CHEMISTRY INVESTIGATORY PROJECT

ON
HARD WATER

By:
Mazen Ur Rahman
Class:
11A
INTRODUCTION:

 Hard water is water that has high mineral content (in contrast with
"soft water"). Hard water is formed when water percolates through
deposits of limestone and chalk which are largely made up of calcium
and magnesium carbonates.

 Hard drinking water may have moderate health benefits, but can pose
critical problems in industrial settings, where water hardness is
monitored to avoid costly breakdowns in boilers, cooling towers, and
other equipment that handles water. In domestic settings, hard water
is often indicated by a lack of foam formation when soap is agitated in
water, and by the formation of limescale in kettles and water heaters.
Wherever water hardness is a concern, water softening is commonly
used to reduce hard water's adverse effects.

A bathtub faucet with built-up calcification from hard water.

Sources of hardness

Water's hardness is determined by the concentration of multivalent cations

in the water. Multivalent cations are 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 Ca2+ and Mg2+. These ions
enter a water supply by leaching from minerals within an aquifer. Common
calcium-containing minerals are calcite and gypsum. A common magnesium
mineral is dolomite (which also contains calcium). Rainwater and distilled
water are soft, because they contain few ions.
The following equilibrium reaction describes the dissolving and formation of
calcium carbonate and calcium bicarbonate (on the right):
CaCO3 (s) + CO2 (aq) + H2O (l) ⇋ Ca2+ (aq) + 2HCO3− (aq)
The reaction can go in either direction. Rain containing dissolved carbon
dioxide can react with calcium carbonate and carry calcium ions away with
it. The calcium carbonate may be re-deposited as calcite as the carbon
dioxide is lost to atmosphere, sometimes forming stalactites and
stalagmites.
Calcium and magnesium ions can sometimes be removed by water
softeners.

Types of Hardness:

 Temporary hardness
Temporary hardness is a type of water hardness caused by the presence of
dissolved bicarbonate minerals (calcium bicarbonate and magnesium
bicarbonate). When dissolved, these minerals yield calcium and magnesium
cations (Ca2+, Mg2+) and carbonate and bicarbonate anions (CO32−,
HCO3−). The presence of the metal cations makes the water hard. However,
unlike the permanent hardness caused by sulphate and chloride
compounds, this "temporary" hardness can be reduced either by boiling the
water, or by the addition of lime (calcium hydroxide) through the process of
lime softening. Boiling promotes the formation of carbonate from the
bicarbonate and precipitates calcium carbonate out of solution, leaving
water that is softer upon cooling.

 Permanent hardness
Permanent hardness is hardness (mineral content) that cannot be removed
by boiling. When this is the case, it is usually caused by the presence of
calcium sulphate/calcium chloride and/or magnesium sulphate/magnesium
chloride in the water, which do not precipitate out as the temperature
increases. Ions causing permanent hardness of water can be removed using
a water softener, or ion exchange column.

Total Permanent Hardness = Permanent Calcium Hardness + Permanent

Magnesium Hardness

Effects:
With hard water, soap solutions form a white precipitate (soap scum)
instead of producing lather, because the 2+ ions destroy the surfactant
properties of the soap by forming a solid precipitate (the soap scum). A
major component of such scum is calcium stearate, which arises from
sodium stearate, the main component of soap:

2 C17H35COO− (aq) + Ca2+ (aq) → (C17H35COO)2Ca (s)

Hardness can thus be defined as the soap-consuming capacity of a water
sample, or the capacity of precipitation of soap as a characteristic property
of water that prevents the lathering of soap. Synthetic detergents do not
form such scums.

A portion of the ancient Roman Eifel aqueduct in Germany. After being in

service for about 180 years, the aqueduct had mineral deposits of up to 20
cm thick along the walls.
Hard water also forms deposits that clog plumbing. These deposits, called
"scale", are composed mainly of calcium carbonate (CaCO3), magnesium
hydroxide (Mg(OH)2), and calcium sulfate (CaSO4). Calcium and magnesium
carbonates tend to be deposited as off-white solids on the inside surfaces of
pipes and heat exchangers. This precipitation (formation of an insoluble
solid) is principally caused by thermal decomposition of bicarbonate ions but
also happens in cases where the carbonate ion is at saturation
concentration. The resulting build-up of scale restricts the flow of water in
pipes. In boilers, the deposits impair the flow of heat into water, reducing
the heating efficiency and allowing the metal boiler components to
overheat. In a pressurized system, this overheating can lead to failure of the
boiler. The damage caused by calcium carbonate deposits varies on the
crystalline form, for example, calcite or aragonite.
The presence of ions in an electrolyte, in this case, hard water, can also lead
to galvanic corrosion, in which one metal will preferentially corrode when in
contact with another type of metal, when both are in contact with an
electrolyte. The softening of hard water by ion exchange does not increase
its corrosivity per se. Similarly, where lead plumbing is in use, softened
water does not substantially increase plumbo-solvency.

In swimming pools, hard water is manifested by a turbid, or cloudy (milky),

appearance to the water. Calcium and magnesium hydroxides are both
soluble in water. The solubility of the hydroxides of the alkaline-earth metals
to which calcium and magnesium belong (group 2 of the periodic table)
increases moving down the column. Aqueous solutions of these metal
hydroxides absorb carbon dioxide from the air, forming the insoluble
carbonates, giving rise to the turbidity. This often results from the pH being
excessively high (pH > 7.6). Hence, a common solution to the problem is,
while maintaining the chlorine concentration at the proper level, to lower
the pH by the addition of hydrochloric acid, the optimum value being in the
range of 7.2 to 7.6.

Softening
Main article: Water softening
It is often desirable to soften hard water. Most detergents contain
ingredients that counteract the effects of hard water on the surfactants. For
this reason, water softening is often unnecessary. Where softening is
practiced, it is often recommended to soften only the water sent to
domestic hot water systems so as to prevent or delay inefficiencies and
damage due to scale formation in water heaters. A common method for
water softening involves the use of ion exchange resins, which replace ions
like Ca2+ by twice the number of monocations (such as sodium or potassium
ions).
Washing soda (sodium carbonate - Na2CO3) is easily obtained and has long
been used as a water softener for domestic laundry, in conjunction with the
usual soap or detergent.

Health considerations
The World Health Organization says that "there does not appear to be any
convincing evidence that water hardness causes adverse health effects in
humans". In fact, the United States National Research Council has found that
hard water actually serves as a dietary supplement for calcium and
magnesium.

Some studies have shown a weak inverse relationship between water

hardness and cardiovascular disease in men, up to a level of 170 mg calcium
carbonate per litre of water. The World Health Organization has reviewed
the evidence and concluded the data was inadequate to allow for a
recommendation for a level of hardness.

Recommendations have been made for the maximum and minimum levels
of calcium (40–80 ppm) and magnesium (20–30 ppm) in drinking water, and
a total hardness expressed as the sum of the calcium and magnesium
concentrations of 2–4 mmol/L.

Other studies have shown weak correlations between cardiovascular health

and water hardness
Some studies correlate domestic hard water usage with increased eczema in
children.
The Softened-Water Eczema Trial (SWET), a multicenter randomized
controlled trial of ion-exchange softeners for treating childhood eczema,
was undertaken in 2008. However, no meaningful difference in symptom
relief was found between children with access to a home water softener and
those without. [18]

EDTA:
Ethylenediaminetetraacetic acid (EDTA), also known by several other names,
is a chemical used for both industrial and medical purposes. It was
synthesized for the first time in 1935 by Ferdinand Münz.

It is an aminopolycarboxylic acid and a colorless, water-soluble solid. Its

conjugate base is ethylenediaminetetraacetate. It is widely used to dissolve
limescale. Its usefulness arises because of its role as a hexadentate ("six-
toothed") ligand and chelating agent, i.e., its ability to sequester metal ions
such as Ca2+ and Fe3+. After being bound by EDTA into a metal complex,
metal ions remain in solution but exhibit diminished reactivity. EDTA is
produced as several salts, notably disodium EDTA and calcium disodium
EDTA.
 Structure:
 DETERMING HARDNESS OF WATER BY EDTA
TITRATION

The ions involved in water hardness, i.e. Ca2+ (aq) and Mg2+ (aq), can
be determined by titration with a chelating agent,
ethylenediaminetetraacetic acid (EDTA), usually in the form of disodium
salt (H2Y2-). The titration reaction is:

Eriochrome Black T is commonly used as indicator for the above

titration.
At pH 10, Ca2+ (aq) ion first complexes with the indicator as CaIn+ (aq)
which is wine red. As the stronger ligand EDTA is added, the CaIn+ (aq)
complex is replaced by the CaY2- (aq) complex which is blue.
The end point of titration is indicated by a sharp colour change from
wine red to blue. Titration using Eriochrome Black T as indicator
determines total hardness due to Ca2+ (aq) and Mg2+ (aq) ions.
Hardness due to Ca2+ (aq) ion is determined by a separate titration at
a higher pH, by adding NaOH solution to precipitate Mg(OH)2(s), using
hydroxynaphthol blue as indicator.
 EDTA TITRATION METHOD

 Aim: To estimate the amount of total hardness present in the given

sample of water by EDTA titration method.
 Apparatus required: 50 ml Burette, 20 ml Pipette, 250 ml conical flask,
100 ml Beaker, 250 ml beaker, Glass funnel.
 Reagents: EDTA solution, Standard CaCO3 solution, Eriochrome Black–
T indicator, Buffer solution.
 Theory: EDTA (Ethylenediamine tetra acetic acid) forms colourless
stable complexes with Ca2+ and Mg2+ ions present in water at pH = 9-
10. To maintain the pH of the solution at 9-10, Buffer solution (NH4Cl +
NH4OH) is used. Eriochrome Black-T (E.B.T) is used as an indicator.
The sample of hard water must be treated with buffer solution and EBT
indicator which forms unstable, wine-red coloured complex s with Ca2+ and
Mg2+ present in water.
.
 PROCEDURE

1. Standardization of EDTA

i. Pipette out 20 ml of standard hard water into a conical flask.

ii. Add 5 ml of buffer solution and few drops of Eriochrome Black-T. The
indicator (which is originally blue colour), would acquire a wine-red
colour.
iii. Titrate with EDTA solution taken in the burette, till the wine red colour
changes to blue (which is the end point). Let the burette reading of
EDTA be V2 ml.
2. Determination of Total hardness
Repeat the above titration method for sample hard water instead of
standard hard water. Let the burette reading of EDTA be V3 ml.
3. Determination of Permanent hardness

Take 100 ml of sample hard water in 250 ml beaker. Boil it to remove

temporary hardness to about half of this volume and cool to room
temperature. Filter through filter paper to remove insoluble CaCO3 and
MgCO3. Make up the volume to the original 100 ml by adding distilled
water. Now pipette out 20 ml of this solution into a clean conical flask. Then
repeat the process of titration steps as mentioned above. Let the burette
reading of EDTA be V4 ml.

OBSERVATIONS

1. Standardisation of EDTA
Burette Reading Vol. of
S.No Vol. of Hard water EDTA
taken (ml) Initial Final Consumed
(V2 ml)
1.

2.

3.
2. Determination of Total hardness:
Burette Reading Vol. of
S.No Vol. of Hard water EDTA
taken (ml) Initial Final Consumed
(V3 ml)

1.

2.

3.

3. Determination of Permanent hardness:

Burette Reading Vol. of
S.No Vol. of Hard water EDTA
taken (ml) Initial Final Consumed
(V4 ml)

1.

2.

3.
 CALCULATIONS

1. Standardization of EDTA
M1V1 = M2V2
Where, M1 = Molarity of standard hard water
V1 = Volume of standard hard water in conical flask
M2 = Molarity of EDTA
V2 = Volume of EDTA consumed (burette reading)

2. Determination of Total hardness

M2V2 = M3V3
Where, M3 = Total hardness of sample water
V1 = Volume of sample hard water in conical flask

3. Determination of Permanent hardness

M2V2 = M4V4
Where, M4= Permanent hardness of sample water
V4 = Volume of sample hard water in conical flask
Note: Multiply M3 and M4 with 105 to covert hardness into parts per million
(ppm).
4. Determination of Temporary hardness
Temporary hardness = Total hardness – Permanent hardness

Result:
The hardness of the given water sample has been found to be as follows:
Total hardness = ------------------------------------ ppm
Permanent hardness = ------------------------------ ppm
Temporary hardness = ----------------------------- ppm