COMPLEXOMETRIC TITRATION

Complex ion- consists of a central metal atom or cation

surrounded by ligands
Ligands : Ligands are anions or neutral molecules possessing
lone pair of electrons .

So,the formation of a complex ion involves the formation of dative

covalent bond/coordinate covalent bond.

Dative covalent bond : donation of a pair of electron from ligand to

the empty orbitals of the central metal atom or ion

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 Ligands
Neutral molecule
Ex: H2O, NH3,CO,NO, CH3NH2
(Aqua, Ammine, Carbonyl……..)

Anions , Ex : F- , Cl-, I-,OH,CN

Cations :?????????????????????

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 Desirable features in ligands
1. Fast reaction with metal ion
2. Quantitative reaction - large Kf overall
3. Sharp change in metal ion concentration close to equiv.
pt.

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TYPES OF LIGANDS
1. Unidentate (monodentate) ligand

Monodentate Ligands - Ligands that have only one

bonding site (one lone pair of electron) that can be
used for coordinate covalent bonding.
Examples: Cl-, Br-, NH3, H2O…etc.
..
H O H

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 Bidentate Ligands - Ligands that have two
bonding sites (2 lone pair of electron) that can be
used for coordinate covalent bonding.
Example : Ethylenediamine
(H2N-CH2-CH2NH2)

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 Polydentate Ligands
Ligands that have TWO or MORE lone pair of electrons
as bonding sites.
Example: EDTA (ethylene diamine tetra acetic acid)–
hexadentate ligands.
A hexadentate ligand has six points at which it can
attach to the central atom

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 Chelate
When a polydentate ligands coordinates with a metal
ion, a ring sructure is formed.
The complex is called a CHELATE
A chelate is a chemical compound composed of a
metal ion and a chelating agent

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 Chelating agent
A chelating agent is a substance whose molecules can
form several bonds to a single metal ion.
In other words, a chelating agent is a multidentate
ligand.
An example of a simple chelating agent is
ethylenediamine.

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 EDTA
EDTA is or Ethylenedinitrilotetraacetic acid
EDTA is a versatile chelating agent.
It is hexadentate ligands ( 6 bonds with a metal ion)
Symbolised as H4Y, (where Y=C10H12N2O8)

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 EDTA (EDTA 4 -)

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 EDTA
In addition to the four charged sites at the carbonyl groups
oxygens, each of the two nitrogens has an unshared pair of
electrons making SIX electron pairs available to form
coordinate covalent bonds.
In forming a complex example with calcium ions, all six
bonding sites bond to calcium forming a large aggregate
consisting of a single EDTA ligand wrapped around the
calcium ions.

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 EDTA

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 Ca(EDTA)]2-

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 one EDTA + one metal ion forms octaheral
structure

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 Chelate
When a polydentate ligands coordinates with a metal
ion, a ring structure is formed. The complex is called a
CHELATE and the polydentate ligand is called a
chelating agent or reagent.

16 crown ethers are multidentate chelating ligands

 Multidentate / polydentate Ligand forming a
1:1 mole ratio with metal cation
Metal: Ligand Complex
Example :
Ca2+ + EDTA = Ca-EDTA
1. Rxn occurs in a single step
2. Gives a sharp change in metal ion
concentration at equivalence point
3. Metal ion is either totally complexed or
no reaction between metal ion and ligand
at all.
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 Disodium Salt of EDTA
1. What is disodium salt of EDTA?
It is the usual sources of EDTA for use in metal analysis
2. Why we use this disodium salt of EDTA and not the
acid form?
 Disodium salt of EDTA is more soluble compare to
its acid form.
 Since EDTA is a weak organic acid it dissolve
slowly in water
3. What is the structure of disodium salt of EDTA?
Frequently symbolized as Na2H2Y

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 Complexation Titrations
In a complexometric titrations commonly the analyte is a
metal cation and the titrant is a ligand
Objective : To determine amounts of metal cations

Titration process

1. Buffer the solution at a suitable pH

2. add Indicator
3. titrate metal with suitable complexing ligand

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 EDTA as titrant

In form of sodium salt of the

ethylenediaminetetraacetic acid (Na2-EDTA).
1. A one-to-one reaction between EDTA salt and
metals ions.
2. EDTA ligand binds strongly to metal ion
3. pH dependent
4. Rapid reaction as complex is stable

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 Dissociation of EDTA
Ethylenediaminetetraacetic acid is frequently
symbolised as H4Y, and the EDTA salt as Na2H2Y.
(where Y=C10H12N2O8)

Ionization of H4Y would depend upon the pH

H4Y = H+ + H3Y- at pH < 1

H3Y- = H+ + H2Y2-
H2Y2- = H+ + HY3-
HY3- = H+ + Y4- at pH = 10
The exact position of the equilibrium is controlled by
controlling the pH of the solution. At pH = 10 , Y4-
21 predominate and at pH< 1 , H4Y will predominate
 END POINT FOR EDTA TITRATION
Metal-Ion Internal Indicator (Eriochrome black T or
EBT)
these indicators are organic dyes that form coloured
chelates with metal ions.
The complexes are often INTENSELY coloured and
can detected by the eyes

Ion-selective Electrode
an ion-selective electrode sensitive to the analyte

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 Example of metal-ion indicator
Eriochrome black T or EBT
EBT function is same as acid-base indicators are useful as
indicators for metal ions only in pH ranges in which
competition with the proton is negligible.

EBT can be symbolised as H3In

In acidic and moderately basic solution, the predominant

acid-base
equilibrium exhibited by the indicator is as follows:
H3In H2In- HIn2- In3-
Red
acidic red moderate basic
blue orange
strongly basic, pH>10
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 acidic basic

1 drop difference of 0.01 M EDTA between the first

and second pictures and between the second and third
pictures.
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 The metal complexes of EBT are generally RED in
colour. To observe a colour change with this indicator,
then it is necessary to adjust the pH to 7 or above
(pH=10) so that the blue form of the indicator HIn2-
predominates.
M2+ + In2-  MIn
blue red
When the titration begins between metal cation and
EDTA, the end point reaction is then (at pH =10) :
MIn + Y4- = HIn2- + MY2-
Red colourless blue colourless

Therefore the end point colour change is from RED to

BLUE.
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 If the pH is below 7, then the colour change is from RED
to RED which is impossible to detect the end point colour
change.
If the pH > 10, then the end point colour change is from
RED to ORANGE which not sharp enough to detect the
colour change.

LIMITATION OF EBT
A limitation of EBT is that its solution decompose slowly
with standing.

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 EDTA commercial usage :
1. used in soaps and detergents as it forms complexes with Ca and
Mg ions. These ions which are in hard water are bound to the
EDTA and cannot interfere with the cleaning action of the soap or
detergent
2. EDTA is also used in foods.
-Certain enzymes are responsible for food spoilage. EDTA is used
to remove metal ions from these enzymes. - used to promote color
retention in dried bananas, beans, chick peas, canned clams, pecan
pie filling, frozen potatoes and canned shrimp.
-used to improve flavor retention in canned carbonated
beverages, beer, salad dressings, mayonnaise, margarine, and
sauces. It inhibits rancidity in salad dressings, mayonnaise, sauces
and salad spreads.
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 Summary complexometric titration
Define : complex ion, ligands, chelates,
EDTA & disodium salt EDTA: Naming, draw the
structure, why we use disodium salt of EDTA
Ratio EDTA and metal
What is EBT? What is the limitation
What is the colour changes of EDTA titration
What is the suitable pH for EDTA titration
What will happen, if less or more than the suitable pH
used.
EDTA commercial usage

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 Activities

Quiz on COMPLEXOMETRIC Titration or

Games on Complexometric titration

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