Define Stability Constant:
The stability constant is the equilibrium constant for the formation of the complex
ion in a solvent from its constituent ions or molecules.
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 expression for Kstab can be deduced in a similar way as the expression for the
equilibrium constant (Kc). 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(𝑵𝑯𝟑)𝟒(𝑯𝟐𝑶)]𝟐+
Kstab =
[𝑪𝒖(𝑯𝟐𝑶)𝟔]𝟐+[𝑵𝑯𝟑]𝟒
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.
If the concentrations of the transition element complex and the reacting
ligands are known, the 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
Worked example
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 /
0.15 0.15 0
mol dm-3
Change in concentration - 0.1.0 -0.10 + 0.10
Equilibrium
0.05 0.05 0.10
concentration / mol dm-3
Step 2: Write the Kstab expression for the reaction:
o Kstab = CuH2O4Cl2 aqCuH2O5Cl+ aq Cl- aq
Step 3: Substitute the equilibrium concentrations into the Kstab expression
and evaluate:
o Kstab = [0.10][0.05] [0.05]
o Kstab = 40
Step 4: Determine the units:
o Kstab = [mol dm-3][mol dm-3] [mol dm-3]
3 -1
o Kstab = dm mol
Answer 2:
The value of Kstab is 40 dm3 mol-1
This is a large value, which suggests:
o The products are favoured
o Therefore, the position of the equilibrium for this step is to the right /
products
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
Worked example
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]–
–
o because the Kstab value for [Ag(CN)2] is the largest value
OR
o [Ag(CN)2]– is the most stable
The lowest concentration will be [Ag(NH3)2]+
+
o because the Kstab value for [Ag(NH3)2] is the smallest value
OR
+
o [Ag(NH3)2] is the least stable
An alternative explanation could be to state that higher Kstab values form a
more stable complex.
