CHEMICAL EQUILIBRIUM

TERMINOLOGY
HOMOGENEOUS REACTIONS are reactions where all the reactants and
products are in the same phase. i.e. all are solids, or all are liquids, or all
are gases.
Example: SO2(g) + O2(g) ⇌ SO3(g) all reactants and products are gases
HETEROGENEOUS REACTIONS are reactions where NOT all species in
the reaction vessel are in the same phase.
Example: CaCO3(s) + HCℓ(aq) → CaCℓ2(aq) + CO2(g) + H2O(ℓ)
Open chemical system: reactants / products can escape from reaction
vessel – container in which reaction takes place is open.
Closed chemical system: reactants / products cannot escape from
reaction vessel – container in which reaction takes place is sealed.
TERMINOLOGY CONTINUED
• REVERSIBLE REACTION occurs when the products can be converted
back to reactants.
• N2(g) + 3 H2(g) ⇋ 2 NH3(g) is an example of a reversible reaction.
• Note the double arrow which indicates that the reaction is reversible.
• They normally take place in closed systems.
• The reactants on the left react to form the products on the right in the
forward reaction.
• The products on the right react to form reactants on the left in the
reverse reaction.
• Both reactions take place simultaneously.
CHEMICAL EQUILIBRIUM
• At the beginning the rate of the forward reaction is high because there is a high
concentration of reactants.
• As the reactants disappear in the forward reaction, the rate of the forward reaction
decreases.
• The rate of the reverse reaction is non existent at the beginning because there is
nothing that can react.
• However as products are formed, the reverse reaction starts off slowly and the rate
increases.
• The rate of the forward reaction decreases while the rate of the reverse reaction
increases.
• Eventually, they meet and the rate of the forward reaction equals the rate of the
reverse reaction. When this happens, we say CHEMICAL EQUILIBRIUM is reached.
• CHEMICAL EQUILIBRIUM is when the rate of the forward reaction equals the rate
of the reverse reaction.
DYNAMIC EQUILIBRIUM
• When you look at a chemical reaction that is in equilibrium, it seems
nothing is happening.
• The number of moles of reactants and products remain constant.
• We say nothing is happening on a macroscopic level.
• However, both reactions are still taking place. They just taking place at
the same speed. Both reactions are taking place at a microscopic level.
• This means that the rate at which a substance disappears in the forward
reaction, equals the rate at which it forms in the reverse reaction.
• The number of moles of the substance thus remains constant.
• We say EQUILIBRIUM is DYNAMIC because eventhough it does not look
like it, both reactions are taking place at the same speed
LE CHATELIER’S PRINCIPLE
• Le Chatelier’s Principle states that:
• When the equilibrium in a closed system is disturbed, the system will re-
instate a new equilibrium by favouring the reaction that will oppose the
disturbance.
• In industry we have to seal containers to prevent the product from escaping.
• However this then means the reaction becomes reversible.
• When equilibrium is reached, there are reactants and products in the
container and we don’t want this.
• Le Chatelier’s Priniple allows us to manipulate the equilibrium so that we
can get as much product as possible.
• If any factor changes, we can apply Le Chatelier’s Principle to determine
how these changes affect the system in equilibrium.
FACTORS AFFECTING LE CHATELIER
1. TEMPERATURE
2. CONCENTRATION
3. PRESSURE
4. CATALYST
TEMPERATURE AND LE CHATELIER
• When a change is made at equilibrium, Le Chatelier says the system will
oppose the change or try to reverse the change.
• When the temperature of a system at equilibrium is increased, the system
will try to decrease the temperature.
• An ENDOTHERMIC REACTION use energy so an endothermic reaction will
decrease the temperature of the system.
• So when we increase the temperature of the system, the system opposes
our change by decreasing the temperature. It does this by FAVOURING the
ENDOTHERMIC REACTION.
• Conversely a DECREASE IN TEMPERATURE will FAVOUR the EXOTHERMIC
REACTION.
• Note: an increase in temperature makes both reactions faster but makes
the endothermic reaction go much faster
EXAMPLE 1
CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g) ΔH > 0

(a) Is the forward reaction endothermic or exothermic? Give a reason for your
answer.
It is endothermic. When ΔH > 0 or positive it means the forward reaction is
endothermic and the reverse reaction is exothermic.
(b) Which reaction is favoured when we decrease the temperature?
A decrease in temperature favours the exothermic reaction. In this example the
exothermic is the reverse reaction. This means the decrease in temperature favours the
reverse reaction
(c) What happens to the concentration of CO when the temperature is decreased?
The reverse reaction is favoured and CO is used up during the reverse reaction. This
means the concentration of CO will decrease.
CONCENTRATION AND LE CHATELIER
• When a change is made at equilibrium, Le Chatelier says the system will
oppose the change or try to reverse the change.
• When the concentration of a substance is increased, the system will try
to decrease the concentration of this same substance.
• It does this by favouring the reaction moving AWAY from this substance.
• If the concentration of a REACTANT IS INCREASED, the FORWARD
REACTION IS FAVOURED.
• If the concentration of a PRODUCT IS INCREASED, the REVERSE
REACTION IS FAVOURED.
• When the concentration of a SUBSTANCE IS DECREASED, the system will
try to increase the concentration by favouring the reaction moving
TOWARD the substance.
EXAMPLE 2
• CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)
(a) Which reaction is favoured if the concentration of CH4 is increased?
The forward reaction
(b) Which reaction is favoured if the concentration of CH4 is decreased?
The reverse reaction
(c) Which reaction is favoured if we increase CO?
Reverse reaction
(d) Which reaction is favoured if we decrease CO?
Forward reaction
(e) What happens to the concentration of H2 if we increase H2O?
If we increase H2O, the forward reaction is favoured. This means H2
concentration will increase.
PRESSURE AND LE CHATELIER
• When a change is made at equilibrium, Le Chatelier says the system will oppose
the change or try to reverse the change.
• Pressure only applies to gases.
• We increase pressure by decreasing volume and we decrease pressure by
increasing volume.
• When we increase the pressure, the system tries to decrease the pressure.
• It does this by producing as little gas as possible.
• When we INCREASE THE PRESSURE, the reaction PRODUCING THE LEAST MOLES
OF GAS will be favoured.
• When we DECREASE THE PRESSURE, the reaction PRODUCING THE MOST MOLES
OF GAS will be favoured.
• When the number of gas moles are the same on each side then pressure has no
effect
EXAMPLE 3
• CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)
(a) Which reaction is favoured when we decrease the pressure?
The forward reaction is producing 4 moles of gas – 1CO and 3H2
The reverse reaction is producing 2 moles of gas – 1CH4 and 1H2O
A decrease in pressure favours the reaction producing the most moles of gas
whch is the forward reaction in this example.
(b) Which reaction is favoured when we increase the pressure?
Reverse reaction
(c) What happens to the concentration od CO if we increase the volume?
Increase volume means decrease pressure means forward reaction is
favoured so CO increases.
CATALYST AND LE CHATELIER
• A CATALYST increases the rate of both reactions but does not favour
one reaction over another.
• Once equilibrium is reached, a CATALYST HAS NO EFFECT.
EXAMPLE 4
• 2A(g) + 3B(aq) ⇌ C(g) + 2D(g) ∆H < 0
(a) Is the reaction homogenous? Give a reason for your answer.
No. There are different phases.
(b) Is the forward reaction endothermic? Give a reason for your answer.
No. ∆H is less than zero so the forward reaction is exothermic.
(c) What will happen to the concentration of D when the following changes are made? Write only
INCREASE, DECREASE OR REMAIN THE SAME.
(i) The temperature is decreased.
INCREASE – decrease in temp favors exo which is forward reaction so D increases
(ii) The concentration of B is increased.
INCREASE – increase in B makes reaction move away from B which is forward reaction so D incr.
(iii) The pressure is decreased.
INCREASE – lower pressure favours reaction producing most moles ie fwd reaction so D increase
(iv) A catalyst is added
REMAIN THE SAME – catalyst has no effect
LE CHATELIER SUMMARY
1. An INCREASE IN TEMPERATURE FAVOURS THE ENDOTHERMIC
REACTION.
2. An INCREASE IN CONCENTRATION OF X FAVOURS REACTION
MOVING AWAY FROM X.
3. An INCREASE IN PRESSURE (VOLUME DECREASE) FAVOURS
REACTION PRODUCING THE LEAST MOLES OF GAS.
4. A CATALYST HAS NO EFFECT
The Equilibrium Constant (Kc)
• The EQUILIBRIUM CONSTANT is a numerical value which tells us
whether a reversible reaction is successful or not.
• When Kc is high, the reaction is successful and when its low the
reaction was not successful.
• Kc =
• Note: solids (s) and pure liquids (l) do not have concentrations so is
not represented in Kc formula.
• In the chemical equation: aA(g) + bB(aq) ⇌ cC(aq) + dD(g)
• Kc =
Examples of Kc formulae
1. CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)
Kc =
2. 2A(g) + 3B(aq) ⇌ C(g) + 2D(g)
Kc =
3. H2(g) + I2(g) ⇌ 2HI(g)
Kc =
4. CaCO3(s) ⇋ CaO(s) + CO2(g)
Kc = [CO2]
5. P4(s) + 6Cℓ2(g) ⇋ 4PCℓ3(ℓ)
Kc =
Factors that influence the equilibrium
constant
1. Only the concentrations of aqueous solutions (aq) and gases (g)
appear in the Kc expression
2. Solids (s) and pure liquids (ℓ) are NOT included in the Kc
expression.
3. The value of Kc DOES change if the temperature of the system
changes.
4. The value of Kc DOES NOT change if:
• the pressure in the system changes;
• the concentration of a reactant or product in the system changes;
• a catalyst is added to the system.
Calculating Kc
Example 5
2SO2(g) + O2(g) ⇋ 2SO3(g)
When equilibrium is reached, it is found that there are 2 moles of SO2, 3
moles of O2 and 6 moles of SO3 in a 500cm3 container. Find the value of
the equilibrium constant.
Solution: volume of container = 500/1000 = 0.5dm3
Concentration of SO2 = = = 4 mol.dm-3
Concentration of O2 = = = 6 mol.dm-3
Concentration of SO3 = = = 12 mol.dm-3
Kc = = = 1.5
Example 6
• Exactly 8 mol SO2 and 10 mol O2 are sealed in a 500 cm3 reaction
vessel which is initially empty. The compounds react to produce SO3.
At equilibrium, the vessel contains 6 mol SO3.
• 2SO2(g) + O2(g) ⇋ 2SO3(g) Find the equilibrium constant.
• Solution: volume of container = 500/1000 = 0.5dm3
Construct
• Balanced the table2SO
equation below:
O2 2SO2 3

Moles at the beginning 8 10 0

• Moles
2SO 3
lost/formed in
reaction
Moles at equilibrium 6
Concentration at
equilibrium
Example 6 continued
• At the beginning there was zero moles of SO3 and at the end there
was 6 moles. This means 6 – 0 = 6 moles of SO3 was formed in the
reaction.
• The moles lost/formed must be proportional
to the balanced equation.
• We subtract to get the moles at equilibrium.
• We then use c = n/v = n/0.5 to get concentration
• at equilibrium.
Example 6 continued
• Now we can calculate Kc.
• Kc = = = 0.64
Example 7
• 6 moles of N2 and 7 moles of H2 are placed in a sealed 250cm3 beaker
at 300K. They react to form NH3 as follows:
• N2 (g) + 3 H2(g) ⇋ 2NH3(g). At equilibrium there are 4 moles of N2.
Determine the value of Kc.
• Solution: volume = 250/1000 = 0.25dm3
• Table:
Example 7 continued
• Subtract 6 – 4 = 2 to get number of moles of N2 used in the reaction.
• The moles lost/formed must be proportional to balanced equation.
• H2: 2/1 x 3 = 6
• NH3: 2/1 x 2 = 4
• Subtract reactants and add products to get the number of moles at equilibrium.
• Use c = n/v = n/0.25 to get concentration at equilibrium
Example 7 continued
• Now we calculate Kc.
• Kc = = = 0.25
• Kc does not have a unit
Example 8
• 0.4 moles of H2 gas and excess sulphur are placed is a sealed 2dm3 container at a
temperature of 350K. At equilibrium the value of Kc is 6.8x10-2. Find the number
of moles of H2S at equilibrium.
• H2(g) + S(s) ⇋ H2S(g)
• Solution: volume = 2dm3 – no need to divide
• Ignore S(s) because it is a solid.
• Table:
Example 8 continued
• Let the number of moles of H2 participating in the reaction be x.
• If we look at the balanced equation, the number of moles of H2S
formed in the reaction will also be x.
• We add and subtract to get moles at equilibrium.
• Concentration = n/v = n/2.
Example 8 continued
• Now for Kc:
• Kc =
• 6.8 x 10-2 =
• 6.8 x 10-2 =
• 6.8 x 10-2 (0.4-x) = x
• 0.0272 – 0.068x = x
• 0.0272 = 1.068x
• x = 0.025 moles
Graphs for chemical systems in equilibrium
• Equilibrium in a chemical system can be represented by a graph of:
1. reaction rate versus time

2. amount of each reagent (number of moles / mass / volume)

3. concentration of each reagent versus time.

In all of these graphs time will be the independent horizontal axis.

Reaction rate vs time graph
• The forward reaction starts off fast and rate decreases.
• The reverse reaction rate increases slowly from zero.
• When the rates are equal equilibrium is reached.
Concentration vs time
The concentration of reactants start high and decrease.
The concentration of products start at zero and increase.
When equilibrium is reached, it levels out but the concentrations of
substances are not the same.
We thus have different horizontal lines – one for each reactant and
product.
How changes at Equilibrium affects the graphs
• When a change is made after equilibrium is reached, the reaction
responds and a new equilibrium is reached.
• We will look at graph changes caused by:
1. TEMPERATURE
2. CONCENTRATION
3. PRESSURE
4. CATALYST
HOW TEMPERATURE CHANGE AFFECTS EQULIBRIUM

• An increase in temperature makes both reactions faster, however it

makes the endothermic reaction much faster and the exothermic
reaction a little faster.
HOW TEMPERATURE CHANGE AFFECTS EQULIBRIUM
• A decrease in temperature makes both reactions slower, however it
makes the endothermic reaction much slower and the exothermic
reaction a little slower.
How adding a reactant changes equilibrium
• An increase in the concentration of a REACTANT will only increase the
FORWARD REACTION and a new equilibrium will be established.
How removing a product affects equilibrium
• Removal of product decreases the reverse reaction dramatically and
thus favours the forward reaction.
How an increase in pressure affects equilibrium
• An increase in pressure favours the reaction producing the least moles.
• Example: 2SO2(g) + O2(g) ⇋ 2SO3(g)
• The forward reaction produces 2 moles of gas.
• The reverse reaction produces 3 moles of gas.
• An increase in pressure favours the forward reaction
How a decrease in pressure affects equilibrium
• An decrease in pressure favours the reaction producing the most moles.
• Example: 2SO2(g) + O2(g) ⇋ 2SO3(g)
• The forward reaction produces 2 moles of gas.
• The reverse reaction produces 3 moles of gas.
• An decrease in pressure favours the reverse reaction
How a catalyst affects equilibrium
• A catalyst makes both forward and reverse reaction faster but does
not favour.
SUMMARY OF GRAPH EQUILIBRIUM CHANGES
How changes affect concentration of reactants and products
Example 9
• Nitrogen and oxygen gases react in a sealed container according to
the following equation: O2(g) + N2(g) ⇋ 2NO(g)
• After the reaction reaches equilibrium, certain changes are made. The
following graph of rate of reaction versus time represents the
situation.
Example 9 continued
(a) Write the equation for the solid line.
O2(g) + N2(g) → 2NO(g)
note the single arrow
(b) Write the equation for the dotted line.
2NO(g) → O2(g) + N2(g)
(c) What is happening between the 10th and 15th minutes?
The system is in equilibrium
(d) What change took place at 15 minutes? Give reason.
Temperature was decreased. Both reaction rates decreased, but
reverse reaction decreases more.
Example 9 continued
(e) Is ∆H positive or negative?
• The temperature was decreased.
• The reverse reaction rate decreased more than the forward reaction.
• The forward reaction was thus favoured.
• Le Chatelier says a decrease in temperature favours an EXOTHERMIC REACTION.
• THE FORWARD REACTION IS THUS EXOTHERMIC.
• ∆H IS THEREFORE NEGATIVE
(f) How will this change in temperature affect Kc?
• The forward reaction is being favoured.
• This means product concentrations (numerator) increase and reactant concentrations
decrease.
• Kc =
• Kc will increase.