Chemical Equilibria

CHEMICAL EQUILIBRIA
A Chemical equilibrium occurs for reversible reactions. Many reactions do

not go to completion and then stop, since the products of the reaction
themselves react to form original reactants.
Therefore, for an equilibrium to be established, there is both a forward and
backward reaction.
Qn. State the characteristics of a chemical equilibrium.

 The reaction in which it occurs should be reversible
 The reaction should occur in a closed system
 Temperature should be constant
 Rate of forward reaction should be equal to the rate of backward
reaction
REVERSIBLE AND IRREVERSIBLE REACTIONS.
Qn. With suitable examples, distinguish between reversible and

irreversible reactions.
A reversible reaction is a reaction that does not go to completion, hence takes

place in both forward and backward directions such that both the reactants and
products are present in the equilibrium.
For example, the reaction between hydrogen gas and gaseous iodine to form
hydrogen iodide
𝐻2 (𝑔) + 𝐼2 (𝑔) 2𝐻𝐼(𝑔)
On the other hand, an irreversible reaction is a reaction that goes to
completion, hence takes place only in the forward direction, such that only the
products are present at the end of the reaction so the reaction can never be at
equilibrium.
For example, the combustion of ethene to form carbon dioxide and water
𝐻2 𝐶 = 𝐶𝐻2 (𝑔) + 3𝑂2 (𝑔) 2𝐶𝑂2 (𝑔) + 2𝐻2 𝑂 (𝑙)
Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

call/whatsapp +256753247098 joskabmtwitt @ BUPASS and MACOS
pg. 1
DYNAMIC EQUILIBRIUM
Qn. What is meant by the term dynamic equilibrium?
A dynamic equilibrium is the equilibrium established when the rate of forward
reaction is equal to the rate of backward reaction, such that the concentration of
reactants and products remains constant.
HOMOGENEOUS AND HETEROGENEOUS REVERSIBLE SYSYTEMS.
Qn. With suitable examples distinguish between a homogeneous equilibrium
system and a heterogeneous equilibrium system.
A homogeneous equilibrium system is one in which all the reactants and products
of a reaction are in the same phase.
For example;
 The reaction between ethanol and ethanoic acid to form ethyl ethanoate
/diethyl ether (esterification)
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑙) 𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5 (𝑙) + 𝐻2 𝑂 (𝑙)
 the reaction between hydrogen gas and gaseous iodine to form hydrogen
iodide
𝐻2 (𝑔) + 𝐼2 (𝑔) 2𝐻𝐼(𝑔)
 Decomposition of Dinitrogen tetroxide to form nitrogen dioxide.
𝑁2 𝑂4 (𝑔) 2𝑁𝑂2 (𝑔)
 Reaction between iodine solution and potassium iodide to form potassium
triiodide complex
𝐼2 (𝑎𝑞) + 𝐼 − (𝑎𝑞) 𝐼3 (𝑎𝑞)
A heterogeneous equilibrium system is one in which two or more phases are
involved.
For example;
 Decomposition of calcium carbonate to form calcium oxide and carbon
dioxide.
𝐶𝑎𝐶𝑂3 (𝑠) 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2 (𝑔)
 Reaction between iron and steam to form triiron tetraoxide and hydrogen
3𝐹𝑒(𝑠) + 4 𝐻2 𝑂 (𝑔) 𝐹𝑒3 𝑂4 (𝑠) + 4𝐻2 (𝑔)

pg. 2
 Reaction between bismuth chloride and water to form bismuth oxychloride
and hydrochloric acid
𝐵𝑖𝐶𝑙3 (𝑎𝑞) + 𝐻2 𝑂 (𝑙) 𝐵𝑖𝑂𝐶𝑙(𝑠) + 2𝐻𝐶𝑙(𝑎𝑞)
Note; if only ions are involved in an equilibrium, an ionic equilibrium is
established.
THE EQUILIBRIUM LAW (LAW OF MASS ACTION)
For a homogeneous equilibrium, represented as;

𝑤𝐴 + 𝑥𝐵 𝑦𝐶 + 𝑧𝐷
[𝐶]𝑦 [𝐷]𝑧
= 𝒂 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 𝒂𝒕 𝒂 𝒈𝒊𝒗𝒆𝒏 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 = 𝒌𝒄
[𝐴]𝑤 [𝐵]𝑥
Where [ ] represents molar concentration at equilibrium
The equilibrium law therefore states that if a reversible reaction is allowed

to reach equilibrium at a particular temperature, the product of the molar
concentrations of the products raised to appropriate powers divided by the
product of the molar concentrations of the reactants raised to appropriate
powers is a constant
The constant being emphasized here is what is called the equilibrium

constant, 𝒌𝒄
THE EQUILIBRIUM CONSTANT
What is meant by the term equilibrium constant(𝒌𝒄 ) ?
Equilibrium constant is the ratio of the product of molar concentration of

products raised to their appropriate powers to the product of molar
concentration or reactants raised to their appropriate powers in a
stoichiometric equation of a reversible reaction at constant temperature.
For reactions involving gases, it is often more convenient to measure and

express the gas concentrations in partial pressures in atmospheres. If this is
done, the equilibrium constant is known as 𝒌𝒑

pg. 3
for example;
𝑎𝑋(𝑔) + 𝑏𝑌(𝑔) 𝑐𝑍(𝑔)
(𝑝𝑍 )𝐶
𝒌𝒑 =
(𝑝𝑋 )𝑎 (𝑝𝑌 )𝑏
EQUILIBRIUM CONSTANT EXPRESSIONS (𝒌𝒄 𝒐𝒓𝒌𝒑 ) AND UNITS

when writing expressions for equilibrium constants, the following should be
noted;
1. Check whether only the concentrations /moles in a given volume are
given or total pressure at equilibrium
2. If only concentration/ moles are given, then an expression for 𝒌𝒄
should be written.
3. If total pressure at equilibrium is given, then expression for 𝒌𝒑 should
be written.
4. Solids do not appear in the equilibrium constant expression since their
concentration is assumed to be constant.
5. For a 𝒌𝒑 expression, only gaseous reactants and products appear.
6. If water is one of the reactants, and its concentration is not given, or
remains unchanged, it is assumed to be present in a large excess hence
does not appear in the equilibrium constant expression. If water is in
gaseous state, then include it in the expression.
7. When only the expression is required, do not write the equation also as
part of the answer
8. In the case of 𝒌𝒄 , strictly square brackets must be used.

pg. 4
Qn. In each of the cases below, write the equation for the
equilibrium, the equilibrium constant expression in terms of either
𝒌𝒄 and 𝒌𝒑 or both , depending on what is indicated in brackets and
state the units.
1. Reaction between ethanol and ethanoic acid in presence of an acid catalyst
(𝒌𝒄 )
2. The reaction between hydrogen gas and gaseous iodine.(both 𝒌𝒄 and 𝒌𝒑 )
3. Decomposition of Dinitrogen tetroxide to form nitrogen dioxide.(both 𝒌𝒄 and
𝒌𝒑 )
4. Reaction between iodine solution and potassium iodide.(𝒌𝒄 )
5. Thermal dissociation of calcium carbonate.(both 𝒌𝒄 and 𝒌𝒑 )
6. Reaction between iron and steam to form triiron tetraoxide and hydrogen
.(both 𝒌𝒄 and 𝒌𝒑 )
7. Hydrolysis of bismuth(III) chloride.(𝒌𝒄 )
8. Reaction between hydrogen and nitrogen.(both 𝒌𝒄 and 𝒌𝒑 )
9. Hydrolysis of ethylethanoate using dilute hydrochloric acid.(𝒌𝒄 )
10. Reaction of phosphorus trichloride and chlorine.(both 𝒌𝒄 and 𝒌𝒑 )
11.Reaction between nitrogen and oxygen.(both 𝒌𝒄 and 𝒌𝒑 )
12.Conversion of Sulphur dioxide to Sulphur trioxide.(both 𝒌𝒄 and 𝒌𝒑 )
13.Reaction between carbon monoxide and hydrogen to form gaseous
methanol.(both 𝒌𝒄 and 𝒌𝒑 )
14. Dissociation of hydrogen iodide.(both 𝒌𝒄 and 𝒌𝒑 )
15.Dissociation of phosphorus(V) chloride to phosphorus(III) chloride and
chlorine.(both 𝒌𝒄 and 𝒌𝒑 )
16.Decomposition of Sulphur trioxide.(both 𝒌𝒄 and 𝒌𝒑 )

pg. 5
EXPERIMENTS ON CHEMICAL EQUILIBRIUM.
Qn. Describe an experiment to determine the equilibrium constant for the

hydrolysis of ethylethanoate using dilute hydrochloric acid.
 A known amount of ethylethanoate (a moles) is mixed with a known amount

of water (b moles)
 The mixture is kept in a sealed tube for some hours at a constant temperature
in presence of a known volume dilute hydrochloric acid to catalyze the
reaction.
 After several hours, the tube is then cooled to attain equilibrium
 A fixed volume of the solution is pipetted and titrated with a standard solution
of sodium hydroxide using phenolphthalein indicator
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝑁𝑎𝑂𝐻(𝑎𝑞) 𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎(𝑎𝑞) + 𝐻2 𝑂 (𝑙)
 The amount of ethanoic acid present at equilibrium is obtained (x moles)
Treatment of results
Let V be the volume of the solution in dm3
If there are x moles of ethanoic acid at equilibrium, there are also x moles of
ethanol at equilibrium since mole ratio of 𝐶𝐻3 𝐶𝑂𝑂𝐻 ∶ 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 = 1: 1
Moles of ester hydrolysed and moles of water used are both equal to x, since
mole ratio is also 1:1
𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 (𝑙) + 𝐻2 𝑂 (𝑙) 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑙)
Initial moles a B 0 0
Moles at a-x b-x X x

equilibrium
concentration 𝑎−𝑥 𝑏−𝑥 𝑥 𝑥
𝑣 𝑣 𝑣 𝑣
[𝐶𝐻3 𝐶𝑂𝑂𝐻][𝐶𝐻3 𝐶𝐻2 𝑂𝐻]

𝒌𝒄 =
[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 ][𝐻2 𝑂]
(𝑥⁄𝑣)(𝑥⁄𝑣)
𝒌𝒄 =
𝑎−𝑥 𝑏−𝑥
(( 𝑣 ) ( 𝑣 ))

pg. 6
𝑥2
𝒌𝒄 =
(𝑎 − 𝑥)(𝑏 − 𝑥)
reaction between ethanoic acid and ethanol.
 A known amount of ethanoic acid (a moles) is mixed with a known
amount of ethanol (b moles)
 A known volume of 2M sulphuric acid is added to the mixture to catalyze
the reaction.
 The mixture is heated in a sealed tube to a higher constant temperature
and the mixture left to cool to attain equilibrium.
 At equilibrium, a fixed volume of the solution is pipetted and titrated
with a standard solution of sodium hydroxide using phenolphthalein
indicator
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝑁𝑎𝑂𝐻(𝑎𝑞) 𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎(𝑎𝑞) + 𝐻2 𝑂 (𝑙)
 The amount of ethanoic acid present at equilibrium is obtained (x moles)
Let V be the volume of the solution in dm3
moles of ethanoic acid at equilibrium=x
moles of ethanoic acid converted to ester and water =(a-x)
since mole ratio of 𝐶𝐻3 𝐶𝑂𝑂𝐻: 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 : 𝐻2 𝑂 = 1: 1: 1
(a-x) moles of 𝐶𝐻3 𝐶𝑂𝑂𝐻 form (a-x) moles of 𝐻2 𝑂 and (a-x) moles of
𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 at equilibrium.
Since mole ratio of 𝐶𝐻3 𝐶𝑂𝑂𝐻 ∶ 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 = 1: 1
Moles of ethanol that react=(a-x)
Moles of ethanol at equilibrium=b-(a-x) =(b-a+x)
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑙) 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 (𝑙) + 𝐻2 𝑂 (𝑙)
Initial moles a B 0 0
Moles at x b-a+x a-x a-x

equilibrium
concentration 𝑥 𝑏−𝑎+𝑥 𝑎−𝑥 𝑎−𝑥
𝑣 𝑣 𝑣 𝑣

pg. 7
[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 ][𝐻2 𝑂]
𝒌𝒄 =
[𝐶𝐻3 𝐶𝑂𝑂𝐻][𝐶𝐻3 𝐶𝐻2 𝑂𝐻]
𝑎−𝑥 𝑎−𝑥
( 𝑣 )( 𝑣 )
𝒌𝒄 =
𝑥 𝑏−𝑎+𝑥
((𝑣 ) ( 𝑣 ))
(𝑎 − 𝑥)2
𝒌𝒄 =
𝑥(𝑏 − 𝑎 + 𝑥)
N.B. Be cautious for some pamphlets with a wrong treatment of results
on this case

dissociation of hydrogen iodide to hydrogen and iodine.
 A known amount of hydrogen iodide (c moles) is put in a sealed glass

tube of a fixed volume (v dm3), heated to a higher constant temperature
and then allowed to settle to attain equilibrium.
 At equilibrium, the tube is rapidly cooled to stop the reaction and fix the
equilibrium such that the equilibrium does not adjust itself to the
equilibrium value at a lower temperature.
 The tube is then broken under an aqueous solution of potassium iodide
to dissolve the iodine present at equilibrium.
 The resultant mixture is titrated with a standard solution of sodium
thiosulphate using starch indicator
𝐼2 (𝑎𝑞) + 2𝑆2 𝑂32− (𝑎𝑞) 2𝐼 − (𝑎𝑞) + 𝑆4 𝑂62− (𝑎𝑞)
 The amount of iodine present at equilibrium is obtained.
Total volume of the tube= v dm3
Number of moles of hydrogen iodide heated= c moles
pg. 8
Degree of dissociation of hydrogen iodide= α
2𝐻𝐼(𝑔) 𝐻2 (𝑔) + 𝐼2 (𝑔)
Initial moles c 0 0
Moles at 2c(1-α) cα Cα
equilibrium
For 1 mole of c(1-α) 𝑐𝛼 𝑐𝛼
HI 2 2
Concentration 𝑐(1−𝛼) 𝑐𝛼 𝑐𝛼
𝑣 2𝑣
at equilibrium 2𝑣
[𝐻2 ][𝐼2 ]
𝒌𝒄 =
[𝐻𝐼]2
𝑐𝛼 2
(2𝑣 )
𝒌𝒄 =
𝑐(1 − 𝛼) 2
( 𝑣 )
𝛼2
𝒌𝒄 =
4(1 − 𝛼)2
reaction between hydrogen and iodine to form hydrogen iodide.
 A known amount of hydrogen (a moles) and a known amount of iodine

(b moles) is put in a sealed glass tube of a fixed volume (v dm3), heated
to a higher constant temperature and then allowed to settle to attain
equilibrium.
 At equilibrium, the tube is rapidly cooled to stop the reaction and fix the
equilibrium such that the equilibrium does not adjust itself to the
equilibrium value at a lower temperature.
 The tube is then broken under an aqueous solution of potassium iodide
to dissolve the iodine present at equilibrium.
 The resultant mixture is titrated with a standard solution of sodium
thiosulphate using starch indicator
𝐼2 (𝑎𝑞) + 2𝑆2 𝑂32− (𝑎𝑞) 2𝐼 − (𝑎𝑞) + 𝑆4 𝑂62− (𝑎𝑞)
 The amount of iodine present at equilibrium is obtained.
pg. 9
Number of moles of iodine converted to hydrogen iodide= x moles
Moles of hydrogen iodide formed = 2x moles
𝐻2 (𝑔) + 𝐼2 (𝑔) 2𝐻𝐼(𝑔)
Initial moles a b 0
Moles at a-x b-x 2x

equilibrium
Concentration (𝑎−𝑥) 𝑏−𝑥 2𝑥

at equilibrium 𝑣 𝑣
𝑣
[𝐻𝐼]2
𝒌𝒄 =
[𝐻2 ][𝐼2 ]
2𝑥 2
(𝑣 )
𝒌𝒄 =
𝑎−𝑥 𝑏−𝑥
( 𝑣 )( 𝑣 )
4𝑥 2
𝒌𝒄 =
(𝑎 − 𝑥)(𝑏 − 𝑥)
reaction between hydrogen and nitrogen to form ammonia.
 A known amount of nitrogen (a moles) and a known amount of hydrogen

(b moles) is put in a sealed glass tube of a fixed volume (v dm3).
 The mixture is heated to a moderately high constant temperature and
then allowed to settle to attain equilibrium.
 At equilibrium, the tube is rapidly broken under ice cold water to stop
the reaction and fix the equilibrium such that the equilibrium does not
adjust itself to the equilibrium value at a lower temperature.
 The resultant mixture is titrated with a standard solution of dilute
hydrochloric acid using phenolphthalein indicator
𝑁𝐻3 (𝑎𝑞) + 𝐻𝐶𝑙(𝑎𝑞) 𝑁𝐻4 𝐶𝑙(𝑎𝑞)
 The amount of ammonia present at equilibrium is obtained.
pg. 10
Number of moles of nitrogen converted to ammonia= x moles
Moles of hydrogen used = 3x since 𝑁2 ∶ 𝐻2 = 1: 3
Moles of ammonia formed = 2x moles
𝑁2 (𝑔) + 3 𝐻2 (𝑔) 2 𝑁𝐻3 (𝑔)
Initial moles a b 0
Moles at a-x b-3x 2x

equilibrium
𝑎−𝑥 𝑏−3𝑥 2𝑥
Concentration
𝑣 𝑣
at equilibrium 𝑣
[𝑁𝐻3 ]2
𝒌𝒄 =
[𝑁2 ][𝐻2 ]3
2𝑥 2
(𝑣 )
𝒌𝒄 =
𝑎 − 𝑥 𝑏 − 3𝑥 3
( 𝑣 )( 𝑣 )
4𝑥 2
𝒌𝒄 =
(𝑎 − 𝑥)(𝑏 − 3𝑥)3

pg. 11
SAMPLE QUESTIONS INVOLVING EQUILIBRIUM CONSTANT.
1. Nitrogen and hydrogen are mixed in a ratio 1:3. At equilibrium at 600 OC

and 10 atmospheres, the percentage of ammonia in the mixture of gases is
15%
(a) Write equation for the reaction
(b) Write an expression for the equilibrium constant.
(c) Calculate the equilibrium constant at that temperature and state its units.
Solution.
(a) 𝑁2 (𝑔) + 3𝐻2 (𝑔) 2𝑁𝐻3 (𝑔)
2
(𝑝𝑁𝐻3 )
(b) 𝒌𝒑 = 3
(𝑝𝑁2 )(𝑝𝐻2 )
(c) 𝑁2 (𝑔) + 3𝐻2 (𝑔) 2𝑁𝐻3 (𝑔)
Initial moles 1 3 0
Moles at
Equilibrium 1-x 3-3x 2x
Total moles at equilibrium= 1-x+3-3x+2x=4-2x
2𝑥 15
At equilibrium, = , 𝑡ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒 𝑥 = 0.261
4−2𝑥 100
2𝑥 0.522
𝑝𝑁𝐻3 = × 10 = × 10 = 1.500
4 − 2𝑥 3.478
1−𝑥 0.739
𝑝𝑁2 = × 10 = × 10 = 2.125
4 − 2𝑥 3.478
3 − 3𝑥 2.217
𝑝𝐻2 = × 10 = × 10 = 6.374
4 − 2𝑥 3.478
(1.500)2
𝒌𝒑 = 𝑎𝑡𝑚−2
(2.125)(6.374)3
𝒌𝒑 = 4.089 × 10−3 𝑎𝑡𝑚−2
2. Stoichiometric amounts of hydrogen and nitrogen were reacted at 50 atm.

At equilibrium, 0.8 moles of ammonia were formed. Calculate:
(i) Amount of hydrogen and nitrogen present at equilibrium
(1.8 and 0.6 moles respectively)
(ii) Value of the equilibrium constant (7.4 × 10-4 atm-2)

pg. 12
3. When 3 moles of hydrogen and 1 mole of nitrogen were mixed and allowed
to attain equilibrium at 100 atm and 400oC, the equilibrium mixture
contained 25% of ammonia by volume. Calculate;
(i) Number of moles of nitrogen and hydrogen at equilibrium.
(0.6 and 1.8 moles respectively)
(ii) Value of 𝒌𝒑 at 400oC (1.87 × 10-4 atm-2)
4. (a) For the reaction,

3𝐻2 (𝑔) + 𝑁2 (𝑔) 2𝑁𝐻3 (𝑔)
Calculate the molar percentage of ammonia in the equilibrium
mixture formed at 400oC and at a pressure of 3 × 107 Pa, when gaseous
hydrogen and nitrogen are mixed in a 3:1 ratio and there is 61% conversion
of nitrogen to ammonia.
(b) (i) Determine the equilibrium constant, 𝒌𝒑 of the reaction.
(ii) Given that the value of 𝒌𝒑 at a given temperature is 2.0 × 10−14 𝑃𝑎2 ,
calculate the pressure at which ammonia is 95% dissociated into its elements
at that temperature .
solution
(a)
𝑵𝟐 (𝒈) + 𝟑𝑯𝟐 (𝒈) 𝟐𝑵𝑯𝟑 (𝒈)
Initial moles 1 3 0
Moles 1 3 0.61
× 0.61 × 0.61
reacted/forme 2 2
d =0.305 =0.915
Moles at 1-0.305 3-0.915
equilibrium =0.695 =2.085 0.61
𝒕𝒐𝒕𝒂𝒍 𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔 𝒂𝒕 𝒆𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎
= 𝟎. 𝟔𝟗𝟓 + 𝟐. 𝟎𝟖𝟓 + 𝟎. 𝟔𝟏 = 𝟑. 𝟑𝟗
𝟎.𝟔𝟏
Molar % of 𝑵𝑯𝟑 𝒂𝒕 𝒆𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎 = × 𝟏𝟎𝟎 = 𝟏𝟕. 𝟗𝟗
𝟑.𝟑𝟗
(b) (i) 𝐴𝑛𝑠𝑤𝑒𝑟 = 7.5425 × 10−16 𝑃𝑎−2

pg. 13
(ii) Try to follow through experiment for dissociation of HI
for the approach to this question.
2 𝑁𝐻3 (𝑔) 𝑁2 (𝑔) + 3𝐻2 (𝑔)
Initial c 0 0
moles
Moles at 2c(1-α) cα 3cα

equilibrium
For 1 mole c(1-α) 𝑐𝛼 3𝑐𝛼
of 𝑁𝐻3 2 2
𝑐𝛼 3𝑐𝛼
Concentrati
𝑐(1−𝛼) 2𝑣
on at 2𝑣
equilibrium 𝑣
Assume volume of bulb is 1 litre.

95% (0.95 moles) ammonia is dissociated meaning that only 5% (0.05
moles) is present at equilibrium of the original 100% (1 mole)
Therefore, c=1, c(1-α) =0.05, so α= 0.95
𝑐𝛼 3𝑐𝛼
Total moles at equilibrium = 𝑐(1 − 𝛼) + +
2 2
0.95 3 × 0.95
= (1 − 0.95) + +
2 2
= 0.05 + 0.475 + 1.425
= 1.95
Let the total pressure be PT
0.05
𝑝𝑁𝐻3 = 𝑃
1.95 𝑇

pg. 14
0.475
𝑝𝑁2 = 𝑃
1.95 𝑇
1.425
𝑝𝐻2 = 𝑃
1.95 𝑇
3
(𝑃𝑁2 )(𝑃𝐻2 )
𝒌𝒑 = 2
(𝑃𝑁𝐻3 )
3
0.475 1.425
( 𝑃𝑇 ) × ( 𝑃𝑇 )
2.0 × 10−14 = 1.95 1.95
2
0.05
( 𝑃𝑇 )
1.95
−14 0.05 2
2.0 × 10 ( )
𝑃𝑇 = √ 1.95
0.475 1.425 3
( )
1.95 1.95
𝑃𝑇 = 1.176 × 10−8 𝑃𝑎
5. (a) Write an equation for the reaction between hydrogen and

nitrogen.
(b) At 500 oC, the equilibrium concentration of hydrogen is 0.250
moll-1 and that of nitrogen is 2.7 moll-1 Calculate the equilibrium
concentration of ammonia at the same temperature given that 𝒌𝒄 =
𝟔 × 𝟏𝟎−𝟐 𝒎𝒐𝒍−𝟐 𝒍𝟐 at 500 oC.
6. When heated, carbon dioxide decomposes according to the

equation:
2𝐶𝑂2 (𝑔) 2𝐶𝑂(𝑔) + 𝑂2 (𝑔)
If at a certain temperature and a pressure of one atmosphere, 60%
of the original carbon dioxide remained undissociated. Calculate
the equilibrium constant 𝒌𝒑 for the reaction. (𝒌𝒑 = 𝟎. 𝟎𝟕𝟒 𝒂𝒕𝒎)
7. 3 moles of hydrogen and 1 mole of iodine were heated together at

500oC until equilibrium was established. Calculate the number of
pg. 15
moles of hydrogen iodide present in the equilibrium mixture at
500oC. (The equilibrium constant , 𝒌𝒄 for the reaction between
hydrogen and iodine is 50)
𝑯𝟐 (𝒈) + 𝑰𝟐 (𝒈) 𝟐𝑯𝑰(𝒈)
Initial 3 1 0
moles
Moles at 3-x 1-x 2x
equilibrium
Taking volume to be 1 litre.
[𝐻𝐼]2
𝒌𝒄 =
[𝐻2 ][𝐼2 ]
(2𝑥 )2
𝟓𝟎 =
(3 − 𝑥)(1 − 𝑥)
2
46𝑥 − 200𝑥 + 150 = 0
−(−200) ± √(−200)2 − (4 × 46 × 150)

𝑥=
2 × 46
𝑥1 = 3.384 𝑎𝑛𝑑 𝑥2 = 0.964
𝑏𝑢𝑡 𝑥 𝑐𝑎𝑛𝑛𝑜𝑡 𝑏𝑒 3.384, 𝑏𝑒𝑐𝑎𝑢𝑠𝑒 𝑖𝑡 𝑔𝑖𝑣𝑒𝑠 𝑎
𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑣𝑎𝑙𝑢𝑒 𝑓𝑜𝑟 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛
𝑎𝑛𝑑 𝑖𝑜𝑑𝑖𝑛𝑒 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
𝑡ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒 𝑥 = 0.964
Moles of hydrogen iodide at equilibrium = 2𝑥 = 2 × 0.964 =
1.938 𝑚𝑜𝑙𝑒𝑠
8. (a) State three characteristics of a chemical equilibrium.

(b) 25 moles of hydrogen and 18 moles of iodine vapour were
heated in a 1 litre sealed tube at 465 oC. When equilibrium was
attained, the tube was rapidly cooled and found to contain 30.8
moles of hydrogen iodide.
(c) Give a reason why the tube was rapidly cooled.
(d) Calculate the:
(i) Value of the equilibrium constant for the reaction taking
place in the flask. (38)
pg. 16
(ii) Degree of dissociation of hydrogen iodide. (α=0.245)
9. 1.54g of hydrogen iodide were heated in a 600cm3 bulb at 530 oC.

When equilibrium was attained, the bulb was rapidly cooled to
room temperature and broken under potassium iodide solution.
The iodine formed required 67 cm3 of 0.1M sodium thiosulphate
solution for complete reaction. Calculate ;
(i) Number of moles of hydrogen iodide in 1.54g
(ii) Number of moles of iodine formed
(iii) Value of 𝒌𝒄 at 530 oC
10. 3.24g of hydrogen iodide were heated at 450 oC in a glass bulb

of volume 800cm3. When equilibrium was attained, the bulb was
rapidly cooled to room temperature and then broken under a
solution of potassium iodide. The iodine formed required 36.0 cm3
of a 0.2M sodium thiosulphate solution in the presence of starch
indicator for complete reaction.
(i) Explain why the bulb was rapidly cooled and broken under
potassium iodide solution
(ii) Calculate the equilibrium constant for the reaction at 450 oC
11.Propene reacts with steam according to the following equation.

𝐶𝐻3 𝐶𝐻 = 𝐶𝐻2 (𝑔) + 𝐻2 𝑂(𝑔) 𝐶𝐻3 𝐶𝐻𝑂𝐻𝐶𝐻3 (𝑔)
At a certain temperature and total pressure of 197.38 atmospheres,
the equilibrium partial pressures of propene and steam are 74.02
and 93.76 atmospheres respectively. Calculate the value of 𝒌𝒑 at
this temperature and state its units. (𝒌𝒑 = 𝟒. 𝟐𝟔𝟓 ×
𝟏𝟎−𝟑 𝒂𝒕𝒎−𝟏 )
12. Dinitrogen tetraoxide dissociates at 40 oC and 1 atm according to

the following equation.
𝑁2 𝑂4 (𝑔) 2 𝑁𝑂2 (𝑔) ∆𝐻 = +57𝑘𝐽𝑚𝑜𝑙 −1
(i) Write an equation for the equilibrium constant , 𝒌𝒑 .
(ii) Draw a well labelled energy level diagram for the
reaction in (i) above

pg. 17
(iii) The reaction mixture in (b) was found to contain 60% by
volume of nitrogen dioxide. Calculate the equilibrium
constant 𝒌𝒑 at 40 oC for the reaction. (𝒌𝒑 =
𝟎. 𝟗𝟎𝟔 𝒂𝒕𝒎)
13. For the following gas equilibrium,

𝑁2 𝑂4 (𝑔) 2 𝑁𝑂2 (𝑔) at 333K, the equilibrium
constant, 𝒌𝒑 is 1.33 atmospheres. Calculate the degree of
dissociation of one mole of dinitrogen tetraoxide at 333K if the
total pressure of the system is 2 atmospheres.
14. When 80.4 g of Phosphorus (V) chloride were placed in a 9.0 litre
vessel and heated at a certain pressure, 8.4 g of chlorine were
formed at equilibrium.
Calculate the:
(i) amount of phosphorus(V) chloride and phosphorus(III)
chloride at equilibrium in moles per litre.
(ii) equilibrium constant, 𝒌𝒄 , for the reaction and state its
units.
Solution
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑃𝐶𝑙5 = 31 + (5 × 35.4) = 208
80.4
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑃𝐶𝑙5 𝑖𝑛 9.0 𝑙𝑖𝑡𝑟𝑒𝑠 =
208
= 0.3865
0.3865
𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑐𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑃𝐶𝑙5 = = 0.0429 𝑀
9.0
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝐶𝑙2 = (35.4 × 2) = 70.8

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑒 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑖𝑛 9.0 𝑙𝑖𝑡𝑟𝑒𝑠
8.4
= = 0.1186
70.8
0.1186
𝑀𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐶𝑙2 = = 0.0132𝑀
9.0

pg. 18
𝑷𝑪𝒍𝟓 (𝒈) 𝑷𝑪𝒍𝟑 (𝒈) + 𝑪𝒍𝟐 (𝒈)
Initial 0.0429 0 0
moles per
litre
Moles at 0.0429-0.0132 0.0132 0.0132
equilibriu =0.0297
m per
litre
15. 2.00 g of Phosphorus (V) chloride were allowed to reach

equilibrium at 200 oC in a 1 dm3 capacity vessel. If the
equilibrium constant of the above reaction is 0.008 mol dm-3at this
temperature and in the conditions stated. Calculate the percentage
dissociation of phosphorus pentachloride at equilibrium.
16. 1.0 mole of phosphorus(V) chloride was strongly heated in a

closed bulb until equilibrium was obtained. The glass bulb was
then rapidly broken under potassium iodide solution. The bulb was
found to contain 40.70% of chlorine.
(a) Write equations for the reactions that took place when:
(i) The glass bulb was strongly heated
(ii) The glass bulb was broken under potassium iodide
solution.
(b) State the reasons why the bulb;
(i) Was rapidly broken
(ii) Was broken under potassium iodide solution
(c) Determine the;
(i) Degree of dissociation of phosphorus(V) chloride
(ii) Equilibrium constant for the reaction.

pg. 19
RELATIONSHIP BETWEEN 𝒌𝒄 AND 𝒌𝒑
Qn. (i) What is the Relationship Between Kc and Kp?
𝒌𝒑 = 𝒌𝒄 𝐑𝑻∆𝒏
Where Kp is the equilibrium constant of pressure,
Kc is the equilibrium constant of concentration,

R is the universal gas constant (8.314 Jmol-1K-1),
T is the temperature and
Δn is the difference between total moles of gas products and the
total moles of gas reactants.
(ii) Derive the relationship stated in (i) above.

Consider a reversible reaction,
𝑦
[𝐶] [𝐷] 𝑧
𝒌𝒄 = … … … … … … … … … … … … . (𝑖)
If the reacting species are gaseous,
(𝑃𝐶 )𝑦 (𝑃𝐷 )𝑍
𝒌𝒑 = … … … … … … … … … … … … … … … . (𝑖𝑖)
(𝑃𝐴 )𝑤 (𝑃𝐵 )𝑥
If the gases are ideal, then according to the ideal gas equation.
𝑃𝑉 = 𝑛𝑅𝑇
𝑛𝑅𝑇 𝑛
𝑃= 𝑏𝑢𝑡 = 𝐶 (𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)
𝑉 𝑣
𝑃 = 𝐶𝑅𝑇 … … … … … … … … … … … . . (𝑖𝑖𝑖)
P is therefore proportional to C
From equation (iii), 𝑃𝐴 = [𝐴]𝑅𝑇 … … … … … … … … … … … .∗1
𝑃𝐵 = [𝐵]𝑅𝑇 … … … … … … … … … … … .∗2
𝑃𝐶 = [𝐶]𝑅𝑇 … … … … … … … … … … … .∗3
𝑃𝐷 = [𝐷]𝑅𝑇 … … … … … … … … … … … .∗4
pg. 20
Substituting for 𝑃𝐴 , 𝑃𝐵 , 𝑃𝐶 𝑎𝑛𝑑 𝑃𝐷 𝑖𝑛 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (𝑖𝑖) 𝑔𝑖𝑣𝑒𝑠;
([𝐶]𝑅𝑇)𝑦 ([𝐷]𝑅𝑇)𝑍
𝒌𝒑 =
([𝐴]𝑅𝑇)𝑤 ([𝐵]𝑅𝑇)𝑥
[𝐶]𝑦 [𝐷]𝑧 (𝑅𝑇)𝑦 (𝑅𝑇)𝑧

𝒌𝒑 = ( 𝑤 𝑥 ) ( )
[𝐴] [𝐵] (𝑅𝑇)𝑤 (𝑅𝑇)𝑥
(𝑅𝑇)(𝑦+𝑧)
𝒌𝒑 = 𝒌𝒄
(𝑅𝑇)(𝑤+𝑥)
𝒌𝒑 = 𝒌𝒄 𝑹𝑻((𝒚+𝒛)−(𝒘+𝒙))
𝒌𝒑 = 𝒌𝒄 𝑹𝑻∆𝒏
Where ∆𝒏 is the total number of moles of gaseous products- total number of

moles of gaseous reactants in a balanced equation.
COMPARING THE REACTION QUOTIENT (Q ) AND 𝒌𝒄 TO

DETERMINE DIRECTION OF A CHEMICAL REACTION.
The reaction quotient is defined as the ratio of the molar concentrations of

the product species over those of the reactant species involved in the
chemical reaction, taking stoichiometric coefficients of the reaction into
account as powers of the concentrations.
The reaction quotient, Q, has the same mathematical form as the
equilibrium-constant expression, but Q is a ratio of the actual concentrations
(not a ratio of equilibrium concentrations).
for a given reaction,
The reaction quotient is given as;
[𝐶]𝑦 [𝐷]𝑧
𝑸=
pg. 21
 At equilibrium, Q = 𝒌𝒄 , and this is defined as the equilibrium
condition.
 If Q > 𝒌𝒄 , the reverse reaction is favoured, the reaction moves from
right to left, until equilibrium is established.
 If Q < 𝒌𝒄 , the forward reaction is favoured, the reaction moves from
left to right, until equilibrium is established.
Qn. For the reaction: N2(g) + O2(g) ⇋ 2NO(g) , the equilibrium constant,
Kc, is 1.0 × 10-5 at 1500 K.
Predict the direction the reaction will move in if the reactants and
products have the following concentrations: [N2] = 0.05 mol l-1 , [O2] =
0.02 mol l-1 , and [NO] = 0.30 mol l-1
Qn. For the reaction: N2O4(g) ⇋ 2NO2(g) , the equilibrium constant, Kc,
is 5.0 × 10-1 at 100°C.
Predict the direction the reaction will move in if the concentration of
N2O4 is 0.02 mol l-1 and the concentration of NO2 is 0.10 mol l-1.
Qn. In the water–gas shift reaction, carbon monoxide produced by
steam-reforming reaction of methane reacts with steam at elevated
temperatures to produce more hydrogen:
CO(g)+H2O(g)⇌CO2(g)+H2(g)
If Kc=0.64 at 900 K. If 0.010 moles of both carbon monoxide and water,

0.0080 moles of carbon dioxide, and 0.012 moles of hydrogen are injected
into a 4.0 litre reactor and heated to 900 K, will the reaction proceed to the
left or to the right ?
Q=0.96. Since (Q > K), so the reaction will proceed to the left, and CO and
H2O will form.
Qn. 1 mole of Sulphur trioxide was introduced into a 1 dm3 vessel. The
vessel was heated to 1000K until equilibrium was attained. At equilibrium,
0.35 mole of Sulphur trioxide was present.
(a) Write:
pg. 22
(i) equation for the decomposition of Sulphur trioxide
(ii) an expression for the equilibrium constant, 𝒌𝒄
(b) Calculate the value of 𝒌𝒄 .
(c) 0.2 mole of Sulphur dioxide, 0.1 mole of oxygen and 0.7 mole
of Sulphur trioxide, were introduced into the vessel in (a) at
1000K.
(i) Calculate the new 𝒌𝒄 value for the reaction.
Using your answers in (a)(ii) and (b)(i) above, state how the position of the
equilibrium was affected
L𝒆́ Chatelier's Principle
Qn. Explain L𝒆́ Chatelier's Principle
The principle states that if a closed system in equilibrium is subjected

to any change, the equilibrium will shift if possible, to a direction which
causes an opposite change.
The system cannot completely cancel the change in the external factor, but
it will move in a direction that will minimize the change.
The external factor may be pressure, temperature ,concentration , adding a

noble gas or a catalyst.

pg. 23
APPLYING L𝒆́ CHATELIER'S PRINCIPLE TO EXPLAIN
EFFECTS OF VARIOUS FACTORS ON THE EQUILIBRIUM OF A
REVERIBLE CHEMICAL REACTION
The factors include concentration, pressure, temperature and catalyst.
a. Concentration
Increasing concentration of any reagent in an equilibrium mixture shifts the
equilibrium in the direction that converts some of the reagent into other
products.
Addition of a reagent that reacts with one of the reactants/products, reduces

the concentration of the reactant/product in an equilibrium mixture and
shifts the equilibrium in the direction to which the reactant/ product is
removed so that it is replaced.
Any change in concentration of one of the species in an equilibrium mixture

changes the position of the equilibrium and the rate of attainment of
the equilibrium but has no effect on the equilibrium constant.
Sample question
Qn. Sulphur dioxide reacts with oxygen according to the equation;
2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) 2𝑆𝑂3 (𝑔)
Explain how the position of the equilibrium, value of the
equilibrium constant and the rate of attainment of equilibrium
would be affected if;
(i) more Sulphur dioxide was added
The concentration of sulphur dioxide increases and the excess
Sulphur dioxide reacts with oxygen to produce Sulphur
trioxide, restoring the proportions of reactants and products so
as to keep the equilibrium constant value constant.
Equilibrium therefore shifts from left to right and equilibrium
constant value remains unchanged. The rate of attainment of
equilibrium increases since there is an increase in the number
of particles in the reaction vessel.
(ii) Sulphur trioxide was added.

pg. 24
The concentration of sulphur trioxide increases and the excess
Sulphur trioxide dissociates to produce Sulphur trioxide and
oxygen, restoring the proportions of reactants and products so
as to keep the equilibrium constant value constant.
Equilibrium therefore shifts from right to left and equilibrium
constant value remains unchanged. The rate of attainment of
equilibrium increases since there is an increase in the number
of particles in the reaction vessel.
(iii) Removing the Sulphur trioxide formed
Removing Sulphur trioxide makes the Sulphur dioxide to react

with oxygen so as to restore the proportions of reactants and
products, keeping the equilibrium constant value constant.
Equilibrium therefore shifts from left to right. The rate of
attainment of equilibrium reduces since there is a reduction in
the number of particles in the reaction vessel.
b. Pressure
Pressure affects mainly gaseous reactions.
Any reaction that occurs with an increase in volume is favoured by a
decrease in pressure.
A reaction that occurs with a decrease in volume is favoured by an
increase in pressure.
Any change in pressure of the system changes the position of the

equilibrium and the rate of attainment of the equilibrium but
has no effect on the equilibrium constant.
Sample questions
Qn. Nitrogen and hydrogen react according to the equation

𝑁2 (𝑔) + 3𝐻2 (𝑔) 2𝑁𝐻3 (𝑔)
would be affected if ;
pg. 25
(i) the pressure was decreased
Note that 𝟏 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝑁2 +
𝟑 𝒗𝒐𝒍𝒖𝒎𝒆𝒔 𝒐𝒇 𝐻2 (𝒂 𝒕𝒐𝒕𝒂𝒍 𝒐𝒇 𝟒 𝒗𝒐𝒍𝒖𝒎𝒆𝒔)𝒑𝒓𝒐𝒅𝒖𝒄𝒆
𝟐 𝒗𝒐𝒍𝒖𝒎𝒆𝒔 𝒐𝒇 𝒂𝒎𝒎𝒐𝒏𝒊𝒂
There forward reaction occurs by a reduction in volume, hence
an increase in pressure.
A decrease in pressure shifts equilibrium from right to left since

backward reaction occurs by an increase in volume. Ammonia
decomposes to form nitrogen and hydrogen so as to restore
proportions of reactants and products, keeping the equilibrium
constant value unchanged. Rate of attainment of equilibrium
decreases because there are fewer gas molecules in a given
volume, molecules are far apart hence there are fewer chances
of successful collisions between particles.
(ii) the pressure was increased
Increase in pressure shifts equilibrium from left to right since

forward reaction occurs by a decrease in volume. Nitrogen will
react with hydrogen to form ammonia so as to restore
proportions of reactants and products, keeping the equilibrium
constant value unchanged. Rate of attainment of equilibrium
increases because there are more gas molecules in a given
volume, molecules are closer together hence there are more
chances of successful collisions between particles.
Qn. When hydrogen iodide is heated it decomposes according to the

equation
2𝐻𝐼(𝑔) 𝐻2 (𝑔) + 𝐼2 (𝑔)
would be affected if the pressure of the reaction was increased
Note that 𝟐 𝒗𝒐𝒍𝒖𝒎𝒆𝒔 𝒐𝒇 𝑯𝑰 𝒑𝒓𝒐𝒅𝒖𝒄𝒆 𝟏 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇𝑯𝟐 +
𝟏 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝑰𝟐 = 𝟐 𝒗𝒐𝒍𝒖𝒎𝒆𝒔 𝒐𝒇 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔

pg. 26
Increase in pressure has no effect on position of equilibrium
since both forward and backward reactions proceed with no
change in volume. Equilibrium constant remains unchanged
but the rate of attainment of equilibrium increases because
there are more gas molecules in a given volume, molecules
are closer together hence there are more chances of
successful collisions between particles.
c. Temperature.
The effect of temperature on an equilibrium depends on whether the

reaction is endothermic ( ∆𝐻 𝑖𝑠 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒) or exothermic (
∆𝐻 𝑖𝑠 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒).
If the reaction is endothermic, increase in temperature favours it
If the reaction is exothermic, then it is favoured by lowering
temperature.
Any change in temperature changes the position of the equilibrium,
rate of attainment of the equilibrium and also the value of the
equilibrium constant.
It is only temperature that affects the value of the equilibrium

constant.
For an exothermic reaction, increase in temperature favours
backward reaction, reducing the equilibrium constant value.
For an endothermic reaction, increase in temperature favours
forward reaction, increasing the equilibrium constant value.
Qn. Ammonia is formed from nitrogen and hydrogen at 25°C and

10 atm.
𝑁2 (𝑔) + 3𝐻2 (𝑔) 2𝑁𝐻3 (𝑔) , ∆𝐻𝜃 = −92𝑘𝐽𝑚𝑜𝑙 −1

would be affected if the reaction is carried out at a temperature of
250°C, while the pressure remains at 10 atm.

pg. 27
Since forward reaction is exothermic, increase in temperature from
25°C to 250°C will make equilibrium shift from right to left, favouring
the backward reaction which is endothermic. The ammonia
dissociates to form nitrogen and hydrogen according to L𝑒́
Chatelier's Principle. This reduces the concentration of ammonia but
increases the concentrations of nitrogen and hydrogen, reducing the
The rate of attainment of equilibrium increases because increase in
temperature will increase both the forward reaction rate and the
reverse reaction rate the collision frequency between colliding
particles.
Qn. Nitrogen reacts with oxygen according to the following equation
𝑁2 (𝑔) + 𝑂2 (𝑔) 2𝑁𝑂(𝑔) ; ∆𝐻𝜃 = 180 𝑘𝐽𝑚𝑜𝑙 −1
would be affected if;
(i) the temperature was increased.
Increase in temperature will make equilibrium shift from left to right,

favouring the forward reaction which is endothermic. The nitrogen
reacts with oxygen to form nitrogen monoxide according to L𝑒́
Chatelier's Principle. This reduces the concentration of nitrogen and
oxygen but increases the concentration of nitrogen monoxide,
increasing the equilibrium constant.
The rate of attainment of equilibrium increases because increase in
temperature will increase both the forward reaction rate and the
reverse reaction rate the collision frequency between colliding
particles.
(ii) the temperature was decreased.
Decrease in temperature will make equilibrium shift from right to left,

favouring the backward reaction which is exothermic. The nitrogen
monoxide dissociates to form oxygen and nitrogen according to L𝑒́
Chatelier's Principle. This increases the concentration of nitrogen

pg. 28
and oxygen but decreases the concentration of nitrogen monoxide,
reducing the equilibrium constant.
The rate of attainment of equilibrium decreases because decrease in
temperature will reduce the collision frequency between colliding
particles.
d. Effect of adding a noble gas

Addition of an inert gas for example argon to an equilibrium neither
affects the concentration of the reactants nor the equilibrium constant.
Qn. When heated, carbon dioxide decomposes according to the equation:
2𝐶𝑂2 (𝑔) 2𝐶𝑂(𝑔) + 𝑂2 (𝑔)
Explain the effect on the equilibrium position and equilibrium
constant and the rate of attainment of equilibrium when;
(i) argon is added to the equilibrium at constant volume
Argon being a noble gas, when added, the total pressure of the system
increases, but there is no change in partial pressure/ concentrations of the
reactants and products. Since the concentration of argon does not apply in
the 𝒌𝒄 or 𝒌𝒑 expression, the equilibrium constant also remains unchanged.
The rate of attainment of equilibrium reduces since some of the particles on
collision do not react.
Hence, when an inert gas is added to the system in equilibrium at
constant volume there will be no effect on the equilibrium or
(ii) neon is added to the equilibrium at constant pressure
Neon being a noble gas, when added to the system at constant pressure,
leads to an increase in the total volume. As a result, partial pressures/
concentrations of the reactants and products decreases. According to Le
Chatelier's Principle, the equilibrium will be shifted from right to left (in
that direction where volume increases). The equilibrium constant remains
unchanged since the partial pressure/concentration of neon does not apply
in the equilibrium constant expression. The rate of attainment of equilibrium
reduces as some of the particles on collision do not react.
Sample questions.

pg. 29
1. Sulphur dioxide reacts with oxygen according to the following
equation.
2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) 2𝑆𝑂3 (𝑔)
(a) State what would be happen to the concentration of Sulphur
trioxide in the equilibrium mixture and give a reason for your
answer if;
(i) the temperature was increased
(ii) nitrogen gas was added to the mixture at a constant pressure.
2. The reaction between nitrogen and hydrogen takes place according to

the following equation.
𝑁2 (𝑔) + 3𝐻2 (𝑔) 2𝑁𝐻3 (𝑔) , ∆𝐻𝜃 = −𝑥 𝑘𝐽𝑚𝑜𝑙 −1

What would happen to the concentration of ammonia if;
(i) Helium was added to the equilibrium mixture at constant
pressure 500 °C?
(ii) The temperature was increased?
3. Iodine is sparingly soluble in water but readily dissolves in potassium

iodide according to the following equilibrium
𝐼2 (𝑎𝑞) + 𝐼 − (𝑎𝑞) 𝐼3− (𝑎𝑞)
(a) Explain why iodine is sparingly soluble in water but very soluble
in potassium iodide
(b) (i) Write an expression for the concentration equilibrium constant,
𝒌𝒄 .
(ii) State any three characteristics of the above equilibrium.
(c) State and explain the effect of adding sodium thiosulphate solution
to the position of equilibrium.
4. Phosphorus pentachloride decomposes at high temperatures
according to the following equation.
𝑃𝐶𝑙5 (𝑔) 𝑃𝐶𝑙3 (𝑔) + 𝐶𝑙2 (𝑔)
State how the value of the equilibrium constant would be affected
and in each case give a reason for your answer if ;

pg. 30
(i) the pressure was increased
(ii) some chlorine was added to the equilibrium
5. When heated at 1atm, carbon dioxide decomposes according to the

equation:
2𝐶𝑂2 (𝑔) 2𝐶𝑂(𝑔) + 𝑂2 (𝑔)
State and explain the effect of ;
(i) heating the carbon dioxide at 2 atmospheres on the
equilibrium concentration of oxygen
(ii) carrying out the decomposition at a lower temperature on
the value of the equilibrium constant, 𝒌𝒑 .
6. Hydrogen and iodine were heated in a 1 litre vessel. Explain what
would happen to the equilibrium position of the reaction, equilibrium
constant, and rate of attainment of equilibrium if;
(i) sodium thiosulphate solution was added to the vessel.
(ii) the pressure was increased
(iii) concentration of iodine was increased
(iv) helium gas was added at constant volume.
(e) Effect of adding a catalyst
A catalyst has no effect on position of equilibrium and value of

equilibrium constant but only alters the rate of backward and
forward reaction equally.
INTERPRETING MAGNITUDE OF 𝒌𝒄 OR 𝒌𝒑 IN RELATION
TO EQUILIBRIUM POSITION.
The magnitude of the equilibrium constant, K, indicates the extent to
which a reaction will proceed:
If K is a large number (k>1) , it means that the equilibrium
concentration of the products is large. In this case, the equilibrium
will shift to the right (resulting in an increase in the concentration
of products)
If K is a small number (k<1) , it means that the equilibrium
concentration of the reactants is large. In this case, the equilibrium

pg. 31
will shift to the left (resulting in an increase in the concentration of
reactants)
If K is about 1, the reaction the equilibrium is reached at some
intermediate mixture.
INDUSTRIAL APPLICATION OF CHEMICAL EQUILIBRIUM.

(Details of these processes must be seen in inorganic chemistry under
chemistry of period 3 elements)
The knowledge of chemical equilibrium is applied industrially in the
following processes;
1. Manufacture of ammonia (the Haber process)
The reaction between dry hydrogen (obtained from natural gas) and
dry nitrogen (from fractional distillation of liquid air) to form ammonia
is exothermic and occurs with a decrease in volume
𝑁2 (𝑔) + 3𝐻2 (𝑔) 2𝑁𝐻3 (𝑔) ; ∆𝐻𝜃 (298𝐾) = −92.4 𝑘𝐽𝑚𝑜𝑙 −1
According to L𝑒́ Chatelier's Principle , the yield of ammonia will be

greatest at low temperature and high pressure. At a low temperature
however, rate of attainment of equilibrium is low and at high pressure, the
cost of the equipment and running costs are high.
Therefore, in practice, a compromise has to be struck. The conditions used

in this process are therefore;
 Pressures between 200-500 atmospheres

pg. 32
 Temperature of about 450-550oC
 Finely divided iron catalyst
2. Manufacture of sulphuric acid (the Contact process)
The conversion of Sulphur dioxide (obtained by burning Sulphur in

air, roasting iron pyrites, copper pyrites or oxidation of zinc blende)
and oxygen (obtained from fractional distillation of liquid air) to
Sulphur trioxide is an exothermic reaction and occurs with a
decrease in volume.
2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) 2𝑆𝑂3 (𝑔); ∆𝐻𝜃 (298𝐾) = −197.6 𝑘𝐽𝑚𝑜𝑙 −1
According to L𝑒́ Chatelier's Principle , the yield of ammonia will be
greatest at low temperature and high pressure. At a low
temperature however, the rate of attainment of equilibrium is very
slow.
Increase in pressure in pressure gives an increased yield of Sulphur
trioxide but the effect is small and the yield is good even at
pressures just above atmospheric pressure but not as high as those
used in the Haber Process.
Therefore, in practice, a compromise has to be struck. The
conditions used in this process are therefore;
 Pressures between 1-3 atmospheres

 Temperature of about 450-500 oC
 Vanadium(V) oxide catalyst

pg. 33

Chemical Equilibria

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Chemical Equilibria

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CHEMICAL EQUILIBRIA

A Chemical equilibrium occurs for reversible reactions. Many reactions do

Qn. State the characteristics of a chemical equilibrium.

REVERSIBLE AND IRREVERSIBLE REACTIONS.

Qn. With suitable examples, distinguish between reversible and

A reversible reaction is a reaction that does not go to completion, hence takes

Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

For a homogeneous equilibrium, represented as;

The equilibrium law therefore states that if a reversible reaction is allowed

The constant being emphasized here is what is called the equilibrium

THE EQUILIBRIUM CONSTANT

What is meant by the term equilibrium constant(𝒌𝒄 ) ?

Equilibrium constant is the ratio of the product of molar concentration of

For reactions involving gases, it is often more convenient to measure and

Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

EQUILIBRIUM CONSTANT EXPRESSIONS (𝒌𝒄 𝒐𝒓𝒌𝒑 ) AND UNITS

Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

Qn. Describe an experiment to determine the equilibrium constant for the

 A known amount of ethylethanoate (a moles) is mixed with a known amount

Moles at a-x b-x X x

[𝐶𝐻3 𝐶𝑂𝑂𝐻][𝐶𝐻3 𝐶𝐻2 𝑂𝐻]

Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

 The amount of ethanoic acid present at equilibrium is obtained (x moles)

Moles at x b-a+x a-x a-x

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Qn. Describe an experiment to determine the equilibrium constant for the

 A known amount of hydrogen iodide (c moles) is put in a sealed glass

 A known amount of hydrogen (a moles) and a known amount of iodine

Moles at a-x b-x 2x

Concentration (𝑎−𝑥) 𝑏−𝑥 2𝑥

 A known amount of nitrogen (a moles) and a known amount of hydrogen

Moles at a-x b-3x 2x

Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

1. Nitrogen and hydrogen are mixed in a ratio 1:3. At equilibrium at 600 OC

2. Stoichiometric amounts of hydrogen and nitrogen were reacted at 50 atm.

Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

4. (a) For the reaction,

(b) (i) Determine the equilibrium constant, 𝒌𝒑 of the reaction.

(b) (i) 𝐴𝑛𝑠𝑤𝑒𝑟 = 7.5425 × 10−16 𝑃𝑎−2

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Moles at 2c(1-α) cα 3cα

Assume volume of bulb is 1 litre.

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5. (a) Write an equation for the reaction between hydrogen and

6. When heated, carbon dioxide decomposes according to the

7. 3 moles of hydrogen and 1 mole of iodine were heated together at

−(−200) ± √(−200)2 − (4 × 46 × 150)

8. (a) State three characteristics of a chemical equilibrium.

9. 1.54g of hydrogen iodide were heated in a 600cm3 bulb at 530 oC.

10. 3.24g of hydrogen iodide were heated at 450 oC in a glass bulb

11.Propene reacts with steam according to the following equation.

12. Dinitrogen tetraoxide dissociates at 40 oC and 1 atm according to

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13. For the following gas equilibrium,

𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝐶𝑙2 = (35.4 × 2) = 70.8

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15. 2.00 g of Phosphorus (V) chloride were allowed to reach

16. 1.0 mole of phosphorus(V) chloride was strongly heated in a

Prepared by JOSEPH JOBS KAYIIRA(BSCED (CHEM/maths)(Hons) josephkayiirab@gmail.com

Where Kp is the equilibrium constant of pressure,

Kc is the equilibrium constant of concentration,