Analysis of hard water

Introduction

Hard water is water that has high mineral content (in contrast
with soft water). Hard water has high concentrations
of calcium, magnesium and iron ions.
These ions are called hardening ion.

In low concentrations, these ions are not considered harmful

for domestic use, but when present in higher concentrations
these ions interfere with the cleansing action of soaps and
accelerate the corrosion of steel pipes, especially those
carrying hot water

Soaps are sodium or potassium salts of higher fatty acids such

as stearic acid, C17H35COOH . Soaps such as C17H35COONa+
are very effective cleansing agents so long as they remain
soluble in water. They react with Ca2+ and Na2+ ions present in
hard water and form an insoluble sticky precipitate of calcium
and magnesium salts of fatty acids known as scum and thus
interfere in the cleansing action of soap.

C17H35COONa+ (aq) + Ca2+ (aq) C17H35COOCa2+ +2Na+

Hardness of water can be defined as the soap – consuming

capacity of water, or the capacity of precipitation of soap as a
characteristic property of water that prevents the lathering of
soap. It is responsible for the formation of boiler scales on tea
kettles and vessels used for heating water. The boiler scale
reduces the efficiency of transfer of heat because it is a bad
conductor of heat. Formation of boiler scale in the pipes
carrying hot water reduces the rate of flow of water in them.
On extreme cases due to overheating the boiler or the pipes
may break due to overheating. The boiler scale consists of
primarily of the carbonates of hardening ions.

Ca2+ (aq) + 2HCO3-(aq) CaCO3(s)+CO2(g)+H2O(l)

The hardening ions enter into water as a result of reaction
between slightly acidic rain water and mineral deposits.
Ground water becomes hard as it flows through underground
lime – stone deposits. The water from the deep wells has
higher degree of hardness as compared with water from
shallow wells because of greater interaction with the lime –
stone deposits.CO2 dissolved in water, makes it slightly acidic
and helps in dissolved lime-stone deposits.

CO2 (aq) + CaCO3(s) + H2O(l) Ca2+ (aq) + 2HCO3-(aq)

Types of hard water

Hard water can be classified into two:-

 Temporary Hard water

 Permanent Hard water

Temporary hardness

Temporary hardness is caused by a combination of calcium

ions and bicarbonate ions in the water. it can be removed by
boiling the water or by the addition of lime (calcium
hydroxide). Boiling promotes the formation of carbonate from
bicarbonate and precipitates calcium carbonate out of the
solution, leaving water that is softer upon cooling.

The following is the equilibrium reaction when calcium

carbonate (CaCO3) is dissolved in water.

CaCO3(s) + CO2(g) +H2O(l) Ca2+ (aq) + 2HCO3-(aq)

Upon heating, less CO2 is able to dissolve into the water. Since
there is not enough CO2 around, the reaction cannot proceed
from left to right, and therefore the CaCO3 will not dissolve
rapidly. Instead, the reaction is forced to the left to
reestablish equilibrium, and solid CaCO 3 is formed.
Boiling the water will remove hardness as long as the solid
CaCO3 that participates out is removed. After cooling, if
enough time passes, the water will pick up CO 2 from the air
and the reaction will again proceed from left to right ,allowing
the CaCO3 re-dissolve into the water.

Permanent hardness

Permanent hardness is hardness that cannot be removed by

boiling. It is usually caused by the presence of calcium and
magnesium sulphates and or chlorides which become more
soluble as the temperature rises. Despite the name,
permanent hardness can be removed using a water softener or
ion exchange column, where the calcium and magnesium ions
are exchanged with the sodium ions in the column.

Hard water causes scaling, which is the left – over mineral

deposits that are formed after the hard water had
evaporated .this is also known as lime scale the scale can clog
pipes , ruin water heaters , coat the inside of tea and coffee
pots and decrease the life of toilet flushing units.

Hardening must be constantly monitored to avoid costly

breakdowns in contact with water. Hardness is controlled by
the addition of chemicals and by large-scale softening with
zeolites (Na2Al2SiO8.xH2O) and ion exchange resins.
Effects of hard water

These are advantages and disadvantages for people who live in

hard water areas.

Disadvantages of hard water

 It is difficult to form lather with soap.
 Scum may form in a reaction with soap thus wasting
soap.
 Lime scale (a hard crust) forms inside kettles. This
wastes energy whenever you boil a kettle.
 Hot water pipes fur up. Lime scale starts to coat the
inside of the pipes which can eventually can get blocked
up.

Advantages of hard water

 Some people prefer the taste.
 Calcium ions in the water are good for children’s teeth
and bones.
 It helps to reduce heart disease.
 A coating of lime scale onside copper pipes or especially
old lead pipes sops poisonous salts dissolving into water

EFFECTS ON SKIN

Some confusion may arise after a first experience with soft

water. Hard water does lather well with soap and leaves a
“clean feeling”. Soft water lathers better than hard water but
leaves a “slippery feeling” on the skin after use with soap.
Some providers of water softening equipment claim that the
“slippery feeling” after showering in soft water is due to “clean
skin” and absence of friction causing soap scum.

However, the chemical explanation is that softened water,

because of its sodium content, has a much reduced ability to
combine with the soap film on the body; therefore, the soap is
much more difficult to rinse off. Solution are to use less soap
or a synthetic liquid body wash.
SOFTENING

It is often considered desirable to soften hard water. This is

because the calcium and Magnesium ions block the oil
emulsifying action of soap due to the formation of insoluble
scum. Large amount of soap have to be used to counteract
this. Most modern soaps and detergents contain ingredients
that at least partly prevent this effect and detergents are
available that are chemically completely unaffected by the
hardness. This makes hardness removal/softening an
optional rather than a necessary water treatment except
possibly in the case of extremely hard water. Where softening
is practiced it is often recommended to soften only the water
sent to domestic hot water systems so as to prevent damage
due to scale formation in water heaters. Another reason for
this is to avoid adding sodium or potassium from the softener
to cold water taken for human consumption while still
providing softening for hot water used in washing and bathing.

PROCESS

A water softener works on the principle of cation or ion

exchange in which hardening ions are exchanged for Sodium
or Potassium ions, effectively reducing the concentration of
hardness to tolerable levels and thus making the water softer
and giving it a smoother feeling.

The most economical way to soften household water is with an

ion exchange water Softener. This unit uses Sodium Chloride
(NaCl) to recharge beads made of the ion exchange resins that
exchange hardness mineral ions for sodium ions. Artificial or
natural zeolites can also be used.

As the hard water passes through the beads, the hardness

mineral ions are preferentially absorbed, displacing the
sodium ions. This process is called ion exchange. When bead
or sodium zeolite has a low concentration of sodium ions left,
it is exhausted, and can no longer soften water. The resin is
recharged by flushing with salt water. The high excess
concentration of sodium ions alter the equilibrium between the
ions in solution and the ions held on the surface of the resin,
resulting in replacement of the hardness mineral ions on the
resin or zeolite with sodium ions. The resulting saltwater and
mineral ion solution is then rinsed away, and the resin is
ready to start the process all over again. This cycle can be
repeated many times. Potassium chloride may also be used to
regenerate the resin beads. It exchanges the hardness ions for
potassium. It also will exchange naturally occurring sodium
for potassium resulting in sodium-free soft water.

Some softening processes in industry use the same method,

but on a much larger scale. These methods create as
enormous amount of salty water that is costly to treat and
dispose of.

MEASUREMENT

The simple way to determine the hardness of water is the

lather/froth test:

When agitated, lathers easily in soft water but not in hard

water. More exact measurements of hardness can be obtained
through a wet titration. Although water hardness usually
measures only the total concentrations of Calcium and
Magnesium (the two most prevalent, divalent metal ions), iron,
Aluminium, and Manganese may also be present at elevated
levels in some geographical locations.

The degree of hardness in water depends on the extent of

hardening ions present in water. The concentration of
hardening ions is a water sample is generally expressed as
though the hardness is due exclusively to CaCO 3. The units or
hardness is mg CaCO3/litre which is same as parts per million
(ppm) CaCO3.
A General Classification Of Hard Water is given below:

Hardness (ppm CaCO3) Classification

<15ppm Very soft water

15ppm-50ppm Soft water
50ppm-100ppm Medium hard water
100ppm-200ppm Hard water
>200ppm Very hard water
 Experiment

Aim
To determine the hardness of a water sample

Requirements
250ml conical flask , funnel , beaker , burette , pipette.
Standard EDTA(Na2H2Y)solution ,buffer
solution(pH=10),Erichrome Black T(EBT) indicator

Theory
The concentration of hardening ions in water can be
determined by a titration technique, the titrant is the
disodium salt of ethylene-diaminetetraaceticacid
In aqueous solution Na2H2Y dissociates into Na+ and H2Y2-
ions.Ca2+ and Mg2+ react with H2Y2- to form stable complexes in
a solution having pH of about 10.a buffer solution containing
ammonia and ammonium ions is used to maintain the pH of
the solution around 10.
For the detection of the end point Erichrome Black T (EBT) is
used as indicator EBT forms complex ions with Ca 2+ and Mg2+,
but binds more strongly to Mg2+ ions. Since only a small
amount of EBT is added, only a small amount of Mg 2+ ions is
used in the formation of complex and no Ca2+ ions are used.

EBT indicator is sky-blue in solution but its complex with Mg 2+

ions, [Mg-EBT]2+, is wine red

Mg2+(aq) + EBT(aq) [Mg-EBT]2+ (aq)

Sky-blue wine
red

Thus, during titration when indicator is added to hard water

,the initial colour is wine red.

When the titrant is added, H2Y2- complexes with free Ca2+ and
Mg2+ present in water and finally removes Mg 2+ ions from the
[Mg-EBT]2+ complex ions. As a result the colour of the solution
from wine red to sky blue.

[Mg-EBT]2+ (aq) + H2Y2-(aq) MgY 2-

+ 2H+(aq) + EBT(aq)
Wine red
sky blue

It may be mentioned here that for the end point to appear,

Mg2+ ions must be present in the solution. Therefore, a small
amount of Mg2+ (as same salt) is added to the buffer solution
and an equivalent amount of Na2H2Y is also added so that the
added Mg2+ ions do not affect the amount of H2Y2- used during
titration.
Indicator

Erichrome Black T(EBT)

End point

Wine red to sky blue colour.

Wine red to sky blue

Procedure

 Take about 100ml of the water sample to be analyzed. If

the water sample contains suspended impurities, it
 should be subjected to simple filtration. If the water
sample is acidic to litmus, add 1M NH 3 drop wise until it
becomes basic to litmus.
 Rinse the burette with Na2H2Y solution and then fill it
with the solution. Record the initial reading.
 Pipette out 25.0ml of the given sample of water in the
conical flask. Add 1ml of the buffer (pH=10) solution and
2 drops EBT indicator. The colour of the solution
becomes wine red at this stage.
 Titrate the above solution with standard Na2H2Y
solution. At the end point the wine red colour disappears
and the solution becomes blue(or purple) in colour. Note
the final reading of the burette. Repeat the titration 3 to
4 times to get a concordant reading.

Observations

Morality of the standard Na2H2Y solution =0.01M.

Volume of water taken for each titration = 20.0ml.

Burette readings
 tap water

S no. Initial reading Final reading Volume of Na2H2Y

used
1 0.0 4.4 4.4ml
2 4.4 8.9ml 4.5ml
3 8.9 13.4ml 4.5ml

Concordant readings – 4.5ml

  pool water

S no Initial reading Final reading Volume of Na2H2Y

used
1 0.0 6.3 6.3ml
2 6.3 12.7 6.4ml
3 12.7 19.1 6.4ml
Concordant readings – 6.4ml

 sea water

S no Initial reading Final reading Volume of Na2H2Y

used
1 0.0 79.9 79.9ml
2 0.0 80.0ml 80.0ml
3 0.0 80.0ml 80.0ml

Concordant readings – 80.0ml

Calculations

 tap water

Let the volume of titrant used be = 4.5 ml

Morality of titrant solution = 0.01M

Moles of titrant used =MxV

1000

=0.01 x
4.5
1000

= 45 x
-6
10
Mass of Na2H2Y = Moles of Ca 2+ = 0.01 x
4.5 = 45 x 10-6

1000

Mass of equivalent CaCO3 = 0 .01 x

4.5 x100g = 45x10-6x102

1000

=45x10-
4
mg

Mass of CaCO3 per litre

= 45 x
-4
10 x 1000

20

=50 x 45 x10-4
=225 x 10-3mg/l

Hardness = = 225
x 10 -3 x 106

= 225
-3 6
x 10 x 10

103

= 225
ppm
Calculations

 Pool water
Let the volume of titrant used be = 6.4 ml
Morality of titrant solution = 0.01M

Moles of titrant used =MxV

1000

=0.01 x
6.4
1000

= 64x
-6
10

Mass of Na2H2Y = Moles of Ca 2+ = 0.01 x

6.4= 45 x 10-6

1000

Mass of equivalent CaCO3 = 0 .01 x

6.4x100g = 64x10-6x102

1000

=64x10-
4
mg

Mass of CaCO3 per litre

= 64 x
-4
10 x 1000

20

=50 x 64 x10-4
=320 x 10-3mg/l
Hardness = = 320
x 10 -3 x 106

= 320x
-3 6
10 x 10

103

=
320 ppm
Calculations

 Sea water

Let the volume of titrant used be = 80 ml

Morality of titrant solution = 0.01M

Moles of titrant used =MxV

1000

=0.01 x
80
1000

= 80 x
-5
10

Mass of Na2H2Y = Moles of Ca 2+ = 0.01 x

80 = 80 x 10-5

1000

Mass of equivalent CaCO3 = 0 .01 x

80 x100g = 80x10-5x102
1000

=80x10-
3
mg

Mass of CaCO3 per litre

= 80 x
-3
10 x 1000

20

=50 x 80 x10-3
=4000 x 10-3mg/l

Hardness = = 4000
x 10 -3 x 106

=
-3 6
4000 x 10 x 10

103

= 4000
ppm

Result

The degree of hardness of the following water samples are:-

 Tap water - 225ml

 Pool water - 320ml
 Sea water - 4000ppm
Index
  Certificate

 Acknowledgements

 Introduction

 Aim, theory and procedure

 Observations and calculations

 Result

Certificate

This is to certify that Eben Mathew of class XII has completed

the investigatory project as per the requirement of CBSE

practical work during the year 2010-2011

……………………..

………………………..

Signature of teacher

Signature of examiner

Acknowledgements

I would like to express my gratitude to my teacher Mrs.

Rajasree karnavar for providing us with an opportunity to

perform this experiment.

I would like to express my appreciation to Mrs. Mary

Thomas our lab assistant for her guiding support

throughout the experiment.

Lastly a sincere thanks to my partners Rahul Mahajan and

Nabeel for the great deal of effort put into this

experiment.

Chemistry Project

Analysis of hard water

 BY: Eben

Mathew

Class: XII-K