7.

0
IONIC EQUILIBRIA

1
7.1 ACIDS AND BASES

Theory of Acids and Bases

Three important theories

1. Arrhenius theory
2. Bronsted-Lowrys theory
3. Lewis theory

2
Theory of Acids and Bases
1. Arrhenius Theory

Acid:
any substance that produces hydrogen ion (H+) or
hydronium ion (H3O+) when dissociating in water.

Example:

HCl (aq) H+ (aq) + Cl (aq)

HCl (aq) + H2O (l) H3O+(aq) + Cl (aq)

3
Base:
any substance that produces hydroxide ions (OH-)
when dissociating in water.

Example:

NaOH (aq) Na+ (aq) + OH(aq)

4
2. Bronsted-Lowry Theory
Acid:
any substance that can donate a proton, (H+) to
other substance

Example:

HNO3 (aq) + H2O (l) NO3 (aq) + H3O+ (aq)

acid

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

acid

5
 Base:
any substance that can accept a proton from
other substance

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

6
Conjugate Acid-base Pairs

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

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

7
Example

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

acid base conjugate conjugate

base acid

The stronger the acid, the weaker is its conjugate

base and the stronger the base, the weaker is its
conjugate acid.

8
Exercise
1. In the following reactions, identify the acid-base conjugate
pairs.

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

base acid conjugate conjugate

acid base

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

base acid conjugate conjugate
acid base

9
c. HBr(aq) + NH3(aq) NH4+(aq) + Br (aq)
acid base conjugate conjugate
acid base

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

base acid conjugate conjugate
acid base

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

acid base conjugate conjugate
base acid

10
2. Write the conjugate base formula for the following acids.
a) HS d) H3PO4
b) HCN e) H 3O+
c) N2H5+ f) CH3NH3+

Answer :
acid conjugate base

a) HS S2- + H+

a) HCN CN- + H+

a) N 2H5+ N 2H4 + H+

a) H3PO4 H2PO4- + H+

a) H3O+ H 2O + H+

a) CH3NH3+ CH3NH2 + H+
11
3. Write the conjugate acid formula for the following bases.
a) HS- d) NH3
b) C6H5COO e) H 2O
c) OH f) H2PO4

12
3. Lewis Theory
Acid:
a substance that can accept a pair of electrons to
form a covalent bond.

The species that can be Lewis acid are

Cations such as H+, Fe2+, Al3+

molecules with incomplete octet central atom
such as BF3, BeCl2
Molecules with central atom that can expand
octet such as PCl3

13
Base:
a substance that can donate a pair of electrons to
form a covalent bond.

The species that can be Lewis base are

anions such as OH-, CN-, Cl-
molecules with lone pairs electrons at
the central atom such as H2O, NH3, ROH
molecules with nonpolar multiple bond such as
alkenes

14
Example

1) H3N: + BF3 H3N BF3

Lewis Lewis
base acid

2) H+ + OH- H 2O
Lewis Lewis
acid base

3) 2Cl-(aq) + SnCl4 (aq) SnCl62-(aq)

Lewis Lewis
base acid

15
Exercise
Classify each of the following species as Lewis acid
or Lewis base.

i. NH3 Lewis base

ii. AlCl3 Lewis acid

iii. BCl3 Lewis acid

iv. Ag+ Lewis acid

v.I- Lewis base

16
Strength of Acids and Bases

Strength of acids and bases depend on the extent of

dissociation

[ ]dissociated
% dissociation = 100%
[ ]initial

[ ]dissociated
Degree of dissociation, =
[ ]initial

17
 Strong Acid
Strong acid is an acid that ionizes completely in
water.

3 ways to write the equation for acid dissociation:

a) HCl (aq) H+ (aq) + Cl (aq)

a) HCl (g) H
2 O (l)
H+ (aq) + Cl (aq)

a) HCl (g) + H2O (l) H3O+ (aq) + Cl (aq)

18
 Example : for 0.10 M HCl

HCl (aq) + H2O (l) Cl (aq) + H3O+ (aq)

[ ]i 0.10 0 0
- 0.10 + 0.10 + 0.10
[ ]f 0.00 0.10 0.10

19
 [HCl]dissociated
% dissociation = 100%
[HCl]initial
0.10=
100%
0.10
= 100 %
[HCl]dissociated
Degree of dissociation, =
[HCl]initial
0.10 =
0.10
= 1.00

20
 The strong acids are ...

The 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

21
 Strong Base
Strong base is a base that ionizes completely in
water.

Example : for 0.50 M NaOH

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

[ ]i 0.50 0 0
- 0.50 + 0.50 + 0.50
[ ]f 0.00 0.50 0.50

22
 [ NaOH ]dissociated
% dissociation = 100%
[ NaOH ]initial
0.50=
100%
0.50
= 100 %

[ NaOH ]dissociated
Degree of dissociation, =
[ NaOH ]initial
0.50=
0.50
= 1.00

23
 The strong bases...

M2O or MOH, where M is group 1 element :

Li, Na, K, Rb, Cs

RO or R(OH)2, where R is Ca, Sr, Ba

24
Weak Acid
Weak acid is an acid that only ionizes partially in
water
Example: CH3COOH, HCOOH

Generallyfor any weak acid, HA the dissociation

reaction is:

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

% dissociation < 100%

<1

25
 Acid dissociation constant expression, Ka

[A ][H3O ]
Ka =
[HA]

Ka value depends on temperature

Normally Ka is measured at 25 C
Value of Ka ; strength of acid

26
 The weak acids are ....

The hydrohalic acids HF

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

e.g: HCN and H2S

Oxoacids in which the number of O atoms equals or

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

Organic acids (general formula RCOOH)

e.g: CH3COOH

27
Weak Base
Weak base is an base that only ionizes partially in
water
Example: NH3, N2H4

Generallyfor any weak base, B the dissociation

reaction is:

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

% dissociation < 100%

<1

28
 Base dissociation constant expression, Kb

[BH ][OH ]
Kb = [B]

Kb value depends on temperature

Normally Kb is measured at 25 C
Value of Kb ; strength of base

29
 The weak bases are ...

Ammonia (NH3)

Amines with general formula RNH2, R2NH, R3N

e.g. : CH3CH2NH2; (CH3)2NH; (CH3)3N

30
Example:
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.

31
Solution:
[4.2]
[HCOOH] dissociated 0.10M
[100]
0.0042 M

HCOOH + H2O H3O+ + HCOO-

[ ]i 0.10 0 0
-0.0042 +0.0042 +0.0042
[ ] 0.0958 0.0042 0.0042

32
 [HCOO- ][H 3O ]
Ka
[HCOOH]
[0.0042M ]2

[0.0958M ]
1.8 10-4 M
Ka for HCOOH is 1.8 x 10-4 M

Ka or Kb for many weak acids or weak bases < 10,

,

To simplify the calculation for ionic equilibrium the

following assumption can be made

[ ]initial [ ]dissociated [ ]initial

33
 The assumption will give correct answer to at
least 2 significant figures if:
value of Ka or Kb < 10 or
% dissociation < 5%

Ka = [H 3O ] [HCOO ]
[HCOOH]

[ ]initial [ ]dissociated [ ]initial

(0.0042 M) 2
=
0.1M
= 1.8 104 M

34
 Try this

1. Acid dissociation constant, Ka for hydrofluoric

acid HF at 25 C is 6.8104 M. For a solution of
0.20 M HF, calculate:
a. the concentration of hydronium ion at
equilibrium
b. degree of dissociation

2. Base dissociation constant, Kb for ammonia

solution, NH3 at 25 C is 1.8105 M. For a
solution of 0.50 M NH3, calculate:
a. the concentration of hydroxide ion at
equilibrium
b. % dissociation
35
Water and the pH Scale
a. The Water Ionization Constant, Kw
When water molecules ionized, transferring a
proton from one water molecule to another
producing a hydroxonium and hydroxide
ion.

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

36
 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 25C

37
For pure water, at 25C,

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

38
a. 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
hydroxonium ion (hydrogen ion)
concentration.

pH = log H3O+

39
 Insimilar way, pOH is the negative logarithm of
the hydroxide ion concentration.

pOH = log OH

40
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

42
Example 1
In a NaOH solution, [OH-] is 2.9 x 10-4 M.
Calculate the pH of the solution at 25 oC.
(10.46)

43
Example 2
The pH of rainwater in a certain region was 5.68.
Calculate the H+ ion concentration of the rainwater.
(2.089 x 10-6)

44
Example 3
Calculate the pH of a 0.15 M acetic acid (CH3COOH)
solution, Ka = 1.8 x 10-5.
(2.79)

45
Example 4
What is the pH of a 0.25 M ammonia solution?
Kb = 1.8 x 10-5.
(11.33)

46
Example 5
The pH of 0.06 M solution of formic acid (HCOOH)
is 3.44. Calculate the Ka of the acid.
(2.211 x 10-6)

47
Exercises
1. The Ka for benzoic acid, (C6H5COOH) is 6.5x10-5.
Calculate the pH of a 0.25 M benzoic acid solution.
(2.39)

1. The pH of an acid solution is 6.20. Calculate the Ka

for the acid. The acid concentration is 0.01M.
(3.98 x 10-11)

3. Calculate the pH for 0.5M C5H5N. Kb = 1.7x10-9

(9.47)

48
1. Calculate pH for the following solution.

Answer
a. 0.55 M CH3COOH (Ka = 1.8x10-5) 2.5
b. 0.23 M NH3 (Kb = 1.8x10-5) 11.31
c. 0.15 M HCl 0.82
d. 0.20 M KOH 13.3
e. 0.45 M HCN (Ka = 4.9 x 10-10) 4.8

49
SALTS
Produced when acid reacts with base.

3 types of salts are :

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

50
 1) Neutral salts
Produced when strong acid reacts with strong base.
e.g
HCl + NaOH NaCl + H 2O
neutral salt

- 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)

51
 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

52
SALT HYDROLYSIS
Salt hydrolysis is a chemical reaction between anion
or cation of a salt with water molecules.

Acidicsalts and basic salts have ions that undergo

hydrolysis in aqueous solution.

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

H3O+ is produced during hydrolysis.

53
2) BASIC SALTS
Normally
is produced from the reaction of weak acid
and strong base.
produce OH- when hydrolyzed
eg : CH3COONa(aq) Na+ (aq) + CH3COO- (aq)

Na+ : comes from strong base

(does not hydrolyzed)

CH3COO- : comes from weak acid and

undergoes hydrolysis

54
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

55
 Example

Sodium cyanide, NaCN is a salt formed when a

strong base, NaOH is reacted with a weak acid, HCN.

a) Write a balanced equation to show the reaction

between NaOH and HCN. Classify the salt
formed.

b) What would be expected pH of the NaCN

solution? Explain the answer using equation(s).

56
3) ACIDIC SALTS
Normallyis produced from the reaction of strong
acid and weak base.
produce H3O+ when hydrolysed.
Eg.

NH4Cl(s) NH4+(aq) + Cl(aq)

Cl- : comes from a strong acid
(does not hydrolyzed)
NH4+ : comes from weak base and
undergoes hydrolysis

57
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

58
 Example

CH3NH3Cl is a salt formed when a weak

base,CH3NH2 is reacted with a strong acid, HCl.

a) Write a balanced equation to show the reaction

between CH3NH2 and HCl. Classify the salt
formed.

b) What would be expected pH of the CH3NH3Cl

solution ? Explain the answer using
equation(s).

59
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 weak acid or weak base with salt that has

its conjugate pair.

2 types of buffer solution:

a. acidic buffer solution
b. basic buffer solution

60
 ACIDIC BUFFER SOLUTION

Has pH < 7.

Anacidic buffer solution is made up of a weak acid

and its salt (containing its conjugate base)

Example:
A solution of CH3COOH and CH3COONa

61
 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-.

Thehigh concentration of CH3COO- will disturb the

equilibrium of the dissociation of ethanoic acid,
CH3COOH.

62
 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)

63
BUFFERS 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.
64
(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.

65
CALCULATION OF pH OF BUFFER SOLUTION
ThepH is obtained by referring to the equilibrium
dissociation of a weak acid, HA.

Considerbuffer solution containing HA and its

conjugate, A-

HA H+ + A-

Comes from Comes from the

weak acids ionisation of a salt

66
We can write the acidic concentration constant,

[H ][A ] Ka[HA ]
Ka or [H ] =
+

[HA] [A ]

By applying log on both sides, we have

[ HA]
-log [H+] = -log Ka + ([-Alog

] )

[A ]
pH = pKa + log
[HA]

Henderson-Hasselbalch equation

67
Example

a. Calculate the pH of a 1.00 L solution containing

0.30 M CH3OOH and 0.1 M CH3COONa.
(Ka CH3COOH = 1.8 x 10-5)

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)?

68
BASIC BUFFER SOLUTION
Has pH > 7

Basicbuffer 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)

69
 NH4Cldissociates 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.

70
 BUFFERS ACTION
Buffer solution maintains its pH by performing
reactions as follow :

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

as an acid.

71
(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

72
(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

73
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 + H 2O BH+ + OH-

74
 The base dissociation constant, Kb
[BH ][OH ] [B]
Kb = [B] or [OH ] = Kb
-

[BH ]

By applying log on both sides:

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

[BH ]
pOH = pKb + log
[B ]
Henderson-Hasselbalch equation

75
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
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

76
Exercises
a) Calculate the pH of a 1 L buffer solution containing
1.5 M CH3COOH and 0.20 M of CH3COONa.
pH = 3.87
b) Calculate the new pH of the buffer after the
addition of 2.0 mL of 0.1 M HCl. PH = 3.87

a) Calculate the new pH of the buffer after the

addition of 2.0 mL of 0.2 M NaOH. pH = 3.87
[ Ka = 1.8 x 10-5 ]

77
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. pH = 8.53

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

of 2.0 mL of 0.1 M HCl. pH = 8.53

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

of 2.0 mL of 0.2 M NaOH pH = 8.54
[ Kb N2H4 = 1.7 x 10-6 ]

78
7.2 ACID-BASE TITRATIONS
Titration
a method for determining the
concentration of a solution using
another solution (known concentration),
called standard solution

Titration Curve
a graph of pH versus volume of titrant

79
Titration apparatus

Titrant

Analyte

80
 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

is the point when the indicator changes colour.

Indicators

is a weak organic acids or bases that change

colour over a range of pH values.
81
Table 1: Some Common Acid-Base Indicators
Colour
Indicator In Acid In Base pH Range
*

Thymol blue Red Yellow 1.2-2.8

Bromophenol blue Yellow Bluish 3.0-4.6
Purple
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 8.3-10.0
pink
82
TYPES OF TITRATIONS
1. Strong acid - strong base titrations
2. Strong acid weak base titrations
3. Weak acid strong base titrations

83
 Strong acid-strong base titration curves

* 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.

84
* The pH rises sharply
when the mole of OH-
that have been added
nearly equal the mole
of H3O+ .

85
* An additional drop or two of
base neutralises the
final tiny excess of acid and
introduces a tiny excess of
base, so pH jumps 6 to 8 unit.

* Beyond this sharp portion, the

pH increases slowly again as
more base is added.

86
 Weak acid-strong base titration curves

* The initial pH is higher

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

87
* A gradually rising portion
of the curve, called the
buffer region, appears
before the sharp rise to
the equivalence point.

88
* The pH at the
equivalence point > 7.0.
The solution contains the
basic salt.

89
 Weak base-strong acid titration curves

* The pH starts above 7.0

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

* The pH decreases gradually

in the buffer region.

90
* After the buffer region,
the curve drops vertically
to the equivalence point.

* Beyond the equivalence

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

91
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

92
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. Identify the final pH

- depends on the [ ] of the titrant (solution in
the burette).
93
Example 1 :
Sketch the titration curve of 25 mL 0.1 M HCl with
0.1 M NaOH.
Step 1 :
Analyte is a strong acid,
HCl dissociates completely

HCl(aq) + H2O(l) Cl (aq) + H3O+(aq)

[H3O+] = [HCl] = 0.1 M

pH = - log [H3O+] = 1.0

94
Step 2 : at equivalence point
- pH equivalence:
- the solution is NaCl (aq)
- both Na+ and Cl- do not hydrolyse
- therefore pH = 7.0
- Volume equivalence:

n HCl
= n NaOH

MHCl VHCl = MNaOH VnaOH

VNaOH = 0.1 x 25 = 25 mL
0.1

95
Step 3 :
Type of titration : strong acid-strong base
pH jump : 3 11

Step 4 :
Titrant is a strong base, NaOH.
NaOH (aq) Na+ (aq) + OH (aq)

[OH-] = [NaOH] = 0.1 M

pOH = - log 0.1 = 1
pH = 14 1 = 13
Final point approaching pH < 13.
96
Example 2 : Sketch the titration curve of 25 mL 0.2
M HCl and 0.1 M NH3.

Step 1 :
Analyte is a strong acid, HCl

HCl (aq) + H2O (l) Cl (aq) + H3O+ (aq)

[H3O+] = [HCl] = 0.2

pH = - log [H3O+] = 0.70

97
Step 2:
at equivalence point
HCl(aq) + NH3 (aq) NH4Cl (aq)

- pH equivalence
- the solution is NH4Cl (aq)
- only NH4+ hydrolyses to form H3O+
- therefore pH < 7.0
- Volume equivalence
n NH = n HCl 3

MNH VNH = MHClVHCl

3 3

VNH = 0.2 x 25 = 50 mL
3

0.1
Step 3 :
Type of titration : strong acid-weak base
pH jump : 3 7

Step 4 :

Titrant is a weak base, NH3.

Final point approaching pH < 11

99
 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.

Types of Titrations pH jump Suitable Indicators

Strong Acid-Strong Base 3 10 Any Indicator except thymol blue

Weak Acid-Strong Base 7 11 Phenolphthalein, cresol red

Strong Acid-weak Base 3 7 Methyl orange, methyl red,

chlorophenol blue, bromophenol blue

Exercise 1
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 Colourless reddish pink

Methyl orange 3.2 4.2 Red Yellow

Bromothymol blue 6.0 7.6 Yellow Blue

phenol red 6.8 8.4 Yellow Red

Exercise 2

The pH range and the colour change for 3 indicator

X, Y and Z is shown in the table below. Determine X,
Y and Z.

Indicator pH range colour change

X 1.2 2.8 Red Yellow

Y 6.0 7.6 Yellow Blue

Z 8.3 10.5 Colourless Yellow

SOLUBILITY EQUILIBRIUM
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.

103
 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.

104
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.

105
 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-]

106
 Soluble
salt such NaCl and KNO3 has an
extremely high value of Ksp .

Thesmaller the value of Ksp the less soluble the

compound in water.

Temperature , solubility , Ksp

107
 Example

Write the solubility product expression and state

the units of Ksp for each of the following ionic
compounds.

a) Ca3(PO4)2 b) Ag2CO3

108
 Example

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.

Ans: [Ag+] = 1.68 x 10-5 M

[CrO42-] = 8.43 x 10-5 M

109
 Example

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

Calculate the solubility product of Ag2S.

Ans: 5.0 x 10-49

110
 Example

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

111
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.

112

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-]

113
 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).
114
 Example

Will precipitate form when 50 mL 0.001 M NaOH

is added to 150 mL of 0.01 M MgCl2.
(Ksp Mg(OH)2 = 2 x 10-11)

115
 Example

Exactly 200 mL of 0.0040 M AgNO3 are added to

800 mL of 0.008 M K2SO4. Will a precipitate form?
(Ksp Ag2SO4 = 1.4x10-5 M3)

116
COMMON ION EFFECT
Commonion 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.

117
 Example

Consider a saturated solution of silver chloride, AgCl

in water.
(Ksp AgCl = 1.6 x 10-10)

118
 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)

- [Ag+] will increase.

- 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.
119
 Example

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)

120