HARDNESS OF

WATER
By the application of complexometric titration

To understand the chemical basis of water hardness, how it originates, and ways it can affect
water distribution
 TO DETERMINE THE TOTAL HARDNESS OF WATER BY
COMPLAXOMETRIC TITRATION.

A PROJECT REPORT

By
MUHAMMAD MURTAZA
(Reg. No. GU15R0080

Submitted to

Dr. Mohamad Taleuzzaman

Glocal School of Pharmacy, Glocal University

Mirzapur Pole , Saharanpur- 247121, U.P

INDIA

Batch:- 2015-2019
 CERTIFICATE

This is certify that the work presented in the project entitled “TO DETERMINE THE
TOTAL HARDNESS OF WATER BY COMPLAXOMETRIC TITRATION .” carried
out by Mr. Muhammad Murtaza at Glocal School of Pharmacy, Glocal University,
Saharanpur , under my guidance and to my satisfaction.

Date : Signature_____________

Place : Dr. Mohamad Taleuzzaman

Glocal School of Pharmacy
Glocal University.

Signature_____________

Dr. Nadeem Ahmed Siddique

HOD glocal school of pharm.
Glocal University
 Acknowledgement

It is difficult to express all that I feel, as words are such that they don’t do adequate
justice for the feelings one has. But silent feelings cannot be expressed, if they are not
given a shape in the form of words. Therefore I wish to grab this opportunity to record
and express my feelings, sentiments and appreciations

I dedicate my project work to my guide Dr. Mohamad Taleuzzaman who provided

inspirational opportunities and energized me to perform this task of lifelong importance I
extend my heartful gratitude to Hon’ble Chancellor Haji Iqbal Sahab , Pro Chancellor
Mohd Wajid Sahab and Vice Chancellor Prof. Om Kumar Harsh ,Glocal University
Saharanpur U.P for providing moral and ethical support as well as for the fulfillment of
requisite needs which arose from time to time throughout the phase of this dissertation
work.

Firstly, I would like to thank Glocal School of Pharmacy, Glocal University who has
granted me this opportunity to prepare a project which has helped me to gain knowledge
beside my studies and which is also definitely going to be useful in future.

And I would like to thank all those who have helped me contribute their valuable insights
and time project.

Thank you
Mr. Muhammad Murtaza
 Introduction
 COMPLEXOMETRY TITRATION
Complexometric titration (sometimes chelatometry) is a form of volumetric
analysis in which the formation of a colored complex is used to indicate the end point of
a titration. Complexometric titrations are particularly useful for the determination of a
mixture of different metal ions in solution. An indicator capable of producing an
unambiguous color change is usually used to detect the end-point of the titration.
Basic theory of complexometry titration with EDTA is the forming of complex
compound between some metal (such as: Ca, Mg, Ni, Zn, Cu, etc) with EDTA. Metals
will forms complex with EDTA at different pH, Ca 2+ and Mg2+ react well at pH 8 – 10.
EDTA (Etilen Diamine Tetra Acetate) is an acid base 4 (H 4Y). but, which is often used is
the natrium salt (Na2H2Y). the forming of complex between metals ions and EDTA
according to pH of solution. Indicator that is used are EBT (Erochrome Black T) and
Kalgamit. That indicator is a weak acid basic 3 (H 3In). dissociating equilibrium of that
indicator will give some colors and forming complex 1 : 1 with total metal ion, so, can
give the color change at the end of reaction.

Reactions

 Indicator : H2In- HIn2- + H+

Red Blue
 With metal ion : Ca2+, Mg2+, Zn2+, Ni2+:
Mg2+ + HIn2- MgIN- + H+
Red grape
 With EDTA : MgIn- + H2Y2- MgH2Y2- MgH2Y + In3-
Red grape
In3- + H2O  HIn- + OH-
Blue
 At equivalent point:
Sum of equivalent Mg2+ = sum of equivalent EDTA
So, the changing color through titration is : solution that contain of metal ion like
the statement above after added by EBT indicator will be change into red grape, after
that, after there’s happen an equivalent between metal ion with EDTA can be seen from
the form of blue from indicator in HIn2-.
In theory, any complexation reaction can be used as a volumetric technique
provided that:
1. The reaction reaches equilibrium rapidly after each portion of titrant is added.

2. Interfering situations do not arise. For instance, the stepwise formation of several
different complexes of the metal ion with the titrant, resulting in the presence of more
than one complex in solution during the titration process.
3. A complexometric indicator capable of locating equivalence point with fair accuracy is
available.
In practice, the use of EDTA as a titrant is well established.

Reagent EDTA

EDTA, ethylenediaminetetraacetic acid, has four carboxyl groups and two amine
groups that can act as electron pair donors, or Lewis bases. The ability of EDTA to
potentially donate its six lone pairs of electrons for the formation of coordinate covalent
bonds to metal cations makes EDTA a hexadentate ligand. However, in practice EDTA
is usually only partially ionized, and thus forms fewer than six coordinate covalent bonds
with metal cations.
Disodium EDTA is commonly used to standardize aqueous solutions of transition
metal cations. Disodium EDTA (often written as Na2H2Y) only forms four coordinate
covalent bonds to metal cations at pH values ≤ 12. In this pH range, the amine groups
remain protonated and thus unable to donate electrons to the formation of coordinate
covalent bonds. Note that the shorthand form Na4-xHxY can be used to represent any
species of EDTA, with x designating the number of acidic protons bonded to the EDTA
molecule.
EDTA forms an octahedral complex with most 2+ metal cations, M2+, in aqueous
solution. The main reason that EDTA is used so extensively in the standardization of
metal cation solutions is that the formation constant for most metal cation-EDTA
complexes is very high, meaning that the equilibrium for the reaction:
M2+ + H4Y → MH2Y + 2H+
lies far to the right. Carrying out the reaction in a basic buffer solution removes H + as it
is formed, which also favors the formation of the EDTA-metal cation complex reaction
product. For most purposes it can be considered that the formation of the metal cation-
EDTA complex goes to completion, and this is chiefly why EDTA is used in titrations /
standardizations of this type.

Indicators
To carry out metal cation titrations using EDTA, it is almost always necessary to
use a complexometric indicator to determine when the end point has been reached.
Common indicators are organic dyes such as Fast Sulphon Black, Eriochrome Black T,
Eriochrome Red B, Patton Reeder, or Murexide. Color change shows that the indicator
has been displaced (usually by EDTA) from the metal cations in solution when the
endpoint has been reached. Thus, the free indicator (rather than the metal complex)
serves as the endpoint indicator. The end point of this titration is the change from blue
color (EBT) to colorless. and when EBT form weak complex with the ca and mg ion
present in the solution but after the addition with titration with EDTA all the metal ion
leaving EBT which formed weak and unstable compound react with EDTA forms stable
and stable complex.
 Hardness of water:
Water hardness is determined by concentration of metallic solids, such as magnesium
and calcium ions, dissolved in a water source. The degree of water hardness is
determined by the concentration of ions in a source; hard water contains a high
concentration of metallic ions while softer water contains a lower concentration. Since
water is a universal solvent, it readily collects ions and impurities when moving over
rocks and soils. The most prevalent ions collected in a water source are Ca+2 and Mg+2 .
The hardness level of water is important for a number of reasons. Although hard water is
not a health risk, it can negatively affect the performance of pipe efficiency, detergents in
laundry, and the use of shampoo and soap for bathing. Deposits of Ca+2 and Mg+2 in
hard water can form limestone deposits that slow and block pipes, which is inefficient
and costly. When washing clothing with hard water, clothing may become scratchy and
harsh as the ions damage the cloth fibers. Hard water can create limestone film deposits
in hair while bathing, as well as causing soap to be less effective at removing dirt and
bacteria from the skin. On a larger scale, metallic ions in water can also cause metal
corrosion and structural weakness of buildings and bridges.
Water hardness is measured either in grains per gallon or parts per million. The
Environmental Protection Agency (EPA) regulates the standards for drinking water
based on primary conditions, which evaluate health and safety, while the secondary
conditions are based on taste, color odor, and corrosivity. The following chart shows
how the U.S. Department of the Interior and Water Quality Association classifies water.
 Classification of Water
Classification mg/l or ppm grains/gal

Soft 0 - 17.1 0–1

Slightly hard 17.1 – 60 1 - 3.5

Moderately hard 60 – 120 3.5 - 7.0

Hard 120 – 180 7.0 - 10.5

Very hard 180 & over 10.5 & over

 Requirements

Tools and materials

  Volumetric flask 500 mL
 Pipette
 Volumetric pipette
 Erlenmeyer
 Burette
 CaCO3
 Aquades
 HCl
 Na-EDTA solution ±
0,01 M
 CaCl2 solution
 EBT

Composition of Water

Water has oftentimes been referred to as the “universal solvent”, because many things can
dissolve in water (Figure 14.4). Many things like salts, sugars, acids, bases, and other organic
molecules can be dissolved in water. Pollution of ocean water is a major problem in some
areas because many toxic substances easily mix with water.
 EXPERIMENTAL PROCEDURE

In this experiment, an EDTA solution is prepared and standardized with standard

calcium solution. The standardized EDTA is then used to analyze an unknown sample.
Standard Calcium Solution
Accurately weigh 0.5 g of dried, pure CaCO3 into a 250 mL beaker. Add approximately
25 mL of distilled H2O, then add 1 mL of conc. HCl carefully (operate in hood!), cover
with watch glass spaced with glass hooks until dissolved. Note: If CaCO3 does not
dissolve completely, add another 0.5 mL of conc. HCl (operate in hood!). Next,
evaporate volume to about 2 mL maintaining watchglass on beaker to expel carbon
dioxide. Rinse watchglass, transfer quantitatively into a 500 mL volumetric flask and
make up volumetrically to 500 mL. Calculate the molarity of your standard calcium
solution.

EDTA Solution Preparation

Weigh out approximately 2 g of reagent grade disodium EDTA into a 250 mL beaker.
Add 0.05 g magnesium chloride hexahydrate, three pellets of NaOH and add about 200
mL of distilled water to dissolve. The EDTA will dissolve slowly over a period of a half
an hour. Magnesium chloride is added to enhance the sharpness of the endpoint (It forms
a more stable complex with the indicator). Filter the EDTA solution into a 0.5 or 1 L
bottle, then add approximately 250 mL of distilled water.

Titration Procedure
Standardization Titration for EDTA
Fill your burette with the EDTA solution. Pipet three 25 mL aliquots of standard calcium
solution into 250 mL Erlenmeyer flasks, add 3 mL ammonium chloride buffer (pH 10)
(operate in hood!) and 2-3 drops of Eriochrome Black T indicator solution. Titrate with
EDTA from violet through wine-red to blue. It is recommended to experiment with a 5
mL aliquot to get an idea of the color and titre. The indicator color changes slowly, thus,
the titrant must be added slowly near the endpoint with thorough stirring. Calculate the
molarity of the EDTA. Now you have your EDTA solution standardized and your
standard EDTA solution should be ~0.01 M.
Titration of Unknown Calcium Sample
Prepare a clean beaker and ask your GA for 100 mL of unknown solution. Titrate with
standard EDTA, 25 mL of unknown solution after addition of 3 mL ammonium chloride
buffer (pH 10) (operate in hood!) and 2-3 drops of Eriochrome Black T indicator
solution following the procedure above. Repeat this in triplicate. Express the
concentration of calcium carbonate in the unknown sample in ppm.
 Determination the sum of the
hardness of water
Sample 1→ Sahaspur

25 mL of
sample water

- Pipette and dropped to Erlenmeyer

- Added 2 mL buffer solution pH 10
- Added 3 drops of BET
- Titration with EDTA 3x

Blue (preciously until

red color
- disappear)

- Calculated the sum of the hardness of water (in the form of

ppm)

EDTA USED

1st reading 2nd reading 3rd reading Mean

4 3.5 3.5 3.6

ml of EDTA used
Average hardness of well water =
( mg/l )= ∗1000
volume of sample (50 ml)

3.6
Total hardness of water =( mg/l )= 50 ml ∗1000 = 72mg/l
 Sample 2→ Selaqui

25 mL of
sample water

- Pipette and dropped to Erlenmeyer

- Added 2 mL buffer solution pH 10
- Added 3 drops of BET
- Titration with EDTA 3x

Blue (preciously until

red color
- disappear)

- Calculated the sum of the hardness of water (in the form of

ppm)

EDTA USED

1st reading 2nd reading 3rd reading Mean

2.5 2.5 2.7 2.5

ml of EDTA used
Average hardness of well water =
( mg/l )= ∗1000
volume of sample (50 ml)

2.5
Total hardness of water =( mg/l )= 50 ml ∗1000 = 50 mg/l
 Sample 3→ Badshahibag

25 mL of
sample water

- Pipette and dropped to Erlenmeyer

- Added 2 mL buffer solution pH 10
- Added 3 drops of BET
- Titration with EDTA 3x

Blue (preciously until

red color
- disappear)

- Calculated the sum of the hardness of water (in the form of

ppm)

EDTA USED

1st reading 2nd reading 3rd reading Mean

11.3 10.5 10.5 10.7

ml of EDTA used
Average hardness of well water =
( mg/l )= ∗1000
volume of sample (50 ml)

10.7
Total hardness of water =( mg/l )= 50 ml ∗1000 =214 mg/l
 Sample 4→ Khushhalpur

25 mL of
sample water

- Pipette and dropped to Erlenmeyer

- Added 2 mL buffer solution pH 10
- Added 3 drops of BET
- Titration with EDTA 3x

Blue (preciously until

red color
- disappear)

- Calculated the sum of the hardness of water (in the form of

ppm)

EDTA USED

1st reading 2nd reading 3rd reading Mean

20 20 19.5 19.8

ml of EDTA used
Average hardness of well water =
( mg/l )= ∗1000
volume of sample (50 ml)

19.8
Total hardness of water =( mg/l )= 50 ml ∗1000 =396 mg/l
 Sample 5→ Glocal University

25 mL of
sample water

- Pipette and dropped to Erlenmeyer

- Added 2 mL buffer solution pH 10
- Added 3 drops of BET
- Titration with EDTA 3x

Blue (preciously until

red color
- disappear)

- Calculated the sum of the hardness of water (in the form of

ppm)

EDTA USED

1st reading 2nd reading 3rd reading Mean

9.5 9.5 10 9.66

ml of EDTA used
Average hardness of well water =
( mg/l )= ∗1000
volume of sample (50 ml)

9.66
Total hardness of water =( mg/l )= 50 ml ∗1000 =193 mg/l
 CONCLUSION
Based on cmoplexometric titration result the hardness of water 72mg/l, 50 mg/l, 214
mg/l, 396 mg/l and 193 mg/l Sahaspur, Selaqui, Badshahibag, Khushhalpur and Glocal
university campus found respectively.
Total hardness of water
450.00

400.00

350.00

300.00

250.00 Sahaspur(72)

200.00

150.00

100.00

50.00

0.00
sample
ATTACHMENT
PICTURE EXPLANATION

Detrmining Standarization Na-EDTA Solution ±0.01M With CaCl2 As Primary Standard

Solution

CaCl2 after adding by Erichrome Black T

(EBT)

CaCl2 after titrated by Na-EDTA solution

it change became blue

Determining total Hardness Water of Well Water

Well water after adding by

(EBT)Erichrome Black T

Well Water after titrated by Na-EDTA

solution it change became blue
 REFERENCES:
1. Mr. Ashutosh Kar. Pharmaceutical Analysis –Volume –I. CBS Publishers &
Distributors.
2. A.H. Beckett & J.B. Stenlake. Practical Pharmaceutical Chemistry .Fourth
Edition part –I.
3. J. Mendham, R.C. Denney, J.D. Barnes, M.J.K Thomas. Vogel’s –Text book of
quantitative chemical analysis 6th Edition