Ammonia, NH3 is a very important compound in industry.

AMMONIA, NH3
Almost everyone has smelled the sharp, penetrating odor of ammonia, NH3. As the active product of smelling salts, the compound can quickly revive the faint of heart and light of head. But more than a sniff of this toxic, reactive, and corrosive gas can make one very ill indeed. It can, in fact, be fatal. Ammonia is pretty nasty stuff. Nevertheless, it is also an extremely important bulk chemical widely used in fertilizers, plastics, and explosives. The melting and boiling points of ammonia, 77.7EC and 33.5EC, respectively, are both considerably higher than the corresponding properties of its chemical cousins, PH3 and AsH3. This failure of NH3 to follow the usual trend of decreasing melting and boiling points with decreasing molecular weights indicates abnormally strong intermolecular attractions. The forces involved stem from hydrogen bonding, a consequence of the high electronegativity of nitrogen and the small size of the hydrogen atom. The NH3 molecule has a large dipole moment, and this is consistent with its geometry, a triangular pyramid. The electronic arrangement in nitrogen obeys the octet rule. The four pairs of electrons (three bonding pairs and one non-bonding lone pair) repel each other, giving the molecule its non-planar geometry. The HNH bond angle of 107 degrees is close to the tetrahedral angle of 109.5 degrees. Because of this, the electronic arrangement of the valence electrons in nitrogen is described as sp3 hybridization of atomic orbitals. The polarity of NH3 molecules and their ability to form hydrogen bonds explains to some extent the high solubility of ammonia in water. However, a chemical reaction also occurs when ammonia dissolves in water. In aqueous solution, ammonia acts as a base, acquiring hydrogen ions from H2O to yield

ammonium and hydroxide ions. NH3(aq) + H2O(l) NH4 +(aq) + OHG(aq) The production of hydroxide ions when ammonia dissolves in water gives aqueous solutions of ammonia their characteristic alkaline (basic) properties. The double arrow in the equation indicates that equilibrium is established between dissolved ammonia gas and ammonium ions. Not all of the dissolved ammonia reacts with water to form ammonium ions. A substantial fraction remains in the molecular form in solution. In other words, ammonia is a weak base. In contrast, the ammonium ion acts as a weak acid in aqueous solution because it dissociates to form hydrogen ion and ammonia.

NH4 +(aq) NH3(aq) + H+(aq)

The ammonium ion is found in many common compounds, such as ammonium chloride, NH4Cl. Typically, ammonium salts have properties similar to the corresponding compounds of the Group IA alkali metals. The commercial production of ammonia by the direct combination of nitrogen and hydrogen is an example of equilibrium in the gaseous state. At 300EC, Kc has a value of 9.6, indicating that at this temperature, an appreciable amount of NH3 forms from N2 and H2. Because the reaction gives off heat ( HE= 92.0 kJ for the equation above), increasing the temperature drives the reaction to the left. Thus, Kc decreases with increasing temperature. The equilibrium mixture at 500EC contains less NH3 than at 300EC or at 100EC. If one is in the business of making ammonia (and money), the object is to make as much NH3 as possible as quickly as possible. The temperature dependence of the equilibrium constant suggests that working at low temperatures is better because more ammonia is obtained at equilibrium. Alas, equilibrium isn't everything! All chemical reactions slow down as the temperature decreases. While a low temperature favors a high equilibrium yield of

ammonia, it also dictates that a long time will be required to obtain the yield. The ideal method is a balance between yield and speed. A great asset in the production of ammonia is a catalyst which speeds the reaction between nitrogen and hydrogen. Early in this century, a German academic chemist, Fritz Haber, and an industrial colleague, Carl Bosch, found that a mixture of Fe2O3 and Fe3O4 catalyzes this reaction at temperatures in the range of 400EC to 600EC. The yield of ammonia was further enhanced by working at gas pressures between 200 and 400 atmospheres. In the balanced equation for the reaction, the number of moles of product (2 NH3) is less than the total number of moles of reactants (N2 + 3 H2). Therefore, high pressures drive the reaction forward, decreasing the number of moles of gas in the mixture. Although now modified and improved, the Haber-Bosch process continues to be the most common method for making ammonia. The nitrogen is obtained from liquefied air, and the hydrogen is usually from natural gas decomposed by heating. The HaberBosch process is also an example of the complex impact of chemistry upon life. At the start of World War I, Germany was dependent upon the natural nitrate deposits of Chile for the nitrogen compounds required to manufacture explosives. The Allied blockade of South American ports soon cut off this supply. Had it not been for the alternative source of nitrogen compounds provided by the direct synthesis of ammonia, Germany most likely would have been forced to surrender several years before 1918. By prolonging the war, the Haber-Bosch process indirectly cost thousands of lives. However, over the years, the fertilizer produced by the same process has increased crop yields around the globe and spared millions from starvation.

The Main Uses of Ammonia

(a)

To manufacture nitrogenous fertilisers such as ammonium sulphate, ammonium nitrate and urea.

(b) (c)

The liquid form is used as a cooling agent (refrigerant) in refrigerators. As a raw material for the manufacture of nitric acid in the Ostwald process.

(d) (e)

To be converted into nitric acid used for making explosives. As an alkali to prevent the coagulation of latex so that latex can remain in the liquid form.

(f) (g) (h)

To produce ammonium chloride used as an electrolyte in dry cells. As a cleaning agent to remove. Used in the manufacture of synthetic fibres such as nylons.

The Manufacture of Nitrogenous Fertilisers

Ammonium Sulphate
Ammonia reacts with sulphhuric acid by neutralization to produce ammonium sulphate. 2NH3 + H2SO4 (NH4)2SO4 Ammonium Sulphate

Ammonium Nitrate
Ammonia reacts with nitric acid by neutralization to produce ammonium nitrate. NH3 + HNO3 NH4 NO3 Ammonium Nitrate

Urea
Ammonia reacts with carbon dioxide at a temperature of 200 C and a pressure of 200 atmospheres to produce urea. 2NH3 + CO2 (NH2)2 CO + H2 O Urea

Liquid Ammonia
Liquid ammonia is suitable for use as a cooling agent (refrigerant) in refrigerators because it has a low boiling point and is very soluble.

Nitric Acid
Nitric acid is used to make explosives such as TNT when nitric acid reacts with organic substances such as methylbenzene (common name: toluene).

Ammonia
Ammonia can neutralize the organic acids that are produced by microorganisms in latex. Thus it is used to maintain latex in the liquid form. Ammonia reacts with hydrogen chloride to produce ammonium chloride which is used as the electrolyte in dry cells.

* In the Ostwald process, ammonia is converted into nitric acid by the following
steps: 1. Ammonia is oxidized to nitrogen monoxide gas in the presence of platinum as the catalyst. Platinum 4NH3 + 5O2 ----------> 4NO + 6H2 O 2. Nitrogen monoxide is further oxidized to nitrogen dioxide. 2NO + O2 3. 2NO2

Nitrogen dioxide is dissolved in water to produce nitric acid. 4NO2 + O2 + 2H2 O 4HNO3

The Properties Of Ammonia

1. 2.

Ammonia is a colourless and pungent gas. It is less dense than air. Ammonia changes moist red litmus paper to blue. Thus ammonia is an alkaline gas.

3.

Ammonia dissolves in water to produce a weak alkali. A 0.1 mol dm ammonia solution has a pH value of about 10. NH3 + H2 O NH4 + + OH-

4.

As ammonia is very soluble in water, an inverted filter funnel is used to prevent the suction of water.

5.

Ammonia gas reacts with hydrogen chloride gas to form white fumes of ammonium chloride. ( This is used as a test for ammonia gas ). NH3 + HCl NH4 Cl

6.

Ammonia is alkaline in property and reacts with dilute acids in neutralization to produce salts. For example: 2NH3 + H2SO4 NH3 + HNO3 (NH4 )2SO4 NH4 NO3

7.

Aqueous solution of ammonia produces OH ions to react with metal ions (except Na ion, K ion and Ca ion) forming precipitates of metal hydroxides. Fe3+ + 3OH- Fe(OH)3 Brown precipitate Mg2+ + 2OH- Mg(OH)2

8.

Some metal hydroxides such as zinc hydroxide and copper (II) hydroxide dissolve in excess aqueous ammonia to form complexes. For example: Zn(OH)2 + 4NH3 Cu(OH)2 + 4NH3 [Zn(NH3 )4]2+ + 2OH[Cu(NH3 )4]2+ + 2OH-

To Investigate The Properties Of Ammonia Gas

Apparatus pH paper, red litmus paper, beaker, glass rod, test tubes, U-tube with soda lime, beaker and delivery tube. Materials Ammonium chloride, calcium hydroxide, concentrated hydrochloric acid, distilled water. Procedure 1 A spatula of ammonium chloride and a spatula of calcium hydroxide are put in a text tube. The test tube is then connected to a U-tube with soda lime as shown in figure below.

The mixture in the test tube is heated. The ammonia gas produced is tested in turn by using (a) a piece of moist red litmus paper (b) a glass rod dipped in concentrated hydrochloric acid

Ammonia gas is collected in inverted test tubes using downwards displacement of air. The test tubes are then stoppered immediately.

A little distilled water is added to the test tube of ammonia gas which is then shaken. The solution formed is tested with a piece of pH paper.

A test tube of ammonia is inverted with its mouth below a beaker of water. The stopper of the test tube is then removed as shown in the figure below. Observation made is recorded.

Results Test 1 With moist litmus paper Observation The red litmus paper changed to a blue colour 2 With hydrogen chloride vapour White fumes are formed Ammonia gas forms white fumes of ammonium chloride with hydrogen chloride gas 3 With pH paper pH paper changed to a blue colour, corresponding to a pH value of about 10 4 A test tube of ammonia is inverted in a beaker of water Water rushes in and fills up the whole test tube Ammonia gas is very soluble in water Aqueous ammonia is a weak alkali Inference Ammonia gas is alkaline

Discussion 1 Ammonia gas is produced when an ammonium salt such as ammonium chloride is heated with an alkali such as calcium hydroxide. (a) The equation for the reaction between ammonium chloride and calcium and calcium hydroxide is 2NH4Cl + Ca(OH)2 (b) CaCl2 + 2NH3 + 2H2 O

The ionic equation for the reaction between ammonium salt and alkali is NH4 + + OHNH3 + H2 O

Soda lime in the U-tube is used as a drying agent to dry the ammonia gas produced. In place of soda lime, amhydrous calcium oxide can also be used as a drying agent. However, concentrated sulphuric acid cannot be used to dry ammonia gas as it will react with ammonia in a neutralisation reaction.

Ammonia gas is collected in inverted test tubes using downwards displacement of air because ammonia is less dense than air.

Ammonia gas is very soluble in water. As such it cannot be collected by a downward displacement of water.

Ammonia gas reacts with hydrogen chloride to form white fumes of ammonium chloride. NH3 + HCl NH4 Cl

Conclusion 1 2 3 Ammonia is an alkaline gas which turns red litmus paper to blue and dissolves in water to form a weak alkali. Ammonia gas reacts with hydrogen chloride to form white fumes of ammonium chloride. Ammonium gas is very soluble in water.

The Industrial Process In The Manufacture Of Ammonia

1.

The Haber Process is the industrial method used to prepare ammonia gas on a large scale using nitrogen gas and hydrogen gas.

In 1918, Fritz Haber was awarded the Nobel prize for his discovery of the industrial manufacture of ammonia gas from hydrogen gas and nitrogen gas.

Nitrogen gas used in the Haber process is obtained from the fractional distillation of liquid air.

Hydrogen gas used in the Haber process can be obtained by two methods: (a) The reaction between steam and heated coke (carbon). H2 O + C CO + H2 The mixture is known as water gas (b) The reaction between steam and natural gas (consists mainly of methane, CH4) 2H2 O + CH4 CO2 + 4H2

In the Haber process: (a) A mixture consisting of one volume of nitrogen gas and three volumes of pure and dry hydrogen gas is compressed to a pressure between 200 500 atmospheres.

(b)

The gas mixture is passed through a catalyst of powdered iron at a temperature of 450 550 oC.

(c)

At this optimum temperature and pressure ammonia gas is produced. N2 + 3H2 2NH3

The gas mixture produced consists of about 17% ammonia gas. The ammonia gas is liquefied when the gas mixture is cooled. The unreacted nitrogen gas and hydrogen gas are pumped back to the catalytic column to be reacted again.

Ammonium Fertilisers

Plants require nitrogen to produce protein. Nitrogen is absorbed by plants in the form of nitrates, NO3- which are soluble in water.

Ammonium fertilisers are chemical fertilisers added to the soil to replace the elements in soil used up by plants.

Ammonium fertilisers contain ammonium ions, NH4 + , that can be converted into nitrate ions by bacteria living in the soil.

The effectiveness of ammonium fertilisers is determined by the percentage of nitrogen by mass in them. The fertiliser with a higher percentage of nitrogen is more effective.

The percentage of nitrogen by mass can be calculated using the following formula:

To Prepare Ammonium Sulphate, (NH4)2SO4, An Ammonium Fertiliser

Apparatus 25 cm3 pipette, 50 cm3 burette, dropper, retort stand with clamp and white tile. Materials 1 mol dm-3 sulphuric acid, 2 mol dm-3 aqueous ammonia solution and methyl orange indicator. Procedure (A) To determine the volume of sulphuric acid required to neutralize 25 cm of ammonia solution. 1 25 cm3 of 2.0 mol dm-3 aqueous ammonia solution is transferred using a 25 cm3 pipette to a clean conical flask. Three drops of methyl orange indicator are added to the alkali and the colour of the solution is noted. 2 A 50 cm3 burette is filled with sulphuric acid and clamped to a retort stand. The initial burette reading (V1 ) is recorded. 3 The conical flask containing 25 cm of the aqueous ammonia is placed below the burette. A piece of white tile is placed below the conical flask for clearer observation of the change in colour. ( Figure below ) 4 Sulphuric acid is added slowly from the burette to the aqueous ammonia solution in the conical flask while the flask is gently swirled. 5 Titration is stoped when methyl orange changes colour from yellow to orange. The final burette reading (V2 ) is recorded. 6 The volume of sulphuric acid required to neutralize 25.0 cm3 of ammonia solution is (V2 - V1) cm .

(B) To prepare ammonium sulphate crystals 1 25 cm3 of 2.0 mol dm-3 aqueous ammonia solution is pipetted into a clean conical flask. 2 (V2 V1 ) cm of sulphuric acid is added from the burette to the aqueous ammonia solution. 3 The mixture in the conical flask is transferred to a beaker and is slowly evaporated until a saturated solution is formed. 4 The saturated solution is left to cool. White crystals of ammonium sulphate are produced. 5 The ammonium sulphate crystals are then removed by filtration, washed with distilled water and dried between filter papers.

Titration of sulphuric acid with ammonia solution

Discussion 1 The equation for the neutralization of aqueous ammonia and sulphuric acid is 2NH3 + H2SO4 2 (NH4 )2SO4

The first titration (Experiment A) is carried out to determine the volume of sulphuric acid required to completely neutralize 25 cm3 of aqueous ammonia.

In the school titration (Experiment B), the methyl orange indicator is not used so that the salt produced is not contaminated with the indicator.

The ammonium sulphate solution produced is not evaporated until dry because ammonium sulphate solid will decompose when heated.

Usually, the mass of ammonium sulphate crystals obtained from the experiment is less than the theoretical value because not all ammonium sulphate crystals can be crystallized from the solution. Some ammonium sulphate remains dissolved in the solution.

Conclusion Ammonium sulphate, an example of ammonium fertilizer, can be prepared by the neutralization reaction between aqueous ammonia and dilute sulphuric acid.

Eppendix

Ammonia products