Equlibrium Lesson

CHEMICAL EQUILIBRIUM
CONTENTS
Concentration change during a chemical reaction
Dynamic equilibrium
Equilibrium constants
Le Chateliers Principle
Haber process

Kinetics
Refers to reaction rates the speed of the reaction, i.e. the change in
concentration of reactants (or products) with respect to time
Equilibrium
Refers to the extent of the reation when no further change occurs,
i.e. the (final) concentration of the product given unlimited time
An equilibrium reaction:
Rateforward
Reactants Products
Ratebackward
At equilibrium, the rate of the forward reaction = the rate of the

backwards reaction
G0 = Standard Gibbs free energy change
R = gas contant
G0 = -RTlnK T = temperature
K = equilibrium constant
Le Chateliers Principle
When a chemical system at equilibrium is disturbed, the system shifts to
counteract the change
Chemical equilibrium
1. Define a reversible reactions, dynamic
equilibrium and determine the equilibrium
constant Kc
2. Use Le Chatelier principle to explain how
different factors affect the equilibria
3. Use Kc to work out the composition of an
equilibrium mixture
Reactions and arrows
The reaction of sodium and chlorine is irreversible.
2Na(s) + Cl2(g) 2NaCl(s)
Irreversible reactions are represented by a single arrow: .
The reaction of nitrogen and hydrogen to form ammonia is

reversible.
N2(g) + 3H2(g) 2NH3(g)
Ammonia can also decompose to form nitrogen and hydrogen.

Reversible reactions that can reach equilibria are represented
by two half arrows: .
CONCENTRATION CHANGE IN A REACTION
As the rate of reaction is dependant on the concentration of reactants... the forward

reaction starts off fast but slows as the reactants get less concentrated
FASTEST AT
THE START
THE STEEPER THE SLOWS DOWN

GRADIENT, THE FASTER AS REACTANTS
THE REACTION ARE USED UP
TOTAL
CONVERSION
In an ordinary reaction; all reactants end TO PRODUCTS
up as products; there is 100% conversion

FASTEST AT
THE START

TOTAL
CONVERSION

FASTEST AT
THE START

TOTAL
CONVERSION
EQUILIBRIUM REACTIONS
Initially, there is no backward reaction but, as products form, it speeds up and

provided the temperature remains constant there will come a time when the backward
and forward reactions are equal and opposite; the reaction has reached equilibrium.
FASTEST AT THE START

NO BACKWARD REACTION
FORWARD REACTION SLOWS DOWN

AS REACTANTS ARE USED UP
BACKWARD REACTION
STARTS TO INCREASE
In an equilibrium reaction, not all the

reactants end up as products; there is not a
100% conversion.
AT EQUILIBRIUM THE BACKWARD
BUT IT DOESNT MEAN THE REACTION AND FORWARD REACTIONS ARE
IS STUCK IN THE MIDDLE EQUAL AND OPPOSITE



BACKWARD REACTION
STARTS TO INCREASE

100% conversion.



BACKWARD REACTION
STARTS TO INCREASE

100% conversion.



BACKWARD REACTION
STARTS TO INCREASE

100% conversion.
What is equilibrium?
If a reversible reaction is carried out in a closed container so
that the reactants and products cannot escape, a state of
dynamic equilibrium can be established.
A + B C + D
This state is dynamic because both the forward and reverse

reactions are ongoing.
It is an equilibrium because:
the rates of the forward and reverse reactions are
the same
the net concentrations of the components of the reaction
mixture remain constant.
DYNAMIC EQUILIBRIUM
IMPORTANT REMINDERS
a reversible chemical reaction is a dynamic process

everything may appear stationary but the reactions are moving both ways
the position of equilibrium can be varied by changing certain conditions
Trying to get up a down escalator gives an excellent idea of a non-chemical

situation involving dynamic equilibrium.
DYNAMIC EQUILIBRIUM
IMPORTANT REMINDERS
a reversible chemical reaction is a dynamic process

everything may appear stationary but the reactions are moving both ways
the position of equilibrium can be varied by changing certain conditions
Trying to get up a down escalator gives an excellent idea of a non-chemical

situation involving dynamic equilibrium.
Summary When a chemical equilibrium is established ...
both the reactants and the products are present at all times
the equilibrium can be approached from either side
the reaction is dynamic - it is moving forwards and backwards
the concentrations of reactants and products remain constant

Dynamic equilibrium
This graph illustrates the dynamic nature of equilibrium.
It shows that both the forward and back reactions are taking
place: they both have non-zero rate. When their rates are equal,
equilibrium is reached.
forward reaction:
2SO2(g) + O2(g) 2SO3(g)
rates are equal at

rate
equilibrium
reverse reaction:
2SO3(g) 2SO2(g) + O2(g)
time
Composition of the reaction mixture
At equilibrium, the proportions of reactants and products
present may not be a 50:50 mix.
The proportion of reactants and

products depend on the
particular reaction, as well as
factors such as temperature,
concentration and pressure.
However, for a given set of

conditions, a particular reaction
will always have the same
proportions of reactants and
products at equilibrium.
THE EQUILIBRIUM LAW
Simply states
If the concentrations of all the substances present at equilibrium are raised to the
power of the number of moles they appear in the equation, the product of the
concentrations of the products divided by the product of the concentrations of the
reactants is a constant, provided the temperature remains constant
The equilibrium constant varies with temperature.
Kc the equilibrium values are expressed as concentrations of mol dm-3

THE EQUILIBRIUM CONSTANT Kc
for an equilibrium reaction of the form...
aA + bB cC + dD
then (at constant temperature) [C]c . [D]d = a constant, (Kc)

[A]a . [B]b
where [ ] denotes the equilibrium concentration in mol dm-3

Kc is known as the Equilibrium Constant
aA + bB cC + dD

[A]a . [B]b

Example Fe3+(aq) + NCS(aq) FeNCS2+(aq)
Kc = [ FeNCS2+ ] with units of dm3 mol-1

[ Fe3+ ] [ NCS ]
aA + bB cC + dD

[A]a . [B]b

VALUE OF Kc
AFFECTED by a change of temperature
NOT AFFECTED by a change in concentration of reactants or products

a change of pressure
adding a catalyst
LE CHATELIERS PRINCIPLE
When a change is applied to a system in dynamic equilibrium, the

system reacts in such a way as to oppose the effect of the change.
Everyday example
A rose bush grows with increased vigour after it has been pruned.
Chemistry example
If you do something to a reaction that is in a state of equilibrium, the equilibrium
position will change to oppose what you have just done
FACTORS AFFECTING THE POSITION OF EQUILIBRIUM
CONCENTRATION
The equilibrium constant is not affected by a change in

concentration at constant temperature. To maintain the
constant, the composition of the equilibrium mixture changes.
If you increase the concentration of a substance, the value of

Kc will theoretically be affected. As it must remain constant at
a particular temperature, the concentrations of the other
species change to keep the constant the same.
CONCENTRATION
example CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)
the equilibrium constant Kc = [CH3COOC2H5] [H2O] = 4 (at 298K)

[CH3CH2OH] [CH3COOH]
CONCENTRATION

increasing
[CH3CH2OH] - will make the bottom line larger so Kc will be smaller
- to keep it constant, some CH3CH2OH reacts with CH3COOH
- this reduces the value of the bottom line and increases the top
- eventually the value of the constant will be restored
CONCENTRATION

increasing
decreasing
[H2O] - will make the top line smaller
- some CH3CH2OH reacts with CH3COOH to replace the H2O
- more CH3COOC2H5 is also produced
CONCENTRATION

increasing
decreasing
[H2O] - will make the top line smaller
- some CH3CH2OH reacts with CH3COOH to replace the H2O
- more CH3COOC2H5 is also produced
SUMMARY
REACTANTS PRODUCTS
THE EFFECT OF CHANGING THE CONCENTRATION ON THE POSITION OF EQUILIBRIUM

INCREASE CONCENTRATION OF A REACTANT EQUILIBRIUM MOVES TO THE RIGHT
DECREASE CONCENTRATION OF A REACTANT EQUILIBRIUM MOVES TO THE LEFT
INCREASE CONCENTRATION OF A PRODUCT EQUILIBRIUM MOVES TO THE LEFT
DECREASE CONCENTRATION OF A PRODUCT EQUILIBRIUM MOVES TO THE RIGHT

SUMMARY
REACTANTS PRODUCTS

Predict the effect of increasing the concentration of O2 on the equilibrium position
2SO2(g) + O2(g) 2SO3(g)
Predict the effect of decreasing the

concentration of SO3 on the equilibrium position
SUMMARY
REACTANTS PRODUCTS

Predict the effect of increasing the concentration of O2 on the equilibrium position
2SO2(g) + O2(g) 2SO3(g) EQUILIBRIUM MOVES TO RHS
Predict the effect of decreasing the

concentration of SO3 on the equilibrium position EQUILIBRIUM MOVES TO RHS
TEMPERATURE
temperature is the only thing that can change the value of the equilibrium constant.
altering the temperature affects the rate of both backward and forward reactions
it alters the rates to different extents
the equilibrium thus moves producing a new equilibrium constant.
the direction of movement depends on the sign of the enthalpy change.
TEMPERATURE
REACTION TYPE DH INCREASE TEMP DECREASE TEMP

EXOTHERMIC - TO THE LEFT TO THE RIGHT
ENDOTHERMIC + TO THE RIGHT TO THE LEFT
TEMPERATURE

Predict the effect of a temperature increase on the equilibrium position of...
H2(g) + CO2(g) CO(g) + H2O(g) DH = + 40 kJ mol-1
2SO2(g) + O2(g) 2SO3(g) DH = - ive

TEMPERATURE

Predict the effect of a temperature increase on the equilibrium position of...
H2(g) + CO2(g) CO(g) + H2O(g) DH = + 40 kJ mol-1 moves to the RHS
2SO2(g) + O2(g) 2SO3(g) DH = - ive moves to the LHS

CATALYSTS
Catalysts work by providing an alternative reaction

pathway involving a lower activation energy.
MAXWELL-BOLTZMANN DISTRIBUTION
NUMBER OF MOLECUES WITH
OF MOLECULAR ENERGY
A PARTICULAR ENERGY
EXTRA MOLECULES
WITH SUFFICIENT
ENERGY TO
OVERCOME THE
ENERGY BARRIER
MOLECULAR Ea
ENERGY
CATALYSTS
An increase in temperature is used to speed up chemical reactions but it can have an

undesired effect when the reaction is reversible and exothermic.
In this case you get to the equilibrium position quicker but with a reduced yield because
the increased temperature moves the equilibrium to the left.
In many industrial processes a compromise temperature is used (see Haber and

Contact Processes). To reduce the problem one must look for a way of increasing the
rate of a reaction without decreasing the yield i.e. with a catalyst.
CATALYSTS
An increase in temperature is used to speed up chemical reactions but it can have an

undesired effect when the reaction is reversible and exothermic.
In this case you get to the equilibrium position quicker but with a reduced yield because
the increased temperature moves the equilibrium to the left.
In many industrial processes a compromise temperature is used (see Haber and

Contact Processes). To reduce the problem one must look for a way of increasing the
rate of a reaction without decreasing the yield i.e. with a catalyst.
Adding a catalyst DOES NOT AFFECT THE POSITION OF EQUILIBRIUM. However, it

does increase the rate of attainment of equilibrium. This is especially important in
reversible, exothermic industrial reactions such as the Haber or Contact Processes
where economic factors are paramount.
HABER PROCESS
N2(g) + 3H2(g) 2NH3(g) : DH = - 92 kJ mol-1
Conditions Pressure 20000 kPa (200 atmospheres)

Temperature 380-450C
Catalyst iron
HABER PROCESS
N2(g) + 3H2(g) 2NH3(g) : DH = - 92 kJ mol-1

Catalyst iron
Equilibrium theory favours

low temperature exothermic reaction - higher yield at lower temperature
high pressure decrease in number of gaseous molecules
HABER PROCESS
N2(g) + 3H2(g) 2NH3(g) : DH = - 92 kJ mol-1

Catalyst iron

Kinetic theory favours

high temperature greater average energy + more frequent collisions
high pressure more frequent collisions for gaseous molecules
catalyst lower activation energy
HABER PROCESS
N2(g) + 3H2(g) 2NH3(g) : DH = - 92 kJ mol-1

Catalyst iron

Kinetic theory favours

high temperature greater average energy + more frequent collisions
high pressure more frequent collisions for gaseous molecules
catalyst lower activation energy
Compromise conditions
Which is better? A low yield in a shorter time or
a high yield over a longer period.
The conditions used are a compromise with the catalyst

enabling the rate to be kept up, even at a lower temperature.
HABER PROCESS
IMPORTANT USES OF AMMONIA AND ITS COMPOUNDS
MAKING
FERTILISERS 80% of the ammonia produced goes to make fertilisers such as
ammonium nitrate (NITRAM) and ammonium sulphate
NH3 + HNO3 > NH4NO3

2NH3 + H2SO4 > (NH4)2SO4
MAKING
NITRIC ACID ammonia can be oxidised to nitric acid
nitric acid is used to manufacture... fertilisers (ammonium nitrate)

explosives (TNT)
polyamide polymers (NYLON)
Dynamic equilibrium: summary
QUESTION
One of the environmentally important reactions involved in
acid rain production has the following equilibrium expression.
From the expression, what would be the balanced chemical
reaction?
Note: all components are in the gas phase.
K = [SO3]/([SO2][O2]1/2)
A. SO3(g) SO2(g) + 2O2(g)

B. SO3(g) SO2(g) + 1/2O2(g)
C. SO2(g) + 2O2(g) SO3(g)
D. SO2(g) + 1/2O2(g) SO3(g)
Answer
D) properly shows the product SO3 on the right and
incorporates the previous exponents from the equilibrium
expression as coefficients in the chemical equation.
Equilibrium Expression
4 NH3(g) + 7 O2(g) 4 NO2(g) + 6 H2O(g)
Write the Equilibrium Expression for the reaction. The
expression will have either concentration units of mol/L
(M), or units of pressure (atm) for the reactants and
products. What would be the overall unit for K using
Molarity and atm units respectively.
4 6
NO2 H 2O
K 4 7
NH3 O2
Ks units = M -1= L/mol or atm-1
QUESTION
The liquid metal mercury can be obtained from its ore
cinnabar via the following reaction:
HgS(s) + O2(g) Hg(l) + SO2(g)
Which of the following shows the proper expression for Kc?
A. Kc = [Hg][SO2]/[HgS][O2]
B. Kc = [SO2]/[O2]
C. Kc = [Hg][SO2]/[O2]
D. Kc = [O2]/[SO2]
Answer
B) correctly presents the product to reactant ratio. Recall that
pure liquids and solids are not shown in the equilibrium
constant expression.

Equlibrium Lesson

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CHEMICAL EQUILIBRIUM

At equilibrium, the rate of the forward reaction = the rate of the

2Na(s) + Cl2(g) 2NaCl(s)

Irreversible reactions are represented by a single arrow: .

The reaction of nitrogen and hydrogen to form ammonia is

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

Ammonia can also decompose to form nitrogen and hydrogen.

As the rate of reaction is dependant on the concentration of reactants... the forward

THE STEEPER THE SLOWS DOWN

As the rate of reaction is dependant on the concentration of reactants... the forward

THE STEEPER THE SLOWS DOWN

As the rate of reaction is dependant on the concentration of reactants... the forward

THE STEEPER THE SLOWS DOWN

Initially, there is no backward reaction but, as products form, it speeds up and

FASTEST AT THE START

FORWARD REACTION SLOWS DOWN

In an equilibrium reaction, not all the

Initially, there is no backward reaction but, as products form, it speeds up and

FASTEST AT THE START

FORWARD REACTION SLOWS DOWN

In an equilibrium reaction, not all the

Initially, there is no backward reaction but, as products form, it speeds up and

FASTEST AT THE START

FORWARD REACTION SLOWS DOWN

In an equilibrium reaction, not all the

Initially, there is no backward reaction but, as products form, it speeds up and

FASTEST AT THE START

FORWARD REACTION SLOWS DOWN

In an equilibrium reaction, not all the

This state is dynamic because both the forward and reverse

a reversible chemical reaction is a dynamic process

Trying to get up a down escalator gives an excellent idea of a non-chemical

a reversible chemical reaction is a dynamic process

Trying to get up a down escalator gives an excellent idea of a non-chemical

Summary When a chemical equilibrium is established ...

the equilibrium can be approached from either side

the reaction is dynamic - it is moving forwards and backwards

the concentrations of reactants and products remain constant

rates are equal at

The proportion of reactants and

However, for a given set of

The equilibrium constant varies with temperature.

Kc the equilibrium values are expressed as concentrations of mol dm-3

for an equilibrium reaction of the form...

then (at constant temperature) [C]c . [D]d = a constant, (Kc)

where [ ] denotes the equilibrium concentration in mol dm-3

for an equilibrium reaction of the form...

then (at constant temperature) [C]c . [D]d = a constant, (Kc)

where [ ] denotes the equilibrium concentration in mol dm-3

Example Fe3+(aq) + NCS(aq) FeNCS2+(aq)

Kc = [ FeNCS2+ ] with units of dm3 mol-1

for an equilibrium reaction of the form...

then (at constant temperature) [C]c . [D]d = a constant, (Kc)

where [ ] denotes the equilibrium concentration in mol dm-3

NOT AFFECTED by a change in concentration of reactants or products

When a change is applied to a system in dynamic equilibrium, the

The equilibrium constant is not affected by a change in

If you increase the concentration of a substance, the value of

example CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)

the equilibrium constant Kc = [CH3COOC2H5] [H2O] = 4 (at 298K)

example CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)

the equilibrium constant Kc = [CH3COOC2H5] [H2O] = 4 (at 298K)

example CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)

the equilibrium constant Kc = [CH3COOC2H5] [H2O] = 4 (at 298K)