Reversible reactions and Equilibrium

REMINDERS about reversible reactions before learning about CHEMICAL EQUILIBRIUM

o A reversible reaction is a chemical change in which the products can be converted back to the original
reactants under suitable conditions.
o This means the reaction can go in either direction i.e.
A + B ==> C + D or C + D ==> A + B
o In a reversible reaction, changing the reaction conditions e.g. concentration, pressure or temperature
will change the net direction the reaction goes i.e. more to the right (forward) or more to left (backward).
This idea becomes important in understanding chemical equilibrium, which is all about the state
of balance between relative amounts of reactants and products in a reversible reaction
situation.
o A reversible reaction is shown by the sign , but on this page you must now think of it as
an equilibrium sign too.
o Conventions used in talking about reversible reactions and a chemical equilibrium
It is really important you understand that the terms right & left AND forward & backward are
used in the context of how the equation of a reversible reaction is presented,
and a half-arrow to the right means the direction of the forward reaction,
and a half-arrow to the left means the direction of the reverse or backward reaction.
If you say the equilibrium is over to the right, you mean there are more products and than
reactants.
If you say the equilibrium is over to the left, you mean there are more of the original reactants
and than products formed.
So, WHAT IS A CHEMICAL EQUILIBRIUM?
When a reversible reaction occurs in a closed system an equilibrium is formed, in which the
original reactants and products formed coexist in the same reaction mixture AND the concentrations of all
components in the mixture remain constant.
o The 'closed system' might be a beaker of a solution containing a reaction mixture in the school
laboratory or gaseous reactants in an enclosed reactor chamber in the chemical industry.
o A closed system quite simply means nothing can escape from the reaction mixture.
In an equilibrium there is a state of balance between the concentrations of the reactants and products and once
a state of chemical equilibrium is reached there is no further change in concentrations BUT the reactions
don't stop!
o Because neither the forward reaction or backward reaction stops, and the concentrations do not
change, the situations is referred to as a dynamic equilibrium.
At equilibrium the rate at which the reactants change into products is exactly equal to the rate at which the
products change back to the original reactants.
o In other words the rate of the forward reaction (L to R) is equal to the rate of the backward reaction (R
to L),
o AND, these forward and backward reactions go on all the time, but sort of cancel each other out.
However the final relative equilibrium amounts/concentrations of the reactants and products depends on the
reaction conditions e.g. the temperature and pressure.

A good example of a chemical equilibrium is the reversible reaction formation of an ester in organic chemistry
Ethyl ethanoate, an ester, is formed by the reaction of ethanoic acid with ethanol e.g.
ethanoic acid + ethanol ethyl ethanoate + water

+ + H2O
Its an equilibrium, and starting with the pure acid plus pure alcohol you get about 2/3rds conversion to the
ester, and the reaction is catalysed by a few drops ofconcentrated sulphuric acid.
o Conversely, if you start with equal amounts ester and water, the reaction will go 'backwards' and
about 1/3rd of the ester and water will change back to the alcohol and acid.
o The point here is that you end up with a chemical equilibrium involving all four reactants & products.
As the equation is written, left to right is called the forward reaction, and right to left the backward reaction.
o The terms forward (L to R) and backward (R to L) must be used in the context of the direction the
reversible reaction equation is written i.e. for the above chemical equilibrium
o forward: CH3COOH + CH3CH2OH ==> CH3COOCH2CH3 + H2O (esterification)
 o backward: CH3COOCH2CH3 + H2O ==> CH3COOH + CH3CH2OH (hydrolysis)
In this example all four components of the equilibrium co-exist with unchanging concentrations unless some
change is imposed on the system
o e.g. change in temperature or addition of any of the four components of the reaction.
o If any such change is imposed on the system, then the reaction will go more to the right or more to the
left to re-establish the equilibrium.
o All four components can co-exist because the energy changes involved are not sufficient to promote the
reaction 100% one way or the other.

WHAT CHANGES THE POSITION OF AN EQUILIBRIUM?

o By 'position of an equilibrium' we mean what are the relative amounts of reactants and products.
o AND, importantly, what changes the position of an equilibrium?
o In other words, what factors affect the position of an equilibrium?
o In a reversible reaction, changing the reaction conditions e.g. concentration, pressure or temperature
will change the net direction the reaction goes i.e. more to the right (forward) or more to left (backward)
and this must inevitably change the position of the equilibrium.
o If you enforce a change on a chemical system at equilibrium, then the system will respond to
alter the equilibrium position, BUT the system responds in a way to minimise the enforced
change.
o The most important factors to consider that strongly influence the position of an
equilibrium are temperature, pressure (if gases) and concentration (if solution).

What are the RULES GOVERNING THE POSITION OF A CHEMICAL EQUILIBRIUM?

For industrial processes, it is important to maximise the concentration of the desired products and minimise the 'leftover'
reactants. A set of rules can be used to predict the best reaction conditions to give the highest possible yield of product.

The three rules outlined below are known as Le Chatelier's Principle. This essentially states that if a change is
imposed on a system, the system will change to minimise the enforced change to re-establish equilibrium.

Rule 1 The effect of temperature change on the position of an equilibrium

Reminder: If a forward reaction is exothermic, the reverse backward reaction is endothermic and vice versa.

Rule 1a: If the forward reaction forming the products is endothermic, raising the temperature favours its
formation increasing the yield of product (lowering the temperature decreases the yield).

So increasing temperature favours the endothermic direction reaction.

The system attempts to absorb the heat and minimise the increase in temperature.

Rule 1b: If the forward reaction forming the products is exothermic, decreasing the temperature favours its formation
(increasing temperature decreases the yield).

So decreasing temperature favours the exothermic direction reaction

The system attempts to release heat to minimise the temperature decrease.

Rule 1 examples
The equilibrium between hydrogen gas, gaseous iodine and gaseous hydrogen iodide.

H2(g) + I2(g) 2HI(g) (plus 10 kJ of heat energy, exothermic L to R)

Increasing temperature favours the endothermic direction, backward reaction, some hydrogen iodide will decompose.

Decreasing temperature favours the exothermic reaction, so more hydrogen and iodine react to form hydrogen iodide.

Rule 2 The effect of changing pressure on the position of an equilibrium

You can increase/decrease the pressure by decreasing/increasing the volume of the gases OR increasing/decreasing
the concentration of gases in the same volume.

Rule 2a: Increasing the pressure favours the side of the equilibrium with the least number of gaseous
molecules as shown by the balanced symbol equation.

So increasing pressure favours the reaction direction to reduce the number of gaseous molecules.

The system is changing to minimise the impact of the increase in pressure by removing some gas molecules.

Rule 2b: Decreasing the pressure favours the side of the equilibrium with the most number of gaseous molecules as
shown by the balanced symbol equation.

So decreasing pressure favours the reaction direction to produce the most gaseous molecules.

The system is changing to minimise the impact of the decrease in pressure by increasing the number of gas molecules.

Rule 2 examples

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

4 gas molecules ==> 2 gas molecules, so to re-establish a dynamic equilibrium ...

Increase in pressures favours the forward reaction to reduce the number of gas molecules, so more ammonia formed.

Decrease in pressure encourages the formation of more gas molecules, so some of the ammonia decomposes into
nitrogen and hydrogen.

(ii) N2O4(g) 2NO2(g)

1 gas molecule ==> 2 gas molecules, so to re-establish a dynamic equilibrium ...

Increase in pressure favours backward direction to reduce the number of gaseous molecules and give more dinitrogen
tetroxide.

Decrease in pressure encourages more gas molecules to form, so the forward reaction gives more nitrogen dioxide.

(iii) N2(g) + O2(g) 2NO(g)

2 gas molecules ==> 2 gas molecules

Change in pressure has no effect on equilibrium position.

PLEASE NOTE

Rules 1 above, and rule 3, below, apply to any reaction, BUT rule 2 above, ONLY applies to a reaction with one
or gaseous reactants or gaseous products.

Increase in pressure does not influence the concentration of substances in a solution or solid mixture because they are
too dense to be significantly compressed i.e. no effective change in concentration.

The situation is quite different in gases where is a lot of space between the molecules to compress them closer
together.

If a reaction involves gases BUT there are equal numbers of gaseous molecules on each side of the equation,
increasing or decreasing pressure has no effect on the position of the equilibrium.

e.g the equilibrium position of the reaction to form hydrogen iodide from hydrogen and iodine

H2(g) + I2(g) 2HI(g)

is unaffected by change in pressure, the are two molecules (or moles) of gas on each side of the equation.

Rule 3 The effect of changing concentration on the position of an equilibrium

Rule 3a: If the concentration of a reactant (on the left) is increased, then some of it must change to the products (on the
right) to maintain a balanced equilibrium position.

Rule 3b: If the concentration of a reactant (on the left) is decreased, then some of the products (on the right) must
change back to reactants to maintain a balanced equilibrium position.

Rule 3 examples

e.g. nitrogen + hydrogen ammonia

o or N2(g) + 3H2(g) 2NH3(g)
o If the nitrogen or hydrogen concentration was increased, some of this extra gas would change to
ammonia.
o If the nitrogen or hydrogen concentration was decreased, some of ammonia would change back to
nitrogen and hydrogen.
o At AS-A2 advanced level things can get more complicated e.g. can you figure out why in terms
of concentration to maintain the equilibrium balance? (and if a gcse student, don't worry if you
can't) ...
o So in terms of enforced change ==> system response:
o Increasing nitrogen concentration ==> decreases hydrogen concentration and increases ammonia
concentration
o Increasing hydrogen concentration ==> decreases nitrogen concentration and increases ammonia
concentration
o Increasing ammonia concentration ==> increases both nitrogen and hydrogen concentrations
o Decreasing ammonia concentration ==> decreases both nitrogen and hydrogen concentration
o Decreasing nitrogen concentration ==> increases hydrogen concentration and decreases ammonia
concentration
o Decreasing hydrogen concentration ==> increases nitrogen concentration and decreases ammonia
concentration
Rule 4 The effect of using a catalyst on the position of an equilibrium

Rule 4: A catalyst does NOT affect the position of an equilibrium.

You just get to the equilibrium position here faster!

A catalyst usually speeds up both the forward and reverse reaction but there is no way it can influence the final
'balanced' concentrations.

However, the importance of a catalyst lies with economics e.g.

(i) bringing about reactions with high activation energies at lower temperatures and so saving the cost on energy,

(ii) and saving time is saving money, i.e. a catalyst increases the efficiency of the chemical process e.g. the Haber
synthesis of ammonia.

Rule 4 examples

Iron catalyst in the synthesis of ammonia.

Vanadium pentoxide catalyst in the Contact Process for manufacturing sulfuric acid.

Both of these chemical processes are faster and made economically more efficient by use of a catalyst, but you don't
get a greater % yield in the final reacted mixture.

SUMMARY

Equilibrium

The concept of dynamic equilibrium

Some reactions are able to go in two directions; forward and reverse. They are known as reversible
reactions.

The forward and reverse reactions occur at the same time, and never stop. As a result, they are called
dynamic reactions.

When the rate of the forward reaction is equal to the rate of the reverse reaction, the reaction is said to
have reached equilibrium.

At equilibrium, the concentrations of the reactants and products are constant, but are not
necessarily equal.

Example: the reaction of iron(III) ions with thiocyanate ions.

Fe3+(aq) + CNS-(aq) FeCNS2+(aq)

Pale yellow iron(III) ions react with colourless thiocyanate (CNS) to produce red iron thiocyanate.
When there are more products than reactants present, the position of equilibrium lies to the right.

Example: in water, only a small proportion of the molecules have split to form ions at
equilibrium.

H2O(l) H+(aq) + OH-(aq)

In this example of water, the equilibrium lies to the left. Only a few molecules have split to form ions.

It doesn't matter whether the reaction starts with 100% reactants or 100% products, the reaction will
always reach the same equilibrium position.

Shifting the equilibrium position

Making changes to the concentration, pressure or temperature of a reaction can alter the position of
the equilibrium.

The rule is that, any change made to a reaction which is in equilibrium, will result in the equilibrium
position moving to minimise the change made (Le Chatelier's principle).

Changes to the concentration of a reactant or product

When chlorine gas dissolves in water, the following equilibrium is produced:

Cl2(g) + H2O(l) Cl-(aq) + ClO-(aq) + 2H+(aq)

If potassium chloride (a source of chloride ions) is added to the equilibrium mixture, the equilibrium will
shift to the left, to remove the chloride ions added.

If potassium hydroxide is added, the hydroxide ions will react with the hydrogen ions and remove them
from the mixture. The equilibrium will now move to the right, to replace the lost hydrogen ions.

Changes to temperature or pressure

A good example of how changes to temperature and pressure alter the position of equilibrium can be
seen in the Haber process (the industrial manufacture of ammonia).

During the manufacture of ammonia, the following equilibrium is present (the position of equilibrium lies
to the left):

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

Temperature

In the Haber process, the forward reaction is an exothermic reaction. Although it is not a substance, in
exothermic reactions heat can be imagined to be a product:

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

If the temperature is increased, then the equilibrium will shift to the left (the endothermic direction), to
remove the extra heat added. This is why only a moderately high temperature (380 - 450C) is used in
the Haber process.

Increasing the temperature always favours the endothermicreaction.Decreasing the

temperature always favours the exothermic reaction.

Pressure

Reactions in which the equilibrium mixture is made up of only liquids and/or solids will not be affected
by changes in pressure.

If there is at least one gas present in the equilibrium mixture, then a change in the pressure may affect
the position of the equilibrium.

Using the balanced equation, it can be seen that there are 4 volumes of reactants and only 2 volumes of
product:

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

1 volume of N2(g) and 3 volumes of H2(g), giving 2 volumes of NH3(g).

If the pressure is increased, the equilibrium will shift towards the right, creating more product.This is
because the volume of the product is smaller than the volume of the reactants, and so the pressure will
reduce to minimise the change.

If the pressure is reduced, the equilibrium will shift towards the left, resulting in more reactants.This is
because the volume of the reactants is greater than the volume of the product, and so the pressure will
increase to minimise the change.

In the Haber process, the actual pressure used is around 250 atmospheres, which favours more product.
 High pressure always favours the side with the lowest volume of gases.
Low pressure always favours the side with the highest volume of gases.
Changes in pressure will not affect the position of equilibrium, if the number of moles of
gases on both sides of the equation are equal. Remember, liquids and solids contribute
nothing to the volume of the equilibrium mixture.

Adding a catalyst
A catalyst reduces the time taken to reach equilibrium, but does not change the position of the
equilibrium. This is because the catalyst increases the rates of the forward and reverse reactions by the
same amount.

In the Haber process, the catalyst used is iron.

The Haber process is a continuous process. Ammonia is constantly being separated from the reaction
mixture and the unreacted nitrogen and hydrogen are recycled back into the reaction vessel. As a result,
equilibrium is never reached. Instead, the equilibrium is constantly shifting to the right, to replace the
ammonia which has been removed.