p-Block Elements (Part-2)

Group 15(Nitrogen Family)

15th group or VA group of the extended form of Concept Ladder

the periodic table consists of 5 elements.

Nitrogen is much less
14 31 75
7
N-nitrogen, 15
P -Phosphorus, 33
As -arsenic, reactive than phosphorous,
122 209 thats why it has greater
51
Sb -antimony and 83
Bi -bismuth. This group
tendency for catenation
than Nitrogen.
these are known as pnicogens and their
compounds as pnictides. (Greek, pniomigs

Rack your Brain

Which element shows anomalous

behaviour among group 15 and
why?

Previous Year’s Questions

Occurrence
Nitrogen is relatively inactive
1. Nitrogen is most abundant in nature both in
element because
free and in the combined state.
[AIPMT]
p-Block Elements (Part-2)

2. Air is the most abundant source of free

(1) its atom has a stable electronic
nitrogen.
3. It forms 75% by mass and 78% by volume of
(2) it has low atomic radius
the air.
(3) its electronegativity is fairly high
4. In combined state, it is found as nitrates such
(4) Bond dissociation energy of its
as chile salt petre (NaNO3), Indian salt petre
molecule is fairly high.
(KNO3) and ammonium compounds.

1.
 5. Nitrogen is found in the form of proteins and
amino acids in living organisms.

Ca9.[PO4]6.CaF2 which is the main constituent

Rack your Brain
of phosphate rocks.
7. Ar, Sb and Bi are commonly associated with
sulphide minerals, ores are Bi2O3 bismuth What is the percentage of
oxide and bismuth sulphide Bi2S3. Nitrogen in air?

Physical property
1. Valence shell
th
group elements
is ns2 np3 , where n = 2 to 6.
2. It increases as we move down Previous Year’s Questions
the group. However, there is small increase in
covalent radii from As to Bi, this is because of Number of electrons shared in the
poor shielding of the valence electrons by the formation of nitrogen molecule is
d- and f-electrons present in the inner shell. [AIPMT]
3. Ionization enthalpy
p-Block Elements (Part-2)

(1) 6 (2) 10
of these elements is much higher than the (3) 2 (4) 8
corresponding elements of group 14 due to
increased nuclear charge and stable exactly

2.
4. It decreases due to a
gradual increase in the atomic radii of the
elements.
5. M.P and B.P. of

As due to increase in their atomic size and

then decreases from Sb and Bi due to their Concept Ladder
tendency to form three covalent bonds
Nitrogen have higher
6. These elements can show
ionisation enthalpy as
negative as well as positive oxidation states.
compare to oxygen and
Going down the group, the stability of +3
carbon because of its half
oxidation state increases while that of +5
oxidation state decreases due to inert pair

7. Down
the group, metallic character increases.

p-Block Elements (Part-2)

3.
 Rack your Brain
All the elements except bismuth show
allotropy. Phosphorus exists in three allotropic
How Phosphorus is categorised
forms such as white or yellow, red or violet and into its white, red and black
black phosphorus. allotropic form?

1.
N2 + O2 2NO

2.
hot
P4 + 20 HNO3 4H3PO4 + 20 NO2 + 4H2O
phosphoric acid Concept Ladder
As4 + 20 HNO3 4H3ASO4 + 20 NO2 + 4H2O
Dinitrogen combines
Arsenic acid
with dioxygen only at
Sb4 + 20 HNO3 Sb4O10 + 20NO2 + 10H2O
very high temperature
Antimony oxide (2000 K) to form nitric
Bi + 6HNO3 Bi (NO3)3 + 3H2O + 3NO2 oxide.
Dinitrogen is a
Bismuth nitrate
colourless, odourless,
3. Hot concentrated nitric acid and sulphuric acid tastless and non-toxic
has no reaction with nitrogen. gas.
p-Block Elements (Part-2)

P4 + 10 H2SO4 4H3PO4 + 10 SO2 + 4H2O

As4 + 10 H2SO4 4H3ASO4 + 10SO2 + 4H2O

2Sb + 6H2SO4 Sb2 (SO4)3 + 3SO2 + 6H2O

2Bi + 6H2SO4 Bi2 (SO4)3 + 3SO2 + 6H2O

4.
 P4 + 3NaOH + 3H2O PH3 + 3NaH2PO2 Concept Ladder
AS4 + 12 NaOH 4Na3AsO3 + 6H2
Oxides of nitrogen have
Salt
open chain structure, while
2Sb + 6NaOH 2Na3SbO3 + 3H2
those of phosphorous
Salt have closed chain or cage
Alkalies have no reaction with nitrogen. structures.

6 Li + N2 2Li3N

3 Mg + N2 Mg3N2

6 Mg + P4 2Mg3P2

6 Ca + P4 2Ca3P2

The elements of group 15 have ns2 np3 as their Rack your Brain

Why NO2 diamerises to form

ways: N2O4?

The atoms of the elements of this group

may accept three electrons from more metallic
elements to form triply charged negative ions
such as nitride, N3– ion and phosphide, P3– ion

small atoms can form highly charged negative

ions because of their greater electronegativities.
The other members of nitrogen family show
little tendency to form triply charged negative Previous Year’s Questions
p-Block Elements (Part-2)

ions and this tendency decreases down the

group because of increase in size and decrease Which of the following oxides is
in electronegativity. These group elements also most acidic?
[AIPMT]
exhibit oxidation states ranging from -3 to +5.
(1) As2O5 (2) P2O5
(3) N2O5 (4) Sb2O5

5.
 Since the atoms of these elements contain Concept Ladder
three unpaired p-electrons so these can pair with
unpaired p-electrons in another atom or atoms Tendency to form
to form three covalent bonds, e.g., NH3, PH3, AsH3, pentahalides decreases
SbH3, BiH3. down in group 15 elements.

Compounds formed by Group 15 Elements

Stability order : NH3 > PH3 > As H3 > SbH3 > BiH3
Basicity : NH3 > PH3 > As H3 > SbH3 > BiH3
H-E-H bond angle : NH3 > PH3 > As H3 > SbH3
Boiling point : SbH3 > NH3 > As H3 > PH3
Reducing character : BiH3 > SbH3 > As H3 > PH3 > NH3

The bond angle in PH3, As H3 and SbH3 is close to

92° which suggests that orbitals used for bonding are Rack your Brain
close to pure p-orbitals.
Nitrogen does not form
pentahalides, why phosphorus
does so?
Oxides with higher oxidation state are more acidic :

Moreover, acidity decreases down the group :

Q.1 What is fuming nitric acid? What colour is it have?

p-Block Elements (Part-2)

A.1 Concentrated nitric acid in which oxides of nitrogen (i.e., NO, NO2, N2O3 etc.)
are dissolved is called fuming nitric acid. Its colour is yellow.

6.
Hali
Ammonia forms NCl3, NBr3.6NH3 and NI3.6NH3 Concept Ladder
(used as explosives) with Cl2, Br2 and I2 respectively.
NCl3
methionine The molecules NH3 & NF3
have same dipole moments
proteins to form toxic methionine sulphoximine,
in opposite direction.
and is no longer used.
Penta halides are more covalent than trihalides
because higher oxidation state leads to high polarising
power.

Nitrogen is present in air to the extent of 78.06

% by volume. N2 is colourless, tasteless, odorless Rack your Brain
and diamagnetic. It is lighter than air, sparingly
soluble in water and a non-supporter of combustion. Why all NX3 compounds unstable
except NF3?

1. In laboratory, nitrogen samples are obtained by

warming ammonium nitrite or by oxidising ammonia
by bromine water, sodium hypochlorite (NaOCl) or
CuO.

Previous Year’s Questions

2NH3 ! 3CuO """

# N2 ! 3Cu ! 3H2O Identify the incorrect statements
8NH3 ! 3Br2 """
# N2 ! 6NH4Br related to PCl5 from the following :
[NEET-2019]
2. Small quantities of very pure N2 is obtained by
(1) PCl5 molecule is non-reactive.
carefully warming sodium azide.
(2) Three equatorial P—Cl bonds
NaN3 """"
300!C
# N2 $ Na
p-Block Elements (Part-2)

make an angle of 120° with each

3. Heating ammonium salts with more oxidizing other.
(3) Two axial P—Cl bonds make an
anion (Cr2O72–, NO2–, NO3–, ClO4–)
angle of 180° with each other.
(NH4 )2 Cr2O7 """
!
# N2 $ Cr2O3 $ 4 N2O (4) Axial P—Cl bonds are longer
NH4NO2 """
!
# N2 $ 2 H2O than equatorial P—Cl bonds.

7.
 Chemical Properties
(a) Ammonia (NH3) Concept Ladder
Ammonia is a colorless gas having characteristic
pungent smell. It is quite poisonous and brings
Haber process also known
tears in eyes. NH3 is highly soluble in water due to
extensive hydrogen bonding.

industrial procedure for the

production of ammonia.
NH3 produced is dried with quick lime CaO. Note
that it cannot be dried with H2SO4, CaCl2 or P4O10 as
they react with the gas instead of drying it.
2.
Finely divided Fe + Mo
N2 H2 NH3 ;
High pressure (200 atm)
low temp. (500°C)

H 46.1kJ / mol

3. NH3

Previous Year’s Questions

Pure nitrogen is prepared in the

laboratory by heating a mixture of
[AIPMT]
Al 2O2 ! 3C ! N2 """
# 2 AlN ! 3CO (1) NH4OH + NaCl
(2) NH4NO3 + NaCl
AlN ! 3H2O """
# Al(OH)3 ! NH3 $
(3) NH4Cl + NaOH
(4) NH4Cl + NaNO2
1. Ammonia is a non-supporter of combustion

continuous heat is supplied.

4NH3 + 3O2 !!! " 2N 2 + 3H 2O

Q.2 What happens when a mixture of ammonium sulphate and sodium nitrate is
p-Block Elements (Part-2)

heated. Write the equation.

A.2
then decomposes to yield laughing gas (N2O).

(NH4 )2 SO4 ! 2 NaNO3 """

# 2 NH4NO3 ! Na 2SO4
Ammonium
nitrate

# 2 N2O ! 4 H2O
2 NH4NO3 """
Ammonium
nitrate 8.
2. Formation of complex ions used in qualitative
analysis: Concept Ladder
2 NH4OH AgCl [Ag NH3 ]Cl H2O
white 2
excess colourless Due to H-bonding NH3
exists in both solid and
4 4 2 4 2 4 liquid states and has higher
Blue
melting and boiling points
than expected on the basis
2NH4OH ZnSO4 Zn OH + (NH4)2SO4
2 of its molecular mass.
white

3 4 3 4 4

3. Reaction with Nessler’s Reagent is used as a

test to detect ammonia:

HgCl 2 ! 2KI """

# 2KCl ! HgI2 """
!2KI
# K2HgI4
Red Nessler 's
colour reage
ent

2K2HgI4 ! 3KOH ! NH3 """

# 2H2O ! 7KI ! NH2 $ Hg $ O $ Hg $ I
Red-Brown
Preccipitate
[Iodide of Million's base]

4. Reaction with chlorine:

NH3 excess Cl 2 NH4Cl N2

NH3 Cl 2 excess NCl 3 HCl

(b) Ammonium Salt

Previous Year’s Questions
All ammonium salts are very soluble in water.
They are usually slightly acidic and decompose
Which one has the lowest boiling
readily on heating producing NH3, N2 or N2O. point?
If the anion (Bx–) is not particularly oxidising [AIPMT]
(1) NH3 (2) PH3
p-Block Elements (Part-2)

(eg. Cl–, CO32– or SO42–) the ammonia is evolved.

(3) AsH3 (4) SbH3
NH4Cl NH3 HCl

NH4 SO4 2NH3 H2SO4

2

9.
 If the anion is more oxidising (e.g.
NO2 ,NO3 , ClO4 , Cr2O27 ) than NH4 is oxidized Concept Ladder
to N2 or N2O.

NH4NO2 N2 2H2O The bond angle (O—N—O)

are not of the same value
NH4NO3 N2O 2H2O in NO2– and NO2+.

NH4 Cr O7
2
N2 4H2O Cr2O3
2
Orange

1. Nitrous oxides N2
It is colourless, non-combustible gas with a
sweetish odour and taste. It is a neutral oxide
and is diamagnetic.

(i) It is prepared by careful thermal decomposition Rack your Brain

of molten ammonium nitrate at about 280°C
Write the name and formula of
NH4Cl ! NaNO3 """"
$NaCl
# NH4NO3 """
%
# N2O ! H2O
neutral oxides of nitrogen.

(ii) 10HNO3 4Zn 4Zn NO3 N2O 5H2O

2
dil.

HSO NH
3 2
HNO3 N2O H2SO4 H2O
sulphamicacid conc.

(iii) 2NO SO2 H2O H2SO4 N2O

moist

900 C
(a) 2N2O 2N2 O2
(b) Reduction of N2O to N2: Previous Year’s Questions
p-Block Elements (Part-2)

N2O Cu CuO N2 Which of the following oxides of

hot
nitrogen is paramagnetic?
N2O Mg MgO N2 [AIPMT]
(1) NO2 (2) N2O3
(3) N2O (4) N2O5

10.
 2N2O C CO2 2N2

10N2O P4 P4O10 5N2

(c) Oxidation:

5N2O 2KMnO4 3H2SO4 K2SO4 2MnSO4 3H2O 10NO

Use

It is used as an anaesthetic by dentists and a

propellant for whipped ice-cream. Concept Ladder

It is a colourless, neutral gas which is NO is paramagnetic in

paramagnetic due to the presence of odd its gaseous state but
electrons. It is sparingly soluble in water. diamagnetic in its liquid or
solid state.
Preparation
(a) NO is prepared in the laboratory by the
reduction of dilute HNO3 with Cu.

8HNO3 3Cu 2NO 3Cu NO3 4H2O

2

(b) Commercial Method

electric arc
N2 O2 2NO
(In Birkeland and Eyde Process)
Ptgauze
Or 4NH3 5O2 4NO 6H2O (Catalytic Oxidation of Ammonia)

(i) It is sparingly soluble in water and its solid-

Rack your Brain
state forms diamagnetic dimer
p-Block Elements (Part-2)

Why in the structure of HNO3

molecule, the N—O bond (121
(ii) NO + 1/2O2 NO2 (brown fumes), thus it is pm) is shorter than N—OH (140
not possible to detect its smell. pm).

[This reaction is also used to detect O2]

11.
 (iii) Action of heat:
900 C Concept Ladder
2NO N2 O2

(iv) Reduction (to N2): N2O3 i.e. Nitrogen trioxide,

is a highly toxic compound
2NO S SO2 N2 and can be partially
dissociated into NO & NO2.
1
NO Cu CuO
N
2 2
(v) Oxidation/Reduction properties

10NO 6KMnO4 9H2SO4 3K2SO4 6MnSO4 6H2O 10HNO3

2NO Cl 2 2NOCl

NO 2HNO3 3NO2 H2O

3. Dinitrogen Trioxide N2O3 Rack your Brain
It exists only in solid state at low temperature
which is pale blue in colour. N2O3 is an acidic Why N2O is diamagnetic in
anhydride of nitrous acid (HNO2). It is diamagnetic. nature?

(a) It can be made by condensing equimolar

amounts of NO and NO2 together at 253 K.

NO NO2 N2O3
Previous Year’s Questions
(b) 2Cu 6HNO3 2Cu NO3 NO NO2 3H2O
2
5N
Which of the following is a nitric
p-Block Elements (Part-2)

(c) As2O3 2HNO3 2H2O NO NO2 2H3AsO4 acid anhydride?

50% [AIPMT]
(1) NO (2) NO2
(3) N2O5 (4) N2O3

12.
 Concept Ladder
(i)
N2O3 s NO2 NO
liquid
NO2 is coloured but
its dimer form N2O4 is
(ii) It being the anhydride of nitrous acid forms colourless in nature.
nitrites with alkalies.

NO NO2 2KOH 2KNO2 H2O

nitrites

(iii) It forms brown coloured FeSO4.NO with FeSO4.

This is used as a test for nitrates called Brown
Ring Test. Rack your Brain
4. Nitrogen Dioxide NO2
It’s a reddish-brown gas and exists at the room Why NO2 is called as mixed
anhydride of nitrous acid?
temperature. Being an odd electron molecule, it
is paramagnetic and dimerises into N2O4 at low
temperature. It is acidic in nature.

10 C 20 C 140 C 620 C
N2O4 N2O4 N2O4 2NO2 2NO O2
solid solid vapour Dark Colour
colourless yellow Reddish Brown less
Brown

Q.3 Why does NO2 dimerize?

p-Block Elements (Part-2)

A.3 NO2 is an odd electron (7 + 2 × 8 = 23) molecule. In the valence shell, N has
seven electrons and hence is less stable. To become more stable by acquiring

dimerization to form N2O4.

13.
 S
(a) In the laboratory it is prepared by heating
dried lead nitrate:
2 Pb(NO3 )2 !!! " 2 Pb # 4 NO2 # 2O2
!# #"## $
Passed through U-tube
cooled in ic
ce to separate
the condensed NO2

(b) It is produced on a large scale by oxidizing NO

in the Ostwald’s Process for the manufacture of
nitric acid.

2NO O2 2NO2 Concept Ladder

NO2 is an intermediate in the

industrial synthesis of nitric
(i) 2NO2 H2O HNO2 HNO3 acid, it is paramagnetic,
Thus, NO2 is called as mixed anhydride bent in shape and used in
of nitrous acid and nitric acid. The reaction of fertilizers.
NO2 with aqueous alkalies is similar to that of a
mixture of HNO2 and HNO3.

2NO2 2NaOH NaNO2 NaNO3 H2O

(ii) Oxidation:

10NO2 3H2SO4 2KMnO4 2H2O K2SO4 2MnSO4 10HNO3

2 2 4 3 2 2
nitrosulphuricacid

(iii) Reduction: Previous Year’s Questions

NO2 SO2 H2O H2SO4 NO

When copper is heated with conc.
2 3
HNO3 it produces
NO2 H2S H2O NO S [NEET-2016]
(1) Cu(NO3)2, NO and NO2
(2) Cu(NO3)2 and N2O
5. Dinitrogen Pentoxide N2O5
p-Block Elements (Part-2)

(3) Cu(NO3)2 and NO2

N2O5 is a colourless crystalline solid which
sublimes readily and is acidic. (4) Cu(NO3)2 and NO

14.
 The solid form consists of (NO2+ + NO3–) which
is ionic and called as nitronium nitrate while in
Concept Ladder
solution it is covalent.

N2O5 i.e. Nitric anhydride

(a) 2HNO3
P2O5
N2O5 H2O Dehydration . is an ore of binary
1000 C
nitrogen oxides, a family
Thus N2O5 is the anhydride nitric acid. of compounds that only
60 90 C contain nitrogen and
(b) AgNO3 Cl 2 AgCl N2O5 O2 oxygen.

(c) 4NO2 O2 2N2O5

Chemical Properties
(i) N2O5 dissolves in H2O with a hissing sound.

N2O5 H2O 2HNO3

Thus it is called as nitric anhydride and Rack your Brain
neutralisation reactions similar to HNO3
Find the covalency of N in N2O5?
N2O5 2NaOH 2NaNO3 H2O

(ii) Since N2O5 NO2 NO O2 it is a very

powerful oxidising agent. It destroys all organic
substances.

5N2O5 I2 10NO2 I2O5

Previous Year’s Questions

1. Nitrous acid HNO2 Urea reacts with water to form A

It is unstable except in dil. aq. solution. It is a which will decompose to form B. B
tautomeric mixture of two forms: when passed through Cu2+(aq), deep
blue colour solution C is formed.
What is the formula of C from the
p-Block Elements (Part-2)

following?
[NEET-2020]
(1) CuSO4 (2) [Cu(NH3)4]2+
(3) Cu(OH)2 (4) CuCO3.Cu(OH)2

15.
 (a) It is made by acidifying a solution of a nitrite Concept Ladder

Ba NO2 H2SO4 2HNO2 BaSO4

2
The N—O bond in NO2– is
(b) Dissolving nitrous anhydride (N2O3) in H2O of shorter than N—O bond in
course forms HNO2: NO3–.

N2O3 H2O 2HNO2

NO2 ion is a weak oxidising agent and gets

reduced to NO which forms a red complex with
haemoglobin and improves the look of meat.

NO2 Fe2 2H Fe3 NO H2O

2NO2 2I 4H I2 2NO 2H2O

However, it is oxidised by KMnO4, Cl2 forming Rack your Brain
NO3– (but to NO2 by H2SO4):

Draw the structure of N2O5–.

HNO2 Cl 2 H2O HNO3 2HCl

2HNO2 H2SO4 SO2 2NO2 H2O

Reaction with Amines :

HNO2 NH 3
NH4NO2 N2 2H2O
ammonia unstable

HNO2 EtNH2 EtOH N2 H2O

1 amine

Secondary and tertiary aliphatic amines form nitrosamines with nitrites:

HNO2 Et 2NH Et 2NO H2O

2 amine
p-Block Elements (Part-2)

HNO2 Et N
3
Et 3NH NO2 Et N N O EtOH
|
3 amine
Et
Nitrites are used to make diazo compounds used in azo dyes:

PhNH2 HNO2 HCl Ph — N NCl 2H2O

aniline

16.
 On standing HNO2 decomposes into NO and
NO2 :

2 2 2

While on boiling it disproportionate: Concept Ladder

III V II
3HNO2 HNO3 2NO H2O N2O5 is a rare example of
a compound that adopts
2. Nitric acid HNO3
two structures depending
Also called as Aqua fortis, it is colourless on the conditions. The
fuming liquid with a pungent smell. Yellow colour solid form is a salt in
occurs on standing due to decomposition into which nitronium nitrate,
NO2. consisting of seperate
nitronium cations [NO2]+
and nitrate anions [NO3]–.

1. In laboratory

2NaNO3 H2SO4 Na2SO4 2HNO3

nitrates conc.

HNO3 vapours are then condensed in a water-cooled receiver.

2. Birkeland and Eyde Process
O2 H2O
N2 O2 2NO 2NO2 HNO3 HNO2 NO2 2H2O

2 2

Q.4 How is nitrogen prepared from ammonia?

p-Block Elements (Part-2)

A.4 Nitrogen is prepared by ammonia according to the following equations :

NH3 (g) ! HCl(aq) """

# NH4Cl(aq)
NH4Cl(g) ! NaNO2 (aq) """
# NH4NO2 (aq) ! NaCl(aq)
NH4NO2 (aq) """
$
# N2 (g) ! 2 H2O(l )

17.
 3. Ostwald Process

3 2 2

2O2 2H2O O2 distillation

4NO 4NO2 4HNO3 4HNO3
50 C
60% 68%
azeotrope

Due to the formation of azeotrope, HNO3

cannot be further concentrated by distillation
and other methods are used like dehydrating
using sulphuric acid vapours.
Previous Year’s Questions
2 4

HNO3 HNO3 conc.

68% 98% Zn gives H2 gas with H2SO4 and HCl
but not with HNO3 because
[AIPMT]
NO3 is a very powerful oxidising agent in
(1) Zn act as oxidisinng agent when
acidic solution. Cu, Ag which are insoluble in HCl
react with HNO3
dissolve in HNO3. Concentrated HNO3 forms NO2
(2) HNO3 is weaker acid than H2SO4
with a reducing agent although. Fe, CO, Al, Ni, Cr
and HCl
and B are rendered passive by concentrated HNO3
(3) in electrochemical series Zn is
due to the formation of a protective oxide layer
above hydrogen
(like Fe3O4 with iron). Dilute HNO3 forms NO with
(4) NO3– is reduced in preference to
a poor reducing agent (Cu, Hg); N2O with a good
hydronium ion.
reducing agent in hot conditions and NH4NO3
with a good reducing agent in cold conditions.
p-Block Elements (Part-2)

Rack your Brain

How conc. HNO3 turns yellow on

expossure to sunlight.

18.
Some reactions with non-metals are:
Concept Ladder
3 2

Aqueous HNO3 can be

concentrated by distillation
upto 68% by mass. Further
concentration to 98% can
be achieved by dehydration
with conc. H2SO4.

Only Mg and Mn react with 2% dil. HNO3

HNO3 (dil.2%) + Mg (or Mn) Mg(NO3)2 +
H2
Solution of 75% HCl and 25% HNO3 is called
Aqua Regia which contains NO+ Cl– ions.
Aqua Regia is capable of dissolving Gold and
Platinum by forming soluble H3AuCl4 and Rack your Brain
H2PtCl6 respectively.
Draw structure of compounds
H2NO2 and H2N2O2. Is there any
possibility of having double bond
between N and O?

Q.5 What is the product formed by the following reaction?

PO ,!
HNO3 """" #
p-Block Elements (Part-2)

4 10

A.5 P4O10 being a strong dehyderating agent, eliminates a molecule of H2O from two
molecules of HNO3 giving dinitrogen pentoxide (N2O5).
4 HNO3 ! P4O10 """
$
# 2 N2O5 ! 4 HPO3

19.
 It exists in many allotropic forms, the
important ones being white, red and black Rack your Brain
phosphorous.
Why Phosphorous only exist in
300 C
inert atmosphere
cage or close chain structure?
Thermodynamically
p-Block Elements (Part-2)

Only white phosphorous reacts with caustic

alkalies to undergoes a disproportion reaction.

P4 3NaOH 3H2O 3NaH PO2 4

PH 3
sodiumhyposphite Phosphine

20.
 Red phosphorus is used in Match - Industry
and white phosphorus as a rat poison. Previous Year’s Questions

Phosphorous is obtained by the reduction of Which of the following phosphorus

calcium phosphate with C in an electric furnace. is the most reactive?
Sand (SiO2) is added to remove the calcium as a [AIPMT]
(1) Scarlet phosphorus
2Ca3 PO4 6SiO2 6 CaSiO3 P4O10 (2) White phosphorus
2
slag
(3) Red phosphorus
(4) Violet phosphorus
2P2O5 10C P4 10CO

Overall reaction :
2Ca 3 (PO4 )2 ! 6SiO2 ! 10C """
# P4 ! 6 CaSiO3 ! 10CO
Oxides of Phosphorous

p-Block Elements (Part-2)

21.
 Other oxides like P4O8 and P4O9 are intermediate
between P4O6 and P4O10 and form a mixture of Concept Ladder
phosphoric acid P(+V) and phosphorous acid
P(+III) on hydrolysis.
Phosphinic acid behaves as
a mono protic acid where
as Ortho Phosphorus acid
is diprotic acid.

Oxo Acids of Phosphorous

All oxo acids of phosphorous can be
categorized into two main acid series namely,
phosphorus acid series and phosphoric acid
series.

The series contain P(+3) and are generally Rack your Brain
reducing agents due to the presence of P – H
bonds which are reducing (as they break down
Find the product formed when
easily to loose H+).
PCl5 reacts with heavy water.
(I) Ortho phosphorous acid H3PO3
It is a dibasic acid formed by hydrolysis of
P4O6.

P4O6 6H2O 4H3PO3

Previous Year’s Questions

Which is the correct statement for

It forms phosphites on hydrolysis which are the given acids?
very strong reducing agents in basic solutions. [NEET-2016]
2
(1) Phosphinic acid is a mono protic
H3PO3 H H2PO3 ; Ka 1.6 10
1 acid while phosphonic acid is a
p-Block Elements (Part-2)

diprotic acid.
H2PO3 H HPO23 ; Ka 7 10 7
2 (2) Phosphinic acid is a diprotic
On heating orthophosphorous acid acid while phosphonic acid is a
disproportionates : monoprotic acid.
!3 !5 "3 (3) Both are diprotic acids
4 H3PO3 ###
$ 3 H3PO4 ! PH3
(4) Both are triprotic acids.

22.
(II) Hypophosphorous Acid H3PO2
Hypophosphorous acid is prepared by alkaline
hydrolysis of (white) phosphorous.

P4 3OH 3H2O PH3 3H PO

2 2
Hypophosphiteion

Structure of P4
Concept Ladder

H4P2O5 is dibasic as metals

can replace the hydrogen
in the pair of attached
H3PO2 is a monobasic acid and a very strong hydroxide ions.
reducing agent.

4Ag H3PO2 2H2O 4Ag H3PO4 4H

(III) Pyrophosphorous Acid H4P2O5

While reaction with PCl5 is

H3PO3 3PCl5 PCl 3

3POCl 3
3HCl
Trichloride Oxychloride

Q.6 H3PO3 undergoes disproportionation reaction but H3PO4 does not?

A.6 The maximum and minimum oxidation states of P are –3 and +5. But the
oxidation state of P in H3PO3 is +3. therefore, it can increase its oxidation to +5
in H3PO3 and decrease its oxidation state to –3 in PH3.
!3 !5 "3
Thus, H3PO3 shows disporportionation reaction : 4 H3PO3 ###
$ 3 H3PO4 ! PH3
p-Block Elements (Part-2)

In contrast, the oxidation state of P in H3PO4 is +5, therefore, it cannot increase

its oxidation state beyond +5 and hence it does not show disproportionation
reaction.

23.
 They usually contain P(+V) and have oxidising
properties. The simplest phosphoric acid is Rack your Brain
orthophosphoric acid.
(I) Orthophosphoric acid H3PO4
How many P—O—P bonds are
It is formed by hydrolysis of phosphorous there in H4P2O7?
pentoxide (P2O5 or P4O10). The scheme for its
hydrolysis is :

In laboratory
2

P4 20HNO3 4H3PO4 20NO2 4H2O

conc.

Impure H3PO4 is prepared in large amounts by

‘Wet Process’.
Previous Year’s Questions
Ca3 PO4 3H2SO4 2H3PO4 3CaSO4
2
P2O5 is heated with water to give
CaSO4 is hydrated to gypsum CaSO4.2H2O and [AIPMT]
PO4 thus produced is used to make (1) hypophosphorous acid
3
fertilizers. (2) phosphorous acid
p-Block Elements (Part-2)

(3) hypophosphoric acid

(4) orthophosphoric acid
1. H3PO4 is hydrogen bonded in aqueous solution
and thus the ‘concentrated acid’ is syrupy and
viscous.

24.
2. It forms meta phosphates on heating:
220 320 C
H3PO4 H4P2O7 Br
2HPO3 Concept Ladder
2
pyrophosphoric metaphosphoric
acid acid

H3PO4 i.e. phosphoric

Sodium metaphosphate is also termed acid has its pure
Graham’s salt or Calgon (Commercial name). It is compound in colourless
soluble in H2O and precipitates Pb2+, Ag+ but not solid form.
Ca2+, Mg2+. Thus, it is used for softening water. When all three
3. It forms 3 series of salts: H+ ions removed,
(a) H3PO4 H H2PO4 ; Ka 1 7.5 10 3 orthophosphate ion
PO4 is form, which is
3-
Dihydrogen phosphates are slightly acidic in
also commenly known
water.
as phosphate.
(b) H2PO4 H HPO22 ; Ka2 6.2 10 8

Monohydrogen phosphates are slightly basic

in water.
2
(c) HPO4 H PO34 ; Ka3 1 10 12

Normal phosphates are appreciably basic in Rack your Brain

water.
4. Phosphates are estimated quantitatively by Name the compound formed as
adding a solution containing NH4OH solution of esters by orthophoric acid.
the phosphate and Mg2+. Magnesium ammonium
phosphate precipitated is ignited and weighed as
Mg2P2O7.

2NH4 2Mg 2 2PO43 2MgNH4PO4 Mg 2P2O7 2NH3 H2O

(II) Hypophosphoric acid H4P2O6
H4P2O6 contains P(+4) and is prepared by
hydrolysis and oxidation of red phosphorous by
NaOCl.
p-Block Elements (Part-2)

25.
 On hydrolysis H4P2O6 forms both H3PO3 and H3PO4
Concept Ladder

A French chemist Philippe

once generated a regular
supply of heat over
Phosphine PH3 Phosphorous (P4) with
PH3 is a colourless, extremely toxic gas which an aqueous solution of
K2CO3, results in colourless
soluble in H2O. Its aqueous solutions are neutral. gaseous substance called
phosphine (due to its

The bond angle in H – P – H is 93.5° which

suggests the presence of almost pure p orbitals.

PH3 can be formed by hydrolysing metal

phosphides or hydrolysing white phosphorous in
basic media.

Ca3P2 6H2O 2PH3 3Ca OH

2

Another method also produces small amounts

Rack your Brain
H . Therefore, PH3 is
2 4
removed in the following manner:
What is the bond angle between
KOH
PH3 HI PH4I KI H2O PH3 H—P—H in phosphine?
Phosphonium Pure
Iodide

Q.7 PH3 has lower boiling point than NH3. Why?

p-Block Elements (Part-2)

A.7 The electronegativity of N (3.0) is much higher than that of P (2.1). Therefore,
NH3 undergoes extensive intermolecular H-bonding and hence it exists as an
associated molecule. To break these H-bonds, a large amount of energy is
needed. On the other hand, PH3 does not undergo H-bonding and thus exists
as discrete molecules. Therefore, the boiling point of PH3 is much lower than
that of NH3.

26.
150°C. Concept Ladder
150 C
PH3 2O2 H3PO4
PH3 possesses the
2. It explodes in contact with traces of oxidising
characteristics to cause
agents like HNO3, Cl2 and Br2.
high environmental
2PH3 16HNO3 P2O5 16NO2 11H2O demages, it acts as a
Lewis base when its lone
3. Solution of PH3 in H2O decomposes in presence
pair electron is donated
of light giving red P and H2.
in reaction with hydrogen
4. Formation of metallic phosphides:
iodide.
3CuSO4 2PH3 Cu3P2 3H2SO4
Black

3AgNO3 PH3 Ag 3P 3HNO3

Black

5. PH3 is weakly basic and forms phosphonium

salts with anhydrous acids while NH3 readily
forms NH4X in aqueous solutions of the acids. Rack your Brain
PH3 HX PH4 X X Cl,Br,I
Why PCl4+ can exists but PCl4-
cannot?
It is used for making ‘Holme’s signal’. CaC2 and
Ca3P2 are contained in containers. Containers are
pierced and thrown in sea when gases evolved,
burn and serve as a signal.

1. PCl5 is a yellowish white powder while PCl3 is

a colourless liquid and is widely used in organic Previous Year’s Questions
chemistry.
A compound ‘X’ upon reaction with
P4 6Cl 2 4PCl 3
White Dry H2O produces a colourless gas ‘Y’
p-Block Elements (Part-2)

P4 8SOCl 2 4PCl 3 4SO2 S2Cl 2 absorbed in a solution of CuSO4 to

Thionyl
give Cu3P2 as one of the products.
Chloride
Predict the compound ‘X’.
P 10Cl 4PCl5 [NEET-2019]
4 2
White Dry,excess (1) Ca3P2 (2) NH4Cl
(3) As2O3 (4) Ca3(PO4)2

27.
 P4 10SO2Cl 2 4PCl5 10SO2
Sulphuryl
Concept Ladder
Chloride

The main use of ammonium

PCl 3 Cl 2 orS2Cl 2 PCl5
sulphate is as a fertilizer for
2. PCl3 fumes in moisture. alkaline solids. Ammonium
ion forms a small amount
PCl 3 3H2O H3PO3 3HCl of acid, which lowers pH
balance of the soil.
While, PCl5 HO2
POCl 3 2HCl
Moist air

POCl 3 3H2O H3PO4 3HCl

3. In solid state it is ionic therefore conducts
electricity, while in gaseous and liquid state PCl5
is trigonal bipyramidal. While in solid state it is
ionic and hence conducts electricity
2PCl5 PCl 4
PCl
6
Tetrahedral Octahedral

4. PF5 forms an unusual trigonal bipyramid

where equatorial and axial bonds interchange Rack your Brain
their positions in short time. This is called pseudo
rotation. Why calcium ammonium nitrate
does not form soil acid where as
ammonium sulphate do?
They are the compounds of N, P and K which
are soluble in H2O and easily assimilated by plants
without causes any damage to them.

(i) Ammonium sulphate ((NH4)2SO4

Ammonium sulphate is made by passing NH3
and CO2 gases into a slurry of CaSO4 in water:

CaSO4
2NH3 CO2 H2O NH4 CO3 CaCO3 NH4 SO4
p-Block Elements (Part-2)

2 2

In soil, the action is:

4 2 4 3

28.
 Excess of nitrogenous fertilizers makes the
soil acidic. Concept Ladder

Ostwalds CaCO3
NH3 HNO3 Ca NO3
Process 2 Urea plays an important
role in the metabolism
NH3 HNO3 NH4NO3 of nitrogen containing
compounds by animals.
Ca(NO3)2.NH4NO3 formed is known as Calcium
Ammonium Nitrate (CAN). It is more soluble in
H2O and does not make soil acidic.
(iii) Nitrolim (CaCN2

C N2
CaCO3 CO2
CaO heat
CaC2 1200 C
Ca N — C N C
White Black
Nitrolim (Grey)
Action in Soil : O
CaCO3 H2O
||
Heat
CaCN2 H2O CO2 H2N — C N H2N C O NH4
NH2CONH2 H2O 2NH3 CO2
Ammonical Carbamate

Nitrolim is a slow fertilizer and produces more

(iv) Urea (NH2CONH2

Urea has high nitrogen content (46%) and is
soluble in H2O. Therefore, it is quick acting but is
easily washed away.

180 200
2NH3 CO2 Chighpressure
NH2COONH4 NH2CONH2 H2O
Ammonium Urea
Carbamate

II. Phosphatic Fe
3
(PO4)2.
CaF2] are insoluble and useless for plants. Thus,
they are processed for formation of useful
p-Block Elements (Part-2)

fertilizers.

3 Ca 3 !PO4 " .CaF2 #######

$ 3 Ca !H2PO4 " % 7 CaSO4 % 2 HF
2 4 %7 H SO (conc .)
2 2
Triple Superphosphate
(of lime)

29.
 Group 16 (Oxygen family)
Introduc Concept Ladder
The elements Oxygen (O), Sulphur (S),
Selenium (Se), Tellurium (Te) and Polonium (Po)
Sulphur has greater
constitute group 16 of the periodic table. tendency for catenatin
Group 16 elements are also known as than oxygen.
Chalcogens, means ore forming, because many
metals are found as oxides and sulphides and a
few as selenides and tellurides.

1. Oxygen is the most abundant element and is

found both in free as well as in combined state.
2. Oxygen makes up 46.6% by mass of the
earth’s crust and dry air contains 21.0% oxygen by Rack your Brain
volume.
Arrange the ions of group 16
3. Sulphur occurs less abundantly and
elements according to their
constitutes 0.034% by mass of the earths crust.
atomic size.
4. Sulphur occurs mainly in combined form of
sulphates and sulphides.
5. Onion, garlic, mustard, eggs, proteins hair and
wool, the organic materials also contain sulphur.
6. Polonium is radioactive in nature.

Electronic co
p-Block Elements (Part-2)

30.
 Concept Ladder

Oxygen is gas while all others are solids.

The value of electron gain
Oxygen molecule is diatomic while the enthalpy with negative sign
molecules of other element are more complex. for sulphur is higher than
Sulphur, selenium and tellurium exists as that of oxygen.
staggered 8-atom rings.

Crown shaped puckered ring of S8.

It increases on moving down the group due to Rack your Brain

increase in the number of electron shells.
Name the element(s) of group 16
The ionization energies of the elements of which is amphoteric in nature.
oxygen family are less than those of nitrogen
family. This is due to the reason that pnicogens has

is stable. As we move from oxygen to polonium,

the ionization energy decreases due to increase
in atomic size.

M.P. and B.P. increases with the increases

in atomic numbers because of the increase in
magnitude of Vander waals forces. Previous Year’s Questions

Elements of group 16 are more electronegative Which is the correct thermal

than corresponding elements of group 15 due to stability order for H2E (E = O, S, Se,
p-Block Elements (Part-2)

their smaller atomic size. Te and Po)?

[NEET-2019]
They have very less metallic character (1) H2Se < H2Te < H2Po < H2O < H2S
due to high ionisation energy. Their metallic (2) H2S < H2O < H2Se < H2Te < H2Po
character increases down the group from oxygen (3) H2O < H2S < H2Se < H2Te < H2Po
to polonium because of decrease in ionization (4) H2Po < H2Te < H2Se < H2S < H2O
energy.

31.
 The elements of oxygen family have high
electron gain enthalpy. The value decreases from
sulphur to polonium.
Concept Ladder
All the elements of 16th group show allotropy.
Oxygen exists in two non-metallic forms i.e. O2
and O3. Sulphur provides a very good example of The boiling point order
an element that exhibits allotropy. among H2O, HCl and NH3
is H2O > NH3 > HCl, it is
Oxygen has some but sulphur has greater because H2O is capable
tendency for catenation. of showing more stronger
H-bonding than NH3, while
H – O – O – H, H–S–S–H HCl has no H-bonding.
(H2O2) (H2S2)

Some properties of group 16 elements.

p-Block Elements (Part-2)

32.
Oxygen and its compounds
Prep Concept Ladder
O2 is a colourless, odourless and tasteless gas
which is partially soluble in water. Liquid dioxygen
is pale blue in colour and the solid is also blue. Oxygen does not show
It is paramagnetic due to presence of unpaired oxidation state of +4 and
electrons. +6, which S does so.
1. It is prepared industrially by the electrolysis
of acidic or alkaline H2O or by Claud’s
Process(fractional distillation of liquid air)
2. In laboratory it is prepared from thermal
decomposition of

MnO2 heat
2KClO3 2KCl 3O2

Pb NO3 PbO 2NO2 1 / 2O2

2

3. It can also be made by catalytic decomposition

of hypochlorites: Previous Year’s Questions
Co2 catalyst
2HOCl 2HCl O2
Which of the following does not
give oxygen on heating?
2CaOCl 2 2CaCl 2 O2
[NEET-2013]
(1) K2Cr2O7 (2) (NH4)2Cr2O7
(3) KClO3 (4) Zn(ClO3)2
Most of the O2 is used in the steel making
industry. Some of it is used in oxy-acetylene
welding and as an oxidant in rockets. It is an
essential constituent of life.

Q.8 Why OF6 does not exist but SF6 exists?

p-Block Elements (Part-2)

A.8 Due to absence of d-orbitals in the valence shell, oxygen cannot show an
oxidation state of +6 and hence does not form OF6. In contrast, S contains
d-orbitals in the valence shell and hence can show a maximum oxidation
state of +6. Since F2 is a very strong oxidising agent, it oxidises sulphur to its
maximum oxidation state of +6 and thus forms SF6.

33.
 [a] Oxides and their general properties
Dioxygen reacts with practically all elements
to form oxides. The reactions are usually
exothermic and once started often continues
spontaneously.
If an element exists in several oxidation Concept Ladder
states, then generally lower ones are basic
and higher ones are acidic.
Tendency to show -2
N2O,NO,N2O3 ,NO2 ,N2O5
oxidation state diminishes
neutral acidic
from S to Po in group 16
CrO, Cr2O3 , CrO3 elements.
basic amphoteric acidic

PbO, PbO2
morebasic lessbasic

The order of acidic strength of oxides can be

obtained as follows:

The further apart two oxides are in the series,

the more stable the compound formed when
they react together.
Example : CaO + H2O + SO3 morestable Rack your Brain
CaSO4 (CaO.SO3)
[b] Ozone O3 Why oxygen exists as a diatomic
O3 is an unstable, dark blue diamagnetic toxic gas at room temperature while
gas. The colour is due to intense absorption of other elements as solid?
red light, It also absorbs strongly in the UV region.
p-Block Elements (Part-2)

For each O atom, of the three sp2 orbitals two

are occupied by two lone pairs and one forms –
bond. The remaining 4 electrons form – bonds.
The system is thus 4e–3 centre bond.

34.
 O3 is prepared by the action of a silent electric Concept Ladder
discharge upon dioxygen in an ozoniser.
Bond order = 1.5 for O – O bonds.
O3 is used as a disinfectant
1. O3 turns starch iodide paper blue. and as a germicide. It is
2. The amounts of O3 in a gas mixture is also used for purifying air
determined by passing gas into KI solution in crowded places such
as cinema halls, tunnels
liberated is titrated with sodium thiosulphate. and underground railway
station.
O3 2K 2I H2O I2 2KOH O2

Alternatively, it is decomposed catalytically

and the change in volume measured.

2O 3
3O 2
2volume 3volume

3. Hg in the presence of ozone is oxidized to

sub-oxide and starts sticking to glass and loses
its meniscus. This is used as a test for ozone Rack your Brain
called ‘Tailing of Mercury’.
4. O3 is an extremely powerful oxidising agent,
Why two O—O bond length in the
second only to F2.
ozone molecule are same?
3PbS 4O3 3PbSO4

2NO2 O3 N2O5 O2

1
2KOH 5O3 2KO3 O H2
2 2
ozonide

5. O3 reduces peroxides
Previous Year’s Questions
O3 BaO2 BaO 2O2
The angular shape of ozone
p-Block Elements (Part-2)

O3 H2O2 H2O 2O2 molecule (O3) consists of

[AIPMT]
Uses
(1) 1 sigma and 1 pi bond
O3 is used as a disinfectant for water.
(2) 2 sigma and 1 pi bond
Its advantage over chlorine is that it avoids
(3) 1 sigma and 2 pi bond
unpleasant smell and taste of chlorine, since any
(4) 2 sigma and 2 pi bond
excess O3 decomposes to O2.

35.
 [c] Hydrogen Peroxide H2O2
Pure H2O2 is a colourless liquid (like water), Concept Ladder
more hydrogen bonded than water (and thus has
highest boiling point)
H2O2 is used as an oxidizer,
1. At one time H2O2 was obtained by electrolysis bleaching agent and
of H2SO4 or (NH4)2SO4 using high current density. antiseptic.
electrolysis
2SO24 S2O82 2e

HSO
2 2 8
2H2O 2H2SO4 H2O2
Peroxodisulphuric
acid

2. Now, it is produced industrially by a cyclic

process.

Rack your Brain

How H2O2 can be produced by

H2O2 is extracted with water as 1% solution using cyclic process?
which is concentrated to 30% solution.
3. In laboratory
cool

2 2 2 4 2 4 2 2 2 4 2 2

2 2 2 3 2 2

1. H2O2 decomposes in presence of impurities

like Fe2+, Fe3+, Ni2+, Pt. to undergoes a Previous Year’s Questions
disproportionation reaction :
p-Block Elements (Part-2)

The O—O—H bond angle in H2O2 is

2H2O2 2H2O O2
[AIPMT]
Glycerol or acetanilide is added to check its (1) 106° (2) 109°28’
decomposition. (3) 120° (4) 97°

36.
2. In most of its reactions H2O2 acts as a strong
oxidising agent (slow in acidic medium while fast Concept Ladder
in alkaline).

H2O2 2Fe2 2Fe3 2H2O H2O2 is a reactive oxygen

4 3 species and the simplest
H2O2 2 Fe CN 2 Fe CN 2OH peroxide, a compound
6 6
Ferrocyanide Ferricyanide having an oxygen – oxygen
single bond structure.
H2O2 SO23 SO24 H2O
3. H2O2 is forced to act as a reducing agent with
stronger oxidising agents and O2 is evolved.

5H2O2 2MnO4 6H 2Mn2 8H2O 5O2

H2O2 is useful to counteract chlorine:
4. H2O2 is a mild bleaching agent for hair feathers
due to the oxidation reaction:

H2O2 H2O O

5. Qualitative Analysis: It is detected qualitatively

Rack your Brain
by its action on KI.
H2O2
2KI 2KOH I2
Name the structure of H2O2?

It is proposed H2O2 is a tautomeric mixture of

two forms:

It shows restricted rotation about O—O bond

due to repulsion between two H’s. The structure is
same in liquid and gaseous forms, but angles and
bond lengths change due to hydrogen bonding. Previous Year’s Questions
p-Block Elements (Part-2)

Hydrogen peroxide molecules are

[AIPMT]
(1) monoatomic and form X22– ions
(2) diatomic and form X– ions
(3) diatomic and form X2– ions
(4) monoatomic and form X– ions

37.
 Sulphur and its Compounds
Concept Ladder
Sulphur has the maximum number of allotropic
structures. The two common crystalline forms
are : -sulphur is insoluble in
(i) -Rhombic Sulphur: water but dissolves to
It is a yellow solid stable at room temperature, some extent in benzene,
M.P. 11.8° alcohol and ether.
(ii) –Monoclinic Sulphur:
It is a colourless solid stable above 95.5°C,
M.P. 120°
At 95.5°C (transition temperature both forms
are stable). Both and forms contain puckered
S8 rings in crown conformation.
(iii) Engels Sulphur ( - sulphur):
It is unstable and has S6 rings in chair
conformation.
Toluene
Rack your Brain
Na2S2O3 conc.HCl 2S 2NaCl O2 H2O
(iv) Plastic Sulphur ( - sulphur): How mono-clinic sulphure is
It is elastic, dark coloured and obtained prepared. Draw its structure?
liquid sulphur into water. It can be moulded with

(v) Colloidal Sulphur:

It is prepared by passing H2S gas into an
oxidising solution like HNO3, FeCl3

2HNO3 H2S S 2NO2 2H2O

Sulphur is obtained from natural gas plants

(which contain) and from metal sulphide ores Concept Ladder
(especially iron pyrites) which produce SO2.

2H2S 3O2 2SO2 2H2O -sulphur is stable below

p-Block Elements (Part-2)

369 K and transform into

SO2 2H2S 2H2O 3S -sulphur above this
Uses temperature.
Almost 90% of S produced is used to
manufacture H2SO4 .The rest is used in vulcanizing
of rubber,making fungicides, gunpowder etc.

38.
[a] Hydrogen sulphide H2S (Sulphuretted
Hydrogen) Concept Ladder
It is a colourless, poisonous gas, soluble in
H2O and smell of rotten eggs.
H2S is more acidic than H2O
It is easier to make H2S by the action of and PH3. Thermal stability
mineral acids on metal sulphides. of H2 o is much higher than
that of H2S.
FeS H2SO4 FeSO4 H2S

Sb2S3 6HCl 2SbCl 3 3H2S

pure

2H2S 3O2 2H2O 2SO2

excess

A saturated solution of H2S is slowly oxidized

by air and Sulphur is deposited. Rack your Brain

2H2S O2 limited 2H2O 2S Why H2S has greater molecular

2. It is a very weak dibasic acid. mass than H2O, former is gas
while latter is present in liquid
2 2 form at room temperature?

NaHS NaOH Na2S H2O

The two salts NaHS, Na2S are basic and
soluble in water.

3. H2S NH3 NH4 HS not NH4 S

2

Yellow (NH4)2S is a mixture of ammonium

polysulphide and is made by dissolving sulphur in Previous Year’s Questions
colourless (NH4)HS/NH3 solution. This solution is
used to precipitate metal sulphides in qualitative
Acidity of diprotic acids in aqueous
analysis.
p-Block Elements (Part-2)

solutions increases in the order

4. H2S is a reducing agent and reduces Cl2 to
Cl–, H2SO to SO2, FeCl3 to FeCl2 and itself gets [NEET-2014]
oxidized to S. (1) H2S < H2Se < H2Te
(2) H2Se < H2S < H2Te
H2S Cl 2 2HCl S (3) H2Te > H2S > H2Se
(4) H2Se < H2Te < H2S
H2S H2SO4 SO2 2H2O S

39.
 [b] Sulphur Dioxide (SO2
SO2 is a colourless poisonous gas with a Concept Ladder
choking smell. It is highly soluble in water and
almost completely present as SO2.6H2O in water
and only 1% as H2SO3. Liquid SO2 has also been H2S acts only as a reducing
used as a non-aqueous solvent. agent while SO2 can act
both as a reducing and
oxidising agent.
1. It is prepared by burning S or H2S in air.

S O2 SO2

2H2S 3O 2
2SO2 2H2O
excess

2. It is also prepared by roasting various metal

sulphides in smelters.

2ZnS 3O2 2ZnO 2SO2 Rack your Brain

4FeS2 11O2 2Fe2O3 8SO2 Why bleaching by SO2 is

temporary?

1. Most of SO2 is oxidized to SO3 by the contact

process and used to manufacture H2SO4.
V2O5
2SO2 O2 2SO3 ; r
H 196.6kJ / mol

2. Bleaching action:

SO2 2H2O H2SO4 2 H

Previous Year’s Questions
Bleaching by SO2 is temporary as reduced
colour is reoxidised by air to give black coloured
matter. Nitrogen dioxide and sulphur
Also, H2SO4 produced during bleaching may dioxide have some properties in
common. Which property is shown
by these compounds, but not by
p-Block Elements (Part-2)

HCl H2O
X — OH SO2 XHSO3 XCl XOH HCl the other?
coloured
colourless
coloured [NEET-2015]
Cl2 (1) Is soluble in water.
produces [O]. (2) Is used as a food preservative.
(3) Forms ‘acid-rain’.
(4) Is a reducing agent.

40.
3. It shows reducing properties in presence of
moisture.
Concept Ladder
SO2 Cl 2 2H2O H2SO4 2HCl

Burning of sulphur or
5SO2 2KIO3 4H2O K2SO4 4H2SO4 I2
sulphide ores in air
Although with stronger reducing agents it acts generates SO2.
as an oxidising agent.

2H2S SO2 2H2O 3S

3Fe SO2 2FeO FeS

Detection of SO2
It may be detected in three ways in the
laboratory :
1. By its choking smell
2
Cr2O7/H+
green.

K2Cr2O7 3SO2 H2SO4 Cr2 SO4 K2SO4 H2O

3
orange green
Rack your Brain

What happen when SO2 gas is

3dz2 orbital of S cannot be used to form passed through an aqueous
bond as its symmetry is wrong. Instead of 3dxz solution of a Fe(III) salt.
orbital on S is used to make the second bond
with 2pz orbital on the second O atom. Although,
it is surprising that both bonds have the same
energy.

Q.9 How SO2 is an air pollutant?

p-Block Elements (Part-2)

A.9 SO2 acts as an air pollutant because of the following reasons : (i) SO2 is
strongly irritating to the respiratory tract. SO2 at a concentration of 5 ppm
causes throat and eye irritation (resulting in cough, tears and redness in eyes).

41.
 [c] Sulphur Trioxide (SO3
It is the anhydride of H2SO4 and is solid at Concept Ladder
room temperature. It has three forms:
All the S—O bonds in
SO3 have equal length
due to resonance.
SO3 exists in 3 allotropic
forms -SO3, -SO3,
In gaseous state, SO3 has a planar triangular -SO3.
structure involving sp2 hybrid sulphur atom. The
lone pair of sulphur atom forms coordinate bond
( ). Therefore, bond angle is exactly 120°. Solid
SO3 possesses either cyclic trimer ( form) or
form).

1. It is manufactured on a huge scale by the Rack your Brain

Contact Process. Practically all of it is converted
to H2SO4 in the same process :
Pt/V2O5 Why SO3 is not absorbed directly
2SO2 O2 2SO3 in water to form H2SO4 in contact
process?
2. Fe2(SO4)3 Fe2O3 + 3SO3

1000 C
1. 2SO3 2SO2 O2

2. SO3 HO2
H SO
2 4
vapour densemist

SO3 is used to prepare oleum (mainly

pyrosulphuric acid H2S2O7)

SO3 g H2SO4 H2S2O7 Concept Ladder

3. SO3 is used to make sulfamic acid NH2SO3H

SO2 may be regarded as an
(the only strong acid that can exist as a solid at
p-Block Elements (Part-2)

anhydride of sulphurous
room temperature).
acid (H2SO3) while SO3 is
NH2CONH2 SO3 H2SO4 2NH2SO3H CO2 regarded as an anhydride
Urea of sulphuric acid (H2SO4).

42.
 Some oxo acids of Sulphur ending in – ous Rack your Brain
have S in the oxidation state (+IV) and form salts
ending in –ite. Some acid ending in –ic have S in
the oxidation state (+VI) and form salts ending in formed by sulphure?
–ate. Four main series exist which are:

The most important acid (according to the

use) in this series is sulphurous acid (H2SO3):

Concept Ladder
It is only known in solution form (like carbonic
acid) and as discussed SO2 solution in water gives
1% H2SO3. Sulphourous acid is an
SO2 H2O H2SO3 intermediate species in the
Chemical Properties of SO32– ion. formation of acid rain from
1. H2SO3 being dibasic forms salt of bisulphites sulphur dioxide.
(HSO3–) and sulphites (SO3–).HSO3– however
undergoes internal dehydration to form
S2O52– ion.
heat
2HSO3 S2O52 H2O
disulphite

2. S(+IV) in SO3– and HSO3– is a moderately strong

reducing agent and forms sulphates on oxidation.

SO23 H2O2 SO42 H2O Previous Year’s Questions

H2SO3 H2O 2FeCl 3 H2SO4 2FeCl 2 2HCl

Which of the following oxoacid of
while with sulphur, sulphites form sulphur has —O—O— linkage
p-Block Elements (Part-2)

thiosulphates: [NEET-2020]
OH (1) H2SO3, sulphurous acid
SO23 S S2O23 (2) H2SO4, sulphuric acid
thiosulphate
(3) H2S2O8, peroxodisulphuric acid
(4) H2S2O7, pyrosulphuric acid

43.
 Sulphites and hydrogen sulphites liberates
SO2 on treatment with dilute acids Concept Ladder
H dil
2 2
3 3 2
H2SO4 is considered as
3. SO32– acts as an oxidising agent with a strong the King of Chemicals. In
RA like H2S. ancient days, it was called
SO23 2S 2
6H 3S 3H2O oil of vitriol (Green Vitriol).

(i) Sulphuric acid [Oil of Vitriol] H2SO4

It is the most important acid used in the
chemical industry. It is a colourless syrupy liquid Rack your Brain
with B.P. 338oC and freezes into crystals at 10.5°C
. It is strongly hydrogen bonded. Write down the main process for
Preparation manufacturing of sulphuric acid.
1. In ancient days it was prepared from
FeSO4.7H2O (Green vitriol).

heat
2 FeSO4 .7H2O Fe2O3 SO2 13H2O H2SO4
green vitriol

2. Lead Chamber Process

Was used to manufacture H2SO4 industrially
but the process is now obsolete as it only produced
78% H2SO4. NO2 is used as a homogeneous
catalyst to oxidise SO2 in the presence of water. Previous Year’s Questions
NO produced combines with air to produce NO2
which is reused. Thus, NO and NO2 act as oxygen Oleum is
p-Block Elements (Part-2)

carriers [AIPMT]
(1) caster oil
(2) oil of vitriol
(3) fuming H2SO4
(4) none of these

44.
 This process is most important commercial
process for the manufacture of H2SO4. It is used
widely.

(i) SO2
or sulphide ores.
(ii) SO2 is then oxidized.

2SO2 g O2 g 2SO3 g Previous Year’s Questions

The forward rxn is exothermic and is favoured Identify the correct formula of
by high pressure, low temperature and excess oleum from the following :
of oxygen. A catalyst (activated V2O5) is used to
p-Block Elements (Part-2)

[NEET-2019]
obtain a reasonable conversion. (1) H2S2O7 (2) H2SO3
(iii) SO3 is then passed into 98% H2SO4 forming (3) H2SO4 (4) H2S2O8
pyrosulphuric acid (H2S2O7) called oleum.
Dilution of oleum with water gives concentrated
H2SO4 (98%).

45.
 1. H2SO4 due to its low volatility is used to
Concept Ladder
manufacture more volatile acids.

2MX 2
H SO
4
2HX H2SO4 H2SO4 has high boiling
M metal;X F,Cl,NO3 point due to H-bonding.
2. H2SO4 is a powerful dehydrating agent It acts as a strong
especially for gases. dibasic acid.
It dehydrates HNO3 forming NO2+ Metals those are more
electropositive than
2H2SO4 HNO3 NO2 H3O 2HSO4
hydrogen react with dil.
It removes elements of H2O from organic H2SO4 to evolve H2 gas
compounds. but less electropositive
metals on heating with
2 2 4 2 conc. H2SO4 evolve SO2.

2 2 4 2 2 4 2

H2SO4 mixes with H2O to evolve large amount

of heat. If H2O is poured into concentrated acid,
the heat evolved causes violent splashing. Thus,
to dilute strong acids like H2SO4, acid is poured
into water while stirring (not water into acid).
3. H2SO4 is a quite strong oxidising agent. Rack your Brain
2Br ! " H2SO4 ### $ 2H2O " SO2 " Br2
(conc .)
Why KMnO4 should not be
2H2SO4 C CO2 2SO2 2H2O dissolved in conc. H2SO4?
(conc .)

4. Pure H2SO4 is a non-aqueous solvent and a

sulphonating agent.

C6H6 HO.SO3H C H SO OH
6 5 2
H2O
Benzenesulphonicacid

Q.10 In solution of H2SO4 when SO3 is bubbled, a compound ‘A’ is formed, which
further reacts with H2O to give H2SO4. Explain this process with equation?
p-Block Elements (Part-2)

A.10 H2SO4 absorbs SO3 forming oleum (A) which reacts with H2O to form H2SO4.
HO
H2SO4 ! SO3 """
# H2S2O7 """
2
# 2 H2SO4
Oleum, A

46.
1. It is used in making superphosphate fertilizer. Concept Ladder
2. It is used in removal of oxides from the surfaces
of metals like Fe, Cu before electroplating or
H2S2O3 is a dibasic acid. It
galvanizing.
does not exist in free state,
3. It is used as a dehydrating agent. oxidising salts are quite stable and
agent and as strong acid. are reducing in nature.
(ii) Thiosulphuric acid (H2S2O3
It is unstable and decomposes in H2O into
a mixture of S, H2S, SO2 and H2SO4 while the
salts (thiosulphates) are stable. Large colourless
hexagonal crystals are formed which are highly
soluble in water.
sodium thiosulphate (Na2S2O3.5H2O) is the
most important thiosulphate also called hypo.

boiling
SO23 S S2O23 Rack your Brain
Neutral/alkaline

How many P—O—P bonds are

1. Hypo solutions are used for iodine titrations there in (i) H4P2O7 (ii) P4O10?
in volumetric analysis.

2Na2S2O3 I2 Na2S4O6 2NaI

In iodometric estimation oxidising agents like

CuSO4, K2Cr2O7 are treated with KI which liberates
I2 which is determined by hypo as above.

2CuSO4 4KI 2K2SO4 Cu2I2 I2

2. Na2S2O3 is used to destroy excess Cl2 on
fabrics after they have been bleached and called
as antichlor. Previous Year’s Questions
p-Block Elements (Part-2)

Na2S2O3 + 4Cl2 + 5H2O 2NaHSO4 +8HCl

Which is the strongest acid in the
It is also used to remove the taste from following?
heavily chlorinated drinking water. [NEET-2013]
(1) HClO4 (2) H2SO3
(3) H2SO4 (4) HClO3

47.
 , AgBr
3
salts.

Na2S2O3

2 2 3 2 2 3 3 2 3 2

Concept Ladder

The chemical name for the

following acids are : (i) H2SO5
(iv) Peroxo Acid Series Peroxymonosulphuric acid
They contain the peroxo linkage —O—O—. or Caro’s acid, (ii) H2S2O8
Peroxydisulphuric acid or
Marshall’s acid, (iii) H2S2O6
Dithionic acid

Q.11 Why is sulphurous acid acts as reducing agent?

A.11 As Sulphur atom contains a lone pair of electrons, sulphurous acid can be
easily oxidised to sulphuric acid. Therefore, it acts as a reducing agent.
H2O ! Br2 ! H2SO3 """
# 2 HBr ! H2SO4

Q.12 Write one chemical reaction to show that conc. H2SO4 can act as an oxidising
p-Block Elements (Part-2)

agent.

A.12 Concentrated sulphuric acid oxidises carbon to CO2.

C ! 2 H2SO4 (conc .) """
$
# CO2 ! 2 SO2 ! 2 H2O

48.
Group 17 (Halogen Family)

The elements Fluorine, Chlorine, Bromine,

Iodine and Astatine constitute group 17 of the
periodic table.

1. Fluorine is less abundant in earth’s crust than

chlorine.
2. Fluorine is available mainly as insoluble

3. Fluorine occurs to the extent of 0.07% of the Concept Ladder

earth’s crust.
Due to its very small
2
2. Cryolite : Na3AlF6 not acts as central
3. Fluorapatite: 3Ca3 (PO4)2 . CaF2 atom in formation
of interhalogen
1. Their valence shell compounds.
It is the most
2
np5 or ns2 npx2 npy2
p-Block Elements (Part-2)

electronegative
npz1 where n = 2 to 6. element in the whole
2. The atomic radii periodic table.

due to increase in number of shells.

49.
 3. Ionization energy of
these elements are higher than those of the Concept Ladder
corresponding elements of group 16 due to
increase nuclear charge. Fluorine is better oxidising
4. With increase in atomic agent than chlorine,
number down the group, the electronegativity although it has less

decreases. The decreasing order of

has highest electron
electronegativity is F > Cl > Br > I.
5. The decreasing order periodic table.
of negative electron gain enthalpy is Cl > F > Br >
I.
6. All the halogens show an

show positive oxidation state also.

7. All the halogens are non-
metallic in nature due to their high ionization Rack your Brain
enthalpies and high electronegativities. The non-
metalic character gradually decreases down the Why electron gain enthalpy of
group.
that of chlorine?
8. Bond dissociation

electronic repulsions present in the small atom

order : Cl2 > Br2 > F2 > I2

9. As the size of the halogen atom Previous Year’s Questions
increases the bond length of X – X bond in X2
molecule increases from F2 to I2. Which one of the following orders
10. It increases is correct for the bond dissociation
p-Block Elements (Part-2)

enthalpy of halogen molecules?

from F to I due to an increase in the VWF of
[NEET-2016]
attraction which increases down in the group. (1) Br2 > I2 > F2 > Cl2
11. The density of halogen increases on (2) F2 > Cl2 > Br2 > I2
moving down the group. (3) I2 > Br2 > Cl2 > F2
12. All halogens are coloured. The colour (4) Cl2 > Br2 > F2 > I2

50.
darkness depends on the rise of atomic number
Concept Ladder
F : Light yellow; Cl : Yellow green;
Br : Raddish brown; I : Deep violet Standard reduction
The colour is due to the adsorption of energy potential of halogens are
from visible light by their molecules to excite positive and decreases
down the group. Thus,
outer electrons for higher energy levels.
halogens acts as strong
Chemical Properties oxidising agents and their
1. Reacti oxidising power decreases
All the halogens are chemically very reactive
elements. This is due to their low dissociation
energy. Fluorine is the most reactive and iodine
is the least reactive halogen.
2.
Thermal stability of hydrides decreases from
HF to HI. i.e. HF > HCl > HBr > HI.
3.
The oxidising power decreases on moving
down the group. i.e. F2 > Cl2 > Br2 > I2.
Conversely, I– is the strongest reducing agent Previous Year’s Questions
while F– is the weakest reducing agent.
4. The variation of the boiling points
All the halogens combine directly with H2 of the hydrogen halides is in the
to form covalent molecular hydrides but their order HF > HI > HBr > HCl.
What explains the higher boiling
to iodine.
5. Bond strength, bond length and thermal [NEET-2015]
(1) There is strong hydrogen bonding
Since, size of halogen atom increases from between HF molecules.
(2) The bond energy of HF molecules
F to I down the group, bond length of H–X bond
is greater than in other hydrogen
increases down the group.
halides.
p-Block Elements (Part-2)

HF < HCI < HBr < HI

Bond energy has inverse relationship with
bond length i.e. larger the bond length, lower the
polarises the HF molecule.
bona strength and vice versa. Thus, order of bond
strength is HF > HCl > HBr > HI is much higher than for other
Bond strength provides a direct idea of elements in the group.
thermal stability. Higher the bond dissociation

51.
 energy greater will be thermal stability. Thus,
Rack your Brain
thermal stability follows the order.
HF > HCl > HBr > HI
Explain why halogens are strong
5.
oxidising agents.
The reducing character of hydrogen halides
increases down the group as, HF < HCl < HBr < HI
2HX H2 + X2

A less thermally stable compound has more

tendency to release hydrogen easily and show
greater reducing property. Since thermal stability
of hydrogen halides decreases from HF to HI,
their reducing power increases from HF to HI.
6.
In gaseous state, hydrogen halides are Previous Year’s Questions
covalent. But in aqueous solutions, they ionize
and behave as acids. The acidic strength of Among the following, the correct
order of acidity is
these acids increases down the group and hence
[NEET-2016]
follows the order.
(1) HClO2 < HClO < HClO3 < HClO4
HF < HCl < HBr < HI (2) HClO4 < HClO2 < HClO < HClO3
(3) HClO3 < HClO4 < HClO2 < HClO
2HF HF2– + H+ (4) HClO < HClO2 < HClO3 < HClO4
HF2– H+ + F22–

Reaction with H2
1. 2H2O + 2F2 4HF + O2

Q.13 Sea is the greatest source of halogens. Comment.

A.13 Sea water contains Cl, Br and I of Na, K, Mg and Ca, but mainly NaCl (2.5% by
p-Block Elements (Part-2)

mass). Dried up sea beds contain NaCl and carnallite, KCl.MgCl2.6H2O. Certain
seaweeds contain upto 0.5% of iodine as sodium iodide and chile saltpetre
(NaNO3) contains upto 0.2% of sodium iodate. Therefore, sea is the greatest
source of halogens.

52.
2. 3H2O + 3F2 6HF + O3
Concept Ladder
3. Cl2 + H2O HCl + HCIO
(Hypochlorous acid)
4. Br2 + H2O HBr + HBrO
provides the largest
(Hypobromous acid) variety of inter-halogen
5. 2HCIO 2HCI + O2, compounds.

2HBrO 2HBr + O2
6. I2 + KI = KI2 + I = I3–
–

200 C
1. H2 + F2 2HF (very violent)
Sunlight
H2 + Cl2 2HCl
Heat
H2 + Br2 Pt. catalyst
2HBr
Rack your Brain
heat
H2 + I2 2HI (Poor yield)
2. Bleaching action of halogen : Cl2 acts as a Arrange hydrogen halides in the
increasing order of there dipole
bleaching agent. Its bleaching action is permanent
moments.
Cl2 water can also acts as ink remover.
3. Reaction with other halides :
2KBr (aq) + Cl2 (g) 2KCl (aq) + Br2 (g)

2 KI (aq) + Cl2 (g) 2KCl (aq) + I2 (g)

Fluorine d
Previous Year’s Questions
sub-group due to the following reasons.
1. Small size of the atom in comparison to the
Which of the following statements
sizes of Cl, Br and I atoms.
is not true for halogens?
2. Higher electronegativity. [NEET-2018]
p-Block Elements (Part-2)

3. Absence of d-orbitals in its valence shell. (1) All form monobasic oxyacids
4. Higher positive reduction potential. (2) All are oxidizing agents.

1. Fluorine shows only a negative oxidation state positive oxidation states.

(4) Chlorine has the highest
electron-gain enthalpy.

53.
p-Block Elements (Part-2)

54.
of –1 due to maximum value of electronegativity.
It never shows any positive oxidation state. The Concept Ladder
other halogen show negative as well as positive
oxidation states, i.e. between –1 and +7. Fluorine and oxygen
2. Fluorine is most reactive as bond dissociation compounds are called
energy of F – F bond is low. X – X bond is stronger
in Cl2 and Br2·

there is no d-orbital in its valence shell. Other

members can have maximum covalency of 7
because of vacant d-orbitals.
4. Fluorine does not have vacant d-orbital in
valence shell therefore it does not combine with
F– –
, Br3–, I5–
Rack your Brain
etc.

Why I2 is more soluble in KI than

2
) in water?

1. Chlorine is widely distributed in nature in

the combined state in the form of chlorides of
various metals.

2. Common Salt (NaCl) is the most important

chloride which occurs in sea water, lakes and in
rocks.
Previous Year’s Questions

1. Sylvine (Potassium Chloride) KCl Which of the following elements

2. Carnalite, KCl, MgCl2, 6H2O is extracted commercially by the
electrolysis of an aqueous solution
p-Block Elements (Part-2)

3. Chlorapatite, 3Ca3(PO4)2 CaCl2

of its comopund?
4. Horn Silver, AgCl [AIPMT]
(1) Cl (2) Br
(3) Al (4) Na
1. By oxidation of conc. HCl

55.
 PbO2 + 4 HCl PbCl2 + 2 H2O + Cl2
Concept Ladder
2 KMnO4 + 16 HCl 2 KCl + 2MnCl2 + 8

H2O + 5 Cl2
Deacon’s process is superior
2. Weldon’s process : By heating pyrolusite with to Weldon’s process as in
conc. HCl Deacon’s process, chlorine
MnO2 + 4 HCl MnCl2 + 2 H2O + Cl2 is obtained by the oxidation
of HCl with air in presence
3. Deacon Process : of cupric chloride heated
HCl(g) is oxidised by atm. oxygen in presence at 400°C.
of a catalyst CuCl2 at 400°C (723 K).
CuCl
4 HCl + O2 """" 2
400!C
# 2 Cl2 + 2 H2O

It is yellowish green gas, poisonous in nature,

soluble in water. Its aqeous solution is known
as chlorine water which on careful cooling gives Rack your Brain
chlorine hydrate Cl2 8H2O.
What is the cause of bleaching
1. Bleaching action and oxidising property. action of chlorine in water?

2. Cl2 + H2O HOCl + HCl

HOCl HCl + O
The bleaching action of chlorine is permanent
and is due to its oxidising nature.

3. SO2 + Cl2 + 2H2O H2SO4 + 2HCl

4. Action of hydrogen : Previous Year’s Questions

H2 + Cl2 2HCl
The correct order of increasing
5. Displacement reactions :
bond angles in the following
2 KBr + Cl2 2 KCl + Br2 species is
p-Block Elements (Part-2)

[AIPMT]
2 KI + Cl2 2 KCl + I2 (1) Cl2O < ClO2 < ClO2–
6. Action of NaOH : (2) ClO2 < Cl2O < ClO2–
(3) Cl2O < ClO2– < ClO2
2 NaOH + Cl2 NaOCl2 + H2O
(4) ClO2– < Cl2O < ClO2

56.
 Ca(OH)2 + Cl2 CaOCl2 + H2O

7. Combination with non metals Concept Ladder

2 As + 3 Cl2 2 AsCl3
2
2 S + Cl2 S2Cl2
is permanent, while that by
2 B + 3 Cl2 2BCl3 SO2 is temporary.

2 Sb + 3 Cl2 2 SbCl3

P4 + 10 Cl2 4 PCl5

P4 + 6 Cl2 4 PCl3

8. Other important reactions

Reaction with ammonia
8 NH3 + 3Cl2 N2 + 6 NH4Cl

Reaction with hydrocarbons Rack your Brain

C2H4 + Cl2 C2H4Cl2

Oxidizing nature of chlorine Arrange the following oxoacids

of chloride in increasing order of
2FeSO4 + H2SO4 + Cl2 Fe2(SO4)3 + 2HCl their acidic strength.
Na2SO3 + Cl2 + H2O Na2SO4 + 2 HCl HOCl, HOClO, HOClO2, HOClO3

H2S + Cl2 2 HCl + S

SO2 + Cl2 + 2 H2O 2 HCl + H2SO4

It is used as :
1. Bleaching agent
Previous Year’s Questions
2. Disinfectant
3. In the manufacture of CHCl3, CCl4, DDT, BHC. Which of the following displaces
(Insecticides) etc. Br2 from an aqueous solution
containing bromide ions?
p-Block Elements (Part-2)

4. In the manufacture of synthetic plastic such

[AIPMT]
as PVC.
(1) I2 (2) I3–
5. Poisonous gas phosgene (COCl2), tear gas (3) Cl2 (4) Cl–
(CCl3NO2), Mustard gas (ClC2H4SC2H4Cl).

57.
 6. Refrigerant such as freon (CCl2F2).
7. Extraction of Metals like Au and Pt. Concept Ladder

HCl also known as muriatic

acid , is an aqueous solution
1. HCl is prepared by dissolving hydrogen
of hydrogen chloride. It is a
chloride gas in water.
colourless solution with a
2. Hydrogen chloride gas required in turn can be distinctive pungent smell.
prepared by the following methods.
sunlight
H2 (g) + Cl2 (g) 2 HCl (g)

HCl gas can also be obtained by burning

hydrogen in chlorine.

1. In the laboratory HCl is prepared by mixture

of NaCl and conc. H2SO4 Rack your Brain
NaCl + H2SO4 NaHSO4 + HCl

NaHSO4 + NaCl Na2SO4 + HCl Explain why ClF3 exists but FCl3
does not?
2. HCl(g) is dried by passing through cone, H2SO4
collected by upward displacement of air.

1. HCl is a covalent compound but when

dissolved in H2O it ionizes to form hydrogen ions
or chloride ions or hydronium ions.

HCl(g) + H2O (l) H3O+ (aq) + Cl–

2. It reacts with metal to form their respective Previous Year’s Questions
chlorides and H2(g).

Metal + HCl Metal + Hydrogen chloride Elements of which of the following

groups will form anions most
Mg + 2HCl MgCl2 + H2 readily?
p-Block Elements (Part-2)

Reaction with NH3 [AIPMT]

(1) Oxygen family
NH3 + HCl !!!
" NH4Cl
(2) Nitrogen family
1. It reacts with metal carbonates, bicarbonates, (3) Halogens
sulphides, sulphites, thiosulophates and nitrites (4) Alkali metals

58.
etc to form their respective chlorides.
Na2CO3 + 2HCl 2NaCl + H2O + CO2 Concept Ladder

NaHCO3 + HCl NaCl + H2O + CO2

As chlorine is second most
NaHSO3 + HCl NaCl + H2O + SO2
electronegative element
CaO + 2HCl CaCl2 + H2O in the periodic table, it
can form compounds as
Mg(OH)2 + 2HCl MgCl2 + 2H2O
carbonates, bicarbonates,
2. It is used for dissolving noble metals like Au, sulphides and nitrates.
Pt etc.
3Pt + 16H+ + 4NO3– + 12Cl 3PtCl42– + 4NO +

8H2O
Au + 4H+ + NO3– + 4Cl– AuCl4– + NO + 2H2O

1. In the preparation of chlorides, chlorine, Rack your Brain

aqua-regia etc.
2. To manufacture glucose from corn strach. Write the components used in
3. In medicine and in galvanizing. the formation of aquaregia.
4. In the production of dyes, paints, photographic
chemicals etc.

1. These compounds are regarded as halides of

more electropositive (i.e. less electronegative)
halogens.

Q.14 How can you prepare Cl2 from HCl and HCl from Cl2. Write reactions only.

A.14 HCl can be oxidised to Cl2 by a number of oxidising agents such as MnO2,
KMnO4, K2Cr2O7, etc.
p-Block Elements (Part-2)

MnO2 ! 4 HCl """

# MnCl 2 ! Cl 2 ! 2 H2O
Cl2 can be reduced to HCl by its reaction with H2 -
light.
Diffused sunlight
H2 ! Cl 2 """""""
# 2 HCl
or Cl ! H S """
# 2 HCl ! S
2 2

59.
p-Block Elements (Part-2)

60.
2. Types of interhalogen compound :
AB type : CIF, BrF, BrCl, ICl, IBr Concept Ladder
AB3 type : CIF3, BrF3, ICl3
AB5 type : BrF5, IF5 In general interhalogen
compounds are more
AB7 type : IF7
reactive than pure halogens

437K A—B bond is weaker than

1. Cl2 + F2 2 CIF
B—B bond.
573K
2. Cl2 + 3F2 2 ClF3

3. I2 + 3Cl2 2 ICl3

4. Br2 + 3F2 2 BrF3

5. I2 + Cl2 2 ICl

6. Br2 + 5SF2 2 BrF5 + 5S

1. Rack your Brain

The central halogen, i.e., the bigger halogen
atom (A) is sp3 hybridised. The molecules are Why interhalogen compounds
linear due to the presence of three lone pairs on are strong oxidizing agents.
A atom.
2. AB3
The central halogen atom is sp3d hybridised.
The molecules have a bent T-shaped geometry
instead of trigonal bipyramidal due to the
presence of two lone pairs.

Concept Ladder
p-Block Elements (Part-2)

Four types of interhalogen

Structure of BrF3 compounds are :
3. AB5 (i) XX’ : ClF, BrF, BrCl etc.
(ii) XX’3 : ClF3, BrF3, IF3 etc.
The central halogen atom is sp3d2 hybridised (iii) XX’5 : ClF5, BrF5, IF5 etc.
leading to a square pyramidal geometry instead (iv) XX’7 : IF7
of octahedral geometry as there present 1 lone
pair on the halogen atom A.

61.
 Concept Ladder

The interhalogen compounds

4. AB7
thermally more stable while
The central halogen atom (A) is sp3d3 the compounds of iodine
hybridised and the molecules shows the expected and chlorine or iodine and
pentagonal bipyramidal shape since there are no bromine are less stable.
lone pairs.

1. These may be gases (ClF, BrF, ClF3, IF7), liquids Rack your Brain
(BrF3, BrF5, IF5) or solids (ICl, IBr, IF3, ICl3).
2. The interhalogen molecules are diamagnetic Write the general formula used
in nature. for formation of interhalogen
compounds.
3. With increase in EN between A and B, thermal
stability of AB type compounds increases. The
more polar is the A – B bond and hence greater is
the thermal stability.
IF > BrF > ClF > ICl > IBr > BrCl
4. A2 or B2 molecules are less reactions than AB
type compounds. Since AB bond is weaker than
A–A & B–B bonds. These order of reactivity of
some interhalogen compounds has been found Concept Ladder
as : ClF3 > BrF5 > IF7 > BrF3 > IF5 > BrF
6. Hydrolysis gives halogen acid and oxyhalogen
p-Block Elements (Part-2)

AB type interhalogen
acid. The oxyhalogen acid is of larger halogen
compounds are ClF, BrF,
atom.
BrCl, ICl, IBr.
AB + H2O HAO + HB

ICl + H2O HIO + HCl

62.
 ICl3 + 2H2O HIO2 + 3HCl
Concept Ladder
BrF5 + 3H2O HBrO3 + 5HF

IF7 + 6H2O H5IO6 + 7HF

Interhalogen compounds are
gases or liquids, volatile and
double bond sites. create fume in air. These can
–CH = CH – +ICl –CHI – CHCl– be hydrolysed and act as
oxidising agents.

1. CIF3 and BrF3

agents.
2. Interhalogen compound are used for the
preparation of polyhalides.
3. CIF3 and BrF3 are used for the
production of UF6 in the enrichment
of 235U.
U(s) + 3ClF3(l) UF6(g) + 3ClF(g) Rack your Brain
4. Interhalogen compounds can be used as non-
aqueous solvents. BrF3 is also used as Lewis acid. What are polyhalides? Write
some examples of polyhalides in
5. Interhalogen compounds of the type XX’
(particularly ICl) are used as halogenating agent. are present.
ICl is used in the estimation of iodine number of
fats and oils.

Q.15 Why interhalogens are more reactive than halogens?

p-Block Elements (Part-2)

A.15 This is because the bond in the interhalogen (X—X’) is weaker than X—X and

orbitals of dissimilar atoms than those between similar atoms. However, due
to low bond dissociation enthalpy of F—F bond, F2 is more reactive than its
interhalogen compounds.

63.
 Central halogen atom of all oxyacids of halogen is sp3 hybridised.

Hypochlorous acid (HClO)

Or
Chlorous acid (HClO2)

Or
Chloric acid (HClO3)

Or Or Or
Linear shape of ClO– ion. Angular shape of ClO2– ion.

Or
Trigonal pyramidal shape of ClO3– ion.
p-Block Elements (Part-2)

Or
Tetrahedral shape of ClO4–

64.
Oxidising power of these oxyacids decreases as
the oxidation number of halogen increases.
Concept Ladder
HClO > HClO2 > HClO3> HClO4
Thermal stability increases with increase in Unlike other halogen
oxidation state of halogen.
HClO < HOClO < HOClO2 < HOClO3 attacks silica and glass.
Hydra – Acids With silica it forms silicon

F2
2 thio salicylic acid.
1. HF is a colourless, corrosive liquid with
pungent smell. It attacks glass and is thus stored
in wax bottles or gutta percha bottles.
2
SiO2 6HF SiF6 2H 2H2O

(This is also used for etching glass.)

HF is kept in laboratory in KF giving K+
[F—H—F]– ions. Rack your Brain

2. H2 and F2 combine with each other very

Why on heating H2F2 with a
violently even in dark to form HF. Thus special
mixture of MnO2 and H2SO4 no
methods are employed in its preparation.
gas is involved?
Industrially it is made by heating CaF2 with
strong H2SO4. The reaction is endothermic,
hence the need for heating as SiO2 impurities
are removed from CaF2 otherwise they consume
much of HF produced.

CaF2 + H2SO4 CaSO4 + 2HF

SiO2 + 4HF SiF4 + 2H2O Previous Year’s Questions

SiF4 + 2HF(aq) H2[SiF6] Which of the statements given

below is incorrect?
3. Two thirds of HF produced are used to
[NEET-2015]
p-Block Elements (Part-2)

(1) O3 molecule is bent.

(2) ONF is isoelectronic with O2N–.
(3) OF2
5

CCl 4 2HF CCl 2F2 2HCl (4) Cl2O7 is an anhydride of

perchloric acid.

65.
 4. In liquid form HF is used as a non - aqueous
solvent. Concept Ladder
2HF l H2F F
HBr and HI cannot be
II. Hydrochloric acid [HCl]
prepared by heating
1. At one time HCl was made exclusively by ‘salt bromides and iodides with
cake’ method. concentrated H2SO4 while
HCl can.
NaCl conc.H2SO4 HCl g NaHSO4

NaHSO4 NaCl HCl g Na2SO4

2. Highly pure HCl is made by bringing H2 and

Cl2 in a special combustion chamber. (Direct
combination is explosive)

Cl2 + H2 2HCl
3. In laboratory : Rack your Brain

4 2 4 4 2 4 How HCl is considered to be

conc.
strong acid.
4. Cl cannot be dried over P2O5 or quick lime
because it reacts with them:

CaO + 2HCl CaCl2 + H2O

P4O10 + 3HCl POCl3 + 3HPO3

Hence it is dried by passing through conc.
H2SO4
5. HCl(g) is colourless, weak reducing agent (is
oxidized by strong oxidising agents like MnO2, Previous Year’s Questions
KMnO4, K2Cr2O7) and highly soluble in water.
Bleaching powder reacts with a few
III HBr and HI
drops of conc. HCl to give
p-Block Elements (Part-2)

1. They are prepared by reaction of phosphoric [AIPMT]

acid on metal bromides or iodides (similar to salt (1) chlorine
cake process) (2) hypochlorous acid
(3) calcium oxide
NaI + H3PO4 HI + NaH2PO4
(4) oxygen

66.
2. The usual laboratory process is :
2P 3Br2 2PBr3 6HBr 2H3PO3 Concept Ladder
Red
6H2O
Re d 2 3 3 3
HF is the weakest acid
3. HBr is not very stable and acts as a strong among hydro halo acids.
reducing agent while HI is least stable and thus a HF < HCl < HBr < HI
more powerful reducing agent.
2HNO3 + 2HI 2NO2 + I2 + 2H2O

HIO3 + 5HI 3I2 + 3H2O

H2SO4 + 2HI SO2 + I2 + 2H2O

Oxides
The bonds in oxides are largly covalent as

between the halogens and oxygen. Most halogen Rack your Brain
oxides are unstable and tend to explode when
subjected to shock. Stability of oxides increases
With what neutral molecule ClO–
down the group and higher oxidation states are
is isoelectronic?
more stable than lower oxidation states.

I Dichloro oxide [Cl2O]

Cl2O is a yellow – brown gas which condenses

to an orange liquid (bp = 2°C). It is the anhydride
of hypochlorous acid (HClO).
Previous Year’s Questions
1. Cl2O is prepared by passing dry chlorine over
freshly precipitated mercuric oxide.
The correct order of increasing
HgO 2Cl 2 HgCl 2 Cl 2O bond angles in the following
p-Block Elements (Part-2)

dry species is :
2. It is soluble in water [AIPMT]
(1) Cl2O < ClO2 < ClO2–
Cl 2O H2O 2HOCl aq
(2) ClO2 < Cl2O < ClO2–
Hypochlrous acid
(3) Cl2O < ClO2– < ClO2
(4) ClO2– < Cl2O < ClO2

67.
 3. It explodes in presence of NH3 or a reducing
agent or on heating.
Concept Ladder
3Cl 2O 10NH3 2N2 6NH4Cl 3H2O
4. It is a strong oxidising agent. ClO2 is a powerful oxidising
and bleaching agent. It
Cl 2O 2HCl 2Cl 2 H2O has an angular structure
II Chlorine Dioxide [ClO2] with O—Cl—O bond angle
of 117.6°. The molecule is
supposed to contain a 3
electrons bond.
It is a yellow gas, condenses to deep red
liquid, explodes above –40°C and in presence of
reducing agents. It is paramagnetic being an odd
electron molecule but does not dimerises as the
odd electron is delocalised.
1. It explodes when mixed with reducing agents.
The safest laboratory preparation is form sodium
chlorate and oxalic acid as this automatically
dilutes the gas with CO2.

2NaClO3 2 COOH 2ClO2 2CO2 COONa 2H2O

2 2

2. 2ClO2 H2O HClO3 HClO2 heat

dark green solution

3. It is used to manufacture NaClO2 which is Rack your Brain

used for bleaching paper textile.
2 ClO2 2NaOH H2O2 2NaClO2 O2 2H2O Write equation when ClO2 reacts
2ClO2 2NaOH NaClO2 NaClO3 H2O with alkalies.
chlorite chlorate

4. ClO2 is a powerful oxidising about and a

bleaching agent and is used to purify water.
p-Block Elements (Part-2)

Q.16 What happens when Cl2 is passed through a hot concentrated solution of a
base like Ba(OH)2?

A.16 On treatment with Ba(OH)2, Cl2 undergoes disproportionation to form barium

chloride, Ba(ClO3)2.
0 $1 !5
6 Ba(OH)2 ! 6 Cl 2 """
Hot
# 5 BaCl 2 ! Ba(ClO3 )2 ! 6 H2O

68.
III Dichlorine Hexoxide [Cl2O6]
Concept Ladder

In vapour state, Cl2O6

exists as ClO3molecule
which is para magnetic
It is a dark red liquid which freeze at –180°C while in liquid state it is
to a yellow solid. It is diamagnetic in nature due in dimeric form having
to absence of unpaired electrons and exists as a even no. of electron hence
diamagnetic in nature.
dimer. The structure is guessed to be as shown
but the exact structure is unknown.

1. It is obtained from ClO2 and O3.

ClO2 O3 ClO3 O2
2ClO3 Cl 2O6
2. Hydrolysis with water or alkali gives chlorate
and perchlorate
Cl 2O6 H2O HClO3 HClO4
Cl 2O6 2NaOH NaClO3 NaClO4 H2O
Chlorate Perchlorate
Previous Year’s Questions
3. It is a strong oxidising agent which explodes on
contact with grease. Which one of the following oxides is
4. Reaction with anhydrous HF is reversible: expected to exhibit paramagnetic
behaviour?
Cl 2O6 HF FClO2 HClO4
[AIPMT]
IV Dichlorine Heptoxide [Cl2O7] (1) CO2 (2) SiO2
Cl2O7 is a colourless oily liquid which is (3) SO2 (4) ClO2
moderately stable and less reactive than others.
It is the only exothermic oxide of Cl and the
anhydride of perchloric acid HClO4. It is anhydride
of perchloric acid and made by dehydrating
p-Block Elements (Part-2)

perchloric acid with P2O5 or H3PO4.

P4O10
2HClO4 Cl 2O7 + H2O

69.
 Bleaching powder is actually written as Concept Ladder
Ca(OCl)2.Ca(OH)2.CaCl2.2H2O. It is a pale-yellow
powder having a strong smell of chlorine and Bleacing powder is also
soluble in water. However, a clear solution is termed as calcium chloro
never formed due to the presence of impurities. hypochlorite, because it is
considered as a mixed salt
It is made by passing Cl2 into slaked lime. of hydrochloric acid and
hypochlorous acid.
Ca(OH)2 + Cl2 Ca(OCl)Cl + H2O

1. Bleaching action

Rack your Brain

Name the porcesses used for

manufacturing of bleaching
2. Oxidising action
powder?

CaOCl2 + H2S CaCl2 + H2O + S

3. It converts acetone into chloroform.

Q.17 Halogens have maximum negative electron gain enthalpy. Explain why?

A.17 respective periods. Therefore, they readily accept one electron to acquire the
p-Block Elements (Part-2)

halogen atom can accepts an electron therefore larger amount of energy is

released, thus halogens have max imum negative electron gain enthalpies.

70.
Group 18 (Noble gases)
Concept Ladder
1. The elements Helium, Neon, Argon, Krypton,
Xenon and Radon constitute group 18 (or zero) of The zero group occupies
the periodic table. the intermediate position
2. All the noble gases, except He have between the elements of
eight electrons (closed shell) with electronic VII A and I A groups.
2
np6 where n = 2 to 6. Helium,
however has only two electrons and hence its
2
.

1. Except radon (radioactive) all noble gases

are present in the atmosphere throughout the
universe in the free state to the extent of 1%
by volume. Helium is also found as natural gas Rack your Brain
Ramsay discovered. He in cleveite (a uranium ore)
p-Block Elements (Part-2)

i.e. on the earth. Why noble gases are monoatomic

2. The gas is obtained when these minerals are in nature?
either heated at 1273 K in vacuum or heated with
H2SO4. Helium and argon are also found in the
dissolved gases of some mineral.

71.
 3. Argon is the most abundant noble gas in the
atmosphere (0.934% by volume). Concept Ladder
The relative abundances of other gases in the
atmosphere are :
Noble gases are also
He = 5.24 × 10–4, Ne = 1.82 × 10–3 termed as inert gases
Ar = 93.4 × 10–2 , Kr = 1.45 × 103 or the rare gases of the
atmosphere.
and Xe = 8.70 × 10–6 % by volume
Physical Properties of Noble Gases
1. Physical state :
All the elements of group 18 are colourless,
odourless and tasteless.
2. Atomic radii :
The atomic radii of noble gases increases on
moving down-the group and their atomic radii Rack your Brain
correspond to the vander waal’s radii.
Order : He < Ne < Ar < Kr < Xe < Rn Explain why electron gain
3. Melting point and boiling point : enthalpy of noble gases is zero?

M.P. and B.P. increases from He to Rn, because

of increase in magnitude of vander waal’s forces.
Order : He < Ne < Ar < Kr < Xe < Rn
4. Ionisation energy and electron gain enthalpy :
Noble gases have stable ns2 np6

tendency to add or lose electron. Therefore

ionisation energy of noble gas is very high. On the
other hand their electron gain enthalpy is zero.
Order : He > Ne > Ar > Kr > Xe > Rn Concept Ladder
5. Solubility in water :
p-Block Elements (Part-2)

They are slightly soluble in water their Noble gases have lowest
solubility generally increases with the increase in boiling point in comparision
atomic number down the group. to the elements of their
Order : He < Ne < Ar < Kr < Xe < Rn respective periods.

72.
 Concept Ladder
atoms are holded by weak VWF.
Helium forms no real
chemical compounds.
8. He has the lowest B.P. (4.18 K) of any known Among noble gases only
Xenon forms chemical
from He to Rn due to increase in inter-molecular compounds.
forces.
9. The zero group of the periodic table constitutes
Helium (He), Neon (Ne), Argon (Ar), Krypton (Kr),
Xenon (Xe) and Radon (Rn).
10. Noble gases do not have chemical reactivity
and at ordinary temperature they are present
in gaseous form and therefore, these are called
Inert gases.
Order : He < Ne < Ar < Kr < Xe < Rn Rack your Brain

Noble gases can form compounds

only with two elements. Name
glass, rubber, plastic, material and some metals.
them?
Order : He > Ne > Ar > Kr > Xe > Rn

meteorological observations.
2. It is also used in gas cooled nuclear reactors. Concept Ladder
3. Liquid helium (boiling point 4.2 K) is used
as Cryogenic agent for carrying out various
Helium — oxygen mixture
experiments at low temperatures.
p-Block Elements (Part-2)

respiration in deep seas

diving and in treatment of
tubes for advertisement display purposes. asthma.

73.
 2. Neon is also used in televisions set, spark
plug, warning signals etc. Concept Ladder

produced by mixing neon with other gases.

The two methods used for
preperation of argon gas
1. Ar is mainly used to provide an inert is Ramsay method and
atmosphere high temp. metallurgical processes Rayleigh method.

electric bulbs. It is also used in the laboratory to

handle substances that are air sensitive.
2. This gas is used in gas chromatography.

coloures in neon sign lamps.

1. Kr and Xe are used in light bulbs designed for

special purpose.
2. These are also used for high speed Previous Year’s Questions
photography.
3. Krypton-85 is used to measure thickness of Identify the incorrect statement,
sheets of metals and plastics. regarding the molecule XeO4 :
[NEET-2013]
(1) XeO4 molecule is square planar.
1. Radon being radioactive is used in nuclear (2) There are four p -d bonds.
processes. (3) There are four sp3-p, bonds.
(4) XeO4 molecule is tetrahedral.
2. It is also used in treatment of cancer and
other tumors.
3. It is used for detecting dislocations and
defects in metals and other solids.
p-Block Elements (Part-2)

Q.18 Why do not helium, neon and argon form chemical compounds?

A.18

74.
Chemistry of Xenon
Xe reacts directly only with F2. Oxygen Concept Ladder

Structures of Xenon

explained by valence bond

agents. They sublime readily at room temperature
approach.
and are hydrolysed even by traces of water. Thus,
they are stored in Ni containers.

XeO3 is a hygroscopic white explosive solid.

XeOF4 is a colourless volatile liquid.
2OH
2NaHXeO4 Na4 XeO6 Xe 2H2O O2
p-Block Elements (Part-2)

oxidise Cl– to Cl2. I– to I2 and Ce(III) to Ce(IV)

75.
 XeF2 PF5 XeF PF6

XeF4 SbF5 XeF3 SbF6 Previous Year’s Questions

XeF4 MF M XeF7 Which compound has planar

structure?
M Na,K,Rb, Cs
[AIPMT]
4. Xe compounds show a variety of shapes: (1) XeF4 (2) XeOF2
(3) XeO2F2 (4) XeO4
XeF2 is linear, XeF4 is square planar, XeF6 is
a capped octahedron, XeO3 is pyramidal, XeOF4
is square pyramidal, XeO2F2 is see saw shaped,
XeOF2 is bent T – shaped, XeO4 is tetrahedral,
XeO3F3 is trigonal bipyramidal and [XeO6]4– ion is
octahedral.

Q.19 What prompted Bartlett to the discovery of noble gas compounds?

p-Block Elements (Part-2)

A.19 Since PtF6 oxidises O2 to O2+, Bartlett thought that PtF6 should also oxidise Xe
to Xe+ because the ionization enthalpies of O2 (1175 kJ mol–1) and Xe (1170 kJ
mol–1) are quite close.

76.
Q.20 In the preparation of H SO2 4
by Contact Process, why is SO3 not absorbed di-
rectly in water to form H2SO4?

A.20 A dense fog of H SO2 4

Q.21 PH3 forms bubbles when passed slowly in water but NH3 dissolves. Explain
why?

A.21 Due to high electronegativity (3.0) and small size of N, NH3 forms H-bonds with
water and hence it is water soluble. Whereas, due to its lower electronegativity
(2.1) of P and its bigger size than N, PH3 does not form H-bonds with H2O. As a
result, it does not dissolve in H2O and hence escapes as bubbles.

Q.22 In PCl , phosphorus is in sp

5
3

equivalent. Justify your answer with reason.

A.22 Since each axial P—Cl bond is repelled by three bond pairs and each equato-
rial P—Cl bond is repelled by only two bond pairs, therefore, axial bonds are

in PCl5 are not equivalent.

Q.23 Why is nitric oxide paramagnetic in gaseous state but the solid obtained on
cooling it is diamagnetic?

A.23 Nitric acid has 15 electrons i.e. it has one unpaired electron and hence it is
paramagnateic in the gaseous state. but in both solid as well as in liquid it
exists as a dimer and hence is diamagnetic in nature.

Q.24 Give the reason to explain why ClF exists but FCl3 does not exist.
p-Block Elements (Part-2)

A.24 Because of bigger size, Cl can accommodate three small F atoms around it
while F being smaller cannot accommodate three bigger sized Cl atoms around
it.

77.
 Q.25 SF 6
is known but SH6 is not. Why?

A.25 H 2
being a very weak oxidising agent cannot oxidise S to its maximum oxidation

its maximum oxidation state of +6, thus SF6 is known but SH6 is not known.

Q.26 The majority of noble gas compounds are those of xenon. Explain.

A.26 Except Rn which is radioactive, Xe has the lowest I.E. among inert gases and
therefore it can be easily oxidised by strong oxidising agents like O and F .
2 2
That is why majority of inert gas compounds are those of Xe.

Q.27 Arrange the hydrides of group 17 elements in order of their increasing acid
strength.

A.27 As the size of halogen increases down the group from F to I, the bond
dissociation energy of the H—X bond decreases. Consequently, the tendency
of H—X bond to release a proton in water increases. In other words, the acid
strength increases in the order : HF < HCl < HBr < HI.

Q.28 Why does argon not form diatomic molecules like oxygen and nitrogen?

A.28 Ar and hence it has no tendency to share electron with other atom of argon to
form diatomic molecules. Oxygen and Nitrogen on the other hand, have
p-Block Elements (Part-2)

unpaired electrons and hence share these electrons with other O and N atom
respectively forming O2 and N2 molecules

78.
Summary

Group 15 (N-family)
1. Hydrides
(i) Bond angle : NH3 > PH3 > AsH3 > SbH3 > BiH3
(ii) Basic character : NH3 > PH3 > AsH3 > SbH3 > BiH3
(iii) Boiling point : PH3 > AsH3 > NH3 > SbH3 > BiH3
(iv) Thermal stability : NH3 > PH3 > AsH3 > SbH3 > BiH3
(v) Reducing character : NH3 < PH3 < AsH3 < SbH3 < BiH3
2. (i) NF3 is not hydrolysed due to absence of vacant d-orbital.
(ii) PF3 and PF5 are not hydrolysed because P—F bond is stronger than P—O bond.
3. NF3 is not lewis base although it has lone pair of e– due to high electronegativity of

4. N2O is called laughing gas.

5. P4S3 is used in strike anywhere matches.
6. Fuming HNO3 is conc. HNO3 + NO2.
7. PH3
8. Holmes signal ships is CaC2 + Ca3P2
9. Match box side has red P + Sb2S3 + sand. Tip of match stick has K2Cr2O7 + S + white
P or KClO3 or red Pb.

Group 16 (O–family)
1. Acidic character
(i) SO2 > SeO2 > TeO2 > PoO2
(ii) SO < SO2 < SO3
2. (i) Pyrosulphuric acid (H2S2O7) has S—O—S linkage.
(ii) Marshall’s acid has O—O linkage.
(iii) S2O82– does not have S—S linkage.
3. Catalyst used in manufacture of H2SO4 by Lead Chamber process is oxides of
nitrogen and in contact process is V2O5.

Group 17 (X–family)
1. Electronegativity : F > Cl > Br > I
p-Block Elements (Part-2)

2. Bond energy : Cl2 > Br2 > F2 > I2

3. Oxidising power : F2 > Cl2 > Br2 > I2
4. I2 is soluble in water due to formation fo I3– polyhalide ion.

79.
 5. Halide of metals in their higher oxidation states are more covalent than those
formed in lower oxidation state. e.g. SnCl4 is more covalent than SnCl2.
6.
stored in copper, wax or guttapercha bottle.
7. KClO3
8. Tincher of iodine is I2
9. F2 is called super halogen due to its high reactivity.
10. Br2 or Cl2 turn moist starch KI paper blue because they displace I2 from KI and this
I2 reacts with starch to give blue complex.
11. AgF is soluble in water but AgCl, AgBr and AgI are not.

Group 18 (Noble gases)

1. Discovery of noble gases.
He – Lockyer and Janassen
Ar – Lord Rayleigh and Ramsey
Kr – Ramsay and Travers
Xe – Ramsay and Travers
Ra – Doron
2. Only He forms interstitial compounds with metals.
3.
in deep sea diving because unlike N, He is not soluble in blood even at high pressure.
p-Block Elements (Part-2)

80.