4d Application of Complexometric Titration

D
Water hardness
A B C
THE DETERMINATION OF WATER HARDNESS
1. EDTA titrations are routinely used to determine
water hardness, in a laboratory.
2. Raw well water and tap water are hard water.
3. Hard water is due to metal ions(minerals) that are
dissolved in the ground water. These minerals
include Ca2+, Mg2+, Fe3+, SO42-, and HCO3-.
4. Water from different sources can have different
hardness values.
5. The EDTA determination of water hardness
results from the reaction of EDTA ligand with all
of the metal ions involved: calcium, magnesium
and iron
6. The “hardness” problem in kettle, water heater
tank etc arise as a result of heating or boiling the
water over a period of time so that the water is
evaporated, and the calcium and magnesium salts
become concentrated and precipitate in the form
of a “scale” on the walls of the container, hence
the term “HARDNESS”. Hard water cause soap
scum, clog pipes and clog boilers
concentration of the
7. In many cases, the
Ca2+ ions is greater than the
concentration of any other metal ion in the ground
water therefore we measure water hardness based
on the concentration of the Ca2+ ions
Degree of hardness of the water
Hardness Concentration of Concentration of Calcium
rating Calcium Carbonate Carbonate (grains/US gallon)
(mg/L)
Soft 0 to <75 0 to <5.2 (0-60 ppm)
Medium 75 to <150 5.2 to <10.5 (61-120 ppm)

hard
Hard 150 to <300 10.5 to <21 (121-180 ppm)
Very hard 300 and greater 21 and greater (>180 ppm)

Determination of Ca alone using EBT as
indicator.
Principle: Ca2+ + EBT = Ca-EBT red complex

Problem: End-point appears before the
equivalent point. This is due to:
The Ca-EBT complex has a small value of formation

constant, Kf .
Thus the Ca_EBT complex can dissociate as Ca2+ is used

up in the titration with EDTA and hence the end-point
appears before the equivalent point.
Remember !! At pH=10
MIn = HIn2-
Red blue
Formation constant = [ Ca - EBT ]
[Ca 2 ] [ EBT ]
 In other words, the determination of Ca with
EDTA using EBT as an indicator produce a
result lower than the correct value.
 Since the end-point is reached before the
equivalence point and the change of colour

from red to blue is very slow, hence Ca2+
alone cannot be determined by using EBT as
indicator.
To overcome the error
A small amount of Mg2+ ion was added to the
standard EDTA solution (before titration begin) so
that Mg-EDTA is formed in the titrant.
The reaction:
Mg2+ + EDTA = Mg-EDTA
The true concentration of EDTA can be determined

by standardization
When the titrant is added to the Ca2+ in the
conical flask, the following reaction takes
place:
Ca2+ + Mg-EDTA = Ca-EDTA + Mg2+
Mg2+ + Ca-EBT = Mg-EBT + Ca2+

red red
Hence the Mg-EBT will remain undissociated
until the equivalence point is reached.
As more EDTA is added, the reaction between Ca
ion and EDTA proceed as long as there is Ca2+
present in solution:
Ca2+ + EDTA = Ca-EDTA
When no more Ca2+ is present, the end point is
reached, then:
Mg-EBT + EDTA = Mg-EDTA + EBT
Red complex blue at
Last drop of EDTA for pH=10
Mg2+
Problems with EDTA titration
 The problems can solve by using :
1. Auxillary Complexing Agent
2. Chemical Masking
1.Auxiliary (supporting) Complexing Agent
 Metals react with EDTA in basic solution in which many of

them form insoluble hydroxides. [ex: Ca(OH)2]
 These hydroxides reacts only slowly with EDTA, making the
titration impossible.
 To avoid this problem, an auxillary complexing agent, such
as NH3 is added to form a temporary complex (soluble) with
the metal.
 The temporary complex will then react with EDTA in the basic
solution.
Auxiliary Complexing Agent- forms a weak complex with the

metal to keep it in solution at higher pH values.
2.Chemical Masking
 A complex is sometime formed to trap metals
that interfere with a chemical reaction.
 Example:
 Ca, Mg + EDTA , where CN- is added as
masking agent.
 CN- is added to mask the interferences of Zn2+
, Cd2+ and Hg2+

COMPLEXOMETRIC CALCULATION
Example 1
A 50.00 mL sample of underground water is
acidified with HCl, boiled to remove CO2, and
neutralised with NaOH. The solution is
buffered to pH 10 and titrated with 0.0124 M
EDTA, using EBT as indicator. If the titration
requires 31.63 mL to reach end-point,
calculate the water hardness as ppm CaCO3.
[ At. Wt. : Ca + 40 , C = 12 , O = 16 ]
Ca2+ + EDTA = Ca-EDTA
mol Ca2+ = 1 mol EDTA
mol CaCO3 = mol EDTA
= MV/1000
= 0.0124 x 31.63
1000
= 0.3922 x 10 -3 mol CaCO3
mg CaCO3
= 0.3922 x 10 -3 mol 100 g 1000mg = 39.22mg
1 mol 1g
ppm CaCO3 = mg /L CaCO3 = 39.22 mg/ 0.050 L
= 784.4 ppm CaCO3 #

Example 2
The Fe in 6.875 mg of an indoor plant food was

oxidized to the +3 state, following which the sample
was diluted to exactly 100 mL. Calculate the
percentage of Fe in the sample if 44.87 mL of the
diluted solution were needed to titrate 15.00 mL
0.0036 M EDTA solution.
[ At. Wt Fe = 56 ]
gram Fe
SOLUTION:
% Fe = gram sample
x 100
Fe3+ + EDTA = Fe – EDTA complex

mol Fe3+ = mol EDTA
mol EDTA = (0.0036 x 15.00)/1000
= 0.054 x 10 -3 mol Fe3+
Molarity of Fe3+ = 0.054 x 10 -3 mol

44.87 x 10 -3 L
= 0.0012 M
mol Fe3+ in 100 mL = 0.0012 x 0.100
= 0.12 x 10 -3 mol Fe3+
Mass (g) Fe3+ = 0.12 x 10 -3 mol 56 g = 6.72 x 10-3g
1 mol
% Fe = 6.72 x 10-3g x 100 = 97.75%

6.875 x 10-3g

4d Application of Complexometric Titration

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D

Soft 0 to <75 0 to <5.2 (0-60 ppm)

Medium 75 to <150 5.2 to <10.5 (61-120 ppm)

Hard 150 to <300 10.5 to <21 (121-180 ppm)

Very hard 300 and greater 21 and greater (>180 ppm)

Principle: Ca2+ + EBT = Ca-EBT red complex

The Ca-EBT complex has a small value of formation

Thus the Ca_EBT complex can dissociate as Ca2+ is used

equivalence point and the change of colour

The true concentration of EDTA can be determined

Mg2+ + Ca-EBT = Mg-EBT + Ca2+

 Metals react with EDTA in basic solution in which many of

Auxiliary Complexing Agent- forms a weak complex with the

, Cd2+ and Hg2+

ppm CaCO3 = mg /L CaCO3 = 39.22 mg/ 0.050 L

= 784.4 ppm CaCO3 #

The Fe in 6.875 mg of an indoor plant food was

Fe3+ + EDTA = Fe – EDTA complex

Molarity of Fe3+ = 0.054 x 10 -3 mol

% Fe = 6.72 x 10-3g x 100 = 97.75%

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