Lewis Theory
Lewis Theory
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.
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.
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: