Thermodynamics of chemical reaction: How to shift reaction equilibrium to right in an equilibrium mixture?

Is your yield of chemical process an issue? Look at difficult chemical reaction of making ammonia if
conversion is an issue. There is lot to learn from the reaction, N2 + 3H2 < = > 2NH3. This reaction is one of the
most difficult reversible chemical reactions. Therefore, this reaction has been chosen to explain what in
general makes it a difficult chemical reaction. Ammonia making is also a success story of overcoming issues in
shifting equilibrium in chemical reactions in general.
Why ammonia making is a difficult reaction? What does the chemical equation predict?
N2 + 3H2 = 2NH3
Predictions

[1] N2 is a diatomic gas with three bonds, Nitrogen atom with atomic number seven, has three electrons in
the outer shell which it shares with another nitrogen atom and makes three covalent bonds. Three covalent
bonds clamp two nitrogen atoms very tightly in a N2 molecule, with very high bond energy, at 946 kj / mol.
This makes N2 molecule needing very high energy to break its bonds and take part in any chemical reaction.
This is why N2 is known as an inert gas. For the same reason activation energy for this reaction is very high.
Typical bond energies of some covalent bonds are given in the image below. N2 has the highest bond energy
because of its triple bond.

[2] The reaction requires four moles of reactants to produce two moles of products, N2 + 3H2 = 2NH3 . In
other words, the reaction requires to proceed from a state of more disorder [larger number molecules] to a
state of relatively less disorder [smaller number of molecules] which is in the direction of decreased entropy.
This is against second law of thermodynamics, which tells any spontaneous reaction must move in the
direction increasing entropy.
[3] As a result of point [2], in the reaction, N2 + 3H2 = 2NH3, ammonia moves reverse from a state of low
entropy to reactants at high entropy. This makes ammonia making reaction - a reversible reaction,
N2 + 3H2 < = > 2NH3

Since the reaction is reversible, increase of reactants concentration does not have any impact on the yield or
conversion as the reaction reaches a state equilibrium soon. Any increase in reactants concentration
simultaneously speeds up the reverse reaction towards an equilibrium and at equilibrium there is no reaction.
Calculation to verify predictions [All thermodynamic data taken from NIST web data book]
N2 + 3H2 = 2NH3
[Standard state is 298k,1bar]

Standard state heat of formation for ammonia = [Product -Reactant] = - 45.90 kj / mol

Standard state entropy for N2 = 191.61 J/k-mol

Standard state entropy for H2 = 130.68 j/k-mol
Total entropy of reactants at standard state = 322j/k-mol
Standard state entropy for NH3 gas = 192.77 j/k-mol

∆S of reaction = [Product – Reactant] = [ 192.77 – 322.0] = - 129.23 j/k-mol or , - 0.12923 kj/k-mol

Gibbs free energy change at standard condition [ 273+25 = 298 k] [Product – Reactant] ,
∆G = -45.92-(298*(-0.12923)) = - 7.4 kj/k-mol
Interpretation of data
Enthalpy

[1] It is an exothermic reaction, ∆H = - 45.92 kj / mol

This is the total heat exchanged between reactants and products during the reaction
What does an exothermic or endothermic reaction tell us?

By looking at enthalpy of reaction, ∆Hrxn, you can predict following:

[1] An increase of temperature in the reaction if the reaction is endothermic will shift the equilibrium to right,
N2 + 3H2 < = > 2NH3, you get more product. Similarly, a decrease in temperature if reaction is exothermic ,
shifts the equilibrium to right, you get more product. Discussed in details later.
[2] When a reaction is endothermic, at the activated complex stage , see the activation energy diagram above,
the energy of product and energy of reactants both reach same level, at this stage, product has two options
[1] take energy from surrounding and go down the hill to ground level in a state of stable low energy or
reverse the reaction, breaks itself into reactants. It is easy for products to break bonds and go back to
reactants. Bottom line is chances of reverse reaction is relatively much more in endothermic reaction than
exothermic reaction.
Entropy

[2] Entropy change in reaction, ∆S of reaction = - 0.12923 kj/k-mol,

Reactants have more entropy than product. Reaction goes from high entropy to low entropy. It is not a
spontaneous reaction according to second law of thermodynamics. ∆S of reaction is near zero. This makes
ammonia to reverse into reactants, nitrogen and hydrogen and move to an equilibrium situation with no
creation of products.
Gibbs free energy

[3] Very little Gibbs free energy change, ∆G = - 7.4 kj/k-mol , suggests non-spontaneity of reaction
Calculation confirms all predictions. The issue in this reaction is its strong tendency to reverse the reaction
towards an equilibrium. This is not specific to ammonia; it can apply to any such reaction.
Haber process: The image below explains Haber process

Until 1910 ammonia making remained a challenge when Haber succeeded in overcoming the hurdles of the
chemical reaction and developed Haber process for large scale ammonia manufacturing by sorting out
chemical and engineering problems.
Briefly, nitrogen from the air with hydrogen derived mainly from natural gas (methane) in the ratio of 1
volume of nitrogen to 3 volumes of hydrogen are fed into the reactor in presence of a catalyst to form
ammonia.

The key issue in ammonia making is that the reaction reverses towards equilibrium. Everything in ammonia
manufacturing is centred around how to shift equilibrium to right, N2 + 3H2 < = > 2NH3 to get more product.

Le Chatelier's principle :
In short, it tells how the position of equilibrium changes, if you change concentration, pressure or
temperature. It is hugely important principle when someone is struggling to improve yield of his chemical
reaction or at early stage, when a reactor is being designed.
Principle:

If a dynamic equilibrium is disturbed by changing the conditions, the position of equilibrium moves to
counteract the change.
This one-line statement often becomes very confusing when one is troubleshooting a yield issue on ground.
Explanation for Haber process conditions

Your objective is 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.
Effect of temperature
N2 + 3H2 < = > 2NH3

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. You get more ammonia. In order to get as much
ammonia as possible in the equilibrium mixture, you need as low a temperature as possible. The downside of
reducing temperature is, while you get more ammonia , your rate of reaction slows down as you reduce
temperature. Therefore, a compromise is necessary.
Compromise

400 - 450°C is a compromise temperature producing a reasonably high proportion of ammonia in the
equilibrium mixture at 15% conversion rate.
Effect of pressure
N2 + 3H2 < = > 2NH3

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. You get more ammonia. That will cause the pressure to fall again.
In order to get as much ammonia as possible in the equilibrium mixture, you need as high a pressure as
possible. 200 atmospheres is the general pressure used.
Downside of increasing pressure very high is 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 and
blocking catalyst surface where they can react. The higher the pressure the better in terms of the rate of a
gas reaction.

Economic considerations
Very high pressures are very expensive to produce on two counts. [1] You need 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 operating costs of your plant
shoots up.
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.

Catalyst
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.
In the absence of a catalyst the reaction is so slow that virtually no reaction happens in any sensible time. The
catalyst reduces the activation energy and 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.
Separating ammonia
When the gases leave the reactor, they are hot and at a very high pressure. Ammonia is easily liquefied under
pressure as long as it isn't too hot, and so the temperature of the mixture is lowered enough for the ammonia
to turn to a liquid. The nitrogen and hydrogen remain as gases even under these high pressures, and can be
recycled.