LEWIS THEORY

In 1923 G.N. Lewis suggested another way of looking at the reaction

between H+ and OH- ions. In the Bronsted model, the OH- ion is the active
species in this reaction- it accepts an H+ ion to form a covalent bond. In the
Lewis model, the H+ ion is the active species-it accepts a pair of electrons
from OH- ion to form a covalent bond.

In the Lewis theory of acid-base reactions, bases donate pairs of electrons

and acids accept pairs of electrons. A Lewis acid is therefore any substance,
such as the H+ ion, that can accept a pair of nonbonding electrons. In other
words, a Lewis acid is an electron-pair acceptor. A Lewis base is any
substance, such as the OH- ion, that can donate a pair of nonbonding
electrons. A Lewis base is therefore an electron-pair donor.

One advantage of the Lewis theory is the way it complements the model of
oxidation-reduction reactions. Oxidation-reduction reactions involve a
transfer of electrons from one atom to another, with a net change in the
oxidation number of one or more atoms.

The Lewis theory suggests that acids react with bases to share a pair of
electrons, with no change in the oxidation numbers of any atoms. Many
chemical reactions can be sorted into one or the other of these classes.
Either electrons are transferred from one atom to another, or the atoms
come together to share a pair of electrons.
The principal advantage of the Lewis theory is the way it expands the
number of acids and therefore the number of acid-base reactions. In the

Lewis theory, an acid is any ion or molecule that can accept a pair of
nonbonding valence electrons. In the preceding section, we concluded that
Al3+ ions form bonds to six water molecules to give a complex ion.

Al3+(aq) + 6 H2O(l) Al(H2O)63+(aq)

This is an example of a Lewis acid-base reaction. The Lewis structure of

water suggests that this molecule has nonbonding pairs of valence electrons
and can therefore act as a Lewis base. The electron configuration of the Al3+
ion suggests that this ion has empty 3s, 3p, and 3d orbitals that can be used
to hold pairs of nonbonding electrons donated by neighboring water
molecules.

Al3+ = [Ne] 3s0 3p0 3d0

Thus, the Al(H2O)63+ ion is formed when an Al3+ ion acting as a Lewis acid
picks up six pairs of electrons from neighboring water molecules acting as
Lewis bases to give an acid-base complex, or complex ion.

The Lewis acid-base theroy explains why BF3 reacts with ammonia. BF3 is a
trigonal-planar molecule because electrons can be found in only three
places in the valence shell of the boron atom. As a result, the boron atom is
sp2 hybridized, which leaves an empty 2pz orbital on the boron atom. BF3 can
therefore act as an electron-pair acceptor, or Lewis acid. It can use the
empty 2pz orbital to pick up a pair of nonbonding electrons from a Lewis
base to form a covalent bond. BF3 therefore reacts with Lewis bases such as
NH3 to form acid-base complexes in which all of the atoms have a filled shell
of valence electrons, as shown in the figure below.
 BRØNSTED–LOWRY THEORY
Brønsted–Lowry theory, also called proton theory of acids and bases, a
theory, introduced independently in 1923 by the Danish chemist Johannes
Nicolaus Brønsted and the English chemist Thomas Martin Lowry, stating
that any compound that can transfer a proton to any other compound is an
acid, and the compound that accepts the proton is a base. A proton is a
nuclear particle with a unit positive electrical charge; it is represented by the
symbol H+ because it constitutes the nucleus of a hydrogen atom.

The Brønsted–Lowry theory definition

In order to resolve the various difficulties in the hydrogen–hydroxide ion

definitions of acids and bases, a new, more generalized definition was
proposed in 1923 almost simultaneously by J.M. Brønsted and T.M. Lowry.
Although the pursuit of exact verbal definitions of qualitative concepts is
usually not profitable in physical science, the Brønsted–Lowry definition of
acids and bases has had far-reaching consequences in the understanding of
a wide range of phenomena and in the stimulation of much experimental
work. The definition is as follows: an acid is a species having a tendency to
lose a proton, and a base is a species having a tendency to gain a proton.
The term proton means the species H+ (the nucleus of the hydrogen atom)
rather than the actual hydrogen ions that occur in various solutions; the
definition is thus independent of the solvent. The use of the word species
rather than substance or molecule implies that the terms acid and base are
not restricted to uncharged molecules but apply also to positively or
negatively charged ions. This extension is one of the important features of
the Brønsted–Lowry definition. It can be summarized by the equation A ⇄ B
+ H+, in which A and B together are a conjugate acid–base pair. In such a pair
A must obviously have one more positive charge (or one less negative
charge) than B, but there is no other restriction on the sign or magnitude of
the charges.

Several examples of conjugate acid–base pairs are given in the table.

EXAMPLES OF CONJUGATE ACID-BASE PAIRS

ACIDS BASE
acetic acid, CH3CO2H acetate ion, CH3CO2−
bisulfate ion, HSO4− sulfate ion, SO42−
ammonium ion, NH4+ ammonia, NH3
ammonia, NH3 amide ion, NH2−
water, H2O hydroxide ion, OH−
hydronium (oxonium) ion, H3O+ water, H2O

A number of points about the Brønsted–Lowry definition should be emphasized:

1. As mentioned above, this definition is independent of the solvent. The ions derived
from the solvent (H3O+ and OH− in water and NH4+ and NH2− in liquid ammonia) are not
accorded any special status but appear as examples of acids or bases in terms of the
general definition. On the other hand, of course, they will be particularly important
species for reactions in the solvent to which they relate.
2. In addition to the familiar molecular acids, two classes of ionic acids emerge from the
new definition. The first comprises anions derived from acids containing more than one
acidic hydrogen—e.g., the bisulfate ion (HSO4−) and primary and secondary phosphate
ions (H2PO4− and HPO42−) derived from phosphoric acid (H3PO4). The second and more
interesting class consists of positively charged ions (cations), such as the ammonium ion
(NH4+), which can be derived by the addition of a proton to a molecular base, in this case
ammonia (NH3). The hydronium ion (H3O+), which is the hydrogen ion in aqueous
solution, also belongs to this class. The charge of these ionic acids, of course, always
must be balanced by ions of opposite charges, but these oppositely charged ions usually
are irrelevant to the acid–base properties of the system. For example, if sodium bisulfate
(Na+HSO4−) or ammonium chloride (NH4+Cl−) is used as an acid, the sodium ion (Na+)
and the chloride ion (Cl−) contribute nothing to the acidic properties and could equally
well be replaced by other ions, such as potassium (K+) and perchlorate (ClO4−),
respectively.
3. Molecules such as ammonia and organic amines are bases by virtue of their tendency
to accept a proton. With metallic hydroxides such as sodium hydroxide, on the other

hand, the basic properties are due to the hydroxide ion itself, the sodium ion serving
merely to preserve electrical neutrality. Moreover, not only the hydroxide ion but also the
anions of other weak acids (for example, the acetate ion) must be classed as bases
because of their tendency to reform the acid by accepting a proton. Formally, the anion of
any acid might be regarded as a base, but for the anion of a very strong acid (the chloride
ion, for example) the tendency to accept a proton is so weak that its basic properties are
insignificant and it is inappropriate to describe it as a base. Similarly, all hydrogen
compounds could formally be defined as acids, but in many of them (for example, most
hydrocarbons, such as methane, CH4) the tendency to lose a proton is so small that the
term acid would not normally be applied to them.
4. Some species, including molecules as well as ions, possess both acidic and basic
properties; such materials are said to be amphoteric. Both water and ammonia are
amphoteric, a situation that can be represented by the schemes H3O+–H2O–OH− and
NH4+–NH3–NH2−. Another example is the secondary phosphate ion, HPO42−,
which can either lose or accept a proton, according to the following equations: HPO42− ⇄
PO43− + H+ and HPO42− + H+ ⇄ H2PO4−. The amphoteric properties of water are
particularly important in determining its properties as a solvent for acid–base reactions.
5. The equation A ⇄ B + H+, used in the Brønsted–Lowry definition, does not represent a
reaction that can be observed in practice, since the free proton, H+, can be observed only
in gaseous systems at low pressures. In solution, the proton always is attached to some
other species, commonly a solvent molecule. Thus in water the
ion H3O+ consists of a proton bound to a water molecule. For this reason all observable
acid–base reactions in solution are combined in pairs, with the result that they are of the
form A1 + B2 ⇄ B1 + A2. The fact that the process A ⇄ B + H+ cannot be observed does
not imply any serious inadequacy of the definition. A similar situation exists with the
definitions of oxidizing and reducing agents, which are defined respectively as species
having a tendency to gain or lose electrons, even though one of these reactions never
occurs alone and free electrons are never detected in solution (any more than free protons
are).

According to the Brønsted–Lowry scheme a substance can function as an acid only in the
presence of a base; similarly, a substance can function as a base only in the presence of
an acid. Furthermore, when an acidic substance loses a proton, it forms a base, called the
conjugate base of an acid, and when a basic substance gains a proton, it forms an acid
called the conjugate acid of a base. Thus, the reaction between an acidic substance, such
as hydrochloric acid, and a basic substance, such as ammonia, may be represented by the
equation:

The Brønsted–Lowry theory enlarges the number of compounds considered to be acids

and bases to include not only the neutral molecules (e.g., sulfuric, nitric, and acetic acids,
and the alkali metal hydroxides) but also certain atoms and molecules with positive and
negative electrical charges (cations and anions). The ammonium ion, the hydronium ion,
and some hydrated metal cations are considered acids. The acetate, phosphate, carbonate,
sulfide, and halogen ions are considered bases.