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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.
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.
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).
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).
Rule 1 examples
The equilibrium between hydrogen gas, gaseous iodine and gaseous hydrogen iodide.
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.
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
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.
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.
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
is unaffected by change in pressure, the are two molecules (or moles) of gas on each side of the equation.
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
A catalyst usually speeds up both the forward and reverse reaction but there is no way it can influence the final
'balanced' concentrations.
(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
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
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.
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.
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.
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).
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.
During the manufacture of ammonia, the following equilibrium is present (the position of equilibrium lies
to the left):
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:
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.
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:
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.
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.