HARD SOFT ACID BASE (HSAB)

THEORY

INTRODUCTION:
The hard soft acid base theory known as HSAB theory is very important in our
modern chemistry. Its also known as the Pearson acid base concept. HSAB is
widely used in chemistry for explaining stability of compounds, reaction
mechanisms and pathways. It assigns the terms hard or soft and acid or
base to chemical species. Hard applies to species which are small, have high
charge states and are weakly polarizable. Soft applies to species which are big,
have low charge states are strongly polarizable.

DEFINITION OF HSAB:
Hard acids: These are metals having low electro negativity values usually 0.7
to 1.6.Exception is H+ ion which is also a hard acid on the basis of very small
size. Similarly ions such as B+3,C+4 are hard acids because of very small size and
high charge.
Hard bases: Donor atoms of very high electro negativity values such as oxygen
and fluorine. The
The gist of HSAB theory is that soft acids react faster and form stronger bonds
with soft bases, where hard acids react faster and form stronger bonds with
hard bases, all other factors being equal. The classification in the original
work was mostly based on equilibrium constants for reaction of two Lewis
bases competing a Lewis acid.
The basic premise of Hard/Soft Acid/Base Theory is very simple: Hard acids
prefer hard bases; soft prefer soft bases. We must define these terms.

CHARACTERS OF HARD ACIDS:

1.
2.
3.
4.
5.

Relatively small atomic/ionic size;

Relatively high charge ( >3+);
High oxidation state;
Low polarizability;
Low electro negativity of the acidic atom. A value in the range 0.1-1.6 is
typical of hard acids.

High charge often results in small size, because the remaining electrons are
contracted toward the nucleus by the substantial excess positive charge.
Examples: the metal cat ions from the s and f blocks, the higher-charged ions
from the left side of the d block. Na+, Mg2+, Fe3+, and Al3+ are examples of hard
acids.
CHARACTERS OF HARD BASES:
1.
2.
3.
4.

Relatively small size of the donor atom;

Very high electro negativity of the donor atom (in the range 3.4 4.0);
High oxidation state;
Low polarizability;

The combination of high electro negativity and small size results in a

nonpolarizable electron cloud surrounding the donor atom. The only 2 donor
atoms with electro negativities in the specified range are oxygen and fluorine.
So the hard bases are those in which the donor atom is either O or F.
Examples: OH, F, Cl, NH3, CH3COO, CO32. are examples of hard bases.
CHARACTERS OF SOFT ACIDS:
1.
2.
3.
4.
5.

Large atomic/ionic size;

Low or zero oxidation state;
high polarizability;
Low charge (1+, 2+);
Intermediate to high electro negativity (1.9-2.5)

Species of large size generally have many electrons, some of which can be
quite far from the nucleus. The low charge of the species results in a
polarizable (distortable) electron cloud.
Examples: Cu+, Hg2+, Au+, Ag+, and Pb2+. are example of soft acids.
CHARACTERS OF SOFT BASES:
1. Large size, leading to polarizability;
2. Low oxidation state;
3. Intermediate to high electro negativity (2.1-3.0).
Examples: S2-, PEt3, RSe-, I-, and Br-. are examples of soft bases. These fall in
groups 15-17 in periods with n>3.

Table: Hard and Soft acids and bases

ACIDS
hard

BASES
soft

hard

soft

Hydronium H
Alkali
metals
Titanium
Chromium
Boron
trifluoride

CH3Hg ,
Mercury Hg2+,
Hydroxide OHHg22+

Hydride

H-

Li+,Na+,K+ Platinum Pt2+

Alkoxide

RO-

Thiolate

RS-

Ti4+
Cr3+,Cr6+

Palladium Pd2+
Silver
Ag+

Halogens
Ammonia

F-,ClNH3

Halogens
Phosphine

IPR3

BF3

borane

Carboxylate CH3COO- Thiocyanate SCN-

Carbocation R3C+

BH3

Pchloranil
bulk
M0
Metals
Gold
Au+

Carbonate

CO32-

Hydrazine N2H4

carbon
monoxide

CO

Benzene

C6H6

In addition to the fundamental hard and soft categories, two additional

categories are useful. Borderline acids are intermediate between hard and soft

acids. Thus they tend to have lower charge and somewhat larger size than hard
acids, and higher charge and somewhat smaller size than soft acids. The 2+ ions
of d block, such as Fe2+, Cu2+, Ni2+, and Zn2+ are borderline acids. Borderline
bases are intermediate between hard and soft bases. Bases in which the donor
atom is N or Cl fall in this category. Thus NH3, Cl-, RCl and pyridine are
borderline bases.

REFINEMENTS OF HSAB THEORY:

FACTORS INFLUENCING HARDNESS/SOFTNESS:
According to the HSAB theory- hard acids prefer hard bases; soft acids prefer
soft bases. There are some refinements to this principle.
1. There are degrees of hardness and softness. Hardness/softness of acids
is affected by several factors. First, the nature of the acceptor atom.
Thus Au+ > Hg2+ > Pb2+ in softness. Hardness increases with distance
from gold. Second, the charge: hardness increases with increasing
charge. For example, Tl3+ is harder than Tl+ . Third, the attached
groups: Attaching soft substituents (bases) to an acceptor atom
increases the softness of the acceptor atom; attaching hard bases
increases the hardness of the acceptor atom.
2. Stronger acids prefer stronger bases. This often complicates
application of the HSAB guidelines. Strengths of acids and bases can
take precedence over hard/soft rules, particularly in cases where only
one soft species is present. For example, Bronsted-Lowry acid base
reactions always involve a hard acid (H+) and mostly hard bases (e.g.,
H2O, OH-) so are not predictable using HSAB.

APPLICATIONS OF HSAB THEORY:

1)
PREDICTING THE PRODUCTS: HSAB theory is useful in
predicting the products of metathesis reactions. Quite recently it has been
shown that even the sensitivity and performance of explosive materials can be
explained on basis of HSAB theory.
2) QUALITATIVE ANALYSIS: The HSAB theory is used in contexts where
a qualitative, rather than quantitative description would help in understanding
the predominant factors which drive chemical properties and reactions.
3) REDUCTION POTENTIALS: The electron has been termed the ultimate
soft base. Viewing electron in these terms, standard reduction potential can be
understood in terms of HSAB theory.
4) GEOCHEMISTRY OF THE ELEMENTS: In nature, hard acids are
found associated with hard bases, and soft acids are found associated with soft
bases. Thus hard acids tend to occur as oxides, silicates, carbonates, and
fluorides, whereas soft acids occur as sulfides, selenides, and tellurides, or as
free elements. Borderline acids often occur as sulfides. Metals found in nature
in combination with the group 16 elements S, Se, and Te are sometimes called
chalcophiles.
5) LIGANDS SELECTING: The HSAB theory is used in transition metal
chemistry, where numerous experiments have been done to determine the
relative ordering of ligands and transition metal ions in terms of their hardness
and softness.
6)TOXICOLOGY AND MEDICINAL CHEMISTRY: Ions of many socalled heavy metals, such as Hg2+ and Pb2+, are highly toxic. Heavy metal ions
are soft acids, and therefore have high affinity for S2-, a soft base. S occurs in
the side chains of two amino acids, methionine and cystine, and is important in
maintaining tertiary structure of proteins and enzymes upon which life depends.
Ingested heavy metal ion seeks out and coordinates with amino acid sulfur,
disrupting protein structure and deactivating the protein. Eventual death is the
usual result of prolonged exposure to heavy metal ions.

7) KORNBLUMS RULE: An application of HSAB theory is the so-called

KORNBLUMS rule which states that in reactions with ambident
nucleophiles, the more electronegative atom reacts when the reaction
mechanism is SN1 and the less electronegative one in a SN2 reaction. This rule
actually predates HSAB theory but in HSAB terms its explanation is that in
a SN1 reaction the carbocation ( a hard acids ) reacts with a hard base and
that in a SN2 reaction tetravalent carbon ( a soft base ) reacts with soft bases.

The End