Equilibrium

CHAPTER 8
Reversible reactions
A reaction in which the products can react to re-form the original reactants is called a reversible
reaction.
In this case heating and adding water are not being carried out at the same time.
Equilibrium -1-
In many chemical reactions the reactants are not used up completely.
Some products are formed but the maximum theoretical yield is not obtained. A mixture of
products and reactants is formed.
The products react together to re-form reactants at the same time as the reactants are forming
products. This type of reversible reaction is called an equilibrium reaction.
Equilibrium -2-
When fizzy drinks are made, carbon dioxide gas is dissolved in the drink under pressure.
When you take the lid off a bottle of fizzy drink, bubbles of carbon dioxide suddenly appear.
When you put the lid back on, the bubbles stop.

The forward reaction happens during manufacture and the backward reaction happens on opening.
Characteristics of equilibrium -1-
An equilibrium reaction has four particular features under constant conditions:
➢ it is dynamic

➢ the forward and reverse reactions occur at the same rate

➢ the concentrations of reactants and products remain constant at equilibrium

➢ it requires a closed system.

Characteristics of equilibrium -2-
2. THE FORWARD AND BACKWARD REACTIONS OCCUR
1. IT IS DYNAMIC
AT THE SAME RATE

The phrase dynamic equilibrium means that

the molecules or ions of reactants and
products are continuously reacting. At equilibrium the rate of the forward reaction
equals the rate of the backward reaction.

Reactants are continuously being changed to

products and products are continuously being Molecules or ions of reactants are becoming
changed back to reactants. products, and those in the products are
becoming reactants, at the same rate.
Characteristics of equilibrium -3-
3. The concentrations of reactants and products remain constant at equilibrium.
Characteristics of equilibrium -4-
4. Equilibrium requires a closed system
A closed system is one in which none of the reactants or products escapes from the
reaction mixture. In an open system some matter is lost to the surroundings.

Many chemical reactions can be studied without placing them in closed containers. They can
reach equilibrium in open flasks if the reaction takes place entirely in solution and no gas is lost.

A closed system. No CO2 escapes. An open system. CaCO3 is continually decomposing

CaCO3 is in equilibrium with CaO and CO2. as the CO2 islost. The reaction eventually goes to
completion.
Position of equilibrium
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 increases relative to the reactants, we say that the position of equilibrium has shifted
to the right.

If the concentration of products decreases relative to the reactants, we say that the position of
equilibrium has shifted to the left.
Le Chatelier’s principle
If one or more factors that affect an equilibrium is changed, the position of equilibrium shifts
in the direction that reduces (opposes) the change.

Changes in both concentration and temperature affect the position of equilibrium. When any of
the reactants or products are gases, changes in pressure may also affect the position of
equilibrium.

If one or more factors that affect a dynamic equilibrium is changed, the position of equilibrium
moves to minimise this change.

We can predict the effect of:

1. changing concentration and pressure by referring to the stoichiometric equation for the
reaction.
2. changing the temperature by referring to the enthalpy change of the reaction.
How does change in concentration affect the position
of equilibrium?
When the concentration of one or more of the When the concentration of one or more of the
reactants is increased: products is increased:
❑ the system is no longer in equilibrium ❑ the system is no longer in equilibrium
❑ the position of equilibrium moves to the ❑ the position of equilibrium moves to the
right to reduce the effect of the increase in left to reduce the effect of the increase in
concentration of reactant concentration of product
❑ more products are formed until equilibrium ❑ more reactants are formed until
is restored. equilibrium is restored.
The effect of pressure on the position of equilibrium -1-
Change in pressure only affects reactions where gases are reactants or products.
The pressure of a gas is caused by the molecules hitting the walls of the container. Each
molecule in a mixture of gases contributes towards the total pressure.
The effect of pressure on the position of equilibrium -2-
The effect of temperature on the position of equilibrium -1-
The effect of temperature on the position of equilibrium -2-
ENDOTHERMIC EXOTHERMIC

➢ an increase in temperature increases the ➢ a decrease in temperature decreases the

energy of the surroundings energy of the surroundings
➢ according to Le Chatelier’s principle, the ➢ according to Le Chatelier’s principle, the
reaction will go in the direction that opposes reaction will go in the direction that opposes
the increase in energy the decrease in energy
➢ so the reaction will go in the direction in ➢ so the reaction will go in the direction in
which energy is absorbed, which is the which energy is released, which is the
endothermic reaction. 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 reduce 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.
Equilibrium expressions and the equilibrium constant, Kc -1-

where m, n, p and q are the number of moles in the equation

Equilibrium expressions and the equilibrium constant, Kc -2-
Kc and concentration changes
If all other conditions remain constant, the value of Kc does not change when the concentration
of reactants or products is altered.

When more hydrogen iodide is added to the equilibrium mixture, the equilibrium is disturbed.
➢ The ratio of concentrations of products to reactants in the equilibrium expression decreases.
➢ To restore equilibrium, both [H2] and [I2] increase and [HI] decreases.
➢ Equilibrium is restored when the values of the concentrations in the equilibrium expression
are such that the value of Kc is once again 6.25 x 10–3.
Kc and pressure changes
Where there are different numbers of gas molecules on each side of a chemical equation, a
change in pressure alters the position of equilibrium.

It is shifted in the direction that results in fewer gas molecules being formed.

However, if all other conditions remain constant, the value of Kc does not change when the
pressure is altered.
Kc and temperature changes
For an endothermic reaction, an increase in For an exothermic reaction, an increase in
temperature shifts the reaction in the temperature shifts the reaction in favour of
direction of more products. more reactants.

➢ the concentrations of H2 and I2 increase as ➢ The concentrations of SO2 and O2 increase as

the temperature increases the temperature increases.
➢ the concentration of HI falls as the ➢ The concentration of SO3 falls as the
temperature increases. temperature increases.
Equilibria in gas reactions: the equilibrium constant, Kp -1-
For reactions involving mixtures of gases, it is easier to measure the pressure than to measure
concentrations.
The total pressure in a mixture of gases is due to each molecule bombarding the walls of the
container.
The pressure exerted by any one gas in the mixture is called its partial pressure.

The total pressure of a gas equals the sum of the partial pressures of the
individual gases.
ptotal = pA + pB + pC …

where pA, pB, pC are the partial pressures of the individual gases in the
mixture.
Equilibria in gas reactions: the equilibrium constant, Kp -2-
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:
Partial pressure and mole fractions
The number of moles of gas is proportional to the volume of the gas at constant temperature. So
it follows that the partial pressure of a gas is proportional to its concentration. The mole fraction
of a gas is given by the relationship:

So the mole fraction of ammonia in a mixture containing 0.5 mol ammonia, 0.9 mol hydrogen and
0.6 mol of nitrogen is:

The partial pressure is related to the mole fraction by the relationship:

partial pressure = mole fraction × total pressure (of all the gases in the mixture)
 Equilibrium and ammonia production
The synthesis of ammonia is carried out by the Haber process.

At high temperatures, when the reaction is faster, the position of equilibrium is to the left because the
reaction is exothermic (ΔH is -).

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

A decrease in temperature decreases the energy of the surroundings. The reaction will go in the
direction in which energy is released.
Equilibrium and the production of sulfuric acid
The synthesis of sulfuric acid is carried out by the Contact process.
Acids, Bases and pH
Acids? What is the pH of acids?

Bases? What is the pH of bases?

Salts? What is the pH of salts?

Neutralisation
A salt is a compound formed when an acid reacts with a base (or alkali). This type of reaction is
called a neutralisation reaction.

From these equations we can see that:

• acid + alkali → salt + water
• sodium sulfate and barium chloride are salts
• the simplest ionic equation for a neutralisation reaction is: H+(aq) + OH-(aq) → H2O(l)
The Brønsted–Lowry theory of acids and bases -1-
A Bronsted–Lowry acid is a proton donor. A Bronsted–Lowry base is a proton acceptor.

Substances like water, which can act as either acids or bases, are described as amphoteric
The Brønsted–Lowry theory of acids and bases -2-
A forward arrow is used as this reaction goes to completion.

An equilibrium arrow is used as this reaction does not go to completion.

Conjugate acids and conjugate bases -1-
If a reactant is linked to a product by the transfer of a proton we call this pair a conjugate pair.
Conjugate acids and conjugate bases -2-
Strong and weak acids and bases
Acids that dissociate almost completely in solution are called strong acids.

Acids that are only partially dissociated in solution are called weak acids.

Bases that dissociate almost completely in solution are called strong bases.

Bases which dissociate to only a small extent in solution are called weak bases.
Distinguishing a weak acid from a strong acid
We can distinguish between a strong and weak acid by their pH values, electrical conductivity
and reactivity. When making these comparisons, we must use dilute solutions of strong and
weak acids of the same concentration.

Refer to Coursebook on page 266

Introducing indicators
An acid–base indicator is a dye or mixture of dyes that changes colour over a specific pH
range.
In simple terms, many indicators can be considered as weak acids in which the acid (HIn)
and its conjugate base (In–) have different colours.

Adding an acid to this indicator solution shifts the position of equilibrium to the left. There
are now more molecules of colour A.
Adding an alkali shifts the position of equilibrium to the right. There are now more ions of
colour B.
The colour of the indicator depends on the relative concentrations of HIn and In–. The
colour of the indicator during a titration depends on the concentration of H+ ions present.
Strong acids with strong bases
Strong acids with weak bases

Because there is a sharp change in pH over the region

3.5 to 7.5 we can use methyl red as an indicator for
this titration.

This is because methyl red changes colour between pH

4.2 and pH 6.3, values that correspond with the region
of sharpest pH change.
Weak acids with strong bases

Because there is a sharp change in pH over the

region pH 7.5 to 11 we can use phenolphthalein
as an indicator for this titration.
Weak acids with weak bases

These results show that there is no sharp fall in the graph

line. No acid–base indicator is suitable to determine the
end-point of this reaction. In the example shown
bromothymol blue:

1. starts changing colour when 19.50 cm3 of acid have been

added

2. finishes changing colour when 20.50 cm3 of acid have

been added.

Such a gradual colour change on addition of acid is not

acceptable when accuracy of reading the end-point to the
nearest 0.05 cm3 is required.