THE HABER PROCESS

This page describes the Haber Process for the manufacture of ammonia from
nitrogen and hydrogen, and then goes on to explain the reasons for the conditions
used in the process. It looks at the effect of temperature, pressure and catalyst on
the composition of the equilibrium mixture, the rate of the reaction and the
economics of the process.

A brief summary of the Haber Process

The Haber Process combines nitrogen from the air with hydrogen derived mainly
from natural gas (methane) into ammonia. The reaction is reversible and the
production of ammonia is exothermic.

A flow scheme for the Haber Process looks like this:

Some notes on the conditions

The catalyst
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.

The pressure

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.

Recycling

At each pass of the gases through the reactor, only about 15% of the nitrogen and
hydrogen converts to ammonia. (This figure also varies from plant to plant.) By
continual recycling of the unreacted nitrogen and hydrogen, the overall conversion is
about 98%.

Explaining the conditions

The proportions of nitrogen and hydrogen

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.

In some reactions you might choose to use an excess of one of the reactants. You
would do this if it is particularly important to use up as much as possible of the other
reactant - if, for example, it was much more expensive. That doesn't apply in this
case.

There is always a down-side to using anything other than the equation proportions. If
you have an excess of one reactant there will be molecules passing through the
reactor which can't possibly react because there isn't anything for them to react with.
This wastes reactor space - particularly space on the surface of the catalyst.

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, 400 - 450C isn't a low temperature!

Rate considerations

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.

The pressure

Equilibrium considerations

Notice that 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.
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.

Rate considerations

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

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

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.

High pressures cost a lot to produce and maintain. That means that the running
costs of your plant are very hig

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 catalyst

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.
Separating the 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.

BOSCH PROCESS
Bosch process is used in the industrial preparation of Hydrogen. Hydrogen is a
very important gas in the chemical industry and can be produced industrially
through a number of methods. It can be produced industrially basically by three
methods: (i) Bosch processes, (ii) From Methane and (iii) Through the
Electrolysis of brine(as a by-product). We shall now take a look at this methods
individually.

In the Bosch process, large quantities of hydrogen are produced from cheap raw
materials such as water and coke. When steam is passed over red hot
coke(carbon) at a temperature of about 1200C, a mixture of carbon(II) oxide
and hydrogen is produced. Excess steam is then mixed with the water
gas[carbon(II) oxide and hydrogen] and passed over a catalyst which could
either be iron(III) oxide or chromium(III) oxide, at a temperature of about 450C.
The resultant effect is that the carbon(II) oxide in the water gas is converted to
carbon(IV) oxide with a further yield of hydrogen.

The first reaction, which is the production of water gas is endothermic, while
the second reaction which is the reduction of steam to hydrogen by carbon(II)
oxide, is exothermic. The carbon(IV) oxide is then removed from the mixture
by dissolving it in water under pressure of 30 atmospheres or in other solvents
such as caustic soda solution. Any unreacted carbon(II) oxide is absorbed in
ammoniacal solution of copper(I) ethanoate.

Hydrogen can also be produced industrially from methane. This process is fast
replacing the Bosch process. Since hydrocarbon such as methane is cheap
unlike coke, it makes more economic sense and improves overall efficiency. In
the first stage of this process, methane is mixed with steam and this mixture is
passed over a nickel catalyst at about 800C. The mixture of carbon(II) oxide and
hydrogen produced is known as synthesis gas. The second stage in this process
is similar to that described above in the Bosch process.

Ni
CH4(g) + H2O(g) CO(g) + 3H2(g)
800C
Hydrogen is also produced industrially by another method known as the
electrolytic method. Here very pure hydrogen is obtained as a by-product in the
electrolysis of brine for the manufacture of sodium hydroxide and chlorine. It
can be also be made by the electrolysis of dilute potassium hydroxide solution.

Test for Hydrogen

You can test if a gas is hydrogen or not by inserting a lighted splinter into a test
tube containing the suspected or unknown gas. If the gas is hydrogen, it would
burn with a pop sound, since hydrogen will always mix with the air as soon as
the test-tube is unstoppered. However, this test must be carried out only with
small quantities of the gas.

The Contact Process

The Contact process is the process during which sulphur trioxide (SO3) is formed from sulphur
dioxide (SO2).
The Sulphur trioxide which is formed is then used to manufacture sulphuric acid.
Sulphur dioxide can be made by either burning sulphur in excess of air or by roasting of sulphide
ores.
The manufacture of sulphur trioxide is a reversible reaction and its enthalpy change is
exothermic.
The following shows a flowchart of the reaction scheme:

2SO2(g) + O2(g) <=> 2SO3(g) H = -196 kJ/mol

Conditions required for the reaction:

1. Temperature: 450 oC
2. Pressure : 1 atm
3. Catalyst: Vanadium (V) oxide, V2O5

Explaining the conditions:

Temperature
A temperature of 450 oC is used in this reaction. This is because the reaction is exothermic such
that a low temperature would favour the forward reaction and produce more sulphur trioxide.
However, a low temperature slows down the rate of the reaction. Thus a compromise
temperature of 450 oC is used.
Pressure
A pressure of only 1 atm is used. According to LCP, an increase in pressure would increase the
yield of the reaction because there are fewer number of moles of gas on the right hand side.
However, a pressure of 1 atm is enough to obtain a very good yield. Thus it would be a waste of
money and resources to increase the pressure.
Catalyst
Vanadium (V) Oxide, V2O5 is used as catalyst in this reaction. It increases the rate of the
reaction, thus reducing the need for a high temperature.

Manufacture of Sulphuric acid

The sulphur trioxide obtained is then used to manufacture concentrated sulphuric acid.
Step 1:
Burning of sulphur

S + O2 --> SO2

Step 2:
Converting sulphur dioxide into sulphur trioxide

2SO2 + O2 <=> 2SO3

Step 3:
Adding concentrated sulphuric acid to sulphur trioxide to form oily product known as oleum.

SO3 + H2SO4 --> H2S2O7

Step 4:
Adding a calculated amount of water to form sulphuric acid.

H2S2O7 + H2O --> 2H2SO4

.2

THE CONTACT PROCESS

This page describes the Contact Process for the manufacture of

sulphuric acid, and then goes on to explain the reasons for the
conditions used in the process. It looks at the effect of
proportions, temperature, pressure and catalyst on the
composition of the equilibrium mixture, the rate of the reaction
and the economics of the process.
A brief summary of the Contact Process

The Contact Process:

makes sulphur dioxide;

convers the sulphur dioxide into sulphur trioxide (the
reversible reaction at the heart of the process);
converts the sulphur trioxide into concentrated sulphuric
acid.

Making the sulphur dioxide

This can either be made by 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.

Converting the sulphur dioxide into sulphur trioxide

This is a reversible reaction, and the formation of the sulphur

trioxide is exothermic.

A flow scheme for this part of the process looks like this:
The reasons for all these conditions will be explored in detail
further down the page.

Converting the sulphur trioxide into sulphuric acid

This can't be done by simply adding water to the sulphur trioxide

- the reaction is so uncontrollable that it creates a fog of
sulphuric acid. Instead, the sulphur trioxide is first dissolved in
concentrated sulphuric acid:

The product is known as fuming sulphuric acid or oleum.

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.
Explaining the conditions

The proportions of sulphur dioxide and oxygen

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. Since the oxygen comes
from the air, this is a very cheap way of increasing the
conversion of sulphur dioxide into sulphur trioxide.

Why not use an even higher proportion of oxygen? This is easy

to see if you take an extreme case. Suppose you have a million
molecules of oxygen to every molecule of sulphur dioxide.

The equilibrium is going to be tipped very strongly towards

sulphur trioxide - virtually every molecule of sulphur dioxide will
be converted into sulphur trioxide. Great! But you aren't going to
produce much sulphur trioxide every day. The vast majority of
what you are passing over the catalyst is oxygen which has
nothing to react with.

By increasing the proportion of oxygen you can increase the

percentage of the sulphur dioxide converted, but at the same
time decrease the total amount of sulphur trioxide made each
day. The 1 : 1 mixture turns out to give you the best possible
overall yield of sulphur trioxide.
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.

In order to get as much sulphur trioxide as possible in the

equilibrium mixture, you need as low a temperature as possible.
However, 400 - 450C isn't a low temperature!

Rate considerations

The lower the temperature you use, the slower the reaction
becomes. A manufacturer is trying to produce as much sulphur
trioxide as possible per day. It makes no sense to try to achieve
an equilibrium mixture which contains a very high proportion of
sulphur trioxide 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 fairly

high proportion of sulphur trioxide in the equilibrium mixture, but
in a very short time.

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 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. However,
the reaction is done at pressures close to atmospheric pressure!

Economic considerations

Even at these relatively low pressures, there is a 99.5%

conversion of sulphur dioxide into sulphur trioxide. The very
small improvement that you could achieve by increasing the
pressure isn't worth the expense of producing those high
pressures.

The catalyst

Equilibrium considerations

The catalyst has no effect whatsoever on the position of the

equilibrium. Adding a catalyst doesn't produce any greater
percentage of sulphur trioxide 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.
Nitric Acid (Ostwalds Process)
Nitric Acid (Ostwalds Process)
Introduction
On industrial process three methods are employed for the manufacture of nitric acid.
Ostwalds Process uses Ammonia as raw material.
Ostwalds Process
When a mixture of ammonia and air is passed through a catalytic chamber containing
electrically heated Platinum Gauze, (NO) nitric oxide is formed. This nitric oxide
combines with more oxygen to form nitrogen dioxide (NO2). This gas is then absorbed
by water to form nitric acid. The plant used in Ostwalds Process consist of following
parts.
1. Catalytic Chamber
A mixture of pure and dry ammonia is passed through a catalytic chamber containing
heated (800C) platinum, which serves as catalyst. Here ammonia is completely oxidized
to nitric oxide.
2. Oxidation Tower
The nitric oxide is passed into oxidation tower where the temperature of gases falls to
200C 250C. At this temperature nitric is oxidized to nitrogen dioxide.
2NO + O2 -> 2NO2
3. Absorption Tower
Now the gases containing NO2 and oxygen are than sent to a series of absorption tower,
which is filled with broken quartz and water is showered from top of the tower. Then
NO2 reacts with H2O in the presence of oxygen to form HNO3.
4NO2 + 2H2O + O2 -> $HNO3

2.

Ostwald Process
Nitric acid is an inorganic or mineral acid. It is a colourless liquid with pungent smell. This mineral acid
is widely used in the manufacturing of inorganic and organic nitrates. Many of the nitro compounds
and nitrates are mainly used for fertilizers, dye intermediates, explosives, and many different organic
chemicals. The chemical formula of nitric acid is HNO3. The structure of nitric acid can be represented
with the help of two resonating structures as given below.

In the molecule of nitric acid, nitrogen atom carries +1 charge with one oxygen atom (-
1charge).

The positive charge and negative charge on same molecule neutralize it and make it stable. Nitric
acid is planar molecule in which all the lie atoms lie in same plane. Nitric acid is precursor for many
ammonia based fertilizers such as ammonium nitrate. Ostwald process is the most common method
for the preparation of nitric acid at industrial level. Overall it involves the conversion of ammonia to
nitric acid through two steps.

Ostwald Process Flow Diagram

Nitric acid is a mono-basic and a strong mineral acid. It is also used in many organic reactions as a
strong oxidizing agent as it can oxidize metals and nonmetals very quickly. Oswald process is used
for the manufacturing of nitric acid. The raw materials of Oswald process are ammonia gas, water and
oxygen gas. Platinum is used as catalyst for Ostwald process. In the first step of Oswald process,
ammonia gets oxidize in a catalytic chamber in the presence of oxygen. The temperature of catalytic
chamber is about 600C and contains platinum gauze. The oxidation of ammonia is an exothermic
and reversible process which results the formation of oxides of nitrogen.

4NH3+5O24NO+6H2O4NH3+5O24NO+6H2O ; HH - 24.8 Kcal/mole

Since it is a reversible reaction therefore low temperature favours the reaction in forward direction and
95% of ammonia is converted into nitric oxide (NO). For decreasing the temperature of chamber, nitric
oxide is passed through a heat exchanger. It helps to reduce the temperature up to 150C. In the
second step, nitric oxide is transferred to another oxidizing tower where it oxidizes to nitrogen
dioxide (NO2)(NO2).
2NO+O22NO22NO+O22NO2

Nitrogen dioxide is further passed to special absorption tower and interacts with water. The absorption
of water by nitrogen dioxide forms nitric acid.
3NO2+H2O2HNO3+NO3NO2+H2O2HNO3+NO
Ostwald Process Catalyst

Wilhelm Ostwald developed the Ostwald process for the preparation of nitric acid in 1902. Ostwald
process involves the oxidation of ammonia in a catalytic chamber which contains platinum gauze.
The oxidation of ammonia is a reversible and exothermic process. It raises the temperature of
chamber up to 600oC.Here platinum gauze acts as catalyst and induces the oxidation of ammonia.
According to Le- chateliers principle, for an exothermic reaction, the temperature must be low for
forward reaction.

4NH3+5O24NO+6H2O4NH3+5O24NO+6H2O ; HH -24.8 Kcal/mol

The oxidation of ammonia and oxides of nitrogen occurs in the presence of platinum catalyst. Nitric
oxide further oxidizes to form nitrogen dioxide. But this reaction occurs at low temperature around
50C and forms nitrogen dioxide (NO2)(NO2).

2NO+O22NO22NO+O22NO2

In 3rd step, nitrogen dioxide absorbs over water to form nitric acid. This step occurs in a special
absorption tower where NO2NO2 gas passed through the tower and absorbed by water.

3NO2+H2O2HNO3+NO3NO2+H2O2HNO3+NO

This nitric acid is very dilute therefore it is recycled in absorption tower to get concentrated nitric
acid by the absorption of more NO2NO2 gas. Last step is concentration step in which vapours
of HNO3HNO3 are passed over concentrated sulphuric acid which is a good dehydrating agent. It
absorbs water at form concentrated nitric acid.
Ostwald Process Equation
Ostwald process is a three step process for the manufacturing of nitric acid. It involves the oxidation
of ammonia gas at high temperature, pressure and in the presence of catalyst that is platinum.

The first step of reaction is oxidation of ammonia in the presence of platinum catalyst. It is an
exothermic process which increases the temperature of primary oxidation chamber. The oxidation of
ammonia results the formation of nitric oxide with water vapour.

4NH3(gas)+5O2(gas)4NO(gas)+6H2O(gas)4NH3(gas)+5O2(gas)4NO(gas)+6H2O(gas)

In second step, nitric oxide oxidizes to form nitrogen dioxide which can occur only at low temperature.
Therefore the temperature of secondary oxidation chamber is very low compare to primary oxidation
chamber. The reaction equation can be written as given below;

2NO(gas)+O2(gas)2NO2(gas)2NO(gas)+O2(gas)2NO2(gas)

In step 3, Nitrogen dioxide (NO2)(NO2) is passed to absorption chamber where it absorbs over water
and forms aqueous nitric acid with nitric oxide.

3NO2(gas)+H2O(liquid)2HNO3(aqueous solution)+NO(gas)3NO2(gas)+H2O(liquid)2HNO3(a
queous solution)+NO(gas)

In this step, the nitrogen dioxide is absorbed with water to create nitric acid (HNO3) as an aqueous
solution. This also yields nitric oxide (NO).

4NO2(gas)+O2(gas)+2H2O(liquid)4HNO3(aqueous solution)4NO2(gas)+O2(gas)+2H2O(liquid)
4HNO3(aqueous solution)

The dilute nitric acid further recycles to form concentrated nitric acid. It also passes over concentrated
sulphuric acid to form concentrated nitric acid.

Ostwald Process Conditions

The Oswald process is mainly based on the temperature conditions and also on the catalyst. First
step of oxidation of ammonia is an exothermic process which increases the temperature of reaction
system. The secondary oxidation of nitric oxide requires low temperature therefore for forward
reaction and product formation, temperature control is required. For the oxidation of ammonia which
is an exothermic reaction, according to LeChatelier's principle, decreasing the temperature, increase
the concentration , and increasing the pressure and volume are necessary for shifting the reaction in
forward direction.
Bergius Process
Coal (which is a mixture of high molecular weight, complex organic
compound deficient in hydrogen) is the raw material. Low ash coal is
powdered well and made into a paste with heavy oil and a catalyst
(tin/nickel oblate).
The paste is heated with hydrogen at 4508C and 200-250 atm for one
and half hours. The coal undergoes hydrogenation to form saturated
hydrocarbons.

Bergius process
which decompose at high temperature and pressure to yield low boiling
liquid hydrocarbons.
The gases from the reaction vessel are led to the condenser where a
liquid resembling crude oil is obtained. The liquid is fractionated to give
(i) Gasoline
(ii) Middle oil and
(iii) Heavy oil.
The heavy oil is used for making paste with fresh coal dust. The middle oil
is hydrogenated in vapor phase to yield more gasoline. The yield of
gasoline is about 60% of coal dust.

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Process of Liquification Of Coal
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