I MSC COORDINATION CHEMISTRY UNIT-III

DETERMINATION OF STABILITY CONSTANTS

 Stability constants of complexes have been measured by different methods.

 The experimental determination of β is an important one but often a difficult task.

 Some of the difficulties encountered in the determination of stability constants of

complexes are given below.

1. Equilibrium constants depends on activities rather than on concentrations. Since

activities and concentrations are numerically equal in very dilute solutions,

concentrations of all species have to be kept low.

2. During measurement of equilibrium concentrations, the equilibrium may get

disturbed.

3. A major problem in the determination of stability constants is the difficulty in

identification of species which are actually present in the solution.

 The selection of the best method to determine the stability constant of a complex is

generally made on the basis of the experimenter's experience. Results of more than one

method are generally compared to et maximum reliability of tea data

List the available methods of stability constant

1. Solubility methods

2. Ion exchange methods

3. Electrochemical methods

4. Polarography methods

5. Spectrophotometric methods

6. The Method of Continuous Variation (Job's Method)

P.RAM KUMAR ASST PROFESSOR DEPARTMENT OF CHEMISTRY

I MSC COORDINATION CHEMISTRY UNIT-III

Spectrophotometric Method

 This method of determining the stability constant of a complex can be considered with
the example
2+
Fe3+ + NCS- Fe(NCS)

 Stability constant for this complex is given by

[𝐹𝑒(𝑁𝐶𝑆)]2 +
𝐾=
[𝐹𝑒 3+ ][𝑁𝐶𝑆−]
 Where the concentration terms represent the actual equilibrium concentrations
 Ferric ion and thiocyanate ion individually are almost colourless in aqueous solution
 The complex [Fe(NCS)]2+is bright-red and its max is 450 mm

The absorption spectra of Fe3+ (aq) and [Fe(NCS)]2+

 Therefore, the concentration of this coloured complex can be estimated by measuring

its absorbance in the visible region using a spectrophotometer.
 The absorbance A is directly proportional to the concentration of absorbing species as
per the Beer Law:
A = ϵcl
ϵ - molar extinction coefficient
c - Concentration of absorbing species
l - path length of the absorbing solution
 The value of ϵ for [Fe(NCS)]2+ can be determined first by measuring the absorbance of a
solution of the complex of known concentration (such a solution can be prepared by
mixing a known amount of Fe3+ with a large excess of NCS-, so that all the Fe3+ is
converted to the complex).
 For determining K, a solution of Fe3+ of known concentration [Fe3+]0 is mixed with a
solution of NCS- of known concentration [NCS-lo.

P.RAM KUMAR ASST PROFESSOR DEPARTMENT OF CHEMISTRY

I MSC COORDINATION CHEMISTRY UNIT-III

 The mixture in which the complex [Fe(NCS)]2+ has been formed is equilibrated.
 Its absorbance (A) at 450 nm is measured. Then K is evaluated as indicated below:

A = ϵ l [Fe(NCS)]2+

 Therefore, equilibrium concentration of complex. [Fe(NCS)]2+= A/ ϵ l

[Fe3+]0 = [Fe3+] + [Fe(NCS)]2+
Uncomplexed Fe3+ + Complexed Fe3+
Equilibrium concentration of Fe3+
[Fe3+] = [Fe3+]0 - [Fe(NCS)]2+
[NCS-]0 = [NCS-] + [Fe(NCS)] 2+
Uncomplexed NCS- + Complexed NCS-
Equilibrium concentration of NCS-
[NCS-] = [NCS-]0 - [Fe(NCS)]2+
[𝐹𝑒(𝑁𝐶𝑆)]2+
Therefore 𝐾 = [𝐹𝑒 3+ ][𝑁𝐶𝑆−]

 The experiment is then repeated with three or more different initial Fe3+ and NCS-
concentrations to check the constancy of K.
 This method does not disturb the equilibrium during absorbance measurement and
hence it is a reliable method of evaluating K value.

The Method of Continuous Variation (Job's Method)

 This method is used for solutions where only one complex is formed.

Determination of formula

 If the sum of the total concentrations [C] of a complexing agent [Cx] and metal ion [CM]
is held constant and only their ratio is varied, then
CM + Cx = C
 A wavelength of light is selected such that where the complex absorbs strongly and the
ligand and metal ions do not.
 A plot of the mole fraction of the ligand in the mixture X versus absorbance gives a
triangular-shaped curve (Fig.).
 The mole fraction of the ligand in the mixture X= Cx/C
 The mole fraction of the metal ion in the mixture = CM/C
Cx /C +CM/C = C/C
1-X= CM/C

P.RAM KUMAR ASST PROFESSOR DEPARTMENT OF CHEMISTRY

I MSC COORDINATION CHEMISTRY UNIT-III

Plot of absorbance versus mole fraction of ligand for complex formation.

 The legs of the triangle are extrapolated until they cross. The mole fraction at the point
of this intersection gives the formula of the complex, since at this point, for the complex
MX
n = Cx/CM = X / (1-X)
 At this point, the ligand and metal are in proper relative concentrations to give maximum
complex formation.
 Performing the experiment at several different wavelength and at several different
values of C would indicate whether there is more than one complex formed in solution;
in such cases n would not be constant
 The curve may be observed to deviate somewhat from the experimental interacting lines.
From the amount of this deviation, the stability content of the complex can be
determined.
Determination of stability constant
For a 1:1 complex, the ratio of the true absorbance (A) to the extrapolated absorbance
(Aext) is the mole fraction of the complex actually formed.

where C= total concentration of the metal or ligand concentration at the point.

 K is the stability constant, CM and Cx are total concentration of metal and ligand
respectively

P.RAM KUMAR ASST PROFESSOR DEPARTMENT OF CHEMISTRY

I MSC COORDINATION CHEMISTRY UNIT-III

Bjerrum’s method

 J.Bjerrum determined the stability constants of a number of ammine complexes of

metals by the Electrochemical method.
 The glass electrode is the fundamental component of the common laboratory pH meter
used to determine the activity of H+ in solution.
 The equilibrium studied with glass electrode must involve changes in pH.
 The ammonia concentration in a solution is related to the [H +] by the equilibrium
constant for the acid dissociation of NH 3. In acidic solutions, the [NH4+] is large with
respect to [NH3]

[1]
 The [NH4+] is practically unchanged as the [H+] is increased.

 In acidic solution, glass electrode measures [H+] can also measure ammonia directly.
 The stability constant for Ag+-NH3 system were determined by this technique

 The concentrations of complexed ammonia, uncomplexed ammonia and uncomplexed

Ag+ are obtained by the following method.
 On substituting these values in the above expressions, K 1 and K2 can be evaluated.
 All solutions prepared at 30°C contained small but various concentrations of Ag+ and
NH3, ([Ag+]0, and (NH3]0.
 The pH of each of these solutions is measured. The concentration of uncomplexed
ammonia, [NH3] is calculated using equation [1].

P.RAM KUMAR ASST PROFESSOR DEPARTMENT OF CHEMISTRY

I MSC COORDINATION CHEMISTRY UNIT-III

 These data are recorded at 30°C in the presence of 2M NH4NO3. The average number (n)
of ammonia molecules bound per Ag+ is determined from these experimental data using
the equation given below:

 This plot indicates that at concentrations of free ammonia greater than 10 -2 M.

[Ag(NH3)2]+ is the predominant species
 Whereas at free ammonia concentrations below 10-4 M, Ag+ is the predominant species
in solution.
 The complex [Ag(NH3)2]+ is present only within a small [NH3] range. From these data, K1
and K₂ values are evaluated. However, the calculations are rather tedious.

P.RAM KUMAR ASST PROFESSOR DEPARTMENT OF CHEMISTRY