Objectives
By the end of the chapter the learner should be able to:
(a) Describe how nitrogen is isolated from air.
(b) Describe how nitrogen is prepared in the laboratory and state its properties and uses.
(c) Describe the laboratory preparation and state the properties and uses of the oxides of nitrogen.
(d) Describe the laboratory preparation of ammonia and state its properties and uses.
(e) Explain the differences in chemical reactions of ammonia gas and its aqueous solution.
(f) Describe the industrial manufacture of ammonia.
(g) Calculate the percentage of nitrogen in nitrogen containing fertilisers.
(h) Describe the laboratory preparation and manufacture of nitric(V) acid and state its uses.
(i) Explain the reactions of both dilute and concentrated nitric(V) acid.
(j) Identify the products formed when different nitrates are heated.
(k) State and explain the pollution effect of nitrogen compounds in the environment
Nitrogen is a non metal in group V of the periodic table. It has an atomic number of seven and has an electron arrangement of 2.5. Nitrogen exists in air as a gaseous element consisting of diatomic molecules. About 78% by volume of the atmosphere is composed of nitrogen making it the most important source of nitrogen.
Nitrogen also occurs combined in Compounds such as sodium nitrate, potassium nitrate and proteins
In the laboratory, nitrogen is isolated from air by first passing the air through concentrated potassium hydroxide or sodium hydroxide which absorbs carbon(IV) oxide.
KOH(aq) + CO2(g) KHCO3(aq)
The remaining part of air is then passed over heated copper turnings to remove oxygen.
2Cu(s) + O2(g) 2CuO(s)
The residual gas is then collected as shown below.
The nitrogen so obtained contains noble gases as impurities.
Nitrogen is obtained on a large scale by fractional distillation of liquid air.
Dust particles are first removed from air through electrostatic precipitation.
The dust-free air is then passed through concentrated sodium hydroxide solution to remove carbon(IV) oxide gas.
The remaining air is passed into a condensation chamber and cooled to –25°C. Water vapour separates out as ice. The residual gas is compressed to a pressure of 200 atmospheres.
Repeated expansion and contraction of the air cools it to a liquid at a temperature of –200°C. The main constituents of liquid air at this stage are nitrogen and oxygen whose boiling points are –196°C and –183°C respectively. Nitrogen has a lower boiling point and therefore distills out first followed by oxygen.
The flow chart below summarises the major steps in the isolation of nitrogen.
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Nitrogen can be prepared by heating a mixture of sodium nitrite and ammonium chloride Ammonium chloride and sodium nitrite react to form ammonium nitrite and sodium chloride.
Ammonium nitrite is unstable and decomposes to form nitrogen and steam.
Ammonium chloride and sodium nitrite react to form ammonium nitrite and sodium chloride.
NaNO2(aq) + NH4Cl(aq) NH4NO2(aq) + NaCl(aq)
Ammonium nitrite is unstable and decomposes to form nitrogen and steam.
NH4NO2(aq) N2(g) + 2H2O(g)
Side Notes
Nitrogen is a colourless, oduorless and tasteless gas that is slightly less dense than air. The boiling point is –96°C. It is slightly soluble in water.
Nitrogen neither burns nor supports combustion. It is neutral and has no effect on moist litmus paper and does not react readily with other elements.
3Mg(s) + N2(g) Mg3N2(s)
When some water is added to the nitride, ammonia gas and magnesium hydroxide are formed.
Mg3N2(s) + 6H2O(l) 3Mg(OH)2(aq) + 2NH3(g)
Several oxides of nitrogen exist. These include:
Nitrogen (I) oxide can be prepared in the laboratory by heating ammonium nitrate. Ammonium nitrate melts and decomposes on heating to form nitrogen(I) oxide and steam.
NH4NO3(s) N2O(g) + 2H2O(g)
Cu(s) + N2O(g) CuO(s) + N2(g)
S(s) + N2O(g) SO(s) + N2(g)
Nitrogen(II) oxide is produced when copper and dilute nitric(V) acid react.
3Cu(s) + 8HNO3(aq) 3Cu(NO3)2(aq) + 4H2O(1) + 2NO(g)
Nitrogen(II) oxide is oxidised by oxygen in the flask to form red-brown fumes of nitrogen(IV) oxide.
2NO(g) + O2 (g) 2NO2 (g)
The fumes gradually disappear as the air in the flask is exhausted. Nitrogen(IV) oxide formed dissolves in the water in the trough.
Nitrogen(II) oxide is a colourless gas. It is slightly soluble in water and has no effect on moist litmus paper.
Nitrogen(II) oxide neither burns nor supports combustion. However it oxidises some strongly heated elements to their oxides.
Magnesium continues to burn in nitrogen(II) oxide. The heat produced decomposes the gas into nitrogen and oxygen. The oxygen produced enables the hot element to continue burning.
2Mg(s) + 2NO(g) 2MgO(s) + N2(g)
2Cu(s) + 2NO(g) 2CuO(s) + N2(g)
P4(s) + 10NO(g) 2P2O5(g) 5N2(g)
Iron(II) sulphate solution turns dark brown when nitrogen(II) oxide is bubbled through it. This is due to the formation of iron(II) sulphate – nitrogen(II) oxide complex, FeSO4.NO.
FeSO4(aq) + NO(g) FeSO4.NO (aq)
Pale gree dark brown
When exposed to air, nitrogen(II) oxide is readily oxidised by oxygen to form red brown fumes of nitrogen(IV) oxide. This reaction is used as the test for nitrogen(II) oxide.
Nitrogen (IV) Oxide can be prepared by the reaction of concentrated nitric(V) acid on copper turnings.
Cu(s) + 4HNO3(l) Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)
Nitrogen(IV) oxide may also be prepared by thermal decomposition of nitrates of metals below sodium in the reactivity series. However, lead(II) nitrate is the most suitable because it is not hydrated.
When concentrated nitric(V) acid is added to copper turnings, a vigorous reaction takes place and red-brown fumes of nitrogen(IV) oxide are evolved.
Cu(s) + 4HNO3(l) Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)
Nitrogen(IV) oxide may also be prepared by thermal decomposition of nitrates of metals below sodium in the reactivity series. However, lead(II) nitrate is the most suitable because it is not hydrated.
When heated, lead(II) nitrate decomposes to form lead(II) oxide, nitrogen(IV) oxide and oxygen. The set up below can be used to prepare nitrogen(IV) oxide from metal nitrates.
2Pb(NO3)2(s) 2PbO(s) + 4NO2(g) + O2(g)
The gases produced are passed through a U-tube surrounded by ice-cold water. On cooling, nitrogen(IV) oxide condenses to form dinitrogen tetraoxide, N2O4, which is a pale-yellow liquid. Oxygen gas is collected over water.
2NO2(g) N2O4 (l)
Reddish-brown pale-yellow
2NO2(g) ⇌ N2O4 (g)
Reddish-brown pale-yellow
2NO2(g)2NO (g) + O2 (g)
Reddish-brown colourless
2NO2(g)+ H2O(l) HNO2(aq) + HNO3(aq)
4Mg(s) + 2NO2(g) 4MgO(s) + N2(g)
2P4(s) + 10NO2(g) 4P2O5(g) + 5N2(g)
The heat produced by the burning element decomposes nitrogen(IV) into nitrogen and oxygen. Oxygen liberated combines with the hot element.
Ammonia, NH3, is a compound of nitrogen and hydrogen. It is a gas at room temperature.
Ammonia is prepared in the laboratory by heating a mixture of an ammonium salt and an alkali. Ammonia is a more volatile base and is displaced by a less volatile base, e.g., NaOH, KOH and Ca(OH)2.
Ca(OH2)(s) + 2NH4Cl(s) CaCl2(s) + 2H2O(l) + 2NH3(g)
The ionic equation for the reaction is:
NH4+(aq)+ OH– (aq) NH3 (g) + H2O (l)
Calcium oxide (quicklime) is used as a drying agent. This is because ammonia reacts with the other common drying agents.
Side Notes
Concentrated sulphuric (VI) acid reacts with ammonia to form ammonium sulphate.
2NH3(g) + H2SO4(l) (NH4)2SO4(aq)
Calcium chloride forms a complex compound with ammonia.
CaCl2(s) + 4NH3(g) CaCl2.4NH3(s)
Ca(OH2)(s) + 2NH4Cl(s) CaCl2(s) + 2H2O(l) + 2NH3(g)
Ammonia is a colourless gas, with a characteristic choking pungent smell. It is less dense than air and therefore it is collected by upward delivery. The gas is very soluble in water.
Ammonia turns moist red litmus paper blue showing that it is alkaline. This is the confirmatory test for ammonia.
When a glass rod dipped in concentrated hydrochloric acid is brought to the mouth of a gas jar full of ammonia, hydrogen chloride fumes react with ammonia to form white fumes of ammonium chloride.
NH3(g) + HCl(g) NH4Cl(g)
Ammonia dissolves in water to form an alkaline solution. To prepare aqueous ammonia,
⚗Practically Speaking🔊 📌
Place a mixture of calcium hydroxide and ammonium chloride in a boiling tube and heat. Allow the gas collected to dissolve in water using a funneled delivery tube.
Side Note
A funnel is used to prevent the water from ‘sucking back’ into the flask by providing a large surface area for absorption of ammonia.
Discourse
Ammonia dissolves in water to form an alkaline solution. A little of the dissolved gas combines with water to form ammonium ions and hydroxide ions.
NH3(g)NH3 (aq)
NH3 (aq)+ H2O (l) NH4+(aq) + OH– (aq)
The hydroxide ion, OH–, gives the solution its alkaline properties.
This experiment illustrates the high solubility of ammonia gas in water. Universal indicator is added to enhance the visibility of the “fountain”.
When a drop of water gets to the jet, it dissolves a lot of the ammonia gas in the flask creating a partial vacuum. When the clip is opened the second time, the water is forced into the flask by the atmospheric pressure leading to the formation of a fountain.
Aqueous ammonia precipitates many metal hydroxides from solutions containing ions of the metal. This property is applied in qualitative analysis of metal ions. These tests can be done practically as follows:
⚗Practically Speaking🔊 📌
Place about 2 cm3 of solutions containing ions of calcium, magnesium, aluminium, zinc, iron, lead and copper in separate test-tubes. To each solution add aqueous ammonia drop by drop. Shake the mixture after each drop. Continue adding aqueous ammonia until it is in excess. Record your observations.
Observations
| Metal ion in solution | Few drops of aqueous ammonia | Excess aqueous ammonia |
| Ca2+ | No white precipitate | No white precipitate |
| Mg2+ | White precipitate | White precipitate does not dissolve. |
| Al3+ | White precipitate | White precipitate does not dissolve. |
| Zn2+ | White precipitate | White precipitate dissolves to form a colourless solution. |
| Fe2+ | Green precipitate | Green precipitate does not dissolve. |
| Fe3+ | Brown Precipitate | Brown precipitate does not dissolve. |
| Pb2+ | White precipitate | White precipitate does not dissolve. |
| Cu2+ | Pale-blue precipitate | Pale-blue precipitate dissolves to form a deep-blue solution. |
Discussion
Aqueous ammonia is a weak alkali and will not precipitate the hydroxide in water if it is slightly soluble, for example, calcium hydroxide. Ionic equations representing precipitation of insoluble metal hydroxides are:
Mg2+(aq) + 2OH–(aq) Mg(OH)2(s)
White precipitate
Al3+(aq)+ 3OH–(aq) Al(OH)3(s)
White precipitate
Zn2+(aq) + 2OH–(aq) Zn(OH)2(s)
White precipitate
Fe2+(aq) + 2OH–(aq) Fe(OH)2(s)
Green precipitate
Fe3+(aq)+ 3OH–(aq) Fe(OH)3(s)
Red brown precipitate
Pb2+(aq) + 2OH–(aq) Pb(OH)2(s)
White precipitate
Cu2+(aq) + 2OH–(aq) Cu(OH)2(s)
Pale-blue precipitate
Zinc hydroxide and copper(II) hydroxide dissolve in excess ammonia due to the formation of complex ions.
Zn(OH)2(s) + 4NH3(aq) [Zn(NH3)4]2++ 2OH– (aq)
White precipitate Tetramine zinc ion (colourless)
Cu(OH)2(s) + 4NH3(aq) [Cu(NH3)4]2+ + 2OH– (aq)
White precipitate Tetramine copper (II) ion (deep blue)
Calcium ions form a white precipitate when 2 M aqueous ammonia is used.
Ammonia gas dissolves in water to form aqueous ammonia. Some of the dissolved ammonia molecules react with water molecules to form ammonium hydroxide.
NH3(aq) + H2O(l) → NH4OH(aq)
Therefore, aqueous ammonia neutralises acids to form ammonium salts and water.
2NH4OH(aq) + H2SO4(aq) → (NH4)2SO4(aq)+ H2O(l)
NH4OH(aq) + HCl(aq) → NH4Cl(aq)+ H2O(l)
NH4OH(aq)+ HNO3(aq) → NH4NO3(aq) + H2O(l)
If dry ammonia is bubbled through dilute acids, ammonium salts are formed.
2NH3(g) + H2SO4(aq) → (NH4)2SO4(aq)
NH3(g) + HCl(aq) → NH4Cl(aq)
NH3(g) + HNO3(aq) → NH4NO3(aq)
Ammonia does not burn in air. However, it burns with a greenish-yellow flame in air enriched with oxygen to form nitrogen and steam.
The set up below can be used to investigate this property of Ammonia.
Ammonia burns with a greenish-yellow flame in air enriched with oxygen to form nitrogen and steam.
4NH2(g) + 3Oz(g) 2N2(g) + 6H2O(g)
Ammonia is oxidised to nitrogen(II) oxide in the presence of a platinum catalyst. This can be demonstrated practically.
⚗Practically Speaking🔊 📌
Place concentrated ammonia solution in a conical flask. Arrange the apparatus as shown. Heat a platinum wire until it is red-hot. Pass oxygen or air through the concentrated ammonia. Place the hot platinum or copper in the flask. Record your observations.
Observation and Discussion
Ammonia is oxidised to nitrogen(II) oxide in the presence of a platinum catalyst.
4NH3(g)+ 5O2 (g)4NO2 (g) + 6H2O(g)
Black solid colourless solution
2NO(g)+ O2(g) 2NO2(g)
Side notes
Ammonia gas can reduce copper(II) Oxide to copper.
When ammonia is passed over heated copper(II) oxide, the black copper(II) oxide turns into a brown solid as copper(II) oxide is reduced to copper metal by ammonia.Water and nitrogen gas is also obtained.
3CuO(s)+ 2NH3 (g)3Cu(s) + N2(g) + 3H2O(l)
Black brown
The colourless liquid collected in the U-tube turns cobalt(II) chloride paper pink. This test confirms the presence of water.
The gas collected has no effect on a moist litmus paper and lime water. It extinguishes a burning splint. The gas is nitrogen.
Ammonia is prepared on a large scale by the Haber Process.
The raw materials
Nitrogen- obtained by the fractional distillation of liquid air.
Hydrogen – obtained from natural gas or as a by-product of cracking long chain alkanes.
The process
Nitrogen and hydrogen gases are mixed in the ratio of 1:3 and passed through a purifier to remove impurities which would otherwise poison the catalyst. The impurities removed are; carbon(IV) oxide, sulphur(IV) oxide and dust particles.
The mixture of nitrogen and hydrogen is then compressed to between 200 and 500 atmospheres and passed into a catalytic chamber maintained at temperatures of between 400°C and 500°C. Iron is used as the catalyst. The reaction is highly exothermic and sustains the temperature in the catalytic chamber.
N2(g) + 3H2(g) 2NH3(g) + Heat
The hot mixture of ammonia and gases which have not reacted are passed into the heat exchanger where cooling takes place. The heat is used to heat the incoming mixture of nitrogen and hydrogen, this makes the process economical.
The ammonia produced is liquefied in the condenser and stored in cylinders. The gases which have not reacted are recycled therefore reducing wastage.
The yield of ammonia is high at higher pressures and low temperature. However, it is expensive to maintain higher pressure. At low temperatures the reaction is slow.
To reduce the production cost optimum conditions of 500°C, 200 atmospheres and iron catalyst are employed.
(i) Ammonium sulphate, (NH4)2SO4
It is the most widely used nitrogenous fertiliser. It is prepared by reacting ammonia and sulphuric acid.
2NH3(g) + H2SO4(aq) (NH4)2SO4(s)
The percentage of nitrogen in ammonium sulphate fertilisers is determined as follows.
Percentage of nitrogen =
=
= 21. 21%
(ii) Ammonium nitrate, NH4NO3
It is used widely due to a high content of nitrogen. It is prepared by neutralising nitric acid with ammonia.
NH3(aq) + HNO3(aq) NH4NO3(aq)
The percentage composition of nitrogen in ammonium nitrate is determined as:
Percentage of nitrogen =
=
= 35.0%
(iii) Ammonium phosphate (NH4)3PO4
Apart from nitrogen, ammonium phosphate also contains phosphorus which is of vital importance for plant growth. It is prepared by neutralising phosphoric acid with ammonia.
3NH3(g) + H3PO4(aq) (NH4)3 PO4(aq)
Percentage of nitrogen in (NH4)3PO4 =
= 28.19%
(iv) Urea (NH2)2 CO
Urea is prepared by passing carbon(IV) oxide through ammonia solution.
CO2(g)+ 2NH3(aq) CO(NH2)2(aq) + H2O(l)
Percentage of nitrogen in urea =
= 46.67%
(v) Calcium ammonium nitrate (CAN)
Calcium ammonium nitrate is a mixture of ammonium nitrate and calcium nitrate.
The percentage composition of nitrogen in calcium ammonium nitrate is about 27%.
From the examples given, urea is a better nitrogenous fertiliser because it contains a higher content of nitrogen.
Nitric(V) acid is prepared by reacting concentrated sulphuric(VI) acid with a nitrate. Potassium nitrate is commonly used as it does not contain water of crystallisation.
When a mixture of potassium nitrate and concentrated sulphuric(IV) acid is heated, fumes of nitric(V) acid are produced. Nitric(V) acid is more volatile and is readily displaced from nitrates by the less volatile sulphuric(VI) acid.
KNO3(s) + H2SO4(l) KHSO4(s) + HNO3(aq)
4HNO3(g) ⇌ 4NO2 (g) + O2(g) +2H2O (g)
colourless reddish-brown
Nitric(V) acid is manufactured by a process that relies on the catalytic oxidation of ammonia.
The raw materials for this process are ammonia, air and water.
A mixture of ammonia and air is first purified to remove dust particles and other impurities that would otherwise ‘poison’ the catalyst.
The mixture is then compressed to a pressure of 9 atmospheres and passed on to the catalytic chamber via the heat exchanger.
As it passes through the heat exchanger, the temperature of the ammonia-air mixture rises to 230°C.
In the catalytic chamber, the temperature of the mixture is raised further to 900°C. It is then passed over a platinum-rhodium catalyst. The ammonia combines with oxygen to form nitrogen(II) oxide. The reaction is highly exothermic.
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
The hot gaseous products from the catalytic chamber are cooled in the heat exchanger. Nitrogen(II) oxide is mixed with more air and is oxidised to nitrogen(IV) oxide.
2NO(g) + O2(g) 2NO2(g)
This reaction is carried out at a temperature of below 45°C to ensure a high yield of nitrogen(IV) oxide.
The mixture of nitrogen(IV) oxide, air and unreacted nitrogen(II) oxide is passed up the absorption tower against a downward flow of hot water. Nitrogen(IV) oxide and water combine to form nitric(V) acid and nitric(III) acid (nitrous acid).
2NO2 (g) + H2O (l)2HNO3(aq) + 2HNO2(g)
Nitric (V) acid Nitric (III) acid
The nitric(III) acid formed is oxidised to nitric(V) acid by excess air.
2HNO2(g)+ O2 (g)2HNO3(aq)
Nitric (III) acid Nitric (V) acid
The mixture that results is 65% nitric(V) acid and 35% water.
A more concentrated acid may be obtained by careful distillation of the solution over phosphorus(V) oxide or concentrated sulphuric(VI) acid that acts as a dehydrating agent.
Concentrated nitric(V) acid is a colourless fuming liquid with a boiling point of 83°C. Commercial nitric(V) acid is 68% pure and has a density of 1.42 g/cm3.
Dilute nitric(V) acid does not produce hydrogen with some metals as expected. This is because any hydrogen produced is at once oxidised by the nitric(V) acid to water. The acid is reduced to one or more of the oxides of nitrogen.
Very dilute nitric(V) acid has little oxidising power and magnesium will displace hydrogen from it.
Mg(s) + 2HNO3(aq) Mg(NO3)2(aq) + H2(g)
With zinc, no hydrogen is produced as the hydrogen is immediately oxidised to water. The acid is reduced to nitrogen(II) oxide.
3Zn(s) + 8HNO3(aq) 3Zn(NO3)2(aq) + 4H2O(l) + 2NO(g)
The nitrogen(II) oxide is colourless but on exposure to air it is oxidised to red-brown nitrogen(IV) oxide.
2NO(g)+ O2 (g)2NO2(g)
colourless red-brown
50% dilute nitric(V) acid does not behave like a typical acid because it reacts with copper to produce copper(II) nitrate, nitrogen(II) oxide and water.
3Cu(s) + 8HNO3(aq) 3Cu(NO3)2(aq) + 2NO(g) + H2O(l)
Dilute nitric(V) acid behaves like a ‘typical’ acid by reacting with carbonates and hydrogen carbonates to produce a nitrate, carbon(IV) oxide and water.
Na2CO3(s) + 2HNO3(aq) 2NaNO3(aq) + CO2(g)+ H2O(l)
ZnCO3(s) + 2HNO3(aq) Zn(NO3)2(aq) + CO2(g) + H2O(l)
CuCO3(s) + 2HNO3(aq) Cu(NO3)2(aq) + CO2(g) + H2O(l)
NaHCO3(s) + HNO3(aq) NaNO3(aq) + CO2(g) + 2H2O(l)
Metal hydroxides and oxides are neutralised by dilute nitric (V) acid to form a metallic nitrate and water only.
NaOH(aq)+ HNO3 (aq)NaNO3(aq) + H2O(l)
CaO(s)+ 2HNO3 (aq)Ca(NO3)(aq) + H2O(l)
White solid colourless solution
CuO(s)+ 2HNO3 (aq)Cu(NO3)(aq) + H2O(l)
Black solid colourless solution
PbO(s)+ 2HNO3 (aq)Pb(NO3)(aq) + H2O(l)
Yellow solid colourless solution
Concentrated nitric(V) acid is a powerful oxidising agent. It oxidisesiron(II) salts to iron(III) salts and is itself reduced to nitrogen(II) oxide. The pale-green iron(II) sulphate solution is oxidised to yellow iron(III) sulphate.
6FeSO4(aq) + 3H2SO4(aq) + 2HNO3(l) 3Fe2(SO4)3 (aq) + 2NO(g) + 4 H2O(l)
Nitrogen(II) oxide is colourless. As it moves up the test-tube it is quickly oxidised by oxygen in the air to red-brown fumes of nitrogen(IV) oxide.
Hot concentrated nitric(V) acid oxidises sulphur to sulphuric(VI) acid and water while it is reduced to nitrogen(IV) oxide.
S(s) + 6HNO3(aq) H2SO4(aq) + 6NO2(g) 2H2O(l)
Copper is oxidised to copper(II) nitrate as the nitric(V) acid is reduced to water and nitrogen(IV) oxide.
3Cu(s) + 8HNO3(aq) 3Cu(NO3)2(aq) + 4H2O(l) + 2NO2(g)
Nitrates are salts that are derived from nitric(V) acid. They are usually prepared by the action of dilute nitric(V) acid on either a base or a carbonate. Some nitrates can be obtained by direct reaction of a metal with concentrated nitric(V) acid.
Hydrated metallic nitrates produce water vapour when gently heated. On strong heating, they all decompose. Sodium nitrate and potassium nitrate melt and decompose on strong heating to produce oxygen gas and the nitrite of the metal.
2NaNO3(s) 2NaNO2(s) + O2(g)
KNO3(s) KNO2(s) + O2(g)
Nitrates of metals below sodium up to copper in the reactivity series decompose on heating to give the metal oxide, nitrogen(IV) oxide and oxygen. Thus:
2Zn(NO3)2 (s) 2ZnO(s)+ 4NO2(g) + O2(g)
yellow when hot
white when cold
2Pb(NO3)2 (s) 2PbO(s) + 4NO2 (g) + O2(g)
white yellow when cold
2Cu(NO3)2 (s) 2CuO(s) + 4NO2 (g) + O2(g)
blue black
Note:When lead(II) nitrate is heated a cracking sound is produced. The cracking sound is due to the air trapped inside the crystal which on expansion causes the crystals to burst producing the sound.
Nitrates of metals below copper decompose on heating to produce the metal, nitrogen(IV) oxide and oxygen. For example silver nitrate decomposes to produce silver, nitrogen(IV) oxide and oxygen gas.
2AgNO3(s) 2Ag(s) + 2NO2(g) + O2(g)
The ease with which metal nitrates decompose increases down the reactivity series of the metals.
Ammonium nitrate when heated decomposes to nitrogen(I) oxide and water.
NH4NO3(s) N2O(g) + 2H2O(g)
Dry nitrogen(I) oxide relights a glowing splint. However, the steam produced does not allow a glowing splint to relight.
The brown ring test for nitrates
Concentrated sulphuric acid is added to a mixture of sodium nitrate and iron (II) sulphate solution. A brown ring is formed at the junction of the two layers that are formed. This is the confirmatory test for nitrates. All nitrates give the same result.
⚗Practically Speaking🔊 📌
Test:Place one spatulaful of sodium nitrate into a clean test-tube. Add 2 cm3 of distilled water and shake the mixture. Add 1 cm3 of freshly prepared iron (II) sulphate and shake the mixture again. Add concentrated sulphuric acid slowly and carefully along the wall of the test-tube.
Discussion
When concentrated sulphuric acid is added to the mixture of sodium nitrate and iron (II) sulphate solution, the acid sinks to the bottom. This is because the acid is denser that the solution. The reaction produces heat. A brown ring is formed at the junction of the two layers. The brown ring is due to the formation of iron(II) sulphate–nitrogen (II) oxide complex, FeSO4.NO.
A safer method of testing for the presence of nitrate ions is by warming a mixture of concentrated sulphuric(VI) acid and the suspected nitrate in the presence of copper turnings.
Test: Place a spatulaful of sodium nitrate in a dry test-tube. Add a few drops of concentrated sulphuric acid. Warm the mixture and add a few pieces of copper turnings.
When sodium nitrate is mixed with concentrated sulphuric acid and the mixture warmed in the presence of copper turnings, brown fumes of nitrogen(IV) oxide are produced. This reaction takes place in two stages.
NaNO3(s) + H2SO4(l) NaHSO4(s) + HNO3(l)
Cu(s) + 4HNO3(l) Cu(NO3)2(aq) + 2H2O(l) + 2NO2(g)
Oxides of nitrogen such as nitrogen(II) oxide and nitrogen(IV) oxide are atmospheric pollutants. Nitrogen(II) oxide is produced in internal combustion engines when nitrogen and oxygen from the air combine at high temperatures.
N2(g) + O2(g) 2NO(g)
In the atmosphere, nitrogen(II) oxide is quickly oxidised to nitrogen(IV) oxide.
2NO(g) + O2(g) 2NO2(g)
The nitrogen(IV) oxide reacts with water in the atmosphere to produce nitric(III) and nitric(V) acids.
2NO2(g) + O2(g) HNO2(aq) + HNO3 (aq)
(Nitric (III) acid) (Nitric (V) acid)
The nitric(III) acid is further oxidised to nitric(V) acid.
2HNO2(aq) + O2(g) 2HNO3(aq)
The nitric(V) acid eventually reaches the ground as acid rain. Acid rain causes the loss of chlorophyll (chlorosis) from plant leaves. This leads to the death of the affected plants.
Acid rain also corrodes stone buildings and metallic structures thereby weakening them and destroying their beauty. Rainwater containing dissolved nitric(V) acid leaches vital minerals from soils. These are converted into soluble nitrates and washed away from the top soil. This leads to poor crop yields.
Nitrogen(IV) oxide undergoes chemical reactions in the air to produce one of the major components of smog. Smog reduces visibility for motorists, irritates the eyes and causes breathing problems.
When nitrate ions from nitrogen containing fertilisers find their way into water bodies they encourage rapid growth of algae. This eventually leads to the reduction in the oxygen content in the water. As a result, aquatic animals such as fish die.
The presence of nitrate ions in drinking water may also cause ill health to humans. This is because in the body, the nitrate ions are converted into carcinogenic compounds.
There is an urgent need to reduce environmental pollution. Some of the measures that can be taken to reduce environmental pollution by nitrogen compounds include:
(a) Recycling unreacted gases in the manufacture of nitric acid to prevent release into the environment.
(b) Treating sewage and industrial effluents to remove nitrogen compounds before releasing them into rivers and lakes.
(c) Fitting the exhaust systems of vehicles with catalytic converters which convert nitrogen oxides into harmless nitrogen gas.
(d) Adding lime to lakes and soils in the surrounding regions to reduce acidity.
(e) Applying fertilisers at the right time and in the correct proportion to prevent them from being washed into water masses.
The first step in the industrial manufacture of nitric acid is the catalytic oxidation of ammonia gas.
In an experiment, a few drops of concentrated nitric acid were added to aqueous iron(II) sulphate in a test-tube. Excess sodium hydroxide solution was then added to the mixture.
The elements nitrogen, phosphorous and potassium are essential for plant growth.
When magnesium was burnt in air, a solid mixture was formed. On addition of water to the mixture a gas which turned moist red litmus paper blue was evolved. Explain these observations. (2 marks)
| Cation of
| Addition of a few drops of Aqueous ammonia. | Addition of excess aqueous ammonia. |
| E | White precipitate | Insoluble |
| F | No precipitate | No precipitate |
| G | White precipitate | Dissolves |
When 8.53g of sodium nitrate were heated in an open tube, the mass of oxygen produced was 0.83g. Given the equation of the reaction as
2NaNO3(s 2NaNO2(s) + O2(g)
Calculate the percentage of sodium nitrate that was converted to sodium nitrite
(Na= 23.0, N = 14.0, O = 16.0) (3 marks)
A sample of fertilizer is suspected to be calcium ammonium nitrate. Describe chemical tests for each of the following ions in the sample:
In an experiment to prepare nitrogen (I) oxide, ammonium nitrate was gently heated in a flask.
The set-up below shows how nitrogen gas is prepared in the laboratory.
50g of ammonium sulphate, (NH4)2SO4, and 30 kg of urea, CO(NH2)2, fertilizers were applied in two equal sizes of plots A and B to enrich their nitrogen content.
Show, by working, which plot was more enriched with nitrogen.
(N = 14; S = 32; O = 16; C 12; H = 1) (3 marks)
Study the flow chart below and answer the questions that follow.
(N = 14.0; O = 16.0; H=1.0) (3 marks)
The scheme below shoes some reaction sequence starting with slid N. Study it and answer the questions that follows.
(a) Write the formula of the complex ion in solution Q. (1 mark)
(b) Write an equation for the reaction in step IV. (1 mark)
When fuels burn in the internal combustion engine at high temperature, one of the products formed is nitrogen (II) oxide.
On heating a pale green solid K, carbon (IV) oxide gas and a black solid M were formed.
On reacting K with dilute hydrochloric acid, carbon (IV) oxide gas and green solution S were formed. When excess aqueous ammonia was added to solution S, a deep blue solution was formed.
(a) Identify the cation in solid K. (1 mark)
(b) Identify the two onions in solution S. (2 marks)
Study the flow chart below and answer the questions that follow:
Dry ammonia gas was passed over heated lead (II) oxide and the product passed over anhydrous Copper (II) sulphate as shown in the diagram below.
State:
Study the set up below and answer the questions that follow
A student used the set up below to prepare a sample of nitrogen gas.
Dry ammonia and dry oxygen were reacted as shown in the diagram below
Potassium nitrate liberates oxygen gas when heated. Draw a diagram of a set-up that shows heating of potassium nitrate and collection of oxygen gas. (3 marks)
In an experiment, concentrated nitric(V) acid was reacted with iron(II) sulphate. State and explain the observations made. (2 marks)
The flow chart in Figure 3 shows the process of obtaining a sample of nitrogen gas. Study it and answer the questions that follow.
(a) Identify X (1 mark)
(b) Write an equation for the reaction with heated copper turnings. (1 mark)
(c) Name an impurity in the sample of nitrogen gas. (1 mark)
The set-up in Figure 4 can be used to prepare nitrogen(II) oxide. Use it to answer the questions that follow.
Study the flow chart in Figure 1 and answer the questions that follow.
Gas N forms a while suspension with aqueous calcium hydroxide.
(a) Name the anion present in the potassium salt. (1 mark)
(b) Write an ionic equation for the formation of solid M. (1 mark)
(c) Give one use of gas N. (1 mark)
(NH4)2HPO4 is a fertiliser used by farmers to boost their crop production.
When burning magnesium ribbon is introduced into a gas jar full of nitrogen, it continues to burn producing a greenish yellow powder.
(a) Write an equation for the reaction between nitrogen and magnesium. (1 mark)
(b) Explain why magnesium continues to bum in nitrogen but sulphur does not. (2 marks)
(c) State one use of nitrogen. (1 mark)
Figure 3 is a flow chart that shows the process that occurs in the manufacture of nitric(v)acid.
P……………………… (1 marks)
Q………………………… (1 marks)
R………………………….. (1 marks)
S……………………………. (1 marks)
(c) When ammonia is reacted with nitric(V) acid, it produces a nitrogenous fertiliser.
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