Name: SAMREEN AHMED KHAN / TANVEER FATIMA

Group: 11
Course Title: CLASSICAL METHOD OF QUANTITATIVE ANALYSIS

Presentation Topic: Quantative Analysis Of Ca++ and Mg++ In a sample solution

Presentation Date: 18-04-2012
 INTRODUCTION :
Analysis of Ca++ and Mg++ in a sample solution can be carried out by volumetric analysis (also
known as Titrimetric analysis) which involves complex formation reaction or complexation reaction.

For this a known volume of sample solution is titrated against standard EDTA solution in the
presence of buffer solution of PH 10 using Eriochrome Black T as an indicator to find out the
volume of standard EDTA solution consumed to form Complex with Mg ++ as well as Ca++ present in
the sample solution.

In second, a known volume of sample solution is treated with 8M KOH solution to precipitate out
Mg++ as Mg(OH)2 and then the content is titrated against standard EDTA solution using Calcon as an
indicator to find out the volume of standard EDTA solution consumed to form Complex with Ca ++
present in sample solution.

Subtraction of volume of standard EDTA solution obtained in first step from the volume of standard
EDTA solution, consumed in second step corresponds to the volume of standard EDTA solution
consumed to form Complex with Mg++ present in sample solution.
 INTRODUCTION OF CALCIUM:

The symbol of Calcium is Ca.

Calcium belongs to 2nd group of periodic table (Alkaline earth metals) soft gray
coloured metal
The atomic number of Ca is 20
The atomic weight of Ca is 40.08
Its main properties are that it is reactive, usually found in combined form in nature.
 Body Content

Total amount of Ca about 1 to 1.5 Kgs

Role in body structure in bone, important divalent cation in body fluids
Form in body Ca++
 Major Function In The Body

Ca++ plays structural role (bone and teeth)

Ca++ plays role in blood coagulation
Ca++ plays a very important role in membrane functions (membrane integrity
messenger role, membrane role, membrane / channel permiability, membrane
adhesiveness)
Its do stimulus response coupling (release of harmones and neurotransmitters, second
messenger function excitation - contraction coupling in skeletal cardiac and smooth
muscle)
 Chemical Properties Of Ca++

The atomic number of Ca++ is 20

The atomic mass of Ca++ is 40.08 g / mol
The electronegativity according to Pauling 1.0
The density is 1.6 g / cm3 at 20oC
The melting point 840oC
The boiling point of Ca++ is 1484oC
The vanderwaals radius of Ca++ is 0.197 nm
The ionic radius of Ca++ is 0.999 nm
The electronic configuration of Ca++ is [Ar] 4S2
The energy of 1st ionization is 589.6 KJ / mol
The energy of 2nd ionization is 1145 KJ / mol
The standard potential is -2.87V
Ca++ was discovered by Sir Humphrey Dary in 1808
 Uses of Calcium:

Calcium is essential for human nutrition

Animals skeletons get their rigidity primarily from Calcium comprised of CaCO3
Calcium is also necessary for plants growth
Calcium is also used as a reducing agent
Calcium compounds are used making line, bricks, cement, glass, paint, paper & sugar etc
 Introduction of Magnesium:

The symbol of Magnesium is Mg

Mgnesium belongs to 2nd group of periodic table Alkaline earth metals
The Atomic number of Mg is 12
The atomic weight of Mg is 24.3050 g / ml
 Magnesium: what is it ???

Magnesium is the 4th most abundant mineral in the body and is essential to good health.
Approximately 50% of total Magnesium is found in bone, the other half is found inside
cells of body tissues and organs.
Only 1% of Magnesium is found in blood.
 Sources Of Magnesium:

It is present in green vegetables such as spinach are good sources of Magnesium because
the centre of the chorophyll molecule contains Magnesium
Some regumes (beans and peas) nuts and seeds and whole unverfined are also good
sources of Magnesium
 Uses Of Magnesium:

Magnesium is commercially important metal with many uses

It is easily machined, cast, forged and welded
Magnesium alloys were used as early as 1910 in Germany. Each structural uses of
Magnesium alloys were in air craft fuselagers, engine parts and wheels
Magnesium can be used as a reducing agent
 Properties of Magnesium:

Magnesium is ductile, silver-white metal

A hexagonal close-packed crystalline structure
It is malleable when heated
It reacts with slowly with cold water
 Chemicals and Reagents:

Magnesium sulphate hepta hydrate (MgSo4.7H2O)

Disodium ethylene tetra diamine tetra acetic acid (H2Y--)
Buffer solution of PH 10
Erichrome Black T (EBT)
Calcon
Potassium hydroxide (KOH)
 EDTA

EDTA is a polyamino carboxylic acid and a colourless, water soluble solid. Its congugate
base is name ethylene diamine tetra acetate. It is widely used to dissolve lime scale.
 MgSO4.7H2O

MgSo4.7H2O is often encounter as hepta hydrate epsomite commonly called Epsom

Salt. Anhydrous MgSO4 is used as a drying agent, since the anhydrous water from is
hygroscopic (readily absorbs water from the air) and is therefore to weight accurately.
 EBT

Eriochrome Black T is a complexometric indicator that is part of the complexometric titrations, e.g.
in the water hardness determination process. It is an azo dye.
In its protonated form, Eriochrome Black T is blue. It turns red when it forms a complex with
calcium, magnesium, or other metal ions.
How Eriochrome Black-T Works
When Eriochrome Black-T complexes with Mg2+ ions, it produces a PINK-RED solution. The
indicator is BLUE when the it is not complexed with Mg2+ (equation 2) and the solution is basic.
As EDTA is added to hard water during the titration it reacts with the divalent ions (e.g. Ca 2+ and
Mg2+) present in the hard water. Once all the divalent ions in solution have reacted with EDTA, the
EDTA reacts with the Mg2+ ions that are complexed with the Eriochrome Black-T indicator, thus
causing the solution to turn BLUE.
Equation 2. In-Mg(aq) In2-(aq) + Mg2+(aq)
 Calcon Indicator

A complexometric indicator is an monochromic dye that undergoes a definite colour

change in presence of specific metal ions. It forms a weak complex with the ions present
in the solution which has a significantly different colour from the form existing outside
the complex. Complexometric indicators are also known as PM indicators
 Q: Why you use PH=10 buffer in EDTA?

Ans: It is necessary to keep the PH at about 10 two reasons:

(a) 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.

(b) The erichrome Black T requires a PH of 8 - 10 for the desire colour change.
 Chemical Equations:

Standardization of EDTA Solution

Ionization of MgSO4.7H2O in aqueous solution.

MgSO4.7H2O Mg++ + SO-- +7H2O

Reaction of Mg++ with Eriochrome Black T at PH 10

Mg++ + HIn-- MgIn- + H+

Reaction of Mg-- - Indicator (Eriochrome Black T) Complex with EDTA at PH 10

MgIn- + H2Y - - [MgY]-- + Hin-- + H+
Analysis of Sample Solution
Reaction of Ca ++ with EBT at PH 10
Ca++ + HIn-- CaIn- + H+

Reaction of Ca++ - Indicator (EBT) Complex with EDTA at PH 10

CaIn- + H2Y- - [CaY] -- + HIn-- + H+

Reaction of Mg++ with EBT at PH 10

Mg++ + HIn-- MgIn- + H+

Reaction of Mg ++ - Indicator (EBT) Complex with EDTA at PH 10

MgIn- + H2Y- - [MgY]- - + HIn- - + H+

Reaction of KOH with Mg ++

KOH + Mg++ Mg(OH)2 + 2K+

Reaction of KOH with Ca++

KOH + Ca+ Ca(OH)2 + 2K+

Ionization of Ca(OH)2 in aqueous solution

Ca(OH)2 Ca++ + 2OH-

Reaction of Ca++ with Calcon indicator at PH 12

Ca++ + Calcon Ca++ - Calcon Complex

Reaction of Ca++ - Indicator (Calcon) Complex with EDTA at PH 12

Ca++ + Calcon + H2Y- - CaY- - + 2H+ + Calcon
 Procedure:

Calculate the weight of MgSO4.7H2O to prepare its 0.01 M standard solution in 100 ml
volumetric flask.
Prepare 0.01 M standard MgSO4.7H2O solution in 100 ml volumetric flask.
Weight x (g) of MgSO4 .7H2O accurately in a vial, transfer to a volumetric flask, dissolve
in distilled water and make the volume of the solution upto the mark with distilled water.
Prepare about 250 ml of about 0.01 M disodium salt of EDTA solution in a beaker.
Weight about y (g) of Na2EDTA on watch glass transferred to a beaker, dissolve in
distilled water and the volume of the solution upto 250 ml with distilled water.
Rinse and fill the burette with Na2EDTA and remove air bubbles from the jet note initial
burette readings.
Transfer 10 ml of 0.01 M MgSO4.7H2O solution to a conical flask, add about 10 ml of
buffer solution of PH 10 and EBT to it and titrate the content of the conical flask against
NA2EDTA solution until red colour changes into blue. Note final burette reading.
Repeat the step until concordant readings obtained and calculate the molality of EDTA.
 Analysis of Sample Solution:

Transfer 10 ml of sample solution to a conical flask, add about 5 ml of about 8M KOH

solution to it. Allow to stand the content of the flask for 5 minutes. Then add a Calcon
indicator to the content of the flask and titrate the content against standard Na 2EDTA
solution until red solution turns purple. Note the burette readings.
Repeat the step until concordant reading obtains.
Transfer 10 ml of sample solution to a conical flask with a pipette, add about 10 ml of
buffer solution of PH 10 and EBT and titrate the content of the flask against standard
Na2EDTA solution until red colour changes into blue. Note the burette readings.
Repeat the step until concordant reading obtains.
 Observations:

Total volume of sample solution = 250 ml

Amount of MgSO4.7H2O = X g / 100 ml
Amount of EDTA = about Y g / about 250 ml
Molar mass of MgSO4.7H2O = 246.4745 g / mol
Molar mass of EDTA = about 372.2360 g / mol
Molar mass of Ca++ = 40.08 g / mol
Molar mass of Mg++ = 24.3120 g / mol
Volume of consumed to Mg++ in sample = r ml
Standardization of EDTA:
Volume of MgSo4.7H2O = 10 ml
Volume of buffer solution of PH 10 = about 10 ml
Indicator = erichrome Black T
Volume of EDTA solution consumed:
S. No Initial reading Final reading Difference Concordant
(ml) (ml) (ml) reading
(ml)

1. A B C

2. B D C C
Volume of sample solution = 10 ml
Volume of KOH solution = about 5 ml about 8M
Indicator = Calcon
Volume of standard EDTA solution consumed:

S. NO Initial reading Final reading Difference Concordant

(ml) (ml) (ml) reading
(ml)

1. H I J

2. J K J J
Analysis of sample solution:
Volume of sample solution = 10 ml
Volume of buffer solution of PH 10 = ml
Indicator = erichrome Black T
Volume of standard EDTA consumed:
S. No Initial reading Final reading Difference Concordant
(ml) (ml) (ml) reading
(ml)

1. D E F

2. E G F F
Calculations:

Determine the amount of MgSO4.7H2O to prepare its 0.01M solution:

Amount of MgSO4.7H2O = (Molarity x Molar mass x Volume) / 1000
= (0.01 x 246.4745 x 100) / 1000
= 0.2464 g / 100 ml
Determine the molarity of prepared MgSO4 in 100 ml
Molarity = (Amount x 1000) / (Molar mass x Volume)
= (X x 1000) / (246.4745 x 100)
= Z M
Determine the amount of EDTA to prepare, its 0.01M solution in 250ml:
Amount of EDTA = (Molarity x Molar mass x Volume) / 1000
= (0.01 x 372.2360 x 250) / 1000
= about 0.9 g / about 250 ml
Standardization of EDTA solution:

1000 ml of standard MgSO4.7H2O solution contains (Z) mol of MgSO4.7H2O

10 ml of standard MgSO4.7H2O solution contains (Zx10) / 1000 mol of MgSO4.7H2O)
= (m) mol of MgSO4.7H2O
1 MgSO4.7H2O = 1 EDTA
(C) ml of EDTA solution contains (m) mol of EDTA
1000 ml of EDTA solution contains (m x 1000) / C mol of EDTA
= (n) mol of EDTA

So, the concentration of prepared EDTA solution is n M

Analysis of sample solution of Ca++ and Mg++
Determination of No. of mole of Ca++ present in 250 ml sample solution:

1000 mlof standard EDTA solution contains n mol of EDTA

J ml of standard EDTA solution contains (J x n) / 1000 mol of EDTA

1 EDTA = 1 Ca++

( 1 mol of Mg++ x O mol of EDTA) / 1 mol of EDTA

= O mol of Ca++

10ml of sample solution contains O mol of Ca++

250ml of sample solution contains (O x 250) / 10 mol of Ca++
= p mol of Ca++
So, the No. of mole of Ca++ in the sample solution is p Mol / 250 ml
Determination of weight of Ca++ present in 250 ml of sample solution:

Weight of Ca++ = (No. of mol of Ca++ x Molar mass of Ca++)

Weight of Ca++ = p x 40.08
Weight of Ca++ = q g / 250 ml

So, the weight of Ca++ in the sample solution is q g / 250 ml

Determination of volume of standard EDTA solution
consumed against Mg present in sample solution ...
++

Volume of standard Disodium Salt of EDTA solution consumed against Mg++ present in
Sample Solution = (Total Volume of Standard Disodium Salt of EDTA Solution
consumed against Ca++ and Mg++ present in sample solutio) - (Volume of Standard
Disodium Salt of EDTA Solution consumed against Ca++ Only present in Sample
Saolution.

Volume of Standard Disodium Salt of EDTA Solution consumed against Mg++ present
in Sample Solution
= (J - F)
= L ml
Determination of No. of mole of Mg present in 250ml ++

sample solution ...

1000ml of standard EDTA solution contains n mol of EDTA

L ml of standard EDTA solution contains (L x n) / 1000 mol of EDTA
= r mol of EDTA
1 EDTA = 1 Mg++

(1mol of Mg++ x r mol of EDTA) / 1 mol of EDTA

= r mol of Mg++

10ml of sample solution contains r mol of Mg++

250 ml of sample solution contains (r x 250) / 10 mol of Mg++

So, the No. of mole of Mg++ present in sample solution is s mol / 250ml
Determination of weight of Mg++ present in 250ml sample
solution ...

Weight of Mg++ = NO. of mol of Mg++ x Molar mass of Mg++

Weight of Mg++ = S x 24.1320
= T g / 250ml

So, the weight of Mg++ present in the sample solution is T g / 250 ml

Result:

The No. of mole of Mg++ present in given sample solution is found to be s mol/250 ml
The weight of Mg++ present in the given sample solution is found to be T g/250ml
The No. of mol of Ca++ present in given sample solution is found to be p mol/250ml
The weight of Ca++ present in the given sample solution is found to be q g/250ml