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CIE A Level Chemistry Your notes

28.5 Stability Constants, Kstab

Contents
Stability Constant, Kstab
Effect of Ligand Exchange on Stability Constant

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Stability Constant, Kstab

Your notes
Define & Write a Stability Constant for a Complex
When transition element ions are in aqueous solutions, they will automatically become hydrated
Water molecules will surround the ion and act as ligands by forming dative covalent bonds to the
central metal ion
When there are other potential ligands present in the solution, there is a competing equilibrium in
ligand exchange and the most stable complex will be formed
For example, a Co(II) ion in solution will form a [Co(H2O)6]2+ complex
Adding ammonia results in the stepwise substitution of the water ligands by ammonia ligands until a
stable complex of [Co(NH3)4(H2O)2]2+ is formed
[Cu(H2O)6]2+ + 4NH3 ⇌ [Cu(NH3)4(H2O)2]2+ + 4H2O
For the substitution reaction above, there are four stepwise constants:
[Cu(H2O)6]2+ + NH3 ⇌ [Cu(NH3)(H2O)5]2+ + H2O K1
[Cu(NH3)(H2O)5]2+ + NH3 ⇌ [Cu(NH3)2(H2O)4]2+ + H2O K2
[Cu(NH3)2(H2O)4]2+ + NH3 ⇌ [Cu(NH3)3(H2O)3]2+ + H2O K3
[Cu(NH3)3(H2O)3]2+ + NH3 ⇌ [Cu(NH3)4(H2O)2]2+ + H2O K4
These stepwise constants are summarised in the overall stability constant, Kstab
The stability constant is the equilibrium constant for the formation of the complex ion in a solvent from
its constituent ions or molecules

Expression of Kstab
The expression for Kstab can be deduced in a similar way as the expression for the equilibrium constant
(K c)
For example, the equilibrium expression for the substitution of water ligands by ammonia ligands in the
Co(II) complex is:
[Cu(H2O)6]2+ + 4NH3 ⇌ [Cu(NH3)4(H2O)2]2+ + 4H2O
⎡⎢ Cu (NH ) (H O) ⎤⎥ 2+
⎢⎣ 3 4 2 ⎥
2⎦
Kstab = ⎡
⎢⎢ Cu (H2 O) ⎥⎤⎥ 2+ ⎡⎢⎣ NH 3 ⎤⎥⎦ 4
⎣ 6⎦

The concentration of water is not included in the expression as the water is in excess
Therefore, any water produced in the reaction is negligible compared to the water that is already
present
The units of the Kstab can be deduced from the expression in a similar way to the units of Kc
The stability constants can be used to compare the stability of ligands relative to the aqueous metal
ion where the ligand is water
The larger the Kstab value, the more stable the complex formed is
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Calculations Involving Stability Constants

If the concentrations of the transition element complex and the reacting ligands are known, the Your notes
expression for the stability constant (Kstab) can be used to determine which complex is more stable
The greater the value of Kstab the more stable the complex is

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Worked example
Your notes
The addition of concentrated hydrochloric acid to copper(II) sulfate solution forms an aqueous
solution containing [CuCl4]2– and [Cu(H2O)6]2+ complex ions. The overall ligand exchange involved is a
series of stepwise reactions as successive ligands are replaced.
The second step in exchanging water ligands with chloride ligands is:
[Cu(H2O)5Cl]+ (aq) + Cl– (aq) ⇌ Cu(H2O)4Cl2 (aq) + H2O (l)
When a 0.15 mol dm–3 solution of [Cu(H2O)5Cl]+ (aq) is mixed with 0.15 mol dm–3 hydrochloric acid, the
equilibrium mixture of Cu(H2O)4Cl2 (aq) was found to be 0.10 mol dm–3.
1. Use this data to calculate Kstab for this step. Include the units for Kstab.
2. Use your answer to (1) to suggest the position of the equilibrium for this step. Explain your answer.
Answer 1
Step 1: Calculate the equilibrium concentration of each ion:

[Cu(H2O)5Cl]+ (aq) Cl– (aq) Cu(H2O)4Cl2 (aq)

Initial concentration / mol dm-3 0.15 0.15 0

Change in concentration - 0.1.0 -0.10 + 0.10

Equilibrium concentration / mol dm-3 0.05 0.05 0.10

Step 2: Write the Kstab expression for the reaction:

CuH O Cl aq
Kstab = CuH O Cl2 + 4 aq2 Cl- aq
2 5
Step 3: Substitute the equilibrium concentrations into the Kstab expression and evaluate:
Kstab = [0 . 05]
[0 . 10]
[0 . 05]
Kstab = 40
Step 4: Determine the units:
-3
Kstab = [mol dm [mol dm ]
-3 -3
] [mol dm ]
Kstab = dm mol3 -1
Answer 2:
The value of Kstab is 40 dm3 mol-1
This is a large value, which suggests:
The products are favoured
Therefore, the position of the equilibrium for this step is to the right / products

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Effect of Ligand Exchange on Stability Constant

Your notes
Effect of Ligand Exchange on Stability Constant
The stability constants (Kstab) of ligands are often given on a log10 scale so that it becomes easier to
compare them with each other
Ligand exchange in a complex occurs to form a more stable complex with a larger Kstab
The stability constants can be used to explain the substitution of ligands in a copper complex

Ligand substitution in a Co(II) complex

When excess ammonia is added to the [CoCl4]2- complex a brown solution is obtained
Ligand exchange of the [CoCl4]2- complex by ammonia

The chloride ligands are substituted by the ammonia ligands to form the more stable ammonia complex
The formation of the ammonia complex could be explained by comparing the stability of the chloride
and ammonia ligands
Stability of chloride and ammonia ligands table

Ligand Stability (log10 Kstab)

Cl– 5.6

NH3 13.1

The stability constant of the ammonia ligand is greater than that of the chloride ligands
The brown ammonia complex is therefore more stable
As a result, the position of the equilibrium is shifted to the right

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Worked example
Your notes
The numerical values for the stability constants, Kstab, of three silver(I) complexes are given.

Silver(I) complex Numerical value of Kstab

[Ag(S2O3)2]3– 2.9 x 1013

[Ag(CN)2]– 5.3 x 1018

[Ag(NH3)2]+ 1.6 x 107

An aqueous solution of Ag+ is added to a solution containing equal concentrations of S2O32– (aq), CN–
(aq) and NH3 (aq). The mixture is left to reach equilibrium.
Deduce the relative concentrations of [Ag(S2O3)2]3–, [Ag(CN)2]– and [Ag(NH3)2]+ present in the
equilibrium mixture. Explain your answer.
Answer
The highest concentration will be [Ag(CN)2]–
This is because the Kstab value for [Ag(CN)2]– is the largest value
OR
[Ag(CN)2]– is the most stable
The lowest concentration will be [Ag(NH3)2]+
This is because the Kstab value for [Ag(NH3)2]+ is the smallest value
OR
[Ag(NH3)2]+ is the least stable
An alternative explanation could be to state that higher Kstab values form a more stable complex

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