Page 1 of 4

Acid-Base and Solubility Equilibria

11.12 Buffer Solutions

Two main types of buffer solutions exist. An acidic buffer which is a mixture of any weak acid and
its salt e.g. CH3COOH/CH3COONa and a basic (alkaline) buffer which is a mixture of a weak base
and its salt e.g. NH3/NH4Cl).

Definition: A Buffer solution is a solution which resists significant change in pH when small
quantities of acid or base are added.

No buffer solution can resist pH change with excess addition of acid or alkali. A buffer solution only
resists pH change on conditions of:
- Addition of small quantities of acid or base or dilution of the buffer solution.
-
How Buffer solutions work in order to resist pH change.
An acidic buffer solution such as CH3COOH/CH3COONa contains a relatively high concentration of
CH3COOH and a relatively high concentration of CH3COONa. The basic buffer solution such as
NH3/NH4Cl contains a relatively high concentration of NH3 and a relatively high concentration of
NH4Cl.
a) An acidic buffer solution resists pH change on addition of acid and alkali
In an acidic buffer, the weak acid is partially ionised while the salt is fully ionised.
CH3COOH(aq) ⇌ H+(aq) + CH3COO-(aq).
Ethanoic acid ethanoate ion
Sodium ethanoate is a salt and fully ionised.
CH3COONa(s) + aq → Na+(aq) + CH3COO-(aq).
Sodium Ethanoate ethanoate ion

- Adding a small quantity of acid to a buffer solution shift the equilibrium above to the left as H +
added combine with CH3COO- to form CH3COOH until the equilibrium is restored. The solution
resists any significant change in pH because CH3COO- is in a relatively high concentration.
CH3COO-(aq) + H+(aq) → CH3COOH(aq)

- Adding a small quantity of alkaline (base) to a buffer solution shift the equilibrium to the right
as OH- added react with H+ to form H2O. More CH3COOH ionise to form H+ and CH3COO- until
the equilibrium is restored. The solution resists any significant change in pH because CH 3COOH
is in a relatively high concentration.
H+(aq) + OH-(aq) → H2O(l)
CH3COOH(aq) ⇌ H+(aq) + CH3COO-(aq).
The overall reaction is: CH3COOH(aq) + OH-(aq) ⇌ CH3COO-(aq) + H2O(l).

b) An basic buffer solution resists pH change on addition of acid and alkali

In an basic buffer, the weak base is partially ionised while the salt is fully ionised.
An alkaline buffer e.g solution containing NH3(aq) and NH4Cl(aq) behaves exactly as an acid buffer.
NH3(aq) exists in solution as NH4OH.
NH4OH(aq) ⇌ NH4+(aq) + OH-(aq).
Aqueous ammonia ammonium ion
Ammonium chloride is a salt and fully ionised.
NH4Cl(s) + aq → NH4+(aq) + Cl-(aq).
Ammonium chloride ammonium ion
- Adding a small quantity of acid to a buffer solution shift the equilibrium above to the right as H+
added combine with OH- to form H2O. More NH4OH ionise until the equilibrium is restored. The
solution resists any significant change in pH because NH4OH is in a relatively high
concentration.
H+(aq) + OH-(aq) → H2O(l)
NH4OH(aq) ⇌ NH4+(aq) + OH-(aq).
The overall equation is: NH4OH(aq) + H+(aq) ⇌ NH4+(aq) + H2O(l).

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
 Page 2 of 4
Acid-Base and Solubility Equilibria

- Adding a small quantity of alkaline (base) to a buffer solution shift the equilibrium to the left as
OH- added react with NH4+ to form NH3(aq) and H2O until the equilibrium is restored. The
solution resists any significant change in pH because NH4+ is in a relatively high concentration.
NH4+(aq) + OH-(aq) → NH3(aq) + H2O(l).

Calculating pH of a Buffer solutions

The pH of a buffer solution can be calculated if:
- The Ka of the acid is known
- The equilibrium concentration of weak acid and its conjugate base (salt) is known.

Two assumptions made in calculating the pH of a buffer solution are:

- The salt in the solution is fully ionised so that the concentration of the RCOO– or NH4+ or RNH3+
is the same as the initial concentration of the salt.
- The weak acid or base is only slightly ionised so that its concentration in equilibrium is about the
same as its initial concentration.

The pH of an acidic buffer solution can be calculated in two ways:

1. Calculate the [H+] using the expression [H+] = and then substitute the [H+] into the
expression pH = -log10[H+] in order to get the pH of the buffer solution.

2. Then calculate the pH using the formula pH =

Example:
Calculate the pH of a buffer solution cotaining 0.60 moldm-3 of ethanoic acid (CH3COOH) and 0.80
moldm-3 sodium ethanoate (CH3COONa). (Ka of CH3COOH = 1.74 x 10-5moldm-3). Ans = 4.88
Assignment:
1. (a) Calculate the pH of a buffer solution made by adding 3.28g of CH3COONa to 1dm3 of 0.01
CH3COOH acid , Ka for CH3COOH acid = 1.7 x 10-5. C = 12, H = 1, 0 = 16, Na = 23
Ans, pH = 5.37
(b) calculate the change in pH when 1 cm3 of 1 moldm-3 of NaOH is added to 1dm3 of buffer
solution above. Ans = 0.33

Uses of buffer solutions

- In agriculture, buffer solutions are used to maintain the pH of the soil constant. A particular pH
range is necessary for healthy plant growth. The presence of salts such as carbonates,
bicarbonates, phosphates and organic acids buffer the soil.
- In the industry, buffer solutions are used in fermentation processes in brewery industries and in
setting the appropriate conditions for dyeing fabrics, treatment of leather, paper, paint, ink and
drugs manufacture used in preparing e.g. antibiotics penicillin. Used to balance pH of
household products such as cosmetics. It is also applied in food preservation.
- In chemical systems, buffer solutions are used in calibration of pH meters, analyses and
syntheses, electroplating, electrophoresis for the separation of amino acids, to measure rate of
reaction which is pH dependent.
- In medicines, used to buffer injections before administering.
- In biochemical systems, buffer solutions help to keep constant pH in various parts of the body.
Carbonic acid (H2CO3) and bicarbonate ion (HCO3-) help to maintain blood pH constant. A
change in pH of blood by 0.2 units can cause instant death.

Lewis acid-base theory

The Lewis acid-base theory involves an electron pair donor-acceptor system resulting to the
formation of a dative covalent.
Definition: An acid is an electron pair acceptor.
Definition: A base is an electron pair donor.
H3N: + BF3 → H3N→BF3.

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
 Page 3 of 4
Acid-Base and Solubility Equilibria

CaO + SO3 → CaSO4 and ionic equation represented as O2- + SO3 → SO42-.

Limitations of Lewis acid-base theory.

- It is difficult to classify Lewis acids or bases in order of strength.
- Catalytic activity of Lewis acids cannot be explained since catalytic activity of an acid is its
ability to provide protons.
Act:
(a) State the necessary condition for a species to be called:
(i) a Lewis acid (ii) a Lewis base
(b) The formation of complexes by transition metals in the presence of ligands is a Lewis acid-base
reaction. Identify the acid and the base and explain your reasoning.

11.14 The Solubility Equilibria

A sparingly soluble salt dissolves in water at a particular temperature and reach a state of dynamic
equilibrium where rate of dissolution is equal to rate of precipitation. AgCl (s) ⇌ Ag+(aq) +
Cl–(aq). The equilibrium constant (Kc) for the above expression is written as:

. The concentration of a solid i.e. [AgCl(s)] is constant =>

Ksp = [Ag+(aq)]eqm[Cl–(aq)]eqm, Ksp = Kc x [AgCl(s)]. Ksp is called the solubility product

Definition: Solubility product (Ksp) is product of the concentration each ion in a saturated
solution of a sparingly soluble salt at 298K, raised to the power of their relative number of moles in
the balanced ionisation equilibrium equation.
For a sparingly soluble salt (AnBm(s)) in dynamic equilibrium at a temperature T°C with its ions
according to the equation AnBm(s) ⇌ nAm+(aq) + mBn–(aq), has Ksp expression as
, units of Ksp given as (moldm-3)n+m , value of Ksp given by the
expression Ksp = (nn)(mm)(s)n+m and its solubility ‘s’ at temperature T°C given by the expression s =

moldm-3 where: n = number of cations and m = number of anions in a formula unit

of the sparingly soluble salt.

For Ca3(PO4)2(s) ⇌ 3Ca2+(aq) + 2PO43–(aq) with solubility ‘S’, x = 3 and y = 2.
Thus Ksp = (33)(22)(S)3+2 (moldm-3)3+2 = (27)(4)(S)5 (moldm-3)5 = 108(S)5 mol5dm-15.
Act:
(a) Calculate the solubility product (Ksp) of Ag2SO4(s) at 25°C given that the solubility of
Ag2SO4(s) at 25°C is 0.015moldm-3. Ans, Ksp = 1.35 x 10-5.
(b) Calculate the solubility of Ag2SO4(s) at 25°C given that the solubility product (Ksp) of
Ag2SO4(s) at 25°C is 1.35 x 10-5 mol3dm-9. Ans = 0.015 moldm-3.
Assignment:
(a) Given that the solubility product (Ksp) of Ca3(PO4)2(s) at 25°C is 1.20 x 10-26 mol5dm-15.
(i) Calculate the solubility of Ca3(PO4)2(s) in moldm-3 at 25°C. Ans = 2.57 x 10-6.
(ii) Calculate the solubility of Ca3(PO4)2(s) in gdm at 25°C. Ans = 7.94 x 10-4.
-3

(iii) Calculate the solubility of Ca2+ in gdm-3 at 25°C. Ans = 3.08 x 10-4.
Ca = 40, P = 31, S = 32 and O = 16.
(b) A saturated solution of CaF2(s) at 25°C contains 8.17 x 10-4g of fluoride (F-) ions in 100 cm3
solution. Calculate the solubility product (Ksp) of CaF2(s) at 25°C. Ans = 4.0 x 10-11.
(c) Calculate the solubility of magnesium hydroxide; Mg(OH)2 in g/dm3 given that its solubility
product (Ksp) is 1.2 x 10-11 . Ans = Ans = 8.36 x 10-3g/dm3.

The smaller the Ksp value, the less soluble the salt and vice versa, only when the salts compared
produce the same number of moles of ions in solution. If the salts compared produce different
number of moles of ions in solution, then the solubility of each salt needs to be calculated and the
salt with a small solubility is the less soluble salt.
Act:

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
 Page 4 of 4
Acid-Base and Solubility Equilibria

(a) The Ksp values of silver iodide; AgCl and zinc hydroxide; Zn(OH)2 are 1.8 x 10-10 mol2dm-6 and
4.5 x 10-17 mol3dm-9 respectively. Which of the compounds is more soluble? Explain.
(b) The Ksp values of lead (II) fluoride; PbF2 and lead (II) chloride; PbCl2 are 3.6 x 10-8 mol3dm-9
and 1.6 x 10-5 mol3dm-9 respectively. Which of the compounds is more soluble? Explain.
(c)
The common ion effect
Solubility of a salt decreases in a solution that already contains one of its ions due to equilibrium
shift to the left. The salt AgCl is more soluble in pure water than in NaCl solution at the same
temperature due to the common ion effect. The common ion here is the chloride (Cl –) ion because
both AgCl and NaCl contain the chloride (Cl–) ion.

Definition: The common ion effect is the reduction in the solubility of a dissolved salt achieved by
adding a solution of a compound which has an ion in common with the dissolved salt.

11.15 Salt Hydrolysis and pH of Salt Solutions

When a salt dissolves in water, the resulting solution may be acidic, neutral or basic.
Definition: Salt hydrolysis is the reaction of the cation or the anion or both ions of the salt with
water to produce acidic or basic solution.

(a) Salt of a strong acid and strong base e.g NaCl, KNO3, Na2SO4.
When NaCl is dissolved in pure water, the resulting solution is neutral (pH = 7). This is because
neither the cation (Na+) nor the anion (Cl–) reacts with water.
NaCl(s) + H2O(l) → Na+(aq) + Cl-(aq).

(b) Salt of a strong acid and weak base e.g NH4Cl, (NH4)2SO4.
When NH4Cl is dissolved in pure water, the resulting solution is acidic (pH < 7). This is because
its cation (NH4+) reacts with water to release H+ ions resulting to an acidic solution.
NH4+(aq) + H2O(l) → NH4OH(aq) + H+(aq).
The overall equation is: NH4Cl(s) + H2O(l) → NH4OH(aq) + HCl(aq).

(c) Salt of a weak acid and strong base e.g CH3COONa, Na2CO3.
When CH3COONa is dissolved in pure water, the resulting solution is basic (pH > 7). This is
because its anion (CH3COO–) reacts with water to release OH– ions resulting to a basic solution.
CH3COO–(aq) + H2O(l) → CH3COOH(aq) + OH–(aq).
The overall equation is: CH3COONa(s) + H2O(l) → CH3COOH(aq) + NaOH(aq).

(d) Salt of a weak acid and weak base e.g CH3COONH4, NH4CN.
When a salt of a weak acid and a weak base e.g. CH3COONH4 dissolves in pure water, the
resulting solution may be basic or acid depending on the strength of the weak acid compared to
the weak base.
CH3COONH4(s) + H2O(l) → CH3COO-(aq) + NH4+(aq).

The anion (CH3COO–) reacts with water to form CH3COOH (a weak acid) while the cation
(NH4+) reacts with water to form NH4OH (a weak base). If Ka for the cation is higher than Kb
for the anion, then the resulting solution will be basic. If Ka for the cation is lower than Kb for
the anion, then the resulting solution will be acidic. Note that Ka for NH 4+ = Kw/Kb for NH3
while Kb for CH3COO- = Kw/Ka for CH3COOH.

(e) Salt of highly charged metallic ions (M3+) e.g. AlCl3, CrCl3, FeCl3.
Salts with metallic ions having high charge densities react with water to produce acidic solutions
(solutions with pH < 7). When AlCl3 dissolves in water ,the solution become acidic, this is
because the high positively charged small Al3+ ions polarises the water molecule to the extent
that an O – H bond is broken to release hydrogen ions in solution.
Al3+(aq) + 3H2O(l) → Al(OH)3(s) + 3H+(aq).

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N