DAY TWENTY TWO

p-Block Elements
(Group-13 to Group-18)
Learning & Revision for the Day

u Periodicity in Properties of p-Block Elements u Group-16 Elements : Oxygen Family

u Group-13 Elements : Boron Family u Group-17 Elements : Halogens Family
u Group-14 Elements : Carbon Family u Group-18 Elements : Noble Gases
u Group-15 Elements : Nitrogen Family

In p-block elements, the last electron enters in the outermost p-orbital. There are six
groups of p-block elements in the periodic table, numbering from 13 to 18. Their valence
shell electronic configuration is ns2 np1 − 6 (except for He). Effective nuclear charge from
first to third period decreases and from fourth period and onwards increases, due to
poor shielding effect. Therefore, ns2 electrons bound closely to the nucleus. Therefore,
the oxidation state two unit less than the group oxidation state becomes progressively
more stable in each group. This is also known as inert pair effect.

Periodicity in Properties of p-Block Elements

l
Non-metals and metalloids exist only in the p-block of the periodic table. On moving
down a group metallic character increases and non-metallic character decreases.
Between metals and non-metals a few metalloids are also present.
l
Second period elements have a tendency to form pπ - pπ multiple bond (double or
triple bond) due to their smaller atomic size and high bond energy.
e.g. C ≡≡ C, C == C, N ≡≡ N, O == O, O == C == O etc.
l
Elements of second period do not expand their covalency due to non-availability of
d-orbitals. Therefore, halides of such elements do not hydrolysed easily.
e.g. BCl3, CCl4 (halides) etc.
l
While elements of third period and onwards only form single bond and can expand
their covalency due to the presence of vacant d-orbitals.
e.g. P4 , S8, [AlF6]3− ion etc.
l
Non-metal oxides are acidic or neutral and metal oxides are basic in nature. Generally,
metalloid oxides are amphoteric. In a period, from left to right acidic character
increases and down a group, basic character increases. Generally, oxides with higher
oxidation state are more acidic in nature.
Properties of Hydrides 2. Oxidation State (+ 3, + 1)
1. Basic character of p-block hydrides decreases on Stability of +3 oxidation state decreases down the group and
moving down a group and acidic character increases. that of +1 oxidation state increases down the group due to
Generally, left to right in a period, acidic character inert pair effect.
increases. e.g. Fourth period and onwards, effective nuclear charge increases
NH3 > PH3 > AsH3 due to poor shielding effect, therefore the radius of gallium
(135 pm) is less than that of aluminium (143 pm) and on
(down the group basic character decreases)
moving down the group inert pair effect increases.
NH3 > H2O > HF
(left to right basic character decreases) 3. Hydrides
2. Thermal stability of hydrides on moving down a group Boron hydrides exist in dimeric or polymeric form. The
decreases due to increase in bond length. simplest boron hydride is diborane, B2 H6. Aluminium forms
Thermal stability of the hydrides decreases down the only one colourless, solid polymeric hydride (AlH3 )n known as
group due to which their tendency to act as reducing alane.
agent increases down the group. Hydrides of Ga and In are not very much stable. B, Al and Ga
3. Bond angle of hydrides on moving down a group, form complex anionic hydrides, e.g. NaBH4 , LiAlH4 and
decreases due to increase in the size of central atom. LiGaH4 . All are strong reducing agents.
Charge density and repulsion interaction also decreases
on moving down a group, e.g.
4. Halides
Halides have incomplete octet, therefore, have a high
H2O > H2S> H2Se
Bond angle tendency to accept electrons and behave as Lewis acid.
BI3 > BBr3 > BCl3 > BF3 (Acidic character)
If central atoms belong to the same period and have the
same hybridisation, then as the number of lone pair BF3 is a colourless gas, BCl3 is a colourless fuming liquid
increases, bond angle decreases. e.g. while BI3 is a white fusible solid. Due to backbonding and
•• •• resonance, the B F bond of BF3 gets a bond order of 1.33.
CH4 > NH3 > H2 O
••
Bond angle 5. Oxides
4. Boiling point of hydrides increases on moving down a On moving down the group, their basic character increases.
group because van der Waals’ forces increases with e.g. B2O3 is weakly acidic, Al2O3 is amphoteric and other
increase in molecular mass except HF, H2O, NH3 etc. HF, oxides are basic in nature.
NH3 and H2O have intermolecular hydrogen bonding as a
result of this they have high boiling point. Preparation, Properties and
Unique behaviour of the first element in each group It
is due to the (i) small size (ii) high electronegativity and
Uses of Boron
(iii) non-availability of d-orbitals in the valence shell of
l
The important minerals of boron are borax
first element in each group. (Na2 B4O7 ⋅ 10 H2O), orthoboric acid (H3 BO3) and kernite
(Na2 B4O7 ⋅ 4 H2O).
l
Preparation Now a days, boron is obtained by electrolysis
Group-13 Elements : of a fused mixture containing boric anhydride, magnesium
Boron Family oxide and magnesium fluoride at 1100°C.
Boron (B), aluminium (Al), gallium (Ga), indium (In) and 2MgO → 2Mg + O2
thallium (Tl) are the members of group-13. Boron is a B2O3 + 3Mg → 2B + 3MgO
non-metal while rest of the members are metals.
Crystalline boron is obtained by the reduction of B2O3
with aluminium powder.
Important Properties B2O3 + 2 Al → 2B + Al2O3
2 1
1. Electronic Configuration (ns , np ) Amorphous boron of low purity is called Moissan boron.
It is black in colour.
GS
l
Physical Properties Boron exists in two allotropic forms,
ns 2 np 1
e.g. amorphous and crystalline. Crystalline boron is
ES chemically inert while amorphous boron is chemically
ns 1 np 2 active. It is a bad conductor of heat and electricity.
 Chemical Properties Amorphous boron on heating with air
Some Important Compounds
l

at 700°C forms a mixture of oxide and nitride.

Some important compounds of group-13 elements or boron
4 B + 3O2 → 2 B2O3 , 2B + N2 → 2BN
family are given below:
Boron is attacked by oxidising acids like conc. H2SO 4 and
HNO3 . 1. Diborane ( B 2 H6 )
H SO
B + 3HNO3  → H3 BO3 + 3NO2
2 4 l
It is a colourless, highly toxic gas with a boiling point of 180 K.
Diborane catches fire spontaneously upon exposure to air.
It dissolves in fused alkalies and liberates hydrogen.
B2 H6 + 3O2 → B2O3 + 3H2O
2B + 6NaOH → 2Na3 BO3 + 3 H2
l
With ammonia, diborane gives borazine.
It reacts with strong electropositive metals at high 3B2 H6 + 6NH3 → 3[BH2 (NH3 )2 ]+ [BH4 ]−
temperature and forms boride such as Mg3 B2 . Heat
  → 2 B3 N3 H6 + 12 H2
3 Mg + B2 → Mg3 B2 Borazine

It is a powerful reducing agent. l

Borazine (B3 N3 H6) is known as “inorganic benzene” in view
3CO2 + 4B → 2B2O3 + 3C of its ring structure with alternative BH and NH groups.
l
However, at high temperature, inorganic graphite (BN)x is
3SiO2 + 4B → 2B2O3 + 3Si
obtained instead of borazine.
l
Uses It is used as control rods in atomic reactors and as a
deoxidiser. Ha Hb Ha

B 97° B 120°
Preparation, Properties and 13
4p
11
9p
Ha m Hb m H
Uses of Aluminium a

The important ores of aluminium are bauxite AlO x (OH)3 − 2 x Structure of diborane
(where, 0 < x < 1) and kaolinite [Al2 (OH)4 Si2O 5]. l
Terminal hydrogens (Ha) in diborane are bonded by 2c − 2e
l
Preparation Bauxite contains SiO2 , iron oxides and (two centred two electrons) bonding and bridge hydrogens
titanium oxide (TiO2 ) as impurities. Leaching of bauxite ore (Hb ) are bonded by 3c − 2e (three centred held by two
is carried out with conc. NaOH solution. Aluminium is electrons) bonding. This type of bonding is also known as
obtained by the electrolysis of Al2O3 mixed with Na3 AlF6 or banana bonding. Orbital structure of B2 H6 is
CaF2 (Hall-Haroult process). Overall reaction is as follows: H H
H
2Al2O3 → 4Al + 3O2
l
Physical Properties It is bluish white lustrous metal and B B
loses its lustre due to the formation of protective oxide film
Al2O3 . It is light, malleable, ductile, good conductor of H H H
electricity and heat.
H H H
l
Chemical Properties It burns in oxygen producing brilliant B B
light. H H H
4Al + 3O2 → 2 Al2O3 ; ∆H = − ve Banana bond

This reaction is used in thermite process for the reduction

l
Due to banana bonding, B2 H6 complete its electron
of oxides of Cr, Mn, Fe etc. deficiency and obtain ethane like structure and
It decomposes boiling water evolving hydrogen. hybridisation of B2 H6 becomes sp3.

2Al + 6H2O → 2Al(OH)3 + 3H2 ↑ 2 M H+ B2 H6 → 2 M +[BH4 ]− (M = Li or Na)

It is rendered passive by nitric acid due to the formation of It is used as a catalyst in polymerisation process, for
thin oxide film. It reacts with non-metals and displaces less welding torch, as reducing agent in organic reactions etc.
reactive metals such as copper, zinc and lead from their salt
solutions. 2. Borax (Na2B4 O7 ⋅10H2O)
l
Uses It is used for making household utensils, frames, [Sodium Tetra Borate Decahydrate]
bodies of aircraft automobiles etc. It is used in making l
It is the most important compound of boron. It is white
paints, as a mordant in dyeing and calico printing. crystalline solid.
Ammonal (mixture of Al powder and ammonium nitrate) is l
Borax dissolves in water to give an alkaline solution.
used as explosive. Magnalium, duralumin and alnico are Na2 B4O7 +7H2O → 2NaOH + 4H3 BO3
important alloys of aluminium. Orthoboric acid
(Weak acid)
l
On heating, it loses their water of crystallisation and swells 4. Boron Trifluoride
up. On further heating, it melts into a liquid which then l
BF3 is a colourless pungent gas (melting point is –127.1°C
solidifies to form a glassy mass like bead.
and boiling point is – 99.9°C) which strongly fumes in
∆ moist air and possesses a pungent smell. It is exceedingly
Na2 B4O7 ⋅ 10H2O → Na2 B4O7
−10 H2O Swell up soluble in water that’s why it is collected over Hg.
(Sodium metaborate) l
BF3 being an electron deficient compound can accept a lone
∆ pair of electrons, thus behaves as Lewis acid, e.g. with
→ 2NaBO2 + B2O3
Boric anhydride
NH3, H2S and F−,it can form complexes as shown below:
144444244444
3
Glassy mass
F H F F
   
l
With acids, it gives orthoboric acid, a weak acid. F — B ← N — H ; F— B ← S — H ; F — B ← F–
Na2 B4O7 + 2HCl + 5H2O → 2NaCl + 4B(OH)3 or H3 BO3     
Orthoboric acid F H F H F
(With NH 3 ) (With H2S) (With F − )
l
Borax contains the tetrahedral units, i.e. [B 4 O 5(OH) 4 ]2− .
Due to its electron accepting tendency, it is used as a
OH catalyst in a number of organic reactions.
_
B
l
BF3 combines with water forming two hydrates, i.e.BF3. H2O
(melting point 10.18°C) and BF3. 2H2O (melting point
O O
6.36°C). It gets hydrolysed in aqueous solutions yielding
HO—B O B—OH boric acid and hydrofluoroboric acid.
O O 4BF3 + 3H2O → H3BO 3 + 3HBF4
_
B The bond length in BF3 are 1.30 Å and are shorter than the
OH sum of the covalent radii (B = 0.80Å and F = 0.72Å). The
bond energy of BF3 is very high (646 kJ mol −1 ) and is higher
Structure of [B4O 5(OH)4 ]2− ion than for any single bond. Based on modern explanation, the
double bond is delocalised.
3. Boric Acid (H3 BO3 )
F F F
l
Boric acid is soft white crystalline solid, soapy to touch and
less soluble in cold water. F B F B F B
l
Boric acid is a weak monobasic acid. It is not a protonic F F F
acid but acts as a Lewis acid.
l
Various resonating structures of BF3 molecules involving
l
On heating it above 370 K, it forms metaboric acid, HBO2
pπ − pπ back bonding.
which on heating yield B2O3 .
l
It is used as building block for production of other boron
Heat Heat
l
H3 BO3 → HBO2 → B2O3 compounds.
Metaboric Boron
acid trioxide
5. Aluminium Chloride (AlCl3 )
l
Structure of boric acid shows that it has a layer structure l
Anhydrous aluminium chloride is a white deliquescent solid
in which planar BO3 units are joined by H-bonds. which fumes in air. Its vapour density corresponds to the
B formula Al2Cl6.
O
O
l
It is covalent and soluble in organic solvents.
B H H B Cl Cl Cl
O O O
Al Al
H H H
Cl Cl Cl
Structure of AlCl3
O O O
B H H B l
Due to the formation of HCl, anhydrous aluminium
O
chloride fumes in moist air.
O
B Al2Cl6(anhy. ) + 6 H2O → 2Al(OH)3 + 6 HCl
Al2Cl6 + 12 H2O → 2AlCl3 ⋅ 6 H2O
l
It is used as an antiseptic, eye wash, as food preservative, in Hydrated aluminium
glass industry and in pottery. chloride (ionic)
l
With ammonia, it gives addition product. 2. Catenation
Al2Cl6 (anhy.) + 12 NH3 → 2[AlCl3 ⋅ 6 NH3 ] The tendency for catenation is maximum in carbon and it
Addition product
decreases down the group due to steady decrease in M—M
l
With NaOH, sodium meta-aluminate is obtained. bond strength.
AlCl3 + 3 NaOH → Al(OH)3 ↓ + 3 NaCl C >> Si > Ge ≈ Sn >> Pb
Al(OH)3 + NaOH → NaAlO2 + 2 H2O 3. Allotropy
Sodium meta -
aluminate l
All the members of group 14 elements (except Pb) show
allotropy.
l
Anhydrous AlCl3 is used.
l
Carbon exhibits many allotropic forms both crystalline
(a) As a reagent in Friedel-Crafts reaction.
as well as amorphous. Diamond, graphite and fullerene
(b) In manufacture of drugs, dyes, perfumes.
are crystalline forms while coal, charcoal and lamp black
(c) In cracking of high boiling fractions of petroleum to form are amorphous forms.
gasoline. l
Diamond is the purest, hardest form of carbon with high
refractive index and density. In it each carbon atom
6. Alums (sp3 hybridised) is tetrahedrally surrounded by four other
l
These are double sulphates having composition
carbon atoms. It is three dimensional polymer has very
M2SO 4 ⋅ M2′(SO 4 )3 ⋅ 24 H2O (M = monovalent basic radicals such high density and very high refractive index. It does not
as Na + , K + etc., and M′ = trivalent basic radicals such as Al3+ , conduct electricity as it has no free electrons. It is used
Cr3+ etc.) in cutting, grinding and drilling instruments and in
making jewellery.
Potash alums; K2SO 4 ⋅ Al2 (SO 4 )3 ⋅ 24 H2O
l
Graphite has two dimensional structure. sp2 hybridised
Sodium alums; Na2SO 4 ⋅ Al2 (SO 4 )3 ⋅24 H2O
carbon atom forms three covalent bonds with three other
Ferric alums; (NH4 )2 SO 4 ⋅ Fe2 (SO 4 )3 ⋅24 H2O carbon atoms in the same plane and the 4th electron of
l
Alums are isomorphous solids and soluble in hot water. Their each carbon remains free and is responsible for electrical
aqueous solutions are acidic due to hydrolysis. conductivity of graphite. The planar hexagonal rings get
l
On heating, alum swells up leaving behind a porous mass, fused together to form sheets of one atom thickness. These
called burnt alum. sheets are held together by weak van der Waals’ forces.
l
Fullerenes are the only pure form of carbon. C 60
200° C
K2SO 4 ⋅ Al2 (SO 4)3 ⋅24 H2O → K2SO 4 ⋅Al2 (SO 4 )3 + 24 H2O molecule contains 12 five membered rings and 20
six-membered rings. The five membered rings are
Red hot
K2SO 4 ⋅Al2 (SO 4 )3 → K2SO 4 + Al2O3 + 3SO3 connected to six membered rings while six membered
rings are connected to both five and six membered
l
It is used to purify water, stop bleeding from cuts, as an
rings. These are used in microscopic ball bearings, light
antiseptic, in leather tanning and as a mordant in dyeing and
weight batteries, in synthesis of new plastics and new
calico printing.
drugs.

Group-14 Elements : Carbon Family 4. Oxidation States

Carbon (C), silicon (Si), germanium (Ge), tin (Sn), and lead (Pb) The common oxidation states are +4 and +2. Carbon also
are the members of group-14. Carbon is the seventeenth most exhibits negative oxidation states, i.e. −4. Down the group,
abundant element by mass in the earth’s crust. C is non-metal, stability of +4 oxidation state decreases and of +2 oxidation
Si, Ge are metalloids and Sn, Pb are metals. state increases due to inert pair effect.

Important Properties 5. Oxides

Some of the important properties of group-14 elements or CO2 , SiO2 and GeO2 are acidic, whereas SnO2 and PbO2 are
carbon family elements are given below: amphoteric in nature.
(i) Among monoxides, CO is neutral, GeO is distinctly
1. Electronic Configuration ( ns2np2 ) acidic whereas SnO and PbO are amphoteric.

Ground State
(ii) Monomeric form of CO2 is stable due to
non-availability of d-orbitals. Carbon has tendency to
ns 2 np 2
form a multiple bond (O == C == O) but SiO2 exists in
Excited State three dimensional polymeric form and has high
ns 1 np 3 melting point and is solid at room temperature.
6. Reactivity Towards Water l
The hydrolysis of SiCl4 occurs due to coordination of OH
with empty 3 d-orbitals in Si-atom of SiCl4 molecule.
Carbon, silicon and germanium are not affected by water. Tin (Sn)
OH
decomposes with steam to form dioxide and dihydrogen gas.
Cl Cl Cl Cl Cl OH
2H2O
Heat Si Si Si
Sn + 2H2O → SnO2 + 2H2 –2H +
–2Cl–
Cl Cl Cl Cl Cl OH
Lead remains unaffected by water, probably because of a OH
protective oxide film formation.
OH
Cl OH HO OH
7. Halides 2H2O
Si Si
GeX 4 is more stable than GeX 2 , whereas PbX 2 is more stable –2H+ –2Cl–
Cl OH HO OH
than PbX 4 and SnCl2 is more stable than SnCl4 . SnCl4 is liquid OH
at room temperature due to covalent character and SnCl2 is
solid at room temperature. 3. Silicones
(i) Except CCl4 , other halides are easily hydrolysed due to l
These are synthetic organosilicon compounds which has
availability of vacant d-orbitals. repeated unit of R2SiO.
OH l
These are prepared from alkyl halides.

e.g. SiCl4 + 4H2O → Si  OH or H4SiO 4 + 4HCl Cu powder
2CH3Cl + Si → (CH3 )2 SiCl2 →
2
(CH3 )2 Si(OH)2
+2H O
HO  570 K −2 HCl
OH
Silicic acid CH3 CH3 CH3
| | |
(ii) Si has vacant d-orbitals, so can expand its covalency and HO—Si —OH + HO—Si —OH + HO—Si —OH
form higher halides [SiF6]2 − but not [SiCl6]2 − because | | |
larger size of chloride ions cannot be accommodated CH3 CH3 CH3
around Si4+ due to limitation of its size.
Polymerisation  − H2O
↓
Some Important Compounds  CH3  CH3
Some of the important compounds of group 14 elements or  
 |  |
carbon family elements are given below: —O  —Si—O —
 —Si—
 |  |
1. Oxides of Carbon  
 CH3  n CH3
Two important oxides of carbon are carbon monoxide (CO) Silicone
and carbon dioxide CO2 . Highly cross-linked silicone polymer is obtained by the
Carbon monoxide can be prepared by the following reactions: hydrolysis of RSiCl3 .
473 K -1273 K l
They are used as sealant, greases, electrical insulators and
C(s) + H2O(g) → CO(g) + H2 (g)
144244 3 for water proofing of fabrics. Being biocompatible, they are
Water gas also used in surgical and cosmetic plants.
1273 K
2C(s) + O2 (g) + 4 N2 (g) → 2CO(g) + 4 N2 (g) 4. Silicates
144 42444 3
Producer gas l
A large number of silicate minerals exist in nature. Some of
Water gas and producer gas are very important industrial fuels. the examples are feldspar, zeolites, mica and asbestos. The
basic structural unit of silicates is SiO 4−
4 .
l
Carbon dioxide can be prepared by complete combustion of – –
carbon and carbon containing fuels in excess of air. O O
l
Carbon dioxide can be obtained as a solid in the form of dry
ice by allowing the liquiefied CO2 to expand rapidly. Dry ice
is used as a refrigerant for ice-cream and frozen food. Si
– – – –
O O O O
2. Silicon Tetrachloride (SiCl4 ) Silicon
–
l
It is tetrahedral and essentially covalent. It is readily O
Oxygen
hydrolysed by water. It fumes in moist air liberating l
The SiO 44 − unit is neutralised by positively charged metal
hydrogen chloride.
ions, if all the four corners are shared with other tetrahedral
SiCl4 + 4H2O → Si(OH)4 + 4 HCl
units.
Generally, the silicates have complex structures but they Oxidation State
mainly differ in
The common oxidation states of these elements are −3, +3
(a) Number of oxygen atoms shared between SiO 4−
4 tetrahedra. and +5. The tendency to exhibit −3 oxidation state decreases
(b) Geometric arrangement of tetrahedra. down the group due to increase in size and metallic character.
The stability of + 5 oxidation state decreases down the group
(c) The number, type and arrangement of metallic cations.
and that of +3 oxidation state increases down the group due to
Different type of silicates are as follows: inert pair effect. Nitrogen with oxygen exhibits +1, +2, +4
(i) Orthosilicates Simple silicates containing SiO 4−
4 oxidation states. Oxidation states from +1 to +4 tend to
tetrahedra. disproportionates in acid solution.
(ii) Pyrosilicate Two tetrahedral units share one O-atom to +3 +5 +2
obtain Si2O76− anion. e.g. 3HNO2 → HNO3 + H2O + 2 NO

(iii) Cyclic silicates Two tetrahedral units share two oxygen

atoms and form (SiO2− 2 n− Physical Appearance
3 )n or (SiO3 )n anion.
Only nitrogen has a tendency to form pπ - pπ multiple bond
(iv) Chain silicates Share two oxygen atoms, (SiO2−
3 )n or (N ≡≡ N) due to the absence of d-orbitals.
(SiO3 )2nn− are obtained.
(v) Sheet silicates Involve sharing of three O-atoms per Chemical Reactivity
tetrahedron to form (Si2O2−
5 )n. N2 has high bond dissociation energy, therefore reactivity of
(vi) Three dimensional silicates All the four corners free N2 is very less. Phosphorus has tendency to form a single
(O-atoms) of SiO 4−
4 tetrahedra are shared with other.
bond due to the presence of d-orbitals and thus, exists in
polyatomic form (P4 ).
(iv) Two important man-made silicates are glass and cement.
P
5. Zeolites
l
If aluminium atoms replace few silicon atoms in three P P
dimensional network of silicon dioxide, the obtained
overall structure is known as alumino silicate and acquires
a negative charge. Cations such as Na+ , K + or Ca2+ balance P
(White phosphorus)
the negative charge. Their examples include feldspar and
zeolites. P4 has cyclic structure, therefore it is highly reactive and can
l
Zeolites are used as a catalyst in petrochemical industries for expand its covalency as in PF6− .
cracking of hydrocarbons. ZSM-5 (a type of zeolite) is used
to convert alcohols directly into gasoline. Hydrated zeolites Preparation, Properties and
are used as ion exchangers in softening of hard water.
Uses of Dinitrogen
Group-15 Elements : Preparation
Dinitrogen is produced commercially by liquefaction and
Nitrogen Family
l

fractional distillation of air. Other methods of preparation

Group 15 elements are nitrogen (N), phosphorus (P), arsenic are as follows:
(As), antimony (Sb) and bismuth (Bi). Nitrogen and NH4Cl(aq ) + NaNO2 (aq ) → N2 (g) + 2 H2O(l ) + NaCl(aq )
phosphorus are non-metals, arsenic and antimony are
metalloids and bismuth is a typical metal. Heat
(NH4 )2 Cr2O7 → N2 + 4H2O + Cr2O3
Ba(N3 )2 → Ba + 3N2
Important Properties
Properties
Electronic Configuration (ns2np3 ) l
Dinitrogen does not react with alkali metals except Li but
GS
reacts with alkaline earth metals to give metal nitride.
Heat Heat
ns 2 np 3 6 Li + N2 → 2Li3 N, 3Mg + N2 → Mg3 N2
ES l
It reacts with dioxygen only at high temperature to form
ns 1 np 3 nd 1 nitric oxide.
2000 K
In case of nitrogen, ground state and excited state will be N2 (g) + O2 (g) → 2 NO(g)
same due to the absence of d-orbitals.
Uses 3. Black phosphorus is obtained from white phosphorus.
200° C
l
Liquid N2 is used as refrigerant. White P → black phosphorus
high pressure
l
It is used in the manufacture of HNO3 , NH3 , CaCN2 (calcium
cyanamide) and other nitrogenous compounds. It may occur in orthorhombic, rhombohedral and cubic
l
It is used for filling electric bulbs. form.

Uses
Preparation, Allotropic forms and l
Red phosphorus is used in match box industry.
Uses of Phosphorus l
Radioactive phosphorus is used in treatment of leukaemia
and other blood disorders.
Preparation l
Yellow phosphorus and zinc phosphide are used as a rat
1. Retort process poison.
Ca3 (PO 4 )2 + 3 H2SO 4 → 2 H3 PO 4 + 3CaSO 4
Phosphorite Orthophosphoric
acid
Some Important Compounds
H3 PO 4 → HPO3 + H2O Some of the important compounds of group 15 or nitrogen
Metaphosphoric acid family elements are given below:
4HPO3 + 10C → P4 + 10 CO + 2 H2O
1. Ammonia (NH3 )
2. Electrothermal process Phosphorus is obtained from
direct reduction of mineral phosphorite by carbon in the Preparation
presence of silica. l
It is prepared by following methods.
1400-1500° C NH2CONH2 + 2 H2O → (NH4 )2 CO3 ⋅ 2 NH3 + H2O + CO2
2 Ca3 (PO 4 )2 + 6SiO2 + 10C → Urea
6 CaSiO3 + P4 + 10 CO
2NH4Cl + Ca(OH)2 → 2NH3 + 2H2O + CaCl2
Allotropic Forms (NH4 )2 SO 4 + 2NaOH → 2NH3 + 2 H2O + Na2SO 4
Phosphorus exists in three allotropic forms, i.e. white or l
On large scale, ammonia is manufactured by Haber’s
yellow, red and black (α and β) phosphorus. These forms are process.
interconvertible. 200 atm
470 K
Black phosphorus ← P4
under pressure White phosphorus
N2 (g) + 3 H2 (g) =
723 K; Catalyst
2NH3 ; ∆H °f = − 46.1 kJ / mol

560 K, inert atm. Catalyst iron oxide with small amounts of K2O and Al2O3 is
→ Red phosphorus
used to increase the rate of attainment of equilibrium.
1. White phosphorus is transparent, soft, poisonous, waxy
solid, shows chemiluminescence and chemically more Properties
reactive. l
Ammonia is covalent N-atom in NH3 is sp3 -hybridised. Due
P4 + 5 O2 → P4O10 or 2 P2O 5 to the presence of lone pair of electrons, it acquires
P4 + 3 NaOH + 3 H2O → 3NaH2 PO2 + PH3 pyramidal shape.
Sodium hypo Phosphine l
NH3 is basic in nature, has tendency to form hydrogen bond,
phosphite
therefore soluble in water and form NH4OH or NH3 (aq ).
6 Mg + P4 → 2Mg3 P2 l
Due to basic nature NH3 is a good complexing agent and
Magnesium phosphide
reducing agent. e.g.
It acts as strong reducing agent. 2FeCl3 (aq ) + 3NH4OH (aq ) → Fe2O3 ⋅ xH2O(s) + 3 NH4Cl
P4 + 10 H2SO 4 → 4 H3 PO 4 + 10SO2 + 4 H2O Brown ppt
2. Red phosphorus is the stable form of phosphorus. It is
ZnSO 4 (aq ) + 2 NH4OH (aq ) →Zn(OH)2 (s) + (NH4 )2SO 4
odourless, non-poisonous and less reactive. White ppt
Heat 2 PCl
2 P + 5 Cl2 → 2+
5 Cu (aq ) + 4 NH3 (aq ) =[Cu(NH ) ] 3 4
2+
(aq )
Blue Deep blue
Heat P S
2 P + 3S → 2 3
Ag+ (aq )+ Cl− (aq ) → AgCl(s)
P + 3 Na → Na3 P Colourless White ppt
It is a polymer consists of chains of P4 tetrahedra linked
AgCl (s) + 2NH3 (aq ) → [Ag(NH3 )2 Cl(aq )
together. White ppt. Colourless
Structure l
Brown ring test for nitrates
NH3 is a covalent molecule in which nitrogen possess 6 FeSO 4 + 3 H2SO 4 + 2 HNO3 → 3Fe2 (SO 4 )3 + 2 NO + 4 H2O
sp3 -hybridisation. But due to the presence of one lone pair it l
NO is absorbed by FeSO 4 and a dark brown ring of
acquires pyramidal structure. The bond angle is 107° due to nitroso-ferrous sulphate is formed (ring test for nitrates).
lp-bp repulsion. l
C12 H22O11 + 36 HNO3 → 6(COOH)2 + 36 NO2 + 23 H2O
Oxalic acid
l
Metals like iron, cobalt, nickel, chromium, aluminium
pm N
1.7 become passive in conc. HNO3 due to the formation of a
10
H 107.8° H
thin protective film of oxide on the surface of the metal.
H

Uses Structure
NH3 is used in refrigeration due to its large heat of evaporation l
Nitrogen present in nitric acid is sp2 -hybridised and has a
and in manufacture of HNO3 , NaHCO3 , ammonium trigonal planar geometry. Structure of HNO3 can be
compounds and nitrogenous fertilizers. represented as

2. Nitric Acid (HNO3 ) 1.2

2Å O O
–

H  O  N1 HON
Preparation + .4
O
– +
1Å O
It was earlier known as aqua fortis. It is prepared by the
following processes.
Uses
l
Laboratory preparation
HNO3 is used in the manufacture of explosives such as TNT,
NaNO3 (s) + H2SO 4 (aq ) → NaHSO 4 (aq ) + HNO3 (aq ) picric acid, nitroglycerine, dynamite etc., fertilizers, such as
l
Ostwald process NH4 NO3 , basic Ca(NO3 )2 etc., artificial silk, dyes, drugs.
Pt gauge
4NH3 (g) + 5O2 (g) → 4NO(g) + 6 H2O(l ) ; ∆H = − ve
1100 K Oxides of Nitrogen
2 NO(g) + O2 (g) → 2 NO2 (g) l
N2O(g) is neutral, colourless gas, with sp-hybridisation and
4 NO2 (g) + O2 (g) + 2 H2O(l ) → 4 HNO3 (aq ) linear geometry (it is also called laughing gas).
Heat
NH4 NO3   → N2O + H2O
Properties
l
Anhydrous HNO3 is a colourless fuming pungent smelling
l
NO(g) is colourless, neutral gas. NO(g) also contains odd
liquid. It acquires yellow colour due to its decomposition. number of electrons (paramagnetic) but in solid or liquid
state NO exists in dimeric form and have paired electrons
Sunlight
4 HNO3 → 4NO2 + 2 H2O + O2 (diamagnetic). It is very reactive and harmful to health.
l
It has corrosive action on skin and causes painful sores. 2 NaNO2 + 2 FeSO 4 + 3 H2SO 4 →
l
It is very strong acid and form salts on reaction with basic Fe2 (SO 4 )3 + 2 NaHSO 4 + 2 H2O + 2 NO
oxides, carbonates, hydroxides etc. l
N2O3 is blue solid. It is acidic and planar with
Na2CO3 + 2 HNO3 → 2 NaNO3 + H2O + CO2 sp2 hybridisation.
It acts as a strong oxidising agent. 250 K
2 NO + N2O 4  → 2 N2O3
l

l
Various reactions given by conc. HNO3 that shows chemical l
NO2 (g) is brown, acidic gas with angular shape and sp2
properties of it are as follows:
hybridisation. NO2 contains odd number of valence
l
Non-metals such as C, S, P and I2 are oxidised to carbonic
electrons (paramagnetic). On dimerisation, it gets
acid, sulphuric acid, orthophosphoric acid and iodic acid
converted to stable N2O 4 molecule with even number of
respectively. e.g.
electrons (diamagnetic).
C + 4HNO3 → H2CO3 + 4NO2 + H2O
673 K
S + 6 HNO3 → H2SO 4 + 6 NO2 + 2 H2O 2 Pb(NO3)2  → 4NO2 + 2 PbO+ O2
l
Metalloids such as Sb is oxidised to antimonic acid, as to l
N2O 4 is colourless solid/liquid. It is acidic with planar
arsenic acid and Sn to stannic acid. geometry and sp2 hybridisation. Its covalency is four (total
Sb + 5 HNO3 → H3SbO 4 + 5 NO2 + H2O number of bonds with central atom).
As + 5HNO3 → H3 AsO 4 + 5 NO2 + H2O Cool

Sn + 4 HNO3 → H2SnO3 + 4 NO2 + H2O

2 NO2 e
Heat
N2O 4
l
N2O 5 is colourless, acidic solid with planar shape and 3. Phosphine (PH3 )
sp2 -hybridisation and four covalency.
Preparation
4 HNO3 + P4O10 → 4 HNO3 + 2 N2O 5
It is prepared by following methods:
(a) Ca3 P2 + 6H2O → 3Ca(OH)2 + 2 PH3
Oxides of Phosphorus
(b) Ca3 P2 + 6 HCl → 3CaCl2 + 2PH3
Phosphorus trioxide and phosphorus pentoxide are the two
oxides of phosphorus. Oxides of phosphorus exist in dimeric (c) P4 + 3 NaOH + 3 H2O → PH3 + 3 NaH2 PO2
forms. (d) PH4 I + KOH → KI + H2O + PH3

1. Phosphorus trioxide (P4 O6 ) Properties

It is prepared from white phosphorus. l
It is a colourless gas with rotten fish like smell and is
Burning highly poisonous. It explodes in contact with traces of
P4 + 3O2 → P4O 6
(limited supply of air) oxidising agents like HNO3 , Cl2 and Br2 vapours.
l
It is a poisonous waxy solid with garlic odour. l
It forms phosphides when passed through the solutions
Heat of CuSO 4 , AgNO3 or HgCl2 .
l
4 P4O 6 → 3P4O 8 + 4P
Phosphorus tetroxide 3 CuSO 4 + 2 PH3 → Cu3 P2 + 3 H2SO 4
l
P4O 6 + 4 Cl2 → 2 POCl3 + 2 PO2Cl 3 HgCl2 + 2 PH3 → Hg3 P2 + 6 HCl
Phosphorus Metaphosphorus l
Phosphine is weakly basic PH3 + HBr → PH+4 Br − .
oxychloride oxychloride
l
P4O 6 + 6 H2O(hot) → 3H3 PO 4 + PH3 Structure
P Phosphine is a covalent molecule having pyramidal
O O structure like ammonia. The bond angle H — P — H is 93°.
123° It can be represented as
O
P P
O 100°
O O P
P 160 pm
H H
Structure of P4 O6 H
Structure of phosphine
2. Phosphorus Pentoxide (P4 O 10 )
It is obtained by burning of white phosphorus in free supply of air. Uses
Burning It is used for making smoke screens, metallic phosphides,
P4 + 5O2 → P4O10
free supply of air holme signals due to spontaneous combustion of PH3 .
l
It is white crystalline, odourless solid which sublimes on
heating. 4. Phosphorus Halides (PCl3 and PCl5 )
2H O
P4O10 →
2
4HPO3 →
22H O
2H4 P2O7 Preparation
Metaphosphoric acid Following methods are used to prepare phosphorus halides.

2 H4 P2O7
2H O
→
2
4 H3 PO 4 (a) P4 + 6Cl2 → 4PCl3
Pyrophosphoric Orthophosphoric (b) P4 + 10Cl2 → 4PCl5
acid acid
(c) P4 + 8SOCl2 → 4 PCl3 + 4 SO2 + 2S2Cl2
l
It is used as most effective dehydrating agent below 100°C.
(d) P4 + 10 SO2Cl2 → 4PCl5 + 10SO2
O
160 p
m
P Properties
O 102
° O
l
PCl5 is a yellowish white powder and in moist air it gets
143 pm O
P P hydrolysed to POCl3 and finally gets converted to
O O 123° O
P phosphoric acid.
O O
PCl5 + H2O → POCl3 + 2 HCl
O
Structure of P4 O 10
POCl3 + 3 H2O → H3 PO 4 + 3HCl
Structure Pyrophosphorus acid = H4 P2O 5
l
PCl5 in gaseous and liquid phases has sp d-hybridisation 3 Hypophosphoric acid = H4 P2O 6
and its shape is trigonal bipyramidal. l
H3 PO3 on heating, disproportionates to give
Cl orthophosphoric acid and phosphine.
Cl 4 H3 PO3 → 3H3 PO 4 + PH3
l
The acids which contain P—H bond, have strong reducing
P Cl properties, thus hypophosphorus acid is a good reducing
agent as it contains two P—H bonds. e.g.
Cl
4 AgNO3 + 2 H2O + H3 PO2 → 4 Ag + 4 HNO3 + H3 PO 4
Cl
The three equatorial P—Cl bonds are equivalent while the Group-16 Elements :
two axial bonds are longer than equatorial bonds.
l
In solid state, PCl 5 exists as an ionic solid, [PCl4 ]+ [PCl6]− in
Oxygen Family
which, the cation, [PCl4 ]+ is tetrahedral and the anion Group 16 elements are sulphur (S), selenium (Se), tellurium
− (Te) and polonium (Po). This is sometimes known as group of
[PCl6] is octahedral.
chalcogens (due to ore forming nature). Oxygen is the most
l
Structure of PCl3 is similar to ammonia. P-atom is abundant of all the elements on earth. Oxygen and sulphur
sp3 -hybridised. are non-metals, selenium and tellurium are metalloids and
polonium is radioactive metal.

P
Important Properties
pm
4

0° The group-16 elements exihibit the properties may be given as:

20

Cl 10 Cl
Cl Electronic Configuration (ns 2 np 4 )
Structure of PCl3
Uses GS
l
PCl3 is used in the manufacture of POCl3 and in preparation ns 2 np 4
of organic compounds. ES
l
PCl 5 is used as a chlorinating agent in organic chemistry. ns 1 np 3 nd 2

Oxoacids of Phosphorus and Nitrogen Oxidation States

l
H2 N2O2 (hyponitrous acid); HNO2 (nitrous acid) and HNO3
Oxidation states exhibited by 16th group elements are −2, +2,
(nitric acid) are the oxoacids of nitrogen. Out of these HNO3
+4, +6 but +4 and +6 are more common. On moving down the
is the most important. HNO2 (conc.) is strong oxidising
group, stability of +6 oxidation state decreases and that of
agent. e.g.
+4 oxidation state increases due to inert pair effect. The
I2 + 10HNO3 → 2HIO3 + 10NO2 + 4H2O 1
oxidation state of O is −1 and − in peroxides and
P4 + 20HNO3 (conc.) → 4H3 PO3 + 20NO2 + 4H2O 2
l
The structure of oxoacids of phosphorus are given below : superoxides respectively. In case of OF2 , O2 F2 , oxidation states
O of oxygen are +2, +1 respectively.
O

P Physical Appearance
P H H
H OH Oxygen has a tendency to form pπ-pπ multiple bond (O ==O)
OH OH
due to the absence of d-orbitals and high bond dissociation
H3PO3 H3PO2
(Orthophosphorus acid) (Hypophosphorus acid) enthalpy. Sulphur has tendency to form single bond due to
sp3, diprotic monoprotic, sp3 the presence of d-orbitals and exist in polyatomic (S8) form.
O O
O Allotropy
P P Oxygen exists in two molecular allotropic forms; the diatomic
HO OH HO O P molecule, O2 (most stable) and the triatomic molecule, O3
OH
O OH OH (ozone comparatively less stable). Sulphur forms numerous
OH allotropes, out of which the yellow rhombic (α-sulphur) and
H3PO4 H4P2O7
(Orthophosphoric acid) (Pyrophosphoric acid) monoclinic (β-sulphur) forms are the most important.
triprotic, sp3 sp3
 369 K above
Rhombic sulphur → Monoclinic sulphur
Properties
l
Colourless, odourless, tasteless gas which is slightly soluble in
At elevated temperatures (1000 K), S2 is the dominant species
water. Liquid oxygen exhibits paramagnetism.
and is paramagnetic like O2 . l
It is non-inflammable but a supporter of combustion.
Hydrides l
O == O, bond dissociation energy is high, therefore it reacts
with metals or non-metals after external heating to start the
Down the group acidic character increases from H2O to H2Se.
reaction.
All the hydrides except water possess reducing property and
3300 K
this character increases from H2S to H2 Te. N2 + O2 → 2 NO
Room temperature
Oxides 4Na(s) + O2(g) → 2 Na2O(s)
All these elements (except O2 ) form MO2 type oxides. SO2 is 4Al (s) + 3O2 (g) → 2 Al2O3 (s)
gas while SeO2 is solid. Reducing property of dioxide
decreases from SO2 to TeO2 . SO2 is reducing while TeO2 is an Uses
oxidising agent. l
In oxyacetylene and oxyhydrogen flames.
l
Liquid O2 is used as a rocket fuel.
Halides l
For life support systems, e.g. in hospitals and in water
The stability of the halides decreases in the order diving for divers, for miners and mountaineers.
F− > Cl− > Br − > I− . l
As an oxidising and bleaching agent.
Amongst hexahalides, hexafluorides are the only stable
2. Ozone
halides. All hexafluorides are gaseous in nature. SF6 is
It is formed in the upper layer of atmosphere by the action of
exceptionally stable for steric reasons. SF4 is a gas, SeF4 is a
UV rays from sun on oxygen. It prevents the UV rays from
liquid and TeF4 is a solid. These fluorides have sp3d
entering the earth’s atmosphere. CFCs, common refrigerants
hybridisation and see-saw geometry. The well known mono deplete the ozone layer.
halides are dimeric in nature. e.g. S2 F2 ,S2Cl2 , S2 Br2 , Se2Cl2 and
Se2 Br2 . These dimeric halides undergo disproportionation as Preparation
given below: It is prepared in ozoniser by subjecting dry and cold dioxygen
2Se2Cl2 → SeCl4 + 3Se to the action of silent electric discharge.
Silent electric discharge
3O2 (g) 2 O3 (g)
Some Important Compounds
Some of the important compounds considered under group 16 Properties
are given below: l
It is pale blue gas with pungent odour. It is diamagnetic and
poisonous.
1. Dioxygen Heat 3O
l
Ozone is unstable; 2O3 → 2
Preparation l
It acts as a powerful oxidising agent. It liberates iodine from
l
Laboratory method neutral KI solution and the liberated I2 turns starch paper
MnO blue.
2 KClO3 →
2
2 KCl + 3O2
∆ 2 KI + H2O + O3 → 2KOH + I2 + O2
l
It is manufactured from liquid air. Air is liquefied by I2 + starch → Blue colour
making use of Joule Thomson effect. Liquid air is a mixture l
Alkaline KI is oxidised to potassium iodate and periodate.
of liquid nitrogen and liquid oxygen. The difference in their
KI + 3O3 → KIO3 + 3O2
boiling points is about 12.8°C, hence they are easily Potassium iodate
separated by fractional evaporation.
KI + 4 O3 → KIO 4 + 4 O2
l
By electrolysis of water (acidified water) Potassium periodate
H2SO 4 0 2 H+ + SO24−
H2S + O3 → H2O + S + O2
+ −
At cathode 2 H + 2 e → H2 l
Mercury loses its meniscus in contact with ozone (tailing of
1 mercury).
At anode 2OH− → H2O + O2 + 2 e −
2 2 Hg + O3 → Hg2O + O2
Uses Properties
l
As a germicide and disinfectant for sterilising water. l
Concentrated sulphuric acid is a strong dehydrating
l
As a bleaching agent for oils, ivory wax and delicate fibre. agent.
For detecting the position of double bond in unsaturated H SO
C12 H22O11 →
2 4
12C + 11 H2O
l

compounds.
l
In destroying odours coming from cold storage room,
l
Hot concentrated sulphuric acid is a moderately strong
slaughter houses and kitchen of hotels. oxidising agent. In this respect, it is intermediate between
phosphoric and nitric acids.

Allotropic forms of Sulphur S + 2 H2SO 4 (conc.) → 3SO2 (g) + 2 H2O

It exists in several allotropic forms. These are as follows: C + 2 H2SO 4 (conc.) → CO2 + 2 SO2 + 2 H2O
1. Rhombic sulphur (α-sulphur) is common crystalline form Uses
of sulphur, yellow in colour, melting point 114.5°C and l
In the manufacture of fertilisers
specific gravity 2.06. Its crystals are prepared by
evaporating sulphur solution in CS2 . It is insoluble in
l
Petroleum refining
water but readily soluble in CS2 . l
In manufacture of pigments, paints and dyestuff
2. Monoclinic sulphur (β-sulphur) is stable above 95.6°C. Its
l
Detergent industry
crystals are amber yellow in colour, melting point 119°C,
l
Metallurgical application
specific gravity 1.98. It is insoluble in CS2 . It is prepared l
Storage batteries
by melting rhombic sulphur in a dish followed by cooling l
As a laboratory reagent
till crust is formed.
95.6° C NOTE H2SO 3 acts as bleaching agent but it is temporary and the
Rhombic sulphur a Monoclinic sulphur. bleached material regains its colour due to oxidation.

At 95.6°C both the forms are stable. This temperature is Oxoacids of Sulphur
called transition temperature. S8 rings in both the forms
The structures of oxoacids of sulphur are as follows:
is puckered and has a crown shape.
O
3. Plastic sulphur is obtained by pouring boiling sulphur
into cold water. It is amber brown in colour, specific
S S
gravity 1.95 and insoluble in CS2 .
HO O HO O
4. Milk of sulphur is obtained by boiling milk of lime with HO HO
sulphur and decomposing the products formed with HCl. Sulphurous acid Sulphuric acid
It is used in medicines. (H2SO3) (H2SO4)
5. Colloidal sulphur is prepared by passing H2S through a
O O O O
solution of an oxidising agent such as nitric acid etc.
2HNO3 + H2S → 2NO2 + 2H2O + S S S S S
Colloidal sulphur changes into ordinary form on heating. O O—O O O O O
OH OH OH OH

Sulphuric Acid (H2SO4 ) Peroxodisulphuric acid

(H2S2O8)
Pyrosulphuric acid (oleum)
(H2S2O7)
Preparation
It is manufactured by contact process which involves three
steps :
Group-17 Elements :
(i) Burning of sulphur ores in air to generate SO2 . Halogens Family
(ii) Conversion of SO2 to SO3 by the reaction with oxygen in l
Group-17 members are fluorine (F), chlorine (Cl), bromine
the presence of a catalyst (V2O 5). (Br), iodine (I) and astatine (At). Astatine is a radioactive
VO
2 SO2 (g) + O2 (g)  
2 5
→ 2 SO3 (g) element.
2 bar, 720 K l
The halogens are highly reactive non-metallic elements.
(iii) Absorption of SO3 in H2SO 4 to give oleum (H2S2O7 ) Fluorine is most electronegative atom and strong
SO3 + H2SO 4 → H2S2O7 (oleum) oxidising agent.
 (ii) Br2O, BrO2 , BrO3 are the least stable bromine oxides and
Important Properties exist only at low temperatures. They are very powerful
Electronic Configuration oxidising agents.
All elements of group have seven electron in their outermost (iii) The iodine oxides, i.e. I2O 4 , I2O 5, I2O7 are insoluble solids
shell ns2 np2 . and decompose on heating. I2O 5 is a very good oxidising
agent and is used in the estimation of carbon monoxide.
GS
ns 2 np 5
(1 unpaired electron accounts for –1 or +1 oxidation state)
Some Important Compounds
Some of the important compounds of group 17 elements.
ES
ns 1 np 3
1. Chlorine (Cl2 )
nd 3
Preparation
Oxidation State It can be prepared by the following methods:
Ground state and excited state in fluorine will be same due to (a) MnO2 + 4 HCl → MnCl2 + Cl2 + 2H2O (Lab method)
absence of d-orbitals and oxidation state of fluorine is CuCl
always –1. (b) 4HCl + O2 →
2
2Cl2 + 2 H2O (Deacon’s process)
Chlorine is obtained by the electrolysis of brine
Chemical Reactivity (concentrated NaCl solution). Chlorine is liberated at anode
All the halogens are highly reactive. Halogens are strong (electrolytic process). It is also obtained as a by product in
oxidising agent and their oxidising power decreases down the many chemical industries.
group.
F2 > O2 > Cl2 > Br2 > I2 Properties
Oxidising power decreases l
It is a greenish yellow gas with pungent and suffocating
− − odour. It is soluble in water.
e.g. F2 + 2 X → 2 F + X 2 ( X = Cl, Br and I)
2 F2 (g) + 2 H2O(l ) → 4HF(aq ) + O2(g)
l
8 NH3 + 3Cl2 → 6NH4Cl + N2

X 2(g) + H2O(l ) → HX (aq ) + HOX (aq )

l
NH3 + 3Cl2 → NCl3 + 3 HCl
Excess Explosive
(where, X = Cl or Br)
l
2NaOH + Cl2 → NaCl + NaOCl + H2O
The reaction of I2 with water is non-spontaneous. However, I− Cold and dil.
can be oxidised by oxygen in acidic medium. l
6NaOH + 3Cl2 → 5 NaCl + NaClO3 + 3H2O
− + Hot and conc.
4 I (aq ) + 4 H (aq ) + O2 (g) → 2 I2 (s) + 2 H2O(l )
l
The order of bond dissociation enthalpy is
l
With dry slaked lime, it gives bleaching powder.
Cl— F > Cl2 > Br2 > F2 > I2 . Ca(OH)2 + Cl2 → CaOCl2 + H2O
l
Here, fluorine shows anomalous behaviour because of its
very small size and high electronegativity. F2 has less bond Uses
enthalpy than Cl2 and Br2 and absence of d-orbitals in l
For bleaching woodpulp, bleaching cotton and textiles.
valence shell. l
In extraction of gold and platinum.
l
Hydrogen halides dissolve in water to form hydrohalic l
In manufacture of dyes, drugs and organic compounds.
acids. The acidic strength of these acids varies as
HF < FCl < HBr < HI. 2. Hydrogen Chloride (HCl)
l
HF is a liquid while rest of hydrogen halides are gases. It
reacts with glass, so it is stored in waxed glass bottles. This
Preparation
property of HF to act on glass is utilised in etching of glass. In laboratory, it is prepared by heating sodium chloride with
concentrated sulphuric acid.
Fluorine forms two oxides, OF2 and O2 F2 , but only OF2 is
420 K
thermally stable at 298 K. O2 F2 oxidises plutonium to PuF6 and NaCl + H2SO 4 → NaHSO 4 + HCl
the reaction is used for removing plutonium as PuF6 from
823 K
spent nuclear fuel. NaHSO 4 + NaCl → Na2SO 4 + HCl
(i) Chlorine forms a number of oxides such as, Cl2O, Cl2O3 , HCl gas can be dried by passing through concentrated
Cl2O 5, Cl2O7 , ClO2 . ClO2 is used as a bleaching agent for sulphuric acid.
paper pulp, textiles and in water treatment.
Properties Some Properties of Interhalogen Compounds
It is a colourless and pungent smelling gas. Its aqueous Physical state
Type Formula Structure
solution is called hydrochloric acid. and colour
When three parts of concentrated HCl and one part of XX’ CIF Colourless gas Linear
concentrated HNO3 are mixed, aqua-regia is formed BrF Pale brown gas Linear
which is used for dissolving noble metals, e.g. gold, IF (very Detected Linear
platinum. unstable) spectroscopically
BrCl (Pure solid Ruby red solid Linear
Uses is known at r.t. ) (α -form)
l
In manufacture of chlorine, NH4Cl and glucose. ICl Brown red solid Linear
l
For extracting glue from bones. ( β -form) Linear
IBr
l
In medicine and as laboratory agent. Black solid
XX ′3 ClF3 Colourless gas Bent T-shaped

Oxoacids of Halogens BrF3 Yellow green

liquid
Bent T-shaped
IF3 Bent T-shaped
Higher oxoacids of fluorine such as HFO2 , HFO3 do not Yellow power
ICl3 (dimerises as Bent T-shaped
exist because fluorine is most electronegative and has
Cl-bridged Orange solid
absence of d-orbitals. +3 oxidation state of bromine and
dimer,I2Cl 6)
iodine is unstable due to inert pair effect, therefore HBrO2
XX ′ 5 IF5 Colourless gas Square pyramidal
and HIO2 do not exist.
but solid below
Decreasing order of acidic nature 77K
HOF > HOCl > HOBr > HOI Colourless liquid Square pyramidal
BrF5
(Hypofluorous (Hypochlorous (Hypobromous (Hypoiodous Colourless liquid Square pyramidal
ClF5
acid) acid) acid) acid)
XX ′7 IF7 Colourless gas Pentagonal
→ HOClO2 > HOBrO2 > HOIO2 bipyramidal
(Chloric acid) (Bromic acid) (Iodic acid)

→ HOClO3 > HOClO2 > HOClO > HOCl Group-18 Elements : Noble Gases
→ HClO 4 > HBrO 4 > HIO 4 l
Elements of group 18 are helium (He), neon (Ne), argon (Ar),
krypton (Kr), xenon (Xe) and radon (Rn) (radioactive).
Structures of various oxoacids of chlorine are as follows:
l
All of these are gases and chemically unreactive. Down the group
H H their ionisation enthalpy decreases, therefore Xe reacts with
O O oxygen and fluorine and forms different compounds. Xenon
and radon are the rarest elements of the group. First prepared
Cl Cl noble gas compound by Neil Bartlett in 1962 is XePtF6.
O O O O O O O
H Cl H Cl O Occurrence
Hypochlorous acid Chlorous acid Chloric acid Perchloric acid
On account of their inert nature, the noble gases always occur in
l
Pseudo halide ions are stronger ligands than halide ions the free state. Argon is the most abundant noble gas in the
and these can function as ambidentate ligands as they atmosphre while radon is not present in atmosphere. He, Ar and
are made up of two hetero atoms. Ne are also found as constituents of dissolved gas of certain
spring water.
Interhalogen Compounds Important Properties
l
When two different halogens react with each other,
interhalogen compounds are formed. These compounds
l
Electronic configuration is (ns2 np6) (except helium).
are covalent and diamagnetic in nature.
GS
l
They are volatile solids or liquids except ClF which is a
gas at 298 K. Interhalogen compounds are more reactive ns 2 np 6
than halogens (except fluorine). ES
ns 1 np 3 nd 4
Chemical Reactivity l
Molecular Structures of Xenon Compounds
l
XeF4 + O2 F2 → XeF6 + O2
180° F F
l
6 XeF4 + 12 H2O → 4Xe + 2 XeO3 + 24 HF + 3 O2
XeF6 + 3 H2O → XeO3 + 6 HF Xe
l
F Xe F
l
Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and F F
XeO2 F2 . XeF2 XeF4
l
XeF2 , XeF4 and XeF6 are colourless crystalline solids and (Xe atom in 1st excited state) (Xe atom in 2nd excited state)
sublime readily at 298 K. They are powerful fluorinating F
F F F
agents.
F F
l
XeF6 is extremely reactive. It cannot be stored in glass or Xe Xe
quartz vessels as it readily reacts with SiO2 present in glass.
F F F F
Summary of Stable Compounds of Xe O
No. of lone XeF6 XeOF4
Oxidation
Compound
state of Xe
Hybridisation pair(s) of Shape (Xe atom in 3rd excited state) (Xe in 3rd excited state)
electrons

XeF2 +2 sp3d 3 Linear

Xe
XeF4 +4 sp3d 2 2 Square F Xe F
planar O O
O
O O
XeF6 +6 sp3d 3 1 Distorted XeO3
XeO2F2
octahedral st st
(Xe in 1 excited state) (Xe in 1 excited state)
XeOF2 +4 sp3d 2 T-shaped
Uses
XeO2 F2 +6 sp3d 1 Distorted
trigonal
l
He is used in filling balloons for meteorological
bipyramidal observations. It is used in gas cooled reactor to produce
powerful super-conducting magnets and as a diluent for
XeOF4 +6 sp3d 2 1 Square oxygen in diving apparatus.
pyramidal
l
Ne is used in discharge tubes and fluorescent bulbs.
3
XeO3 +6 sp 1 Pyramidal l
Ar is used in filling bulbs and to produce inert atmosphere
in various metallurgical operations.
246 40 DAYS ~ JEE MAIN CHEMISTRY DAY TWENTY TWO

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

1 Boric acid is called acid because its molecule 10 The catenation tendency of C, Si and Ge is in the order
(a) contains replaceable H+ion Ge < Si < C. The bond energies (in kJ mol−1) of C—C,
(b) gives up a proton Si—Si and Ge—Ge bonds are respectively
(c) accepts OH− from water releasing proton j JEE Main (Online) 2013

(d) combines with proton from water molecule (a) 348, 297, 260 (b) 297, 348, 260
2 Heating of an aqueous solution of aluminium chloride to (c) 348, 260, 297 (d) 260, 297, 348
dryness will give 11 Strong reducing behaviour of H 3PO 2 is due to
(a) Al(OH)Cl 2 (b) Al 2O3 (c) Al 2 Cl 6 (d) AlCl 3 (a) Low oxidation state of phosphorus
3 Boron cannot form which one of the following anions? (b) presence of two  OH groups and one P H bond
(c) Presence of one  OH group and two P H bonds
j AIEEE 2011
(d) high electron gain enthalpy of phosphorus
(a) BF63 − (b) BH−4
12 Nitrogen shows different oxidation states in the range
(c) B(OH)−4 (d) BO −2
(a) 0 to +5 (b) −3 to +5
4 Mark the oxide which is amphoteric in character. (c) −5 to +3 (d) −3 to+3
(a) CO2 (b) SiO2 (c) SnO2 (d) CaO
13 A hydride of nitrogen which is acidic is
5 Graphite is a soft, solid lubricant, extremely difficult to (a) NH3 (b) N2H4
melt. The reason for this anomalous behaviour is that (c) N2H2 (d) N3H
graphite 14 The compound that does not produce nitrogen gas by
(a) is an allotropic form of diamond the thermal decomposition is j
JEE Main 2018
(b) has molecules of variable molecular masses like (a) Ba(N3 )2 (b) (NH4 )2 Cr2O7
polymers (c) NH4NO2 (d) (NH4 )2 SO4
(c) has carbon atoms arranged in large plates of rings of
strongly bound carbon atoms with weak interplate 15 Extra pure N2 can be obtained by heating
bonds (a) NH3 with CuO (b) NH4NO3
(d) is a non-crystalline substance (c) (NH4 )2 Cr2O7 (d) Ba(N3 )2

6 Carborundum is obtained when silica is heated at high 16 The number of σ bonds in P4O10 is
temperature with (a) 6 (b) 16
(c) 20 (d) 7
(a) carbon (b) carbon monoxide
(c) carbon dioxide (d) calcium carbonate 17 PH3, the hydride of phosphorus is
7 Among the following substituted silanes the one which (a) metallic (b) ionic
(c) non-metallic (d) covalent
will give rise to cross linked silicon polymer on
hydrolysis, is 18 When concentrated HNO3 is heated with P2O5 it forms
(a) R 3 SiCl (b) R 4 Si (a) N2O (b) NO
(c) R SiCl 3 (d) R 2 SiCl 2 (c) NO2 (d) N2O5

8 Name of the structure of silicates in which three oxygen 19 Among the following, the number of compounds that can
atoms of [SiO4 ] 4−
are shared is react with PCl5 to give POCl3 is
(a) pyrosilicate (b) sheet silicate O2, CO2, SO2, H2O, H2SO4, P4O10.
(c) linear chain silicate (d) three dimensional silicate
(a) 1 (b) 2
9 In curing cement plasters water is sprinkled from time to (c) 3 (d) 4
time. This helps in
20 When conc. H2SO4 is heated with P2O5, the acid is
(a) keeping it cool converted to
(b) developing interlocking needle like crystals of hydrated (a) sulphur trioxide
silicates (b) sulphur dioxide
(c) hydrating sand and gravel mixed with cement (c) sulphur
(d) converting sand into silicic acid (d) a mixture of sulphur dioxide and sulphur trioxide
21 The pair in which phosphorus atoms have a formal 33 The solubility order of alkali metal fluoride in water is
oxidation state of +3 is j JEE Main 2016 j JEE Main (Online) 2013

(a) pyrophosphorus and hypophosphoric acids (a) LiF < RbF < KF < NaF (b) RbF < KF < NaF < LiF
(b) orthophosphorus and hypophophoric acids (c) LiF > NaF > KF > RbF (d) LiF < NaF < KF < RbF
(c) pyrophosphorus and pyrophosphoric acids
(d) orthophosphorus and pyrophosphorus acids 34 Which one has the highest boiling point? j JEE Main 2015
(a) He (b) Ne (c) Kr (d) Xe
22 White phosphorus on reaction with NaOH gives PH3 as
one of the products. This is a 35 Argon is used in arc welding because of its
(a) dimerisation reaction (b) disproportionation reaction (a) low reactivity with metal
(c) condensation reaction (d) precipitation reaction (b) ability to lower the melting point of metal
(c) flammability
23 The molecule having smallest bond angle is j AIEEE 2012
(d) high calorific value
(a) NCl 3 (b) AsCl 3 (c) SbCl 3 (d) PCl 3
36 The structure of XeO3 is
24 Which of the following statements is incorrect? j AIEEE 2011 (a) linear (b) planar
(a) The stability of hydrides increases from NH3 to BiH3 in (c) pyramidal (d) T-shaped
group 15 of the periodic table 37 XeF4 and XeF6 are expected to be
(b) Nitrogen cannot form dπ-pπ bond
(a) oxidising (b) reducing
(c) Single N—N bond is weaker than the single P—P bond (c) unreactive (d) strongly basic
(d) N2O4 has two resonance structures
38 Which of the following acids possesses oxidising,
25 Which one of the following compounds has the smallest reducing and complex forming properties?
bond angle in its molecule? (a) HCl (b) HNO2 (c) H2 SO4 (d) HNO3
(a) OH2 (b) SH2 (c) NH3 (d) SO2
39 Match the species given in Column I with properties
26 The number of S––S bonds in sulphur trioxide trimer given in Column II.
(S 3O9 ) is
Column I Column II
(a) three (b) two (c) one (d) zero
A. Diborane 1. Used as a flux for soldering metals
27 Which of the following are peroxoacids of sulphur?
(a) H2 SO5 and H2 S2O8 (b) H2 SO5 and H2 S2O7 B. Gallium 2. Crystalline form of silica
(c) H2 S2O7 and H2 S2O8 (d) H2 S2O6 and H2 S2O7 C. Borax 3. Banana bonds
28 Which of the following is the wrong statement? D. Aluminosilicate 4. Low melting, high boiling,useful for
(a) O3 molecule is linear j
JEE Main (Online) 2013 measuring high temperatures
(b) Ozone is violet black in solid state E. Quartz 5. Used as catalyst in petrochemical
(c) Ozone is diamagnetic gas industries
(d) ONCl and ONO − are not isoelectronic
Codes
29 Which of the following statements regarding sulphur is
incorrect? j
AIEEE 2011 A B C D E
(a) 3 4 1 5 2
(a) S2 molecule is paramagnetic (b) 4 3 1 5 2
(b) The vapour at 200°C consists mostly of S8 rings
(c) 4 3 5 2 1
(c) At 600°C, the gas mainly consists of S2 molecules
(d) 1 2 5 4 3
(d) The oxidation state of sulphur is never less than +4
in its compounds Directions (Q. Nos. 40-42) Each of these questions
30 Which among the following is the most reactive? contains two statements : Statement I and Statement II. Each
(a) Cl 2 (b) Br2 j
JEE Main 2015 of these questions also has four alternative choices, only one
(c) I2 (d) ICI of which is the correct answer. You have to select one of the
codes (a), (b), (c), (d) given below:
31 The correct order of the thermal stability of hydrogen (a) Statement I is true, Statement II is true; Statement II is a
halides (H X ) is correct explanation for Statement I
(a) HI > HCl > HF > HBr (b) HCl < HF > HBr < HI (b) Statement I is true, Statement II is true; Statement II is
(c) HF > HCl > HBr > Hl (d) Hl > HBr > HCl > HF not a correct explanation for Statement I
32 Among the following oxoacids, the correct decreasing (c) Statement I is true; Statement II is false
order of acid strength is j
JEE Main 2014 (d) Both the Statement I and II are false
(a) HOCI > HCIO2 > HCIO3 > HCIO4 40 Statement I Boron always forms covalent bond.
(b) HCIO4 > HOCI > HCIO2 > HCIO3 Statement II The small size of B 3+ favours formation of
(c) HCIO4 > HCIO3 > HCIO2 > HOCI
covalent bond.
(d) HCIO2 > HCIO4 > HCIO3 > HOCI
 41 Statement I In water, orthoboric acid behaves as a (b) Assertion and Reason both are correct statements but
weak monobasic acid. Reason is not the correct explanation of the Assertion
Statement II In water, orthoboric acid acts as a proton donor. (c) Assertion is correct and Reason is incorrect
(d) Both Assertion and Reason are incorrect
42 Statement I Between SiCl4 and CCl4, only SiCl4 reacts
with water. 43 Assertion (A) Silicones are water repelling in nature.
Statement II SiCl4 is ionic and CCl4 is covalent. Reason (R) Silicones are organosilicon polymers, which
have (—R 2SiO— ) as repeating unit.
Direction (Q. Nos. 43 and 44) In the following questions,
Assertion (A) followed by Reason (R) is given. Choose the 44 Assertion (A) Nitrogen and oxygen are the main
correct answer out of the following choices. components in the atmosphere but these do not react to
(a) Assertion and Reason both are correct statements and form oxides of nitrogen.
Reason is the correct explanation of the Assertion Reason (R) The reaction between nitrogen and oxygen
requires high temperature.

DAY PRACTICE SESSION 2

PROGRESSIVE QUESTIONS EXERCISE

1 Identify the incorrect statement among the following. (c) Between NH3 and PH3 , NH3 is a better electron donor
(a) Ozone reacts with SO2 to give SO3 because the lone pair of electrons occupies sp 3 orbital
and is more directional
(b) Silicon reacts with NaOH (aq) in the presence of air to
give Na 2 SiO3 and H2O (d) Between NH3 and PH3 , PH3 is a better electron donor
because the lone pair of electrons occupies spherical ‘s’
(c) Cl 2 reacts with excess of NH3 to give N2 and NH4 Cl
orbital and is less directional
(d) Br2 reacts with hot and strong NaOH solution to give
NaBr, NaBrO4 and H2O 6 The formation of O+2 [PtF6 ] is the basis for the formation of
xenon fluorides. This is because
2 Reduction potentials of some ions are given below.
(a) O2 and Xe have comparable sizes
Arrange them in the decreasing order of oxidising power.
(b) both O2 and Xe are gases
Ion ClO−4 IO−4 BrO−4 (c) O2 and Xe have comparable I.E.
Reduction potential (d) Both (a) and (c)
E È / V E È = 119
. V E È = 1.65 V E È = 174
. V 7 The hydrides of the first elements in groups 15-17 namely
(a) CIO−4 > IO−4 > BrO−4 (b) IO−4 > BrO−4 > CIO−4 NH3, H2O and HF respectively shows abnormally high
(c) BrO−4 > IO−4 > CIO−4 (d) None of these values for melting and boiling points. This is due to
3 Which of the following statements is true? (a) small size of N, O and F
(b) the ability to form extensive intermolecular H-bonding
(a) H3PO3 is a stronger acid than H2 SO3
(c) the ability to form extensive intramolecular H-bonding
(b) In aqueous medium, HF is a stronger acid than HCl (d) effective forces of interaction
(c) HClO4 is weaker acid than HClO3
(d) HNO3 is a stronger acid than HNO2 8 An inorganic compound ‘X ’, made of two most occurring
elements in the earth’s crust and used in building
4 Which one of the following reaction of xenon compounds construction, when reacts with carbon forms a diatomic
is not feasible? molecule, which is poisonous in nature. Compound ‘X ’ may be
(a) XeO3 + 6HF → XeF6 + 3H2O (a) SiO2 (b) Al 2O3
(b) 3XeF4 + 6H2O → 2Xe + XeO3 + 12HF + 1.5O2 (c) CaO (d) CO2
(c) 2XeF2 + 2H2O → 2Xe + 4HF + O2
(d) XeF6 + RbF → Rb[XeF7 ] 9 Which one of the following reactions does not occur ?
(a) F2 + Cl − → 2F − + Cl 2 (b) Cl 2 + 2F − → 2Cl − + F2
5 Among the following, the correct statement is : (c) Br2 + 2I− → 2B r − + I2 (d) Cl 2 + 2Br − → 2Cl − +Br2
(a) Between NH3 and PH3 , NH3 is a better electron donor
10 B(OH) 3 + NaOH 0NaBO + Na[B(OH)4 )] + H2O
2
because the lone pair of electrons occupies spherical ‘s’
orbital and is less directional How can this reaction is made to proceed in forward
(b) Between NH3 and PH3 , PH3 is a better electron donor direction?
because the lone pair of electrons occupies sp 3 orbital (a) Addition of cis 1, 2-diol (b) Addition of borax
and is more directional (c) Addition of trans 1, 2-diol (d) Addition of Na 2HPO4
11 An inorganic compound containing (3c-2e − ) and (2c-2e − ) 14 Consider the following statements.
bonds when reacts with NH3, at a certain temperature, I. NCl5 does not exist while PCl5 does
gives a compound ‘X ’ which is isostructural with benzene II. Both O+2 and NO are paramagnetic
and when reacts at high temperature forms a substance ‘
III.Three C — O bonds are not equal in carbonate ion.
Y ’. The substance ‘Y ’ is
IV. Lead prefers to form tetravalent compound.
(a) B 2H6 (b) B 3N3H6
Which of the above statements are incorrect?
(c) inorganic graphite (d) B 2H6 ⋅ 2NH3
(a) I and III (b) I, III and IV
12 In which of the following arrangements, the sequence is (c) II and III (d) III and IV
not strictly according to the property written against it? 15. The molecule BF3 and NF3 both are covalent compounds,
(a) CO2 < SiO2 < SnO2 < PbO2 : increasing oxidising power but BF3 is non-polar and NF3 is polar. The reason is that
(b) HF < HCl < HBr < HI : increasing acid strength (a) boron is a metal and nitrogen is a gas in uncombined
(c) NH3 > PH3 < AsH3 < SbH3 : increasing basic strength state
(d)B < C < O < N : increasing first ionisation enthalpy (b) BF3 bonds have no dipole moment whereas NF3 bond
have dipole moment
13 The correct order of pseudohalide, polyhalide and
(c) atomic size of boron is smaller than that of N2
interhalogen are
(d) BF3 is symmetrical molecule whereas NF3 is
(a) BrI−2 , OCN− , IF5 (b) IF5 , BrI2− , OCN−
unsymmetrical
(c) OCN− , IF5 , BrI−2 (d) OCN− , BrI2 , IF5

ANSWERS
SESSION 1 1 (c) 2 (b) 3 (a) 4 (c) 5 (c) 6 (a) 7 (a) 8 (b) 9 (b) 10 (a)
11 (c) 12 (b) 13 (d) 14 (d) 15 (d) 16 (b) 17 (d) 18 (d) 19 (d) 20 (a)
21 (d) 22 (b) 23 (c) 24 (a) 25 (a) 26 (d) 27 (a) 28 (a) 29 (d) 30 (d)
31 (c) 32 (c) 33 (d) 34 (d) 35 (a) 36 (c) 37 (a) 38 (b) 39 (a) 40 (b)
41 (a) 42 (c) 43 (a) 44 (a)
SESSION 2 1 (d) 2 (c) 3 (d) 4 (a) 5 (c) 6 (d) 7 (b) 8 (a) 9 (b) 10 (a)
11 (a) 12 (c) 13 (d) 14 (d) 15 (d)

Hints and Explanations

SESSION 1 Due to the absence of 2d-orbital, maximum covalency is four.
1 Due to the small size of boron atom and presence of six Thus, BF63− is not formed.
electrons. Boric acid accepts a pair of electron from OH − ion of BH−4 (BH3 + H− ); B(OH)−4 (B(OH)3 + OH− ) and BO −2 are formed.
H2O thereby releasing a proton.
4 SnO 2 is amphoteric. It dissolves in acids as well as in alkalies e.g.
2 Aqueous solution of AlCl 3 is acidic due to hydrolysis.
AlCl 3 + 3H2O Al(OH) 3 + 3HCl
- SnO 2 + 2H2SO 4 → Sn(SO 4 )2 + 2H2O
On strong heating, Al(OH) 3 is converted into Al 2O 3 . SnO 2 + 2NaOH → Na 2SnO 3 + H2O
2Al(OH) 3 ∆ Al O + 3H O
→ 2 3 2 5 Graphite has carbon atoms arranged in large hexagonal layers
3 5B with weak van der Waals’ interactions between the layers.
1s2 2s2 2 p1
Ground state High temp.
6 SiO 2 + 3 C → SiC + 2CO
2300 K Carborundum
2s1 2 p2
Excited state

Fourth lone pair is accomodated in this empty orbital

Maximum covalency = 4
 7 RSiCl 3 , gives cross-linked silicon 16 The number of σ-bonds in P4O10 is 16. Lone pair and bond pair repulsion
polymer on hydrolysis. decreases bond angle. However, the
There are also four π-bonds present in
Cl OH bond-pairs of electrons are much farther
P4O10 molecule.
H2O away from the central atom in SbCl 3
R Si Cl R Si OH O than they are in NCl 3 . Thus, lone pair
Cl OH causes even greater distortion in PCl 3 ,
P
AsCl 3 and SbCl 3 . Hence, bond angle
Si Si O O
decreases from NCl 3 (maximum) to
O SbCl 3 (minimum).
O O O
O P P O
Polymerisation
R Si O Si R 24 (a) Thermal stability of the hydrides
O O decrease as we go down the group in
O O n
P periodic table for group 15 (N-family).
Si Si BiH3 < SbH3 < AsH3 <PH3 < NH3
O Least stable Most stable
(P4O10 molecule)
8 The structure of silicates has been M–H – 255 247 322 391
found with the help of X-ray diffraction bond energy (kJ mol −1 )
17 PH3 is a covalent hydride.
techniques. Sheet silicates are formed
when three oxygen atoms (bridging ∆ 2N O + 4HPO
(b) Due to the absence of d-orbital, nitrogen
18 4HNO 3 + 2P2O 5 → 2 5 3 cannot from dπ-pπ bond, thus it is
O-atoms) of each (SiO 4 )4− unit are
shared. Hence, the general formula of correct.
19 PCl 5 produces POCl 3 with the following
sheet silicates is (Si 2O 5 )2n− .
reagents. (c) The N—N bond (BE 160 kJ mol −1) is
weaker than P—P bond (BE 209 kJ mol −1)
9 The hydration of calcium aluminates 2 PCl 5 +SO 2 → POCl 3 +SOCl 2
and silicates involved in the setting of thus, it is correct.
PCl 5 +H2O → POCl 3 +2HCl
cement is an exothermic process, hence (d) N2O 4 can form two resonance structures.
cement structures have to be cooled 2PCl 5 + H2SO 4 → SO 2Cl 2
O O O O
during setting by sprinkling water. + 2POCl 3 + 2HCl
N N N N
10 Higher the catenation tendency, 6PCl 5 + P4O10 → 10POCl 3
O O O O
higher is the bond energy. 20 When conc. H 2SO 4 is heated with
∴ The bond energies of C  C, Si  Si P2O 5 , the acid is converted into Thus, it is correct.
and Ge  Ge bonds are respectively
sulphur trioxide. 25 Bond angles are OH2 (104° ), H2S (92° ),
348, 297 and 260 kJ mol −1.
2H2SO 4 + 2P2O 5 → 2SO 3 + 4HPO 3 NH3 (107° ) and SO 2 (119.5°).
11 Due to the presence of one  OH
group and two P — H bonds, H 3 PO 2 21 Orthophosphorus acid, H3PO 3 26 S3O 9 is as
act as reducing agent. O
O
O O
 S S
12 Nitrogen shows all the oxidation states HO  P  OH
ranging from −3 to + 5 in its compounds.  O O
H O O
13 N3H is acidic. It shows following x S
resonating structures. H3 PO3 = 3 + x + 3(−2 ) = 0 or x = + 3
O O
[N ≡≡ N+ — N− ]− → [N− — N+ ≡≡ N]− Pyrophosphorus acid, H4P2O 5 :
O O Hence, number of S—S bond = 0.
14 The thermal decomposition of given
compounds is shown below:  
HO  P O  P OH 27 O
∆
(NH4 )2 Cr2O7 → N2 + 4H2O+ Cr2O3  
H O O S OH (H2SO5)
H H
∆
NH4NO2 → N2 + 2H2O x
H4 P2 O 5 = 4 + 2 x + 5 (− 2) = 0 O
∆ O O
(NH4 )2 SO4 → 2NH3 + H2 SO4 4 + 2 x − 10 = 0 ⇒ x = + 3
BO(N3 )2 → Ba + 3N2 22 White phosphorus on reaction with H O O S S O O H
Thus, only (NH4 )2 SO4 does not gives NaOH gives PH3 as one of the product (H2S2O8)
O O
N2 on heating while rest of the given in disproportionation reaction.
compounds give N2 on their thermal 3
P4 + 3NaOH +3H2O → 3NaH2PO 2 + PH3 28 O3 molecule is sp -hybridised and
decomposition.
N  has bent shape.
Heat
15 Ba(N3 )2 → Ba(s ) + 3N2 (g ) Group = 15
P  29 (a) S2 molecule is paramagnetic due to
Azide salt of barium can be used to 23  Valence  = 5
As electrons unpaired electrons in MO and is

Sb 
obtain purest form of N2 . The blue-coloured compound, thus true.
decomposition product contain solid (b) The vapour at 200°C consists
Ba as by product along with gaseous MCl 3 has sp3 hybridised M-element
mostly of S8 rings, thus correct.
nitrogen. with one lone pair.
 (c) At 600°C, the gas mainly consists 33 For a substance to dissolve, the 40 Boron always form covalent bond
of S2 molecules, thus correct. hydration energy must be greater than because boron requires very high
(d) Oxidation states of sulphur are: lattice energy. Due to the small size of energy to form B 3+ and again B 3+ due
−2 in H2 S Li + ion, the hydration energy of LiF is to its very small size, have high
considerably high, but it has low polarising power, thus cause greater
0 in S8 polarisation and eventually significant
solubility in water because of its higher
+2 in S 2 O 2−
3 lattice energy. covalent characteristics
(Fajan’s rule.)
+ 4 in SO 2 On moving down the group lattice
energy decreases which results in 41 In water, orthoboric acid behave as a
+ 6 in SO 3
increased solubility. Thus, the order of weak monobasic Lewis acid.
Thus, incorrect oxidation state can solubility for alkali metal fluorides in H H
be less than 4. water is O O O –
O
B H B + H
30 Cl 2 ,Br2 and I2 are homonuclear diatomic LiF < NaF < KF < RbF. O H
: OH2
molecule in which electronegativity of 34 As we move down the group of noble O H O
H H _
the combining atoms is same,so they gases, molecular mass increases by HO OH
are more stable and less reactive which dipole produced for a moment B H+
whereas, I and Cl have different and hence London forces increases HO OH
electronegativities and bond between from He to Xe. Therefore, more amount
them are polarised and hence, reactive. of energy is required to break these 42 Statement I is true but Statement II is
Therefore, interhalogen compounds are false (SiCl 4 is also covalent bonded).
forces, thus boiling point also increases
more reactive. form He to Xe. 43 Silicones are a group of organosilicon
Time Saving Technique In this type of polymers which have (R 2SiO) as a
35 Argon is used in arc welding to cause
question of halogen, only go through the repeating unit.
the inert atmosphere around,
polarity of the molecule. As we know, i.e. without interaction with metal. This suggests that silicones are
diatomic molecule does not have surrounded by non-polar alkyl groups
polarity but molecules with dissimilar 36 In XeO 3 , total electron pairs that are water repelling in nature. They
sizes have polarity resulting in more = 4 (3 bp + 1lp), have wide applications it is used for
reactivity. i.e. sp3 -hybridisation ⇒ pyramidal shape. water proofing of fabrics.
31 As the size of the halogen atom 44 Nitrogen is an inert gas because of the
increases from F to I, the bond length presence of strong bond. That’s why
Xe
of H — X increases. This increase in although there is 78% N2 in the
O O
bond length decreases the bond atmosphere but nitrogen oxide in not
O formed under ordinary conditions.
strength and thus the thermal stability.
Therefore, the order is 37 XeF4 oxidises potassium iodide. But when temperature is high enough
HF > HCl > HBr > HI. XeF4 + 4I− → 2I2 + 4F − + Xe i.e. = 2000 K, it reacts with oxygen to
XeF6 oxidises hydrogen like other form nitrogen oxide.
32 Decreasing order of strength of ≈ 2000K
oxoacids
xenon fluorides. N2 + O 2   → 2NO

HCIO 4 > HCIO 3 > HCIO 2 > HOCI 38 HNO 2 posseses oxidising, reducing Thus, Assertion and Reason are true
and complex forming properties as in it and Reason is the correct explanation
Reason Negative charge is more of the Assertion.
delocalised on ClO −4 due to resonance, oxidation number of nitrogen is +3 (i.e.
hence, ClO −4 is more stable (and less in between –3 to +5).
SESSION 2
basic). 39 A → 3, B → 4, C → 1, D → 5, E → 2
O 1 Br2 reacts with hot and strong NaOH to
A. BH3 is unstable froms diborane B 2H6
give NaBr, NaBrO 3 and H2O.
Cl Cl Cl by (3c —2e − ) electron bond show
–O – O Cl O– banana bond. 2 Higher the reduction potential stronger
O
O
O
O
O O–
B. Gallium with low melting point and high the oxidising agent, i.e. option (c) is
boiling points makes it useful to correct.
Hence, we can say as the number of measure high temperatures.
+
O
oxygen atom (s) around Cl-atom C. Borax is used as a flux for soldering 3 H →— O →→— N ,
increases as oxidation number of metals for heat,scratch resistant O−
Cl-atom increases and thus, the ability coating in earthernwares.
H →— O →— N ==O
of loose the H+ increases. D. Alumino silicate used as catalyst in
petrochemical industries. Polarity along O H in HNO 3 is more in
E. Quartz is a crystalline form of silica. comparison to  O  H in HNO 2 .
 4 XeF6 has much tendency to hydrolyse. between B(OH)3 and NaOH gets a large surface area and hence, the
The reverse reaction is more spontaneous. hydrolysed to regenerate B(OH) 3 and ability to donate the electron pair
XeF6 + 3H2O → XeO 3 + 6HF NaOH. (basicity) decrease.
Hydrolysis 13 Pseudohalide are the combination of
5 NH3 is better electron donor because Na + [B(OH)4 ]− → NaOH
more than one electronegative atoms
the lone pair of electrons occupies
+ B(OH) 3 that have one unit negative charge. e.g.
sp3 -orbital and is more directional.
OCN– , CN– .
CH2__OH HO O H + HO__CH2
6 The first ionisation energy of xenon is + B Polyhalide ions The complex ions
quite close to that of oxygen and the CH2__OH HO HO__CH2 which are formed by reaction of
molecular diameter of xenon and cis 1,2-diol orthoboric acid halogens among themselves are called
oxygen are almost identical. Based on _ polyhalide ions, e.g. I−3 , BrI−2 .
the above facts it is suggested that _ 3H O CH2__O O__CH2
2 +
since, oxygen combines with PtF6 , so H B 14 I. In nitrogen, d-orbitals are absent
xenon should also form similar CH2__O O__CH2 hence, it does not form NCl 5 .
Chelate complex
compound with PtF6 . Thus, NCl 5 does not exist but PCl 5
If some quantity of polyhydroxy does.
7 Hydrides like NH3 , H2 O and HF have
compounds like cis 1,2-diol, catechol, II. O+2 and NO are isoelectronic and
extensive intermolecular hydrogen glycerol etc., is added to the reaction contains one unpaired electron
bonding due to which they show high mixture, then the B(OH) 3 combines each, thus both are paramagnetic.
melting and boiling point. with such polyhydroxy compounds to III. In carbonate ion CO2−
3 all three
8 The two most abundant elements in the give chelated complex compound. Due
to complex compound formation, C — O bonds are identical due to
earth’s crust are Si and oxygen and the resonance.
stability increases and due to higher
compound made by them is SiO 2 . This
stability of complex, reaction moves in
compound is used in building forward direction.
– –
O O –
construction. C—
—O C—
—O
–
11 B 2H6 contains (3c-2e − ) and (2c-2e − )
–
SiO 2 + 2C → Si + 2CO O O
Poisonous
bonds.
9 With progressive increase in atomic
Low temp.
number, the reduction potential of B 2H6 +2NH3 → B 2H6 ⋅ 2NH3 –
O –
halogens decreases, thus oxidising 200°C C— O
power also decreases. → B 3N3H6 –
O
‘X’
Hence, a halogen with lower atomic Inorganic benzene
number will oxidise the halide ion of IV. Pb2+ is more stable than Pb4+ due
High temp.
higher atomic number and therefore, B 2H6 + NH3 → (BN) x to inert pair effect, hence, prefers
will liberate them from their salt ‘ Y’ to form divalent compounds.
Inorganic
solution. Hence, the reaction, graphite Thus, the incorrect statements are
Cl 2 + 2F − → 2Cl − + F2 12 The correct increasing basic strength III and IV.
is not possible. SbH3 < AsH3 <PH3 <NH3 15 BF3 is symmetrical planar, although it
10 B(OH) 3 + NaOH 2 NaBO 2
NH3 is the most basic because of its has polar bonds but resultant dipole
+ Na + [B(OH)4 ]− + H2O small size, the electron density of moment is zero. In NF3 lone pair cause
electron pair is concentrated over distortion hence polarity arises.
This reaction is reversible reaction
small region. As the size increases,
because sodium metaborate,
the electron density gets diffused over
Na + [B(OH)4 ]− formed by the reaction