HHCKLA Buddhist

Leung Chik Wai College

HKDSE Chemistry

Topic X: Chemical Equilibrium

Name: ____________________

Class: ______________ ( )
 Unit 39 - An introduction to chemical equilibrium

1. Reversible and Irreversible reaction

A. Irreversible reactions 7- TIE
• The reaction proceeds in __________
one direction only.
• Reactions will go to __________________.
completion
• Examples:
i. Metals + dilute hydrochloric acid

-dTdgnT
ii. Acid-alkali neutralization

B. Reversible reactions
I either
• The reaction proceeds in __________
two directions.
• Reactions will not go to completion.

• forward reaction.
The reaction from left to right (i.e. A + B → C + D) is called the ________________
• backward reaction.
The reaction from right to left (i.e. C + D → A + B) is called the ________________
• Examples:
i. Esterification

Ethanoic acid reacts with ethanol to form ethyl ethanoate.

Ethyl ethanoate will also react with water to give ethanoic acid and ethanol.

ii. Ionization of ethanoic acid

Weak acids slightly ionize in water.

2
Practice
Consider the following reaction: R Xp
2SO2(g) + O2(g) 2SO3(g)
Title P TR
(a) Is the reaction reversible? Explain your answer.
react to form 503
Yes .
Because 502 ,
Oz

503 decomposes to form

502 , Oz

(b) Is the decomposition of SO3 considered as the forward or backward reaction in the above reaction?

backward reaction

(c) State the reactants and products of the forward and backward reactions respectively.

Forward reaction: 2502cg , t Oz (g ) → 2503 Ig )

Reactants : 502 , Oz

Products: 503

Backward reaction: 2503 F- Oz

( g) ( g,
t 2502cg )
Reactants: Sos
Oz SOL
Products: ,

3
 AFB
→ Reversible reaction
2. Chemical equilibrium
Forward

↳ TO
Ÿ At equilibrium,
observable change
1. No ____________________________ in the system

#Ig
A backward reaction
forward reaction = rate of _____________
2. Rate of _____________
3. Both reactions are continuing (i.e. dynamic in nature)
Backward
Ÿ Example: Decomposition of N2O4 molecules into NO2 molecules

conc

Reversible
.

Rate of forward Rate of backward

Colour intensity [N2O4(g)] [NO2(g)]
reaction reaction
(a) 0 Highest 0 Highest 0
(b) Increase decrease increase Decrease Increase
Brown colour Remain Remain
(c)
persists Equal FAA unchanged unchanged
↳
At (c), the system has reached equilibrium.
Equilibrium

Figure 1. The establishment of equilibrium starting with N2O4

4
 Reversible
ur
*

Figure 2 Concentration-time graph Figure 3 Reaction rate-time graph

Ÿ At equilibrium,
unchanged
1. the concentrations of all reactants and products remain _____________, but not necessarily the
ummm
same.
~
forward and _____________
2. The rates of _____________ backward reaction are equal.

Ÿ Dynamic equilibrium can be reached from either direction of a reversible reactions.

(i.e. can start with NO2 instead of N2O4)

Experiment Initial concentration (M) Equilibrium concentration (M)

N2 O4 NO2 N2 O4 NO2
1 0.0500 0 0.0429
2 0 0.1000 0.0141

• Characteristics:
* i. It is dynamic;
ii. The rate of forward reaction is equal to the rate of backward reaction;
iii. It requires a closed system;

"n④%D④%
iv. It can be reached from either the forward or backward direction;
v. At equilibrium, he concentrations of reactants and products remain unchanged.

4¥ ,
5
• Types of equilibrium
A. homogeneous equilibrium
Same
All reactants and products are in the _____________ phase
E.g. H2(g) + I2(g) 2HI(g)

B. heterogeneous equilibrium
Two or more phases are present in the equilibrium
E.g. 2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)

6
 Practice
1. Which of the following graphs correctly shows the change in reaction rate for an equilibrium
system over time?

O
D X

"

x O
2. Consider the following reversible reaction:
N2O4(g) 2NO2(g)
At dynamic equilibrium, which of the following statements is/are correct?
→
-
r

q
(1) The rate of decomposition of N2O4 molecules is equal to the rate of combination of NO2 molecules.
(2) The concentrations of N2O4 and NO2 are equal.
(3) The colour intensity of the reaction mixture remains constant. V
urn
A (1) only B (2) only

O
C (1) and (3) only D (2) and (3) only

3. Solid calcium carbonate is heated strongly as shown in the set-up below:

CaCO3(s) CaO(s) + CO2(g) *
A dynamic equilibrium cannot be established because
A calcium carbonate cannot be decomposed.

O
B it is an open system.
C calcium oxide does not react with carbon dioxide.
D the forward reaction is exothermic.

7
4. Equilibrium law
• Consider the following reaction,
aA + bB cC + dD
The equilibrium law can be expressed as:

Episode
[ Reactant)

where Kc is the equilibrium constant;

[A]eqm, [B]eqm, [C]eqm and [D]eqm are the equilibrium concentrations;
a, b, c and d are the stoichiometric coefficients in the balanced equation
solid
Note: Pure _____________ liquid
and _____________ should not be included in the equilibrium law

Practice E. t Ig ) .

lag )
1. Write the expression for the equilibrium constant, Kc, of the below reactions.
a) 2SO2(g) + O2(g) 2SO3(g)
in

Kc :
[S03cg
[ 502cg, ] [ 021GB
-

b) N2(g) + 3H2(g) 2NH3(g)

Kc = [NH3lg#
EN zig) ) [ Hzcg ,]
3

c) Fe3+(aq) + SCN–(aq) FeSCN2+(aq)

"
ko : [ Fe SCN lap )
-

[ fest lag ] [ Scrap)

,

d) 2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)

Kc -
-
E H2O
cop] [ (
02cg ] ,

8
5. Calculations involving equilibrium
Example (EASY)
Consider the following equilibrium involving two nitrogen oxides.

O2NO(g) + O (g) O2NO (g)

2 2

Calculate the equilibrium constant, Kc, from the given equilibrium concentrations at 25°C.
[NO(g)]eqm = 1.5 x 10-11 mol dm-3
[O2(g)]eqm = 8.9 x 10-3 mol dm-3
[NO2(g)]eqm = 2.2 x 10-6 mol dm-3

ke : [N02ig ¥K
[ NO
cgs32-LO.io#
(2.2×6-6)
2

T.si/g.gxio-3)
=

unit of
conc =moldm
✓
.

( M)
⑦
*Unit of Kc
[N0zi
Kc =

[ N0cgDZ[ Orgs)

=
=

Ty -

motif
↳ M
-
'
' '
dm
-

→ mot

9
Practice
1) Consider the oxidation of sulphur dioxide to sulphur trioxide:
2SO2(g) + O2(g) 2SO3(g)
Kc
Calculate the equilibrium constant for the reaction if the equilibrium concentrations of SO2(g), O2(g)
run
and SO3(g) are 1.75 mol dm–3, 1.50 mol dm–3 and 2.25 mol dm–3 respectively. (1.10)

Kc =
[S03cgs
-

[ 502cg ] [ 02cg ]
, ,

( 2.255 MY
Mt
= '

Mf
→

2¥
-
- -
-

I 1.755 ( 1.5 )
'

mold -53 )
-

-3
(
mot 1dm
-

= l . 10

2) A mixture of nitrogen and chlorine gases was kept in a 5 dm3 reaction flask at a certain temperature.
N2(g) + 3Cl2(g) 2NCl3(g)

O
The equilibrium mixture was found to contain 0.0070 mol of N2(g), 0.0022 mol of Cl2(g) and 0.9500
mol of NCl3(g). Calculate the equilibrium constant for this reaction. (3.03x1011)
Kt
conc
-
-
t
dm }
Kc = [NCl3lg
[ Nzcg , ] [ clzcg ]3
,

( 0.95542 "
Zdmb
= -

mot
-

( 0.0ft ) ( 0.0¥)
3
=
3.03×10

unit
Mm÷ 7¥ -

=p: -
Z

( Idm 3)
-

10
mo
6
mot -2dm
 What we have learned?

Forward
2N 02cg )
1. Characteristics of equilibrium N2O4cg ) 7-
Backward

O t
O nun

2. Calculation of Kc
Nz 04cg , F moldm-31M
2N
02cg ) conc =

a
.

9
Expression of Kc: 2
Mtl
[ Nozcg,]
Kc
[ product ) =
-
=
M
#
= - = -

[ reactant ) [ Nz 0419')
-3
→ moldm
A Ale ) t Bls ) F Ccg )
( s ) - le ) do not include in ke
✓
Practice
MI
conc =

dm 3

At equilibrium, 3 moles of sulphur dioxide, 2 moles of oxygen gas and

µ
1.5 moles of sulphur trioxide were found in 2 dm sealed reaction vessel.
Calculate the Kc of the reaction.
'
[ SO
3cg ,]
ke =
-

502cg ]
'

[ , x ( 02cg)

iii. ¥
'
=

I x
II)
*
'
=
ti
-

I
( mo 1dm 3)
-

mody3
Example (MEDIUM)
The colourless gas N2O4 and the brown gas NO2 exist in equilibrium as shown by the following
equation: N2O4(g) 2NO2(g)
-

Fittro
In an experiment, 0.80 mol of N2O4 was introduced into a 5 dm3 container and allowed to reach
um
equilibrium with NO2 at a certain temperature. At equilibrium, the concentration of N2O4 was 0.09 mol
um
dm–3. Calculate the Kc for this reaction. (0.218)

N2O4(g) ) 2NO2(g)
Mol
Initial conc. 0.8mW
Fms w
F¥Hb Fdm3=
0.16M O
Change in conc.
0.07 t 0.07×2=0.14
Tgif
-

Our
*Eqm conc.
0.09M 0.14
T T

ke =
[NO"9 =
€45
0.218 moldm
'S
=
[ Nz04lg , ] ( 0.09 ) =

11
 mot
Practice Conc :

dm }
3
1) A 1 dm container contains 1.00 mol of phosgene, which decomposes at a certain temperature
according to the following equation: t
COCl2(g) CO(g) + Cl2 (g)
(a) At equilibrium, the concentration of Cl2 is 0.028 mol dm-3. What are the concentrations of CO and
COCl2 respectively? (
F¥Hb
( Oct
2cg )
E ( 0cg , t
12cg ,
initialed

chang¥¥z8|t8
Egm conc I
=
-

O 028
0.972
-

0.028 0.028

'
0.028 moldm
-3 [ COCK ]= o.97zm.edu
[ Co ] : ;

Kc
(b) Calculate the equilibrium constant. (8.07 x 10-4)

[ C0lgD[ Clacgs ] (0-028)/0.028 )

Kc ,
-
=
-

10.972)
[ Coclzcg ] ,

-3
= 8
.I4
-
mofdm

12
2) A mixture of 2.5 mol H2(g) and 5.0 mol I2(g) is placed in a 5 dm3 at 450°C and allowed to reach
equilibrium with HI(g). At equilibrium, the concentration of HI(g) is 0.934 mol dm–3. Calculate the
equilibrium constant for the reaction. (49.6)

F ZHI Cg
MI
Hzlg Izig ) conc :

) t , dm3

ange/=-o467µ4/t94
0.5 O
p¥Hb'initial
=/ =

Atta

Egm conc 0.5-0.467 I -

0.467 0.934
'

0.033 =
0.533
EHF
-

THICGD
'

Ko
-

-
-

[ IzcgDIHug , ]

=
( 0.93472
-

( 0.533 ) ( 0.033)

=
49.6
=

13
Example (DIFFICULT)

3+
O
At a given temperature, the equilibrium constant, Kc, for the following reaction is 137.5 mol–1 dm3.
– 2+
O
Fe (aq) + SCN (aq) FeSCN (aq)
In an experiment, 500 cm3 of 0.200 mol dm–3 Fe(NO3)3 was mixed with 500 cm3 of 0.200 mol dm–3
KSCN at the above given temperature. Calculate the equilibrium concentrations of all species in the
that
-

mot any
Kt SCN
-

conc -

→
-

mixture.
-

,
}
} dm
'
500cm
's vote 1000cm
500cm
?

md÷
0.2M
°h ? [ conc]
FEIN 03730
l ? + ksuvl ? à
-

Fest 3h05
,
I
Initial Eqmt
3+ –
Fe (aq) + SCN (aq) FeSCN2+(aq)
Initial conc. I5¥ol =
O 't
H=o , o
(1000/1000) (1000/1000)
Change in conc.
-

X
-

X TX

*Eqm conc.
10.1 -
X) 10.1 -
X ) TX

0.0764
X =
0*31 or

Write the expression of equilibrium law and substitute,

Solve the problem using quadratic equation.

µ=[FeSCNY9 = 137.5

EFe4ap5LSCN )
-

cap

1×110.1×110.1) -

X
= 137.5

x
- =
137.5
0.01 -
0.2×-1×2
X = 1.375-27.5×-1137.5×2
1. 375-28.5×-1137.5×2=0
0.131 or 0.0764
X =

( rejected)

\
[ Fest lag ] ,
-

-
O I .
-
X =
0.1 -

0.0764 = 0.0236M

[ SCN caps] 0.0764=0.0236

-
=
0.1 -

X 0.1 M
-

14
[ " 0764M
Fescn cap] x o
= = .
Practice
1) At 450°C, the equilibrium constant for the following reaction is 50.0.
H2(g) + I2(g) 2HI(g)
In an experiment, 0.15 mol of H2 and 0.15 mol of I2 were placed in a 5 dm3 container. The mixture was
allowed to react at 450°C. Calculate the concentration of each substance at equilibrium. (X = 0.0234)

Hzcg )
F
t
Izcg , ZHI
Lg )
D. 15h01
Otfdnm!

#X
initial O 03 0.03 O
-
-

7dm
- - -

conc ,

Egm conc 0.03 X -

0.03 X -

Ot 2x -

2x

[HT 50
Ko
=
'

[
Ings][ Hugs)

(2×51003×110.03-11)=50
11=0.0234
=

}
6.6×10-3 mohdm
'

'
'
'
[ Hug , ] : 0.03 -

0.0234 =

' '
0.0234=6.6×10
-

[ Izcg , ]
-

- 0.03 -

moldwi
'
[ HI ig , ] 0.0468
'

210.0234) -

moldm

15
2) 4.00 mol of HI(g) were placed in an evacuated 5.00 dm3 flask and then heated to 800 K. The system
was allowed to reach equilibrium. The Kc of the reaction is 0.016. (X = 0.0808)
2HI(g) H2(g) + I2(g)
Calculate the equilibrium concentrations of each species.
ZHI
Ig )
I
Hzcg ) t
Izcg )

o.€X|tX
initial
#
conc ¥ -

-
0.8 O O

Egm conc
0.8 -

2X X X

Kc ,
ET-21917.lt/zig#
?
[ HI cop ]

0.016 =
¥)
( 0.8-2×12

X 0.135 (
rejected )
= -

or

0.0808
=

'

[ 0.0808 moldui
Ing, ] X
'
' = =
.

]
[ Hugs ) :
X =
0.0808 moldni

( HI , ] -

0.8 2x 0.8 210.0808)

ig
- -

- =

-3
= 0.639 molden

16
3) A mixture of CO(g) and H2(g) was allowed to reach equilibrium at a certain temperature:
CO(g) + 2H2(g) CH3OH(g)
The initial concentrations of CO and H2 were 0.50 mol dm-3 and 1.00 mol dm-3 respectively. At
equilibrium, the concentration of CO was 015 mol dm-3. Calculate the equilibrium constant at this
-

temperature. (25.9)
( 0cg ) t 2Hz ( ) E CH 304cg )
g

ty€€35/35x7/O35
initial conc 0.50 1.00 O
#

I 0.70
01-0.35=0.3
-

0.15
Egm conc
= 0.35

[ CH 3014cg ) )
Kc :
a-
[ Hugs) -10cg ) ,

Kc = 10.35L
(0.35/0.15)

25.9 Zdmb
-

= mot
-

17
4) Carbon dioxide decomposes to carbon monoxide and oxygen as shown in the equation below:
2CO2(g) 2CO(g) + O2(g)
Initially, there was 0.001 mol of CO2(g) in a 1.0 dm3 reaction vessel at a certain temperature. When an
equilibrium was established, it was found to contain 1 × 10–4 mol dm–3 of CO(g). Calculate the
equilibrium constant, Kc, of the reaction at this temperature. (6.2 x 10 -7 )

202cg ) E 200cg ) t 02cg)

¥4#xi
initial conc O.TO/---o.oo/ O O

Egm conc 9×10-4 1×10-4 5×10-5

'
[ 02cg ] , -40cg ,]
Kc : -

[ cozcgg ]2
4)
2

5)
-

(
-

=
( 5×10 1×10
-

(9×10-4)
b
6.2×10-7 motdm
-

18
 5. At 1000 K, the Kc value for the dissociation of F2(g) is 1.2 × 10–4 mol dm–3.
F2(g) 2F(g)
(a) Write the expression for the equilibrium constant, Kc, of the reaction.
(b) If the initial concentration of F2(g) is 0.2 mol dm–3, calculate the equilibrium concentrations of
F2(g) and F(g) at 1000 K. (x = 2.43 x 10 ) -3

[Fig ]
2
,

( al ke
-

[ Fzcg ,]

(b) f- F 2- Flop
zig ,

÷÷÷÷t#
0.2 O

0.2 -

X 2X

'
[ Fig ,]
ke : -

[ Fugs )

1. 2×10-4 =

12×510.2 -

X)

X
= -

2.46×10-3 ( rejected ) or

2. 43×10-3
=

's
'
[
Fig) ) (2.43×0-3)=4.86×15 molders
'

2x 2
'
'
: -

-3
[ Fzlg ) ) = 0.2 -

X = 0.2-2.43×153--0.198 mot dm

19
 6. At 373 K, N2O4(g) decomposes to NO2(g) and NO2(g) combines to form N2O4(g) until an
equilibrium is reached. The equilibrium concentration of NO2(g) is found to be 3.0 × 10–3 mol dm- and
3

the equilibrium constant, Kc = 0.2 mol dm–3.

(a) Write a chemical equation for the reaction.
-3
(b) Calculate the initial concentration of N2O4(g). (1.55 x 10 )

F
( a ) Nz 04
Ig ) 2N
02cg )

( b)
Nao 4cg , ZNO
2cg )

i :÷÷÷tfnox#
'

X o

X
-
1.5×10-3 3.0×10-3

[ NO 2cg ,]2
Kc - -

[ NzO4lg ) )

0.2 =
13.0×10--3/2
( x -

1.5×10-7
X =
1.55×10-3
=

1.55×153 moldni ?
.
.

. Initial concentration of Nzoycg , is

20
 Unit 40 - Factors affecting chemical equilibrium system

At B F C
1. Effect of change in concentration
• Chemical equilibria will respond the change in concentration by shifting the position.
O
• Change in concentration does not affect the value of ________.
Ke
• Example:
?
→
Kc
-

-
137.5 mot
-
'
dm I 300k )

The colour of the equilibrium mixture is orange-yellow.

Case I
When more of either reactant (Fe3+ or SCN-) is added to the equilibrium mixture, the orange-yellow
dark red
solution becomes ____________.
à Indicates the equilibrium position has shifted to the ____________.
right
product side

T
'
T
Case II
When Fe3+(aq) is removed, the orange-yellow solution is becoming paler and eventually pale
yellow
____________ in colour.
left
à Indicates the equilibrium position has shifted to the ____________.

reactant side

21
Practice
1. Consider the equilibrium system established between CrO42–(aq) and Cr2O72–(aq) in acidic solution.
2CrO42–(aq) + 2H+(aq) Cr2O72–(aq) + H2O(l)
yellow
④ 9 orange
(a) When a few drops of dilute sulphuric acid are added to the equilibrium mixture, the mixture
mm
becomes more orange in colour. To which direction does the equilibrium position shift when the acid
is added?

Shift to the right/ product side.

Na OH
(b) The addition of a few drops of dilute sodium hydroxide solution to the equilibrium mixture can
mum
shift the equilibrium position to the left. Suggest the colour of the resultant equilibrium mixture.

Yellow in color.

2. When bromine dissolves in water at room temperature, the following equilibrium is established.
Br2(aq) + H2O(l) HOBr(aq) + H+(aq) + Br-(aq)
yellowish brown colourless
(a) The addition of a few drops of dilute hydrochloric acid shifts the equilibrium position to the left.
Suggest the colour of the resultant equilibrium mixture.

(b) To which direction will the equilibrium position shift when a few drops of KOH(aq) are added to
the equilibrium mixture?

22
2. Reaction Quotient, Qc
• position
Qc predicts the _______________ of shift in equilibrium.
• Qc is calculated from the _______________
concentration at any particular moment.
• Consider the following reaction, At B F C
Eg .

① initial right
Egm conc
l
Qc can be expressed as: I ① initial O O left
(C)
'
Cold ③ initial l l 3
"" "
CATCH 's r

Comparison Direction of shift of equilibrium Qc

:[Prod > Kc
Qc < Kc ( Reactant)
Right 1 product side
q
Qc > Kc ,
left 1 reactant side
Qc = Kc
Equilibrium
Practice
1. The following equilibrium was originally established in an evacuated 5.00 dm3 flask at 100°C.
SO2Cl2(g) SO2(g) + Cl2(g)
Kc = 0.078 mol dm–3 at 100°C
However, the equilibrium has been disturbed and there are now 0.40 mol of SO2Cl2, 0.08 mol of SO2,
- -

and 0.06 mol of Cl2 in the flask.

-

3
(a) What is the reaction quotient, Qc, immediately after the equilibrium has been disturbed? (2.43x10 )
-

mum

Qc =
[ Chigi [ 502cg ) , conc : MI
dm 's
-

[ Sozclzcgs )
=

-5
food ) ( oge) = 2.4×10-3 moldm-3
( o) =

(b) To which direction will the equilibrium position shift?

Qcckc

Equilibrium position shifts to the right .

23
2. The equilibrium constant, Kc, for the following reaction is 128.4 mol–1 dm3 at a given temperature.
Fe3+(aq) + SCN–(aq) FeSCN2+(aq)
A 2.0 dm3 sealed flask contains 0.0320 mol of Fe3+(aq), 0.0600 mol of SCN–(aq), and 0.1020 mol of
FeSCN2+(aq) at that temperature.

(a) Calculate the reaction quotient to show that the system is not at equilibrium. (106.25)

(b) To which direction will the equilibrium position proceed to reach equilibrium?

3. In a sealed reaction vessel at a certain temperature, ethyne and hydrogen react to give ethene.
C2H2(g) + H2(g) C2H4(g)
The equilibrium constant, Kc, of the above reaction is 0.072 mol–1 dm3.
Initially, [C2H2(g)] = 0.4 mol dm–3, [H2(g)] = 0.02 mol dm–3 and [C2H4(g)] = 3.2 × 10–4 mol dm–3.

(a) Calculate the reaction quotient, Qc, for the initial conditions. (0.04)

(b) Determine the direction in which the reaction proceeds to establish an equilibrium.

24
 Many chemicals produced in industry are made in processes involving
chemical equilibrium. At BIC 130°C :
Kc : I mot
- '
dms )
( 50°C dm' )
'
Kc
-

3. Effect of change in temperature :

2. mot
Industrial production of nitric acid
Higher temperature, equilibrium is reached rapidly.
• ____________
Nitric acid is a very important chemical. It is commonly used in producing
• Kc
Change in temperature changes the value of _______.
ammonium nitrate — a very popular nitrogenous fertilizer (Figure 41.8).
• Example
NH3(aq) + HNO3(aq) NH4NO3(aq)
CASE I

an The finalConsider theindustrial

step in the followingproduction
reaction, of nitric acid is shown in the
the
ous
equation below: O
colourless
3NO (g) + Hbrown
O( ) 2HNO3(aq) + NO(g)
2 2

In the process, nitrogen monoxide is removed from the chemical

system by a further reaction with oxygen. The removal of nitrogen
monoxide shifts the equilibrium
endothermic DR¥¥
position to the right. As a result, more
The reaction is __________________.
nitric acid, the desired product, is produced.
When the temperature increases, the value of Kc ____________
increases and more products form.
forward
à Indicates an increase in temperature favours the _________________ reaction.
Industrial production of ammonia — the Haber left
à Indicates a decrease in temperature, the equilibrium position shifts to the ____________.
process AS2011(II)6(a) reactant
side
In *Haber process,
CASE IInitrogen and hydrogen combine to give ammonia as
shown in theConsider
followingthe
reversible
followingreaction:
reaction,
[NO(g)]
–1
ent, Qc, N2(g) + 3H2(g) 2NH3(g) H = –92 kJ mol
ilibrium
ilibrium The reaction is exothermic. Tix '¥
CE2000(II)25
,
a result, CE2002(II)25
O3(aq), decreases and less products form.
When the temperature increases, the value of Kc ____________

@ forward
à Indicates a decrease in temperature favours the _________________ reaction.
à Indicates an increase in temperature, the equilibrium position shifts to the ____________.
left
21 41
side
reactant
Summary

25
Practice
1. Consider the following equilibrium reaction.
2SO2(g) + O2(g) 2SO3(g) ∆H= –196 kJ mol–1

(a) Is the forward reaction an exothermic or endothermic change?

Exothermic reaction.

IEEE Amount
(b) Predict the yield of SO3 when
(i) the temperature is raised.
① loves
Decreased. An increase in temperature favors backward
reaction. The equilibrium position shifts to the left.①

(ii) the temperature is lowered.

①
Increased. A decrease in temperature favors the forward
reaction. The equilibrium position shifts to the right. ②

2. Consider the following equilibrium system in which the forward reaction is endothermic.
Co2+(aq) + 4Cl–(aq) CoCl 2–(aq) ∆H = +ve
pink blue

(a) Predict the colour change of the mixture if

(i) the temperature of the equilibrium mixture is increased,

(ii) the temperature of the equilibrium mixture is decreased.

(b) What is the change in the Kc value of the equilibrium system when the temperature increases?
Explain your answer.

26
 nitric acid, the desired product, is produced.

Industrial production of ammonia — the Haber

4. Effect of change in pressure/ volume
process AS2011(II)6(a)
• For reaction involving ______________ mixture.
gaseous
*
In Haber process, nitrogen and hydrogen combine to give ammonia as
• Example
shown in theConsider
following
thereversible
followingreaction:
reaction,
NO(g)]
–1
nt, Qc, N2(g) + 3H2(g) 2NH3(g) H = –92 kJ mol
brium
brium CE2000(II)25
esult, CE2002(II)25
3(aq),
CASE I
increases
When the volume decreases, the pressure of the gaseous mixture ____________.

21 41

mol –3
3 = 0.04 mol dm
m For the same equilibrium mixture, what happens when we pull up the
centration of H2(g).
piston?
(g)

See Figure 41.5.

Since there is a greater amount of moles of gases on the left-hand-side of the equation,
2x
l product
right
movable piston side
à The equilibrium position shifts to the ____________________________.

T pressure * ,
→ it ,
pressure decreases
f the equation.
movable piston
w
with a increase
in volume w
b pressure ,
htt
4 moles Zmoles
CASE II
gas molecule

) mol dm
–3 gas molecule

action vessel, concentration of HI(g)

Figure 41.5 Moving the piston upwards increases the volume of the container and hence the
pressure of the gaseous mixture decreases.
–3 2
411 mol dm )
–3 –3 –3
dm )(4.43 × 10 mol dm )
A decrease in pressure has the opposite effect. It will cause the
equilibrium position to shift to the left (i.e. the side with a greater
number of moles of gases).
When This tends
the volume to oppose
increase, the change
the pressure in pressure
of the gaseous decreases
mixture ____________.
by increasing the à
total
Thenumber of moles
equilibrium of gases
position present.
tends to shifts to the side with a greater number of mole of gases.
Increase à The equilibrium
in volume position
or decrease in pressure shifts
shifts left / reactant side
to the ____________________________.
the equilibrium position
) 2HI(g)
to the left which contains a greater number of moles of gases.

–3
43 × 10 0.0411
+y –2y
N2(g) + 3H2(g) 2NH3(g)
1 mole 3 moles 2 moles
W
–3
× 10 + y 0.0411 – 2y
w
k it

y)
Equilibrium reactions with the same number of 27

moles of gases on both sides of the equation

H20 Example 41.4 AS2006(A)4(a) DSEPP2012(IA)26

Effect of change in pressure or volume on an equilibrium system

Practice
1.The
Thegas
gassyringe
syringeshown
shownbelow
belowcontains
containsa agaseous
gaseousmixture
mixtureofofNN
2O4(g) and NO2(g) at equilibrium at
2O4(g) and NO2(g) at equilibrium at
roomtemperature.
room temperature.
N2O4(g) 2NO2(g)
colourless brown

rubber cap
← pluger
Tpressure ,
*→ y -

Y X

①
a gaseous mixture of gas syringe
N2O4(g) and NO2(g)

What colour change in the gaseous mixture will be observed if the plunger of the syringe is pushed
What colour change in the gaseous mixture will be observed if the plunger of the syringe is pushed
quickly from mark X to mark Y? Explain your answer.
quickly from mark X to mark Y? Explain your answer.

Solution
The decrease in volume/ increase in pressure causes the
Theequilibrium
brown colourposition
of the mixture
shifts will turnleft/
to the deeper for a moment
reactant side. and will then gradually become
paler.
WhenThe
the concentration
plunger is pushedofquickly
N2O4from mark X toHence,
increases. mark Y, the
therereaction
is a decrease in volume
mixture turnsand the
concentration NO2(g) increases immediately.
of the browngradually.
paler/ colourless
A decrease in volume or increase in pressure causes the equilibrium position to shift to the left
to reduce the total number of moles of gases in the system. As a result, the concentration of N2O4(g)
increases and the concentration of NO2(g) decreases.

2. Consider the formation of sulphur trioxide from sulphur dioxide and oxygen:
2SO2(g) + O2(g) 2SO3(g)
Cla prac
Predict the shift in equilibrium position whence
A41.4
(a)(a)
Thethe volume
equilibrium of the
position mixtureConsider
shifts is reduced, and
the formation of sulphur trioxide from sulphur dioxide and oxygen:
to the right/product side.
(b) The equilibrium position shifts 2SO2(g) + O2(g) 2SO3(g)
to the left/reactant side. Predict the shift in equilibrium position when
(a) the volume of the mixture is reduced, and
(b) the pressure of the equilibrium system is reduced.

(b) the pressure of the equilibrium system is reduced.

15 41

28
 5. Le Chatelier’s Principle
• To predict the change of conditions on equilibrium position.
• Equilibrium system shifts in a direction to counteract the change.
ur
t.A-tatx.EE
• Examples:

÷¥¥
"
Case I
Consider the following equilibrium

increases
Addition of extra Fe3+(aq) to the equilibrium mixture, the concentration of Fe3+(aq) ____________.
r ht consume the newly added Fe3+(aq)
'

The equilibrium position shifts to the ____________.to

"
dark red
Eescv
"Tag
More _________________
, form, the solution becomes _________________ in colour.

Case II
Consider the following equilibrium

endothermic MKII
The reaction is _________________. .

When the temperature of equilibrium system increases, it would respond by removing heat.
tight to remove heat.
The equilibrium position shifts to the ____________

Cockfcaq blue
, form, the solution becomes ____________
More _________________ in colour.

Limitations
goosefoots
• Always involves gaseous mixtures
Occur when more than one factor is changed at the same time.
endometria
•
• Example: N2O4(g) 2NO2(g) ΔH = +58.1 kJ mol–1 ←

tht
(i) Increase in temperature: equilibrium shifts to the _____________ to lower the temperature.
(ii) Increase in pressure: equilibrium shifts to the _____________ to reduce the pressure.
à Contradiction
pressure , .

29
 Industrial production of ammonia — the Haber
process AS2011(II)6(a)
In *Haber process, nitrogen and hydrogen combine to give ammonia as
Application
shown in•theProduction
following reversible
of ammoniareaction:Haber process
- ______________________
NO(g)]
–1
ent, Qc, N2(g) + 3H2(g) 2NH3(g) H = –92 kJ mol
librium
*
librium CE2000(II)25
Ammonia
CE2002(II)25is removed once it forms
Exo IKEA ,
Equilibrium shifts to the right to
result,
O3(aq), increase pressure favours the forward reaction
An___________ produce more ammonia, increasing the
decrease temperature favours the forward reaction
A _________ yield of the products

21 41
• maintenance cost
Although high pressure increases the yield of ammonia, the ________________________ is high.
slower
Although low temperature increases the yield of ammonia, the reaction rate would be ___________.
o
optimal pressure (200 atm) and temperature (450 C) are set to ______________
Hence, ______________
compromise
,y
the yield, rate of reaction and economic considerations.
F
TENE
Practice
1. The following equation shows the reaction taking place in the Haber process:
N2(g) + 3H2(g) 2NH3(g)
(a) State the catalyst used in the Haber process.

(b) Given that the yield of ammonia increases when temperature decreases, deduce whether the
forward reaction is exothermic or endothermic.

(c) (i) State the advantage of using high pressure for this equilibrium system.

(ii) However, the process is seldom operated at too high pressure. Explain briefly.

30
Past paper
1. [AL 01 I Q3]
(a) In an enclosed reaction vessel at 1100 K and in the presence of a catalyst, an initial 1:1 mole ratio
mixture of SO2 (g) and O2 (g) was allowed to attain equilibrium:

(iii) State, with explanation, the effect of each of the following changes on the position of the above
equilibrium.
(I) Reducing the volume of the reaction vessel

Footpad
(II) Injecting helium gas while keeping the volume of the reaction vessel unchanged.

(2 marks)

2. In an experiment, excess aqueous ammonia is added to an aqueous solution of copper(II) sulphate.

The following equilibrium is established and the resulting solution is deep blue in colour.
[DSE PP Q.13]

(a) Write an expression of Kc for this reaction. (1 mark)

(b) If the above equilibrium mixture contains 0.0020 mol dm–3 of Cu2+(aq) ions, 0.0014 mol dm–3 of
NH3(aq) and 0.0800 mol dm–3 of Cu(NH3)42+(aq) ions, calculate Kc under the conditions of the
experiment. (1.04 x 10 13 )

31
3. Consider an equilibrium mixture of the following chemical reaction:

(a) Write an expression for the equilibrium constant Kc for the reaction. (1 mark)

(b) At a certain temperature, the equilibrium constant Kc for the reaction is 1.08 x 103 dm3 mol-1. The
equilibrium mixture is prepared by mixing 20.0 cm3 of 0.030 M Fe(NO3)3(aq) with 10.0 cm3 of
0.030 M KSCN(aq) in an acidic medium. Calculate the concentration of Fe(SCN)2+(aq) in the
equilibrium mixture at that temperature. (3 marks) (x = 9.21 x 10-3 )

(c) It is known that the equilibrium constant Kc increase when temperature increases. Suggest and
explain whether the enthalpy change of the reaction is positive, negative or zero. (1 mark)

(d) When a little amount of Na2SO3(s) is added to the equilibrium mixture, the colour of the mixture
becomes paler. Explain this observation. (2 marks)

32
 33
PERIODIC TABLE
GROUP
atomic number
0
1 2
H He
I II 1.0 III IV V VI VII 4.0
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.9 9.0 10.8 12.0 14.0 16.0 19.0 20.2
11 12 relative atomic mass 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
23.0 24.3 27.0 28.1 31.0 32.1 35.5 40.0
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.1 40.1 45.0 47.9 50.9 52.0 54.9 55.8 58.9 58.7 63.5 65.4 69.7 72.6 74.9 79.0 79.9 83.8
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.5 87.6 88.9 91.2 92.9 95.9 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 * 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 ** 104 105
Fr Ra Ac Rf Db
(223) (226) (227) (261) (262)
* 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 (145) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 (231) 238.0 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)
**