Chapter vi

chemical equilibrium
Physical Chemistry II (Extended)
EPHC2P0
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CHAPTER 6 OUTLINE
6.1 Describing a Dynamic Chemical Equilibrium
6.2 Homogeneous & Heterogeneous Equilibria
6.3 Applying Stoichiometry on a Chemical Equilibrium Mixtures
6.4 The Equilibrium Constants (Kc and Kp)
6.5 Equilibrium Constants (Kc ) Calculations
6.6 Determining the Equilibrium Concentrations
6.7 Determining the Equilibrium Concentrations – Quadratic Equations
6.8 Reaction Quotient: Predicting the Direction of the Reaction
6.9 Changing the Reaction Conditions: Le Chatelier’s Principle
6.9.1 Removing Products or Adding Reactants
6.9.2 Changing Pressure and Temperature
6.9.3 Effect of a Catalyst
Chapter 6 - Chemical Equilibrium 2
6.1 Chemical Equilibrium
• Chemical Equilibrium: is the state reached by a reaction mixture when two opposing
reactions (forward and reverse reactions) occur at the same time and rate and become equal.

• These reversible reactions never go to completion. Given a General: aA + bB cC + dD

Chapter 6 - Chemical Equilibrium 3

6.1 The Concept of Chemical Equilibrium
• Therefore, Chemical Equilibrium occurs when the forward and reverse reactions
proceed at the same rate.
• Once the equilibrium is achieved, the amount of each reactant and product remains
constant.
• Consider the following decomposition for a system at Equilibrium:

Chapter 6 - Chemical Equilibrium 4

6.2 Homogenous and Heterogeneous Equilibria
• Homogeneous Equilibrium – is an equilibrium that involves reactants & products which
are in a single-phase. Example: Catalytic Methanation equation:-
CO (g) + 3H2 (g) CH4 (g) + H2O (g)

• Heterogeneous Equilibrium – is an equilibrium that involves reactants & products which

are in more than one phase. Example: Iron filings reacting with steam to produce Iron oxide:
3Fe (s) + H2O (g) Fe3O4 (s) + 4H2 (g)
• Note: The concentrations of pure solids and liquids are omitted in the equilibrium-constant
expressions.

Chapter 6 - Chemical Equilibrium 5

6.3 Applying Stoichiometry on Equilibrium Mixtures
1. Suppose CO and H2 react according to the following reaction: CO(g) + H2 (g) CH4(g) + H2O (g)
When 1.0 mol of CO and 3.0 mol H2 are placed in 10.0 L vessel at 1200 K and allowed to come to
equilibrium the mixture is found to contain 0.387 mol of H2O. Calculate the molar concentration of
each of the substances present in the equilibrium mixture.

2. Consider the reversible reaction of SO2 with oxygen to form sulfur trioxide at 1500 K as follows:
SO2 (g) + O2 (g) 2SO3 (g)
Suppose 0.400 mol of SO2 and 0.200 mol of O2 are injected into a closed 1.00 L container. When
equilibrium is established, 0.056 mol of SO3 has been formed. Determine the molar concentrations of
the equilibrium mixture.

3. For a reverse reaction, 0.50 mol of SO3 is introduced in a 1.00 L container and 0.212 mol of O2 is
formed. Calculate the equilibrium concentrations for the reaction.
Chapter 6 - Chemical Equilibrium 6
6.3 Practice Exercise Solution

Chapter 6 - Chemical Equilibrium 7

6.3 Practice Exercise Solution Continued
1. Alternatively

Chapter 6 - Chemical Equilibrium 8

6.4 The Equilibrium Constants (Kc and Kp)

6.4.1 Equilibrium Constant (Kc)

It is the value obtained for the equilibrium–constant expression when the equilibrium
concentrations are substituted. Kc might have no units.

Given the balanced general equation: aA + bB cC + dD

• Kc = [C]c[D]d
[A]a[B]b

Chapter 6 - Chemical Equilibrium 9

6.4.1 Express the Equilibrium Constant (Kc) Exercises
1. CO (g) + 3H2(g) CH4 (g) + H2O (g)
2. CH4 (g) + H2O (g) CO (g) + 3H2(g)
3. N2 (g) + 3H2 (g) 2NH3 (g)
4. ½ N2 (g) + 3Τ2 H2 (g) NH3 (g)
5. 2NO2 (g) + 7H2 (g) 2NH3(g) + 4H2O (g)

Practice Exercise Solution:

1. CO (g) + 3H2(g) CH4 (g) + H2O (g)

Chapter 6 - Chemical Equilibrium 10

6.4.2 Equilibrium Constant (Kp)
6.4.2 Equilibrium constant (Kp) – is an equilibrium constant for a gaseous reaction, similar to
Kc, but in which concentrations of gases are replaced by partial pressures (in atm).

Consider the following catalytic methanation equation:

CO(g) + 3H2(g) CH4(g) + H2O (g)

The equilibrium expression in terms of partial pressures becomes:

Kp = ꝭCH4.ꝭH2O
ꝭCO.ꝭH23

The value of Kp is different from that of Kc.

From the relationship PV = nRT; Kp = Kc (RT)∆n and

∆n = nproducts – nreactants

Chapter 6 - Chemical Equilibrium 11

6.4 Equilibrium Constant (Kc & Kp) Calculations
1. For the Catalytic Methanation equation:- CO (g) + 3H2 (g) CH4 (g) + H2O (g)

Kc = 3.92, R = 0.0821 L.atm/(K.mol) and T is 1200 K. Determine Kp.

2. In the synthesis of ammonia from nitrogen and hydrogen Kc = 9.60 at 300oC

N2 (g) + 3H2(g) 2NH3 (g). Calculate Kp for this reaction.

3. For the equation: 2SO3(g) 2SO2 (g) + O2 (g) at a temperature of 1000 K, Kc has the value of

4.08 x10-3. Calculate the value of Kp

• Practice Exercise Solution

Chapter 6 - Chemical Equilibrium 12

6.5 Equilibrium Constants (Kc ) Calculations:
1. Nitrogen and hydrogen are placed in a empty 5.00 L container at 500oC. When equilibrium
is established; 3.01 mol of N2 (g), 2.10 mol of H2 (g) and 0.565 mol of NH3 are present.
Evaluate Kc for the following reaction at 500oC: N2 (g) + 3H2 (g) 2NH3 (g)

2. When 10.0 moles of N2O are put into a 2.0 L container at some temperature, where it decomposes
according to: 2N2O (g) 2 N2 (g) + O2 (g). At equilibrium, 2.20 mol of N2O remain.
Calculate the value of Kc for the reaction.

3. Hydrogen iodide, HI, decomposes at moderate temperatures according to the equation:

2HI(g) H2 (g) + I2(g). When 4.00 mol HI was placed in a 5.00 L vessel at 458oC. The
equilibrium mixture was found to contain 0.442 mol I2. Determine the Kc for the decomposition of
HI at this temperature.

4. Hydrogen sulfide dissociates as follows: 2H2S(g) 2H2(g) + S2 (g). When 0.10 mol H2S
was put in a 10 L vessel and heated to 1132oC, it gave an equilibrium mixture containing
0.0285 mol H2.
Chapter 6 - Chemical Equilibrium 13
6.5 Equilibrium Constants (Kc ) Practice Exercise
1. Solution

Chapter 6 - Chemical Equilibrium 14

6.6 Determining the Equilibrium Concentrations
1. A gaseous mixture contains 0.30 mol CO, 0.1mol H2 and 0.020 mol H2O plus an unknown amount
of CH4 in each liter. Calculate the concentration of CH4 in this mixture at 1200 K. The equilibrium
constant (Kc ) is 3.92.
2. Phosphorus pentachloride, PCl5 gives an equilibrium mixture of PCl3 and Cl2 when heated:
PCl5 PCl3 + Cl2 . A 1.00 L vessel contains an unknown amount of PCl5 and 0.020 mol each of
PCl3 and Cl2 at equilibrium and the temperature is 250oC. Calculate the number of moles of PCl5 that
are in the vessel if Kc for this reaction is 0.0415 at 250oC.

3. An equilibrium mixture in a 1.00 L container contains 0.25 mol of PCl5 and 0.16 mol of PCl3.
Calculate the equilibrium concentration of Cl2 present and Kc = 1.9: PCl3 + Cl2 PCl5

4. For the following reaction: Kc = 49.0 at a certain temperature. If 0.40 mol of each A and B are placed
in a 2.0 L container at that temperature. Calculate the concentrations of all the species that are
present at equilibrium. Chapter 6 - Chemical Equilibrium 15
6.6 Determining the Equilibrium Concentrations
• Practice Exercise Solution

Chapter 6 - Chemical Equilibrium 16

6.7 Determining Equilibrium Concentrations – Quadratic Equations

−𝑏± 𝑏2 −4𝑎𝑐
Remember, according to the Quadratic Equation: 𝑥=
2𝑎

1. Hydrogen and Iodine react according to the equation:H2(g) + I2(g) 2HI(g). Suppose 1.00
mol of H2 and 2.00 mol of I2 are placed in a 1.00 L vessel. Calculate the number of moles of
substances in the gaseous mixture when it comes to equilibrium at 458oC and Kc = 49.7.

2. Consider A + B ↔ C + D at a certain temperature. If 0.600 mol of A and 0.200 mol of B are

mixed in a 2.0 L container and allowed to reach equilibrium. Calculate the equilibrium
concentration of all the species and Kc = 49.0.

3. Phosphorus pentachloride, PCl5 gives an equilibrium mixture of PCl3 & Cl2 when heated:
PCl5 PCl3 (g) + Cl2 (g). Determine the equilibrium composition of the gaseous mixture at
160oC if the initial concentration of PCl5 is 1.0 mol/L and Kc = 0.0211.
Chapter 6 - Chemical Equilibrium 17
6.7 Determining Equilibrium Concentrations – Quadratic Equations

Practice Exercise Solution

Chapter 6 - Chemical Equilibrium 18

6.7 Determining Equilibrium Concentrations – Quadratic Equations
• Practice Exercise Solution Continued…

Chapter 6 - Chemical Equilibrium 19

6.8 Reaction Quotient (Qc)
• It is an expression that has the same form as the equilibrium – constant expression but
whose concentration values are not necessarily those at equilibrium.
• It is the mass action expression under any set of conditions (not necessarily at equilibrium).
• Its magnitude is relative to Kc and it determines the direction in which the reaction must
occur to establish equilibrium.

For the Balanced General Equation: aA + bB cC + dD

• Qc = [C]ci [D]di
[A]ai [B]bi Where i indicates concentrations at a particular instant.

Chapter 6 - Chemical Equilibrium 20

6.8 Reaction Quotient (Qc) – Continued…
• If Qc > Kc The reaction will go to the Left. The Reverse reaction predominates or prevails
until equilibrium is established. More Reactants will be formed.
• If Qc = Kc The reaction mixture is At Equilibrium.
• If Qc < Kc The reaction will go to the Right. The Forward reaction predominates or prevails
until equilibrium is established. More Products will be formed.

Chapter 6 - Chemical Equilibrium 21

6.8 Reaction Quotient (Qc) – Calculations
1. Suppose a gaseous mixture has the following composition at 1200 K: 0.0200 M CO, 0.020 M H2,
0.001 M CH4 and 0.001 M H2O: CO (g) + 3H2 (g) CH4 (g) + H2O (g) Determine the reaction
quotient (Qc) and the direction of the reaction when Kc = 6.25.
2. A 50.0 L vessel contains: 1.00 mol N2, 3.00 mol H2 and 0.500 mol NH3. Determine whether
ammonia will be formed or dissociated when the mixture goes to equilibrium, Qc = 19.68:
N2 (g) + 3 H2 (g) 2NH3 (g)
3. At a very high temperature, Kc = 65.0 for the following reaction: 2HI (g) H2 (g) + I2 (g)
The following concentrations were detected from the mixture: [HI] = 0.500 M, [H2 ] = 2.80 M and
[I2] = 3.40 M. Determine if the system is in equilibrium of not. If not, state the direction of the
reaction for the equilibrium to be established.
4. A 10.0 L vessel contains 0.0015 mol CO2 and 0.10 mol CO. Determine the direction of the reaction
if a small amount of carbon is added to this vessel and the temperature is raised to 1000oC. Also,
determine if more carbon dioxide will form or not. The reaction is CO2 (g) + C (s) 2 CO(g)
Chapter 6 - Chemical Equilibrium 22
6.8 Reaction Quotient (Qc) – Practice Exercise
1. Solution

Chapter 6 - Chemical Equilibrium 23

6.9 Disturbing a System at Equilibrium – Le Chatelier’s Principle

• Le Chatelier’s Principle states that when a system at equilibrium is disturbed/stressed by the

change in concentration, pressure or temperature, the system shifts in equilibrium
composition in the direction that reduces or counteracts this change of variable.
• Therefore, this is a guiding principle for the changes and disturbances in reaction conditions at
equilibrium.
• There are three ways to alter/change the equilibrium composition of a gaseous reaction
mixture and possibly increase the yield of the product:

1. Changing the Concentration by Moving Products Adding Reactants in a Reaction Vessel.

2. Changing Pressure and Volume of Gaseous Reactants and Products.
3. Changing Temperature

Chapter 6 - Chemical Equilibrium 24

6.9.1 By Changing the Concentration
(Removing Products or Adding Reactants) - TABLE

Chapter 6 - Chemical Equilibrium 25

6.9.1 By Changing the Concentration (Removing Products or Adding
Reactants) - EXERCISE

1. Predict the direction of the reaction when H2 is removed from a mixture (lowering its concentration)
in which the following equilibrium has been established: H2 (g) + I2 (g) 2HI (g)

2. Consider each of the following equilibria which are disturbed as indicated. Predict the direction of
the reaction.
(a) The equilibrium: CaCO3 (s) CaO (s) + CO2 (g) is disturbed by increasing the concentration of
CO2.
(b) The equilibrium: 2Fe (s) + 3H2O (g) Fe2O3 (s) + 3H2 (g) is disturbed by increasing the
concentration of hydrogen.

3. Predict the effect of each of the following changes on the amount of ammonia (NH3) present at
equilibrium:
(a) Forcing of adding more H2 into the system.
(b) Removing some NH3 from the system: N2 (g) + 3H2 (g) 2NH3 (g)
Chapter 6 - Chemical Equilibrium 26
 6.9.1 Practise Exercise
• Solution

Chapter 6 - Chemical Equilibrium 27

6.9.2 By Changing the Partial Pressure and Volume of
Gaseous Reactants and Products – TABLE

Chapter 6 - Chemical Equilibrium 28

6.9.2 By Changing the Partial Pressure and Volume of Gaseous Reactants
and Products - EXERCISE
1. Predict the effect of increasing the pressure by decreasing the volume given the following equilibrium:
N2 (g) + 3H2 (g) 2NH3 (g)

2. Make the same prediction for the following reaction: H2 (g) + I2 (g) 2HI (g)

3. Observe the following equations and decide whether an increase of pressure (obtained by decreasing the
volume) will INCREASE, DECREASE or HAVE NO EFFECT on the amounts of products.
(a) CO (g) + Cl2 (g) COCl2 (g)
(b) 2H2S (g) 2H2 (g) + S2 (g)
(c) C (graphite) + S2 (g) CS2 (g)

4. Determine if it is possible to increase the amount of the product in each of the following reactions by
increasing the pressure. Explain
(a)CO2 (g) + H2 (g) CO (g) + H2O (g)
(b)4CuO (s) 2Cu2O (s) + O2 (g)
(c)2SO2 (g) + O2 (g) 2SO3 (g)
Chapter 6 - Chemical Equilibrium 29
6.9.2 Practise Exercise
• Solution

Chapter 6 - Chemical Equilibrium 30

6.9.3 By Changing the Temperature – Table & Exercises

1. Carbon monoxide is formed when carbon dioxide reacts with solid carbon (graphite):
C (graphite) + CO2 (g) 2CO (g) ∆Ho = –172.5 kJ
Determine if high or low temperature will be more favorable for the formation of carbon monoxide.

2. Consider the possibility of converting CO2 and CO by the endothermic reaction:

CO2 (g) + H2 (g) CO (g) + H2O (g) ∆Ho = + 256.8 kJ
Determine if high or low temperature will be favorable for the formation of carbon monoxide.
Chapter 6 - Chemical Equilibrium 31
6.9.3 Practise Exercise
• Solution

Chapter 6 - Chemical Equilibrium 32

THE END!!!

Chapter 6 - Chemical Equilibrium 33