Nitrogen

Nitrogen is one of the gases that make up the atmosphere and has the molecular formula, N 2. It is about
78% by volume of atmospheric air. Also living matter contains nitrogenous organic compounds usually
as proteins.

Preparation of Nitrogen

(1). From the Atmospheric Air

Air is composed mainly of oxygen, carbon- dioxide and nitrogen. Both oxygen and carbon(IV) oxide can
be removed from a volume of air, leaving behind nitrogen, by passing the volume of air into either
sodium hydroxide or calcium hydroxide solution (to absorb the CO2 content), and then passing the
resulting gas through a mass of heated copper (to remove the oxygen content - copper reacts with
oxygen when heated to give CuO).

The gas left is nitrogen, with some noble gases (about 1% by volume).

Note: nitrogen obtained from air is not pure - it contains the noble gases of the air, hence it is denser
than pure nitrogen.

Alternatively, nitrogen can be obtained from the atmospheric air by absorbing both carbon(IV) oxide and
oxygen together by shaking air with a solution of benzene -1,2,3- triol in sodium hydroxide solution.

Oxygen is absorbed by benzene -1,2,3 triol to form an oxidation product of itself, while carbon(IV) oxide
is absorbed by sodium hydroxide solution.

(2). Preparation of Nitrogen by action of heat on:

(a). Ammonium dioxonitrate(III) solution - NH4NO2 readily decomposes slowly on slight warming at
ordinary temperature to liberate nitrogen.

Note: NH4NO2 is not kept in stock because it will decompose. Also, it is not advisable to heat NH4NO2
solution directly, because the reaction might be explosive.

To produce nitrogen by this method, a mixture of suitable substances which would produce NH4NO2,
and subsequently produce the required nitrogen are warmed slightly.

Example, a mixture of dioxonitrate(III) salt and an ammonium salt are warmed to initially produce
ammonium dioxonitrate(III), NH4NO2, which immediately decomposes to give the desired nitrogen.

It is common to use sodium dioxonitrate(III) solution and ammonium chloride solution.

NaNO2(aq) + NH4Cl(aq) → NH4NO2(aq) + NaCl(aq)

Then NH4NO2(aq) → N2(g) + 2H2O(l)

(b). Ammonium dichromate(VI), (NH4)2Cr2O7

(3). The action of chlorine on excess ammonia.

3Cl2(g) + 8NH3(g) → N2(g) + 6NH4Cl(s)

(4). By passing ammonia gas over heated copper (II)oxide.

2NH3(g) + 3CuO(s) → 3Cu(s) + 3H2O(g) + N2(g)

(5). By reduction of oxides of nitrogen by heated copper.

Example, 2Cu(s) + 2NO(g) → 2CuO(s) + N2(g)

(6). Production of nitrogen from liquid air:

The process of liquefying air and obtaining nitrogen is explained here: What is Air?

Properties of Nitrogen

Nitrogen shows the following properties:

Physical Properties

1. Nitrogen is a colourless and tasteless gas.

2. It is a little lighter than air).

3. It is only slightly soluble in water.

4. It has a boiling point of 77 K at 1 atmosphere

5. It has a freezing point of 63 K.

Chemical properties

The nitrogen atom has two s and three p electrons in its outermost shell. Three pairs of shared electrons
bond the two atoms together in the N2 molecule:

:N:::N:

The great strength of this triple bond is responsible for the stability of the N2 molecule and the
consequent relative inertness of elementary nitrogen.

The dissociation of 1 mole of N2 molecules involves the absorption of very high energy (171 kcal). The
same quantity of energy is released when 2 moles of nitrogen atoms form 1 mole of N2 molecules.
This is the basic reason for the instability of many nitrogen compounds. Some of the compounds are so
unstable that they decompose with explosive violence.

Most chemical explosives are nitrogen compounds and elementary nitrogen is a product of their
decomposition. Some reactions of nitrogen are:

1. Nitrogen combines directly with certain metals, such as Ca, Al, Mg and Fe at very high temperatures
and pressures.

Example, Magnesium when red hot combines with nitrogen to form a magnesium nitride.

3Mg(s) + N2(g) → Mg3N2(s)

Note: when water is added to the nitride, it hydrolysis to liberate ammonia.

Mg3N2(s) + 6H2O(l) → 3Mg(OH)2(s) + 2NH3(g)

2. Nitrogen reacts with hydrogen and oxygen at high temperatures and pressures. With hydrogen - the
reaction is reversible, and a catalyst is used.

Ammonia is produced.

N2(g) + 3H2(g) reversible reaction arrow 2NH3(g)

With oxygen - at very high temperatures (about 2000oC), nitrogen reacts with oxygen to form
nitrogen(II)oxide.

N2(g) + O2(g) → 2NO(g)

Note: this reaction is also given during thunder and lightening.

Test for Nitrogen

Nitrogen is not reactive. That is, it is inert at ordinary temperatures. Hence, it becomes extremely
difficult to test chemically.

However, a certain gas can be confirmed to be nitrogen by eliminating other possibilities, such as:
combustion (nitrogen does not burn or support combustion); action with lime water (nitrogen does not
show any effect); with litmus paper and with acidified KMnO4 (nitrogen does not show any effect).

Uses of Nitrogen

Nitrogen can be used in the following ways:

1. For the manufacture of synthetic ammonia - this is the single largest use for nitrogen.

2. For the making of calcium cyanamide.

3. To provide inert atmosphere as a protection against oxidation for processes such as the canning of
foods.
Ammonia and Its Properties
Ammonia molecules consist of one nitrogen and three hydrogen atoms, and has the formula, NH3.

Laboratory Preparation of Ammonia

Ammonia is prepared in the laboratory by the heating of a fine mixture of an ammonium salt (usually
NH4Cl) and an alkali (usually Ca(OH)2).

Ca(OH)2(s) + 2NH4Cl(s) → CaCl2(s) + 2H2O(l) + 2NH3(g)

Note: the principle behind the reaction is this: more volatile alkalis, such as ammonia are liberated from
their salts when less volatile alkalis act on them.

Hence, NH4Cl or NH4SO4 and Ca(OH)2, NaOH or KOH may be used together. The ammonia formed is
dried using an unusual drying agent - calcium oxide, cao (quicklime).

This is because NH3 reacts with the usual drying agents: - It reacts with conc. H2SO4 to form a salt.
Example,

2NH3(g) + H2SO4(l) → (NH4)2SO4(s)

It reacts with calcium chloride forming a complex solid compound, i.e.,

CaCl2(s) + 4NH3(g) → CaCl2 . 4NH3(s)

Commercial Production of Ammonia

Ammonia is made commercially by the direct combination of nitrogen and hydrogen using a catalyst -
finely reduced (or divided) iron impregnated with aluminium oxide. A lower temperature of about 45oC and
high pressure condition (between 200 to 500 atm are used.

This process is called the Haber process.

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

Properties of Ammonia
Ammonia shows the following properties:

Physical Properties

1. Ammonia is a colourless gas.

2. It is less dense than air (V.D.= 8.5 - hence it is collected by upward delivery).

3. It is very soluble in water and is therefore used in the fountain experiment - it is a soluble gas

4. It is alkaline in nature, i.e., it is a soluble base, showing properties of alkalis.

Chemical Properties

1. Reaction with oxygen - it burns in oxygen with a greenish - yellow flame to form water vapour and
nitrogen.

4NH3(g) + 3O2(g) → 6H2O(g) + 2N2(g)

In excess of oxygen, nitrogen oxide is formed instead of nitrogen.

4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)

2. As a reducing agent - although NH3 is not a strong reducing agent, it reduces heated CuO, while it is
itself oxidized to water and nitrogen.

3CuO(s) + 2NH3(g) → 3Cu(s) + 3H2O(l) + N2(g)

3. Reaction with chlorine - in excess ammonia, chlorine reacts with ammonia firstly to produce HCl and
N2, then the excess NH3 react with the HCl to form white fumes of ammonium chloride.

2NH3(g) + 3Cl2(g) → 6HCl(g) + N2(g) then,

6NH3(g) + 6HCl(g) → 6NH4Cl(s) overall:

3Cl2(g) + 8NH3(g) → 6NH4Cl(s) + N2(g)

4. Reaction with carbon(IV)oxide - ammonia reacts with CO2 to produce urea, (NH2)2CO.

2NH3(g) + CO2(g) → (NH2)2CO(s) + H2O(l)

5. Thermal decomposition - at high temperature and prolonged sparking, ammonia decomposes to N2 and
H2

6. As a precipitating agent - the hydroxides of most metals are precipitated from solutions of their salts by
aqueous ammonia.

Example of such hydroxides are Fe(OH)3 - reddish brown; Pb(OH)2 - white; Cu(OH)2 - blue; and Zn(OH)2 -
white gelatinous.

Note: in excess ammonia solution,Cu(OH)2 and Zn(OH)2 are dissolved. This can be used to identify both
Cu and Zn ions. Cu(OH)2 dissolves to form a deep-blue complex compound, while Zn(OH)2 dissolves to
form a colourless, complex compound.

Test for Ammonia

Ammonia can be identified through the following tests:

 Smell - it has a characteristic choking smell.

 Action on litmus paper - turns moist, red litmus paper blue (It is alkaline).
 Reaction with conc. HCl - it forms a white fume NH3(g) + HCl(g) → NH4Cl(g)

Uses of Ammonia
Here are ways by which ammonia can be used:

(1). Solution of ammonia is used in laundry work. It removes temporary hardness and removes also acids
left on under clothing from evaporation of sweat.

(2). For the manufacture of trioxonitrate(V) acid.

(3). In the fertilizer industry - NH3 is used in the manufacture of urea which is used in the production of
nitrogenous fertilizers, such as (NH4)2SO4 and ammonium tetra oxophosphate(V), (NH4)3PO4 - this is the
most important use of ammonia.

(4). As refrigerant.

Ammonium Salts and their Uses

Ammonium salts are electrovalent compounds, containing the ammonium ion, NH4+, in combination with a
corresponding amount of an acidic ion, such as Cl-, NO3-, CO32- and SO42-. Ammonium salts of strong
acids are hydrolyzed in their aqueous solutions to give acidic solutions.

This is because NH3 is a weak base. Action of heat on ammonium salts - ammonium salts are always
decomposed by heat, and some of them sublime, that is, moving straight from solid to gas without going
through the liquid state.

And when the gas is cooled, it solidifies without becoming liquid. A very good example is ammonium
chloride, NH4Cl.

Note: ammonium salts from acids having a high proportion of oxygen are usually decomposed when
heated. Example, ammonium dioxonitrate(III)

NH4NO2(s) → N2(g) + 2H2O(g) - Ammonium trioxonitrate(V)

NH4NO3(s) → N2O(g) + 2H2O(g)

Uses of Ammonium Salts

Ammonium salts has the following uses:

1. NH4Cl - two of the important uses of this salt are: (a). In the leclanche votaic cell. (b). As a flux in
soldering.

2. (NH4)2SO4, NH4NO3 and (NH4)3PO4 are mainly used as fertilizers.

3. (NH4)2CO3 is used as a constituent of ‘smelting salts’, since it decomposes readily to ammonia,

carbondioxide and water.

Oxidation of Ammonia
Ammonia is oxidized to nitrogen(IV) oxide in the presence of excess air and platinum/rhodium gauze as
catalyst.

The reaction is exothermic and the temperature of the system is maintained once it starts.
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(l)

The NO cools rapidly and combines with more oxygen (from the excess air) to form nitrogen(IV) oxide.

2NO(g) + O2(g) → 2NO2(g)

If the NO2 formed is passed into hot water, in the presence of more air, trioxonitrate(V) acid is formed.

2H2O(l) + 4NO2(g) + O2(g) → 4HNO3(aq)