7.1 Chemical Equilibria

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CIE AS Chemistry Your notes
7.1 Chemical Equilibria: Reversible Reactions &

Dynamic Equilibrium
Contents
Chemical Equilibria
Le Chatelier's Principle
Equilibrium Constants, Kc & Kp
Equilibrium Constant Calculations
Changes Affecting the Equilibrium Constant
Equilibria in Industrial Processes
Page 1 of 26
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Chemical Equilibria
Your notes
Reversible Reactions & Dynamic Equilibrium
Reversible reaction
Some reactions go to completion where the reactants are used up to form the products and the
reaction stops when all of the reactants are used up
In reversible reactions the products can react to reform the original reactants
To show a reversible reaction, two opposing half arrows are used: ⇌
How reactions can be reversible
The diagram shows an example of a forward and backward reaction that can be written as one equation
using two half arrows
Dynamic equilibrium
In a dynamic equilibrium the reactants and products are dynamic (they are constantly moving)
In a dynamic equilibrium:
The rate of the forward reaction is the same as the rate of the backward reaction in a closed
system
The concentrations of the reactants and products are constant
Page 2 of 26
Your notes
The diagram shows a snapshot of a dynamic equilibrium in which molecules of hydrogen iodide are
breaking down to hydrogen and iodine at the same rate as hydrogen and iodine molecules are reacting
together to form hydrogen iodide
Diagrams showing reactant and product concentration as a reaction approaches
equilibrium
Page 3 of 26
The diagram shows that the concentration of the reactants and products does not change anymore
once equilibrium has been reached (equilibrium was approached using reactants)
Your notes
The diagram shows that the concentration of the reactants and products does not change anymore
once equilibrium has been reached (equilibrium was approached using products)
A closed system is one in which none of the reactants or products escape from the reaction mixture
In an open system, matter and energy can be lost to the surroundings
When a reaction takes place entirely in solution, equilibrium can be reached in open flasks as a
negligible amount of material is lost through evaporation
If the reaction involves gases, equilibrium can only be reached in a closed system
Thermal decomposition of calcium carbonate in a closed system
Page 4 of 26
The diagram shows a closed system in which no carbon dioxide gas can escape and the calcium
carbonate is in equilibrium with the calcium oxide and carbon dioxide
Your notes
Thermal decomposition of calcium carbonate in an open system
The diagram shows an open system in which the calcium carbonate is continually decomposing as the
carbon dioxide is lost causing the reaction to eventually go to completion
Exam Tip
A common misconception is to think that the concentrations of the reactants and products are equal.
However, they are not equal but they remain constant at dynamic equilibrium (i.e. the concentrations
are not changing).
The concentrations will change as the reaction progresses, only until the equilibrium is reached.
Page 5 of 26
Your notes
Position of the equilibrium
The position of the equilibrium refers to the relative amounts of products and reactants in an
equilibrium mixture.
When the concentration of reactants increases, the position of equilibrium shifts to the right
When the concentration of products increases, the position of equilibrium shifts to the left
Le Chatelier’s principle
Le Chatelier’s principle says that if a change is made to a system at dynamic equilibrium, the position
of the equilibrium moves to minimise this change
The principle is used to predict changes to the position of equilibrium when there are changes in
temperature, pressure or concentration
Effects of concentration
Effects of concentration table
Change How the equilibrium shifts
Increase in concentration of a reactant Equilibrium shifts to the right
Decrease in concentration of a reactant Equilibrium shifts to the left
Increase in concentration of a product Equilibrium shifts to the left
Decrease in concentration of a product Equilibrium shifts to the right
Page 6 of 26
Worked example
Your notes
Changes in equilibrium position
Use the reaction below:
CH3COOH (l) + C2H5OH (l) ⇌ CH3COOC2H5 (l) + H2O (l)

Explain what happens to the position of equilibrium when:
1. More CH3COOC2H5 (l) is added
2. Some C2H5OH (l) is removed
Answer
Answer 1: More CH3COOC2H5 (l) is added
The position of the equilibrium moves to the left and more ethanoic acid and ethanol are
formed
The reaction moves in this direction to oppose the effect of added ethyl ethanoate, so the
ethyl ethanoate decreases in concentration
Answer 2: Some C2H5OH (l) is removed
The position of the equilibrium moves to the left and more ethanoic acid and ethanol are
formed
The reaction moves in this direction to oppose the removal of ethanol so more ethanol (and
ethanoic acid) are formed from ethyl ethanoate and water
Worked example
Changes in equilibrium position
Use the reaction below:
Ce4+ (aq) + Fe2+ (aq) ⇌ Ce3+ (aq) + Fe3+ (aq)

Explain what happens to the position of equilibrium when:
1. Water is added to the equilibrium mixture.
Answer
There is no effect as the water dilutes all the ions equally so there is no change in the ratio of
reactants to products
Effects of pressure
Changes in pressure only affect reactions where the reactants or products are gases
Effects of pressure table
Page 7 of 26

Your notes
Equilibrium shifts in the direction that produces a smaller number of
Increase in pressure
molecules of gas to decrease the pressure again
Equilibrium shifts in the direction that produces a larger number of

Decrease in pressure
molecules of gas to increase the pressure again
Worked example
Changes in pressure
Predict the effect of increasing pressure on the following reactions:
1. N2O4 (g) ⇌ 2NO2 (g)

2. CaCO3 ⇌ CaO (s) + CO2 (g)
Answer
Answer 1:
The equilibrium shifts to the left as there are fewer gas molecules on the left
This causes a decrease in pressure
Answer 2:
The equilibrium shifts to the left as there are no gas molecules on the left but there is CO2 on
the right
This causes a decrease in pressure
Worked example
Changes in pressure
Predict the effect of decreasing pressure on the following reaction:
2NO2 (g) ⇌ 2NO (g) + O2 (g)

Answer
The equilibrium shifts to the right as there is a greater number of gas molecules on the right
This causes an increase in pressure
Effects of temperature
Effects of temperature table
Page 8 of 26
Increase in temperature Equilibrium moves in the endothermic direction to reverse the change
Your notes
Decrease in temperature Equilibrium moves in the exothermic direction to reverse the change
Worked example
Changes in temperature
Predict the effect of increasing the temperature on the following reaction:
H2 (g) + CO2 (g) ⇌ H2O (g) + CO (g) ΔH = +410.2 kJ mol-1

Answer
The reaction will absorb the excess energy
Since the forward reaction is endothermic, the equilibrium will shift to the right
Worked example
For the following reaction, increasing the temperature increases the amount of CO2 (g) at constant
pressure.
Ag2CO3 (s) ⇌ Ag2O (s) + CO2 (g)

Explain whether the reaction is endothermic or exothermic.
Answer
The reaction absorbs the excess energy
Since more CO2 (g) is formed, the equilibrium has shifted towards the right
Therefore, the reaction is endothermic
Remember: Endothermic reactions favour the products
Effects of catalysts
A catalyst is a substance that increases the rate of a chemical reaction (they increase the rate of the
forward and reverse reaction equally)
Catalysts only cause a reaction to reach its equilibrium faster
Catalysts therefore have no effect on the position of the equilibrium once this is reached
Page 9 of 26
Equilibrium Constants, Kc & Kp

Your notes
Equilibrium Constant: Concentrations
Equilibrium expression & constant
The equilibrium expression is an expression that links the equilibrium constant, Kc, to the
concentrations of reactants and products at equilibrium taking the stoichiometry of the equation
into account
So, for a given reaction:
aA + bB ⇌ cC + dD
Kc is defined as:
⎡⎢ C ⎤⎥ c ⎡⎢ D ⎤⎥ d
Kc= ⎡ ⎤a
⎣ ⎦ ⎣ ⎦
⎢⎣A ⎥⎦ ⎡⎢ B ⎤⎥ b
⎣ ⎦
Where:
[A] and [B] are the equilibrium concentrations of A and B, in mol dm-3
[C] and [D] are the equilibrium concentrations of C and D, in mol dm-3
a, b, c and d are the respective number of moles of each reactant and product
Solids are ignored in equilibrium expressions
The Kc of a reaction is specific and only changes if the temperature of the reaction changes
Page 10 of 26
Worked example
Your notes
Deduce the equilibrium expression for the following reactions:
1. Ag+ (aq) + Fe2+ (aq) ⇌ Ag (s) + Fe3+ (aq)

2. N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
3. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
Answer
1. Ag+ (aq) + Fe2+ (aq) ⇌ Ag (s) + Fe3+ (aq)

⎡⎢ 3+
( aq ) ⎥⎦
⎤
Fe
Kc = ⎡ 2+ ⎣ ⎤ ⎡⎢ +
⎢⎣ Fe ( aq ) ⎥⎦ ⎣ Ag ( aq ) ⎥⎦
⎤
2. N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

⎤2
⎢⎣ NH3 ( g ) ⎥⎥⎦
⎡⎢
Kc = ⎡
⎢⎣ N 2 ( g ) ⎤⎥⎦ ⎡⎢⎣ H 2 ( g ) ⎤⎥⎦ 3
3. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

⎤2
⎢⎣ SO 3 ( g ) ⎥⎥⎦
⎡⎢
Kc = ⎡
⎢⎣ SO 2 (g) ⎤⎥⎦ 2 ⎡⎢⎣ O 2 (g) ⎤⎥⎦
Page 11 of 26
Mole Fraction & Partial Pressure

Partial pressure Your notes
For reactions involving mixtures of gases, the equilibrium constant Kp is used as it is easier to measure
the pressure than the concentration for gases
The partial pressure of a gas is the pressure that the gas would have if it was in the container all by itself
The total pressure is the sum of the partial pressure:
Ptotal = PA + PB + PC + .......
Ptotal = total pressure
PA, PB, PC = partial pressures
How partial pressures contribute to total pressure
Partial pressures can be added together to calculate the total pressure

Mole fraction
The mole fraction of a gas is the ratio of moles of a particular gas to the total number of moles of gas
present
number of moles of a particular gas
Mole fraction =
total number of moles of all the gases in the mixture
Page 12 of 26
To calculate the partial pressures of each gas the following relationship can be used:
Partial pressure = mole fraction × total pressure
Your notes
The sum of the mole fractions should add up to 1.00, while the sum of the partial pressures should add
up to the total pressure
Page 13 of 26
Equilibrium Constant: Partial Pressures

Equilibrium expressions involving partial pressures Your notes
Equilibrium expressions in terms of partial pressures are written similarly to those involving
concentrations with a few differences:
Comparing Kp and Kc expressions
The process of writing the expressions is similar, but there is a different presentation and different
information required
Page 14 of 26
Worked example
Your notes
Deducing equilibrium expressions of gaseous reactions
Deduce the equilibrium expression for the following reactions:
1. N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

2. N2O4 (g) ⇌ 2NO2 (g)
3. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
Answer
1. N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
p 2 NH3
Kp =
p 3 H2 × p N2
2. N2O4 (g) ⇌ 2NO2 (g)
p 2 NO 2
Kp =
p N2O 4
3. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
p 2 SO 3
Kp =
p 2 SO 2 × p O 2
Page 15 of 26
Equilibrium Constant Calculations

Your notes
Equilibrium Constant: Calculations
Calculations involving Kc
In the equilibrium expression, each figure within a square bracket represents the concentration in mol
dm-3
The units of Kc therefore depend on the form of the equilibrium expression
Some questions give the number of moles of each of the reactants and products at equilibrium
together with the volume of the reaction mixture
The concentrations of the reactants and products can then be calculated from the number of moles
and total volume using:
number of moles
concentration ( mol dm −3 ) =
volume ( dm 3 )
Page 16 of 26
Worked example
Your notes
At equilibrium, 500 cm3 of the following reaction mixture contains 0.235 mol of ethanoic acid, 0.0350
mol of ethanol, 0.182 mol of ethyl ethanoate and 0.182 mol of water.

Use this information to calculate a value of Kc for this reaction.
Answer
Step 1: Calculate the concentrations of the reactants and products:
0. 235
[CH3COOH (l)] = = 0.470 mol dm-3
0. 500
0. 0350
[C2H5OH (l)] = = 0.070 mol dm-3
0. 500
0. 182
[CH3COOC2H5 (l)] = = 0.364 mol dm-3
0. 500
0. 182
[H2O (l)] = = 0.364 mol dm-3
0. 500
Step 2: Write out the balanced chemical equation with the calculated concentrations beneath
each substance:
0.470 mol dm-3 0.070 mol dm-3 0.364 mol dm-3 0.364 mol dm-3
Step 3: Write the equilibrium constant for this reaction in terms of concentration:
⎡⎢ ⎤ ⎡ ⎤
⎢⎣ H 2 O ⎥⎥⎦ ⎢⎢⎣ CH 3 COOC 2 H 5 ⎥⎥⎦
Kc = ⎡⎢ ⎤ ⎡ ⎤
⎢⎣ C 2 H 5OH ⎥⎥⎦ ⎢⎢⎣ CH 3 COOH ⎥⎥⎦
Step 4: Substitute the equilibrium concentrations into the expression:
0. 364 × 0. 364
Kc =
0. 070 × 0. 470
Kc = 4.03
Step 5: Deduce the correct units for Kc:
(mol dm −3 ) (mol dm −3 )
Kc =
(mol dm −3 ) (mol dm −3 )
All units cancel out
Therefore, Kc = 4.03
Note that the smallest number of significant figures used in the question is 3, so the final answer
should also be given to 3 significant figures
Some questions give the initial and equilibrium concentrations of the reactants but products
Page 17 of 26
An initial, change and equilibrium table should be used to determine the equilibrium concentration of
the products using the molar ratio of reactants and products in the stoichiometric equation
Your notes
Page 18 of 26
Worked example
Your notes
Ethyl ethanoate is hydrolysed in water.
CH3COOC2H5 (l) + H2O (l) ⇌ CH3COOH (l) + C2H5OH (l)

0.1000 mol of ethyl ethanoate are added to 0.1000 mol of water. A little acid catalyst is added and the
mixture is made up to 1 dm3.
At equilibrium, 0.0654 mol of water are present.
Use this information to calculate a value of Kc for this reaction.
Answer
Step 1: Write the balanced chemical equation, with the concentrations beneath each substance,
into an initial, change and equilibrium (ICE) table:
CH3COOC2H5
+ H2O (l)
(l) ⇌ CH3COOH (l) + C2H5OH (l)
Initial moles 0.1000 0.1000 0 0
Change –0.0346 –0.0346 +0.0346 +0.0346
Equilibrium
0.0654 0.0654 0.0346 0.0346
moles
Step 2: Calculate the concentrations of the reactants and products:

0. 0654
[H2O (l)] = = 0.0654 mol dm-3
1. 000
0. 0654
[CH3COOC2H5 (l)] = = 0.0654 mol dm-3
1. 000
0. 0346
[C2H5OH (l)] = = 0.0346 mol dm-3
1. 000
0. 0346
[CH3COOH (l)] = = 0.0346 mol dm-3
1. 000
Step 3: Write the equilibrium constant for this reaction in terms of concentration:
⎡⎢ C H OH ⎤⎥ ⎡⎢ CH COOH ⎤⎥
⎣ 2 5 3
Kc = ⎡
⎦ ⎢⎣ ⎥⎦
⎤ ⎡
⎢ ⎤
⎢⎣ H 2 O ⎥⎦ ⎢ CH 3 COOC 2 H 5 ⎥
⎥
⎣ ⎦
0. 0346 × 0. 0346
Kc =
0. 0654 × 0. 0654
Page 19 of 26
Kc = 0.28
Step 5: Deduce the correct units for Kc:
Kc = Your notes
Therefore, Kc = 0.28
Calculations involving Kp
In the equilibrium expression the p represent the partial pressure of the reactants and products in Pa
The units of Kp therefore depend on the form of the equilibrium expression
Worked example
The equilibrium between sulfur dioxide, oxygen and sulfur trioxide is as follows:
2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

At constant temperature, the equilibrium partial pressures are:
SO2 = 1.0 x 106 Pa
O2 = 7.0 x 106 Pa
SO3 = 8.0 x 106 Pa
Calculate the value of Kp for this reaction.
Answer
Step 1: Write the equilibrium constant for the reaction in terms of partial pressures:
p 2 SO 3
Kp =
p 2 SO 2 × p O 2
( 8. 0 × 10 6 ) 2
Kp =
( 1. 0 × 10 6 ) 2 × ( 7. 0 × 10 6 )
Kp = 9.1 x 10–6
Step 3: Deduce the correct units of Kp:
Pa 2
Kp =
Pa 2 × Pa
So, the units of Kp are Pa-1
Therefore, Kp = 9.1 x 10-6 Pa-1
Some questions only give the number of moles of gases present and the total pressure
The number of moles of each gas should be used to first calculate the mole fractions
The mole fractions are then used to calculate the partial pressures
The values of the partial pressures are then substituted in the equilibrium expression
Page 20 of 26
Worked example
Your notes
The equilibrium between hydrogen, iodine and hydrogen bromide is as follows:
H2 (g) + I2 (g) ⇌ 2HI (g)

At constant temperature, the equilibrium moles are:
H2 = 1.71 x 10–3
I2 = 2.91 x 10–3
HI = 1.65 x 10–2
The total pressure is 100 kPa.
Calculate the value of Kp for this reaction.
Answer
Step 1: Calculate the total number of moles:
Total number of moles = 1.71 x 10-3 + 2.91 x 10-3 + 1.65 x 10-2
Total number of moles = 2.112 x 10-2
Step 2: Calculate the mole fraction of each gas:
1. 71 × 10 −3
H2 = = 0.0810
2. 112 × 10 −2
2. 91 × 10 −3
I2 = = 0.1378
2. 112 × 10 −2
1. 65 × 10 −2
HI = = 0.7813
2. 112 × 10 −2
Step 3: Calculate the partial pressure of each gas:
H2 = 0.0810 x 100 = 8.10 kPa
I2 = 0.1378 x 100 = 13.78 kPa
HI = 0.7813 x 100 = 78.13 kPa
Step 4: Write the equilibrium constant in terms of partial pressure:
p 2 HI
Kp =
p H 2 × p I2
Step 5: Substitute the values into the equilibrium expression:
78 . 13 2
Kp =
8. 10 × 13 . 78
Kp = 54.7
Step 6: Deduce the correct units for Kp:
Pa 2
Kp =
Pa × Pa
Therefore, Kp = 54.7
Page 21 of 26
Other questions related to equilibrium expressions may involve calculating quantities present at
equilibrium given appropriate data
Your notes
Worked example
An equilibrium is set up in a closed container between equal volumes of gaseous reactants A and B to
form a gaseous product C.
A (g) + B (g) ⇌ 2C (g)

The total pressure within the container, at 50 oC, is 3 atm.
The equilibrium partial pressure of A, at 50 oC, is 0.5 atm.
What is the equilibrium partial pressure of C at this temperature?
Answer
There are equal volumes of reactants A and B in a 1 : 1 molar ratio
This means their partial pressures will be the same.
B therefore also has an equilibrium partial pressure of 0.5 atm
Total pressure = Σ (equilibrium partial pressures)
Therefore, the sum of all the partial pressures must equal to 3 atm
0.5 + 0.5 + pc = 3 atm
pc = 2 atm
Page 22 of 26
Changes Affecting the Equilibrium Constant

Your notes
Changes that Affect the Equilibrium Constant
Changes in concentration
If all other conditions stay the same, the equilibrium constant Kc is not affected by any changes in
concentration of the reactants or products
For example, the decomposition of hydrogen iodide:
2HI ⇌ H2 + I2
The equilibrium expression is:
⎣H2⎦ ⎣I2⎦
⎡⎢ ⎤⎥ ⎡⎢ ⎤⎥
Kc = ⎡ ⎤ 2 = 6.25 x 10–3
⎢⎣ HI ⎥⎦
Adding more HI makes the ratio of [ products ] to [ reactants ] smaller

To restore equilibrium, [H2] and [I2] increase and [HI] decreases
Equilibrium is restored when the ratio is 6.25 x 10-3 again
Changes in pressure
A change in pressure only changes the position of the equilibrium (see Le Chatelier’s principle)
If all other conditions stay the same, the equilibrium constant Kc is not affected by any changes in the
pressure of the reactants and products
Changes in temperature change the equilibrium constant Kc
For an endothermic reaction such as:
⎡⎢ ⎤⎥ ⎡⎢ ⎤⎥
⎢ H 2 ⎥ ⎢ I2 ⎥
2HI (g) ⇌ H2 (g) + I2 (g) Kc = ⎣ ⎡ ⎦ ⎤⎣ 2 ⎦
⎢⎣ HI ⎥⎦
With an increase in temperature:

[H2] and [I2] increases
[HI] decreases
Because [H2] and [I2] increase and [HI] decreases, the equilibrium constant Kc increases
For an exothermic reaction such as:
⎡⎢ ⎤3
⎢⎣ SO 3 ⎥⎥⎦
2SO2 (g) + O2 (g) ⇌ 2SO3 (g) Kc = ⎡
⎢⎢ SO 2 ⎤⎥⎥ 2 ⎡⎢⎢ O 2 ⎤⎥⎥
⎣ ⎦ ⎣ ⎦
With an increase in temperature:
[SO3] decreases
[SO2] and [O2] increases
Because [SO3] decreases and [SO2] and [O2] increase, the equilibrium constant Kc decreases
Page 23 of 26
Presence of a catalyst
If all other conditions stay the same, the equilibrium constant Kc is not affected by the presence of a Your notes
catalyst
A catalyst speeds up both the forward and reverse reactions at the same rate so the ratio of [ products ]
to [ reactants ] remains unchanged
Worked example
Factors affecting Kc
An equilibrium is established in the following reaction:
AB (aq) + CD (aq) ⇌ AC (aq) + Bd (aq) ΔH = +180 kJ mol-1

Which factors would affect the value of Kc in this equilibrium?
Answer
Only a change in temperature will affect the value of Kc
Any other changes in conditions would result in the position of the equilibrium moving to oppose
this change
Adding a catalyst increases the rate of reaction meaning the state of equilibrium will be reached
faster but has no effect on the position of the equilibrium and, therefore, Kc is unchanged
Worked example
Factors which increase Kp value
What will increase the value of Kp for the following equilibrium?
2A (g) + B (g) ⇌ 2C (g) ΔH = +6.5 kJ mol-1

Answer
Only temperature changes permanently affect the value of Kp
An increase in temperature shifts the reaction in favour of the products
The [ products ] increases and [ reactants ] decreases, therefore, the Kp value increases
Page 24 of 26
Equilibria in Industrial Processes

Your notes
Haber & Contact Processes
Equilibrium reactions are involved in some stages of large-scale production of certain chemicals
An understanding of equilibrium and Le Chatelier’s principle is therefore very important in the chemical
industry
Haber process
The Haber process involves the synthesis of ammonia according to:
N2 (g) + 3H2 (g) ⇌ 2NH3 (g) ΔHr = -92 kJ mol-1
Le Chatelier’s principle is used to get the best yield of ammonia
Maximising the ammonia yield

Pressure
An increase in pressure will result in the equilibrium shifting in the direction of the fewest molecules of
gas formed to reduce the pressure
In this case, the equilibrium shifts towards the right so the yield of ammonia increases
An increase in pressure will cause the particles to be closer together and therefore increasing the
number of successful collisions leading to an increased reaction rate
Very high pressures are expensive to produce therefore a compromise pressure of 200 atm is chosen
Temperature
To get the maximum yield of ammonia the position of equilibrium should be shifted as far as possible to
the right as possible
Since the Haber process is an exothermic reaction, according to Le Chatelier’s principle the
equilibrium will shift to the right if the temperature is lowered
A decrease in temperature will decrease the energy of the surroundings so the reaction will go in the
direction in which energy is released to counteract this
Since the reaction is exothermic, the equilibrium shifts to the right
However, at a low temperature the gases won’t have enough kinetic energy to collide and react and
therefore equilibrium would not be reached therefore compromise temperature of 400-450 oC is
used in the Haber process
A heat exchanger warms the incoming gas mixture to give molecules more kinetic energy such that
the gas molecules collide more frequently increasing the likelihood of a reaction
Removing ammonia
Removing ammonia by condensing it to a liquid causes the equilibrium position to shift to the right to
replace the ammonia causing more ammonia to be formed from hydrogen and nitrogen
The removed ammonia is stored at very low temperatures and there is no catalyst present with the
stored ammonia so the decomposition reaction of ammonia to decompose back into hydrogen and
Page 25 of 26
nitrogen will be too slow

Catalysts Your notes
In the absence of a catalyst the reaction is so slow that hardly anything happens in a reasonable time!
Adding an iron catalyst speeds up the rate of reaction
Contact process
The Contact process involves the synthesis of sulfuric acid according to:
2SO2 (g) + O2 (g) ⇌ 2SO3 (g) ΔHr = -197 kJ mol-1
Le Chatelier’s principle is used to get the best yield of sulfuric acid
Maximising the sulfuric acid yield

Pressure
An increase in pressure will result in the equilibrium shifting in the direction of the fewest molecules of
gas formed to reduce the pressure
In this case, the equilibrium shifts towards the right so the yield of sulfuric acid increases
In practice, the reaction is carried out at only 1 atm
This is because Kp for this reaction is already very high meaning that the position of the equilibrium is
already far over to the right
Higher pressures than 1 atm will be unnecessary and expensive
Temperature
The same principle applies to increasing the temperature in the Contact process as in the Haber
process
A compromise temperature of 450 oC is used
Removing sulfuric acid
SO3 is removed by absorbing it in 98% sulfuric acid
The SO3 reacts with the solution and more H2SO4 is formed
Catalysts
The Contact process uses vanadium(V) oxide as a catalyst to increase the rate of reaction
Page 26 of 26

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CIE AS Chemistry Your notes

7.1 Chemical Equilibria: Reversible Reactions &

Change How the equilibrium shifts

Increase in concentration of a reactant Equilibrium shifts to the right

Decrease in concentration of a reactant Equilibrium shifts to the left

Increase in concentration of a product Equilibrium shifts to the left

Decrease in concentration of a product Equilibrium shifts to the right

CH3COOH (l) + C2H5OH (l) ⇌ CH3COOC2H5 (l) + H2O (l)

Ce4+ (aq) + Fe2+ (aq) ⇌ Ce3+ (aq) + Fe3+ (aq)

Change How the equilibrium shifts

Equilibrium shifts in the direction that produces a larger number of

1. N2O4 (g) ⇌ 2NO2 (g)

2NO2 (g) ⇌ 2NO (g) + O2 (g)

H2 (g) + CO2 (g) ⇌ H2O (g) + CO (g) ΔH = +410.2 kJ mol-1

Ag2CO3 (s) ⇌ Ag2O (s) + CO2 (g)

Equilibrium Constants, Kc & Kp

1. Ag+ (aq) + Fe2+ (aq) ⇌ Ag (s) + Fe3+ (aq)

1. Ag+ (aq) + Fe2+ (aq) ⇌ Ag (s) + Fe3+ (aq)

2. N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

3. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

Mole Fraction & Partial Pressure

Partial pressures can be added together to calculate the total pressure

Equilibrium Constant: Partial Pressures

1. N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

1. N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

2. N2O4 (g) ⇌ 2NO2 (g)

3. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

Equilibrium Constant Calculations

CH3COOH (l) + C2H5OH (l) ⇌ CH3COOC2H5 (l) + H2O (l)

CH3COOC2H5 (l) + H2O (l) ⇌ CH3COOH (l) + C2H5OH (l)

Initial moles 0.1000 0.1000 0 0

Change –0.0346 –0.0346 +0.0346 +0.0346

Step 2: Calculate the concentrations of the reactants and products:

2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

H2 (g) + I2 (g) ⇌ 2HI (g)

A (g) + B (g) ⇌ 2C (g)

Changes Affecting the Equilibrium Constant

Adding more HI makes the ratio of [ products ] to [ reactants ] smaller

With an increase in temperature:

AB (aq) + CD (aq) ⇌ AC (aq) + Bd (aq) ΔH = +180 kJ mol-1

2A (g) + B (g) ⇌ 2C (g) ΔH = +6.5 kJ mol-1

Equilibria in Industrial Processes

Maximising the ammonia yield

nitrogen will be too slow

Maximising the sulfuric acid yield

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