ACID-BASE EQUILIBRIA

DEFINITIONS OF ACIDS AND BASES

1. Arrhenius Acids and Bases (Svante Arrhenius) – definition emphasis is on increase of

concentration of certain ions in aqueous solutions.

Acids increase hydrogen ion (H+) concentration when dissolved in water

Examples: HCl, H2SO4, H3PO4

Bases increase hydroxide ion (OH-) concentration in water

Examples: NaOH, Mg(OH)2

2. Brønsted-Lowry Acids and Bases (Johannes Brønsted and Thomas Lowry) – definition emphasis
is on proton transfer.

Acids donates a proton to another substance.

Bases accepts a proton from another substance.

Because of this definition of acids and bases, acid-base reactions

• always involves acid-base pairs
Example:

HNO2 + H2O ↔ NO2- + H3O+

Proton donor Proton acceptor
Acid Base

• may or may not occur in water

HCl + NH3 ↔ Cl- + NH4+
Proton donor Proton acceptor
Acid Base

Substances may also act as either a proton donor or a proton acceptor, depending on which
species it is paired with. This substances are called amphiprotic substances.

Example: Water is an amphiprotic substance.

HNO2 + H2O ↔ NO2- + H3O+
Proton donor Proton acceptor
Acid Base

NH3 + H2O ↔ NH4+ + OH-

Proton acceptor Proton donor
Base Acid

Conjugate Acid-Base Pairs

In an acid-base equilibria, the forward and reverse reaction involves proton transfer. For example:

HNO2 + H2O ↔ NO2- + H3O+

In the forward reaction, HNO2 acts as the acid and H2O acts as the base. In the reverse reaction,
NO2- acts as the base and H3O+ acts as the acid. Notice that HNO2 and NO2- differ only in one H+
ion. The same is true for H2O and H3O+. They are called conjugate acid-base pairs.

HNO2 + H2O ↔ NO2- + H3O+

Acid Base Conjugate base Conjugate acid
If an acid readily donates protons, it is said to be a relatively strong acid. Otherwise, it is a
relatively weak acid. If an acid is relatively strong, its conjugate base is relatively weak. If an acid
is relatively weak, its conjugate base is relatively strong.

In a certain acid-base equilibria, the favored direction of a reaction is always towards the one that
would form the weaker acid and weaker base. For example,

NH3 + H2O ↔ NH4+ + OH-

Base Acid Acid Base

Since NH3 is a weaker base than OH- and H2O is a weaker acid than NH4+, the reaction will favor
the reverse direction.

Autoionization of Water and the pH scale

Since water can act as an acid or a base, it can react with itself in an acid-base reaction in a process
called autoionization.

H2O + H2O ↔ H3O+ + OH-

Base Acid Acid Base

If we write the equilibrium constant expression of the above reaction, we have

Kw = [H3O+][OH-] or [H+][OH-]

At 25 °C, the value of Kw (ion-product constant for water) is 10-14. If the [H3O+] = [OH-], a substance
is said to be neutral. However, if [H3O+] > [OH-], a substance is said to be acidic and if [H3O+] <
[OH-], a substance is said to be basic.

Since the [H3O+] or [H+] concentration in water and aqueous solutions are very small, we usually
express them in the negative logarithm of [H+], or pH. For example, at 25°C, for pure water where
the amount of [H3O+] = [OH-], the concentration of [H3O+] is 1.0 x 10-7 M. It can also be expressed
as:

pH = -log [H+] = -log [1.0 x 10-7] = 7.00

Because of this relationship, the more acidic a certain substance is, its pH value becomes lower
than 7. The pH value becomes greater than 7 when a certain substance becomes more basic.

Similarly, we can express [OH-] concentrations as pOH. For example, in a neutral substance with
a [OH-] concentration of 1.0 x 10-7 M,

pOH = -log [OH-] = -log [1.0 x 10-7] = 7.00

Consequently, the more acidic a certain substance is, its pOH value becomes greater than 7. The
pOH value becomes lower than 7 when a certain substance becomes more basic.

Since Kw = 10-14, and Kw = [H3O+][OH-], we can express this also as a p-value:

Kw = [H+][OH-] = 10-14
-log Kw = -log [H+] + -log [OH-] = -log 10-14

pKw = pH + pOH = 14

Strengths of Acids and Bases

Strong acids and bases are those that dissociate completely. The seven most common strong
acids include six monoprotic acids (HCl, HBr, HI, HNO3, HClO3, and HClO4), and one diprotic acid
(H2SO4). The most common soluble strong bases are the ionic hydroxides of the alkali metals,
such as NaOH, KOH, and the ionic hydroxides of heavier alkaline earth metals, such as Sr(OH) 2.

Since these acids and bases dissociate completely, their pH can be calculated readily. For
example, a solution of 0.1 M HCl has a concentration of H+ = [0.1 M]. This means that

pH = -log [0.1 M] = 1

For the diprotic acid H2SO4, the [H+] is simply twice the H2SO4 concentration. Thus, a 0.05 M H2SO4
has a [H+] = 0.1 M.

To calculate the pH of strong bases, we can first calculate its pOH, then subtract the pOH from 14.
Thus, a 0.001 M solution of NaOH has a pOH = 2. Therefore, the pH of the solution is 12.

Weak acids and bases

Weak acids are acids which do not dissociate completely in water. How strong or weak an acid is
is based on how readily they dissociate. This can be examined by determining their acid
dissociation constants (Ka), which is the equilibrium constants for acids. For example, for HClO 2

HClO2 + H2O ↔ ClO2- + H3O+

Ka = [ClO2-][H3O+] / [HClO2] = 1.0 x 10-2

For benzoic acid, C6H5COOH

C6H5COOH + H2O ↔ C6H5COO- + H3O+

Ka = [C6H5COO-][H3O+] / [C6H5COOH] = 6.3 x 10-5

The larger the value of Ka, the more readily the acid dissociates, and therefore it is relatively
stronger. In the given example, HClO2 is relatively stronger than C6H5COOH. However, both of
them are weak acids since they do not dissociate completely.

To calculate the pH of weak acids, we apply the techniques used in calculating concentrations of
reactions in equilibrium. For example, the pH of a certain 0.001 M benzoic acid solution can be
calculated as follows:

Reaction C6H5COOH + H2O ↔ C6H5COO- + H3O+

Initial 0.001 0 0
Change -x +x +x
Equilibrium 0.001-x x x

[C6H5COO-][H3O+] / [C6H5COOH] = 6.3 x 10-5

[x][x] / [0.001-x] = 6.3 x 10-5
x = 2.51 x 10-4
[H+] = 2.51 x 10-4
pH = -log [H+] = -log [2.51 x 10-4] = 3.60

Weak bases are bases which do not dissociate completely in water. How strong or weak a base is
is based on how readily they dissociate. This can be examined by determining their base
dissociation constants (Kb), which is the equilibrium constants for bases. For example, for NH3

NH3 + H2O ↔ NH4+ + OH-

Kb = [NH4+][OH-] / [NH3] = 1.8 x 10-5

For pyridine, C5H5N

C5H5N + H2O ↔ C5H5NH+ + OH-

Kb = [C5H5NH+][OH-] / [C5H5N] = 1.7 x 10-9

The larger the value of Kb, the more readily the base dissociates, and therefore it is relatively
stronger. In the given example, NH3 is relatively stronger than C5H5N. However, both of them are
weak bases since they do not dissociate completely.

To calculate the pH of weak bases, we apply the techniques used in calculating concentrations of
reactions in equilibrium. For example, the pH of a certain 0.001 M ammonia solution can be
calculated as follows:

Reaction NH3 + H2O ↔ NH4+ + OH-

Initial 0.001 0 0
Change -x +x +x
Equilibrium 0.001-x x x

[NH4+][OH-] / [NH3] = 1.8 x 10-5

[x][x] / [0.001-x] = 1.8 x 10-5
x = 2.51 x 10-4
[OH-] = 1.6 x 10-3
pOH = -log [OH-] = -log [1.6 x 10-3] = 2.80
 pH = 14 – pOH = 14 – 2.80 = 11.2

Ka and Kb

Consider the following conjugate acid-base pairs and their reactions with water:

NH3 + H2O ↔ NH4+ + OH-

Kb = [NH4+][OH-] / [NH3]

NH4+ + H2O ↔ NH3 + H3O+

Ka = [NH3][H+] / [NH4+]

If we multiply Kb and Ka of the conjugate acid pairs, we get:

Kb x Ka = [NH4+][OH-] / [NH3] x [NH3][H+] / [NH4+]

Kb x Ka = [H+][OH-] = Kw

The above result holds for any conjugate acid–base pair. In general, the product of the acid-
dissociation constant for an acid and the base-dissociation constant for its conjugate base equals
the ion-product constant for water.

3. Lewis Acids and Bases (G. N. Lewis) – definition emphasis is on electron pair transfer.

Acids accepts an electron pair from another substance.

Bases donates an electron pair to another substance.

In many cases, Lewis acids have incomplete octet (such as many cations) or have multiple bonds.
Lewis bases, on the other hand, have electron pairs or have more than eight valence electrons.