By Shameer Mohamed E , Asst Professor SS and AC , COA Padannakkad

Nitrogenous Fertiliser

A Fertilizer can be defined as a mined or manufactured material containing one or more essential plant nutrients in potentially available forms and in
commercially valuable amounts.

Differences between manures and Fertilizers:

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
Elements essential for plant growth:

Macronutrients: N, P, K, Ca, Mg and S These are the essential elemental needed by crops in large quantities

Micronutrients : Fe , Zn ,Cu ,Mn , Mo, B ,Cl, etc., They needed in very less quantities but are essential

Primary nutrients: N, P and K , Secondary nutrients: Ca, Mg and S

The mineral fertilizers are normally produced in Factories run by simple operation by a few people with less investment to huge factories involving
heavy investment. .

Classification of fertilizers

STRAIGHT FERTILIZERS : Straight fertilizers are chemical substances that contain only one nutrient element in absorbable form by plants. The straight
fertilizers include 1) Nitrogenous, 2) Phoshphatic and 3) Potassic fertilizers.

Complete fertiliser-Fertiliser material which contain all three major nutrients (ie N,P,K) may be in blend or mixture form

A few example given as follows 18:18:18 NPK mixture , 19:19:19, NPK mixture, 10:5:20 NPK mixture (for coconut)

Incomplete fertiliser -Fertiliser material which lack any one of the three nutrients

A few example given as follows UAP - Urea Ammonium phosphate 20:20:0:13 Factom phos

Mixed or complex fertiliser-Contain more than one major nutrient produced by the process of chemical reaction. Eg NPK complex fertiliser

1. NITROGENOUS FERTILIZERS

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
Nitrogenous fertilizers are chemical substances that contain the nutrient element nitrogen in absorbable form by plants chiefly as ammonium (NH4+)
or nitrate (NO3-) or which yield these from after conversion .

Origin and reserves:

1) Nitrogen reserves on the earth are abundant. The earth’s atmosphere consists of nearly 80 percent of nitrogen by volume.

2) Deposits of natural nitrates present in vast areas in CHILE and PERU of pacific coast of South America. The nitrogen containing salt of these deposits
are called chile salt peter.

3) Majority of the nitrogenous fertilizers are produced synthetically from atmospheric N via ammonia synthesis .

Though crop plants are surrounded by atmospheric nitrogen (N2).They cannot split this highly stable molecule and convert it into utilizable forms

But this splitting (splitting of N2) is done only by certain microorganisms in the presence of specific enzymes (nitrogenase) through the process known
as Biological nitrogen fixation (BNF). Fixing of atmospheric nitrogen by human being in big factories is known as Industrial Nitrogen fixation

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
Manufacturing process: of AMMONIA:

The synthesis of ammonia (NH3) is the basis for nitrogen fertiliser industry .The production of Ammonia is done by the process is called Haber –Bosch
process.

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
 In the Haber –Bosch process the reaction between molecular atmosphere nitrogen and hydrogen, takes place at a pressure of 200 atmospheres and a
temperature of 550 0C .

N2 (g) +3H2 (g) 2NH3 (g)

Synthesis of ammonia being an exothermic reaction produces heat, so, that production of N2 and H2 requires large quantities of energy.

Raw materials:

Atmospheric air is the source of N2. The raw material for H2 in the manufacture of ammonia include water , natural gas ,naphtha ,fuel oil or heavy
petroleum fractions , coal and coke oven gas.

i) Water :

The electrolysis of water to generate H2 requires an electric power. This method is adopted wherever abundant supply of electricity is available with
cheep rate.

ii) Natural gas :

.About 64 % of ammonia produced in the world is from natural gas. Natural gas is a mixture of gases viz., methane ,ethane ,butane , propane ,pentane
and CO2 etc., of all these gases methane constitutes major portion varying 74 to 94 per cent by volume .

iii) Naphtha :

The light distillate fraction of petroleum which is produced during the refining of crude oil . About 75% of nitrogen produced in India utilizes NAPHTHA
for hydrogen source.

iv) Fuel oil

Fuel oil contains various products obtain from primary distillation.

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
Other two sources are coal and coke oven gas

UREA (NH2CO NH2)]

Urea is used as a fertilizer for crops and also as protein supplement for farm animals. Major share of nitrogen in India from Urea. It has got very high
nutrient content (46% of nitrogen). It can be applied to soil also as foliar spray to crops. Urea can also be applied as foliar spray with a concentration of
2%. It give quickest response to the crops. It is hygroscopic – Hence to be stored in moisture proof bags. It is white chrystalline

Urea absorb moisture from atmosphere, if RH is >70%

Manufacturing process of Urea

Raw materials needed are 1. Ammonia 2. Carbon dioxide

Ammonia is manufacturd by Haber Bosch process (see previous page )

F.WHOLER (German chemist ),first prepared urea in the year 1828 (The first synthesised organic chemical from inorganic chemical is urea)

But commercial production of urea as fertiliser started in 1922.

The commercial production of fertiliser urea as follows

Liquid ammonia and carbon dioxide gas are pumped continuously into a reactor maintained at temperature ranging 180-200 0C and pressure ranging
2500 to 3500 Psi. The reaction is exothermic. The reaction product , is a mixture of urea ,ammonia, carbon dioxide , ammonium carbamate and water
.The mixture is then flows in to a carbamate strippers, where liquid phase of urea , water containing small quantities of ammonium carbamate
,ammonia and gaseous phase of ammonia, carbon dioxide and water vapour are separated .The aqueous urea solution contains around 70-80 per cent
urea . Then it is concentrated to produce solid urea.

2NH3 +CO2 NH2COONH4

Unstable intermediate product – Ammonium carbonate

NH2COONH4 CO (NH2)2 + H2O

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
Occurs at 180-200o C and 2500-3500 psi

 Biuret:

When concentrated urea solution is exposed to high temperatures during evaporation in prilling process, biuret is formed by mixing of two urea
molecules. Biuret is toxic to plants.

NH2 CO NH2 + NH2 CO NH2 NH2 –CO-NH-CO-NH2 + NH3

Maximum permissible content of Biuret in urea is 1.5%. Above this level toxic to plant

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
Physical properties of Urea

1. White organic compound with low bulk density i.e., 0.7 kg /L

2. It is a solid fertilizer usually granulated

3. Having specific gravity of 1.335

Chemical properties of Urea

1. Richest source of N (46%) in amide form. 2. Soluble in water and solubility is 100 g /100 g of water at 2000 C

Reaction urea in soil

Urea is easily hydrolyses to ammonia soon after its application to the soil in the presence of urease enzyme produced by micro
organisms and then urea is converted to ammonium carbonate and then by microbial oxidation into ammonium and nitrate ions and these
forms are absorbed by plant . Some of the ammonia and nitrate formed is lost due to leaching , volatilization and denitrification and these
losses are responsible for the low recovery of urea by rice which is generally 40-50 per cent.

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
Acidity due to different N fertiliser

H + is released during nitrification of NH4+ based nitrogenous fertiliser. This will cause decrease the p H of the soil.

For example, Application of 100 kg urea to soil results acidity in soil , which requires 80 kg of CaCO3 to neutralize the acidity created in that particular
soil. This is known as acid equivalent of urea

Dose of urea for Foliar spraying is 3 to 5 % .

Acid forming fertiliser- when this kind of fertiliser applied to soil , soil become more acidic Eg Ammonium sulphate, Ammonium nitrate, Urea

In the case of Base forming fertiliser when it applied to soil , the soil become more basic Eg, Calcium nitrate and KNO3

Neutral fertiliser- when applied this fertiliser to soil , the pH of the soil wont change

Eg CAN- Calcium ammonium nitrate

Ammonium sulphate (NH4)2SO4

It contains N- 20.6 - 21 % and S - 24%

It is white crystalline and with good keeping quality. It is a quick acting fertiliser and soluble in water

It is retained in the soil colloid (since NH4 in cationic form). Since soil colloid is having negative charge, hence NH4+ ions are absorbed in soil

 Loss by leaching is less

 When applied to alkaline soil, Ammonium in ammonium sulphate fertiliser will be lost through volatilisation process

Reaction of Ammonium sulphate in soil

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
 When applid to the soil, ammonium ion in ammonium sulphate will under go cation exchange with soil colloid especially with Ca ion. Thus ca sulphate
is formed, which leached from the soil . The Ammonium ion in the soil colloid may be taken up by plants or may under go nitrification to form nitrate
ion. During the nitrification of the ammonium ion, Hydrogen ion will be formed , hence pH of soil will be decreasing . Hence continual use of
ammonium sulphate will cause acidity of soil also cause loss of Ca from soil

 It is acid producing fertiliser

 Acid equivalent of Ammonium sulphate is 110

 (ie 110 kg Lime is needed to neutralise the acidity caused by application of 100kg of Amm sulphate)

Manufacturing process of Ammonium sulphate

1. Gypsum process or leuna process:

Raw materials :

NH3 ,CO2 and Gypsum

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
  Anhydrous ammonia is absorbed in water and CO2 is pumped at 5 atmospheres .The Ammoniam carbonate is formed which is made to react
with Gypsum.Then ammonia sulphate and calcium carbonate are formed . The calcium carbonate being insoluble ,precipitated out ,the
ammonium sulphate solution is filtered out,

 Reactions:

 NH3 +H2O⇋ NH4OH

 2 NH4OH +CO2 → (NH 4)CO3 + H2O

 (NH 4)CO3 +CaSO4 2H2O⇋(NH4)2SO4+CaCO3

2. By product process: [Raw materials Coal and Sulphuric acid ]

 During the production of iron and steel the bituminous coal is subjected to destructive distillation (heating coal (980 0C). During this process coke
is obtained which is used for iron and steel industry. The by product coke oven gas is evolved contains 10 per cent ammonia. This coke oven gas
is cooled and bubbled through water ,then liquor ammonia is formed ,which is distilled and passed into saturators containing weak H2SO4 .Thus
Ammonium sulphate crystals are formed which are centrifuged ,washed and drained.

 Reaction:

2NH3 (g) +H2SO4 → (NH4)2 SO4

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
3. Neutralization process:

 [Raw materials NH3 and H2SO4]

 Gaseous ammonia produced in Haber and Bosch process is directly neutralized with sulfuric acid to produce ammonium sulphate.

 2NH3 (g)+H2SO4(liquid ) → (NH4)2SO4

Advantage of urea over Ammo sulphate

 During manufacture of Ammonium sulphate, Sulphur or Gypsum is needed which to be imported which involve high foreign exchange

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
  Contain high % of N in urea

 Hence cost handling and transport per unit weight of N is less

 Urea relatively less acid forming than Amm sulphate

 Urea can be used for foliar spray where as amm sulphate cannot be used for foliar spray

Ammonium chloride (NH4Cl) fertiliser

 It is White crystalline. It contains Nitrogen - 25%. The nitrogen iin Ammoniacal form. It is good fertiliser for paddy. It is resistant to leaching

 In India it is mainly for industrial purpose

 Not recommended for tomoto and tobocco due to chloride injury

 Act as decalcifying fertiliser

 when applied to calcareous soil (soil containing CaCO3 ) , CaCl2 is formed and which is leached from the root zone

Manufacturing process of Amm chloride

 NaCl is treated with NH4 and CO2 to form Amm chloride and Na carboanate

 Nacl +CO2+ NH3+ H2O NH4Cl +NaHCO3

Calcium ammo nitrate (CAN) fertiliser

 It is combination of Amm nitrate and ca carbonate

 contains 25 % nitrogen with equal quantity of each NH4+ and NO3- forms of nitrogen

 NH4+ nitrogen 12.5%

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
  NO3- nitrogen 12.5%

 It is a neutral fertilizer and leaves neither acidic nor basic residues on soil application

 it contains 8.1 % of calcium

 It is readily soluble in water

Manufacturing process:

 Anhydrous NH3 and HNO3 are heated to get ammonium nitrate liquor of 82 to 83 %. It is further concentrated to 92 to 94 % by heating with
steam in a vacuum concentrator

 NH3 (g) +HNO3 → NH4NO3

 The concentrated ammonium nitrate solution is sprayed on lime stone powder then granules of Calcium ammonium nitrate are obtained
.which is cooler by air , and coated with soap stone dust (Talc) in a coating drum.

 The final product is a mixture of calcium carbonate and ammonium nitrate.

 NH4NO3 +Ca CO3 → NH4NO3 CaCO3

Amm sulphate nitrate (ASN)

 26% N and 13 % S

 Manufactured by reacting Un hydrous Ammonia with HNO3 and H2SO4

 Has good storage and handling properties. It is very good for direct applicaton. It can be used in blended fertilisers

Amm nitrate- NH4 NO3

 Contains 33-34 % N. Not manufactured in India. It has got high solubility. It suited for fertigation and foliar application

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
  It is produced by reacting ammonia gas with conc HNO3

 nitro chalk - Trade name of the product of the mixture of Amm nitrate and 40 % lime stone or dolomite

Sodium nitrate (NaNO3)

It is known as Chilean Nitrate. It is the oldest nitrogenous fertiliser. It is obianed from Salt peter of Chile.

Properties

Causes fire hazards

Quickly leached from soil

N 16%

Na 27 %

It is a Basic fertiliser

Importance of urea as nitrogenous fertilizer

1. High nitrogen content 44 to 46 per cent

2. Good physical condition

3. Less cost per unit of nitrogen in production, storage and transportation

4. when applied to soil , urea is less acidic as compared to ammonium sulphate

5. Suitable for foliar application

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
 6. Lack of corrosiveness

Slow release N fertiliser

 Majority of N fertiliser applied to soil have been lost due to different process like Ammonium volatilisation , leaching etc

 Efficiency of applied N fertiliser to the soil is 60-70%

 Main loss of nitrogen is by Amm volatilisation , leaching

 Maximum loss pf nitrogen by leaching of Nitrate N

 Aim of slow release N fertiliser to minimise loss of applied fertiliser

 Also to prevent frequent application of fertiliser

They are three types,

1. Coated N fertiliser
Due to coating with substance like Lac, neem, sulphur etc ,urea will be released to soil (root zone) very slowly by diffusion process

N will be supplied to plants at controlled rate for longer period

Examples

a. Sulphur coated urea- (SCU)

S will be oxidised to H2SO4 ( in presence of S oxidising bacteria) thereby reduce activities of nitrifiiers

b. Lac coated urea (LCU)

c. Neem coated urea (NCU)

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
 2. N substance of low water solubility
a. Urea formaldehyde or urea form – It contain 38% N
Manufactured by reacting urea with formaldehyde

b.CDU- ( Crotonylidene Diurea) it contain 30% N

Manufactured by reacting urea with acetaldehyde

C. Thio urea 36.8 % . It contain N

d. Oxamide. It contain 31.8 %N

3. Nitrification inhibitor
This will slows down the nitrification reaction in soil , there by retard the conversion of ammoniacal nitrogen to nitrate nitrogen in soil

They block the bacteria responsible for nitrification ie nitrosomonas and nitrobactor

 A nitrification inhibitor should be non toxic to plants, soil , micro organism, animals, fish and mammals

It should be able to move with fertiliser or fertiliser solution so that it will be distributed uniformly through out the soil contacted by Nitrogen
fertiliser

Examples are following

 N serve chemically it is -2 chloro 6 trichloromethyl pyridine. It is known as Nitrapyrine

 AM 2 amino 4 chloro 6 methyl pyrimidine

Advantages of slow release fertiliser

 Aim of slow release N fertiliser to minimise loss of applied N fertiliser

 Also helps to avoid frequent application of N fertiliser
 Increase efficiency of applied N
 Avoid luxury consumption of N

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad
  Reduce the activities of Nitrifiers

Choice of nitrogenous fertiliser in different soil types

 In submerged soil Ammoniacl or ammonia forming fertiliser is good. This is because Ammonia is the most stable form of Nitrogen under
submerged condition

 In acidic upland soil, Ammoniacal fertiliser is good, This is because ammonia ion (NH4+ ion) absorbed in soil colloid. Hence leaching loss will be
reduced

 In highly acidic upland soil urea is preferred than Ammonium sulphate

 In alkaline upland soils of low rain fall situation nitrate fertiliser is preferred than Ammonium fertiliser, because ammonium present in the
fertiliser may undergo voltalisation under alkaline condition

Prepared by Shameer Mohamed E, Asst Professor, Dept of Soil science and Agricultural chemistry, Kerala Agricultural University, College of Agriculture,
Padannakkad