Tutorial 7

Compleximetry

Objectives
1.Define complex formation reaction.
2.Differentiate between types of ligands.
2.Define properties of EDTA titrations.
3.Describe different types of EDTA titrations.
4.Determination of water hardness.
5.Describe how to increase EDTA selectivity.
6. Apply EDTA titrations.
2

Complex formation reaction

Is the reaction of a metal ion with electron donnating group or
nucleophile to form a metal-ligand complex.

Metal

Ligand

Ex.: Cu2+ + 4:NH3

complex
[Cu(NH3)4]2+

The metal ion acts as Lewis acid (electron acceptor) and is used as
a titrant for complex forming agent (Ligand) which acts as a Lewis
base (neutral group or negatively charged group {stronger Lewis
base}) that can donate electrons.

The coordination number (n) of the metal ion represents the

number of coordinate bonds around the central metal, which is
the number of monodentate ligands coordinated to the metal
ion.
Cu2+ + 4NH3
[Cu(NH3)4]2+
n= 4
Coordinate bond is the bond formed between electron
donnating group (ligand) and an electron acceptor (metal ion).

Types of ligands:

Monodentate ligands: contain only one center of

donnation e.g.: CN-, F-, :NH3, H2O:
Bidentate ligands: contain 2 centers of donnation.
e.g. ethylene diamine H2N:-CH2-CH2-:NH2
Multidentate ligands: contain more than 2 centers of
donnation. Ethylene diamine tetraacetic acid (EDTA).

Each element cant donate more than one lone pair of

electrons.

EDTA:a multidentate ligand

EDTA is a tetrabasic acid that has six potential sites for bonding
with a metal ion, four carboxyl groups and the two amino groups ,
each of the latter with unshared pair of electrons. Thus EDTA is a
hexadentate ligand

EDTA is not a selective reagent :as it can complex with all metal
ions with a ratio 1:1 regardless of the charge on the cation.
e.g. Ag+ + Y4- ---- AgY3Al3+ + Y4- ---- AlY-

The stability of the formed complexes is highly

dependent on the pH of the medium:

Tri and tetravalent valent metal ions such as Bi3+, Fe3+, Cr3+, Th4+, V4+ form
highly stable EDTA complexes. These can be titrated with EDTA in acid
medium pH 1-3 using 0.2N HNO3 to adjust pH.
Ca2+ can be titrated in highly alkaline medium pH>12 using
murexide as indicator.
Divalent metal ions such as Pb2+, Cd2+, Zn2+ can be titrated in acidic
medium using hexamine buffer and xylenol orange as indicator.
Most of divalent metal ions as Mg2+,Ca2+, Ba2+, Pb2+, Zn2+ can also be titrated in
alkaline medium (pH 10) using ammoniacal buffer and Eriochrome black T
as indicator
The main determining factor in the pH dependence is the stability of the formed
complex in comparison to the free EDTA in a given pH; the complexes should have
higher stability constants so that the titration is possible.

Types of EDTA titrations

A. Direct titration:

Many metal ions can be titrated using EDTA taking into account choosing
a suitable indicator and pH medium.

This type has a very important application in the determination of:

hardness of water (hard water cant form foam with soap)

There are two types of water hardness:

Temprorary Hardness, this can be removed by boiling and it is due to
carbonate salts.
Permenant hardness, this cant be removed by boiling and this is mainly
due to other types of salts that are not affected by heating as sulphates,
silicates.etc

Hardness of Water:

Water hardness is represented in terms of the presence of

Ca2+ and Mg2+ salts.

Total Ca2+ and Mg2+ are determined by direct titration with

EDTA at pH 10 using ammoniacal buffer and EBT as
indicator.

Ca2+ alone can be determined at pH 12 using 0.4N NaOH

and murexide as indicator.

B. Back titration:
1.Back titrations are useful for the determination of cations that form
stable EDTA complexes and for which no suitable indicator is
available as in case of determining Thallium.
2. The method is also useful for cations as Cr(III) and Co(III) that
react only slowly with EDTA. A measured excess is added and
after the reaction , the excess EDTA is titrated against standard zinc
or magnesium.
3. It can also be used when the analyte forms precipitates at the
required pH of its titration.

C. Displacement titration:

In displacement titrations ,an unmeasured excess of a solution

containing the magnesium or zinc complex of EDTA is introduced
into the analyte solution.

The analyte which forms more stable complex than that of

magnesium or zinc will undergo the following displacement reaction:
MgY2- + M2+ --- MY2- + Mg2+
Where M2+ can be Hg(II), Pd(II), Ti(II), Mn(II) and V(II).

The liberated Mg2+ or Zn

solution.

2+

can be then titrated with standard EDTA

Displacement titrations are used on lacking sharp end point or

when no suitable indicator is available.

How to increase selectivity of EDTA

Control of pH
At highly acidic
medium , pH 1-3, only
tri, and tetravalent
metals can be detected

At highly basic
Medium pH> 12,
Calcium and Barium
can be determined
using murexide
indicator and NaOH to
Adjust pH.

Precipitation

Masking with
Cyanide

If a metal is precipitated as
hydroxide on adding buffer
or NaOH, EDTA cant react
with metal so it will be
masked.
e.g. Mg2+, Sr2+, Ba2+, Pb2+

Metals that can react with

CN- are: Ag(I), Cu(II), Hg(II),
Cd(II), Zn(II), Co(II), Ni(II),
Fe(II), Fe(III), Cr(III).

Metals that cant react with

CN- are: Ca, Sr, Ba, Mg, In,
Pb and Mn

( N.B. , in highly basic medium, most of the metals will

ONLY Zn and Cd cyano
precipitate as hydroxides which is more stable than forming complexes that the metal
a complex with EDTA, i.e. cant be titrated with EDTA)
ions can be released
(demasked) from the
complex using
formaldehyde, acetone or
chloral hydrate

Questions
Suggest a suitable method to determine
each metal in the following mixture:
1. Fe2+,Zn2+,Ca2+
1- Back titration to find the equivalent volume for total metals.
2- On a new portion, add CN- , Fe2+ and Zn2+ will be masked,
therefore by direct titration, the volume of EDTA will be
equivalent to Ca2+.
3- On the same flask, add acetone, Zn2+ will be de-masked,
therefore by direct titration, the volume of EDTA will be
equivalent to Zn2+.
4- By subtraction, u can obtain the equivalent volume to Fe2+.

2-Cr3+,Cu2+,Cd2+,Mg2+
1- Back titration to find the equivalent volume for total metals.
2- On a new portion, adjust the medium at highly acidic pH,
(by direct titration, the volume of EDTA will be equivalent to
Cr3+.
3- On a new portion, add CN- , Cu2+ , Cd2+ and Cr3+ will be
masked, therefore by direct titration, the volume of EDTA will
be equivalent to Mg2+.
4- On the same flask, add acetone, Cd2+ will be de-masked,
therefore by direct titration, the volume of EDTA will be
equivalent to Cd2+.
5- By subtraction, u can obtain the equivalent volume to Cu2+.

3.Cd2+, Fe2+,Fe3+,Ca2+
1- Back titration to find the equivalent volume for total metals.
2. On a new portion, adjust the medium at highly acidic pH.
By direct titration, the volume of EDTA will be equivalent to
Fe3+.
3. On a new portion, add CN- , Fe3+,Fe2+ and Cd2+ will be
masked, therefore by direct titration, the volume of EDTA will
be equivalent to Ca2+.
3- On the same flask, add acetone, Cd2+ will be de-masked,
therefore by direct titration, the volume of EDTA will be
equivalent to Cd2+.
4- By subtraction, u can obtain the equivalent volume to Fe2+.

4.Cd2+ , Ca2+, Ni2+,Mn2+

1- Back titration to find the equivalent volume for total metals.
2. . On a new portion, adjust the PH to be highly alkaline (PH>12)
using NaOH and murexide. By direct titration, the volume of EDTA
will be equivalent to Ca2+ .
3. On a new portion, add CN- , Cd2+ and Ni2+ will be masked, therefore
by direct titration, the volume of EDTA will be equivalent to Ca2+ and
Mn2+.

By subtraction: volume of 3-2, you can obtain the equivalent

volume to Mn2+.

3- On the same flask, add acetone, Cd2+ will be de-masked, therefore

by direct titration, the volume of EDTA will be equivalent to Cd2+.
4- By subtraction, u can obtain the equivalent volume to Ni2+.

For each of the following COMPLEX FORMING AGENTS, draw the mode of chelation with a metal ion:
1. Note that the final complex should have a coordination number of 6.

O
+

For each of the following COMPLEX FORMING AGENTS, draw the mode of chelation with a metal ion:
1. Note that the final complex should have a coordination number of 6.
Metal ion interacts w ith this ligand w ithin the ratio of 1:2.
What is the coordination number?

H2N

O
M

O
O

NH2
n=4