The Amount of Calcium in

Hard Water Sample

Water's hardness is determined by the concentration of
multivalent cations in the water. Multivalent cations are
cations (positively charged metal complexes) with a charge
greater than 1+. Usually, the cations have the charge of 2+.
Common cations found in hard water include Ca
2+
and Mg
2+
.
Hard Water
Temporary hard water: Temporary hardness of water can be
reduced either by boiling the water, or by the addition of lime
(calcium hydroxide) through the softening process of lime
softening. e.g. water containing Ca(HCO
3
)
2
, Mg(HCO
3
)
2
Permanent hard water: Permanent hardness of water is
hardness (mineral content) that cannot be removed by boiling. e.g.
water containing CaSO
4
, MgSO
4
, CaCl
2
, MgCl
2
Hardness of water can be expressed by total amount of CaCO
3
(unit: ppm)
Hard water may cause industrial safety problem. e.g. As the
water temperature increases, the more mineral deposits will
appear in the water. It will cover the inner layer of the boiler to
interrupt the heat transfer.
EDTA (Ethylene Diamine Tetraacetic Acid) is a hexadentate (six-
toothed) ligand and chelating agent, i.e. its ability to sequester
metal ions such as Ca
2+
and Fe
3+
. After being bound by EDTA,
metal ions remain in solution but exhibit diminished reactivity.
O
Ca
O
O
N
N
O
O
CH
2
CH
2
CH
2
O
CH
2
CH
2
C
H
2
O
O
2-
N CH
2
H
2
C
H
2
C
HOOC
HOOC
CH
2
N
CH
2
CH
2
COOH
COOH
EDTA
Metal EDTA chelate
(metal:EDTA=1:1)
Fractional composition diagram for EDTA
OH
N N
OH O
3
S
O
2
N
The indicator EBT (Eriochrome Black T) (HIn
2
)
reacts with Mg
2+
to form the complex MgIn

with
wine red color. After chelating Mg
2+
by EDTA, the
color of indicator (HIn
2
) changes to sky blue color.
H
2
Y
2
(aq)Ca
2+
(aq) CaY
2
(aq) 2H
+
(aq)
H
2
Y
2
(aq)MgIn

(aq)
wine red
MgY
2
(aq)HIn
2
(aq)H
+
(aq)
sky blue
EBT (Eriochrome Black T)
The purpose of adding buffer solution (pH 10)
EBT indicator requires an environment at pH
above 7.3 for the desired color change:

H
2
In

HIn
2
+ H
+
K = 510
7
(wine red) (sky blue)
7.3 pH 10
] In [H
] [HIn
10 5
] In [H
] ][H [HIn
2
2
7
2
2

-
-
-
-
-
EBT is blue in a buffered solution at pH 10, it turns
red when Ca
2+
ions were added.
Suitable pH values for titration of Ca
2+
, Mg
2+
with
EDTA are above 7.6 and 10.0, respectively:
K
MY
2 : formation constant
of EDTA-metal complex
K
CaY
2 : 1.7510
10
K
MgY
2 : 1.7210
8
electronic balance
beaker (250 mL)
volumetric flask (100 mL)
pipette
pipet filler
burette
flask (125 mL)
Apparatus & Materials
calcium carbonate HCl
(aq)
EBT (Eriochrome Black T) MgCl
2
buffer solution (pH 10)
Chemicals
The Amount of Calcium in Hard Water Sample
250 mL
ddH
2
O
25 mL ddH
2
O
10 mL buffer (pH 10)
10 drop of EBT
15 drop of 0.03 M
MgCl
2(aq)
10 mL
ddH
2
O
12 drop of HCl
(aq)
(prepare it in the hood)
(add additional water
to the mark of the flask)
0.016 M Ca
2+

solution
(blank
titration)
10 mL buffer (pH 10)
10 drop of EBT
15 drop of 0.03 M
MgCl
2(aq)
0.016 M Ca
2+

solution
Ca
2+
solution
(unknown
concentration)
10 mL buffer (pH 10)
10 drop of EBT
15 drop of 0.03 M
MgCl
2(aq)
(repeat titration twice)
(repeat titration again)
2.0 g
EDTA 2Na
(s)
(Step A) Calibration
of EDTA Solution
(Step B) Estimation of Hardness of Water
(Step A) Calibration of EDTA2Na Solution
weight of CaCO
3
g
[Ca
2+
] M
Ca
2+
m mol
exhausted volume of EDTA solution for blank titration
mL
volume of EDTA added mL
volume after subtracting volume of blank titration mL
average volume mL
[EDTA] M
Results
(Step B) Estimation of Hardness of Water
I II
volume of EDTA added mL
volume after subtracting volume of blank titration mL
average volume mL
mmole of EDTA mmol
[Ca
2+
] M
hardness of water ppm CaCO
3