Applications of 'SHAB'

Principle
CHEM-01131
Hard and soft acid-base principle has several important applications, which are as follows:

1. (a) Stability of complexes having same ligand:

Pearson (1963) explained the relative stability of complexes on the basis of hard and soft acid-
base principle. Thus, a complex AB is most stable when both A and B are either hard or soft.

B: + A B→A
Lewis base Lewis acid Complex
(e- pair donor) (e- pair acceptor)

If one of the species is hard and other is soft, the complex formed will not be stable. For example, AgI 2-1, is
stable whereas AgF₂-1 is unstable. This is because AgI2-1, is formed by the combination of Ag+ ion (soft acid)
and I- ion (soft base) whereas AgF₂-1, is formed by the combination of Ag+ ion (soft acid) and F- ion (hard
base):

Ag+ + 2I- AgI2-

soft acid soft base stable

Ag+ + 2F- AgF2-

soft acid hard base unstable
Similarly, [CoF6]-3 ion (Co+3 ion hard acid and F- ion hard base) is stable whereas [CoI6]-3ion (Co+3 ion hard acid and I- ion soft
base) is unstable.

Co+3 + 6F- [CoF6]-3

Hard acid hard base stable

Co+3 + 6I- [CoI6]-3

Hard acid soft base unstable
(b) Stability of complex compounds having different ligands:
If a complex compound has more than one type of ligands attached to central metal ion, its stability is decreased if
one ligand is of different nature as compared to others. For example.
[Co(NH3)5 F]+2 complex is stable whereas [Co(NH3)5 I]+2 complex is unstable. This is because Co +³ is a hard acid. Both
NH3 and F- are hard bases whereas I- is soft base. Therefore, on the basis of hard-soft acid base principle, the former
complex is stable than the later.
[Co(NH3)5 F]+2
Co+³ → hard acid
NH3 →hard base
F- →hard base
 Whereas
[Co(NH3)5 F]+2
Co+³ → hard acid
NH3 →hard base
I- →soft base
2. Prediction of chemical reactions:
The hard and soft acid-base principle predicts the possibility of certain chemical reactions. For example:

CsF + LiI CsI + LiF

(Soft acid (hard acid (soft acid (hard acid
+ + + +
Hard base) soft base) soft base) hard base)

The reaction takes place in the forward direction because soft acid Cs + ion prefers to combine with soft base I - to form
CsI and hard acid Li+ ion prefers to combine with hard base F- ion to form LiF, other examples are:
 BeI2 + HgF2 BeF2 + HgI2
(Hard acid (soft acid (hard acid (soft acid
+ + + +
Soft base) hard base) hard base) soft base)

3. Occurrence of minerals :
The occurrence of minerals in is also according to SHAB principle. The metals such as magnesium, calcium and
aluminum occur in nature as MgCO3, CaCO3, and Al2O3 respectively. This is because acid cations Mg +2, Ca+2, Al+3 and
anions CO3-2, O-2 are all hard. These metals do not occur in nature as sulphides because S -2 ion is a soft base.
On the other hand the metals like silver, mercury are found as sulphides (Ag 2S, HgS) because acid cations Ag+, Hg+2 and
anions S-2 are all soft. The borderline acids such as Ni +2, Cu+2 and Pb+2 occur in nature both as carbonates and sulphides

4. Prediction of nature of bonding in complex ions formed by ambidentate ligands:

The unidentate ligands which can bind to the central metal ion through two donor atoms are called as ambidentate
ligands. For example, in thiocyanate SCN- group both sulphur and nitrogen may act as donor atoms. It co-ordinates
through sulphur atom to form the complex [Pt(SCN) 6]-2 whereas it co-ordinates through nitrogen atom to form
[Co(NCS)6]-3. The reason for this is that Pt+4 ion is a soft acid so it prefers to co-ordinate through the softer sulphur
atom of –SCN-, on the other hand Co+3 is a hard acid so it prefers to co-ordinate through harder nitrogen atom of –
NCS-.
5. Poisoning of metal catalysts:
The soft metals like Pt, Pd, V, Cr, Mo etc. act as catalyst in different chemical reactions. These catalysts are easily
poisoned CO, unsaturated hydrocarbons, organo-phosphine R3P or organo-arsenes R3As (all soft bases). This soft-
soft interaction hinder the catalytic activity of metal atom.
Hard bases do not act as catalytic poisons.
6. Rates of chemical reactions:
The concept of hard and soft acids and bases also related to the rates of chemical reactions. The rates of electrophilic
and nucleophilic reactions depends upon the hardness and softness of the acids and bases.

H+ + CH3HgOH CH3Hg+ + H 2O
fast

H+ + CH3HgSH CH3Hg+ + H 2S
slow
7. Precipitation reactions:
The softer acids like Ag+, Hg+, Hg+2 etc., and border line acids like Fe +2, Ni+2, Cu+2, Zn+2, Pb+2 etc., can be
precipitated as sulfides from their aqueous solutions since S -2 ion is a softer base.

8. The relative strength of halogen acids:

The hard base F- is strongly bonded to the hard acid H+ so HF shall be a highly stable compound. Hence, the
increasing order of acidic strength of halogen acids will be:
HF<HCI <HBr < HI

9.Biological applications:
Chemical-induced toxicity in biological systems has successfully been applied, by soft and hard acids and bases.
Most soft acids and soft bases are harmful to alive organisms. This is because they can combine with soft acids and
soft bases present inside the body. For example:
CO is a soft base that combines with soft acid iron in the hemoglobin and reduces its oxygen-carrying capacity.