MODULE 2 CONT’D……………………

Perform calculations involving equilibrium constant

in terms of concentration, (Kc)

In some equilibrium calculations we may be given the amount, in grams or moles

present at equilibrium. When doing these calculations, we first need to calculate
the concentration of each of these substances.

EXAMPLE 1: In this example we are given the number of moles of each of the
reactants and products at equilibrium together with the volume of the reaction
mixture. Ethanol reacts with ethanoic acid to form ethyl ethanoate and water.

1. 500cm3 of the reaction mixture at equilibrium contained 0.235mol of

ethanoic acid and 0.0350mol of ethanol together with 0.182mol of ethyl
ethanoate and 0.182mol of water. Use this data to calculate a value of Kc
for this reaction.

STEP 1: Calculate the concentration of each substance in moldm-3.

Concentration of ethanoic acid:

If 500 cm3 contains 0.235 moles ethanoic acid

Then 1000 cm3 contains = 0.235 moles x 1000 cm3 = 0.470 moles

500cm3

Therefore, the concentration of ethanoic acid = 0.470 moldm-3

Concentration of ethanol:
If 500 cm3contains 0.0350moles of ethanol

Then 1000 cm3 contains = 0.0350 moles x 1000 cm3 = 0.070 moles

500cm3

Therefore, the concentration of ethanol = 0.070 moldm-3

Concentration of ethyl ethanoate:

If 500 cm3 contains 0.182 moles of ethyl ethanoate

Then 1000 cm3 contains = 0.182 moles x 1000 cm3 = 0.364 moles

500cm3

The concentration of ethyl ethanoate is 0.364 moldm-3

Concentration of water:

If 500 cm3 contains 0.182 moles of water

Then 1000 cm3 contains = 0.182 moles x 1000 cm3 = 0.364 moles

500cm3

The concentration of water is 0.364 moldm-3

STEP 2: Write the equilibrium constant for this reaction in terms of

concentrations.
STEP 3: Substitute the equilibrium concentrations into the expression.

STEP 4: Determine the units of the equilibrium constant:

EXAMPLE 2: In this example we are only given the initial concentrations of the
reactants and the equilibrium concentration of the product.

2. A mixture of 0.0500moldm–3 propanone and 0.0500moldm–3 hydrogen

cyanide is left to reach equilibrium at room temperature. At equilibrium
the concentration of the product is 0.0233moldm–3. Calculate Kc for this
reaction.

USING THE I.C.E. TABLE METHOD to calculate the concentration of the

reactants at equilibrium:

CH3COCH3 HCN CH3C(OH)(CN)CH3

Initial 0.0500 moldm-3 0.0500 moldm-3 0

concentration
Change in - 0.0233 - 0.0233 + 0.0233
concentration
Equilibrium 0.0267 moldm-3 0.0267 moldm-3 0.0233 moldm-3
concentration
Based on your balanced equation, for every 1 mole of CH3C(OH)(CN)CH3
(product) formed, 1 mole of CH3COCH3 is consumed.

Therefore, the concentration at equilibrium for CH3COCH3 is 0.0500 – 0.0233

moldm-3 = 0.0267 moldm-3

Based on your balanced equation, for every 1 mole of CH3C(OH)(CN)CH3

(product) formed, 1 mole of HCN is consumed.

Therefore, the concentration at equilibrium for HCN is 0.0500 – 0.0233

moldm-3 = 0.0267 moldm-3

STEP 2: Write the equilibrium constant for this reaction in terms of concentrations.

STEP 3: Substitute the equilibrium concentrations into the expression.

STEP 4: Determine the units of the equilibrium constant.

EXAMPLE 3: In this example we are given the initial and equilibrium
concentrations of the reactants but not the products.

3. 0.1000mol of ethyl ethanoate are added to 0.1000mol of water. A little

acid catalyst is added, and the mixture made up to 1dm3 with an inert
solvent. At equilibrium 0.0654mol of water are present. Calculate Kc for
this reaction.

Since the volume of the mixture is 1dm3, then initial concentration of ethyl
ethanoate and water is 0.1000 moldm-3.

USING THE I.C.E. TABLE METHOD to calculate the concentration of the

reactants and products at equilibrium:

CH3COOC2H5 H 2O CH3COOH C2H5OH

Initial 0.1000 moldm-3 0.1000 moldm-3 0 0

concentration
Change in - x - x +x +x

concentration
Equilibrium moldm-3 0.0654 moldm-3 moldm-3 moldm-3

concentration

Change in concentration of water can be calculated as:

Initial concentration – Change in concentration = Equilibrium concentration

0.1000 moldm-3 – x = 0.0654 moldm-3

x = 0.0346 moldm-3

Concentration of ethyl ethanoate (CH3COOC2H5) at equilibrium is:

0.1000 moldm-3 – 0.0346= 0.0654 moldm-3 (Because based on the mole ratio
from the balanced equation 1 mole of CH3COOC2H5 reacts with 1 mole water, so
the equilibrium concentration of CH3COOC2H5 is also 0.0654moldm–3)
Concentration of ethanoic acid (CH3COOH) at equilibrium is:

Initial concentration + Change in concentration

0 + 0.0346 moldm-3 = 0.0346 moldm-3

Concentration of ethanol (C2H5OH) at equilibrium is:

Initial concentration + Change in concentration

0 + 0.0346 moldm-3 = 0.0346 moldm-3

STEP 2: Write the equilibrium constant for this reaction in terms of

concentrations.

STEP 3: Substitute the equilibrium concentrations into the expression.

STEP 4: Determine the units of the equilibrium constant.

 Understand the term partial pressure and define the
term Kp.
Equilibrium constants are normally expressed in terms of concentrations using
the symbol Kc. For reactions involving gases, however, it is usually more
convenient to use the partial pressures of gases rather than their molar
concentrations.

The pressure exerted by the molecules of a particular gas in a mixture of gases

is called the partial pressure of that gas. The partial pressure of a gas is
proportional to its concentration.

Partial pressure = Total pressure x mole fraction

Total pressure = P1 + P2 + P3………. ( total partial pressures of all the gases in a

mixture)

Mole fraction = number of moles of a particular gas

total number of moles of gases in the mixture

Kp is the equilibrium constant in terms of partial pressures. The units for Kp

can be expressed in pascals (Pa) or atmospheres (atm). Usually, you would be
using atmospheres as the unit, to simplify your calculations.

1 pascal (Pa) = 1 Nm-2

1 atm = 1.01 x 105 Pa

Construct equilibrium expressions in terms of partial

pressures and deduce the units of Kp
We write equilibrium expressions in terms of partial pressures in a similar way
to equilibrium expressions in terms of concentrations. But there are some
differences:

• we use p for partial pressure.

• the reactants and products are written as subscripts after the p.
• the number of moles of particular reactants or products is written as a
power after the p.
 • square brackets are not used.
• we give the equilibrium constant the symbol Kp (the equilibrium constant
in terms of partial pressures).

Example 1:

Example 2:
 Perform calculations involving Kp.

Example 1: In this example we are given the partial pressure of each gas in
the mixture.

Step 2 Substitute the partial pressures.

Step 3 Determine the units.

Example 2: In this example we are given the partial pressure of two of the three
gases in the mixture as well as the total pressure.

Step 3 Substitute the partial pressures.

Step 4 Determine the units.

 State Le Chatelier's principle
Le Chatelier’s principle states,” If one or more factors that affect an
equilibrium is changed, the position of equilibrium shifts in the direction that
reduces (opposes) the change.”

The position of equilibrium refers to the relative amounts of products and

reactants present in an equilibrium mixture.

If a system in equilibrium is disturbed (e.g.by a change in temperature) and

the concentration of products is increased relative to the reactants, we say
that the position of equilibrium has shifted to the right.

If the concentration of products is decreased relative to the reactants, we

say that the position of equilibrium has shifted to the left.

These are the links to two videos which explain Le Chatelier’s Principle and the
factors which affect the position of equilibrium for a reaction:

https://youtu.be/7zuUV455zFs

https://youtu.be/XhQ02egUs5Y
 Apply Le Chatelier's principle to explain
the effects of changes in temperature,
concentration and pressure on a system in
equilibrium.

How does change in concentration affect the position of

equilibrium?

For example, look at the reaction:

What happens when we add more ethanol?

✓ The concentration of ethanol is increased.

✓ According to Le Chatelier’s principle, some of the ethanol must be removed to
reduce the concentration of the added ethanol.
✓ The position of equilibrium shifts to the right.
✓ More ethanol reacts with ethanoic acid and more ethyl ethanoate and water are
formed.

What happens when we add more water?

✓ The concentration of water is increased.

✓ According to Le Chatelier’s principle, some of the water must be removed
to reduce the concentration of the added water.
✓ The position of equilibrium shifts to the left.
✓ So more water reacts with ethyl ethanoate and more ethanoic acid and
ethanol are formed.

What happens when we remove some water?

✓ The concentration of water is decreased.

 ✓ According to Le Chatelier’s principle, some water must be added to
increase its concentration.
✓ The position of equilibrium shifts to the right.
✓ So more ethanoic acid reacts with ethanol and more water and ethyl
ethanoate are formed.

The effect of pressure on the position of equilibrium

For example, consider the reaction:

There are three moles of gas molecules on the left of the equation and two on
the right.

What happens when we increase the pressure?

✓ The molecules are closer together, because the pressure is higher.

✓ According to Le Chatelier’s principle, the reaction must shift in the direction
that reduces the number of molecules of gas.
✓ The position of equilibrium shifts to the right.
✓ So more SO2 reacts with O2 to form SO3.

What happens when we decrease the pressure?

✓ The molecules are further apart, because the pressure is lower.

✓ According to Le Chatelier’s principle, the reaction must shift in the direction
that increases the number of molecules of gas.
✓ The position of equilibrium shifts to the left.
✓ So more SO2 and O2 molecules are formed by the decomposition of SO3
molecules.

Note that:
✓ if there are equal numbers of molecules of gas on each side of the
equation, the position of equilibrium is not affected by a change in
pressure
 ✓ in a reaction involving gases and solids (or liquids), it is only the
molecules of gases that count when determining how pressure affects
the position of equilibrium.

The effect of temperature on the position of equilibrium

For example:

The decomposition of hydrogen iodide is an endothermic reaction.

What happens to the position of equilibrium when the

temperature increase?

✓ an increase in temperature increases the energy of the surroundings

✓ according to Le Chatelier’s principle, the reaction will go in the direction
that opposes the increase in energy
✓ so the reaction will go in the direction in which energy is absorbed, which
is the endothermic reaction
✓ the position of equilibrium shifts to the right, producing more H2 and I2.

If an endothermic reaction is favoured by an increase in temperature, an

exothermic reaction must be favoured by a decrease in temperature:

✓ a decrease in temperature decreases the energy of the surroundings

✓ according to Le Chatelier’s principle, the reaction will go in the direction
that opposes the decrease in energy
✓ so the reaction will go in the direction in which energy is released, which
is the exothermic reaction.

Do catalysts have any effect on the position of equilibrium?

A catalyst is a substance that increases the rate of a chemical reaction.

Catalysts speed up the time taken to reach equilibrium, but they have no effect
on the position of equilibrium once this is reached. This is because they increase
the rate of the forward and reverse reactions equally.

Apply Le Chatelier’s principle to the Haber Process and

the Contact Process

HABER PROCESS

The synthesis of ammonia is carried out by the Haber process. The equilibrium
reaction involved is:

We can use Le Chatelier’s principle to show how to get the best yield of
ammonia.

What happens if we increase the pressure?

✓ When we increase the pressure, the reaction goes in the direction that
results in fewer molecules of gas being formed.
✓ The equilibrium shifts in the direction that reduces the pressure.
✓ In this case there are four molecules of gas on the left-hand side and
two on the right-hand side. So the equilibrium shifts towards the right.
✓ The yield of ammonia increases.

What happens if we decrease the temperature?

✓ A decrease in temperature decreases the energy of the surroundings.

✓ The reaction will go in the direction in which energy is released.
✓ Energy is released in the exothermic reaction, in which the position of
equilibrium favours ammonia production.
✓ This shifts the position of equilibrium to the right. The value of Kp
increases.
 What happens if we remove ammonia by condensing it to a liquid?

We can do this because ammonia has a much higher boiling point than
hydrogen and nitrogen.

✓ The position of equilibrium shifts to the right to replace the ammonia

that has been removed.
✓ More ammonia is formed from hydrogen and nitrogen to keep the value
of Kp constant.

What happens if we use a catalyst?

✓ Using an iron catalyst will speed up the reaction rate but has no effect on
the equilibrium yield (of ammonia).

OVERALL, the yield of ammonia is increased by increasing the pressure,

decreasing the temperature and removing ammonia through condensation.

This is a link to a video which explains the Haber process:

https://youtu.be/NWhZ77Qm5y4

CONTACT PROCESS

The synthesis of sulfuric acid is carried out by the Contact process. The main
equilibrium reaction involved is:

We can use Le Chatelier’s principle to show how to get the best yield of sulfur
trioxide.

What happens when we increase the pressure?

When we increase the pressure, the reaction goes in the direction that results
in fewer molecules of gas being formed, to reduce the pressure.

There are three molecules of gas on the left-hand side and two on the right-
hand side, so the equilibrium shifts towards the right.
However, in practice, the reaction is carried out at just above atmospheric
pressure and not at a high pressure because:

✓ The yield of SO3 produced for SO2 is fairly high at fairly low
temperatures.
✓ Highly corrosive sulphur oxides are less easily contained in the reactor
vessel at high pressure.
✓ Using very high pressure is also very expensive.

What happens if we decrease the temperature?

✓ Decreasing the temperature shifts the position of equilibrium to the

right.
✓ A decrease in temperature decreases the energy of the surroundings so
the reaction will go in the direction in which energy is released.
✓ This is the exothermic reaction, in which the position of equilibrium
favours SO3 production. The value of Kp increases.

This is a link to a video which explains the Contact process:

https://youtu.be/xjLUJ-7m5v8
Define the term solubility product, Ksp and explain
the principles underlying solubility product

Solubility
Many ionic compounds dissolve in water but some are only slightly soluble or
appear to be insoluble. But even ‘insoluble’ ionic compounds form some ions in
solution to a very small extent. We say that a solution is saturated when no more
solute will dissolve in it at a particular temperature. Solubility is a property which
describes the maximum amount of solute which dissolves in a given volume of
solvent at a particular temperature and solubility is measured in moldm-3 (or
sometimes in g/100g water).

Now, when a sparingly soluble or ‘insoluble’ salt is added to water, an equilibrium

is established between the ions in solution and the ions in the solid. The ions move
from the solid to solution at the same rate as the they move from solution to
solid. For example in the diagram below, we observe at equilibrium ions move from
saturated silver iodide solution to silver iodide solid at the same rate as they
move from solid to solution.
The chemical equation for this reaction which is at equilibrium is:

AgI (s) Ag+ (aq) + I- (aq)

Therefore, the related equilibrium expression is:

K = [Ag+(aq)] [I-(aq)]
[AgI(s)]

However, the concentration of a solid is constant, so we can write the

equilibrium expression as:

Ksp = [Ag+] [I-]

Ksp is the solubility product constant. Solubility product is an expression

showing the equilibrium concentration of ions in a saturated solution of a
sparingly soluble salt, after a precipitate has formed. It takes into account the
relative number of each ion in solution.

EXAMPLES of equilibrium expressions for solubility product:

1. Co(OH)2 (s) Co2+(aq) + 2OH- (aq)

Ksp = [Co2+] [OH- ]2

2. Al2O3 (s) 2Al3+(aq) + 3O2-(aq)

Ksp = [Al3+]2 [O2-]3

The UNITS of solubility product

We calculate the units of Ksp in the same way as for general equilibrium
expressions involving Kc:

Example:

Ksp = [Co2+] [OH- ]2 units are :

Ksp = (moldm-3) X (moldm-3)2 = mol3 dm-9

Perform calculations involving solubility product

EXAMPLE 1: Determining solubility product from solubility.

A saturated solution of lead iodide, PbI2, contains 0.076 g PbI2 in 100 g solution.
Calculate Ksp for lead iodide. Molar mass of lead iodide = 461.0 gmol-1

STEP 1: Calculate the solubility / concentration of the solution in moldm-3.

If 461.0 g contains 1 mole of PbI2

then 0.076 g contains: 1 mole x 0.076 g = 0.000164859 moles

461.0 g

NOTE: 100g of water has a volume of 100 cm3 / 100 ml

If 100 cm3 contains 0.000164859 moles

Then 1000 cm3 contains: 1000 cm3 x 0.000164859 moles = 0.00164859 moles

100 cm3

Therefore, the concentration of the solution is = 0.00164859 moldm-3

Rounded up to 3 sig. figs.: 1.65 x 10-3 moldm-3

Step 2: Calculate the concentration of each ion in solution.

PbI2 (s) Pb2+ (aq) + 2I– (aq)

Mole ratio of PbI2 to Pb2+ is: 1:1

Therefore, concentration of Pb2+ = 1.65 x 10-3 moldm-3

Mole ratio of PbI2 to I- is 1:2

Therefore, concentration of I- = 2 (1.65 x 10-3 moldm-3) =3.30 x 10-3 moldm-3

Step 3: Write the equlibrium expression.

Ksp = [Pb2+] [I–]2

Step 4: Substitute the values.

Ksp = (1.65 x 10-3 moldm-3) X (3.30 x 10-3 moldm-3)2

= 1.80 x 10-8

Step 5: Determine the units.

= (moldm-3) x (moldm-3)2 = mol3 dm-9

THEREFORE, Ksp = 1.80 x 10-8 mol3 dm-9

EXAMPLE 2: Determining solubility from solubility product.

Calculate the solubility in moldm-3 of calcium sulphate, CaSO4.

Ksp = 2.0 x10-5 mol2 dm-6.

Step 1: Write down the equilibrium expression.

CaSO4 (s) Ca2+ (aq) + SO42- (aq)

Ksp = [ Ca2+] [SO4 2-]

Step 2: Substitute the values.

Let’s represent solubility of CaSO4 as “s”

Mole ratio of CaSO4 to Ca2+ is 1:1, so the solubility of Ca2+ can be represented as
“s.”

Mole ratio of CaSO4 to SO42- is 1:1, so the solubility of SO42- can be represented
as “s.”

Therefore: 2.0 x10-5 mol2 dm-6 = s x s 2.0 x10-5 mol2 dm-6= s2

Step 3: Complete the calculation and determine units.

√2.0 x10-5 = s

s = 4.47 x 10-3 moldm-3

Solubility of Calcium sulphate: is 4.47 x 10-3 moldm-3

 The common ion effect…………….
The common ion effect is the reduction in the solubility of a dissolved salt
caused by adding a solution of a compound which has an ion in common with
the dissolved salt.

Example 1: Ksp = [Ba2+] [SO42-] = 1.0 x 10-10 mol2 dm-6

The image below illustrates the common ion effect, when considering the
solubility of BaSO4 in 0.1 moldm-3 Na2SO4 (aq):

[Ba2+] = s’ moldm-3

[SO42-] = 0.1 moldm-3 because the very small concentration of SO42-ions

from barium sulphate is ignored)

s’ x 0.1 moldm-3 = 1.0 x 10-10 mol2 dm-6

s’ = 1.0 x 10-9 moldm-3

Solubility of BaSO4 in 0.1 moldm-3 Na2SO4 (aq) is 1.0 x 10-9 moldm-3

Predicting Precipitation……….

Ionic product refers to the product of multiplying together the concentrations

of two aqueous ions raised to the appropriate powers of the coefficients in the
chemical balanced equation, before any precipitate has formed.

Therefore, because the value of the ionic product is greater the value of the
solubility product, then a precipitate will form.
Therefore, a precipitate can be formed when the value of the ionic product
is equal to the value of the solubility product.
Relate the solubility product principle to the

selective precipitation of substances.

Precipitation and Qualitative analysis

Kidney stones formation due to selective precipitation

Determining solubility product by experiment

COMPULSORY READINGS FROM TEXTBOOK, “Cambridge AS and

A level chemistry coursebook, 2nd Edition.”

• Explain the terms acid and base using Bronsted-Lowry theory. READ

PAGES 131-132.

• Explain the differences in behaviour of strong and weak acids and bases,

using Bronsted-Lowry theory. READ PAGES 133-134.