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COMPLEXOMETRIC TITRATIONS

Objectives
1. Understanding complexometric titrations (titrations method to determine metal). 2. Acknowledging EDTA.

Introduction
Many metal ions form slightly dissociated complexes with various ligands (complexing agents). The formation of complexes can also serve as the basis of accurate and convenient titrations for metal ions in which the titrant is a complexing agent. Complexometric titrations are useful for determining a large number of metals. Very useful complexing agent in titrations with metal EDTA.

Complexes
Complexes play an important role in many chemical and biochemical processes. E.g.: heme molecule in blood (nitrogen) form strong ligand or complexing bonds with iron atom. Iron in turn bonds readily with oxygen. Many cations will form complexes in solution with a variety of substances that have a pair of unshared electrons (N,O,S atoms in the molecule) capable of satisfying the coordination number of the metal.

The metal ion is a Lewis acid. The complexer is a Lewis base. The number of molecules of the complexing agent (ligand) will depend on the coordination number of the metal and on the number of complexing groups on the ligand molecule. E.g.: 4 ammonia molecule will complex one Cu2+ ion.

Chelates
Complexing agents such as ammonia are rarely used as titrating agents (a sharp end point is difficult to achieve). Certain complexing agents that have two or more complexing groups on the molecule form well-defined complexes and can be used as titrating agents. The most generally useful titrating agents are aminocarboxylic acids (nitrogen and carboxylate groups serve as ligands).

Chelating agent: an organic agent that has two or more groups capable of complexing with a metal ion. Chelate: the complex formed. Chelating agent ligand. Titration with a chelating agent is called a chelometric titration (a type of complexometric titration).

EDTA
The most widely used chelating agent in titrations: ethylenediaminetetraacetic acid (EDTA). Each of the two N and each of the four carboxyl groups contains a pair of unshared electrons capable of complexing with a metal ion. Thus, EDTA is a hexadentate ligand.

Metal-EDTA Titrations
A titration is performed by adding the chelating agent to the sample. The more stable the chelate, the lower the pH at which the titration can be performed. Important: allows the titration of some metals in the presence of others whose EDTA chelates are too weak to titrate at the lower pH.

pH < 4 (highly acidic) (group 1) 47 (group 2) >7 (group 3)

Metals Fe3+ , In3+ , Th4+ , Sc3+ , Hg2+ , Ga3+ , Lu3+ VO2+ , Ni2+ , Cu2+ , Y3+ , Pb2+ , Sm3+ , Zn2+ , Cd2+ , Al3+ , Co2+ , La3+ , Fe2+ , Mn2+ Ca2+ , Sr2+ , Mg2+

At the intermediate pH range, the third group will not titrate. However, the second group of metals can be titrated in the presence of the third group. In the most acidic pH range, only the first group will titrate and can be determined in the presence of others.

Indicators
Indicators are themselves chelating agents. Usually dyes of the o,o-dihydroxy azo type. Eriochrome Black T is a typical indicator. Metal-indicator complex must be less stable than the metal-EDTA complex (or else the EDTA will not displace it from the metal). Must not be too weak (or the EDTA will start replacing it at the beginning of the titration). In general: the metal-indicator complex should be 10 to 100 times less stable than the metal-titrant complex.

E.g.: titration of Mg2+ with EDTA, indicator Eriochrome Black T. - a small amount of indicator is added to the sample solution, and it forms a red complex with part of the Mg2+ . - the colour of the uncomplexed indicator is blue. - as soon as all the Mg2+ is titrated, the EDTA displaces the indicator from the magnesium, causing a change in the colour from red to blue.

Application
The most important complexometric titration in the clinical laboratory is regarding the determination of calcium in blood. Chelating agents such as EDTA are used in the treatment of heavy metal poisoning, e.g. when children ingest chipped paint that contains lead.

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