Complexometric Reactions and Titration
Complexometric Reactions and Titration
Complexometric Reactions and Titration
Many metal ions form slightly dissociated complexes with various ligands (complexing
agents).
Complexes used to mask undesired reactions.
Its formation can serve as the basis of accurate and convenient titrations for metal
ions.
Complexometric titrations are useful for the determination of a large number of
metals.
Most complexing agents are weak acids or weak bases whose equilibria
influenced by the pH.
Nomenclature
Ligand
Neutral or anionic species with unpaired electrons that can bond to a metal ion. Common
ligands are CN-, NH3, OH-, and halides.
Complex
An association of a central metal ion and surrounding ligands in solution - also called
coordination complex.
Coordination number
The number of bonds with the central metal ion, usually 2, 4, or 6.
Chelate
A specific type of complex in which at least one ligand contains more than one atom with
unpaired electrons so it can make multiple bonds with the central metal ion. Ligands that
make two bonds are called bidendate, ligand that make three bonds are tridendate, and so
on.
donor).
When a complex is formed, the solvating molecules (H 2O) are replaced one by one by the
new ligands (in the above example: NH3). The complex formation takes place step by
step where every step corresponds to the substitution of one H2O by NH3 .
Example:
K1, K2, K3 and K4 are the stepwise stability constants. These equilibrium constants are
described by a general expression
Chelates:
A Chelating agent (the Ligand) is an organic agent that has tow or more groups which are
capable of complexing with a metal ion. The complex formed is called a Chelate. The
titration with a chelating agent is called a Chelometric titration a type of Complexometric
titration.
The most generally useful titrating agent is amino carboxylic acids, in which nitrogen and
carboxylate groups serve as ligands. The amino nitrogens are more basic and are
protonated (NH3+) more strongly than carboxylate groups. When these groups bind o
the metal atoms, they will lose their protons. The metal complexes formed with these
multidentate complexing agents are often 1:1 regardless of the charge on the metal ions,
because there are sufficient complexing groups on one molecule to satisfy the
coordination sites of the metal ions.
The most widely used chelating agent in titration is Ethylene Diamine Tetra Acetic acid –
EDTA.
HY3- + H2O Y 4-
+ H3O +
Ethylenediaminetetraacetic acid (EDTA)
A pair of unshared electrons capable of complexing with a metal ion is contained on each
of two nitrogens and each of the four COOH groups. Thus, there are six complexing
groups in EDTA. EDTA can be represented by the symbol H4Y since it is a tetraprotic
acid and the H in H4Y refer to the four ionisable hydrogen.
EDTA equilibria:
We can represent EDTA as having four Ka values corresponding to the stepwise
dissociation of the four protons:
Formation constant:
Consider the formation of the EDTA chelate of Ca+2. This can be represented by
Ca+2 + y-4 ↔ CaY2
The effect of pH on EDTA equilibria:
The equilibrium is shifted to the hydrogen ion concentration is increased due to
competition for the chelating anion by the hydrogen ions.
OH OH
-
O3S N N
O 2N
pK1=6.3
pK1=11.6
The metal indicator complex should be 10-100 times less stable than the metal-titrant
complex so metal titrant will displace the indicator from the metal giving good and sharp
end point.
EBT can not be used to indicate the direct titration of Ca 2+ alone with EDTA, however,
because the indicator forms too weak complex with Ca2+ to give a sharp end point.
The Ca2+ titrates first since its EDTA chelate is more stable. When Mg-EDTA is added to
the sample, the Ca2+ in the sample displaces the EDAT from Mg2+ so that the Mg2+ is free
to react with the indicator. At the end point, an equivalent amount of EDTA displaces the
indicator from Mg+2 (Ca2+ Titer) causing the color change, and no correction is required
for the added Mg-EDTA.
EDTA