HARD AND SOFT ACIDS AND BASES

Reactions of different metals with a ligand

Mn2+

nL

[MLn]

Generally stability of the complexes increases in the order

Ba2+ < Sr2+ < Ca2+ < Mg2+ < Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ >Zn2+

The order is partly due to ligand field effects and partly due to decrease in size across
the series.

Certain ligands form their most stable complexes with alkali metals, alkaline earth
metals and metals in high oxidation states such as Ti 4+, Cr3+, Fe3+ Co3+, and Al3+ as
well as H+, all of which are called class a metal ions
Other ligands prefer heavier metal ions in low oxidation states like Cu +, Ag+, Hg+,
Hg2+, Pd2+ and Pt2+ and are referred to as class b metal ions

Ligands Classification

Class a ligands- those with tendency to form more stable complexes with class a
metal ions
Class b ligands- those with tendency to form more stable complexes with class b
metal ions

Stability of different ligands to form complexes with a particular metal ion may be
summarised as follows:

Tendency to complex with class a metal ions:

N > P > As > Sb

O >> S > Se > Te
F > Cl > Br > I

Tendency to complex with class b metal ions

N << P < As < Sb

O << S < Se ~ Te
F < Cl < Br < I

Order is based on the constant K by which they bond with the metal complex.

e. g. phosphines (PR3) and thioethers (SR2) are class b as they coordinate more easily
with ions like Hg2+, Pd2+ and Pt2+.

Ligands like ammonia, amines, water and fluoride ions form stable complexes with class a
metal ions like Be2+, Ti4+ and Co3+ and are class a ligands

Pearsons Principle: Hard acids prefer to bind to hard bases and soft acids to soft
bases.

Hard acids class a metal ions

Hard bases - class a ligands

Soft acids - class b metal ions

Soft bases class b ligands

Consider the reaction

BH+

+ CH3Hg+

CH3Hg+ + H+

Where B is a base
There is competition for B between the soft acid CH3Hg+ and the hard acid H+. Addition of
the hard base will drive the eqbm to the left while a soft base will push it to the right.

Classification of hard or soft is relative, e.g.

Cs+ is softer than Li+ (class a)

N is softer than O (class a)
Se is softer than S (class b)
Pyridine (py) is much softer than NH3 such that py is considered borderline

Acid Base Strength and Hardness and Softness

In competitive reactions, it is possible for a strong acid or base to displace a weaker acid
or base even though this appears to violate the principle of hard and soft acids and
bases.
Examples include:

SO32- +
softer
base

HF

HSO3- + F-

Keq = 1014

hard-hard

SO32- is stronger Lowry-Bronsted base than F-

OH- + [CH3HgSO3]hard
base

CH3HgOH + SO32-

Keq = 10

soft-soft

There are cases where the hardness-softness dominate, e.g.

CH3HgF+
soft-hard

HSO3hard-soft

[CH3HgSO3]- +
soft - soft

HF Keq~ 103
hard-hard

Symbiosis of Hardness with softness

R2SBF3

+ R2O
hard

R2OBH3

R 2S
soft

R2OBF3
soft

R2SBH3
hard

R2S

R2O

The hardness or softness of an atom can be influenced by other atoms bonded to it. In the
above case, the boron atom in BF3 is harder than the boron in BH3 because F- is hard
whereas H- is soft

Electronegativity and Hardness and Softness

Generally:

The more electronegative the species, the harder the species.

The lower the electronegativity of the species, the softer the species

Note that Li and \H may not be very electronegative but the cations Li + and H+, because of
their small sizes, have relatively high electronegativities, thus hardness decrease down the
groups

O > S > Se > Te

F . Cl > Br > I

Also hardness increase from left to right across the periodic table:

F>O>N>C

Theoretical Basis of Hardness and softness

Attempts have been made to explain hardness and softness in terms of ionic and covalent
bonding using Drago-Wayland equation:

-H = EAEB

CACB

Where H is enthalpy of the reaction

EAEB is enthalpy change associated with ionic bonding
CACB is enthalpy change associated with covalent bonding
EA, CA is parameters associated with the acid
EB, CB is parameters associated with the base

According to the equation

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EAEB term dominates when hard acid- hard base interactions are involved
CACB dominate when soft acid-soft base interactions are involved.

Thus an acid that is highly charged and small is expected to form a more stable bond with
a base that is highly electronegative. Similarly, Lewis acids that are large and of low
charge tend to favour covalent bonding with soft bases.

Summary
Hard prefers hard
Soft prefers soft
Hard acids are highly charged and small
Hard bases are highly electronegative
Soft acids and soft bases are more polarisable than hard acids and bases
Soft acids and bases are larger in size
Soft acids and bases tend to form bonds that are more covalent.

Acids and Base Conceipts

Arrhenius Definition:
An Arrhenius acid is a substance that when added to water increases the
concentration of H1+ ions present. The chemical formulas of Arrhenius
acids are written with the acidic hydrogens first. HCl is an example of an
Arrhenius acid

An Arrhenius base is a substance that when added to water increases the

concentration of OH1- ions present. NaOH is an example of an Arrhenius
base.

Arrhenius acids are frequently referred to as proton donors, hydrogen

ion donors, or hydronium ion donors, depending on whether we are trying
to emphasize the species liberated by the acid (proton or hydrogen ion)
or the species present in solution (hydronium ion). To represent the
transfer of the H1+ ion to water to form the hydronium ion, we must
include H2O in the chemical equation for acid ionization.

Bronsted-Lowry Definition:
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Acid is substance that can donate a hydrogen ion is often referred to as proton
donor
The Brnsted base is defined as any substance that can accept a hydrogen ion i.e.
proton acceptor.
Acid
HCl

Base
+

NaHCO3

Salt
H2CO3

NaCl

Lux-Flood Definition:

Acid is an oxide O2- acceptor

Base is an oxide O2- donor
Definition limited to high temperature melts of oxides.
e.g
CaO

SiO2 CaSiO3

Also acid defined as an acidic anhydride and base also as a basic anhydride
H2SiO3 SiO2 + H2O
Ca(OH)2 CaSiO3 + H2O

Lewis Acid Definition:

A Lewis acid is defined as the reactant in a chemical reaction that accepts an electron pair
from another reactant.
A Lewis base is defined as the reactant in a chemical reaction that donates an electron
pair to another reactant.
The definition covers Lowry-Bronsted and Lux-Flood conceipts as well as all reactions in
which no ions are formed and no hydrogen ions or other ions are transferred.

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Usanovichs Definition:
Acid- any chemical species which reacts with bases, gives up cations, or accepts anions or
electrons
Base- any chemical species which reacts with acids, gives up anions (e.g CaO as Ca2+ + O2where Ca2+ is a spectator ion) or electrons, or combines with cations.

Generally:
An acid is defined in terms of donating a reactive positive species( such as H + or any other
cation) or accepting a negative species such as O 2-, a pair of electrons, an electron etc).
A base is defined in terms of donating a reactive negative species (such as a pair of
electrons, O2-, solvent anion) or accepting a positive species ( e.g. H + , metal ion).

Solvent System Definition:

In the solvent system, an acid is defined as a species that increases the concentration of
the characteristic cation of the solvent and a base as a species that increases the
concentration of the characteristic anion.

Na2O + H2O 2OH- + 2Na+

OH- is the characteristic anion hence Na2O is the base, H2O is the acid

Theory based on autoionisation of solvents

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In Protic systems

2H2O H3O+ (hydronium) + OH- (hydroxide)

2NH3 NH4+ (ammonium) + NH2 (amide
In aprotic systems
N2O4 NO+ (nitrosonium) + NO3 (nitrate)
2SbCl3 SbCl2+ (dichloroantimonium) + SbCl4- (tetrachloroantimonate)
Kw = [H3O+][OH-]
K AB = [A][B] where A is the acid and B is the base

Solvent Levelling

The extent to which a dissolved substance can act as an acid or base depends
largely on the solvent. The substance for example only shows acidic properties if
its proton donating properties exceeds those of the solvent.

HF will be forced to accept protons from the stronger proton donor, HClO 4 . HF
thus will act as a base. Similarly, HNO3 is forced to accept protons from HClO4 and
liquid HF as solvents.

In Aqueous solutions, the mineral acids all donate protons to water (water has a
weaker tendency to donate protons)
HA + H2O H3O+ + AWater has a leveling effect on all stronger acids
Strong acids, less strong and weak acids in water all react completely with ammonia
forming NH4+ in liquid ammonia as a solvent.

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Strong acids
HClO4 + NH3 NH4+ + ClO4HNO3 + NH3 NH4+ + NO3-

Less strong acid

H2SO4 + 2NH3 NH4+ + SO42-

Weak
COOH + NH3 NH4+ + COO-

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Types of solvents
Protic solvents: Solvent with dissociable hydrogen e.g water, ammonia, sulfuric acid
Non-Polar Aprotic Solvents: Solvents which do not autoionize e.g. CCl4, and
cyclohexane etc.
Polar aprotic solvents: solvents which do not autoionize. These solvents generally
have high dielectric constants and high polarity. This class of solvents are good
electron donors reacting with a number of Lewis acids.
e.g. dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dioxane and
hexamethylphosphorotriamide.

CoCl2 + 6DMSO [Co(DMSO)6]Cl2

SbCl5 + CH3CN CH3CNSbCl5

They can also behave as acceptor solvents e.g.

PPh3CCl + SO2 Ph3C+ + SO2Cl-

Solvent properties are determined by three factors

(i)

Polarity- e.g diethyl ether has polarity 4.3

(ii)

Donor number (DN)- a measure of the basicity or donor ability of the

solvent. It is the negative of the reaction enthalpy for the formation
of a complex between the solvent and a reference acid. Consider the
reaction:
SbCl5 + :B Cl5Sb_B

H
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DN is negative H, i.e -H. The higher the value of DN, the stronger
the Lewis base
(iii)

Acceptor number (AN)- a measure of the solvent acidity, also a

measure of electrophilic behavior of the solvent.

Solvent
Nitromethane
Acetone
THF
DMSO
Pyridine

DN
2.70
17.0
20.0
29.8
33.1

AN
12.5
8.0
19.3
14.2

Highly Polar Aprotic Solvents: They are usually highly reactive. They can react
with water, silica containers (glass), or dissolve electrodes of gold and platinum
Examples of highly polar aprotic and autoionising solvents include;
(i)

Bromine trifluoride, BrF3

(ii)

Phosphorous oxychloride, OPCl3

(iii)

The dielectric constant of a solvent is a relative measure of its polarity. For

example, water (very polar) has a dielectric constant of 80.10 at 20 C while nhexane (very non-polar) has a dielectric constant of 1.89 at 20 C.[11] This
information is of great value when designing separation, sample preparation and
chromatography techniques in analytical chemistry.

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