Introduction:

What is meant by complexometry?

It is a form of volumetric analysis in which the formation of a colored complex is used for
indication of end point in titration. Complexometric titrations are particularly useful for the
determination of a mixture of different metal ions in solution. An indicator is capable of
producing definite color change which is used to detect the end point of the titration. A complex
is a molecule or ion formed by the reaction of two or more ions or molecules capable of
independent existence. The most important complexation reactions from an analytical point of
view are those between a metal ion in solution and a complexing agent. A metal atom can
usually form a bond with one or more donor atoms which have at least one unshared pair of
electrons. The number of donor atoms which bond with a given atom depends on the number of
electron pairs that the metal ion can accept, in other words, the coordination number of the metal
ion. Complexing agents can provide more than one pair of electrons called as multi-dentate
ligands which are also called chelating agents. Complexometric titrations are particularly useful
for determination of a mixture of different metal ions in solution. An indicator with a marked
color change is usually used to detect the end-point of the titration. Complexometric titration is a
solution containing the free metal ion of interest is titrated with a solution of chelating agent until
all of the metal ions are completely complexed. The endpoint is usually measured with an
indicator ligand that forms a colored complex with the free metal ion.

Figure 1.1: graphical representation of volume of EDTA used in a titration

EDTA and its properties:

An essential agent in coordination chemistry which are chelating is ethylene-di-amine-tetra-

acetic acid. The basic form of this acid of the given complexes with particulate all metal ions.

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EDTA considered as hexa-dentate with the complexes are membered rings of four to five
molecules and their stability was significantly contributed. We faced difficulty in using it as a
primary standard. For obtaining the precise composition of the di-hydrate ion it is available in
pure form, and had dried at 80°C. While EDTA standardization is titrated against a solution of
the metal ion which is used to be determined with the help to eliminate the errors in end-point by
realizing that the electron pairs of the carboxylic acid groups of EDTA by which an acid is
dissociated are only available for metal ion only. Hence complex of many metal ions was formed
with hydroxide ion which was competed with the agent by sites of metal atom which is the
complexes was also reduced at higher pH. An optimum pH will be effected by chelating agent
and metal ion for the titration by depending upon the pKa values for agent and the metal-
hydroxide complexes are constant in formation.

EDTA, ethylene-edi-amine-tetra-acetic acid consist two groups which is of amines and four
group of carboxyl was considered as electron pair which are donor. Hence EDTA is partially
ionized only and thus formed six coordinate covalent bonds with metal.

For the aqueous solutions of transition metal of disodium ion was used in it commonly. In
disodium EDTA coordinate covalent bonds to metal cat-ion was formed at pH values lesser than
12. The protonation of amine groups was remained in this pH range and thus for coordinate
covalent bonds it is not possible to donate electrons pair to the metal atom by designing the
number of positive ions was bonded to the EDTA molecule is essentially considered.

EDTA is complex molecule, which are octahedral in structure and has positive two charges on it
in aqueous solution. The formation of metal atoms of EDTA complexes at high efficiency with
the equilibrium constant proportion was in solution

M2+ + A4B → MA2B + 2H+

Process has carry out in a solution basic which removes hydronium ion known as buffer solution,
and favors EDTA metal cation complex reaction product particularly.

The equilibrium involved in EDTA titration:

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 1. The stability of complex formed would be greater the stability if constant for all
complexes had larger the charge in concentration of free metal at given point and the
end point would be more précised.
2. It contains following steps by the identification of complexes and greater would be
the complex in the curve of titration at point which is given for the end point
clarification.
3. In a complexometric titration by using buffer solution that must have constant pH.
For the hydronium ion pH plays an important role in chelation. Basic ligands had
bind to ions of hydrogen with high amount pH. These ions had able to displace by
ligands during the formation of chelates with metal atom.

Figure 1.2: structure representation of complex structures

Eneiochrome Black-T

It is used as indicator in a sample solution and metal ligands bound with Erio-chrome Black T
molecule by disappearance of hydronium ions from phenol ion and bonding between metal ion
as well as oxygen molecule and also with the di-imide group. This indicator is used to form red
wine stable complex in solution of samples with some cations such as calcium, nickel,
magnesium, zinc etc. Most of the titration of EDTA occured in solution of buffers with the pH
equals to eight to ten in a range where it is prevail form of EBT.

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 Figure 1.2: EBT in a solution of buffer is commonly blue in color

Blunt Titration

By the method complex metal atom till the end point had indicated and the process was normally
related with the titrations which are acid-base. For example injection of sod. lactate and calcium
gluconate for testing of CaCl2 and tablets of calcium lactate.

Back Titration

By this process EDTA was added to the metal solution in an sufficient amount by analyzing it
and it was titrated back with solution with an example for determining the Mn+2 as well as Zn +2
ions in a solution.

With EDTA the given metal atom wouldn’t be initiated by maganese hydroxide precipitation and
to solution which is considered to be acidic. Magnese and ammonia is used to adjust the pH of
buffer equals to ten and after chelation excess EDTA remained and back titration is carried out
with zinc metal solution which was added in burette and u Erio-chrome complex as an indicator
was used in the given sample. This scheme was convenient to back titration in acidic analysis for
example zinc oxide. .

Application of Complexometry:

For the determining of hardness in water this method was used by mineral ion accumulation with
increase in pH of water. By adding the reduce amount of EDTA in a solution of hard water Kf
reduce during the titration.

By changing the pH and reduced in the concentration of metal ions softening of hard water can
occurred.

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In industries hard water can cause serious problems settings and hence settling is a place where
water hardness can be tested and also used to prevent spoilage of food by metal atoms.

Minerals that cause hard water have a wide impact on households. Hard water interferes with
almost every cleaning task from laundering and dishwashing to bathing and personal grooming.
Clothes laundered in hard water may look dingy and feel harsh and scratchy. Dishes and glasses
washed in hard water may become spotted as they dry. Hard water may cause a film on glass
shower doors, shower walls, and bath-tubs.

Calcium occur H2O naturally. It is available as calcium solution in it but it may also occur as
calcium hydroxide in aqueous solution or as calcium sulphide in seawater. Calcium is an
important determinant of water harness, and it also functions as a pH stabilizer, because of its
buffering qualities. Calcium also gives water a better taste.

. Calcium is also present in muscle tissue and in the blood. It is required for cell membrane
development and cell division, and it is partially responsible for muscle contractions and blood
clotting. Calcium regulates membrane activity, it assists nerve impulse transfer and hormone
release, stabilizes the pH of the body, and is an essential part of conception. In order to stimulate
these body functions a daily intake of about 1000 mg of calcium is recommended for adults. This
may be achieved by consuming dairy, grains and green vegetables.

Calcium carbonate has a positive effect on lead water pipes, because it forms a protective lead
(II) carbonate coating. This prevents lead from dissolving in drinking water, and thereby
prevents it from entering the human body

Figure 1.4: classification of hard water

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Conclusion:

Complexomertic titration is useful for the formation of complex metal ions in a solution and its
solution is comparatively different for the other solution which was titrated normally because
complex titration is a formation of ligand and more effective compounds was used in it such as
EDTA and EBT. As EDTA is also called as amino poly-carboxyic acid and used as chemical
analysis, in water softening of boilers and as cleaning agent in removing of hard water in large
scales.

. Figure 1.5: shows the indication of complexomtric titration start and end point