Course Name:

Volumetric and gravimetric Analytical chemistry

Course Code: 4022133-3
 Lecture 10 contents

Complexmetric Titration
EDTA
Metal indicator
Application of Complexmetric Titration
 Complexometric reaction
Complex metric reaction is the reaction between metal ion
Mn+ with neutral or negatively charged groups that are
called ligands.
Mn+ + nL ↔ MLn
Metal ion Ligand Complex
(Lewis acid) (Lewis base)

Ligand: atom, ion or group which has one or more

unshared electron pair available for bond formation e.g.
neutral groups: water, ammonia, CO
negative groups: Cl-, Br-, CN-, OH-
 Complexometric titration

Complexometric titration is a form of

in which the formation of a colored complex is used to indicate the
end point of a titration.

-This complex is slightly ionized in solution, like weak

electrolyte and sparingly soluble salt.
 EDTA
Hexadentate Ligand:
The Ligand attached to metal at 6 sites
e.g.EDTA is a polyprotic acid containing four carboxylic
acid groups (acidic hydrogens) and two amine groups
with lone pair electrons.

EDTA
 Titration curve
Three Regions of EDTA Titration
The curves are easily calculated by dividing the curve up into
domains:
•The pM before equivalence.
• The pM at equivalence.
•The pM after equivalence.
 Titration using Ethylene di-amine tetra-acetic acid (EDTA)

- EDTA forms complexes with Varity of metals (divalent, trivalent,

tetravalent) (except gp. VI "Alkali gp.")

- All metal –EDTA complexes have a 1:1 stoichiometry (irrespective to

the charge of the metal ion)

- The general reactions for the formation of metal – EDTA

complexes as follows:

M2+ + H2Y2- MY2- + 2 H+

M3+ + H2Y2- MY- + 2 H+
M4+ + H2Y2- MY + 2 H+

Mn+ + H2Y2- (MY)n-4 + 2 H+

 Requirements for direct EDTA titrations:

M-EDTA complex must be more stable than M-Ind. complex in

buffered medium.
The compound to be determined is water soluble.
The reaction between EDTA and metal must be rapid. If the
reaction is slow it must be catalyzed.
Mn+ should not be ppt. at the pH of titration. If Mn+ is ppt. as
MOH, auxiliary reagent must be added to prevent pptn. of M n+.
 Factors affecting stability of complex
Effect of central metal ion :
1- Ionic size (metal radius):
Smaller an ion (small radius of metal) ⎯→
greater its electrical field ⎯→ more stable
complex
2-Ionic charge (metal charge):
Metal of higher charge give more stable
complexes. e.g. Ferricyanide [hexacyanoferrate
III] is more stable than Ferrocyanide
[hexocyanoferrate II].
 Factors affecting stability of complex

Effect of central metal ion :

3- Electronegativity :
The higher acidity (electronegativity) of metal
(Mn+) ⎯→ the higher stability of complex.
e.g,metal which has incomplete outer shell (has
high acidity) have more tendency to accept
electrons  more stable complex. e.g. Ca2+ , Ni2+
, Zn2+ , Mn2+ , Cu2+
 Factors affecting stability of complex

Effect of Ligand:
1- Basic character:
The higher the basicity (strong base is good electron
donor)  the higher the ability of ligand to form complex.
e.g. ligand contain electron donating atom.
e.g. N > O > S > I- > Br- > Cl- > F-

2- The extent of chelation:

Multidentate ligands form more stable complexes than
monodentate.
 Factors affecting stability of complex
Effect of Ligand:
3- Steric effect:
Large, bulky ligand form less stable complexes
than smaller ones due to steric effect. e.g.
ethylene diamine complexes are more stable than
those of the corresponding tetramethyl ethylene
diamine.
 Metal Ion Indicators
Metal Ion Indicator: a organic dyes that form colord
chelates with metal ion

Mn+ + Ind. ⎯→ M – Ind.

M – Ind. + EDTA ⎯→ M – EDTA + free Ind.
 Conditions of metal –indicator reaction
Act as ligand to form complex with metal (act as Lewis
base and the metal acts as Lewis acid).
The reaction between metal and ind. must be reversible.
The metal-ind. complex should be less stable than the
metal-EDTA complex.
The color of free form different than color of complex
one.
Changes its color according to the pH of the medium.
 Indicator
Murexide: Ammonium salt of Purpuric acid or
ammonium purpurate
• It can be represented by H4 Ind. -

OH - OH -
• H4 Ind.- H3 Ind.2- H2 Ind.3-
H+ H+
Reddish violet Violet Blue
pH : <9 9-11 > 11
 Indicator

Eriochrome Black T (EBT)

• It can be represented by H2Ind -
• The color of Ind. change with the change of pH.
• EBT contains 2 replaceable phenolic hydrogen.
OH - OH -
• H2 Ind.- H Ind.2- Ind.3-
H+ H+
Wine red Blue Yellow
pH : <7 7-11 > 11
 Example
Titration of Mg2+ by EDTA
Eriochrome Black T Indicator
M-In + EDTA = M-EDTA + free In
(red) (colorless) (colorless) (blue)

End Point indicated by a color change from red to blue

Addition of EDTA

Before Near After

Equivalence point
 Metal Ion Indicators

Indicator pH range Metal ion titrated

Eriochrome Black T Mg, Ca, Mn, Zn, Cd,

7.5-10.5
(ErioT) Ba, Pb

Murexide 6-13 Ca, Ni, Co, Cu

PAN 2-11 Cu, Zn, Hg

Salicylic acid 2-3 Fe

Xylenol orange 5-6 Zn, Cd,Hg

 selectivity

The selectivity of a ligand for one metal ion over another

refers to the stability of the complexes formed. The higher the
formation constant of the metal-ligand complex, the better
the selectivity of the ligand for the metal relative to similar
complexes formed with other metals.

The following procedures will help to increase the

selectivity :
 selectivity

1- Suitable control of the pH of the solution.

A mixture of bismuth and lead ions can be successfully titrated

by firs ttitrating the bismuth at pH 2 with xylenol orange as
indicator, and then adding hexamine to raise the pH to about 5,
and titrating the lead.
 selectivity
2-Use of masking agents.

Masking agents are reagents which prevent interfering ion

from reaction without physical separation.
By the use of masking agents, some of the cations in a
mixture can often be 'masked' so that they can no longer
react with EDTA or with the indicator.

An effective masking agent is the cyanide ion.

 selectivity
3-Selective demasking.
Demasking agents are reagents which regain the ability of masked
ion to enter the reaction with ind. and EDTA.
The cyanide complexes of zinc and cadmium may be demasked
with formaldehydeacetic acid solution or, better, with chloral
hydrate .

The use of masking and selective demasking agents permits the

successive titration of many metals.
 Example
Thus a solution containing Mg+2, Zn+2, and Cu+2 can be titrated
as follows:
1. Add excess of standard EDTA and back-titrate with standard
Mg+2 solution using solochrome black as indicator. This gives
the sum of all the metals present.
2. Treat an aliquot portion with excess of KCN and titrate as
before. This gives Mg+2 only.
3. Add excess of chloral hydrate (or of formaldehyde-acetic acid
solution, to the titrated solution in order to liberate the Zn +2
from the cyanide complex, and titrate until the indicator turns
blue. This gives the Zn+2 only.
The Cu+2 content may then be found by difference.
 Applications of Complexometric Titrations
EDTA Titration
Direct determination of water hardness:
• Water hardness is due to the presence of Ca2+ & Mg2+ salts.
• EDTA forms complex with Ca2+ & Mg2+, Ca-EDTA complex is more stable than Mg-
EDTA complex.
• At pH 12 EDTA forms complex with Ca2+ only.
• Total Ca2+ & Mg2+:
• Total Ca2+ and Mg2+ determined by titration with EDTA at pH 10 using ammonia
buffer and EBT as ind.
• Upon titration with EDTA, Ca2+ will be chelated first, then Mg2+.
• For Ca2+ only:
• Direct titration with EDTA at pH 12 using 8% NaOH and Murexide.
• Mg2+ is pptd. as Mg(OH)2 leaving Ca2+ which is titrated with EDTA
• For Mg2+ :
• Total – Ca2+ = Mg2+
 Applications of Complexometric Titrations
EDTA Titration
Direct determination of Cu2+ with EDTA
• The complex of Cu2+ with EDTA is more stable than its complex with murexide
ind.
• Cu2+ + H3Ind.2- ⎯→ CuH2Ind.- + H+
• CuH2Ind.- + H2Y2- ⎯→ CuY2- + H3Ind.2- + H+
yellow violet
Direct determination of Zn2+ by EDTA
• - The complex of Zn2+ with EDTA is more stable than its complex
with EBT ind.
• Zn2+ + H Ind.2- ⎯→ Zn Ind.- + H+
• Zn Ind.- + H2Y2- ⎯→ ZnY2- + H Ind.2- + H+
wine red Blue
 Back Titration

• Addition of known xss. of st. EDTA to the sample

• The medium is buffered.
• xss. EDTA is titrated with standard soln. of another metal ion e.g. Mg2+
or Zn2+
It is used in the following cases:
• Insoluble substances e.g. BaSO4 , Ca(C2O4)2 , PbSO4 , Mg3(PO4)2 … etc.
Usually soluble in hot EDTA.
• The reaction between Mn+ & EDTA is slow (incomplete) e.g. Fe3+ , Al3+ ,
Cr3+ , Th4 , … etc.
• The Mn+ is pptd. at the pH suitable for titration e.g. Al(OH)3.