COMPLEXOMETRIC

TITRATION

Dr Mohammad Kaisarul Islam

Department of Pharmaceutical Chemistry, DU

1 Complexometric Titration_Dr Mohammad Kaisarul Islam

  Complexometric titration is a form of volumetric analysis in which the
formation of a coloured complex is used to indicate the end point of a
titration. Complexometric titrations are particularly useful for the
determination of a mixture of different metal ions in a solution.
 A titration based on the formation of a coordination complex is known
as a complexometric titration.
 Complex formation titrations are used to titrate cations via complex
formation reagents.

Conditions for Titration:

1. Reaction Proceed rapidly
2. Well-defined stoichiometry
3. Large equilibrium Constant

2 Complexometric Titration_Dr Mohammad Kaisarul Islam

 The earliest examples of metal–ligand complexation titrations are Liebig’s
determinations, in the 1850s, of cyanide and chloride using, respectively,
Ag+ and Hg2+ as the titrant. Practical analytical applications of complexation
titrimetry were slow to develop because many metals and ligands form a
series of metal–ligand complexes. Liebig’s titration of CN– with Ag+ was
successful because they form a single, stable complex of Ag(CN)2–, giving a
single, easily identified end point. Other metal–ligand complexes, such as
CdI42–, are not analytically useful because they form a series of metal–

ligand complexes (CdI+, CdI2(aq), CdI3– and CdI42–) that produce a

sequence of poorly defined end points.

3 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Metal ligand Complexes
 Complexation Titrations are based on the reaction of a metal ion with a
chemical agent to form a metal-ligand complex.
 Complexation Titrations are essentially Lewis acid-base reactions, in which
an electron pair is donated from one chemical to another.
 The ligands used in complexometric titrations are also known as chelating
agents.
- Ligand that attaches to a metal ion through more than one ligand atom
 Most chelating agents contain N or O; elements that contain free electron
pairs that may be donated to a metal

4 Complexometric Titration_Dr Mohammad Kaisarul Islam

 The tendency of complex formation is controlled by the formation
constant (kf) of the reaction between the metal ion (Lewis acid) and the

ligand (Lewis base). As the formation constant (kf) increases, the

stability of the complex increases.

5 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Types of complexing agents (Classification of ligands according to the
no. of sites of attachment to the metal ion)

 Unidentate (Monodentate) or Simple Ligand: The ligand attached to

metal at one site e.g., H2O, NH3, CN–, Cl– , I–, Br –, (i.e., forming one
coordinate bond, or capable of donating one unshared pair of electrons)

NH3
2+

H3N Ag NH3 Cu2+ + 4NH3 H3N Cu NH3

NH3
• Bidentate Ligand: The ligand attached to metal at two sites.

NH2 NH2 H2N

H2C H2C CH2
2+
Cu + 2 Cu
H2C H2C CH2
NH2 NH2 H2N

6 Complexometric Titration_Dr Mohammad Kaisarul Islam

 • Tridentate Ligand: The Ligand attached to metal at 3 sites
• Tetradentate Ligand: The Ligand attached to metal at 4 sites
NH2

H2C CH2
H2 H H2 H2
C N C C NH2
H 2C NH
H2N C C N C
H2 H2 H H2

H2N CH2

Diethylene triamine Triethylene tetramine

Tetradentate or Hexadentate ligands are more

satisfactory as titrants than ligands with a lesser
number of donor groups because their reactions
with cations are more completely and because
they tend to form 1:1 complexes.

7 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Chelation

Chelate : It is a complex formed between the ligand containing two or

more donor groups and metal to form ring structure. (heterocyclic rings
or chelate rings).
Chelating agents: organic molecules containing two or more donor
groups which combine with metal to form complex having ring structure.
Chelates are usually insoluble in water but soluble in organic solvent.
Sequestering agent : Ligands which form water soluble chelates e.g.,
EDTA.

8 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Factors affecting stability of complex

Effect of central metal ion:

 Ionic size (metal radius):

Smaller an ion  greater its electrical field  more stable complex

 Ionic charge (metal charge): Metal of higher charge give more stable
complexes; e.g., Ferricyanide [hexacyanoferrate III] is more stable than
Ferrocyanide [hexocyanoferrate II].

 Electronegativity: The higher acidity (electronegativity) of metal (Mn+)

 the higher stability of complex.

 Metal which has incomplete outer shell (has high acidity) have more
tendency to accept electrons  more stable complex. e.g., Ca2+, Ni2+,
Zn2+, Mn2+, Cu2+

9 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Effect of Ligand:

 Basic character: The higher the basicity (strong base is good electron
donor)  the higher the ability of ligand to form complex. e.g. ligand
contain electron donating atom; e.g. N > O > S > I- > Br- > Cl- > F-

 The extent of chelation: Multidentate ligands form more stable

complexes than monodentate.

 Steric effect: Large, bulky ligand form less stable complexes than
smaller ones due to steric effect. e.g. ethylene diamine complexes are
more stable than those of the corresponding tetramethyl ethylene
diamine.
CH3
H2 H2
H2N C N C CH3
C NH2 H3C C N
H2 H2
CH3
10 Complexometric Titration_Dr Mohammad Kaisarul Islam
 Properties of EDTA (Ethylenediaminetetraacetic acid)
EDTA is one of the most common chelating agents used for complexometric titrations
in analytical chemistry.
 EDTA has 6 hydrogen atoms (2 atoms from amine group & 4 atoms from
carboxylic group). So in its structure it gives 6 free electron pairs that it can
donate to metal ions. Thus,
- High Kf values - 6 acid-base sites in its structure

 EDTA is an example of a multidentate (many-toothed)

ligand, which can bind metal ions through multiple
atoms.

11 Complexometric Titration_Dr Mohammad Kaisarul Islam

  EDTA is an amphoteric substance.
 It can both donate and accept protons.
 The four hydrogen atoms shown in the above line structure are acidic. Because
of this, the formula of EDTA is often abbreviated H 4Y, where H4 represents the
four acidic hydrogen atoms and Y represents the remaining structure.
 At very low pH, EDTA will be present in its completely protonated form H 6Y2+.
 At very high pH, EDTA will be present in its completely deprotonated form, Y 4-.
O O O

O OH O OH O O
+ +
NH H OH NH OH N OH
HO N HO N HO N
HO O HO O HO O

O O O
EDTA in 1* form (Abbreviated -
EDTA in 2* form (Abbreviated EDTA in 1 form (Abbreviated
H6Y+2; predominant at pH <0) H5Y2; predominant at pH = 0.75) H3Y-; predominant at pH = 2.33)

O O O

O O O O O O
N OH N OH N O
O N O N O N
HO O O O O O

O O O
EDTA in 2 form (Abbreviated H2Y-2;
-
EDTA in 3- form (Abbreviated EDTA in 4- form (Abbreviated
predominant at pH = 4.41) HY-3; predominant at pH = 8.2) Y-4; predominant at pH >12)

12 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Types of EDTA titrations

1. Direct Titration: Simply add an indicator to the solution of the metal ion and
titrate with EDTA. Before starting the titration, it is needed to check the pH of
the solution.
2. Indirect titration: EDTA can be used as titrant for anions. Anions can be
precipitated with suitable metal ion. Filter and wash the ppt with proper
solution. Then boil in excess EDTA to complex the metal ion (ppt).
3. Back Titration: An excess of EDTA is added to the metal ion solution, and
the excess EDTA is titrated with a known concentration of a second metal
ion. The second metal ion must form a weaker complex with EDTA than the
analyte ion.
4. Displacement titration: The analyte is treated with an excess of a second
metal bound to EDTA. The analyte ion displaces the second metal from the
EDTA complex, and then the second metal is titrated with EDTA.

13 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Metal–EDTA Formation Constants
To illustrate the formation of a metal–EDTA complex, let’s consider the
reaction between Cd2+ and EDTA:
where Y4– is a shorthand notation for
Cd 2+
(aq) +Y 4−
(aq) ⇌ CdY 2−
(aq) the fully deprotonated form of EDTA.

Because the reaction’s formation constant,

is large, its equilibrium position lies far to the right.

14 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Formation or dissociation of complexes is affected by pH.

1. In acidic medium: i.e.  [H+]   ionization of

EDTA   stability of metal – EDTA complex 
shift the reaction backward.
2. In slightly alkaline solution  the reaction is
forward   stability of complexes (chelates).
3. In strong alkali  pptn. of metal as hydroxide.

15 Complexometric Titration_Dr Mohammad Kaisarul Islam

 EDTA Titration

Titratlon of mixtures, selectivity, masking and demasking agents

 EDTA is a very unselective reagent because it complexes with numerous doubly,
triply and quadruply charged cations.
 When a solution containing two cations which complex with EDTA is titrated
without the addition of a complex-forming indicator, and if a titration error of 0.1%
is permissible, then the ratio of the stability constants of the EDTA complexes of
the two metals M and N must be such that KM/KN > 106 (if N is not to interfere with
the titration of M).
 Strictly, of course, the constants K M and KN considered in the above expression
should be the apparent stability constants of the complexes.

The following procedures will help to increase the selectivity :

(a) Suitable control of the pH of the solution
(b) Use of masking and demasking agents

16 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Masking may be defined as the process in which a substance, without physical
separation of it or its reaction products, is so transformed that it does not enter
into a particular reaction.
Demasking is the process in which the masked substance regains its ability to
enter into a particular reaction. By the use of masking agents, some of the
cations in a mixture can often be 'masked' so that they can no longer react with
EDTA or with the indicator.
An effective masking agent is the cyanide ion; this forms stable cyanide
complexes with the cations of Cd, Zn, Hg(II), Cu, Co, Ni, Ag, and the platinum
metals, but not with the alkaline earths, manganese, and lead.
It is therefore possible to determine cations such as Ca2+, Mg2+, Pb2+, and Mn2+
in the presence of the above-mentioned metals by masking with an excess of
potassium or sodium cyanide.
The cyanide complexes of zinc and cadmium may be demasked with
formaldehyde/acetic acid solution or chloral hydrate. The use of masking and
selective demasking agents permits the successive titration of many metals.
17 Complexometric Titration_Dr Mohammad Kaisarul Islam
 Detection of End Point

 Metal indicator (Metallochromic Indicator)

 Acid-base Indicator
 Turbidity end point (appearance of turbidity)
 Instrumental method

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 Colorimetric indicators (metallochromic indicators)
CH3

N
OH N
N
OH
OH N
OH

O2N
O 2N
SO3H
SO3H

Eriochrome Black T Calgamite

OH CH3 CH3

OH O OH
AsO3H2
SO3 HO2C CO2H
N N
N N HO2C CO2H

SO3

SO3

Arsenazo I
Xylenol Orange

19 Complexometric Titration_Dr Mohammad Kaisarul Islam

 Metal Indicators (Metallochromic Ind)

 They are organic dyes which form colored chelates (complexes),

which exhibit a color in the free form and a different color in the
complex form.
Mn+ + Ind.  M – Ind.
M – Ind. + EDTA  M – EDTA + free Ind.
 Act as ligand to form complex with metal (act as Na+ -
O
O O S O
Lewis base and the metal acts as Lewis acid).
- N+
O
 The reaction between metal and indicator must be
OH
reversible. N
N
 The metal-ind. complex should be less stable than C OH

the metal-EDTA complex.

Eriochrome Black T
 Changes its color according to the pH of the
medium.
20 Complexometric Titration_Dr Mohammad Kaisarul Islam