University of Science and Technology

of Southern Philippines
of Southern Philippines
DETERMINATION OF HARDNESS IN WATER
(Total Hardness, Calcium Hardness & Magnesium Hardness)

Bangga, P.1, Baquiran, A.K.2, Bonglay, P.A.3, Manla, T.A.4, Masong, A.R.5, Olaer, L.J.6,
Lomonsod, K.7*, Landiao, M.A.8*
1Department of Food Science and Technology, University of Science and Technology of Southern Philippines
Email of corresponding author: banggap@yahoo.com

Abstract

Hardness is the tendency of water not to react with soap or tendency of water not
to form a scale, which is due to the presence of divalent cat-ions mainly Mg+2. In
order to determine the hardness some indicators will be used. Water hardness is an
expression for the sum of the calcium and magnesium cation concentration in a
water sample.

These cations form insoluble salts with a reagent in soap, decreasing its cleaning
effectiveness. The standard way to express water hardness is in ppm CaCO3 which
has the formula weight of 100.1 g/mole. An excellent way to determine water
hardness is to perform a complexometric titration using a standard
ethylenediaminetrtaacetic acid (EDTA) solution.

Due to steric hindrances, EDTA will complex with calcium and magnesium in a one-
to-one molar ratio. The indicator will a give a blue color if endpoint is reached.
Hardness is most frequently measured through application of the principle of
chelation. Metals are capable of sharing electron pairs with a molecule or ion to
form a coordination bond. These ions or molecules are called chelating agents if has
more than one free electron pairs to share.

As the number of these bonds increase the stability of a chelate increase, one of the
most used chelating agent in analytical chemistry is ethylene diamine terta-acetic
acid (EDTA). This chelating agent used is metallochromic which can be used also as
an indicator.

1. Introduction

Water that has high mineral content is
known as Hard Water. Hard water contains
bicarbonate, chlorides and sulphates of
calcium and magnesium.
When treated hard water with soap, it gets
precipitated in form of insoluble salts of
calcium and magnesium. Hardness of Water
is a measure of the total concentration of
the calcium and magnesium ions expressed
as calcium carbonate. There are two types
of hardness: Temporary Hardness and
Permanent Hardness. Temporary hardness
is due to the presence of bicarbonates of
calcium and magnesium. It can be easily
removed by boiling. While Permanent
hardness is due to the chlorides and
sulphates of calcium and magnesium. This
type of hardness cannot be removed by
boiling.
Hardness of water is a measure of its to change from claret or violet to blue. At
capacity to precipitate soap and is caused the equivalence point is:
by the presence of divalent cations of
mainly Calcium and Magnesium. n(Ca2+ + Mg2+) =n(EDTA)

Hardness EDTA as mg/L CaCO3 = The results are given in amount of

[( )( 3 1 )(1000)] substance concentration (molarity).

Mg+2 Hardness as mg/L CaCO3 =

Total Hardness Ca+2 Hardness
2. Materials And Method

I.A. Principle II.A. Total hardness in water sample

Materials
This is a complexometric titration of calcium
and magnesium with an aqueous solution of II.A.1 APPARATUS REQUIRED
disodium salt of EDTA at pH value of 10 and
Mordant black 11 as an indicator, which 1. Burette with Burette stand and
forms a claret or a violet colour in the porcelain title
presence of calcium and magnesium ions. 2. Pipettes with elongated tips
3. Pipette bulb
The sodium salt of EDTA dissociated into 4. Conical flask (Erlenmeyer Flask)
ions in aqueous solution 5. 250 mL graduated cylinders
6. Standard flask
Na2Y2H2*2H2O(s) 2Na+(aq)+H2Y2-(aq)+2H2O(I)
7. Wash bottle
8. Beaker

II.A.2 CHEMICALS REQUIRED

1. Ammonium Chloride
2. Ammonium Hydroxide
3. EDTA (Disodium Salt of EDTA)
4. Erichrome sulphate
5. Magnesium sulphate

During the titration EDTA reacts first with

free calcium and magnesium ions in the
solution

Me2+(aq) + H2Y2-(aq) MeY2-(aq) + 2 H+(aq)

Me2+(Ca2+, Mg2+)

And at the end or equivalent point EDTA

reacts with the calcium and magnesium ions
superseded from their complexes, which
were created with the indicator molecules,
liberating indicator and causing the colour
 III.C Determination of Magnesium
Hardness in water sample

II.B. Determination of Calcium III.C.1 APPARATUS REQUIRED

hardness in water sample
1. Burette
II.B.1 APPARATUS REQUIRED 2. 20 mL pipette
3. 250 mL conical flasks
1. Burette with Stand & Porcelain tile 4. 100 mL volumetric cylinder
2. Pipettes with elongated tips
3. Conical flask III.C.2 CHEMICALS REQUIRED
4. 250 mL Graduated Cylinder
5. Standard Flask 1. EDTA
6. Beakers 2. Buffer
7. Wash Bottles 3. MgCl2.6h2O
4. Eriot Indicator

3. PROCEDURES
II.B.2 CHEMICALS REQUIRED
III.A. Total hardness in water
1. Ammonium Purpurate
2. Sodium Chloride III.A.1 PREPARATION OF REAGENT
3. Sodium Hydroxide
4. EDTA Buffer Solution Preparation

1. Switch on the electric balance, keep

the weighing pan, set the reading to
zero.
2. Measure 50 mL of distilled water and
transfer it to the beaker
3. Weigh 1.179 gms
4. Transfer the contents to the beaker
having 50 mL distilled water and
dissolve it thoroughly
5. Weigh 16.9g of ammonium chloride
6. Add it to the contents in the beaker.
And dissolve it thoroughly.
7. Weigh 780mg of magnesium
sulphates and transfer it to the
beaker.
8. Measure 143 mL of ammonium
hydroxide solution using measuring
cylinder and add it to the contents in
the beaker.
 9. Place the funnel over the 250mL
standard flask and transfer the
dissolved contents from beaker
10. Make the volume up to 250mL mark
by adding distilled water, transfer
the solution to a clean reagent bottle
labelled as buffer solution. This
buffer solution is used to maintain
the pH of water sample between 9
and 10.
Erichrome Black T
1. Weigh 0.5g of erichrome black T
2. Transfer it to 100mL standard flask
using funnel
3. Add distilled water in the standard
flask and make the volume exactly
up to 100mL marl
4. Put the lid and shake the contents
well.
5. Transfer the solution to a clean
reagent bottle named EBT
Standard EDTA solution (0.02 M)
1. Switch on the electronic balance,
keep the weighing pan, and set the
reading to zero.
2. Weigh 3.723g of EDTA sodium salt
3. Transfer the entire content 1000mL
standard flask
4. Fill with distilled water up to 1000
mL mark
5. Put the lid and shake the contents
well
6. For easy handling take the EDTA
solution in a 250 mL beaker
III.A.2 TESTING OF WATER SAMPLE
1. Pipette 20mL of water sample and
transfer it to a clean 250mL conical
flask
2. Add 2mL ammonia buffer solution to
the water sample so that the pH will
be maintained between 9 and 10.
3. Add few drops of EBT indicator to
the conical flask and the sample
turns to wine red in color
4. Before starting the titration rinse the
burette with few mL of EDTA. Fill the
burette with 0.02M EDTA solution
and adjust to zero then fix it in
burette stand.
5. Titrate the sample against the EDTA
solution in the burette till all calcium
and magnesium ions present in the
sample reacts with the EDTA. The
appearance of blue colour indicates
that all Ca & Mg ions are complexed
with EDTA and forms a metal EDTA
complex i.e., the end point of the
titration.
6. Note down the burette reading
7. The value of titration is 29.8mL
8. Repeat the titration for concordant
values
III.B. Determination of Calcium in
water sample
III.B.1 PREPARATION OF REAGENT
Standard EDTA Solution (0.02 M)
1. Switch on the electronic balance,
keep the weighing pan, and set the
reading to zero.
2. Weigh 3.723g of EDTA sodium salt
3. Transfer the content to the water
sample. Place the lid and mix the
content thoroughly until all EDTA
sodium salt dissolve in water
4. Make the volume exactly 1000 mL
by adding distilled water. Transfer
the solution to a clean reagent bottle
named EDTA solution.
5. This. 0.02 molar EDTA solution is
going to be used as a titrant in this
experiment.
Ammonium purpurate
1. Weigh 0.5g of Ammonium Purpurate
2. Transfer it to a dry beaker
3. Weigh 100g of sodium chloride
4. Transfer it to the beaker having
ammonium purpurate mix the
contents thoroughly. Use it as a dry
powder.
Sodium Hydroxide (1N) solution
1. Take 100 mL of distilled water in a
beaker
2. Weigh 4gm m of sodium hydroxide
powder
3. Transfer it to the distilled water in
the beaker and mix it thoroughly.
4. Then transfer the entire content to
100 mL standard flask
5. Rinse the glass rod and funnel with
distilled water
6. Make the volume 100mL by adding
distilled water up to the mark
7. Take the sodium hydroxide solution
in 100mL beaker for easy handling.
III.B.2 TESTING OF SAMPLE
1. Pipette 20mL of water sample and
transfer it to a clean 250 mL conical
flask
2. Measure 2mL of 1N sodium
hydroxide solution using measure
cylinder. Add it to the water sample
in conical flask so that the pH will be
maintained between 12 and 13.
3. Add few amount of Ammonium
purpurate indicator to the water
sample. Now the sample turns into
pink color. This color change is due
to the calcium and magnesium
contents present in water.
4. Before starting the titration rinse the
burette with few mL of EDTA
solution and discard it. Fill the
burette with 0.02M EDTA solution.
Adjust the reading to zero, then fix it
in burette stand. Ensure that, there
is no any air bubble inside the
burette.
5. Titrate the water sample against the
EDTA solution in the burette till all
calcium and magnesium ions present
in the sample reacts with the EDTA
to form a metal EDTA complex by
changing the color of the sample to
purple.i.e, the end point.
6. Note down the burette reading
III.C Determination of Magnesium by
Titration with EDTA
III.C.1 PREPARATION OF STANDARD
0.01 M NA2H2EDTA SOLUTION
1. Weigh about 3.8 g of the disodium
EDTA salt ( Na2H2Y 2H2O) . Into a 1
liter volumetric flask, dissolve and
dilute to the mark with de-ionized
water and mix well.
III.C.2 STANDARDIZATION OF THE
EDTA SOLUTION
1. Pipet exactly 25 mL of standard Zn
solution into each of three
Erlenmeyer flasks. Add 20 mL of
pH 10 buffer (in the hood), 15 mL
of water, stir, and add a few
crystals of the Eriochrome Black T
indicator. It is critical to add only
enough indicator to produce a light
wine-red color.
2. Titrate with your EDTA solution
until the color changes from wine-
red to a clear blue.
3. Use these results to determine the
molar concentration of the EDTA
solution for use in the titration of
your unknown Mg solution.
III.C.3 DETERMINATION OF
UNKNOWN MAGNESIUM
 1. Your unknown for this experiment
is a solution. When you obtain
your unknown, you need to
quantitatively transfer it to a
100mL volumetric flask and dilute
it to the mark, resulting in the
prepared unknown solution. You
are to report the results of this
prepared unknown.
2. Transfer exactly 10mL of the
prepared unknown solution into 3
or 4 erlenmeyer flasks. Add
approximately 15mL of pH 10
buffer in the hood and 20 or 25mL
of distilled, de ionized water to
each flask.
3. Add a few crystals of Eriochrome
Black T indicatorit is a crucial
that you only add enough
indicator to produce a light, wine-
red color.
4. Titrate each solution with your
standardized EDTA solution to a
clear blue color.
5. Report your results as percent
magnesium (%w/v) in your
prepared unknown sample. Also
report the 95% confidence
interval.

IV. Calculations

IV.D.1 TOTAL HARDNESS IN WATER

The hardness of water is due in part to the presence of Ca2+ ions in water. The
concentration of Ca2+ ions is usuallyexpressed as ppm CaCO3 in the water sample. This
is equivalent to 1 gram of CaCO3 in 106 grams of sample. In the lab 1 ppm CaCO3 is
expressed as 1 mg CaCO3 per 1 Liter of sample or ppm is mg CaCO3 per L of sample.

The procedure is done in 3 steps:

1. Preparation of a standard Ca2+ solution

For example:
0.405 g of CaCO3 is dissolved in HCl and diluted to a volume of 250.00 mL. What is the
molarityof calcium ions in the solution?

CaCO3(s) + 2HCl(aq) Ca2+(aq) + 2Cl1-(aq) + H2O(l) + CO2(g)

1 1
(405gCaCO3)(100.093 )(1 ) = 0.004505
3 3

0.00405
Molarity of Ca = 0.250
=0.0162 M Ca

2. Standardization of EDTA with the standard calcium solution

For example:
A 25.00 mL aliquot (a portion or part) of the standard calcium solution reacts with 27.25
mL of the EDTA solution. What is the molarity of the EDTA?

0.0162 0.02500 1
( )( )( ) = 0.000405
1 1
 0.000405
Molarity of EDTA = 0.02725
= 0.0149

3) Analysis of an unknown Ca2+ sample with the standardized EDTA solution.

For example:
A 50.00 mL unknown solution requires 25.55 ml of the standardized EDTA solution for
complete reaction. What is the Ca2+ concentration in the unknown reported as ppm
CaCO3?

0.0149 0.02555 1
( )( )( ) = 0.000381
1 1

13 100.093
0.000381( )( ) = 0.03813
1 13

3 10003
3 = = 0.03813 ( ) = 0.03813
13

3 10003 1
3 = = 0.03813 ( )( ) = 762
1.0003 0.05000