CHAPTER

Ionic Equilibria
7
7.1 Acids and Bases
7.2 Acid-Base Titration
7.3 Solubility Equilibria

SK015 NURUL SYAFIQAH ZAKARIYA

1
 7.1 Acids and Bases
At the end of this topic, students should be able to:

a) Define acid and base according to Arrhenius and

Bronsted-Lowry theories.
b) Identify conjugate acid and conjugate base according to
Bronsted-Lowry theory.
c) Relate pH and pOH to the ionic product of water, Kw at 25
°C.
d) Define strong acid and base, weak acid and base, pH,
pOH and pKw.
e) Calculate the pH values of a strong acid and base.
f) Relate the strength of a weak acid and a weak base to2
the respective dissociation constant, Ka and Kb.
 7.1 Acids and Bases

g) Perform calculations involving pH, dissociation

constant, initial concentration, equilibrium
concentration and the degree of dissociation, a.
h) Explain qualitatively salt hydrolysis using hydrolysis
equations and classify the salts formed from the
reaction between:
i. strong acid and strong base
ii. strong acid and weak base
iii. Weak acid and strong base
i) Define buffer solution.
j) Descibe how a buffer solution controls its pH.
 7.1 Acids and Bases
k) Write the Henderson-Hasselbalch equation for a given
buffer solution.
l) Calculate the pH of buffer solutions using the
Henderson-Hasselbalch equation before and after the
addition of strong acid or base.
 Theory of acids and bases

Three important theories of defining acids and bases

1. Arrhenius theory
2. Bronsted-Lowry’s theory
3. Lewis theory

5
1. Arrhenius Theory

Acid is any substance that dissociates in water to

produce hydrogen ions (H+) or hydronium ions (H3O+).

Example:

HCl (aq) ¾¾® H+ (aq) + Cl- (aq)

HCl (aq) + H2O (l) ¾¾® H3O+(aq) + Cl- (aq)

6
1. Arrhenius Theory

Base is any substance that dissociates in water to

produce hydroxide ions (OH-).

Example:

NaOH (aq) ¾¾® Na+ (aq) + OH- (aq)

7
2. Bronsted-Lowry Theory
Acid is any substance that can donate a proton (H+)
to other substances.

Example:

HNO3 (aq) + H2O (l) ¾¾® NO3- (aq) + H3O+ (aq)

acid

NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq)

acid

8
2. Bronsted-Lowry Theory

Base is any substance that can accept a proton from

other substances

Example:
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
base

CO32- (aq) + H2O (l) HCO3- (aq) + OH- (aq)

base

H2O is able to act as an acid or a base : AMPHOTERIC

9
Conjugate acid-base pairs

Conjugate base
A species that remains when one proton (H+) has been
removed from the Bronsted acid.

Conjugate acid
A species that remains when one proton (H+) has been
added to the Bronsted base.

10
Example

HCO3- (aq) + H2O (l) CO32- (aq) + H3O+(aq)

acid base conjugate conjugate
base acid

Note:
— A weaker acid has a stronger conjugate base.
— It is due to the ability of the acid to transfer its proton.
— The acid donates its proton less readily because its
conjugate base holds it more strongly.

11
 Exercise 1

1. In the following reactions, identify the acid-base conjugate

pairs.

a. ClO- (aq) + H2O (l) HOCl (aq) + OH- (aq)

b. CH3NH2 (aq) + H2PO4- (aq) CH3NH3+(aq) + HPO42- (aq)

12
c. HBr(aq) + NH3(aq) NH4+(aq) + Br- (aq)

d. PO43-(aq) + H2O(l) HPO42-(aq) + OH-(aq)

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

13
 Exercise 2

2. Write the conjugate base formula for the following acids.

a) HS- d) H3PO4
b) HCN e) H3O+
c) N2H5+ f) CH3NH3+

14
 Exercise 3
3. Write the conjugate acid formula for the following bases.

a) HS- d) NH3
b) C6H5COO- e) H2O
c) OH- f) H2PO4-

15
 Strength of acids and bases

Strength of acids and bases depend on the extent of

dissociation.

[ ]dissociated
% dissociation = ´ 100%
[ ]initial

[ ]dissociated
Degree of dissociation, a =
[ ]initial

16
 Strong acid
— Strong acid is an acid that ionizes completely in
water.

— 3 ways to write the equation for acid dissociation:

a) HCl (aq) ¾¾® H+ (aq) + Cl- (aq)

H 2O (l)
b) HCl (g) H+ (aq) + Cl- (aq)

c) HCl (g) + H2O (l) ¾¾® H3O+ (aq) + Cl- (aq)

17
 Example : Dissociation of 0.10 M HCl

HCl (aq) + H2O (l) ¾® Cl- (aq) + H3O+ (aq)

[ ]i (M) 0.10 0 0
Δ[ ] (M) - 0.10 + 0.10 + 0.10
[ ]f (M) 0.00 0.10 0.10

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 [HCl]dissociated
% dissociation = ´ 100%
[HCl]initial
= 0.10
100%
0.10
= 100 %
[HCl]dissociated
Degree of dissociation, a =
[HCl]initial
= 0.10
0.10
= 1.00

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Example of strong acids:

• Hydrohalic acids HCl, HBr and HI

• Oxoacids in which the number of O atoms exceeds

the number of ionizable protons by two or more.
e.g: HNO3 and HClO4

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 Strong base
— Strong base is a base that ionizes completely in
water.

Example : Dissociation of 0.50 M NaOH

H2 O
NaOH (aq) Na+ (aq) + OH- (aq)

[ ]i (M) 0.50 0 0
Δ[ ] (M) - 0.50 + 0.50 + 0.50
[ ]f (M) 0.00 0.50 0.50

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 [ NaOH ]dissociated
% dissociation = ´ 100%
[ NaOH ]initial

= 0.50 100%
0.50
= 100 %

Degree of dissociation, a = [ NaOH ]dissociated

[ NaOH ]initial
= 0.50
0.50
= 1.00

22
Example of strong bases:

• M2O or MOH, where M is group 1 element :

eg: Li, Na, K, Rb, Cs

• RO or R(OH)2, where R is Ca, Sr, Ba

23
 Weak acid
— Weak acid is an acid that only ionizes partially in
water
Example: CH3COOH, HCOOH

— Generally for any weak acid, HA the dissociation

reaction is:

HA (aq) + H2O (l) A- (aq) + H3O+(aq)

— % dissociation < 100%

— a<1

Remark: indicates partial dissociation 24

— Acid dissociation constant expression, Ka

[A ][H3O ]
Ka =
[HA]

— Ka value depends on temperature

— Normally Ka is measured at 25 °C
— Value of Ka ↓ ; a ↓ strength of acid ↓

25
Example of weak acids:

i) Hydrofluoric acid, HF

ii) Acids in which H is not bonded to O or to halogen

e.g: HCN and H2S

iii) Oxoacids in which the number of O atoms equals or

exceeds by one the number of ionizable protons
e.g: HNO2 and HClO

iv) Organic acids (general formula RCOOH)

e.g: CH3COOH

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 Weak base
— Weak base is a base that only ionizes partially in
water
Example: NH3 and N2H4

— Generally for any weak base, B the dissociation

reaction is:

B (aq) + H2O (l) BH+ (aq) + OH- (aq)

— % dissociation < 100%

— a<1

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— Base dissociation constant expression, Kb

[BH ][OH ]
Kb =
[B]

— Kb value depends on temperature

— Normally Kb is measured at 25 °C
— Value of Kb ↓, a ↓, strength of base ↓

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Example of weak bases:

i) Ammonia (NH3)

ii) Amines
RNH2
eg: CH3CH2NH2 ethanamine
R2NH
eg: (CH3)2NH N-methylmethanamine
R3N
eg: (CH3)3N N, N-dimethylmethanamine

29
 Exercise 4
At 25 °C, 4.2% of 0.10 M formic acid, HCOOH dissociated
in aqueous solution.

Calculate the acid dissociation constant, Ka for formic acid.

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31
— Ka or Kb for many weak acids or weak bases < 10-5.

— Saying that the degree of dissociation is too small, a ↓↓

— To simplify the calculation for ionic equilibrium the

following assumption can be made:

[ ]initial - [ ]dissociated » [ ]initial

— The assumption will give correct answer to at least 2

significant figures if:
i. value of Ka or Kb < 10-5 or
ii. % dissociation < 5%
 Exercise 5
Acid dissociation constant, Ka for hydrofluoric acid HF at
25 °C is 6.8´10-4 M. For a solution of 0.20 M HF,
calculate:
i. the concentration of hydronium ion at equilibrium
ii. degree of dissociation

33
 Exercise 6
Base dissociation constant, Kb for ammonia solution, NH3
at 25 °C is 1.8´10-5 M. For a solution of 0.50 M NH3,
calculate:
i. the concentration of hydroxide ion at equilibrium
ii. % dissociation

35
 Water ionization constant, Kw

• When water molecules ionized, transferring a

proton from one water molecule to another
producing a hydronium ion, H3O+ and
hydroxide ion, OH-.

2H2O (l) H3O+ (aq) + OH- (aq)

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 2H2O (l) H3O+ (aq) + OH- (aq)

The equilibrium constant expression can be written as

follows:
Kw = [H3O+] [OH-]

Kw is the ionization constant for water at 25°C

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For pure water, at 25°C,

[H3O+] = [OH-] = 1 x 10-7 M

Kw = [H3O+] [OH-]
= (1 x 10-7) (1 x 10-7)

\ Kw = 1 x 10-14 M2

Note:
Temperature ↑, Kw ↑ because the dissociation of
water is an endothermic process

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 The pH scale

• The pH scale is used to express acidity.

• The pH of a solution is defined as the negative

logarithm (log) of the hydronium ion (hydrogen ion)
concentration.

pH = - log [H3O+] or pH = - log [H+]

— In similar way, pOH is the negative logarithm of the

hydroxide ion concentration.

pOH = - log [OH-]

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In pure water,

Kw = [H3O+] [OH-] = 1 x 10-14 M2

[H3O+] = [OH-] = 1 x 10-7 M

pH = pOH = - log (1 x 10-7 )

pH = pOH = 7

pH + pOH = 14

41
At 25 oC,

• Acidic solution : pH < 7.0 ; pOH > 7.0

• Basic solution : pH > 7.0 ; pOH < 7.0

• Neutral solution : pH = 7.0 ; pOH = 7.0

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 Exercise 7
In a NaOH solution, [OH-] is 2.9 x 10-4 M.
Calculate the pH of the solution at 25 oC.

43
 Exercise 8
The pH of rainwater in a certain region was 5.68.
Calculate the H+ ion concentration of the
rainwater.

44
 Exercise 9
Calculate the pH of a 0.15 M acetic acid (CH3COOH)
solution, Ka = 1.8 x 10-5.

45
 Exercise 10
What is the pH of a 0.25 M ammonia solution?
Kb = 1.8 x 10-5.

47
 Exercise 11
The pH of 0.06 M solution of formic acid (HCOOH)
is 3.44. Calculate the Ka of the acid.

49
 Exercise 12
The Ka for benzoic acid, (C6H5COOH) is 6.5x10-5. Calculate
the pH of a 0.25 M benzoic acid solution.

51
 Exercise 13
The pH of an acid solution is 6.20. Calculate the Ka for the
acid. The acid concentration is 0.01M.

53
 Exercise 14
Calculate the pH for 0.5 M C5H5N.
Kb = 1.7x10-9

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 Exercise 15
Calculate pH for the following solution.
a. 0.55 M CH3COOH (Ka = 1.8x10-5)
b. 0.23 M NH3 (Kb = 1.8x10-5)
c. 0.15 M HCl
d. 0.20 M KOH
e. 0.45 M HCN (Ka = 4.9 x 10-10)

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 Salts

— Salts are produced when acid reacts with base.

— 3 types of salts are :

1) neutral salts
2) acidic salts
3) basic salts

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 1) Neutral salts

— Produced when strong acid reacts with strong base.

e.g
HCl + NaOH NaCl + H2O
neutral salt
— Dissociation of salt
NaCl(aq) Na+ (aq) + Cl- (aq)
- Na+ comes from strong base
- Na+ does not react with water (does not hydrolyzed)
- Cl- comes from strong acid
- Cl- does not react with water (does not hydrolyzed)

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— So, pH of a solution depends on the ionization of water

H2O (l) H+ (aq) + OH- (aq)

Kw = [H3O+] [OH-] = 1 x 10-14 M2

[H+ ] = [ OH- ] = 1.0 x 10-7 M

pH = 7

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 SALT HYDROLYSIS
— Salt hydrolysis is a chemical reaction between anion or
cation of a salt with water molecules that produces OH-
ion or H3O+ ion.

— The pH value of a solution depends on whether OH- or

H3O+ ion is produced during hydrolysis.

— Acidic salts and basic salts have ions that undergo

hydrolysis in aqueous solution.

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2) Acidic salts
— An acidic salt is produced from the reaction of a strong
acid and a weak base and yields H3O+ when
hydrolysed.
— Dissociation of salt
NH4Cl(s) ¾¾® NH4+(aq) + Cl-(aq)
Cl- : comes from a strong acid
(does not hydrolyzed)
NH4+ : comes from weak base and
undergoes hydrolysis

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Hydrolysis of NH4+ :

NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

— The solution is acidic because hydrolysis of NH4+

produces H3O+

— pH of the acidic salt solution is < 7.0

— Hence, NH4Cl is acidic salt.

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 Exercise 16
CH3NH3Cl is a salt formed when a weak base,CH3NH2 reacts
with a strong acid, HCl.
a) Write a balanced equation to show the formation of
CH3NH3Cl.
b) Determine the type of salt and its pH.

67
3) Basic salts
— A basic salt is produced from the reaction of a weak
acid and a strong base and yields OH- ion when
hydrolyzed.
— Dissociation of salt
CH3COONa(aq) Na+ (aq) + CH3COO- (aq)

Na+ : comes from strong base

(does not hydrolyzed)

CH3COO- : comes from weak acid and

undergoes hydrolysis

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Hydrolysis of CH3COO- :

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

— The solution is basic because the hydrolysis of

CH3COO- produces OH-

— pH of the basic salt solution is > 7.0

— Hence, CH3COONa is basic salt.

70
 Exercise 17
Sodium cyanide, NaCN is a salt formed when a strong base,
NaOH reacts with a weak acid, HCN.
a) Write a balanced equation for the formation of NaCN.
b) Determine the type of salt and its pH.

71
 Buffer solution
— A solution that maintains its pH when a small amount
of a strong acid or a strong base is added to it.

— It contains a weak acid or a weak base with salt that

has its conjugate pair.

— 2 types of buffer solution:

1) acidic buffer solution
2) basic buffer solution

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1) Acidic buffer solution

— Has pH < 7.

— An acidic buffer solution is made up of a weak acid

and its salt (containing its conjugate base)

Example:
A solution of CH3COOH and CH3COONa
(weak acid) (salt)

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— The dissociation reactions are:

CH3COOH (aq) H+(aq) + CH3COO-(aq)

CH3COONa(aq) ® CH3COO-(aq) + Na+(aq)

— CH3COONa dissociates completely and produces

high concentration of CH3COO-.

— The high concentration of CH3COO- will disturb the

equilibrium of the dissociation of ethanoic acid,
CH3COOH.

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— Equilibrium of acid shifts backward, less
CH3COOH dissociates.

— Solution now has high concentrations of

CH3COOH (from weak base) and its conjugate
base ion CH3COO- (from salt).

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ACIDIC BUFFER’S ACTION
— Since buffer solution contains CH3COOH that acts
as acid and the conjugate ion CH3COO- that acts
as base, buffer solution will maintain its pH by
performing reactions as follows:

(i) Adding a small amount of acid to the solution:

§ CH3COO- (conjugate base) will neutralize it.
§ CH3COO-(aq) + H3O+ (aq) ® CH3COOH(aq) + H2O(l)

§ The amount of weak acid, CH3COOH increased a

little but since the dissociation of acid is small, the
pH of the solution is not much affected.
77
(ii) Adding a small amount of base to the solution :
§ the acid, CH3COOH will neutralize it.

CH3COOH(aq) + OH-(aq) ® CH3COO-(aq) + H2O(l)

§ The amount of weak acid, CH3COOH decreased

a little but addition amount CH3COO- will cause the
equilibrium position to move to the left and
replace the amount of acid used

§ So,the pH of the solution is not much affected.

78
CALCULATION OF pH OF BUFFER SOLUTION
§ The pH is obtained by referring to the equilibrium
dissociation of a weak acid, HA.

§ Consider buffer solution containing HA and its

conjugate, A-

HA H+ + A-

Comes from Comes from the

weak acids ionisation of a salt

79
We can write the acidic concentration constant,

[H ][A ] or Ka[HA]
Ka [H ]
[HA] [A ]

By applying –log on both sides, we have

[HA]
-log [H+] = -log Ka + ( - log )
[A ]

pH = pKa + log [A ]
[HA]

Henderson-Hasselbalch equation

80
Example
a. Calculate the pH of a 1.00 L solution containing 0.30 M
CH3OOH and 0.10 M CH3COONa.
(Ka CH3COOH = 1.8 x 10-5)

81
b. What is the pH when 10 mL of 0.01 M HCl is added
to the buffer solution in (a)?
c. What is the pH when 1 mL of 0.1 M NaOH is added to
the buffer solution in (a)?
2) Basic buffer solution
— Has pH > 7

— Basic buffer solution is made up of a weak base

and its salt (containing its conjugate)

— Example: A basic buffer solution of NH3 and

NH4Cl

— The dissociation reactions are:

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

NH4Cl(aq) ® NH4+(aq) + Cl-(aq)

86
— NH4Cl dissociates completely and produce high
concentration of NH4+ ions

— The high concentrations of NH4+ disturb the

equilibrium of the dissociation of NH3.

— Equilibrium of base shift backwards, less NH3

dissociate.

— Solution now has high concentrations of NH3 and

its conjugate acid ion NH4+, originated from salt.

87
BASIC BUFFER’S ACTION
— Buffer solution maintains its pH by performing
reactions as follow :

— NH3 acts as base and the conjugate ion, NH4+ acts

as an acid.

88
(i) Adding a small amount of acid to the solution

◦ NH3 (base) will neutralize it.

NH3(aq) + H3O+(aq) NH4+(aq) + H2O

◦ The amount of NH4+ will increase a little but this

will cause the equilibrium to shift to the left and
replace the NH3 used, the pH of solution is not
much affected

89
(ii) Adding a small amount of base to the solution

◦ NH4+ (conjugate acid) will neutralize it.

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

◦ The amount of NH3 will increase a little but since

the dissociation of NH3 is small, the pH of solution
is not much affected

90
CALCULATION OF pH OF BUFFER SOLUTION

— The pOH and pH can be calculated by using the

Henderson-Hasselbalch equation.

— Consider the following base dissociation reaction:

B + H2O BH+ + OH-

91
— The base dissociation constant, Kb

[BH ][OH ] or [B]

Kb [OH ] K b
[B] [BH ]

By applying – log on both sides:

[B]
-log [OH] = -log Kb + ( -log )
[BH ]

pOH = pKb + log [BH ]

[B ]
Henderson-Hasselbalch equation

92
Example
A buffer solution is prepared by mixing 400mL 1.5 M NH4Cl
solution with 600 mL of 0.10 M NH3 solution.
[ Kb = 1.8 x 10-5 ]
a)Calculate the pH of buffer

93
b) Calculate the new pH of the buffer after the addition
of 2.0 mL of 0.10 M HCl
c) Calculate the new pH of the buffer after the addition of
2.0 mL of 0.15 M NaOH
 Exercise 18

a) Calculate the pH of a 1 L buffer solution containing 1.5 M

CH3COOH and 0.20 M of CH3COONa.

b) Calculate the new pH of the buffer after the addition of 2.0

mL of 0.1 M HCl.

c) Calculate the new pH of the buffer after the addition of 2.0

mL of 0.2 M NaOH.
[ Ka = 1.8 x 10-5 ]

99
 Exercise 19

a) Calculate the pH of the solution prepared by mixing 500

mL 0.1 M hydrazinium chloride, N2H5Cl with
500 mL 0.2 M hydrazine, N2H4.

b) Calculate the new pH of the buffer after the addition

of 2.0 mL of 0.1 M HCl.

c) Calculate the new pH of the buffer after the addition of

2.0 mL of 0.2 M NaOH
[ Kb N2H4 = 1.7 x 10-6 ]
100
 7.2 Acid-Base Titration
At the end of this topic , students should be able to:

a) Describe the titration process.

b) Distinguish between the end point and equivalence point.
c) Sketch and interpret the variation of pH against titrant volume
for titrations between:
i. strong acid-strong base
ii. strong acid-weak base
iii. weak acid-strong base
c) Identify suitable indicators for acid-base titrations.
 Introduction

Titration
A method for determining the concentration of a solution
using another solution (known concentration), called
standard solution.

Standard solution is a solution with known concentration.

Titration Curve
A graph of pH versus volume of titrant.

102
Titration apparatus

Titrant

Analyte

103
The equivalence point
The point at which the number of moles of OH- ions
added to a solution is equal to the number of moles of
H+ ions originally present.

The end point

The point at which is the indicator changes colour.

104
Indicators
A weak organic acids or bases that change colour over a
range of pH values.

INDICATOR COLOUR pH range

In Acid In Base
Thymol blue Red Yellow 1.2 – 2.8
Bromophenol blue Yellow Bluish Purple 3.0 – 4.6
Methyl orange Orange Yellow 3.1 – 4.4
Methyl red Red Yellow 4.2 – 6.3
Chlorophenol blue Yellow Red 4.8 – 6.4
Bromothymol blue Yellow Blue 6.0 – 7.6
Cresol Red Yellow Red 7.2 – 8.8
Phenolphthalein Colourless Reddish Pink 8.3 – 10.0

105
 How to determine the suitable indicator for titrations?

• Choose an indicator which the endpoint pH range lies on

the steep portion of the titration curve.

• This choice ensures that the pH at the equivalent point will

fall within the range over which indicator changes color.

Type pH jump Suitable Indicator

Strong acid - Strong base 3 – 11 Any indicator except thymol blue

Strong acid – Weak base 3 – 7 Methyl orange, methyl red, chlorophenol

blue, bromophenol blue
Weak acid – strong base 7 - 11 Phenolphthalein, cresol red
 Exercise 20

What is the colour of the solution when 3 drops of the below

indicators are added separately to water (pH = 7) ?

Indicator pH range Colour Change

Phenolphthalein 8.2 – 10.0

Methyl orange 3.2 – 4.2

Bromothymol 6.0 – 7.6

blue
Phenol red 6.8 – 8.4
 Type of titration
1) Strong acid – strong base titrations
2) Strong acid – weak base titrations
3) Weak acid – strong base titrations

Based on this graph, can you

predict is the analyte an acid,
or a base?

108
What the curve tells you?
Strong acid-strong base titration curve

The pH starts out low,

reflecting the high [H3O+]
of the strong acid, and
increases gradually as
acid is being neutralised
by the added base.

110
The pH rises sharply
when the mole of OH-
that have been added
nearly equal the mole
of H3O+.

111
An additional drop or two of
base neutralises the final tiny
excess of acid and introduces
a tiny excess of base.
pH jump : 3 - 11

Beyond this sharp portion, the

pH increases slowly again as
more base is added.

112
Strong acid-strong base titration curve

The initial pH is higher

than strong acid-strong
base titration curve
because the weak acid
dissociates only slightly,
less H3O+ is present.

113
A gradually rising portion of
the curve, called the buffer
region, appears before the
sharp rise to the equivalence
point.
pH jump: 7 - 11

114
The pH at the
equivalence point > 7.0.
The solution contains the
basic salt.

115
 Weak base-strong acid titration curve

The pH starts above 7.0

(~11) because the weak
base dissociates only
slightly.

The pH decreases gradually

in the buffer region.

116
After the buffer region, the
curve drops vertically to
the equivalence point.
pH jump: 3 - 7

Beyond the equivalence

point, the pH decreases
slowly as excess H3O+ is
added.

117
 How to sketch a titration curve?
Steps :
1. Calculate the initial pH of the solution
- Identify the analyte (solution in the conical flask).
Whether strong acid, weak acid, strong base or
weak base.

2. Determine the equivalence point :

- Volume and pH

118
3. pH jump (steep portion / sharp portion)
- depends on the type of the titration

Type pH jump
Strong acid - Strong base 3 – 11

Strong acid – Weak base 3 – 7

Weak acid – strong base 7 - 11

4. Calculate the final pH of the solution

- Depends on the [ ] of the titrant (solution in the burette).

119
 Exercise 21

Sketch the titration curve of 25.0 mL 0.10 M HCl and

0.10 M NaOH.
 Exercise 22
Sketch the titration curve of 25.0 mL 0.10 M NH3 and
0.10 M HCl.
 Exercise 23
Sketch the titration curve of 25.0 mL 0.10 M CH3COOH and
0.10 M NaOH.
 7.3 Solubility Equilibria
At the end of this topic , students should be able to:

a) Define solubility, molar solubility and solubility product, Ksp.

b) Calculate Ksp from concentration of ions and vice versa.
c) Predict the possibility of precipitation of slightly soluble ionic
compounds by comparing the values of ion-product, Q to Ksp.
d) Define and explain the common ion effect.
e) Perform calculations related to common ion effect.
 Introduction

— Some salts are soluble but most are insoluble

or slightly soluble in water.

— A saturated solution is a solution that contains

the maximum amount of solute that can
dissolve in a solvent.

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— The solubility of a salt is the amount of solid that
dissolved in a known value of saturated solution.

— The unit of solubility used may be g L-1 or mol L-1

— Molar solubility is the maximum number of moles of

solute that dissolves in a certain quantity of solvent at a
specific temperature.

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 The Solubility Product Constant, Ksp

— Ksp is the product of the molar concentrations of the

ions involved in the equilibrium, each raised to the
power of its stoichiometric coefficient in the equilibrium
equation.

— Ksp is called the solubility product constant.

— The degree of solubility of a salt is shown by the

value of Ksp.

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— Consider the equilibrium system below :

MX (s) M+ (aq) + X- (aq)

Kc = [M+] [X-]
[MX]

Kc [MX] = [M+] [X-]

*since [MX] is a constant ;

Ksp = [M+] [X-]

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— Soluble salt such NaCl and KNO3 has an extremely
high value of Ksp .

— The smaller the value of Ksp the less soluble the

compound in water.

— Temperature ↑ , solubility ↑, Ksp ↑

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 Exercise 24

Write the solubility product expression and state the units

of Ksp for each of the following ionic compounds.

a) Ca3(PO4)2 b) Ag2CO3

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 Exercise 25

The solubility product of silver chromate(VI), Ag2CrO4 is

2.4 x10-12 mol3dm-9. Calculate the concentration of Ag+(aq)
and CrO42-(aq) in the saturated solution.

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 Exercise 26

The solubility of silver sulphide, Ag2S is 5.0x10-17.

Calculate the solubility product of Ag2S.

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 Exercise 27

Calculate the solubility of copper (II) hydroxide,

Cu(OH)2, in g L-1.

Ksp Cu(OH)2 = 2 x 10-20 M3,

Mr Cu(OH)2 = 97.57g mol-1

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Predicting the formation of a precipitate

Precipitate is an insoluble solid formed in and separates

from the solution.

A mixture of two solutions will produce a precipitate or not

depending on the ion product, Q present.

Q has the same form as Ksp but the concentrations of

ions are taken at any given time.

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The solubility equilibrium equation for a slightly soluble
salt, MA :

MA (s) M+ (aq) + A- (aq)

Ksp = [M+] [A-]

If we mix a solution containing M+ ions with one

containing A- ions, the ion product, Q is given by :
Q = [M+] [A-]

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 Three possible situations:
Q < Ksp;
Solution is not saturated.
Solid will dissolve and no precipitate formed.

Q = Ksp;
Saturated solution formed.
System is in equilibrium.

Q > Ksp;
Solution is supersaturated;
Ions will form precipitate until the ionic concentration
product of the system equals the Ksp (until the system
reaches equilibrium).
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 Exercise 28

Will precipitate form when 50 mL 0.0010 M NaOH is

added to 150 mL of 0.010 M MgCl2?
(Ksp Mg(OH)2 = 2.0 x 10-11)

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 Exercise 29

Exactly 200 mL of 0.0040 M AgNO3 are added to 800 mL

of 0.0080 M K2SO4. Will a precipitate form?
(Ksp Ag2SO4 = 1.4x10-5 M3)

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 Common Ion Effect

— Common ion is an ion that is common to two or

more components in a mixture of an ionic
solution.

— Common ion effect is the shift in equilibrium

caused by the addition of a compound having
an ion in common with the dissolved
substances.

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Example:

Consider a saturated solution of silver chloride, AgCl in water.

(Ksp AgCl = 1.6 x 10-10)

The equilibrium system is:

AgCl (s) Ag+ (aq) + Cl- (aq)

If AgNO3 is added to the saturated AgCl solution :

AgNO3 (aq) Ag+ (aq) + NO3- (aq)
(common ion)

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The addition the common ion of Ag+ causes the [Ag+]
increases.

- Equilibrium position will shift backward (according to

the Le Chatelier's Principle).
- Solubility of AgCl will decrease.
- So, the addition of a common ion will reduce the
solubility of a slightly soluble salt.

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 Exercise 30

Calculate the solubility of AgCl (mol L-1) in :

a. liquid water
b. 0.05 M of silver nitrate solution.
(Ksp AgCl = 1.6 x 10-10)

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