CHEMICAL EQUILIBRIUM

24 OCTOBER 2020
 TERMS TO KNOW
o Dynamic Equilibrium: state at which the forward and reverse reactions continue to
take place simultaneously, at the same rate.
o Closed System: refers to a system isolated from its surrounding environment in such a
way that there is no mass transferred into or out of the system.
o Open System: a system in which mass and energy can be transferred into or out of the
system during the reaction.
o Homogenous equilibrium: all the substances in the system are in the same phase.
o Heterogeneous equilibrium: the substances in the system are in different phases.
o Reversible reaction: a reaction that does not go to completion and it occurs in both the
reverse and forward directions. (products can be converted back to reactants)
FACTORS AFFECTING EQUILIBRIUM
o If a system is in equilibrium, it will stay that way indefinitely, unless something happens
to upset the equilibrium situation.
o In 1885 , Henry Le Chatelier came up with the following prince to explain the system’s
response to change:
Le Chatelier’s principle states that the change in any of the factors that determine the
equilibrium conditions of the system will cause the system to change in such a manner as
to reduce or counteract the effect of the change.
Factors that affect equilibrium position include:
o Concentration

o Temperature

o Pressure
Concentration
o We will be using the terms, “ the reverse reaction is favoured” or “the forward reaction
is favoured. If the forward reaction is favoured that means the rate of reaction for the
forward reaction is greater than the rate of reaction for the reverse reaction.
o As a result the concentration of the substances on the left hand side of the equation will
decrease and the concentration of the substances on the right hand side will increase.
o If the forward reaction is favoured, we say the equilibrium shifts to the right.
 Concentration of the
Concentration of the substances on the
substances on the left right hand side
hand side decrease increase

Forward reaction is favoured

 
𝐴( 𝑔 ) + 𝐵( 𝑔 ) ⇋ 𝐶 ( 𝑔 ) + 𝐷 ( 𝑔 )

Concentration of the
Concentration of the substances on the
substances on the left right hand side
hand side increase decrease

reverse reaction is favoured

 Worked example
Consider
o   the following equilibrium situation:

a) What would happen if you increased the concentration of A?

The system will respond to counteract the increase in the concentration of the A, therefore it will
assume the path that will lead to the decrease of the concentration of the substances on the left hand
side. Therefore the equilibrium will shift to the right/ forward reaction will be favoured

b) What would happen if you decreased the concentration of B?

The system will respond to counteract the decrease in the concentration of the B, therefore it will
assume the path that will lead to the increase of the concentration of the substances on the left hand
side. Therefore the equilibrium will shift to the left/ reverse reaction will be favoured

c) What would happen if you increased the concentration of C?

The system will respond to counteract the increase in the concentration of C, therefore it will assume
the path that will lead to the decrease of the concentration of the substances on the right hand side.
Therefore the equilibrium will shift to the left/ reverse reaction will be favoured
d. What would happen if you decreased the concentration of D?
The system will respond to counteract the decrease in the concentration of D, therefore it
will assume the path that will lead to the increase of the concentration of the substances on
the right hand side. Therefore the equilibrium will shift to the right/ forward reaction
will be favoured
problem
Consider
o   the following equilibrium reaction:

What would the effect on the equilibrium system be if:

a) is added to the system? Explain.
b) is added to the system? Explain.
c) is removed to the system? Explain.
d) is added to the system? Explain.
 Temperature
Recall
o   that:
o A + value means that the forward reaction is endothermic.
o A value means that the forward reaction is exorthemic.
Once you have determined whether the forward reaction is endothermic or
exothermic, you can conclude that the reverse reaction id the opposite.
An increase in temperature always favours the endothermic reaction in an
equilibrium reaction.
A decrease in temperature always favours the exothermic reaction in an
equilibrium reaction.
 Worked examples
Consider
o   the following equilibrium situation:

means that the forward reaction is exothermic and the reverse reaction is endothermic.
exothermic

endothermic

a) What would the effect on the equilibrium position if the temperature in the container was decreased?
Explain
According to Le Chatelier, the position of equilibrium will move in such a way as to counteract the
change. This means the position of equilibrium will move so that the temperature is increased again,
thus increasing the heat energy in the system. Exothermic reactions release heat energy, so the
exothermic reaction, which in this case is the forward reaction, will be favoured. As a result the
concentration of H2 and N2 will decrease and the concentration of NH3 will increase. Equilibrium
position will shift to the right.
a) What would the effect on the equilibrium be if the temperature in the container was increased?
Explain.
According to Le Chatelier, the position of equilibrium will move in such a way as to counteract
the change. This means the position of equilibrium will move so that the temperature is decreased
again, thus decreasing the heat energy in the system. Endothermic reactions absorb heat energy,
so the endothermic reaction, which in this case is the reverse reaction, will be favoured. As a
result the concentration of H2 an N2 will increase and the concentration of NH3 will decrease.
Equilibrium position will shift to the left.
 problems
Consider
o   the following equilibrium situation:

a) What would the effect on the equilibrium position if the temperature in the container was decreased?
Explain
b) What would the effect on the equilibrium be if the temperature in the container was increased? Explain.
Consider the following equilibrium reaction:

c) What would the effect on the equilibrium be if the temperature in the container was increased? Explain.
d) What would the effect on the equilibrium position if the temperature in the container was decreased?
Explain
 Pressure
o  
When assessing how pressure affects equilibrium, we specifically look at the number of moles of
gas in each side of the equation. The reason is that the change in pressure does not noticeably
affects solids and liquids.
o Increasing the pressure favours the reaction that proceeds towards the fewer number of moles of
gas.
o decreasing the pressure favours the reaction that proceeds towards the greater number of moles
of gas.

Example
Consider the following equilibrium situation

a) What would the effect on the equilibrium be if the pressure in the container was increased?
Explain.
The equilibrium will shift in the direction that reduces the pressure. The reaction shifts to the side with
the fewer number of moles of gas. In this case the forward reaction will be favoured and the equilibrium
will shift to the right. As a result the concentration of N2 and H2 will decrease and for NH3 it will
increase.
What would the effect on the equilibrium be if the pressure in the container was decreased? Explain.
The equilibrium will shift in the direction that increases the pressure. The reaction shifts to the side with
the greater number of moles of gas. In this case the reverse reaction will be favoured and the
equilibrium will shift to the left. As a result the concentration of N2 and H2 will increase and for NH3 it
will decrease.
 Problems
o  
a) What would the effect on the equilibrium be if the pressure in the container was increased? Explain.
b) What would the effect on the equilibrium be if the pressure in the container was decreased? Explain.

c) What would the effect on the equilibrium be if the pressure in the container was increased? Explain.
d) What would the effect on the equilibrium be if the pressure in the container was decreased? Explain.
 Catalysts
o Since catalysts affect the rate of both forward and reverse reactions equally, catalysts
do not affect the equilibrium position.
o If a catalyst is added to a system that is not yet in equilibrium, then equilibrium will
be reached sooner with a catalyst compared to a system without one.

The common ion effect

If a compound is added to a system in equilibrium and that compound contains an ion
that is already present in the system, than the reaction that uses up that ion will be
favoured.
 Worked example
The
o   following system is in equilibrium:

NaCl is now added to the equilibrium mixture. State and explain what observations you
would make.
Solution:
The addition of NaCl involves the common ion , as NaCl dissociates into and ions. The
system will use up some of the ions that have been added. As a result, the reverse reaction
will be favoured and the solution will turn blue.
 Problems

Consider
o   the following equilibrium reaction:

What would the effect on the equilibrium system be if some is added to the
system.
 Problems cont…..
In the equation:

how would the following affect the equilibrium position and the concentration of
 SO3?
Change that took place Effect on equilibrium Effect on the concentration
position of SO3
Increasing the concentration of SO2 a) b)
Removing SO3 c) d)
Increasing pressure e) f)
Decreasing the concentration of O2 g) h)
Decreasing temperature i) j)
 The equilibrium constant expression
the 
o equilibrium constant can be defined as being an expression, or ratio, of the
concentration of the products over the concentration of the reactants for a reaction that is
in equilibrium.

Where: Kc=equilibrium constant (no units)

concentration of products ()
= concentration of reactants ()
A large Kc value means there are more products than reactants present in the container at equilibrium, and
a small Kc value means that there are more reactants than products present at equilibrium.
 Formulating the equilibrium constant expression
Take
o   note of the following when writing and equilibrium constant expression:
o The equation must be balanced first.
o Only gases(g) and aqueous solutions(aq) are included in the Kc equation.
o Kc changes as temperature changes

Kc for this equilibrium expression is written as

 Examples
o   down the expressions for the equilibrium constant for the following equilibrium reactions
Write
 Problems
Write down the expressions for the wquilibrium constant for
o 
o

the following equilibrium reactions:

 Calculating the equilibrium constant
The
o   equilibrium concentration can be calculated only if the concentrations of the substances
at equilibrium are known.
Hydrogen and iodine are mixed in a close vessel and kept at a temperature of . After reaching
equilibrium, the reaction mixture was analysed and found to be:

Calculate the value of the equilibrium concentration at this temperature.

 Problems
1.  
o Consider the following equilibrium reaction at

After reaching equilibrium, the reaction mixture was analysed and found to be:

Calculate the value of the equilibrium concentration at this temperature.

2. At equilibrium in the following reaction

The value of
Calculate the value of x
More equilibrium constant calculations
o The concentration of substances in the reaction vessel are not the same at
the beginning of the reaction as at equilibrium.
o In order for us to calculate the equilibrium constant, we need to find the
concentration of both products and reactants at equilibrium.
 EXAMPLE
1 mol of A and 2 mol of B react in a 2dm3 container. If at equilibrium 0.75 mol of C has formed, calculate the
value of Kc.

 
𝐴( 𝑔 ) + 2 𝐵 ( 𝑔) ⇋ 𝐶 ( 𝑔 )
Start/initial moles 1 2 0
Mole ratio 1 2 1
Used/formed =1*0,75 =2*0,75 0,75
=0,75 =1,5

Equilibrium 1-0,75 2-1,5 0+0,75

Equilibrium 1-0,75 2-1,5 0+0,75
=0,25 =0,5 0,75
=0,25 =0,5 0,75

Concentration
Concentration
 Example cont….
o   reaction mixture originally contained 4g of A and 5g of B. if at equilibrium, 3.5g of A remains unreacted,
A
calculate the value of Kc for the reaction at this temperature. The volume of the container is o.5 dm3.
(Mr(A)=12g. and Mr(B)=25 ).

Start
Mole ratio
Used/formed

Equilibrium

Concentration