Topic 10: Manufactured Materials Ammonia, Sulphuric Acid and Nitric Acid

Learning Outcomes: 1 . Describe the industrial process of producing ammonia, sulphuric acid and nitric acid 2. State the uses of ammonia, sulphuric acid and nitric acid in our daily life 3. Prepare ammonium salt fertilizer

Ammonia
Introduction Ammonia (NH3) is an important compound of nitrogen and hydrogen, can take the form of a strong smelling liquid or gas. It is a colourless gas with a choking smell, and a weak alkali which is very soluble in water.Most popularly, consumer and commercial products use the alkaline substance to clean grime or fertilize crops. Even in low concentrations, inhaling ammonia or getting the solution on your skin can cause burning, fainting, or death, so always use caution when handling this chemical. Ammonia has one nitrogen atom and three hydrogen atoms tightly bonded. A tiny amount of ammonia forms when organic matter decomposes, so the gas can be found naturally in our atmosphere. Most of the ammonia used is produced through artificial means, however, by bonding the four atoms together by sheer force. Then the gas can be pressurized to form a liquid for easy distribution to manufacturing plants. It is produced by the natural decomposition of animal and vegetable bodies. The death and decay of plants and animals cause the nitrogen compounds present in them to get decomposed, giving ammonia. Ammonia also occurs in the soil in the form of ammonium salts. As a gas, ammonia is lighter than air, so it won't pool indoors like other dangerous gases, such as propane. While it has a very pungent, distinctive odor, it's clear and difficult to combust unless highly concentrated. This makes ammonia safer than other chemicals for household use, as most people will recognize the smell and leave a toxic area to prevent fainting.. Preparation of Ammonia Ammonia is prepared by the following methods: From ammonium chloride Ammonia gas is usually prepared in the laboratory by gently heating ammonium chloride (NH4Cl) and slaked lime [Ca(OH)2].

Fig: 13.3 - Preparation of ammonia Ammonia gas is lighter than air, necessitating its collection by the downward displacement of air. Because it is highly soluble in water it cannot be collected over it. Passing ammonia gas over quicklime (CaO) dries it. Being a basic gas, ammonia cannot be dried by passing it through concentrated sulphuric acid or phosphorus pentoxide (P2O5), as it reacts with them to form ammonium sulphate or ammonium phosphate respectively.

Calcium chloride also cannot be used for drying ammonia gas as it forms ammoniates with CaCl2.

Ammonia and the Haber process Ammonia is manufactured by combining nitrogen and hydrogen in an important industrial process called the Haber process. The Haber process The raw materials for this process are hydrogen and nitrogen. Hydrogen is obtained by reacting natural gas - methane - with steam, or through the cracking of oil. Nitrogen is obtained by burning hydrogen in air. Air is 80 per cent nitrogen; nearly all the rest is oxygen. When hydrogen is burned in air, the oxygen combines with the hydrogen, leaving nitrogen behind. Nitrogen and hydrogen will react together under these conditions:

a high temperature - about 450C a high pressure - about 200 atmospheres (200 times normal pressure) an iron catalyst ammonia 2NH3(g) 2

The reaction is reversible. nitrogen + hydrogen N2(g) + 3H2(g)

The flow chart shows the main stages in the Haber process. The reaction is reversible, and some nitrogen and hydrogen remain mixed with the ammonia. The reaction mixture is cooled so that the ammonia liquefies and can be removed. The remaining nitrogen and hydrogen are recycled.

The Haber process for making ammonia

MANUFACTURE OF AMMONIA (HABER PROCESS)

Reactants : Nitrogen and hydrogen in the ratio of 1 : 3 by volume. Sources of reactants : Nitrogen gas is obtained by fractional distillation of liquid air. Hydrogen gas is obtained from water gas (Bosch process) or from natural gas. Reaction : N2 + 3H2 2NH3 + heat

Favourable conditions : Temperature : Optimum temperature is 450-500 C. Pressure : Above 200 atm. Catalyst : Finely divided iron. Promoter : Traces of molybdenum or A1203. Rate of conversion : 8% to 12% of the reacting gases get converted to ammonia.

The reaction is reversible, exothermic and proceeds with a decrease in volume.

Recovery of ammonia Ammonia is separated from the unreacted nitrogen and hydrogen by : 1. Liquefaction, as ammonia compared to N2 and H2 is easily liquefiable. 2. Absorbing in water because NH3 is highly soluble in water, while N2 and H2 are very slightly soluble. Note : Since the reaction is exothermic, the heat evolved further maintains the temperature. External heating is, therefore, not required after the reactants are initially heated. Process : Nitrogen and hydrogen are dried, purified and then mixed in the ratio of 1 : 3 respectively at a relatively high pressure. This mixture is passed in an electrically heated catalytic chamber containing finely divided iron with aluminium oxide or a little amount of molybdenum at a temperature of 500C. Mixture of ammonia formed along with residual nitrogen and hydrogen exchanges their heat with the incoming unreacted nitrogen and hydrogen mixture. Catalyst Poison : The presence of carbon dioxide, carbon monoxide and traces of sulphur compounds H2S) poisons the catalyst. The removal of these catalytic poisons from nitrogen and hydrogen is very essential. The hot mixture of the outgoing gases contains nearly 10% ammonia. The mixture is passed through the cooling pipes (condenser). Ammonia liquefies first, whereas nitrogen and hydrogen do not liquefy easily. The unchanged nitrogen and hydrogen are recirc{ulated} through the plant to get more ammonia. Note : (i) The reaction is exothermic, hence low temperature will favour the synthesis. However, at low temperature, the reaction proceeds slowly. In practice, the optimum temperature has been found to be in the range of 450C to 500C. (ii) Four volumes of reactants produce two volumes of product, hence high pressure favours the formation of ammonia. The optimum pressure is found to be 200 to 900 atm. Practically, a pressure of about 250 atm. is used. (iii) Catalyst and promoter: The speed of the reaction can be improved by using a catalyst which is finely divided iron, obtained by the reduction of iron oxide. Flow chart of Haber Process

A promoter is used to increase the efficiency of the catalyst, which is molybdenum or A1203. The main uses of ammonia: 1) Ammonia is used in the industrial preparation of nitric acid by Ostwald's process. 2) Fertilisers, such as ammonium sulphate, ammonium nitrate, ammonium phosphate, urea etc. are manufactured with the help of ammonia. Most of the ammonia we produce goes to fertilizing crops by providing absorbable nitrogen to plants 3) It is used in the manufacture of other ammonium salts, such as ammonium chloride, ammonium carbonate, ammonium nitrite etc. 4) It finds use in the manufacture of nitrogen compounds such as sodium cynamide, plastics, rayon, nylon, dyes etc. Manufacturers of plastics, pesticides, and dyes use the liquid at some point in their synthesizing process. 5) It is used in the manufacture of sodium carbonate by Solvay's process. (Ammonia and carbon dioxide are treated with aqueous sodium chloride, crystals of sodium hydrogen carbonate are formed. They are heated to yield sodium carbonate). 6) Ammonia acts as refrigerant in ice plants. Evaporation of a liquid needs heat energy. About 17g of liquid ammonia absorb 5700 calories of heat from the surrounding water. This cools the water and ultimately freezes it to ice. 7) Ammonia is used to transport hydrogen. Hydrogen is dangerous to transport, as it is highly combustible. So it is converted to ammonia, liquefied, transported and then catalytically treated to obtain hydrogen. Refrigerate rooms or trucks 8) Many ammonium salts are used in medicines. Inhaling the fumes produced by rubbing ammonium carbonate in the hands can revive people who have fainted. 9) It is used as a cleansing agent. Ammonia solution emulsifies fats, grease etc. so it can be used to clean oils, fats, body grease etc. from clothes. It is also used to clean glassware, 6

porcelain, floors etc. Commercial cleansers, with 25-30% ammonia, are extremely dangerous due to their corrosivity. Under careful oversight, liquid ammonia is also used to etch metal like aluminum and copper. Many window sprays, oven foam, toilet bowl cleansers, wax removers, and other household cleaners contain around 5-10% ammonia. Different types of cleaners should never be mixed in the same application. For example, ammonia and bleach form a very dangerous gas, called chloramine, that shouldn't be inhaled 10) It is used as laboratory reagent and dissolve other elements in chemistry labs. The uses of ammonia are summarized given in figure 6.12.

Ammonium sulphate fertilizer: Ammonium sulphate is usually one of the possible organic salts having the formula as (NH4)2SO4. It is a odourless white powder, whose melting point is 2350 - 2800C. It is a very good nitrogenous fertilizer, which will enrich the soil with 21% nitrogen led to the flawless growth of the soil. It is also used as a catalyst and in medicines, in electroplating and in many chemicals. But the most commercial applications of ammonium sulphate is in the field of fertilizing. Fertilizer is a material which is added to the soil to improve its productivity. It increases the fertility of the soil. The nitrogen, phosphorus and potassium are required in a desirable quantiy to improve the fertility of a soil. Ammonium sulphate fertilizer contains 21% nitrogen . 7

Synthesis of Ammonium Sulphate Fertilizer: Ammonium sulphate can be prepared by the following two ways: By combining sulphuric acid with two moles of ammonia, we get ammonium sulphate. The chemical equation is shown as under: 2NH3 + H2SO4 (NH4)2SO4 By combining Gypsum with ammonium carbonate, we will get ammonium sulphate and the precipitate of calcium carbonate. The chemical equation is shown as under: (NH4)2CO3 + CaSO4 (NH4)2SO4 + CaCO3 Ammonium sulphate can be used as a rich fertilizer or can be called as a lawn fertilizer. Uses of Ammonium Sulphate Fertilizer:

It is usually a water soluble fertilizer and provides the land with 21% nitrogen as well as 29% sulphur. After using the fertilizer, water that area well. Whenever this fertilizer is applied to the lawn, it helps in growing the grass more readily. If the fertilizer is applied in more quantity, then it will lead to the extra growth. So, we have to take care of the amount of the fertilizer to be applied.

Also when the fertilizer is applied, monitor the PH of the soil and depending on which add lime to the soil if needed. This fertilizer is easy to store, is inexpensive and even do not melt in case of high humidity. Kept the fertilizer away from the water ways or water containers because it can lead to the algae growth. It is generally used as an artificial fertilizer for the alkaline soils.

Nitric acid
The most important and useful oxoacid of nitrogen is nitric acid. Its molecular formula is HNO3 and molar mass 53 g mol-1. 8

Industrial Preparation On a commercial scale, nitric acid is manufactured through the Ostwald's process - the process of catalytic oxidation of ammonia. Ostwald's process The conversion of ammonia into nitric acid in this process is done through the following steps: Step1 Oxidation of ammonia to nitric oxide Ammonia is oxidized by air in the presence of Pt catalyst at 800C to give nitric oxide.

Step 2 Oxidation of NO to NO2 The nitric oxide is oxidised by air at temperature below 100C, to give nitrogen dioxide (NO2)

Step 3 Formation of nitric acid Nitrogen dioxide is then converted to nitric acid by absorbing NO2 in water, in the presence of air.

Nitric acid is prepared in large scale from ammonia and air (Fig.6.14).

The plant The manufacturing plant for the production of nitric acid by the Ostwald's process, has the following components and processes.

Fig: 1 - Ostwald's process for the manufacture of nitric acid

Converter The converter is made of aluminium and fitted with platinum - rhodium gauze cylinder (23 cm x 34 cm). The cylinder is closed at the bottom with a silica lid. The gauze is initially heated to 800C electrically. Thereafter no external heating is required as oxidation of ammonia is an exothermic reaction. A mixture of ammonia and clear air (volume ratio = (1:8) is then passed through the gauze from the top, and the products leave from the bottom. Every 1000 cm2 area of the gauze produces about 500 kg of nitric oxide, every 24 hours.

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Fig: 2 - Converter for the Ostwald's process

Oxidation tower When nitric oxide, containing nitrogen and some water vapors, come out of the converter, they are cooled to about 100C by passing them through coolers. In the oxidation tower, nitric oxide is mixed with more air and it gets converted to NO2.

Absorption tower NO2 is allowed to enter the absorption tower from the lower end. The tower is packed with quartz pieces and water is sprinkled from the top. Here, NO2 is absorbed into water in the presence of air to yield nitric acid.

Commercial nitric acid has a brown color due to dissolved NO2. The procedure of bubbling dry air through warm commercial nitric acid, is to drive away the dissolved nitrogen dioxide so that the acid becomes colorless. Concentrating nitric acid Aqueous nitric acid obtained by this method can be concentrated by distillation to 68.5% by mass. Further concentration to 98% acid can be achieved by dehydration with concentrated sulphuric acid. Anhydrous nitric acid can be obtained by distillation of concentrated aqueous nitric acid with phosphorus pentoxide (P2O5 or P4O10).

Uses of Nitric acid The important uses of nitric acid are as follows: 11

1) Nitric acid plays a significant role in the manufacture of various products such as:

Explosives like trinitrotoluene (T.N.T.) nitro glycerine, gun cotton, ammonal etc. Fertilizers such as calcium nitrate, ammonium nitrate etc. Nitrate salts such as calcium nitrate, silver nitrate, ammonium nitrate. Dyes, perfumes, drugs etc. from coal tar products. Sulphuric acid by Lead Chamber process.

2) It is used in the purification of silver, gold, platinum etc. 3) Nitric acid is used in etching designs on copper, brass, bronze ware etc . 4) It is used to prepare "aqua regia" to dissolve the noble elements. 5) It is used as a laboratory reagent. Remember : Ammonal is a mixture of ammonium nitrate and aluminium powder. The uses of nitric acid are summarized in figure 6.18.

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Sulphuric acid
Sulphuric acid, H2SO4, is one of the most important industrial chemicals. It is an oily liquid having a boiling point of 335 C, which evolves much heat on dilution with water. Millions of tons of sulphuric acid are made every year by the CONTACT PROCESS, which converts raw sulphur, oxygen and water to sulphuric acid.

Step 1: Melted sulphur is burned in a furnace, using air, producing sulphur dioxide, SO2. Step 2: The SO2 gas is passed through a tower called a precipitator in order to remove dust and other impurities which might interfere with the catalyst. Step 3: The SO2 is then washed with water, in a scrubbing tower. Step 4: The SO2 is then dried in a drying tower. Step 5: After passing through a heating chamber, the SO2, which is still mixed with air, is passed through a reactor. There, using vanadium pentoxide, V2O5, as catalyst, the SO2 is converted to sulphur trioxide, SO3.

Step 6: Finally, the SO3 is absorbed in concentrated sulphuric acid, giving the socalled oleum or pyrosulphuric acid. This is the diluted with water to give about 98% pure H2SO4.

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Industrial Preparation of Sulphuric Acid: Purification Unit The mixture of sulphur dioxide and oxygen is passed thro dusting tower which remove dust particles .Steam is blown downward in the dusting tower. The gases are passed over cooling pipes which cools the gases. Then it is passed thro scrubbing tower, where water is sprayed down ward. The further impurities will be removed. Then it is passed thro drying tower in which concentrated sulphuric acid is sprayed downward Which removes the moisture present in the gaseous mixture and they become dry. Then it is passed thro arsenic tower which contains ferric hydroxide which removes arsenic oxide. Testing box. The out coming gas is tested for its purity by the passage of light thro darkened box. Catalytic Oxidation of Sulphur dioxide. The purified gas is passed over contact tower for the catalytic oxidation of sulphudioxide to sulphur trioxide. It is an iron tower packed with vanadium pentoxide as catalyst. Which is heated to 450degree Celsius. At 1to2atmospheres. 2 SO2 + O2-------- 2SO3 +DH 98% of sulphurdioxide will be converted to sulphur trioxide. Vanadium pent oxide is cheaper and less easily poisoned by impurities It is shredded and mixed with potassium oxide as a promoter to enhance the catalyst. The contact mass is porous So the gases can enter to the interior of the granules. The reaction is exothermic which maintains the temperature of the catalyst to 450' 500'. So the catalyst is heated only at the initial stage. The forward reaction is favoured by increasing the pressure of the reactants because the reaction takes place with decrease in volume. But if the pressure increased it may cause damage to lead pipes and acid resisting towers.. Even the catalyst will undergo decom[position. So 1-2 atmosphere pressure is used. Absorption Tower Though sulphur trioxide is highly soluble in water, it cannot be done. It is highly exothermic resulting in the formation of a dense fog of sulphuric acid particle which do not condense easily The sulphur trioxide obtained in the above step is passed over absorption tower to which stream of concentrated sulphuric acid will be poured. In this tower sulphur trioxide combines with sulphuric acid yielding oleum H2S2O7. 5. dilution of oleum This is done in dilution tank . Here oleum combines with soft water H2S2O7 + H2O ------ 2H2SO4 15

Sulfuric acid is called the "King of Chemicals", and rightly so, because there is no other manufactured chemical which is used by such a large number of industries. The detailed list of all the elements and compounds manufactured by using Sulfuric acid is as follows:1. It is used in the preparation of Iodine, Carbon dioxide, Carbon monoxide, and Hydrogen gases. Uses of Sulfuric acid in Metallurgy 2. It is used to form sulphates from metallic compounds. These sulphates can be eaily electrolysed to give pure metal. 3. It is used for removing impurities like oxides and carbonates from metal sheets before they undergo processes like galvanization, electroplating, etc. This process is called pickling of metals. Used in Lead Accumulators 4. Sulfuric acid is a very good electrolyte in the aqueous state and is used in batteries that have electrodes of lead as the elctrolyte. These batteries are called Lead accumulators or the lead acid batteries and are the most suitable type of rechargable batteries for cars as their powerto-weight ratios are high. 5. Sulfuric acid is used in refining of petroleum products, eg, petrol, kerosene, lubricants, etc. 6. Ammonium sulfate, a compound used widely as an artificial fertilizer, is manufactured by the combination reaction of Sulfuric acid and Ammonia. NH3 + H2 SO4 (NH4)2SO4

7. Super phosphate of lime, another widely used fertilizer for soils is produced by the action of sulfuric acid on Phosphate rock:Formula of Super phosphate is [Ca(H2PO4 )2 + CaSO4] 8. Rayon, nylon and many dyes and drugs manufactured by using Sulfuric acid. 9. Explosives like T.N.T (tri nito toluene) and Picric acid. 10. Sulfuric acid, being a non-volatile acid, is used to manufacture volatile acids like Nitric acid, Hydrochloric acid, and acetic acid. (as compared to sulfuric acid). This is because when volatile acids are produced from non-volatile acids, both the acids do not mix together as one being volatile vaporizes off at less temperature whereas the non-volatile acid does not vaporize at low temperatures. 16

11. Sulphate compounds are widely used in many industries like Sodium sulphate in the glass industry and Ferrous sulphate in the ink industry. sulfuric acid is used to produce many sulphates as well as other compounds in the chemical industry. Uses of sulphuric acids in our daily life

In the manufacture of fertilizers, ammonium phosphate and calcium super phosphate.

In the manufacture of rayon and nylon and also in the preparation of dyes and drugs from coal tar derivatives. In the manufacture of the explosives such as Tri-nitro toluene , Tri-nitro glycerine and picric acid. In the manufacture of nitric acid, hydrochloric acid and phosphoric acid. In the manufacture of sodium sulphate for glass industry and ferrous sulphate for ink industry. In the purification of petrol, kerosene, and lubricants. It is used in metallurgy for extraction of metals. Leaching of metallic compounds gives sulphates which on electrolysis gives the metal in pure form .It is used for pickling of metals. It is used in storage of batteries. It is used as a laboratory reagent for the preparation of iodine, carbon monoxide and hydrogen.

References http//www.Ammonia,%20Nitric%20Acid,%20and%20Sulphuric%20Acid.htm http://www.tutorvista.com/content/chemistry/chemistry-iii/p-block-elements/nitricacid.php

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