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Subject Chemistry

Paper No and Title 3 and Inorganic Chemistry-I (Stereochemistry,

Metal-Ligand Equilibria and Reaction Mechanism
of Transition Metal Complexes)
Module No and 15 and Determination of Constant by Job's method
Title
Module Tag CHE_P3_M15

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 2

TABLE OF CONTENTS

1. Learning Outcomes

2. Introduction

3. Binding Constants

4. Methods for obtaining the stoichiometry of complex

5. Continuous-variation method

6. Limitations

7. Summary

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 3

1. Learning Outcomes

After studying this module, you shall be able to know about

 Formation and Stability of Inorganic Complexes in Solution

 Optical Methods for obtaining the stoichiometry of complex (determination of the
composition of complexes)
 Jobs method
 Limitations of jobs method

2. Introduction

The optical properties of complexes are governed by the formation of coordinate bonds
between ligands and metal ions. The complexation in solution can easily be detected by
various analytical instruments viz. uv-visible spectrophotometer, fluorimeter etc at very
low concentrations. The basic conditions laid by Lambert-Beer law should be obeyed to
selective determination of any species in solution.

3. Binding Constants
The binding constant (also known as association constant) is a type of the equilibrium
onc ant st(K). It is associated with the binding reaction of Metal (M) and ligand (A)
molecules.

M + A ⇌ MA

At the equilibrium binding constant for forward reaction and dissociation constant for
backward reaction is

Kf[M][A] = Kb[MA]

The overall constant of the reaction is called binding constant

Ka = Kf/Kb = [MA]/[M][A]

The units of Kf and Kb are of M−1 s−1 and s−1, respectively, while the binding constant
(Ka) is of unitless values

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 4

4. Methods for obtaining the stoichiometry of complex

Methods for obtaining the stoichiometry of complex (determination of the

composition of complexes)
nA + mM  AnMm
There are three common optical methods for the determination of the composition of
complexes
Continuous-variation method (Job’s method)
This method is based on the measurement of absorption of a series of solutions in which
molar concentrations of two reactants vary but their sum remains constant.
Mole-ratio method
This method is based on the measurement of absorption of a series of solution in which the
analytical concentration of one reactant is held constant while that of other is varied.
Slope-ratio method
In this method, the reaction can be forced to completion with a large excess of either metal
or ligand. It is used for studying weak complexes.

5. Continuous-variation method
Job's Method: This method is also known as the method of continuous variation. The
principle of the method is that the mole-ratio of the metal ion and the ligand is varied
between 0 and 1 at constant total concentration C = CL+CM and the absorbance of the
solutions of different composition is measured. The absorbance is then plotted against the
mole fraction of the ligand(xL). If only one complex species has been formed, with
composition MLn and the absorbance is measured at a wavelength where neither the metal
ion nor the ligand but only the complex absorbs, then n, the average number of ligands
bound by one metal ion, can be calculated from the abscissa of the maximum of the curve
(xmax):
𝑥𝑚𝑎𝑥
𝑛=
1 − 𝑥𝑚𝑎𝑥

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 5

This is a very common method for determination of composition of complexes. Equimolar

mixture of metal and ligand are taken and are mixed to give a series of solution having the
same total concentration of metal and ligand, but varying the concentration of metal and
ligand. Table below shows such a set of solutions

TM 10-2 M TA 10-2 M (TA + TA)  10-2 M

1) 10 0 10

2) 9 1 10

3) 8 2 10

4) 7 3 10

5) 6 4 10

6) 5 5 10

7) 4 6 10

8) 3 7 10

9) 2 8 10

10) 1 9 10

11) 0 10 10

Consider a complex reaction:

M  nA  MAn

(1 - x) x

K
MAn  or[MAn]  K M An
(1)
M An
Suppose x is the mole fraction of ligand and

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 6

(1 - x) is the mole fraction of metal present in the solution.

The total number of moles of reactants present in solution at equilibrium if ,N (no. of moles
of meal + no. of moles of ligand) in one liter of solution, [M] the free metal,[L] free ligand
and concentration of complex are given by the equations

M   TM  MAn   1  x N  MAn  (2)

A  TA  nMA n   xN  nMA n  (3)

Where TM and TL are the total metal and ligand concentrations.

Differentiating w.r.t. x and applying the condition of equilibrium for maximum complex
formation:

dMA n  d M 
(1) 0 (2)  N
dx dx {[M] = (1-x)N}

dA
(3) N
dx {[A] = (x)N}


d
dx

MAn  0 

 M d An  An dM  0

dx dx

 An dM  nMAn1 d

A  0 (4)
dx dx

dM dA
Substitute the value of and in (4)
dx dx

An  N  nMAn1 N  0
 
N nMA
n 1

 A  0
n

  NAn  nNMAn1
CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-
Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 7

 A  nM
Substitute the value of A & M from equation 2 and 3::

xN  nMA n   n1  x N  MA n 

 xN  nMA n   n1  x x  nMA n 

 xN  nMA n   nN  nNx  nMA n 

 xN  nNx  nN  nMAn  nMAn 

 Nn1  x   xN

x
 n
1 x
So, on drawing the graph between absorbance of prepared series of solution and their
corresponding mole fraction, the exact ratio of metal and ligand at equilibrium can be
observed at maxima of the graph. For all the cases of graph drawn below, consider
absorbance on ordinate and mole fraction on abscissa

1.2

1.0

0.8
Absorbance

0.6

0.4

0.2

0.0

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Mole fraction of metal ions

Figure 1: For 1:1 case between metal and ligand

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 8

1.2

1.0

0.8

Absorbance
0.6

0.4

0.2

0.0

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Mole fraction of metal ions

Figure 2: For 1:2 case between metal and ligand

1.2

1.0

0.8
Absorbance

0.6

0.4

0.2

0.0

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Mole fraction of metal ions

Figure 3: For 1:3 case between metal and ligand

Let at this pt x 0.5 ligand is 0.5 and metal is 0.5.

 total mole fraction is 1 i.e. it is 1:1 complex.

For 1:2, x = 0.67 & 1:3, x = 0.75

For strong ionic compounds, pH should be maintained during the measurement of the
spectra.

Job's method is also used for calculating approx. value of .

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 9

As
= Degree of formation of complex.
Am

From the degree of formation of complex, the value of free metal and free ligand are
calculated and stability const. of complex is also calculated.

Determination of  by Job's method

A MA n 
 (5)
Am TM

At Am, the whole complex has been formed and whole of the metal ion is consumed.

M  TM  MA n 
 0  TM  MAn 

 TM  MAn 

From (5), MA n  

TM A
AM

 K=
MA n 
MAn
A / A m  TM
=
MA An
A
 TM
Am
K=
TM  MA n TA  n[MA n ]n
A / A m  TM
 K n
 
TM  A / A m  TM  TA  n A  TM 
 Am 

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 10

A / A m  TM
 K
   
 TM 1  A  TA  n A  TM  
  A  
  m  Am 

A / Am
 K
A m  A A M TA  mATm n
A m n1

A.A m 
n
 K
A m  A A m TA  nATM n
Hence, by knowing the values of A, Amax, n, TM and TA, the value of the stability constant,
K can be calculated.

The greater the stability of the complex, the sharper is the peak of the curve and the greater
is the error caused by incorrect reading of the ordinate values. On the other hand, if the
stability of the complex is small, the curve becomes flat and the drawing of the tangents
becomes uncertain.

The Job’s method is the most commonly used method due to its simplicity and rapidity. Its
applicability, however, is limited.

6. Limitations

1) This method is applicable to one type of equilibria i.e., only one type of complex
formation in the solution.

2) This is applicable to moderate stable complexes; it means it cannot be applied to

very weak complexes.

3) If the complexes are colourless, then spectrophotometric method cannot be used.

Measure the absorbance of prepared series of solution, according to Lambert's - Beer's law.

4) pH and ionic strength must be maintained constant

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method
 11

7. Summary

 The binding constant (also known as association constant) is a type of the

equilibrium constant (K).

 Continuous-variation method (Job’s method), Mole-ratio method and Slope-ratio

method are the common methods for obtaining the stoichiometry of complex

(determination of the composition of complexes).

 Job’s method is based on the measurement of absorption of a series of solutions in

which molar concentrations of two reactants vary but their total sum remains

constant.

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition Metal
Complexes)
Module No. 15: Determination of Constant by Job's method