CHEMISTRY

PRACTICAL FILE
{Analysis of Hard
Water}
Class: XI-F
Roll No . - 20
 Experiment 1
AIM: To determine the hardness of a water sample by measuring the
amount of calcium present. This analysis will utilize the method of
titration.

{THEORY }
Introduction:
All natural waters have salts dissolved in them. It is these salts that give water a
unique taste. Quality of drinking water has a direct relationship with the human
health and life. Sometimes the water can contain too much of these salts and can
cause problems when the water is used for drinking or washing. You may have
experienced this problem if you have taken a bath with water that contained too
many calcium and magnesium salts. It must have been evident that you cannot get the
soap to lather and form suds. When this happens, we say that the water is “hard.” If
iron, fluoride, chloride, etc. are present in water above permissible limits, they may
cause several health problems. For example, if fluoride is present above permissible
limit, people of the region may suffer from flourosis. Hardness of water is due to the
presence of calcium and magnesium ions.

Students may collect samples of water from different sources. They can detect the
presence of different ions by usual methods of analysis. Total hardness of water can
be estimated by standard procedure of complexometric titration. Titration is a
process of adding standard solution until reaction completes. Upon completion, it’s
identified by the colour change of the indicator. Estimation of Cl– , F– and Fe2+ is
difficult at this level. Therefore existing data from approved labs can be taken for the
purpose of investigation.

OBJECTIVE

In this experiment, we will analyze a sample of water to measure the amount of

calcium (or the water hardness) by performing titrations on water samples you
provide from home or other sources. This experiment will require us to perform a
titration so an in-depth explanation regarding it is necessary.
Types of Titrations
1. Neutralization titrations
2. Complex formation/ Complexometric titrations
3. Precipitation titrations
4. Oxidation-reduction Titrations
 Cleansing of Equipments
 Titration flask is only washed using distilled water.
 Burette is first washed by using distilled water, and then it’s washed
using a titrant (Solution which is having known concentration).
 Pipette is first washed by using distilled water, and then it’s washed
by using the analyte (solution whose concentration has to be
checked).

 Complexometric titration is a form of volumetric

analysis in which the formation of a coloured complex
is used to indicate the end point of a titration.
 These titrations are particularly useful for the
determination of a mixture of different metal
ions in a solution.

Applications of EDTA Chelation (Complexation)

EDTA has many uses:
 Chemical Analysis of Metals
 Medical Removal of Heavy Metals in Accidental
 Poisonings
 Boiler Water Softening by Chelation
 Removal of Hard Water Scale by Cleaning Agents
 Addition to Shampoo to Soften Water
 Addition to Prepared Food to Prevent Spoilage by Metal Ions
 Solubilisation of Metal Ions in Fertilizers and Vitamin
Supplements

EDTA is not used in residential water softening or home laundry products

because it is too expensive and because it is so effective, it would remove calcium
from our bodies if it got into the drinking water supply.

Complex Formation:
 Complex: metal + ligand
 Ligand  It has at least one pair of unshared electrons available for bond
formation.
 Complex formation has a specific colour.
 Electron donor <Eg: H2O, NH3, Cl-, Br, I-
o An ion or a molecule which forms a covalent bond with a cation or a
neutral metal atom by donating a pair of electrons, which is then shared
by the two atoms.
  Complex formation reactions are reversible. So, we
have a formation constant, (Kf).
 Most chelating agents contain either N or O.
o Elements that contain free electron pairs that may be
donated to a metal.
 Formation Constant (Kf)
 The equilibrium constant for the reaction between a
metal ion (M+n) and a chelating agent (L -P) is known
as a formation constant or stability constant.

How Complexometric Titration differ from normal Titration?

Complexometric Normal
At the end point, a colourful complex At the end point, precipitate solution may
formation is seen. form.
Used by metal indicator and metal ion Normally acid base indicator can be used
indicator. or sometimes, it’s necessary to use the
indicator.

EDTA Titrations

Properties of EDTA

1. EDTA (Ethylenediaminetetraacetic acid)

 This is one of the most chelating agents used
complexometric titrations in analytical chemistry.
 EDTA has 6 hydrogen atoms, 2 atoms from ammine
group and 4 atoms from carboxylic group. Thus, its
structure gives 6 free electron pairs that it can
donate to metal ions.
o High Kf values
o 6 acid-base sites in its structure
2. EDTA is an example of a multidentate (many-toothed)
ligand which can bind metal ions through multiple
atoms.

3. EDTA is an amphoteric substance.

4. It can both donate and accept protons.
5. The four hydrogen atoms shown in the above line
structure are acidic.
6. Due to this, the formula of EDTA is often abbreviated
as H4Y, where H4 represents the four acidic hydrogen
atoms and Y represents the remaining structure.
7. At very low pH, EDTA will be present in its completely
protonated form H6Y2+.
8. At very high Ph, EDTA will be present in its completely
deprotonated form Y4-.
EDTA can be represented as different types:
 However, the reaction in this titration is not a neutralization reaction as in
the acetic acid titration. In this case, an EDTA (ethylenediamine tetra-
acetic acid) solution is the titrant, which will react or capture (also called
chelate) the calcium ions in the water as shown in equation 1 below.
O
- -
OOCCH2 CH2COO
N 2+ NON
- +
OOCCH2 Ca
CH2COO Ca OOO O
N - O
O Eqn. 1
4- 2-
(EDTA ) (CaEDTA )
The reaction between calcium ions and EDTA only occurs at a high pH;
therefore, a solution which has a constant pH of 10 (called a buffer) will to be
added to the water sample.
Just as in the acid-base reactions, you must use an indicator to identify when
the reaction is complete. In this experiment, Eriochrome black T, a metal ion
indicator, will be used to visualize the endpoint.
OH OH
-
O3S N N

O2N

Eriochrome black T
Water containing certain ions react with soap forming a
precipitate called scum.
For example:

2 NaC15H31COO + Ca2+ --> Ca(C15H31COO)2 + 2 Na+

Contemporary society deals with this problem in two ways. One way is to
use detergents whose calcium salts are soluble. Another is to treat the water
by softening -- usually replacing calcium and magnesium with sodium.

Hardness is reported as mg CaCO3 because dissolved limestone is the major

cause of hardness in most regions. (Dissolved Mg2+ and sometimes Fe2+ also
contribute.)

Calmagite has a red color when complexed with Mg2+ and a blue color when
Mg2+ is chelated by the EDTA. Ca2+ is more tightly bound to EDTA then
Mg2+. Consequently, the color change for Mg2+ occurs after all Ca2+ is
chelated.

Eriochrome Black T indicator has a red color when complexed with Ca2+ or
Mg2+. It is blue when these ions are removed. A change from red to blue is
the basis of the endpoint.

The EDTA is a weak acid. A pH 10 buffer is used to keep the acid groups
deprotonated. (The EDTA can be envisioned to wrap itself around the
divalent cation.)
Results:
It’s essential that all data is recorded and collected.
We repeat the titrations until results that are within 0.1 ml are obtained. These are called
concordant results. The average of the concordant results is used in calculations.
At Least Three Trials are
Mandatory
Additional Trials Only if Necessary

Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Trial 6

Final Volume (mL) 24.20 23.15 24.20

Start Volume (mL) 00.00 00.00 00.05

Titration Volume (mL)

24.20 23.15 23.15

Avg. of Concordant results

23.17 ± 0.1

Burette Readings
a. Tap water

S no. Initial Reading Final Reading Volume

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

Concordant Readings – 4.5 mL

b. Pool Water

S no. Initial Reading Final Reading Volume

1 0.0 6.3 6.3
2 6.3 12.7 6.4
3 12.7 19.1 6.4
Concordant Readings – 6.4 mL

c. Sea Water
 S no. Initial Reading Final Reading Volume
1 0.0 79.9 79.9
2 6.3 80.0 80.0
3 12.7 80.0 80.0
Concordant Readings – 80 mL