GROUP - 15

NITROGEN FAMILY

Covalent
Symb Pauling’s
Element Electronic structure Physical state Nature Radius
ol (pm) electronegativity
Nitrogen N [He] 2s2 2p3 Gas Non – metal 74 3.0
Phosphorus P [Ne] 3s2 3p3 Waxy solid Non – metal 110 2.1
Arsenic As [Ar]3d10 4s2 4p3 Solid Metallod 121 2.0
Antimony Sb [Kr] 4d10 5s2 5p3 Solid Metalloid 141 1.9
Bismuth Bi [Xe] 4f14 5d10 6s2 6p3 Solid Metal 152 1.9

General Electronic Configuration: ns2 np3

The valence p-subshell has three half-filled p-orbitals in accordance with the Hund’s rule. Therefore,
these elements are expected to be quite stable.

Allotropy: Except for nitrogen and bismuth, the remaining members show allotropy.

Phosphorus - White, red, black, scarlet and violet

Arsenic - Grey, yellow and black
Antimony - Yellow and black

Catenation: catenation is the self-linking property of an element. As a result, a number of the atoms of the
same element can be linked by covalent bonds.

Catenation is not noticed in nitrogen because the size of the nitrogen atom is quite small and two atoms of
nitrogen can be linked to each other by covalent bonds resulting in N2 molecule (N ≡ N) which is quite stable.

Molecular nitrogen (N2) is very little reactive chemically because of very small atomic size of nitrogen and
also small bond length for the triple bond. As a result, bond dissociation enthalpy is quite high and bond
cleavage is not so easy. However, it can be made to combine with hydrogen, oxygen and even certain
metals under drastic condition of temperature and pressure. This is called chemical fixation of nitrogen.

Chemical properties:

1. OXIDATION STATES: Nitrogen and phosphorus show oxidation states of -3 in their compounds since
their electro negativities are high and atomic sizes are comparatively small. They form anions such as
nitride ion (N3-) and phosphide ion (P3-). For example, (Mg3N2) and (Mg3P2).

In general all the members have tendency to show variable oxidation states of +3 and +5 in their
compounds. The stability of +3 oxidation state increases and that of +5 oxidation state decreases
down the group on account of inert pair effect.
 Inert Pair Effect: The inert pair effect represents

“the reluctance of the valence s-electrons (ns 2 np3) to be available for bonding as
compared to the valence p-electrons due to their greater penetration in the
nucleus.”

In nitrogen family the inert pair effect is maximum in bismuth (Bi) due to very large nuclear charge.
Therefore, a molecule of BiCl3 can exist but not of BiCl5.

2. HYDRIDES: (MH3)

Bond Decomposition Bond energy

m.p. (K) b.p. (K)
MH3 length Temperature (M – H) Bond angle
(approx) (approx)
(pm) (0C) (kJ mol-1)
NH3 102 1300 389 195 239 107.50
PH3 142 440 318 140 186 93.50
AsH3 152 280 247 158 211 91.50
SbH3 171 150 255 185 255 91.30
BiH3 25 290 900

Characteristics of Hydrides:

(I) Basic strength:

Hydrides are Lewis bases due to the presence of lone pair of electrons on the central atom. The basic strength
decreases in the order: NH3 > PH3 > AsH3 > SbH3 > BiH3

Explanation: Nitrogen atom has the smallest size and a very high electron density.
Therefore its electron releasing tendency for the basic strength is the maximum. Down
the group, there is a gradual increase in atomic size and decrease in electron density
on the central atom. As a result, the electron releasing tendency or basic strength of
the hydrides decrease in the order

NH3 > PH3 > AsH3 > SbH3 > BiH3

(II) Thermal stability:

The thermal stability of the hydrides of group-15 elements decreases from NH3 towards BiH3. Whereas NH3
and PH3 are quite stable, the other hydrides are comparatively less stable. BiH3 is so highly unstable that it
decomposes even at room temperature.

Explanation: The thermal stability is inversely proportional to the M – H bond length in

hydrides of group-15 elements. The bond length increases from NH3 to BiH3 because of
the increase in the size of the central atom. As a result, the bond dissociation enthalpy
decreases and the thermal stability also decreases from NH3 to BiH3.
(III) Reducing nature:

The reducing nature of the hydrides of group-15 elements is expressed in terms of hydrogen releasing tendency.
This tendency is found to increase from NH 3 to BiH3. This means that NH3 is the weakest reducing agent while
BiH3 is the strongest one.

Explanation: the reducing nature is related to thermal stability. Lesser the thermal stability, more will be the
reducing nature. Since NH3 is the most stable among the hydrides of the group-15 elements, it is the weakest
reducing agent. Actually ammonia fails to act as the reducing agent. BiH3 is the most reducing in nature since it
is least stable thermally. Reducing nature increases from ammonia to bismuthine.

(IV) Boiling points:

With the exception of ammonia, the boiling points of the hydrides of group-15 elements show an increasing
trend. Ammonia has higher boiling point than phosphine and arsine against expectation.

Explanation: The molecular size of the hydrides increases down the group and as a
result, van der Waal’s forces of attraction also increase. However, the boiling point of
ammonia is more than that of phosphine and arsine because of the presence of
intermolecular hydrogen bonding in the molecule. In fact, N – H bond is reasonable
polar which leads to the formation of hydrogen bonding. As the polarity of the P – H
bond is almost negligible; phosphine does not form hydrogen bonds. Therefore its
boiling point is less than that of ammonia.

3. HALIDES: (MX3 & MX5)

With the exception of NCl3, NBr3, and NI3, all other trihalides are stable.

Explanation: The cause of instability of the trihalides of nitrogen is because of weak N –

Cl, N – Br and N – I bonds on account of large difference in the atomic sizes of
nitrogen and halogen atoms

Pentahalides are less common as compared to trihalides.

Nitrogen does not form pentahalides of the type MX5.

Explanation: Nitrogen does not form pentahalides due to the absence of d-orbitals in the
valence shell.

4. OXIDES:

Oxides of Nitrogen:

N forms different oxides with oxygen in a number of oxidation states.

Nitrous oxide (N2O) or Nitrogen (I) oxide
Nitrogen monoxide (NO) or Nitrogen (II) oxide
Dinitrogen trioxide (N2O3) or Nitrogen (III) oxide
Nitrogen dioxide (NO2) or Nitrogen (IV) oxide
Nitrogen pentoxide (N2O5) or Nitrogen (V) oxide

Oxides of Phosphorus:

P forms two oxides namely Phosphorus trioxide (P4O6) and Phosphorus pentoxide (P4O10).
These oxides exist in the form of dimers.

Structure of P4O6

Structure of P4O10

DINITROGEN (N2)

Reactions of preparation:

NH4Cl + NaNO2 → NH4NO2 + NaCl

NH4NO2 → N2 + 2H2O
 (NH4)2Cr2O7 → Cr2O3 + N2 + 4H2O

2NH3 + 3CuO → 3Cu + N2 + 3H2O

2NH3 + 3CaOCl2 → 3CaCl2 + N2 + 3H2O

Bleaching powder

Ba(N3)2 → Ba + 3N2
Barium azide

2NaN3 → 3Na + 3N2

Sodium azide

Reactions of chemical properties:

CaC2 + N2 → CaCN2 + C
Calcium carbide Calcium cyanamide

CaCN2 + 3H2O → CaCO3 + 2NH3

The mixture of Calcium cyanamide and carbon is commonly known as NITROLIM which is
used as a nitrogen fertilizer.

Al2O3 + 3C + N2 → 2AlN + 3CO

AlN + 3H2O → Al(OH)3 + NH3

Al(OH)3 upon heating gives pure alumina, Al2O3 (Serpeck’s process of purification of bauxite
ore).

AMMONIA (NH3)

Reactions of preparation:

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

(NH4)2SO4 → 2NH3 + H2SO4

(NH4)3PO4 → 3NH3 + HPO3 + H2O

NH4Cl + NaOH → NH3 + NaCl + H2O

(NH4)2SO4 + 2NaOH → 2NH3 + Na2SO4 + 2H2O

Mg3N2 + 6H2O → 2NH3 + Mg(OH)2

Haber’s process of manufacture of ammonia:

N2 + 3H2 2NH3 + Heat

The favorable conditions for the forward reaction are derived from Le-Chatelier’s principle. These are:

(a) Low temperature should favor the formation of ammonia as the forward reaction is
exothermic. But an optimum temperature of nearly 700K is necessary to keep the reaction in
progress.
(b) High pressure (about 200 atm) is required to favor the formation of ammonia because
pressure decreases in the forward direction.
(c) Catalyst can accelerate the rate of reaction. Finely divided iron oxide is used as catalyst with
traces of molybdenum acting as a promoter for the catalyst.

Ammonia gas can not be dried by using concentrated sulfuric acid, anhydrous calcium chloride or
phosphorus pentoxide because ammonia reacts with all of these dehydrating agents.

2NH3 + H2SO4 → (NH4)2SO4

8NH3 + CaCl2 → CaCl2.8NH3
(Addition compound)

P4O10 + 6H2O → 4H3PO4

3NH3 + H3PO4 → (NH4)3PO4

Therefore, ammonia gas is dried by placing over quick lime (CaO).

Reactions of chemical properties:

Ammonia forms complexes with certain cations of d-block elements such as Ag+, Cu2+, Cd2+ ions which
are Lewis acids.

Ag+ + 2NH3 → [Ag(NH3)2]+

Cu2+ + 4NH3 → [Cu(NH3)4]2+

Cd2+ + 4NH3 → [Cd(NH3)4]2+

Reaction with chlorine:

8NH3 + 3Cl2 → 6NH4Cl + N2

(Excess)
NH3 + 3Cl2 → NCl3 + 3HCl
(Excess) Nitrogen trichloride

Action with Nessler’s reagent:

2K2HgI4 + NH3 + 3KOH → H2N – Hg – O – Hg – I + 7KI + 2H2O

Nessler’s reagent Iodide of Millon’s base

Certain metal ions such as Fe3+, Cr3+, Al3+ etc. are precipitated as hydroxides when their aqueous salt
solutions are reacted with ammonium hydroxide. For example,

FeCl3 + 3NH4OH → Fe(OH)3 + 3NH4Cl

(Brown ppt.)

AlCl3 + 3NH4OH → Al(OH)3 + 3NH4Cl

(White ppt.)

CrCl3 + 3NH4OH → Cr(OH)3 + 3NH4Cl

(Green ppt.)

NITRIC ACID (HNO3)

Nitrogen forms two oxo acids, namely nitrous acid (HNO2) and nitric acid (HNO3).

Laboratory preparation: NaNO3 + H2SO4 → NaHSO4 + HNO3

Manufacture of Nitric Acid:(Ostwald Process)

4NH3 + 5O2 → 4NO + 6H2O (In converter)

2NO + O2 → 2NO2 (In oxidation chamber)

2NO2 + H2O → 2HNO3 + NO (In absorption tower)

Dilute nitric acid can be concentrated to about 68% by distilling under reduced pressure.

The acid obtained as a result of concentration is brown in color due to some dissolved NO 2 gas in it
and is called fuming nitric acid (HNO3 + NO2). The gas can be removed by bubbling dry air through
it for some time. Completely anhydrous acid can be obtained by distilling the aqueous acid over
phosphorus pentoxide (P4O10).

Properties:
 Decomposition: 2HNO3 → 2 H2O + 4 NO2 + O2

Oxidizing Properties: A very powerful oxidizing agent

Conc. Acid 2HNO3 → 2 H2O + 4 NO2 + [O]

Dilute Acid 2HNO3 → H2O + 2NO + 3[O]

Some of the oxidizing reactions of nitric acid:

[A] Oxidation of non-metals:

Non-metals are not normally oxidized by nitric acid. However, concentrated nitric acid can oxidize most
of them:

C + 4 HNO3 → H2CO3 + 4 NO2 + H2O

I2 + 10 HNO3 → 2 HIO3 + 10 NO2 + 4 H2O
P4 + 20 HNO3 → 4 H3PO4 + 20 NO2 + 4 H2O
S8 + 48 HNO3 → 8 H2SO4 + 48 NO2 + 16 H2O

H2CO3 = Carbonic acid

HIO3 = Iodic acid
H3PO4 = Phosphoric acid
H2SO4 = Sulphuric acid

[B] Oxidation of metals:

For Na, K, Ca, Mg, Al, Zn, Fe, Co, Ni etc.

Metal + HNO3 → Metal nitrate + Reduction product + H2O
Zn + 4 HNO3 (conc.) → Zn(NO3)2 + 2 NO2 + 2 H2O
4 Zn + 10 HNO3 (dil.) → 4 Zn(NO3)2 + N2O + 5 H2O
Pb + 4 HNO3 (conc.) → Pb(NO3)2 + 2 NO2 + 2 H2O
3 Pb + 8 HNO3 (dil.) → 3 Pb(NO3)2 + 2 NO + 4 H2O
Fe + 6 HNO3 (conc.) → Fe(NO3)3 + 3 NO2 + 3 H2O
Fe + 10 HNO3 (very dil.) → 4 Fe(NO3)3 + NH4NO3 + 3 H2O

For Cu, Ag, Hg etc.

Metal + HNO3 → Metal nitrate + NO2 (or NO) + H2O

Cu + 4 HNO3 (conc.) → Cu(NO3)2 + 2 NO2 + 2 H2O

3 Cu + 8 HNO3 (very dil.) → 3 Cu(NO3)2 + 2 NO + 4 H2O
Ag + 2 HNO3 (conc.) → AgNO3 + NO2 + H2O
3 Ag + 4 HNO3 (very dil.) → 3 AgNO3 + NO + 2 H2O

Oxidation of compounds:
H2S + 2 HNO3 (conc.) → S + 2 NO2 + 2 H2O
 3 H2S + 2 HNO3 (dil.) → 3S + 2 NO + 4 H2O
SO2 + 2 HNO3 (conc.) → 3 H2SO4 + 2 NO2
3 SO2 + 2 HNO3 (dil.) + 2 H2O → 3 H2SO4 + 2 NO
3 Ag + 4 HNO3 (very dil.) → 3 AgNO3 + NO + 2 H2O

Ferrous salts are oxidized to ferric salts:

2 FeSO4 + 2HNO3 (conc.) + H2SO4 → Fe2(SO4)3 + 2 NO2 + 2 H2O
6 FeSO4 + 2 HNO3 (dil.) + 3 H2SO4 → 3 Fe2(SO4)3 + 2 NO + 4 H2O

Uses of nitric acid:

1. Used in the manufacture of fertilizers

2. Used in the manufacture of explosives like T.N.T., Dynamite, Picric acid etc.
3. Used as a useful laboratory reagent.

************************************************************************************

PHOSPHORUS

White Phosphorus:

This allotropic form of phosphorus becomes yellow on exposure to air. It exists as P4 molecules in
which each phosphorus atom is linked to three other atoms by covalent bonds and has alone pair of
electrons present on it.

White phosphorus is a white, waxy transparent solid. This allotrope is

thermodynamically unstable at normal condition and will gradually change to
red phosphorus. This transformation, which is accelerated by light and heat,
makes white phosphorus almost always contain some red phosphorus and
appear yellow. For this reason, it is also called yellow phosphorus.

Red Phosphorus:

Red phosphorus may be formed by heating

white phosphorus to 250°C or by exposing
white phosphorus to sunlight. Phosphorus after this treatment exists as an amorphous network of atoms
which reduces strain and gives greater stability. Red phosphorus is much less reactive than white
phosphorus. It does not ignite in air until heated to 300°C, and it is insoluble in water, alkali and carbon
disulfide. It does not react so readily with the halogens, but can be oxidized by nitric acid to phosphoric
acid.

Reactions:

P4 + 5 O2 → P4O10
 P4 + 6 Cl2 → 4 PCl3
P4 + 10 Cl2 → 4 PCl5
P4 + 3 S8 → 8 P4S3
P4 + 6 Mg → 2 Mg3P2
P4 + 12 Na → 4 Na3P

P 4 S3 Tetraphosphorus trisulfide

Reaction with aqueous alkalies:

P4 + 3 NaOH + 3 H2O → PH3 + 3 Na2H2PO2

Reducing nature:
P4 + 10 H2SO4 → 4 H3PO4 + 10 SO2 + 4 H2O
P4 + 20 HNO3 → 4 H3PO4 + 20 NO2 + 4 H2O

PHOSPHENE (PH3)

Preparation:
Na3P + 3 H2O → 3 NaOH + PH3
Ca3P2 + 6 H2O → 3 Ca(OH)2 + 2 PH3

Laboratory preparation:
P4 + 3 NaOH + 3 H2O → PH3 + 3 Na2H2PO2

OXO ACIDS OF PHOSPHORUS

Name Formula Oxidation state of P Basicity

Hypophosphorus acid H3PO2 +1 Monobasic
Phosphorus acid H3PO3 +3 Dibasic
Hypophosphoric acid H4P2O6 +4 Tetrabasic
Orthophosphoric acid H3PO4 +5 Tribasic
Pyrophosphoric acid H4P2O7 +5 Tetrabasic
Metaphosphoric acid HPO3 +5 Monobasic

Structures of Oxoacids of Phosphorus:

Page 10 of 33
 GROUP - 16

OXYGEN FAMILY

 Elements:

Oxygen (O) - Non-metal

Sulphur (S) - Non-metal
Selenium (Se) - Metalloid
Tellurium (Te) - Metalloid
Polonium (Po) - Metal (Radioactive)

 Electronic configurations:

General electronic configuration of this group is ns2 np4

The valence p-subshell has two half-filled p-orbitals in accordance with the Hund’s rule.
Therefore, these elements are expected to be quite reactive.

 Physical State:

Oxygen - A gas at room temperature

Sulphur - Solid
Selenium - Solid
Tellurium - Solid
Polonium - Solid

 Allotropy: All the elements show allotropy. For example,

Oxygen - Ordinary oxygen gas and ozone

Sulphur - Rhombic, monoclinic and many more forms

 Multiple bonds: Oxygen the first element in the family has a tendency to form multiple bonds
(pπ – pπ) with oxygen, carbon, nitrogen etc. due to its very small size. The
tendency to form multiple bonds decreases down the group. This is due to the fact
that elements other than oxygen in this family have larger atomic sizes. Sulphur,
selenium, tellurium and polonium are generally linked to each other by single
covalent bonds such as – S – S – S – and – Se – Se – Se – etc. and result in the
puckered ring structures containing eight atoms (S8, Se8, Te8 etc.).

 Chemical properties:

1. OXIDATION STATES: The elements of oxygen family can acquire noble gas electronic
configuration either by the gain of two electrons or by sharing two electrons with the atoms of
other elements. Therefore, they show both negative and positive oxidation states in their
compounds.
 The first element oxygen is highly electronegative in nature. It shows –2 oxidation state in the
compounds such as metal oxides (K2O, Na2O, CaO etc). However there are few exceptions,

(i) In OF2, oxygen shows +2 oxidation state because F is more

electronegative than O.

(ii) In H2O2, the oxidation state of oxygen is –1.

Tendency to show –2 oxidation state decreases down the group.

Sulphur and the rest of the elements are less electronegative than oxygen. Therefore, their atoms
can not take up electrons easily. They can acquire ns2 np6 by sharing two electrons with the
atoms of other elements and hence, exhibit +2 oxidation state in their compounds. In addition to
this, their atoms have also vacant d-orbitals in their valence shell to which electrons can be
promoted from the p-orbitals of the same shell. As a result, they can also show +4 and +6
oxidation states. For example Sulphur has +2, +4 and +6 oxidation states in SF 2, SF4 and SF6
respectively.

2. HYDRIDES: (MH2)

H2O H2S H2Se H2Te H2Po

Water Hydrogen Selenium Tellurium Polonium
sulfide hydride hydride hydride

Characteristics of Hydrides:

(I) Physical Sate: Except water which is a liquid at room temperature, other hydrides are
pungent smelling gases.

Water is a liquid at room temperature because of the presence of

intermolecular hydrogen bonds between H2O molecules which leads
to association resulting in liquid state. In H2S molecules hydrogen
bonding is not present because of the low polarity of S – H bond.
Therefore it is a gas at room temperature.

(II) Acidic character: Hydrides are weakly acidic in nature and dissociate in aqueous
solution to release H+ ions.

The acidic character increases down the group in the order:

H2O < H2S < H2Se < H2Te

Explanation: Oxygen atom has the smallest size and a very high electron
density. Therefore the bond dissociation energy of O – H bond is maximum.
Down the group, there is a gradual increase in atomic size and hence M – H
bond dissociation energy gradually decreases with increasing size of the
 central atom. As a result the bond cleavage or release of H+ becomes
easier from H2O to H2Te .

Furthermore, extremely low acidic strength of H2O is also due to the

presence of intermolecular hydrogen bonding in the molecules as a result
of which the hydrogen atoms get trapped in the hydrogen bonds.

(II) Reducing nature: All the hydrides with the exception of water are reducing in nature.
The reducing character increases down the group.

(III) Boiling points: With the exception of water, which has a very high boiling point because
of the hydrogen bonding, the boiling points of the hydrides of group – 16 elements
increases from H2S to H2Te. This is due to the fact that the molecular size of the
hydrides increases down the group and as a result, van der Waal’s forces of
attraction also increase.

3. HALIDES: The members of the oxygen family form halides which are covalent in nature.
Some of the halides are described here:

With oxygen: OF2 Cl2O, Cl2O5, Cl2O7 Br2O, Br2O3 I2O5

With Sulphur: Monohalides S2Cl2 S2Br2 (In the form of dimers)

Dihalides SCl2

Tetrahalides SF4 SCl4

Hexahalides SF6 (Only fluorine is involved)

4. Oxides: Structure of oxides of Sulphur

Sulphur dioxide:
 DIOXYGEN (O2)

Reactions of preparation:

By heating certain oxygen rich metal oxides:

2Ag2O → 4 Ag + O2
2 HgO → 2 Hg + O2
2 Pb3O4 → 6 PbO + O2
2 PbO2 → 2 PbO + O2
3 MnO2 → Mn3O4 + O2

By thermal decomposition of some oxygen rich salts:

2 KClO3 → 2 KCl + O2
2 KNO3 → 2 KNO2 + O2
2 CaOCl2 → 2 CaCl2 + O2

By the action of conc. Sulphuric acid on certain oxygen rich compounds

2 K2Cr2O7 + 8 H2SO4 → 2 K2SO4 + 2 Cr2(SO4)3 + 8 H2O + 3 O2
4 KMnO4 + 6 H2SO4 → 2 K2SO4 + 4 MnSO4 + 6 H2O + 5 O2
2 MnO2 + 2 H2SO4 → 2 MnSO4 + 2 H2O + O2

Chemical properties:

Action with non-metals: (upon heating)

2 H2 + O2 → 2 H2O
N2 + O2 → 2 NO
S8 + O2 → 8 SO2
2C + O2 → 2 CO
C + O2 → CO2
P4 + 5 O2 → P4O10

Action with metals:

4 Na + O2 → 2 Na2O
2 Ca + O2 → 2 CaO
2 Mg + O2 → 2 MgO
4 Al + 3 O2 → 2 Al2O3
4 Fe + 3 O2 → 2 Fe2O3
 SIMPLE OXIDES
Oxides are the binary compounds of oxygen with other elements.
 The oxides of the metals are generally basic in nature.
 The oxides of non-metals are acidic in nature.
 The oxides having characteristics of both acidic and basic oxides are known as amphoteric
oxides.
 Certain oxides are neutral in nature.

Acidic oxides:
CO2 + H2O → H2CO3
SO2 + H2O → H2SO3
N2O5 + H2O → 2 HNO3
P4O10 + 6 H2O → 3 H3PO4

Basic oxides:
Na2O + H2O → 2 NaOH
CaO + H2O → Ca(OH)2
MgO + H2O → Mg(OH)2
Fe2O3 + 3 H2O → 2 Fe(OH)3

Amphoteric oxides:
Al2O3 + 6 HCl → 2 AlCl3 + 3 H2O

Neutral oxides: Neither acidic nor basic in nature. For example, CO, N2O, NO, H2O etc.

Mixed oxides:The metal oxides in which two oxides of the same metal with metal in different oxidation
states, are mixed with each other. For example:

Ferrosoferric oxide (Fe3O4 = FeO + Fe2O3)

Red Lead (Pb3O4 = 2 PbO + PbO2)

Special information:

Oxides have also been classified into different types base don oxygen contents. They are:

Simple oxides: Oxygen is present in the same proportion as permitted by the normal oxidation
state (- 2). For example, Na2O, MgO, CO2. However in oxygen difluoride (OF2)
oxidation state of oxygen is +2.

Poly-oxides: More oxygen is present than permitted by the valency of the other element. These
have been further classified into peroxides, super-oxides and dioxides.
 (i) Peroxides: These contain peroxide ion (O22-). For example, Na2O2, BaO2,
H2O2 etc. The oxidation state of oxygen is (-1). The oxygen atoms are
linked by peroxide linkage ( – O – O – ).

(ii) Super-oxides: These contain super-oxide ion (O2-). For example, KO2,
RbO2. The oxidation state of oxygen is ( – ½).

(iii) Dioxides: These appear to the same as peroxides (For example, PbO2,
MnO2) but are different from them in the sense that they do not contain
peroxide linkage and two oxygen atoms are linked directly to the metal
atom by double bond (O = Pb = O).

(iv) Sub-oxides: They contain less oxygen than permitted by normal valency.
For example, N2O.

OZONE (O3)

Ozone is a form of elemental oxygen. In its most stable form, elemental oxygen exists as diatomic
molecules (O2). The molecules of ozone contain three oxygen atoms (O3) and are unstable with respect
to O2. Ozone is a very reactive gas, and even at low concentrations it is irritating and toxic. It occurs
naturally in small amounts in the Earth's upper atmosphere, and in the air of the lower atmosphere after a
lightning storm.

Ozone is much more reactive than O2. It is a very powerful oxidizing agent, second among elements
only to fluorine. It can oxidize many organic compounds and is used commercially as bleach for waxes,
oils, and textiles, and as a deodorizing agent. Because it is a powerful germicide, it is also used to
sterilize air and drinking water.

Preparation of ozone:
Ozone is usually manufactured by passing a silent (sparkles) electrical discharge through pure, cold and
completely dry O2 gas or through dry air, in an apparatus called Ozonizer. The resulting mixture of
ozone and O2 or air is usually suitable for most industrial applications of ozone. Because ozone is very
unstable and reactive, the preparation of pure ozone is both difficult and hazardous and is seldom
attempted.

In the laboratory, two ozonizers are commonly used. These are Siemen’s Ozonizer and Brodie’s
Ozonizer.
Chemical properties:

Oxidizing character: It acts as very strong oxidizing agent [ O3 → O2 + O ]

Oxidation of Compounds:
PbS + 4 O3 → PbSO4 + 4 O2
CdS + 4 O3 → CdSO4 + 4 O2
ZnS + 4 O3 → ZnSO4 + 4 O2
MnS + 4 O3 → MnSO4 + 4 O2

2 HCl + O3 → Cl2 + H2O + O2

2 HI + O3 → I2 + H2O + O2

2 FeSO4 + H2SO4 + O3 → Fe2(SO4)3 + H2O + O2

2 K2MnO4 + H2O + O3 → 2 KMnO4 + 2 KOH + O2
2 K4[Fe(CN)6] + H2O + O3 → 2 K3[Fe(CN)6] + 2 KOH + O2

Oxidation of Metals:
2 Ag + O3 → Ag2O + O2
2 Hg + O3 → Hg2O + O2

Oxidation of non-metals:
I2 + 5 O3 + H2O → 2 HIO3 + 5 O2
P4 + 10 O3 + 6 H2O → 4 H3PO4 + 10 O2

Bleaching Character:

Vegetable + O3 → Colorless oxidized matter (Bleached) + O2

coloring matter

Depletion of Ozone Layer:

The presence of ozone blanket in the upper atmosphere also called ozonosphere prevents the harmful
ultra-violet radiations from reaching earth. These ultraviolet radiations are extremely harmful to the
living beings. Ozone depleting substances (ODS) are being released in the atmosphere by high flying
jets and rockets. These are converting ozone into oxygen. Actually, these are chemical substances like
chlorofluorocarbons (chlorofluoromethane – Freons) nitrogen oxides, chlorine, carbontetrachloride etc.

Nitrogen oxides such as nitrogen dioxide directly convert ozone into oxygen,

NO2 + O3 → NO + 2 O2

Chlorofluorocarbons undergo dissociation in the presence of light to produce chlorine free radicals
which catalyze the conversion of ozone into oxygen,

Cl2CF2 → Cl + CClF2
 (Freon)

Cl + O3 → ClO + O2

ClO + O → Cl + O2

Because of the destruction of ozone in the ozonosphere, its concentration has fallen down. This is also
called ozone – hole since the high radiation ultraviolet rays are in apposition to pass through the ozone
layer and reach our planet. The ultraviolet rays will lead to health hazards in the coming years if no
check on depletion of ozone layer is made. Some of the diseases likely to be caused as a result of the
depletion of ozone layer are as skin cancer, loss of sight and ill effect on immune system.

SULPHUR

Sulphur exists as a covalently bonded, molecular solid at room temperature with the formula S 8. These
large molecules each have many electrons , so the Van der Waals forces are quite strong and the melting
point is quite high (119oC). There are two ways of packing the sulphur rings, so solid sulphur exists in
two crystalline forms:

(i) Rhombic Sulphur (or α – Sulphur)

(ii) Monoclinic Sulphur (or β – Sulphur)

Both these forms are crystalline in nature and crystals consist of eight atoms of Sulphur (S8) in a
puckered ring structure. In the two forms of sulphur, the molecules are identical. The only difference
between the rhombic and monoclinic types is the arrangement of the molecules in space.

Comparison of two allotropic forms of Sulphur:

Rhombic Monoclinic

Yellow transparent crystals Amber colored needles

Melting point 113 oC Melting point 119 oC

Obtained when Sulphur crystallizes from solution Obtained when Sulphur solidifies above 95.6 oC
 Sulphur Dioxide (SO2)

Preparation:

When heated in air, Sulphur burns with a blue flame forming the colorless gas Sulphur dioxide.

S8 + 8 O2 → 8 SO2

Other methods of preparation:

Cu + H2SO4 → CuSO4 + SO2 + 2 H2O
Na2SO3 + 2 HCl → NaCl + SO2 + H2O

Properties:

It is highly soluble in water and its solution is acidic.

SO2 + H2O → Na2SO3

It reacts with bases like NaOH or KOH because of its acidic nature.
SO2 + 2 NaOH → Na2SO3 + H2O
SO2 + 2 KOH → K2SO3 + H2O

Reducing nature: In solution or in the presence of moisture, it behaves as a reducing agent.

SO32- + H2O → SO42- + 2H+ + 2e-

2 KMnO4 2 MnSO4
+ 5 SO2 + H2O → K2SO4 + + 2 H2SO4
(Pink) (Colorless)

K2Cr2O7 Cr2(SO4)3
+ 3 SO2 + H2SO4 → K2SO4 + + H2O
(Orange) (Green)

SULFURIC ACID (H2SO4)

Sulphuric acid is often called King of Chemical.

Manufacture: On large scale it is prepared by Contact Process. It is completed in the following steps:

1. Formation of Sulphur dioxide by burning either Sulphur or iron pyrites in excess of air
2. Catalytic oxidation (catalyst V2O5) of Sulphur dioxide into Sulphur trioxide
3. Absorption of Sulphur trioxide in 98% Sulphuric acid
4. Dilution of Oleum with water to get concentrated sulphuric acid
 S + O2 → SO2
FeS2 + 11 O2 → 2 Fe2O3 + 8 SO2
2 SO2 + O2 2 SO3
SO3 + H2SO4 → H 2 S2 O 7
H2S2O7 + H2O → 2 H2SO4

H2S2O7 is known as OLEUM.

Chemical properties:

It is a dibasic acid and hence it forms two series of salts called bisulphates and sulphates.
H2SO4 + NaOH → NaHSO4 + H2O
H2SO4 + 2 NaOH → Na2SO4 + 2 H2O

Dehydrating agent: Sugar gets charred acoompanied by the smell of burning sugar due to the black
mass consisting of carbon particles.
Conc. H2SO4
C12H22O11 12 C + 11 H2O
→
Action with Metals:
Zn + H2SO4 (dil.) → ZnSO4 + H2
Mg + H2SO4 (dil.) → MgSO4 + H2

All the metals (except gold and platinum) evolve Sulphur dioxide upon heating with conc. H2SO4
Cu + H2SO4 (conc.) → H2SO4 + SO2 + 2 H2O

Action with Non-metals: Conc. H2SO4 also oxidizes a number of non-metals since it is a powerful
oxidizing agent:
C + 2 H2SO4 (conc.) → CO2 + 2 SO2 + 2 H2O
S8 + 16 H2SO4 (conc.) → 16 H2O + 24 SO2 +
P4 + 10 H2SO4 (conc.) → H3PO4 + 10 SO2 + 4 H2O

Action with Salts:

With dilute H2SO4: It decomposes salts like carbonates, bicarbonates, sulphates, sulphides etc.
Na2CO3 + H2SO4 (dil.) → Na2SO4 + H2CO3
NaHCO3 + H2SO4 (dil.) → Na2SO4 + H2CO3
Na2S + H2SO4 (dil.) → Na2SO4 + H2S
Na2SO3 + H2SO4 (dil.) → Na2SO4 + H2SO3

With conc. H2SO4: It decomposes fluorides, chlorides. Nitrates, oxalates etc upon heating to liberate the
corresponding acids:
CaF2 + H2SO4 (conc.) → CaSO4 + 2 HF
 NaCl + H2SO4 (conc.) → NaHSO4 + HCl
NaNO3 + H2SO4 (conc.) → NaHSO4 + HNO3
Na2C2O4 + H2SO4 (conc.) → Na2SO4 + H2C2O4

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 GROUP - 17

HALOGEN FAMILY

 Elements:

Fluorine (F) - Non-metal

Chlorine (Cl) - Non-metal
Bromine (Br) - Non-metal
Iodine (I) - Non-metal
Astatine (At) - Non-metal (Radioactive)

 Electronic configurations:

General electronic configuration of this group is ns2 np5

The valence p-subshell has only one half-filled p-orbital in accordance with the Hund’s rule.
Therefore, these elements are highly reactive and exist as diatomic molecules.

 Physical State:

Fluorine - Gas
Chlorine - Gas
Bromine - Volatile liquid
Iodine - Volatile solid
Astatine - Solid

 Electron gain enthalpy:

Halogens have maximum negative electron gain enthalpy in the corresponding periods (i.e. the highest
tendency to form negatively charged ions). This is due to the fact that the atoms of these elements have
only one electron less than stable noble gas configurations. As a consequence, they readily accept one
electron to acquire noble gas electronic configuration. Electron gain enthalpy of the elements of the
group becomes less negative down the group (i.e. the tendency to form anions decreases down the
group).

However, the negative electron gain enthalpy of fluorine is less than that of
chlorine (i.e. the tendency to form F- is less than that of Cl- formation). It is due
to small size of fluorine atom. As a result, there are strong inter-electronic
 repulsions in the relatively small 2p orbitals of fluorine and thus, the incoming
electron does not experience much attraction.

 Electronegativity:

They have very high electronegativity. The electronegativity decreases down the group. Fluorine is
the most electronegative element in the periodic table.

 Bond dissociation enthalpy:

In the halogen molecule (X – X), the bond dissociation enthalpies are expected to decreases with the
increase in the bond length values.

Exception: The bond dissociation enthalpy for F – F bond is expected to be more

than for Cl – Cl bond. But its actual value is less. This is because of high inter-
electronic repulsions between non-bonding (lone pairs of) electrons present on
the atoms which are much closer to each other in the fluorine (F2) molecule than
in the chlorine (Cl2) molecule.

 Chemical properties:

o OXIDATION STATES: All the halogens exhibit –1 oxidation state. However, chlorine,
bromine and iodine exhibit + 1, + 3, + 5 and + 7 oxidation states also.

The fluorine atom has no d orbitals in its valence shell and therefore cannot expand its octet.
Being the most electronegative, it exhibits only –1 oxidation state.

o OXIDIZING NATURE: Since the halogens have strong electron accepting tendencies, they are
powerful oxidizing agents. F2 is the strongest oxidizing halogen and it oxidizes other halide ions
in solution or even in the solid phase. In general, a halogen oxidizes halide ions of higher atomic
number.

F2 + 2X– → 2F– + X2 (X = Cl, Br or I)

Cl2 + 2X– → 2Cl– + X2 (X = Br or I)
Br2 + 2I– → 2Br– + I2

Therefore the relative oxidizing power in decreasing order is:

F2 > Cl2 > Br2 > I2

o REACTIVITY TOWARDS HYDROGEN: The members of the halogen family combine with
hydrogen directly under different conditions to form corresponding hydrohalides (HX). The
affinity for hydrogen decreases from fluorine to iodine.

Characteristics of Hydrogen halides (HX):

(a) Physical state:

 HF HCl HBr HI
Liquid Gas Gas Gas

The liquid state of hydrogen fluoride (HF) is attributed to the

presence of intermolecular hydrogen bonding in the molecules due to
their highly polar nature. They get associated and exist as liquid. But
hydrogen bonding is not present in other halogen acids and hence
their molecules do not get associated. They exist in the gaseous state
at room temperature.

(b) Thermal stability: The stability of hydrogen halides decreases down the group from
HF to HI. This means that HF is the maximum stable while HI is the least stable acid.
This is because H – X bond dissociation enthalpies decreases from HF to HI. There fore
HI can be cleaved most easily.

(c) Reducing nature: Greater the thermal stability, weaker will be the reducing nature.
This is because, cleavage of H – X bond becomes difficult when
thermal stability increases. Therefore, HF is the weakest reducing
agent, whereas HI has the maximum reducing strength. Both HF and
HCl act as oxidizing agents and not as reducing agents.

(d) Acidic strength: In gaseous state hydrogen halides are covalent in nature but
become ionic in aqueous solution and behave as acids. The acidic strength follows
the following order:

HI > HBr > HCl > HF

Bond dissociation enthalpy is maximum for HF and least for HI.

Therefore, HF is the weakest acid while HI is the strongest acid. The
weak acidic nature of HF is also attributed to the presence of
intermolecular hydrogen bonding as a result of which hydrogen
atoms get trapped in the hydrogen bonds.

4. REACTIVITY TOWARDS OXYGEN: Chlorine, bromine and iodine form oxides in which
the oxidation states of these halogens range from +1 to +7.

Oxidation state Fluorine Chlorine Bromine Iodine

-1 OF2 - - -
+1 - Cl2O Br2O -
+3 - Cl2O3 - -
+4 - ClO2 BrO2 I2O4
+5 - - - I2O5
+6 - Cl2O6 - -
+7 - Cl2O7 - I2O7

Oxides of halogen are covalent in nature and are powerful oxidizing agents. They explode
violently upon heating. Chlorine oxides, Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive
 oxidizing agents and tend to explode. ClO2 is used as a bleaching agent for paper pulp and
textiles and in water treatment. Structures of some oxides of chlorine:

5. OXO ACIDS OF HALOGENS:

Oxidation state F Cl Br I General name

+1 HFO HClO HBrO HIO Hypohalous acid
+3 - HClO2 - - Halous acid
+5 - HClO3 HBrO3 HIO3 Halic acid
+7 - HClO4 - HIO4 Perhalic acid

Relative acidic strength of oxo-acids of halogens:

(a) Acidic strength of oxoacids of different halogens with same oxidation state decreases
with the increase in the atomic number.

HClO > HBrO > HIO

More is the electronegativity, greater will be its electron attracting tendency facilitating
the release of H+ ion from the O – H bond. Therefore, HClO is the strongest acid because
the Cl is the most electronegative while HIO is the weakest acid since I is the least
electronegative among all the halogens.

(b) Acid strength of the oxoacids of the same halogen atom increases with the increase in
the oxidation number of the halogen atom. The different oxo acids of chlorine have the
following order of relative acidic strengths:

HClO4 > HClO3 > HClO2 > HClO

Structures of oxoacids of chlorine:

6. INTERHALOGEN COMPOUNDS: Halogens mutually combine to form a number of
covalent compounds called interhalogen compounds. In most of these compounds, fluorine
generally acts as the electronegative element. There are four types of interhalogen compounds
based upon the oxidation states of the halogen atoms involved which act as electropositive
elements.

XY XY3 XY5 XY7

ClF ClF3 ClF5 -

BrF , BrCl BrF3 BrF5 -

ICl , IBr , IF ICl3 , IF3 IF5 IF7

Shapes of Interhalogen Compounds:

BrF3

BrF BrF5

IF7 ClF3

ClF5
 CHLORINE (Cl2)

Preparation: It can be prepared by any one of the following methods:

(i) By heating manganese dioxide with concentrated hydrochloric acid.

MnO2 + 4HCl → MnCl2 + Cl2 + 2 H2O

A mixture of common salt and concentrated H2SO4 is used in place of HCl.

4 NaCl + MnO2 + 4 H2SO4 → MnCl2 + 4 NaHSO4 + Cl2 + 2 H2O

(ii) By the action of HCl on potassium permanganate.

2 KMnO4 + 16 HCl → 2 KCl + 2 MnCl2 + 5 Cl2 + 8 H2O

Manufacture of chlorine:

(i) Deacon’s process: By oxidation of hydrogen chloride gas by atmospheric oxygen in the
presence of CuCl2 (catalyst) at 723 K.

4 HCl + O2 → 2 Cl2 + 2 H2O

(ii) Electrolytic process: Chlorine is obtained by the electrolysis of brine (concentrated NaCl
solution). Chlorine is liberated at anode. It is also obtained as a by–product in many chemical
industries.

Chemical Properties:

Reaction with metals: Forms chlorides of the respective metals

2 Al + 3 Cl2 → 2 AlCl3
2 Na + Cl2 → 2 NaCl
2 Fe + 3 Cl2 → 2 FeCl3

Reaction with non-metals: Forms chlorides of the respective non-metals

P4 + 6 Cl2 → 4 PCl3
S8 + 4 Cl2 → 4 S2Cl2
Reaction with hydrogen: It has great affinity for hydrogen. It reacts with compounds containing
hydrogen to form HCl.
H2 + Cl2 → 2 HCl
H2S + Cl2 → 2 HCl + S
C10H16 + 8 Cl2 → 16 HCl + 10 C

Reaction with ammonia: (See also: Properties of Ammonia)

8 NH3 (excess) + 3 Cl2 → 6 NH4Cl + N2

NH3 + 3 Cl2 (excess) → 3 HCl + NCl3

Reaction with alkalies: With cold and dilute alkalis chlorine produces a mixture of chloride and
hypochlorite but with hot and concentrated alkalis it gives chloride and chlorate.
2 NaOH (cold & dil.) + Cl2 → NaCl + NaOCl + H 2O

6 NaOH (hot & conc.) + 3 Cl2 → 5 NaCl + NaClO3 + H 2O

Oxidation reactions: Chlorine acts as a strong oxidizing agent.

2 FeSO4 + H2SO4 + Cl2 → Fe2(SO4)3 + 2 HCl
Na2SO3 + H2O + Cl2 → Na2SO4 + 2 HCl
SO2 + 2 H2O + Cl2 → H2SO4 + 2 HCl
I2 + 6 H2O + 5 Cl2 → HIO3 + 10 HCl

Bleaching action: Chlorine water on standing loses its yellow color due to the formation of
HCl and HOCl. Hypochlorous acid (HOCl) so formed, gives nascent oxygen which is
responsible for oxidizing and bleaching properties of chlorine. It is a powerful bleaching agent;
bleaching action is due to oxidation.

Cl2 + H2O → 2 HCl + O

Colored substance + [O] → Colorless substance

It bleaches vegetable or organic matter in the presence of moisture. Bleaching effect of chlorine
is permanent.
 Hydrogen Chloride (HCl)

Its aqueous solution is called hydrochloric acid.

Important chemical properties:

Hydrochloric acid decomposes salts of weaker acids, e.g., carbonates, hydrogencarbonates,

sulphites, etc.
Na2CO3 + 2 HCl → 2 NaCl + CO2 + H2O
NaHCO3 + HCl → NaCl + CO2 + H2O
Na2SO3 + 2 HCl → 2 NaCl + SO2 + H2O

Aqua-regia: When three parts of concentrated HCl and one part of concentrated HNO3 are
mixed, aqua regia is formed which is used for dissolving noble metals, e.g., gold, platinum
Au + 4 H+ + NO3- + Cl- → AuCl4- + NO + 2 H2O
3 Pt + 16 H+ + 4 NO3- + 18 Cl- → 3 PtCl6- + 4 NO + 8 H2O

******************************************************************************************
 GROUP - 18

NOBLE GASES

 Elements:

Helium - (He)
Neon - (Ne)
Argon - (Ar)
Krypton - (Kr)
Xenon - (Xe)
Radon - (Rn) Radioactive element.

 Electronic configurations:

General electronic configuration of this group is ns2 np6

The valence p-subshell is completely filled, i.e., they have complete octet. Therefore, these elements
are highly inert and exist in atomic form.

 Physical State: All the elements are gases at room temperature.

Noble gases have very low boiling points.

Noble gases being monoatomic have no interatomic forces except weak

dispersion forces and therefore, they are liquefied at very low temperatures.
Hence, they have low boiling points.

 Chemical properties:

The noble gases have highly symmetrical and stable electronic configuration of their atoms. Therefore,
they do not combine with each other. However, recent researches have shown that under certain
conditions, higher members of the family such as krypton and xenon can take part in the chemical
combination.

In 1962, Bartlett, prepared a complex compound by reacting oxygen with powerful

oxidizing agent platinum hexafluoride.

O2 (g) + PtF6 (g) → O2+ [PtF6] -

Dioxygenylhexachloroplatinate (V)
In this reaction, PtF6 has oxidized O2 to O2+ ion. Bartlett thought that PtF6 should also
oxidize Xe to Xe+ since first ionization enthalpy of xenon (1176 kJ mol -1) is quite close to
that of O2 (1180 kJ mol-1). He was successful in preparing the compound Xe[PtF6] which
is red solid, by heating xenon and platinum hexafluoride,

Xe (g) + PtF6 (g) → Xe+ [PtF6] -

Therefore, Xe+ [PtF6] - was the first ever compound of a noble gas element to be synthesized.

Now, more than 80 xenon compounds have been made with xenon chemically bonded to fluorine and
oxygen.

Xenon Fluorides

There are three xenon fluorides:

Xenon difluoride (XeF2)

Xenon tetrafluoride (XeF4)
Xenon hexafluoride (XeF6)

These can be obtained by the direct interaction between xenon and fluorine under appropriate
experimental conditions.

Properties:

1. Hydrolysis:

Complete hydrolysis yields XeO3

6 XeF4 + 12 H2O → 2 XeO3 + 24 HF + 4 Xe + 3 O2
XeF6 + 3 H 2O → XeO3 + 6 HF

Partial hydrolysis yields oxyfluorides

XeF4 + H 2O → XeOF2 + 2 HF
XeF6 + H 2O → XeOF4 + 2 HF
XeF6 2 H 2O → XeO2F2 + 4 HF
The fluorides of xenon, XeF 2, XeF4 and XeF6 react with fluoride ion acceptors like PF 5, SbF5, AsF5 to
form adducts in which the fluorides (XeF2, XeF4 and XeF6) change to cationic species whereas the
fluoride ion acceptors form fluoroanions.

Structures:

Oxidation State of
Compound Formula Structure
state of Xe hybridization of Xe

Xenon difluoride XeF2 +2 sp3d Linear

Xenon
XeF4 +4 sp3d2 Square planar
tetrafluoride
Xenon Distorted
XeF6 +6 sp3d3
hexafluoride octahedral*
Xenon
XeOF2 +4 sp3d T - shaped
oxydifluoride
Xenon Square
XeOF4 +6 sp3d2
oxytetrafluoride pyramidal

Xenon trioxide XeO3 +6 sp3 Pyramidal

Distorted octahedral*: On the basis of hybridization, the molecule should have pentagonal bipyramidal
structure. However, this structure has not yet been confirmed. Thus, it is preferably believed to have
distorted octahedral structure.

Xenon difluoride (XeF2)

Xenon tetrafluoride (XeF4)

Xenon hexafluoride (XeF6)

Another way of representing structures of Xenon compounds: