Group 15 Elements (Nitrogen Family) Overview

Chapter-1
p-BLOCK (GROUP 15, 16, 17, 18)

GROUP 15 ELEMENTS (NITROGEN FAMILY)
General Characteristics
1. Introduction. The elements nitrogen, phosphorus, arrsenic, antimony and bismuth constitute group
V A of the periodic table. These are p-block elements having the configuration ns2, np3 as given
in the following table :
Element At. No Electronic Configuration

Nitrogen 7 [He] 2s2, 2p3
Phosphorus 15 [Ne] 3s2, 3p3
Arsenic 33 [Ar] 3d10, 4s2, 4p3
Antimony 51 [Kr] 4d10, 5s2, 5p3
Bismuth 83 [Xe] 4f14, 5d10, 6s2, 6p3
Where as nitrogen and phosphorus have noble gas electronic kernels beneath their valence shells,
arsenic, antimony and bismuth have eighteen electrons in their penultimate shell in addition to two
electrons in their valence shell.
2. Gradation in Properties. There is a general gradation in their properties as discussed below :
(1) Physical State. Nitrogen is a gas, phosphorus is a solid which can vaporise readily. The
remaining members (As, Sb and Bi) are solids.
(2) Density and Boiling point. Density and boiling point increase gradually on descending the group
(3) Ionization energy. The ionization energy decreases regularly on descending down the group.
However, penultimate shell of N and P has eight electrons [(n–1) s2p6] while those of As, Sb
and Bi have eighteen electrons [(n–1) sp2p6d10]. The extra d-electrons do not screen the outer
s-electrons effectively. The screening by various electrons is in the order s > p > d > f. The
orbital electrons are, therefore, held more firmly by the nucleus in the case of As, Sb and Bi.
consequently their atoms are smaller and they have ionization energies higher than expected.
The ionization energy of Bi is further affected by the presence of fourteen poorly shielding f-
electrons in its anti-penultimate shell.
N P As Sb Bi
Atomic Radii (PM) 70 110 120 140 150
Ionization Energy KJ/mol 16920 11220 10880 9636 9776
Electronegativity 3.0 2.1 2.0 1.9 1.9
(4) Size of the atoms. Covalent radii of the atoms do not increase regularly from N to Bi as shown
in Table above
This is because the d-electrons in As, Sb and Bi do not shield the nuclear charge effectively as
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2 p-block Elements (Group, 15, 16, 17, 18)
discussed under ionization energy. The outer electrons are, therefore, more firmly held by the
nucleus. Consequently atoms with d10 inner shells, are smaller in size than would otherwise be
expected. In the case of Bi the inclusion of f14 inner shell (more poorly shielding) further affects
the atomic size.
(5) Electronegativity. Electronegativity decreases gradually on descending down the group from N
to Bi
(6) Valency. In their valence shell each one of these elements possesses two paired s-electrons
and three unpaired p-electrons. By using noble gas electronic configuration. Except nitrogen
all other elements of this group contain d-orbitals also. As a result, these can form five covalent
bonds. Thus P, As and Sb exhibit 5-covalent state. This is not possible in nitrogen due to
absence of d-orbitals.
(7) Oxidation States. All these elements having five electrons in their outer shell exhibit a
maximum oxidation state of five towards oxygen when all the five outer electrons are used.
When the two ns2 electrons tend to remain inert (the inert pair effect) and only p-electrons
are used in bonding, trivalency results. They show oxidation states of –3 in hydrides (MH3).
Nitrogen generally shows oxidation states of +3 and –3 whereas phosphorous Arsenic antimony
and Bismuth shows an oxidation states of –3, +3, and +5 due to the presence of vacant
d-orbitals.
(8) Inert Pair Effect. Elements of this sub-group show variable valency exhibiting two states :
(i) Oxidation number = Group number ( = 5)
(ii) Oxidation number = Group number minus two = 5 – 2 = 3
Loss of electrons from an atom of an elements can take place in two ways.
(i) All its s and p electrons may be lost forming a compound in which its oxidation number equals
the Group number ; for example, in tin(iv) and antimony (v) compounds. Such compounds are
covalent, not ionic.
(ii) The outermost s-electrons are not lost very frequently and the oxidation number of the element
is then equal to Group number minus two, for example in thalium (I), lead (II) and bismuth (III)
compounds.
The pair of electrons in these elements is said to have become inert. The inert pair effect is most
prominent in the heavier elements of a group such as Tl (Group III), Pb (Group IV) and Bi (Group V).
(9) Type of bonds formed. Due to high ionization energies, they do not form highly charged ions.
In majority of cases, the bonds are covalent bond. Thus the bonding in metallic phosphides and
arsenides is largely covalent. This tendency increases with increase in oxidation number. In a few
cases, Sb and Bi give Sb3+ and Bi3+ ions but these are rapidly hydrolysed to SbO+ and BiO+ ions
in water.
Bi3+ + 3H2O BiO+ + 2H3O+
The elements in this group could attain noble gas configuration by gaining three electrons to
from M3– ions. However, energy required to form such ion would be extremely large. Only
nitrogen is definitely known to give such an anion (N3–) when it combines with highly
electropositvie metals, e.g., Na3N.
(10) Metallic and Non-Metallic Character. The metallic (electro-positive) character increases
as we descend the group. Thus N and P are non-metals. As and Sb are metalloids which show
a number of metallic properties and Bi is a true metal. The same is shown by the fact that
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p-block Elements (Group, 15, 16, 17, 18) 3
normal oxides of nitrogen and phosphorus are strongly acidic, those of As and Sb are
amphoteric, while bismuth oxide is largely basic.
The +5 oxidation states of the elements are generally more acidic than the +3 states, as may
be seen from a comparison of HNO2 and HNO3 as well as H3PO3 and H3PO4.
(11) Hydride. They form hydrides of the formula MH3. Ammonia, NH3 forms as associated and
high-boiling liquid with basic character. These properties may be ascribed to the high
electronegativity and lone pair of electrons of the N atom which give rise to hydrogen bonding
and the basic character of NH3. It is evident that melting and boiling points of NH3 are much
higher compared to those of PH3, AsH3 and SbH3.
Phosphine PH3, is a much weaker base than NH3 and arsine (AsH3) and stibine (SbH3) are
weaker still. The boiling point order is BiH3 > SbH3 > NH3 > AsH3 > pH3.
Stability of these hydrides decreases gradually from NH3 to BiH 3 as shown by their
temperatures of decomposition given below :
NH 3 PH 3 AsH 3 SbH 3 BiH 3
1573 K 673 K 553 K 423 K (very unstable)
Bond angles in these hydrides are close to 90º showing a high degree of p character of M–
H bonds and s character of the lone pair of electrons. The H–N–H bond angle in ammonia
is 107.8º, a value close to tetrahedral angle. It suggests sp3 hybridization with the lone pair of
electrons occupying the fourth position
The hydrides of P, As and Sb are strong reducing agents and react with solutions of metal ions
to give phosphides, arsenides and stibnides. They are inflammable and extremely poisonous.
Ammonia forms NH4+ salts very readily PH3 forms salts with HCl and HI only under
anhydrous conditions, while other hydrides do not form analogous salts. Ammonia also forms
coordination complexes with metal ions from the Co, Ni, Cu and Zn groups. This represents
its strong donor properties.
(12)Halides. They form trihalides of the formula MX3. All the possible trihalides of N, P, As, Sb
and Br are known except NBr3 and NI3 which have been obtained as ammoniates, e.g.
NBr3.6NH3.
These halides are predominantly covalent and have a pyramidal structure like NH3. BiF3 is,
however, ionic while SbF3 and other bismuth halides are partially ionic. NF3 is extremely stable,
while NCl3 is explosive and is readily hydrolysed.
NCl3 + 3H2O NH3 + 3HOCl
The difference is due to the fact that during the first stage in hydrolysis an extra bond is formed
and while Cl can expand its octet by using d orbitals, F and N cannot. Hence NCl3 is
hydrolysed while NF3 is not trihalides of P, As and Sb hydrolyse readily since they can expand
their octets.
PCl3 + 3H2O H3PO3 + 3HCl
BiCl3 and BiBr3 are much more ionic but give BiO+ ion in solution.
SbCl 3 + H 2 O SbOCl + 2HCl
BiCl3 + H2O Bi (OH)3 + 3HCl
Nitrogen does not form pentahalides as given by the subsequent elements, e.g., PCl 5, SbCl5.
Phosphorus forms five bonds due to sp3d hydbridization, not possible in nitrogen due to the
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absence of vacant d-orbitals to expand their valency.

The pentahalides have a trigonal bi pyramid shape in which some angles are 90oC and other 120o.
PF5 is stable. PCl5 exists in equilibrium with PCl3 however PBr5 and PI5 are highly unstable.
PCl5 hydrolysis PCl5 + 4H2O H3PO4 + 5HCl
(13)Oxides. Nitrogen forms a number of oxides, e.g., N2O (nitrous oxide), NO (nitric oxide), N2O3
(nitrogen sesquioxide), NO2, N2O4 (nitrogen dioxide, dinitrogen tetroxide), N2O5 (dinitrogen
pentoxide) and NO3, N4O6 (nitrogen trioxide, dinitrogen hexoxide–very unstable). First two of
them are neutral and the rest are acidic. Phosphorus gives trioxide (P4O6), dioxide (PO2)n and
pentoxide (P4O10). These are acidic in nature.
P4O6 + 6H2O 4H3PO3
2PO2 + 3H2O H3PO3 + H3PO4
P4O10 + 6H2O 4H3PO4
Corresponding oxides given by As, Sb and Bi are :
As4O6 Sb4O6 Bi2O3
As4O10 (SbO2)n (Basic)
(Acidic) Sb4O10
(Amphoteric)
As4O10 and Sb4O10 lose oxygen on heating and form trioxides.
(14)Strength and Solubility of their Oxy-acids. Strength of acids and their solubility in water
decreases regularly. For example,
HNO 3 H 3 PO 4 H 3 AsO 4 H 3 SbO 4 H 3 BiO 3 or Bi(OH) 3
Strong Weak Weaker Amphoteric basic Amphoteric basic
(soluble) (soluble) (soluble) (insoluble) (insoluble)
There are the other oxaacids
(a) Nitrogen
(i) Hyponitrous acid H2N2O2 or HNO
(ii) Nitrous acid HNO2
(iii) Nitric acid HNO3
(iv) Pernitric acid HNO4
Structure
HON = NOH Hyponitrous acid
HO – N = O Nitrous acid
HO – N = O
Nitric acid
O
H–O–O–N=O
Pernitric acid
O
Miscellaneous
(1) Nitrogen fixation. Nitrogen is important for life processes, as it is a constituent of plant and
animal proteins and genetic material. Any process by which atmospheric nitrogen is converted

into a useful nitrogen compound is referred to as nitrogen fixation. Assimilation of atmospheric

nitrogen (N2) by plants occurs through two important Nitrogen Fixation process :
(i) During thunder storms, nitrogen and oxygen of the air combine to form nitrogen oxides,
which are eventually converted into nitric acid and nitrates in the soil.
(ii) Soil bacteria in the root nodules of some plants such as beans fix atmospheric nitrogen
into compounds that the plant can readily utilize. This biochemical process involves an
enzyme called Nitrogenase in which the active sites contain molybdenum and iron atoms.
(2) Compound of nitrogen.
Ammonia. Ammonia is manufactured by the Haber process represented by the equilibrium :
N2(g) + 3H2(g) 2NH3(g); r H° = 92.2 kJ mol–1
In accordance with Le Chateller’s principle, high pressure would favour the formation of
ammonia. The optimum conditions for the production of ammonia are a pressure of 200 × 105
Pa (about 200 atm), a temperature of around 700 K and the use of a catalyst such as iron
oxide with small amounts of K2O and Al2O3 to increase the rate of attainment of equilibrium.
A convenient laboratory preparation of ammonia consists of heating an ammonium salt with
a strong alkali (e.g., NaOH) either in the solid form or dissolved in water. It can also be
prepared by the hydrolysis of magnesium nitride.
Mg3N2 + 6H2O  3Mg(OH)2 + 2NH3
Ammonia is a colourless gas with a pungent odour. Its freezing and boiling points are 198.4
K, and 239.7 K respectively. In the solid and liquid states, it is associated through hydrogen
bonds as in the case of water and that accounts for its high melting and boiling points. The
ammonia molecule is trigonal pyramidal with the nitrogen atom at the apex. It has three bond
pairs and one lone pair as shown below.
pm N
1.7
10
H 107.8° H
H

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Ammonia gas is highly soluble in water. Its aqueous solution is weakly basic due to the
equilibrium :
NH3(aq) + H2O(l) NH4+(aq) + OH–(aq)
It forms ammonium salts with acids, e.g. NH 4Cl, (NH4) 2SO4, etc. As a weak base, it
precipitates the hydroxides of many metals from their solutions e.g.
Fe3+ (aq) + 3NH4OH (aq)  Fe(OH)3 + 3NH4–(aq).
The presence of a lone pair of electrons on the nitrogen atom of the ammonia molecule makes
it a Lewis base. It forms coordinate linkage with metal ions and the formation of such complex
compounds find applications in qualitative analysis as in the case of Cu2+ ions :
Cu 2  (aq) + 4NH3(aq) [Cu(NH3 ) 4 ]2  (aq)

(blue) (deep blue)
Ammonia is used mostly to produce various nitrogenous fertilizers (ammonium nitrate, urea,
ammonium phosphate and ammonium sulphate) and in the manufacture of some inorganic
nitrogen compounds, the most important one being nitric acid. Liquid ammonia is also used as
a refrigerant.
(3) Oxides of Nitrogen. Oxides of nitrogen provide a fascinating picture from the point of view
of their varied structures and diverse chemical behaviour. They range from N2O (oxidation state
of nitrogen +1) through NO, N2O3, NO2, N2O4 to N2O5 (oxidation state of nitrogen +5).
The ability of nitrogen to form p – p multiple bonds dictates the structures of its oxides. They
are also good example for illustrating the concept of resonance. Nitrogen monoxide is an odd-
electron molecule. Because of the presence of an unpaired electron, it undergoes partial
dimerization in the liquid state and exists as dimer in the solid state. Nitric oxide readily reacts
with oxygen (itself a free-radical with two unpaired electrons) to give brown fumes of nitrogen
dioxide (NO2).
2NO(g) + O2(g)  2NO2(g)
Nitrogen oxides react with water to give oxoacids of nitrogen. Thus N 2O3 and N2O5 may be
regarded as anhydrides of nitrous (HNO2) and nitric acid (HNO3) respectively. Nitrogen dioxide
reacts with water to give both nitrous and nitric acids.
2NO2 + H2O  HNO3 + HNO2
Because of its rather unreactive nature, dinitrogen monoxide (N2O) is used as an anaesthetic,
particularly in dentistry. Nitric oxide and nitrogen dioxide are important in the manufacture of
nitric acid and nitrate fertilizers.
Liquid N2O4 finds use as an oxidizer for rocket fuels in missiles and space vehicles. Oxides
of nitrogen are emitted into the atmosphere during the burning of oil and coal in power stations
and are also present in automobile exhaust fumes. They are the main cause of air pollution
in major cities and near power stations burning fossil fuels. They contribute to acid rain and
photochemical smog.
Nitric oxide (NO), in spite of its reactive and harmful nature occurs in biological systems
in traces. It acts as a neurotransmitter and plays a significant role in controlling blood
pressure by relaxing blood vessels. It also provides protection from bacterial infections.
(4) Nitric Acid. Nitric acid is manufactured by the catalytic oxidation of ammonia in what is
known as Ostwald Process which can be represented by the sequence of reactions shown
below:
4NH 3 (g)  5O 2 (g) 
Pt / Rh
Catalyst
4NO(g)  6H 2 O(g)
2NO(g) + O2(g) 
1120 K
 2NO2(g)
3NO2(g) + H2O(l)  2HNO3(aq) + NO(g)


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Ammonia is mixed with air and the mixture containing ~10% ammonia is passed through a
metal gauze made of 90% platinum and 10% rhodium at a temperature of 500K and 9 × 10 5
Pa (9 bar) pressure. The product mixture containing nitrogen monoxide is cooled below 420
K when the unreacted oxygen in the air reacts with NO to give NO2. The final stage involves
the absorption of NO2 in water to give nitric acid and NO gas, which is recycled. The aqueous
nitric acid obtained by this method can be concentrated by distillation to ~68.5% by weight.
Further concentration to 98% acid can be achieved by dehydration with concentrated sulphuric
acid.
The nitrate ion, NO3–, is isoelectronic with the carbonate ion, CO32–, and likewise planar. The
nitrate ion can be represented by the resonance structures shown below :
Concentrated nitric acid is a strong oxidizing agent and attacks most metals except noble metals
such as gold and platinum. Some metals (e.g., Cr, Fe, Al) do not dissolve in concentrated nitric
acid because of the formation of a passive film on the surface. The products of reduction
depend upon the concentration of the acid, temperature and the nature of the material
undergoing oxidation. The principal product is nitric oxide (NO), when dilute nitric acid is used
and nitrogen dioxide (NO2), when concentrated HNO3 is used,
3Cu + 8HNO3  3Cu(NO3)2 + 2NO + 4H2O
(dilute)
Cu + 4HNO3  Cu(NO3)2 + 2NO2 + 2H2O
(conc.)
Zinc reacts with dilute nitric acid to give ammonium nitrate :
4Zn + 10HNO3  4Zn(NO3)2 + NH4NO3 + 3H2O
Concentrated nitric acid also oxidizes nonmetals and their compounds. Iodine is oxidised to iodic
acid, carbon to carbon dioxide sulphur to H2SO3 and H2SO4 and phosphorus to phosphoric acid.
Nitric acid is reduced to nitrogen dioxide (NO2).
I2 + 10HNO3  2HIO3 + 10NO2 + 4H2O
C + 4HNO3  CO2 + 2H2O + 4NO2
1/8 S8 + 6HNO3  H2SO4 + 6NO2 + 2H2O
(conc.)
1/4 P4 + 5HNO3  H3PO4 + 5NO2 + H2O
(conc.)
The familiar brown-ring test for nitrates depends on the ability of Fe 2+ to reduce nitrates to
nitric oxide, which reacts with Fe2+ to form a brown coloured complex. The test is usually
carried out by adding dilute ferrous sulphate to an aqueous solution containing nitrate ion, and
then carefully adding concentrated sulphuric acid along the sides of the test tube so that a
separate layer is formed. A brown ring at the interface between the solution and sulphuric acid
indicates the presence of nitrate ion in solution.
NO3– + 3Fe2+ + 4H+  NO + 3Fe3+ + 2H2O
[Fe(H2O)6]2+ + NO  [Fe(H2O)5(NO)]2+ + H2O
(brown)

Uses of Nitric Acid. The major use of nitric acid is in the manufacture of ammonium nitrate
for fertilizers and other nitrates for use in explosives and pyrotechnics. It is also used for the
preparation of nitroglycerin, trinitrotoluene, and other organic nitro compounds. Another major
use is in the pickling of stainless steel and etching of metals and as an oxidizer in rocket fuels.
Phosphorus
Source
Phosphorite – Ca3(PO4)2
Chlorapatite – 3Ca3 (PO4)2.CaCl2
Fluorapatite – 3Ca3 (PO4)2.CaF2
Preparation
Electrothermic Process :- Phosphorus is manufactured by heating a mixtures of phosphorite, sand and
coke. The different reactions taking place are.
2Ca3(PO4)2 + 6SiO2  6CaSiO3 + P4O10
P4O10 + 10C P4 + 10CO
Allotropic Forms
(a) White or Yellow
P P P
(b) Red –P P– P P– P P–
P P P
(c) Scarlet
(d) Metallic
(e) Violet
(f) -black phosphorus
(g) -black phosphorus
Properties
(1) It reacts with oxygen to form two types of oxides.
4P + 3O2 2P2O3
4P + 5O2 2P2O5
(2) It reacts with chlorine to form phosphorus trichloride and phosphorus pentachloride
2P + 3Cl2 2PCl3
2P + 5Cl2 2PCl5
(3) It reacts with sulphur to form phosphorus (iii) sulphide

2P + 3S P2S3
(4) It reacts with metals to form phosphides
(a) 3Na + P Na3P
(b) 3Ca + 2P Ca3P2
(5) It disproportionates to form hypo phosphite and phosphine.
4P + 3NaOH + 3H2O 3NaH2 PO2 + PH3

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(6) With copper sulphate it forms cupric phosphide.

4P + 3CuSO4 + 6H2O Cu3P2 + 2H3PO3 + 3H2SO4
(7) It is oxidised by H2SO4 and HNO3 to H3PO4 (orthophosphoric acid).
2P + 5H2SO4 2H3PO4 + 5SO2 + 2H2O
P + 5HNO3 H3PO4 + H2O + 5NO2
248º  250ºC
(8) Yellow P 
Inert Atm
 Red P
Phosphorus trioxide (P4O6)

Preparation
It is obtained by burning phosphorus in limited supply of oxygen.
P4 + 3O2 P4O6
Properties
(1) White wax like solid with garlic like odour.
(2) On heating it gives P4O8.
4P4O6 210ºC 3P4O8 + P4
(3) It hydrolyses to phosphorus acid in cold water. However with hot water it gives H 3PO4
P4O6 + 6H2O (Cold) 4H3PO3
P4O6 + 6H2O (hot) 3H3PO4 + PH3
(4) It is oxidised to phosphorus pentaoxide by oxygen
P4O6 + 2O2 P4O10
(5) It reacts with chlorine to form phosphoryl chloride and metaphosphoryl chloride.
P4O6 + 4Cl2 2POCl3 + 2PO2Cl

Phosphorus Pentoxide
Preparation
It is obtained by burning phosphorus in excess of oxygen
P4 + 5O2 P4O10
P  O may be taken as P = O
Properties
(1) It is hydrolysed to metaphosphoric acid and orthophosphoric acid in cold and hot water respectively.
P4O10 + 2H2O (cold) 4HPO3
P4O10 + 6H2O (hot) 4H3PO4
(2) It is converted to metaphosphoric acid by sulphuric and nitric acid.
(a) P4O10 + 2H2SO4 2SO3 + 4HPO3
(b) P4O10 + 4HNO3 2N2O5 + 4HPO3
(3) It is a good dehydrating agent
(a) P4O10 + 4CH3COOH 2(CH3CO)2 O + 4HPO3
(b) P4O10 + 2CH3CONH2 2CH3CN + 4HPO3
(c) P4O10 + (C6H10O5)n 6n C + 5n H2O + P4O10
(4) It is reduced by carbon to phosphorus
P4O10 + 10 CP4 + 10CO
(5) Being an acidic oxide it reacts with basic oxide to form salt i.e. phosphate salt e.g.
P4O10 + 6CaO 2Ca3(PO4)2
Phosphorus acids
Phosphorous
Hypophosphorous H3PO2 (+1)
orthophosphorous H3PO3 (+3)
Hypophosphoric H 4P 2O 6 (+4)
Orthophosphoric H3PO4 (+5)
Pyrophosphoric H 4P 2O 7 (+5)
Metaphosphoric HPO 3 (+5)

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Structure
O
H–P–O–H
H3PO2
H
O
H–O–P–O–H
H3PO3
H
Their preparations and properties are dealt seperately.
O O
HO – P – P – OH
H 4P 2O 6
OH OH
OH
HO – P = O
H3PO4
OH
O O
HO – P – O – P – OH
H 4P 2O 7
OH OH
HO – P = O
HPO3
O
Phosphorus acid or (Phosphonic acid), H3PO3

Preparation
(1) By action of water on P4O6
P4O6 + 6H2O 4H3PO3
(2) By action of water on PCl3
PCl3 + 3H2O H3PO3 + 3HCl
Properties
(1) White deliquescent crystalline solid.
(2) It decomposes to ortho phosphoric acid and phosphine at 200ºC
4H3 PO3 3H3PO4 + PH3
(3) Reducing Properties :- It is a strong reducing agent.
(a) 2AgNO3 + H3PO3 + H2O 2Ag + 2HNO3 + H3PO4
(b) 2HgCl2 + H3PO3 + H2O Hg2Cl2 + 2HCl + H3PO4
(c) 2HgCl2 + H3PO3 + H2O Hg2Cl2 + 2HCl + H3PO4
(d) CuSO4 + H3PO3 + H2O Cu + H2SO4 + H3PO4
(e) SO2 + 2H3PO3 2H3PO4 + S
(f) H3PO3 + 3PCl5 PCl3 + 2POCl3 + 3HCl
(g) I2 + H2O + H3PO3 H3PO4 + 2HI
(h) 2KMnO4 + 3H2SO4 + 5H3PO3 K2SO4 + 2MnSO4 + 3H2O + 5H3PO4

Phosphoric acid (Orthophosphoric acid) (H3PO4)

Preparation
(1) By action of water on P4O10
P4O10 + 6H2O 4H3PO4
(2) By action of HNO3 on Phosphorus
P + 5HNO3 H3PO4 + H2O + 5NO2
(3) By treating phosphorite rock with H2SO4
Ca3(PO4)2 + 3H2SO4 3CaSO4 + 4H3PO4
Properties
(1) Colourless syrupy liquid
(2) Orthophosphoric acid on heating to 250ºC gets converted to pyrophosphoric acid which further gets
converted to metaphosphoric acid.
2H3PO4 250ºC H4P2O7 + H2O
H4P2O7 316ºC 2HPO3 + H2O
Pyrophosphoric acid (H4P2O7)

Preparation
It is obtained by heating orthophosphoric acid.
2H3PO4 250ºC H4P2O7 + H2O
Properties
(1) White Crystalline solid
(2) Pyrophosphoric acid is hydrolysed to orthophosphoric acid.
H4P2O7 + H2O 2H3PO4
(3) It decomposes to water and metaphosphoric acid at 316ºC.
H4P2O7 2HPO3 + H2O
Metaphosphoric acid (HPO3)

Preparation
By heating orthophosphoric acid or pyrophosphoric acid
H3PO4 
600ºC
 HPO3 + H2O
H4P2O7 
600ºC
 2HPO3 + H2O
Properties
(1) Transparent glassy solid
(2) Reacts with water to give H3PO4
HPO3 + H2O  H3PO4

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Phosphine
Preparation
(1) Phosphine is obtained by the hydrolysis of calcium phosphide and Aluminium phosphide.
(a) Ca3P2 + 6H2O 3Ca (OH)2 + 2PH3
(b) 2AlP + 3H2SO4 Al2 (SO4)3 + 2PH3
(2) When Phosphonium Iodide is reacted with NaOH we get phosphine.
PH4I + NaOH PH3 + NaI + H2O
(3) Phosphorus acid decomposes to phosphine and orthophosphoric acid.
4H3PO3 PH3 + 3H3PO4
(4) It is prepared from the disproportionation reaction phosphorus with sodium hydroxide.
4P + 3NaOH + 3H2O PH3 + 3NaH2PO2
Properties
(1) Colourless gas with a smell of rotten fish.
(2) Phosphine is converted to P2O5 when heated with O2 at 150ºC.
2PH3 + 4O2 150ºC P2O5 + 3H2O

(3) PH3 decomposes at 440ºC to phosphorus and hydrogen
440°C
2 PH3 2P + 2H2
(4) It reacts with halogen acid (HX) to give phosphonium compound PH4X.
PH3 + HX PH4X
(5) It reacts with halogen to give phosphorus halide
PH3 + 3Cl2 PCl3 + 3HCl
PH3 + 4Cl2 PCl5 + 3HCl
(6) Reducing Properties : - Phosphine acts as a reducing agent e.g.
3HgCl2 + 2PH3 Hg3P2 + 6HCl
3CuSO4 + 2PH3 Cu3P2 + 3H2SO4
6AgNO3 + PH3 + 3H2O 6Ag + 6HNO3 + H3PO3

GROUP 16 ELEMENTS OXYGEN FAMILY

General Characteristics.
1. Introduction.– The elements oxygen, sulphur, selenium, tellurium and polonium constitute group VIA
(or 16) of the periodic table. The first four elements are collectively called CHALCOGENS. These
are p-block elements having the configuration ns2, np4 as give in Table below.
Table
Element At. No. Electronic structure
Oxygen 8 [He] 2s2, 2p4
Sulphur 16 [Ne] 3s2, 3p4

Selenium 34 [Ar] 3d10, 4s2, 4p4
Tellurium 52 [Kr] 4d10, 5s2, 5p4
Polonium 84 [Xe] 4f14, 5d10, 6s2, 6p4
2. Periodicity in Properties of Group VIA Elements. As in gp 14 and 15 the properties of these

elements also show a regular gradation from a typical non-metal (oxygen) to a typical metal
(polonium). They show allotropy and in this regard surpass even the elements of group 15. Oxygen
exists as O2 and is a gas whereas sulphur exists as S8 and is a solid. All other elements (Se, Te,
Pe) are also solids.
(1) Non-metallic Character. O, S, Se and Te are non-metals but the non-metallic character is
the strongest in O and S and weaker in Se and Te. They are collectively known as chalcogens
or ore forming elements since many metals occur as oxides or sulphides, e.g., Cu 2O, Cu2S,
Ag2S. Polonium is markedly metallic and being radioactive it is shortlived (t1/2 = 138.4 days).
(2) Ionization Energy. High values of ionization energy indicate that the formation of positive ions
is extremely difficult and the elements are predominantly non-metallic in character. The values
decrease gradually from oxygen to polonium
(3) Electron Affinity. Electron affinity values indicate that O– shows a considerably high resistance
to form O2–. However, the simple ionic oxides of electropositive metals (e.g., alkaline earth
emtals) all contains O2– ion insead of O– ion. This can be explained by consideration of Born-
haber cycle for the formation of the solid ionic oxide.
1 Hf
M(s) + O2(g) MO(s)
2
H1 1 H H5 (Lattice energy)
3
2 O(g) H4
O2–
M(g)
H2 M2+(g) +
H1 = Sublimation energy

H2 = Ionization energy
H3 = Bond energy of O2
H4 = Electron affinity
H5 = Lattice energy

- 15 -
The lattice energy released. on forming the crystal more than compensates the adverse effect of
second electron affinity value (O– to O2–) and high bond energy values.
Table
Alkaline earth metal oxide Lattice energy, kJ mol –1
MgO –3923
CaO –3517
SrO –3312
BaO –3120
Also, the lattice energies of sulphides, selenides and tellusides are lower. It means their formation
becomes increasingly difficult,
(4) Electronegativity. Non-metallic character of the elements is also reflected by the high
electronegativity values. The values decrease from oxygen to polonium.
(5) Oxidation States. All of them have the electronic structure ns2, np4 and in their bid to assume
noble gas configuration they form metal oxides which are ionic and contain O2– ions, thus giving
oxygen an oxidation state of –2.
Oxygen shows general oxidation states of –2, +2, –1, –1/2 –2 in oxides. +2 in fluorides, –1 in
peroxides and –1/2 in superoxides.
Oxygen is divalent since it has only two unpaired electrons, its electronic structure being 1s 2, 2s2,
2px2, 2py1, 2pz1
Since its second shell is limited to 8 electrons (i.e., since there are no d orbitals in this shell) and
too much energy is needed to excite an electron into a higher shell, it is never more than divalent.
In the case of S, Se, Te and Po, d orbitals are available for bonding and they can form four or
six bonds by unpairing electrons. For example, in the case of sulphur unpairing of electrons to form
2, 4 or 6 bonds can be explained as follows :
The +4 oxidation states due to unpairing of p-electrons and +6 oxidation state due to unpairing of
both p and s-electron. The tendency to form +6 oxidation state decreases down the group due to
inert pair effect.
S, Se and Te are typically tetravalent in their compounds with oxygen. However, in their compounds
with fluorine their maximum oxidation state of +6 is exhibited.
(6) Bond Lengths. The covalent bonds between S and O, or Se and O (e.g., in SO2 and SeO2)
have bond lengths much shorter than expected of single bond. This is explained by considering
them as double bonds formed by the sideways overlap of a p-orbital on the oxygen with a d-
orbital on the sulphur in addition to the original bond. the p - d interaction accounts for
the short bond length.
(7) Molecular Structure. Oxygen forms a stable diatomic molecule while S, Se, Te and Po have
more complex molecules. This accounts for oxygen being a gas and the others being solids.
Sulphur and selenium have S8 molecules with puckered ring structure at room temperature.
(8) Polymorphism. All of these elements are polymorphic, i.e., exist in more than one allotropic
form. Oxygen occurs as two non-metallic forms O2 and O3 (ozone). Sulphur exists in a
number of forms, all non metallic, e.g., rhombic, monoclinic and plastic sulphur. Selenium has
two forms, red (non-metallic) and grey (metallic). Tellurium exists in two forms, non-metallic
and the more stable metallic form. Polonium occurs in two forms and (bvoth metallic).

(9) Hydrides. All of these elements form stable volatile bivalent hydrides, H2O, H2S, H2Se, H2Te
and H2Po. The stability of the hydrides decreases graduallly from H2O to H2Po. Out of these
H2S, H2Se and H2Te are prepared by the action of metallic sulphides, selenides and tellurides
whereas H2Po is obtained by treating a mixture of magnesium and polonium with dilute acid.
FeS + H2SO4 H2S + FeSO4
All these hydrides, except water which is odourless, have unpleasant odour and are poisonous in
nature. Poisonous nature gradually increases from H2S to H2Po. The volatility increases markedly
from H2O to H2S and then decreases. Abnormally low volatility (i.e., high boiling point) of water
is due to its association as a result of hydrogen bonds both solid and liquid states.
The boiling point order is H2O > H2Te > H2Se > H2S
They are feebly acidic in character, the acidic strength increases from H2O to H2Te. This cannot
be explained in terms of Electronegativity differences. The probable reason is that in HX (where
X is O, S, Se or Te), large the size of X, weaker its bond with H, and more easily does the
hydrogen ion get lost in aqueous solution.
(9) Halides. Elements S, Se and Te show a maximum valence of six in their fluorides, SF6, SeF6
and TeF6, which are colourless gases. The hexafluorides have an octahedral structure due to
sp3d2 hybridization of group VIA atom.
The low boiling points of the halides indicate a high degree of covalency in these moelcules.
Many tetrahalides are known which possess presumable trigonal bipyramidal stucture. Such a
structure is well established in case of TeCl4.
There are four unpaired electrons in tellurium atom (excited state) which form four bonds with
four chlorine atoms ; there is sp3d hybridization as a result of which TeCl4 has a bipyramid structure
with one position occupied by a lone pair of electrons.
F
F
156 pm
165 pm
F F
5 pm F
15
S 90°
S 102°
173° F F
F
F
F (b)
(a)
Dihalides form tetrahedral molecules due to sp3 hybridization. The bond angle is less than 109º 28'
due to distortion caused by lone pairs of electrons.
The bond angle is 103o in SCl2, 101.5o in OF2 and 98o in TeBr2.
Dimeric monohalides are given by sulphur and selenium. These tend to disproportionate and are
hydrolysed slowly.
2Se2Cl2 SeCl4 + 3Se
2S2Cl2 + 2H2O 3S + SO2 + 4HCl

- 17 -
The structure of monohalides is similar to that of hydrogen peroxide. The bond angle is 104 o
probably due to sp3 hybridization distorted by two lone pairs.
(10)Oxides. All of them form oxides of the type MO2, e.g., SO2, SeO2, TeO2 and PoO2. there
is, however, considerable different in their individual structure. SO2 is a gas of the structure
formula given in the margin and forms discrete molecule even in the solid state. The S–O
double bonds arise from p – d bonding. The bond angle 119.5 o is very near 120o expected
of sp2 hybridization as explained below.
SeO2 is solid at room temperature. In the gaseous state it has the same structure as SO 2 but the
solid form consists of infinite chains which are not planar.
S, Se and Te also form trioxide SO2 SeO2 and TeO2. Sulphur trioxide gas has planar triangular
structure given in the marign.
SO2 is soluble in water forming SO32– ions
SO3 also dissolves but form SO42– ions
Sold SO3 is trimeric
(11) Oxy-acids. Sulphur, selenium, and tellurium form similar oxy-acids and salts as shown below:
H2SO3 Sulphurous acid H2SeO3 Selenous acid
H2SO4 Sulphuric acid H2SeO4 Selenic acid
O S O
S S S S
HO O HO O HO O O OOH
HO HO HO OH
Sulphurous acid Sulphuric acid Thiosulphuric acid Peroxomonousulphuric aic
O O O
O
S S S
S O
O O O O
O
OH HO HO
HO
Peroxodisulphuric acid Dithionic acid
The strength and stability of these acids diminish progressively from sulphur to tellurium. Sulphuric,
selenic and telluric acids form double salts with alkaline earth or other divalent metals of the general
formula M'2RO4.M"RO4.6H2O. where R=sulphur triad ; M' = alkali metal or ammonium, and
M' = a divalent metal, e.g. iron, cobalt, nickel, zinc, copper, cadmium, magnesium and manganese.
Their preparations and properties are dealt separately.
(12)Compounds with Carbon. All of these elements form compounds with carbon. Oxygen and
sulphur form two compounds each viz, CO and CO2 ; and CS and CS2 respectively. Selenium
and tellurium give CSe2 and CTe2 respectively.
(13)Catenation. Oxygen and, to a greater extent, sulphur differ from the rest of the elements in
their ability to catenate, i.e., for chains of atoms. For example, sulphur gives H2S2, the thionates,
SxO62– and the sulphur moelcule itself is S8. Oxygen has a maximum chain length of three in
ozone. Selenium and tellurium also form short chains as, for example, Se2Cl2.

The highest catenation capability of sulphur is related to highest bond strength

H 2 O 2 , H–O–O–H
H 2 S 2 , H–S–S–H
H 2 S 2 , H–S–S–S–H
H 2 S 4 , H–S–S–S–S–H
The B.E. high bond energy of S-S when compared to O-O bond energy
(14)Paramagnetism. Oxygen is exceptional is having two unparied electrons in its molecule and
hence shows paramagnetism, i.e. it is weakly attracted by a magnet. Conventionally it was
earlier represented by the following formula :
:O::O: or O=O
in which all the electrons are paired and hence the molecule should have a diamagnetic character.
In order to account for the paramagnetic character of oxygen it is represented by the following
structure
:O:::O:
in which oxygen atoms are joined by one covalent bond and two three electron bonds.
Oxygen
The electronic configuration of oxygen in its ground state is 1s2 2s2 2p4. There are three naturally
occurring isotopes of oxygen, 168 O  99.762%  , 8 O(0.038%) and 8 O(0.200%) . Like hydrogen,
17 18
oxygen exists in the elemental form as a diatomic molecule (O2). Dioxygen (O2) is unique among
diatomic molecules. It contains an even number of electrons (16) but two of them are unpaired.
Dioxygen is, therefore, paramagnetic. Oxygen has two allotropes dioxygen (O2) and trioxygen
(O3), which is called ozone.
Occurrence
Just as hydrogen is the most abundant element in the cosmos, oxygen is the most abundant element
on earth. Oxygen constitutes nearly 50% by weight of the crust of the earth, water bodies and the
atmosphere. In the earth’s crust, oxygen occurs in the combined state, mainly in the form of silicates,
carbonates and oxides of metals. Water consists of 88.8% oxygen by weight. Dioxygen makes up
about 23.2% by weight of the atmosphere.
Preparation
In the laboratory, dioxygen is obtained by the thermal decomposition of oxygen-rich compounds such
as KMnO4 or KClO3. The thermal decomposition of KClO3 requires a temperature of 670-720 K.
The temperature can be lowered to ~420 K by the use of MnO2 as a catalyst :
2KClO3(s)   3O2(g) + 2KCl(s)
heat
MnO2
Another method to prepare dioxygen in the laboratory is by the reaction of water with sodium peroxide:
2Na2O2(s) + 2H2O(l)  O2(g) + 4NaOH(aq)
Electrolysis of water produces both dihydrogen and dioxygen in a pure state. The most economical
method of production of dioxygen on an industrial scale is the fractional distillation of liquid air. In this
method, dinitrogen (b.p. 77K) is boiled away leaving behind dioxygen (b.p.90 K). Production of
dioxygen in the world is more than 100 tonnes per year.
Uses of Dioxygen
One of the major uses of dioxygen is in making steel and in metal fabrication where it functions as an
aid to combustion. Another important use is in the production of oxygen-containing organic chemicals
(e.g., ethylene oxide from ethene). Dioxygen is essential for life support systems (e.g., in hospitals, in
underwater diving). Liquid dioxygen is used as an oxidizer in rockets for space explortaion and
in the launching of satellites. It is used on a large scale for the production of TiO2 and synthesis
gas (CO + H2). Dioxygen is used for sewage treatment, river revival and paper pulp bleaching.

- 19 -
Ozone
In addition to the diatomic molecule, O2, elemental oxygen exists as a triatomic species, O3, known as
ozone. Ozone is a pale blue gas with a characteristic pungent odour. It condenses to a deep blue liquid
(b.p. 161.2 K) and to a violet black solid (m.p. 80.6 K). Ozone is formed when energy is supplied to
dioxygen in the form of UV radiation or silent electric discharge.
3O2(g) 2O3(g); H298 = 142.7 kJ mol–1
The ozone molecule has an angular structure. Both the oxygen-oxygen bonds are of equal
length (128 pm). This distance is intermediate between that of a O-O single bond (148 pm) and
that of a O = O double bond (110 pm). The bonding in ozone is best described as a resonance
hybrid.
In contrast to dioxygen which is paramagnetic, ozone is diamagnetic. Ozone is much more
reactive than dioxygen. It acts as a powerful oxidizing agent with the liberation of dioxygen. The
typical reactions are :
PbS(s) + 4O2(g)  PbSO4(s) + 4O2(g)
2KI(aq)  O3(g) + H2O(l)  2KOH(aq) + I2(aq) + O2(g)
The oxidation of potassium iodide by ozone can be conveniently used for the quantative estimation of
ozone.
Ozone is formed in the upper atmosphere by a photochemical reaction involving dioxygen. Ozone
absorbs radiation strongly in the ultraviolet region of the spectrum between 220-290 nm and this
protects the earth and its inhabitants from the harmful ultraviolet radiation of the sun. Without this
protective layer, more ultraviolet radiation will reach the surface of the earth and cause damage to
plant and animal life.
In recent years, there is world-wide concern about the depletion of the ozone layer in the
stratosphere caused by the presence of chlorofluorocarbons (CFC’s). These volatile compounds
have been used for some years as aerosol propellants and as refrigerants. Chlorofluorocarbons are
long-lived molecules and diffuse into the stratosphere where they are decomposed by ultraviolet
radiation to produce chlorine. The chlorine atoms react with ozone, this causes a decrease in the
concentration of ozone at a rate faster than its formation from O2. Another case of ozone depletion
is release of nitrogen oxides (NOx) into the stratosphere by the supersonic jet aeroplanes. NO
molecule can react with ozone to give O2.
NO(g) + O3(g)  NO2(g) + O2(g)
Three scientists, P.J. Crutzen, M.J. Molina and F.S. Rowland received the 1995 Nobel Prize in
chemistry for their pioneering work in this area. As a result of their work, there is a great awareness
all over the world to find alternatives for CFC’s and to limit the NOx emissions into the stratosphere.
Ozone is used as a disinfectant (for purifying drinking water) and as a bleaching agent. It also finds
use as a chemical reagent in organic chemistry.
Sulphur
Source
It occurs in nature as sulphides of metals (e.g. FeS2, PbS, ZnS) and sulphates (e.g. CaSO4, 2H2O,
MgSO4 7H2O) and native element. Other important source of S are crude oil and natural gas.

Uses of S, Se & Te
Most of the sulphur produced is used for the manufacture of sulphuric acid and other industrially
important sulphur compounds. The most important application of Se is as a photoconductor in
photocopying (xerox) machines, though the major use is as a decolouriser of glass. Tellurium
is mostly used as an additive in metallurgy (manufacture of iron and steel, non-ferrous metals and
alloys). Tellurium and polonium are highly toxic, the latter more so because of its intense radioactivity.
Allotropy
(A) Sulphur
(a) Ortho rhombic, (b) -monoclinic, (c) -monoclinic.
The stable form at room temperature is ortho rhombic sulphur, which transforms to monoclinic sulphur
when heated above 369-K. Both ortho rhombic and monoclinic sulphur are molecular solids; S 8
molecules are packed up to give different crystal structure for the two forms. The S8 ring in both the
forms is puckered and has a crown shape. Chain polymers called catena-Sn are known. Unstable
small molecules, Sn(n = 2-5) exist in liquid sulphur at elevated temperatures and in sulphur vapour. At
1000 K, S2 is the dominant species. Like dioxygen (O2), S2 is paramagnetic.
204 p S 205.7 pm
S m S S S
S 107° S
102.2°
S S
S (b)
S S
(a)
S
(B) Selenium
Selenium exists in eight allotropic forms of which three are red monoclinic forms containing Se8 rings.
The thermodynamically stable form is grey hexagonal ‘metallic’ selenium which consists of polymeric
helical chains. The common form of the element is the amorphous black selenium. Grey selenium is
the only allotrope of selenium which conducts electricity. Tellurium has only one crystalline form with
a chain structure similar to that of grey Se.
Extraction
(1) From Alkali wastes
CaS + H2O + CO2  CaCO3 + H2S
2H2S + O2  Burn
 2H2O + S
(2) From Spent oxides of Coal gas
2FeS3 + 3O2  2Fe2O3 + 6S
(3) From iron pyrites
Distillation
3FeS2 Fe3S4 + 2S
3FeS2 + 5O2  Fe3O4 + 3SO2 + 3S
FeS + CO2  FeO + CO + S

- 21 -
Properties
(1) Tasteless, odourless yellow solid.
(2) Sulphur is oxidised to SO2 by conc. H2SO4.
S + 2H2SO4 (Conc.)  3SO2 + 2H2O
(3) It is oxidised to H2SO4 by conc HNO3
S + 6HNO3 (Conc.)  H2SO4 + 6NO2 + 2H2O
(4) It disproportionates in the presence of NaOH to S2– and S2O32–
4S + 6NaOH  2Na2S + Na2S2O3 + 3H2O
(5) It reacts with metals and non metals to form their sulphides
(a) H2 + S  H2S
(b) Cl2 + 2S  S2Cl2
(c) C + 2S  CS2
(d) 2As + 3S  As2S3
(e) Fe + S  FeS
(f) 2H2O (steam) + 3S (boiling)  2H2S + SO2
(g) K2S + 4S  K2S5
Hydrogen Sulphide (H2S)

Preparation
(1) It is prepared in the laboratory by the action of dilute acids on sulphide e.g.
FeS + H2SO4  FeSO4 + H2S
(2) Sb2S3 + 6HCl  2SbCl3 + 3H2S
Properties
(1) It is a colourless gas with the smell of rotten eggs
(2) H2S  H2 + S
(3) H2S forms two types of salts S2– and HS–
NaOH + H2S  NaHS + H2O
NaSH + NaOH  Na2S + H2O
(4) With metals like Ag, Zn, Sn it forms their sulfide.
(a) 2Ag + H2S  Ag2S + H2
(b) Zn + H2S  ZnS + H2
(c) Sn + H2S  SnS + H2
(5) It precipitates the basic radicals of 2nd group in qualitative analysis
HgCl2 + H2S  HgS + 2HCl
(6) In alkaline medium it precipitates the IVth gorup radials
MCl2 + H2S  MS + 2HCl [N = Ni, Co, Mn and Zn]
(7) It is oxidised by O2 to give S and SO2
2H2S + O2  2H2O + 2S
2H2S + 3O2  2H2O + 2SO2
(8) Reducing properties :- H2S acts a good reducing agent. It reacts as follows
Hence H2S + [O]  H2O + [S]
(a) Fe2(SO4)3 + H2S  2FeSO4 + H2SO4 + S

(b) It decolourizes acidic KMnO4.

2KMnO4 + 3H2SO4 + 5H2S  K2SO4 + 2MnSO4 + 8H2O + 5S
(c) It turns pot. dichromate solutions green
K2Cr2O7 + 4H2SO4 + 3H2S  K2SO4 + Cr2(SO4)3 + 7H2O + 3S
(d) It reacts with SO2 to give S.
SO2 + 2H2S  H2O + 3S
(e) It reduces H2SO3 to sulphur
H2SO3 + 2H2S  3H2O + 3S
(f) It reacts with H2SO4 to give SO2 and S
H2SO4 + H2S  2H2O + SO2 + S
(g) It reduces nitric acid to NO2
2HNO3 + H2S  2H2O + 2NO2 + S
(h) It reduces PbO2 to PbO
PbO2 + H2S  PbO + H2O + S
Sulphur dioxide
Preparation
(1) By action of H2SO4 (Conc.) on copper turning :- When copper is heated with conc H2SO4, SO2
is liberated
Cu + 2H2SO4  CuSO4 + 2H2O + SO2
(2) By reducing H2SO4 :- H2SO4 when heated with Hg C or S then SO2 is liberated
Hg + 2H2SO4  HgSO4 + SO2 + 2H2O
C + 2H2SO4  CO2 + 2SO2 + 2H2O
S + 2H2SO4  3SO2 + 2H2O
(3) By action of sulphuric acid on Na2SO4 or NaHSO3
Na2SO3 + H2SO4  Na2SO4 + H2O + SO2
NaHSO3 + H2SO4  NaHSO4 + H2O + SO2
(4) By heating iron pyrite in air
4FeS2 + 11O2  2Fe2O3 + 8SO2
Properties
(1) Colourless gas with peculiar suffocating odour.
(2) Sulfur dioxide decomposes to SO3 and S.
3SO2  2SO3 + S
(3) SO2 converts Magnesium to MgO.
2Mg + SO2  2MgO + S
(4) SO2 converts potassium to potassium sulphite
4K + 3SO2  K2SO3 + K2S2O3
(5) It reacts with O2 to give SO3
2SO2 + O2 Pt. 2SO3
(6) SO2 reacts with Cl2 to form sulfuryl chloride
SO2 + Cl2  SO2Cl2
(7) In the presence of moisture however it gives H2SO4 and HCl
SO2 + 2H2O + Cl2  H2SO4 + 2HCl

- 23 -
(8) Moist SO2 acts as a bleach

SO2 + 2H2O  H2SO4 + 2H (responsible for bleaching action)
(9) It oxidises Fe to FeO
3Fe + SO2  2FeO + FeS
(10) It oxidises H2S to S
2H2S + SO2  2H2O + 3S
(11) It reacts with PbO2 to give PbSO4
PbO2 + SO2  PbSO4
(12) Sulfur dioxide reduces KMnO4 (acidified)
2KMnO4 + 2H2O + 5SO2  K2SO4 + 2MnSO4 + 2H2SO4
(13) It turns K2Cr2O7 solutions green.
K2Cr2O7 + 3SO2 + H2SO4  K2SO4 + Cr2(SO4)3 + H2O
(14) It reduces Ferric salts to ferrous salts.
2FeCl3 + SO2 + 2H2O  2FeCl2 + H2SO4 + 2HCl
(15) It reacts with H2O2 to give H2SO4
H2O2 + SO2  H2SO4
Silphur Trioxide
Preparation
(1) Sulphur trioxide is obtained by the dehydrations of sulphuric acid.
6H2SO4 + P4O10  4H3PO4 + 6SO3
(2) It can be obtained by the oxidation of sulphur dioxide in the presence of platinum as catalyst.
2SO2 + O2 
Pt.
 2SO3
Properties
(1) Sulphur trioxide decomposes at 1000ºC to form sulphur dioxide and oxygen
2SO3 
1000ºC
 2SO2 + O2
(2) Sulphur trioxide reacts with sulphuric acid to form oleum.
H2SO4 + SO3  H2S2O7
(3) It reacts with HCl to form Chlorosulphuric acid.
HCl + SO3  ClSO2OH
(4) It oxidises HBr to Br2
2HBr + SO3  H2O + SO2 + Br2
(5) It dissolves in water to form sulphuric acid.
H2O + SO3  H2SO4
(6) It reacts with basic oxides to form salts.
Na2O + SO3  Na2SO4
CaO + SO3  CaSO4
Sulphurous acid
Preparation
Sulphurous acid is obtained by dissolving sulphur dioxide in water.
SO2 + H2O  H2SO3

Properties
(1) Dibasic acid :- It is a diabasic acid and hence can form two types of salts bisulphites and sulphites
H2SO3  H+ + HSO3– (Bisulphite)
HSO3–  H+ + SO3–2 (Sulphite)
(2) Reducing properties
(a) In sulphurous acid sulphhur is in +4 oxidation state. It can therefore be oxidised to +6 oxidation
state by stronger oxidising agents like Cl2, KMnO4, K2Cr2O7, KIO3 etc.
2H2SO3 + O2  2H2SO4
(b) H2SO3 + H2O + Cl2  H2SO4 + 2HX
(c) 2FeCl3 + H2SO3 + H2O  2FeCl2 + 2HCl + H2SO4
(d) 2KMnO4 + 5H2SO3  K2SO4 + 2MnSO4 + 3H2O + 2H2SO4
(e) K2Cr2O7 + 3H2SO3 + H2SO4  K2SO4 + Cr2(SO4)3 + 4H2O
(f) 2KIO3 + 5H2SO3  2KHSO4 + 3H2SO4 + I2 + H2O
(3) Oxidising properties :- It can also act as a oxidising agent and can oxidise H2S to sulphur.
H2SO3 + 2H2S  3H2O + 3S
Sulphuric acid
Preparation
(1) Contact Process :- The various steps involved in this process are.
(a) Oxidation
V2O5
2S + 3O2 2SO3 (Heterogeneous catalyst is used)
450º - 600ºC
(b) Conversion to Oleum
SO3 + H2O  H2SO4
H2SO4 + SO3  H2S2O7 (Oleum)
(c) Conversion of Oleum to H2SO4
H2S2O7 + H2O  2H2SO4 (96–98% purity)
(2) Lead chamber process
The various steps involved in this process are given below :
2NO + O2  2NO2
NO2 + SO2 + H2O  H2SO4 + NO (Homogeneous catalyst is used)
2H2SO4 + NO + NO2  2NO+ HSO4– + H2O
High
2NOHSO4 + H2O Temperature
2H2SO4 + NO + NO2
Properties
(1) Colourless oily liquid, good conductor of heat and electricity, extremely corrosive its chemical reactions
are as result of following characteristic
(a) low volatility
(b) strong acidic characters
(c) strong affinity for water
(d) ability to act as an oxidizing agent

- 25 -
(2) It decomposes on heating to form SO3 and H2O

H2SO4  H2O + SO3
(3) It forms two types of salts. Sulphates and bisulphates
(a) H2SO4  H+ + HSO4–
HSO4–  H+ + SO4–2
(b) NaOH + H2SO4  NaHSO4 + H2O
NaHSO4 + NaOH  Na2SO4 + H2O
(4) Copper reacts with conc. H2SO4 to forms SO2
Cu + 2H2SO4  CuSO4 + H2O + SO2
(5) It precipitates heavier metals as sulphates
Pb (NO3)2 + H2SO4  PbSO4 + 2HNO3
BaCl2 + H2SO4  BaSO4 + 2HCl
SrCl2 + H2SO4  SrSO4 + 2HCl
(6) As dehydrating reagent : H2SO4 has great affinity for water and acts as a good dehydrating
agent. Concentrated acid must be added slowly into water with constant stirring.
(a) C12H22O11 + H2SO4  12C + [H2SO4.11H2O]
(b) H2C2O4 + H2SO4  CO + CO2 + [H2SO4.H2O]
(c) HCOOH + H2SO4  CO + [H2SO4.H2O]
(d) 2C2H5OH + H2SO4  C2H5OC2H5 + [H2SO4.H2O]
C2H5OH + H2SO4  C2H4 + [H2SO4.H2O]
(7) As oxidising agent
(a) It oxidises carbon to carbon dioxide
C + 2H2SO4  CO2 + 2SO2 + 2H2O
(b) It oxidises sulfur to sulfur dioxide
S + 2H2SO4  3SO2 + 2H2O
(c) It oxidises KI to I2 and KBr to Br2
KI + H2SO4  KHSO4 + HI
2HI + H2SO4  2H2O + SO2 + I2
2HBr + H2SO4  2H2O + SO2 + Br2
(d) It oxidises S–2 to S
H2S + H2SO4  2H2O + SO2 + S
(8) Displacement reactions :- It is less volatile acid hence displaces more volatile acids (such as HCl,
HNO3, H2CO3, H3PO4, H2C2O4, H2S etc.) from their metal salts.
(a) FeS + H2SO4  FeSO4 + H2S
(b) CaC2O4 + H2SO4  CaSO4 + H2C2O4
(c) Ca3 (PO4)2 + 3H2SO4  3CaSO4 + H3PO4
(d) Na2 CO3 + H2SO4  Na2SO4 + H2O + CO2
(e) 2NaNO3 + H2SO4  Na2SO4 + 2HNO3
(f) 2NaCl + H2SO4  Na2SO4 + 2HCl
(9) Other reactions : - There are many special reaction given by sulphuric acid which is given as below
(a) It sulphonates benzene to benzene sulphonic acid
C6H6 + H2SO4  C6H5SO3H + H2O

(b) PCl5 halogenates H2SO to ClSO2Cl

PCl5 + H2SO4  ClSO2.OH + PCl3 + HCl
ClSO2OH + PCl5  ClSO2Cl + POCl3 + HCl
(c) It decomposes potassium ferrocyanide to K 2SO4, FeSO4 and CO
K4[Fe(CN)6] + 6H2SO4 + 6H2O  2K2SO4 + FeSO4 + 3(NH4)2 SO4 + 6CO
(d) KClO3 gives HClO4 and ClO2 on reaction with H2SO4
3KClO3 + 3H2SO4  3KHSO4 + HClO4 + 2ClO2 + H2O
O
||
O  S  O  Na 
Sodium Thiosulphate |
S Na 
(1) Sodium thiosulphate is obtained by boiling of Na2SO3 with S or with Na2S + I2.
Na2SO3 + S  Na2S2O3
Na2SO3 + Na2S + I2  Na2S2O3 + 2NaI
(2) When sodium hydrogen sulphide is reacted with sodium hydrogen sulphite, sodium thiosulphate is
obtained.
2NaHS + 4NaHSO3  3Na2S2O3 + 3H2O
(3) When sodium carbonate is heated with SO2 then Na2SO3 is formed due to the displacement of CO2
by SO2. Na2SO3 obtained when heated with sulphur gives Na2S2O3.
Na2CO3 + SO2  Na2SO3 + CO2
Na2SO3 + S  Na2S2O3
Properties
(1) Colourless crystalline solid.
(2) Sodium thiosulphate on heating decomposes to sodium polysulphide and sodium sulphate.
Above
4Na2S2O3 Na2S5 + 3Na2SO4
220ºC
(3) It is reduced to sulphur when reacted which HCl.
Na2S2O3 + 2HCl  2NaCl + H2O + SO2 + S
(I) GENERAL CHARACTERISTICS OF HALOGENS

1. Position of Halogens in the Periodic Table. The halogen group comprises the elements fluorine,
chlorine, bromine, iodine and the artifically produced astatine (atomic number 85). They constitute
group VIIA (or group 17) of the periodic table (chlorides, bromides and iodides) in sea water. Their
inclusion in the same group of the periodic table is justified by the fact that they show very close
similarities and there is a regular gradation in their both physical and chemical properties as
discussed below :
(1) Electronic Configuration All of these elements have seven electrons in their outer shell, the
electronic configuration of the valence shell in the ground state being ns 2np5 as gien in the
following table below:

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Table
Element Symbol Electronic Configuration
Fluorine F [He] 2s22p5
Chlorine Cl [Ne]3s23p5
Bromine Br [Ar]3d104s24p5
Iodine I [Kr]4d105s25p5
Astatine At [Xe] 4f145d106s26p5
(2) Oxidation States. The oxidation state which may be exhibited by chlorine, bromine and iodine
are –1, +1, +3, +5 and +7. From their electronic configurations in the ground state and various
excited states we find that 1, 3, 5 or 7 electrons are available for bonding.
Electronic Configurations of the halogen atoms in the ground and excited states are :
ns np
Ground state
ns np nd
st
1 exited state
+3 oxidation state
2nd exited state

+5 oxidation state
3rd exited state

+7 oxidation state
In the second excited state, the main tendency of the halogen atom is to complete its octet by either
(a) formation of a covalent bond, or (b) formation of the negative ion X –. The ground state refers
to oxidation states exhibited as –1 or +1, depending upon whether the element combining with
halogen is less electronegative or more electronegative than the halogen. Higher oxidation state are
exhibited in the excited states.
The fluorine atom has no d orbitals in its valence shell and cannot, therefore, have any excited
states. Hence it cannot have any of higher oxidation states. It being the most electronegative element
known the only oxidation state exhibited by fluorine is –1.
The higher oxidation states of Cl, Br and I are realized mainly when the halogen atom is in
combination with the small and highly electronegative fluorine and oxygen atoms, e.g., in inter-
halogen compounds and in oxides or oxy-acids.
In the case of bromine the penultimate shell (3s2 3p6 3d10) being weekly screening, the energy
requried to promote an electrons from the s orbital to the vacant d orbital is markedly higher than
in the case of chlorine. The explains the inability of bromine to attain the +7 oxidation state.
The oxidation state of +4 and +6 occur in the oxides and oxyacids of chlorine and bromine.
This could be explained on the basis that chlorine can form effective multiple bonds with oxygen.
(3) Physical State. Halogens in the uncombined state exist as diatomic covalent molecules and
only week van der Walls forces which explain the volatile nature of these elements. Their
melting points and boiling points increase while volatility decreases with increase in atomic
number. The densitites increase from fluorine to iodine.
Fluorine < Chlorine < Bromine < Iodine F2 Cl2 Br2 I2
Gas Gas Fuming Liquid Volatile Solid

(4) Size. Size of the atoms and ions increases gradually from fluorine to iodine as seen from Table.
F Cl Br I
Covalent Radii (PM) 72 99 114 133
(5) Ionization Energy. The ionization energies of halogens are all very high, which indicates that
there is little tendency to lose electrons. The ionization energy decreases gradually from fluorine
to iodine. The ionization energy for fluorine is the highest since the electrons are firmly held
in its small atom. Iodine atom being very large its ionization energy is the lowest.
IE (KJ/mol) 1681 1256 1143 1009
E.A. (KJ/mol) 333 349 325 296
(6) Colour. Halogens are all coloured. This is due to absorption of visible light their by molecules
resulting in the excitation of outer electrons to higher energy levels. The excitation energy
requried by the small fluorine atom is large and that required by the large iodine atom is less.
The small F2 molecules absorb high-energy violet radiation and appear yellow whereas large
I2 molecules absrorb low-energy yellow and green radiations and appear violet in colour.
Similarly we can account for greenish yellow colour of chlorine and red colour of bromine.
(7) Bond Energy. The halogens for diatomic molecules. The bond energy in a fluorine molecule
is very low, about 159 kJ mol–1. This is due to repulsion between non-bonding electrons. In Cl2,
molecules there is a possibility of multiple bonding involving d orbitals. This accounts for the
highest bond energiy of Cl2. The B.E. order is Cl2 > Br2 > F2 > I2.
(8) Electronegativity. The electronegativity of the halogens is very high. Fluorine has the highest
electronegativity (=4). The electronegativity decreases gradually from fluorine to iodine
Electronegativity F = 4.0 Cl = 3.0 Br = 2.8 I = 2.5.
(9) Electron affinity. The electron affinity order follows Cl > F > Br > I as given in table
(10)Oxidizing Power. An important feature of the halogens is the oxidizing property. Though
electron affinity (i.e., tendency of an atom to gain electron) of chlorine is maximum fluorine
to iodine. This is because the oxidizing power depends on several energy terms (shown in a
Born haber cycle) and the sum of these values (energy evolved) decreases from fluorine to
iodine.
1 X (g) + e– X–caq
2 2
Born Haber cycle
X(g) X–(g)
Fluorine and chlorine being gases, heats of fusion and evaporation are omitted for them. For liquid
bromine, heat of fusion is not considered and heat of evaporation corresponds to kJ mol –1. for
Br2 (l) Br2(g). For iodine, heats of fusion and evaporation are kJ mol–1 for I2 (l) and + kJ mole–1
for I2  I2 (g), respectively. Heats of fusion, evaporation and dissociation are positive (energy
absorbed while values for electrons affinity and heat of hydration are negative (energy evolved).
Heat of dissociation is very low and heat of hydration is very high for fluorine. Using the Born-
Haber cycle and summing up all the energy terms enthalpy values (total energy evovled) follow the
order :
F > Cl > Br > I

- 29 -
For F, Cl, Br, I, the sum of ethalpy value energy evolved X2 X– aq. work out to be 760, 605,
560 and 409 kJ mol–1. It expalins oxidizing powers as deduced above are also evident from relative
1
redox potentials X + e– X– for F, Cl, Br and I respectively are 2.87 V. 1.26 V, 1.09 V and 0.54 V..
2 2
The relative oxidizing powers of halogens are well illustrated by their reactions with water. The
strongest oxidizing agent fluorine oxidizes water to oxygen with large evolution of heat.
F2(g) + H2O(l)  2H+(aq) + 2F–(aq) + O2(g) ; G = –795 kJ mol–1.

Chlorine and bromine react with water to form hydrogen halide and hypohalous acid ; no oxygen
is liberated.
X 2 (g) + H 2 O(l)  HX(aq) + HOX(aq)
(where H = Cl or Br)
The reaction of iodine with water is endothermic.
In means the energy is needed for the forward reaction to occur. In fact, the reverse reaction takes
place and oxygenoxidizes iodide ion to iodine. Hence the oxidising power is as follows
F2 > Cl2 > Br2 > I2
(11) Reducing Power of the Halogens Acids. Oxidizing power of the halogen decreases from
flurine to iodine. The converse of this trend of oxidizing properties among the halogens is seen
in the halogen acids which are reducing agents. The reducing power increases from H2F2
(hydrofluoric acid) to HI (hydriodic acid). Thus H2F2 is very stable and is not oxidized. HCl
is oxidized only by MnO2, KMnO4. etc. (strong oxidizing agents). HBr and Hl are strong
reducing agents and are oxidized readily.
(12) Reactivity. The halogens are very reactive elements and react with metals and many non-
metals. Fluorine is the most reactive and chlorine oxidize elements further than bromine and
iodine ; for example in their compounds with phosphorus and sulphur,
PBr3 ; PCl5 ; SBr2 ; SCl2 and SF6
chlorine and fluorine bring out higher valences. The general order of reactivity of halogens is
F2 > Cl2 > Br2 > I2
The great reactivity of fluorine is due to high electronegativity, small size of its atom, extremely high
oxidizing power and low energy of the F–F bond. Due to the high electronegativity it forms very
strong bonds with other elements. Highly electropositive alkali metals and alkaline earth metals burn
spontaneously in fluorine at room temperature forming fluorides, e.g., NaF and CaF2.
(13)Affinity for Hydrogen. They all combine with hydrogen to give halogen acids but their affinity
for hydrogen decreases from fluorine to iodine. Fluorine combines with it even in cold and dark,
chlorine combines is sunlight, bromine does so only on heating while iodine combines only when
heated with it is presence of a catalyst.

Fluorine has such a high affinity for hydrogen that is explodes or reacts very vigorously with
hydrogen compounds like water and hydrocarbons even in the dark. Chlorine decomposes water
in sunlight, Bromine decomposes water in sunlight but very slowly. Iodine does not decompose water
at all.
(1) Acid strength of halogen acids. HCl, HBr and HI are fully ionized in aqueous solutions and
are thus strong acid.s Ionization constant of hydrofluoric acid is very small. It is, therfore, a
weak acid. The weakly acidic nature of hydrofluoric acid is largely due to very strong H–F
bond.
(2) High melting and boiling points of hydrofluoric acid. The melting and boiling points of various
acids are :
H2F2 HCl HBr HI
Melting points 190 K 162 K 187 K 222.2 K
Boiling points 292.5 K 189 K 206 K 237.5 K
Anomalously high melting and boiling points of hydrogen fluoride are due to the association of its
molecules through hydrogen bonding.
(13)Reaction with Halides. Fluorine decomposes chlorides, bromides and iodides liberating
corresponding halogens. Chlorine decomposes bromides and iodides only. Bromine decomposes
only iodides while iodine decomposes none.
OXYACIDS OF HALOGENS
Fluorine does not form any oxyacid because it is more electronegative than oxygen. Other halogens form
four series of oxyacids with formulae HXO, HXO2, HXO3 and HXO4. These are respectively known as
hypohalous, halous, halic and perhalic acids or halic (I), halic (III), halic (V) and halic (VII). The list of these
acids is given in the following table. Some of these acids are quite unstable and are known only in solutions or
as their salts.
Oxidation
state of Chlorine Bromine Iodine Name of acid Name of salt
halogens
+1 HCIO HBrO HIO Hypohalous Hypohalite XO–
+3 HCIO 2 – – Halous Halite XO2–
+5 HCIO 3 HBrO3 HIO 3 Halic Halate XO3–
+7 HCIO 4 HBrO4 HIO 4 Perhalic Perhalate XO4–
H 5 IO 6

- 31 -
O O
O
H Cl H Cl
(a) (b)
H H
O O
Cl Cl
O O O
O O
(c) (d)
The acidic strengths order is in HXO4 > HXO3 > HXO2 > HXO for different halogens in same
oxidation state HClO4 > HBrO4 > HIO4
Some important general trends in oxyacids of halogens.
1. In oxyacids, hydrogen is present as –OH group.

2. All the hypohalous acids (HXO) are unstable and readily form HXO 3. Among these, the relative
order of stability is
HClO > HBrO > HIO
3. In halic acids (HXO3), iodic acid is the most stable.
4. Thermal stability. The thermal stability of both the acids and their salts increases with the
increasing oxidation state of the halogen or with the increase in the number of oxygen atom, i.e.,
stability of the oxyhalide anion increases from ClO–, ClO2–, ClO3– to ClO4–. This is due to the fact
that with the increasing number of oxygen atoms in the series, the number of electrons involved
in forming s and p bonds increases. Thus in the most stable perchlorate ion, ClO4–, all the valence
orbitals and electrons of chlorine atom are involved in the formation of bonds.
The stability of perchlorate ion, ClO4– may also be said due to greater multiplicity of the Cl–O bond.
O O O O O
O O
.. Cl Cl
Cl: :Cl :
O O O
Dumb-bell Bent-chain Pyramid Tetrahedron
Hypochtorite Chlorite Chlorate Perchlorate

5. Oxidising power. As the stability of the anions increases from ClO– to ClO4–, the oxidising power
decreases from ClO– to ClO4–. Thus, under usual conditions, hypochlorite are the strongest oxidising
agents.
6. Relative acidity. The acidic character of oxyacids increases with increase in oxidation number. For
example, acidity of oxyacids of chlorine decreases in the following order.
HClO4 > HClO3 > HClO2 > HClO (Relative acidic character)
Explanation. It is a well-known fact that the strength of an acid is related to the strength of its conjugate
base, i.e. stronger the acid, the weaker will be its conjugate base and vice versa. In other words, the strength
of the conjugate bases of the above four acids follows the following order.
ClO4– < ClO3– < ClO2– < ClO– (Relative basic character)
Thus ClO4 is the weakest base and hence, HClO4 (conjugate acid of ClO4–) is the strongest acid. The
–
weak basic character of ClO4– in turn is due to maximum possibility of delocalisation of negative charge by
extended p  – d  bonding. The ClO4– anion has a maximum number of oxygen atoms which can participate
in extension of the  bonds. Hence the charge on the ClO4– ion is delocalised which greatly stabilizes the ion
and thus decreases its tendency to accept a proton.
Alternatively, the relative acidity of these acids can be explained on the basis of more stability of the Cl–
O bond with the increase in oxidation number of the chlorine, i.e. the strength of Cl – O bond in the oxyanions
follows the order.
ClO4– > ClO3– > ClO2– > ClO– (Relative stability of the Cl – O bonds)
Thus stronger the Cl – O bond of an anion, weaker is the O – H bond of the conjugate acid and hence
stronger is the acid. Relative acidity of oxyacids having different halogen but the same oxidation state
decreases with the increase in atomic number. Thus, the oxyacids of chlorine are more acidic than the
corresponding oxyacids of bromine which in turn are more acidic than that of iodine. This is due to the fact
that as the atomic number of halogen increases, the electronegativity decreases but size increases. Thus the
tendency of the halogen to draw electrons from X O – H bond due to inductive effect decreases from
Cl to I with the result removal of proton from the O – H group also decreases. Consequently, the oxyacids
of iodine are the weakest acids among the corresponding oxyacids of halogens.
Basic (Cationic) Properties of Iodine

As in other groups of p-block elements, the basic or cationic properties of halogens increase on descending
the group. Thus, among halogens, fluorine is the most electronegative element and has no basic properties,
i.e., it has no tendency to form positive ions. Iodine among halogens being the least electronegative (most
electropositive or metallic), shows maximum basic character which is evident by the existence of positive
iodine. This is in accordance with the ionisation energy of iodine; ionisation energy of iodine is lowest among
halogens; actually the IE1 of iodine is neary equal to that of mercury (I = 10.44 eV ; Hg = 10.43 eV). So the
properties of iodine indicate that it is capable of forming positive ions, i.e. it shows basic properties. Iodine
may exist as unipositive ion (I+) and tripositive ion (I3+); evidences in favour of both are available.
Evidences for unipositive ion, I+.

(i) Molten iodine monochloride conducts electricity. On electrolysis, iodine is liberated at the cathode,
and both iodine and chlorine at the anode. Liberation of iodine at the cathode confirms the positive
character of iodine. These observations indicate that ICl ionises in the following way.
2ICl I+ + ICl2–
At cathode: 2I+ + 2e– I2 ; At anode: 2ICl2– I2 + 2Cl2 + 2e–

- 33 -
(ii) Molten iodine cyanide behaves in a similar way, but in pyridine it gives iodine only at the cathode
which suggests the following simple type of ionisation.
ICN I+ + CN–
(iii) Iodine monochloride iodinates acetanilide to 4-iodoacetanilide and salicylic acid to 3, 5-di-iodosalicylic
acid. This suggests that the electrophile, iodonium ion (I+) must have been formed during the
substitution reaction.
(iv) When iodine dissolved in an inert solvent is passed down through a cationic ion exchange resin iodine
is retained on the resin.
H+ Resin + I2 I+ Resin + HI
The amount of positive iodine absorbed by resin can be estimated by elution with potassium iodide.
I+ Resin + KI K+ Resin + I2
Evidence for tripositive ion, I3+.
(i) Molten iodine trichloride, ICI3 conducts electricity liberating iodine and chlorine at both electrodes.
This explains following type of ionisation.
2ICl 3 ICl2+ + ICl4–
(ii) Various ionic compounds containing I3+ have been obtained. For example, iodine triacetate is obtained
by the oxidation of iodine with fuming nitric acid in presence of acetic anhydride.
Recently, evidence has also been obtained for the existence of cationic bromine and chlorine which are
stable in highly acidic medium.
Interhalogen Compounds or Interhalogens

Each halogen can combine with other halogens to form several compounds amongst themselves. These are
known as interhalogens or interhalogen compounds. The main reasons for the formation of these compounds
is the large electronegativity and size differences among the halogens. Thus fluorine, the most electronegative
element and the smallest halogen, forms the maximum number of interhalogens (halogen fluorides). Interhalogen
compound having maximum number of halogen atoms is IF7. There are four types of interhalogen compounds.
The less electronegative halogen A is always written first.
Type Interhalogen compound Shape
AB CIF, BrF, BrCl Linear
AB 3 CIF3, BrF3, IF3, ICl3 T shaped, distorted trigonal pyramidal due to 2 lone pair
of electrons (sp3d )
AB 5 CIF5, BrF5 Distorted octahedral, square pyramidal due to 1 lone

pair of electrons (sp3d 2)
AB 7 IF 7 Pentagonal bipyramidal (sp3d3)
Pseudohalides and Pseudohalogens

Pseudohalides are the uni-negative groups which show certain characteristics of halide ions. Similarly,
pseudohalogens are the covalent dimers of the pseudohalogenoids (cf. halogens, X2 are the dimers of
halides ions, X–). So far, only four pseudohalogens have been isolated. The most important pseudohalide is
CN– and thus its corresponding pseudohalogen is cyanogen (CN)2. Other pseudohalide ions are SeCN–
(selenocyanate), SCN– (thiocyanate), N3– (azide), OCN– (cyanate), ONC– (isocyanate).

Similarity between fluorine and oxygen.

(1) Fluorides and oxides resemble each other closely. e.g., in solubility, volatility and fusibility. For
example, hydrogen fluride (H2F2) and water (H2O) resemble in the followign aspects :
(a) Both have associated molecules as a result of hydrogen bonding.
(b) Both have anomalously high boiling points.
(c) Both have the same range of fluidity.
(2) Heats of formation of many fluorides and corresponding oxides are similar.
(3) Elements show higher valences in both fluorides and oxide. For example, valence of sulphur
in SO2 and SF6 is 6 while in SCl2 or SBr it is only 2.
(4) Both fluorine and oxygen combine directly with carbon while no other halogen combines with
carbon directly.
Similarity of fluorine and oxygen may be attributed to the following factors :

(i) Their atomic and ionic radii are closely similar.
(ii) The atoms of both elements are restricted to an octet of electrons in their valence shells.
(iii) Both of them are highly electronegative elements.
Flourine
Preparation
(1) Moissan’s Method :- Here F2 is prepared by the electrolysis of potassium hydrogen fluoride in
anhydrous HF and during this process F2 is liberated at anode and H2 at cathode.
KHF2  2HF + 2K + F2
2K + 2HF  2KF + H2
Electrolyte  Anhydrous liquid HF + 20% KHF2
Electrode  Pt - Ir alloy
Vessel  Pt – Ir alloy kept immersed in methyl chloride (–23ºC)
(2) Dennis method -
Electrolyte  Pure and dry KHF2
Electrodes  Graphite rod
Vessel  Copper Vessel
Reactions
2KHF2  2HF + 2K + F2 (anode)
2K + 2HF  2KF + H2 (cathode)
(3) Chemical method
K2MnF6 + 2SbF5  2KSbF6 + MnF6 + 1/2 F2
Properties
(1) Fluorine is a very storng oxidising agent. It oxidises metals and non-metals.
(a) 2Na + F2  2NaF
(b) Ca + F  CaF2
(c) Pt + 2F2  PtF4
(d) 2B + 3F2  2BF3
(e) C + 2F2  CF4
(f) P4 + 10F2  4PF5

- 35 -
(g) S + 3F2  SF6

(h) H2 + F2  2HF
(2) The reduction potential of F2 is very high which makes it displace other non metals
(a) 2H2O + 2F2  4HF + O2
3H2O + 3F2  6HF + O3
(b) 2HCl + F2  2HF + Cl2
(c) H2S + 4F2  2HF + SF6
(d) 2NH3 + 3F2  6HF + N2
(e) CH4 + 2F2  CF4 + 4HF
(f) It either displaces oxygen or oxidises it to OF2
2NaOH + 2F2  2NaF + OF2 + H2O
(dil)
(g) 4NaOH + 2F2  4NaF + O2 + 2H2O
(Conc.)
(h) Since it has ability to displace oxygen form H2O so in aqueous solutions it can oxidise KClO3
or HIO3.
H2O + F2  2HF + [O]
KClO3 + O  KClO4
HIO3 + O  HIO4
Chlorine
Preparaion
(1) Cl2 has a very strong reduction potential. So it can not be displaced by weak oxidising agents but
with strong oxidising agents it is displaced from HCl as Cl 2.
(a) By action of HCl on MnO2, PbO2 and Pb3O4
MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O
PbO2 + 4HCl  PbCl2 + 2H2O + Cl2
Pb3O4 + 8HCl  3PbCl2 + 4H2O + Cl2
(b) By action of HCl on KMnO4
2KMnO4 + 16HCl  2KCl + 2MnCl2 + 8H2O + 5Cl2
(c) By action of HCl on K2Cr2O7
K2Cr2O7 + 14HCl  2KCl + 2CrCl3 + H2O + Cl2
(d) By action of HCl on CaOCl2
CaOCl2 + 2HCl  CaCl2 + H2O + Cl2
(2) From chlorides on heating or treatment with oxidising agent
PtCl4 480ºC Pt + 2Cl2
200ºC
2AuCl3 2Au + 3Cl2
450ºC
2CuCl2 2CuCl + Cl2
2NaCl + MnO2 + 3H2SO4  2NaHSO4 + MnSO4 + 2H2O + Cl2
(3) Deacon’s Process
Cu2Cl2
4HCl + O2 2H2O + 2Cl2
450ºC

Properties
(1) Greenish yellow gas with strong suffocating odour
(2) Cl2 acts as a good oxidising agent in aqueous solutions.
Cl2 + H2O  HCl + HClO
(3) Cl2 oxidises sodium sulphite to sodium sulphate.
Na2SO3 + H2O + Cl2  Na2SO4 + 2HCl
(4) It oxidises SO2 to H2SO4
SO2 + 2H2O + Cl2  H2SO4 + 2HCl
(5) It oxidises ferrous salts to ferric salts.
(a) 2FeCl2 + Cl2  2FeCl3
(b) 2FeSO4 + H2SO4 + Cl2  Fe2(SO4)3 + 2HCl
(6) H2S is oxidised to sulphur by Cl2 in aqueous medium.
H2S + Cl2  2HCl + S
(7) H2S is oxidised to sulphur by Cl2 in aqueous medium.
H2S + Cl2  2HCl + S
(8) It oxidises I– to I2 and Cl– to Cl2
(a) 2Kl + Cl2  2KCl + I2
(b) 2KBr + Cl2  2KCl + Br2
(9) It reacts with metals and non-metals to form chlorides (Ionic chlorides with metals and covalent
chlorides with non-metals)
(a) 2Na + Cl2  2NaCl (Ionic)
(b) 2P + 3Cl2  2PCl3 (Covalent)
(c) 2P + 5Cl2  2PCl5 (Covalent)
(10) It reacts with SO2 to form sulfuryl chloride.
SO2 + Cl2  SO2 Cl2
(11) It reacts with carbon monoxide to form phosgene.
CO + Cl2  COCl2
(12) It reacts with NH3 when passed in limited supply to form N2 and Ammonium chloride.
(a) 8NH3 + 3Cl2  N2 + 6NH4Cl
(b) When passed in excess it reacts with NH3 to form Nitrogen thrichloride.
NH3 + 3Cl2  NCl3 + 3HCl
(13) It reacts with calcium hydroxide to form beaching powder
Ca(OH)2 + Cl2  CaOCl2 + H2O
(14) With NaOH in cold dilute conditions it disproportionates to sodium chloride and sodium hypochlorite.
(a) Cl2 + 2NaOH  NaClO + H2O + NaCl
(Cold and dilute)
(b) With hot concentrated sodium hydroxide is disproporionates to form sodium chloride and sodium
chlorate.
3Cl2 + 6NaOH  5NaCl + NaClO3 + 3H2O
(Hot and concentration)

- 37 -
Other Reactions
C2H4 + Cl2 h.v. C2H4Cl2
C2H6 + Cl2 h.v. C2H5Cl + HCl
Red p.
CH3COOH + Cl2 CH2ClCOOH + HCl (Hell volhard Zelinsky Reaction)

Bromine
Preparation
(1) From carnallite - Carnallite (KCl MgCl2.6H2O) contains a small amount of potassium and magnesium
bromide. The mother liquor obtained after separation of crystals of KCl and MgCl 2 called bittern is
treated with Cl2.
MgBr2 + Cl2  MgCl2 + Br2
(2) From sea water - Sea water contins about 0.006% of Br2. It is separated by passing Cl2 through the
water.
MgBr2 + Cl2  MgCl2 + Br2
Liberated Br2 is passed through Na2CO3
3Na2CO3 + 3Br2  5NaBr + NaBrO3 + 3CO2
This on acidification liberates bromine.
5NaBr + NaBrO3 + 6HCl  6NaCl + 3Br2 + 3H2O.
Properties
(1) It is dark red mobile liquid.
(2) Its reaction are similar to chlorine however reactivity is low.
(3) It reacts with NH3 to form nitrogen gas
8NH3 + 3Br2  N2 + 6NH4Br.
Iodine
Preparation
(1) By reaction of iodine with chlorine
2KI + Cl2  2KCl + I2
2KI + MnO2 + 3H2SO4  2KHSO4 + MnSO4 + 2H2O + I2
(2) Form sea weeds
2NaI + MnO2 + 3H2SO4  2NaHSO4 + MnSO4 + 2H2O + I2
(3) From caliche - Caliche is crude chile saltpetere it contains small amount of NaHSO3.
2NaIO3 + 5NaHSO3  2Na2SO4 + 2NaHSO4 + H2O + I2
Properties
(1) Greyish black solid with metallic lustre
(2) It reacts with NH3 to give NI3.NH3.
NI3.NH3 is unstable and decomposes readily to form N2 and HI
2NH3 + 3I2  NI3.NH3 + 3HI
(3) It reacts with cold, dilute NaOH to form sodium iodide and sodium hypoiodite.
(a) NaOH + I2  NaI + NaOI
(Cold and dil)

(b) It reacts with hot and conc NaOH to give NaI and NaIO3.
6NaOH + 3I2  5NaI + NaIO3 + 3H2O
(Hot and conc.)
(4) It reacts with sodium thiosulphate to sodium tetrathionate.
2Na2S2O3 + I2  Na2S4O6 + 2NaI
(5) Because of low reduction potential it is readily oxidised by KClO 3 to KIO3.
2KClO3 + I2  2KIO3 + Cl2
(6) Nitric acid oxidises Iodine to HIO3.
10HNO3 + I2  2HIO3 + 10NO2 + 4H2O
(7) Iodine dissolves in KI where as Cl2 and Br2 do not.
KI + I2  KI3
(8) Iodine reacts with starch to form a complex which is blue in colours.
I2 + Starch  Starch – iodine complex
(Deep blue in colour)
Hydrofluoric acid
Preparation
(1) From Fluorspar :- When Calcium fluoride reacts with sulphuric acid it gives Hydrogen fluoride.
CaF2 + H2SO4  CaSO4 + 2HF
(2) From Fremy’s Salt
Pt – Cu retort
KHF2 KF + HF
Properties
(1) Liquid at room temperature
(2) Hydrogen fluoride reacts with glass hence cannot be stored in glass bottle.
(a) SiO2 + 4HF  SiF4 + 2H2O
(b) SiF4 + H2F2  H2SIF6
(3) Sodium silicate reacts with HF to form NaF and SiF4.
Na2SiO3 + 6HF  2NaF + SiF4 + 3H2O
Calcium silicate reacts with H2F2 to form calcium fluorosilicate.
CaSiO3 + 3H2F2  CaSiF6 + 3H2O
Halogen acids HCl, HBr and HI

Preparation
(1) By combination of elements
H2 + Cl2  2HCl
(2) From Chlorides
Chlorides on treatment with H2SO4 give HCl
NaCl + H2SO4  Na2SO4 + 2HCl
[HBr and HI can not be obtained by this method because they will reduce H 2SO4 to SO2]
2HBr + H2SO4  SO2 + Br2 + 2H2O

- 39 -
2HI + H2SO4  SO2 + I2 + 2H2O

Hence H3PO4 is used in the place of H2SO4
2KBr + H3PO4  K2HPO4 + 2HBr
2KI + H3PO4  K2HPO4 + 2HI
Properties
(1) All the halogen acids are colourless gases with pungent odours.
(2) HBr and HI reat with Cl2
2HBr + Cl2  2HCl + Br2
2HI + Cl2  2HCl + I2
(3) Reaction with NH3 [HCl, HBr and HI being acidic react with NH3 to form their Ammonium salts)
NH3 + HCl  NH4Cl
NH3 + HBr  NH4Br
NH3 + HI  NH4I
(4) Reaction with MnO2 [HCl, HBr and HI are oxidised to Cl2, Br2 and I2 respectively when reacted
with MnO2)
MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O
MnO2 + 4HBr  MnBr2 + 2H2O
MnO2 + 4HI  MnI2 + I2 + 2H2O
(5) Reaction with CuSO4 - HCl and HBr do not react
2CuSO4 + 4HI  CuI2 + I2 + 2H2SO4
(6) Reaction with HgCl2
HgCl2 + 2HI  HgI2 + 2HCl
(7) Reaction with H2SO4 [HBr and HI are oxidised to Br2 and I2 respectively by H2SO4]
2HBr + H2SO4  SO2 + 2H2O + Br2
2HI + H2SO4  SO2 + 2H2O + I2
Bleaching Powder
Preparation
(1) In Hasen-Clever Plant
Ca(OH)2 + Cl2  CaOCl2 + H2O
Properties
(1) It is yellowish white solid having chlorine like smell
(2) Bleaching powder decomposes to form O2
CoCl2
2CaOCl2 2CaCl2 + O2

(3) When reacted with H2O to liberates Cl2.
CaOCl2 + H2O  Ca(OH)2 + Cl2

(4) Bleaching powder is decomposed to Cl2 by dilute H2SO4.
CaOCl2 + H2SO4  CaSO4 + H2O + Cl2
(5) It reacts with carbondioxide to form calcium carbonate and Cl 2.
CaOCl2 + CO2  CaCO3 + Cl2
(6) The chlorine liberated in above reaction can be used to oxidises I– to I2 thereby liberating I2.This I2
can be estimated by Na2S2O3 thus we can measure the available chlorine in bleaching powder.
2KI + Cl2  2KCl + I2
(7) Reaction with ethyl alcohol and acetone
The chlorine liberated from bleaching powder may be used to convert C2H5OH and CH3CHO to
chloroform.
CaOCl2 + H2O  Ca(OH)2 + Cl2
CH3CH2OH + Cl2  CH3CHO + 2HCl
CH3CHO + 3Cl2  CCl3 CHO + 3HCl
2CCl3.CHO + Ca(OH)2  (HCOO)2 Ca + CHCl3
CH3COCH3 + Cl2  CCl3COCH3 + 3HCl
CCl3COCH3 + Ca(OH)2  (CH3COO)2 Ca + 2HCl3.
Noble Gases
Group 18 of the periodic table consists of six elements – helium, neon, argon, krypton, xenon and radon
which are collectively known as the Noble Gases.
All the noble gases except radon occur in the atmosphere. Their total abundance in dry air is ~1%
by volume of which argon is the major cmponent. Neon, argon, krypton and xenon are obtained as by-
products of liquefication of air and separation of its constituents by fractional distillation. The main commercial
source of helium is natural gas. Helium is the second most abundant element in the universe (23%
compared to 76% hydrogen) although its terrestrial abundance is very low. Radon is obtained as the
decay product of 226Ra.
226
88 Ra  86
222
Rn  24 He
Noble gas compounds proved elusive for many years. The real chemistry of noble gases began in 1962
with the isolation of an orange yellow solid by Neil Bartlett from the reaction of xenon with PtF 6. Bartlett
had noticed that PtF6 reacts with oxygen to form O2+[PtF6]– and since the ionization enthalpies of O2 and
Xe are close to each other [Xe 1170; O2 1175 kJ mol–1], he reasoned that PtF6 would react with xenon to
form Xe+[PtF6]–*. Since this exciting discovery, several other xenon compounds, mainly with the most
electronegative elements-fluorine and oxygen, have been synthesised. The compounds of krypton are
fewer; only the difluoride (KrF2) has been studied in detail. Compounds of radon have not been isolated
but only identified by radiotracer techniques. No true compounds of Ar, Ne or He are known.

- 41 -
Xenon forms three binary fluorides, XeF2, XeF4 and XeF6 by the direct union of elements under appropriate
experimental conditions. XeF2 can also be prepared by irradiating a mixture of xenon and fluorine with
sunlight or light from a high pressure mercury arc lamp:
Xe(g) + F2(g) 

673 K, 1 bar
 XeF2(s)
(xenon in excess)
Xe(g) + 2F2(g) 

873 K, 7 bar XeF4(s)
(1:5 ratio)
Xe(g) + 3F2(g) 

573 K, 60  70 bar
 XeF6(s)
(1 : 20 ratio)
XeF2, XeF4 and XeF6 are colourless crystalline solids subliming readily at 298 K. They are powerful
fluorinating agents. They are readily hydrolysed by even traces of water. The hydrolysis of XeF 2 can be
represented by the equation :
2XeF2(s) + 2H2O(l)  2Xe(g) + 4HF(aq) + O2(g)
The structures of the three xenon fluorides can be deduced from VSEPR (Valence shell electron pair
theory). XeF2 and XeF4 have the linear and square planar structures, respectively. XeF6 has seven electron
pairs (6 bonding pairs and one lone pair) and would thus have a distorted octahedral structure as found
experimentally in the gas phase. In the solid state, XeF6 contains tetrameric and hexameric units in which
square pyramidal XeF5+ units are linked by bent F– pyramidal bridges. Xenon fluorides react with fluoride
ion acceptors to form cationic species and fluoride ion donors to form fluoroanions.
XeF2 + PF5  [XeF]+[PF6]–
XeF4 + SbF5  [XeF3]+[SbF6]–
XeF6 + MF  M+ [XeF7]–
[M = Na, K, Rb or Cs]


Group 15 Elements (Nitrogen Family) Overview

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Group 15 Elements (Nitrogen Family) Overview

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Chapter-1

p-BLOCK (GROUP 15, 16, 17, 18)

Element At. No Electronic Configuration

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absence of vacant d-orbitals to expand their valency.

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into a useful nitrogen compound is referred to as nitrogen fixation. Assimilation of atmospheric

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Cu 2  (aq) + 4NH3(aq) [Cu(NH3 ) 4 ]2  (aq)

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(a) White or Yellow

(3) It reacts with sulphur to form phosphorus (iii) sulphide

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(6) With copper sulphate it forms cupric phosphide.

Phosphorus trioxide (P4O6)

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Phosphorus acid or (Phosphonic acid), H3PO3

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Phosphoric acid (Orthophosphoric acid) (H3PO4)

H4P2O7 316ºC 2HPO3 + H2O

Pyrophosphoric acid (H4P2O7)

2H3PO4 250ºC H4P2O7 + H2O

Metaphosphoric acid (HPO3)

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2PH3 + 4O2 150ºC P2O5 + 3H2O

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GROUP 16 ELEMENTS OXYGEN FAMILY

Oxygen 8 [He] 2s2, 2p4

Sulphur 16 [Ne] 3s2, 3p4

2. Periodicity in Properties of Group VIA Elements. As in gp 14 and 15 the properties of these

H1 = Sublimation energy

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2S2Cl2 + 2H2O 3S + SO2 + 4HCl

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Sulphurous acid Sulphuric acid Thiosulphuric acid Peroxomonousulphuric aic

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The highest catenation capability of sulphur is related to highest bond strength

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Hydrogen Sulphide (H2S)

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(b) It decolourizes acidic KMnO4.

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(8) Moist SO2 acts as a bleach

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(2) It decomposes on heating to form SO3 and H2O

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(b) PCl5 halogenates H2SO to ClSO2Cl

Na2SO3 + Na2S + I2  Na2S2O3 + 2NaI

2NaHS + 4NaHSO3  3Na2S2O3 + 3H2O

Na2CO3 + SO2  Na2SO3 + CO2

(I) GENERAL CHARACTERISTICS OF HALOGENS

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2nd exited state

3rd exited state

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