Chemistry Unit 4 Part 3 Reallyacademics

IAL Edexcel Chemistry Unit 4 (WCH14):
Rates, Equilibria and Further Organic Chemistry

(Part 3/5)
REALLYACADEMICS
Preface
● This series will be divided into 5 parts corresponding to the 5 topics in the 2018
specification
○ PART 1 - TOPIC 11: Kinetics
○ PART 2 - TOPIC 12: Entropy and Energetics
○ PART 3 - TOPIC 13: Chemical Equilibria
○ PART 4 - TOPIC 14: Acid-base Equilibria
○ PART 5 - TOPIC 15: Organic Chemistry: Carbonyls, Carboxylic Acids and Chirality
● This series will provide you with a means of last minute revision on [WCH14] IAL
Edexcel Chemistry Unit 4
● This series will aim to provide you with an revision in under 50 MINS
● All information here is a summary of the New Specification Book
● This series will not serve as a primary study material but as an adjunct to help you
recall and prepare as a last minute revision
● YOU CAN ALSO SUPPLEMENT THIS WITH MY OTHER VIDEOS ON FREQUENTLY ASKED
QUESTIONS OF UNIT 4
Syllabus
1. Be able to deduce an expression for Kc , for homogeneous and heterogeneous systems, in terms of
equilibrium concentrations
2. Be able to deduce an expression for Kp for homogeneous and heterogeneous systems, in terms of
equilibrium partial pressures in atm
3. Be able to calculate a value, with units where appropriate, for the equilibrium constants (K c and Kp) for
homogeneous and heterogeneous reactions, from experimental data
4. Understand how, if at all, a change in temperature, pressure or the presence of a catalyst affects the
equilibrium composition in a homogeneous or heterogeneous system
5. Understand that the value of the equilibrium constant is not affected by changes in concentration or
pressure or by the addition of a catalyst
6. Know the effect of changing the temperature on the equilibrium constant (K c and Kp) for both exothermic
and endothermic reactions
7. Understand that the effect of temperature on the position of equilibrium is explained using a change in
the value of the equilibrium constant
8. Understand the effect of a change in temperature on:
a. The value of ∆Stotal
b. The magnitude of the equilibrium constant, since ∆Stotal = R lnK
9. Be able to apply knowledge of the value of equilibrium constants to predict the extent to which a reaction
takes place
1. Be able to deduce an expression for Kc , for homogeneous
and heterogeneous systems, in terms of equilibrium
concentrations
2. Be able to deduce an expression for Kp for homogeneous
and heterogeneous systems, in terms of equilibrium
partial pressures in atm
3. Be able to calculate a value, with units where appropriate,
for the equilibrium constants (Kc and Kp) for homogeneous
and heterogeneous reactions, from experimental data
Equilibrium constant Kc
● A number that expresses the relationship between the amounts of
products and reactants present a equilibrium in a reversible chemical
reaction at a given temperature
● There are two ways of obtaining a value for the equilibrium constant:
○ The first is by experimentation
○ The second is by calculation using thermodynamic equations
● For a general reaction:
Finding equilibrium constant Kc in homogeneous reactions
● A homogeneous reaction is one in which all the reactants and products
are in the same phase.
● Example in the next slide:
Example 1
1. 2.00 mol of ethanoic acid and 2.00 mol of ethanol are mixed and allowed to
reach equilibrium with ethyl ethanoate and water at 298 K. The amount of
ethanoic acid at equilibrium is found to be 0.67 mol. Calculate Kc for the
reaction at 298K.
Example 2
1. 0.100 mol of N2O4 is placed into a 0.100 dm3 flask and allowed to reach
equilibrium with NO2 at 398K. At equilibrium, there is 0.071 mol of N 2O4.
Calculate Kc at this temperature.
Finding equilibrium constant Kc in heterogeneous reactions
● Heterogeneous reactions in which at least one of the reactants and/or
products is in a different phase to the others.
● For example:
○ The equation would be:
○ However, the conc. of a solid at a given temperature is determined by its density, which
has a constant value. Hence, the expression can be simplified to:
Example Question 1
The equilibrium constant, Kc, for the reaction:
has a value of 4.92 x 10-5 mol dm-3 at 700 K.

A mixture of water vapour and carbon is heated to 700 K in a closed vessel
and allowed to reach equilibrium with hydrogen and carbon monoxide.
Write an expression for Kc and use it to calculate the equilibrium
concentration of H2 and CO in the above equilibrium mixture, at 700 K, when
the equilibrium concentration of H2O is 2.00 x 10-2 mol dm-3.
Example Question 1: Answer
Finding equilibrium constant Kp in a homogeneous reaction
● For reversible reactions involving gases we can express the concentrations of
the reactants and products in terms of their partial pressures.
● Partial pressure is the pressure that the gas would exert if it alone occupied
the volume of the mixture.
● The total pressure is equal to the same of all partial pressures:
● The general reaction:
○ The Kp equation would be

Calculating partial pressures
● The partial pressure of an individual gas in a mixture of gases is calculated
by multiplying its mole fraction by the total pressure, for example:
○ Where xA = the mole fraction of gas A in the mixture

Example Question 1
1. 1.00 mol of PCl5 vapour is heated to 500K in a sealed vessel. The
equilibrium mixture, at a pressure of 6 atm, contains 0.60 mol of chlorine.
Calculate Kp for the reaction:
Example Question 2
The reaction between carbon monoxide and chlorine to form phosgene,
COCl2, is reversible. The equation for the reaction is:
Some carbon monoxide and chlorine are allowed to react and reach a position
of equilibrium. The equilibrium partial pressures of the mixture are:
A. What is meant by the term ‘partial pressure’?

B. Write an expression for Kp for this reaction and calculate its value, giving
the units, if any.
A. The pressure that an individual gas would exert if it alone occupied the
total volume of the gaseous mixture.
Finding equilibrium constant Kp in heterogeneous reactions
● Solids that are in equilibrium with gases are not considered in the K p
equation.
● Consider the reaction:
○ The equilibrium constant in terms of partial pressures is given by:
○ This equation suggests that for a particular temperature, the pressure of carbon dioxide
in the equilibrium mixture is constant regardless of the masses of calcium carbonate and
calcium oxide present.
4. Understand how, if at all, a change in temperature, pressure or the
presence of a catalyst affects the equilibrium composition in a
homogeneous or heterogeneous system
5. Understand that the value of the equilibrium constant is not
affected by changes in concentration or pressure or by the addition of
a catalyst
6. Know the effect of changing the temperature on the equilibrium
constant (Kc and Kp) for both exothermic and endothermic reactions
7. Understand that the effect of temperature on the position of
equilibrium is explained using a change in the value of the
equilibrium constant
Factors affecting Kc and Kp
● The values of Kc and Kp are not affected by concentration or pressure change or by the use of a
catalyst. However, they are affected temperature change.
● Concentration and pressure changes and the addition of a catalyst affect the rate of the
reaction but not the position of the equilibrium.
● Temperature affects the position of the equilibrium by changing the position of the
equilibrium.
● If the forward reaction is exothermic, an increase in temperature will decrease the rate of the
forward reaction because the equilibrium shifts to the left to oppose the change.
○ This will decrease the concentrations of products and increase the concentrations of reactants, therefore the
equilibrium constant (Kc or Kp) decreases
● If the forward reaction is endothermic, an increase in temperature will increase the rate of the
forward reaction because the equilibrium shifts to the right to oppose the change.
○ This will increase the concentration of products and decrease the concentrations of reactants, therefore the
equilibrium constant increases
Example Question 1
A dynamic equilibrium is set up between carbon monoxide, hydrogen and
methanol. The equation for the reaction is:
State the effect that an increase in pressure, at constant temperature, has on

the value of Kc and also on the position of equilibrium. Justify your answers.
A dynamic equilibrium is set up between carbon monoxide, hydrogen and methanol. The equation
for the reaction is:
State the effect that an increase in pressure, at constant temperature, has on the value of K c and also
on the position of equilibrium. Justify your answers.
Answer
● The value of Kc will not change, since its value changes only with a change in temperature.
● If the pressure is increased, then the volume of the reaction mixture will decrease. This will
result in an instantaneous equal increase in the concentration of each component.
● However, the increase in the magnitude of [CH3OH(g)][H2(g)]2 will greater than the increase in
the magnitude of [CH3OH(g)]
● So, the value of the expression will temporarily decrease
● In order to return its value to that of Kc, the equilibrium has to shift to the right, to increase the
magnitude of the numerator.
Example Question 2
A dynamic equilibrium is set up between carbon monoxide, hydrogen and methanol.
The equation for the reaction is:
When the reaction is carried out at a higher temperature, the value of Kc decreases.
Explain whether the forward reaction is exothermic or endothermic.
A dynamic equilibrium is set up between carbon monoxide, hydrogen and methanol.
The equation for the reaction is:
When the reaction is carried out at a higher temperature, the value of Kc decreases.
Explain whether the forward reaction is exothermic or endothermic.
Answer
● If Kc has decreased, then the position of equilibrium has moved to the left.
Since the shift has been caused by an increase in temperature, the
reverse reaction must be endothermic. Hence, the forward reaction must
be exothermic
Understand the effect of a change in temperature on:
A. The value of ΔStotal
B. The magnitude of the equilibrium constant, since
ΔStotal = R lnK
Be able to apply knowledge of the value of equilibrium
constants to predict the extent to which a reaction takes
place
Effect of temperature change on the value of ΔStotal
● There is very little change in ΔSsystem with a change in temperature,
unless there is a change in state of one of the reactants or products.
● However, there are significant changes to ΔSsurroundings because the
reaction is given by:
Example
The decomposition of calcium carbonate into calcium oxide and carbon dioxide at different temperatures
At 293 K (20oC)
At 1173K (900oC)
So the decomposition of calcium carbonate is not spontaneous at 293 K, but it is when heated to 1173 K
Gibbs free-Energy (ΔG)
● ΔG is an indicator of reaction feasibility. ΔG (free energy change) is related
to equilibrium constant, K:
○ This shows that reactions are feasible when the reaction has a large value for the
equilibrium constant. It is therefore possible to predict the feasibility of a reaction at a
known temperature if the equilibrium constant is known.
● The relationship of ΔStotal to equilibrium constant is given by the
equation:
Example Questions
Example Question 1
Nitrogen and hydrogen react together to form ammonia in a reversible reaction that
can reach a position of equilibrium. The equation for the reaction is:
At a fixed temperature and a total pressure of 5.00 atom, a sealed vessel of volume
20.0 dm3 contained 1.00 mol of N2(g), 2.00 mol of H2(g) and 1.00 mol of NH3(g)
A. Calculate the value, stating units, of the equilibrium constant, Kc, for this
reaction.
B. Calculate the value, stating units, of the equilibrium constant, Kp, for this
reaction.
Example Question 2
The composition of an equilibrium mixture produced at 2 atm pressure is
shown here:
A. Give the expression for the equilibrium constant, Kp, for the reaction and
calculate its value. Include units in your answer.
B. The total entropy change, in J mol-1 K-1, is related to the equilibrium
constant by the equation shown below. Calculate the total entropy
change for this reaction. (R=8.31 J mol-1 K-1)
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IAL Edexcel Chemistry Unit 4 (WCH14):

Rates, Equilibria and Further Organic Chemistry

○ The equation would be:

has a value of 4.92 x 10-5 mol dm-3 at 700 K.

● The general reaction:

○ The Kp equation would be

○ Where xA = the mole fraction of gas A in the mixture

A. What is meant by the term ‘partial pressure’?

○ The equilibrium constant in terms of partial pressures is given by:

State the eﬀect that an increase in pressure, at constant temperature, has on

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