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IONIC EQUILIBRIA
ACID-BASE EQUILIBRIA
Arrhenius theory of acid and base
Acid
Is a substance which on dissolving in water produces hydrogen ions.
Base
 Is a substance which on dissolving in water produces Hydroxyl ions
 Is a substance which combines with an acid to form a salt and water
Brønsted – Lowry theorem
Acid
Is a substance which donates a proton (proton donor)
Base
Is a substance which accepts a proton (proton acceptor)
Examples include;
a) HCl(aq)+ NH3(aq) → Cl− + NH
Acid; Base; conjugate conjugate
Base of acid of
HCl NH3

(b) HCl + H2O → H3 + C

Conjugate conjugate
Acid; base;
(Hydronium/oxorium/hydroxonium)
(c.) H2O+NH3→ ŌH + NH
Conjugate conjugate
Base; acid;
NB
i. Strong acids
Are acids which do not readily donate a proton to another molecule (base) eg H2SO4, etc
ii. Weak acids
Are acids which easily lose its proton with difficult eg CH3COOH ie
CH3COOH(aq) CH3OŌ (aq) + H+
H2SO3 (aq) H++ HSO
iii. Strong base ;
A base which has a high affinity for protons eg NaOH
Lewis acid theory
Acid;
 Is a substance which can accept a pair of electrons.
Base
Is a substance which donates a pair of electrons in a dative covalent bond
Eg (i) F3B + NH3→ F3B ← :NH3
acid base

(ii) Cu(aq) + 4NH3 (aq)

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IONISATION CONSTANTS OF ACIDS AND BASES

a) Ionisation constants of weak acids (Ka)
Consider a weak monobasic acid(HA) of concentration C which ionizes in solution as follows;
HA(aq) H+ (aq) + A− (aq)
HA(aq) + H2O (l) A− (aq) + H3O+ (aq)
Ka = , but =C

Ka = At equilibrium; =

Ka =

Ka =
Eg .CH3COOH (aq) CH3CO (aq) +H+ (aq)
Ka = At equilibrium = , If = C mold

Ka =
Relationship between Ka and degree of Dissociation, α
Consider a weak monobasic acid( HA) of concentration C and degree of dissociation, α
HA(aq) H+ (aq) + A− (aq)
Initial moles; C − −
Moles reacted ; Cα Cα Cα
Equilibrium moles C − Cα Cα Cα
Ka = = = = ,
For weak acids, α is small, ≅1
Ka = =C

α=

Example
1. The acid dissociation constant of a dibasic acid is 4.39 × 1 at 2 C, Calculate the
degree of ionization of a 0.01M solution of the acid. UNEB 2010
Solution
For weak acids, Ka = , But also for weak acids; α <<<< 1,
≅1
Ka = C
4.39 × 1 = 0.01

α=

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𝛂 = 0.066
α = 6.6%
Activity
1. Calculate the degree of dissociation of a 0.01M ethanoic acid if K is 1.0 × 1 at 298K
b) Ionisation constant for weak bases; Kb
Consider a weak base BOH of concentration C which ionizes in solution as follows.
BOH (aq) B+(aq) +ŌH(aq)
Kb = but [BOH] = C moldm-3

Kb = At equilibrium; [ ] = [ŌH];

Kb =
Assumptions
 At equilibrium; [ ] = [ŌH];
 Concentration of unionized base is equal to the original concentration; because proportion of
molecules ionized is small.
Relationship between Kb and α
Consider a weak base BOH of concentration C and degree of dissociation, α
BOH (aq) B+(aq) +ŌH(aq)
Initial concentration C − −
Reacted moles Cα Cα Cα
Equilibrium concn C – Cα Cα Cα
Kb = = = =
But for weak bases; α <<<< 1, ≅1
Kb = C

α=

Activity
1. Write;
i. An equation for the ionization methylamine in water
ii. The expression for the base dissociation constant, Kb for Methylamine
2. At 250C Ammonia has a base ionization constant, Kb of 1.8×10−5moldm−3
a) Write an expression for Kb of Ammonia
b) Calculate the concentration of ŌH in 0.1M Ammonia solution at 250C
State any assumptions made ( 1997 No. 11 Paper 1, part of question)
IONISATION OF WATER
Pure water undergoes self-ionization as follows
H2O(l) H+ (aq)+ŌH(aq)
By law of mass action;
Keq =
Keq [H2O] = [H+][ŌH]
Since the degree of ionization of water is small; [H2O(l)] = constant

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Keq . constant = [H+][ŌH], but Keq . constant = Kw (ionization product of water/ionic product of water)
Kw =[H+][ŌH]
But pure water contains equal concentration of H+ and ŌH ions (1 × 10−7moldm-3)
Kw = (1 × 10−7moldm-3)(1 × 10−7moldm-3)
Kw = (1 × 10−14moldm-6)

pH
Is the negative logarithm to the base 10 of the hydrogen ion concentration of a solution.
pH = −
OR;
is the logarithm to base 10 of the reciprocal of the hydrogen ion concentration of a solution. i.e. pH =

a) pH of water:
pure water contains equal concentration of hydroxyl and hydrogen ions (1 × 10−7moldm-3); pH
=− =−
pH = 7
b) pH of acids:
i. strong acids:
pH of strong acids depends only on its concentration because strong acid is fully ionized;
Examples
1. Calculate the pH of a 0.02M H2SO4
Solution
[H2SO4] =0.02M
H2SO4 → 2H+(aq)+ SO (aq)

1 mole of H2SO4 form 2 moles of H+

0.02moles of H2SO4 form (0.02) moles of H+
= 0.04 moldm-3
+ -3
[H ] =0.04 moldm
pH = −
=−
= 1.40
2. Calculate the pH value of 2× 10−3moldm−3 of HNO3
Solution
HNO3 (aq) H+ + NO
1 mole of HNO3 (aq) produces 1 mole H+
[HNO3] = [H+] = 2 × 10−3moldm−3
ACTIVITY
1. Calculate the pH of the following concentration of the following acids
(a). 0.05moldm−3 HCl (b) 0.025moldm-3 Sulphuric acid
NB: A strong acid of concentration > 1.0moldm-3; pH value < 0 eg for 2M HCl; pH = −0.3;
ii) pH of weak acids
Consider ionization of weak acid HA whose concentration is C moldm-3, and the degree of ionization α

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HA(aq) H+(aq)+ (aq)

By law of mass action;
Ka =
But at equilibrium; [H+] = [ ]
Ka =
] 2 = K aC
]= ----------- (i)

Also; α ------------ (ii)

Examples
1. Calculate the [H+] and the pH of a 0.01M solution of ethanoic acid. (Ka =1.8 × 10−5moldm−3)
Solution
Concn of CH3COOH = 0.01moldm−3, Ka = 1.8 × 10−5
From [H+] =
[H+] =
[H+] = 4.24 × 10−4moldm−3
pH = − ]
=− 10−4)
= 3.37
2. The pH of a 0.001M solution of ethanoic acid is 3.59. Calculate the;
i. dissociation constant of the acid.
ii. Degree of dissociation at the concentration given.

Solution
i. pH = − ]
3.59 = − ]
] = −3.59
+
[H ] =
= 2.57 × moldm−3
From [H+] =
] 2 = K aC
Ka = =
= 6.61 × 10−5moldm−3

ii. α= = = 0.26
ACTIVITY
1. A solution of 0.05M propanoic acid had a pH of 4. Calculate its degree of dissociation and hence
dissociation constant Ka
c) pH of bases
pH of bases can be obtained from the ionization pH of water. ie ;

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Kw = [ ][ ]
Taking − on both sides of the expression
− log Kw = −
− log Kw = − + −
pKw = pH + pOH
from Kw = 1 ×
pKw= −
pKw= −
pKw = 14
i. pH of strong bases
Examples
1. Calculate the pH of 0.001M Potassium hydroxide
KOH(aq) K+(aq) + H(aq)
1 moleof KOH produces 1 mole of H ions
-3
[KOH] = [ H] = 0.001moldm
pOH = −log (0.001)
pOH = 3
But from pKw = pH + pOH
14 = pH + 3
pH = 14 – 3 = 11
OR:
Kw = [ H][ ]
1× 10− 14 = [ H][ ]
[ ]= = = 1 × 10-11
pH = −log [ ]
= −log(1 × 10-11)
pH = 11
ii. pH of weak bases
Consider a weak base BOH of concentration Cmoldm-3 and degree of dissociation, α
BOH(aq) B+(aq) + H(aq)
By law of mass action,
Kb = =
At equilibrium, [B+] =[ H]
Kb =
[ H] =

α=
Example
1. Calculate the pH of 0.1M aqueous ammonia whose Kb is 1.5 × 10-6.

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Solution
NH3(aq) + H2O (l) NH (aq) + H(aq)

Kb = , At equilibrium [ H] = [NH (aq)]

Kb =

1.5 × 10-6 =

= 1.5 × 10-6
[ H] = = 3.87 × 10 −4 moldm−3
pOH = −log (3.87 × 10 −4)
= 3.41
From pH = pKw – pOH
= 14 – 3.41 = 10.587
ACTIVITY
1. 0.01M solution of phenylamine is 7.5% ionized
(a) Write the expression for dissociation of phenylamine
(b) Calculate;
(i) Kb
(ii) pH of the solution
BUFFER SOLUTION
Buffer solutions are solutions which resist changes in their pH when small amounts of acid or base is
added to them.
Types of buffer solutions
(i)acidic buffer
 consists of solution of a weak acid and its salt eg acetic acid and sodium acetate, supplying a
conjugate base of weak acid
 Maintain nearly a constant pH value less than 7
(ii) Basic buffer
 Consists of a solution of a weak base and its salt. Eg ammonium hydroxide and ammonium
chloride, supplying a conjugate acid of weak base.
 Maintain nearly a constant pH value above 7
a) Action of acidic buffer:
Consider a solution of weak acid(acetic acid) and its highly ionisable salt ( sodium acetate)
 Acetic acid is a weak acid, is not fully ionized while sodium acetate is a strong
electrolyte, fully ionized.
CH3COOH(aq) CH3CO (g) + (aq)

CH3COONa(aq) CH3CO (g) + Na+(aq)

 Solution contains excess of acetate ions and a large amount of unionized acetic acid, and
a small amount of hydrogen ions.
 Addition of to this solution (inform of acid eg HCl) will combine with the acetate
ions forming unionized acetic acid.

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CH3CO (aq)+ (aq) CH3COOH (aq)

 are removed by excess ethanoate ions already present, solution retains its constant pH
value.
 H ions to this solution from a base, it will be removed by reacting with the
unionized acetic acid.
CH3COOH(aq) + H(aq) CH3CO (aq) + H2O(l)
 the solution also maintains its pH value.
pH calculations of acidic buffers
 Consider a buffer solution consisting of acetic acid and sodium acetate
CH3COOH(aq) CH3CO (g) + (aq)

CH3COONa(aq) CH3CO (g) + Na+(aq)

Ka =

[ ]=
Assumptions:
 CH3COONa is a strong electrolyte; fully ionizes; = [salt]
 CH3COOH is a weak acid, [CH3COOH] = [acid]
Therefore [ ]=
Taking –log on both sides of the expression;
−log [ ] = − log

−log [ ] = −logKa + − log

pH = pKa − log

pH = pKa + “The Henderson – Hassel balch equation”

Examples
1. (a) Calculate the pH of a buffer solution which consists of 4.1g of Sodium ethanoate per litre of
solution and 0.01M ethanoic acid whose Ka = 1.7× 10−5moldm-3
solution
Relative molecular mass of CH3COONa =(2×14)+(2×O16)+(3×1)+ 23= 82
1 mole of CH3COONa weighs 82g
X moles of CH3COONa weighs 4.1g
X=( ) = 0.05moldm-3
[acid] = 0.01
CH3COOH(aq) CH3CO (aq) + H+(aq)
CH3COONa(aq) CH3CO (aq) + Na+(aq)
From the Henderson – Hassel balch equation;
pH = pKa +

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pH = −logKa+

pH = − +
pH = 5.47
(b). Calculate the pH change of the solution above if;
(i) 1cm3 of 1M NaOH is added
(ii) 1cm3 of 1M HCl is added
Solution
1000cm3 of NaOH contain 1 mole
1cm3 of solution contains moles of NaOH
= 0.001 moles of NaOH
[NaOH] = [ ] = 0.001 moles
ions reacts with unionized acetic acid, decreases the concentration of acid, increasing the
concentration of salt (CH3CO )
CH3COOH (aq) + (aq) CH3CO (aq) + H2O
New [salt] = 0.05+ 0.001= 0.051 mol l-1
New [acid] = 0.01 – 0.001 = 0.009 mol l −1
From pH = pKa +

pH = − +
pH = 4.7696 + 0.753 = 5.523
change in pH = 5.523 – 5.47
change in pH = 0.053 units
(b) 1000cm3 of HCl contain 1 mole
1cm3 of HCl contains moles
-3
[HCl] = [ ] = 0.001moldm
H+ ions reacts with acetate ions , decreasing the concentration of salt , increasing the concentration of
salt caid.
CH3CO (aq) + H+(aq) CH3COOH(aq)
New [salt] = 0.05 – 0.001 = 0.049moldm-3
New [acid]= 0.01 + 0.001 = 0.011 moldm-3
From pH = pKa +

pH = − +
pH = 5.418
change in pH = 5.418 – 5.47 = − 0.052 units
2. Calculate the mass of Sodium ethanoate that should be added to 0.1M ethanoic acid at 25OC to give a
solution of pH 5.5.
State any assumptions made (Ka of ethanoic acid = 1.8 × 10−5moldm-3)
Solution
From pH = pKa +

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5.5 = −log Ka +

5.5 = −log (1.8 × 10−5) +

log [salt] = − 0.245
[salt] = 0.569mol l−1
RMM of CH3COONa = 82.
1 mole of CH3COONa weighs 82g
0.569 moles of CH3COONa weigh (82 × 0.569 ) = 46.62g
Mass of CH3COONa = 46.62g
Activity UNEB 2001(paper 1 no.15, 1999(p1 No. 12), 2007 p1. 13a)
(b) Action of basic buffers
Consider a solution of weak base(ammonium hydroxide) and its highly ionisable salt( Ammonium
chloride)
-NH4OH partially ionizes while NH4Cl fully ionizes both producing NH

NH4OH(aq) NH (aq) + H(aq)

NH4Cl(aq) NH (aq) + Cl−(aq)

-Solution contains excess of NH , a large amount of unionized ammonium hydroxide, and a small
amount of hydroxyl ions.
-Addition of a small amount of strong acid, HCl ,hydrogen ions added are removed by ammonium
hydroxide;
NH4OH(aq) + H+(aq) NH (aq) + H2O
-Solution suffers no change in pH
-Addition of a small amount of a base, H added are removed by reacting with NH forming unionized
ammonium hydroxide/ ammonia and water, thus
-pH remains constant;
NH (aq)+ H(aq) NH4OH(aq) (NH3(aq) + H2O (l))
pH calculation of Basic buffers:
 Consider a buffer solution consisting of ammonium hydroxide and ammonium chloride.
NH4OH(aq) NH (aq) + H(aq)

NH4Cl(aq) NH (aq) + Cl−(aq)

By law of mass action; Kb =

Kb =

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Assumptions
i. Concentration unionized NH4OH is equal to the concentration of base.
ii. NH4Cl fully ionizes,[NH ] = [salt]

Therefore = Kb

=− +−

= pKb −

= pKb+

pOH = pKb + But pKw = pH + pOH

pH = pKw - pKb +

Examples
1. A solution consists of 0.01M ammonia solution and 2.13g of ammonium chloride in a litre of solution
(Kb for NH4OH = 1.8 × 10−5moldm-3)
a) Calculate the pH of the solution
b) pH change of solution on addition of 1cm3 of 1M HCl
Solution
Relative molecular mass of NH4Cl =53.5
1 mole of NH4Cl weighs 53.5g
X mole of NH4Cl will weigh 2.13g
X = [NH4Cl] = = 0.0398mol l−1

From pOH = pKb + = −log (1.8 × 10−5) + = 5.345

pKw = pH + pOH , pH = pKw − pOH = 14-5.345= 8.655

b) moles of HCl
1000cm3 of solution contains 1 mole of HCl
1cm3 of solution contains moles
HCl(aq) H+(aq) + Cl
1 mole of acid produces 1 mole of H+(aq)
Concentration of H+ = 0.001moles
H+(aq) +NH4OH(aq) NH (aq) + H2O (l)
New [salt] = 0.0398 + 0.001 =0.0408 mol l−l

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New [Base] = 0.01 – 0.001 = 0.009mol l−l

pOH = −log (1.8 × 10−5) + log
pOH = 5.401
pH = 14 – 5.401 = 8.59885
pH change = 8.655 – 8.59855
pH change = 0.056units
2. calculate the pH of the solution which was made by adding 30cm3 of 0.1M HCl to 80cm3 of 0.1M
ammonia solution (Kb = 1.8 × 10−5moll-1)
Solution
Moles of acid
1000cm3 of solution contains 0.1moles of acid
30cm3 of solution contains
= 0.003moles
Moles of NH4OH
1000cm3 of solution contains 0.1moles of base
80cm3 of solution contains
= 0.008moles

NH4OH(aq) + HCl(aq) NH4Cl(aq) + H2O

Moles of acid that reacted = 0.003 = [salt]
Moles of base that reacted = 0.003
Moles of excess base = 0.008 – 0.003
= 0.005 moles
Excess NH4OH and salt formed (NH4Cl) forms a basic buffer:
pOH = pKb + log

pOH = −log (1.8 × 10−5) + log

pOH = 4.523
pKw = pH + pOH
pH = 14 – 4.523
pH = 9.477
Activity
1. 0.01M ammonia solution was 4.5% ionized when dissolved in water
a) Write the expression for the ionization of ammonia in water
b) Calculate the base dissociation constant, Kb
c) Calculate the concentration of ammonium chloride in grams per litre that must be added to
the solution in (a) to give a pH of 8.83.
2. UNEB 2012 (2) NO. 3C
APPLICATIONS OF BUFFER SOLUTIONS:
 Controlling the pH of the reactions in industrial processes eg in fermentation process.
 electroplating metals
 Maintaining the pH of blood plasma constant i.e. 7.4 eg carbonic acid and its conjugate base
,HCO
 Used in preparations of standard solutions of definite pH
 Used in preservationof food.
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 Control pH of shampoos.
SALT HYDROLYSIS
Is a process whereby a salt dissolved in water produces cations and anions which interact with water
producing more H+ and H ions so that pH of the resultant solution is either greater than or less than 7.
(a) Hydrolysis of salt of strong base and weak acid.
These salts include;
 Sodium acetate (CH3COONa) , Sodium carbonate (Na2CO3), Sodium cyanide (NaCN)
When Sodium acetate is dissolved in water;
 Salt being a strong electrolyte; is highly dissociated and water is slightly dissociated.
H2O (l) H+ (aq) + (aq)
Unionized
water
CH3COONa(aq) CH3CO (aq) + Na+(aq)
 Acetate ions react with hydrogen ions from water resulting in the excess of hydroxyl ions
CH3CO (aq) + H2O(l) CH3COOH(aq) + H(aq)
 More water molecules ionize to restore water equilibrium producing more hydroxyl ions in
excess; solution will have pH greater than 7;
a) Hydrolysis constant Kh for a salt of a weak acid
Consider salt BA formed from combination of a weak acid HA and a strong base, BOH
(aq)+ H2O(l) HA(aq) + H (aq)
By law of mass action; Kh = --------- (i) (Assumption H2O is large in excess)
At equilibrium [HA+] = [ H]
Kh =
Since = [salt]
Kh =
Relationship between Kh, Ka, Kw
Multiplying the denominator and numerator of the expression (i) by the concentration of hydrogen ions;
Kh = ×

Kh = . H] [H+]

But [ ][H+] = Kw and Ka =

Kh = Kw

Kh =

Degree of hydrolysis of a salt of weak acid and strong base:

-Is the fraction of the total salt that undergoes hydrolysis when equilibrium has been established;
Consider a salt of initial concentration, C moldm−3, degree of hydrolysis, h

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(aq)+ H2O(l) HA (aq)+ H(aq)

Initial conc C − −
Moles ch ch ch
Hydrolysed
Eqm moles (C − Ch) ch ch
By law of mass action: Kh =
At equilibrium [ H] = [HA]
Kh = = =

Kh = ; For dilute solution, h is very small, 1 – h ≅ 1

h= Examples
1. Calculate the degree of hydrolysis of 0.1M solution of potassium cyanide. (dissociation constant of
hydrogen cyanide at 250C is 7.2 × 10−10 moldm−3)
Solution
From Kh = =

= 1.388889 × 1 moldm−3

But h =

h=
h = 0.012 = 1.2%

2. Calculate the pH of solution of sodium ethanoate made by dissolving 8.4gdm-3 in water (Kh = 5.5 ×
10−10) moldm−3)

Solution
CH3COONa(aq) CH3CO (aq) + Na+(aq)
CH3CO (aq) + H2O(l) CH3COOH(aq) + H(aq)

Kh=

But at equilibrium [CH3COOH] = [ ]

Kh = ----------------------(i)
RFM of CH3COONa = 82
1 mole of CH3COONa weighs 82g
X mole of CH3COONa weighs 8.4g
X= = 0.1024 moldm−3
From (i) = 0.1024 × 5.5 × 10−10

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= 7.5 × 1 moldm−3
pOH = −log [
=−
pOH= 5.125
pH = pKw – pOH
pH = 14 – 5.125
pH = 8.875
ACTIVITY
1. When a certain mass of sodium propanoate was dissolved in 1 litre of water, 10cm3of this solution
required 7.0cm3 of 6.0 × 10−3 M for complete neutralization. Calculate the mass of sodium propanoate
dissolved in 1 litre of water ( K h = 6.0 × 1 )
2. The pH of a solution formed by dissolving 7.2g of sodium benzoate in 1litre of water is 8.6. Calculate
the hydrolysis constant of sodium benzoate
b) Hydrolysis of a salt from strong acid and weak base eg NH4Cl;
When NH4Cl is dissolved in water;
-Salt being a strong electrolyte; is highly dissociated; and water partially ionizes.
NH4Cl(s) + (aq) NH4+(aq) + Cl−(aq)
H2O(l) + H+(aq) + H (aq)
- NH reacts with ions from ionized water forming unionized NH4OH
-concentration of hydroxyl ions is decreased.
-More water molecules ionize producing more hydrogen ions; molar concentration of hydrogen ions
exceed the hydroxyl ions , pH becomes less than 7.
Hydrolysis constant of a salt from a weak base and strong acid
NH4Cl (s) + (aq) NH (aq) + Cl

NH (aq) + H2O(l) NH4OH (aq) + (aq)

OR NH (aq) + H2O(l) NH3(aq) + H3O (aq)

Kh =

At equilibrium ]
Kh =

Kh =

[ ]=
Degree of hydrolysis:

h=

Kw =
Activity.

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1. Given that the dissociation constant of ammonium chloride at 250C is 1.8 × 10−5 .Calculate the
hydrolysis constant and the degree of hydrolysis of ammonium chloride in 0.001M solution. What will
be the hydrogen ion concentration of the solution?
2 (a). The pH of ammonium nitrate solution is 5.45. Explain this observation.
b) Calculate the hydrolysis constant of ammonium nitrate.
3. Methyl ammonium chloride undergoes hydrolysis according to the equation.
CH3NH3+ (aq)+ H20(l) CH2NH2(aq) + H3O+(aq)
a) Write the expression for its hydrolysis constant.
b) When 6.7g of methyl ammonium chloride was dissolved in 500cm3 of water, the pH was
2.33. Calculate the hydrolysis constant of the salt.
c) Calculate the volume of the above solution that would react completely with 10cm3 of 0.25M
Sodium hydroxide solution..
4. Calculate the pH of 0.001M solution of phenyl ammonium chloride whose Kh = 1.8 × 10−3 moldm−3.
ACID – BASE INDICATORS/ HYDROGEN ION INDICATORS
 Are substances that change colour according to the hydrogen concentration of the solution, in
which they are added.
 Are weak acids or weak bases , therefore ;
- are slightly dissociated when dissolved in water.
- Its colour depends on the colour of the undissociated molecule and anion
produced(negatively charged.)
INDICATOR FUNCTIONING
(a). Phenolphthalein (HPh)
HPh(aq) + H2O(l) H3O+(aq) + Ph−(aq)
Colourless pink
Undissociated molecule anion produced;

In acidic solution with high concentration of H+,

 Hydrogen ions remove Ph−, equilibrium shifts from right to left.
 Solution contains an excess of HPh molecules; showing colourless
In alkaline solution, with high concentration of ,
 Addition of removes the hydroxonium ions, producing water, decreasing the concentration of
+
H3O .
 Decrease in H3O+ concentration disturbs the equilibrium; more of the HPh ionizes producing Ph−
molecules; solution appears pink.
(b). Methylorange
HA(aq) H+(aq) +A−(aq)
Red yellow
In acidic solution, with high concentration of Hydrogen ions,
 Hydrogen ions remove A− ions, equilibrium shifts right to left.
 Solution contains an excess of HA molecules showing red colour;
In alkaline solution, with high concentration of hydroxyl ions;
 Addition of hydroxyl ions remove the hydrogen ions, producing water; decreasing concentration
of hydrogen ions.
 More HA ionize producing A- ions; colour of methyl orange appears yellow
QUESTION
a) Explain what is meant by the term acid – base indicator.
b) Explain how phenolphthalein acts as an indicator.
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INDICATOR CONSTANT (Kxn)

Consider unionized form of indicator, HIn which is a weak acid
HIn(aq) H+(aq) + In−(aq)
Colour x Colour y
By law of mass action;
KIn =
WORKING RANGES OF INDICATORS
 Is the range of hydrogen ion concentration/pH ; over which different indicators change colour.
From KIn = , [ ]=
Taking negative logarithm on both sides
=−

=− +−

pH = pKIn −

pH = pKIn + Henderson – Hasselbalch equation for Indicators

For colour Y; [In−] = 10[HIn]

⟹ pH = pKIn + ,
pH = pKIn + 1
For colour X; [HIn]= 10[In−]
⟹ pH = pKIn +
pH = pKin– 1
pH = pKIn ± 1

Therefore range of pH over which indicator changes colour is pH = pKIn ± 1,

e.g for phenolphthalein, PKin (9.4), for pink (colour y), 9.4+1= 10.4; for colourless (colour x) 9.4-1=8.4,
range of 8.3-10.4.
Table showing some indicators, their colours and pH ranges
Indicator PKIn pH range Colour
Acid Base

Thymol blue 1.51 1.2-2.8 red yellow

Methyl orange 3.70 3.0-4.5 red yellow
Methyl red 5.10 4.2-6.3 red yellow
Phenolphthalein 9.4 8.3-10.0 colourless pink
Bromo thymol blue 7.0 6.0-7.3 yellow blue
NB:
− Universal indicator is a mixture of indicators which give a gradual change in colour over a wide
range of pH.
pH CHANGES DURING ACID – BASE TITRATIONS
 Depends on the nature of acid and base used eg;

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Strong base against strong acid (HCl Vs NaOH)

pH

10 C

7 (4 − 10)

4
B

2 A
Volume of base added (cm3)
-. At A, pH is low, HCl is a strong acid which completely ionizes producing many hydrogen ions.
AB;
− Slow pH rise, hydrogen ion from acid is removed from hydroxyl ion added.
BC;
− Asharp rise in pH, (4−10), is due to a small amount of Sodium hydroxide added at the end point;
when equivalent amounts of acid and base are added
− pH at end point 7; neutral salt formed is not hydrolysed.
− Methyl red, phenolphthalein, Bromothymol blue are the most suitable indicators used.
CD
− Rise in pH is due to excess NaOH added after the end point
Example
1. 20.0cm3of a 0.02M sodium hydroxide was added to 30cm3of 0.025M sulphuric acid.
Calculate the;
a) Molar concentration of the hydrogen ions in the initial sulphuric acid.
b) Molar concentration of the hydrogen ions in the resultant solution
c) pH of the resultant solution (Uneb 1999 (No 5)

Solution
a) H2SO4(aq) 2H+(aq) + SO (aq)

1 mole ofH2SO4 produces 2 moles of H+

0.025moles of H2SO4 produces (2 × 0.025)
= 0.05M
b) Moles of Sulphric acid
1000cm3 of solution contains 0.025moles of H2SO4
30cm3 of solution contains moles
−4
= 7.5 × 10 moles
Moles of sodium hydroxide
1000cm3 of solution contains 0.02 moles of NaOH.
20.0cm3 of solution contains moles
= 4 × 10−4 moles

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2NaOH(aq) + H2SO4(aq) Na2SO4(aq)+ 2H20(l)

2 moles of NaOH reacts 1 mole of H2SO4
Moles of H2SO4 that reacted = × 4.0× 10−4 moles = 2×10−4 moles
Moles of unreacted/ excess H2SO4 =7.5 ×10−4− 2×10−4 = 5.5×10−4 moles
Total volume of solution = (20 + 30) cm3
= 50.0cm3
50cm of solution that contains 5.5×10−4 moles of H2SO4
3

1000cm3 of solution contains moles

Molar concentration = 0.011M
Molar concentration of H+= (2 × 0.011)M
= 0.022M
c) pH = −
pH = −
pH = 1.66
2. Calculate the pH obtained by addition of 20cm3 of 0.1M NaOH to 40cm3 of 0.1M HCl
Solution
Moles of Hydrochloric acid;
1000cm3 of solution contain 0.1 moles of HCl
40cm3 of solution contains moles = 4 ×10−4 moles
Moles of sodium hydroxide;
1000cm3 of solution contain 0.1moles of NaOH
20cm3 of solution contains moles = 2 ×10−3moles
NaOH(aq) + HCl(aq) NaCl(aq)+ H20 (l)
From the reaction equation, 1 mole of NaOH reacts with 1 mole of HCl
Moles of HCl that reacted = moles of sodium hydroxide, 2×10−3 moles
Moles of unreacted/excess HCl = (4 ×10−3− 2×10−3) = 2 ×10−3moles
Total volume of solution = (20 + 40) cm3 = 60.0cm3
60cm3 of solution that contains 2×10−3 moles of HCl
1000cm3 of solution contains moles = 0.033M
HCl(aq) H+(aq) + Cl−(aq)
1 mole of HCl ionizes to produce 1 mole of H+
[H+] = 0.0333M
pH = −
pH = −
pH = 1.48

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STRONG ALKALI VS WEAK ACID (CH3COOH VS NaOH)

Titration curve of weak acid Vs strong base
pH

14 D

10
C

8 B

2 A

Volume of NaOH added (cm3)

− pH of the ethanoic acid is slightly higher compared to that of HCl. Ethanoic acid is a weak acid, only
partly ionized in solution producing few hydrogen ions.
− Addition of NaOH, H from the NaOH reacts with H+ of the solution, leading to an increase in pH
along AB
− pH at endpoint, when equivalent amounts of NaOH and CH3COOH are present is greater than 7 ie 9
reason
− NaOH reacts with ethanoic acid to produce sodium ethanoate
CH3COOH(aq) + NaOH(aq) CH3COO + H2O
− Salt formed undergoes hydrolysis producing excess H ions;
+
CH3COONa(aq) CH3CO (aq) + Na (aq)

CH3CO (aq) + H2O ⇌ CH3COOH(aq) + H(aq)

− Excess H produced rises the pH along BC from 8 – 10.
− Between CD rise in pH is due to the excess NaOH added
− Phenolphthalein is the most suitable indicator.

Example
1. Calculate the pH of the solution obtained when 20cm3 of 0.1M NaOH is added to 10.0cm3 of 0.1M
CH3COOH (Ka = 1.8 × 10−5moldm−3)
Solution
Moles of ethanoic acid
1000cm3 of solution contains 0.1 mole of CH3COOH
100cm3 of solution will contain moles = 0.01 moles

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Moles of NaOH
1000cm3 of solution contains 0.1 mole of NaOH
20cm3 of solution will contain 0.002 moles
CH3COOH(aq)+ NaOH(aq) CH3COONa(aq) + H2O(l)
1 mole of acid reacts 1 mole of NaOH to produce 1 mole of salt
0.002 moles of acid reacts 0.002 moles of NaOH to produce 0.002 moles of salt
Moles of unreacted / excess acid = 0.01 – 0.002 = 0.008moles
Total volume of solution = 100 + 20 = 120cm3
120cm3 of solution contains 0.008 moles
1000cm3 of solution contains moles
= 0.067 moles l−1
Salt formed and unreacted acid form a buffer solution;
pH = pKa +
[salt] = ?
120cm3 of CH3COONa contains 0.002moles
1000cm3 of CH3COONa contains moles = 0.01667M

⟹ pH = − +
= 4.14

activity UNEB: 2001 paper 2 (4b)

Titration of strong acids and weak base (HCl Vs NH4OH)
pH
14
D
C
6.5
3.5
B

2A Volume of NH4OH added

A:

Low pH , HCl is a strong acid which fully ionizes in solution; giving a high concentration of
hydrogen ions
AB;
As the NH4OH is added;- H ions from the base reacts with hydrogen ions in solution, pH rises
BC;
-pH rises from 3.5 to 6.5, ammonium solution reacts with HCl producing ammonium chloride.
-pH at end point is below 7;

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Reason;-
NH4OH + HCl (aq) NH4Cl(aq) + H2O(l)
-Salt formed undergoes hydrolysis in water
NH4Cl(aq) NH (aq)+ Cl−(aq)

NH (aq)+ H2O(aq)⇌NH4OH(aq) + H+(aq)

-Hydrolysis leaves excess of H+ ions; hence pH less than 7
-Further rise in pH along CD is due to excess of NH4OH is added.
-Methyl orange is a suitable indicator.
Example
Calculate the pH of a solution when 100cm3 of 0.1M NH4OH is added to 20 cm3 of 0.1M HCl (Kb for
NH3 = 2.12 ×1 )
Solution
Moles of NH4OH
1000cm3 of solution contains 0.1 moles of NaOH
100cm3 of solution contains moles = 0.01 moles
Moles of HCl
1000cm3 of solution contains 0.1 moles of HCl
20cm3 of solution contains moles = 2 × 10−3
NH4OH(aq)+ HCl(aq) NH4Cl(aq) + H2O(l)
From the equation of reaction above,
Excess moles of base = (0.01 – 0.002) = 0.008 moles
Total volume = (100 + 20) = 120cm3
120 cm3 of solution contains moles of NH4OH

1000 cm3 of solution contains moles of NH4OH

= 0.0167M

From pOH = pKb +

⟹ pOH=− +
pOH = 4.07
⟹from pKw = pH + pOH

pH= pKw− pOH

= 14 – 4.07
pH = 9.93
Activity . Uneb 2012 (paper 2 , 3b)

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Titrations of weak acids and weak bases eg CH3COOH and NH4OH

-pH range between 6.5 – 7.5
-no suitable indicator can be used; there is no sharp change in pH art any point

pH
14−

Volumeof NH4OHadded (cm3)

SOLUBILITY PRODUCT
Consider a sparingly soluble salt silver bromate , AgBrO3
-AgBrO3 added to water, a saturated solution( containing both the ions & undissolved solute ) is formed
-Equilibrium is established between ions and excess undissolved solute , AgBrO3
AgBrO3(s) ⇌Ag+(aq) + BrO (aq)

Excess
undissolved
Solute

By law of mass action, Kc =

Kc =

But; = constant
Kc × = Ksp (solubility product)

Therefore, Ksp =

Generally for a saturated solution of a sparingly soluble salt

AxBy(s)⇌xA+y(aq) + yB_x(aq)

Ksp = [A+y [B−x]y

Definition
-Solubility product (Ksp) is the product of the concentration of ions raised to their powers of
stoichiometric coefficients in a saturated solution of a sparingly soluble salt of an ionic compound of a
given temperature;
ACTIVITY.
Write an expression for the solubility product of;
(i). Bi2S3 (ii). AgCl (iii). PbI2 (iv). Ca(OH)2

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Limitations of solubility product/condtions of solubility product

-Valid for only saturated solutions
-Only valid at constant temperature
-Only applied for sparingly soluble salts
Example
1. The solubility of Calcium hydroxide in water at 20OC is 2.78gdm−3. What is the solubility product
(Ca = 40, O = 16, H =1)
Solution:
Relative formula mass of Ca(OH)2 = 40 + (16 × 2) + (1×2) = 74
1 mole of Ca(OH)2 weighs 74g
X mole of Ca(OH)2 will weigh 2.78
∴ Molarity = = 0.038dm−3
[Ca(OH)2 ] = 0.038dm−3
Ca(OH)2 (s)⇌Ca2+(aq) + 2 (aq)
[Ca2+] = 0.038dm−3
[ ] = 2 × 0.038 = 0.076moldm−3
Ksp = [Ca2+] [ ]2
= 0.038 × (0.076
Ksp= 2.19 × 10−4mol3dm−9

2. The solubility product of silver Carbonate at 200C is 8 × 10−2 mol3dm−9. What is the solubility at
this temperature?
Solution
From, Ag2CO3(s) ⇌ Ag+(aq) + CO (aq)

If the solubility of Ag2CO3(s) is S moldm−3

[Ag+] = 2S moldm−3
[CO ] = S moldm−3

Ksp = [Ag+][ CO ]
8 × 10−2 = (2S)2S
8 × 10−2 = 4S3
Solubility = 0.27moldm−3
Activity:
1. Calculate the solubility of silver ethanedioate (Ag2C2O4) in water. (Ksp of Ag2C2O4 = 5× 10−12
mol−3dm−9)
2.The solubility of AgCl at 180C is 1.46 × 10-3gdm-3. What is the solubility product (Ag = 108, Cl = 35.5)
3. The solubility product of calcium Phosphate at 250C is 6 × 10−29mol5dm−15. Calculate the solubility of
Calcium phosphate in gdm−3 at 250C.
FACTORS AFFECTING THE SOLUBILITY OF SPARINGLY SOLUBLE SALT.
(i) Common ion effect:
-Is the precipitation of a sparingly soluble ionic compound from a saturated solution by addition of
another soluble compound containing a similar ion
Consider a saturated solution of PbSO4;

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PbSO4⇌ Pb2+(aq) + SO (aq)

Addition of Pb(NO3)2 solution;

-More Pb2+ ions, a common ion is produced; increasing the concentration of Pb 2+ in the equilibrium.
-To restore the equilibrium, excess Pb2+ from Pb (NO3)2 reacts with SO to precipitate PbSO4
-This decreases solubility of PbSO4
Example:
1. Calcium iodate, Ca(IO3)2 is sparingly soluble in water. Write an,
(a) (i) equation for the solubility of Ca (IO3)2
(ii) expression for the solubility product Ksp of Ca(IO3)2
(b) If the Ksp of Ca(IO3)2 at 250C is 1.95× 10−4 moldm−3. Calculate the solubility in moldm−3.
Calculate the solubility in moldm−3 at 250C.
i. In water
ii. 0.1M solution of NaIO3.
(c) Comment on your answer in (b) above UNEB 2006(1) No. 17
Solution
1 (a)(i) Ca(IO3)2(s)⇌Ca2+(aq) + 2IO (aq)

(ii) Ksp = [Ca2+][IO ]2

(b) (i). From , Ca(IO3)2(s)⇌Ca2+(aq) + 2IO (aq)

Let the solubility of Ca(IO3)2 be m moldm−3

⟹ [Ca2+] = m [IO ] = 2m
From Ksp = [Ca2+][IO ]2
⟹ 1.9 ×10−4 = (m)(2m)2
4m3 =1 .9 ×10−4

m=
= 0.036moldm−3
Solubility of Ca (IO3)2 is 0.036moldm−3 in water
(ii) 0.1M of NaIO3

NaIO3(aq)⇌ Na+(aq) + IO (aq)

Let the new solubility of Ca(IO3)2 in iodate solution be S’ moldm-3

Ca(IO3)2(s)⇌ Ca2+(aq) + 2IO

Solubility of Ca2+ = S’ moldm-3

Solubility of IO = (2S’ + 0.1)

But S’ ≪≪≪ 0.1, (2S’ + 0.1) ≅ 0.1

Ksp = [Ca2+] [IO ]

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1.95×10−4 = S’ (0.1)2
Solubility of Ca(IO3)2 in iodate solution S’ = 0.0195moldm−3

(c.) Comment
− Solubibilty of Ca(IO3)2 in NaIO3 is lower than that in water; because in NaIO3 concentration of

IO is higher; therefore IO react with Ca2+ to precipitate out Ca(IO3)2.

Activities:
UACE 2000(1) no 12, 2005(1) no 17, 2004(1) no 17, 2003(1) no 17, 2001(1) no 16(a, b(i).
ii) Complex ion formation:
-Increases solubility of a sparingly soluble salt i.e.
Consider solubility of AgCl in water,
AgCl(s) + ⇌ Ag+(aq) + Cl-(aq)
− Addition of ammonia solution, ammonia reacts with silver ions, forming diamine silver ion
complex .
Ag+(aq) + 2NH3(aq)⇌ [Ag(NH3)2]+
− Concentration of Ag+ decreases;
− to restore equilibrium, AgCl solid ionizes to produce more Ag+ ions, increasing the solubility.
Example.
a) State how the solubility of Ag2SO4 is affected if the following substances were added;
i) Na2SO4
ii) NH4OH
b) Explain your answer in (a) (UACE, 2001(1) no.16 (b)
Solution
a) (i). solubility would decrease
(ii) Solubility would increase
b) a(i)
− Na2SO4 is a strong electrolyte; therefore strongly ionizes in aqueous solution to form a higher
concentration of SO ions

− Ag+ react with excess SO ions ; forming solid silver sulphate, Ag2SO4; hence decreasing

solubility.
(ii) Ammonia react with Ag+ to form a complex; decreasing the concentration of Ag+ in
solution; therefore more silver sulphate dissolves to restore the equilibrium, hence increasing
solubility of the salt.

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APPLICATION OF COMMON ION EFFECT

i. Purification of common salt: (NaCl)
-NaCl contains small quantities of MgCl2 and CaCl2 as impurities.
-This causes it to be deliquesecent (absorb water from the atmosphere and appear damp)
-Pure NaCl is obtained by passing HCl gas into a saturated solution of impure NaCl (Addition of
HCl gas provides Cl− which precipitate only pure NaCl)
ii. Salting out of soap:
Saturated solution of soap, sodium stearate (Nast) contains the following ions;
Nast(s)⇌Na+(aq) + St −(aq)
During saponification (soap making), concentrated solution of NaCl is added
More Na+ are produced, excess Na+ react with St− to precipitate soap
Na+(aq) + St−(aq) NaSt (s)
APPLICATIONS OF SOLUBILITY PRODUCT ON QUALITATIVE ANALYSIS
-Used in predicting precipitation of salts eg sulphides, hydroxides, chlorides, etc
NB: For saturated solution, ionic product is equal to solubility Product; therefore can be used to
predict whether or not precipitation occurs.
Therefore if,
i. Ionic product is greater than the solubility product, solution is supersaturated, precipitation
will occur
ii. If ionic product is less than the solubility product , solution is unsaturated, precipitation will
occur not occur.
Example:
1. Predict whether or not precipitation occurs when 0.001moldm-3 solution of Ca2+ is mixed with an
equal volume of a 0.001moldm-3 solution of SO at 25OC. (Ksp of CaSO4 = 2×10-5mol2dm-6 at
25OC). Show your working.
Solution
-Mixing equal volumes of the two ions, molar concentration of the ions are halved, because each
solution is diluted by mixing with the other.
new[SO ]= = 0.0005moldm-3

new [Ca2+] = = 0.0005moldm-3

Ionic product immediately after mixing
Ionic product = [Ca2+] [SO ]
= 0.0005 × 0.0005
= 2.5 × 10-7mol2dm-6
Ionic product, 2.5 × 10-7 mol2dm-6 is less than the solubility product; no precipitation occurs.

2. 20cm3 of 0.01M Barium chloride solution and 20cm3 of 0.005M solution of Sodium Sulphate are
mixed at 25OC. Determine whether or not precipitation occurs( Ksp of Barium sulphate is 1x10-20
mol2dm-6).
Solution
BaCl2(aq)⇌ Ba2+(aq) + 2Cl−(aq)
0.01 0.01
Na2SO4) ⇌2Na+ + SO
0.005 0.005

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Mixing 2 equal volumes, the concentration of the ions are halved,

[Ba2+] = = 5×10−3moldm-3

[SO ] = = 2.5× 10−3moldm-3

Ionic product = [Ba2+] [SO ]

= (2.5× 10 ) (5×10−3) =1.25×10−5mol2dm−6
−3

Ionic product, 1.25×10−5mol2dm−6 is greater than the solubility constant value, there precipitation will
occur.
ACTIVITY
1. A solution containing Ag+ was added to a solution containing 0.005M Chromate ions and
0.005M Cl−. State which of the salts, AgCl or Ag2CrO4 was precipitated first. Give a reason for your
answer.
2. A solution is 0.01M in cuprous ion, (Cu+) and 0.001M in lead (II) ion. Cl− is slowly added, will
lead (II) Chloride (Ksp = 1.6×10−5mol3/l2) or CuCl (Ksp = 3.2× 10−7mol3/l2) precipitate first? Show
your working.
Experimental determination of solubility product
Solubility product can be determined directly by;
 Direct titration or Titrimetric method
 Ion exchange
 Conductivity measurements
a) Direct titration
i. Ca(OH)2
− A Known volume of water is placed in a bottle and a known mass of Ca(OH)2is added to it.
− The bottle is corked, shaken for about 35 minutes,at fixed temperature; allowed to settle for
equilibrium to be attained.
− Know volumes of clear solution are then pippeted into a conical flask, titrated with a standard
solution of HCl using methyl orange indicator.
− Knowing the number of molecules of HCl, number of moles and concentration of H can be
calculated.
Ca(OH)2 + 2HCl(aq) CaCl2(s) + 2H2O(l)
− Concentration of Ca2+ can be determined from
[[Ca2+] = ½[ H] from mole ratio
⟹ Ksp = [Ca2+][ H]2
ii. Potassium Iodate in water
− A known volume of distilled water is placed in a bottle and a known mass of Potassium
iodate is added.
− The bottle is stoppered, shaken for a period of time, at fixed temperature, allowed to settle to
reach equilibrium.
− After equilibrium has been attained, known volumes of the clear saturated solution are
pipetted into a conical flask containing potassium iodide with dilute H2SO4
IO + 5I− + 6H+ 3I2 (aq) + 3H2O

− Iodine liberated is then titrated with standard thiosulphate solution using starch as an
indicator

Compiled by Lawrence arum +256-7505133312/717503108, HOD at K.SS, Also taught at KISUBI

MAPEERA, ST JOSEPH’S GIRLS NSAMBYA, KAKIRA S.S, LAKE SIDE COLLEGE LUZIRA . Page 28
 Lawrence arum , [email protected], +256-750513312

2S2O (aq) + I2 (g) S4O (aq)+ 2I− (aq)

− Titrate until when the solution turns blue, repeat and note the average volume of the
thiosulphate solution used.
− Knowing the concentration of the thiosulphate, mole of Iodine liberated can be determined,
from which concentration of iodate ions can be obtained.
[IO ] = [K+]
Ksp= [IO ] [K+]

Compiled by Lawrence arum +256-7505133312/717503108, HOD at K.SS, Also taught at KISUBI

MAPEERA, ST JOSEPH’S GIRLS NSAMBYA, KAKIRA S.S, LAKE SIDE COLLEGE LUZIRA . Page 29