Instructor

Analytical Chemistry (CHEN 223)

Dr. Shaikh Manirul Haque (Associate Professor)
Department of Chemical Engineering, Jubail Industrial College

Reference Book: Gary D. Christian, 7th Edition

Chapter 4 – Complexometric Reactions and Titrations

*For correspondence, e-mail: Haque_m@[Link]

1 Saturday, October 28, 2023

 Complexes are compounds formed from combination of metal ions with ligands
(complexing agents).

 A metal is an electron deficient species while a ligand is an electron rich, and thus,
electron donating species.

 A metal will thus accept electrons from a ligand where coordination bonds are formed.
Electrons forming coordination bonds come solely from ligands.

2
 A ligand is called a monodentate if it donates a single pair of electrons (like :NH3). While a
bidentate ligand (like ethylenediamine, :NH2CH2CH2H2N:) donates two pairs of electrons.
Ethylenediaminetetraacetic acid (EDTA) is a hexadentate ligand.

 The ligand can be as simple as ammonia which forms a complex with Cu2+, for example, giving the
complex Cu(NH3)42+. When the ligand is a large organic molecule having two or more of the
complexing groups, like EDTA, the ligand is called a chelating agent and the formed complex, in
this case, is called a chelate.

3
 The tendency of complex formation is controlled by the formation constant of the reaction
between the metal ion (Lewis acid) and the ligand (Lewis base). As the formation constant
increases, the stability of the complex increases.
Let us look at the complexation reaction of Ag+ with NH3:

Ag+ + NH3  Ag(NH3)+ kf1 = [Ag(NH3)+]/[Ag+][NH3]

Ag(NH3)+ + NH3  Ag(NH3)2+ kf2 = [Ag(NH3)2+]/[Ag(NH3)+][NH3]

4
Kf1 x kf2 = [Ag(NH3)2+]/[Ag+][NH3]2

Now look at the overall reaction:

Ag+ + 2 NH3  Ag(NH3)2+

kf = [Ag(NH3)2+]/[Ag+][NH3]2

5
 It is clear fro inspection of the values of the kf that:

Kf = kf1 x kf2

For a multistep complexation reaction, we will always have the formation

constant of the overall reaction equals the product of all step wise formation
constants.

6
The formation constant is also called the stability constant and if the equilibrium is
written as a dissociation the equilibrium constant in this case is called the instability
constant.
Ag(NH3)2+  Ag+ + 2 NH3

kinst = [Ag+][NH3]2/[Ag(NH3)2+]

Therefore, we have:
Kinst = 1/kf

7
Example
A divalent metal ion reacts with a ligand to form a 1:1 complex. Find the
concentration of the metal ion in a solution prepared by mixing equal volumes of 0.20
M M2+ and 0.20 M ligand (L). kf = 1.0x108.
Solution
The concentration of metal ions and ligand will be half that given as mixing of equal
volumes of the ligand and metal ion will make their concentrations half the original
concentrations since the volume was doubled.

8
 [M2+] = 0.10 M, [L] = 0.10 M

M2+ + L  ML2+

9
Kf = ( 0.10 –x )/x2
Assume 0.10>>x since kf is very large
1.0x108 = 0.10/x2, x = 3.2x10-5
Relative error = (3.2x10-5/0.10) x 100 = 3.2x10-2 %
The assumption is valid.
[M2+] = 3.2x10-5 M

10
Example
Silver ion forms a stable 1:1 complex with trien. Calculate the silver ion concentration
at equilibrium when 25 mL of 0.010 M silver nitrate is added to 50 mL of 0.015 M
trien. Kf = 5.0x107
Solution
Ag+ + trien  Ag(trien)+
mmol Ag+ added = 25x0.01 = 0.25
mmol trien added = 50x0.015 = 0.75

11
The reaction occurs in a 1:1 ratio
mmol trien excess = 0.75 – 0.25 = 0.50
[Trien] = 0.5/75 M
[Ag(trien)+] = 0.25/75 M

12
Kf = ( 0.25/75 – x )/(x * 0.50/75 + x)
Assume 0.25/75>>x since kf is very large
5.0x107 = (0.25/75)/(x * 0.50/75)
x = 1.0x10-8
Relative error = (1.0x10-8/(0.25/75)) x 100 = 3.0x10-4 %
The assumption is valid.
[Ag+] = 1.0x10-8 M

13
• An organic agent that has two or more groups capable of complexing with a metal ion is called a
chelating agent.

• The complex formed is called a chelate.

• The chelating agent is called the ligand.

• Titration with a chelating agent is called a chelometric titration, perhaps the most important
and practical type of complexometric titrations.

14
 Each of the two nitrogens and each of the four carboxyl
groups contains a pair of unshared electrons capable of
complexing with a metal ion. Thus, EDTA contains six
complexing groups.
We will represent EDTA by the symbol H4Y. It is a tetraprotic acid, and the hydrogens in H4Y refer to the
four ionizable hydrogens belonging to the four carboxylic acid groups. At sufficiently low pH, the nitrogens
can also be protonated and this diprotonated EDTA can be considered a hexaprotic acid. However, this
occurs at a very low pH and EDTA is almost never used under such conditions. It is the unprotonated ligand
Y4- that forms complexes with metal ions, that is, the protons are displaced by the metal ion upon
complexation.

15
The Chelon Effect

The question is which is more stable a chelate formed from a chelating agent with four
chelating groups or a complex formed from the same metal with four moles of ligand
having the same donating group?

16
This can be simply answered by looking at the thermodynamics of the process. We know from
simple thermodynamics that spontaneous processes are favored if an increase in entropy results.
Now look at the dissociation of the chelate and the complex mentioned above, dissociation of
the chelate will give two molecules while dissociation of the complex will give five molecules.
Therefore, dissociation of the complex results in more disorder and thus more entropy. The
dissociation of the complex is thus more favored and therefore the chelate is more stable as its
dissociation is not favored.

17
EDTA Titrations

 Ethylenediaminetetraacetic acid disodium salt (EDTA) is the most frequently used chelate in complexometric
titrations.

 Usually, the disodium salt is used due to its good solubility. EDTA is used for titrations of divalent and polyvalent
metal ions.

 The stoichiometry of EDTA reactions with metal ions is usually 1:1. Therefore, calculations involved are simple and
straightforward.

 Since EDTA is a polydentate ligand, it is a good chelating agent and its chelates with metal ions have good stability.

18
EDTA Equilibria
We can represent EDTA as having four Ka values corresponding to the stepwise dissociation of the four
protons.

19
 Figure illustrates the fraction of each form of EDTA as a function of pH.
 Since the anion Y4− is the ligand species in complex formation, the complexation
equilibria are affected markedly by the pH.
 H4Y has a very low solubility in water, and so the disodium salt Na2H2Y.2H2O is
generally used, in which two of the acid groups are neutralized. This salt dissociates in
solution to give predominantly H2Y2−.

20
21
22
Let CH4Y represent the total concentration of all forms of uncomplexed EDTA, then

23
The Formation Constant
Reaction of EDTA with a metal ion to form a chelate is a simple reaction. For
example, EDTA reacts with Ca2+ ions to form a Ca-EDTA chelate forming the
basis for estimation of water hardness. The reaction can be represented by the
following equation:
Ca2+ + Y4- = CaY2- kf = 5.0x1010
Kf = [CaY2-]/[Ca2+][Y4-]
The formation constant is very high and the reaction between Ca2+ and Y4- can
be considered quantitative. Therefore, if equivalent amounts of Ca2+ and Y4-
were mixed together, an equivalent amount of CaY2- will be formed.

24
 The question now is how to calculate the amount of Ca2+ at equilibrium?
CaY2-  Ca2+ + Y4-
However, [Ca2+] # [Y4-] at this point since the amount of Y4- is pH dependent and Y4- will
disproportionate to form all the following species, depending on the pH
CT = [H4Y] + [H3Y-] + [H2Y2-] + [HY3-] + [Y4-]
Where, CT is the sum of all species derived from Y4- which is equal to [Ca2+].
Therefore, the [Y4-] at equilibrium will be less than the [Ca2+] and in fact it will only be a
fraction of CT where:
4 = [Y4-]/CT
4 = ka1ka2ka3ka4/([H+]4 + ka1 [H+]3 + ka1ka2[H+]2 + ka1ka2ka3[H+] + ka1ka2ka3ka4)

25
Formation Constants for EDTA Complexes

Cation KMY Cation KMY

Ag+ 2.1 x 107 Cu2+ 6.3 x 1018
Mg2+ 4.9 x 108 Zn2+ 3.2 x 1016
Ca2+ 5.0 x1010 Cd2+ 2.9 x 1016
Sr2+ 4.3 x 108 Hg2+ 6.3 x 1021
Ba2+ 5.8 x 107 Pb2+ 1.1 x 1018
Mn2+ 6.2 x1013 Al3+ 1.3 x 1016
Fe2+ 2.1 x1014 Fe3+ 1.3 x 1025
Co2+ 2.0 x1016 V3+ 7.9 x 1025
Ni2+ 4.2 x1018 Th4+ 1.6 x 1023
26
The Conditional Formation Constant
We have seen that for the reaction
Ca2+ + Y4-  CaY2-
We can write the formation constant expression
Kf = [CaY2-]/[Ca2+][Y4-]
However, we do not know the amount of Y4- at equilibrium but we can say that since 4 = [Y4-
]/CTthen we have:
[Y4-] = 4CH4Y
Substitution in the formation constant expression we get:
Kf = [CaY2-]/[Ca2+]4CH4Y or at a given pH we can write
Kf' = [CaY2-]/[Ca2+]CH4Y = Kf4
Where Kf' is called the conditional formation constant. It is conditional since it is now
dependent on pH.

27
Titration Curves
In most cases, a titration is performed by addition of the titrant (EDTA) to the metal ion
solution adjusted to appropriate pH and in presence of a suitable indicator. The break
in the titration curve is dependent on:

1. The value of the formation constant.

2. The concentrations of EDTA and metal ion.
3. The pH of the solution
As for acid-base titrations, the break in the titration curve increases as kf increases and
as the concentration of reactants is increased. The pH effect on the break of the
titration curve is such that sharper breaks are obtained at higher pH values.

28
 Minimum pH for effective titrations
29 of various metal ions with EDTA.