EXPERIMENT 15

ESTIMATION OF MAGNESIUM AND 1

1

CALCIUM IONS IN A MIXTURE BY

COMPLEXOMETRY

Structure

15.1 Introduction
Objectives
15.2 'Principle
15.3 Requirements
15.4 Procedure
15.5 O b s e ~ a t i o n s
15.6 Calculations
15.7 Result

In Chemistry Lab-I and Chemistry Lab-I1 courses, you performed titrimetric or

gravimetric estimations of only single cation present in any substance. In this
experiment and Experiments 15 and 16, you will perform titrimetric or gravimetric
estimations of two cations together. For example, you will determine i) magnesium
and calcium by complexometry; ii) copper and zinc, and iii) copper and nickel by
gravimetry. Now we will concentrate on complexometric titration method.

Numerous methods are available for titrimetric determination of various cations by

titrations of their salts with certain organic reagents called complexones. These
complexones are imino-polycarboxylic acids, having excellent complex forming
ability with a number of cations. The simplest of the complexones is iminodiacetic
acid, HN(CH2COOH)z Other complexones can be assumed to be higher derivatives
of this family. The most important member of this family of reagents is
ethylenediaminetetraacetic acid, abbreviated as E D T A The structure of EDTA is
shown in Fig. 15.1.

Flg. 15.1: The structure of EDTA

EDTA can form complexes with a number of cations like alkaline earth metals and
man non-ferrous metal ions like cu2+, zn2+, pb2+, Co2+, ~ n ~~ +i ~, z r+4 +, and
Y
HP ,etc.
EDTA is only slightly soluble in water. However, its disodium salt is freely soluble in
water. Dihydrate of the disodium salt is available commercially in a state of high
purity under the brand names 'Versen' o r Trilon-B'. It can be used as a primary
standard. EDTA, generally, forms 1:l complexes with metal ions. In reactions,
EDTA and its disodium salt are represented as H4Y and Na H Y, respectively.
2.2
Reaction of the dispdium salt with a bivadent cation can be written as follows:
 Estimation of Magnesium and
Calcium Ions in a Mixture by
Complexometry

It is apparent from the above equation that there is always a competition in solution
between the metal ions and the hydrogen ions in seeking the negative sites on
EDTA. The equilibrium condition is determined by the strength of the bond between
the metal ion and the ligand, and the relative concentrations of metal ions versus
hydrogen ions. In other words, we can say that the stability of the metal-EDTA
complex will be governed by the hydrogen ion concentration or pH of the solution.
Minimum p H values for the stability of EDTA complexes of some selected metal
ions are listed in Table 15.1
t

Table 15.1: Stability with respect to pH of some Metal EDTA complexes

-
SI.No. Metal ion Minimum pH at which complex
is stable
1. Bi3+,2 r 4 + ,HP+,~ h ~ + 1-3

You can see from the Table that in general, EDTA complexes with alkaline earth
metal ions are stable in alkaline solution, whilst complexes with tri- and tetra-valent
metal ions are stable in strongiy acidic solutions.

EDTA is a multidentate ligand as it can donate six paris of electrons - two pairs from
the two nitrogen atoms and four pairs from the four terminal oxygens of the -COO-
groups. Such multidentate ligands prefer to form complexes having ring type
structures. As you know, these complexes are called chelates and such ring forming
ligands are called chelating agents.

The structure of a chelate of a divalent metal ion with EDTA is shown in Fig. 15.2.

Fig. 15.2: The slrudure of a chelate of M

'
+ and EDTA

Objectives

After studying and performing this experiment, you should be able to:
estimate ca2+and M ~ together
~ + by complexometry, and
describe complexones and perform complexometric titration

15.2 PRINCIPLE
In complexometric determination of magnesium and calcium ions in their mixture,
EDTA is used as a titrant and Solochrome Black (Eriochrome Black T)as an
indicator. When indicator solution, which is blue in colour, is added to the solution
containing magnesium and calcium ions, wine red coloured metal ion-indicator
Chemistry Lab-V complexes of varying stability are formed. The magnesium-indicator complex is more
stable than the calcium indicator complex but less stable than the magnesium-EDTA
complex which in turn is less stable than the clacium-EDTA complex. Consequently,
when EDTA solution is added, it reacts first with the free calcium ions, then with the
free magnesium ions, then with the calcium indicator complex and finally with the
magnesium-indicator complex. Since the magnesium-indicator complex is wine-red
in colour and the free indicator is blue between p H 7 and 11, the colour of the
solution changes from wine-red to blue at the end point.

In this experiment, we titrate one portion of the test solution containing both
magnesium and calcium ions with EDTA using Solochrome Black indicator at pH 10
and the volume consumed is noted. This gives the volume of EDTA required for the
titration of both magnesium and calcium ions. Then another equal portion of test
solution is taken, but this time the medium is kept strongly alkaline. In strong
alkaline medium, magnesium ions are precipitated and the calcium ions are left free
in the solution. This solution is then titrated with EDTA for calcium ions only using I

Murexide as indicator. The volume of EDTA consumed is the volume required for

I
titration of calcium ions only. By substracting the volume of EDTA consumed by
calcium ions from the volume of EDTA required for both magnesium and calcium
ions, we get the volume required for magnesium ions.

As EDTA is a primary standard, its molarity is known. Then using the molarity
equation, MIVl = M2V2, the molarity of magnesium and calcium ions can be
calculated.

15.3 REQUIREMENTS
You will need the following apparatus, chemicals and solutions for this experiment.

Apparatus Chemicals
Beaker 250 cm3 1NO. Ammonia liquor
Burette 50 cm3 1 No. Ammonium chloride
Burette stand 1 No. Calcium chloride
Conical flask 250 cm3 1No. Disodium salt of EDTA
Funnel 1No. Magnesium sulphate
Pipette 20125 cm3 1 No. Murexide indicator .
Pipette graduated 10 cm3 1 No. Sodium hydroxide
Volumetric flask 250 cm3 1 No. Solochrome Black indicator
Wash bottle 1 No.
Weighing bottle 1No.
Solutions provided :

1. Test solution :It can be prepared by dissolving accurately 2-3 g of calcium

chloride and 1-2 of MgS04 into minimum quantity of dil. HC1 and making up the
8
volume to 250 cm with distilled water.

2. NH:, - NH4Cl buffer solution of pH 10 :This can be prepared by dissolving 64g of

NH4C1 in distilled water, adding 570 cm3 of ammonia solution (sp.gr. 0.88) and
diluting to ldm3 with disttled water.

3. Solochrone Black indicator (0.5%mass /volume) :0.50 g indicator is weighted

and dissolved in 100 cm3 ethanol.

4. Mureride indicator :It can be used as solid, in 0.05g quantity in each titration.
The indicator solution may be prepared by suspending 0.5g of the powered solid in
 water, shaking thoroghly, and allowing undissolved protion to settle. The saturated Estimation of Magnesium and
Calcium Ions in a Mixture by
supernant liquid is used for titrations. Every day the old supernatant liquid decanted Cornplexometry
and the residue treated with water as before to provide a fresh solution of indicator.
3-4 drops of this solution are used for each litration.
i.
5. 0.1 M NaOH solution : Dissolve 4 g of NaOH in 1 dm3 of distilled water.

15.4 PROCEDURE
The experimental procedure involves the following steps:

1) Preparation of standard 0.M EDTA solution: As said earlier, EDTA is available

as a dihydrate of its disodium salt ( N ~ ~ H ~ Y . ~ HTake
~ o )already
. dried disodium salt
of EDTA from your counsellor. Take rough mass of a glass weighing bottle, transfer
about 9.5 g of the salt to the weighing bottle and weigh accurately. Transfer the salt
to a clean and dry volu,metric flask of 250 cm3 capacity through a glass funnel. Find
out the accurate mass of the weighing bottle after transferring the salt. The
difference between the two masses gives the actual mass of the salt taken. Record
these values in your observation note book for calculating the exact concentration of
the solution. Now dissolve the salt in deionised or distilled water. Make up to the
mark with distilled water and shake thoroughly to make a homogeneous solution.

' 'I
1: 2) Titration of the test solution

i) Fix a clean burette in a burette stand.

Fill the burette with the EDTA salt solution after rinsing it with this solution
In this titration wlour change
develops a little late, hence,
ii) titration should be done slowly.
and mount the burette o n a stand. Note the reading in the burette and record If necessary, add 2-3 drops more
it in the Observation Table I under the column 'Initial reading'. of indicator at the final stage of
titrat~on.This will provide
iii) Pipette out 25 cm3 of test solution in a 250 cm3 conical flask. Add 10 cm3 of necessary contrapi i n colour.
0.1 M NaOH solution and 3-4 drops of Murexide indicator solution. Dilute it
to 50 cm3 with distilled water. Now titrate with EDTA solution until the
colour changes from red to purple. Repeat the titration-3-4 times to obtain
concordant values. Record the values in Observation Table I under the
column 'Final Reading'. This gives volume (V,) of EDTA required for
calcium ions only.
iv) Pipette out 25 cm3 of another portion of the test solution containing both
magnesium and calcium ions, in a 250 cm3 conical flask. Add 5 cm3 of buffer
solution (pH = 10) and dilute it to 50 cm3 with distilled water. Ensure that
the smell of ammonia persists. If necessary add 2-3 drops of liquor ammonia. Solution should be warmed to
50-6O0C, but under no
Add Solochrome Black indicator (3-4 drops) and warm up to 50-60'~. Now, circumstances it should be
titrate with EDTA solution till the wine red colour of the solution changeslto boiled.
bluish. Note the final reading in the burette and record it in the Observation
Table I1 under the colunin 'Final reading'. Repeat the titration 3-4 tim& till
concordant values are obtained. This gives the volume (V2) of EDTA
required for both calcium and magnesium ions.

15.5 OBSERVATIONS
Approximate mass of the weighing bottle = ml =. .............. g

+
Mass of the weighing bottle EDTA salt = m2 =. .............. g
(before transferring the salt)

Mass of the weighing bottle -

- m3 =. .............. g
(after transferring the salt)
Chemistry Lab-V Observation Table 1
Titration of the test solution with EDTA using Murexide indicator

Sl. Volume of test Burette reading Volume of EDTA

No. solution in cm3 Initial Final salt, Vl in cm3
(Final-Initial)
1. 25
2. 25
3. 25
4. 25

Observation Table 11
Titration of the test solution with EDTA using Solocbrome Black indicator

I I
SI.
No.
Volume of test
solution in cm3
Burette reading
Initial Final
Volume of EDTA
salt, V2 in cm3
(Final-Initial)
1. 25
2. - 25

15.6 CALCULATIONS
Molarity of EDTA salt solution
Mass of EDTA salt transferred (m) = m2 - m3= .............. g
Molar mass (M,) of sodium salt of EDTA = 372.3 g mol-'

Volume of EDTA salt solution prepared = 2.50 cm3

Molarity of EDTA salt solution = loo' mol dm-3

M1 Mmx250

Concentration of Calcium ions in solution

Volume of calcium ion solution = V2 = 25 cm3
Molarity of Calcium ion solution = M2 = ?
Volume df EDTA salt solution required for calcium ions = Vl cm3 (From Table I)
m x 4
Molarity of EDTA salt solution = M1 = -
372.31
Now, using the molarity equation, MIVl = M2V2, we get,

Hence, concentration of calcium ions = molarity x molar mass of ca2+

mx4xVl
- mol dm-3x (40.08 g mol-l)
3 7 2 . 3 1 25
~
Concentration of Magensium ions in solution ,Estimation'of Magnesium and
Calcium Ions in a Mixture by
Volume of magnesium ion so~btion= V3 = 25 cm3 Complexometry

Molarity of magnesium ion solution = M3 ='?'

volume of EDTA salt solution required for magnesium ions = (V2 - Vl) cm3
mx4
Molarity of EDTA salt solution =MI = -
372.31
Now, using the molarity equation, we get,
M l (V2 - Vl) = M3 v3

- m x 4 x (V2 -.Vl) mol dm-3

372.31 x 25
Hence, concentration of magnesium ions=molarityxmoar mass of M ~ ~ +
4 X (V2 - V1)
- m X372.31 x 25 mol dm" x (24.32 g mol-')

15.7 RESULT
You can report your result in the following form:

1. Calcium content in the solution =........... g dm"

2. Magnesium content in the solution =.......,... g dm-3