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Hard and Soft Acids and Bases (Hsab)

The document discusses Pearson's classification of Lewis acids and bases as either hard or soft. Hard acids and bases are small and less polarizable, preferring to combine with other hard species. Soft acids and bases are larger and more easily polarizable, preferring soft binding partners. Pearson suggested that hard acids bind most stably to hard bases, and soft acids to soft bases. Examples of applications include explaining the relative strengths of hydracids and the stability of complexes in aqueous solutions. However, the hard/soft distinction is a generalization and does not provide a quantitative scale of acid/base strengths.

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55 views5 pages

Hard and Soft Acids and Bases (Hsab)

The document discusses Pearson's classification of Lewis acids and bases as either hard or soft. Hard acids and bases are small and less polarizable, preferring to combine with other hard species. Soft acids and bases are larger and more easily polarizable, preferring soft binding partners. Pearson suggested that hard acids bind most stably to hard bases, and soft acids to soft bases. Examples of applications include explaining the relative strengths of hydracids and the stability of complexes in aqueous solutions. However, the hard/soft distinction is a generalization and does not provide a quantitative scale of acid/base strengths.

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nolimitsjustfashion
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HARD AND SOFT ACIDS AND BASES (HSAB)

Pearson’s classification of Lewis acids and Lewis bases into hard and soft acids
and bases.

R. G. Pearson (1963) has classified the Lewis acids and Lewis bases as hard

and soft acids and bases. R. G. Pearson extended and generalized the

qualitative correlation between Lewis acids and Lewis bases by classifying

them into two categories Hard and Soft.

The class –‘a’ metals which are small and less polarizable, prefer to

combine with non- metals or ligands which are also small and not very

polarizable , pearson called such metals as Hard Acids and the corresponding

ligands as soft Bases.

Similarly the class ‘b’metals having large size ,more or easily polarisable,

prefers to combine with non-metals or ligands having similar properties

Pearson called such metals as soft acids and the ligands as soft base The

attempt of classification of acidsand bases as hard and soft by Pearson is

known as Hard and soft Acids and Bases .(HSAB) or pearson’s concept

Principle of Pearson’s concept :

Pearson suggested a simple rule (Sometimes called Pearson’s principle )

for predicting the stability of complexes formed between hard and soft acids

and bases. “Hard acids prefer to bind (co-ordinate) with hard bases and soft

acids prefer to bind with soft bases and gives stable complex compound ”. It

should be noted that the statement given above is not a theory or an

1
explanation but it is simple rule of thumb which enables us to predict the

relative stabilities of acid-bases adducts qualitatively.

Third categories whose characteristics are intermediate between those of hard

and soft acids/bases are called borderline acids/bases.

Hard acids Soft acids


d-orbitals are either vacant or non-existent Nearly full d-orbitals
Smaller in size Larger in size
Not so easily polarizable Easily polarizable
These are mostly light metal ions generally These are mostly heavy metal ions
associated with high positive oxidation state. generally associated with low (or
even zero) positive oxidation state.

Hard Acids Borderline Acids Soft Acids


+ + + + 2+ 2+ 2+ 2+ 2+ 2+ 2+
H , Li , Na , K , Be , Ca , Sr , Fe , Co , Ni , Cu , Cu , Ag+, Au+, Tl+,
+

Mn2+, Al3+, Ga3+, In3+, La3+, Lu3+, Zn2+ Hg+, Pb2+, Cd2+, Pt2+,
Cr3+, Co3+, Fe3+, As3+, Si4+, Ti4+, Pb2+, Sn2+, Sb3+, Bi3+, Hg2+, Pt4+, TI3+, BH3,

2
U4+, Ce3+, Sn4+, VO2+, UO22+, Rh3+, SO2, NO+, GaH3 GaCl3, InCl3, carbenes
3+
MoO3 , BF3  - acceptor ligands
I+, Br+, O, Cl, Br, I, N
Zero valent metal
atoms.

Hard bases Soft bases


Donor atoms having low polarisabilities Donor atoms that can be easily polarized
and high electronegativity and have low electronegativity.

Hard Bases Borderline Bases Soft Bases


H2O, OH , F–, CH3COO–, PO 3–,
–
C6H5NH2, R2S, RSH, RS–, I–, SCN–,
4
– – –
SO42–, 2–
Cl , CO 3, ClO , 4NO , 3
C6H5N, N 3–, NO2, S2O32–, R3P, R3As, CN–,
ROH, RO–, R2O, NH3, NH2, SO32–, N2, Br– RCN, CO, C2H4, C6H6, H–
N2H4

According to HSAB principle, hard acids form stable complexes with hard bases and soft acids with soft
bases.

3
APPLICATIONS OF HSAB PRINCIPLE
With the help of HSAB a large number of chemical reactions can be understood.

1. Relative strength of Hydracids HF,HCL,HBR and HI :

In aqueous solution the relative strength of HF,HCI,HBr and HI can be predicted.

The reaction of acids with water is:

HX+H2O→H 3O++X-
The hardest base F- will be most successfully and strongly bonded to the hard acid H + Hence HF
Will be highly stable.It is therefore least dissocated.Hence acid strength increases as :

HF < HCI < HBr < HI

2. Relative stabilities of complexes in Aqueous Solutions :

HSAB entails that[ Cd(CN )]2- is more


4
stable that [Cd(NH3) ]2+ According to HSAB
4
principle hard

prefers hard and soft prefers soft.Hence the soft acid Cd2+
will prefer to corrdicate soft base CN-It is clear from the Kinst constants where
cyano complex has K = 1.4x10-19 while for ammine complex it is 7.5x10-8 .Thus
inst
cyano is stable.

3. To Predict the Course of Reaction :

i) H+ CH3HgOH→H2O+CH3Hg+

ii) H+ +CH3HgSH→H2S+CH3Hg+

The reaction (i) goes to right as the hard acid H+ binds strongly to hard base OH- to produce stable
product H2O

On the other hand the reaction (ii) is favoured to left where soft base SH will tend to remain
combined with soft acid CH Hg+ instead of joining to hard acid H+
3

4
LIMITATIONS OF HSAB PRINCIPLE

Hard and soft classification is useful concept no doubt but it has some tricky limitations as

pointed out below.

1. The prime limitation f the HSAB concept is that it is widely general and has no any direct

quantitative scale of acid base strength .

2. The inherent acid base strengths are not accounted for e.g.OH- and F- ions are both hard

bases where OH- is nearly 1013 times stronger base than F ions .Correlation between

hardness and inherent acid base strength is yet to be developed.

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