Group 3

Alano, Pamela
Alipio, Rianne
Borromeo, Lorenz
De Leon, Jasen Emil
De Sagun, David
Lunas, Louise Dianne
San Luis, Rommel Jr.











Instructor:
Engr. Jocelyn Balisnomo
Experiment No. 3



ESTIMATION OF THE TOTAL HARDNESS OF A WATER SAMPLE USING EDTA


I. Objectives:

Use a complexometric titration to determine the total concentration of calcium and
magnesium ions in a water sample.

II. Materials:

Laboratory Apparatus: Reagents:
Graduated Cylinder Hard Water Sample
Spatulas for solid indicator Standardized EDTA solution
Aspirator Ammonia Buffer Solution (pH 10)
Volumetric Flask Distilled Water
Beakers Eriochrome Black T Indicator
White Card
Erlenmeyer Flask
Base Burette
Iron Stand
Burette Clamp
Funnel
Wash Bottle
Acid Pipette

III. Procedures:

1. Wash the pipette, burette and Erlenmeyer flask with deionise/distilled
water. Rinse the burette with the EDTA solution and the pipette with the
hard water.
2. Using the funnel, fill the burette with the EDTA solution. Open the tap
briefly to fill the part below the tap. Remove the funnel. Adjust the level
of the solution to the zero mark. Make sure that the burette is vertical.
3. Use the pipette to transfer 50ml of the hard water sample to the conical
flask.
4. Add 0.03g of the solid indicator to the contents of the flask in the
following manner: Add gradually to the flask, swirling each addition. A
deep wine red color is obtained.
5. Carry out one rough titration to find the approximate end point,
followed by a number of accurate titrations until two titres agree to

within 0.1ml. At the end point, the color should be dark blue, with no
tinge of wine-red color.
6. From the data, calculate the total hardness of the water sample.

IV. Computations

A. Preparation of CaCO
3
concentration of HCl

C
HCl
= (37g/100g)(1.18g/1ml)(1000ml/1L)(1mol HCl/36.45g HCl)
C
HCl
= 11.98M

Dilution of HCl:
11.98M(V
1
)=(1M)(12ml)
V
1
=0.99ml of 11.98M HCl needed

Reaction:
CaCO
3
+HCl --->Ca
+2
+CO
2
+H
2
O +2Cl
-

Titer Concentration (CaCO
3
solution)
250mg CaCO
3
/250ml solution =
1mg CaCO
3
/ml


B. Preparation of EDTA solution

Titer Concentration (EDTA solution)
1000mg CaCO
3
/250ml solution =
4mg EDTA/ml

%MgCl
2
.6H
2
O (w/w) = 0.01 = (g MgCl
2
.6H
2
O/30g + g MgCl
2
.6H
2
O)
Mass of MgCl
2
.6H
2
O = 0.3 g

C. Standardization of EDTA solution

Reaction:
Ca
+2
+EDTA-
4
------>CaEDTA
-2

Aliquot: 25ml of CaCO
3
(1mg CaCO
3
/ml)
= 25mg CaCO
3


Ammonia Buffer (for NH
3
):
20ml(16.5M)=(C
m
)(500ml)
C
m
=0.66M
(150ml)(0.66M)=(16.5M)(V)
V=6ml


Indicator: 0.5g /100 ml ethanol)(10ml)= 0.05g

Standardization of EDTA Solution

Volume of EDTA used
V
0
= 0.00ml
V
F
= 19.2 ml
V
U
= V
F
V
0
= 19.2 ml

Aliquot used:
25.00ml of CaCO
3
(1mg CaCO
3
/ml) = 25.00mg CaCO
3
needs 19.2 ml of EDTA Solution

Calculations: (EDTA Titer)
E
T
= 25.00mg CaCO
3
/19.2 ml EDTA solution = 1.302 mg CaCO
3
/ml EDTA



V. Results:

Table of Results

Volume of the Hard
Water Sample
(VIVA Mineral
Water)
50ml
Concentration
(Titer) of
EDTA solution
1.302 mg
CaCO
3
/ml
EDTA
1
st
Titration 7.3 ml EDTA
2
nd
Titration 7.2 ml EDTA
3
rd
Titration 7.3 ml EDTA
Concordant
Value
7.3 ml

TOTAL HARDNESS (mg/L CaCO
3
) = 7.3ml EDTA (


)(

)
=

)
=

Viva Mineral Water (Ca
+
) concentration =

(


)

=

*The Viva Mineral Water claims that its calcium ion concentration (Ca
+
) in mg/L is 54mg/L or
134.85mg CaCO
3
/L. Based on our analysis, the estimated CaCO
3
result was 190.1 mg/L. We can
then conclude that the bottled Viva mineral water is quite harder than they claim it to be.

VI. Answers to Questions:

1. Why is it important that the reaction between the EDTA and the metal
ions in solution is (i) rapid and (ii) go to completion?
These are general requirements of any titrimetic reaction. If the
reaction is not almost instantaneous the colour change of the indicator will lag
behind the end point and too large a titre would be recorded. If the reagents do
not react completely, no conclusion about the concentration of one of the
solutions can be obtained from the volume of it that reacts with a known
concentration and volume of the other.

2. The water sample could contain metal ions other than Ca
2+
and Mg
2+
.
How would the reliability of the result be affected if this were the case?
Suggest two other metal ions that could be present in the water.
Since alkali metal ions such as sodium or potassium ions do not
complex with edta reagent, the results would be unaffected by their presence
in the water sample. If, however, there were, for example, iron or aluminium
ions present, the value recorded for total hardness by this method would be
expected to be too high.

3. This reagent cannot distinguish between temporary and permanent
hardness, List the compounds of calcium and magnesium that cause
hardness, and indicate those which cause temporary hardness.
MgSO
4
, MgCl
2
, Mg(HCO
3
)
2
, CaSO
4
, CaCl
2
and Ca(HCO
3
)
2
are the
water-soluble compounds of magnesium and calcium that cause hardness.
Mg(HCO
3
)
2
and Ca(HCO
3
)
2
cause temporary hardness.

4. Suggest a method of establishing the amount of permanent hardness in a
water sample.
A known volume of hard water is boiled to precipitate the temporary
hardness-causing hydrogencarbonate compounds as carbonates. These are
removed by filtration. The filter paper is washed with deionised water.
The filtrate is made up to an exact volume with deionised water and the
edta titration carried out again. The result is used to calculate the
permanent hardness of the water sample.

5. What is the function of the buffer solution?

All reactions between metal ions and EDTA are pH dependent. For
divalent ions, solutions must be kept basic (buffered) for the reaction to go to
completion.
Eriochrome black T indicator requires a pH of 8 to 10 for the desired color
change.

VII. Conclusion

Determination of Hardness of Water
Hard water is due to metal ions(minerals) that are dissolved in the ground water. These
minerals include Ca
2+
, Mg
2+
, Fe
3+
, SO
4
2-
, and HCO
3
-
. This is due to rain moving through the vast
amount of limestone, CaCO
3
that occurs in our area to the aquifer. This is why we measure
hardness in terms of CaCO
3
; The concentration of the Ca
2+
ions is greater than the concentration
of any other metal ion in our water.
Environmental Levels and Human Exposure

Water

Concentrations of up to 100 mg of calcium per litre are fairly common in natural sources
of water; sources containing over 200 mg of calcium per litre are rare. Magnesium salts are
soluble, natural water sources typically containing concentrations of up to 10 mg/litre. Such
sources rarely contain more than 100 mg of magnesium per litre, and it is usually calcium
hardness that predominates. In drinking-water, hardness is in the range 10500 mg of calcium
carbonate per litre. Estimated daily intakes of 2.3 and 52.1 mg of magnesium in soft- and hard-
water areas, respectively, have been reported, based on adults drinking 2 litres of water per day.

Food

Virtually all foods contain calcium and magnesium, and dietary intake is the principal
route of exposure. Typical diets provide about 1000 mg of calcium per day and 200400 mg of
magnesium per day. Dairy products are a particularly rich source of calcium, whereas
magnesium tends to be associated more with meat and foodstuffs of plant origin. Estimated total
exposure and relative contribution of drinking-water. The typical dietary contribution of calcium
and magnesium is over 80% of the total daily intake. Of this, approximately 30% of calcium and
35% of magnesium will be absorbed. For calcium and magnesium, the typical contribution from
water is 520%.

Effects on Human
There does not appear to be any convincing evidence that water hardness causes adverse
health effects in humans. In contrast, the results of a number of epidemiological studies have
suggested that water hardness may protect against disease. However, the available data are
inadequate to prove any causal association.