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What are fertilizers?

Fertilizer is natural or artificial substance containing the chemical elements that improve growth
and productiveness of plants. Fertilizers enhance the natural fertility of the soil or replace the
chemical elements taken from the soil by previous crops. The use of manure and composts as
fertilizers is probably almost as old as agriculture. Modern chemical fertilizers include one or
more of the three elements that are most important in plant nutrition: nitrogen, phosphorus,
and potassium. Of secondary importance are the elements sulfur, magnesium, and calcium.

Types of fertilizers
The following points highlight the six important types of fertilizers. The types are:

1. Nitrogenous Fertilizers
2. Organic Nitrogenous Fertilizers
3. Phosphate Fertilizers
4. Potassic Fertilizers
5. Compound Fertilizers
6. Complete Fertilizers (NPK)

1. Nitrogenous Fertilizers:
The nitrogenous fertilizers are divided into four groups — nitrate, ammonia and ammonium
salts, chemical compounds containing nitrogen in the amide form, and plant and animal
byproducts.

(i) Sodium Nitrate:

It occurs in natural deposits in northern Chile and is refined before use. The refined product
contains about 16% nitrogen in the nitrate form, which renders it directly available to plants. For
this reason it is applied as a source of nitrogen, specially to young plants and garden vegetables,
which need readily available nitrogen for quick growth.
Sodium nitrate is easily soluble in water and is quickly leached out from the soil. It is particularly
useful for acidic soils. Its continued and abundant use in soils causes de-flocculation and develop
a bad physical condition in the regions of low rainfall.

(ii) Ammonium Sulphate:

It is the most widely used fertilizer in the country. It is a white crystalline salt, containing 20 to
21 % ammoniacal nitrogen. It is very suitable for wetland crops, for example, paddy and jute.
Ammonium sulphate is easy to handle and is stored well under dry conditions.It is also suitable
for wheat, cotton, sugarcane, potatoes and many other crops grown on a wide variety of soils. Its
continuous use increases soil acidity and lowers the yield. Its application to acid soils improves
the yield of tea plantation considerably. It is advisable to use this fertilizer along with bulky
organic manures to avoid its ill effects.

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Ammonium sulphate can be applied before sowing, at sowing time, or as a top dressing to the
growing crop. It should not be applied during germination, as in concentrated form it affects the
germination very adversely.

(iii) Ammonium Nitrate:

Ammonium nitrate is a white crystalline salt, containing 33 to 35% nitrogen, 50% as nitrate
nitrogen and another 50 percent as the ammonium form. In the ammonium form it is not leached
out easily from the soil. It is quick-acting and highly hygroscopic and cannot be stored. Under
certain conditions, it is explosive and, therefore, should be handled cautiously.
‘Nitro Chalk’ is the trade name of the product formed by mixing ammonium nitrate with about
40% of limestone or dolomite. It contains 20.5% nitrogen, 50% in the form of ammonia and half
as nitrate. Its continuous use makes the soil acidic. The presence of lime makes it useful for acid
soils.

(iv) Ammonium Sulphate Nitrate:

It is a mixture of ammonium sulphate and ammonium nitrate. It is available in a white crystalline

form or as dirty white granules. It contains 26% nitrogen, three-fourths of it in the ammoniacal
form and the rest as nitrate nitrogen.
It highly soluble in water and very quick-acting and non-explosive. It is useful for all crops. It
slightly acidifies the soil. It is applied before sowing, during sowing or as a top dressing, but it is
unsuitable for application along with the seeds.

(v) Ammonium Chloride:

It is quite crystalline compound possessing a good physical condition. It contains 26%

ammoniacal nitrogen. It is extensively used on paddy in Japan. It is used largely in- industries in
India. It is similar to ammonium sulphate in action. It is not recommended for certain types of
crops like tomatoes, tobacco, etc., as they may be injured by chlorine.

(vi) Urea:

Urea is a white crystalline organic compound. It is highly concentrated nitrogenous fertilizer

containing 45 to 46% of organic nitrogen. It is highly hygroscopic and cannot be stored well in
humid regions. To overcome this difficulty it is also produced in granular pellet forms coated
with a non-hygroscopic inert material.
It is highly soluble in water and rapidly leached out from the soil. It is very quick-acting and
rapidly changed into ammonia when applied. It is applied during sowing or as top-dressing but
never during germination. It is suitable for most crops and can be applied to all types of soils.

(vii) Calcium Ammonium Nitrate:

It is a fine, light brown or gray granular fertilizer. It is prepared from ammonium nitrate and
ground limestone. It is almost neutral and can be applied even to acid soils. Its nitrogen content
varies from 25 to 28 percent. Of the total nitrogen 50 percent remains in the ammoniacal form
and the remaining 50 percent in nitrate form.

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2. Organic Nitrogenous Fertilizers:

These fertilizers include plant and animal by-products, such as oil cakes, fish manure and dried
blood from slaughter-houses. Before use by the crops these materials are converted by bacterial
fermentation into utilizable ammonium-nitrogen and nitrate-nitrogen. These fertilizers are,
therefore, slow acting, but supply available nitrogen for a longer period to the crops.
Oil-cakes are usually supplied as organic fertilizer throughout the country. They contain not only
nitrogen but also some phosphoric acid and potash. A large quantity of organic matter is also
present in the oil-cake. In addition to the three fertilizing constituents like, N, P2O5 and K2O, the
oil-cakes contain 2 to 15 percent of oil.
Dried blood or blood meal contains 10 to 12 percent highly available nitrogen and 1 to 2
percent phosphoric acid. It is effective on all types of crops and all types of soils.
Fish manure is available either as dried fish or as fish meal or powder. After extraction of oil
from the fish the residue can be used as a manure, Fish manure contains 5 to 8 percent organic
nitrogen and 4 to 6 percent of phosphoric acid. It is quick acting and suitable for all crops and
soils. It is usually used as powder.

3. Phosphate Fertilizers:
Phosphate fertilizers are classified as natural phosphates, treated phosphates, by-product
phosphates and chemical phosphates.

(i) Rock Phosphate:

It occurs as natural deposits of rock in different countries. Very little rock phosphate is used
directly as a fertilizer. Much more of it is used to manufacture superphosphate, the phosphoric
acid of which is water soluble and becomes available to the crops.

(ii) Super phosphate:

It is the most widely used phosphoric fertilizer in India. It is now manufactured from ground
phosphate rocks treating with sulphuric acid. The brownish- gray product after treatment
contains mono-calcium phosphate and calcium sulphate (Gypsum) in practically equal quantities.
There are three grades of super phosphate:
Single superphosphate containing 16 to 20 percent phosphoric acid; di-calcium phosphate, 35 to
38 percent; and triple superphosphate, 44 to 49 percent.
Single superphosphate is the most commonly available grade in Indian market. The fertilizer is
suitable for all crops and can be applied to all soils. It should be used along with organic manures
in acid soils. It should be applied before or at sowing or transplanting.

(iii) Basic Slag:

Basic slag is a by-product of steel factories. It contains 6 to 20 percent of phosphoric acid (P2O5).
The European slag contains 15 to 18 percent P2O5 and used as a popular phosphatic fertilizer in
central Europe. But slag from Indian steel mills is poor in P2O5 and is not used as a fertilizer. The
European slag is suitable for acid soils as it is alkaline in reaction. For effective use, it must be
pulverized before application.

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(iv) Bone-Meal:

The ground bone is called bone-meal. It is now widely used as phosphate fertilizer.
It is available in two forms:
(a) raw bone-meal
(b) steamed bone-meal.

The steaming up bones under pressure removes fats, nitrogen and glue making substances. It
contains 25 to 30 percent phosphoric acid. Steamed bones are more brittle and can be readily
ground. As it is slow acting, bone-meal should not be used as a top dressing. It must be
incorporated into the soil in order to become available. It is applied either at sowing time or a
few days before sowing and should be broadcast. It is particularly suitable for acid soils.
It is used for all crops. In some places of the country charred and powdered bones are used as
manure. Charring destroys about 50 percent of nitrogen, but the whole of P2O5 remains in a
quickly available form.

4. Potassic Fertilizers:
In India most of the soils contain sufficient amount of potash. So, potassic fertilizers are applied
only to those soils which are deficient in potash.
Potassic fertilizers are used as:
(a) muriate of potash (potassium chloride)
(b) sulphate of potash (potassium sulphate).

(i) Muriate of Potash:

It is a gray crystalline material containing 50 to 63 percent of potash (K2O), the whole of which
is available to the crops. It remains absorbed on the colloidal surfaces and is not leached out from
the soil. It is applied at sowing time or before sowing.

(ii) Sulphate of Potash:

It is more costly as it is prepared by treating potassium chloride with magnesium sulphate. It

contains 48 to 52 percent K2O. It dissolves readily in water and becomes available to the crops
almost immediately after application. It can be applied at any time up to sowing. In certain crops
like tobacco, chillies, potato and fruit-tree it is considered better than muriate of potash.

5. Compound Fertilizers:
These fertilizers contain two or three plant nutrients simultaneously. When both nitrogen and
phosphorus are deficient in soil, a compound fertilizer, e.g., amorphous, can be used. It contains
16 percent nitrogen and 20 percent P2O5. Two different fertilizers can be mixed in correct
proportion to produce the compound fertilizer.

6. Complete Fertilizer (NPK):

Compound fertilizers are not always well adapted to different kinds of soils. For that reason
mixed fertilizers containing two or more materials in suitable proportions are used according to

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the needs of different soils. Mixtures usually fulfil the nutrient deficiencies in a more balanced
manner and require less labour to apply than different fertilizers used separately.
These mixtures containing all the three principal nutrients (N, P and K) are called complete
fertilizers as most soils usually remain deficient in these three elements. A special mixture for
different crops are also produced by the manufacturers.
In some cases insecticides, fungicides and weed-killers, such as DDT, BHC and mercury or
copper salts and 2, 4-D are mixed into the complete fertilizers. The component fertilizers must be
compatible to ensure mutual reaction. Uneven mixing must be avoided. Bone- meal, muriate of
potash and sulphate of potash can be mixed with all fertilizers.

Bio-fertilizers: Types and Importance of Bio-fertilizers

Chemical fertilizers are being used in increasing amounts in order to increase output in high
yielding varieties of crop plants. However, chemical fertilizers cause pollution of water bodies as
well as ground water, besides getting stored in crop plants. Therefore, environmentalists are
pressing for switch over to organic farming. Organic farming is the raising of unpolluted crops
through the use of manures, bifertilizers and biopesticides that provide optimum nutrients to crop
plants, keeping pests and pathogens under control. Bio-fertilizers are micro-organisms which
bring about nutrient enrichment of soil by enhancing the availability of nutrients to crops. The
micro-organisms which act as bio-fertilizers are bacteria, cyanobacteria (blue green algae) and
mycorrhizal fungi. Bacteria and cynobacteria have the property of nitrogen fixation while
mycorrhizal fungi preferentially withdraw minerals from organic matter for the plant with which
they are associated. Nitrogen fixation is the process of conversion of molecular or dinitrogen into
nitrogen compounds. Insoluble forms of soil phosphorus are converted into soluble forms by
certain micro-organisms. This makes the phosphorus available to the plants. Phosphate is also
solubilised by some bacteria and by some fungi that form association with plant roots.

The various bio-fertilizers are as follows.

(i) Free Living Nitrogen Fixing Bacteria:

They live freely in the soil and perform nitrogen fixation. Some of them are saprotrophic, living
on organic remains, e.g., Azoto- bacter, Bacillus polymyxa, Clostridium, Beijerinckia. They are
further distinguished into aerobic and anaerobic forms.
The property of nitrogen fixation is also found in photoautotrophic bacteria, e.g.,
Rhodopseudomonas, Rhodospirillum, Chromatium. Inoculation of soil with these bacteria helps
in increasing yield and saving of nitrogen fertilizers. For example, Azotobacter occurring in
fields of Cotton, Maize, Jowar and Rice, not only increases yield but also saves nitrogen fertilizer
to the tune of 10-25 kg/ha. Its inoculation is available under the trade name of azotobactrin.

(ii) Free Living Nitrogen Fixing Cyanobacteria:

A number of free living cyanobacteria or blue-green algae have the property of nitrogen fixation,
e.g., Anabaena, Nostoc, Aulosira, Totypothrix, Cylindrospermum, Stigonema. Cyanobacteria are
photosynthetic. Therefore, they add organic matter as well as extra nitrogen to the soil.
Aulosira fertilissima is considered to be the most active nitrogen fixer of Rice fields in India
(Aiyer et al, 1972). Cylindrospermum licheniforme grows in Sugarcane and Maize fields.
Cyanobacteria are an extremely low cost biofertilisers. In Tamil Nadu, the technique of

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cyanobacteria inoculation to rice fields is being followed. Phosphate, Molybdenum and

Potassium are supplied additionally.

(iii) Loose Association of Nitrogen Fixing Bacteria:

Certain nitrogen fixing bacteria like Azospirillum live around the roots of higher plants without
developing any intimate relationship. It is often called rhizosphere association. The bacteria
obtain some plant exudate and use the same as part of their food requirement. The bacteria fix
nitrogen and exude a part of the fixed nitrogen for use by the plant. The phenomenon is termed
as associative mutualism (= associative symbiosis).

(iv) Symbiotic Nitrogen Fixing Bacteria:

They form a mutually beneficial association with the plants. The bacteria obtain food and shelter
from plants. In return, they give a part of their fixed nitrogen to the plants. The most important of
the symbiotic nitrogen fixing bacteria is Rhizobium (pi Rhizobia). It forms nodules on the roots
of legume plants. There are about a dozen species of Rhizobium which form association with
different legume roots, e.g., R. leguminosarum, R. lupini, R. trifolii, R. meliloti, R. phaseoli.
These bacteria, also called rhizobia, live freely in the soil but cannot fix nitrogen except for a
strain of Cowpea Rhizobium (Me Comb et al, 1975). They develop the ability to fix nitrogen
only when they are present inside the root nodules. In the nodule cells, bacteria (bacteroids) lie in
groups surrounded by membrane of the host which is lined by a pink-red pigment called
leghaemoglobin. Presently cultures of Rhizobium specific for different crops are raised in the
laboratory.
Frankia, a nitrogen fixing mycelial bacterium (actinomycete), is associated symbiotically with
the root nodules of several nonlegume plants like Casuarina, Alnus (Alder) Myrica, Rubus etc.
Leaves of a few plants (e.g., Ardisia) develop special internal cavities for providing space to
symbiotic nitrogen fixing bacteria, Xanthomonas and Mycobacterium. Such leaves are a constant
source of nitrogen fertilizer to the soil.

(v) Symbiotic Nitrogen Fixing Cyanobacteria:

Nitrogen fixing cyanobacteria (blue- green algae) form symbiotic association with several plants,
e.g., cycad roots, lichens, liverworts, Azolla (fern). Out of these, Azolla-Anabaena association is
of great importance to agriculture.
Azolla pinnata is a small free floating fresh water fern which multiplies rapidly, doubling every
5-7 days. The fern can coexist with rice plants because it does not interfere with their growth. In
some South-East Asian countries, especially China, the rice fields are regularly provided with
Azolla.
Anabaena azollae resides in the leaf cavities of the fern. It fixes nitrogen. A part of the fixed
nitrogen is excreted in the cavities and becomes available to the fern. The decaying fern plants
release the same for utilization of the rice plants. When field is dried at the time of harvesting,
the fern functions as the green manure, decomposing and enriching the field for the next crop.

(vi) Microphos Biofertilizers:

They release phosphate from bound and insoluble states, e.g., Bacillus polymyxa, Pseudomonas
striata, Aspergillus species.

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(vii) Mycorrhiza (pl-Mycorrhizae Frank,. 1885):

It is a mutually beneficial or symbiotic association of a fungus with the root of a higher plant.
The most common fungal partners of mycorrhiza are Glomus species. Mycorrhizal roots show a
sparse or dense wooly growth of fungal hyphae on their surface. Root cap and root hairs are
absent.
The shape is irregular, tuberous, nodulated or coralloid. The fungus remains restricted to the
cortex of the root. The vascular strand and growing point are not affected. Mycorrhiza often
remains in the upper layers of the soil where organic matter is abundant. Depending upon the
residence of the fungus, mycorrhizae are of two types— ectomycorrhiza and endomycorrhiza.

(a) Ectomycorrhiza (= Ectotrophic Mycorrhiza):

The fungus forms a mantle on the surface of the root. Internally, it lies in the intercellular spaces
of the cortex. The root cells secrete sugars and other food ingredients into the intercellular spaces
for feeding the fungal hyphae. The exposed fungal hyphae increase the surface of the root to
several times. They perform several functions for the plant—

(i) Absorption of water,

(ii) Solubilisation of organic matter of the soil humus, release of inorganic nutrients, absorption
and their transfer to root,
(iii) Direct absorption of minerals from the soil over a large area and handing over the same to
the root. Plants with ectomycorrhiza are known to absorb 2-3 times more of nitrogen,
phosphorus, potassium and calcium,
(iv) The fungus secretes antimicrobial substances which protect the young roots from attack of
pathogens. Ectomycorrhiza occurs in the trees like Eucalyptus, Oak (Quercus), Peach, Pine, etc.
The fungus partner is generally specific. It belongs to basidiomycetes.

(b) Endomycorrhiza (- Endotrophic Mycorrhiza):

Fewer fungal hyphae lie on the surface. The remaining live in the cortex of the root, mostly in
the intercellular spaces with some hyphal tips passing inside the cortical cells, e.g., grasses, crop
plants, orchids and some woody plants. In seedling stage of orchids, the fungal hyphae also
provide nourishment by forming nutrients rich cells called pelotons. Intracellular growth occurs
in order to obtain nourishment because unlike ectomycorrhiza, the cortical cells do not secrete
sugars in the intercellular spaces.
The hyphal tips passing into cortical cells either produce swollen vesicles or finely branched
masses called arbuscules. Therefore, endomycorrhiza is also called VAM or vesicular-arbuscular
mycorrhiza. The major benefits of VAM to the plant are the supply of inorganic nutrients as well
as enhanced water absorption. Phosphate which is mostly present in the unavailable form in the
soil, becomes abundantly available to the plant. A single fungus may form mycorrhizal
association with a number of plants, e.g., Glomus.

Importance of Bio-fertilizers:

(i) They increase the yield of plants by 15-35%.

(ii) Bio-fertilizers are effective even under semi-arid conditions,
(iii) Farmers can prepare the inoculum themselves,
(iv) They improve soil texture,
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(v) Bio-fertilizers do not allow pathogens to flourish,

(vi) They produce vitamins and growth promoting bio-chemical’s,
(vii) They are non-polluting.

Manufacture of some chemical fertilizers

1. THE UREA MANUFACTURING PROCESS
Urea is produced from ammonia and carbon dioxide in two equilibrium reactions:
2NH3 + CO2 = NH2COONH4
ammonium carbamate

NH2COONH4 = NH2CONH2 + H2O

urea

The urea manufacturing process, shown in Figure, is designed to maximise these reactions while
inhibiting biuret formation:

2NH2CONH2 = NH2CONHCONH2 + NH3 biuret

This reaction is undesirable, not only because it lowers the yield of urea, but because biuret burns
the leaves of plants. This means that urea which contains high levels of biuret is unsuitable for
use as a fertiliser.

Step 1 - Synthesis A mixture of compressed CO2 and ammonia at 240 barg is reacted to form
ammonium carbamate. This is an exothermic reaction, and heat is recovered by a boiler which
produces steam. The first reactor acheives 78% conversion of the carbon dioxide to urea and the
liquid is then purified. The second reactor recieves the gas from the first reactor and recycle
solution. Conversion of carbon dioxide to urea is approximately 60% at a pressure of 50 barg.
The solution is then purified in the same process as was used for the liquid from the first reactor.

Step 2 - Purification The major impurities in the mixture at this stage are water from the urea
production reaction and unconsumed reactants (ammonia, carbon dioxide and ammonium
carbamate). The unconsumed reactants are removed in three stages3 . Firstly, the pressure is
reduced from 240 to 17 barg and the solution is heated, which causes the ammonium carbamate
to decompose to ammonia and carbon dioxide:
NH2COONH4 = 2NH3 + CO2
At the same time, some of the ammonia and carbon dioxide flash off. The pressure is then
reduced to 2.0 barg and finally to -0.35 barg, with more ammonia and carbon dioxide being lost
at each stage. By the time the mixture is at -0.35 barg a solution of urea dissolved in water and
free of other impurities remains. At each stage the unconsumed reactants are absorbed into a
water solution which is recycled to the secondary reactor. The excess ammonia is purified and
used as feedstock to the primary reactor.

Step 3 - Concentration 75% of the urea solution is heated under vacuum, which evaporates off
some of the water, increasing the urea concentration from 68% w/w to 80% w/w. At this stage

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some urea crystals also form. The solution is then heated from 80 to 110o C to redissolve these
crystals prior to evaporation. In the evaporation stage molten urea (99% w/w) is produced at
140o C. The remaining 25% of the 68% w/w urea solution is processed under vacuum at 135o C
in a two series evaporator-separator arrangement.

Step 4 - Granulation Urea is sold for fertiliser as 2 - 4 mm diameter granules. These granules are
formed by spraying molten urea onto seed granules which are supported on a bed of air. This
occurs in a granulator which receives the seed gransules at one end and discharges enlarged
granules at the other as molten urea is sprayed through nozzles. Dry, cool granules are classified
using screens. Oversized granules are crushed and combined with undersized ones for use as
seed. All dust and air from the granulator is removed by a fan into a dust scrubber, which
removes the urea with a water solution then discharges the air to the atmosphere. The final
product is cooled in air, weighed and conveyed to bulk storage ready for sale.

2. Ammonium nitrate

The industrial production of ammonium nitrate entails the acid-base

reaction of ammonia with nitric acid

HNO3 + NH3 → NH4NO3

Ammonia is used in its anhydrous form (i.e., gas form) and the nitric acid is concentrated. This
reaction is violent owing to its highly exothermic nature. After the solution is formed, typically
at about 83% concentration, the excess water is evaporated to an ammonium nitrate (AN) content

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of 95% to 99.9% concentration (AN melt), depending on grade. The AN melt is then made into
"prills" or small beads in a spray tower, or into granules by spraying and tumbling in a rotating
drum. The prills or granules may be further dried, cooled, and then coated to prevent caking.
These prills or granules are the typical AN products in commerce.
The ammonia required for this process is obtained by the Haber process from nitrogen and
hydrogen. Ammonia produced by the Haber process is oxidized to nitric acid by the Ostwald
process. Another production method is a variant of the Odda process:
Ca(NO3)2 + 2 NH3 + CO2 + H2O → 2 NH4NO3 + CaCO3
The products, calcium carbonate and ammonium nitrate, may be separately purified or sold
combined as calcium ammonium nitrate.
Ammonium nitrate can also be made via metathesis reactions:
(NH4)2SO4 + Ba(NO3)2 → 2 NH4NO3 + BaSO4
NH4Cl + AgNO3 → NH4NO3 + AgCl

3. Calcium ammonium nitrate

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Molecular formula: 5Ca (NO3)2·NH4NO3·10H2O. It is a new Nitrogenous and Calcareous

fertilizer with characteristics of high efficiency and quickly make-up Nitrogen, applied in
greenhouse and large-area farmland. It improves the soil and granulates the soil making it
anti-caking. It guarantees fruits in gay colors and increases carbohydrate contents in fruits.
The term "calcium ammonium nitrate" is applied to multiple different, but closely related
formulations. One variety of calcium ammonium nitrate is made by adding powdered limestone
to ammonium nitrate; another, fully water-soluble version, is a mixture of calcium
nitrate and ammonium nitrate, which crystallizes as a hydrated double salt:
5Ca(NO3)2•NH4NO3•10H2O.

4. Ammonium phosphate

Ammonium phosphate is an ammonium salt of orthophosphoric acid. It is a highly unstable

compound with the formula (NH4)3PO4. Because of its instability, it is elusive and of no
commercial value. A related "double salt", (NH4)3PO4.(NH4)2HPO4 is also recognized but is too
unstable for practical use. Both triammonium salts evolve ammonia. In contrast to the unstable
nature of the triammonium salts, the diammonium phosphate (NH4)2HPO4 monoammonium
salt (NH4)H2PO4, are stable materials that are commonly used as fertilizers to provide plants with
fixed nitrogen and phosphorus.
Triammonium phosphate can be prepared in the laboratory by treating 85% phosphoric acid with
30% ammonia solution.
H3PO4 + 3 NH3 → (NH4)3PO4
(NH4)3PO4 is a colorless, crystalline solid. The solid, which has the odor of ammonia, is readily
soluble in water. The salt converts to diammonium hydrogen phosphate (NH4)2HPO4.

Ammonium dihydrogen phosphate (ADP), also known as monoammonium

phosphate (MAP) is a chemical compound with the chemical formula (NH4)(H2PO4). ADP is a

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major ingredient of agricultural fertilizers. Monoammonium phosphate is soluble in water and

crystallizes from it as the anhydrous salt in the tetragonal system, as elongated prisms or
needles. It is practically insoluble in ethanol. Solid monoammonium phosphate can be
considered stable in practice for temperatures up to 200 °C, when it decomposes into
gaseous ammonia NH3 and molten phosphoric acid H3PO4.[9] At 125 °C the partial pressure of
ammonia is 0.05 mm Hg. A solution of stoichometric monoammonium phosphate is acidic
(pH 4.7 at 0.1% concentration, 4.2 at 5%). Monoammonium phosphate is industrially prepared
by the exothermic reaction of phosphoric acid and ammonia in the correct proportions:[12]
NH3 + H3PO4 → NH6PO4
Crystalline MAP then precipitates.

Diammonium phosphate (DAP) (chemical formula

(NH4)2HPO4, IUPAC name diammonium hydrogen phosphate) is one of a series
of water-soluble ammonium phosphate salts that can be produced when ammonia reacts
with phosphoric acid. Solid diammonium phosphate shows a dissociation pressure of ammonia
as given by the following expression and equation:

MAP DAP

Ammonium polyphosphate can be prepared by reacting concentrated phosphoric acid

with ammonia. However, iron and aluminum impurities, soluble in concentrated phosphoric acid,
form gelatinous precipitates or "sludges" in ammonium polyphosphate at pH between 5 and
7. Other metal impurities such as copper, chromium, magnesium, and zinc form granular
precipitates. However, depending on the degree of polymerization, ammonium polyphosphate
can act as a chelating agent to keep certain metal ions dissolved in solution.
Ammonium polyphosphate is used as a food additive, emulsifier, and as a fertilizer.

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5. Superphoosphates:

Monocalcium phosphate is an inorganic compound with the chemical

formula Ca(H2PO4)2 ("AMCP" or "CMP-A" for anhydrous monocalcium phosphate). It is
commonly found as the monohydrate ("MCP" or "MCP-M"), Ca(H2PO4)2·H2O. Both salts are
colourless solids. They are used mainly as superphosphate fertilizers and are also
popular leavening agents. Material of relatively high purity, as required for baking, is produced
by treating calcium hydroxide with phosphoric acid:

Ca(OH)2 + 2 H3PO4 → Ca(H2PO4)2 + 2 H2O

Samples of Ca(H2PO4)2 tend to convert to dicalcium phosphate:
Ca(H2PO4)2 → Ca(HPO4) + H3PO4
Superphosphate fertilizers are produced by treatment of "phosphate rock" with acids.
Using phosphoric acid, fluorapatite is converted to Ca(H2PO4)2:
Ca5(PO4)3F + 7 H3PO4 → 5 Ca(H2PO4)2 + HF

This solid is called triple superphosphate. Several million tons are produced annually for use
as fertilizers. Residual HF typically reacts with silicate minerals co-mingled with the phosphate
ores to produce hexafluorosilicic acid (H2SiF6). The majority of the hexafluorosilicic acid is
converted to aluminium fluoride and cryolite for the processing of aluminium. These materials
are central to the conversion of aluminium ore into aluminium metal. When sulfuric acid is used,
the product contains phosphogypsum ( CaSO4·2H2O) and is called single superphosphate.

Dicalcium phosphate is the calcium phosphate with the formula CaHPO4 and its
dihydrate. The "di" prefix in the common name arises because the formation of the HPO42– anion
involves the removal of two protons from phosphoric acid, H3PO4. It is also known as dibasic

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calcium phosphate or calcium monohydrogen phosphate. Dicalcium phosphate is used as

a food additive, it is found in some toothpastes as a polishing agent and is a biomaterial.
Dibasic calcium phosphate is produced by the neutralization of calcium
hydroxide with phosphoric acid, which precipitates the dihydrate as a solid. At 60 °C the
anhydrous form is precipitated:
H3PO4 + Ca(OH)2 → CaHPO4
To prevent degradation that would form hydroxyapatite, sodium pyrophosphate or trimagnesium
phosphate octahydrate are added when for example, dibasic calcium phosphate dihydrate is to be
used as a polishing agent in toothpaste.
In a continuous process CaCl2 can be treated with (NH4)2HPO4 to form the dihydrate:
CaCl2 + (NH4)2HPO4 → CaHPO4•2H2O
A slurry of the dihydrate is then heated to around 65–70 °C to form anhydrous CaHPO4 as a
crystalline precipitate, typically as flat diamondoid crystals, which are suitable for further
processing.
Dibasic calcium phosphate dihydrate is formed in "brushite" calcium phosphate cements
(CPC's), which have medical applications. An example of the overall setting reaction in the
formation of "β-TCP/MCPM" (β-tricalcium phosphate/monocalcium phosphate) calcium
phosphate cements is:
Ca3(PO4)2 + Ca(H2PO4)2•H2O + 7 H2O → 4 CaHPO4•2H2O

Tricalcium phosphate (sometimes abbreviated TCP) is a calcium salt of phosphoric

acid with the chemical formula Ca3(PO4)2. It is also known as tribasic calcium
phosphate and bone phosphate of lime (BPL). It is a white solid of low solubility. Most
commercial samples of "tricalcium phosphate" are in fact hydroxyapatite.
It exists as three crystalline polymorphs α, α', and β. The α and α' states are stable at high
temperatures. Tricalcium phosphate is produced commercially by
treating hydroxyapatite with phosphoric acid and slaked lime. It cannot be precipitated directly
from aqueous solution. Typically double decomposition reactions are employed, involving a
soluble phosphate and calcium salts, e.g. (NH4)2HPO4 + Ca(NO3)2.] is performed under carefully
controlled pH conditions. The precipitate will either be "amorphous tricalcium phosphate",
ATCP, or calcium deficient hydroxyapatite, CDHA, Ca9(HPO4)(PO4)5(OH), (note CDHA is
sometimes termed apatitic calcium triphosphate). Crystalline tricalcium phosphate can be
obtained by calcining the precipitate. β-Ca3(PO4)2 is generally formed, higher temperatures are
required to produce α-Ca3(PO4)2.
An alternative to the wet procedure entails heating a mixture of a calcium pyrophosphate and
calcium carbonate:
CaCO3 + Ca2P2O7 → Ca3(PO4)2 + CO2

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6. Potassium chloride:
Potassium chloride (also known as KCl or potassium salt) is a metal halide salt composed
of potassium and chlorine. It is odorless and has a white or colorless vitreous crystal appearance.
The solid dissolves readily in water, and its solutions have a salt-like taste. It could be obtained
from ancient dried lake deposits. KCl is used as a fertilizer, in medicine, in scientific
applications, and in food processing. The majority of the potassium chloride produced is used for
making fertilizer, called potash, since the growth of many plants is limited by potassium
availability. The two main types of potash are muriate of potash (MOP, potassium chloride) and
sulphate of potash (SOP, potassium sulphate). While SOP typically sells at a premium to MOP,
the vast majority of potash fertilizer worldwide is sold as MOP.
Potassium chloride is extracted from minerals sylvite, carnallite, and potash. It is also extracted
from salt water and can be manufactured by crystallization
from solution, flotation or electrostatic separation from suitable minerals. It is a by-product of the
production of nitric acid from potassium nitrate and hydrochloric acid.
The vast majority of potassium chloride is produced as agricultural and industrial grade potash
in Saskatchewan, Canada, as well as Russia and Belarus. Saskatchewan alone accounted for over
25% of the world's potash production in 2017.

Laboratory methods:

Potassium chloride is inexpensively available and is rarely prepared intentionally in the

laboratory. It can be generated by treating potassium hydroxide (or other potassium bases)
with hydrochloric acid:
KOH + HCl → KCl + H2O

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This conversion is an acid-base neutralization reaction. The resulting salt can then be purified by
recrystallization. Another method would be to allow potassium to burn in the presence of
chlorine gas, also a very exothermic reaction:
2 K + Cl2 → 2 KCl

7. Potassium sulfate:
Potassium sulfate (US) or potassium sulphate (UK), also called sulphate of
potash (SOP), arcanite, or archaically potash of sulfur, is the inorganic compound with
formula K2SO4, a white water-soluble solid. It is commonly used in fertilizers, providing
both potassium and sulfur. The dominant use of potassium sulfate is as a fertilizer. K2SO4 does
not contain chloride, which can be harmful to some crops. Potassium sulfate is preferred for
these crops, which include tobacco and some fruits and vegetables. Crops that are less sensitive
may still require potassium sulfate for optimal growth if the soil accumulates chloride from
irrigation water.
Approximately 1.5 million tons were produced in 1985, typically by the reaction of potassium
chloride with sulfuric acid, analogous to the Mannheim process for producing sodium
sulfate.[7] The process involves intermediate formation of potassium bisulfate, an exothermic
reaction that occurs at room temperature:
KCl + H2SO4 → HCl + KHSO4
The second step of the process is endothermic, requiring energy input:
KCl + KHSO4 → HCl + K2SO4

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Compound fertilizer
Compound fertilizers, which contain N, P, and K, can often be produced by mixing straight
fertilizers. In some cases, chemical reactions occur between the two or more components. For
example, monoammonium and diammonium phosphates, which provide plants with both N and
P, are produced by neutralizing phosphoric acid (from phosphate rock) and ammonia :
NH3 + H3PO4 → (NH4)H2PO4
2 NH3 + H3PO4 → (NH4)2HPO4
Many soils require adding several essential nutrients to alleviate plant deficiencies. Farmers may
opt to select a combination of single-nutrient fertilizers or apply a fertilizer that combines several
nutrients into each particle. These combination fertilizers (compound or complex) can offer
advantages of convenience in the field, economic savings and ease in meeting crop nutritional
needs.
Production:
Manufacturers make compound fertilizers by using basic fertilizer materials, such as ammonia
(NH₃), ammonium phosphate, urea, sulfur (S) and potassium (K) salts. There are many methods
used for making these fertilizers, with the specific manufacturing processes determined by the
available basic components and the desired nutrient content of the finished product. Here are
four brief examples.

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● Compaction methods (agglomeration) involve binding small fertilizer particles together

using compaction, a cementing agent or a chemical bond. Various nutrient ratios can be
combined using undersized particles that may not be suitable for other applications.
● Accretion-based fertilizers are made by repeatedly adding a thin film of nutrient slurry,
which is continually dried, building up multiple layers until the desired granule size is
reached.
● Pipe-cross reactors are used to chemically melt NH₃, acids containing S or phosphorus
(P), and other nutrients—such as K sources and micronutrients—into a solid fertilizer
with the desired nutrient content.
● The nitrophosphate process involves reacting phosphate rock with nitric acid to form a
mixture of compounds containing N and P. If a K source is added during the process, a
solid fertilizer with N, P and K will result.

Agricultural use

Compound fertilizers contain multiple nutrients in each individual granule. They differ from a
blend of fertilizers mixed together to achieve a desired average nutrient composition. This
difference allows farmers to spread compound fertilizer so that each granule delivers a mixture
of nutrients as it dissolves in the soil and eliminates the potential for segregation of nutrient
sources during transport or application. The multiple-nutrient granules of compound fertilizers
also allow the farmer to achieve uniform distribution of micronutrients throughout the root zone.
These fertilizers are especially effective for applying an initial nutrient dose in advance of
planting. There are certain ratios of nutrients available from a fertilizer dealer for specific soil
and crop conditions. This approach offers advantages of simplicity in making complicated
fertilizer decisions, but does not allow farmers the flexibility to blend fertilizers to meet specific
crop requirements. Turf managers and homeowners often find compound fertilizers especially
desirable.

Mixed Fertilizers
Mixed fertiliser typically refers to a fertiliser containing two or more of the elements of nitrogen,
phosphorus and potassium (NPK) which are essential for promoting plant growth and high crop
yields. They are obtained by thoroughly mixing the ingredients either manually or
mechanically.NPK mixture fertilisers are formulated and recommended by agricultural scientists
to enhance the output of crops by giving it specific and exclusive blend of plant nutrients. They
are slow releasing by nature and remain in the field for a long time. They are tailor made as per
the soil and are crop specific.
Mixed fertilisers have a number of advantages, a few of them being:

● Use of mixed fertilisers results in reduction of labour costs as applying a mixture

consumes lesser time as compared to applying the components separately.
● Micro nutrients which help in increasing soil organic matter content are applied in small
amounts to the soil. They can be incorporated in fertiliser mixtures. This facilitates
uniform soil application of plant nutrients.
● If a proper mixture suits a particular soil type and crop, the use of a fertiliser mixture
leads to balanced manuring. It results in higher crop yield.

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● Being in granulated form, mixtures have a better physical condition and hence their
application is easier.
● Residual acidity of of fertilisers can be controlled by using neutralisers in the mixture.

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