SEMINAR ON COMPLEXOMETRY TITRATION

Presented by,
Sudhindra.g

Under the Guidance of Dr. Satish Kumar Shetty

CONTENT
 Definition
 Chelates
 Ligand
 CLassification of ligand
 Titration curve
 Complexometric titration involving EDTA
 Methods of End Point Detection
 Types of Complexometric Titrations
1. Direct Titration
2. Back titration
3. Replacement of one complex by another
4. Alkalimetry titration of metals
Definition:
Complexometric titration is the volumetric
method of analysis in which the simple metal
ion is converted into complex by addition of
reagent known as ligand or complexing agent
and is used to estimate polyvalent ions i.e.,
divalent, trivalent.
CHELATE:
 Chelate is a complex that is formed by the
combination of a polyvalent metal ion with a
molecule which contain two or more groups that
can donate electrons.

Example: copper with a co-ordination no 4 forms

 Cationic amine complex

 Neutral complex with glycine

 Copper bonds with the both oxygen of carboxyl

group and nitrogen of amine group
LIGAND :
 A complexing agent is an electron donating ion or molecule
capable of forming one or more covalent or coordinate bonds
(dative bond) with metal ions, producing a complex which has
different properties from that of metal ions.

 A ligand uses a lone pair of electrons (Lewis base) to bond to the

metal ion (Lewis acid)

 All an ions, and molecules such as NH3, H2O, NO, CN-, and
halides are called as Ligands, because they can donate pair of
electrons to metal ion.
Ag+ + 2 CN- ⇌ [Ag (CN) 2]-
Hg2+ + 2 Cl- ⇌ HgCl2
 Classification of Ligands
Unidentate ligand
Ligands that are bound to metal ion only at one place are called
unidentate ligands.
Bidentate ligand
 If the ligand has two co-ordinating site then it is called as
Bidentate Ligand.
E.g.: ↓ ↓
H2N −CH2−CH2−NH2
Ethylene diamine [bidentate]
Tridentate ligand
 If the ligand has three coordinating site then it is called as
Tridentate Ligand.
E.g.: -↓ ↓ ↓
H2N −CH2−CH2−NH− CH2−CH2−NH2
Multidentate ligand
 Ligand having many sites is called Multidentate Ligand.
E.g.:-EDTA- disodium salt.
 TITRATION CURVES
 So in the EDTA titrations if pM (negative logarithm of the
free metal ion concentration pM = -log[Mn+ ]) is plotted
against the volume of EDTA solution added .

 And a point of inflexion occurs at equivalence point in some

instance it may exceed 10pM units.
There are two factors that are important in determining the magnitude of
break in titration curve at end point.

1. The stability of complex formed: The greater the stability constant

for complex formed, larger the charge in free metal concentration
(pM) at equivalent point and more clear would be the end point.

2. Effect of pH:. Control of pH is important since the H+ ion plays an

important role in chelation. Most ligands are basic and bind to H+ ions
throughout a wide range of pH. Some of these H+ ions are frequently
displaced from the ligands (chelating agents) by the metal during
chelate formation.
 Equation below shows complexation between metal ion and H+
ion for ligand:

 Thus, stability of metal complex is pH dependent.

 Lower the pH of the solution, lesser would be the stability of

complex.

 Only metals that form very stable complexes can be titrated in

acidic solution, and metals forming weak complexes can only be
effectively titrated in alkaline solution.
COMPLEXOMETRIC TITRATION
INVOLVING EDTA

 The spatial structure of the EDTA which has 6 donor atoms

enables it to satisfy the coordination number of 6 frequently
encountered with the metal ion and forms strain less five
membered rings on chelation .EDTA can form a hexadentate
ligand.
 Effect of pH on complex formation
 Ethylenediamine tetra-acetic acid ionizes in four stages
(pK1=2.0, pK2=2.67, pK3=6.16 and pK4=10.26).

 since the actual complexing species is Y4-, complexes will form more
efficiently and be more stable in alkaline solution.

 On the other hand, at lower pH values when the concentration of Y4- is lower,
the stability constant of the complexes will not be so high.

 Complexes of most divalent metals are stable in ammonia solution.

 Trivalent metal complexes are usually still more firmly bound and stable in
strongly acid solutions.

Example:- cobalt(III) edetate complex is stable in concentrated hydrochloric

acid.
 STABILITY OF COMPLEXES

 The general eqn: for the formation of a 1:1 chelate

complex , MX is

 Where M is the metal ion and X is the chelating ion

 Therefore stability constant K = [MX] / [M] [X]
 Methods of End Point Detection

End point in complexometric titration can be detected by the

following methods:

1. Indicators
2. Spectrophotometric detection
3. Amperometric titration
4. Potentiometric titration
 METAL ION INDICATORS

 The end point in complexometric titrations is shown by means of

pM indicators.

 If K is the stability constant,

K = [MX]/[M][X]
then, [M] = [MX]/[X]K
or log [M] = log [MX]/[X] – log K
and pM = log [X]/[MX] – pK
 The pM indicator is a dye which is capable of acting as a
chelating agent to give dye-metal complex .

 The complex is different in colour from the dye itself and also
has a lower stability constant than the chelate metal complex..

 As soon as there is a slight excess of edetate , the metal dye

complex decomposes to produce free dye , this is
accomplished by a colour change.

 The colour of dye and of the metal complex vary with the pH
therefore it is also essential to buffer the solution to maintain
the required pH during titration.
Mechanism of action of indicator
 Let the metal be denoted by M, indicator by I and chelate by
EDTA.

 At the onset of the titration, the reaction medium contains the

metal-indicator complex (MI) and excess of metal ion.

 When EDTA titrant is added to the system, a competitive

reaction takes place between the free metal ions and EDTA.
Since the metal-indicator complex (MI) is weaker than the
metal-EDTA chelate, the EDTA which is being added during
the course of the titration is chelating the free metal ions in
solution at the expense of the MI complex.
 Finally, at the end point, EDTA removes the last traces of the
metal from the indicator and the indicator changes from its
complexed colour to its metal free colour.
EXAMPLES FOR pM INDICATORS
 Some examples of metal ion indicators

MUREXIDE

 Murexide is a ammonium salt of purpuric acid solution.

pH =9(H4D) reddish- violet
pH 9 to pH 11 (H3D2 -) violet , and above
pH 11(H2D3 -) blue-violet .
 Murexide from complexes with many metal ions .

 Only these with Cu, Ni,Co,Ca,and the lanthanides are

sufficiently stable to find the application in analysis .
 There colours in alkaline solutions are orange (copper),
yellow (nickel and cobalt) & red (calcium).

 Murexide may be employed for direct EDTA titration of

calcium at pH=1 the colour change at the end points is from
red to blue–violet .
Solochrome Black (Eriochrome black T )

 In strongly acidic solutions the dye tends to polymerise to a red-brown product,

and therefore the indicator is rarely applied in the EDT A titration of solutions
more acidic than pH = 6.5.

 The sulphonic acid group gives up its proton long before the pH range of 7-12,
which is of more interest for metal-ion indicator use.

 Only the dissociation of the two hydrogen atoms of the phenolic groups need,
and so the dyestuff may be represented by the formula H2D-. The two pKa values
for these hydrogen atoms are 6.3 and 11.5 respectively.
Below pH = 5.5, the solution of Solochrome Black is red (due to
H2D-).

Between pH 7 and 11 it is blue (due to HD2-).

And above pH = 11.5 it is yellowish-orange (due to D3-).

In the pH range 7-11 the addition of metallic salts produces

colour change from blue to red.

M2+ + HD2- (blue) →MD- (red) + H+

 Xylenol Orange

 This indicator is prepared by the condensation of O-

cresolsulphonephthalein (Cresol Red) with formaldehyde and
iminodiacetic acid.

 Special feature is dyestuff retains the acid-base properties of

Cresol Red and displays metal indicator properties even in
acid solution (pH = 3-5).
 Acidic solutions of the indicator are coloured lemon-yellow
and those of the metal complexes coloured red.

 Direct EDTA titrations of Bi, Th, Zn, Cd, Pb, Co, etc., are
readily carried out and the colour change is sharp.
 Mordant black II

 Indicator is blue in colour at pH 10.

 On complexation with metal ions pink colour is formed.

 Below pH 6.3 and above 11.5 it is reddish in colour hence it is

used at pH 10.

 It is used in the estimation of metal ions like Calcium,

Magnesium, Zinc, Cadmium, Lead and Mercury.

 It can’t be used with oxidizing ions like ferric, cerric or with

reducing ions like stannous and titannous.
 It can’t be used with ions like copper, aluminum, cobalt, silver
as these ions form more stable complexes with indicator than
with chelating agent.
 TYPES OF COMPLEXOMETRIC
TITRATIONS

1. Direct titration

2. Back titration

3. Replacement of one complex by another

4. Alkalimetric titration of metals

1. Direct Titration

 The solution containing the metal ion to be determined is

buffered to the desired pH and few drops of indicator is added.

 The contents are titrated against standardized disodium edetate

solution till the end point shown by the colour change.

 A blank titration is carried out omitting the substance to be

determined, but contains all the other solutions like buffer &
indicator.

 The volume of edetate consumed in blank titration is subtracted

from that obtained in the original estimation.
Examples of such estimation:
 Bismuth - Nitrate, carbonate, oxynitrate, sub nitrate.

 Calcium - Chloride, gluconate, lactate, carbonate.

 Magnesium - Carbonate, oxide, stearate, sulphate, trisilicate.

 Zinc - Sulphate, oxide.
 Assay of magnesium sulphate
Principle:
 Magnesium sulphate forms stable complex with disodium
edetate in presence of strong ammonia-ammonium chloride
buffer.
 It is assayed by direct titration method.
 Mordant black mixture is used as indicator for detection of end
point {red to blue} and standard 0.05 M disodium edetate is
employed as titrant.
Materials required:

 Standard disodium edetate 0.05 M, Magnesium sulphate

sample (0.4 g),
 Ammonia-ammonium chloride buffer (10ml), Mordant black
mixture as indicator.
 Mg2+ + EDTA → Mg EDTA
Mg2+ + [H2X]2- → [Mg X ]2- + 2 H +
. . . Mg SO4 ≡Mg2+≡Na2H2X.2 H2O
. . . 120.38 gm Mg SO4 ≡ 1000 ml M

Assay:
► Weigh accurately about 0.3 g and dissolve in 50 ml of water.

► Add 10 ml of strong ammonia-ammonium chloride solution, and

titrate with O.05M EDTA using 0.1 g of mordant black 11 mixture
as indicator, until the pink colour is discharged from the blue.

Each ml of O.05M disodium ethylenediaminetetraacetate is equivalent

to 0.00602 g of MgS04
 BACK TITRATION

Back titration is necessary in the following cases:

 Metals which are precipitated as hydroxides in the pH used
 For insoluble substances like Lead sulphate, Calcium oxalate
 Those react slowly with disodium acetate
 Those form stable metal chelate complex than with indicator
Method:
 In this method, a known excess of disodium edetate, buffer
solution and few drops of indicator is added.
 The complexation is favored by heating, then cooled and the
excess edetate is back titrated against magnesium sulphate or
zinc sulphate.
Example
Aluminum Hydroxide gel, dried- aluminum hydroxide gel
Calcium phosphate
Assay of ALUMINIUM HYDROXIDE GEL
 Weigh accurately about 5 g and dissolve in 3 ml of HCl by
warming on a water-bath; cool to below 20° and dilute to
100.0 ml with water.

 Pippet 20.0 ml of above solution, add 40 ml of O.05M EDTA

+ 80 ml of water + 0.15 ml of methyl red solution, and
neutralize by the drop wise addition of NaOH.

 Warm on a water-bath for thirty minutes, add 3 g of hexamine,

and titrate with O.05M lead nitrate, using 0.5 ml of Xylenol
orange solution as indicator.

Each ml of 0.05 M EDTA is equivalent to 0.002549 g of Al203

 REPLACEMENT OF ONE COMPLEX
BY ANOTHER
 In this method the metal, which is to be analyzed, displaces
quantitatively the metal from the complex.
 When direct or back titrations do not give sharp end points, the metal
may be determined by the displacement of an equivalent amount of
Mg or Zn from a less stable EDTA complex.

 Mn displaces Mg from Mn EDTA solution.

 The freed Mg metal is then directly titrated with a standard EDTA
solution.

 In this method, excess quantity of Mg EDTA chelate is added to Mn

solution.
 Mn quantitatively displaces Mg from Mg EDTA chelate.

 This displacement takes place because Mn forms a more

stable complex with EDTA.

 By this method Ca, Pb, Hg may be determined using

Eriochrome blackT indicator

Example: Calcium, Cadmium, lead and mercury can be

determined by this method
 Assay of CALCIUM GLUCONATE
TABLETS
Ca++ + Mg-EDTA → Ca-EDTA + Mg++
Mg++ + EDTA → Mg-EDTA

 Transfer an accurately weighed quantity of about 0.5 g of calcium

gluconate to a 250 ml conical flask.

 Add 50 ml water to dissolve it.

 Add 5 ml of magnesium sulphate (0.05 M) and 10 ml of strong

ammonia-ammonium chloride solution.

 Titrate the mixture with disodium edetate solution (0.05M) using

mordant black mixture as indicator to blue colour.
Each ml of 0.05 M disodium edetate ≡ 0.02242 g of calcium
gluconate.
4. Alkalimetry titration of metals

 It is clear from the metal-EDTA complex formation

reaction that protons from disodium edetate are liberated
resulting in formation of acid.

 The liberated acid is titrated with standard alkali. Either

visual pH indicator or Potentiometric method is adopted
for detecting the endpoint.

 That is when a solution of disodium EDTA, Na2H2Y is

added to a solution containing metallic ions; complexes
are formed with the liberation of two equivalent hydrogen
ions.

Mn++ H2Y2-⇌ (MY)(n-4) + 2H+

 REFERENCES

 The text book of Pharmaceutical

Analysis by Kenneth A. Connors.
 The text book of Pharmaceutical
Analysis by P.Parimo.
 The text book of quantitative chemical
analysis by Vogel’s 5th edition .
 Fundamentals of analytical chemistry
7th edition by Skoog.
 Pharmaceutical drug analysis by
Ashutosh kar.