Ionic Equilibria

Brönsted–Lowry Theory
According to the Brönsted–Lowry theory, an acid is a substance,
charged or uncharged, that is capable of donating a proton, and a base is a
substance, charged or uncharged, that is capable of accepting a proton from
an acid. The relative strengths of acids and bases are measured by the
tendencies of these substances to give up and take on protons.
In the Brönsted–Lowry classification, acids and bases may be anions
such as HSO4- and CH3COO-, cations such as NH4+ and H3O+, or neutral
molecules such as HCl and NH3. Water can act as either an acid or a base
and thus is amphiprotic. Acid–base reactions occur when an acid reacts with
a base to form a new acid and a new base. Because the reactions involve a
transfer of a proton, they are known as protolytic reactions or protolysis.
In the reaction between HCl and water, HCl is the acid and water the
base:

Acid1 and Base1 stand for an acid–base pair or conjugate pair, as do

Acid2 and Base2. Because the bare proton, H+, H3O+, known as
the hydronium ion.
Lewis Electronic Theory
The most familiar of which is the electronic theory of Lewis.
According to the Lewis theory, an acid is a molecule or an ion that accepts
an electron pair to form a coordinated bond. A base is a substance that
provides the pair of unshared electrons by which the base coordinates with
an acid.
 The Lewis theory is finding increasing use for describing the
mechanism of many organic and inorganic reactions.
Acid–Base Equilibria
Chemical equilibrium maintains the concentrations of the reactants
and products constant. Most chemical reactions proceed in both a forward
and a reverse direction if the products of the reaction are not removed as
they form.
The ionization or proteolysis of a weak electrolyte, acetic acid, in
water can be written in the Brönsted–Lowry manner as

According to the law of mass action, the velocity or rate of the

forward reaction, Rf, is proportional to the concentration of the reactants:

The speed of the reaction is usually expressed in terms of the

decrease in the concentration of either the reactants per unit time. The terms
rate, speed, and velocity have the same meaning here. The reverse reaction

expresses the rate, Rr, of re-formation of un-ionized acetic acid.

The symbols k1 and k2 are proportionality constants commonly known
as specific reaction rates for the forward and the reverse reactions,
respectively,

Ionization of Weak Acids

According to the concept of equilibrium, the rate of the forward
reaction decreases with time as acetic acid is depleted, whereas the rate of
the reverse reaction begins at zero and increases as larger quantities of
hydrogen ions and acetate ions are formed. Finally, a balance is attained
when the two rates are equal, that is, when

The concentrations of products and reactants are not necessarily

equal at equilibrium; the speeds of the forward and reverse reactions are
what are the same. Because equation (7-7) applies at equilibrium,
equations (7-5) and (7-6) may be set equal:

and solving for the ratio k1/k1, one obtains

In dilute solutions of acetic acid, water is in sufficient excess to be

regarded as constant at about 55.3 moles/liter (1 liter H2O at 25°C weights
997.07 g, and 997.07/18.02 = 55.3). It is thus combined with k1/k2 to yield a
new constant Ka, the ionization constant or the dissociation constant of
acetic acid.

according to the Brönsted–Lowry nomenclature, the term ionization

constant, Ka, is not satisfactory and is replaced by the name acidity
constant. Similarly, for charged and uncharged bases, the term basicity
constant is now often used for Kb, In general, the acidity constant for an
uncharged weak acid HB can be expressed by

-
 using the symbol c to represent the initial molar concentration of
acetic acid and x to represent the concentration [H3O+]. The latter quantity
is also equal to [Ac-] because both ions are formed in equimolar
concentration. The concentration of acetic acid remaining at equilibrium
[HAc] can be expressed as c - x. The reaction [equation (7-4)] is

and the equilibrium expression (7-10) becomes

where c is large in comparison with x. The term c - x can be replaced

by c without appreciable error, giving the equation

which can be rearranged as follows for the calculation of the

hydrogen ion concentration of weak acids:

Ionization of Weak Bases

Nonionized weak bases B, exemplified by NH3, react with water as
follows:

which, by a procedure like that used to obtain equation (7-16), leads to

When a salt formed from a strong acid and a weak base, such as
ammonium chloride, is dissolved in water, it dissociates completely as
follows:
 The Cl- is the conjugate base of a strong acid, HCl, which is 100%
ionized in water. Thus, the Cl- cannot react any further. In the Brönsted–
Lowry system, NH4+ is considered to be a cationic acid, which can form its
conjugate base, NH3, by donating a proton to water as follows:

In general, for charged acids BH+, the reaction is written as

and the acidity constant is

Salts of strong bases and weak acids, such as sodium acetate,

dissociate completely in aqueous solution to given ions:

The sodium ion cannot react with water, because it would form
NaOH, which is a strong electrolyte and would dissociate completely into
its ions. The acetate anion is a Brönsted–Lowry weak base, and

In general, for an anionic base B-,

The Ionization of Water
The concentration of either the hydrogen or the hydroxyl ion in
acidic, neutral, or basic solutions is usually expressed in terms of the
hydrogen ion concentration or, more conveniently, in pH units.
In a manner corresponding to the dissociation of weak acids and
bases, water ionizes slightly to yield hydrogen and hydroxyl ions. As
previously observed, a weak electrolyte requires the presence of water or
some other polar solvent for ionization. Accordingly, one molecule of water
can be thought of as a weak electrolytic solute that reacts with another
molecule of water as the solvent. This autoprotolytic reaction is
represented as

The law of mass action is then applied to give the equilibrium expression

ions, [H2O]2 is considered as a constant and is combined with k to

give a new constant, Kw, known as the dissociation constant,
the autoprotolysis constant, or the ion product of water:

The value of the ion product is approximately 1 × 10 -14 at 25°C; it

depends strongly on temperature,
Substituting equation (7-30) into (7-29) gives the common
expression for the ionization of water:

In pure water, the hydrogen and hydroxyl ion concentrations are

equal, and each has the value of approximately 1 × 10 -7 mole/liter at 25°C.
Relationship Between Ka and Kb
A simple relationship exists between the dissociation constant of a
weak acid HB and that of its conjugate base B-, or between BH+ and B,
when the solvent is amphiprotic. This can be obtained by multiplying
equation (7-12) by equation (7-27):

and

or

Ionization of Polyprotic Electrolytes

Acids that donate a single proton and bases that accept a single
proton are called monoprotic electrolytes. A polyprotic (polybasic) acid is
one that is capable of donating two or more protons, and a polyprotic base
is capable of accepting two or more protons. A diprotic (dibasic) acid, such
as carbonic acid, ionizes in two stages, and a triprotic (tribasic) acid, such as
phosphoric acid, ionizes in three stages. The equilibria involved in the
protolysis or ionization of phosphoric acid, together with the equilibrium
expressions, are

In any polyprotic electrolyte, the primary protolysis is greatest, and

succeeding stages become less complete at any given acid concentration.
 The negative charges on the ion HPO42- make it difficult for water to
remove the proton from the phosphate ion, as reflected in the small value
of K3. Thus, phosphoric acid is weak in the third stage of ionization, and a
solution of this acid contains practically no PO43- ions.
Each of the species formed by the ionization of a polyprotic acid can
also act as a base. Thus, for the phosphoric acid system,

Ampholytes
The species H2PO4- and HPO42- can function either as an acid or a
base. A species that can function either as an acid or as a base is called
an ampholyte and is said to be amphoteric in nature. In general, for a
polyprotic acid system, all the species, with the exception of H nA and An-,
are amphoteric.
Amino acids and proteins are ampholytes of particular interest in
pharmacy. If glycine hydrochloride is dissolved in water, it ionizes as
follows:

The species +NH3CH2COO- is amphoteric in that, in addition to

reacting as an acid as shown in equation (7-51), it can react as a base with
water as follows:
 The amphoteric species +NH3CH2COO- is called a zwitter ion and
differs from the amphoteric species formed from phosphoric acid in that it
carries both a positive and a negative charge, and the whole molecule is
electrically neutral. The pH at which the zwitter ion concentration is a
maximum is known as the isoelectric point. At the isoelectric point the net
movement of the solute molecules in an electric field is negligible.

Sörensen's pH

The pH of a solution can be considered in terms of a numeric scale

having values from 0 to 14, which expresses in a quantitative way the
degree of acidity (7 to 0) and alkalinity (7-14). The value 7 at which the
hydrogen and hydroxyl ion concentrations are about equal at room
temperature is referred to as the neutral point, or neutrality. The neutral pH
at 0°C is 7.47, and at 100°C it is 6.15 .
A better definition of pH involves the activity rather than the
concentration of the ions:

pK and pOH

where pK is often called the dissociation exponent.

The pK values of weak acidic and basic drugs are ordinarily
determined by ultraviolet spectrophometry and potentiometric titration.
They can also be obtained by solubility analysis and by a partition
coefficient method.