Principles of chemical equilibria

A balanced condition within a system of chemical reactions. When in chemical equilibrium, substances
form and break down at the same rate, and the number of molecules of each substance becomes definite
and constant.
A reaction rate determines how fast a reaction proceeds, and is mathematically defined as the change in
concentration of a species over the change in time.

Reactions do not only proceed forward; reactions often occur in a mixture of forward and reverse, and are
termed reversible reactions, where the products can react to produce the original reactanys again..
Because 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.

Reactions should not be conceptualized as one substance completely changing into another; rather, they
should be visualized as having two components acting in opposite directions. In this scenario, there is a
point where the two components are acting at equal rates; this is referred to as equilibrium. At
equilibrium, the reaction rates of the forward and reverse reactions are equal.
Dynamic equilibrium

A dynamic equilibrium is a chemical equilibrium between a forward reaction and the reverse reaction
where the rate of the reactions are equal. A dynamic equilibrium occurs when you have a reversible
reaction in a closed system. Reactants are converted to products and products are converted to reactants at
an equal and constant rate. Reactions do not necessarilyand most often do notend up with equal
concentrations. Equilibrium is the state of equal, opposite rates, not equal concentrations.

In a closed system no substances are either added to the system or lost from it. Energy can, however, be
transferred in or out at will.

You can show dynamic equilibrium in an equation for a reaction by the use of special arrows.

The change from left to right in the equation is known as the forward reaction. The change from right to
left is the back reaction. It is important to realise that this doesn't just mean that the reaction is reversible.
It means that you have a reversible reaction in a state of dynamic equilibrium.

CHARACTERISTICS OF A SYSTEM IN DYMANIC EQUILIBRIA

(a) the system is closed and the temperature is uniform and constant throughout

(b) The concentration (or pressure) of reactants and products remains constant (or unchanged) over time.
(c) The rate of forward reaction is equal to the rate of reverse reaction (both forward and reverse
reaction proceed at an equal rate).

(d) microscopic processes (the forward and reverse reaction) continue in a balance which yields no
macroscopic changes (so no change/reaction appears to be happening)
(e) the equilibrium position can be approached from the left (starting with reactants) or from the right
(starting with products)
(f) Reaction quotient (Q) is equal to the equilibrium constant (K).

Types of equilibria (dynamic)

Homogeneous equilibrium has everything present in the same phase. The usual examples include
reactions where everything is a gas, or everything is present in the same solution. No state symbols have
been given, but they will be all (g), or all (l), or all (aq) if the reaction was between substances in solution
in water.

A good example of a gaseous homogeneous equilibrium is the conversion of sulphur dioxide to sulphur
trioxide at the heart of the Contact Process:

A heterogeneous equilibrium has things present in more than one phase. The usual examples include
reactions involving solids and gases, or solids and liquids.

Le Chatelier's Principle or "The Equilibrium Law

A principle stating that if a constraint (such as a change in pressure, temperature, or concentration of a

reactant) is applied to a system in equilibrium, the equilibrium will shift so as to tend to counteract the
effect of the constraint.

Ex. An equilibrium established between four substances A, B, C and D.

What would happen if we changed the conditions by

1 Concentration
a Increasing the concentration of A?

According to Le Chatelier, the position of equilibrium will move in such a way as to counteract the
change. That means that the position of equilibrium will move so that the concentration of A decreases
again - by reacting it with B and turning it into C + D. The position of equilibrium moves to the right.

b Decreasing the concentration of A?

According to Le Chatelier, the position of equilibrium will move so that the concentration of A increases
again. That means that more C and D will react to replace the A that has been removed. The position of
equilibrium moves to the left.


N.B. If you remove one of the products of the reaction as soon as it is formed. If, for example, you
removed C as soon as it was formed, the position of equilibrium would move to the right to replace it. If
you kept on removing it, the equilibrium position would keep on moving rightwards - turning this into a
one-way reaction.
2. Temperature

For this, you need to know whether heat is given out or absorbed during the reaction.

Assume that our forward reaction is exothermic (heat is evolved):

This shows that 250 kJ is evolved (hence the negative sign) when 1 mole of A reacts completely with 2
moles of B.

N.B For reversible reactions, the value is always given as if the reaction was one-way in the forward
direction.

The back reaction (the conversion of C and D into A and B) would be endothermic by exactly the same
amount.

a increasing the temperature?

According to Le Chatelier, the position of equilibrium will move in such a way as to counteract
the change. That means that the position of equilibrium will move so that the temperature is
reduced again.

Increasing the temperature of a system in dynamic equilibrium favours the endothermic reaction.
The system counteracts the change you have made by absorbing the extra heat.

A system is in equilibrium at 300C, and you increase the temperature to 500C. How can the reaction
counteract the change you have made? How can it cool itself down again?
To cool down, it needs to absorb the extra heat that you have just put in. In the case we are looking at, the
back reaction absorbs heat. The position of equilibrium therefore moves to the left. The new equilibrium
mixture contains more A and B, and less C and D.

b decreasing the temperature?

The equilibrium will move in such a way that the temperature increases again. Decreasing the
temperature of a system in dynamic equilibrium favours the exothermic reaction. The system
counteracts the change you have made by producing more heat.

Suppose the system is in equilibrium at 500C and you reduce the temperature to 400C. The reaction
will tend to heat itself up again to return to the original temperature. It can do that by favouring the
exothermic reaction.

The position of equilibrium will move to the right. More A and B are converted into C and D at the lower
temperature.

3 Pressure, This only applies to reactions involving gases:

a increasing the pressure?

According to Le Chatelier, the position of equilibrium will move in such a way as to counteract the
change. That means that the position of equilibrium will move so that the pressure is reduced again.

Pressure is caused by gas molecules hitting the sides of their container. The more molecules you have in
the container, the higher the pressure will be. The system can reduce the pressure by reacting in such a
way as to produce fewer molecules.

Example: There are 3 molecules on the left-hand side of the equation, but only 2 on the right. By forming
more C and D, the system causes the pressure to reduce.

Increasing the pressure on a gas reaction shifts the position of equilibrium towards the side with fewer
molecules.
Example 1: Haber Process

N 2 +3H 2 2NH 3 N2+3H22NH3

If this mixture is transferred from a 1.5 L flask to a 5 L flask, in which direction does a net change occur
to return to equilibrium? Answer?

b decreasing the pressure?

The equilibrium will move in such a way that the pressure increases again. It can do that by producing
more molecules. In this case, the position of equilibrium will move towards the left-hand side of the
reaction.

c What happens if there are the same number of molecules on both sides of the equilibrium
reaction?

In this case, increasing the pressure has no effect whatsoever on the position of the equilibrium. Because
you have the same numbers of molecules on both sides, the equilibrium can't move in any way that will
reduce the pressure again.

Effect of catalyst on equilibrium

Catalyst has no effect upon the equilibrium concentration of the reactants and products. In fact, a catalyst
accelerates the forward and backward reactions to the same extent and therefore simply helps in the
attainment of the equilibrium state faster.

Contact process and Haber process

The Contact Process equilibrium- Manufacture of sulphur trioxide

The major industrial process used to make sulphuric acid, by oxidizing sulphur dioxide in the presence of
a solid catalyst and absorbing the resulting sulphur trioxide in water.
The raw materials needed to make sulfuric acid are:

sulfur
 air

water

Step one

Burning sulphur in an excess of air:

. . . or by heating sulphide ores like pyrite in an excess of air:

In either case, an excess of air is used so that the sulphur dioxide produced is already mixed with oxygen
for the next stage.
sulfur + oxygen sulfur dioxide

S(l) + O2(g) SO2(g)

Notice that this is not a reversible reaction. Remember that (l) means liquid and (g) means gas.
Step 2 making sulphur trioxide

This is a reversible reaction, and the formation of the sulphur trioxide is exothermic.

Notice that this reaction is reversible. The conditions needed for it are:

a catalyst of vanadium(V) oxide, V2O5

a temperature of around 450C

atmospheric pressure

Understanding the conditions

The mixture of sulphur dioxide and oxygen going into the reactor is in equal proportions by volume.

Avogadro's Law says that equal volumes of gases at the same temperature and pressure contain equal
numbers of molecules. That means that the gases are going into the reactor in the ratio of 1 molecule of
sulphur dioxide to 1 of oxygen.

That is an excess of oxygen relative to the proportions demanded by the equation.



According to Le Chatelier's Principle, Increasing the concentration of oxygen in the mixture causes the
position of equilibrium to shift towards the right.

The temperature

Equilibrium considerations

You need to shift the position of the equilibrium as far as possible to the right in order to produce the
maximum possible amount of sulphur trioxide in the equilibrium mixture.

The forward reaction (the production of sulphur trioxide) is exothermic.

According to Le Chatelier's Principle, this will be favoured if you lower the temperature. The system will
respond by moving the position of equilibrium to counteract this - in other words by producing more heat.

The pressure

Equilibrium considerations

Notice that there are 3 molecules on the left-hand side of the equation, but only 2 on the right.

According to Le Chatelier's Principle, if you increase the pressure (by decreasing the volume) the system
will respond by favouring the reaction which produces fewer molecules. That will cause the pressure to
fall again.

In order to get as much sulphur trioxide as possible in the equilibrium mixture, you need as high a
pressure as possible. High pressures also increase the rate of the reaction.

You will remember that the equation for this is:

This time the Kc expression will include some visible powers:

Although everything is present as a gas, you still measure concentrations in mol dm -3. There is another
equilibrium constant called Kp which is more frequently used for gases. You will find a link to that at the
bottom of the page.
Step 3

In the final stage, sulfur trioxide reacts with water to make sulfuric acid:

H2O(l) + SO3(g) H2SO4(aq)

Notice that this is not a reversible reaction, just like the first stage. Remember that (aq) means aqueous or
dissolved in water.

the sulphur trioxide is first dissolved in concentrated sulphuric acid:

The product is known as fuming sulphuric acid or oleum (H2S2O7) in an absorption tower.

This can then be reacted safely with water to produce concentrated sulphuric acid - twice as much as you
originally used to make the fuming sulphuric acid.

The Haber Process equilibrium- Manufacture of ammonia

Ammonia can be synthesized from nitrogen and hydrogen in accordance with the reaction.

The equilibrium constant of this reaction may be written as,

Understanding and explaining the conditions

The catalyst

In the absence of a catalyst the reaction is so slow that virtually no reaction happens in any sensible time.
The catalyst ensures that the reaction is fast enough for a dynamic equilibrium to be set up within the very
short time that the gases are actually in the reactor. However, catalyst does not affect the position of
equilibrium. Hence, in the case of Haber Process an iron catalyst is used.
The catalyst is actually slightly more complicated than pure iron. It has potassium hydroxide added to it
as a promoter - a substance that increases its efficiency.

Why iron? An iron catalyst is used to speed up the reaction by lowering the activation energy required to
carry out the reaction, this has no effect on the equilibrium of the reaction, but allows the system to reach
equilibrium quicker. Other materials such as ruthenium and osmium were used, however iron-based
catalysts tend to be economically superior to these especially in cost.

Equilibrium considerations

The catalyst has no effect whatsoever on the position of the equilibrium. Adding a catalyst doesn't
produce any greater percentage of ammonia in the equilibrium mixture. Its only function is to speed up
the reaction.

Rate considerations

In the absence of a catalyst the reaction is so slow that virtually no reaction happens in any sensible time.
The catalyst ensures that the reaction is fast enough for a dynamic equilibrium to be set up within the very
short time that the gases are actually in the reactor.

The pressure

In the reaction, there are 4 molecules on the left-hand side of the equation, but only 2 on the right.
According to Le Chatelier's Principle, if you increase the pressure the system will respond by favouring
the reaction which produces fewer molecules. That will cause the pressure to fall again. Taking
equilibrium position into consideration, in order to get as much ammonia as possible in the equilibrium
mixture, you need as high a pressure as possible. 200 atmospheres is a high pressure, but not amazingly
high.Hence, the reaction will be more product favoured.

However, building a very high pressure condition is very expensive and might cause the business to be
less profitable. So, the optimum pressure is 200atm. The pressure varies from one manufacturing plant to
another, but is always high. You can't go far wrong in an exam quoting 200 atmospheres.

Rate considerations and pressure

Increasing the pressure brings the molecules closer together. In this particular instance, it will increase
their chances of hitting and sticking to the surface of the catalyst where they can react. The higher the
pressure the better in terms of the rate of a gas reaction.

Economic considerations and pressure

Very high pressures are very expensive to produce on two counts.

1. You have to build extremely strong pipes and containment vessels to withstand the very high pressure.
That increases your capital costs when the plant is built.
2. High pressures cost a lot to produce and maintain. That means that the running costs of your plant are
very high.

The compromise

200 atmospheres is a compromise pressure chosen on economic grounds. If the pressure used is too high,
the cost of generating it exceeds the price you can get for the extra ammonia produced.

The proportions of nitrogen and hydrogen/ The concentration

The mixture of nitrogen and hydrogen going into the reactor is in the ratio of 1 volume of nitrogen to 3
volumes of hydrogen.

Avogadro's Law says that equal volumes of gases at the same temperature and pressure contain equal
numbers of molecules. That means that the gases are going into the reactor in the ratio of 1 molecule of
nitrogen to 3 of hydrogen.

That is the proportion demanded by the equation.

The temperature

Equilibrium considerations

You need to shift the position of the equilibrium as far as possible to the right in order to produce the
maximum possible amount of ammonia in the equilibrium mixture.

The forward reaction (the production of ammonia) is exothermic.

According to Le Chatelier's Principle, this will be favoured if you lower the temperature. The system will
respond by moving the position of equilibrium to counteract this - in other words by producing more heat.

In order to get as much ammonia as possible in the equilibrium mixture, you need as low a temperature as
possible. However, a very low temperature will cause reaction to occur very slowly and hence, not
efficient. Therefore, 400 - 450C (though not really a low temperaturature) is a compromise temperature
producing a reasonably high proportion of ammonia in the equilibrium mixture (even if it is only 15%),
but in a very short time.

Rate considerations and temperature

The lower the temperature you use, the slower the reaction becomes. A manufacturer is trying to produce
as much ammonia as possible per day. It makes no sense to try to achieve an equilibrium mixture which
contains a very high proportion of ammonia if it takes several years for the reaction to reach that
equilibrium.
You need the gases to reach equilibrium within the very short time that they will be in contact with the
catalyst in the reactor.

The compromise

400 - 450C is a compromise temperature producing a reasonably high proportion of ammonia in the
equilibrium mixture (even if it is only 15%), but in a very short time.

Synopsis

The characteristics of the reaction are:

Firstly, the reaction proceeds with a decrease in volume. Therefore, an increase in pressure should favour
the forward reaction. The equilibrium between nitrogen, hydrogen and ammonia at 200C has been studied
at different pressures and the following data has been obtained.