) What is the [EDTA] in
its solution?
3. If we titrate a 100 mL unknown sample with EDTA in question 2, it takes
23.24 mL of EDTA solution. How many ppm CaCO
3
present in this sample?
4. The dissociation constant of EBT in water as below:
H
2
In

HIn
2

+ H
+
K = 510

7
(red) (blue)
The complex of metal ion and EBT is purple red, and the titration with EDTA
makes the color of the complex from purple red to blue. In what pH range can
we observe the color change of the titration to avoid the interfere of the color
of H
2
In

(red)?
5. A 10-mL sample containing Mg
2+
, Ca
2+
is titrated with 26.81 mL of 0.003474
M EDTA to end point. Take another 10-mL of the same sample to react with
H
2
C
2
O
2
to precipitate out CaC
2
O
2
. If we dissolve the CaC
2
O
2
and titrate it
with 11.63 mL of EDTA to end point, how many mg of Ca
2+
, Mg
2+
present in
the 10-mL sample?