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 mol6 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 dm3)-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 (mol6 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 mol4 dm12

[Zn(NH3)4]2+ Kst = 3.8  109 mol4 dm12

[Cu(NH3)4]2+ Kst = 1.1  1013 mol4 dm12

[CuCl4]2+ Kst = 4.2  105 mol4 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 mol6 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 = 6.3102 mol1 dm3

[Cu(H2O)3Cl]+(aq) + Cl(aq) [Cu(H2O)2Cl2](aq) + H2O(l)

K2 = 40 mol1 dm3

[Cu(H2O)2Cl2](aq) + Cl(aq) [Cu(H2O)Cl3](aq) + H2O(l)

K3 = 5.4 mol1 dm3

[Cu(H2O)Cl3](aq) + Cl(aq) [CuCl4]2(aq) + H2O(l)

K1 = 3.1 mol1 dm3

[Cu(H2O)4]2+(aq) + 4Cl(aq) [CuCl4]2(aq) + 4H2O(l)

Kst = K1  K2  K3  K4 = 4.2  105 mol4 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+