Chemical Equilibrium

Chapter 5
 Many chemical reactions do not go to
completion

In such reactions there are always at any

point during the reaction both reactants and
products present
Haber process
Haber process
 Haber process
• Reactions that can go in either direction (forwards- favouring product
formation, backwards- favouring reactant formation) are called
reversible (double arrow).
 Haber process

In reversible reactions
Equilibrium both the forward and
reverse reactions are
occurring.
Molar Concentration

N2

H2

NH3
Equilibrium is reached
when the rate of the
forward and reverse
reactions are the same.

Time
 Haber process

Equilibrium At equilibrium, the forward

and reverse reactions are
proceeding at the same
rate.
Rate

Time
 Chemical Equilibrium
• Chemical equilibrium exists when two reactions (forward and
backward reactions) occur simultaneously at the same rate.
• At equilibrium there is a mixture of both the reactants and products
present.
• Chemical equilibria are dynamic- the forward and reverse reactions
are still ongoing even when equilibrium has been reached.
 Haber process
• Haber could manipulate the equilibrium by applying
Le Chaterlier’s principle in the production of
ammonia and thereby increase the yield of this
commodity chemical.
• Le Chaterlier’s principle: “If a system at equilibrium is
disturbed by a change in temperature, pressure, or
the concentration of one of the components, the
system will shift its equilibrium position so as to
counteract the effect of the disturbance.”
 Stoichiometry and Chemical Equilibria
• When initial amounts of the reactants in a reaction and the
equilibrium amount of a reactant or product is known, the
concentrations or number of moles of all the reactants and products
at equilibrium can be determined by using the stoichiometry of the
equation.
Consider
2 SO2(g) + O2(g) 2 SO3(g)

Suppose 0.2 mol of SO2 and 0.1 mol of O2 are injected into a 1 dm3
container. The reaction proceeds until equilibrium is reached after
which it was found that 0.025 mol of SO3 had formed. How many moles
of each substance is present at equilibrium?
 Stoichiometry and Chemical Equilibria
Suppose 0.2 mol of SO2 and 0.1 mol of O2 are injected into a 1 dm3 container.
The reaction proceeds until equilibrium is reached and it was found that 0.025
mol of SO3 had formed. How many moles of each substance is present at
equilibrium?
2 SO2 + O2 2 SO3
I (initial n) 0.2 mol 0.1 mol 0
C (change in n) -2x -x +2x
E (n at equilibrium) (0.2 -2x) (0.1-x) 0.025

We know we have 0.025 mol SO3 at equilibrium therefore +2x = 0.025 mol SO3
Solve for x:
x = 0.025 mol SO3/ 2
x = 0.0125 mol SO3

At equilibrium, mol SO2= (0.2 - 0.025) = 0.175 mol SO2

mol O2 = (0.1-0.0125) = 0.0875 mol O2
 Problems
The following reaction was allowed to come to equilibrium:
CO(g) + H2O(g) CO2(g) + H2(g)
The initial amount of CO present in a 1 L container was 1.2 mol and 0.6
mol of H2O. At equilibrium 0.9 mol of CO was present. Determine the
number of moles of each compound present at equilibrium.
 Problems
The following reaction was allowed to come to equilibrium:
CO(g) + H2O(g) CO2(g) + H2(g)
The initial amount of CO present in a 1 L container was 1.2 mol and 0.6 mol of
H2O. At equilibrium 0.9 mol of CO was present. Determine the number of
moles of each compound present at equilibrium.

CO(g) + H2O(g) CO2(g) + H2(g)

I (initial n) 1.2 mol 0.6 mol 0 mol 0 mol

C (change in n) -x -x +x +x
E (n at equilibrium) (1.2-x) (0.6-x) (+x) (+x)

We know we have 0.9 mol CO at equilibrium therefore 1.2-x = 0.9 mol CO

Solve for x:
x = 1.2 – 0.9 = 0.3 mol CO

At equilibrium, mol H2O = (0.6 - 0.3) = 0.3 mol H2O

mol CO2 = 0.3 mol CO2
mol H2 = 0.3 mol H2
 The Equilibrium Constant, Kc
• The Equilibrium constant, Kc is defined as the mathematical product
of the equilibrium concentrations (in M) of the products, each raised
to the power that corresponds to the coefficient in the balanced
chemical equation, divided by the mathematical product of the
equilibrium concentrations of the reactants, each raised to the
power of the coefficients in the balanced equation.

• A general expression for Kc can be formulated using the following

reaction:

aA + bB cC + dD
This is called the
Equilibrium constant
expression!
 Take note for Kc
• To write a equilibrium constant expression, the reaction must be
balanced.
• The concentrations to be used in calculating Kc are the equilibrium
concentrations (M)
• The subscript c refers to concentration (Kc)
• The unit of Kc
• The value of Kc is unique for a particular reaction and temperature.
• For a reaction at constant temperature, Kc stays constant.

Products
Kc =
Reactants
 Problems
Write equilibrium constant expressions for Kc in each of the
following reactions:
N2O4(g) 2NO2(g)
SO3(g) + H2(g) SO2(g) + H2O(g)
N2(g) + 3H2(g) 2NH3(g)
 Problems
Write equilibrium constant expressions for Kc in each of the following
reactions:
N2O4(g) 2NO2(g)

SO3(g) + H2(g) SO2(g) + H2O(g)

2 2

3 2

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

3

2 2
 Calculating Equilibrium constants
• If the equilibrium concentrations are known, the value of Kc can be
determined by substituting the equilibrium concentrations into the
expression for Kc.
Consider:
An equilibrium mixture of N2, H2 and NH3 at 200 °C had [N2]= 0.20 M, [H2]=
0.07 M and [NH3]= 0.06 M. Calculate the equilibrium constant.
N2(g) + 3H2(g) 2NH3(g)

Does Kc have a unit? Let us consider and see what

happens, Kc has the unit M-2. Do you agree with me? However
you will notice in your textbook that Kc has no units, it is called
dimensionless. Do you agree with this?
 What does the value of Kc mean?
• If Kc >>1: Equilibrium lies to the right, products are favoured
• If Kc <<1: Equilibrium lies to the left, reactants are favoured

Products
Kc >>1
Reactants

Reactants Kc <<1
Products
 Calculating Equilibrium constants
SO3 and H2 are mixed in a container of fixed volume. Their initial concentrations are
0.02 M and 0.03 M respectively. When the reaction has reached equilibrium there was
found to be 0.002 M SO2. Calculate the equilibrium constant for the reaction.
SO3(g) + H2(g) SO2(g) + H2O(g)

2
3
2
2
 Problems
0.5 mol N2O4 was placed in a 1.0 dm3 container and heated to produce
NO2, the reaction reached equilibrium and it was determined that
there was 0.15 mol of NO2 present. Calculate the equilibrium constant
for the reaction.
N2O4(g) 2NO2(g)
 Problems
0.5 mol N2O4 was placed in a 1.0 dm3 container and heated to produce NO2, the
reaction reached equilibrium and it was determined that there was 0.15 mol of NO2
present. Calculate the equilibrium constant for the reaction.
Convert mol to concentration, because it’s a 1L container the mole values are
numerically equal to concentration.

N2O4(g) 2NO2(g)

2
2 4

2
2

0.01323
 The Equilibrium Constant, Kp and the
relation to Kc
• The concentrations of reactants and products in the gas phase can
also be expressed using their partial pressures.
• There is a direct relationship between the pressure and
concentration of a gas as illustrated in the ideal gas law.

In the above equation c= n/ V, the molar concentration, R =8.314 L.

kPa/ mol. K (the ideal gas constant) and T= temperature in Kelvin.
 The Equilibrium Constant, Kp
• A general expression for Kp for the following reaction is:

aA + bB cC + dD

P is the equilibrium
partial pressures in
bar.
 Problems
Write equilibrium constant expressions for Kp in each of the
following reactions:
N2O4(g) 2NO2(g)
SO3(g) + H2(g) SO2(g) + H2O(g)
N2(g) + 3H2(g) 2NH3(g)
 Problems
Write equilibrium constant expressions for Kp in each of the following
reactions:
N2O4(g) 2NO2(g)
2
𝑁𝑂

𝑁𝑂

SO3(g) + H2(g) SO2(g) + H2O(g)

𝑆𝑂 𝐻𝑂

𝑆𝑂 𝐻

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

2
𝑁𝐻
3
𝑁 𝐻
 Problems
Work through example 17-14 on page 261 in your textbook.
 The Equilibrium Constant, Kp and the
relation to Kc
• In general Kp is not equal to Kc since partial pressure is not equal to
concentration.
aA(g) + bB(g) cC(g) + dD(g)

• The equation that relates Kc and Kp is:

With ∆n = (c+d) – (a+b)

Kc=Kp only when the same number of moles of gas appears on the left
and right hand side of the equation (∆n=0)
 Problems
In the production of ammonia the pressures of all species was
determined at equilibrium (200 K) to be:
N2(g) + 3H2(g) 2NH3(g)
PNH3= 1 bar
PN2= 0.002 bar
PH2= 0.0013 bar
Calculate Kp and use the value to also calculate Kc for the reaction.
 Problems
In the production of ammonia the pressures of all species was
determined at equilibrium (200 K) to be:
N2(g) + 3H2(g) 2NH3(g)
PNH3= 1 bar, PN2= 0.002 bar, PH2= 0.0013 bar. Calculate Kp and use the
value to also calculate Kc for the reaction.
You can use the equilibrium constant expression: to calculate the value
of Kp. Remember Kp is in atm so convert bar to atm.
and 𝒑 𝒄
∆𝒏 , With ∆n = (n
gas products) – (ngas reactants) = (c) – (a+b) to calculate the
value for Kc. But, make Kc the subject of the equation.
Step 1: Calculate Kp
= = 2.336 x 1011

Step 2: Calculate Kc, check if the correct R value was used.

= 2.336 x 1011 x (0.0821 L.atm/mol.K x 200 K)-(2-4) = +2

Kc = 6.282 x 1013
 Problems
A mixture of CH4 and H2O is passed over a nickel catalyst at 1000 K. The
emerging gas is collected in a 5.00 dm3 flask and is found to contain
8.62 g of CO, 2.60 g of H2, 43.0 g of CH4 and 48.4 g of H2O. Assuming
that equilibrium has been reached, calculate Kc and Kp for the reaction.
 Problems
A mixture of CH4 and H2O is passed over a nickel catalyst at 1000 K. The emerging gas is
collected in a 5.00 dm3 flask and is found to contain 8.62 g of CO, 2.60 g of H2, 43.0 g of CH4
and 48.4 g of H2O. Assuming that equilibrium has been reached, calculate Kc and Kp for the
reaction.
Step 1: Balanced equation
CH4 (g) + H2O (g) CO(g) + 3H2(g)

Step 2: Calculate mol of all compounds and then calculate molarity of all compounds (NB!!!
even though I don’t include the formulas and units here, you should include it in all your
calculations NB!!!)
mol (CH4) = 2.681 mol, M(CH4) = 0.5362 M
mol (H2O) = 2.689 mol, M(H2O) = 0.5378 M
mol (CO) = 0.3079 mol, M(CO) = 0.06158 M
mol (H2) = 1.300 mol, M(H2) = 0.2600 M

Step 3: Calculate Kc
[ . ] [ . ]
= 0.003753
[ . ] [ . ]

Step 4: Calculate Kp
𝒑 𝒄
∆𝒏
, With ∆n = (ngas products) – (ngas reactants) = (c+d) – (a+b)
Kp = 0.003753 x (0.0821 L.atm/mol.K x 1000 K)4-2=2
Kp = 25.30
 Heterogeneous and Homogeneous
Equilibria
• When writing expressions for Kc and Kp the concentration terms for
pure solids (s) and liquids (l) are left out.
aA(g) + bB(s) cC(l) + dD(g)

aA(g) + bB(g) cC(l) + dD(s)

 Problems
Write Kc and Kp expressions for the following reactions:
C(s) + H2O(g) CO(g) + H2(g)
2HgO(s) 2Hg(l) + O2(g)
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)
CaCO3(s) CaO(s) + CO2(g)
 Problems
Write Kc and Kp expressions for the following reactions:
C(s) + H2O(g) CO(g) + H2(g)
,

2HgO(s) 2Hg(l) + O2(g)

,

Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)

,

CaCO3(s) CaO(s) + CO2(g)

,
 Reaction Quotient, Q
• At any point during the progress of a reaction (not at equilibrium)
it is possible to calculate the ratio of concentrations of products
and reactants.
• The ratio will have the same form as the equilibrium constant
expression but is called the reaction quotient, Q.
aA + bB cC + dD
 Reaction Quotient, Q
• If Qc= Kc then the reaction is at equilibrium.
• If Q < K the forward reaction (product formation) will be favoured
until equilibrium is reached (reaction will shift to the right).
• If Q > K, the reverse reaction (reactant formation) will be favoured
until equilibrium is reached (reaction will shift to the left).

Q K Q
K K
Forward Reverse
Q
Q <<Kc Q = Kc Q >>Kc
 Problems
At 450 °C, Kc= 50.5 for the reaction
H2(g) + I2(g) 2HI(g)
Predict in which direction the reaction needs to proceed in order to
reach equilibrium if there is 0.002 mol HI, 0.01 mol H2 and 0.05 mol I2
in a 1.5 dm3 container.
 Problems
At 450 °C, Kc= 50.5 for the reaction
H2(g) + I2(g) 2HI(g)
Predict in which direction the reaction needs to proceed in order to reach
equilibrium if there is 0.002 mol HI, 0.089 mol H2 and 0.05 mol I2 in a 1.5 dm3
container.
Step 1: convert moles to molarity (NB!!! even though I don’t include the
formulas and units here, you should include it in all your calculations NB!!!)
M (H2) = 0.05933 M
M (I2) = 0.03333 M
M (HI) = 0.001333 M

Step 2: calculate Qc
( . )
= 8.986 x 10-4
( . ) ( . )

Step 3: Make conclusion regarding values of Kc and Qc

Qc < Kc therefore, product formation is favoured until equilibrium is established
 Problems
Work through example 17-4 on page 243
 Calculating Equilibrium Concentrations
• It is possible to determine unknown equilibrium concentrations if Kc
is known.
Consider
A 1 litre flask is filled with 1 mol H2 and 1 mol I2 at 448 °C. The value for
Kc is known to be 50.5. What are the equilibrium concentrations of H2, I2
and HI?
H2(g) + I2(g) 2HI(g)
A 1 litre flask is filled with 1 mol H2 and 1 mol I2 at 448 °C. The value for
Kc is known to be 50.5. What are the equilibrium concentrations of H2, I2
and HI?
H2(g) + I2(g) 2HI(g)

x = 1.39 or x = 0.78 (cannot be 1.39, we only started with 1 M of H2, I2)

[H2]= (1-0.78)= 0.22 M
[I2]= (1-0.78)= 0.22 M
[HI]= 2(0.78)= 1.56 M
 Problems
Work through example 17-6 on page 244 and 245 and example 17-7
page 246
NB!!! Please make sure you understand these two examples because
you will get one of them (or both) or something similar in your tests (not
test, tests!!) NB!!!
 Effect of changes on the equilibrium,
Le Chatelier’s Principle
• Equilibrium reactions are dynamic.
• Le Chaterlier’s principle: “If a system at equilibrium is disturbed by
a change in temperature, pressure, or the concentration of one of
the components, the system will shift its equilibrium position so as
to counter act the effect of the disturbance.”
 Le Chatelier- Concentration Changes
• Concentration changes: If the equilibrium is disturbed by adding more
reactants to the system, the system will counteract the change by
reacting the additional reactants. Therefore the forward reaction
(product formation) is favoured (equilibrium will shift to the right).
 Le Chatelier- Concentration Changes
• Concentration changes: If the equilibrium is disturbed by removing
reactants from the system, the system will counteract the change
by favouring the reverse reaction (reactant formation) and thereby
replacing the lost reactants (equilibrium will shift to the left).
 Le Chatelier- Pressure Changes
• Pressure changes: If the Volume of the container is decreased- an
increase in pressure is exerted by the reactants and product
molecules. The system will try and counteract this change by
decreasing the number of molecules (the less molecules, the less
pressure is exerted). The system will move to the side that
represents fewer molecules.

Ratio of Molecules
Since the right hand side of
4:2 the reaction represents the
least amount of molecules,
when pressure is increased,
the forward reaction will be
favoured (equilibrium shifts
to the right).
 Le Chatelier- Pressure Changes
• Pressure changes: If the Volume is increased, the pressure will be
decreased in the system. The system will counteract this change
by favouring the side of the reaction that will increase the number
of molecules to try and maintain the initial pressure experienced
by the system.

Ratio of Molecules
4:2 When the pressure is
decreased, the system will
try and increase the
pressure again. In order to
do that, it will favour the
side of the reaction that
represents the most
amount of molecules.
Le Chatelier- Pressure Changes
Change Direction of Shift
Volume decrease, pressure Towards the smaller number of
increase moles of gas

Volume increase, pressure Towards the larger number of

decrease moles of gas

1 kg 2 kg
 Le Chatelier- Pressure Changes
Important to Remember
• Compounds in the liquid and solid phase are ignored when
determining the effect of pressure changes on the equilibrium.
• If the total pressure of a gaseous system is raised by merely adding
an inert gas (a gas that does not take part in the reaction) the
equilibrium is not disturbed because the partial pressures of each
of the reacting gasses remains constant.
 Le Chatelier- Temperature Changes
• Temperature changes: To determine the effect of temperature
changes on an equilibrium system, the enthalpy change (∆H) value is
taken into account.

• Enthalpy change is the heat energy change for a reaction.

• It is always indicated in the direction of the forward reaction (product
formation).
• If ∆H is positive, the net forward reaction is endothermic. Some of the
heat energy of the system is used to form the products and the
temperature of the system will decrease.
• If ∆H is negative, the forward reaction is regarded as exothermic and
the temperature of the system will increase.
• If the forward reaction is endothermic, the reverse reaction will
always be exothermic and vice versa.
 Le Chatelier- Temperature Changes

• In the above reaction the forward reaction has a negative ∆H value

indicating that this reaction is exothermic with the reverse reaction
being endothermic.
• Temperature changes: If the temperature was increased in the
system, the system will counteract this change by favouring the
reaction which will utilize the extra heat (endothermic reaction).
Therefore, the reverse reaction will be favoured for the above
reaction.
• Temperature changes: If the temperature is decreased of the system,
the reaction that will generate more heat will be favoured to replace
the missing heat and raise the temperature again. Therefore the
forward reaction will be favoured in the above reaction.
 Le Chatelier- Catalysts
• A catalyst is a substance that increases the rate of reactions without
participating in the reaction itself.
• Similarly in equilibrium systems, catalysts increase the rates of both
the forward and reverse reactions and allow equilibrium to be
reached faster.
• The rate of both the forward and reverse reactions increase equally.
• Catalysts do not result in a shift of the equilibrium to favour either
the forward or reverse reactions in equilibrium systems.
 Problems
Consider the following equilibrium system and state which reaction
(forward or reverse) will be favoured with each change
2SO2(g) + O2(g) 2SO3(g) ∆H= -99.1 kJ/mol
i) The container expands
ii) O2 is removed from the system
iii) SO3 is removed from the system
iv) The temperature is raised
v) A catalyst is added to the system
 Problems
Consider the following equilibrium system and state which reaction (forward or
reverse) will be favoured with each change
2SO2(g) + O2(g) 2SO3(g) ∆H= -99.1 kJ/mol

The container expands

The volume increases and pressure decreases, the reverse reaction will be
favoured because it has more moles of gas
O2 is removed from the system
Reverse reaction will be favoured, because the system will try to increase the
oxygen amount to reach equilibrium
SO3 is removed from the system
Forward reaction will be favoured, the system will try to replenish the SO3
concentration.
The temperature is raised
The reaction is exothermic, heat is released. The reverse reaction will be
favoured. Because the system will try to remove some of the extra heat.
A catalyst is added to the system
No change because the system is already at equilibrium. The catalyst does not
change Q or Kc.
 Problems
Work through example 17-8 on page 249, example 17-9 page 251 and
example 17-10 on page 254.