ABSTRACT

Many industrial and domestic water users are concerned about the hardness of their
water. Hard water requires more soap and synthetic detergents for home laundry and
washing and contributes to scaling in boilers and industrial equipment. Hard water is
water that has high mineral content and formed when water percolates through deposits
of calcium and magnesium-containing minerals such as limestone, chalk and dolomite.
Hard water does cause soap scum, clog pipes and clog boilers.

Soap scum is formed when the calcium ion binds with the soap. This causes an insoluble
compound that precipitates to form the scum. Soap actually softens hard water by
removing the Ca2+ ions from the water. Therefore, it is important for us to carry out
determination of calcium from the water sample by complexometric titration.

This method which is complexometric titration is used to find the calcium content of
milk, the ‘hardness’ of water and the amount of calcium carbonate in various solid
materials. The method uses a very large molecule called EDTA which forms a complex
with calcium ions. Eriochrome black T act as indicator will remains blue as all the Ca2+
ions present are complexed with the EDTA. The endpoint is reached when the colour of
solution changed from faint red to light blue.
Based on experiment, the concentration of calcium in a water sample X is determined by
using the complexometric titration with EDTA. The average ppm of calcium we get in
this experiment is 5.1728 ± 0.588 and the % (w/v) of calcium is 0.000517 %. The results
means the amount of calcium in mg/L and in % (w/v) that is presented in water sample X.
The water hardness indicated the water quality and the amount of calcium ions present in
the water sample. Hence it is a soft water and it probably came from mineral water.
 INTRODUCTION
The determination of water hardness is a useful test that provides a measure of quality of
water for households and industrial uses. Originally, water hardness was defined as the
measure of the capacity of the water to precipitate soap. Hard water is not a health
hazard. People regularly take calcium supplements. Drinking hard water contributes a
small amount of calcium and magnesium toward the total human dietary needs of
calcium and magnesium. When hard water is heated, CaCO3 precipitates out; this then
clogs pipes and industrial boilers. This leads to malfunction or damage and is expensive
to remove. Hence, we are carrying out complexometric titration to determine the amount
of calcium in sample given so that the hardness of water is then classified.

Complexometric titration is a quantitative analysis in which the formation of a colored

complex is used to indicate the end point of a titration. This method uses a very large
molecule called EDTA which forms a complex with calcium ions. EDTA is short for
ethylenediaminetetraacetic acid. A blue dye called Eriochrome Black T is used as the
indicator. For the titration, the sample solution containing the calcium and magnesium
ions is reacted with an excess of EDTA. The indicator is added and remains blue as all the
Ca2+ ions present are complexed with the EDTA. The endpoint is reached when the colour
of solution changed from faint red to light blue. This is because when sufficient EDTA is
added and the metal ions are chelated by EDTA, leaving the free indicator molecule to
remains the characteristic blue colour as endpoint. The reaction between calcium ions and
EDTA is shown as follow:

Ca2++ H2EDTA2- → CaEDTA2- + 2H+

To ensure consistent results of titrations, the pH of the solutions must be controlled by

using buffer solution. Thus, NH3 – NH4Cl act as a buffer with pH 10 to prevent the
interferences by most metals. Therefore, the sample is avoided from interferences and
calcium ions can be determined more accurate.

There are several advantages of complexometric titrations in comparison with other kinds
of titration. Since EDTA is stable, soluble and has definite composition it is preferable to
other titrants. The selectivity in such titrations can be easily accomplished by judicious
choice of pH. For instance, at pH 11, Mg, Br, Ca, Ba can be titrated while at pH 4.0-7.0
Mn, Fe, Co, Ni, Zn, Cd, Al, Pb, Cu, Ti can be titrated and finally at pH 1.0- 4.0 metals
like Hg, Bi, Co, Fe, Cr, Ga, In, Sc, Ti and Th can be titrated. Stability constant of calcium
complex is higher than magnesium therefore calcium reacts first in this titration. This is
a very established, reliable, and accurate method but it take time to complete as done
manually.
 MATERIALS AND METHODS

The apparatus and reagents needed for complexometric titration:

Apparatus: Reagents:
Burette (50 mL) Disodium EDTA, Na2H2Y.2H2O
Pipette (25 mL) Calcium carbonate, CaCO3
Volumetric flasks (250 mL) Sodium hydroxide, NaOH
Erlenmeyer flasks (250 mL) Dilute hydrochloric acid, HCl(20%)
Measuring cylinder (50 mL) Magnesium chloride, MgCl2.6H2O
NH3-NH4Cl Buffer solution pH 10
Eriochrome Black T indicator (5%)
Deionized Distilled water
Water sample (provided in lab)

Procedure:

A. Preparation of Standard Calcium Solution and EDTA Solution

250 mL Calcium solution: 0.25 g dried CaCO3 is weighed accurately to the
nearest 0.1 mg. The solid is completely dissolved in a minimum amount of dilute 20% of
HCl until the solution is clear. The solution is quantitatively transferred into a 250 mL
volumetric flask and diluted to the mark with distilled water.
250 mL EDTA solution: 1.0±0.001 g of Na2H2Y.2H2O (the actual weight of the
EDTA is recorded to the nearest mg) is approximately dissolved in 30 mL distilled water.
Then, 0.025±0.001 g of MgCl2.6H2O and a few pellets of NaOH are added to the
solution. The solution is transferred to a 250 mL volumetric flask and diluted to the mark
with distilled water.

B. Standardization of EDTA Solution

25 mL of the Calcium solution is pipetted into a 250 mL conical flask and 1 mL of
buffer solution is added before 4 drops of Eriochrome Black T indicator into the same
conical flask. The Calcium solution is titrated with the EDTA when the colour change
from faint red to light blue is observed. The titration is repeated to obtain at least 3
accurate readings. The average molarities of the EDTA solution are calculated.
C. Determination of Calcium in Water Samples
50 mL of each water sample is approximately obtained. 10 mL of the sample is
pipetted into a conical flask and titrated with EDTA solution by using the procedure B as
described. The sample volume doubled to 20 mL for subsequent titration if the end point
is reached in less than 5 mL. The titration is repeated up to 3 times. The concentration of
Calcium in each sample in units of molar and ppm is reported.
 RESULTS
I. Standard Calcium Solution

Weight of CaCO₃ = 0.2518 g

Weight of EDTA = 0.9807 g
Weight of MgCl2.6H2O = 0.0254 g
Molarity of CaCO₃ = 0.01 M

Molar mass of CaCO₃ = [40 + 12 + (16x3)] gmol-1

= 100g mol-1

0.2518 g
Number of moles of CaCO3 =
100 g/mol
= 0.0025 mol

number of moles solute

Molarity of CaCO3 =
number of liter of solution
= 0.0025mol / 0.25L
= 0.01M

II. Standardization of EDTA Solution

Titration 1 2 3
Initial Burette Reading (mL) 0.0 19.3 0.0
Final Burette Reading (mL) 19.3 42.6 23.9
Volume of EDTA used (mL) 19.3 23.3 23.9
Molarity of EDTA (M) 0.0130 0.0107 0.0105
Mean for molarity of EDTA (M) 0.0114

Titration 1: Titration 3:
MCaCO₃VCaCO₃ = MEDTAVEDTA MCaCO₃VCaCO₃ = MEDTAVEDTA
0.01 M x 25.0mL = MEDTA x 23.9 mL
0.01 M x 25.0 mL = MEDTA x 19.3 mL MEDTA = 0.0105 M
MEDTA = 0.0130 M
Titration 2: Mean = 0.0130+ 0.0107+ 0.0105
MCaCO₃VCaCO₃ = MEDTAVEDTA 3
0.01 M x 25.0 mL = MEDTA x 23.3 mL = 0.0114 M
MEDTA = 0.0107 M

Standard deviation =

√
(0. 0130 - 0. 0 114) 2 + (0. 0 107 - 0. 0 114)2 + (0. 0 105 - 0.0 114) 2
3−1

=1.389 x 10-3 M

Average Mean of EDTA used (mean ± S.D.) = (0.0114 ±1.389 x 10-3) M

III. Determination of Ca in sample

Titration 1 2 3 4
Volume of sample (mL) 10.0 10.0 20.0 20.0
Initial Burette Reading (mL) 0.0 5.8 14.5 23.0
Final Burette Reading (mL) 5.3 10.0 23.0 31.8
Volume of EDTA used (mL) 5.3 4.2 8.5 8.8

Molarity of Calcium :

CaCO₃ Ca2+ + CO32-

0.01moldm-3 0.01moldm-3 0.01moldm-3

MCa=0.01 MCa=0.01 MCa=0.01

Titration 1:

Molarity of Calcium undiluted : Parts per million(ppm) :

MCaVCa = MEDTAVEDTA 6.042 x10 -3 mol

MCa(10.0) = 0.0114(5.3) dm 3
MCa =6.042 x10-3M =
( 6.042x10-3 molx1Lx 103 ) g
1L
=6.042mg/L

Titration 2:

Molarity of Calcium undiluted : Parts per million(ppm) :

 MCaVCa = MEDTAVEDTA 4.788 x10 -3 mol
MCa(10.0) = 0.0114(4.2) dm
3

MCa =4.788 x10-3M ( 4.788x10 -3 molx1Lx 103 ) g

=
1L
=4.788 mg/L

Titration 3:

Molarity of Calcium undiluted : Parts per million(ppm) :

MCaVCa = MEDTAVEDTA 4.845x10 -3 mol

MCa(20.0) = 0.0114(8.5) dm 3
MCa =4.845 x10-3M ( 4.845x10 -3 molx1Lx 103 ) g
=
1L
=4.845 mg/L

Titration 4:

Molarity of Calcium undiluted : Parts per million(ppm) :

MCaVCa = MEDTAVEDTA 5.016 x10 -3mol

MCa(20.0) = 0.0114(8.8) dm 3
MCa =5.016 x10-3M ( 5.016x10-3 molx1Lx 103 ) g
=
1L
=5.016 mg/L

6.042+ 4.788+4.845+5.016
Mean =
4

= 5.1728

Standard deviation =

√
2 2 2 2
( 6.042 -5.1728 ) + ( 4.788 -5.1728 ) + ( 4.845 -5.1728 ) + (5.016-5.1728 )
4−1
= 0.588

ppm of calcium (average ± S.D.) = 5.1728 ± 0.588

% (w/v) of calcium = (5.1728mg/1L)x (10mLx1L/1000mL)

 = 0.0517mg
= (0.0517x10-3g)/ 10mL x 100%
=0.000517 %

DISCUSSION
Complexometric titratio is a form of volumetric analysis in which the formation of a
colored complex is used to indicate the end point of a titration. In this experiment, the
analyte are standard calcium solution and water sample X while the titrant is the
standardized EDTA solution. This method is based on the fact that certain organic
compounds form stable complexes with metal ions in solution. In a complexometric
titration, a solution containing the free metal ion of interest is titrated with a solution of
chelating agent until all of the metal ions are completely complexed. The endpoint is
usually measured with an indicator ligand that forms a colored complex with the free
metal ion. The chelating agent is EDTA solution and the metal ion are calcium and the
color formed is light blue from paint red. The result of this experiment shows that water
sample contains 5.1728 ± 0.588ppm of calcium ion.

Hard water typically contains high concentrations of Ca, Mg (and other) cations, which
interfere with the use of the water for many applications. The determinations of levels of
these ions in untreated (natural) water are very common procedures in commercial
laboratories. For some purposes it is only necessary to know the total hardness. This is
related to the total amount of Mg and Ca in the water, and is usually expressed in terms of
part per million (ppm).

All reactions between metal ions and EDTA are pH dependent, and for divalent ions,
solutions must be kept basic and buffered for the reaction to go to completion. We must
use buffer for titration and also the Eriochrome black T indicator requires a pH of 8 to 10
for the desired color change from faint red to light blue

CaIn- + H+ Ca2+ + HIn2-

(Red) (Blue)

The major objective in this experiment is to determine the calcium in ppm by using
complexometric titration. This lab was done because determination of calcium by
complexometric titration is easier to handle and it is a type of experiment that can be used
to measure water hardness. In this experiment, we use formula M1V1=M2V2 to calculate
the molarity of calcium and molarity of EDTA. The average ppm of calcium we get in
this experiment is 5.1728 ± 0.588. Our result is quite accurate since standard deviation is
quite small (<10%).

Table: The Water Hardness Classification

Description Hardness in mg/l as Hardness in mg/l as

calcium calcium carbonate
Soft 0 - 20 0 – 50
Moderately soft 20 - 40 50 – 100
Slightly hard 40 - 60 100 – 150
Moderately hard 60 - 80 150 – 200
Hard 80 - 120 200 – 300
Very hard Over 120 Over 300
*Based on the Water Quality Association.

mg/l = milligrammes per litre = 1 part per million

There are two types of water hardness which is temporary and permanent. Temporary
hardness is due to the bicarbonate ion, HCO3-, being present in the water. This type of
hardness can be removed by boiling the water to expel the CO2. Permanent hardness is
due to the presence of the ions Ca2+, Mg+2, Fe3+ and SO4-. This type of hardness cannot be
eliminated by boiling. The water with this type of hardness is said to be permanently
hardness. Generally, we will classify our water sample according to the table above to
determine whether the water is soft or hard. In this experiment, our water sample X is
classified as soft water since the average ppm of calcium is 5.1728 ± 0.588. The source of
the sample probably is mineral water.

We found that we did manage to minimize the risk of making errors. Some precautions
should be taken, for example avoiding parallex error during reading the burette reading
and the EDTA solution is titrated slowly and drop by drop to ensure the equivalent point
is reached and don’t not exceed the equivalent point.

As the indicator doesn’t not change the colour of the solution from red to others when the
equivalent point is exceed. So titration for the EDTA solution should be slowly and drop
by drop. Besides, we had a little problems in weighting the magnesium chloride since the
weight required is small in quantitative but we did managed to overcome it. Personal
judgment such as colour of the solution and estimation of the burette reading in this
experiment is important and we try to avoid the error. From the calculation of standard
deviation and the volume used in each titration, we can conclude that the personal error
that we get in this experiment is minimized.

CONCLUSION
By doing this experiment we are now can apply the technique to carry out
complexometric titration. This experiment has shown how the amount of calcium present
in sample can be found. The amount of calcium carbonate (CaCO3) in 50mL sample X is
5.1728 ppm. We have classified it as a soft water and it probably came from mineral
water. The determination of water hardness is a useful test that provides a measure of
quality of water for households and industrial uses. Originally, water hardness was
defined as the measure of the capacity of the water to precipitate soap. Hard water is not a
health hazard. Drinking hard water contributes a small amount of calcium and
magnesium toward the total human dietary needs of calcium and magnesium. In general,
there are many applications where ability to easily determine water hardness is very
important.
 LIST OF REFERENCES
1. Skoog, D.A, West, D.M & Holler, F.J,(1996) “Fundamentals of Analytical
Chemistry, 6th Edition, Savnders College Publishing, USA.

2. Christian G.D(1994), “Analytical Chemistry”, 5th Edition, John Wiley & Son, Inc.
New York.

3. Williard,H.H.;Merritt,L.L.,Jr.;Dean,J.A.;Settle,F.A.,Jr.(1981),Instrumental
Methods of Analysis,6th Edition;Van Nostrand:New York .

4. The ACS Style Guide;Dodd,J.S.,Ed,(1997);American Chemical Society, 2nd

Edition,Washington,D.C.