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REPORT OF TOPIC:
NITROGEN
1. L Th Thu Tho
2. Nguyn Bo Lun
3. Nguyn Vn Sen
4. Trn Duy Tin
5. Trn Th Trc o
6. Thch Th Ngc Thi
7. L Hong Giang
8. H Th Nh Thy
9. Trn Hu Phc n
Table of content:
Page
Introduction
..3
The Haber process
..5
Ammonia gas
............................................................12
Nitric acid
.
........................................................16
Artificial fertilisers
.
19
Index..
....................................26
The Haber process forms the basis of the artificial fertiliser industry, as it is
used to produce ammonia gas. The process was developed by the German scientist Fritz
Haber in 1913. He was awarded a Nobel Prize in 1918 for his work. The process involves
reacting nitrogen and hydrogen. It was first developed to satisfy the need for explosives
during World War I, as explo-sives can be made from ammonia.
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.
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.
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 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 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.
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.
During industrial production of ammonia, the reaction never reaches equilibrium
as the gas mixture leaving the reactor is cooled to liquefy and remove the ammonia. The
remaining mixture of reactant gases are recycled through the reactor. The heat released
by the reaction is removed and used to heat the incoming gas mixture.
Uses of Ammonia
Industry
Use
Fertilser
production of:
Chemicals
synthesis of:
nitric acid, HNO3, which is used in making explosives
such as TNT (2,4,6-trinitrotoluene), nitroglycerine
which is also used as a vasodilator (a substance that
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Explosives
nylon,-[(CH2)4-CO-NH-(CH2)6-NH-CO]-,and
polyamides
Refrigeration
used for making ice, large scale refrigeration plants, airconditioning units in buildings and plants
Pharmaceuticals
other
A Brief History
At the beginning of the 20th century there was a shortage of naturally occurring,
nitrogen-rich fertilisers, such as Chile saltpetre, which prompted the German Chemist
Fritz Haber, and others, to look for ways of combining the nitrogen in the air with
hydrogen to form ammonia, which is a convenient starting point in the manufacture of
fertilisers.This process was also of interest to the German chemical industry as Germany
was preparing for World War I and nitrogen compounds were needed for explosives.
The hydrogen for the ammonia synthesis was made by the water-gas process (a
Carl Bosch invention) which involves blowing steam through a bed of red hot coke
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resulting in the separation of hydrogen from oxygen. The nitrogen was obtained by
distillation of liquid air, then by cooling and compressing air.
These days, the hydrogen is produced by reforming light petroleum fractions or
natural gas (methane, CH4) by adding steam:
CH4(g) + H2O(g)
( )
700
CO(g) + 3H2(g)
Enough steam is used to react with about 45% of the methane (CH4), the rest of
the methane is reacted with air:
2CH4(g) +
2() + 42()
()
2CO(g) + 4H2(g) + 4N2(g)
All the carbon monoxide (CO) in the mixture is oxidised to CO2 using steam and
an iron oxide catalyst:
CO(g) + H2O(g)
H2(g) + CO2(g)
The carbon dioxide (CO2) is removed using a suitable base so that only the
nitrogen gas (N2) and hydrogen gas (H2) remain and are used in the production of
ammonia (NH3).
In ammonia production the hydrogen and nitrogen are mixed together in a ratio
of 3:1 by volume and compressed to around 200 times atmospheric pressure.
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Ammonia gas
I. Natural States
Ammonia is found in trace quantities in the atmosphere, being produced from
the putrefaction (decay process) of nitrogenous animal and vegetable matter. Ammonia
and ammonium salts are also found in small quantities in rainwater, whereas ammonium
chloride (sal-ammoniac), and ammonium sulfate are found in volcanic districts; crystals
of ammonium bicarbonate have been found in Patagonian guano. The kidneys secrete
NH3 to neutralize excess acid. Ammonium salts are found distributed through fertile soil
and in seawater. Ammonia is also found throughout the Solar
System on Pluto, Mars, Jupiter, Saturn, Uranus, and Neptune. Substances containing
ammonia, or those that are similar to it, are called ammoniacal.
II. Physical Properties of Ammonia
Ammonia is a colorless gas.
It has a pungent odor with and an alkaline or soapy taste. When inhaled suddenly,
it brings tears into the eyes.
It is lighter than air and is therefore collected by the downward displacement of
air.
It is highly soluble in water: One volume of water dissolves about 1300 volumes
of ammonia gas. It is due to its high solubility in water that the gas cannot be collected
over water.
It can be easily liquefied at room temperature by applying a pressure of about 810 atmosphere.
Liquid ammonia boils at 239.6 K (- 33.5C) under one atmosphere pressure. It
has a high latent heat of vaporization (1370 J per gram) and is therefore used in
refrigeration plants of ice making machines.
Liquid ammonia freezes at 195.3 K (-77.8C) to give a white crystalline solid.
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With halogens
Ammonia reacts with halogens but the type of halogen and reaction conditions
determine the nature of products.
Chlorine
Nitrogen and ammonium chloride are formed with a limited amount of chlorine.
In the presence of excess of chlorine, nitrogen trichloride is formed.
Bromine
It gives ammonium bromide and nitrogen
Iodine
When rubbed with solid iodine, a dark colored precipitate of nitrogen
tri-iodide is obtained
After drying, if NH3.NI3 is struck against a hard surface or hit with a hammer, it
explodes producing iodine vapors.
With carbon dioxide (formation of urea)
Ammonia when heated under pressure with CO2 gives urea.
Alkali metal dissolved in liquid ammonia gives a blue solutions, which upon
standing slowly, liberate hydrogen. The blue color of such solutions is due to the
presence of solvated electrons (e- (NH3)n). For instance, with sodium
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mining industry for extraction of metals such as copper, nickel and molybdenum from
their ores.
Ammonia is used in several areas of water and wastewater treatment, such as
pH control, in solution form to regenerate weak anion exchange resins, in conjunction
with chlorine to produce potable water and as an oxygen scavenger in boiler water
treatment.
Ammonia is used in stack emission control systems to neutralize sulfur oxides
from combustion of sulfur-containing fuels, as a method of NOx control in both catalytic
and non-catalytic applications and to enhance the efficiency of electrostatic precipitators
for particulate control.
Ammonia is used as the developing agent in photochemical processes such as
white printing, blue printing and in the diazo duplication process.
Ammonia is a widely used refrigerant in industrial refrigeration systems found
in the food, beverage, petro-chemical and cold storage industries.
Ammonia is used in the rubber industry for the stabilization of natural and
synthetic latex to prevent premature coagulation.
The pulp and paper industry uses ammonia for pulping wood and as a casein
dispersant in the coating of paper.
The food and beverage industry uses ammonia as a source of nitrogen
needed for yeast and microorganisms.
The decomposition of ammonia serves as a source of hydrogen for some
fuel cell and other applications.
Ammonia is used by the leather industry as a curing agent, as a slime
and mold preventative in tanning liquors and as a protective agent for leathers
and furs in storage.
Weak ammonia solutions are also widely used as commercial and
household cleaners and detergents.
15
Nitric acid
I.Physical properties.
Pure nitric acid is a colorless liquid,fuming strongly in air and there are density
ratio is 1,52.It solidifies at -41oC and boils at 86oC.Pure nitric acid unstable, prone to
decomposition under the effect of light and heat:
4HNO3 = 4NO2
+ O2 +2H2O
Concentrated nitric acid soluble in water in any proportions.It make up with water
mixture of co boiling contains 69.2% acidic and boiling at 121,8oC under normal
pressure.
II.Chemical properties.
1.The acidic:
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3Cu
Pb
4HNO3()
4Mg
10HNO3(aq)
5Mg
12HNO3(aq) =
+ N2 + 6H2O
The passivation:
Though manganese (Mn), chromium (Cr), iron (Fe) and aluminum (Al) soluble
in dilute nitric acid solution, but for cold concentrated acid to produce a metal oxide
layer to protect them from further oxidized this phenomenon is the passivation.
React with non-metals:
when react to the non-metallic elements except silicon and halogen the elements
often be oxidized to the highest oxidation state and create nitrogen dioxide for
concentrated acid and nitrogen oxide for dilute acid.
S
3C
P
4HNO3(aq) = 2H2O
+ 3CO2 + 4NO
H2 O
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Artificial fertilisers
ARTIFICIAL FERTILISERS
Artificial or inorganic fertilisers are manufactured chemicals, usually from
hydrocarbons or from mining minerals, and were responsible for a revolution in
agriculture, increasing yields tremendously.
Inorganic fertilizers are mineral salts that contain plant nutrients. There are 13
mineral nutrients essential for the growth and development of plants. Including 3 macro
elements are: N, P, K; 3 secondary elements are: Ca, Mg, S and 7 trace elements: Fe,
Mn, Zn, Cu, Mo, B, Cl. In addition, there are some other elements required for each type
of tree, such as Na, Si, Co, Al.
Inorganic fertilizers include major categories:
Inorganic fertilizers Macro: Nitrogen - Phosphate - Potassium - Lime
compost
- synthetic fertilizers and compound fertilizers
Secondary inorganic fertilizer
Inorganic fertilizer micronutrients
Nitrogen:
Nitrogen fertilizer are essential and very important for the tree. Protein is
involved in elemental composition of clorophin, protit, amino acids, enzymes and
vitamins in plants.
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Urea CO (NH4) 2
Lan has an important role in the life of the plant. Phosphorus is present in the cell
nucleus, is essential for the formation of new parts of the tree.
Lan engaged in component enzymes, proteins, involved in the synthesis of amino
acids
Phosphorus stimulates root growth, making deep roots into the soil and spread
around, creating more favorable conditions for resistant plants and less-term lodging.
Lan stimulate tillering, budding, flowering promoting early results and more.
Phosphorus increases resistance characteristics of plants to unfavorable factors:
anti-rust, anti-drought, soil acidity, against some pests etc ...
In some soils in our country, phosphorus becomes the limiting factor for crop
yields. Especially in most of the rice land in the southern provinces. Lack of phosphorus
not only reduce crop yield but also limited the effectiveness of the fertilizer.
The performance of high phosphorous fertilizer. On some soils in the Central
Highlands 1 kg P2O5 fertilizer efficiency gain 4.3 to 7.5 pounds of coffee beans, 8.5 kg
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of rice. In the newly reclaimed acid sulphate soils, performance of higher phosphate, 1
kg of P2O5 bring 90 kg of rice, fertilizer at 40-60 kg P2O5 / ha.
Excessive phosphate fertilizer in many cases can cause the plants to lack some
trace elements. Therefore, fertilizer micronutrients, especially Zn.
* Domestic phosphate
* Sub-apatite
* Superphosphate
* Tecmo phosphate (FMP, P Van Dien)
* Phosphate precipitation:
Potassium:
In terms of volume, the plant needs more K than N. But because the land
is relatively more K than N and P, so people pay little attention to the K fertilizer for
plants.
Compost and pleasure mixed with NPK ratios in different combinations were
selected to suit each type of soil and plant groups. Many cases of compost and manure
mixture also has all the elements Mg, Ca, S and other trace elements.
On the market are the following fertilizers:
- Type 2 N and P elements NPK ratio: 18: 46: 0 and 20: 20: 0.
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* Sub-NP
* Analysis of NK
* Sub-PK
* Assignment of N, P, K
* Things to note when mixing:
- Fertilizers containing ammonium as ammonium sulfate, urea, ammonium
chloride, ammonium nitrate fertilizer may not be mixed with alkaline reaction as
calcium, phosphate Van Dien, phosphorite powder, ash. Because if these fertilizers
mixed together will make NH3 volatilization loss of nitrogen.
- Phosphate soluble in water, such as superphosphate, DAP is not mixed with
lime.
- Sub-soluble, hygroscopic, lumps as nitrate, urea, potash is mixed just before
use.
- Supe phosphatic acid can release some sort of harmful substances such as
nitrates produce bags bags, which should be noted in shipping.
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The end.
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