Hard-Soft Acid-Base (HSAB) Theory

Classifying Lewis acids and bases into:

(i) Hard acid

(ii) Soft acid

Ralph G. Pearson (iii) Hard base

(iv) Soft base

Hard acids (hard metal ions) form more stable

complexes with hard bases (hard ligands), while soft
acids (soft metal ions) shows a preference for soft
bases (soft ligands)
 e.g.
AgF(s) + H2O → Ag+(aq) + F-(aq) Ksp = 205

AgCl(s) + H2O → Ag+(aq) + Cl-(aq) Ksp = 1.8x10-10

AgBr(s) + H2O → Ag+(aq) + Br-(aq) Ksp = 5.2x10-13

AgI(s) + H2O → Ag+(aq) + I-(aq) Ksp = 8.3x10-17

Ksp = solubility product

Reasons: different solvation energy of the anions

Interaction with Ag+: I > Br > Cl > F
Lithium halides have solubilities roughly in
the reverse order: LiBr > LiCl > LiI > LiF
LiI is out of order, probably because of the poor soublity of the
large iodide ion but it is still 100 times more soluble than LiF

Strong interactions in Li-F overcome

the solvation of water
•These interactions between cations and anions can
be expressed in term of hard and soft acids and bases
(HSAB)

•Electrons in polarizable molecules/ions can be

attracted or repelled by charges on other molecules

•Hard acids and bases are small and nonpolarizable

•Soft acids and bases are larger and more polarizable

•Interactions btw 2 hard or 2 soft species are stronger

than those btw 1 hard and 1 soft species
Characteristic Properties of Hard and Soft Acids and Bases

Properties Hard Soft Soft Hard

acids acids bases bases
Electronegativity 0.7 -1.6 1.9-2.5 2.1 – 3.0 3.4 – 4.0

Ionic radius (pm) <90 >90 >170 ~120

Ionic Charges ≥ +3 ≤ +2
 Explanation for HSAB Principle
•Large difference in electronegativity btw hard acids and
hard bases – strong ionic bonds

•Soft acids and bases have similar electrongeativity –

favors covalent bonds (the large size and low charge of
the atoms, although not favorable for covalent bonding,
are even less favorable for ionic bonding)

•Soft acid-hard base or hard acid-soft base

combinations – the relative electronegativity and ionic
sizes are not optimal for either ionic or covalent
bonding. The bonding is polar covalent.

•Polar covalent compounds tend to be reactive if they

can react to give an ionic product and a covalent
product.
e.g.

R
Polar covalent ionic
O
R R2 C O- MgBr
covalent
+ CH3
H 3C Mg Br
Polar covalent
Hard acids Borderline Soft acids
Acids
H+, Li+, Na+, K+, B(CH3)3, BH3, Tl+,
Be2+, Mg2+, Ca2+, Fe2+, Co2+, Ni2+, Tl(CH3)3,
Sr2+, BF3, B(OR)3, Cu2+, Zn2+, Rh3+, Cu+, Ag+, Au+,
Al3+, Al(CH3)3, Ir3+, Ru3+, Os2+, Cd2+, Hg22+,
AlCl3, AlH3, Cr3+, Hg2+, CH3Hg+,
Mn2+, Fe3+, Co3+ Pd2+, Pt2+, Br2, I2
Ga3+, Sc3+ , In3+,
Sc3+,
Ions with Metals with zero
oxidation state of oxidation state
4 or higher i.e.
Ti4+, Zr4+,
Hard bases Borderline Soft bases
bases
F-, H2O, OH-, O2-, Cl-, Br-, NO2-, N32-, H-, I-, H2S, HS-,
ROH, RO-, R2O, SO32-, C6H5NH2, S2-, RSH, RS-,
CH3COO-, NO3-, C5H5N, N2 R2S, CN-, RCN,
ClO4-, CO32-, CO, S2O32-,
SO42-, PO43-, PR3, P(OR)3,
NH3, RNH2, N2H4 AsR3
Predict whether reactants or products
are favored in the following equlibirum

Nb2S5 + 5 HgO Nb2O2 + 5 HgS

Consider a reaction in which both Lewis acids are soft
and both Lewis bases are soft

CdSe + HgS CdS + HgSe

HSAB principle can be used to predict the position of

the equilibrium because it is possible to assign
relative softness to different soft acids and bases

Less soft acids tend to combine with less

soft bases; softer acids prefer softer bases