FERTILIZERS , = 10-763 as well as minor plant nutrients; plants may need light, heat, watet, carbon dioxide, oxygen ete for optimum growth. .” NUTRIENT FUNCTIONS The role of various nutrients in the plant growth has been studied extensively but is not yet fully understood. Some of the important findings are, however, briefly given below: Nitrogen- Nitrogen is the most important nutrient for plants, It is the first fertilizer clement of mac- ronutrients usvally applied in commercial fertilizers. Nitrogen is very important nutrient for plants and it seems to have the quickest and most pronounced effect. It also forms a constituent of every living cell in the plant. Plants for their growth require sixteen elements, namely, carbon, hydrogen, oxygen, potas- sium, phosphorus, nitrogen, calcium, magnesium, sulphur, zinc, boron, copper, manganese, molybdenum, chlorine and iron. Out of these three, namely éarbon, hydrogen and oxygen are derived from air and water and so these are called natural nutrients. Nitrogen, phosphorus and potassium are consumed in large amounts by the plints for their growth and so these are called primary nutrients. Calcium, magnesium and sulphur which occur to a limited extent in all soils, are calied secondary nutrients. Rest of the elements are required by the plants ia minute amounts and so these are called micro nutrients. Soil takes up the-nitrogen in the form of ammonium or-nitrate ions and forms amino acids with carbon compounds in the’ compiex-chemical system in the plant These amino acids are then converted into proteins and enzymes. Proteins thus formed make part of the protoplasm, while enzymes act as catalysts for various reactions taking. place in the plants. Nitrogen is’ also a. special constituent of the chlorophyll, without which photosynthesis is not possible. Nitrogen makes up 16-18% of the plant protein and constitutes,1-4% of the dry weight of plants and is required in large amounts of any of the plant nutrients. The main sources of nitzogea are (a) Fertilizers-(b) Organic nitrogen compounds formed in the soil by recurring natural processes, and (c) Atmosphere. The riatural sources are however, not sufficient for adequate plant: growth and so artificial nitrogen compounds in the form of. fertilizers are added to the soil for making the soil productive. “ In fact, air contains 78% nitrogen, but plants can not use it directly. But the plants belonging to the family of leguminoceae, can play host to a special group of nitrogen fixing bacteria such as Rhizobium. This bacteria is capable of converting atmospheric nitrogen into organic form that can be used by host plants. Some common examples of legumes are pulses, soyabean, groundnut, berscem, clovers and -guar. Nitrogen is not only essential constituent of protein and chlorophyll, but it is also involved in photosyn- thesis, respiration and protein synthesis, The most important functions of nitrogen are : (a) Nitrogen tends primarily to encourage above ground vegetative growth and it imparts dark green colour to the plants, (b) Nitrogen regulates to a considerable extent the utilisation of potassium, phosphorus and other constituents. (c) Nitrogen promotes vegetative growth and improves the quality of the produce including fodder, leafy vegetable and food crops. (d),Nitrogen increases the tillering of cereal crops. (¢) “When nitrogen is present in sufficient amounts in the soil, plants acquire healthy green colour which is neither too dark nor too light, growth of the plant is fairly rapid and crop natures normally and gives high yields. (f) Nitrogen increases the protein content of food and fodder, It also increases the plumpness of grain in the cereal crops. + Abundant supply of nitrogen may, however, cause some adverse effects, which include : (a) It delays ripening by encouraging more vegetative growth. The leaves acquire a dark green colour, become thick and leathery and in some cases crinkled. They may also become soft and shappy. The plants become more susceptible to attack of certain fungi and their resistance to disease decreases. (b) In case of cereal crops. the straw becomes weak, and the crop very often lodges and straw and grain ratio is increased. (c) Excess nitrogen deteriorates the quality of some crops such as potato, barley and sugarcane. (d) It detays reproductive growth and may adversely offect fruit and grain quality. The deficiency of nitrogen may also cause some adverse effects, which include: (a) The plant become yellowish or light green and remains stunted. (b) The leaves and young fruits tend to drop prematurely. (c) A nitrogen deficient plant ripens prematurely and crop gives poor yield. (d)INDUSTRIAL CHEMISTRY 764 ‘The keels or cereals and the seed of other crops do not attain their normal size, and become shrivelled and light in weight. (e) Root growth is severely affected. (f) It delays reproductive growth, but increases profuse vegetative growth. (g) The flower bud often turns pale and sheds prematurely. ‘ Phosphorus - Phosphorus is the second fertilizer element and it is essential constituent of every living cell and for the nutrition of plant and animal. It takes active part in all types of metabolism of plant. It is essential constituent of many enzymes and also structural component of membrane system of cells, the chloroplasts and the mitochondria. ~ It is required in. much lesser amounts than nitrogen. Most soils contain phosphate in the form of complex calcium phosphate, iron and aluminium complexes and organic compounds. Such sources are insoluble and so the plants can make very little'use of them. It has been found that certain high energy phosphate bonds are involved in the respiratory and pho- tosynthetic processes. These bonds transfer energy in some Of the plants metabolic processes without which the plant could not live. The need of phosphorus is also necessary for the health of the plant. It is a constituent of nucleic acids, phytins and phospholipids. It is also found in seeds and fruits. The phos- phorus has also been found to contribute to the-formation of the reproductive parts in the early life of the plant, Liebig (1940) first emphasized the need for phosphates and his work led to the commercial production of phosphate fertilizers. The main functions of phosphorus include: (a) It stimulates ‘root development and growth in the seedling stage and hence help to establish the seedling quickly. (b) It enhances leaf development and encourages greater growth of shoots and roots. (c) It enhances the development of reproductive parts and thus brings about early:maturity of crops particularly the cereals and counteracts the effect of excess nitrogen. (d) It develops resistance to certain diseases. (e) It increases the number of tiller in-cereal cops and also increases the’ ratio of grain to siraw. As a result, the yield is increased. (f)'It increases the straw of cereal crops and helps in preventing the lodginig. (g) It influences cell division.and formation of fat and albumin. (h) It stimulates the flowering, ‘fruit settirlg and seed formation and the development of roots, particularly pf root crops. (i) It has a ‘special action on leguminous crops. It induces nodule formation of such crops and rhizobial activity. In other words, it helps in fixing more atmospheric nitrogen in root nodules, . Excessive phosphorus, however, has some adverse effects, which include: (a) Profuse root growth, particularly to the lateral and fibrous rootlets. (b) It Wevelops normal growth having green leaf colour. (c) It may cause trace element deficiencies in some cases, particularly those of iron and tinc. (d) Unlike nitrogen, excess of phosphorus is not harmful. . A deficiency of phosphorus may cause the following important adverse effects: (a) Roots and shoot growth is restricted and plants become thin and spindly. (b) Leaves may shed prematurely and there may be considerable delaying In flowering and fruiting, (c) The leaves of cereal Crops become dull greyish green in colour. The deficiency is shown by slow growth and low yields. (d) ‘Stunted growth even under abundant supply of nitrogen and potash, and premature ripening of crops. (e) The tering of cereal crops decreases as a result of which yield becomes slow. (f) Potato tubers have shown rusty brown lessions, * x , : Potassium- Potassium, the third fertilizer element acts as a chemical traffic policeman, root booster, food former, sugar and starch transporter, protein builder, breathing regulator, water stretcher and as a disease retarder, but it is effective only in presence of conutrients such as nitrogen and phosphorus. ‘The function of potassium is not clearly known, but it as been found that it is essential for healthy growth of plants and can not be replaced even by closely related elements as sodium and lithium. In the plant, it either occurs as a psrt of the anion of organic acid or as a soluble inorganic salt in the tissues. Formation and movement of carbohydrates. in plant is contributed by potassium and a deficiency of po- tassium quickly reduces the carbohydrate contents. The potassium content of plants ranges from about 05-25% of the dry weight. Potassium has also been found to contribute to-the vigour and resistance of plants. The iwportant functions of potassium are given below: (a) it is an essential element for the development of chlorophyll. (b) It is essential for photosynthesis,FERTILIZERS : 10-765 that is, for converting CO; and water into sugars and for translocation of sugars and also for starch formation, Potassium is, therefore, of special value for crops-like sugarcane and potatoes which are rich in sugar and starch. (c) Potassium is absolutely necessary for tuber development. (d) Potassium improves the health and.vigour of the plant, enabling it to withstand adverse climate conditions. (e) It increases the crop resistance to certain diseases and counteract the adverse effects of excess nitrogen. (f) Potassium is necessary for the production of best quality of grains and fruits. (g) Potash plays an important role in the production of quality vegetables. (h) It strengthens the straw of cereals and keeps the plants green. Thus it reduces lodging in cereal crops. (i) Potassium improves the quality of some crops such as tobacco, potatoes, sugarcane, vegetables and fruits. (j) Potassium also works ageinst undue ripening influences of phosphorus. In general, potassium exerts a balancing effect on both nitrogen and phosphorus. Hence it is especially important in mixed fertilizers. (k) Potassium increases the plumpness and boldness of grains and seeds. (1) Potassium acts as an enzyme activator. (m) Potassium improves water balance, promotes metabolism and increases the production of carbohydrates. The potassium deficiency may cause the following important effects. (a) Deficiency of potassium may cause chlorosis, i.e. yellowing of leaves and leaf scorch in the case of fruit trees. (b) Deficiency of potassium is also responsible for dying back tips of shoots. The older leaves have been found to show-the deficiency symptoms earlier. (c) Potassium deficient plants show a decreased rate of photosynthesis. (d) Potassium deficient plant becomes stunted in growth with shortening of intermodes and bushy in'cppearance. (e) Potato plant shows an abnormal dark green colour of foliage followed by brownish. (f) Deficiency of potash results in blackeniag of tubers and damage in shortage and transit, . ; Calcium Calcium acts as a plant nutrient and also as a soil amendment to correct soil acidity. It is found as a plant constituent in the cell walls of leaves in the form of calcium pectate. Calcium is closely associated with the growth of the flowers and a deficiency of calcium also prevents normal development of buds and tips. Calcium is also found in cell sap either in the ionic form or as salts of organic acids. Application of calcium to the soils in the form of CaCO; corrects the soils acidity rather than supplying 1 nutrient, Calcium is.a structural component of chromosomes. It has been established as an essential element for plants in 1939. The main functions of calcium include : (a) It promotes root development and growth of plant because it is involved in root elongation and cell division. (b) It is helpful in translocation of sugar in the plants. (c) It enhances the nodule formation in leguminous plants and thereby rhibial activity is increased, (d) It neutralises organic acids which may become poisonous to the plants. (e) It induces stiffness of straw and hence leads to the prevention of undesirable lodging of plants. (f) It is an essential cofactor or an activator of various enzymes including lipase and apyrase. (h) It acts as a buffer in plant systems and ameliorates the toxic effects of other nutrients if they are at toxic levels in the plant. (i) The structure of soil having calcium becomes good and cation exchange capacity increases. (j) It improves the intake of other plant nutrients, especially nitrogen and trace elements such as Fe, Zn,.Cu, Mn, and B by correcting the pH of the soil: Excessive amounts of calcium, however, decrease the availability of many micronutrients. The defi- ciency of calcium may cause the following important adverse effects. * (a) The normal growth of the plant is arrested. (b) Roots may become short, stubby and brown. (c) ts deficiency may cause soil to be acidic. (d) The acidity of saps of cells increases abnormally and it hampers the physiological function of the plant. As a result, plant suffers illness and causes the death of plant at last. {e) Leaves may become wrinkled and the young leaves of cereal crops remain folded. () . Young leaves of terminal buds die back at the tips and,margins. It should be noted that calcium deficiency resembles.boron deficiency. ‘ : . Magnestum — Magnesiumfacts as a carrier of-phosphate and, therefore, plays an important part in the formation’ of phospholipids'and in the synthesis of nucleoproteins, Magnesium is also a mineral con- stituent of chlorophyll and makes up’2.7% of the weight of chlorophyll. Several photosynthetic enzymes - - present in chlorophyll require magnesium as an activator. Magnesium Is usually required by-plants in relatively small quantities. Hence its deficiency in soil is observed later than that of potassium. DeficiencyFERTILIZERS 10-769 to determine the most effective and economical materials for supplying these nutrients. Taking this fact into consideration and because of relatively large consumption of macronutrients in agriculture, much time has been devoted mainly to nitrogen, phosphorus and potassium fertilizers. Nitrogen is usually supplied eithér in the ammonical or in the nitrate form, For most agricultural situations it makes litle difference which form is used, because the ammonical form is converted rapidly to nitrates in the soil by the action of nitrifying bacteria. In spscial cases, ¢.g., in case of low soil tem- perature, nitrification- may be delayed, For example, urea requires a little longer to reach nitrate stage, because it must first hydrblyse to the ammonical form. Inorder to get good results, a number of im- provements have been-made-in technology. Some of them include : (a) Caking and hygroscopicity. (b) Fire and detonation hazards. (c) Nitrogen loss after application *: to the soit: (d):Nonunifom. release of nitrogen 10 the plant during the growth period. In addition to these, continuous efforts are in progress to reduce production cost and to increase - concentration. Phosphates are supplied in two major forms to the plant-as calcium phosphate or ammonium phosphates. Dicalcium phiosphate is the principal phosphate constituent in two major fertilizers. One is nitric phosphate, a product made by dissolving phosphate ore in nitric acid, neutralising with ammonia and drying and granulating the resulting slurry. The other is ammoniated superphosphate. Dicalcium phosphate is formed when. monocalcium phosphate in super phosphate is treated with ammonia. In both the: processes, formation of some calcium phosphate more basic than dicalcium phosphate causes unde- sirable results, which are avoided as much as possible . .Mono calcium phosphate is classed with ammonium phosphate in solubility. For phosphates of low solubility, best results are.obtained with finely divided material on acid soil. Development work on-phosphate fertilizers, is aimed mainly. at reducing cost of production and in- creasing nutrient:content.A new product, which contains phosphate in the polyphosphate rather than the ‘usual orthophosphate form has also been introduced in the industry and is expected to give good results. Unlike nitrogen and phosphorus, the selection of potash compound for fertilizers is no problem, because potash is available in natural deposits. For example, KCI occurs is large deposits. It is soluble and readily available to plants with further treatment: After mining’ the low cost of KCl makes potassium the least costly of any of the nutrients in the product. Another potash material, potassium sulphate occurs mainly as double salt, KSOs.2MgSOg (Langbeinite). It.is either used as such or treated to remove associated salt. Secondary nutrients are.not really a part of fertilizers industry and therefore, do not enter very much imo consideration. For example, calcium and magnesium are supplied by application of limestone or dolomite limestone osed to correct soil acidity. Calcined limestone has also becn used. Calcium is also supplied in the form of byproducts, such + furnace slags, as gypsum etc. Sulphur is supplied as ammonium sulphate and potassium sulphate, and in the calcium sulphate found in one form of superphosphate. Micronutrients are usually supplied as soluble sulphates. : : NEED FOR FERTILIZERS © . After repeated cultivation, a stage is, however, reached when the soil becomes less productive, if ‘supply of the above nutrients js not provided, Thus, in order tq make up this deficiency,certain elements in the form of their compounds. have to be added to the soil to make reproductive. These substances are known as fertilizers. Thus fertilizers are those substances which must be added to the soil inorder | to remove the deficiency of essential elements required for plant growth. The need of fertilizing a * and is therefore three fold: : =. (To supplement what has been eaten up by the plants. + (b)’ To supply them an additional tonic and good food, so that they may grow more health and ; produce'a better yield, ¢ (©) _ To manitain the pH of the, soil in the vicinity of 7-8 and thereby facilitate optimum growth * and health . 4FERTILIZERS OT Because low pH of the soil is not conductive to plant growth, the adverse acidity effect 18 compensates by adding lime to the soil. Lime not only eliminates effectively the acids (H,SO4, HNO) etc) in the soil, bot also precipitates the toxic materials without affecting the structure of the soil. The harmful high pH! effects are’ removed by treatment with aluminium sulphate, ammonium phosphate, ammonium sulphate etc, through graded acidification of the soil by hydrolysis. CLASSIFICATION OF FERTILIZERS Inorganic fertilizers are classified according to the role they play in soil chemistry, the number and types of nutrient elements they contain, their physicochemical properties and in particular, thei solubility in soil water, their physiological effect on the soil to which the fertilizer has been applied, method used for manufacturing them etc. Fertilizers are classified as direct or indirect fertilizers according to their agrochemical nature. Direct fertilizers are those which contain the nutrient elements in the form of compounds which are directly assimilated by plants. Indirect fertilizers are those substances which are added to the soil inorder to improve its chemical, mechanical or biological propefties. Ground dolomite and limestone, used to decrease soil acidity and gypsum used to improve the properties of soils with a high salt content, are the examples of indirect fertilizers. Direct fertilizers are classified as phosphatic, nitrogenous, potash, magnesium etc., according to the nutrient element present in therh. According to the number of basic nutrient elements such as phosphorus, nitrogen and potassium in them, fertilizers are classified as sirnple fertilizers, containing only one nutrient clement, or double or triple fertilizers, containing two or three elements respectively. The triple fertilizers are also called complete fertilizers, because they contain all the principal nutrient elements nitrogen. phosphorus and potassium. Microfertilizers are those which contain the elements such as boron, manga- nese, zinc and copper. These fertilizers are required in very small amounts to stimulate the plant growth. Fertilizers containing several nutrient elements and obtained by mechanical mixing of various fertilizers are known as mixed ones. Fertilizers containing several nutrient elements which are produced by chemical reactions are known as complex fertilizers. : Fertilizers are classified as water soluble or soluble in soil acids according to their solubility in the moisture in the soil. All nitrogenous and potash fertilizers are soluble in water. These fertilizers are readily assimilated by plants, but they are quickly washed out of the soil by surface water. Most phos- phates are the fertilizers soluble in soil acids. They are dissolved much slower, but are retained in the soil much longer. Fertilizers are classified as physiologically acid, physiologically alkaline, or physio- logically neutral, according to their physiological effect on the soil to which they are added. The phys iologically neutral fertilizers do not change the pH cf the soil. According to their form or physical properties, fertilizers are subdivided into. powder form and granulated form. Granulated fertilizers arc less hygroscopic and they do not cake during storage. They are not subjected to weathering after being introduced into the soil and are retained by the soil for 2 longer time, that is, they are not washed out quickly by rains. Moreover, granulated fertilizers can be added to the solid using fertilizer machines or seed drills. STRAIGHT AND MIXED FERTILIZERS For most crops application of more than one nutrient is required, The farmer could purchase single nutrient materials and apply them separately or mix them together before application, Materials can also be supplied simultaneously, but combining nutrient materials to make mixed (multi nutrient) fertilizers is more common now, Mixed fertilizers are prepared by mixing appropriate amounts of ammonium salts, superphosphates, potassium salts etc. and in this manner they supply more than one essential elements to the soil, Straight fertilizers are sometimes used in special situations, such as giving the plant an additional supply of nitrogen after it is used up, thereby reducing leaching loss and ensuring an adequate supply of nitrogen throghout the growth periad, Potash is ofien added to pastures as a straight material. Phosphate is also applied straight, but to much lesser extent than in mixed fertilizers. The amount of nitrogen in straight form is more than six times as that of phosphate or potash.“NOUSTRIAL CHEMISTRY CxH;PO.),+Cx(HCOs) 2 2CaHPO,+2H,C0, CaHPOD: + ACAHCO;), = Cay(PO,), + 4H;CO, Dicalcium phosphate is slowly dissolved in soil water containing carbonic acid and becomes available to growing plant. The tricalcium phosphate, being insoluble, remains in the soil as fixed phosphate. POTASSIUM FERTILIZERS Potassium containing feniizers are KNOs, KCI and K,SOu. Potassium is most conveniently expressed as K,0. KNO; or chile saltpeire has already been discussed. KCI is obtained, by the evaporation of dead sea brine * solar energy. During the process of evaporation, the concentration increases from 1.2 in the brine to 23% in liquor which crystallizes in the pan. After refining, about 97% pure KCI can be obtained, KCI contains about 63.17% K;0 and K content of about 52.44%. Potassium chloride is most common potassium fertilizer having potash (K20) in ehloride form. It is sold in the market as Muriate of potash. It is cheaper than all other potassium fertilizers and so itis ceatensively used by the farmers and cultivators throughout the world It can also be prepared by ores such as carnallite, KCLMgClz6H,0, and kainite, KCLMgSO,3H,0 by crystallisation and floatation method. Potassium chloride is commonly marketed as commercial fertilizer in granules or powder form. It contains 50-60% potash, the whole of which is readily available to the plants. I is readily soluble in.water and hence it 1s rated as readily available, It undergoes ionisation into K* ions and CI” ions.in the soil and like NHj ions, K" ions are absorbed by the soil. As such itis not fost from the soil although it is highly soluble in water. It has litle or no effect on soil pH. ‘a Table (4) Major fertilizer compounds ‘Compound Formula ‘% Nutrient content i = Element Oxide { Nitrogen | Ammonia NH 2.3 | Ammonium Nitrate INH,NOS 348 Ammonium Sulphate (119.80. fm [Urea INH,CONH, 467 7 NaNOv —_fiss 7 [Calcium Nitrate IcaNOp,” ~ fiat ‘Ammmonivin Chloride NHLCI «(362 Phosphate 7 Monocalium Phosphte— [CAHAPO)WHLO__ [246 __|se2 Dicalcium Phosphate |CaHPO, 22.8 52.2 [Potash T Potassium Chloride KCL 523 63.2 1 Potassium Sulphate _ KO, 447 54.0 — Multi Nutrients 1 |Mono ammonium Phosphate_{(NH,)H,PO, 12.2 (N), 26.9 (P) (61.8 Diamnece [(NH);HPO. [21.2 (N), 23.5. (P)__ [53.8 _ Potassium chloride has been applied as fertilizer to a wide range of soils and crops. But in case of potato and tobacco large doses of KCI have been considered to lower the quality of the product. Hencees : synthesis by the process of photosynthesis is hampered in presence of copper deficiency. Gum pockets under the bark and die back of shoots in citrus are the predominant symptoms of copper deficiency: The fruits are subjected to cracking and die back of terminal growth can occur. Molybdenum = It has also been proposed to be associated with the functioning of one or more of the plant enzyme systems, especially nitrate reducing enzymes. . Molybdenum and manganese have been found to be essential for certain nitrogen transformation in microorganisms and in plants. Molybdenum has been found to be essential for the process of nitroges: fixation both symbiotic as well as non-symbiotic. _ Molybderiuim has been found to enhance the symbictic nitrogen fixation as well as protein synthesis. It also regulates the activities of various enzymes. ‘The deficiency of molybdenum produces whip cauliflower and downward cupping in radish. Most-of the vegetable crops are prone to molybdenum deficiency. The deficiency of molybdenum reduce: the activity of the symbiotic and non-symbiotic nitrogen fixirig organism. Molybdenum deficient legumes will not nodule well or fix the normal amounts of nitrogen expected of them. . Chlorine It is the most recent addition to the esscntial nutrient list. It has been observed that the deficiency of chlorine can cause wilt chlorosis (yellowing of green plants) and necrosis. Chlorine in smal! amounts also stimulate growth of crops like barley, alfalfa and tobacco. : Chlorine.is thought to be associated:with thé evolution of ‘oxygen during photosynthesis. Burning of leaf tips of margin, bronzing, premature yellowing and.lcaf fall arg the chloride toxicity-symptoms, Non-essential elements — Certain non essential elements, such as sodium, silicon, aluminium etc. are also found in plants. No evidence has yet been found that meets any of the requirements for essentiality. . MICRONUTRIENTS Out of 16 essential plant nutrients required for the development of plant growth, seven are requi . in much smaller amounts and hence‘they are known as micronutrients. These include mangarese, zi copper, molybdenum, boron, iron and chlorine. Multipt: cropping with high yielding varieties of crop ‘one of the most important reasons of removal of micronutrients from the soil. In secent years, they becos more important because of conserving and increasing the fertility and productivity of soil. Under the deficiency of micronutrients, (a) The growch of plant is hampered. (b) Thé plants are subjected to attack by diseases, and (c) The yield of the crop decreases.accordingly. ° . . Repeated application of one trace element can in deficiency of other elements. Micronutrients are most essential for the growth, development and reproduction of plants. Different crops need varied quantities of micronutrients in their different stages of growth, The main functions of micronutrients are given Lelow: (a) They help in the photosynthesis of green plants. (b) They also"take part in thé synthésis of chlo- rophyll. (c) They act as catalyst in oxidation reduction reactions within the plant, The deficiency of such micro-nutrients may cause shedding of flowers, improper fertilization; poor seed setting etc. (d) They are also responsible for regulating the’ activities of various enzymes. (e) Some of them are essential for the synthesis of vitamin'A and other compounds in the plc: i and in the absorption of nitrogen in. the soil..(g) They «! phorus. (h) They maintain potassium and calcium ratio TNOUSTAIAL CHEMISTRY the plants, (i) They are involved in the biosyn- voces of certain plants. (j) They help in protein synthesis in chloroplast. (x) They enhance the symbiotic nitrogen fixation. (1) They are helpful in proper utilisation of nitrogen and phosphorus. FERTILIZE\. TYPE One of the major problems of those who have developed the modern fertitlzer industry has beenjatroduced through a sprayer nozzle. The inner space of tl cylinder is the neutralizing part of the unit, while the annular space between the outer and inner cylind: is the evaporating part. The reactants move through the neutralizer in a counter current flow. Heat is ‘moved from the reaction zone through the wall of the internal cylinder. The removal of heat in neu! ‘sation is required not only for evaporation ‘of water, but also to prevent the thermal decomposition ©‘ the ammonium nitrate formed. The steam liberated when the water evapo-rates (secondary steam) i: used further asm heat carrying agent The solution of ammonium nitrate formed (contains about 70° NHiNOs) flows over the upper rim of the cylinder into the evaporator part, where water is evapor 45 a result of heat transfer from the nev tralisation part of apparatus to the evaporation part, contain): a system of multiple-body vacuum evar orators. In the after neutralizer, the weakly acidic solution is additionally neutrelized wit In the multiple body vacuum evaporator where the heat carryin, vent (steam) is economized by using the secondary steam of the neutralizer, the concentration 0! the solution if brought upto 98-99% of NH,NO3. A melt of ammonium nitrate is formed which is sferted first to the separator and then to a prilling or granulating tower. The nitrate is granulated by sp’ ing the melt with the aid of a rotating dise a hollow reinforced concrete tower 30-35 m. high. The { ‘ing drops of the melt solidify in the form of granules in the stream of cold air blown through tuyeres in'o the lower part of the tower, the granules drop cn to a conveyor belt, which transports product to the cicying and packing sections. (O Some plants produce NHsNOs in the form of erystal'ive aggregates or flakes instead of granules, by crystallising the melt on the surface of a rotary drum coc!cd from the inside with water. (g) The no-evaporation, single stage method of manufa:(uring NH4NO is based on a rapid reaction between ammonia and 60% HNOs under a pressure of 4 atm, y)ccheaded in interchangers. The vapour-liquid emulsion Jeavjng the reactor is “separated into its compos''c parts in a separator and the 97-98% NH,NO3 melt is transferred to a granulator. : (h) Because of a number of negative features of NHANC;, it is advisable to use it as the basis for making complex and mixed fertilizers. Calcium ammonium nitrate, amimonium sulphate nitrate etc. are made by mixing ammonium nitrate with limestone and with «raonium sulphate, (i) Nitrogenous-potash-phosphatic fertilizers can be made by melting NHyNOs with salts of potassium and phosphorus. Ammonium nitrate is also ‘used for making Ji;uid fertilizers, by dissolving it in liquid atamonia or ammonia liquor. AMMONIUM SULP LATE ‘Ammonium sulphate containing 21% nitrogen is another important nitrogenous fertilizer. It can de obtained as a byproduct or may be manufactured synthetical ‘Ammonium sulphate is obtained as a byproduct in the «cl industry in which ammonia (another byproduct) from coke ovens is absorbed in sulphuric acid. ‘Ammonium sulphate. is also manufactured ’by reacting syr'ctic ammonia with sulphuric acid, Weste streams from various chemical and metallurgical incvstries are another source of ammonium sulphate. For example, ammonia leaching of ores, production of pigments and synthetic fibres, maavfiicture of caprolactam etc. produce byproduct solutions containing amsonium sulphate. Flue gases are another source of the ammonium sulphate. ‘i. metallurgical smelters and coal burning power plants liberate large quantities of SO; that pollute the atin *phere, The sulphur dioxide is collectee end converted into sulphuric acid, Ammonium sulphate is then ; c ; 7 OH Various methods of drying are available, in one m:.hod, the material is cooled to below 90°F and the remaining moisture is reraoved in a second dryer In another method, known as short tower - cilling, ymmonium nitrate solution concentrated to about 99.5% rather than the usual 95% is prilled ‘ti usual way in a short tower, making use of the fact that strong solution solidifies Fister. Dhe levi trace of water may be removed by the process of evaporation than removing it in dryer. However, the quality of ammonium nitrate obtained by this method is not ax good 2s it should be. : In Stengel process, super heated ammonin vapour (145°C) and concentrated nitric acid preheated to 170°C are allowed react in a packed tower and the reaction mixture is then passed into a cyclone designed to separate steam and solution quickly. Air is blown through the tnelt as a result of which water is removed from the niclt to a greater extent anc a melt containing only about 0.25% moisture is produced ctly. The melt can be used directly, prilled in a short tower or passed into a cooled steel belt to give a thin layer of solid nitraté. The latter is subscavently broken up to give granular crystals. In Bamag process, nitric acid and ammonia gas are pumped into a melt of ammonium nitrate at about 150°C, which is then cooled and converied into solid NH,NO3.- ‘ In crystallisution method, 83% solution is crystallised and the crystals are removed by centrifiyging and then dried. This method has-two major ¢isadvantages. . +(a) Difficulty in growing crystals of adequate size at a satisfactory rate. (b) Poor ; hysicat conditions. . Protucticn economics - Production cos: of ammonium nitrate depends mainly oft the cost of raw materials ampuonia and nitric acid. . Handling - Tue latest practice is to store in bulk in buildings equipped with dehumidification equip- ments. Explosive aature - A major drawback of smmonium nitrate is its explosive nature, It is very sensitive to heat and shock. The:principal method usec ‘or reducing the explosive nature or hazard of ammonium nitrate is to mix some thing with it. The risk of explosipn may, therefore, be,avoided by mixing it with chalk (CaCO, obtained as a byproduct in the manufacture of ammonium sulphate). A mixture of NH4NOy and CaCCy, called nitrochalk contains 16% nitrogen and does not explode, The ammonium sulphate an:! ammoniv.n phosphate have also been used for the same purpose. The amounts of calcium carbonate ands ammonitim sulphate used with ammonium nitrate reduce detonation sensitivity of NH,NO) to a lars. extent. ‘actual practice, nitrochalk can be prepared by mixing ammonium nitrate solution with dry* calcium carbonate and sprayed from-the top of a tower. A semisolid mixture is first obtained which on cooling sets to hard mass. It is dried, crushed and passed over screen to yield nitrochalk The use of NH,NO) or nitrochalk avoids overdependence on sulphur or sulphur bearing ores which are lesé available in India. ‘The mixing of CaCO with NH,NO; prevents the ammonium salt from making the soil acidic. ‘Ammonium nitrate can, therefore, be usc! safely by avoiding contact with oxidisable materials, keep- ing NH,NO) + 148.65 ‘The heat of neutralisation is utilized in evaporating water from the NH,NOy solution. If the process is carried out with the use of the reaction heat to evaporate t!.> water, then by using $8-60% HNO3, it is possible to obtain directly a melt of ammonium nitrate (with » concentration of 95-97% NH,NO,) without the evaporation stage. (e),In recent years, the most extensively used scheme is that in which the solution’ is partially concentrated by evaporation at the expense of the heat of neutralisation, ‘The main part of water is evap- orated in a neutcaliser, which consists of a cylindrical vessel r3..4e of stainless steel with a second cylinder inside it. Gaseous NHy and nitric acid are continuously fed into the inner cylinder, where nitric acid is