Analytical Chemistry

Second year -Semester IV

2020 - 2021

Almadain College for Medical Sc. & Tech.

Alkhair Adam Khalil, B.Pharm, M. Pharm

 Complexation reactions
• Definition of a complex: it is a reaction
product of electron donating group and a
metal ion.
• The electron donating group is called “ligand”
or “complexing agent”. It may be a neutral
molecule as H2O or NH3, or it may be an anion
like CN-, Cl-, or SCN-.
• The metal cation is called the central atom.
• The central atom is either divalent, trivalent or
tetravalent.
• If the ligand donate one pair of electrons, it is
called mono-dentate ligand.
• If it donate 2 pairs, it is bidentate
• If it donate 3 pairs, it is tridentate.
• Generally a ligand that donate more than 1
pair of electrons, it is called a multi-dentate
ligand.
• When a multi-dentate ligand reacts with metal
ion, the complex produced is chemically stable
and it is cyclic in nature, this complex is called
a “chelate” and the ligand is called “chelating
agent” or “chelon”.
• The overall charge on the complex depends
upon the ligand, it may be +ve, -ve or neutral.
• The complex may contain one or more central
atom. Normally it contains one central atom
(mono-molecular complex). It can be
dimolecular or trimolecular.
 Chemical bond in complex
• Normally it is co-ordinate bond. But
sometimes it may be covalent or mixture of
the two types, e.g. hexacyanoferrate(iii)
(ferric cyanate), contains 3 co-ordinate bonds
and 3 covalent bonds:
• If the ligand is negatively charged, the charge on
the complex is normally negative, and it is equal
to the difference between the number of bonds
around the central atom and the valence of the
central atom itself.
• If the ligand is neutral, the charge of the complex
is +ve, and it is equal to the valence of the
central atom, e.g. [Cu(NH3)4] 2+.
• The maximum number of bonds around the
central atom is called the co-ordination number
and it is governed by the valence of the central
atom, and most important by the steric
hindrance.
 Complex formation
• Complexation reactions 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
 Metal Ligand Metal-Ligand Complex

• Complex formation reactions are reversible. So

there have formation constant (Kf)
Formation Constant (Kf)
The equilibrium constant for the reaction
between a metal ion (M+n) and a chelating agent
(L-P) is known as a formation constant or
[stability constant].
Ma   Y b  M bYa

[M bYa]
Kf  a
[M ] [Yb ]
 Formation Constants for EDTA Complexes
Cation KMY Cation KMY
+
Ag x 107 2.1 +
Cu2 x 1018 6.3
+
Mg2 x 108 4.9 +
Zn2 x 1016 3.2
+
Ca2 x1010 5.0 +
Cd2 x 1016 2.9
+
Sr2 x 108 4.3 +
Hg2 x 1021 6.3
+
Ba2 x 107 5.8 +
Pb2 x 1018 1.1
+
Mn2 x1013 6.2 +
Al3 x 1016 1.3
+
Fe2 x1014 2.1 +
Fe3 x 1025 1.3
+
Co2 x1016 2.0 V
+ 3
x 1025 7.9
+
Ni2 x1018 4.2 +
Th4 x 1023 1.6

10
Haemoglobin
Vitamin B12
(Cyanocobalamin)
 Complexometric Titrations
• One of the most common chelating
agents used for Complexometric
titrations in analytical chemistry is a
multi-dentate ligand “EDTA”
(Ethylenediaminetetraacetic acid)
 EDTA Titrations
Properties of EDTA
1. EDTA has 6 hydrogen atoms. 2 atoms from
ammine groups & 4 atoms from carboxylic
groups. So in its structure it gives 6 free
electron pairs that it can donate to metal ions.
- High Kf values
- 6 acid-base sites in its structure
2. EDTA is an example of a multi-dentate
(many-toothed) ligand, which can bind
metal ions through multiple atoms.

EDTA chelating a metal ion

3. EDTA is an amphoteric substance.
4. It can both donate and accept protons.
5. The four hydrogen atoms shown in the
above line structure are acidic.
6. Because of this, the formula of EDTA is
often abbreviated H4Y, where H4 represents
the four acidic hydrogen atoms and Y
represents the remaining structure.
7. At very low pH, EDTA will be present in its
completely protonated form H6Y2+.

8. At very high pH, EDTA will be present in its

completely deprotonated form, Y4-.
• The suitable species for complex formation
with a metal ion is the ionized form, in alkaline
medium, but not highly alkaline (pH < 10)
because this may precipitate the central atom
itself.
• To keep EDTA highly ionized we use ammonia -
ammonium chloride buffer keeping the pH 9
to 10.
• Reaction of EDTA is always 1:1 with one
central atom.
Effect of pH on stability of EDTA complexes

• Divalent cations form stable complex with

EDTA in “Ammonical solution (pH = 10).
• Alkaline earth metals [Ca2+, Mg2+] complexes
with EDTA decomposes bellow pH = 7.
• Firmly bound divalent cations [Ni2+, Cu2+]
make a stable complexes with EDTA in slightly
acidic solution (pH = 6.0 to 6.5).
• Trivalent cations [Co3+, Al3+] form a stable
complexes in highly acidic pH. (dilute HCl - pH=
2 – 3)
• Tetravalent cations [Th4+] form stable
complexes in concentrated HCl (pH = 0 – 1)
• The standard solution used for titration is the
disodium salt of EDTA.
• Because it is more soluble.
• Na2[H2Y2- ].2H2O

• M2+ + H2Y2- [MY]2- + 2H+

• M3+ + H2Y2- [MY]1- + 2H+
• M4+ + H2Y2- [MY] + 2H+