Reagents

Eriochrome black- T Indicator, 0.01 M EDTA solution, four water samples, basic buffer solution
( NH4OH and NH4Cl)

Apparatus

Conical flask, burette with burette stand, pipettes, beaker , measuring cylinders

Aim

To determine the total hardness of a given water sample by complexometric titration (EDTA method)

Introduction

Hard water is a water substance that contains cations which has a charge of +2 alsoCa2+ and Mg2+.
These ions stand for calcium and magnesium. ... Water hardness that is caused by bicarbonates and
carbonates from the calcium and magnesium are called temporary hardness.

The harder the water the more soap or detergent you need to get things clean .So if you live in an
area with hard water and you want to wash your clothes, dishes, or yourself, it will be harder to get
these things clean than if you live in an area with soft water (water without a lot of dissolved
minerals).

What is hard water?

Water having high mineral content (between 120-180 PPM) – mostly Calcium and Magnesium is
considered as hard water. Anything below this limit is mildly hard, and over this is very hard.

What are the sources of hard water?

Essentially, water used for consumption comes from two sources: groundwater and surface water.
Often, ground water sources like bore wells, tube wells, hand-pumps and wells have high amounts of
dissolved impurities and minerals. This is because water is a universal solvent and absorbs these
substances as it travels through the earth crust & beneath the ground.

Surface water from rivers and lakes supplied by municipalities usually have low amounts of dissolved
impurities and minerals such as calcium and magnesium.

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.

When hard water is treated with soap, hard water doesn't give ready and permanent lather.
It gets precipitate in the form of insoluble salts of calcium and magnesium (scum).

2C15H31COONa + Ca2+---- >(C15H31COO)2Ca + 2Na+

Water free from soluble salts of calcium and magnesium is called soft water. It gives lather with soap
easily.

There are two types of hardness:

Temporary hardness

Hardness caused by the presence of dissolved carbonate minerals(calcium carbonate and

magnesium carbonate).

When dissolved, these minerals yield calcium and magnesium cations(Ca2+,Mg2+) and carbonate
and Bicarbonate anions (Co3+,HCO3 -).

The presence of the metal cations make 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 precipitate 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
boiling the case, it is usually caused by the presence of calcium and magnesium sulphate and/or
chlorides in the water, which become more soluble as a temperature rises. Despite the name, the
hardness of the water can be easily removed using a water softener, or ion exchange column

Measurement

Hardness can be quantified by instrumental analysis. The total water hardness is the sum of the
molar concentrations of Ca2+ and Mg2+, in mol/L or mmol/L units. Although water hardness usually
measures only the total concentrations of calcium and magnesium (the two most prevalent divalent
metal ions), iron, aluminium, and manganese can also be present at elevated levels in some
locations. The presence of iron characteristically confers a brownish (rust-like) colour to the
calcification, instead of white (the color of most of the other compounds).

Hard/soft classification

Because it is the precise mixture of minerals dissolved in the water, together with the water's pH and
temperature, that determine the behavior of the hardness, a single-number scale does not
adequately describe hardness. However, the United States Geological Survey uses the following
classification into hard and soft water.

Effects of Hard Water

_Effects of hard water on household equipment

There are several adverse effects of hard water in house hold equipments such as lime scale form in
coffee makers, tea kettles, hot water heaters, steam irons, washing machines, faucets, shower heads,
inside of pipes, taps etc.
For example, when lime scale is formed inside of pipes, it decreases the flow through the pipes. In
the long run pipes can get completely clogged. As a result sometimes it may be required to replace
the pipes.

When “hard” water is heated in a water heater, a scale is formed. This scale reduces the heating
efficiency. This in turn increases energy and maintenance costs of the water heater.

Effects of hard water on health

There are no established effects of hard water on health. In areas where hardness is very high, the
possibility of kidney stones has been linked to hard water. But it has some effects on skin and hair.
Bathing in hard water could cause dry itchy skin and rough hair. Mineral deposits left on the body can
also suck moisture right out of the skin.

Effects of hard water in preparation of foods and beverages

Preparation of food and beverages requires water of certain quality as the taste and quality of the
food or beverage is largely determined by the quality of water. Water used in food and beverage
processing should be free from any contaminants and microorganisms. Presence of hardness in
water not only alters the taste, color and odor but also reduces the life span of equipments, with
problems of corrosion and scale buildup, leading to higher costs and lower profits.

Temporary hardness present in the water can be removed by using the following methods: -

1 By heating :

Salts like calcium bicarbonate and magnesium bicarbonate, when dissolved in water causes
temporary hardness. While heating, soluble salts of calcium and magnesium (bicarbonates) change
into insoluble salts. The chemical equations are as follows:

Ca(HCO3)2 → CaCO3 + CO2 + H2O

Mg(HCO3)2 → MgCO3 + CO2 + H2O

2 Treating with lime water:

The temporary hardness of water can be removed by treating it with lime water. The chemical
equations are as follows:

Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O

Mg(HCO3)2 + Ca(OH)2 → CaCO3 + MgCO3 + 2H2O

Removal of Permanent Hardness

Permanent hardness cannot be removed by heating only. Soluble salts of calcium and magnesium are
turned to insoluble salts by the following methods.
*1 Treatment with washing soda

Soluble salts of calcium and magnesium change into insoluble salts due to the treatment with
sodium carbonate (washing soda).

CaCl2 + Na2CO3 → CaCO3 + 2NaCl

MgSO4 + Na2CO3 → MgCO3 + Na2SO4

2 Calgon Process

A complex salt,sodium hexametaphosphate(NaPO3)6 is used for softening hard water.

Ca2+ + (NaPO3)6---->Na2[Ca2(PO3)6]

3 By Ion Exchange Method

• Inorganic ion exchange method

~Permutit Process:~

Permutit is the trade name for an artificially prepared sodium zeolite or sodium aluminium
orthosilicate obtained by fusing together sodium carbonate silica and alumina. Its composition
resembles Na2Al2SiO8 or Na2Z, where, Z stands for Zeolite = Al2SiO8. It possesses the higher quality
of reactivity with calcium and magnesium ions forming insoluble calcium or magnesium zeolites.

2Na2Z + Ca++ → CaZ2 +4Na

Thus by passing hard water through a cylinder packed with permutit, all the ions of soluble salts of
calcium and magnesium responsible for the hardness of water are retained and replaced by sodium
ions. In due course, however, the permutit is exhausted or losses its capacity of reacting with these
salts by having given up all its sodium ions. This can be regenerated by soaking in a 10% solution of
common salt when the reverse change takes place and calcium and magnesium ions pass into
solution and sodium zeolite is formed again.

CaZ2 + 2NaCl → Na2Z + CaCl2

MgZ2 + 2NaCl → Na2Z + MgCl2

The resulting calcium and magnesium chlorides are washed out and the regenerated permutit is
used over again.

•Organic Method

In this method,we use acidic or basic ion exchange resins.

a)Acidic resin(Cation exchanger) contains acidic group like -COOH

RCOOH+Ca2+ +Cl- ------>(RCOOH)2Ca +H+ Cl-

RCOOH+Ca2+ + SO42- ----->(RCOOH)2Ca+H+ +SO42-

b)Basic resin(Anions exchanger)contains basic groups like-NH2

RNH3+OH- +SO42- ----->(RNH3)2SO4 +OH-

RNH3+OH- +Cl- ---->RNH3Cl +OH-

[21:22, 11/10/2018] Sumijio:

Working principle

•Eriochrome Black T

Eriochrome Black T is a complexometric indicator that is used in complexometric titrations, e.g. in the
water hardness determination process. It is an azo dye.

It's Chemical formula is

C20H12N3O7SNa

In its protonated form, Eriochrome Black T is blue. It turns red when it forms a complex with calcium,
magnesium, or other metal ions

-> Applications

When used as an indicator in an EDTA titration, the characteristic blue end-point is reached when
sufficient EDTA is added and the metal ions bound to the indicator are chelated by EDTA, leaving the
free indicator molecule.
[21:35, 11/10/2018] Sumijio: •Ethylenediaminetetraacetic acid (EDTA)

It's Chemical formula is

C10H16N2O8.

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.

The main reason that EDTA is used so extensively in the standardization of metal cations solution is
that the formation constant for most metal cation EDTA complex is very high, meaning that the
equilibrium for the reaction lies far to the right

M2+ + H4Y ---->MH2Y+2H+

[21:47, 11/10/2018] Sumijio: Etar niche eta o include kore diyo okay

(iii) Solution of Ammonia:

It may be used for softening water, when the fabrics to be treated would be harmed by soda. If used
in excess, ammonia may destroy the Iustre of rayon's, discolour and injure animal fabrics and loosen
the dyes of coloured articles. Since, it is not possible to be very certain of the quantity to be used;
this is not practicable for softening water.

(iv) Borax:

It is useful for softening water containing over 20% of hardness. Borax is usually used to reduce the
alkalinity of soap solution rather than to soften water

It is useful for softening water containing over 20% of hardness. Borax is usually used to reduce the
alkalinity of soap solution rather than to soften water

A water sample is buffered to pH 10.1 and taken into a conical flask.If an Indicator like EBT, when
added to a solution containing calcium and magnesium ions,it gives wine red coloured unstable
complex with Ca2+ and Mg2+ ions of the sample water.

Now when this wine red coloured solution is

•Ethylenediaminetetraacetic acid (EDTA)

It's Chemical formula is

C10H16N2O8.

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.

The main reason that EDTA is used so extensively in the standardization of metal cations solution is
that the formation constant for most metal cation EDTA complex is very high, meaning that the
equilibrium for the reaction lies far to the right

M2+ + H4Y ---->MH2Y+2H+

tar niche eta o include kore diyo okay

(iii) Solution of Ammonia:

It may be used for softening water, when the fabrics to be treated would be harmed by soda. If used
in excess, ammonia may destroy the Iustre of rayon's, discolour and injure animal fabrics and loosen
the dyes of coloured articles. Since, it is not possible to be very certain of the quantity to be used;
this is not practicable for softening water.

(iv) Borax:

It is useful for softening water containing over 20% of hardness. Borax is usually used to reduce the
alkalinity of soap solution rather than to soften water

It is useful for softening water containing over 20% of hardness. Borax is usually used to reduce the
alkalinity of soap solution rather than to soften water

A water sample is buffered to pH 10.1 and taken into a conical flask.If an Indicator like EBT, when
added to a solution containing calcium and magnesium ions,it gives wine red coloured unstable
complex with Ca2+ and Mg2+ ions of the sample water.

Now when this wine red coloured solution is

This reagent is a weak acid that

can lose four H (in bold) on complete neutralization; its structural formula is:

A water sample is buffered to pH 10.1 taken into a conical flask . If an indicator like EBT, when added
to a solution containing calcium and magnesium ions it gives wine red coloured unstable Complex
with

Ca2+ and Mg 2+ ions of the sample water.

Now in this wine red coloured solution is titrated against stronger ligand EDTA solution, Ca2+/Mg2+
ions preferably forms a stable EDTA-

Ca2+/Mg2+ complex , since it cannot under these conditions distinguish between Ca2 + and Mg2+,
removing them from association with EBT,to form a stable metal-EDTA complex by forming six special
bonds with the cations(Ca2+ and Mg2+), called coordination covalent bonds, and liberates the free
Eriochrome Black-T.

As the titration is carried out at a pH of 10, in a NH3/NH4

buffer, which keeps the EDTA (H4Y)

mainly in the form HY3–, where it complexes the Group 2 ions very well but does not tend to

react as readily with other cations such as Fe3+ that might be present as impurities in the water.
Taking H4Y and H3In as the formulas for EDTA and Eriochrome Black T, respectively, the

equations for the reactions which occur during the titration are:

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.

Precautions

1 . Don't pipette out the buffer solution using measuring cylinder, automatic pipette or pipette with
a sucker

2.Always store EDTA solution and buffer solution in a plastic or resistant glass container.

3. Discard the buffer solution if it is turbid or if it is stored for a very long period of time.

4. Take necessary precautions for preventing inhalation of ammonia from the buffer
5. Do not allow the samples to freeze. Begin analysis present 6 hours of sample collection.

6. Do not store EDTA in glass stopper flasks as a solution tends to freeze stoppers

7. Avoid skin contact with chemicals

Bibliography

a)www.google.com

b)en.wikiledia.com

c)chemmovies.unl.edu

d)www.sjsu.edu

e)nitttrc.ac.in

f)www.slideshare.net

g)www.quora.com

h)www.titrations.info