Displacement of Ligands and Relative Stability
of Complex Ions
Stronger ligand
[Fe(H2O)6]2+(aq) + 6CN–(aq)
Hexaaquairon(II) ion
Weaker ligand
[Fe(CN)6]4–(aq) + 6H2O(l)
Hexacyanoferrate(II) ion
Reversible reaction Kst 1024 mol6 dm18
Equilibrium position lies to the right
Stronger ligand
[Ni(H2O)6]2+(aq) + 6NH3(aq)
Hexaaquanickel(II) ion
Weaker ligand
[Ni(NH3)6]2+(aq) + 6H2O(l)
Hexaamminenickel(II) ion
The greater the equilibrium constant,
the stronger is the ligand on the LHS and
the more stable is the complex on the RHS
The equilibrium constant is called the
stability constant, Kst
Spectrochemical Series
• A partial spectrochemical series listing of ligands from small
Δ to large Δ is given below.
• I− < Br− < S2− < SCN− < Cl− < NO3− < N3− < F− < OH− < C2O42− ≈
H2O < NCS− < CH3CN < py (pyridine) < NH3 < en
(ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-
phenanthroline) < NO2− < PPh3 < CN− ≈ CO
Consider the general equilibrium system below,
[M(H2O)x]m+ + xLn [M(L)x](m-xn)+ + xH2O
[[M(L)x ] ]
(m xn)
Kst Units = (mol dm3)-x
[[M(H2O)x ] ][L ]
m n x
Kst measures the stability of the complex, [M(L)x](m-xn)+,
relative to the aqua complex, [M(H2O)x]m+
monodentate
bidentate
multidentate
Relative strength of some ligands
TAS Expt 6 bonding with copper(II) ions
Equilibrium Kst ((mol dm–3)–n)
[Cu(H2O)4]2+(aq) + 4Cl–(aq) 4.2 × 105
[CuCl4]2–(aq) + 4H2O(l)
[Cu(H2O)4]2+(aq) + 4NH3(aq) 1.1 × 1013
[Cu(NH3)4]2+(aq) + 4H2O(l)
[Cu(H2O)4]2+(aq) + 2H2NCH2CH2NH2(aq) 1.0 × 1018.7
[Cu(H2NCH2CH2NH2)2]2+(aq) + 4H2O(l)
[Cu(H2O)4]2+(aq) + EDTA4–(aq) 1.0 × 1018.8
[CuEDTA]2–(aq) + 4H2O(l)
What is the Kst of the formation of [Cu(H2O)4]2+(aq) ?
[Cu(H2O)4]2+ + 4H2O [Cu(H2O)4]2+ + 4H2O
[[Cu(H2O)4 ]2 ]
Kst 1
[[Cu(H2O)4 ] ]
2
Factors affecting the stability of complexes
1. The charge density of the central ion
Equilibrium Kst (mol6 dm18)
[Co(H2O)6]2+(aq) + 6NH3(aq) 7.7 × 104
[Co(NH3)6]2+(aq) + 6H2O(l)
[Co(H2O)6]3+(aq) + 6NH3(aq) 4.5 × 1033
[Co(NH3)6]3+(aq) + 6H2O(l)
[Fe(H2O)6]2+(aq) + 6CN–(aq) ≈ 1024
[Fe(CN)6]4–(aq) + 6H2O(l)
[Fe(H2O)6]3+(aq) + 6CN–(aq) ≈ 1031
[Fe(CN)6]3–(aq) + 6H2O(l)
Factors affecting the stability of complexes
2. The nature of ligands
Ability to form complex : -
CN > NH3 > Cl > H2O
[Zn(CN)4]2 Kst = 5 1016 mol4 dm12
[Zn(NH3)4]2+ Kst = 3.8 109 mol4 dm12
[Cu(NH3)4]2+ Kst = 1.1 1013 mol4 dm12
[CuCl4]2+ Kst = 4.2 105 mol4 dm12
Factors affecting the stability of complexes
3. The pH of the solution
In acidic solution, the ligands are protonated
lone pairs are not available
the complex decomposes
[Cu(NH3)4]2+(aq) + 4H2O(l) [Cu(H2O)4]2+(aq) + 4NH3(aq)
H+(aq)
Equilibrium position shifts to the right NH4+(aq)
Consider the stability constants of the following silver
complexes:
Ag+(aq) + 2Cl–(aq) [AgCl2]–(aq)
Kst = 1.1 × 105 mol–2 dm6
Ag+(aq) + 2NH3(aq) [Ag(NH3)2]+(aq)
Kst = 1.6 × 107 mol–2 dm6
Ag+(aq) + 2CN–(aq) [Ag(CN)2]–(aq)
Kst = 1.0 × 1021 mol–2 dm6
What will be formed when CN–(aq) is added to a
solution of [Ag(NH3)2]+?
[Ag(CN)2](aq) and NH3
Consider the stability constants of the following silver
complexes:
Ag+(aq) + 2Cl–(aq) [AgCl2]–(aq)
Kst = 1.1 × 105 mol–2 dm6
Ag+(aq) + 2NH3(aq) [Ag(NH3)2]+(aq)
Kst = 1.6 × 107 mol–2 dm6
Ag+(aq) + 2CN–(aq) [Ag(CN)2]–(aq)
Kst = 1.0 × 1021 mol–2 dm6
What will be formed when NH3(aq) is added to a solution
of [Ag(CN)2]–?
No apparent reaction
FeSO4(aq) is used as the antidote for cyanide poisoning
[Fe(H2O)6]2+(aq) + 6CN(aq) [Fe(CN)6]4 + 6H2O(l)
Kst 1 1024 mol6 dm18 Very stable
Only free CN is poisonous
Why is Fe2(SO4)3(aq) not used as the antidote ?
Fe3+(aq) is too acidic.
[Fe(H2O)6]3+(aq) + H2O(l)
[Fe(H2O)5OH]2+(aq) + H3O+(aq)
[Cu(H2O)4]2+(aq) + Cl(aq) [Cu(H2O)3Cl]+(aq) + H2O(l)
K1 = 6.3102 mol1 dm3
[Cu(H2O)3Cl]+(aq) + Cl(aq) [Cu(H2O)2Cl2](aq) + H2O(l)
K2 = 40 mol1 dm3
[Cu(H2O)2Cl2](aq) + Cl(aq) [Cu(H2O)Cl3](aq) + H2O(l)
K3 = 5.4 mol1 dm3
[Cu(H2O)Cl3](aq) + Cl(aq) [CuCl4]2(aq) + H2O(l)
K1 = 3.1 mol1 dm3
[Cu(H2O)4]2+(aq) + 4Cl(aq) [CuCl4]2(aq) + 4H2O(l)
Kst = K1 K2 K3 K4 = 4.2 105 mol4 dm12
K1 > K2 > K3 > K4
Reasons :
1. Statistical effect
On successive displacement, less water
ligands are available to be displaced.
K1 > K2 > K3 > K4
Reasons :
2. Charge effect
On successive displacement, the Cl
experiences more repulsion from the
complex
[Cu(H2O)4]2+ Cl attraction
[Cu(H2O)Cl3] Cl repulsion
Colours of some copper(II) complexes
Colour of the
Formula of copper(II) complex
complex
[Cu(H2O)4]2+ Pale blue
[CuCl4]2– Yellow
[Cu(NH3)4]2+ Deep blue
[Cu(H2NCH2CH2NH2)]2+ Violet
[Cu(EDTA)]2– Sky blue
The displacement of ligands are usually
accompanied with easily observable colour changes
Coloured Ions
The colours of many gemstones are due to the
presence of small quantities of d-block metal ions
Coloured Ions
• Most of the d-block metals
form coloured compounds
due to the presence of the
incompletely filled d orbitals in the
d-block metal ions
Which aqueous transition metal ion(s) is/are
not coloured ?
3d10 : Zn2+, Cu+; 3d0 : Sc3+, Ti4+
