Irreversible and Reversible Reactions

Irreversible
and
Reversible
Reactions
1
Irreversible Reactions
Chemical reactions that take place in
one direction only
It goes on until at least one of the
reactants is used up
complete reaction
Irreversible Reactions
Examples : 2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
HCl(aq) + H2O(l) H3O+(aq) + Cl(aq)
2Mg(s) + O2(g) 2MgO(s)
Cl2(g) + 2OH(aq) ClO(aq) + Cl(aq) + H2O(l)
Q.1
2Na(s) + 2H2O(l)
2Mg(s) + O2(g)
2NaOH(aq) + H2(g)
2MgO(s)
Conditions for reversible reactions : Closed reaction vessels to prevent

escape of gases
High temperature to favour the reversed
processes
Q.1
HCl(aq) + H2O(l)
H3O+(aq) + Cl(aq)
Conditions for reversible reactions : Concentration of HCl(aq) > 6 M
Q.1
Cl2(g) + 2OH(aq)
ClO(aq) + Cl(aq) + H2O(l)
Conditions for reversible reactions : Closed reaction vessels to prevent

escape of Cl2
Dilute OH(aq) at T 20C to prevent side
3Cl (g)reaction
+ 6OH(aq) ClO (aq) + 5Cl(aq) + 3H O(l)
2
Hot and
concentra
ted
6
Reversible Processes
Vapour
Solid
Liquid
Changes of physical phases are reversible

7
Reversible Reactions
Chemical reactions that can go in two
opposite directions
Incomplete reactions
Q.2
CH3COOH(aq) + H2O(l)
NH3(aq) + H2O(l)
Cl2(aq) + H2O(l)
CH3COO(aq) + H3O+(aq)
NH4+(aq) + OH(aq)
HCl(aq) + HOCl(aq)
CH3COOH(l) + C2H5OH(l)
3H2(g) + N2(g)
2NH3(g)
CH3COOC2H5(l) + H2O(l)
Examples of reversible reactions

CrO42-(aq) + 2H+(aq)
yellow
Cr2O72-(aq) + H2O(l)
orange
1. When HCl(aq) is added to CrO42(aq)

Observation : The yellow solution turns orange.
10

yellow
orange
1. When HCl(aq) is added to CrO42(aq)

Interpretation : CrO42(aq) reacts with H+ to give Cr2O72(aq)
There is no further colour change when
rate of forward rx = rate of backward rx
11

yellow
orange
2. When NaOH(aq) is added to Cr2O72(aq)

Observation : The orange solution turns yellow.
12

yellow
orange

Interpretation : H+ ions are being removed by NaOH
rate of forward rx
rate of backward rx > rate of forward rx
13
a net change of Cr2O72(aq) to CrO42(aq)

yellow
orange

Interpretation : There is no further colour change when
rate of backward rx = rate of forward rx
14

BiCl3(aq) + H2O(l)
colourless
BiOCl(s) + 2HCl(aq)
White ppt
1. When H2O(l) is added to BiCl3(aq)

Observation : The colourless solution turns milky.
15

BiCl3(aq) + H2O(l)
colourless
BiOCl(s) + 2HCl(aq)
White ppt
1. When H2O(l) is added to BiCl3(aq)

Interpretation : BiCl3(aq) reacts with H2O(l) to give BiOCl(s)
There is no further change when
16

BiCl3(aq) + H2O(l)
colourless
BiOCl(s) + 2HCl(aq)
White ppt
2. When HCl(aq) is added to BiOCl(s)

Observation : The milky solution becomes clear.
17

BiCl3(aq) + H2O(l)
colourless
BiOCl(s) + 2HCl(aq)
White ppt

Interpretation : [HCl(aq)]
a net consumption of BiOCl(s)
18

BiCl3(aq) + H2O(l)
colourless
BiOCl(s) + 2HCl(aq)
White ppt

Interpretation : There is no further change when
19
Q.3
Br2(aq) + H2O(l)
Red-orange
H+(aq) + Br-(aq) + HOBr(aq)

colourless
1. When NaOH(aq) is added to Br2(aq)

Prediction : The red-orange solution turns colourless.
20
Q.3
Br2(aq) + H2O(l)
Red-orange
colourless

Interpretation : Before the addition,
21
Q.3
Br2(aq) + H2O(l)
Red-orange

colourless

Interpretation : H+ ions are being removed by NaOH(aq)
rate of forward rx > rate of backward rx
a net consumption of Br2(aq)
22
Q.3
Br2(aq) + H2O(l)
Red-orange

colourless

Interpretation : There is no further change of colour when
23
Q.3
Br2(aq) + H2O(l)
Red-orange
colourless
2. When HCl(aq) is added

Prediction : The colourless solution turns red-orange.
24
Q.3
Br2(aq) + H2O(l)
Red-orange
colourless

Interpretation : Addition of HCl increases [H+(aq)]
a net production of Br2(aq)
25
Q.3
Br2(aq) + H2O(l)
Red-orange
colourless

26
Q.3
Br2(aq) + H2O(l)
Red-orange
colourless
3. When AgNO3(aq) is added

Prediction : A pale yellow ppt is formed.
The red-orange solution turns colourless.
27
Q.3
Br2(aq) + H2O(l)
Red-orange

colourless

Interpretation : Ag+(aq) react with Br-(aq) to give pale yellow
ppt of AgBr(s).
rate of backward rx < rate of forward rx
a net consumption of Br2(aq)
28
Q.3
Br2(aq) + H2O(l)
Red-orange

colourless

29
Phenolphthlein is a weak acid that ionizes

slightly in water to give H3O+(aq)
+ H3O+(aq)
Colourless
30
Red
What is the colour of phenolphthalein

when pH < 8.3 ?
+ H3O+
(aq)
Colourless
31
Red
When pH < 8.3 (e.g. deionized water),

The colourless form predominates
+ H3O+(aq)
Colourless
32
Red
When NaOH(aq) is added,

[H3O+(aq)]
a net production of the red form
+ H3O+(aq)
Colourless
33
Red
There is no further colour change when

+ H3O+(aq)
Colourless
34
Red
When pH > 10,

The red form predominates
+ H3O+(aq)
Colourless
35
Red
When 8.3 < pH < 10,

Both forms have similar concentrations pink
+ H3O+(aq)
Colourless
36
Red
Reversible reactions and dynamic equilibrium

For a reversible reaction,
reactants
products
a state of dynamic equilibrium is said to be

established when
Apparently, there is no change in the
concentrations of reactants and products.
Reactions continues at molecular level.
37
Dynamic Equilibrium
No change in the
position of the girl
An example of dynamic equilibrium

38
Reversible reactions and chemical equilibrium

ALL chemical reactions are considered as
reversible processes with different extents
of completion.
39

H < 0
At equil., k[reactant]eq = k[product]eq
Ea > Ea
k >> k [reactant]eq << [product]eq
Forward rx is more complete than backward rx

Ea
40
Ea

H > 0
Ea > Ea
Forward rx is less complete than backward rx
Ea
41
Ea
Chemical Equilibrium vs Chemical Kinetics

Chemical equilibrium is about how far a reaction
can proceed.
Chemical kinetics is about how fast a reaction
can proceed.
42
Chemical Equilibrium vs Chemical Kinetics

The rate of rx depends on Ea or Ea
The extent of completion of rx depends on H
Ea
43
Ea
Evidence for Dynamic Equilibrium

NaNO3(s)
NaNO3(aq)
saturated
At fixed T, [NaNO3(aq)] is a constant

Addition of
24
NaNO3(s)
Detection of radioactivity in satd solution

Interchange of NaNO3 between the satd
solution and the solid
44
Features of Chemical Equilibria

1. A system in chemical equilibrium consists of
a forward reaction and a backward reaction
both proceeding at the same rate.
2. All macroscopic properties (such as
temperature, pressure, concentration,
density, colour, etc.) of an equilibrium
system remain unchanged.
45
Q.4 (i)
H2(g) + I2(g)
2HI(g)
Time taken to
reach the
equilibrium state
46
Q.4 (ii)
H2(g) + I2(g)
2HI(g)
The equilibrium
concentrations
need not be
equal
Time taken to reach the
equilibrium state
47
Q.5
48
Constant flame colour and

temperature
Q.5
CO2 and H2O

Open system
Not at equilibrium state
Air
Steady state
Fuel
49
3. Equilibria can only be achieved in closed

systems with no exchange of matter with
their surroundings.
50
Q.6 A
Observation : Br2(g)
Br2(l)
51
The brown vapour escapes until all

brown liquid disappears
Interpretation : Br2 escapes from the system. Thus,
the rate of condensation is always
less than the rate of evaporation.
Q.6 B
Observation : No observable change

Interpretation : -
Fe3O4(s) + 4H2(g)
500
C
3Fe(s) + 4H2O(g)
52
H2(g) and H2O(g) escape from

the system leaving only
Fe3O4(s) and Fe(s). Thus,
both forward and backward
reactions stop due to
absence of reactants.
Q.6 C
Observation : The amount of solid KCl
Interpretation : Water escapes by evaporation.
KCl(s)
53
[KCl(aq)] , making the rate of

precipitation greater than the
KCl(aq) rate of dissolution.
Q.6 D
Observation : A pleasant smell is detected.
The volume of the mixture
54
Interpretation : The more volatile ester

escapes, causing a drop in
volume of both reactants.
4. The state of equilibrium can be attained

from either the forward or the backward
direction.
5. The equilibrium composition under a given
set of conditions is independent of the
direction from which the equilibrium is
approached.
In other words, the same set of equilibrium
concentrations of reactants and products
can be obtained from either side of the
reversible reaction under the same set of
conditions (See Q.7).
55
Q.7
nH = nI = 1.0 nHI = 1.0
H2(g)
2HI(g)
ninitial
nequil
ninitial
nequil
I2(g)
0.5
0.5-0.78/2
0.5
0.5-0.78/2
= 0.11
= 0.11
(1.0-0.78)/2 (1.0-0.78)/2
= 0.11
56
= 0.11
0
0.78
1.0
0.78
Equilibrium position and equilibrium

composition
For a system with a more complete forward
reaction,
A + B
the equilibrium position is said to lie more to

the right hand side.
The equilibrium composition is richer in C,
i.e. [C]equil is much higher than [A]equil and [B]equil.
57
Equilibrium position and equilibrium

composition
For a system with a less complete forward
reaction,
A + B
the equilibrium position is said to lie more to the

left hand side.
The equilibrium composition is richer in A and B,
i.e. [A]equil and [B]equil are much higher than [C]equil.
58
Equilibrium
Law
59
Equilibrium Law
For any chemical system in dynamic
equilibrium, the concentrations or partial
pressures of all the substances present are
related to one another by a mathematical
expression which is always a constant at fixed
temperature.
60
For the chemical system in equilibrium,

aA + bB
cC + dD
Equilibrium constant
expressed in concentration
Kc depends on temperature and
the nature of reaction
61
Equilibrium constant and reaction quotient

aA + bB
cC + dD
Equilibrium
constant
Reaction
quotient
62
Qc
c
d
[C] [D]
a
b
[A] [B]
aA + bB
cC + dD
Equilibrium
constant
Reaction
quotient
Qc
[C]c [D]d
[A]a [B]b
Qc = K c
the system is at equilibrium
63
aA + bB
cC + dD
Equilibrium
constant
Reaction
quotient
Qc
[C]c [D]d
[A]a [B]b
Qc > K c
the system is NOT at equilibrium
64
The reaction proceeds from right to

left until Qc = Kc.
aA + bB
cC + dD
Equilibrium
constant
Reaction
quotient
Qc
[C]c [D]d
[A]a [B]b
Qc < K c
the system is NOT at equilibrium
65
The reaction proceeds from left to

right until Qc = Kc.
aA + bB
cC + dD
Equilibrium
constant
Reaction
quotient
Qc
[C]c [D]d
[A]a [B]b
Large Kc
The forward reaction is more complete
The equilibrium position lies to the right.
66
The equilibrium mixture is richer in the

substances on the R.H.S. of the equation.
aA + bB
cC + dD
Equilibrium
constant
Reaction
quotient
Qc
[C]c [D]d
[A]a [B]b
Small Kc
The forward reaction is less complete
The equilibrium position lies to the left.
67
The equilibrium mixture is richer in the

substances on the L.H.S. of the equation.
Kc gives no indication about the rate

of reaction
Q.8
The rate of reaction depends on Ea
68
Relationship of Kc to the Stoichiometry of Equations
A+B
69
A+B
KC1
KC-1
[C]
[A][B]
[A][B]
[C]
1
Kc1
units
mol1 dm3
mol dm3
A+B
xA + xB
KC1
[C]
[A][B]
units
mol1 dm3
xC
[C]
x
KC2
(K
)
c1
x
x
[A] [B]
x
70
molx dm3x
A+B
1
A+
y
Kc3
71
KC1
C
1
B
y
[C]
[A][B]
units
mol1 dm3
1
C
y
[C]
1
y
1
y
[A] [B]
1
y
Kc1
1
y
mol
1
y
dm
3
y
Q.9
(1) A
(2) B
(3) C
72
[B]
K1
[A]
[C]
K2
[B]
[D]
K3
[C]
[C] [B] [C]
K4
= K1K2
[A] [A] [B]
(4) A
(4) = (1) +
(2)
K4 = K1 K2
Q.9
B
[B]
K1
[A]
[C]
K2
[B]
[D]
K3
[C]
(1) A
(2) B
(3) C
(5) A
(5) = (1) + (2) +

(3)
73
[D] [B] [C] [D]

K5
= K1K2K3
[A] [A] [B] [C]
K5 = K1 K2 K3
Q.10
(1) H2(g) + Cl2(g)
(2) N2(g) + 3H2(g)
2HCl(g)
2NH3(g)
(3) N2(g) + 4H2(g) + Cl2(g)

(4) NH3(g) + HCl(g)
2NH4Cl(s)
NH4Cl(s)
(4) = [(3) 1 (2) (1)]

70
6
18
K3 2
3.9 10 mol dm

K4
33
5
2
6
(2.5 10 )(6.0 10 mol dm )
K1K2
= 5.11015 mol2 dm6
74
1
2
Determinatio
n of
Equilibrium
Constants
75
Equilibrium System: (TAS Expt. 11)

CH3COOH(l) + CH3CH2OH(l)
CH3COOCH2CH3(l) +
H2O(l)
Kc
76
[CH3COOCH2CH3 (l)]eqm [H2O(l)]eqm
[CH3COOH(l)]eqm [CH3CH2OH(l)]eqm
Equilibrium System:
CH3COOCH2CH3(l) +
Reactant/
Experiment 1
Experiment 2
H
Product
2O(l)
Amount at
Amount at
Amount at
Amount at
beginning
(mol)
equilibrium
(mol)
beginning
(mol)
equilibrium
(mol)
CH3COOH(aq)
0.250
0.083
0.296
0.098
CH3CH2OH(aq)
0.250
0.083
0.296
0.098
H2SO4(l)
0.020
0.020
0.020
0.020
CH3COOCH2
CH3(aq)
0.000
0.250 0.083
= 0.167
0.000
0.198
H2O(l)
0.000
0.167
0.000
0.198
77
Equilibrium System:
CH3COOCH2CH3(l) +
experiment
1:
HFor
O(l)
2
(0.167 )(0.167 )
V 4.05
Kc V
0.083 )(0.083 )
1 (
V
V
78
Equilibrium System:
CH3COOCH2CH3(l) +
experiment
2:
HFor
O(l)
2
(0.198 )(0.198 )
V 4.08
Kc V
0.098 )(0.098 )
1 (
V
V
79
Equilibrium System:
CH3COOCH2CH3(l) +
Kc Kc
H2O(l)
Average value of K c
4.05 4.08
2
= 4.065 (no unit)
80
Equilibrium System:
CH3COOCH2CH3(l) +
H2O(l)
Conc. H SO acts as a positive catalyst
2
81
It can shorten the time taken to reach

the state of equilibrium but has no
effect on the extent of completion of
the reaction.
With
catalyst
Without
catalyst
Same extent of
completion
Same equilibrium
composition
82
Equilibrium
Constant in
Terms of Partial
Pressures
83
For gaseous systems in dynamic equilibria,

it is more convenient to express the equilibrium
constants in terms of partial pressures.
aA(g) + bB(g)
cC(g) + dD(g)
PC PD
Kp
a
b
PA PB
c
84
Relationship between Kc and Kp

PV = nRT
n
P RT = [Gas]RT
V
At fixed T,
85
P [Gas]
Consider the equilibrium system :

aA(g) + bB(g)
Kp
PC PD
PA PB
cC(g) + dD(g)
[C]c (RT) c [D] d (RT) d
[A] a (RT) a [B]b (RT)b

Kc (RT) (cd)(a b)
If a + b = c + d,
86
Kp = Kc
Simple Calculations Involving Kc and Kp

0.50 mole of CO2(g) and 0.50 mole of H2(g) are
mixed in a 5.0 dm3 flask at 690 K and are
allowed to establish the following equilibrium.
CO2(g) + H2(g)
CO(g) + H2O(g)
Kp = 0.10 at 690 K
R = 0.082 atm dm3 K1 mol1
Find partial pressures of all gaseous components
87
CO2(g) + H2(g)
Initial
0.50
no. of
moles
No. of moles 0.50 - x
at equil.
CO(g) + H2O(g)
0.50
0.50 - x
x
x
( 5.0
)( 5.0
)
Kc 0.50 x 0.50 x Kp 0.10
( 5.0 )( 5.0 )
x = 0.12
88
CO2(g) + H2(g)
at equil.
0.38
0.50 - x
0.38
CO(g) + H2O(g)
x
0.12
0.12
nT = 0.38 + 0.38 + 0.12 + 0.12 = 1.00
nT RT
PT
V
(1.00 mol)(0.082 atm dm3 K -1 mol-1 )(690 K)
5.0 dm3
= 11.316 atm
89
CO2(g) + H2(g)
at equil.
0.38
0.50 - x
0.38
CO(g) + H2O(g)
x
0.12
0.12
nT = 0.38 + 0.38 + 0.12 + 0.12 = 1.00
90
0.38
PCO2 XCO2 PT
11.316 atm = 4.30 atm
1.00
0.38
PH2 XH2 PT
11.316 atm = 4.30 atm
1.00
0.12
PCO PH2O
11.316 atm = 1.36 atm
1.00
Q.11
At fixed V & T,
PSO2
PO2
nSO2
nO2
Pn
=3
2SO2(g) + O2(g)
2SO3(g)
Initial partial
pressure
3x
Partial pressure
at equilibrium
1.5x
x 1.5x/2
= 0.25x
1.5x
91
Q.11
2SO2(g) + O2(g)
Partial pressure
at equilibrium
1.5x
0.25x
2SO3(g)
1.5x
PT = 373 kPa = 1.5x + 0.25x + 1.5x

x = 115 kPa
(PSO3 ) 2
(1.5x) 2
1
Kp
=
0.035
kPa
(PSO ) 2 (PO ) (1.5x) 2 (0.25x)
2
92
Q.12
At fixed V & T,
PCl5(g)
Initial partial
pressure
Partial pressure
at equilibrium
0.14x
Pn
PCl3(g) + Cl2(g)
0
0.86x
0
0.86x
PT = 101 kPa = 0.14x + 0.86x + 0.86x

x = 54.3 kPa
93
Q.12
Partial pressure
at equilibrium
PCl5(g)
PCl3(g) + Cl2(g)
0.86x
0.14x
0.86x
x = 54.3 kPa
Kp
PPCl3 PCl2
PPCl5
(0.86x)
0.14x
94
= 287 kPa
Q.13
N2(g)
95
O2(g)
2NO(g)
Initial no. of
moles
2.0
1.0
No. of moles
at equilibrium
2.0 - x
1.0 x
2x
Concentration
at equilibrium
2.0 x
2.0
1.0 x
2.0
2x
2.0
Q.13
N2(g)
Concentration
at equilibrium
2.0 x
2.0
O2(g)
2NO(g)
1.0 x
2.0
Kc
2x
2.0
2
=
K
=
1.2
10
p
2.0 x 1.0 x

2.0 2.0
x = 0.073
[N2] = (2.0 0.073)/2.0 = 0.96 mol dm3
96
2x
2.0
Q.13
N2(g)
Concentration
at equilibrium
2.0 x
2.0
O2(g)
2NO(g)
1.0 x
2.0
Kc
2x
2
2.0
(2x)
=
K
=
1.2
10
p
2.0 x 1.0 x
(2.0)(1.0)

2.0 2.0
x is small, 2.0 x 2.0 and 1.0 x 1.0
97
2x
2.0
Q.13
N2(g)
Concentration
at equilibrium
2.0 x
2.0
O2(g)
2NO(g)
1.0 x
2.0
Kc
2x
2
2.0
(2x)
=
K
=
1.2
10
p
2.0 x 1.0 x
(2.0)(1.0)

2.0 2.0
x = 0.077
[N2] = (2.0 0.077)/2.0 = 0.96 mol dm3
98
2x
2.0
Homogeneous Equilibrium
Equilibrium system involving ONE phase only
N2(g) + 3H2(g)
2NH3(g)
Cl2(aq) + 2Br(aq)
2Cl(aq) + Br2(aq)
99
Homogeneous Equilibrium
Glacial
ethanoic acid
Absolute
alcohol
Dissolve both
products
CH3COOH(aq) + C2H5OH(aq)
Immiscible Two phases
100
Q.14
Cu2+(aq) + 4NH3(aq)
Kc
101
Cu(NH3)42+(aq)
[Cu(NH ) (aq)]eqm
2
3 4
[Cu (aq)]eqm [NH3 (aq)]

2
4
eqm
Q.14
N2(g) + 3H2(g)
Kp
2NH3(g)
P P
NH3
N2
102
H2
Q.14
Kc
103
[CH3COOC2H5 (l)]eqm [H2O(l)]eqm

[CH3COOH(l)]eqm [C2H5OH(l)]eqm
Q.14
H+(aq) + OH(aq)
Kc
H2O(l)
[H2O(l)]eqm
[H (aq)]eqm [OH (aq)]eqm
At pH 7, density of water 1000 g dm3
1000 g
18 g mol1
3
[H2O(l)]
=
55.5
mol
dm
1 dm3
104
Q.14
H+(aq) + OH(aq)
Kc
H2O(l)
[H2O(l)]eqm
[H2O(l)] 55.5 M In large excess

a constant
1
K

'
c
105
Q.15(a)
Calculate the molarity of water in 12.39 M
hydrochloric acid.
Given: Density of 12.39 M hydrochloric acid is
1.19 g cm3 at 298 K
Mass of 1 dm3 of 12.39 M HCl(aq)
= 1.19 g cm3 1000 cm3 = 1190 g
Mass of HCl present
= 12.39 mol (1 + 35.5) g mol1 = 452.2 g
106
Q.15(a)
Calculate the molarity of water in 12.39 M
hydrochloric acid.
Given: Density of 12.39 M hydrochloric acid is
1.19 g cm3 at 298 K
Mass of water present
= (1190 452.2) g = 737.8 g
737.8 g
18.0 g mol1
[H2O(l)]
= 41.0 M
3
1 dm
107
Q.15(b)
737.8 g
18.0 g mol1
[H2O(l)]
= 41.0 M < 55.5 M
3
1 dm
At very high acid concentrations, H2O is

NOT in large excess.
It is NOT justified to consider [H2O]equil as a
constant in ALL aqueous solutions.
108
Q.15(b)
HCl(aq)
H+(aq) + Cl(aq)
12.38 M
H+(aq) + OH(aq)
< 12.38 M
109
H2O(l)
41.0 M
Heterogeneous Equilibrium
Equilibrium systems involving two or more
phases
H2O(l)
H2O(g)
Kp PH2O
Kp depends on temperature only

at fixed T, vapour pressure of water (Kp)
is a constant, irrespective of the amount
of water present.
110
Kc
[H2O(g)]equil
[H2O(l)]equil
[H2O(l)]equil
nH2O
VH2O
mH2O
18 g mH2O
18 g
VH2O VH2O
18 g
[H2O(l)]equil = constant (at fixed T)
111
Kc
[H2O(g)]equil
[H2O(l)]equil
Kc [H2O(l)]equil Kc' [H2O(g)]equil
PH2O [H2O(g)]equil RT
PH2O K RT
'
c
= Kp (at fixed T)
112
In a solution, and in a gas, the concentration

changes as the particles (molecules, atoms or
ions) become closer together or further apart.
In a solid or a liquid, the particles are at fixed
distance from one another;
this means that the concentration is also
fixed.
In effect, the concentration of a solid or a
liquid is equivalent to its density (also known as
the effective reacting concentration).
113
In heterogeneous equilibria, the effective

reacting concentration of a pure liquid or a
pure solid is a constant and is independent of
the amount of liquid or solid present
Since collisions of reacting particles occur
at the boundary of phases.
A change in the surface area of a solid or a
liquid (by changing the amount) affects the
rates of forward and backward reactions to
the same extent.
114
Changing the amount of a pure solid or a pure

liquid in a heterogeneous equilibrium mixture
does NOT disturb the equilibrium.
Conclusion : [X(s)] and [X(l)] do NOT appear in the

equilibrium constant expressions of
heterogeneous equilibria.
115
Q.16
Mg(s) + Cu2+(aq)
Kc
116
Mg2+(aq) + Cu(s)
[Mg (aq)]eqm
2
[Cu (aq)]eqm
2
Q.16
CaCO3(s)
CaO(s) + CO2(g)
Kp PCO2
117
Q.16
Ag+(aq) + Cl(aq)
AgCl(s)
1
Kc
[Ag (aq)]eqm [Cl (aq)]eqm
118
Q.16
Fe3O4(s) + 4H2(g)
Kp
3Fe(s) + 4H2O(g)
P
H2O
H2
119
Q.16
Br2(l)
Br2(g)
Kp PBr2
120
Partition
Equilibrium of a
Solute Between
Two Immiscible
Solvents
121
Partition (Distribution) Equilibrium
The equilibrium established when a

non-volatile solute distributes itself
between two immiscible liquids
A(solvent 2)
122
A(solvent 1)

Water and hexane are immiscible with
each other.
Hexane
Water
123

I2 dissolves in both solvents to different
extent.
Hexane
Water
124

When dynamic equilibrium is established,
rate of movement = rate of movement
Hexane
Water
125
Suppose the equilibrium concentrations of iodine

in H2O and hexane are x and y respectively,
x
KD
y
Hexane
Water
126
Suppose the equilibrium concentrations of iodine

in H2O and hexane are x and y respectively,
x
KD
y
When dynamic equilibrium is established
the ratio of concentrations of iodine in water
and in hexane is always a constant.
KD : partition coefficient or
distribution coefficient
127
Changing the concentrations by the same extent

does not affect the quotient.
x 2x 3x 4x 0.5x
KD
y 2y 3y 4y 0.5y
the rates of the two opposite processes are

affected to the same extent.
However, changing the concentrations by the
same extent changes the colour intensity of the
solutions.
128
Partition Coefficient
The partition law can be represented by
the following equation:
concentration of solute in solvent 1
KD
concentration of solute in solvent 2
[solute]solvent 1
[solute]solvent 2
(no unit)
Units of concentration : mol dm-3, mol cm-3, g dm-3, g cm-3

129
The partition coefficient of a solute
between solvent 2 and solvent 1 is given by
[solute]solvent 2
KD
[solute]solvent 1
The partition coefficient of a solute

between solvent 1 and solvent 2 is given by
[solute]solvent 1
KD
[solute]solvent 2
130
Depends on temperature ONLY.
Not affected by the amount of solute
added and the volumes of solvents
used.
TAS Experiment No. 12
131
[CH3COOH]water
[CH3COOH]water
[CH3COOH]2-methylpropan-1-ol
TAS Expt 12
slope [CH3COOH]water / [CH3COOH]2methylpropan1ol
= KD
132
[CH3COOH]2-methylpropan-1-ol
Partition law holds true

1. at fixed temperature
2. for dilute solutions ONLY
For concentrated solutions,
interactions between solvent and
solute have to be considered and the
concentration terms should be
expressed by activity (effective
concentration)
133
Partition law holds true

3. when the solute exists in the same
form in both solvents.
i.e. no association or dissociation of solute
C6H5COOH(benzene)
C2
134
C6H5COOH(aq)
C1
C1 and C2 are determined by titrating the

acid in each solvent with standard sodium
hydroxide solution.
[C6H5COOH]water(C1)
[C6H5COOH]benzene(C2)
/ mol dm-3
/ mol dm-3
0.06
0.483
0.124
0.12
1.92
0.063
0.14
2.63
0.053
0.20
5.29
0.038
C1/C2
Not a constant
135
Interpretation : Benzoic acid tends to dimerize (associate)

in non-polar solvent to give (C6H5COOH)2
H
O
C
C
O
Benzoic acid dimer
The solute does not have the same

molecular form in both solvents
Violation of Partition law

136
Interpretation : 2C6H5COOH(benzene)
C2 (1 )
(C6H5COOH)2(benzene)
1
2 C 2
= degree of association of benzoic acid

[C6H5COOH]total = [C6H5COOH]free + [C6H5COOH]associated
C2
C2(1-)
C2
Determined by titration with NaOH

137
Q.17(a)
The interaction between benzoic acid and
benzene molecules are weaker than the
hydrogen bonds formed between benzoic
acid molecules.
Thus benzoic acids tend to form dimers
when dissolved in benzene.
In aqueous solution, benzoic acid molecules
form strong H-bond with H2O molecules
rather than forming dimer.
138
Q.17(b)
In aqueous solution, there is no association
as explained in (a).
Also, dissociation of acid can be ignored
since benzoic acid is a weak acid
(Ka = 6.3 10-5 mol dm-3).
139
Q.17(c)
2C6H5COOH(benzene)
(C6H5COOH)2(benzene)
C2 (1 )
C2
K
[C2 (1 )]2
1
2
C2
1
2
C6H5COOH(benzene)
C2 (1 )
C1
KD
C2 (1 )
140
C6H5COOH(aq)
C1
C2
K
2
[C2 (1 )]
1
2
is a constant at fixed T
C2
'
C2 (1 )
K C2
2K
C1
C1
KD
'
C2 (1 ) K C2
141
C1
C2
KDK K
'
''
[C6H5COOH]water(C1) [C6H5COOH]benzene(C2) /
/ mol dm-3
mol dm-3
C1
C2
0.06
0.483
0.086
0.12
1.92
0.087
0.14
2.63
0.086
0.20
5.29
0.087
~constant
142
Applications of partition law
Solvent extraction
Chromatography
Two classes of separation
techniques based on partition
law.
143
Solvent extraction
+ hexane
I2 in KI(aq)
I22 in hexane
Colourless
Hexane
I22 in KI(aq)
To
It
Itdissolves
iscan
remove
immiscible
be recycled
II22from
but
with
not
an
easily
water.
KI.
aqueous
(e.g. by
solution
distillation)
of KI, a
What
feature
should
the
solvent
have?
At equilibrium,
suitable
solvent
is added.
Organic
Organic
solvents
(volatile)
solvents
preferred.
are preferred.
rate of movement of I2 =are
rate
of movement
of I2
By partition law,
144
[ I 2 ]hexane
K
[ I 2 ]KI ( aq )
Solvent Extraction
Hexane
layer
Aqueous
layer
Before
shaking
145
After
shaking
Iodine can be extracted from water by

adding hexane, shaking and separating the
two layers in a separating funnel
Determination of I2 left in both layer

Titrated with standard sodium thiosulphate
solution
I2 + 2S2O3
146
2I + S4O62
Determination of I2 left in the KI solution

For the aqueous layer,
starch is used as the indicator.
For the hexane layer,
starch is not needed because the colour of I2 in
hexane is intense enough to give a sharp end
point.
147
In solvent extraction, it is more

efficient (but more time-consuming) to
use the solvent in portions for repeated
extractions than to use it all in one
extraction.
Worked example
148
Worked example : 50g X in 40 cm3 ether solution

10g X in 25 cm3 aqueous solution
[X]
ether of X between ether

(a) By partition
Calculatelaw,
the partition
K D coefficient
[X]water
and water at 298 K.
[ X ]ether
149
50
50
M
0.04 0.04 M
[ X ]water
10
10
M
0.025 0.025M
50
M is the molecular mass
ofMX
0
.
04
KD
3.125
10
0.025M
Worked example : 50g X in 40 cm3 ether solution

10g X in 25 cm3 aqueous solution
Or simply,
150
50
40
10
25
3.125
(b)(i)
30 cm3 ether
5g of X in 30 cm3
aqueous solution
xg of X in 30 cm3
ether solution
(5-x)g of X in 30 cm3
aqueous solution
Determine the mass of X that could be extracted by shaking a

30 cm3 aqueous solution containing 5 g of X with a single 30
cm3 portion of ether at 298 K
151
(b)(i)
30 cm3 ether
5g of X in 30 cm3
aqueous solution
xg of X in 30 cm3
ether solution
(5-x)g of X in 30 cm3
aqueous solution
K 3.125
x
30
5 x
30
x 3.79
5 x
3.79 g of X could be extracted.

152
(b)(ii) First extraction

15 cm3 ether
5g of X in 30 cm3
aqueous solution
x1g of X in 15 cm3
ether solution
(5-x1)g of X in 30
cm3 aqueous solution
K 3.125
153
x1
15
5 x1
30
2 x1
x1 3.05
5 x1
(b)(ii) Second extraction

15 cm3 ether
(5-x1)g of X in 30 cm3
aqueous solution
x2g of X in 15 cm3
ether solution
(5-x1-x2)g of X in 30
cm3 aqueous solution
K 3.125
154
x2
15
5 x1 x2
30
2 x2
x2 1.19
5 3.05 x2
total mass of X extracted

= (3.05 + 1.19) g = 4.24 g > 3.79 g.
Repeated extractions using smaller portions
of solvent are more efficient than a single
extraction using larger portion of solvent.
However, the former is more time-consuming
155
Important extraction processes : 1. Products from organic synthesis, if contaminated

with water, can be purified by shaking with a suitable
organic solvent.
2. Caffeine in coffee beans can be extracted by
Supercritical carbon dioxide fluid (decaffeinated
coffee)
2. Impurities such as sodium chloride and sodium
chlorate present in sodium hydroxide solution can be
removed by extracting the solution with liquid
ammonia. Purified sodium hydroxide is the raw
material for making soap, artificial fibre, etc.
156
Q.18(a)
200 cm3 alcohol
Alcohol layer
Aqueous layer
100 cm3 of 0.500 M

ethanoic acid
Calculate the % of ethanoic acid extracted at 298 K by
shaking 100 cm3 of a 0.500 M aqueous solution of
ethanoic acid with 200 cm3 of 2-methylpropan-1-ol;
157
Q.18(a)
Let x be the fraction of ethanoic acid extracted to the
alcohol layer
No. of moles of acid in the original solution
= 0.500 0.100 = 0.0500 mol
[acid]alcohol
0.0500x
0.200
[acid]water
0.0500(1 x)
0.100
K 3.05
0.0500x
0.200
158
0.0500(1 x)
0.100
x = 0.396 = 39.6%
Q.18(b)
Let x1, x2 be the fractions of ethanoic acid extracted to
the alcohol layer in the 1st and 2nd extractions
respectively.
0.0500(1 x1 )
0.100
st
3.05 x1 0.247
1 extraction
0.0500x1
0.100
2nd extraction
0.0500(1 x1 x2 )
0.100
3.05 x2 0.186
0.0500x2
0.100
% of acid extracted=0.247+0.186=0.433=43.3%
159
Q.19
Let x cm3 be the volume of solvent X required to extract
90% of iodine from the aqueous solution and y be the no.
of moles of iodine in the original aqueous solution.
[I2 ]solventX
K 120
[I2 ]water
0.9y
x
0.1y
100
x = 7.5
7.5 cm3 of solvent X is required
160
Chromatography
A family of analytical techniques for
separating the components of a mixture.
Derived from the Greek root chroma,
meaning colour, because the original
chromatographic separations involved
coloured substances.
161
Chromatography
In chromatography, repeated extractions
are carried out successively in one
operation (compared with fractional
distillation in which repeated distillations
are performed) which results, (as shown
in the worked example and Q.18), in an
effective separation of components.
162
All chromatographic separations are

based upon differences in partition
coefficients of the components
between a stationary phase and a
mobile phase.
163
The stationary phase is a solvent

(often H2O) adsorbed (bonded to the
surface) on a solid.
The solid may be paper or a solid such
as alumina or silica gel, which has
been packed into a column or spread
on a glass plate.
164
The mobile phase is a second solvent

which seeps through the stationary
phase.
Three main types of chromatography

1.
Column chromatography
2.Paper chromatography
3.Thin layer chromatography
165
Stationary phase : Water adsorbed on the
adsorbent (alumina or silica gel)
Mobile phase : A suitable solvent (eluant) that

seeps through the column
166
Sample
Partition of components takes

place repeatedly between the
two phases as the components
are carried down the column
by the eluant.
The components are separated
into different bands according
to their partition coefficients.
167
Eluant
The component with the
highest coefficient
between mobile phase and
stationary phase is carried
down the column by the
mobile phase most quickly
and comes out first.
168
Suitable for large scale
treatment of sample
For treatment of small
quantities of samples, paper
or thin layer chromatography
is preferred.
169
Paper chromatography
Stationary phase : -
Water adsorbed on
paper.
Mobile phase : A suitable solvent
The best solvent for a
particular separation
should be worked out by
trials-and-errors
X
(adsorbed water)
170
stationary phase
X(solvent)
mobile phase
The solvent moves up
the filter paper by
capillary action
Components are carried
upward by the mobile
solvent
Ascending
chromatography
171
172
Different dyes
have different KD
between the mobile
and stationary
phases
They will move
upwards to
different extent
173
The components separated
can be identified by their
specific retardation
factors, Rf, which are
calculated by
Rf distance travelled by spot

distance travelled by solvent
174
filter
paper
separated
colours
spot of
coloured
dye
solvent
Using chromatography to separate the colours in a sweet.
175
Solvent front
176
b
Rf (blue)
a
c
Rf (red)
a
d
Rf (green)
a
a chromatogram
separated
colours
177
Paper Chromatography
The Rf value of any particular substance
is about the same when using a particular
solvent at a given temperature
The Rf value of a substance differs in
different solvents and at different
temperatures
178
Paper Chromatography
Amino acid
Solvent
Cystine
Mixture of
phenol and
ammonia
0.14
Mixture of
butanol and
ethanoic acid
0.05
Glycine
0.42
0.18
Leucine
0.87
0.62
Rf values of some amino acids in two

different solvents at a given temperature
179
Two-dimensional paper chromatography
180
Two-dimensional paper chromatography
All spots (except proline)

appears visible (purple)
when sprayed with
ninhydrin (a developing
agent)
181
Thin layer chromatography

Stationary phase : Water adsorbed on a thin
layer of solid adsorbent
(silica gel or alumina).
Mobile phase : A suitable solvent
X(adsorbed water)
stationary phase
182
X(solvent)
mobile phase
Q.20
Suggest any advantage of thin layer
chromatography over paper chromatography.
A variety of different adsorbents can be used.
The thin layer is more compact than paper,
more equilibrations can be achieved in a
few centimetres (no. of extraction ).
A microscope slide is long enough to provide
effective separation
183
Factors
Affecting
Equilibrium
184
THREE factors affecting chemical equilibria.

1. Changes in pressure
2. Changes in concentration
No effect on
Kc or Kp
Alter the equilibrium position by

changing the equilibrium composition
3. Changes in temperature
Alter the equilibrium position by
changing the equilibrium constant
185
THREE ways of interpretation
186
1.
Kc or Kp approach
2.
Kinetic approach
3.
Le Chateliers Principle
Effects of changes in pressure

increase in pressure
A(g)
B(g)
C(g)
decrease in pressure
P by reducing V
Equilibrium position shifts to the right
P by increasing V
187
Equilibrium position shifts to the left
Interpretation : Kp approach
A(g)
B(g)
Pequil 1
PA
PB
P1
2PA
2PB
188
C(g)
PC
Kp
PAPB
PC
2PC
2PC
1 PC Kp

Qp

Kp
2PA 2PB 2 PAPB 2
A(g)
Pequil 1
PA
B(g)
PB
C(g)
PC
Equilibrium position shifts to the right until

Qp = Kp
P1
2
189
2PA
2PB
2PC
2PC
1 PC Kp

Qp

Kp
2PA 2PB 2 PAPB 2
A(g)
Pequil 1
PA
B(g)
PB
C(g)
PC
Equilibrium position shifts to the right until

Qp = Kp
Pequil 2
2PA - x
2PB x
2PC + x
2PC x
PC
Qp
Kp
2PA x 2PB x PAPB
190
Interpretation : kinetic approach

A(g)
B(g)
C(g)
Both the rates of forward and backward

reactions are increased by doubling the partial
pressures of all gaseous components of the
system.
However, the rate of forward reaction is
increased more.
There is a net forward reaction
191
Equilibrium position shifts to the right
Q.21
A(g)
B(g)
k1
k-1
C(g)
R1 = k1[A][B]
R-1 = k-1[C]
V
R1 = k1(2[A])(2[B]) = 4R1
R-1 = k-1(2[C]) = 2R-1
192
More
affected
Q.21
A(g)
B(g)
k1
k-1
C(g)
R1 = k1[A][B]
R-1 = k-1[C]
V2
R1 = k1([A])([B]) = R1
R-1 = k-1([C]) = R-1
193
More
affected
Le Chateliers Principle
If a system at equilibrium is forced to
change, the equilibrium position of the
system will shift in a way to reduce (or
oppose) the effect of the change.
194
Q.22(a)
A(g)
B(g)
Change : PT
Response : PT
195
C(g)
Q.22(b)/(c)
A(g)
B(g)
Two moles
196
C(g)
One mole
Q.22(d)
A(g)
B(g)
Two moles
C(g)
One mole
One mole of gas exert less pressure.
197
Q.22(e)
A(g)
B(g)
Two moles
C(g)
One mole

The forward reaction lowers the pressure
of the system.
198
Q.22(f)
A(g)
B(g)
Two moles
C(g)
One mole

The forward reaction lowers the pressure
of the system.
Equilibrium position shifts to the right.
199
Q.22(g)
A(g)
B(g)
Change : PT
Response : PT
200
C(g)
N2O4(g)
pale yellow
2NO2(g)
brown
Sealed nozzle
Syringe
N2O4(g), NO2(g)
Immediately after pushing in the plunger

The gas mixture turns darker brown due to a
sudden increase in concentrations of both gases
201
N2O4(g)
pale yellow
Sealed nozzle
2NO2(g)
brown
Syringe
N2O4(g), NO2(g)
After a few seconds
202
The gas mixture turns paler

because the system reduces the pressure by
shifting the equilibrium position to the left (the
side with less gas molecules).
N2O4(g)
pale yellow
2NO2(g)
brown
Sealed nozzle
Syringe
N2O4(g), NO2(g)
Immediately after pulling out the plunger

The gas mixture turns paler due to a sudden
decrease in concentrations of both gases
203
N2O4(g)
pale yellow
Sealed nozzle
2NO2(g)
brown
Syringe
N2O4(g), NO2(g)
After a few seconds
204
The gas mixture turns darker brown because

the system the pressure by shifting the
equilibrium position to the right (the side with
more gas molecules).
Q.23(a)/(b)
H2(g) + CO2(g) H2O(g) + CO(g)
Cause : in PT by reducing VT
Effect : No effect on the equilibrium position
Cause : in PT by increasing VT
Effect : No effect on the equilibrium position
205
Q.23(c)/(d)
H2(g) + CO2(g) H2O(g) + CO(g)
Cause : in PT by increasing PH2
Effect : Equilibrium position shifts to the
right
Cause : in PT by increasing PCO
Effect : Equilibrium position shifts to the left
206
Q.23(e)
H2(g) + CO2(g) H2O(g) + CO(g)
Cause : in PT by introducing He(g)
Effect : No effect on equilibrium position
Reason : The partial pressures of reactants
and products remain unchanged.
207
Q.23(a)/(b)
PCl5(g)
PCl3(g) + Cl2(g)
right
208
Q.23(c)/(d)
PCl5(g)
PCl3(g) + Cl2(g)
Cause : in PT by increasing PPCl

right
Cause : in PT by increasing PCl
209
Q.23(e)
PCl5(g)
PCl3(g) + Cl2(g)

210
Q.23(a)/(b)
Fe3O4(s) + 4H2(g)
3Fe(s) + 4H2O(g)
211
Q.23(c)/(d)
Fe3O4(s) + 4H2(g)
3Fe(s) + 4H2O(g)
Cause : in PT by increasing PH2

right
Cause : in PT by increasing PH O
2
212
Q.23(e)
Fe3O4(s) + 4H2(g)
3Fe(s) + 4H2O(g)

213
For the systems

H2(g) + CO2(g) H2O(g) + CO(g)
Fe3O4(s) + 4H2(g)
3Fe(s) + 4H2O(g)
Changing PT by altering VT has no effect on

the equilibrium position
214
For the systems

H2(g) + CO2(g) H2O(g) + CO(g)
Pequil 1
PH2
PCO2
PH2O
PCO
P1
2PH2
2PCO2
2PH2O
2PCO
Kp
PH2OPCO
PH2 PCO2
Qp
2P 2P
2P 2P
H2O
H2
= Kp
215
CO
CO2
For the systems

Fe3O4(s) + 4H2(g)
Pequil 1
P1
2
Kp
P
H2O
H2
3Fe(s) + 4H2O(g)
PH2
PH2O
2PH2
2PH2O
Qp
2P
2P
H2O
H2
= Kp
216
For the systems

H2(g) + CO2(g) H2O(g) + CO(g)
Fe3O4(s) + 4H2(g)
3Fe(s) + 4H2O(g)
Kinetic approach
The rates of forward and backward reactions
are affected to the same extent.
217
For the systems

H2(g) + CO2(g) H2O(g) + CO(g)
Fe3O4(s) + 4H2(g)
3Fe(s) + 4H2O(g)
By Le Chateliers principle
Since the system has the same no. of gas
molecules on either side,
No adjustment made by the system can
reduce the change.
No shifting of equil. position
218
For the systems

H2(g) + CO2(g) H2O(g) + CO(g)
PCl5(g)
PCl3(g) + Cl2(g)
in PT by changing VT has no effect on the

equilibrium position
However, the partial pressures and thus the
equilibrium composition change by altering VT
219
Q.24
Decrease in PCO2
CO2(aq)
CO2(g)
Once the bottle is opened, CO2 escapes from

the system and its partial pressure drops.
The system responds by releasing CO2 from
the aqueous solution.
220
Effects of pressure changes on equilibrium

systems involving ONLY solids and/or liquids
are negligible since solids and liquids are
incompressible (with fixed density at fixed T)
H2O(s)
221
H2O(l)
Q.25
Extremely high P
H2O(s)
More open
H2O(l)
More closely
packed
The great increase in pressure causes the

more open structure of ice to collapse to give
the more closely packed structure of liquid
water.
222
The Effect of Changes in Concentration on

Equilibrium
Bi3+(aq) + Cl(aq) + H2O(l)
colourless
BiOCl(s) + 2H+(aq)
white ppt
Test 1 : Add HCl

Result : The white ppt disappears
The equil. position shifts to the left
223
colourless
BiOCl(s) + 2H+(aq)
white ppt
Interpretation : Kc approach
2
[H
(aq)]
equil
*
Kc 3
[Bi (aq)]equil[Cl (aq)]equil[H2O(l)]equil
Since H2O is in large excess
[H (aq)]2 equil
Kc
[Bi3 (aq)]equil[Cl (aq)]equil
224
colourless
BiOCl(s) + 2H+(aq)
white ppt
[H (aq)]2 equil
Kc
[Bi3 (aq)]equil[Cl (aq)]equil
Addition of HCl(aq)
Both [H+(aq)] and [Cl(aq)] to the same extent
[H (aq)]2
Qc 3
Kc
[Bi (aq)][Cl (aq)]

225
The equilibrium position shifts to the left to

restore the Kc
colourless
BiOCl(s) + 2H+(aq)
white ppt
Kinetic approach : Both the rates of forward and backward

reactions increase but the backward reaction
increases more.
A net backward reaction is observed
The equilibrium position shifts to the left
226

Bi3+(aq) + 3Cl(aq) + H2O(l)
BiOCl(s) + 2H+(aq)
BiOCl(s) + 2HCl(aq)
Addition of HCl(aq)
The system responds in such a way as to reduce
the amount of HCl added
the equilibrium position shifts to the left
227
The Effect of Changes in Concentration on

Equilibrium
colourless
BiOCl(s) + 2H+(aq)
white ppt
Test 2 : Add large excess of H2O

Result : The white ppt reappears
The equil. position shifts to the right
228
colourless
BiOCl(s) + 2H+(aq)
white ppt
Interpretation : Kc approach
[H (aq)]2 equil
Kc
[Bi3 (aq)]equil[Cl (aq)]equil [H2O(l)]equil
Addition of large excess of H2O

[H (aq)]2
Qc
*Kc
3
[Bi (aq)][Cl (aq)][H2O(l)]
229
Equilibrium position shifts to the right such

that *Qc = *Kc
colourless
BiOCl(s) + 2H+(aq)
white ppt
Interpretation : Kinetic approach

[H2O(l)]
equilibrium position shifts to the right
230
colourless
BiOCl(s) + 2H+(aq)
white ppt
By Le Chateliers principle : [H2O(l)]

The system shifts to the right to reduce the
water added.
231
The Effect of Changes in Temperature on

Equilibrium
A change in temperature of an equilibrium

system results in an adjustment of the
equilibrium system to
a new equilibrium position with
a new equilibrium constant.
232
Examples : -
Exothermic reaction:
N2(g) + 3H2(g)
2NH3(g)
H 0 92 kJ mol1
Temperature (K)
500
600
700
800
Kp (atm-2)
90.0
3.0
0.3
0.04
Kp decreases as T increases
233
Examples : -
Exothermic reaction:
2C(graphite) + O2(g)
2CO(g)
H 0 211 kJ mol1
Temperature
(K)
Kp (atm)
298
500
700
900
1100
1.5
1048
3.1
1032
1.2
1026
3.1
1022
1.5
1020
Kp decreases as T increases
234
Examples : -
Endothermic reaction:
N2O4(g)
2NO2(g)
H 0 58 kJ mol1
Temperature (K)
200
300
400
500
Kp (atm)
1.8 10-6
0.174
51
1510
Kp increases as T increases
235
Examples : -
Endothermic reaction:
N2(g) + O2(g)
2NO(g)
H 0 100 kJ mol1
Temperature (K)
700
1100
1500
Kp (no unit)
5 10-13
4 10-8
1 10-5
Kp increases as T increases
236
Vant Hoff Equation

H o
lnK
C
RT
H
log10K
C'
2.303RT
o
C and C are constants related to S

o
o
S
S
C
C'
R
2.303R
237
H
lnK
C
RT
o
If the forward process is exothermic,
H
H 0 and R
TK
o
An increase in T shifts the equilibrium

position to the left
238
(in the endothermic direction)
H
lnK
C
RT
o
If the forward process is exothermic,
H
H 0 and R
TK
o
An decrease in T shifts the equilibrium

position to the right
239
(in the exothermic direction)
H
lnK
C
RT
o
If the forward process is endothermic,
H
H 0 and R
TK
o
An increase in T shifts the equilibrium

position to the right
240
(in the endothermic direction)
H
lnK
C
RT
o
If the forward process is endothermic,
H
H 0 and R
TK
o
An decrease in T shifts the equilibrium

position to the left
241
(in the exothermic direction)
Conclusion :
1. An increase in temperature shifts the
equilibrium position in the endothermic
direction.
2. A decrease in temperature shifts the
equilibrium position in the exothermic
direction.
Consistent with Le Chateliers principle
242
Q.26(a)
Forward reaction is exothermic
lnK
H o
slope 0
R
y - intercept C
243
(If C > 0)
1 1
(K )
T
Q.26(a)
lnK
Forward reaction is exothermic

H o
slope 0
R
y - intercept C
244
(If C < 0)
1 1
(K )
T
Q.26(a)
Forward reaction is endothermic
lnK
y - intercept C
(If C > 0)
H o
slope 0
R
1 1
(K )
T
245
Q.26(a)
Forward reaction is endothermic
y - intercept C
(If C < 0)
H o
slope 0
R
lnK
246
1 1
(K )
T
Q.27
50C
Increase in T
N2O4(g)(pale yellow)
247
Decrease in T
2NO2(g)(brown)
Q.27(a)
Increase in T
N2O4(g)(pale yellow)
2NO2(g)(brown)
Decrease in T
in T shift the equilibrium position to the
right.
Thus, the forward oreaction is endothermic
H 0
By Le Chateliers principle, the system tends

to decrease the T by shifting in the
endothermic direction.
248
Q.27(b)(i)
Assume no change in equilibrium position
n is fixed
PT inside the syringe = atomospheric pressure
PT is fixed
VT
V373K
249
V373 K 373 K
V273 K 273 K
373 K
3
3
(1 dm ) 1.37 dm
273 K
Q.27(b)
(ii)
N2O4(g)
2NO2(g)
equilibrium position shifts to the right

total no. of moles of gas molecules
total volume of the system further
250
Increase in T
Q.27
V(dm )
3
N2O4(g)
2NO2(g)
Actual in V
1.37
Ideal gas expansion
1.00
251
273
373
T(K)
Interpretation of the Effects of Temperature

Changes on Equilibrium in Terms of Chemical Kinetics
AB + X
A + BX
Potential energy
Ea
H 0
Ea
AB+X
A+BX
252
Reaction co-ordinate
For the forward reaction (exothermic)
kT2
kT1
AT2 e Ea/RT2
AT1 e
Ea /RT1
Ea /RT2
e
Ea/RT1 e
e
Ea 1 1
( )
R T2 T1
Ea (T2 T1 )
RT1T2
Potential energy
Ea > 0 &
T2 T1 > 0
Rate as T
Ea
Ea
AB+X
A+BX
253
>1
For the backward reaction (endothermic)
kT2 '
kT1 '
AT2 'e
AT1 'e
Ea '/RT2
Ea '/RT1
Ea '/RT2
e
Ea '/RT1 e
e
Ea ' 1 1
( )
R T2 T1
Potential energy
Ea (T2 T1 )
RT1T2
Ea > E a &
Ea
Ea
T2 T1 > 0
AB+X
A+BX
254
Ea '(T2 T1 )
RT1T2
Conclusion :
An in temperature the rates of endothermic
and exothermic reactions to different extents.
The rate of endothermic reaction is affected
more by temperature changes.
255
Q.28
X(l)
X(g)
o
vap
Prediction : An in T shifts the equilibrium position to

the right (in endothermic direction)
Interpretation : An in T increases Kp
Thus, more X(l) evaporate until Qp = Kp
256
Q.28
X(s)
X(g)
o
sub
Prediction : An in T shifts the equilibrium position to

the right (in endothermic direction)
Interpretation : An in T increases Kp
Thus, more X(s) sublime until Qp = Kp
257
H o and the Extent of Completion of Reaction

H
log10K
C'
2.303RT
o
if H < 0 (forward reaction is exothermic)

o
and C is negligibly small

log10K > 0
K > 1 (the exothermic reaction is more complete
258
H o and the Extent of Completion of Reaction

H
log10K
C'
2.303RT
o
if H > 0 (forward reaction is endothermic)

o
and C is negligibly small

log10K < 0
K < 1 (the endothermic reaction is less
complete)
259
Example : Estimate the values of K at 298 K for the

equilibrium systems in which the H of the
forward reactions are (i) 100 kJ mol1 and (ii)
100 kJ mol1 respectively.
(Given : R = 8.314 J K1 mol1)
(i)
o
H
log10K
C'
2.303RT
- (-100 1000 J mol-1 )

Ho
2.303RT 2.303 8.314 J K -1 mol-1 298 K

260
K 3 1017
(Units not known)
Example : Estimate the values of K at 298 K for the

equilibrium systems in which the H of the
forward reactions are (i) 100 kJ mol1 and (ii)
100 kJ mol1 respectively.
(Given : R = 8.314 J K1 mol1)
(ii)
o
H
log10K
C'
2.303RT
- (100 1000 J mol-1 )

Ho
2.303RT 2.303 8.314 J K -1 mol-1 298 K

261
K 3 1018 (Units not known)
Conclusion : Exothermic processes are Far More Complete

than endothermic processes.
262
Q.29
The total pressures of the following equilibrium
system are 2.333104 Nm2 and 6.679104 Nm2 at
282.5 K and 298.1 K respectively.
NH4HS(s)
NH3(g) + H2S(g)
Since all gases arises from NH4HS(s)
PNH3 PH2S
263
1
PT
2
NH4HS(s)
At 282.5 K
lnKp ln(PNH3 )eqm (PH2S )eqm
NH3(g) + H2S(g)
o
H
1
2
C
ln( PT )
2
8.314 282.5
At 298.1 K
(1)
H
1
2
C (2)
lnKp ' ln(PNH3 ')eqm (PH2S')eqm ln( PT ')
2
8.314 298.1
(2) (1)
PT '
H o
1
1

ln
8.314 282.5 298.1

PT
6.679 10
ln
4
2.333
10
264
H o
1
1

8.314 282.5 298.1
H o = +94.41 kJ mol1
Effects of catalysts on Equilibrium

It can be shown that catalysts have no effect
on the equilibrium position since they affect
the rates of both forward and backward
reactions to the same extent.
(Refer to Notes on Chemical Kinetics, p.37
Q.29)
A catalyst has no effect on the equilibrium
position but can change the time taken to
attain the equilibrium state.
265
Q.30
Less time
Time
takentotoattain
attainequilibrium
equilibrium
Concentration
[A
]
266
[B]
t2
t1
Time
Q.31
A(g) + B(g)
H > 0
Rate of reaction
Forward
reaction
in T
in PT by reducing VT
VT T
(adiabatic compression)
Backward
reaction
t1
267
C(g)
e.g. expanding universe
Time
Q.31
A(g) + B(g)
C(g)
H > 0
Rate of reaction
Forward
reaction
Adding a +ve catalyst

Backward
reaction
t2
268
Time
Q.32 H2(g) + I2(g)

t1 : 1.2HI(g)
adding a catalyst
H < 0
Concentration
2. in PT by adding an
an inert gas at fixed VT
[HI(g)
]
[H2(g)]
[I2(g)]
269
t1
t2
t3
t4
Time
Q.32 H2(g) + I2(g)

2HI(g)
in PT by reducing VT has no
Concentration
[HI(g)
]
H < 0
effect on the equilibrium

position but changes the
equilibrium composition
[H2(g)]
[I2(g)]
270
t1
t2
t3
t4
Time
Q.32 H2(g) + I2(g)

2HI(g)
t : in P by reducing V
4
H < 0
T
Concentration
[HI(g)
]
[H2(g)]
[I2(g)]
271
t1
t2
t3
t4
Time
Q.32 H2(g) + I2(g)

2HI(g)
H < 0
Concentration
t2 : in T at fixed VT
[HI(g)
]
[H2(g)]
[I2(g)]
272
t1
t2
t3
t4
Time
Q.32 H2(g) + I2(g)

2HI(g)
H < 0
Concentration
t3 : Input of H2(g) at fixed VT

[HI(g)
]
[H2(g)]
[I2(g)]
273
t1
t2
t3
t4
Time
Q.33
CO(g) + 2H2(g)
274
CH3OH(g)
H < 0
Changes
Effect on
equilibrium
position
Effect on Kp
in PT by
reducing VT
Shifts to the
right
No effect
in T
Shifts to the
left
Kp
Q.33
CO(g) + 2H2(g)
Changes
Doubling PCO and
PCH3OH
Doubling
PH2
PCH3OH
275
and
CH3OH(g)
H < 0
Effect on
equilibrium
position
Effect on Kp
No effect
No effect
Shifts to the
right
No effect
Soluble in water
Q.33
CO(g) + 2H2(g)
276
CH3OH(g)
H < 0
Changes
Effect on
equilibrium
position
Effect on Kp
A positive
catalyst is added
No effect
No effect
A little H2O(l) is
added
Shifts to the
right
No effect
Q.34 A(g) + B(g)
277
C(g)
H = 0
Changes
Effect on
equilibrium
position
Effect on Kp
in T at fixed PT
No effect
No effect
in T at fixed PT
No effect
No effect
Q.34 A(g) + B(g)
278
C(g)
H = 0
Changes
Effect on
equilibrium
position
Effect on Kp
in T at fixed VT
Shifts to the
right
No effect
in T at fixed VT
Shifts to the
left
No effect
Summary of the Effects of Changes

of Various Factors on Equilibrium
aA(g) + bB(g)
Factor
Increase in
concentration of
reactants A or B
Increase in
concentration of
products C or D
279
cC(g) + dD(g)
Equilibrium
position
Shifts to right
Equilibrium
constant
No change
Shifts to left
No change

aA(g) + bB(g)
Factor
Increase in
pressure by
reducing the
volume of the
container
Isothermal
compression
280
cC(g) + dD(g)
Equilibrium
position
Shifts to right if
(c + d) < (a + b)
Shifts to left to
(a + b) < (c + d)
No change if
a+b=c+d
Equilibrium
constant
No change

aA(g) + bB(g)
Factor
Increase in
temperature
281
cC(g) + dD(g)
Equilibrium
position
Shifts to right if
the forward
reaction is
endothermic
Shifts to left if
the forward
reaction is
exothermic
Equilibrium
constant
Kp if the
forward reaction
is endothermic
Kp if the
forward reaction
is exothermic

aA(g) + bB(g)
Factor
Addition of a
catalyst
282
Equilibrium
position
No change
cC(g) + dD(g)
Equilibrium
constant
No change
16.1 Irreversible and Reversible Reactions (SB p.89)
Back
In the following reversible reaction:
A
B
(a)Give the letter that represents the reactant
of the
forward reaction.
(b) Give the letter that represents the
reactant of the backward reaction.
(c)Which is the forward reaction, A B or B
A ?
(a) A
(b) B
(c) A
283
Answer
16.2 Dynamic Nature of Chemical Equilibrium (SB p.91)
Back
List some characteristics of chemical equilibrium.
Answer
Some characteristics of chemical equilibrium include:
284
It can only be achieved in a closed system.
It can be achieved from either forward or backward

reactions.
It is dynamic in nature.
The concentrations of all chemical species present in a

system at equilibrium state remain constant as long as the
reaction conditions are unchanged.
16.3 Examples of Chemical Equilibrium (SB p.92)
Back
A trace amount of carbon monoxide labelled
with radioactive carbon-14 is added to the
following equilibrium system:
H2O(g) + CO(g)
H2(g) + CO2(g)
Explain why radioactive carbon dioxide

molecules are formed.
285
Chemical equilibrium is dynamic in nature. When a trace

amount of carbon monoxide labelled with radioactive
carbon-14 is added to the equilibrium system, the
equilibrium position shifts to the right. Therefore,
radioactive carbon dioxide molecules are formed.
Answer
16.4 Equilibrium Law (SB p.94)
Back
What is a closed system? Why can chemical equilibrium
only be established in a closed system?
Answer
A closed system means that there is no transfer of matter
between the system and the surroundings. If the system is
open, some of the reactants or products can enter or leave the
system. As a result, the equilibrium state can never be
reached.
286
Write the equilibrium expression (for Kc) and

unit of equilibrium constants for the following
equilibrium system.
(a) 2O3(g)
(a)
[O 2 ( g)]3eqm
Kc
[O 3 ( g)] 2eqm
Unit of Kc: mol dm-3
287
3O2(g)
Answer

equilibrium system.
(b) N2(g) + 3H2(g)
(b)
Kc
[NH3 (g)] 2eqm

[N2 (g)] eqm [H2 (g)]3eqm
Unit of Kc: mol-2 dm6

288
2NH3(g)
Answer
Back
equilibrium system.
(c) C(graphite) + H2O(g)
H2(g)
(c)
[CO( g)] eqm [H2 (g)] eqm

Kc
[H2 O(g)] eqm
Unit of Kc: mol dm-3
289
CO(g) +
Answer
16.5 Determination of Equilibrium Constants (SB p.98)
In the determination of the equilibrium constant

(Kc) of:
Fe2+(aq) + Ag+(aq)
Fe3+(aq) + Ag( s)
100 cm3 of 0.100 M AgNO3(aq) and 100 cm3 of

0.100 M FeSO4(aq) are mixed in a dry conical
flask. The mixture is then allowed to stand
overnight and filtered. The concentration of Ag +
(aq) is found by titration. 25.00 cm3 of the
filtrate is titrated with 0.050 M KCNS(aq) and
6.10 cm3 of the KCNS( aq) is required for
complete reaction.
290
(a)Calculate the equilibrium concentrations of

Ag+(aq), Fe2+(aq) and Fe3+(aq).
(a) Ag (aq) + CNS (aq) AgCNS(aq)
Number of moles of KCNS(aq)
= 6.10 dm 3 0.050 M
1000
+
Answer
= 3.05 10-4 mol

Number of moles of Ag+(aq) in 25 cm3 of the filtrate
at equilibrium = 3.05 104 mol
-4
[Ag+(aq)]eqm = 3.05 10 mol
25 10 - 3 mol
291
= 0.012 2 mol dm-3
(a) Fe2+(aq) and Ag+(aq) are consumed at the same rate.

[Fe2+(aq)]eqm = [Ag+(aq)]eqm = 0.012 2 mol dm3
[Fe2+(aq)]initial
0.100 mol dm -3 (100 10 -3 ) dm 3
=
(100 100) 10 - 3 dm 3
= 0.05 mol dm-3
[Fe3+(aq)]eqm = [Fe2+(aq)]initial [Fe2+(aq)]eqm
= (0.05 0.012 2) mol dm-3
= 0.0378 mol dm-3
292
(b) Calculate the equilibrium constant (K c).
Answer
(b)
[Fe 3 (aq)] eqm

Kc
[Fe 2 (aq)] eqm [ Ag (aq)] eqm
3
0.0378
mol
dm
=
0.0122 mol dm 3 0.0122 mol dm - 3
= 253.96 mol-1 dm3
293
Back
(c)What is the significance of
(i) using a dry conical flask?
(ii)
allowing the mixture to stand
overnight?
(c)
294
Answer
(i)
The significance of using a dry conical flask is
to make sure the reaction mixture in the conical flask is
not diluted by the presence of water.
(ii) The reaction mixture is allowed to stand overnight in
order to give sufficient time for the reaction mixture to
reach the equilibrium state.
For the reversible reaction of hydrogen and

iodine at equilibrium:
H2(g) + I2(g)
2HI(g)
If the initial amount of H2(g) is a mol, I2(g) is

b mol and the amount of H2(g) or I2(g)
reacted is x mol, express the equilibrium
constant (Kc) in terms of a, b and x.
Answer
295
Back
Let the volume of the reaction mixture be V dm3.
Reactant /
Product
Initial number of
moles (mol)
Change in
number of
moles (mol)
Number of moles
at equilibrium
(mol)
H2(g)
-x
ax
I2(g)
-x
bx
HI(g)
2x
2x
[HI(g)]
Kc
[H2 ( g)] eqm [I2 (g)] eqm
2
eqm
296
2x 2
)
4x 2
V
ax bx
(a x )(b x )
(
)(
)
V
V
(
For the Haber process,

N2(g) + 3H2(g)
2NH3(g)
If the initial amount of N2(g) is a mol, H2(g) is

b mol and the amount of N2(g) reacted is x
mol, express the equilibrium constant (Kc) in
terms of a, b and x.
Answer
297
Back
Let the volume of the reaction mixture be V dm3.
Reactant /
Product
Initial number of
moles (mol)
Change in
number of
moles (mol)
Number of moles
at equilibrium
(mol)
N2(g)
-x
ax
H2(g)
-3x
b 3x
NH3(g)
2x
2x
[NH3 (g)]
Kc
[N2 (g)] eqm [H2 (g)]3eqm
2
eqm
298
2x 2
)
V
a x b 3x 3
(
)(
)
V
V
(
4x 2
4x 2
V
V3
2
V
2
(a x )(b 3 x )3
V
a x (b 3 x )3
A student mixed 10 cm3 of 2.0 103 M

Fe(NO3)3(aq) with 10 cm3 of 2.0 103 M
KNCS(aq).
Fe3+(aq) + NCS(aq)
[Fe(NCS)]2+(aq)
When the system reaches the equilibrium,

the concentration of [Fe(NCS)]2+(aq) is 1.4
104 M. Determine the equilibrium constant
(Kc) of the reaction.
Answer
299
3
3
-3
3
Initial concentration of Fe3+(aq) = 2.0 10 mol dm 10 10 dm
(10 10) 10 - 3 dm 3
= 1.0 10-3 mol dm-3

2.0 10 3 mol dm 3 10 10 -3 dm 3
Initial concentration of NCS-(aq) =
(10 10) 10 - 3 dm 3
= 1.0 10-3 mol dm-3
Fe3+(aq) +
NCS-(aq)
[Fe(NCS)]2+(aq)
At start:
1.0 10-3 M
1.0 10-3 M
Amount changed:
-x M
x M
At equilibrium: (1.0 10-3 x) M (1.0 10-3 x) M
300
0M
xM
xM
Back
From the given data, the equilibrium concentration of [Fe(NCS)]2+

(aq) is 1.4 104 M, thus x = 1.4 104 M.
[Fe3+(aq)]eqm = (1.0 103 1.4 104) mol dm3
= 0.86 103 mol dm3
[NCS-(aq)]eqm = (1.0 103 1.4 104) mol dm3
= 0.86 103 mol dm3
1.4 10 4
3
3
Kc = (0.86 10 )(0.86 10 )
= 189.3 dm3 mol-1
301
Back
What is the implication for an equilibrium reaction

having an equilibrium constant much smaller than 1.0?
Answer
The equilibrium constant of a reaction is related to the

ratio of the concentration of products to the
concentration of reactants at equilibrium. When the
equilibrium constant of a reaction is much greater than
1, the reaction goes nearly to completion. Conversely,
when the equilibrium constant of a reaction is much
smaller than 1, the reaction hardly goes to completion.
302
At 400 K, 0.250 mole of PCl3(g) and 0.009

mole of PCl5(g) were mixed in a 1 dm3 flask.
After the system was left overnight, an
equilibrium was established and 0.002 mole
of chlorine gas was found in the flask.
Determine the equilibrium constant (Kc) of
the reaction:
Answer
PCl5(g)
303
PCl3(g) + Cl2(g)
Back
Reactant /
Product
Initial no. of
moles (mol)
Change in no.
of moles (mol)
No. of moles at
equilibrium
(mol)
PCl5(g)
0.009
-x
0.009 x
PCl3(g)
0.250
+x
0.250 + x
Cl2(g)
+x
At equilibrium, 0.002 mole of Cl2(g) was found in the flask.
X = 0.002 mol
304
[PCl 3 (g)][Cl2 (g)]

Kc =
[PCl5 (g)]
(0.250 0.002) mol dm 3 0.002 mol dm -3
=
(0.009 - 0.002) mol dm - 3
= 0.072 mol dm-3
16.6 Equilibrium Constant in Terms of Partial Pressures (SB p.101)
The following equilibrium reaction

2NOBr(g)
2NO(g) + Br2(g)
is studied at 298 K. The partial pressures of

NOBr(g), NO(g) and Br2(g) at equilibrium
were found to be:
PNOBr = 246 Nm2
PNO = 450 Nm2
PBr2 = 300 Nm2
305
Answer
Calculate the value of Kp for the reaction
at
298 K.
2NOBr(g)
2NO(g) + Br2(g)
The expression of Kp is:

(PNO ) 2 (PBr )
Kp
(PNOBr )2
2
Substituting the partial pressures into the expression, we have:

( 450 )2 (300 )
Kp
(246 ) 2
= 1 003.9 Nm2
306
Back
The decomposition of dinitrogen tetroxide to

form nitrogen dioxide is a reversible
reaction.
N2O4(g)
2NO2(g)
When the reaction reaches an equilibrium

state, the partial pressure of N2O4(g) was
found to be 2.71 atm. Calculate the partial
Answer
pressure of NO2(g) at equilibrium given
that
the value of Kp is 0.133 atm.
307
N2O4(g)
2NO2(g)
The expression of Kp is:

Kp
PNO
PN O
2
0.133
Substituting the value of Kp and the partial pressure of N2O4(g) into

the expression,
2
PNO = K PN O
p
= 0.133 2.71
2
=
0.360
atm
PNO
= 0.600 atm
2
308
Back
Equal amounts of hydrogen and iodine are

allowed to reach an equilibrium at 298 K:
H2(g) + I2(g)
2HI(g)
If 80% of the hydrogen is converted to

hydrogen iodide at the equilibrium, what is
the value of Kp at this temperature?
Answer
309
Assume that the initial number of moles of H2(g) is 1 mol.

H2(g)
I2(g)
At start:
1 mol
1 mol
At equilibrium: (1 0.8) mol (1 0.8) mol
= 0.2 mol
= 0.2 mol
0.2 mol
Mole fraction of H2(g) =
(0.2 0.2 1.6) mol
= 0.1 1.6 mol
Mole fraction of I2(g) = (0.2 0.2 1.6) mol

= 0.1
310
2HI(g)
0 mol
(0.8 2) mol
= 1.6 mol
Mole fraction of HI(g) =
1.6 mol
(0.2 0.2 1.6) mol
= 0.8
Let P be the total pressure of the system.
PHI2
Kp
PH PI
(0.8 P) 2
(0.1 P)(0.1 P)
= 64
2
311
Back
16.7 Equilibrium Position (SB p.103)
Determine the equilibrium constant (Kc)

from the following data on the equilibrium
system
2SO2(g) + O2Equilibrium
(g)
2SO3(g) at(mol
873dm
K.-3)
Experiment
concentration
[SO2(g)]
[O2(g)]
[SO3(g)]
1.60
1.30
3.62
0.71
0.50
1.00
Answer
312
Back
The expression of Kc is:
[SO 3 (g)] 2eqm
Kc
[SO 2 (g)] 2eqm [O 2 (g)] eqm
From experiment 1:
3.62 2
Kc
1.60 2 1.30
= 3.94 dm3 mol-1
From experiment 2:
1.00 2
Kc
0.72 2 0.50
= 3.97 dm3 mol-1
Since Kc is a constant at a specific temperature, the values of Kc
313
from experiments 1 and 2 are very close, and the average value of
Kc at 873 K is 3.955 dm3 mol1.
Answer
For the following reversible reaction:

CH 3COOCH2CH3(l) +
H2O(l)
Calculate the equilibrium constant (Kc) using
Expt
Initial no. of moles (mol)
No. of moles
the following data.
at eqm (mol)
CH3CHOOH(l)
CH3CH2OH(l)
CH3COOH(l)
1.00
1.00
0.33
1.00
4.00
0.07
314
(Assume that the equilibrium is established in
The equilibrium constant for the equilibrium is expressed as:

[SO 3 (g)] 2eqm
Kc
[SO 2 (g)] 2eqm [O 2 (g)] eqm
For experiment 1:
At start:
At eqm:
At start:
At eqm:
315
1.00 mol
0.33 mol
1.00 mol
0.33 mol
CH3COOCH2CH3(l) + H2O(l)
0 mol
0 mol
(1.00 0.33) mol (1.00 0.33) mol
= 0.67 mol
= 0.67 mol
0.67 mol dm 3 0.67 mol dm 3

Kc
4.12
3
3
0.33 mol dm 0.33 mol dm
Back
For experiment 1:
At start:
At eqm:
1.00 mol
0.07 mol
4.00 mol
(4.00 0.93) mol
= 3.07 mol
CH3COOCH2CH3(l) + H2O(l)
At start:
At eqm:
0 mol
0 mol
(1.00 0.07) mol (1.00 0.07) mol
= 0.93 mol
= 0.93 mol
0.93 mol dm 3 0.93 mol dm 3
Kc
4.02
3
3
0.07 mol dm 3.07 mol dm
Since Kc is a constant at a specific temperature, the average value of
316
Kc from experiments 1 and 2 is 4.07.
16.8 Partition Equilibrium of a Solute Between Two Immiscible

Solvents (SB p.104)
An organic compound X has a partition

coefficient of 30 in ethoxyethane and
water.
[X]
ethoxyetha
ne
K
30
D
[X]
water
There is 3.1 g of X in 50 cm3 of water. 50
cm3 of ethoxyethane is then added to
extract X from water. How much X is
extracted using ethoxyethane? Answer
317

Solvents (SB p.106)
Let a g be the mass of X extracted using 50 cm3 of ethoxyethane,

then the mass of X left in water is (3.1 a) g.
a
g cm 3
50
3.1 - a
[X] water
g cm 3
50
a
K D 50
3.1 - a
50
a
30 50
3.1 - a
50
[X]ethoxyethane
318
a = 3.0
Back

Solvents (SB p.106)
At 298 K, 50 cm3 of an aqueous solution

containing 6 g of solute Y is in equilibrium
with 100 cm3 of an ether solution containing
108 g of Y.
Calculate the mass of Y that could be
extracted from 100 cm3 of an aqueous
solution containing 10 g of Y by shaking it
with
(a) 100 cm3 of fresh ether at 298 K;
Answer
(b) 50 cm3 of fresh ether twice at 298 K.
319

Solvents (SB p.106)
[ Y ] ether
[ Y ] water
108 g
100 cm 3
= 1.08 g cm-3
6g
50 cm 3
= 0.12 g cm-3
[Y] ether
KD
[Y] water
1.08 g cm -3
0.12 g cm - 3
=9
320

Solvents (SB p.106)
(a) Let m g be the mass of Y extracted using 100 cm3 of ether, then
the mass of Y left in the aqueous layer is (10 m) g.
m
K D 100
10 - m
100
m
9 100
10 - m
100
m=9
9 g of Y can be extracted using 100 cm3 of fresh ether.
321

Solvents (SB p.106)
(b) Let m1 g be the mass of Y extracted using the first 50 cm3 of

ether, then the mass of Y left in the aqueous layer is (10 m1) g.
m1
K D 50
10 - m1
100
m1
9 50
10 - m1
100
m1 = 8.182
Mass of Y extracted using the first 50 cm3 of ether = 8.182 g
Mass of Y left in the aqueous layer = (10 8.182) g = 1.818 g
322

Solvents (SB p.106)
Let m2 g be the mass of Y extracted using the second 50 cm3 of

ether, then the mass of Y left in the aqueous layer is (1.818 m2) g.
m2
50
KD
1.818 - m 2
100
m2
50
9
1.818 - m 2
100
m2 = 1.487
323
Mass of Y extracted using the second 50 cm3 of ether = 1.487 g

Mass of Y left in the aqueous layer = (1.818 1.487) g = 0.331 g

Solvents (SB p.106)
Total mass of Y extracted = m1 + m2

= (8.182 + 1.487) g
= 9.669 g
Back
324

Solvents (SB p.108)
The partition coefficient (KD) of an unknown

organic compound A between 1,1,1trichloroethane and water is expressed as:
Concentrat
ionof A in 1,1,1
- trichloroe
thane
(gcm-3)
KD
15
-3
Concentrat
ionof A in water
(gcm )
Calculate the mass of A that can be extracted

from 60 cm3 of an aqueous solution initially
containing 6 g of A using 100 cm3 of fresh
1,1,1-trichloroethane.
Answer
325

Solvents (SB p.108)
326
Let m be the mass of A extracted using 100 cm3 of 1,1,1trichloroethane, then the mass of A left in 60 cm3 of aqueous
layer is (6 m).
m
K D 100
6m
60
m
Back
15 100
6m
60
m = 5.77 g
5.77 g of A is extracted using 100 cm3 of 1,1,1trichloroethane.

Solvents (SB p.110)
(a)A student wrote the following explanation for

the different Rf values found in the
separation of two amino acids, leucine (Rf
value = 0.5) and glycine (Rf value = 0.3), by
paper chromatography using a solvent
containing 20% of water.
Leucine is a much lighter molecule than
glycine.
Answer
Do you agree with this explanation?
Explain
your answer.
327

Solvents (SB p.110)
(a) The difference in Rf value of leucine and glycine is due to

the fact that they have different partition between the
stationary phase and the mobile phase. Therefore, they
move upwards to different extent. The Rf value is not
related to the mass of the solute.
328

Solvents (SB p.110)
(b) Draw a diagram to show the expected

chromatogram of a mixture of A, B, C and D
using a solvent X, given that the Rf values of
A, B, C and D are 0.15, 0.40, 0.70 and 0.75
respectively.
Answer
329

Solvents (SB p.110)
Back
(b)
330
16.9 Significances of Equilibrium Constants (SB p.111)
The reaction N2(g) + 3H2(g)

2NH3(g)
has an equilibrium constant of 0.062 dm6 mol2
at 500 oC. Predict the net chemical change, if
there is any, for the following concentrations
of reactant(s) and product(s).
(a) [NH3(g)] = 0.001 mol dm3, [N2(g)] = 0.001
Answer
3
mol dm3 and [H2(g)] = 0.002 mol dm
331
(a)
[NH3 ( g)] 2
Qc
[N2 (g)][H2 (g)]3
0.0012
0.001 0.002 3
= 125 000 mol-2 dm6
Since Qc > Kc, the reaction proceeds from the right (product
side) to the left (reactant side) until the equilibrium is
reached.
332
The reaction N2(g) + 3H2(g)

2NH3(g)
has an equilibrium constant of 0.062 dm6 mol2
at 500 oC. Predict the net chemical change, if
there is any, for the following concentrations
of reactant(s) and product(s).
(b) [NH3(g)] = 0.001 mol dm3, [N2(g)] = 1 mol
dm3 and [H2(g)] = 0.08 mol dm3 Answer
333
Back
(b)
[NH3 (g)] 2
Qc
[N2 (g)][H2 (g)]3
0.0012
1 0.08 3
= 0.001 95 mol-2 dm6
Since Qc < Kc, the reaction proceeds from the left (reactant
side) to the right (product side) until the equilibrium is
reached.
334
16.10 Factors Affecting Equilibrium (SB p.113)
Back
For the equilibrium system:
As4O6(s) + 6C(s)
6CO(g)
As4(g) +
predict how the equilibrium position

will shift in response to the following
changes:
Answer
(a) removing CO(g)
(a)
Le Chateliers
principle, the equilibrium
(b)According
addingto more
As4(g)
position will shift to the right.
(b) According to Le Chateliers principle, the equilibrium
position will shift to the left.
335
(a) For the reaction H2(g) + I2(g)

2HI(g), the
following data are
determined at 490 oC,
[H2(g)] = 0.22 mol dm3; [I2(g)] = 0.22 mol
dm3 and [HI(g)] = 1.56 mol dm3
Calculate the equilibrium constant (Kc) at
(a) H2(g) + I2(g)
2HI(g)
Answer
o
490 C.
[HI(g)] 2
(1.56) 2
Kc
50.3
[H2 (g)][I2 (g)] (0.22)(0.22)
336
(b) If an additional 0.200 mol dm3 of H2(g) is

added to the above equilibrium mixture
while keeping volume and temperature
constant, what will happen? Calculate
the equilibrium concentrations of all
species when equilibrium is reached.
Answer
337
(b)
H2(g)
I2(g)
At eqm: 0.22 mol dm-3

0.22 mol dm-3
Now: (0.22 + 0.2) mol dm-3 0.22 mol dm-3
[HI( g)] 2
(1.56) 2
Qc
26.34
[H2 (g)][I2 (g)] (0.42)(0.22)
2HI(g)
1.56 mol dm-3
1.56 mol dm-3
Since the value of the reaction quotient (Qc) is less than that of the
equilibrium constant (Kc), the system is not at equilibrium. In order to
re-establish the equilibrium, the value of the reaction quotient should
be increased until it equals Kc. It can be predicted that more H2(g)
and I2(g) will react to form more HI(g).
338
Back
(b)
H2(g)
I2(g)
Now: (0.22 + 0.2) mol dm-3

0.22 mol dm-3
At eqm: (0.42 - x) mol dm-3 (0.22 x) mol dm-3
2HI(g)
1.56 mol dm-3
(1.56 + 2x) mol dm-3
[HI(g)] 2
(1.56 2x ) 2
Kc
[H2 ( g)][I2 (g)] (0.42 x )(0.22 x )

Since Kc remains constant, we obtain:
(1.56 2x ) 2
50.2
(0.42 x )(0.22 x )
By solving the quadratic equation, x = 0.06 or 0.77.
If x equals 0.77, the concentration of H2(g) and I2(g) at equilibrium will
be negative. Therefore, the correct answer of x is 0.06.
[H2(g)]eqm = 0.42 mol dm3 - 0.06 mol dm3 = 0.36 mol dm3
339
[I2(g)]eqm = 0.22 mol dm3 - 0.06 mol dm3 = 0.16 mol dm3
[HI(g)]eqm = 1.56 + 2 0.06 mol dm3 = 1.68 mol dm3
Consider the following reaction at equilibrium:

2CrO42-(aq) + 2H+(aq)
H2O(l)
Cr2O72-(aq) +
Explain the changes of the graph at time t 0, t1,

t2 and t3 respectively.
Answer
340
When CrO42(aq) and H+(aq) are mixed at t0, they react

continuously to form Cr2O72(aq) and H2O(l ). At t1, an
equilibrium between them is established. At t2, when more H+
(aq) is added to the system, the equilibrium can no longer be
maintained. In order to attain the equilibrium again (i.e. at t 3),
the additional H+(aq) must be removed by shifting the
equilibrium to the right to form more Cr2O72(aq) and H2O(l).
Back
341
The diagram on the

right shows the effect
of increasing pressure
on the equilibrium
2NO2(g)
N2O4(g). The equilibrium
constant Kp for the
reaction is 0.92 atm1 at
a given temperature.
342
(a)Calculate the partial pressures of NO2(g)

and N2O4(g) at equilibrium if the total
Answer
pressure
is 1 atm.
(P )
(a)
Kp
N 2 O4
eqm
(PNO ) 2 eqm
Let the partial pressure of NO2(g) at equilibrium be p atm, then
2
the partial pressure of N2O4(g) at equilibrium is (1 p) atm.

1 p
0.92 2
p
p = 0.632 or 1.719 (rejected)
PNO2 = 0.632 atm
PN2O4 = (1 0.632) atm = 0.368 atm
343
(b) Calculate the partial pressures of NO 2(g)

and N2O4(g) if the total pressure at
equilibrium is 2 atm.
Answer
(b) Using the same method as in (a),
2p
p2
p = 1.028 or 2.115 (rejected)
PNO2 = 1.028 atm
0.92
PN2O4 = (2 1.028) atm = 0.972 atm
344
(c) Compare the results of (a) and (b), and

state the effect of an increase in
pressure on the equilibrium.
Answer
(c) Comparing the results in (a) and (b), PN2O4 is more

than doubled while PNO2 is less than doubled when the
total pressure increases from 1 atm to 2 atm. Thus,
the equilibrium position shifts to the side with a smaller
number of molecules when the pressure increases.
345
(d) Explain why the brown colour of the

equilibrium mixture fades out when the
pressure of the equilibrium system is
increased. Assume there is no
temperature change.
(Hint: The colour of NO2(g) is dark brown
Answer
and that of N2O4(g) is pale brown or
(d) The impact of the increased
pressure is reduced by
colourless.)
shifting the equilibrium position to the right-hand side of
2NO2(g)
N2O4(g). More NO2(g), which is brown in
colour, is used up. More N2O4(g), which is colourless, is

346
formed. A colour change from brown to pale brown (or

colourless) can be observed.
Back
(e) Given that the enthalpy change for the

reaction 2NO2(g)
N2O4(g) is 58 kJ,
predict the colour change when a glass
syringe containing the equilibrium mixture
is put into a beaker of hot water for about
30 seconds, and then a beaker of water
with a large amount of crushed ice for
(e) When the equilibrium mixture is put into hot water (the Answer
temperature
another 30 seconds.
increases), the equilibrium will shift to the left and more NO 2(g) will
be formed. Thus, the colour of the mixture will change to a darker
brown. When the equilibrium mixture is put into ice water (the
temperature decreases), the equilibrium will shift to the right and
more N2O4(g) will be formed. As a result, the colour of the mixture
347
will change to pale brown (or colourless).
1. Consider the following reaction at

equilibrium:
3NO2(g) + H2O(g)
(a)
above,
for the
(a)
Referring to the chemical equation

write a
mathematical expression
Answer
equilibrium
constant,
K
.
2
p
P
P
Kp
HNO 3 ( g )
NO ( g )
3
PNO
( g ) PH O ( g )
2
348
2HNO3(g) + NO(g)

equilibrium:
3NO2(g) + H2O(g)
2HNO3(g) + NO(g)
(b)
If the partial pressure of H2O(g) is
increased at constant temperature, what
(b) (i)in
Decreasethe partial
changes, if any, occur
(ii) Increase
pressures of
(i)
NO2(g)?
(ii) HNO3(g)?
349
(iii) NO(g)?
(iii) Increase
Answer

equilibrium:
3NO2(g) + H2O(g)
2HNO3(g) + NO(g)
(c)
If the partial pressure of H2O(g) is
increased at
constant temperature, will
the value of Kp increase,
decrease
or
Answer
(c) The value of Kp will remain the same.
remain the same?
350
2. The equilibrium partial pressures of N2O4(g)

and NO2(g) were found to be 0.364 atm and
0.636 atm respectively for the following
reversible reaction at 100 oC.
2NO2(g)
N2O4(g)
(a)
Calculate the equilibrium constant,
Answer
K(a)
,
for
the
reaction.
PN O
p
Kp
351
2
NO 2
0.900 atm
2. The equilibrium partial pressures of N2O4(g)

and NO2(g) were found to be 0.364 atm and
0.636 atm respectively for the following
reversible reaction at 100 oC.
2NO2(g)
N2O4(g)
(b)
The vessel containing the
equilibrium mixture is compressed to onehalf original volume suddenly.
Predict
what would happen. Calculate the Answer
equilibrium partial pressures of N2O4(g) and
NO2(g).
352
(b) After compression to one-half the original volume, all

the gas pressures will be doubled. Therefore, the
partial pressures of N2O4(g) and NO2(g) will be 0.728
atm and 1.272 atm respectively.
2NO2(g)
N2O4(g)
Q
353
PN O
2
2
NO 2
0.450 atm
(b) Since the value of the reaction quotient is less than

that of the equilibrium constant, the system is not at
equilibrium. The reaction proceeds from the left to the
right until the equilibrium is reached. As a result, more
N2O4(g) will be formed.
At start:
At eqm:
2NO2(g)
N2O4(g)
1.272
1.272 2x
0.728
0.728 + x
K p 0.90
354
(0.728 x )
(1.272 2x ) 2
(b) By solving the quadratic equation, x = 0.143 8 or 1.405 9.

x = 0.143 8
PNO2 = 1.272 2 0.143 8 = 0.984 4 atm
PN2O4 = 0.728 + 0.143 8 = 0.871 8 atm
Back
355
Predict how the equilibrium position is affected

when the equilibrium system
N2O4(g)
2NO2(g)
H = +58 kJ
is subjected to the following changes:

(a) addition of NO2(g)
(b) removal of N2O4(g)
(c) addition of He( g)
(d) increase in volume of the container
(e) decrease in temperature
356
Answer
(a)
(b)
(c)
(d)
(e)
The equilibrium position shifts to the left.

The equilibrium position shifts to the left.
The equilibrium position remains unchanged.
The equilibrium position shifts to the right.
The equilibrium poistion shifts to the left.
Back
357
The equilibrium constant (Kp) of the

following reaction is 1.6 104 atm2 at 673
K and 1.4 105 atm2 at 773 K.
N2(g) + 3H2(g)
2NH3(g)
Determine the mean enthalpy change of

formation of
1 mole of ammonia from its elements in the
temperature ranges from 673 K to 773 K.
(Given: R = 8.31 J K
358
mol )
1
Answer
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At 673 K,
ln(1.6 10 4 ) cons tan t
H
.........(1)
8.31 673
At 773 K,
H
ln(1.4 10 ) cons tan t
.........( 2)
8.31 773
Combining (1) and (2),
4
ln(1.6 10 4 )
359
H
H
ln(1.4 10 5 )
5593
6424
H = 105 329 J mol-1
= -105.3 kJ mol-1
Determine graphically the enthalpy change

of formation of NO2(g) from N2O4(g) using
the following data:
Temperature (K)
Kp (atm)
298
0.115
350
3.89
400
47.9
500
1700
600
17 800
(Given: R = 8.314 J K1 mol1)

360
Answer
361
1/T (K-1)
ln Kp
3.36 10-3
-2.16
2.86 10-3
+1.36
2.50 10-3
+3.87
2.00 10-3
+7.44
1.67 10-3
+9.79
A graph of ln Kp against
slope
362
H
.
R
1
T
produces a straight line with
Slope =
7.44 9.79
(2.00 1.67 ) 10 3
= -7121.2
H
R = -7121.2
H = 7121.2 8.314
= 59 206 J mol-1
= 59.2 kJ mol-1
Back
363
Haber process is an important industrial

process to manufacture ammonia with the
use of nitrogen and hydrogen. Ammonia has
numerous uses like making fertilizers and
explosives. The reaction between nitrogen
and hydrogen is a reversible reaction. It
takes place with release of thermal energy.
N2(g) + 3H2(g)
364
2NH3(g)
92.6 kJ
H =
(a)Based on your knowledge about

chemical equilibrium, predict the
Answer
necessary conditions to
increase the yield
(a) Since the reaction is exothermic, a lower temperature will shift

the equilibrium to the right-hand side and hence increase the
yield of ammonia.
As shown in the chemical equation, there are totally four
nitrogen and hydrogen molecules on the left-hand side of the
equation and only two ammonia molecules on the right-hand
side. A higher pressure will shift the equilibrium position to the
right and more ammonia will be produced. Also, increasing the
concentration of the reactants (i.e. nitrogen and hydrogen) or
removing the product (i.e. ammonia) from the reaction mixture
will shift the equilibrium position to the right and thus the yield of
ammonia will be increased.
365
(b) The actual operating conditions of the

Haber process are a temperature of
about 450 oC, a pressure of about 400
atm and the presence of a catalyst (e.g.
iron). Justify the conditions used.
Answer
366
Back
(b) The use of high pressure is as predicted in (a). This not only shifts
the equilibrium position to the right but also increases the rate of the
reaction. The use of catalysts shortens the time for the reaction to
reach the equilibrium while it has no effect on the equilibrium
constant.
The use of a high temperature is contradictory to the prediction
made in (a). It can be explained based on the rate of the reaction
which in turn determines the rate of manufacture of ammonia.
Although the equilibrium position shifts to the right at a lower
temperature, the rate of the reaction is very low (i.e. a longer time is
required to reach the equilibrium state). The use of a moderate
temperature is a compromise between the rate and the yield of the
reaction. At 450 C, the reaction is reasonably fast and the yield of
367
ammonia is optimum.

Irreversible and Reversible Reactions

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Irreversible and Reversible Reactions

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Irreversible

Conditions for reversible reactions : Closed reaction vessels to prevent

Conditions for reversible reactions : Concentration of HCl(aq) > 6 M

ClO(aq) + Cl(aq) + H2O(l)

Conditions for reversible reactions : Closed reaction vessels to prevent

Changes of physical phases are reversible

Examples of reversible reactions

1. When HCl(aq) is added to CrO42(aq)

Examples of reversible reactions

1. When HCl(aq) is added to CrO42(aq)

Examples of reversible reactions

2. When NaOH(aq) is added to Cr2O72(aq)

Examples of reversible reactions

2. When NaOH(aq) is added to Cr2O72(aq)

a net change of Cr2O72(aq) to CrO42(aq)

Examples of reversible reactions

2. When NaOH(aq) is added to Cr2O72(aq)

Examples of reversible reactions

1. When H2O(l) is added to BiCl3(aq)

Examples of reversible reactions

1. When H2O(l) is added to BiCl3(aq)

Examples of reversible reactions

2. When HCl(aq) is added to BiOCl(s)

Examples of reversible reactions

2. When HCl(aq) is added to BiOCl(s)

Examples of reversible reactions

2. When HCl(aq) is added to BiOCl(s)

H+(aq) + Br-(aq) + HOBr(aq)

1. When NaOH(aq) is added to Br2(aq)

H+(aq) + Br-(aq) + HOBr(aq)

1. When NaOH(aq) is added to Br2(aq)

H+(aq) + Br-(aq) + HOBr(aq)

1. When NaOH(aq) is added to Br2(aq)

H+(aq) + Br-(aq) + HOBr(aq)

1. When NaOH(aq) is added to Br2(aq)

H+(aq) + Br-(aq) + HOBr(aq)

2. When HCl(aq) is added

H+(aq) + Br-(aq) + HOBr(aq)

2. When HCl(aq) is added

H+(aq) + Br-(aq) + HOBr(aq)

2. When HCl(aq) is added

H+(aq) + Br-(aq) + HOBr(aq)

3. When AgNO3(aq) is added

H+(aq) + Br-(aq) + HOBr(aq)

3. When AgNO3(aq) is added

H+(aq) + Br-(aq) + HOBr(aq)

3. When AgNO3(aq) is added

Phenolphthlein is a weak acid that ionizes

What is the colour of phenolphthalein

When pH < 8.3 (e.g. deionized water),

When NaOH(aq) is added,

There is no further colour change when

When pH > 10,

When 8.3 < pH < 10,

Reversible reactions and dynamic equilibrium

a state of dynamic equilibrium is said to be

An example of dynamic equilibrium

Reversible reactions and chemical equilibrium

Reversible reactions and chemical equilibrium

At equil., k[reactant]eq = k[product]eq

k >> k [reactant]eq << [product]eq

Forward rx is more complete than backward rx