Ch # 7 Nitrogen and Phosphorus

7.1 INTRODUCTIONS:

Group VA (15) of the periodic table consists of nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) and
bismuth (Bi). The constitute a well defined series showing a regular change of properties with the atomic
number. The gradual transition from non-metallic to metallic character with the in a group is no better
illustrated than in this group. The first two elements, N and P, are typical non-metallic, Sb and Bi are definitely
metals, while As may be considered as a metalloid. All the elements have five electrons in their outer most shell
with two electrons in the s-orbital and three electrons in the p-orbital as shown in table 7.

Table 7.1 Electronic configuration of Group VA (15) Elements.

Element Symbol At. No. Electronic Configuration

Nitrogen N 7 1s2, 2s2 2p3
Phosphorus P 15 1s2, 2s2 2p6, 3s2 3p3
Arsenic As 33 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p3
Antimony Sb 51 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6, 5s2 5p3
Bismuth Bi 83 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6, 5s2 5p6 5d10, 6s2 6p3

liquid N2

Atomic Spectral lines of nitrogen

Crystal structure: hexagonal

 Figure 13.2 The bonding in a nitrogen molecule, N2.

It is evident from the above configurations that all these elements possess s2p3 configuration in the valance
shell. The three p-electrons are equally distributed in accordance with the Hund’s rule amongst the three
orbitals and since the orbitals are exactly half-filled, the elements are fairly stable and not so reactive, e.g.,
nitrogen behaves almost as an inert element. The penultimate shell of nitrogen contains s2 electrons (saturated),
of phosphorus s2p6 electrons (saturated), of arsenic s2p6d10 electrons (saturated), while antimony and bismuth
contains s2p6d10 electrons (unsaturated). This shows why nitrogen differs from phosphorus and these two from
the remaining members of this groups.

Some of the important physical properties of group VA (15) elements are summarized in Table 7.2.

Table 7.2. Some Physical Properties of Group VA (15) Elements

Property N P As Sb Bi
Atomic number 7 15 33 51 83
Atomic weight 14.00 30.97 74.92 121.75 208.98
Density (g/cm3) 1.026 1.82 to 2.31 4.7 to 5.7 6.7 9.6
Ionization potential (eV) 14.48 10.9 10.5 9 8
Melting Point °C -209.8 44.1 814 631 271
Boiling Point °C -195.8 280 615 1380 1450
Atomic radius (nm) 0.074 0.110 0.121 0.141 0.146
Electronegativity 3.0 2.1 2.0 1.9 1.8

7.2 GRADUATION OF THE CHARACTERISTIC PROPERTIES WITHIN GROUP VA ELEMENTS

The graduation in the physical and chemical properties of the elements with the rise of atomic number is as
fellow:

(i). Physical State: Nitrogen is a gas, phosphorus is a soft waxy solid, and arsenic is hard but lusterless solid
while antimony and bismuth are hard solids with metallic luster.

(ii). Atomic number and Ionic Sizes: The steady increase in size with increasing atomic number is apparent in
the group. A comparison of the sizes of the atoms in different oxidation states is of special interest. The size of
the radius for an atom in -3 oxidation state is very large and it is much smaller for +5 oxidation state. This is in
accordance with the gradual increase in the metallic character from top to bottom in the group.

(iii). Ionization Potential and Electronegativity: With increase in size, these elements have increasing
tendency to lose valence electrons and their ionization Potential shows a progressive decrease. The
electronegativity decrease from nitrogen (= 3.0) to bismuth (= 1.9) nitrogen to bismuth 3 ─ 1.9.

(iv). Density: There is a pronounced increase in hardness and density in going from P to Bi. d = m/V

(v). Melting and Boiling Points: The melting point (expect for Sb and Bi) and the boiling points both increase
as we move down the group. The melting point of Bi is usually low. Low melting point of Bi suggests that there
is little possibility of the availability of the pair of electrons in s-orbital. The elements of this group are more
volatile than their intermediate neighbours.
(vi). Metallic Character: Due to the decrease in the values of ionization energies from N to Bi, the metallic
character of these elements increases in the same direction. For example, the first two elements are exclusively
nonmetals, the next two elements viz. As and Sb are metalloids, while the last element namely Bi is typically a
metal.

(vii) Catenation: Nitrogen and phosphorus have a tendency to form M─M links. For example, N-atoms are
linked together in hydrazine (H2N─NH2) and azide N ─ N ─ N)- skeleton. In case of phosphorus P-P links are
limited only to two atoms (e.g., P2H4) while As has no tendency for catenation.

(viii). Oxidation States: The common oxidation state of these element are ─3, +3 and +5. This is in agreement
with the number of electrons in the outer shell. The tendency to acquire three electrons and to be in -3 oxidation
state is most pronounced in the case of nitrogen. It decreases with increasing atomic number until bismuth
forms no stable compound in which its oxidation state is ─3. In the +3 oxidation state, the inert pair s2, is of
importance. The oxidation state becomes progressively more important from phosphorus to bismuth. Only Bi
and Sb form simple cations Bi3+ and Sb3+ in aqueous solutions.

Some of the elements of this group also show other oxidation states. e.g., nitrogen show +1, +2, and +4 and
phosphorus shows +1, and +4, in addition to the normal States.

(ix). Formation of Hydrides: All the element of this group from the Hydrides like MH3 (M = N, P, As, Sb, Bi),
M2H4 (M = N, P). The stability of the Hydrites decreases with the rise of atomic weight. Nitrogen form the
most stable ammonia (NH3) while the existence of bismuth hydride is doubtful and it has been obtained only in
the traces.

(x) Formation of Oxides: All the element from oxides of the general formulae X2O3, X2O4 and X2O5 in which
the oxidation states are +3, +4 and +5 respectively. Their acidic character decreases with increasing atomic
weight. The oxides of nitrogen (N2O3, N2O4 and N2O5) and phosphorus (P2O3, P2O4 and P2O5) are purely acidic
in character; those of arsenic and antimony are amphoteric while that of bismuth (Bi2O3) is predominantly
basic.

(xi). Formation of Halides: These element form two types of halides namely trihalides (MX3) and pentahalides
(MX5). With the exception of BiF3, all other trihalides have covalent character which decreases down the group.
Nitrogen and bismuth cannot form pentahalides, because nitrogen cannot expand its octet due to the non-
availability of d-orbitals and phosphorus has inert pair effect.

(xii). Formation of Oxy-acids: With the exception of bismuth, all other elements form oxy-acids in various
oxidation states. Oxy-acids of nitrogen and phosphorus are quite common and useful. The strength and
solubility of oxy-acids having the element in the same oxidation state (e.g., HNO3 and H3PO4, H3AsO4,
H3SbO4) decreases gradually.

7.3 PECULIAR PROPERTIES OF NITROGEN

Nitrogen which is the first element of VA group differs considerably, like carbon (first element of IVA group),
from the other element of this group. This is because of the following inherent properties of nitrogen: (a) small
size (b) high electronegativity, and (c) non-availability of d-orbitals. The main points of difference are:

(i). Nitrogen is a gas while other elements are solid.

(ii). Nitrogen molecule is diatomic (N2) while other elements are tetra-atomic and are, therefore represented as
P4, As4, and Sb4.

(iii). Nitrogen does not show allotropy while other elements (expect Bi) show allotropy.

(iv). Nitrogen occurs in the free state while none of the other elements occurs in the free state.

(v). The covalency limit for nitrogen is 4 while the other elements can raise their covalency to 5 and 6 by
expansion of outer shell.

(vi). Nitrogen cannot form complexes by accepting electrons but the other elements having suitable d-orbitals
available can form complexes by accepting elements.

(vii). Nitrogen with its small size and high electronegativity can acquire three electrons to give the nitride ion
N3+. This tendency is very much suppressed in the subsequent elements.

(viii). Nitrogen is peculiar in showing a wide range of oxidation states, e.g., +1 in N2O, +5 in HNO3 and ─3 in
NH3. Other elements do not show a variety of oxidation states.

(ix). The nitrogen molecule contains triply bonded nitrogen atoms (N N) and is very stable. The other
elements which are found in different allopatric forms can form molecules of different complexity.

(x). Usually large number of binary compounds of nitrogen with oxygen are known, e. g., N2O, NO, N2O3, NO2,
N2O4 and N2O5. Some of which, e.g., N2O, NO and N2O4 have no counterparts in the other elements.

7.4 FIXATION OF NITROGEN

The conversion of atmospheric nitrogen into useful nitrogenous compounds by natural or artificial methods is
called fixation of nitrogen. Nitrogen present in these nitrogenous compounds is called fixed or combined
nitrogen.

Nitrogen present in the atmosphere is the source of various nitrogenous compounds such as proteins, amino
acids, nucleic acids which are essential for animal and plant kingdom. Neither animals nor the plants can
assimilate free nitrogen. Animals obtain the nitrogen supply from compounds present in plants, while plants
secure the required nitrogen from nitrates present in the soil or from fertilizers. The nitrogenous compounds
taken up by plants are converted into proteins in the presence of light. Proteins are essential for animal life.
Thus, plants form a useful link between animals and soil substance.

The chief source of numerous nitrogen compounds is the atmospheric nitrogen. The atmospheric nitrogen is
fixed by the following natural and artificial methods.

Figure 13.2: The triple bonding in a nitrogen molecule, N2.

1. Natural Fixation
(a) By Electric Discharge

The nitrogen and oxygen present in air combine together to form nitric oxide under the influence of electric
discharges. Nitric oxide is oxidized by excess of oxygen present in the atmosphere to form nitrogen dioxide
which further combines with water to form nitric acid. This acid is washed down by rain into the soil, where it
reacts with soil limestone or alkali to form calcium nitrate which is food of plants.

N2(g) + O2(g) → 2NO(g)

Nitrogen (II) Oxide

2NO(g) + O2(g) → 2NO2(g)

Nitrogen (IV) Oxide

2NO2(g) + H2O(l) + 1/2O2(g) + 2HNO3(aq)

Nitric acid

2HNO3 + 2H2O + O2 → 4HNO3

2HNO3 + CaCO3 → Ca(NO3)2 + 2H2O + CO2

Figure 13.3 Nitrogen oxides are formed when lightning strikes

The complete oxidation of the nitrogen gas takes place in three steps:

Step 1: Lightning provides the high activation energy needed for the
oxidation of the unreactive nitrogen

gas to form nitrogen(II) oxide:

N2(g) + O2(g) → 2NO(g)

Nitrogen (II) Oxide

The nitrogen(II) oxide formed is then further oxidised by oxygen in
the air to give nitrogen(IV) oxide, NO2.

Step 2:

2NO(g) + O2(g) → 2NO2(g)

Nitrogen (IV) Oxide

Nitrogen(IV) oxide dissolves in water droplets in the air, and reacts with
more oxygen, to form a dilute

solution of nitric acid. The dilute acid falls to the Earth in rain:

Step 3:

This sequence of reactions in the atmosphere forms part of the natural

nitrogen cycle. In this way, nitrogen from unreactive, insoluble nitrogen
gas can get into the soil in a soluble form that plants can
absorb. The plants can then use the nitrate ions, NO3−, from the dilute
nitric acid to make proteins. These proteins are essential for healthy
growth of the plants.

2NO2(g) + H2O(l) + 1/2O2(g) + 2HNO3(aq)

Nitric acid

2HNO3 + 2H2O + O2 → 4HNO3

(b) By Symbiotic Bacteria

There are also some bacteria, known as symbiotic bacteria which grow in small nodules in the roots of plants of
family Leguminaceae (pea gram etc). These bacteria can assimilate atmospheric nitrogen directly and convert it
into products useful for plant growth.

Plants give out ammonical compounds to the earth on decay, which under the action of nitrosifying and
nitrifying bacteria from nitrites and nitrates. Most of the ammonia and ammonium compounds are produced,
however, as a result of the decomposition of urea, amino acids etc., which are secreted by the animal body.

H2N─CO─NH2 + H2O → (NH4)2CO3

These substances are formed in the animal body by the digestion of nitrogenous plant proteins taken by THE
animals as food. Again, there are some dentrifying bacteria also present, which break up these nitrites and
nitrates and ammonical compounds to nitrogen which goes up to the atmosphere from where it started in the
beginning and thus the cycle is complete. Ammonia to nitrite, and nitrite to nitrate and again nitrate to nitrogen
are not only bacterial processes but photochemically too, and both these agencies help in the completion of the
cycle. This whole phenomenon is known as nitrogen cycle (Fig. 7.1.)

Fig. 7.1. Nitrogen Cycle

2. Artificial Fixation

(a) Fixation of Nitrogen as HNO3

Under the influence of high tension electric arc, nitrogen of the air combines with oxygen to form nitric oxide.
The equilibrium mixture is suddenly cooled when it combines with more of oxygen to form nitrogen peroxide.
This may be absorbed in water in presence of excess air to get nitric acid which may be used for nitrogenous
fertilizers.

(b) Fixation of Nitrogen as NH3

Under the influence of certain catalysts nitrogen combines with hydrogen to form ammonia. A mixture of
nitrogen and hydrogen in the ratio 1:3 is compressed to a pressure of 200 - 500 atmosphere and is passed over a
catalysts (Fe) heated to about 550 °C. This is Haber’s process for the manufacture of ammonia which can be
converted into ammonium salts by treatment with suitable acids.

N2(g) + 3H2(g) → 2NH3(g)

Haber’s process for the manufacture of ammonia

 Figure 13.4 A dot-and-cross diagram showing the covalent bonding in an ammonia molecule and its
pyramidal shape.

(c) Fixation of Nitrogen as Nitrides

Nitrogen combines with Mg and Al at high temperature to give nitrides which are employed as a source of
ammonia, since these nitrides are decomposed by H2O and NH3 is evolved.

3Mg + N2 → Mg3N2

2Al + N2 → 2AIN

AIN + 3H2O → Al(OH)3 + NH3

7.5. OXIDES OF NITROGEN:

Nitrogen is unique in forming a number of oxides corresponding with the formal oxidation states for
nitrogen of +1, +2, +3, +4 and +5 (N2O, NO, N2O3, N2O4, N2O5). Except N2O5, all are gases at ordinary
temperature.

Nitrous Oxide N2O:

Preparation

(i) It is prepared by heating a mixture of sodium nitrate and ammonium sulphate.

2NaNO3 + (NH4)2SO4 → Na2SO4 + 2N2O + 4H2O

(ii) When hydroxylamine salts are oxidized by sodium nitrite, copper sulphate or permanganate, nitrous oxide is
always evolved.

NH2OH . HCI + NaNO2 → NaCl + N2O + 2H2O

(iii) When nitric acid is reduced by stannous chloride and hydrochloric acid, nitrous oxide is obtained.

4SnCl2 + 8HCl + 2HNO3 → 4SnCl4 + 5H2O + N2O

Properties

(i) It is a colorless gas with pleasant odor and sweet taste. It is fairly soluble in water and alcohol. When inhaled
with oxygen, it begets peculiar sort of consciousness with nervous excitement so that it has been named as
laughing gas.

(ii) It is neutral to litmus.

(iii) It supports the combustion of substances like sulphur, phosphorus, sodium, magnesium etc. just as well as
oxygen. This is because of its ready decomposition into its elements.

S + 2N2O → SO2 + 2N2

C + 2N2O → CO2 + 2N2
Mg + N2O → MgO + N2
2Na + N2O → Na2O + N2
(iv) A mixture of hydrogen and nitrous oxide (equal volume) explodes with violence

N2O + H2 → N2 + H2O

Structure:

It is a linear and unsymmetrical molecule with a very small value of dipole moment (= 0.116 D). Thus N2O is a
resonance hybrid of the following structures:

In structure (a) the central N+ is sp hybridized. Each of the two linear sp hybrids orbitals has one electron.
The remaining two 2p-orbitals which do not take part in hybridization also have one unpaired electron. The two
sp hybrids overlap with suitable 2p orbitals of oxygen atom on one side and of nitrogen on the other side to give
two σ-bonds. The remaining two 2p-orbitals of N+ overlap with suitable 2p orbitals of oxygen and of nitrogen to
form two π-bonds. The bond lengths in the molecule are as:

Nitric Oxide, NO
Preparation

(i) It is easily prepared by heating copper turnings with concentrated nitric acid.

3Cu + 8HCO3 (conc.) → 3Cu(NO3)2 + 2NO + 4H2O

The action of Ag, Zn and Hg metals on nitric acid is also similar.

(ii) It is also prepared when a mixture of N2 and O, is passed through an electric arc:

N2 + O2 ⇌ 2NO
(iii) Pure nitric oxide is obtained when a mixture of ferrous sulphate and potassium nitrate is treated with conc.
sulphuric acid

2KNO3 + 6FeSO4 + 4H2SO4 → 3Fe2(SO4)3 + 2NO + 4H2O

Properties

(i) It is a colorless gas, heavier than air and very sparingly soluble in water. The gas is neutral to litmus solution.

(ii) It combines with O2 to form brown fumes of nitrogen peroxide.

2NO + O2 → 2NO2

(iii) It reacts with burning charcoal, S, P to give oxides.

2NO + S → SO2 + N2
2NO + C → CO2 + N2

(iv) It reacts with ferrous sulphate, potassium sulphate etc. to form addition products.

FeSO4 + NO → FeSO4.NO

K2SO4 + 2NO → K2SO4.2NO

(v) It reduces acidified solution of KMnO4 to MnSO4 and HNO3 to NO2-.

6KMnO4 + 9H2SO4 + 10NO → 3K2SO4 + 6MnSO4 + 10HNO3 + 4H2O

2HNO3 + NO → 3NO2 + H2O

(vi) It oxidizes SO2 to H2SO4 and H2S to S.

2NO + SO2 + H2O → H2SO4 + N2O

H2S + 2NO → H2O + S + N2O

(vii) It combines with Cl2 and Br2 to form nitrosyl chloride and nitrosyl bromide respectively.

2NO + Cl2 → 2NOCl

2NO + Br2 → 2NOBr

(viii) When passed through a strong solution of caustic potash it forms nitrite.

2KOH + 4NO → N2O + 2KNO2 + H2O

Structure

Valence bond theory says that NO molecule is a resonance hybrid of the following structures.
It is an odd electron molecule since it contains an odd number of electrons. NO molecule in the gaseous state has
one unpaired electron which makes this molecule paramagnetic. According to magnetic evidence the odd electron
in NO molecule spends half of its time on N-atom and half of its time on O-atom. This situation can be presented
by assuming that NO molecule contains one three-electron bond and two electron bonds as shown below:

In the solid state NO is known to form a loose dimer, N2O2 with structure as:

Dinitrogen Trioxide, N2O3:

Preparation

(i) Nitrogen trioxide is prepared by the production of nitric acid with arsenious oxide.

As2O3 + 2HNO3 → N2O3 + As2O5 + H2O

(ii) It is also prepared by cooling a mixture of nitric oxide and nitrogen peroxide at -21 °C

NO + NO2 → N2O3

Properties

(i) It is a red color gas. On condensing, it gives a dark blue liquid. On heating it dissociates into NO and NO2-

N2O3 → NO + NO2

(ii) It is acidic in nature and reacts with sodium hydroxide to form sodium nitrite

2NAOH + N2O3 → 2NANO2 + H2O

(iii) It is also called nitrous anhydride, i.e., anhydride of HNO 2, since it gives HNO2 when treated with H2O

N2O3 + H2O → 2HNO2

(iv) It reacts with sulphuric acid with the formation of nitrosonium hydrogen sulphate.

N2O3 + 2H2SO4 → 2NO+(HSO4-) + H2O

Structure

Since in liquid and gaseous state N2O3 dissociates to give NO and NO2 it may be assumed that structure
of N2O3 involves a link between NO and NO2 via a π-bond. Thus the structure of N2O3 may be shown as:
This structure is confirmed by the tracer studies which have shown that when nitrogen dioxide labeled with
N15(N15O2) is mixed with N14O a rapid exchange between N15 and N14 takes place as shown below:

N14O + N15O2 ⇌ N15O + N14O2

N2O3 molecule is diamagnetic in spite of its intense blue color and hence it is not an odd electron molecule.

Nitrogen Dioxide, NO2 and Nitrogen Tetroxide, N2O4

NO2

Preparation

(i) When nitric oxide mixes with air, it gives out red fumes which are mainly of nitrogen dioxide.

2NO + O2 → 2NO2

(ii) In the laboratory, it is prepared by the action of heat on lead nitrate.

2Pb(NO3)2 → 2PbO + 4NO2 + O2

(iii) It is also prepared by the action of copper on conc. HNO3.

Cu + 4HNO3 → Cu(NO3)2 + 2NO2 + 2H2O

Properties

(i) Nitrogen dioxide is a reddish brown gas with a pungent smell. This oxide is also called nitrogen peroxide. At
14 °C it has a deep brown colour and a density which corresponds to the formula, NO2-. As the temperature falls,
its colour goes on fading. On further cooling, it condenses to pale yellow liquid (b.p. = 22°C) which freezes to
colorless crystals (m.p. = -9°C). The density of the solid corresponds to the formula, N2O4. Quite evidently,
progressive association of molecules occurs with the decrease in temperature.
2NO2 (Dark brown) ⇌ N2O4 (Colorless)

(ii) The colour of nitrogen dioxide begins to fade above 140 °C also. This is due to its dissociation into NO and
O2-.
 2NO2 ⇌ 2NO + O2

(iii) It is soluble in water and acidic towards litmus. When dissolved in water, it forms a mixture of nitrous and
nitric acids. It is, therefore, a mixed anhydride.

N2O4 + H2O → HNO2 + HNO3

(iv) It neutralizes alkali solution with the formation of mixture of nitrite and nitrate, thus proving its acidic
nature.

2NaOH + 2NO2 → NaNO2 + NaNO3 + H2 O

(v) It acts as a strong oxidizing agent. Thus, it liberates iodine from potassium iodide and turns starch iodide
paper blue.

KI + 2NO2 → 2KNO2 + I2

Its reactions (as an oxidizing agent) with other inorganic compounds are given as:

NO2 + H2S → NO + H2O + S

NO2 + CO → CO2 + CO2 + NO
2FeSO4 + H2SO4 + NO2 → Fe2( SO4)3 + H2 O + NO
NO2 + 2Na → Na2 O + NO
2Cu + NO2 → Cu2 O + NO
5NO2 + 2P → P2 O5 + 5NO
2NO2 + S → SO2 + 2NO
2NO2 + C → CO2 + 2NO

(vi) It also acts as a reducing agent. Thus it decolorizes permanganate.

2MnO4 + 10NO2 + 2H2O → Mn2+ + 4H+ + 10NO3-

Structure

NO2 molecules has V-shaped structure with O-N-O bond angle = 132° and N-O distance = 1.19 Å. This
structure shows that NO2 has one unpaired electron and hence it is an odd electron molecule. Thus NO2 is
paramagnetic and can be regarded as resonance hybrid of the following structures.

The dimer N2O4 is planar with long N-N bond (= 1.75 Å) and O-N-O bond angle (= 132°). The planer structure
of N2O4 admits some +δ positive charge on each N-atom. The repulsion between the adjacent +δ positive
charges make N-N bond longer than a single bond.
Nitrogen Pentaoxide, N2O5

Preparation

(i) It is prepared by the action of dry chlorine over dry silver nitrate at 90 °C in the beginning and then at 60 °C.

4AgNO3 + 2CI2 → 4AgCI + 2N2O5 + O2

(ii) It may be obtained by taking out water molecules from absolutely dry nitric acid by P 2O5. The vapors of N2
O5 so obtained are cooled in a U-tube which is cooled by solid CO2 and ether.

2HNO3 + P2O5 → N2O5 + 2HPO3

Properties

(i) N2O5 forms colourless hard crystals which are deliquescent and melt at 30 °C. It is very unstable and may
explode even without heating.

(ii) It decomposes to give NO2 and O2.

2N2O5 → 4NO2 + O2

(iii) It dissolves in water giving nitric acid and is, therefore, called nitric anhydride.

N2O5 + H2O → 2HNO3

(iv) It reacts with iodine to from iodine pentoxide.

I2 + N2O5 → I2O5 + N2

Structure

X-ray studies of N2O5 suggest that it is an ionic solid and hence is nitronium nitrate NO2+NO3- But in its
vapour state it exists as a symmetrical molecule having the following structure.
N-O-N bond is almost linear i.e., N-O-N bond angle = 180°

7.6. POLE OF NITROGEN OXIDES IN ENVIRONMENTAL POLLUTION

The atmosphere consists of a mixture of gases (e.g., N2, O2, CO2, Ar, etc.) and it extends upto about 500
kms above the surface of the earth. These important gaseous constituents of the earth play important roles in
sustaining life on earth. Oxygen supports on earth, nitrogen is an essential macro-nutrient for plants (via nitrogen
fixation and fertilizer manufacture) and carbon dioxide is essential for photosynthetic activity of plants. In
addition to these, carbon monoxide, nitrogen oxide (N2O, NO2), Sulphur dioxide and ozone are also present to
small extent. Any major disturbance in the atmospheric composition either by extra-ordinary or anthropogenic
activities, may lead to disastrous consequences or may even endanger the very survival of life on the earth. The
latter gases if present in excessive amount act as air pollutants. Pollutants are the substances that are present in
excess amounts and have detrimental effects on the environment.

According U.S. Public Health Service, “air pollution may defined as the presence in the outdoor atmosphere of
one or more contaminates in such quantities and of such duration as may be injurious to human, plant or animal
life, or property.”

The important air pollutants are:

(a) Carbon monoxide (CO)

(b) Carbon dioxide (CO2)
(c) Sulphur oxides (SO2, SO3)
(d) Nitrogen oxides (NOx)
(e) Hydrocarbons (HC)
(f) Particulate matter (sand, dust, etc.)

The above pollutants are continually released into atmosphere through natural as well as anthropogenic activities.
The magnitude of the problem of air pollution has increased alarmingly due to population explosion,
industrialization, urbanization, automobiles and other human activities for great comfort. We shall discus here
only the role of nitrogen oxides in air pollution.

Oxides of Nitrogen

Out of eight possible oxides of nitrogen, only N2O, NO and NO2 are the important constituents of the atmosphere.
Although the concentration of N2O is more in the atmosphere, NO and NO2 are more significant from air pollution
point of view and they are usually represented together as NO x. Oxides of nitrogen may be formed either by
natural or artificial fixation of nitrogen from the atmosphere or from nitrogen compounds present in organic
matter. The annual global release of NOx from man made sources is about 5 × 107 tonnes, which is only slightly
less than that discharged by natural bacterial activity. Oxides of nitrogen are produced by combustion of coal, oil,
natural gas and other organic matter. Thus, NOx is introduced into atmosphere form automobile exhaust,
incinerators, furnace stacks, coal-based power plants and other similar sources.

When the fuels are burnt in air, some of the nitrogen in the air is oxidize to NO. The amount of NO formed
depends on the temperature of flame and the rate of cooling of the combustion products. Rapid cooling of
combustion products prevents the dissociation of NO. The oxidation of NO to NO 2 is also favored at higher
temperatures (~100 oC) but the amount of NO2 formed is usually not more than 0.5% of the total NOx present.
Some of the reactions involved are as follows:

N2 + O 2 → 2NO
O3 + NO → NO2 + O2
2NO + O2 → 2NO2
NO2 + hv → 2NO + O
O2 + hv → O + O
O + O2 + M → O3 + M
O3 + NO → NO2 + O2
2NO2 + O3 → N2O5 + O2
2NO2 + 2H2O + O2 → 4HNO3

Photochemical smog is initiated by the photochemical dissociation of NO2 and the consequent secondary
reactions involving unsaturated hydrocarbons, other organic compounds and free radicals, leading to the
formation of organic peroxides and ozone. This phenomenon takes place during sunny days with low wind and
low level inversion. The photochemical smog and consequent formation of aerosols reduce the visibility, cause
irritation to eyes and damage plant and rubber goods.

Photochemical smog (Smoke + Fog)

Photochemical smog is characterized by brown, hazy fumes, which irritate eyes, lungs, leads to cracking of rubber
and cause damage to vegetation.

The following steps are involved photochemical smog.

1. Emission of NOx and hydrocarbons by vehicles and industry in the atmosphere.

2. Absorption of sunlight causing photodissociation of NOx.

3. Consumption of NOx and simultaneous build up of the oxidants such as O3, O, O2 and peroxides.

4. Oxidation of hydrocarbons to produce a wide variety of products aerosols.

5. Atmospheric oxidants include H2O2, organic peroxides (ROOR), organic hydroperoxides (ROOH) and
peroxyacyl, nitrate or PAN.

Olefins and NOx damage plants, leaves and causes bronzing of surfaces.

The following reactions are involved in photochemical SMOG formation.

i) NO2 ℎv → NO + O
ii) O2 + O + M → O3 + M

O3 + NO → NO2 + O2

iii) O + RH → R + Other products

O3 + RH → R + other products

iv) N + R +O→ NO2 + R

Figure 15.8: The vast numbers of cars on the roads pollute our atmosphere. Nitrogen oxides from traffic contribute
to photochemical smog, as well as acid rain.

A variety of Sulphur compounds are also released into atmosphere from both natural and anthropogenic sources.
The most important of these are the sulphur oxides and hydrogen sulphides.

Among natural sources volcanoes provide 67% of the oxides of sulphur.

Sunlight plays an important role in smog formation. Hence this type of smog is referred as photochemical smog.
The eye irritation is caused by smog is due to the formation of formaldehyde and acrolein from hydrocarbons.

Industrial smog consists primarily of ash and smoke, oxides of nitrogen, SO 2, oil and H2SO4 mist and is referred
to as ‘acid rain’. Industrial operations such as coke refineries, smelters, etc., result in the liberation of SO2 in
atmosphere. Sulphur dioxide can undergo oxidation to SO3 caused by air or NO2. Sulphur trioxide reacts with
water vapours to produce H2SO4 mist. The control of industrial smog can be made by passing SO2 through
scrubbers containing line or MgO when 83-85% SO2 can be removed.

Ca(OH2) + SO2 → CaSO3 + H2O

MgO + SO2 → MgSO3

Figure 13.7: Photochemical smog hangs over Los Angeles in certain weather conditions.The word ‘smog’ is
derived from the two words ‘smoke’ and ‘fog’.

Biochemical effects of the photochemical oxidants

Ozone and PAN are the major photochemical oxidants present in the smog. O 3 and PAN are harmful to plants,
animals and humans.

Oxidize cellular constituents. PAN and ozone toxicity is produced via generation of free radicals. The free radicals
produced may damage DNA and thus alter cellular genetic integrity too. The toxic effects of ozone are manifested
after inhalation and absorption in the lungs causing accumulation of fluids in the lungs (pulmonary edema),
damaging lung capillaries and mortality if continued or high level exposure occur. Both O 3 and photochemical
smog cause irritation of the eyes and respiratory tract. The free radicals produced by O 3 and other photochemical
oxidants attack the sulphydryl groups on the enzymes and also inactive enzymes like isocitric dehydrogenase,
malic dehydrogenase and glucose-6-phosphate dehydrogenase, which are so much involved and essential for
citric acid cycle and generation of cellular energy. O3 may also inhibit the activity of some enzyme involved in
synthesis of cellulose and lipids in plants. Among the sulphur containing amino-acids, cysteine is strongly
attacked by PAN.

Control of NOx Emissions

Control of NOx emissions from anthropogenic activities is completed on the following lines:

Use of two stage catalytic converters can minimize the NOx from automobile emissions. NOx is reduced to N2
and NH3 in the first converter at elevated temperature in the presence of catalysts such as Pt, Pd and Ruthenium.

Similarly, NOx from power plant emissions can be reduced by 90% by using a two-state combustion process. The
fuel can be first fired at relatively high temperature using only about 90% of the stoichiometric air required so
that only minimum quantity of NO is formed under these conditions. Then combustion of fuel may be completed
at a relatively low temperature in excess of air. NO is not formed under these conditions.
Figure 13.8 This limestone carving has been chemically weathered by acid rain.

Figure 15.7: These trees have been badly damaged by acid rain.

7.7. OXYACIDS OF NITROGEN

Typical oxyacids of nitrogen are:

1. Hyponitrous acid, HNO, or H2N2O2 (+1 oxidation state of N)
2. Nitrous acid, HNO2 (+3 oxidation state of N)
3. Nitric acid, HNO3 (+5 oxidation state of N)

In addition to these nitroxylic acid, H2NO2 and hyponitric acid H2N2O3 are also known.

1. Hyponitrous Acid, HNO, H2N2O2

Preparation

It can be prepared by the following methods:

(i) Free acid is prepared by treating silver hyponitrile with a solution of HCl in dry ether or with H2S.

Ag2N2O2 + 2HCl → H2N2O2 + 2AgCl

Ag2N2O2 + H2S → H2N2O2 + AgS

(ii) it can be obtained by oxidation of hydroxylamine in the presence of CuO, Ag2O or HgO.

2NH2OH + 2Ag2O → H2N2O2 + 2Ag + 2H2O

(iii) it can also be prepared by the alkali hydrolysis of sodium hydroxylamine sulphonate.

2(SO3Na)NHOH + 4KOH → K2N2O2 + 4H2O + 2KNaSO3

From the alkali hyponitrile solution, silver hyponitrite is obtained by adding silver nitrate solution.

Properties

(i) Hyponitrous acid yields hygroscopic crystals and in the pure state, while leaflets which explode, when rubbed.

(ii) It is soluble in water, alcohol, ether and benzene.

(iii) It is a weak dibasic acid and hence forms two types of salts viz. acid salts like Ba(HN2O2)2 and normal salts
(called hyponitrites) like BaN2O2.

(iv) In air, it decomposes to furnish a mixture of nitrous and nitric acids;

2H2N2O2 + 3O2 → 2HNO2 + 2HNO3

(v) It decomposes on warming to water and nitrous oxide

H2N2O2 → H2O + N2O

(vi) It is a reducing agent and oxidized to nitrate by acidified KMnO4.

5H2N2O2 + 8KMnO4 + 12H2SO4 → 10HNO3 + 4KSO4 + 8MnSO4 + 12H2O

Structure

The acid is dibasic one, since it gives both acidic and normal salts. The decomposition of its salts and ester gives
N2, showing that the acid has an azo -N=N-group. Infra-red spectra of silver, sodium and mercuric hyponitrite
favour the following structure of anion.
2. Nitrous Acid, HNO2

Preparation

The free existence of nitrous acid is not very definite because it is unstable and readily decomposes. However, it
is prepared by the following methods.

(i) When nitrogen trioxide is dissolved in water at the ice temperature, a blue liquid thus obtained consists in main
of this nitrous acid.

N2O3 + H2O ⇌ 2HNO2 (at 0 °C)

(ii) It can also be obtained when barium nitrite is treated with ice cold sulphuric acid.

Ba(NO2)2 + H2SO4 → 2HNO2 + BaSO4

The insoluble BaSO7 is removed by filtration.

Properties

(i) Nitrous acid is not very stable and at lower temperature decomposes as:

3HNO2 ⇌ HNO3 + 2NO + H2O

On raising the temperature nitric oxide and nitrogen peroxide are formed:

2HNO2 ⇌ NO + NO2 + H2O

(ii) It decomposes ammonia, urea and other compounds with -HN2 group.

CO(NH2) + HNO2 → CO2 + 2O2 + 3H2O

NH3 + HNO2 → NH4NO2 → N2 + 2H2O

(iii) At lower temperature, it acts on aromatic amines to give diazo compound.

C6H5NH2 + HCl + HNO2 → C6H5N2Cl + 2H2O

(iv) It is a good oxidizing agent on account of the ease with which it can take part with an atom of oxygen.

For example:

2HNO2 + H2S → 2H2O + 2NO + S

2HNO2 + 2KI → 2KOH + I2 + NO

SnCl2 + 2HCl + 4HNO2 → SnCl4 + 2NO + 2H2O

 FeSO4 + H2SO4 + 4HNO3 → Fe2(SO4)3 + 2NO + 2H2O

2HI + 3HNO2 → I2 + 2NO + 2H2O

NaAsO3 + 2HNO2 → H2O + 2NO + Na3AsO4

(v) It can be easily oxidized to nitric acid and as such reduces strong oxidizing agents.

For example:

HNO2 + O → HNO3

For example:

HNO2 + Br2 + H2O → 2HBr + HNO3

KMnO4 + 3H2SO4 + 5HNO2 → K2SO4 + 2MnSO4 + 5HNO3 + H2O

HNO2 + H2O2 → HNO3 + H2O

K2Cr2O7 + 4H2SO4 + 5HNO2 → K2SO4 + 2Cr(SO4)3 + 3HNO3 + 4H2O

(vi) It reacts with alkalies to form nitrites. Nitrites are much more stable then nitrous acid.

NaOH + HNO2 → NaNO2 + H2O

Structure:

Nitrous acid gives two types of organic derivatives. The nitrites (e.g.; methyl nitrites, CH3-ONO) and nitro
compound (e.g., nitro-methane, CH3-NO2). On this basis two corresponding tautomeric forms of the acid are
supposed to exist which are:

L.H. Jones, from IR study of HNO2 vapours came to the conclusion that the acid has a trans configuration with
the dimensions shown below;

X-ray and Raman studies of crystalline AgNO2 have shown that NaNO2 have shown that NO2 ion has an
angular structures which is resonance hybrid of the following two structures.
Nitric Acid HNO3;

Nitric acid is a chemical of great commercial importance because of its use in the manufacture of explosives
like nitroglycerine, trinitrotoluene, gun cotton, picric acid etc. in the manufacture of nitrates which are used as
fertilizers and in the manufacture of dyes, drugs and artificial silk.

Fuming nitric acid contaminated with yellow nitrogen dioxide

Preparation

(1). From Nitrates, Nitric acid is prepared on large scale by heating Chile saltpeter (NaNO3) with concentrated
sulphuric acid. The mixture is placed in a cast iron retort and subjected to distillation at a temperature of about
200 °C.

NaNO3 + H2SO4 → NaHSO4 + HNO3

Potassium nitrate has also been employed. The yellow color of HNO 3 is due to the presence of NO2 in it which
can be removed by distillation in vacuum.

(2). From air Birkland Eyde process, Nitrogen and oxygen of the atmosphere can be made to combine by
passing an electric discharge through the air or the air may be passed through an electric arc (temp. 3500 °C).
This process at first gives nitric oxide, which is then quickly cooled to 500 °C. Which is further combines with
oxygen to give about 2% nitrogen peroxide.

N2 + O2 → 2NO ΔH = ─43.2 k cals

2NO + O2 → 2NO2

The vapours are then washed down by water trickling in absorption towers filled with quartz stones when nitric
acid is produced:

2NO2 + H2O → HNO3 + HNO2

3HNO2 → HNO3 + 2NO + H2O

Before the gases escape in air, they are led through towers containing lime or caustic alkali which recover all
oxides or nitrogen.
NO2 + NO + 2NaOH → 2NaNO3 + H2O

Ca(OH)2 + 2HNO3 → Ca(NO3)2 + 2H2O

(iii). From Ammonia (Ostwald’s process).

1. Oxidation of NH3 to NO

In this method a mixture of ammonia gas with air in the ratio 1:8 is passed through a catalyst chamber
packed with platinum gauze maintained at temperature of 800 °C. The ammonia is oxidized to nitric oxide.

4NH3 + 5O2 → 4NO + 6H2O + ΔH = 215k cals

There exothermic reaction proceeds without supply of heat except the initial heating. About 90% NH3 is
converted to NO under these conditions.

2. Oxidation of NO to NO2

NO is converted to NO2 in the presence of air or oxygen and passed through the absorption tower as mentioned
above in arc process.

2NO(g) + O2(g) → 2NO2(g) + ΔH = 27.8 k cals

3. Absorption of NO2 in water

2NO2 + H2O → 2HNO3 + NO

4. Concentration of HNO3

Side reactions

NH3+3/4O2 → 1/2N2+3/2H2O ∆H = -75.7Kcal

NH3 → 1/2 N2 +3/2H2

NH3+O2 → 1/2N2 O+3/2H2O

NH3+3/2NO → 5/4N2 +3/2H2O ∆H = -107.9Kcal

The acid so obtained is dilute which can be concentrated to 68% by distillation, when constant boiling mixture
is formed. This constant boiling mixture of HNO3 has a specific gravity of 1.42 and is the commercial
concentrated HNO3. More concentrated acid needed for certain uses is produced by distillation with conc.
H2SO4 which holds back the water. The distillate is 98% HNO3 having density 1.5.
Fuming nitric acid is made by distilling conc. HNO3 with a little starch. The starch reduces some acid to NO2
which dissolves in the remaining acid to form fuming nitric acid. It is yellow in colour due to NO 2. It is a much
more powerful oxidizing agent and nitrating agent than conc. HNO3.
Ostwald Process - Principle, Nitric Acid Production

Manufacture of Nitric Acid by Ostwald’s Process

Ostwald Process - Manufacturing of Nitric Acid

diagram of Ostwald method for preparation of .

Fig.7.2 Ostwald’s Process For Manufacture Of HNO3
 Nitric acid plant in Uzbekistan

Properties:

Pure nitric acid is a colourless liquid with a characteristic choking smell. It boils at 86 °C and freezes at -42 °C
into a transparent crystalline mass. It is soluble in water in all proportions.
1. Oxidizing Property

Nitric acid is a strong oxidizing agent because of the ease with which it decomposes to give nascent oxygen.
The oxidizing properties of the acid are

2HNO3 → 2NO2 + H2O + O

indicated by its action on non-metals, metalloids, metals and on various compounds as shown below:

(i) It oxidizes non-metals like sulphur, phosphorus, carbon, and iodine to their corresponding oxy-acids.

S + 6HNO3 → H2SO4 + 6NO2 + 2H2O

C + 4HNO3 → H2CO3 + 4NO2 + H2O

P + 5HNO3 → H3PO4 + 5NO + 4H2O

I2 + 10HNO3 → 2HIO3 + 5NO2 + 10H2O

(ii) Metalloids like arsenic and antimony are oxidized to corresponding oxy-acids.

As + 5HNO3 → H3AsO4 + 5NO2 + H2O

(iii) Most of the metals with the exception of gold and platinum are attacked by nitric said. Some like tin and
antimony gives oxides while the others form nitrates. During the reaction, a part of the acid is reduced to give
products like NO2, NO, N2, H2O or HN3 and the nature of products depends upon the concentration of the acid,
temperature and nature of the metal. For example;

(a) Copper with dilute nitric acid gives nitric oxide.

3Cu + 8 HNO3 → 3Cu(NO3)2 + 2NO + 4H2O

With concentrated nitric acid, it forms nitrogen peroxide.

Cu + 4HNO3 → Cu(NO3)2 + 2NO2 + 2H2O

Silver (Ag), mercury (Hg) and lead (Pb) give similar reactions.

(b) Tin with dilute nitric acid forms stannous nitrate and ammonium nitrate.

4Sn + 10HNO3 → 4Sn(NO3)2 + 3H2O + NH4NO3

 Figure 13.6 Ammonium nitrate is spread as pellets onto the soil.

With concentrated acid, it gives meta-stannic acid and nitrogen peroxide

Sn + 4HNO3 → H2SnO3 + H2O + 4NO2

(c) Zinc with dilute acid gives ammonium nitrate.

4Zn + 10HNO3 → 4Zn(NO3)2 + 3H2O + NH4NO3

With dilute acid, it produces N2O while with concentrated acid its gives NO2

(d) Magnesium and manganese are the only metals that liberate hydrogen from dilute acid.

Mg + 2HNO3 → 4Mg(NO3)2 + 3H2

(e) Gold and Platinum dissolve in a mixture of 1 part HNO3 and 3 parts HCl know as aqua regia. The
dissolution occurs as a result of the action of nascent chlorine on the metals.

2HNO3 + 3HCl → NOCl + 3H2O + 2Cl

Au + 2HNO3 + 3HCl → AuCl + NO + 2H2O

(iv) It also oxidizes a number of compounds, for example,

SO2 + 2HNO3 → H2SO4 + 2NO2

H2S + 2HNO3 → 2H2O + 2NO2 + S

6FeSO2 + 2HNO3 + 3H2SO4 → 2Fe(SO4)3 + 4H2O + 2NO2

The nitric acid formed gives a dark brown ring (Ring test for nitrate)

2. Nitrating property:
It reacts with organic compound and forms their nitro-derivatives. The reaction takes place in the presence of
stronger acid like conc.H2SO4. In the presence of an acid which is stronger than nitric acid, NO 2+ (nitronium
ions) are produced.

HNO3 + 2H2SO4 → NO2+ 2HSO4- + H3O+

When NO2+ ions replace the hydrogen ions in organic compounds, nitration is said to take place. Thus

C6H6 + HNO3 → C6H6NO2 + H2O

Trinitrotoluene (TNT) is also formed by nitrating toluene in presence of conc. H2SO4.

C6H6NO2 + HNO3 → (NO2)3C6H2CH3 + 3H2O

3. Acidic property:

Nitric acid is a strong acid. It ionizes in aqueous solution as:

HNO3 → H+ + NO3─

It decomposes metal oxides, carbonates, bicarbonates, sulphides, sulphites, bisulphites and hydroxides forming
metal nitrates.

CuO + 2HNO3 → Cu(NO3)2 + 2H2O

CaCO3 + 2HNO3 → Ca(NO3)2 + 2H2O + CO2
NaHCO3 + HNO3 → NaNO3 + H2O + CO2
Na2S + 2HNO3 → NaNO3 + H2S
H2S + 2HNO3 → 2H2O + 2NO2 + S
KOH + HNO3 → KNO3 + H2O
NaHSO3 + HNO3 → NaNO3 + SO2 + H2O
Uses:

It is used:

(i) in the manufacture of nitrates which are important chemicals of commerce. Basic calcium nitrate is used as
fertilizer. Silver nitrate is used in photography and sodium nitrate is used in the manufacture of gun powder.
(ii) in the manufacture of explosive like nitroglycerin, dynamic, trinitrotoluene, picric acid TNT, and cordite etc.
(iii) in the manufacture of artificial silk, dyes, medicine and perfumes.
(iv) in the purification of gold and silver.
(v) as a important reagent in the laboratory.
(vi) in the manufacturer of H2SO4.
(vii) in the preparation of aqua regia.
(viii) Nitric acid is used to manufacture the fertilizer ammonium nitrate.

Structure:

HNO3 is a monobasic acid and is supposed to exist in the following two resonating forms:
Two major resonance representations of HNO3

As indicated by electrons diffraction studies. The molecule of nitric acid in vapour state, possesses a planar
structure as shown below:

7.8. Role of Oxyacids Of Nitrogen In Environmental Pollution.:

It has been stated in the earlier section that NOx emissions into the atmosphere is eventually converted into
HNO3 and HNO2 due to a series of photochemical reactions and chemical reactions catalysed by other species
present in the atmosphere. The reaction may take place in the following sequence:

2NO + O2 → 2 NO2

NO + O3 → NO2 + O2

2NO2 + O3 → N2O5 + O2

4NO2 + O2 + 2H2O → 4HNO3

N2O5 + H2O → 2HNO2

HNO2 and HNO3 may also undergo photochemical dissociation as follows:

HNO2 + hv → NO2 + H‫٭‬

HNO2 + hv → NO + HO‫٭‬

HNO3 + hv → NO2 + HO‫٭‬

In the stratoshphere, NO2 may react with the HO radicals forming HNO3,

NO2 + HO‫٭‬ → HNO3

The acid droplets so formed are neutralized with bases e.g., participate lime, NH3 etc. These salts and the
remaining HNO3 droplets alongwith H2SO4 drops and HCl released into the atmosphere by man-made and
natural emissions give rise to acidic precipitation, which is popularly known as “Acid Rain”. (H2SO4 is also an
important constituent of acid rain which is formed by SOx emission into atmosphere)

Acid rain represent one of the major consequences of air pollution because of large SOx and NOx emissions
from big industrial areas into the atmosphere. The longer the remain of SO x and NOx in the atmosphere, the
greater the chance of their oxidation to H2SO4 and HNO3 by the various photochemical and catalyst chemical
reactions.

Effects of Acid Rain:

Acid rain may cause extensive damage to materials and terrestrial ecosystems such as water, fish, vegetation,
stone, steel, paint, soil and mankind as follows:

(i) Damage to building and structural materials as well as valuable ancient sculptures, carved from marble, lime-
stone, sand-stone etc., because of pitting and mechanical weaking due to attack by acidic components.

(ii) Potential effects on aquatic system such as an acidification, decreased alkalinity and mobilization of metals
like aluminium.

(iii) Foliar damage to crops and forests, leaching of nutrients from leaves and alternation of seed germination
characteristics.

(iv) Corrosive damage to steel, zinc, oil-based paints and automobile coatings.

(v) Acidification of soils with the consequent effects on microbial and soil fauna and fixation of nitrogen.

(vi) Skin, hair and lungs of human beings may be affected. The heavy metals released by acid rain also may
cause potential threat to human health. Acidification of drinking water reservoir and concurrent increase in
heavy metals concentrations may cause injurious effects.

Figure 13.8 This limestone carving has been chemically weathered by acid rain.
Figure 15.7: These trees have been badly damaged by acid rain.

Remedial Measures:

The phenomenon of acid rain is highly interactive problem and remedial by measure to control it are very
expressive. The only practical approach to counter the problem of acid rain is to reduce SOx and NOx emissions.

Reduction of NOx emissions from stationary combustion source can be achieved by modification of furnance
and burner design and or modification of operation conditions. The combustion modification techniques
available now include using 2-stage combustion, precisely controlling air injecting system during combination,
recirculating flue gases, and or by altering design of firing Chambers. NOx emissions from mobile combustion
sources may be achieved by lowering the combustion temperatures in engine and catalytic removal of NOx from
exhaust gases using device such as 3-way system reduces CO, hydrocarbons and NOx simultaneously.

7.9 Oxyacids Of Phosphorus:

Typical oxyacids of phosphorus are:

1. Hyophosphorus acid H3PO2 (+1 oxidation state of P)

2. Orthophosphorus acid H3PO3 (+3 oxidation state of P)
3. Pyrophosphorus acid H4P2O5 (+3 oxidation state of P)
4. Metaphosphorus acid (HPO2)n (+3 oxidation state of P)
5. Hypophosphoric acid H4P2O6 (+4 oxidation state of P)
6. Orthophosphoric acid H3PO4 (+5 oxidation state of P)
7. Orthophosphoric acid H4P2O7 (+5 oxidation state of P)
8. Metaphosphoric acid (HPO3)n (+5 oxidation state of P)
The two series of phosphorus acids, phosphorus and phosphoric are derived from the lower, +1, +3 and higher
+5 oxidation states of phosphorus respectively. All these acids have P-OH bonds where hydrogen IS ionizable
but the hydrogen atoms in R-H bonds (found in phosphorus acid) are not ionizable. The phosphorus acids are
less well-known.

Light red waxy white dark red and violet

Spectral lines of phosphorus

body-centred cubic (bcc)

1. Hypophosphoric Acid H3PO2.

Preparation:

(i) When white phosphorus is boiled with baryta solution, barium hypophosphite is formed which on treatment
with sulphuric acid gives H3PO2.

2P4 + 2Ba(OH)2 + 6H2O → 3Ba(H2PO2)2 + 2PH3

Ba(H2PO2)2 + H2SO4 → H3PO2 + BaSO4↓

The solution is filtered and the filtrate is evaporated and cooled below 0 °C to get crystal of H3PO2.

(ii) It can also be obtained by the oxidation of phosphine with iodine.

PH3 + 2I2 + 2H2O → H3PO2 + 4HI

Properties:
(i) It is a colourless crystalline solid having specific gravity = 1.492 and melting point 26 °C. It is readily
soluble in water and is monobasic acid.

(ii) When strongly heated, it is decomposed to phophine.

3H3PO2 → PH3 + 2H3PO3

(iii) The acid and its salts are powerful reducing agents. The potential equation for these reduction is

3H3PO2 + 2H2O → PH3 + 2H3PO3

For example:

4AgNO3 + H2O + H3PO2 → 4HCl + H3PO4

2Cl + 2H2O + H3PO2 → 4HCl + H3PO4

4CuSO4 + 6H2O + 3H3PO2 → CuH + H3PO4 + 4H2SO4

(iv) Active metals like Zn, Mg etc. dissolve in the acid and H2 is evolved

Zn + 2H2PO2 → Zn(H2PO3)2 + H2

Structure: -

H3PO2 is a monobasic acid, i.e., it has only one ionizable hydrogen atoms. IR spectrum shows the presence of
P-H bonds. This is in accordance with the following tetrahedral structure.

The structure of Hypophosphorus acid (Phosphinic acid)

2. Orthophosphorus Acid, H3PO3:

Preparation:

(i) It is prepared by the reaction of water on PCl3 or phosphorus trioxide.

PCl3 + 3H2O → H3PO3 + 3HCl

Phosphorus(V) chloride also under goes hydrolysis when added to water:

PCl5(s) + 4H2O(l) → H3PO4(aq) + 5HCl(g)

Both products are soluble in water and are highly acidic.

Figure 10.14: Solid phosphorus(V) chloride is hydrolysed in water, releasing white fumes of hydrogen chloride
gas.

P4O6 + 6H2O → 4H3PO3

(ii) It is also obtained by heating PCl3 with oxalic acid.

PCl3 + 3H2C2O4 → H3PO3 + 3CO2 + 3HCl

Properties:

(i) It forms white deliquescent crystal (m.p = 73.5 °C) and is extremely soluble in water.
(ii) It is a dibasic acid and ionizes as
H3PO3 ⇌ H2PO3- K1 = 1×10-2
H2PO3- ⇌ HPO32- K2 = 2 10-7

From the mode of its ionization shown above it is evident that the acid gives two types of salts viz.

Primary phosphate (e.g., MH2PO3) and secondary phosphate (e.g.M2HPO3)

(iii) When heated to 200 °C. it gives orthophosphoric acid and phosphine.
4H3PO3 → 3H3PO4 + PH3

(iv) It is a strong reducing agent. The potential equation is:

H3PO3 + H2O → H3PO4 + 2H

For Example:

CuSO4 + H3PO3 + H2O → H3PO4 + Cu + H2SO4

I2 + H3PO3 + H2O → H3PO4 + 3HI

2HgCl2 + H3PO3 + H2O → Hg2Cl2 + 2HCl + H3PO4

2H3PO3 + SO2 → 2H3PO4 + S

2AgNO3 + H3PO3 + H2O → 2Ag + 2HNO3 + H3PO4

Structure

The diprotic nature and its reducing properties indicate the following tetrahedral structure for it.

The structure of Phosphorous acid (or phosphonic acid)

3. Orthophosphoric Acid, H3PO4

Preparation:

(i) Commercial orthophosphoric acid is prepared by treating bone ash (calcium phosphate) with sulphuric acid.
After reaction, the precipitate of CaSO4 is filtered and the solution is evaporated to get colorless crystal of H3PO4.
Ca3(PO4)2 + 3H2SO4 → 3CaSO4 + 2H3PO4

(ii) It is prepared in the laboratory by dissolving red phosphorus in nitric acid diluted with equal volume of water.
P4 + 10HNO3 + H2O → 4H3PO4 + 5NO + NO2

(iii) It may also be obtained by the hydrolysis of P4O10 OR PCl5.

P4O10 + 6H2O → 4H3PO4
PCl5 + 4H2O → H3PO4 + 5HCl

Properties:

Phosphoric acid (orthophosphoric acid, monophosphoric acid or phosphoric(V) acid).

(i) Orthophosphoric acid forms hard, solid, colorless, odorless, deliquescent, rhombic crystals. Commercial acid
is 82.89% pure. It is soluble in all proportions. Its density is 1.87 and melts at 42 °C.
(ii) It is tribasic acid and ionizes as follow:
H3PO4 → H2PO4- + H+ K1 = 8 10-3
H2PO-4 → HPO42- + H+ K2 =6 10-8
HPO42- → PO43- + H+ K3=1 10-12

The acid therefore, forms three types if salts with alkalis.

For Example:

H3PO4 + NaOH → NaH2PO4 + H2O

H3PO4 + 2NaOH → Na2HPO4 + 2H2O
H3PO4 + 3NaOH → Na3PO4 + 3H2O

(iii) When heated to 250 °C, It gives pyro phosphoric acid, H4P2O7
 2H3PO4 → H4P2O7 + H2O

(iv) It liberate hydrobromic and hydroiodic acid forms bromides and iodides.
3NaBr + H3PO4 → Na3PO4 + 3HBr

3NaI + H3PO4 → Na3PO4 + 3HI

(v) It acts as a base in the presence of very strong acid, e.g., HCIO 4
H3PO4 + HClO4 → [P(OH)4][ClO4]

(vi) It reacts with barium chloride to give a white precipitate of barium orthophosphate in neutral medium.

2BaCl2 + 2H3PO4 → Ba(PO4)2 + 6HCl

(vii) It has no oxidizing properties below 400 °C but at higher temperature it is fairly reactive towards metals and
is reduced.
(viii) When phosphoric acid and phosphate are treated with ammonium molybdate and excess of conc. HNO 3 a
yellow precipitate of ammonium phosphomolybdate is obtained on warming to about 60 °C.
H3PO4 + 12(NH4)2MoO4 → (NH4)3PO4∙12MoO3 + 21NH4NO3 + 12H2O

(Yellow ppt.)

Structure:

It is a tribasic acid, and has following tetrahedral structure.

Uses

(i) Pure orthophosphoric acid has pharmaceutical applications and is used in the preparation of nervous tonics.
(ii) It serves as a stabilizer for H2O2.
(iii) It is used for the manufacture of fertilizers. dyes, enamels and proclaim cement.
(iv) It is used in the dental fillings.
7.10 Halides of Phosphorus:

Phosphorus combines with halogens to give two series of halides in which it is trivalent and pentavalent. PX 3 and
PX5 are formed depending upon phosphorus or halogens being in excess. The existence of phosphorus pentiodide
PI5 is however, doubtful. Two additional halides P2Cl4 and P2I4 are known as presumably derived from P2H4.
Stable mix halides are also known trivalent as well as in pentavalent states. All Halides undergo hydrolysis
forming halogen acids and oxyacid’s of phosphorus. The fluorides are less readily hydrolyzed.

Important trihalides: PF3, PF2Cl, PFCl2, PCl3, PF2Br, PFBr2, PBr3, PI3.

Important pentahalides: PF5, PBr5, PCl5, PF3Cl2, PF2Br3.

Here we shall discuss only PCl3 and PCl5

1. Important Trichloride, PCl3

History: Phosphorus trichloride was first prepared in 1808 by the French chemists Joseph Louis Gay-
Lussac and Louis Jacques Thénard by heating calomel (Hg2Cl2) with phosphorus. Later during the same year, the
English chemist Humphry Davy produced phosphorus trichloride by burning phosphorus in chlorine gas.

Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure,
it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus
compounds. It is toxic and reacts readily with water to release hydrogen chloride.
Preparations:

It is the most trihalides. It is obtained by passing chlorine over white/red phosphorus. The phosphorus burns with
a pale green flame and PCl3 distills and is condensed as a colorless liquid. Since it is attacked by air and water, it
is necessary to displace the air from the apparatus with the steam of CO 2.

P4 + 6Cl2 → 4PCl3

Properties:
(i) PCl3 is a colorless liquid boiling at 74 °C. It can be frozen to a solid, m.p, -111.8 °C
(ii) It fumes strongly in air and is vigorously hydrolyzed by water forming phosphorus acid and hydrochloric acid.
PCl3 + 3H2O → H3PO3 + 3HCl

(iii) It reacts with organic compounds containing a hydroxyl groups.

C2H5OH + PCl3 → H3PO3 + 3C2H5Cl

(iv) With excess of chlorine, it gives PCl5

PCl3 + Cl2 → PCl5

(v) It reacts with SO3 forming phosphoryl chloride and sulphur dioxide.
PCl3 + SO3 → POCl3 + SO2

(vi) It reacts with thionyl chloride forming phosphoryl chloride and PCl5.
3PCl3 + SOCl2 → POCl3 + PSCl3 + PCl5

Structure:

PCl3 molecule has a pyramidal structure as shown below:

Uses of Phosphorus Trichloride – PCl3
 The Largest use for phosphorus trichloride (PCl3) is for making phosphorus oxychloride by oxidising it
with oxygen.
 Used as an important intermediate in the production of phosphate ester insecticides.
 Used as a chlorinating agent for converting alkyl alcohols to alkyl chlorides and organic acids to organic
acid chlorides and also as a catalyst.
 Used in the production of important compounds like phosphorous pentachloride, phosphoryl chloride,
thiophosphoryl chloride, pseudohalogens and phosphonic acids.

PCl3 is important indirectly as a precursor to PCl5, POCl3 and PSCl3, which are used in many applications,
including herbicides, insecticides, plasticisers, oil additives, and flame retardants.
For example, oxidation of PCl3 gives POCl3, which is used for the manufacture of triphenyl
phosphate and tricresyl phosphate, which find application as flame retardants and plasticisers for PVC. They are
also used to make insecticides such as diazinon. Phosphonates include the herbicide glyphosate.
PCl3 is the precursor to triphenylphosphine for the Wittig reaction, and phosphite esters which may be used as
industrial intermediates, or used in the Horner-Wadsworth-Emmons reaction, both important methods for
making alkenes. It can be used to make trioctylphosphine oxide (TOPO), used as an extraction agent, although
TOPO is usually made via the corresponding phosphine.
PCl3 is also used directly as a reagent in organic synthesis. It is used to convert primary and
secondary alcohols into alkyl chlorides, or carboxylic acids into acyl chlorides, although thionyl
chloride generally gives better yields than PCl3.[18]

2. Phosphorus Pentachloride, PCl5

Preparation

(i) Phosphorus pentachloride is prepared by the action of dry chlorine (excess) on phosphorus trichloride.

PCl3 + S2Cl2 → PCl5 + 2PSCl3

To push the equilibrium to the right, the temperature must be kept low and excess chloride must be present.

(iii) It can also be prepared by burning white phosphorus in excess of chlorine or by reaction of sulphur
monochloroide on PCl3.
3PCl3 + S2Cl2 → PCl5 + 2PSCl3

Properties:

(i) Phosphorus pentachloride is almost colorless crystalline solid with pungent odour in pure state.
(ii) It sublimes below 100 °C and then dissociates on heating. Dissociation is completed above 300 °C.
PCl5 → PCl3 + Cl2

(iii) It react with water violently yielding first phosphorus oxychloride and then orthrophophatic acid.
PCl5 + H2O → POCl3 + 2HCl

POCl3 + 2H2O → H3PO4 + 3HCl

(iv) It react with hydroxyl compound and replace the –OH group by chlorine atoms. For example:
C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl
CH3COOH + PCl5 → CH3COl + POCl3 + HCl
H2SO4 + PCl5 → SO2Cl2 + 2POCl3 + 2HCl

(v) Many metals like Zn, Cd, and Pt. etc. are converted into chloride when heated with PCl5.
Zn + PCl5 → ZnCl2 + PCl3

(vi) It react with SO3 it give sulphuryle chloride.

SO3 + PCl5 → SO2Cl2 + POCl3

Structure:
Solid PCl5 is ionic. Its crystal lattice contains positive tetrahedral PCl4+ ion negative octahedral PCl6 - ions. In the
vapor state, it consists of discrete PCl5 molecules which have a trigonal bipyramidal geometry. The axial P-Cl
distance = 2.19 Å and equatorial P-Cl = 2.04 Å.

7.11 Fertilizers:

Definition:

Chemical fertilizers are a class of substances which are added to the soil to make up and to provide the
elements necessary for the growth of plants. These may include naturally occurring inorganic or organic
substances or such substances prepared synthetically. These are in a way considered superior to the natural
manures like decayed animal wastes and leaf and plant manures which cannot supply the various elements in
correct and suitably adjusted proportions according to the needs of the plants.

Besides carbon, hydrogen and oxygen which the plants take from air and water, other major requirements of
growing plants are nitrogen, phosphorus and potassium. These elements are required by the plants for their
normal growth, proper maintenance and highly yield of produce, in bulk because they are not only the
constituents of plants roots, enzymes, co-enzymes, hormones or activators but also make the very plant roots,
stem, leaves, fruits, vegetables, grains, seeds etc. In addition to N, P and K, plants need a number of elements
for their proper growth and maintenance, in very small quantities which act as activators for enzymes, e.g., Mn,
Mg, Co, Zn, Cu, Fe, etc. These are called trace elements, Their deficiency in the soil normally does not take
place and are, therefore, not required to the regularly added to the soil except certain areas or region which may
be deficient in one or more of these elements.

Besides the above mentioned elements, there are some elements and compounds such as gypsum which make
the availability of fertilizers to the plants easier. These substances are known as stimulants.

Role of Fertilizers in Agriculture:

Plants need the various substances such as water, nitrogen compounds, phosphorus compounds, potassium
compounds etc., all in fair quantities, for their proper growth and maintenance. Iron, lime, magnesium and sulphur
compounds are also required in small quantities. These substances stimulate the processes of metabolism in the
plant cell, growth of plants and specially its fruits, increase the content of valuable materials (e.g. starch, proteins
etc.) and increase resistance to frost draught and various diseases. By consuming these elements, the soil becomes
exhausted. Each year fertilizers (or manures), which are chemicals substances which serving as food materials to
the soils, are added to the soil to replenish the loss suffered by it on account of growth of plants. The plants, so
essential to our life, require food for nourishment. All these plant foods are supplied by nature. Plants draw their
requirement from the soil by means of their roots.

Application of fertilizers to the soils increase the fertility of the soils-hence plants products have to be
sustained on normal land by replenishing and can be increased above normal level by applying larger amounts of
fertilizers. Fertilizers also help to maintain the pH of the soil near 7 to 8 which is optimal for plant health and
growth. Today the increase of food production has become essential on account of the enormous growth of
population. This is a problem of every country and the challenge of increased production is being met by larger
production of fertilizers.

Classification of fertilizers:

Fertilizers are classified according to the nature of the element/elements like N, P and K, they provide to
the soil. This classification gives the following types of fertilizers:

(1) Nitrogen fertilizers: These fertilizers mainly supply nitrogen to the plants of soil. Ammonium sulphate,
calcium ammonium nitrate, urea etc. are the examples of nitrogenous fertilizers.

(2) Phosphatic fertilizers: These fertilizers provide phosphorus to the soil. Superphosphate of lime, triple
superphosphate and phosphate slag are the example of phosphatic fertilizers.

(3) Potash fertilizers: These fertilizers supply potassium to the plants. KCl, KNO3, K2SO4 etc. are the important
examples.

(4) NP fertilizers: These fertilizers contain two elements namely nitrogen and phosphorous. These are obtained
by mixing together nitrogenous and phosphatic fertilizers in suitable proportions. Examples of NP fertilizers
are: dihydrogen ammoniated phosphate, NH4H2PO4, calcium superphosphate nitrate, Ca (H2PO4)2. 2Ca (NO3)2.

(5) Complete fertilizers: These fertilizers supply all the three essential elements namely nitrogen phosphorus
and potassium to the soil and are produced by mixing nitrogenous, phosphatic and potash fertilizer in suitable
proportions. It is observed that these fertilizers produce much better results. These are also known as mixed
fertilizers or NPK fertilizers.

1. Nitrogenous fertilizers:

These fertilizers mainly supply nitrogen to the plant or soil. Most of them are synthetic products and nitrogen is
present in the fertilizers either as NO3─ ion or amide or NH4+ ion. All the nitrogenous fertilizers are soluble in
water and are readily available to plants. Typically nitrogenous fertilizers are.
1. Ammonia (82%N)
2. Urea (46%N)
3. Ammonium nitrate (33%N)
4. Ammonium sulphate (21%N)
5. Ammonium chloride (26%N)
6. Ammonium sulphur nitrate (26%N)
7. Calcium ammonium nitrate (26%N)
8. Mono-ammonium phosphate (11%N)
9. Di-ammonium phosphate (16%N)
10. Nitro phosphate (20%N)

1. Ammonia:
Ammonia usually exists as a colorless but may be preserved as colorless liquid or ice like solid. It can be obtained
by either off the following methods.

Figure 13.4: Adot-and-cross diagram showing the covalent bonding in an ammonia molecule and its triangular
pyramidal shape.

(i) From ammonium salt:

Ammonia is prepared in the laboratory by heating an ammonium salt with a base.

2NH4+ + OH → 2NH3 + H2O

OR

2NH4+ + CaO → Ca2+ + 2NH3 + H2O

Figure 13.6: Preparing ammonia gas from an ammonium salt, NH4Cl, and a base, Ca(OH)2.

(ii) From Ammonical Liquor: Coal contain about 1.5 percent of decayed nitrogen of ancient vegetable and
when coal is carbonized, ammonia passes along with the coal gas in form of its compound with H2S, HCN,
HCl, H2SO4 etc. and comes in the ammonical liquor. When this liquor is heated with lime in a current of steam,
some of the ammonia salts are decomposed by the action of heat alone and rest under the influence of lime to
give out ammonia gas.

NH4HS ↔ NH3 + H2S

2NH4Cl + Ca(OH)2 → CaCl2 + 2NH3 + 2H2O

(iii) From air: The nitrogen obtained from air is converted to ammonia by the Haber’s process or Cyanamid
process.

(a) Haber’s Process:

Even though the synthesis of ammonia is exothermic, it is a very slow reaction.

N2(g) + 3H2(g) → 2NH3(g) ΔH° = −92 kJ mol−1

There are three ways in which the rate can be increased: an increase in pressure, an increase in temperature and
the use of a catalyst. All three are used in the Haber Process.

Most of the commercial ammonia is now prepared by fixing atmospheric nitrogen. When nitrogen and hydrogen
are passed over an iron crystal at 500°C under a pressure of about 200 atm; ammonia is formed.

N2(g) + 3H2(g) → 2NH3(g) ∆H = 46 kJmol-1

In the actual process the required hydrogen is obtain from water gas and nitrogen from the fractional distillation
of liquid air. The mixture of nitrogen and hydrogen (1:3 by volume) is also obtained from an appropriate mixture
of water gas and producer gas by blowing steam and air over hot coke alternately. Steam is added to mixture and
the whole is passed over heated iron oxide at 500 °C and 20-30 atmospheric pressure, carbon monoxide being
converted to carbon dioxide.
 CO(g) + H2O → CO2(g) + H2(g)

CO2 is removed by water under pressure and residual CO by ammonical sodium formate (at 250 atm) or by
ammonical cupreous chloride. By suitable adjustment of the process, a mixture of nitrogen and hydrogen in the
required proportion of 1:3 is obtained.
The gas mixture is compressed and then passed into the catalytic chamber which consist of a steel tower
containing thin walled steel tube packed with the catalyst. The incoming gases pass up in between these tubes so
as to get heated and then enter down through them. The temperature of the catalytic tube is maintained at 500 °C
by heating them electrically. The issuing gas containing about 10 percent ammonia is cooled and liquid ammonia
condenses. The unconverted nitrogen and hydrogen are returned to the inlet and passed again over the catalyst.
According to Le-Chateliers principle, the most favorable conditions for the synthesis of ammonia are:

(i) High pressure due to decrease in volume (200 atm).

(ii) Low temperature due to exothermic nature of the reaction. (500-600 °C in the presence of suitable catalyst).

(b) Cyanamid process:

In this process the air is passed or calcium carbide heated to about 800 °C when nitrogen combine to form
calcium Cyanamid.

CaC2 + N2 → CaCN2 + C

Properties and uses:

Ammonia is colorless gas with characteristic smell. It can be liquefied in a bath maintained at -40 °C). The liquid
boils at -33.2 °C. Liquid ammonia resemble water in its physical behavior, being highly associated because of the
polar nature and strong hydrogen bonding. Ammonia is utilized for

Uses of ammonia
(i) Manufacture of urea
(ii) Manufacture of ammonium sulphate

(iii) Manufacture of ammonium nitrate, and

(iv) Oxidation to nitric acid
Ammonia forms the basis of nitrogen fertilisers and explosives.
(v) In acidic soils ammonia is injected directly into the ground; in other soils it is used in the form of
ammonium sulfate, ammonium nitrate or urea.
(vi) Ammonia can be catalytically oxidised by air to give NO, which reacts with oxygen to produce NO 2, which
is dissolved in water in the presence of more air to give nitric acid, HNO 3.
(vii) Nitric acid is used to manufacture the fertiliser ammonium nitrate and to make explosives, such as TNT,
dynamite and cordite.

2. Urea:
Urea (carbamide) is a high quality of nitrogenous fertilizer with 46.6% nitrogen contents. It is also used as a
nitrogen containing admixture to animal feed. It is synthesized from ammonia (NH3) and carbon dioxide (CO2).
The manufacturing process consists of the following steps:

(i) Production of NH3

(ii) Production of CO2

(iii) Chemical reaction between NH3 and CO2

(iv) Distillation and processing to end product.

(i) Production of NH3:

(a) Haber’s process: N2 is obtained from air by burning any combustible material which utilize O2 leaving N2 or
by liquefaction of air. H2 gas is obtained by cracking of natural gas or by heating the natural gas with steam in
the presence of Ni as catalyst.

(N2 + O2) air + C → CO2 + N2

CH4 → C + 2H2
𝑁𝑖
CH4 + 2H2O → CO2 + 4H2

CO2 is obtained as a byproduct which is used in the manufacture of urea. N2 and H2 gases obtained from the above
methods are mixed in the ratio 1:3 heated to optimal temperature 450-500°C and pressure 200atm. In the presence
of Fe2O3-Al2O3 as a catalyst.

N2 + 3H2 ↔ 2NH3
 (b) From Coal: When coal is heated in closed retorts to red heat (1000°C) in the absence of air or O2, it produces
coal gas, coal tar and coke as major fractions. Ammonium salts such as (NH4)2CO3, (NH4)2S, (NH4)HS, NH4CN,
(NH4)2SO4 and NH4Cl present in ammonical liquor, are obtained as byproduct, which on heating or treatment
with lime produce NH3 gas.
NH4HS heat→ NH3 + H2S
2NH4Cl + Ca(OH)2 → 2NH3 + CaCl2 + 2H2O

(ii) Production of CO2: Carbon dioxide is obtained by igniting C obtained from natural gas.

C + O2 → CO2

(iii) Reaction between NH3 and CO2: NH3 and CO2 obtained are reacted with each other in reaction tower as
under:

CO2 + 2NH3 ↔ NH2COONH4 ammonium carbamate

On dehydration, ammonium carbamate produces liquid urea.

∆
NH2COONH4 → NH2CONH2 (urea) + H2O

The conversion ratio increases with temperature.

(iv) Processing to end product: According to Solvay Process 1 part compressed CO2 is reacted with part 2 liquid
NH3 at 180 °C and 200atm pressure. The reaction between NH3 and CO2 results in a liquid mass known as
ammonium carbamate. Dehydration of the carbamate take place in tower made of alloy steel. This result in the
formation of liquid urea. The conversion ratio increases with temperature. Since urea formed is in liquid state, hence
high pressure is needed. The urea solution is concentrated in an evaporator and the urea is produced in the form of
crystals or it is granulated in prilling tower, where concentrated solution is allowed to fall from the top of a high
tower while a hot blast of air is blown in a counter current way. This evaporates excess water and urea granules also
called "prills" about 1/16 to 1/8 inches in diameter fall at the bottom where they are packed.

Fig. 7.4 Flow sheet diagram for urea manufacture

Uses of Urea
Urea has the highest nitrogen content equal to 46.6%. This percentage of nitrogen is much higher than any other
fertilizer. It does not change the pH of the soil and can be used to all types of soils and crops, since after its
assimilation by plants through the interaction of nitrifying bacteria, it leaves behind only CO 2 in the soil.

NH2 NH2

O = C +H2O→ C*O_{2} + 2N*H_{3}

Ammonia is then converted to nitrates by oxidation.

3. Ammonium Sulphate (NH4)2SO4.

(i) Ammonium sulphate, (NH4)2SO4 is manufactured by passing ammonia gas into 60 percent sulphuric acid solution.

N*H_{3} + H_{2}*S*O_{4} → (N*H_{4}) 2 SO 4

The mixture of ammonia and steam is bubbled through a lead lined tank containing 60% H 2SO4. From this reaction, crystals of
ammonium sulphate are obtained.

(ii) It may be made on large scale by passing NH3 into a suspension of gypsum powder in water and then passing CO2 through
the liquid. CO₂ is obtained by heating CaCO3.

CaCO3→ CaO + CO2 2NH3 + H2O + CO2 + CaSO4 → (NH4)2SO4 + CaCO3 (soluble) (ppt)

The precipitate of CaCO3 is filtered off and the filtrate containing (NH4)2SO4 is concentrated by evaporation under vacuum
and cooled when crystals of (NH4)2SO4 are obtained. These crystals are packed in bags and sold in the market.

(iii) It can also be obtained from ammonical liquor which is obtained as by-product in the manufacture of coke. Besides organic
compounds, this liquor contains free NH3 and ammonium salts such as (NH4)2CO3, (NH4)2S, NH4CN, (NH4)2SO4, NH4HS
and NH4Cl. Volatile salts are decomposed by boiling alone, while fixed salts are decomposed by lime water, Ca(OH)2. The
total ammonia in combination is about 17 g/l. The liquor is heated in stills, first by steam and then with Ca(OH)2.
 NH 4 ) 2 CO 3 2N*H_{3} + C*O_{2} + H_{2}*O NH 4 HS N*H_{3} + H_{2}*S (NH4)2SO4 + Ca
(OH)2 2NH4Cl + Ca (OH)2 → 2NH3 + CaSO4 + 2H2O → 2NH3 + CaCl2 + 2H2O

The mixture of ammonia and steam so produced is passed through a lead-lined tank containing 60% H2SO4, when crystals of
ammonium sulphate separate on cooling.

2N*H{3} + H_{2}*S*O_{4} (NH 4 ) 2 SO 4

Properties and Uses

Ammonium sulphate forms large colorless transparent rhombic crystals of density 1.77 and highly soluble. Besides
being a useful fertilizer it is used as a reagent in the laboratory, in the preparation of the other ammonium salts and
in the preparation of alums. It contains 24-25% NH3 which is converted to nitrates by nitrifying bacteria in the soil.
It is less hygroscopic than urea and NH4NO3 and, therefore, has better storage properties. It can supply nitrogen to
the soil and is particularly useful for potato and rice crops.

The primary use of ammonium sulfate is as a fertilizer for alkaline soils for agriculture purpose.

Ammonium sulfate precipitation is a common method for protein purification by precipitation in laboratory.

It is used as an acidity regulator in flours and breads.

3. Ammonium Sulphate

(i) Ammonium sulphate, (N*H_{4}) 2 SO 4 is manufactured by passing ammonia gas into 60 percent sulphuric acid
solution.

N*H_{3} + H_{2}*S*O_{4} → (N*H_{4}) 2 SO 4

The mixture of ammonia and steam is bubbled through a lead lined tank containing 60% H_{2}*S*O_{4} From this
reaction, crystals of ammonium sulphate are obtained.

(ii) It may be made on large scale by passing NH3 into a suspension of gypsum powder in water and then passing
C*O_{2} through the liquid. CO₂ is obtained by heating CaCO3.

CaCO3→ CaO + CO2 2NH3 + H2O + CO2 + CaSO4 → (NH4)2SO4 + CaCO3 (soluble) (ppt)
The precipitate of CaCO3 is filtered off and the filtrate containing (N*H_{4}) 2 SO 4 is concentrated by evaporation
under vacuum and cooled when crystals of (N*H_{4}) 2 SO 4 are obtained. These crystals are packed in bags and
sold in the market.

(iii) It can also be obtained from ammonical liquor which is obtained as by- product in the manufacture of coke.
Besides organic compounds, this liquor contains free NH3 and ammonium salts such as (N*H_{4}) 2 CO 3 ,
(N*H_{4}) 2 S , NH4CN, (N*H_{4}) 2 SO 4 , NH4HS and NH4Cl. Volatile salts are decomposed by boiling alone,
while fixed salts are decomposed by lime water, Ca (OH) 2 . The total ammonia in combination is about 17 g/l. The
liquor is heated in stills, first by steam and then with Ca (OH)2.

NH 4 ) 2 CO 3 2N*H_{3} + C*O_{2} + H_{2}*O NH 4 HS N*H_{3} + H_{2}*S

(NH4)2SO4 + Ca (OH)2 2NH4Cl + Ca (OH)2 → 2NH3 + CaSO4 + 2H2O → 2NH3 + CaCl2 + 2H2O

The mixture of ammonia and steam so produced is passed through a lead-lined tank containing 60% H2SO4, when
crystals of ammonium sulphate separate on cooling.

2N*H{3} + H_{2}*S*O_{4} (NH 4 ) 2 SO 4

(ii) Properties and Uses

Ammonium sulphate forms large colorless transparent rhombic crystals of density 1.77 and highly soluble. Besides being a
useful fertilizer it is used as a reagent in the laboratory, in the preparation of the other ammonium salts and in the
preparation of alums. It contains 24-25% NH3 which is converted to nitrates by nitrifying bacteria in the soil. It is less
hygroscopic than urea and N*H_{4}*N*O_{3} and, therefore, has better storage properties. It can supply nitrogen to the soil
and is particularly useful for potato and rice crops.

4. Ammonium Nitrate

Ammonium nitrate, N*H_{4}*N*O_{3} is an important nitrogenous fertilizer containing 33% nitrogen. It is manufactured by
the neutralization reaction between N*H_{3} and HNO3. The manufacturing process consists of the following steps: 02.4

………………………………………………………………………………………………………………………
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 ………………………………………………………………………………………………………………………
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(i) Production of NH3

N2 (obtained from liquefaction of air) and H₂ (obtained by the electrolysis of water) are mixed together in the ratio of 1:3
and are converted into NH3 by Haber's process in the presence of F*e_{2}*O_{3} - A*l_{2}*O_{3} as catalyst. N 2 +3H 2
500^ C 200atm . 2NH
3……………………………………………………………………………………………………………………
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…………………..…………………………………………………………………………………………………..

(ii) Production of HNO3

A part of NH3 produced as above is used in the manufacture of HNO3 by the Ostwald's process. In this process NH3 and air
are mixed together in the ratio of 1:10 by volume. The mixture is introduced into a converter having a cage of five platinum
gauge (80 mesh) which is kept electrically heated between 800-900°C. By this treatment NO is produced. 4NH3 + 502 800-
900°C Pt gauge 4NO + 6 H2O

NO is cooled and mixed with air so that it is oxidized to nitrogen peroxide, NO2. NO2 is dissolved in water to get the solution
of HNO3.

2NO + O_{2} -> 2N*O_{2} 3NO 2 +H 2 O longrightarrow 2HN*O_{3} + NO

NO produced in the above process is reoxidized to NO2 which can be used to prepare HNO3 by dissolving it into H₂O as
shown above.

(iii) Reaction between NH3 and HNO3.

Solution of HNO3 obtained as above is concentrated and heated to about 75°C and is then allowed to fall in the form of a
fine spray from the top of a tower called neutralizer while NH3 gas pre-heated to about 70 ^ 0 * C is introduced from the
bottom of the neutralizer. This operation results in the neutralization of HNO3 by NH3 and formation of N*H_{4}*N*O_{3}
. NH 3 +HNO 3 longrightarrow N*H_{4}*N*O_{3} N*H_{4}*N*O_{3} is obtained in the form of a liquor at the bottom of
the neutralizer. This liquor contains about 84% NH4NO3. This liquor is taken to vacuum concentrator where this gets
concentrated upto 94-96%. The solution of N*H_{4}*N*O_{3} is stirred with finely powdered lime stone (CaCO 3 ) in a
granulator to make it a granulated product. Lime stone is added as a filler. Its function is to render N*H_{4}*N*O_{3} safe
to handle, since it is an explosive
substance.……………………………………………………………………………………………………………
………………………………………………………………………………………………………………………
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 ………………………………………………………………………………………………………………………
………..

Properties and Uses: pp 333

Figure 13.6 Ammonium nitrate is spread as pellets onto the soil.

NH4NO3 is an important nitrogenous fertilizer and contains about 33% nitrogen. It is simple N*H_{4}*N*O_{3} and cheap in
its manufacture. It is directly assimilated by plants and does not undergo any changes in soils. It is highly soluble in water and
as such finds its way into the soil very easily.

2. Phosphate Fertilizers pp334

Phosphatic fertilizers provide phosphorus to the soil and plants. They come next to nitrogenous fertilizers keeping the
deficiency status of Pakistani soils and requirement of principle crops. The two fertilizers therefore should be used in a
mixture or in the form of compounds containing both components. Phosphorus is a constituent element of phosphatic
enzymes which are responsible for energy metabolism.

It is generally considered that plants absorb most of the phosphorus in the primary orthophosphate ion H_{2}*P O 4 ^ - Small
amounts of secondary ortho-phosphate ion HP*O_{4} ^ - 2 are also absorbed. Lower pH values favour the absorption of
H_{2}*P O 4 ^ - form. Phosphorus is associated with early maturing of crops, especially the shortage is accompanied by
marked reduction in plant growth. It is considered essential to seed and fruit formation. Typical phosphatic fertilizers are:

1. Calcium superphosphate (16 + (- 20)% * P_{2}*O_{5})

2. Triple superphosphate (42 + (- 46)% * P_{2}*O_{5})

3. Phosphatic slag ( 14 + (- 22)% * P_{2}*O_{5} and 40% lime)

1. Calcium Superphosphate (CaH6O9P2)

Superphosphate is the soluble phosphate of calcium. It is a mixture of calcium dihydrogen phosphate, Ca (H_{2}*P*O_{4}) 2
and gypsum, CaSO4.2H2O. It is manufactured by treating calcium phosphate or phosphate rock or bone ash with calculated
quantity of commercial H_{2}*S*O_{4} The manufacturing process consists of the following steps:

(i) Preparation of phosphate rock

(ii) Preparation of H_{2}*S*O_{4}

(iii) Mixing of H_{2}*S*O_{4} with phosphate rock (processing)

(i) Preparation of Phosphate rock

Preparation of Phosphate rock. Phosphate rock mainly consists of tricalcium phosphate, Ca 3 (P*O_{4}) 2 with varying
amounts of impurities, chief of which include fluorine CaCO3. Phosphate rock with more fluorine is called fluorapetite,
3C*a_{3} (PO 4 ) 2 .CaF 2 . The mineral is crushed or powdered before its treatment with acid.

(ii) Preparation of H2SO4.

Preparation of H_{2}*S*O_{4} 70% strong H_{2}*S*O_{4} is needed. This can be manufactured from sulphur which is now
abundantly available in Pakistan from desulphurization plants used in natural gas and petroleum industry.

(iii) Processing

The manufacturing process for superphosphate includes a chemical reaction between powdered phosphate rock and 70%
H2SO4. The phosphate rock is well powdered and is placed in a cost iron mixer. Now a calculated quantity of chamber
H_{2}*S*O_{4} is added to it. The whole mass is stirred by means of paddles for 2 to 5 minutes and then dumped
mechanically into one of the brick lined pits or dens D₁ or D2 through the valves V_{1} or V_{2} . Here the mixture is left for
about 24 hours. The reaction which actually started in the mixture continues in the pot or den and the temperature gradually
rises to 100-110°C because of the exothermic nature of the reaction.

Ca3(PO4)2 + 2H2SO4 + 5H2O → Ca(H2PO4)2H2O + 2(CaSO4.2H2O) + Heat (insoluble) (superphosphate)

Since the phosphate rock invariably contains CaCO3 and CaF2 as impurities, they react with H_{2}*S*O_{4} to evolve CO2 and
HF. CaCO3 + H2SO4 CaF2 + H2SO4 CaSO4 + CO2 + H2O → CaSO4 + 2HF

Free HF reacts with silica (Si*O_{2}) present as impurity in the phosphate rock to produce SiF4 which at once gets
decomposed in presence of H_{2}*O forming hydrofluosilic acid, H_{2}*Si*F_{6} . 4HF+SiO 2 longrightarrow Si*F_{4} +
2H_{2}*O 3Si*F_{4} + 2H_{2}*O -> Si*O_{2} + 2H_{2}*Si*F_{6}

The evolution of these gases makes the whole mass of superphosphate porous due to their escape through the solid mass.
The resulting porous mass is easier to be powdered subsequently, otherwise it is very difficult to grind and powder hard non-
porous mass. However, these

commercial uses.
C*O_{2} is used in beverages and HF in glass making and cutting. This method is known as Den's process.

There is another continuous process known as Broad-feld process. In this process well grinded phosphate rock is mixed with
the acid and is continuously and simultaneously introduced into cost iron cylinder with inside revolving blades. Then the well-
mixed material is delivered mechanically into a mechanical den, then reaction time is 1.5 hours. The product has a granulated
structure and is good for plant use.

Properties and Uses

It contains about 16-20% of P2O5 depending on the purity of phosphate rock used in its manufacture. It active
ingredient is calcium dihydrogen phosphate. Normal phosphate, Ca 3PO4)2 being insoluble, cannot be assimilated by
plants, while superphosphate, Ca(H2PO4)2.H2O dissolves in soil moisture and is, thereby easily assimilated by plants.
Thus its use as fertilizer is preferred over normal phosphate.

2. Triple Superphosphate

Calcium dihydrogen phosphate and as monocalcium phosphate, [Ca(H2PO4) 2 .H2O]

It is called triple superphosphate because it furnishes three times as much available phosphorus to the plant as
compared to superphosphate per mole of phosphate rock, i.e., 46-48% P2O5. Normal superphosphate contains CaSO4
in a quite high percentage along with active ingredient, Ca(H2PO4)2, which decreases the percentage of phosphorus in
the mixture. Triple superphosphte is prepared by reacting phosphatic rock with phosphoric acid in place of sulphuric
acid, thus avoiding the formation of CaSO4 and achieving 3 times the amount of available phosphorus.

Ca3(PO4)2 + 3H2SO4 → 3CaSO4 + 2H3PO4

Ca3(PO4)2 + 4H3PO4 → 3Ca(H2PO4)2

triple superphosphate
 Granular triple superphosphate is prepared by mixing pulverized rock phosphate with phosphoric acid in a two-
stage reactor. The resultant slurry is sprayed into the granulator. The granules from the granulator are dried and
screened. The final product is conveyed to bulk storage where the material is cured for 4-6 weeks during which a
further reaction between phosphoric acid and rock phosphate takes place which increases the available P 2O5 as plant
food. During ageing, some amount of water evaporates. After the ageing period, the triple phosphate is dried by hot
flue gases. The dried triple phosphate is screened by vibrating screens and then is made ready for sale.
 Flow diagram for triple superphosphate manufacturing by slurry-type granulation process (Nielsson, 1987)

Triple superphosphates [TSPs, Ca(H2PO4)2·H2O] were produced by exothermic reactions of oyster shells and
different concentrations of phosphoric acid (10, 20, 30, 40, 50, 60, and 70% w/w) in a molar ratio of 1:2.

https://pmc.ncbi.nlm.nih.gov/articles/PMC8412895/

Fertilizer Industry in Pakistan

There are 10 fertilizer units operating in the country (Punjab 6, Sindh 2, and NWFP 2) with an installed capacity of
45516 thousand tonnes. Out of these 10 units, four units having capacity of 2621 thousand tonnes are in the private
sector and six units having 1930 thousand tonnes, capacity are in public sector. The overall production of fertilizers
have declined to 3019478 MT during July-March 1997-98 as compared to 3089191 MT during the same period last
year, depicting an overall decline of 2.26 percent over last year. The production of fertilizers like urea, nitrophosphate
and ammonium sulphate increased by 1.09 percent, 13.51 percent and 0.36 percent respectively during July-March
1996-97 while the production of superphosphate and ammonium nitrate declined by 99.86 percent and 14.60 percent
during the same period.

The overall domestic production during the year 1997-98 was about 3894 thousand product tonnes compared to
4017 thousand tonnes in 1996-97 showing a decrease of 3.1 percent. Domestic production met only 65.2 percent of
the country's product requirements during 1997-98. The gap between fertilizer demand and domestic production is
filled through imports. Fertilizer imports are, therefore, a regular activity of the fertilizer sector, which entains a burden
on the country's foreign exchange. A total quantity of 1227 thousand tonnes of mainly six products were supplied
through imports which represented a decrease of 22.2 percent, as compared to 1996-97.

Broad-field process

There is another continuous process known as Broad-field process. In this process well grinded phosphate rock
is mixed with the acid and is continuously and simultaneously introduced into cost iron cylinder with inside
revolving blades. Then the well-mixed material is delivered mechanically into a machinal den, then reaction time
is1.5 hours. The product has a granulated structure and is good for plant use.
 Figure 1: Plant used for superphosphate

Properties and Uses

It contains about 16-20%of P2O5depending on the purity of phosphate rock used in its manufacture. It actives
ingredient is calcium dihydrogen phosphate. Normal phosphate, Ca3(PO4)2 being insoluble, cannot be
assimilated by plants, while superphosphate, Ca(H 2PO4)2H2O dissolves in soil moisture and its, thereby easily
assimilated by plants. Thus, its use a fertilizer is preferred over normal phosphate.

2. Triple Superphosphate

It is called triple superphosphate because it furnishes three times as much available phosphorus to the plant as
compared to superphosphate per mole of phosphate rock i.e., 46-48% P2O5. Normal superphosphate contains
CaSO4 in a quiet high percentage along with active ingredient, Ca(H2PO4)2, which decrease the percentage of
phosphorus in the mixture. Triple superphosphate is prepared by reacting phosphatic rock with phosphoric acid
in place of sulphuric acid, thus

avoiding the formation of CaSO4 and achieving 3 times the amount of available phosphorous.

Ca3(PO4)2+3H2SO4 3CaSO4+2H3PO4

Ca3(PO4)2+4H3PO4 3Ca(H2PO4)2

triple superphosphate

Granular triple superphosphate is prepared by mixing pulverized rock phosphate with phosphoric acid in a
two-stage reactor. The resultant slurry is sprayed into the granulator. The granules from the granulator are dried
and screened. The final product is conveyed to bulk storage where the material is cured for 4-6 weeks during
which a further reaction between phosphoric acid and rock phosphate takes place which increases the available
P2O5 as plant food. During ageing, some amount of water evaporates. After the ageing period, the triple
phosphate is dried by hot flue gases. The dried triple phosphate is screened by vibrating and then is made ready
for sale.

Fertilizer Industry in Pakistan

There are 10 fertilizer units operating in the country (Punjab 6, Sindh 2, and NWEP 2) with installed capacity
of 45516 thousand tonnes. Out of these 10 units, four units having capacity of 2621 thousand tonnes are in the
private sector and six units having 1930 thousand tonnes, capacity are in public sector. The overall production of
fertilizers have deadline to 3019478 MT during July-March 1997-98 as compared to 3089191 MT during the
same period last year, depicting an overall decline of 2.26 precent over last year. The production of fertilizers like
urea, nitrophosphate and ammonium sulphate increased by 1.09 precent, 13.51 precent and 0.36 precent
respectively during July-March 1996-97 while the production of superphosphate and ammonium nitrate declined
by 99.86 precent and 14.60 precent during the same period.

The overall domestic production during the year 1997-98 was about 3894 thousand products tonnes compared
to 4017 thousand tonnes in 1996-97 showing a decrease of 3.1 precent. Domestic production met only 65.2 percent
of the country’s product requirement during 1997-98. The gap between fertilizer demand and domestic production
is filled through imports. Fertilizers imports are, therefore, a regular activity of the fertilizer sector, which entains
a burden on the country’s foreign exchange. A total quantity of 1227 thousand tonnes of mainly six products were
supplied through imports which represented a decrease of 22.2 precent, as compared to 1996 -97.
FERTILISER ISSUES

Ammonia (NH3) is a simple compound that can be made using nitrogen

gas (N2). It is used to make ammonium compounds that are very
 important fertilisers. Ammonium salts commonly used in fertilisers include
ammonium chloride (NH4Cl), ammonium nitrate (NH4NO3), ammonium
phosphate (NH4)3PO4 and ammonium sulfate (NH4)2SO4.

Nitrogen is removed from the soil when plants absorb nitrates through
their roots as they grow . When farmers harvest their crops, the
nitrogen is not replaced, as the plants do not die naturally
and rot back into the soil. So farmers use fertilisers, mainly
ammonium compounds, to replace this essential nitrogen in the soil.

Nitrogen-based fertilisers must be soluble in water for plants to absorb

the nitrate ions they provide. This has created an environmental
problem. The nitrates can be washed, or leached, out of
the soil by rain into groundwater . These nitrates can then end
up in rivers and lakes. Once in rivers and lakes, the nitrates promote
the growth of algae (a simple water plant) on the surface,
causing eutrophication (F igure 13.1).

Figure 13.1: F ertilisers leached from farmland have caused eutrophication in

this river .
When fertilisers are washed from the soil into rivers:

A bloom of algae can spread across the surface, blocking out the light
for other plant life in the water .

When the plants and algae die, bacteria in the water feed on them,
decomposing the plant material.

The bacteria multiply rapidly with so much food available, using up

the dissolved oxygen in the water .

Fish extractdissolved oxygen from water, taken in through their gills.

Without this dissolved oxygen they die, affecting the whole ecosystem.

Eutrophication isn’t the only problem with fertilisers being leached from
the soil. Nitrates have also been detected in our drinking water,
especially in agricultural areas. People are worried that nitrates in

drinking water cause ‘blue baby’ syndrome (when a newborn baby’s blood is
starved of oxygen), as well as stomach cancer . But others argue
that links between nitrates and diseases have not been proven and
that recommended nitrate levels are set unrealistically low .

Farmers can help limit the amount of nitrates in watercourses by

adding the most economical amounts of fertilisers at the right time of
year . This will minimise the leaching of excess fertiliser from the
soil and into our rivers and lakes.

Questions for discussion

Working with another learner or group of learners:

Discuss the statement ‘Nitrogen-based fertilisers do more harm than good.’

Then feedback any conclusions you make to the whole group.

Try to make suggestions that could help reduce any harmful effects caused by
the large-scale use of fertilisers.