Acid – Base Equilibria

Chemistry Unit 1 D.Hines

1. The Bronsted-Lowry definition of acids and bases

There are many definitions of acids and bases in existence, but the most useful one is the Bronsted-Lowry definition:

An acid is a substance which can behave as a proton donor. A proton can be represented as a hydrogen ion, H+.

Any substance which contains hydrogen bonded to a more electronegative element can thus behave as an acid:

HCl(aq) → H+(aq) + Cl-(aq)

Or HCl(g) + H2O(l) → H3O+(aq) + Cl-(aq)

When hydrogen chloride gas dissolves in water, almost all of it ionizes to hydronium ions and chloride ions. Therefore
hydrochloric acid is described as a strong acid.

A base is a substance which can behave as a proton acceptor. Any species which has a lone pair of electrons can thus
behave as a base:

NH3 + H+ NH4+

OH- + H+ H2O

When ammonia dissolves in water to produce ammonium hydroxide, the ammonia accepts a proton (H+ ions from H2O.

NH3(g) + H2O(l) NH4+(aq) + OH-(aq)

When ammonia gas dissolves in water only some of it ionizes in water, therefore ammonia is described as a weak base.

Water can act as an acid or base, therefore it is amphoteric.

2H2O(l) H3O+(aq) + H+(aq)

2. Conjugate acid-base pairs

Since all the above reactions are reversible, the species formed when an acid gives up a proton can accept a proton and
thus behave as a base. The species formed when a base accepts a proton can give up a proton and behave as an acid:

Acids and bases thus come in pairs; every acid can lose a proton to become a base and every base can accept a proton to
become an acid. Species related in this way are known as conjugate acid-base pairs.

Eg Cl- is the conjugate base of HCl; HCl is the conjugate acid of Cl -

Eg NH3 is the conjugate base of NH4+; NH4+ is the conjugate acid of NH3

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+ (aq)

Acid base conjugate base conjugate acid

The ion left when an acid has given away its proton is called a conjugate base. The ion formed when a base has accepted
a proton is called a conjugate acid.

Strong and weak acids and bases

Acids are classified into two categories based on their ability to ionize in aqueous solutions. They are strong acids and
weak acids.

A strong acid ionizes completely in aqueous solutions producing a high concentration of hydrogen ions.

HNO3(aq) → H+(aq) + NO3-(aq)

Or HNO3(aq) + H2O(l0 → H3O+(aq) + NO3-(aq)

Hydrochloric acid, nitric acid and sulphuric acids are all strong acids.

Weak acids ionize (dissociate) only partially in solution. The position of equilibrium lies to the left. There are many more
molecules of acid present than ions, the concentration of hydrogen ions is low. Organic acids such methanoic acid,
ethanoic acid and citric acid are weak acids. CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+ (aq)

1
Bases

Bases are also classified as strong and weak bases. Bases that dissolve in water are referred to as alkali. Strong bases
ionize completely in water. For example; NaOH(aq) → Na+(aq) + OH-(aq)

Examples of strong bases are group (I) hydroxides and oxides.

Weak bases ionize (dissociate) only partially in solution. For example:

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

CH3NH2(aq) + H2O(l) CH3NH3+(aq) + OH-(aq)

In this reaction, the equilibrium lies to the left indicating that the ammonia is not completely ionized. Only a small
concentration of hydroxide ions is generated in solution and there are more molecules of base than ions.

Calculating pH

The relative strength of acids can be compared by measuring the concentration of hydrogen ions. The concentration of
hydrogen ions in a solution can range from 10 -15 to 10 mol dm-3. Using a logarithmic scale can reduce this wide range to a
narrow range. Using negative logarithmic would produce a positive value for these concentrations. The pH scale is thus
used to measure acidity and range from 0 to 14. Very concentrated acids can pH values below 0 and concentrated alkalis
can have pH values above 14.

The p notation

The p notation (as in pH) is a modified logarithmic scale used by chemists to express small values simply. The p stands
for negative logarithm to base ten. Therefore pH means negative logarithm to base ten of hydrogen ions in a solution.

pH= -log10 [H+]

The lower the pH, the more acidic is a solution.

[H+] 10-14 10-12 10-10 10-8 10-7 10-6 10-4 10-2 10-0

pH 14 12 10 8 7 6 4 2 0

Strongly alkaline alkaline neutral acidic strongly acidic

The concentration of the hydroxide ion can be measured similarly using a pOH scale.

pOH = -log10 [OH-]

The relationship between pH and pOH is pH + pOH = 14

The p notation can also be used in relation to other equilibrium constants. e.g

pOH = -log10 [OH-] pKa = -log [Ka] pKw = -log10[Kw]

Simple pH calculations

The pH of strong acids

Strong acids are completely ionized in water. So the pH can be easily calculated and the concentration of H+ ions can be
found using stoichiometry.

Example 1

a. Calculate the pH of 0.1 M HCl solution.

b. Calculate the pH of 0.1 M H2SO4 solution
c. Calculate the pH of 0.01 M of H3PO4

Converting pH to [H+]

pH = -log10[H+]

anti log (-pH) = [H+], which is

[H+] = anti log (-pH)

2
Example 2

a. Calculate the hydrogen ion concentration of a solution of pH 10.5

b. Calculate the concentration of HCl with a pH of 1.3.
c. Calculate the concentration of NaOH of pH = 11.
d. Calculate the concentration of KOH of pH = 13

Calculate the pH of a strong base

To calculate the pH of a strong base it is necessary to determine the hydroxide ion concentration in mol dm -3 and
determine the pOH using pOH = -log[OH-]. From here pH can then be determined using;

pH + pOH = 14, therefore

pH = 14 – pOH

Example 3

a. Calculate the pH of a solution of KOH of concentration 0.0250 M.

b. Calculate the pH of a solution of Ba(OH) 2 of concentration 0.0130 M.
c. Calculate the pH of a 0.23 M Ca(OH)2 solution.

The ionic product of water, Kw

Most common acid-base reactions take place in aqueous solution, and thus acids and bases are generally defined by the
way in which they react with water.

1. Auto-ionisation of water
Water can behave both as an acid and a base: in aqueous solution a small fraction of the water molecules undergo acid-
base reactions with each other to produce the equilibrium:

2H2O(l) H3O+(aq) + H+(aq)

It can be simply put H2O(l) H+(aq) + OH-(aq)

This is known as the auto-ionisation of water. The equilibrium expression for this reaction can be written:

Kc = [H+][OH-]

[H2O]

The concentration of water under these conditions is not changed significantly, since the proportion of water which
dissociates into its ions is small. The water concentration can thus be assumed to be constant and it can be incorporated
into Kc:

Kw = [H +][OH-]
+ -
Kc[H2O] = [H ][OH ]

Kw = [H+][OH-]

The expression [H+][OH-] is known as the ionic product of water and has a value of 1.0 x 10-14 mol2dm-6 at 25oC. This
value is a constant at a given temperature. The ionic product of water is slightly higher at higher temperatures,
suggesting that the dissociation is endothermic.

In pure water, the [H+] and [OH-] concentrations are equal.

It follows that [H+][OH-] = [H+]2 = Kw = 1.0 x 10-14 mol2dm-6

So [H+] = [OH-] = Kw = 1.0 x 10-7 moldm-3.

Any solution in which the concentrations of H+ and OH- are equal is said to be neutral.

Calculating the pH of water:

We can use the ionic product expression for water to prove why the pH of water is 7

[H+][OH-] = 1.00 x 10-14

And [H+] = [OH-]

3
So [H+]2 = 1.00 x 10-14

And [H+] = √1.00 x 10-14 = 1.00 x 10-7 M

Therefore pH = -log10[H+]

= - (1.00 x 10-7)

=7

In pure water, [H+] = [OH-] = 1 x 10-7 M and the pH = 7.

It follows that the pH of acidic solutions is less than 7 and the pH of alkaline solutions is greater than 7.

Using Kw to calculate the pH of alkalis

We can use Kw to calculate the pH of strong bases. We need to know the concentration of hydroxide ions in the solution
and value of Kw.

The concentration of OH- ions can be deduced from the concentration of H+ ions and vice versa. The following table
shows some examples:

[H3O+] [OH-] Type of

solution

0.1 1 x 10-13 Acidic

1 x 10-3 1 x 10-11 Acidic

1 x 10-7 1 x 10-7 Neutral

1 x 10-9 1 x 10-5 Alkaline

1 x 10-11 1 x 10-3 Alkaline

Example 4
Use the equilibrium systems below to answer (a) to (c) below.

H2CO3(aq) + H2O(l) HCO3-(aq) + H3O+(aq)

HCO3-(aq) + H2O(l) CO3-(aq) + H3O+(aq)
a. Explain the meaning of the term conjugate acid-base pair
b. Write the formula of the conjugate base and acid of HCO3-(aq)
c. Write the formula of the conjugate base and acid of CO3-(aq)
Example 5

Ammonia forms a weak basic solution in water

a. Write an equation for the reaction between ammonia and water
b. Write an expression for the equilibrium constant for the reaction