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COMPLEXOMETRIC TITRATION

K. G. Baheti
Y. B. Chavan College of Pharmacy
Complexation Titrations are based on the reaction of a metal ion with a
chemical agent to form a metal-ligand complex.

Metal Ligand Metal-Ligand Complex

Complexometric titration is a type of titration based on complex formation between


the analyte and titrant.

Metal – Lewis Acid or Electron-pair acceptor


Ligand – Lewis Base or Electron-pair donor

 Most chelating agents contain N or O


- Elements that contain free electron pairs that may be donated to a metal
A. Direct titration.
B. Back-titration

Back titration is performed in following conditions


1. Many metal may recipitate from the solution in the pH range necessary for the
titration,
2. Metal may form inert complexes
3. suitable metal indicator is not available.
4. Solubility of metals in the given solvent.

Condition for titration:


1. Excess of standard EDTA solution is added and the excess of the EDTA is back-
titrated with a standard metal ion solution.
2. The titration solution is buffered to the desired pH.
3. Metal ion used for back titration are zinc chloride or sulphate or of magnesium
chloride or sulphate
4. Metal indicator responds to the zinc or magnesium ions introduced in the back-
titration.
C. Replacement or substitution titration.

1. Substitution titrations may be used for metal ions that do not react (or react
unsatisfactorily) with a metal indicator
2. Metal ions which form EDTA complexes that are more stable than those of other
metals such as magnesium and Calcium.
The metal cation Mn+ to be determined may be treated with the magnesium complex
of EDTA, when the following reaction occurs :

The amount of magnesium ion set free is equivalent to the cation present and can be
titrated with a standard solution of EDTA and a suitable metal indicator.

Example : Determination of calcium. In the direct titration of calcium ions, solochrome


black gives a poor end point; if magnesium is present, it is displaced from its EDTA
complex by calcium and an improved end point results.
Stability of complexes is
Magnesium –indicator complex is more stable than Ca-indicator but less stable than
Mag –EDTA complex
Calcium _EDTA > Magnesium -EDTA> Magnesium –Indicator
E.g. Calcium lead and mercury
D. Alkalimetric titration.
When a solution of disodium EDTA, Na2H2Y, is added to a solution containing metallic
ions, complexes are formed with the liberation of two equivalents of hydrogen ion:

The hydrogen ions thus set free can be titrated with a standard solution of sodium
hydroxide using an acid-base indicator or a potentiometric end point.

The solution of the metal to be determined must be accurately neutralized before


titration; this is often a difficult matter on account of the hydrolysis of many salts, and
constitutes a weak feature of alkalimetric titration.
Problems
1. Do ligands act like Lewis acids or Lewis bases? Why?
2. Do ligands form ionic bonds with the central metal atom?
3. What are chelating agents?
4. What is a monodentate ligand?
5. Describe polydentate ligands and provide an example.
6. What are hexadentate ligands?
7. Name this complex [Cu(NH3)4]SO4.
8. Name this complex [Co(en)3](NO3)2.(en = ethylene diamine)
Answers
Ligands act like Lewis bases because they share their electron pairs (electron
donors) with the central metal atom.
No, ligands do not form ionic bonds the with the central metal atom. Rather, they
form covalent bonds with the central metal atom because they share electron pairs.
Chelating agents are ligands that have two or more atoms with donating electron
pairs that are able to attach a metal ion at the same time. These chelating ligands are
monodentate and tridentate ligands
A monodentate ligand is a ligand that uses only one pair of electrons to bond to the
central metal atom or ion.
Polydentate ligands are ligands which are able to donate more than two electron
pairs to the central metal they bond to. EDTA is an example of a polydentate ligand.
Hexadentate ligands are ligands which have six lone pairs of electrons which can all
bond to the central metal atom.
tetraamminecopper(II) sulfate
Tris(ethylenediamine)cobalt(II) nitrate
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 with EDTA
Preparation and Standardization of 0.1 M Disodium Edetate (EDTA)

Preparation: · Take about 100 ml of water in a cleaned and dried 1000 ml volumetric flask. ·
Add about 37. 2 gm of Disodium edetate with continues stirring. · Add more about 700 ml
of water mix. · Make up the volume 1000 ml with water. Mix solution thoroughly.

EDTA can be standardized against many reagents, be it metallic magnesium, calcium


carbonate, metallic bismuth and so on. For best results it is good to standardize EDTA
solution against the same cation and using the same method as will be later used during
sample analysis. Note, that EDTA solution can be prepared without a need for
standardization, as EDTA itself can be obtained in form pure enough.
Reaction taking place during titration is
Mg2+ + EDTA4- → MgEDTA2-
Titration is done in pH 10 solution.
Procedure: Weight exactly about 0.24g of metallic Mg ribbon. Dissolve metal in 25 mL of 1M
HCl solution and dilute in volumetric flask to exactly 1L. Transfer 25 mL of magnesium
solution to Erlenmeyer flask. Add 75 mL of distilled water.
Add 2 mL of pH 10 ammonia buffer solution.
Add a pinch of Eriochrome Black T ground with sodium chloride (100 mg of indicator plus 20
g of analytical grade NaCl).
Titrate with EDTA solution till the color changes to blue.
Standardization can also be done with calcium carbonate and zinc metal
Complexometric titration with EDTA

Ethylenediamminetetraacetic acid, has four carboxyl groups and two amine groups that
can act as electron pair donors, or Lewis bases. The ability of EDTA to potentially donate
its six lone pairs of electrons for the formation of coordinate covalent bonds to metal
cations makes EDTA a hexadentate ligand. However, in practice EDTA is usually only
partially ionized, and thus forms fewer than six coordinate covalent bonds with metal
cations. Disodium EDTA, commonly used in the standardization of aqueous solutions of
transition metal cations, only forms four coordinate covalent bonds to metal cations at pH
values less than or equal to 12 as in this range of pH values the amine groups remain
protonated and thus unable to donate electrons to the formation of coordinate covalent
bonds.
In analytical chemistry the shorthand "Na2H2Y" is typically used to designate disodium
EDTA. This shorthand can be used to designate any species of EDTA. The "Y" stands for
the EDTA molecule, and the "Hn" designates the number of acidic protons bonded to the
EDTA molecule. EDTA forms an octahedral complex with most 2+ metal cations, M2+, in
aqueous solution. The main reason that EDTA is used so extensively in the standardization
of metal cation solutions is that the formation constant for most metal cation- EDTA
complexes is very high, meaning that the equilibrium for the reaction :

M2+ + H4Y → MH2Y + 2H+

Carrying out the reaction in a basic buffer solution removes H+ as it is formed, which also
drives the reaction to the right. For most purposes it can be considered that the formation
of the metal cation-EDTA complex goes to completion, and this is chiefly why EDTA is used
in titrations / standardizations of this type.
Indicator

To carry out metal cation titrations using EDTA it is almost always necessary to use a
complexometric indicator, usually an organic dye such as Fast Sulphon Black,
Eriochrome Black T, Eriochrome Red B or Murexide, to determine when the end point
has been reached. These dyes bind to the metal cations in solution to form colored
complexes. However, since EDTA binds to metal cations much more strongly than does
the dye used as an indicator the EDTA will displace the dye from the metal cations as it
is added to the solution of analyte. A color change in the solution being titrated
indicates that all of the dye has been displaced from the metal cations in solution, and
that the endpoint has been reached.
Applications of Complexometric titration
Zinc in water/ food /soil/ointment can be determined by complexometric
titration

The important electrolyte like calcium can be determined by complexometric


titration in powder form/ solution form/ in pharmaceuticals preparation.

Useful for the determination divalent, trivalent and tetravalent ions

The metals ions in the mixture for can be determined by complexometric


titration.
What Is A Coordination Compound?

A coordination complex is the product of a Lewis acid-base reaction in which neutral


molecules or anions (called ligands) bond to a central metal atom (or ion) by coordinate
covalent bonds.

Ligands are Lewis bases - they contain at least one pair of electrons to donate to a metal
atom/ion. Ligands are also called complexing agents.

Metal atoms/ions are Lewis acids - they can accept pairs of electrons from Lewis bases.
Within a ligand, the atom that is directly bonded to the metal atom/ion is called the
donor atom.

A coordinate covalent bond is a covalent bond in which one atom (i.e., the donor atom)
supplies both electrons. This type of bonding is different from a normal covalent bond in
which each atom supplies one electron.

If the coordination complex carries a net charge, the complex is called a complex ion.
Compounds that contain a coordination complex are called coordination compounds.

Coordination compounds and complexes are distinct chemical species - their properties
and behavior are different from the metal atom/ion and ligands from which they are
composed.

The coordination number is the number of donor atoms bonded to the central metal
atom/ion.

Examples of coordination complex

molecular formula of Lewis base/ coordination


Lewis acid donor atom
complex ligand number
[Ag(NH3)2]+ NH3 Ag+ N 2
[Zn(CN)4]2- CN- Zn2+ C 4
[Ni(CN)4]2- CN- Ni2+ C 4
[PtCl6]2- Cl- Pt4+ Cl 6
[Ni(NH3)6]2+ NH3 Ni2+ N 6
Double salts Co-ordinate compound
Double salts are molecular compounds A complex compound is a compound
which are formed by the evaporation of formed from a lewis acid and a lewis base.
solution containing 2 or more salts in They don't dissociate into its constituent
stoichiometric proportions. They dissociate ions in solutions
into their constituent ions in solution

2SO4.Al2(SO4)3.24H2O --> 2K^+ + 2Al^3+ + Fe(CN)2 + 4KCN ---> K4[Fe(CN)6]


4SO4^2- + 24H2O this is how it dissociates

*the properties of the double salt same as the properties of the complex compounds
their constituents. are different from their constituents
* they loose their identity in aqueous complex compounds do not completely
solution or any other solvent. loose their identity in aqueous solution.

DOUBLE SALTS:- double salt exist only in COMPLEX COMPOUND:-complex


solid state and dissociate into ions in compounds exist in solid state as well as in
aqueous solution or any other solvent. water or any other solvent

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