Acids and Bases

Acid-base concepts, measuring of acid-base

strength, hard and soft acids and bases.

Professor Dr. Md. Ashraful Islam Molla

Department of Applied Chemistry & Chemical Engineering
Faculty of Engineering and Technology
University of Dhaka, Dhaka–1000
Figure 1: HCl is an Arrhenius acid. NaOH is an Arrhenius base. 2
Limitations of Arrhenius Concept

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 Acidity and Basicity of Molecules
1. Relative order of the acidity of CH4, NH3, H2O and HF molecules.

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 Cady-Esley Concept: General Theory of Solvent System
An acid is a solute that, either by direct association or by reaction with the
solvent, gives the cation characteristic of the solvent.
A base is a solute that either by direct association or by reaction with the
solvent, gives the anion characteristic of the solvent.
If, for example, we consider the solvent H20, its characteristic cation and anion
are H3O+ and OH− respectively as shown below:

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 Usanovich Concept
An acid is any chemical species which is capable of combining with anions or electrons or
giving up cations.
Conversely, a base is any chemical species which is capable of giving up anions or electrons or
combining with cations.
Some examples of acid-base reactions in terms of Usanovich concept are given below:

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 Hard/Soft Acid/Base
Lewis acids and bases can be classified by designating them as hard or soft. Acids and bases
are not strictly hard or soft, since many ions and compounds are classified as
intermediate. The categorizations are based on three factors: (1) charge density, or charge-to-
size ratio (2) polarizability (3) covalent vs. ionic nature of interactions.
Hard Acids/Bases:
In general, hard acids and bases have a high charge density, are not very polarizable, and form
bonding interactions that are more ionic in nature. These atoms and ions tend to have high
charge and/or small radius.
 Typical Hard Acids: Metal ions with high positive charges and smaller ionic sizes tend to be
hard acids. Early transition metal ions in the 3d series tend to be hard Lewis acids.
 Typical Hard Bases: Small anions and neutral molecules; heteroatoms of the second row
of the periodic table are typically hard (N,O,F). Some examples of hard acids and bases
include: H+, O2−, OH−, F−, Fe3+, and Al3+. Oxygen atoms are always hard, and N atoms
are usually hard.

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Soft Acids/Bases: In general, soft acids or bases have a low charge density, are more
polarizable, and form bonds that are more covalent in nature. These atoms/ions tend to have
low charge and/or large radius.
 Typical Soft Acids: Transition metals with (+1) charge (such as Cu+) or that are in the late
4d and 5d series (like Cd2+ and Hg2+), are classified as soft. Soft acids often include
transition metals in the second and third row of the periodic table that have a +1 or +2
charge, as well as late transition metals (especially those in the 4d and 5d series) with
filled or almost completely filled d orbitals.
 Typical Soft Bases: Larger anions and neutral molecules. For example, I− and S2− are soft
bases.
Examples of Hard and Soft Acids and Bases
Acids Bases
H+ NH3, RNH2, N2H4
Li+, Na+, K+ H2O, ROH, R2O
Hard Be2+, Mg2+, Ca2+, VO2+ OH−, F−, Cl−, CH3CO2−
Al3+, Sc3+, Cr3+ CO32−
Ti4+ PO43−
BF3, Al2Cl6, CO2, SO3
Cu+, Ag+, Au+, Tl+, Hg22+ H−
soft
Pd2+, Pt2+, Hg2+ CN−, SCN−, I−, RS−
GaCl3, GaBr3, GaI3 CO, R2S 22
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“HOMO” stands for Highest occupied
molecular orbital while “LUMO” stands
for Least unoccupied molecular orbital.
The HOMO is the highest energy MO that
has any electrons in it. The LUMO is the
next highest energy orbital (it will be
empty). The LUMO is the lowest energy
place to put or excite an electron.
Frontier orbitals are those at the frontier
between occupied and unoccupied. They
are often taken to be the highest energy
occupied and lowest energy unoccupied
molecular orbitals, called the HOMO and
LUMO levels.

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The frontier orbital concept conceptualizes chemical bonding and reactivity in terms of the interactions
between frontier orbitals on the chemical species undergoing an interaction (e.g. molecules, atoms,
ions, or groups as they interact to form a bond or undergo a reaction). Frontier orbitals are those at the
frontier between occupied and unoccupied. They are often taken to be the highest energy occupied
and lowest energy unoccupied molecular orbitals, called the HOMO and LUMO levels.

In particular, the frontier orbital concept envisions a Lewis acid-base interaction as involving an
interaction between some of the frontier orbitals of the Lewis acid and base, specifically the donation of
electrons from the base's HOMO level into the acid's LUMO level. For example, in the frontier orbital
approach, adduct formation between NH3 and BH3 involves the donation of electrons from
ammonia’s a2 HOMO into BH3’s a1 LUMO level.

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Thank You All

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