Chapter 23

The p-Block Elements

Chapter Contents
z Introduction Introduction
The elements in which last electron enters into p-subshell are called as
z Boron Family p-block elements. The number of p-orbitals are three and, therefore, the
maximum number of electrons that can be accommodated in a set of
z Group 14 Elements: p-orbitals is six, hence p-block contains six groups. The general
The Carbon Family electronic configuration of these elements is ns2np1 – 6 (except for He).
p-block elements can be either metals, metalloids or non-metals.
z Group 15 Elements: Maximum oxidation state shown by p-block elements is equal to the
Nitrogen Family sum of valence electrons (i.e., sum of s-and p-electrons) or the group
number minus 10 known as group oxidation state.
z Group 16 Elements: Absence of d-orbitals in the elements of second period and presence
Oxygen Family of d- and f-orbitals in rest of elements have significant effects on
the properties as a result lower oxidation state will be more stable.
z Group 17 Elements : This effect is known as inert pair effect.
Halogen Family Boron (of group 13) forms three covalent bonds in its compounds
hence need two more electrons to complete its octet, hence its
z Group 18 Elements : compounds are electron deficient or Lewis acid.
Noble Gases Carbon (of group 14) occurs both in free state and combined state
in nature. All living systems contain carbon. Carbohydrates, fats,
proteins, vitamins, hormones, nucleic acids etc. all contain carbon.
The first member of each of these groups also displays the ability of
forming p-p bonds to itself (C=C, CC, NN) and also to other
elements of second period (C=O), CN, N=O and so on).
Nitrogen (of group 15) occurs as adiatomic gas N2 it makes about
78% by volume of the atmosphere N2 mainly occurs as nitrates
NaNO3 (Chile-saltpetre) and KNO3 (Indian saltpetre). Nitrogen is the
essential constituents of proteins, amino acids and nucleus acid.
Group 16 are also called chalcogens (ore forming) O, S are typical
non-metals, Se, Te are metalloids and Po is metallic and radioactive.
Group 17 are known as halogens (sea salt forming) F2, Cl2, Br2, I2
and astatine are all non-metallic elements.
Group 18 consists of six monoatomic gases i.e., helium (He), Neon
(Ne), Argon (Ar), Krypton (Kr), Xenon (Xe) and Radon (Rn). Except Rn
other gases are known as Rare gases. These gases do not show
reactivity at ordinary temperature and are known as Inert gases.

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Table : General Electronic Configuration and Oxidation States of p-Block Elements

Group 13 14 15 16 17 18
2 6
ns np
General electronic configuration 2
ns np
1
ns2np2
2
ns np
3
ns np
2 4
ns2np5 (1s2 for He)

First member of the group B C N O F He

Group oxidation state +3 +4 +5 +6 +7 +8

Other oxidation state +1 +2, –4 +3, –3 +4, +2, –2 +5, +3, +1, –1 +6, +4, +2

BORON FAMILY
Group III A contains six elements : boron, aluminium, gallium, indium, thallium and ununtrium. The penultimate
shell (next to the outermost) conains 1s 2 in boron, 2s 2 2p 6 (8 electrons) in aluminium and
(n – 1)s2 (n – 1)p6 (n – 1)d10 (18 electrons) in other elements. This shows why boron differs from aluminium
and both boron and aluminium having noble gas kernel differ from other four elements.
Boron is a non-metal and always form covalent bonds. Boron family is known as most heterogeneous family
as there is no regular trend in all properties, as it comes after d-block, lanthanoid contraction, poor shielding
of d-orbital, they have large deviation in properties.
The heavier members of this group show inert pair effect. Boron compounds, especially the hydrides are
electron deficient compounds which can accept a lone pair of electrons hence behave as Lewis acids.

Physical Properties
General electronic configuration is ns2np1.

Atomic Number Atomic Radii Element Configuration Metallic Character

2 1
5 85 pm B [He] 2s 2p Non-metal
2 1
13 143 pm Al [Ne] 3s 3p Metal
10 2 1
31 135 pm Ga [Ar] 3d 4s 4p Metal
10 2 1
49 167 pm In [Kr] 4d 5s 5p Metal
14 10 2 1
81 170 pm Tl [Xe] 4f 5d 6s 6p Metal

Decrease in metallic character in gallium is because of shielding effect. In Gallium 10 electrons are filled in
d orbitals hence have less shielding so size decreases and metallic character decreases.
Aluminium is most metallic among boron family due to its least electronegativity.

Atoms B Al Ga In Tl

Electronegativity 2 1.5 1.6 1.7 1.8

Due to poor shielding of 3d and 4d and

lanthanoid contraction.
Atomic Size
Atomic size of boron family is smaller than alkaline and larger than carbon family. Down the group atomic
size increases irregularly. Gallium is smaller than aluminium due to poor shielding of 3d orbital.

Ionization Energy : Ionization enthalpy, the general trend do not decrease smoothly down the group.
Ionization energy decreases from B to Al, but increases from Al to Ga.

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Element First Ionization energy in kJ/mole

Boron 801
Aluminium 577
Gallium 579
Indium 558
Thallium 589

Decreasing order of 1st ionization energy is as follows

B > Tl > Ga > Al > In

Oxidation States
Oxidation states are possible from +3 to –5. Stability of +3 oxidation state decreases down
the group due to inert pair effect, as well as stability of +1 oxidation state increases.

Note : Indium in +1 oxidation state is reducing agent.

Chemical Properties
1. Reactivity towards air
Amorphous boron and aluminium metal on heating in air forms trioxide and forms nitride at very high
temperature. Gallium and indium are not affected with air while thallium does.
B2O3  Acidic oxide
Al2O3  Amphoteric oxide
Ga2O3  Amphoteric oxide
In2O3  Basic oxide
Tl2O3  Basic oxide

4E(s)  3O2 (g)  2E2O3 (s)

2E(s)  N2 (g)  2EN(s) (Where E = B, Al, Ga, In, Tl)

B2O3 is called boric anhydride as it is anhydride of boric acid.

2. Reactivity towards acids
Boron is not affected by acids agents like HCl and dil. H2SO4 while all other elements react with conc.
H2SO4 and HNO3. Ga and Al develop protective layer of oxide with conc. HNO3.
2 Al(s)  6HCl(aq)  2 Al3  (aq)  6 Cl (aq)  3H2 (g)
2B(s)  3H2SO4 (aq)  2H3BO3  3SO2 (g)

B(s)  3HNO3 (aq)  3H (aq)  BO33 (aq)  3NO2 (g)

3. Reactivity towards alkalies

Except indium and thallium all other elements react with alkali solutions
2M(s)  2NaOH(aq)  2H2O 
 2NaMO2 (s)  3H2 (g) (M = Al or Ga)
Example, Al also reacts with aq. Alkali and liberates dihydrogen.

2 Al(s)  2NaOH(aq)  6H2O(l)  2Na [Al(OH)4 ] (aq)  3H2 (g)

Sodium tetrahydroxoaluminate (III)

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4. Reactivity towards halogens

Trihalides are formed when these elements react with halogens. All these halides exist as discrete
molecular species which are sp2 hybridised and covalently bonded. TlI3 is unstable.
AlCl3 achieves stability by forming a dimer.

Cl 20 Cl 22 Cl
6p 1
m pm
101º
Al 79º Al 118º

Cl Cl Cl

Acidic strength is inversely proportional to back-bonding, as back-bonding decreases from BF3 to BI3 as given
below
BF3 > BCl3 > BBr3 > BI3
Hence, Lewis acidic strength will increase as under
BF3 < BCl3 < BBr3 < BI3
p-p back-bonding is strongest in BF3 because both B and F involve 2p orbital in back-bonding.

IMPORTANT TRENDS AND ANOMALOUS PROPERTIES OF BORON

Trihalides of these elements are covalent in nature and are hydrolysed in water and produces species like
tetrahedral [M(OH)4]– and octahedral [M(H2O)6]3+ except in boron.

 
NH3  BF 3 H3N BF3  NH3 BF3

In this reaction, hybridisation of BF3 changes to sp3 as one more bond is formed with nitrogen. Here shape
changes to tetrahedral (irregular).

BF3  HF  H [BF4 ]

In above reaction, [BF4]– is having sp3 hybridisation with tetrahedral geometry.

Due to absence of d-orbital maximum covalency of B is 4 while other elements of that group have d-orbitals
hence, maximum covalency can be expected beyond 4.
Borax is a white crystalline solid and can be prepared by boric acid.

4H3BO3  Na2 CO3  Na2B 4 O7  6H2O  CO2 

Example 1 : Give electronic configuration of Ga.

Solution : Group configuration is ns2np1
Ga is in 4th period
Hence, electronic configuration is 4s24p1

Example 2 : Why boron compounds behave as lewis acid?

Solution : Boron compounds have three covalent bonds hence, require two electrons to complete octet hence,
electron deficient compounds.

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Example 3 : Write oxidation state of boron family.

Solution : Group oxidation state of boron family is +3.

SOME IMPORTANT COMPOUNDS OF BORON

The important minerals of boron are
(i) Borax : Na2B4O7·10H2O
(ii) Colemanite : Ca2B6O11 : 5H2O OH

(iii) Boric acid : H3BO3 B

1
1. Borax O O

Na2B4O710 H2O / Na2 [B4O5 (OH)4]8 H2O 2Na HO B 2 4 B OH  8H O

2

O
Number of B in sp2 hybridisation = 2 (1, 3) O O
3 3
Number of B in sp hybridisation = 2 (2, 4) B
Oxidation state of all boron present = +3 state
OH
n-factor = 2
Number of B—O—B bonds = 5
Number of B—O bonds = 14
Number of bridging oxygen between two boron = 5
It furnishes two OH– from 2nd and 4th, then octet of B cannot be completed. After cleavage it will be
highly unstable structure.
On heating borax first looses water molecules and swells up and gives sodium metaborate which on
further heating turns into a transparent liquid which solidifies into glassy bead.
Pt
Na2B4 O7 10H2O 
loop
 Na2B4 O7  10H2 O NaBO2  B2O3
Anhydrous borax Glassy bead


This glassy bead reacts with CuO or CoO to give blue bead and reacts with TiO to give yellow bead.
Glassy bead  CuO 
 Cu(BO2 )2
Blue bead

Glassy bead  CoO 

 Co(BO2 )2
Blue bead

Glassy bead  TiO 

 Ti(BO2 )2
Yellow bead

2. Orthoboric acid (H3BO3)

It is prepared by treating concentrated sulphuric acid with borax.

Na2B4O7  H2SO4  5H2O 

 Na2SO4  4H3BO3

It is white, soft, needle-like crystals having a soapy touch.

It does not loose 3H+ but accepts one lone pair from H2O, so n-factor = 1. This is a monobasic Lewis
acid as oxygen gives one electron to boron, so it acquires positive charge and becomes unstable, so
it furnishes 1H+ and gets stable.

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O H
 + –
H O B + H2O
 H [B(OH)4]
O H
In H [B(OH)4] hybridisation of boron is sp3.
+ –

100C 160 Re d hot

H3BO3   HBO2   H2B4 O7   B 2 O3
Orthoboric Metaboric Tetraboric Boric Oxide
acid acid acid

H
O

H B
O O
H H
O O
H B H H
O O

B O
H H H B
O O O O
H H
Fig. Structure of boric acid; the dotted lines represent hydrogen bonds.
It is used as an antiseptic, in manufacturing of enamels, as food preservative and in glass industry. Boric
acid is layered structure. B(OH)3 units are joined by hydrogen bonds and form two dimensional sheet.
3. Hydrides of boron
B2H6 (Diborane)
Preparations of diborane are :
(i) 3LiAlH4  4BF3 
 2B2H6  3 AlF3  3LiF
(ii) 2NaBH4  I2 
 B2H6  2NaI + H2
450K
(iii) 6NaH  2BF3  B2H6  6NaF

Bonding in diborane:

H H H
H H
H
B B 
120º B 97º B

H
H H H H
H

H 119 H 13 H
pm m 4p m
4p m 9p
13 11

120º B 97º 97º B 120º

m 13 119
4 m
9p pm 4p pm
H 11 H 13 H

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It is 3 centre 2 electron bonding called banana bonding or bridge bonding.
Number of atoms present in same plane = 6
Number of terminal hydrogen = 4
Number of bridging hydrogen = 2
Since boranes have vacant p or vacant d-orbitals in central boron atom hence, it reacts with water and
thus shows hydrolysis.

B2H6 (g)  6H2O(l) 

 2B(OH)3 (aq)  6H2 (g)

NH3(Excess)
B 2H 6 + –
B2 H6 ·2NH3 [(H 3N  BH 2  NH 3 ) and BH 4 ]
NH3(Excess)
at high temperature Boron nitride (Inorganic graphite)
B2H6 : NH3 = 1 : 2
at high temperature
B3N3H6 [(Inogranic benzene)

Note :
Diborane is colourless gas and bursts into flame in air and is stable at low temperatures in the absence
of moisture and grease. Boranes either belong to Bn Hn + 4 or Bn Hn + 6 series.

Example 4 : How many B atoms are sp2 hybridised in borax structure?

Solution : 2 (Two)

Example 5 : Give colour of bead when glassy bead reacts with TiO.

Solution : Yellow bead

Example 6 : Why is basicity of orthoboric acid one?

Solution : It does not lose 3H+ while it accepts one lone pair of electrons from H2O.

USES OF BORON AND ALUMINIUM AND THEIR COMPOUNDS

Boron Compounds
Boron is a hard solid having high melting point low density and very low electrical conductivity. Some important
boron compounds are :

(a) Boron fibers : It is mixed with plastic to form a material which is lighter than aluminium but tougher
and stiffer than steel hence it is used in body armour, missiles and aircrafts.

(b) Boron-10 (10B) isotope : Boron carbide rods or boron steel are used to control nuclear reactions as
neutron absorbers.

5B
10
 0n
1  5B
11

(c) Borax : It is used in manufacture of enamels and glazes for pottery and tiles. It is also used in making
optical glasses and also borosilicate glasses which is very resistant to heat and shock. It is used as
an antispectic.

(d) Boric acid : It is used in glass industry, in food industry as preservative. It is also used as an antiseptic
and eye wash under the name ‘boric lotion’. It is also used in manufacture of enamels and glazes for pottery.
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Aluminium Compounds
Aluminium and its alloy are used in packing industry, utensil industry, aeroplane and transportation industry etc.
1. Alumina (Al2O3)
(a) Used in chromatography.
(b) Used in making bauxite bricks which are used for lining furnaces.
2. Aluminium chloride (AlCl3)
Used in manufacture of dyes, drugs and perfumes and also in manufacture of gasoline. It is also used
as catalyst in Friedel Craft reaction.
3. Potash Aluminium [K2SO4Al2(SO4)324 H2O] or [KAl(SO4)2.12H2O]
Used in purification of water, leather tanning, as antiseptic and as a mordant.

Note :
z Use of aluminium and its compounds for domestic purposes is now reduced considerably because
of their toxic nature.
z Ultrmarine is a compound of aluminium which is an artificial Lapis-Lazuli (rare mineral having fine
blue colour). It is a complex silicate of sodium and aluminium having 12% of sulphur which is
used in calico printing and in making blue paints.

Example 7 : Why boron fibre is used in body armour?

Solution : On mixing with plastic it forms a material which is lighter than aluminium but tougher and stiffer
than steel hence, used in body armour.

Example 8 : How boron isotope controls nuclear reactions?

Solution : 5B
10
 0n
1  5B
11

Example 9 : Name an aluminium compound that can be used in chromatography.

Solution : Alumina

EXERCISE
1. Number of B–O–B bond in borax is
(1) Four (2) Five
(3) Three (4) Zero
2. Among the group 13 the only element which is non-metallic
(1) B (2) Al
(3) Ga (4) In
3. Products formed are
Polyether
2NaBH4 + I2   
(1) HI, NaI and H2 (2) B2H6, NaI and HI
(3) B2H6, NaI and H2 (4) H3BO3 + H2

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4. What is the hybridisation state of B and N in inorganic benzene respectively?
(1) sp2 and sp3 (2) sp3 and sp2
(3) Both have sp2 (4) Both have sp3
5. Which type of hydride is BH3?
(1) Electron deficient (2) Electron precise
(3) Electron excess (4) Lewis base
6. Which one of the following is the correct statement ?
(1) The hydroxide of boron is basic in nature
(2) The hydroxide of boron is neutral in nature
(3) The hydroxide of boron is acidic in nature
(4) Boron shows maximum oxidation state of +1 due to inert pair effect
7. Which of the following statement is correct regarding B2H6?
(1) Each boron atom is sp 3 hybridised
(2) B2H6 is electron deficient
(3) B2H6 has banana bond
(4) All of these
8. Boric acid is polymeric due to
(1) Its acidic nature
(2) The presence of hydrogen bonds
(3) Its monobasic nature
(4) Its geometry
9. Which of the following element has exceptionally high melting point?
(1) Al (2) Ga
(3) B (4) In
10. In which of the following compounds banana bond is present?
(1) BCl3 (2) B2H6
(3) B(OH)3 (4) All of these

GROUP 14 ELEMENTS: THE CARBON FAMILY

Group IV A contains six elements : carbon, silicon, germanium, tin, lead and ununquadium . The penultimate
shell (prior to outermost) contains 1s2-grouping in carbon, 2s22p6 (8 electrons) in silicon and (n – 1)s2 (n –
1)p6 (n – 1)d10 (18 electrons) in other elements. This shows why carbon differs from silicon in some respects
and these two differ from rest of the members of this group.
General electronic configuration is ns2np2.
Silicon is second most abundant element in earth crust (27.7%). Carbon is the seventeenth most abundant
element in earth crust. Carbon is important element of all living organisms. Till yet more than 5 million organic
compounds have been discovered, 40,000 new organic compounds are discovering every year.

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Silicon is used in cement, glass, transistors, semiconductors.

Tin is used in alloys.
Tin mainly occurs as cassiterite, SnO2 and lead occurs as galena, PbS.
Germanium is used in transistors.
Lead is used in glass, paints and varnish

Element Electronegativity
C 2.5
Si 1.8
Ge 1.8 three members have
same electronegativity.
Sn 1.8
Pb 1.9

Still properties of silicon differs from germanium due to poor shielding effect of 3d subshell and properties of
germanium differs from tin due to poor shielding effect of 4f subshell (Lanthanoid contraction).
Properties of tin are different from lead due to poor sheilding effect of 5f subshell (Actinoid contraction).
Order of electronegativities is C > Pb > Si = Ge = Sn
All elements of this family except carbon have tendency to show maximum covalency of six due to absence
of vacant d-orbitals.

Note :
Most abundant element in earth crust is oxygen (46.6%) by mass. Second most abundant element is silicon
(27.7%). Third most abundant element is aluminium (8%) and fourth abundant element is iron.

Physical Properties
Atomic Number Element Atomic radii (pm) Electronic configuration Metallic character
2 2
6 C 77 [He] 2s 2p Non-metal
2 2
14 Si 117 [Ne] 3s 3p Non-metal
10 2 2
32 Ge 122 [Ar] 3d 4s 4p Metalloid
10 2 2
50 Sn 140 [Kr] 4d 5s 5p Metals
10 14 2 2
82 Pb 146 [Xe] 5d 4f 6s 6p Metals

The elements of this group form covalent bonds with each other and therefore there are strong binding forces
between their atoms in both solid and liquid states.

Consequently the melting and boiling points of group 14 elements are much higher in comparison to group
13 elements. The atomic radius, ionic radius and density increase when one moves from top to bottom in a
group in periodic table while melting point decreases from B to Ga and then increases from (Ga to In)

Atomic Size
Size of this family is smaller than boron family but larger than nitrogen family, down the group atomic size
increases regularly. There is a considerable increase in covalent radius from C to Si, thereafter from Si to
Pb, a small increase in radius is observed. This is due to the presence of completely filled d & f orbitals in
heavier members.

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Ionization Energy
Ionization energy of this group is higher than boron family and lower than nitrogen family. Down the group
ionization energy decreases irregularly.

Element First Ionization energy in kJ/mole

C 1086
Si 786
Ge 760
Sn 707
Pb 715

Decreasing order of first ionization energy is as follows:

C > Si > Ge > Pb > Sn
Large decrease in ionization potential from C to Si is due to increase in size of atom. Ionization energy
decreases from silicon is due to less screening effect of d10 electrons in Ge and Sn, and due to d10f14
electrons in Pb.
Ionization energy increases from Sn to Pb, it increases slightly due to Lanthanide contraction and increase
of 32 units of nuclear charge in Pb over Sn.

Catenation
Catenation power of carbon family is higher than boron family and nitrogen family. Down the group, catenation
tendency decreases.
Catenation tendency is highest in carbon among all elements of family while silicon has second highest
tendency of catenation among all elements of family and the decreasing tendency of catenation is as follows:
C >> Si > Ge  Sn, Pb do not show catenation.
All the elements of the carbon family with the exception of lead exhibit allotropy and this tendency decreases
from C to Pb. It is due to decreasing bond energy.

Bond C—C Si—Si Ge—Ge Sn—Sn

Bond energy (kJ/mol) 348 297 260 240

Chemical Properties
1. Reactivity towards air
All members of this group form monoxide of the general formula MO such as CO, SiO, SnO and PbO.
All members of this group form dioxides of molecular formula MO2 such as CO2, SiO2, GeO2, SnO2 and
PbO2.
CO2 is monomeric, SiO2 is 3-D network solid.
Dioxides (CO2, SiO2 and GeO2) are acidic whereas dioxides (SnO2 and PbO2) and mono-oxides
(SnO and PbO) are amphoteric. Mono-oxide CO is neutral while GeO is distinctly acidic.
2. Reactivity towards water
In this family carbon, silicon and germanium are unaffected by water while lead becomes inert towards
water due to formation of protective oxide film. Tin is converted into tin dioxide and hydrogen gas is
libreated on reaction with steam.

Sn  2H2O(g)   SnO2  2H2

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3. Reactivity towards halogen

Element in pure state Type of bonding Melting Point
C Covalent 4100ºC
Si Covalent 1420ºC
Ge Covalent 945ºC
Sn Metallic 232ºC
Pb Metallic 327ºC

On moving down the group from carbon to lead stability of +4 oxidation state decreases while stability
of +2 oxidation state increases and hence decreases oxidising power decreases down the group due
to inert pair effect.
These elements form two types of hallides - MX2 and MX4. Most of the MX4 are covalent. SnF4 and PbF4
are ionic in nature.
Thermal stability decreases with increasing atomic size or molecular mass of tetrahalide or due to
decreasing polarity.
CX4 > SiX4 > GeX4 > SnX4 > PbX4 and
CF4 > CCl4 > CBr4 > CI4
In these componds:
Hybridisation  sp3
Geometry  Regular tetrahedral
Polarity  non-polar
Bond angle  109º 28
PbI4 is not stable as I is strong reducing agent which reduces Pb+4 to Pb+2 and also stability of +4
–

oxidation state of Pb is lesser than +2 state.

Hydrolysis of halides
The chlorides except CCl4 are hydrolysed readily by water

SiCl4  4H2O  Si(OH)4  4HCl

Silicic acid

Hydrolysis of silicon tetrafluoride gives silicic acid and fluorosilicic acid

3 SiF4  4H2O  Si(OH)4  2H2 SiF6
(Silicic acid) (Fluorosilicic acid)

Due to unavailability of vacant d-orbitals, carbon tetrahalides cannot increase its co-ordination number
hence does not form complexes while those having vacant d-orbitals form.

Example 10 : On moving down the group in carbon family stability of group oxidation state +4 decreases why?

Solution : Due to inert pair effect.

Example 11 : SiO2 is solid while CO2 is gas. Why?

Solution : CO2 is monomeric linear structure while SiO2 is 3-D network solid.

Example 12 : Why [SiCl6] – cannot exist?

Solution : Because six large Cl– cannot be accommodated around silicon ion.

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Example 13 : Give correct order of increasing first ionization energy in carbon family.
Solution : C > Si > Ge > Pb > Sn

ANOMALOUS BEHAVIOUR OF CARBON

Carbon shows anomalous behaviour due to its smaller size, higher electronegativity, higher ionization enthalpy
and unavailability of d orbitals.
Carbon atom forms double or triple bonds involving p-p bonding. Carbon has also the property to form closed
chain compounds with O, S and N atoms as well as forming p-p multiple bonds with other elements
particularly N, S and O.
When we move down the group size increases and electronegativity decreases hence catenation tendency
decreases. Order is
C >> Si > Ge  Sn
Note :
Carbon has smallest atomic radius, lowest atomic volume and highest melting and boiling points amongst
the elements of group 14. CO2 is a gas while the dioxides of other elements are solids. It has the highest
ionization energy and most electronegative element of group 14. Carbon is the element among the group
which can form maximum number of hydrides and is the only element of group which does not dissolve in
aqueous NaOH to evolve hydrogen gas.

ALLOTROPES OF CARBON
Carbon shows allotropism due to catenation and p-pbond formation. Carbon exists in two allotropic forms
– crystalline and amorphous. The crystalline forms are diamond and graphite while the amorphous forms are
coal, charcoal and lamp-black. The third form is fullerenes discovered by Kroto, Smalley and Curl.
Tin has maximum number of allotropes.

Diamond
In diamond each carbon is joined to other four carbon tetrahedrally and carbon-carbon bond length is 1.54Å
and bond angle is 109º28 having sp3 hybridisation on each carbon. All four electrons in carbon are involved
in bonding hence, it is good conductor of heat but bad conductor of electricity.
It is hardest natural substance known. It is transparent and has a specific gravity 3.52 and its refractive index
is high (2.45).

C C C C 154 pm

C C C C

C C C C

C C C C

Fig. The structure of diamond

Difficult to break due to extented covalent bonding.
Diamond is used for making cutters. Blades of diamond are used in eye surgery and as an abrasive for
sharpening hard tools. Impure diamonds (black) are used in knives for cutting glass.

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Graphite
141.5 pm
2
Each carbon is sp hybridised. It has layered structure. These layers
are attracted by van der Waals force. Each carbon has one free

340 pm
electron in p-orbital, so it is a good conductor of electricity. All
electrons get delocalized in one layer and form -bond. Electron
jumps from one orbital to another hence it is a good conductor of
heat and electricity. In graphite carbon-carbon bond length is 141.5
pm and distance between adjacent graphite layer is 340 pm.

Graphite is used as a lubricant at high temperature. Oil gets burn

or denatured at high temperature but graphite does not get denatured
even at high temperature so, preferred over oil and grease.

Fig. The structure of graphite

Note :
z Graphite is of two forms :  and .
z In -graphite, layers are arranged in sequence ABAB... with the third layer exactly above first layer.
z In -graphite, the layers are arranged as ABCABC... the two forms are interconvertible.
z Graphite is thermodynamically more stable than diamond and its free energy of formation is 1.9 kJ less,
than diamond. However entropy of graphite is more than diamond.

Fullerene
It was made as a result of action of a laser beam or strong heating of a sample of graphite in presence of
inert atmosphere. The sooty material mainly contains C60 with C70 (small amount).
Most common fullerene is C60 called Buckminsterfullerene which has football-like structure. It contains 20
hexagonal six-membered ring and 12 pentagonal five-membered ring. Every ring in this structure is aromatic.
It is used to make ball bearings. All the carbon atoms are equal and they undergo sp2 hybridisation. Fullerenes
are the only pure form of the carbon because they have smooth structure without having dangling bonds.

Fig.The structure of C60, Buckminsterfullerene :

Note that molecule has the shape of a soccer ball (football).

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Coal
It is the crude form of carbon. It has been formed in nature as a result of slow decomposition of vegetable
matter under the influence of heat, pessure and limited supply of air.
The successive stages of transformation are : peat, lignite, bituminous, steam coal and anthracite.
Bituminous is hard stone, burns with smoky flame. The superior quality is anthracite which burns with
non-smoky flame.
Lamp black or carbon black : It is obtained by burning substances rich in carbon content such as kerosene,
petroleum, turpentine oil, acetylene etc. in a limited supply of air.

Example 14 : Name two elements of carbon family which have nearly same catenation tendency.
Solution : Ge and Sn.

Example 15 : Which element of the carbon family does not dissolve in aqueous NaOH to evolve hydrogen gas?
Solution : Carbon.

Example 16 : Given three reasons for anomalous behaviour of carbon.

Solution : Small size, high electronegativity, unavailability of vacant d-orbitals.

Example 17 : Which is thermodynamically more stable - diamond or graphite?

Solution : Graphite.

Uses of carbon
Graphite : In making lead pencils, electrodes of electric furnances, as a moderator in nuclear reactor, as a
lubricant in machinery.
Charcol : In removing offensive odour from air, in removing fused oil from crude spirit, in decolourising sugar
syrup, in gas masks etc.
Carbon black : For making printing inks, black paints, Indian inks, boot polishes and ribbons of typewriters.
Coal : For the manufacture of coal gas, coal tar, coke and synthetic petrol.

SOME IMPORTANT COMPOUNDS OF CARBON AND SILICON

Carbon Monoxide
Preparation :
(a) Formed due to incomplete combustion of carbon.

2C(s)  O2 (g)  2CO(g)
(b) Dehydration of formic acid.
373 K
HCOOH 
conc. H SO
 H2 O  CO
2 4

(c) Passing steam over coke.

437–1273 K
C(s)  H2O(g)  CO(g) + H2 (g) (Synthesis gas)

Water gas

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(d) Passing air over coke.

1273 K
2C(s)  O2 (g)  4N2 (g) 
 2CO(g)  4N2 (g)

Producer gas

It is colourless, odourless and water insoluble and is a strong reducing agent.

CO molecule acts as a donor and reacts with certain metals when heated to form metal carbonyls. It is also
called silent killer because reacts 300 times with haemoglobin than O2.

Carbon Dioxide
It is prepared by
(a) Thermal decomposition of calcium carbonate.

CaCO3  CaO  CO2
(b) Action of calcium carbonate with dil. HCl.
CaCO3 (s)  2HCl(aq) 
 CaCl2 (aq)  CO2 (g)  H2 O(l)

(c) Combustion of carbon containing fuels.


C  O2  CO2

CH4  2O2  CO2  2H2O
It is colourless, odourless and acidic gas as it combines with water to form carbonic acid which helps to
maintain pH of blood. Plants make food from it.
h
6CO2  6H2O 
Chlorophyll
 C6H12O6  6 O2

Green plants convert atmospheric CO2 into glucose (carbohydrates) by photosynthesis. By this process, CO2
is reduced from atmosphere.
If CO2 underpressure is allowed to escape through a nozzle, a white solid is obtained that is called dry ice
or cardice.
It can be used as refrigerant for frozen food or ice cream under the commercial name drikold.
Gaseous CO2 is used in soft drinks it is also used as fire extinguisher as it is non-supporter of combustion
and heavy. With water it gives weak dibasic acid called carbonic acid which dissociates in two steps as below.
 HCO3 (aq)  H3 O (aq)


H2CO3 (aq)  H2O(l) 
HCO3 (aq)  H2O(l) 
 CO32 (aq)  H3O (aq)



H2CO3 / HCO3 buffer system helps to maintain pH of blood between 7.26 to 7.42. It combines with alkalies
to form metal carbonates.

Silicon Dioxide
It is commonly known as silica and is nearly non-reactive because of its very high silicon-oxygen bond
enthalpy. It is resistant to acids, halogens, metals and dihydrogen.
It is attacked by HF and NaOH.
SiO2  2NaOH 
 Na2SiO3  H2O
SiO2  4HF  SiF4  2H2O
The entire solid crystal may be considered as giant molecule in which eight-membered rings are formed with
alternate silicon and oxygen atoms.

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Uses : SiO2 (silica gel) is used as a drying agent and as a support for chromatographic materials and catalysts.
Kieselghur, an amorphous form of silica is used in filtration plants.

Si O Si O Si O Si

O O O O

Si O Si O Si O Si

Silicones
Alkyl chloride reacts with silicon at 537 K in presence of copper catalyst to give dialkyl dichlorosilane with
other substituted chlorosilane.
Cu powder
2RCl  Si 
570 K
 R2SiCl2

Which on hydrolysis gives dialkyl dihydroxy silane.

 2H O
R2SiCl2  2  R Si(OH)
 2HCl 2 2 (Here R is methyl group)

Which on polymerisation gives silicones.

R R R R R R
Polymerisation
HO Si O H + HO Si O H + HO Si OH Si O Si O Si O
–H2O

R R R R R R
Silicone

Silicones are water repellants, good electrical insulators, stable towards heat, non-toxic resistant to chemicals.
Silicone oils remain viscous at different temperature.

These can be used in surgical and cosmetic plants. It is a polymer having ( Si O )n monomer. It can
be used as lubricant.

Silicates
Oxide anion of silicon is known as silicates.

1. Orthosilicates (SiO4–4 )
O

Si or

O O
O
Here is silicon and is oxygen. Here Si is sp3 hybridised.
Sodium orthosilicate is Na4SiO4 Zirconium silicate is ZrSiO4
Calcium orthosilicate is Ca2SiO4

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2. Pyrosilicates ( Si2O76 )

O O

Si Si

O O O
O O

No charge
(Neutral)

Sodium Pyrosilicate is Na6Si2O7 Calcium Pyrosilicate is Ca3Si2O7

Other examples of silicates are cyclic silicate (SiO32 )n , chain silicates (Si2O3 )n2n (Si4 O11 )n6n etc.
Some examples of natural silicates are feldspar, zeolites, mica and asbestos. Synthetic silicates are
glass and cement.

Note :

CLASSIFICATION OF SILICATES
(i) Orthosilicates : These do not share any corner. The anions are discrete SiO44– units.
Examples - Zircon (ZrSiO4) and Forestrite (Mg2SiO4).
(ii) Pyrosilicate : Here, two tetrahedral share one corner to form Si2O76– anion. The structure
posessed by them is called island structure. Example - Thortveitite (Sc2Si2O7).
(iii) Cyclic or ring silicates : Here two corners of each tetrahedron are shared to form closed rings.
The anionic unit are (SiO32–)n. Examples - Wollastonite- Ca3Si3O9, Beryl - Be3Al2Si6O18.
(iv) Chain silicates : Here two corners of each tetrahedron are shared to form a linear chain. The
anionic unit is again (SiO32–)n. Linear silicate chain is present in pyroxenes. Example -
6
Spodumene - LiAl(SiO3)2. If two chains are cross linked, the double stranded silicates (Si 4 O11 )n
are called amphiboles. Example - asbestos.
(v) Sheet silicates : These silicates are formed by the sharing of three corners of each
tetrahedron. The anion has a two dimensional sheet structure with general formula (Si2O52–)n.
Example - Clay
(vi) Three dimensional silicates : These are formed by the sharing of all the four corners.
Example - All the crystalline forms of silica. Example : Zeolites, Feldspar

Tetrahedral unit (ii)

(i)

Cyclic silicate
(iii)
(iv)

Sheet silicate
(vi)
Chain silicate (Pyroxene)
(v)

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Zeolites
If Al atoms replace few silicon atoms in 3D-network of SiO2, overall structure known as aluminosilicates
acquires a negative charge.
Cations such as Na+, K+, Ca2+ etc balance the negative charge. e.g., feldspar and Zeolites.
Uses
(i) Softening hard water by ion-exchanging.
(ii) Converting alcohols directly into gasoline (ZSM-5).
(iii) As catalyst in petrochemical industries.

Glass
It is a transparent or translucent amorphous supercooled solid soution of silicates and borates. Its composition
is variable as it is not a true compound it is also referred as pseudo solid.

Example 18 : What is hybridisation of carbon in CO2?

Solution : sp hybridisation.

Example 19 : Write use of silicones.

Solution : Used in surgical and cosmetics.

Example 20 : Why silicon dioxide is non-reactive?

Solution : Due to very high silicon-oxygen bond enthalpy.

EXERCISE
11. Most stable allotrope of carbon thermodynamically is
(1) Fullerene (2) Diamond
(3) Graphite (4) Coke
12. What is the correct order of I.E.?
(1) C < Si < Ge < Pb < Sn
(2) C > Si > Pb > Ge > Sn
(3) C > Si > Ge > Sn < Pb
(4) C > Si > Ge > Sn > Pb
13. In group 14, which element show inert pair effect?
(1) Si (2) Pb
(3) C (4) Ge
14. Which of the following is neutral oxide?
(1) CO
(2) CO2
(3) SiO2
(4) Na2O

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15. Which of the following halide cannot hydrolysed?

(1) CCl4 (2) SiCl4
(3) GeCl4 (4) SiF4
16. Which polymorph of carbon act as hardest allotrope?
(1) Diamond
(2) Fullerene
(3) Graphite
(4) All of these
17. SiC is popular with name
(1) Acetylide (2) Methanide
(3) Carborundum (4) Plumbago
18. On heating oxalic acid with H2SO4, we get
(1) H2CO3
(2) CO2 and O2
(3) CO2 and CO
(4) H2CO3 + CO2 + O2
19. Which allotrope of carbon leads to the formation of bucky ball?
(1) Graphite
(2) Diamond
(3) Fullerene
(4) Nano tube
20. Which of the following is correct structure of anion of pyrosilicates?
–

–
(1)
– –

– –

– –
(2)
– –

(3) – –

– –

– –

– –
– –
(4)
– –

– –

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GROUP 15 ELEMENTS : NITROGEN FAMILY
General electronic configuration  [inert gas] ns2np3
As exactly half-filled p-orbital, hence electronic configuration is extra stable.

Nitrogen (7N)
Non-metals
Phosphorous (15P)
Arsenic (33As)
Metalloids
Antimony (51Sb)
Bismuth (83Bi) Typical metal

Commonly called Pnictogens means chocking elements.

Occurrence
Nitrogen :
 Atmosphere comprises 78% by volume of N2.
 In form of proteins in plants and animals.
 Earth crust : Chile saltpeter (NaNO3)
Indian saltpeter (KNO3)
Phosphorus :
 Minerals of apatite family [Ca9(PO4)6CaX2]
(X = F, Cl or OH)
E.g., Fluorapatite [Ca9(PO4)6CaF2].
These are main components of phosphate rocks.
 Also phosphorus is present in bones, living cell, plant matter.
Arsenic, Antimony, Bismuth :
 Present mainly as sulphide minerals.
Table : Atomic and Physical Properties of Group 15 Elements
Property N P As Sb Bi
Atomic number 7 15 33 51 83
–1
Atomic mass / g mol 14.01 30.97 74.92 121.75 208.98
2 3 2 3 10 2 3 10 2 3 14 10 2 3
Electronic configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p
Ionization enthalpy I 1402 1012 947 834 703

 i H /(kJ mol)1 II 2856 1903 1798 1595 1610

III 4577 2910 2736 2443 2466

Electronegativity 3.0 2.1 2.0 1.9 1.9
a
Covalent radius / pm 70 110 121 141 148
b b b c
Ionic radius / pm 171 212 222 76 103c
Melting point / K 63* 317d 1089 e 904 544
d f
Boiling point / K 77.2* 554 888 1860 1837
–3 g h
Density / [g cm (298 K)] 0.879 1.823 5.778 6.697 9.808
a E III single bond (E = element); b E 3– ; c E 3+; d White phosphorus; e Grey  -form at 38.6 atm; f Sublimation temperature;
g At 63 K; hGrey -form; * Molecular N2.

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Atomic Properties of Group 15

Nitrogen is a diatomic gas, while other elements are polyatomic solid.

 Boiling point : Increases down the group, but that of Sb is greater than Bi.

 Melting point : Increases upto arsenic and then decreases upto bismuth.

 Allotropy : All elements of group 15 show allotropy except nitrogen.

Anomalous properties of nitrogen

Nitrogen differs from rest of the members of Group 15 due to its small size, high electronegativity, high ionization
enthalpy and absence of vacant d orbitals.

(1) Nitrogen exists as diatomic molecule with triple bond, thus its bond enthalpy (941.4 kJ/mol) is very high.
But P, As, Sb form single bond, while bismuth forms metallic bond in elemental state.

(2) Catenation tendency is weaker in nitrogen as single N–N bond is weaker than single P–P bond, as high
interelectronic repulsion of non-bonding electrons, owing to small bond length in nitrogen.

(3) Nitrogen has unique ability to form p–p multiple bond with itself and other elements having small size
and high electronegativity (e.g., C, O). But heavier elements do not form p–p bond as their atomic orbitals
are so large and diffuse that they can not have effective overlapping.

(4) Nitrogen shows maximum covalency of four, because of absence of vacant d orbitals. Thus, nitrogen
cannot form d–p bond, but heavier elements can like P, As can from d–p [e.g., R 3P = O,
R3P = CH2], [R = alkyl group] and d–d bond with transition metals, when compounds like P(C2H5)3
and As(C6H5)3 act as ligands.

Chemical Properties and Trends in Chemical Reactivity

Oxidation State
Common oxidation state of Group 15 elements are –3, +3 and +5.
Tendency to show –3 oxidation state decreases down the group due to increase in size and metallic character.
Bi hardly forms any compound in –3 oxidation state.
The stability of +5 oxidation state decreases and that of +3 oxidation state increases down the group due to
inert pair effect. The only well characterised Bi (V) compound is BiF5.
Nitrogen shows +1, +2, +4 oxidation state also when it reacts with oxygen. All oxidation state from +1 to +4
disproportionate in acid solution in case of nitrogen, e.g.,

3HNO2  HNO3  H2O  2NO

Phophorous also shows +1 and +4 oxidation states in some oxoacids. All intermediate oxidation state
disproportionate in both acid and alkali into –3 and + 5.
However +3 oxidation state for As, Sb, Bi become increasingly stable with respect to disproportionation.

Covalency
Nitrogen shows maximum covalency of four, as only four orbitals (one s and three p) orbitals are available for
bonding. The heavier element with vacant d orbital can show covalency more than four. e.g., in PF6 , P has
covalency of six.

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Reactivity towards Hydrogen :
All Group 15 elements form hydrides of the type EH3. (E = N, P, As, Sb or Bi.)
NH3, PH3, AsH3, SbH3, BiH3

Thermal Stability decreases



decreases
Bond dissociation enthalpy  

Basicity decreases


Reducing character increases

 

Bond angle decreases



Boiling Point : PH3 < AsH3 < NH3 < SbH3 < BiH3.

Table : Properties of Hydrides of Group 15 elements

Property NH3 PH3 AsH3 SbH3 BiH3

Melting point / K 195.2 139.5 156.7 185 –
Boiling point / K 238.5 185.5 210.6 254.6 290
(E–H) Distance / pm 101.7 141.9 151.9 170.7 –
HEH angle (º) 107.8 93.6 91.8 91.3 –
T –1
f H /kJ mol –46.1 13.4 66.4 145.1 278
T –1
diss H (E–H) / kJ mol 389 322 297 255 –

Reactivity towards Oxygen :

All Group 15 elements form oxides of type E2O3 and E2O5. The oxide in higher oxidation state is more acidic
than in lower oxidation state. In a particular state the acidic character decreases down the group.
Oxides of E2O3 type of N and P – Purely acidic
As and Sb – Amphoteric
Bi – Basic
Tendency to form pentoxide decreases down the group due to inert pair effect.
Oxides :
Acidic Character Increases
Ac idic Char ac te r D ec rea se s

N 2O NO N 2O 3 NO 2 N 2O5

P2O 3 P2O5

As2O3 As 2O 5

Sb2O3 Sb 2O 5

Bi2O 3 Bi2O5

*NO2 is mixed anhydride

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Reactivity towards Halogens :

Elements of group 15 reacts to form halide of type EX3 and EX5.
All trihalides except that of nitrogen are stable.
In case of nitrogen only NF3 is known to be stable.
Except BiF3, other trihalides are predominantly covalent.
Nitrogen does not form pentahalide due to absence of vacant d subshell. Pentahalide are more covalent than
trihalides.
Hydrolysis of ECl3 :
NCl3 + 3H2O  NH3 + 3HOCl
PCl3 + 3H2O  H3PO3 + 3HCl
2AsCl3 + 3H2O  As2O3 + 6HCl
SbCl3 + H2O  SbOCl + 2HCl
BiCl3 + H2O  BiOCl + 2HCl
Reactivity towards Metals :
Group 15 elements react with metals to form binary compounds showing –3 oxidation state e.g.,
Ca3N2, Ca3P2, Na3As, Zn3Sb2, Mg3Bi2

DINITROGEN

Preparation
1. Commercially by liquefaction and fractional distillation of air, liquid N2 (b.p. 77.2 K) distills out first leaving
O2 (b.p. 90 K)
2. In laboratory it is prepared by :

NH4 Cl(aq)  NaNO2 (aq)  N2 (g)  2H2O(l)  NaCl(aq)

Small amount of NO and HNO3 are also formed in this reaction as impurities can be removed by passing
the gas through aqueous H2SO4 containing K2Cr2O7.
3. By thermal decomposition of (NH4)2Cr2O7
Heat
(NH4 )2 Cr2O7  N2  4H2O  Cr2O3

4. Very pure N2 can be obtained by the thermal decomposition of sodium or barium azide.

Ba(N3 )2  Ba  3N2


2NaN3  2Na  3N2

Properties
1. It is colourless, odourless, tasteless and nontoxic gas. It has two stable isotopes N14 and N15.
2. It has very low solubility in water (23.2 cm3 per litre of water at 273 K and 1 bar P) and low freezing
and boiling point.
3. Dinitrogen is inert at room temperature because of high bond enthalpy of N  N bond. With increase in
temperature reactivity increases.
It directly combines with some metals to form predominantly ionic nitrides.

6Li  N2  2Li3N

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
3Mg  N2  Mg3N2

4. It combines with H2 at about 773 K in presence of catalyst (Haber’s process) to form ammonia
773K

N2 (g)  3H2 (g)  
 2NH3 (g) ; Hf  46.1 kJ/mol
5. At high temperature (2000 K)


N2 (g)  O2 (g)  
 2NO(g)
Uses :
(i) In manufacture of NH3 and other industrial chemical containing N2 (e.g., calcium cyanamide).
(ii) Used to create inert atmosphere (e.g., in iron and steel industry)
(iii) Liquid N2 is used as refrigerant to preserve biological materials, food items and in cryosurgery.

AMMONIA
Ammonia is present in small quantities in air and soil, formed by decay of nitrogenous organic compounds
e.g., urea.

NH2CONH2  2H2O  (NH4 )2 CO3 


 2NH3
  H2 O  CO2

On small scale, it is obtained from ammonium salts which decompose when treated with caustic soda or
lime,

2NH4 Cl  Ca(OH)2  2NH3  2H2O  CaCl2

(NH4 )2 SO4  2NaOH  2NH3  2H2O  Na2SO4

On large scale, ammonia is manufactured by Haber’s process.

 2NH3 (g) ;  H Θ = – 46.1 kJ/mol–1
N2 (g)  3H2 (g)  f

In accordance with Le Chatelier’s principle, the optimum conditions for the formation of NH3 are :
High pressure : 200 × 105 Pa (about 200 atm).

Temperature :  700 K.
Catalyst : Iron oxide with small amount of K2O and Al2O3. Earlier, Iron with molybdenum used as catalyst.

Properties
Physical :
Ammonia is colourless gas with pungent odour. Freezing point = 198.4 K. Boiling point = 239.7 K.
As it is associated through hydrogen bonding in solid and liquid states it has higher melting and boiling point,
than expected on the basis of its molecular mass.
Structure :
The NH3 molecule is trigonal pyramidal having sp3 hybridized N with a lone pair of electrons.

pm N
1.7
10
H 107° H
H

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Chemical :
Ammonia is highly soluble in water. Its aqueous solution is weakly basic due to formation of OH– ions.

 NH4 (aq)  OH (aq)

NH3 (g)  H2O (l) 

It forms ammonium salt with acids e.g., NH4Cl, (NH4)2SO4 etc.

As a weak Lewis base, it precipitates hydroxide of many metals from their salt solutions e.g.,
FeCl3 (aq)  3NH4OH (aq)  Fe2O3  xH2O  3NH4Cl (aq)
(brown ppt.)

ZnSO4 (aq)  2NH4OH (aq)  Zn(OH)2  (NH4 )2 SO4 (aq)

(white ppt.)
As NH3 is a Lewis base (due to lone pair of electron on N), it donates electron pair and forms linkage with
metal ions and this helps in detection of metal ions such as Cu2+, Ag+.

Cu2 (aq)  4NH3 (aq) 

 [Cu(NH3 )4 ]2 (aq)
(blue) (deep blue)

Ag (aq)  Cl (aq)  AgCl (s)

( colourless ) ( white ppt.)

AgCl (s)  2NH3 (aq)  [Ag(NH3 )2 ]Cl (aq)

(White ppt.) (colourless)

Note :

Some more reactions of NH3

(Test for NH3) Sodamide (Bronze Colour)

NaNH2
(Iodide of Millon's base)
NH2.HgO.HgI
(Brown) (BN)x Boron Nitride
Na (Inorganic graphite)
Ne
at

ss
He

le
K2

d N2 + H2O
Re 2 H6

r 's
Hg

te
d
B

re mi
I4

ag Li
N2 en O2
NaOCl t Ex
+ NaCl + H2O ce
NH3 ss
NO + H2O
Cl2
B 2H
6

0K Limited
45 PbO CuO N2 + NH4Cl
Exce

(Hot) (Hot)
B3N3H6
(Borazine)
ss

(Inorganic benzene)
NCl3 + HCl
N2
N2
+ Cu + H2O
+ Pb + H2O

Uses of NH3
(i) To produce nitrogenous fertilizers [NH4NO3, NH2CONH2, (NH4)3PO4, (NH4)2SO4].
(ii) To manufacture some inorganic nitrogen compounds like nitric acid (HNO3).
(iii) Liquid ammonia is used as refrigerant.

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OXIDES OF NITROGEN
Nitrogen froms a number of oxides in different oxidation states. The detail is given below :
Table : Oxides of Nitrogen

Oxidation Physical
Common methods of
Name Formula state of appearance and
preparation
nitrogen chemical nature
Heat
Dinitrogen oxide N 2O +1 NH4NO3 N2O + 2H2O Colourless gas,
[Nitrogen(I) oxide] Neutral
Nitrogen monoxide NO +2 2NaNO2 + 2FeSO4 + 3H2SO4 Colourless gas,
[Nitrogen(II) oxide] Fe2(SO4)3 + 2NaHSO4 + 2H2O + 2NO Neutral

250K
Dinitrogen trioxide N 2O3 +3 2NO  N2O4 2N2O3 Blue solid, Acidic
[Nitrogen(III) oxide)
673K
Nitrogen dioxide NO2 +4 2Pb(NO3 )2 4NO2  2PbO + O2 Brown gas, Acidic
[Nitrogen(IV) oxide]
Cool
Dinitrogen tetroxide N 2O 4 +4 2NO2 N 2 O4 Colourless solid /
Heat
[Nitrogen(IV) oxide] liquid, Acidic
Dinitrogen pentoxide N 2O 5 +5 4HNO3  P4O10 4HPO3 + 2N2O5 Colourless solid,
[Nitrogen(V) oxide] Acidic

Table : Lewis dot main resonance structures and bond parameters of oxides of nitrogen.

Formula Resonance Structures Bond Parameters

N2O N N O N N O N N O
113 pm 119 pm
Linear
NO N O N O N O
115 pm

O O O O 105º O
O 11
N2O3 4
pm
N N N N N N 130º
186 pm
O O 117º O
121 pm
Planar
N N N
NO2 120 pm
O O O
O O 134º O
Angular
O O O O O O
175 pm 1 pm
N2O4 N N N N 12
N N 135º

O O O O O Planar O

O m
O O O O 1 pm 9p O
O O 15 O 11
N2O5 N N N N N N 134º
112º
O O O O O O
Planar

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Example 21 : Though nitrogen exhibits +5 oxidation state, it does not form pentahalide. Give reason.
Solution : Nitrogen has s and p orbitals only. As it does not have d orbital to expand its covalency beyond four.

Example 22 : PH3 has lower boiling point than NH3. Why?

Solution : Unlike NH3, PH3 is not associated through hydrogen bonding in liquid state.

Example 23 : Write reaction of thermal decomposition of sodium azide.

Solution : 2NaN3  2Na + 3N2

Example 24 : Why does NH3 act as lewis base?

Solution : Nitrogen atom in NH3 has one lone pair of electron which is available for donation, hence Lewis base.

Example 25 : Why does NO2 dimerise?

Solution : NO2 contains odd number of valence electron. On dimerisation it gets converted to stable N2O4
with even number of electrons.

NITRIC ACID
Nitrogen forms oxoacids such as :
H2N2O2 (Hyponitrous acid), HNO2 (Nitrous acid) and HNO3 (Nitric acid).
HNO3 is the most important.

Preparation
 In laboratory HNO3 prepared by heating KNO3 or NaNO3 and conc. H2SO4 in glass retort.

NaNO3  H2SO4  NaHSO4  HNO3

 Large scale (by Ostwald’s process)

(i) Based on catalytic oxidation of NH3 by atmospheric oxygen.

Pt / Rh gauge catalyst
4NH3 (g)  5O2  4NO(g)  6H2O(g)
500K,9 bar
(from air)

(ii) Nitric oxide combines with O2 giving NO2.



2NO(g)  O2 (g) 
 2NO2 (g)

(iii) Nitrogen dioxide so formed dissolves in water to give HNO3.

3NO2 (g)  H2O(l)  2HNO3 (aq.)  NO(g)

Aqueous HNO3 can be concentrated by distillation upto ~68% by mass. Further concentration upto 98%
achieved by dehydration with conc. H2SO4.

Properties
It is colourless liquid. (Freezing point : 231.4 K and boiling point : 355.6 K)
Lab. HNO3 contains ~68% of HNO3 by mass and has specific gravity 1.504.

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Structure :
In the gaseous state HNO3 has planar structure.

H O

m
1p
102º

96

12
pm
O N 130º
140.6 pm

O
In aqueous solution, HNO3 behaves as strong acid giving hydronium and nitrate ions.

HNO3 (aq)  H2O(l)  H3 O (aq)  NO3 (aq)

Concentrated nitric acid is strong oxidising agent and attacks most metals except noble metals such as gold
and platinum.
The products of oxidation depend upon the concentration of the acid, temperature and the nature of material
undergoing oxidation.

 3Cu  8HNO3 (dilute)  3Cu(NO3 )2  2NO  4H2O

Cu  4HNO3 (conc.)  Cu(NO3 )2  2NO2  2H2O

 4Zn  10HNO3 (dilute)  4Zn(NO3 )2  5H2O  N2O

Zn  4HNO3 (conc.)  Zn(NO3 )2  2H2O  2NO2

Due to formation of passive film of oxide on the surface of some metals like Cr, Al do not dissolve in
concentrated nitric acid.
 Conc. HNO3 also oxidises non-metals and their compounds.

I2  10HNO3  2HIO3  10NO2  4H2O

C  4HNO3  CO2  2H2O  4NO2

S8  48HNO3  8H2SO 4  48NO2  16H2O

(conc.)

P4  20HNO3  4H3PO 4  20NO2  4H2O

(conc.)

Brown Ring Test for Nitrates :

This depends on the ability of Fe2+ to reduce nitrates to nitric oxide, which reacts with Fe2+ to form brown-
coloured complex.

This test is done by adding dil. FeSO4 to an aqueous solution containing NO3 , and then adding conc. H2SO4
along the sides of test tube. Brown ring at interface between solution and H2SO4 layer indicates the presence

of NO3 in solution.

NO3  3Fe2   4H  NO  3Fe3   2H2O

[Fe(H2O)6 ]2   NO  [Fe(H2O)5 (NO)]2   H2O

brown

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Uses of HNO3 :
1. In the manufacture of ammonium nitrate for fertilisers and other nitrates for use in explosives and
pyrotechnics.
2. Also used for the preperation of nitroglycerin, trinitrotoluene (TNT) and other organic nitro compounds.
3. Other uses are in pickling of stainless steel, etching of metals and as an oxidiser in rocket fuels.

ALLOTROPIC FORMS OF PHOSPHORUS

The important allotropic forms of phosphorus are white, red and black.

1. White phosphorus :

(a) It consists of discrete tetrahedral P4 molecule.

(b) It is less stable and more reactive than other solid phases because of P
angular strain in P4 molecules, having angle of 60º.
60°
(c) It is translucent white waxy solid.
P P
(d) It is poisonous, insoluble in water but soluble in CS2 and glows in dark
(chemiluminescence). P
(e) It dissolves in boiling NaOH solution in inert atmosphere giving PH3.

P4  3NaOH  3H2O  PH3  3NaH2PO2

(Sodium hypophosphite)

(f) It readily catches fire in air to give dense white fumes of P4O10.

P4  5O2  P4 O10

2. Red phosphorus
P P P
(a) It is polymeric consisting of chains of P4
tetrahedra linked together.

(b) It is obtained by heating white phosphorus P P P P P P

at 573 K in inert atmosphere for several
days. P P P
(c) When red P is heated under high pressure, a series of phases of black P is formed.

(d) Red P has iron grey lustre.

(e) It is odourless, non-poisonous and insoluble in water and CS2.

(f) Chemically it is much less reactive than white P.

(g) It does not glow in dark.

3. Black phosphorus

(a) It has two forms : -black and -black phosphorus.

(b) -black phosphorus is formed when red phosphorus is heated in a sealed tube at 803 K. It can
sublime in air and has opaque monoclinic or rhombohedral crystals.

(c) -black phosphorus is prepared by heating white phosphorus at 473 K under high pressure. It does
not burn in air upto 673 K.

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PHOSPHINE, PH3

Preparation
 By reaction of calcium phosphide with water or dil. HCl.

Ca3P2  6H2O  3Ca(OH)2  2PH3

Ca3P2  6HCl  3CaCl2  2PH3

 Lab preparation : By heating white P with conc. NaOH in an inert atmosphere of CO2.

P4  3NaOH  3H2O  PH3  3NaH2PO2

(Sodium hypophosphite)

When pure it is non-inflammable but becomes inflammable due to presence of P2H4 or P4 vapours.
To purify it from impurities, it is absorbed in HI to form phosphonium iodide (PH4I), which on treating with
KOH gives phosphine.

PH4I  KOH  KI  H2O  PH3

Properties
 PH3 is colourless gas with rotten fish smell and is highly poisonous.
 It explodes in contact with traces of oxidising agent like HNO3, Cl2 and Br2 vapours.
 It is slightly soluble in water, solution of PH3 in water decomposes in presence of light giving red P and
H2.
 When absorbed in CuSO4 or HgCl2, phosphides are obtained.

3CuSO4  2PH3  Cu3P2  3H2SO4

3HgCl2  2PH3  Hg3P2  6HCl

 PH3 is weakly basic and like NH3, give phosphonium compounds with acids.

PH3  HBr  PH4Br

Uses of PH3
1. Used in Holme’s signals, due to spontaneous combustion of phosphine. Containers containing CaC2 and
Ca3P2 are pierced and thrown in sea when gases evolve burn and serve as signal.
2. Also used in smoke screens.

PHOSPHORUS HALIDE
Phosphorus forms halides of type PX3 (X = F, Cl, Br, I) and PX5 (X = F, Cl, Br)

Phosphorus Trichloride, PCl3 :

Preparation :


P4  6Cl2  4PCl3
(white P) (dry)

P4  8SOCl2  4PCl3  4SO2  2S2Cl2

(white P) Thionyl chloride

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Properties :
 Colourless oily liquid and hydrolyse in the presence of moisture.

PCl3  3H2O  H3PO3  3HCl

 It reacts with organic compounds containing –OH group.

3CH3 COOH  PCl3  3CH3 COCl  H3PO3

3C2H5 OH  PCl3  3C2H5 Cl  H3PO3

Structure :
It has sp3 hybridised P and has pyramidal structure.

Cl Cl Cl

Phosphorus pentachloride, PCl5 :

Preparation :

P4  10Cl2  4PCl5

(white) (excess)

P4  10SO2Cl2  4PCl5  10SO2

Sulphuryl chloride

Properties :
It is yellowish white powder and in moist air, it hydrolyses to POCl3 and finally forms phosphoric acid.

PCl5  H2O  POCl3  2HCl

POCl3  3H2O  H3PO4  3HCl

 When heated, it sublimes but decomposes on stronger heating.


PCl5  PCl3  Cl2

 It reacts with organic compound containing –OH group.

C2H5 OH  PCl5  C2H5 Cl  POCl3  HCl

(Phosphorous oxychloride
or phosphoryl chloride)

CH3 COOH  PCl5  CH3 COCl  POCl3  HCl

 Finely divided metals on heating with PCl5 give corresponding chloride.

2Ag  PCl5  2AgCl  PCl3

Sn  2PCl5  SnCl4  2PCl3

 It is used in the synthesis of some organic compounds e.g., C2H5Cl, CH3COCl.

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Structure :
Cl
 In gaseous and liquid phases, it is sp3d hybridised and Cl
240 pm
has trigonal bipyramidal structure. The two axial bonds
are longer than three equatorial bonds. This is due to
fact that axial bond pair suffer more repulsion as 202
P pm
compared to equatorial bond pairs.
Cl Cl
 In solid state, it exists as an ionic solid [PCl 4 ] +
[ P C l 6 ] – . [P C l 4 ] + is tetrahedral and [PCl 6 ] – is
octahedral. Cl

Oxides of Phosphorus :
It forms two oxides P4O6 and P4O10.

P4O6 : P4  3O 2  P4 O 6
(Limited )

..
P
O O
O
Structure : :P P:
O
O O
P
..
It is white solid with garlic odour. It dissolves in cold and hot water to form phosphorus acid and phosphoric
acid respectively.

P4O6 + 6H2O  4H3PO3

(cold)

P4O6 + 6H2O  3H3PO4 + PH3

(hot)

P4O10 : P4 + 5O 2  P4O10
(excess)

O
||
P
O O
O
O P P O
||

||

Structure :
O
O O
P
||
O
It is a white solid with snow like appearance and sublimes on heating. It readily dissolves in both cold
and hot water.

P4O10 + 2H2O  4HPO3 (Meta phosphoric acid)

(cold)

P4O10 + 6H2O  4H3PO4 (Phosphoric acid)

(hot)

It is a powerful dehydrating agent.

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OXOACIDS OF PHOSPHORUS
Phosphorus forms number of oxoacids. The formulae, method of preparation and structures of important
oxoacids of phosphorus are given below :
Table : Oxoacids of Phosphorus

Oxidation state Characteristic bonds

Name Formula Preparation
of phosphorus and their number
Hypophosphorous acid H3PO2 +1 One P – OH white P4 + alkali
(Phosphinic) Two P – H
One P = O
Orthophosphorous H3PO3 +3 Two P – OH P2 O 3 + H 2 O
acid (Phosphonic) One P – H
One P = O
Pyrophosphorous acid H4P2O5 +3 Two P – OH PCl3 + H3PO3
Two P – H
Two P = O
Hypophosphoric acid H4P2O6 +4 Four P – OH Red P4 + alkali
Two P = O
One P – P
Orthophosphoric acid H3PO4 +5 Three P – OH P4O10 + H2O
One P = O
Pyrophosphoric acid H4P2O7 +5 Four P – OH On heating
Two P = O phosphoric acid
One P – O – P
Metaphosphoric* acid (HPO3)3 +5 Three P – OH Phosphorus acid
Three P = O + Br2, heat in a
Three P – O – P sealed tube
* Exists in polymeric forms only. Characteristic bonds of (HPO3)3 have been given in the Table.

The compositions of the oxoacids are interrelated in terms of loss or gain of H2O molecule or O-atom.
The structures of some important oxoacids are given below :
O
O O O O
P P
P P P
HO OH H OH
HO O H OH
OH OH OH
OH OH H
H3PO4 H4P2O7 H3PO3 H3PO2
Orthophosphoric acid Pyrophosphoric acid Orthophosphorous acid Hypophosphorous acid

O O O
O OH O
P P
HO OH P P P
O O O O O O
P OH O OH
O OH
Polymetaphosphoric acid, (HPO3)n
Cyclotrimetaphosphoric acid, (HPO3)3

Fig : Structures of some important oxoacids of phosphorus

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In oxoacids, phosphorus is tetrahedrally surrounded by other atoms. They contain at least one P = O and one
P–OH bond. The one with lower oxidation state (less than +5) also has either P–P (e.g., in H4P2O6) or P–H
(e.g., H3PO2). In + 3 oxidation state, P shows disproportionation e.g., orthophosphorus acid


4H3PO3  3H3PO 4  PH3

The acids containing P–H bond have strong reducing properties. Thus hypophosphorus acid having two
P–H bonds is a good reducing agent and reduces AgNO3 to metallic silver.

4AgNO3  2H2O  H3PO2  4Ag  4HNO3  H3PO4

These P–H bonds are not ionisable to give H+ and do not involve in basicity of the acids.
Only those H atoms attached with oxygen in P–OH form are ionisable and cause basicity. Thus H3PO3
containing two P–OH bonds is dibasic and H3PO4 with three P–OH bonds is tribasic.

Example 26 : How can it be proved that PH3 is basic in nature?

Solution : PH3 can react with acid like HI,

PH3  HI  PH4I

As PH3 has lone pair of electron, hence it acts as Lewis base.

Example 27 : Why does PCl3 fume in moisture?

Solution : PCl3  3H2O  H3PO3  3HCl

PCl3 on hydrolysis gives fumes of HCl.

Example 28 : Are all the five bonds in PCl5 equivalent? Justify your answer.
Solution : PCl5 has trigonal bipyramidal structure, the two axial bonds are longer, as they experience more
repulsion than three equatorial bonds.

Example 29 : How do you account for reducing behaviour of H3PO2 on the basis of its structure?

O
P
Solution :
H OH
H

The two H atoms bonded directly to phosphorus atom impart reducing characters.

Example 30 : Draw structure of pyrophosphoric acid.

O O
P P
Solution : H4P2O7 : HO O OH
HO OH

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EXERCISE

21. Catenation property of group 15 elements follow the order

(1) N >> P > As > Sb > Bi
(2) P >> N > As > Sb > Bi
(3) N < P < As < Sb < Bi
(4) P < N < As < Sb < Bi
22. Melting point of hydrides of nitrogen family follows the order
(1) NH3 < PH3 < AsH3 < SbH3
(2) PH3 < NH3 < AsH3 < SbH3
(3) PH3 < AsH3 < NH3 < SbH3
(4) PH3 < AsH3 < SbH3 < NH3
23. Which of the following halides of group 15 is not hydrolysed?
(1) NF3 (2) NI3
(3) PF3 (4) Both (1) & (3)
24. Brown ring test is used for the identification of

(1) PO43 (2) NO3

(3) SO24 (4) HCO3

25. White phosphorus occurs as discrete P4 units, where P atoms lie at the corners of a regular tetrahedron.
The PPP bond angle is
(1) 90°` (2) 109°28
(3) 60° (4) 120°
26. Orthophosphorus acid on heating gives
(1) Hypophosphorus acid (2) Orthophosphoric acid
(3) Phosphene gas (4) Both (2) & (3)
27. Which of the following is correct?
(1) H3PO3 is dibasic and reducing
(2) H3PO3 is dibasic and non-reducing
(3) H3PO4 is tribasic and reducing
(4) H3PO3 is tribasic and non-reducing
28. The correct order of decreasing acidic strength of oxyacids of group 15 element is
(1) HNO3 > H3SbO4 > H3AsO4 > H3PO4
(2) H3PO4 > H3AsO4 > H3SbO4 > HNO3
(3) HNO3 > H3PO4 > H3AsO4 > H3SbO4

(4) HNO3 > H3AsO4 > H3PO4 > H3SbO4

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29. The bond angle is maximum in
(1) NH3 (2) PH3
(3) AsH3 (4) SbH3

2
30. When excess of NH3(aq) is added to a blue solution containing Cu(aq) ions

(1) Solution turns red due to formation of Cu+ ions

2
(2) Solution becomes red due to formation of Cu(NH3 )4  aq

2
(3) Solution become deep blue due to formation of Cu(NH3 )4  aq

(4) Solution becomes colourless due to excess colourless NH3

GROUP 16 ELEMENTS : OXYGEN FAMILY

General electronic configuration : [inert gas] ns2np4

Oxygen (8O)
Non-metals
Sulphur (16S)
Selenium (34Se)
Metalloids
Tellurium (52Te)
Polonium (84Po) Radioactive metal (half-life 13.8 days)

Group 16 is known as chalcogens, means ore forming elements such as oxides and sulphides.

Occurrence
Oxygen :

Most abundant of all the elements on earth. It forms about 46.6% by mass of earth’s crust. Dry air contains
20.946% oxygen by volume.

Sulphur :
In earth curst only 0.03–0.1%

 Combined sulphur exists primarily as sulphates as : gypsum (CaSO42H2O), epsom salt (MgSO47H2O),
baryte (BaSO4).

 Sulphides such as : galena (PbS), zinc blende (ZnS), copper pyrites (CuFeS2).

 Traces of sulphur occur as H2S in volcanoes.

 Organic materials such as eggs, proteins, garlic, onion, mustard, hair and wool contain sulphur.

Selenium and Tellurium :

Found as metal selenides and tellurides in sulphide ores.

Polonium :

Occurs as decay product of thorium and uranium minerals.

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Table : Some Physical Properties of Group 16 elements

Property O S Se Te Po

Atomic number 8 16 34 52 84
–1
Atomic mass/g mol 16.00 32.06 78.96 127.60 210.00
Electronic configuration [He]2s 2 2p4 [Ne]3s 2 3p4 [Ar]3d 104s2 4p 4 [Kr]4d10 5s 25p4 [Xe]4f14 5d 106s2 6p 4
a
Covalent radius /(pm) 66 104 117 137 146
2– b
Ionic radius, E /pm 140 184 198 221 230
Electron gain enthalpy, –141 –200 –195 –190 –174
/egH kJ mol–1
Ionisation enthalpy 1314 1000 941 869 813
–1
(iH1 )/kJ mol
Electronegativity 3.50 2.44 2.48 2.01 1.76
–3 c d e
Density /g cm (298 K) 1.32 2.06 4.19 6.25 –
f
Melting point / K 55 393 490 725 520
Boiling point / K 90 718 958 1260 1235
Oxidation states* –2, –1, 1, 2 –2, 2, 4, 6 –2, 2, 4, 6 –2, 2, 4, 6 2, 4

a Single bond; b Approximate value; c At the melting point; d Rhombic sulphur; e Hexagonal grey; f Monoclinic form, 673 K.
* Oxygen shows oxidation state of +2 and +1 in oxygen fluorides OF2 and O2F2 respectively.

Physical Properties of Group 16

 All these elements exhibit allotropy.

 The melting and boiling point increase with increase in atomic number down the group. The large difference
in melting and boiling points of oxygen and sulphur is due to their atomicity.

 Oxygen exists as diatomic molecule (O2) and sulphur as polyatomic molecule (S8).

Anomalous behaviour of oxygen in Group 16

This is due to its small size and high electronegativity.

 Presence of strong hydrogen bonding in H2O, which is absent in H2S.

 Due to absence of d orbital in oxygen, limits its covalency to four and in practice, rarely exceeds to two.
Other elements can show covalency more than four.

Chemical Properties and Trends in Chemical Reactivity

 Oxidation State :

Since electronegativity of oxygen is very high, it shows only negative oxidation state as –2 (except in
OF2, where it is + 2). Stability of –2 state decreases down the group. Polonium hardly shows –2 state.

Other elements of the group show +2, +4, +6, where +4 and +6 are more common. S, Se, Te show +4
state with oxygen and +6 with fluorine. Bonding in +4 and +6 are primarily covalent.

Down the group stability of +6 decreases and that of +4 increases due to inert pair effect.

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 Reactivity with Hydrogen :
Table : Properties of Hydrides of Group 16 Elements
Property H2O H2S H2Se H2Te
m.p / K 273 188 208 222
b.p / K 373 213 232 269
H–E distance / pm 96 134 146 169
HEH angle (º) 104 92 91 90
–1
f H /kJ mol –286 –20 73 100
–1
diss H (H–E) / kJ mol 463 347 276 238
a –6 –7 –4 –3
Dissociation constant 1.8 × 10 1.3 × 10 1.3 × 10 2.3 × 10

a Aqueous solution, 298 K

All elements of Group 16 form hydride of type H2E (E = S, Se, Te, O)

H2O H2S H2Se H2 Te

increases
Acidic character  
(As bond dissociation energy decreases)

decreases
Thermal stability 

increases
Reducing character  
Note : Water does not show reducing property
Boiling point : H2S < H2Se < H2Te < H2O
Melting point : H2S < H2Se < H2Te < H2O
 Reactivity with oxygen :
All elements form oxides of type EO2 and EO3 (E = S, Se, Te, or Po). O3 and SO2 are gases, but SeO2
is solid. From SO2 to TeO2 reducing property decreases. TeO2 is an oxidising agent. Sulphur, selenium
and tellurium also form EO3 type oxide. Both type of oxides are acidic in nature.
Tendency to form EO3 decreases down the group due to inert pair effect.

 Reactivity towards Halogens :

(i) Group 16 elements form halides of type EX6, EX4 and EX2, (E = Group 16 element) (X = Halogen).
Stability of halides decreases from F– > Cl– > Br– > I–.
(ii) Among hexahalides, hexafluorides are only stable halide. SF6 is exceptionally stable for steric reason.
Hexafluorides are gaseous in nature, sp3d2 hybridised central atom and has octahedral structure.

F
F F

F F
F

(iii) Among tetrafluorides, SF4 is gas, SeF4 is liquid and TeF4 is solid. They have sp3d hybridised central
atom and have trigonal bipyramidal geometry. One of equitorial positions is occupied by lone pair
of electron, so its shape becomes see-saw.
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F
F

F
F

(iv) All elements except selenium form dichlorides and dibromides. They are sp3 hybridised and have
tetrahedral structure. Monohalides like S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2 are dimeric in nature
and undergo disproportionation.
2Se2Cl2  SeCl4  3Se

Example 31 : Name the radioactive element of Group 16.

Solution : Polonium.

Example 32 : Elements of Group 16 show lower value of 1st ionization enthalpy compared to Group 15, why?
Solution : Due to extra stable half-filled p orbitals of Group 15, larger amount of energy is required to remove
electron as compared to group 16.

Example 33 : H2S is less acidic than H2Te, why?

Solution : Down the group, E–H bond dissociation enthalpy decreases and hence acidic character increases.

Example 34 : Give hybridisation and structure of SF4.

Solution : sp3d, trigonal bipyramidal geometry and see-saw structure.

DIOXYGEN

Preparation
In lab O2 can be obtained by

1. By heating oxygen containing salt as chlorates, nitrates and permanganates.


2KClO3 
 2KCl  3O2
MnO2

2. By thermal decomposition of oxides of metals.

2Ag2O(s)  4Ag(s)  O2 (g)

2HgO(s)  2Hg(l)  O2 (g)

2Pb3 O4 (s)  6PbO(s)  O2 (g)

2PbO2  2PbO(s)  O2 (g)

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3. By decomposition of H2O2.
finely divided metals
2H2O2 (aq) 
 2H2O (l)  O2 (g)
and MnO2

On large Scale, O2 is prepared from electrolysis of H2O releasing O2 at anode.

Industrially, O2 is obtained from air by removing CO2 and H2O vapours and gases are liquefied and fractionally
distilled to give N2 and O2.

Properties
 O2 is colourless and odourless gas.
 Solubility in water is approx. 3.08 cm3 in 100 cm3 water at 293 K, sufficient for marine and aquatic life.
 It liquefies at 90 K and freezes at 55 K.
 It has three stable isotopes : O16, O17 and O18.
 O2 is paramagnetic and this can be explained on basis of MO theory.
Dioxygen directly reacts with nearly all metals and non-metals (except Au, Pt and some noble gases). These
reactions are exothermic, however to initiate reaction, some external heating is required as bond dissociation
enthalpy of O=O is high (493.4 kJ/mol).
Some reactions are :
2Ca  O2  2CaO

4Al  3O2  2Al2O3

P4  5O2  P4 O10

C  O2  CO2

2ZnS  3O2  2ZnO  2SO2

CH4  2O2  CO2  2H2O

V O
2 5
2SO2  O2   2SO3

CuCl
4HCl  O2 
2  2Cl
2  2 H2 O

Uses of O2 :
1. It is an important gas for normal respiration and combustion.
2. O2 is used in oxyacetylene welding.
3. For manufacturing of many metals and steel.
4. O2 cylinders are used in hospitals, high altitude flying and in mountaineering.
5. Combustion of fuels, e.g., hydrazines in liquid oxygen provides thrust in rockets.

SIMPLE OXIDES
Binary compound of oxygen with other elements. Oxides vary widely in nature and properties.
Simple oxides can be classified as :
(i) Acidic Oxide :
Non metal oxides are acidic but oxides of some metals in higher oxidation state also show acidic
character. They combine with water to give acid e.g.,

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SO2, Cl2O7, CO2, N2O5, Mn2O7 , CrO3 , V2O5

  
metal oxide

For example, SO2 combines with water to give sulphurous acid.

SO2  H2O  H2SO3
Sulphurous acid

(ii) Basic Oxide :

In general metallic oxides are basic. These oxides give base with water e.g.,
Na2O, CaO, BaO etc.
For example, CaO combines with water to given Ca(OH)2, a base.
CaO  H2O  Ca(OH)2

(iii) Amphoteric Oxide :

Some metallic oxides show dual behaviour of both acid as well as alkali e.g., Al2O3

Al2O3 (s)  6HCl (aq)  9H2O (l)  2[Al(H2O)6 ]3  (aq)  6Cl (aq)

Al2O3 (s)  6NaOH (aq)  3H2O (l)  2Na3 [Al(OH)6 ] (aq)

(iv) Neutral oxides :

They are neither acidic nor basic e.g., CO, NO, H2O and N2O
(v) Mixed oxides :
Oxides containing more than one cations with different oxidation states are called mixed oxides.
e.g., Pb3O4, MgAl2O4, Fe3O4 etc.

OZONE
It is allotropic form of oxygen. Being too reactive it cannot remain in atmosphere at sea level. At height of
20 km, it is formed from atmospheric oxygen in the presence of sunlight. Ozone layer prevents earth’s surface
from excessive exposure of UV radiations.

Preparation
On passing dry stream of O2 through silent electrical discharge, so as to prevent decomposition of O3.

3O 2  2O 3 ;  H298K  142 kJ / mol 

(10% formed)

The product is known as ozonized oxygen.

If concentration of O3 required is greater than 10%, a battery of ozonisers can be used and pure ozone can
be condensed.

Properties
 O3 is pale blue gas, dark blue liquid and violet black solid.
 It has characteristic smell and in small concentration it is harmless. But in concentration above 100 ppm
breathing becomes uncomfortable resulting in headache and nausea.

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 O3 is thermodynamically unstable with respect to oxygen, as its decomposition liberates heat. Its
conversion to O2 is favourable as G is negative. [H = –ve and S = + ve]
 Due to ease to release nascent oxygen O3 acts as strong oxidising agent, [O3  O2 + O].

e.g., PbS(s)  4O3 (g)  PbSO4 (s)  4O2 (g)

2I (aq)  H2O  O3 (g)  2OH (aq)  I2 (s)  O2 (g)

 Quantitative estimation of O3 :
On reaction of O3 with excess of KI buffered with borate buffer (pH 9.2), I2 is liberated which can be titrated
against standard sodium thiosulphate.
2KI(aq)  H2O(l)  O3 (g)  2KOH(aq)  I2 (s)  O2 (g)

 Nitrogen oxides (especially NO) emitted from exhaust systems of supersonic jet aeroplanes might slowly
deplete the concentration of O3 in upper atmosphere.
NO(g)  O3 (g)  NO2 (g)  O2 (g)

Use of freons (in aerosol sprays and as refrigerants) can also damage ozone layer.
Some more reactions of O3 :
O2

2RCHO O2
( i)

H2O2
R

(ii
)Z
–
C

n/
H

H
=

O
CH

Ag2O
–

Ag
R

3+
Fe Fe 2+
O3
Hg
O
I 2/H
2
P/H

S/H

Hg2O (Tailing)
HIO3
2

(Test of O3)
2
O
O

H2SO4
H3PO4

Structure
It has angular structure and two oxygen-oxygen bond length in ozone are identical (128 pm) and bond angle
117º.

O O or O
O O O O O O

Uses :

1. Used as germicide, disinfectant and for sterilising water.

2. Used for bleaching oils, ivory, flour, starch, etc.

3. As oxidising agent in manufacturing of KMnO4.

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ALLOTROPES OF SULPHUR
The various allotropes of sulphur are :

1. -sulphur) :
Rhombic sulphur (

It is yellow in colour, melting point 385.8 K and specific gravity 2.06. It is stable form of sulphur at room
temperature.

It is formed on evaporating the solution of roll sulphur in CS2. It is insoluble in water, readily soluble in
CS2 and dissolves to some extent in benzene, alcohol and ether.

2. -sulphur) :
Monoclinic sulphur (

Its melting point is 393 K and specific gravity 1.98.

 It is prepared by melting rhombic sulphur in a dish and cooling, till crust is formed. Two holes are
made in crust and remaining liquid is poured out. On removing crust, colourless needle-shaped
crystals of -sulphur is formed.
 Monoclinic suphur is stable above 369 K and below 369 K -sulphur is stable. At 369 K both forms
are stable and this temperature is called transition temperature.
Both rhombic and monoclinic suphurs have S8 molecules, these are packed to give different crystal
structure. S8 form is puckered and has crown shape.

S 20
4p
S S
m
107º
S S
S
S S
 Several other modifications containing 6–20 sulphur atoms per ring are synthesised. In cyclo-S6, the
ring adopts chair form.

205.7 pm
S S
102.2º
S S

 At elevated temperatures (1000 K), S2 is dominant species and is paramagnetic like O2.

SULPHUR DIOXIDE
Preparation
It is formed when sulphur is burnt.
S(s)  O2 (g)  SO2 (g)

In laboratory : SO32 (aq)  2H (aq)  H2O (l)  SO2 (g)

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Industrially : As by-product of roasting of sulphide ores.

4FeS2 (s)  11O2 (g)  2Fe2O3 (s)  8SO2 (g)

The gas after drying is liquefied under pressure and stored in steel cylinders.
Properties
 SO2 is colourless gas with pungent smell and is highly soluble in water. It liquefies at room temperature
under pressure of two atmosphere and boils at 263 K.
 SO2 when passed through water, forms sulphurous acid.
 H2SO3 (aq)
SO2 (g)  H2O(l) 

 It readily reacts with sodium hydroxide.

2NaOH  SO2  Na2SO3  H2O
Na2SO3  H2O  SO2  2NaHSO3

 It reacts with Cl2 in the presence of charcoal which acts as catalyst.

SO2 (g)  Cl2 (g)  SO2Cl2 (l)

(sulphuryl chloride)

 It is converted into SO3 by the action of O2 in the presence of V2O5.

V O
2SO2 (g)  O2 (g) 
2 5  2SO (g)
3

 Moist SO2 acts as reducing agent e.g.,

2Fe3  SO2  2H2O  2Fe2  SO24  4H

5SO2  2MnO4  2H2O  5SO24  4H  2Mn2

(pink colour) (colourless)

The above reaction is used as test for SO2.

Note :
Some more reactions of SO2 :

2+
Fe
SO2 acting as reducing agent
SO2Cl2

Fe3+
Cl2 SO3
O2

H2S SO2 Ca(

OH
)2
S + H2O
Mg Fe CaSO3 + H2O
(Milky)

MgS
FeS + FeO
+MgO

SO2 acting as oxidizing agent

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Structure of SO2
It is angular and is resonance hybrid of the following two canonical forms :

S S
O O O O

Uses of SO2 :
1. In refining petroleum and sugar.
2. In bleaching wool and silk.
3. As an anti-chlor, disinfectant and preservative.
4. In preperation of H2SO4, NaHSO3, CaHSO3.
5. Liquid SO2 used as solvent to dissolve organic and inorganic compounds.

OXOACIDS OF SULPHUR

Sulphur forms a number of oxoacids such as H2SO3, H2S2O3, H2S2O4, H2S2O5, H2SxO6 (x = 2 to 5),
H2SO4, H2S2O7, H2SO5, H2S2O8 . Some of these acids are unstable and cannot be isolated. They are known
in aqueous solution or in the form of their salts. Structures of some important oxoacids are shown.

O O O O
O

S S S S S
S
HO O O O O O
HO O O O O
HO OH OH HO
HO HO
Sulphurous acid Sulphuric acid Peroxodisulphuric acid Pyrosulphuric acid (Oleum)
(H2SO3) (H2SO4) (H2S2O8) (H2S2O7)

Fig. : Structure of some important oxoacids of sulphur

SULPHURIC ACID
One of the most important industrial chemicals.
Manufacturing : By Contact Process which involves three steps :
(i) Burning of sulphur or sulphide ores in air to generate SO2.
The SO2 is purified by removing impurities such as arsenic compound.

(ii) Conversion of SO2 to SO3 by reaction with oxygen in the presence of V2O5 (catalyst).

V O
2SO2 (g)  O2 (g) 2 5
  2SO3 (g) ; H = – 196.6 kJ/mol

Reaction is exothermic, reversible and forward reaction leads to decrease in volume. Therefore, low
temperature and high pressure are favourable conditions. In practice 720 K and 2 bar pressure is used.

(iii) Absorption of SO3 in H2SO4 to give oleum (H2S2O7)

SO3  H2SO4  H2S2O7

(oleum )

Finally dilution of oleum with water gives H2SO4 of desired concentration. H2SO4 obtained is 96–98% pure.

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Properties of Sulphuric Acid

Physical Properties:
(i) Concentrated sulphuric acid is a dense, oily liquid also known as oil of vitriol.
(ii) Concentrated sulphuric acid has a specific gravity of 1.84 and a boiling point of 611 K. The high
boiling point and high viscosity indicate that sulphuric acid has associated structure due to hydrogen
bonding as shown below:

HO O HO O
Hydrogen
S bond S

HO O HO O

(iii) The concentrated acid is soluble in water and the dissolution process is highly exothermic. So acid is
always diluted by adding acid to the water slowly and not by adding water to acid. This is done because
in the later case, lot of heat is produced which causes the acid to spurt out of the container.

Chemical Properties
1. Decomposition. Sulphuric acid is quite stable but on strong heating it dissociates as
H2SO4  SO3 + H2O
2. Acidic nature.
(i) It is a typical acid and it turns blue litmus red.
(ii) It ionises in water as
Water
H2SO4 H+ + HSO4–

HSO4– H+ + SO42–
(iii) It reacts with metals, oxides and carbonates etc. as:
Zn + H2SO4  ZnSO4 + H2
CaO + H2SO4 CaSO4 + H2O
2NaOH +H2SO4  Na2SO4 + H2O
Na2CO3 + H2SO4  Na2SO4 + H2O + CO2 
3. Dehydrating agent. Concentrated sulphuric acid is a good dehydrating agent as it has a great affinity
for water. Some of its properties which illustrate its strong affinity for water are:
(i) Charring of sugar

Conc.H2SO4
C12H22O11   12C  11H2O

(ii) Action with formic acid and oxalic acid

Conc. H SO
HCOOH   
2

4
 CO  H2O
Formic acid

COOH
Conc.H2SO4
CO + CO2 + H2O
COOH
Oxalic acid

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(iii) Dehydration of ethyl alcohol

CH2
Conc.H2SO4
C2H5OH + H 2O
443 K
CH2
4. Oxidising agent. Hot concentrated sulphuric acid is moderately strong oxidising agent. Its oxidizing
behaviour is intermediate between phosphoric and nitric acid. Both metals and non-metals are oxidised
by concentration sulphuric acid which is reduce to SO2.

H2SO 4  H2O  SO 2  [O]

Nascent oxygen

It oxidises a number of substances as :

(a) C + 2[O]  CO2

(b) 1/8 S8 + 2[O]  SO2

(c) 2HBr + [O]  H2O + Br2

(d) H2S + [O]  H2O + S

(e) Cu + [O] + H2SO4  CuSO4 + H2O

5. Action with metal salts. Sulphuric acid decomposes the salts like nitrates and chlorides to liberate
their acids on heating.

NaNO3 + H2SO4  NaHSO4 + HNO3

NaCl +H2SO4  NaHSO4 + HCl

6. Miscellaneous reactions

(i) The salts of barium, calcium, strontium and lead form precipitates with sulphuric acid.

BaCl2 + H2SO4  BaSO4  + 2HCl

White ppt

Pb(NO3)2 +H2SO4  PbSO4  + 2HNO3

White ppt

(ii) Aromatic compounds react with conc. H2SO4 to form sulphonic acids.

C6H6 + H2SO4  C6H5SO3H + H2O

Benzene Benzene

sulphonic acid

Uses of sulphuric acid

It is an important industrial chemical and is used in many industries. Its major uses are:
(i) For preparation of fertilizers like ammonium sulphate, super–phosphate of lime etc.
(ii) For the manufacture of rayon
(iii) In storage batteries and lead accumulators
(iv) As a dehydrating agent
(v) For pickling (cleaning of metal surfaces before electroplating)

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Example 35 : Which form of sulphur shows paramagnetic behaviour?

Solution : In vapour state, sulphur exists as S2, which has two unparied electron in * orbitals like O2, hence
paramagnetic.

Example 36 : What happens when

(i) Conc. H2SO4 is added to calcium fluoride.

(ii) SO3 is passed through water.

Solution : (i) CaF2  H2SO4  CaSO4  2HF

(ii) SO3  H2O  H2SO4

Example 37 : Give one example each of Acidic, Basic, Amphoteric and Neutral Oxides.
Solution : Acidic oxide  SO2
Basic oxide  MgO
Amphoteric oxide  Al2O3
Neutral oxide  CO

Example 38 : Draw structure of peroxodisulphuric acid.

O O

S S
Solution : H2S2O8 : O O
O O
OH OH

EXERCISE
31. The correct order of acidity of hydrides of oxygen family
(1) H2O > H2S > H2Se > H2Te
(2) H2O < H2S < H2Se < H2Te
(3) H2S > H2O > H2Se > H2Te
(4) H2S < H2O < H2Se < H2Te
32. S and O both are non-metals in the oxygen family, but their melting points are largely different,
O = 90 K and S = 718 K. This is because
(1) S is larger in size than O
(2) S exhibits more oxidation state + 2, + 4 and + 6 whereas O exhibits only – 2 and + 2 oxidation states
(3) O exists as diatomic molecule whereas S exists as polyatomic molecule (S8)
(4) S has more allotropes than O

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33. Which of the following is not a reducing oxide?

(1) SO2 (2) SeO2
(3) TeO (4) SO3
34. Which of the following compounds does not exist?
(1) SF6 (2) S2Cl2
(3) SCl2 (4) SeBr2
35. O3 molecule is a resonance hybrid of the two structures I and II.

O O

O O O O
I II

The two oxygen-oxygen bond lengths in ozone molecule are

(1) Identical
(2) Slightly different
(3) Largely different
(4) Cannot be measured due to resonance
36. S8 ring of both rhombic sulphur and monoclinic sulphur has crown shaped structure. The S – S – S bond angle
in S8 ring is
(1) 109°28 (2) 107°
(3) 104° (4) 120°
37. In the contact process of manufacturing of H2SO4, the catalyst used is
(1) P2O5 (2) V2O5
(3) Rh (4) NO
38. Number of S = O bonds in pyrosulphuric acid are
(1) Two (2) Four
(3) Five (4) Six
39. H2SO4 in aqueous medium ionises in two steps.

H2SO4 (aq) + H2O (l)  H3O+ (aq) + HSO4– (aq), K a1  x

HSO4– (aq) + H2O (l)  H3O+ (aq) + SO42–, K a2  y

What is relation between x and y?

(1) x < y (2) x  y
(3) x > y (4) x >> y
40. What is the product when Mg react with SO2?
(1) MgO (2) MgSO4
(3) MgS (4) Both (1) & (3)

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GROUP 17 ELEMENTS : HALOGEN FAMILY
General electronic configuration : [inert gas] ns2np5.
Fluorine (9F); Chlorine (17Cl); Bromine (35Br); Iodine (53I)
Astatine (85At)  Radioactive element.
Collectively known as halogens (Greek halo means salt and genes means born i.e., salt producers). They
are highly reactive non-metallic elements. Great similarity among Group 17 elements observed.
Occurrence
Fluorine : Mainly as insoluble fluorides.
Fluorspar – CaF2, Cryolite – Na3AlF6, Fluoroapatite – 3Ca3(PO4)2CaF2.
Small quantities are also present in soil, river water plants, bones and teeth of animals.
 Sea water contains chlorides, bromides and iodides of Na, K, Mg, Ca, but mainly NaCl (2.5% by mass).
Deposits of dried up seas contain NaCl and carnallite ( KClMgCl26H2O).
 Certain forms of marine life contain iodine in their system, various seaweeds contain 0.5% iodine, chile
saltpetre contains up to : 0.2% sodium iodate.
Table : Atomic and Physical Properties of Halogens

a
Property F Cl Br I At

Atomic number 9 17 35 53 85
–1
Atomic mass / g mol 19.00 35.45 79.90 126.90 210
Electronic
configuration
Covalent radius / pm
–
Ionic radius X / pm
Ionisation enthalpy
–1
/ kJ mol
Electron gain
–1
enthalpy / kJ mol
b
Electronegativity
– –1
HydH(X ) / kJ mol

Melting point / K
Boiling point / K
–3
Density / g cm
Distance X – X / pm
Bond dissociation
–1
enthalpy / (kJ mol )
e
E /V

aRadioactive; b Pauling scale; c For the liquid at temperatures (K) given in the parentheses; d solid; e The
half-cell reaction is x2(g) + 2e–  2X–(aq).

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Physical Properties
All halogens are coloured.
Fluorine (F2)  Yellow gas
Chlorine (Cl2)  Greenish yellow gas
Bromine (Br2)  Reddish liquid
Iodine (I2)  Violet colour solid
The colour is due to absorption of different quanta of radiation in visible region which results in excitation of
outer electrons to higher energy level, thus different colours are observed.
 With increase in atomic number boiling and melting point steadily increase.
 Bromine and iondine are sparingly souble in water but soluble in solvents like CHCl3, CCl4, CS2,
hydrocarbons to give coloured solutions.
 Anomaly is observed among bond dissociation enthalpy. From Cl2 to I2 it decreases as expected. But
bond dissociation enthalpy of F2 is less than that of Cl2, as large electron-electron repulsion among lone
pairs in F2 where they are close to each other in comparison to Cl2.
Bond dissociation enthalpy : Cl2 > Br2 > F2 > I2.

Chemical Properties
Anomalous behaviour of fluorine :
Due to its small size, high electronegativity, low F–F bond dissociation enthalpy, non-availability of vacant
d orbital and higher value of electrode potential. Fluorine shows some difference in properties from the rest of
the members of the group. Also ionic and covalent radii, melting and boiling point and electron gain enthalpy
are lower than expected.
 Most reactions of fluorine are exothermic due to small and strong bonds formed by it.
 It forms only one oxoacid, while other halogens form number of oxoacids.
 HF is a liquid below 293 K due to strong hydrogen bonding, other hydrogen halides are gases at room
temperature.
Oxidation State :
All the halogens exhibit –1 oxidation state. However, chlorine, bromine and iodine exhibit +1, +3, +5 and +7
oxidation states also, as explained below :
Halogen atom in ns np nd
ground state 1 unpaired electron accounts
(other than fluorine)
for –1 or +1 oxidation states
3 unpaired electron account
First excited state for +3 oxidation states
5 unpaired electron account
Second excited state for +5 oxidation states
7 unpaired electron account
Third excited state
for +7 oxidation states

Fluorine :
Being the most electronegative element, it shows oxidation state of –1 only. As fluorine does not have any
d orbitals in valence shell, hence cannot expand its octet.

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Higher oxidation state of chlorine, bromine and iodine are realised when these halogens form compounds
with small and high electronegative elements like fluorine and oxygen atoms, e.g., interhalogens, oxides and
oxoacids. Oxidation state of +4 and +6 occur in oxides and oxoacids of chlorine and bromine.
Chemical Reactivity :
All halogens are highly reactive. They react with metals and non-metals to form halides. Reactivity of halogen
decreases down the group.
Halogens show strong oxidising nature. F2 is the strongest oxidising halogen and it oxidises other halide ions
in solution and even in solid phase.

F2  2X  2F  X2 ; (X  Cl, Br or I)

Cl2  2X  2Cl  X2 ; (X  Br or I)

Br2  2I  2Br   I2

Decreasing oxidising ability of halogens in aqueous solution down the group is evident from standard electrode
potentials, which is dependent on the parameters indicated below:

o
1 1 Ho  egHo Hhyd
X2 (g) 
2 diss  X(g)   X (g)   X (aq)
2

 The relative oxidising power of halogens illustrated by reactions with water.

F2 oxidises water to oxygen whereas Cl2 and Br2 react with water to form hydrohalic acid and hypohalous
acids.

2F2 (g)  2H2O (l)  4H (aq)  4F (aq)  O2 (g)

X2 (g)  H2O (l)  HX (aq)  HOX (aq); (X = Cl or Br)

The reaction of iodine with water is nonspontaneous. I– can be oxidised by oxygen in acidic medium.
Which is just reverse of the case of fluorine.

4I (aq)  4H (aq)  O2 (g)  2I2 (s)  2H2O (l)

Reactivity towards Hydrogen :

They react with hydrogen to give hydrogen halide. Affinity for hydrogen decreases from fluorine to iodine. They
dissolve in water to form hydrohalic acids.
HF HCl HBr HI

increases
Acidic strength  

increases
Reducing power  

decreases
Bond dissociation enthalpy 
decreases
Stability 

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Table : Properties of Hydrogen Halides

Property HF HCl HBr HI

Melting point / K 190 159 185 222
Boiling point / K 293 189 206 238
Bond length (H – X) / pm 91.7 127.4 141.4 160.9
–1
diss HΘ / kJ mol 574 432 363 295
pKa 3.2 –7.0 –9.5 –10.0

Reactivity towards Oxygen :

 Fluorine forms two oxides OF2 and O2F2. Only OF2 is thermally stable at 298 K. They are actually oxygen
fluorides, as fluorine is more electronegative than oxygen. Both OF2 and O2F2 are strong fluorinating
agents. O2F2 oxidises plutonium to PuF6 and used in removing plutonium from spent nuclear fuel.

 Chlorine, bromine and iodine form oxides in which halogen shows oxidation state from +1 to +7,
combination of kinetic and thermodynamic factors lead to decrease stability of oxides by halogens,
I > Cl > Br. Higher oxides are more stable than lower ones.
 Chlorine oxides Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive oxidising agents and tend to explode.
ClO2 is used as bleaching agent for paper pulp, textiles and in water treatment.

 Bromine oxides (Br2O, BrO2, BrO3) are least stable halogen oxides and exist only at low temperature.
They are powerful oxidising agents.

 Iodine oxides (I2O4, I2O5, I2O7) are insoluble solids and decompse on heating. I2O5 is strong oxidising
agent and used in estimation of CO.
Reactivity towards Metals :

Halogens form metal halides on reaction with metals e.g.,

Mg(s)  Br2 (l)  MgBr2 (s)

The ionic character of halides decrease in order

MF > MCl > MBr > MI (M = Monovalent metal)

 The metal in higher oxidation state will be more covalent than the one in lower oxidation state e.g., SnCl4,
PbCl4, SbCl5 and UF6 are more covalent then SnCl2, PbCl2, SbCl3 and UF4 respectively.

Example 39 : Why do halogens have maximum negative electron gain enthalpy in the respective periods of the
periodic table?
Solution : Halogens have the smallest size and high effective nuclear charge in their respective periods. Thus
they readily accept one electron to have noble gas configuration.

Example 40 : Although egH of fluorine is less negative than that of chlorine, but fluorine is a stronger oxidising
agent than chlorine, why?
Solution : This is due to
(i) Low bond dissociation enthalpy of F–F bond.
(ii) High hydration enthalpy of F–.

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Example 41 : Fluorine exhibits only –1 oxidation state whereas other halogens show +1, +3, +5 and +7 oxidation
states also. Explain.
Solution : Fluorine being the most electronegative element cannot have positive oxidation state. Other halogens
have d orbitals, therefore can expand their octet.

Example 42 : Give correct order of boiling point of hydride of group 17.

Solution : HCl < HBr < HI < HF

CHLORINE

Preparation
(i) By heating manganese dioxide with conc. HCl.

MnO2  4HCl  MnCl2  Cl2  2H2O

Also, 4NaCl  MnO2  4H2SO4  MnCl2  4NaHSO4  2H2O  Cl2

(ii) By the action of HCl on KMnO4.

2KMnO4  16HCl  2KCl  2MnCl2  8H2O  5Cl2

Manufacturing of chlorine
(i) Deacon’s process :
By oxidation of HCl (g) by atomspheric oxygen in presence of CuCl2 (catalyst) at 723 K.

CuCl
4HCl  O2 
2  2Cl
2  2H2 O
723 K

(ii) Electrolytic process :

Chlorine is obtained by electrolysis of brine (conc. NaCl solution) where Cl2 is liberated at anode. Also
as by-product in chemical industries.
Properties
 It is greenish yellow gas with pungent and suffocating odour. It is 2–5 times heavier than air. It can be
liquefied easily into greenish yellow liquid which boils at 239 K. It is soluble in water.
 It reacts with number of metals and non-metals to form chlorides.
2Al  3Cl2  2AlCl3 ; P4  6Cl2  4PCl3

2Na  Cl2  2NaCl ; S8  4Cl2  4S2Cl2

2Fe  3Cl2  2FeCl3 ;

 It has great affinity for hydrogen.

H2  Cl2  2HCl

H2S  Cl2  2HCl  S

C10H16  8Cl2  16HCl  10C

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 On reaction with NH3.

8NH3  3Cl2  6NH4 Cl  N2

(excess)

NH3  3Cl2  NCl3  3HCl

(excess) (explosive)

 On reaction with alkali they form mixture of chloride and hypochlorite or chlorate.

2NaOH + Cl2  NaCl  NaOCl + H2O

(cold & dilute) (Sodium hypochlorite)

6NaOH + 3Cl2  5NaCl  NaClO3 + 3H2O

(hot & conc.) (Sodium chlorate)

 With dry slaked lime it gives bleaching powder.

2Ca(OH)2  2Cl2  Ca(OCl)2  CaCl2  2H2O

Composition of bleaching powder is Ca(OCl)2CaCl2Ca(OH)22H2O

 Chlorine gives substitution products with saturated hydrocarbons and addition products with unsaturated
hydrocarbons e.g.,
UV
CH4  Cl2 
 CH3 Cl  HCl

Room temp.
C2H4  Cl2 
 C2H4 Cl2
 Chlorine water on standing loses its yellow colour due to formation of HCl and HOCl. HOCl so formed,
gives nascent oxygen, responsible for oxidising and bleaching properties of chlorine.
(i) Oxidising action :
2FeSO4  H2SO4  Cl2  Fe2 (SO4 )3  2HCl

Na2SO3  Cl2  H2O  Na2SO4  2HCl

SO2  2H2O  Cl2  H2SO4  2HCl

I2  6H2O  5Cl2  2HIO3  10HCl

(ii) Bleaching action :

Cl2  H2O  2HCl  [O]

Coloured substance + [O]  Colourless substance.

Its bleaching action is permanent and is due to oxidation. It bleaches vegetable or organic matter
in presence of moisture.
Uses :
1. For bleaching woodpulp used in manufacturing paper and rayon.
2. In the extraction of gold and platinum.
3. Manufacturing dyes, drugs and organic compounds such as CCl4, CHCl3, DDT, refrigerants, etc.
4. In sterilising drinking water.
5. Preparation of poisonous gases such as phosgene (COCl2), tear gas (CCl 3NO 2), mustard gas
(ClCH2CH2SCH2CH2Cl).

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HYDROGEN CHLORIDE
Preparation
In laboratory : By heating NaCl with conc. H2SO4.

420 K
NaCl  H2SO 4 
 NaHSO4  HCl

823 K
NaHSO 4  NaCl 
 Na2SO 4  HCl

HCl gas dried by passing through conc. H2SO4.

Properties
Colourless and pungent smelling gas. It is easily liquefied to colourless liquid (b.p. 189 K) and freezes to white
crystalline solid (f.p. 159 K)

 It is extremely soluble in water and ionises as :

HCl (g)  H2O (l)  H3 O (aq)  Cl (aq); K a  107

Its aqueous solution called as hydrochloric acid. High value of Ka shows it is strong acid in water.

NH3  HCl  NH4 Cl

white fumes

 When three parts of conc. HCl and one part of conc. HNO3 are mixed, aqua regia is formed, which is
used for dissolving noble metals e.g., gold, platinum.

Au  4H  NO3  4Cl  AuCl4  NO  2H2O

3Pt  16H  4NO3  18Cl  3PtCl62  4NO  8H2O

 HCl decomposes salts of weaker acids, e.g., carbonates, bicarbonates, sulphites, etc.
Na2CO3  2HCl  2NaCl  H2O  CO2

NaHCO3  HCl  NaCl  H2O  CO2

Na2SO3  2HCl  2NaCl  H2O  SO2

Uses :

1. In manufacturing chlorine, NH4Cl and glucose from corn starch.

2. For extracting glue from bones and purifying bone black.

3. In medicines and as a laboratory reagent.

OXOACIDS OF HALOGENS

Due to high electronegativity and small size, fluorine forms only one oxoacid, HOF known as Fluoric (I) acid
or hypofluorous acid. Other halogens form number of oxoacids, most of them cannot be isolated in pure state.
They are stable only in aqueous solution or in form of their salts.

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Oxoacids of Halogens

Decreasing acidic strength

Halic (I) acid HOF HOCl HOBr HOI

Increasing acidic strength

(Hypohalous acid) (Hypofluorous acid) (Hypochlorous acid) (Hypobromous acid) (Hypoiodous acid)

Halic (III) acid – HOCIO – –

(Halous acid) (chlorous acid) – –

Halic (V) acid – HOCIO2 HOBrO2 HOIO2

(Halic acid) – (chloric acid) (bromic acid) (iodic acid)

Halic (VII) acid – HOCIO3 HOBrO3 HOIO3

(Perhalic acid) – (perchloric acid) (perbromic acid) (periodic acid)

O
H H
H Cl

Hypochlorous acid O O

Cl Cl
O O O
O O
H Cl O O

Chlorous acid Chloric acid Perchloric acid

Fig. : The structures of oxoacids of chlorine

INTERHALOGEN COMPOUNDS

When two different halogens react with each other, interhalogen compounds are formed. They can have general
composition as XX , XX  , XX  and XX
3 5 7

where X = larger size halogen and less electronegative.

X = Small size halogen and more electronegative.

As the ratio between radii of X and X increases, the number of atoms per molecule also increases. Iodine(VII)
fluoride should have maximum number of atoms as ratio of radii between I and F should be maximum, so its
formula is IF7.

Preparation

The interhalogen compounds can be prepared by the direct combination or by the action of halogen on lower
interhalogen compounds. The product formed depends upon some specific conditions, e.g.,

437 K
Cl2 + F2 
 2ClF; l2 + 3Cl2  2ICl3 ;
(equal volume) (excess)

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573 K
Cl2 + 3F2 
 2ClF3 ; Br2  3F2  2BrF3
(excess) (diluted with water)

l2 + Cl2  2ICl; Br2  5F2  2BrF5

(equimolar) (excess)

Properties
Some properties of interhalogen compounds are given in
Some Properties of Interhalogen Compounds

Type Formula Physical state and colour Structure

XX1 ClF Colourless gas –

BrF Pale brown gas –

a Detected spectroscopically gas –
IF
b Gas –
BrCl
Ruby red solids (-form) –
ICl
Brown red solid (-form) –
IBr Black solid –

XX3 ClF3 Colourless gas Bent T-shaped

BrF3 Yellow green liquid Bent T-shaped

IF3 Yellow powder Bent T-shaped

c
ICl3 Orange solid Bent T-shaped
XX5 IF5 Colourless gas but solid below 77 K Square pyramidal

BrF5 Colourless liquid Square pyramidal

ClF5 Colourless liquid Square pyramidal

Pentagonal
XX7 IF7 Colourless gas
bipyramidal
a Very unstable; b The pure solid is known at room temperature; c Dimerises as
Cl-bridged dimer (I2Cl6)

 These are all covalent molecules and are diamagnetic in nature. Their physical properties are in between
that of constituent halogens, except that their melting and boiling point are little higher than expected.

 In general interhalogen compound are more reactive than halogens, except fluorine. As X – X bond in
interhalogen is weaker than X–X bond in halogens except F–F bond.

 All these undergo hydrolysis giving halide ion derived from smaller halogen and hypohalite (when XX),
halite (when XX3 ), halate ( XX5 ) and perhalate ( XX7 ).

XX  H2O  HX  HOX

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Uses :

These compounds can be used as

(i) Non-aqueous solvents.

(ii) Fluorinating agents.

(iii) ClF3 and BrF3 are used for the production of UF6 in enrichment of U235.

U (s)  3ClF3 (l)  UF6 (g)  3ClF (g)

Note :

Pseudohalide ions and Pseudohalogens.

Ions which consist of two or more atoms of which at least one is nitrogen and have properties similar to
those of halide ions are called pseudohalide ions. Some of these pseudohalide ions can be oxidized to
form covalent dimers comparable to halogens (X2).
Such covalent dimers of pseudohalide ions are called pseudohalogens. Some important pseudohalide ions
and pseudohalogens are given below :
Pseudohalide ions Pseudohalogen

CN –, cyanide ion (CN)2, cyanogen

OCN –, cyanate ion (SCN)2, thiocyanogen

SCN –, thiocyanate ion (SeCN)2, selenocyanogen

SeCN – selenocyanate ion ----

NCN2-, cyanamide ion ----

N3–, azide ion ----

OCN–, fulminate ion ----

Example 43 : Write balanced equation for reaction of Cl 2 with hot and conc. NaOH. Is this reaction a
disproportionation one? Justify.

Solution : 3Cl2  6NaOH  5NaCl  NaClO3  3H2O

As ‘Cl’ changes from zero to –1 and +5. Hence it is disproportionation.

Example 44 : Give two uses of Cl2.

Solution : (i) In manufacturing CCl4, DDT, CHCl3 etc.
(ii) Sterilising drinking water.

Example 45 : When HCl reacts with finely powdered iron, it forms ferrous chloride and not ferric chloride, why?

Solution : Fe  2HCl  FeCl2  H2

Liberation of H2 prevents the formation of FeCl3.

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NEET The p-Block Elements 167

Example 46 : Deduce the molecular shape of BrF3 on the basis of VSEPR theory.
Solution : The two lone pairs occupy corners of a trigonal
bipyramid (equatorial positions).
F
So its shape would be slightly bent (T).

Br F

EXERCISE

41. Electron affinity of halogens follows the order

(1) F < Cl < Br < I
(2) F > Cl > Br > I
(3) Cl > F > Br > I
(4) Cl > Br > I > F
42. The oxidation states shown by halogen are – 1, + 1, + 3, + 5 and + 7. The oxidation state(s) shown by all
the halogens is
(1) – 1 and + 3 (2) – 1, + 1 and + 3
(3) Only – 1 (4) Only + 3
43. When F2 gas reacts with H2O, it forms
(1) O2 gas (2) O2F2 gas
(3) HOF (4) Both (2) & (3)
44. F2 combines with O2 to form OF2 and O2F2 which are
(1) Oxygen fluorides (2) Oxides of fluorine
(3) Anhydride of HOF (4) Both (2) & (3)
45. The order of acidity of oxides of chlorine
Cl2O Cl2O3 Cl2O5 Cl2O7
I II III IV
is
(1) I < II < III < IV (2) I > II > III > IV
(3) I > III > II > IV (4) IV > I > II > III
46. Deacon’s process is used for the manufacture of
(1) HNO3 (2) I2
(3) Cl2 (4) Br2

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168 The p-Block Elements NEET

47. Aqua regia, which is used for dissolving noble metals like gold and platinum etc. is
(1) 1 : 3 mixture of conc. HCl and conc. HNO3
(2) 3 : 1 mixture of conc. HCl and conc. HNO3
(3) 1 : 1 mixture of conc. HCl and conc. HNO3
(4) 3 : 1 mixture of dil. HCl and conc. HNO3
48. Halogens react with oxygen to form many oxoacids, commonly named as hypohalous acid, halous acid, halic
acid and perhalic acid. The halogen(s) which form(s) halous acid is/are
(1) F2
(2) Cl2
(3) Cl2, Br2 and I2
(4) F2, Cl2 and Br2
49. The number of peroxide linkages in perchloric acid is
(1) Zero
(2) One
(3) Two
(4) Four
50. Which is the correct order of bond length?
(1) F2 < Cl2 < Br2 < I2
(2) Cl2 < F2 < Br2 < I2
(3) I2 < Br2 < F2 < Cl2
(4) Br2 < I2 < F2 < Cl2

GROUP 18 ELEMENTS : NOBLE GASES

General electronic configuration : [inert gas] ns2np6
(Except He : 1s2)
Helium (2He) ; Neon (10Ne); Argon (18Ar); Krypton (36Kr); Xenon (54Xe); Radon (86Rn)
All these are gases and chemically unreactive.
As they form very few compounds hence termed as noble gas.
Occurrence
 All noble gas except radon occur in atmosphere. This abundance in dry air is  1% by volume of which
argon is main constituent.
 He and Ne are sometimes found in minerals of radioactive origin e.g., pitchblende, monazite, cleveite.
 Main commerical source of He is natural gas.
 Xenon and radon are rarest elements of the group.
 Radon obtained as radioactive decay product of Ra226.
226  Rn222 4
Ra88 86
 2
He

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NEET The p-Block Elements 169

Table : Atomic and Physical Properties of Group 18 Elements

Property He Ne Ar Kr Xe Rn*
Atomic number 2 10 18 36 54 86
Atomic mass/ g 4.00 20.18 39.95 83.80 131.30 222.00
–1
mol
2 2 6 2 6 10 2 6 10 2 14 10
Electronic 1s [He]2s 2p [Ne] 3s 3p [Ar]3d 4s 4p [Kr]4d 5s [Xe]4f 5d
6 2 6
configuration 5p 6s 6p
Atomic radius / pm 120 160 190 200 220 –
Ionisation enthalpy 2372 2080 1520 1351 1170 1037
–1
/ kJ mol
Electron gain 48 116 96 96 77 68
–1
enthalpy / kJ mol
–4 –4 –3 –3 –3 –3
Density (at STP) / 1.8 × 10 9.0 × 10 1.8 × 10 3.7 × 10 5.9 × 10 9.7 × 10
–3
gcm
Melting point / K – 24.6 83.8 115.9 161.3 202
Boiling point / K 4.2 27.1 87.2 119.7 165.0 211
–4 –3 –4 –6
Atmospheric 5.24 × 10 1.5 × 10 0.934 1.14 × 10 8.7 × 10 –
content (% by
volume)

* Radioactive

Physical Properties
 They are monoatomic, colourless, odourless and tasteless.
 Sparingly soluble in water
 Very low melting and boiling points as weak dispersion forces present.
 Helium has lowest boiling point (4.2 K) of any known substance. It has unusual property of diffusing
through commonly used laboratory materials like rubber, glass or plastics.

Chemical Properties
Noble gases are least reactive. Their chemical inertness is due to
(i) Completely filled valence shell.
(ii) High ionization enthalpy and more positive electron gain enthalpy.

In 1962, Neil Bartlett prepared a red compound O2 PtF6 and realised that the ionization enthalpy of molecular
oxygen (1175 kJ/mol) is identical with xenon (1170 kJ/mol) and he became successful in preparing similar red
colour compound of xenon by mixing Xe with PtF6 i.e., XePtF6 .
Thus number of compounds of Xe, especially with electronegative elements like F and O have been synthesised.
Compounds of krypton are fewer. Only KrF2 has been studied. Compounds of radon have not been isolated
but only identified (e.g., RnF2) by radiotracer technique. No true compound of Ar, He and Ne are yet known.
(a) Xenon-fluorine compounds :
Three binary fluorides of Xe is XeF2, XeF4, XeF6 prepared.

673 K, 1 bar
Xe(g)  F2 (g) 
 XeF2 (s)
(Excess)

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170 The p-Block Elements NEET

873 K, 7 bar
Xe(g)  2F2 (g) 
 XeF4 (s)
(1 : 5 ratio)

573 K, 60-70 bar

Xe(g)  3F2 (g) 
 XeF6 (s)
(1 : 20 ratio)

XeF6 is also prepared by :

143 K
XeF4  O2F2 
 XeF6  O2

 XeF2, XeF4 and XeF6 are colourless crystalline solids and sublime readily at 298 K. They are powerful
fluorinating agents. Readily hydrolysed by traces of water.

2XeF2 (s)  2H2O(l)  2Xe(g)  4HF(aq)  O2 (g)

 Xenon fluorides react with fluoride ion acceptors to form cationic species and fluoride ion donors to
forms fluoroanions

XeF2  PF5  [XeF] [PF6 ]

XeF4  SbF5  [XeF3 ] [SbF6 ]

XeF6  MF  M [XeF7 ] ; (M = Na, K, Rb or Cs)

(b) Xenon-Oxygen Compounds :

Hydrolysis of XeF4 and XeF6 with water gives XeO3.

6XeF4  12H2O  4Xe  2XeO3  24HF  3O2

XeF6  3H2O  XeO3  6HF

Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2.

XeF6  H2O  XeOF4  2HF

XeF6  2H2O  XeO2F2  4HF

XeO3 is a colourless explosive solid and has a pyramidal molecular structure. XeOF4 is a colourless
volatile liquid and has a square pyramidal molecular structure.

F F
F
F
Xe F F
Xe Xe

F F F
F
F F

(a) Linear (b) Square planar (c) Distorted octahedral

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NEET The p-Block Elements 171

O
F
F
Xe
Xe
O O
F F
O

(d) Square pyramidal (e) Pyramidal

Fig. : The structures of (a) XeF2 (b) XeF4 (c) XeF6 (d) XeOF4 and (e) XeO3

Uses of Noble Gases

Helium :
It is non-inflammable and light gas. Hence used in
(i) Filling balloons for meterological observations.
(ii) Also used in gas-cooled nuclear reactors.
(iii) Liquid helium (b.p. 4.2 K) used as cryogenic agent for carrying experiments at low temperatures.
(iv) It is used to produce and sustain powerful superconducting magnets which form part of NMR
spectrometers and MRI (Magnetic Resonance Imaging) systems for clinical diagnosis.
(v) Used as diluent for oxygen in modern diving apparatus as it has low solubility in blood.
Neon :
Used in discharge tube and fluorescent bulbs for advertising display purpose. Neon bulbs are used in botanical
gardens and in greenhouses.
Argon :
(i) Used to provide inert atmosphere in high temperature metallurgical processes (arc welding of metals or
alloys) and for filling electric bulbs.
(ii) Used in laboratory for handling air-sensitive substances.
No significant uses of Xenon and Krypton. They are used in light bulbs designed for special purposes.

Example 47 : Why elements of Group 18 known as noble gases?

Solution : Elements of Group 18 have valence shell orbitals completely filled and therefore react with few
elements only under certain conditions.

Example 48 : Noble gases have low boiling points, why?

Solution : Noble gases being monoatomic have weak dispersion forces and therefore liquefied at very low
temperature.

Example 49 : Does the hydrolysis of XeF6 lead to redox reaction?

Solution : No, the products of hydrolysis are XeOF4 and XeO2F2, where the oxidation state of all the elements
remains same as it was in the reacting state.

Example 50 : Give equation for preparation of Radon from Radium.

226  -decay 222 4

Solution : 88
Ra 
 86
Rn  2
He

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172 The p-Block Elements NEET

Note :

1. Inert pair effect : Reluctance of s-subshell to participate in bond formation. Thus down the group
stability of lower oxidation state increases and that of higher oxidation state decreases.

2. Catenation : Tendency of self linkage of element. It depends on element-element bond strength.

3. Acetylide : Ionic carbide which yield actylene on hydrolysis.

4. Methanide : Ionic carbide which yield methane on hydrolysis.

5. Allylide : These carbide evolve allylene on hydrolysis .

6. CO2 is gas whereas, SiO2 (Silica) has three dimensional structure which makes it solid.
7. The P4 units of white phosphorus are held together by weak van der Waal forces of attraction. As a result,
its ignition temperature (303 K) is very low and easily catches fire in air. It is, therefore, kept under water.
8. P4S3 is used in safety matches or strike anywhere matches. The head of a safety match stick
contains KClO3, KNO3 or Pb3O4 alongwith Sb2S3 and ground glass pieces while the sides of a match
box contain red P and sand powder.
9. Sulphur exists in three allotropic forms i.e., rhombic, monoclinic and plastic sulphur. Rhombic sulphur
is the most stable form of sulphur.
10. Both rhombic and monoclinic sulphur are soluble in CS2 but plastic sulphur is insoluble.
11. Sulphuric acid or oil of vitriol is manufactured either by lead chamber or contact process. Lead
chamber process gives H2SO4 of 80% strength while contact process gives H2SO4 of 100% purity.
12. Like SO2, Cl2 also bleaches vegetable colouring matter in the presence of moisture. The bleaching action
of Cl2 is due to oxidation and hence is permanent while that of SO2 is due to reduction and
hence is temporary.
13. The noble gases occupy about 1% by volume of the atmosphere. However, argon is the most abundant
of all the noble gases in the atmosphere.
14. Water containing dissolved air dissolve lead, forming water soluble lead hydroxide. This solvent effect
of water is known as plumbo solvency. Litharge or massicot is PbO, red lead is Pb3O4 or PbO2.
2PbO (double oxide). Lead is soluble in acetic acid. Pb (CH3COO)2 is called sugar of lead. Basic
lead carbonate is known as white lead.
15. Phosphorus is the tenth element in order of abundance in the earth’s crust and occurs to the
extent of 1120 ppm. All the known minerals of phosphorus are orthophosphate.
16. The metaphosphoric acid (HPO3) can be obtained by heating ammonium phosphate. It can also be obtained
by heating microcosmic salt, NaNH4. HPO4. It is known as glacial phosphoric acid. It is a monobasic
acid.
17. PCl5 is molecular in the gas phase and ionic in the solid phase, [PCl4]+ [PCl6]–. PBr5 is also ionic in
solid state but exists as [PBr4]+ [Br]–.
18. In general, in the oxidation of SO2, SeO2, TeO2 etc to their higher oxides, all the three O atoms of O3
are used up. Ozone is known as dry bleach as it bleaches in the absence of moisture.
19. Gun powder is a mixture of sulphur, charcoal and KNO3.
20. The colour of halogens is because of absorption of visible light, as a result, valence electrons are excited
from the higher energy occupied * molecular orbital to the lowest energy un-occupied * molecular orbital.
21. Both ClO– and HOCl are good oxidising agents. Sodium hypochlorite solutions are used as laundry bleach.
Clorox is a 5.25% solution of NaOCl in water.

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NEET The p-Block Elements 173

22. Tincture of iodine contains I2 + KI + rectified spirit.

23. Oxides of chlorine are Cl2O, ClO2, ClO3 (Cl2O6) and Cl2O7. Among halogens, maximum number of oxides
are formed by chlorine. Cl2O7 is the most stable and Cl2O is the least stable oxide of chlorine. The only
exothermic oxide is Cl2O7. ClO2 and ClO3 are paramagnetic oxides, while ClO3 is paramagnetic but Cl2O6
is diamagnetic. The order of stability follows the order Cl2O < ClO2 < Cl2O6 < Cl2O7. The oxidising power
of oxides follows the order Cl2O > ClO2 > Cl2O6 > Cl2O7.
24. Reasons for the difference in the bond angles of H2O, H2Se, H2S and H2Te. Though oxygen, sulphur,
tellurium etc. belong to the same group viz group 16, yet their bond angles decrease as follows:
H2O H2S H2Se H2Te
104.5º 92.1º 91º 90º
This can be explained as follows :

The outer shell electronic configuration of O, S, Se and Te is ns2 np4 or ns2 npx2 np1y np1z .

They undergo sp3 hybridisation forming four hybrid orbitals, two of which are occupied by lone pairs of
electrons. The expected bond angle is, therefore, 109.5º. But the lone pairs repel bond pairs thereby
decreasing the angle.
Due to smaller size and high electronegativity of O-atom, the bond pairs are closer and hence the
repulsions between them are larger. As a result, the repulsions by the lone pairs on the bond pairs
decrease the angle to only 104.5º. (from 109.5º). As we move from oxygen to tellurium, the size of the
atom increases and electronegativity decreases. As a result, the bond pairs move away from the central
atom. Hence the repulsions between the bond pairs decrease and the repulsion by the lone pairs on the
bond pairs increase so that the bond angle decreases much more (i.e. to nearly 90º from 104.5º)
25. Photosensitive elements : Selenium exists in two crystalline allotropic forms viz grey (metallic) and
red (non-metallic). Tellurium exists only in one stable form which is grey. Grey form of selenium and
tellurium consist of parallel chains held by weak metallic bonds. In the presence of light, the weak metallic
bonds are excited and as a result, the number of free electrons increases and so does the conductivity.
That is why Se and Te are called photosensitive metals.
26. Brief Review of discovery of noble gases.
(i) Discovery of argon (by Henry Cavendish in 1785). This was the first noble gas to be discovered.
Electric spark was passed through air mixed with excess of oxygen. Nitrogen was completely
converted into NO2 which was absorbed in NaOH solution and the excess oxygen present was
absorbed by passing through potassium pentasulphide solution (K2S5). The residual gas left was
named as argon (the lazy one).
(ii) Discovery of helium (by Janssen and Lockyer in 1868 in sun’s atmosphere spectroscopically and
by Ramsay in 1885 on the earth by heating the uranium mineral Cleveite). The name helium comes
from the Greek word helius which means sun.
(iii) Discovery of neon, krypton and xenon (by Ramsay and Travers by fractional distillation of liquid air).
(iv) Discovery of radon (by Dorn in 1900) by disintegration of radium.

ˆ ˆ ˆ

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 t
en
nm nment
sig ssig
As A Assignment

Assignment
8. Select the correct statement(s) regarding borax
SECTION - A [NCERT Pg. 320]
NCERT Based MCQs (1) Boron is both sp2 and sp3 hybridised
1. The abnormally smaller size of Ga among its group (2) Its aqueous solution is basic in nature
can be explained by [NCERT Pg. 317]
(3) Oxidation state of boron is +3
(1) Poor shielding of p orbitals
(4) All of these
(2) Poor shielding of d orbitals
9. A compound ‘A’ when reacts with LiAlH4 it gives
(3) Poor shielding of d and f orbitals two compounds B and C along with LiF.
(4) Poor shielding of f orbitals Compounds A, B and C respectively are
[NCERT Pg. 321]
2. The oxide which is amphoteric in nature is
[NCERT Pg. 324] (1) HF, H2 and AlF3
(1) CO2 (2) SnO2 (2) BF3, H2 and AlF3
(3) SiO2 (4) GeO2 (3) BF3, B2H6 and AlF3
3. Which among the following is not a silicate? (4) B2H6, BF3 and AlF3
[NCERT Pg. 330]
10. Orthoboric acid is a monobasic acid because
(1) Mica (2) Zeolite [NCERT Pg. 321]
(3) Feldspar (4) Carborundum
(1) It forms H3O+ and H3BO2 ions in water
4. Which of the following compounds on hydrolysis
will form cross linked silicones? [NCERT Pg. 329] (2) It forms H3O+ and BO32  ions in water
(1) CH3SiCl3 (2) (CH3)2SiCl2
(3) It forms H3O+ and [B(OH)2]– ions in water
(3) (CH3)3SiCl (4) SiCl4
(4) It forms H3O+ and [B(OH)4]– ions in water
5. In Al2Cl6, the bond angle of Al – Cl – Al bond is
[NCERT Pg. 319] 11. The stability order of +2 oxidation state among Si,
Ge, Sn and Pb is [NCERT Pg. 324]
(1) 79° (2) 90°
(1) Pb < Sn < Ge < Si
(3) 101° (4) 118°
(2) Sn < Pb < Ge < Si
6. Which of the following is passive towards conc.
HNO3? [NCERT Pg. 319] (3) Si < Ge < Sn < Pb

(1) Al (2) Mg (4) Ge < Si < Sn < Pb

(3) Na (4) K 12. With respect to graphite and diamond, the

incorrect statement is [NCERT Pg. 326]
7. When boric acid reacts with sodium carbonate a
white crystalline solid X is formed which on heating (1) Graphite has higher electrical conductivity than
above 750°C gives [NCERT Pg. 320] diamond
(1) Na2B2O5 + B2O3 (2) Diamond is thermodynamically more stable
(2) Na2B4O7 than graphite
(3) NaBO2 + Na2BO3 (3) Graphite has higher bond order than diamond
(4) NaBO2 + B2O3 (4) Graphite is softer than diamond

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NEET The p-Block Elements 175
13. Which of the following is not isostructural with (1) It is non-poisonous in nature
SiCl4? [NCERT Pg. 325] (2) It does not glow in dark
(1) NH4+ (2) AlCl4– (3) It is less reactive than white phosphorous
(3) BCl3 (4) SiO44– (4) It readily catches fire in air to give dense white
fumes of P4O10
14. Lewis acid among the following is
[NCERT Pg. 321] 20. The chemical formula of the compound that
contains one P — OH, two P — H and One P = O
(1) B2H6 (2) [B(OH)]4
bond in its one molecule is [NCERT Pg. 185]
(3) CH4 (4) CCl4
(1) H3PO3
15. Which of the following forms a more stable (2) H4P2O5
complex with haemoglobin? [NCERT Pg. 328]
(3) H3PO4
(1) CO (2) CO2
(4) H3PO2
(3) O2 (4) H2
21. The hybridisation state of phosphorus atom in PCl5
16. The correct order of acidic character of given is [NCERT Pg. 183]
oxides is [NCERT Pg. 177, 178]
(1) sp 3
(1) NO > N2O3 > NO2 > N2O5
(2) sp 3d
(2) NO > NO2 > N2O3 > N2O5
(3) sp 3d 2
(3) NO > N2O3 > N2O5 > NO2
(4) dsp3
(4) N2O5 > NO2 > N2O3 > NO
22. All of the given statements are correct except
17. Compound X is prepared by Haber’s process and
is used to produce nitrogenous fertilisers like urea. [NCERT Pg. 187]
The shape of compound and the hybridisation state
(1) Negative electron gain enthalpy of S is greater
of central atom in (X) are [NCERT Pg. 176]
than that of Se
(1) sp 3, trigonal pyramidal
(2) Fluorine has higher electronegativity than
(2) dsp 3, square planar oxygen
(3) sp 3d 2, octahedral (3) Elements of group 16 have higher ionisation
enthalpy than elements of group 15
(4) sp 2, linear
18. All of the given statements are true for nitric acid (4) On moving down the group, the atomic size
except [NCERT Pg. 179, 180] generally increases

(1) It is a colourless liquid X

23. Consider the given reaction, PbS   PbSO 4
(2) In aqueous solution, HNO3 behaves as strong
and if X is a thermodynamically unstable compound
acid giving hydronium ion and nitrate ion
then X is [NCERT Pg. 191]
(3) Conc. HNO3 is a strong oxidising agent and
attacks most metals except noble metals (1) O2

(4) The product of oxidation does not depend on (2) O3

concentration of acid, temperature or nature of (3) I2
material undergoing oxidation
(4) SO2
19. Consider the given figure [NCERT Pg. 181]
24. The shape of XeOF4 is [NCERT Pg. 210]
P P P (1) Pyramidal
P P P P P P (“X phosphorous”) .

P P P (2) Square pyramidal

(3) Tetrahedral
All the given properties are possessed by type ‘X’
phosphorus except (4) Octahedral

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176 The p-Block Elements NEET

25. The compound in which nitrogen exhibits lowest 2. NaOH can absorb
oxidation state is [NCERT Pg. 172]
(1) N2O5 (2) N2O
(1) N3H (2) NH3
(3) NO (4) All of these
(3) N2H4 (4) NH2OH
26. The correct order of the reducing strength of the 3. H2N–CONH2 + HNO2  gas
given compounds is [NCERT Pg. 173] Gas can be
(1) PH3 < NH3 < AsH3 < SbH3 < BiH3 (1) N2 (2) N2O
(2) NH3 < AsH3 < PH3 < SbH3 < BiH3 (3) NO (4) NO2
(3) NH3 < PH3 < AsH3 < SbH3 < BiH3
Cu + HNO3 Cu(NO3)2 + gas A
(4) BiH3 < SbH3 < AsH3 < PH3 < NH3 4. dil
< 250
Product C
Cu + HNO3 Cu(NO3)2 + gas B
27. Which of the given acids is most acidic in nature?
Conc
[NCERT Pg. 205]
Correct for the above reaction is
(1) HClO4 (2) HClO3
(1) A = NO (2) C = N2O3
(3) HClO2 (4) HClO
(3) B = NO2 (4) All of these
28. Interhalogen which is very unstable among the
Cold
following is [NCERT Pg. 206] 5. P2O5  H2O   Pr oduct A
(1) ICl (2) BrCl Product A is
(3) IF (4) IBr (1) Orthophosphoric acid (2) Metaphosphoric acid
29. Which of the given noble gases has highest (3) Pyrophosphoric acid (4) Hypophosphoric acid
positive electron gain enthalpy? [NCERT Pg. 208]
6. Number of P–O–P bonds present in P4O6 are
(1) Kr (2) Xe
(1) 4 (2) 5
(3) Rn (4) Ne
(3) 6 (4) 8
30. When sulphur is oxidised using conc H2SO4 the
obtained major product is [NCERT Pg. 196] 7. The hybridisation of S in SF4 is:

(1) SO2 (2) H2S2O8 (1) dsp2 (2) sp3

(3) sp3d (4) sp3d2
(3) H2SO4 (4) H2S
8. Oxidation state of NO in brown ring complex is
SECTION - B
(1) 0 (2) +1
Objective Type Questions
(3) +2 (4) –1
1. NH3 + Cl 2 A + HCl 9. Which of the following does not contain S–S
(excess) H2O
linkage?
(B) + HOCl (1) H2S2O3 (2) H2S2O6
H2O + CrCl3
(3) H2S2O8 (4) All of these
C
(green ppt.) 10. O3 can oxidise

Correct for the above reaction is (1) K4[Fe(CN)6] (2) BaO2

(1) A = NH4Cl, B = NCl3, C = Cr(OH)3 (3) HgO (4) KMnO4

(2) A = NCl3, B = N2, C = Cr2O3 11. The anhydride of HClO4 is

(3) A = N2, B = NH3, C = Cr2O3 (1) Cl2O (2) ClO2

(4) A = NCl3, B = NH3, C = Cr(OH)3 (3) Cl2O6 (4) Cl2O7

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NEET The p-Block Elements 177
12. Consider the following statements
18. NCl3  3H2O  ' A '
(a) OF2 is an acid anhydride
Correct for above reaction is
(b) Bleaching action of SO2 is due to reduction
(1) Hydrolysis occurs due to d-orbital of Cl
(c) Ozone reacts with moist iodine to form HIO3
(2) Product A is NH3
Incorrect among the following is/are
(3) Product A is N2
(1) (a), (b) (2) (b), (c)
(4) Both (1) and (2)
(3) (a), (c) (4) (a) only 19. Incorrect reaction among the following is/are
13. Acidified KIO3 converts into I2 by

(1) NH4NO3   N2O  H2O
(1) O3

(2) KMnO4 (2) (NH4 )2Cr2O7   Cr2O7  O2
(3) SO2
 250K
(3) NO + NO2   N2O3
(4) H2SO4
14. Which of the following pair are mixed anhydride? (4) NO2 + H2O  HNO2 + HNO3
(1) Cl2O, ClO2 20. Ammonia can be identified by
(2) ClO2, Cl2O6 (1) K2HgI4 (2) CuSO4(aq)
(3) NO2, Cl2O6 (3) Red litmus paper (4) All of these
(4) Both (2) & (3)
21. Fe  dil HNO3  Fe(NO3 )2  ' A ' H2O
15. Correct match among the following are
(a) ClO4– > ClO3– > ClO2– > ClO– Stability order Cu  dil HNO3  Cu(NO3 )2  'B' H2O

(b) Cl2 > Br2 > F2 > I2 Bond strength

Ag  conc. HNO3  AgNO3  'C'
(c) OF2 < OCl2 < ClO2 Bond angle
Product A, B, C will be
(d) l– > Br– > Cl– Reducing power
(1) A = NO2, B = NO, C = N2O
(1) (a), (b), (d) (2) (b), (d)
(2) A = N2O, B = NO, C = NO2
(3) (a), (c), (d) (4) All of these
16. Hydrolysis of which of the following is not the (3) A = NO, B = N2O, C = NO2
example of redox reaction? (4) A = NO2, B = NO2, C = N2O
(1) XeF2 (2) XeF4 22. Product formed during hydrolysis of P4O10 is/are
(3) XeF6 (4) All of these (1) HPO3 (2) H4P2O7
17. a. NH3 > PH3 > AsH3 Thermal stability (3) H3PO4 (4) All of these
b. NH3 < PH3 < AsH3 Reducing power 23. Number of P–O–P bonds present in
c. NI3 > NBr3 > NCl3 Lewis basic character cyclotrimetaphosphoric acid (HPO3)3 are
d. N2O5 > P2O5 > As2O5 Acidic character (1) 1 (2) 2
Correct order is (3) 3 (4) 6
(1) a, b & c 24. Which of the following gas is used for artificial
(2) a, b, c and d respiration?

(3) c & d (1) CO2 + O2 (2) CO + O2

(4) a & d (3) H2 + O2 (4) All of these

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178 The p-Block Elements NEET

25. Consider the following statement 32. Total number of lone pair of electron on Xe atom in
XeOF4 is
a. KI  O3  KOH  O2  I2
neutral (1) 0 (2) 1

b. CO can be estimated by I2O5 (3) 2 (4) 3

33. Which of the following is most acidic ?
c. Pb3O4, Fe3O4 are mixed oxide
(1) HClO4 (2) HClO3
d. Bleaching action of SO2 is due to reducing
nature (3) HClO2 (4) HClO

Correct statement is/are 34. Which of the following is not a disproportionation

reaction?
(1) a, c & d
(1) MnO2 + 4HCl  MnCl2 + 2H2O + Cl2
(2) b, c & d
(2) Cl2 + 2NaOH  NaCl + NaClO + H2O
(3) a & b only (3) 4H3PO3  3H3PO4 + PH3
(4) All of these (4) 3HNO2  HNO3 + 2NO + H2O
26. On heating oxalic acid with concentrated H2SO4, 35. Which of the following is not correct?
the gas evolved is
(1) White phosphorus is soluble in CS2
(1) SO2 (2) CO 2 only (2) Holme’s signal uses Ca3P2 and CaC2
(3) CO only (4) CO + CO2
(3) Nitrogen exhibits +5 oxidation state but it does
27. Fluorine reacts with water to give not form pentahalide
(1) HF only (2) HF, O2 or O3 (4) NH3 has lower boiling point than PH3
(3) O2 only (4) O3 only 36. The element in group-15 having maximum melting
point is
28. Incorrect statement from the following is
(1) Sb (2) Bi
(1) Cl2 disproportionate in NaOH aq. solution
(3) As (4) P
(2) Cl2 have permanent bleaching action
37. The shape and hybridisation of some xenon-
–
(3) ClO < ClO 2 < ClO 3 < ClO4 basic nature oxyfluorides are given below. Which of these is
incorrect?
(4) ClO 4 < BrO 4 > IO4 oxidising power (1) XeOF2 – Bent T-shaped and sp3d
29. Deacon’s process is (2) XeOF4 – Square pyramidal and sp3d2

CuCl2 /723 K (3) XeO2F2 – See-saw and sp3d

(1) 4HCl  O2   2H2 O  2Cl2
(4) XeO3F2 – Square planar and sp3
(2) MnO2 + 4HCl  MnCl2 + H2O + Cl2
38. The catalyst used in Contact process is
(3) Ca(OH)2 + Cl2  Ca(OCl)2 (1) SO2Cl2 (2) MnO2
(4) Na2S2O3 + H2O + Cl2  Na2SO4 + 2HCl + S (3) V2O5 (4) H2O2
30. Bleaching action of Bleaching powder is due to the 39. Which of the following is not correct?
formation of
(1) Cane sugar, on heating with concentrated
(1) OCl– (2) O2 H2SO4 produces carbon

(3) Cl2 (4) Cl– (2) In brown ring compound [Fe(H2O)5 NO]SO4,
the oxidation number of Fe is +1
31. XeF6 on complete hydrolysis gives
(3) Brown ring test is used for the identification of
(1) XeO3 (2) XeO NO–3 ion.
(3) XeO2F2 (4) Xe (4) N2O5 is the anhydride of HNO2
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NEET The p-Block Elements 179
40. Clatherates are not formed by 48. Which of the following has maximum bond angle?
(1) He (2) Ne (1) H2S (2) H2O
(3) Ar (4) Both (1) & (2) (3) H2Te (4) H2Se
41. Which of the following compound does not have S – 49. Which of the following statements is incorrect?
S bond ?
(1) Oxygen is more electronegative than sulphur
(1) Solid S3O9 (2) Na2S4O6
(2) Bond energy of F2 is less than Cl2
(3) Na2S2O3 (4) H2S2O6
(3) HOCl is stronger acid than HOBr
42. How many lone pairs are present in P 4 O 6
(4) Ka >>> Ka for H2SO4 in water
molecule? 2 1

50. Which one of the following does not exist?

(1) 4 (2) 8
(1) XeOF4 (2) NeF2
(3) 16 (4) 12
(3) XeF2 (4) XeF4
43. On heating K4[Fe(CN)6] with concentrated H2SO4
gives the gas 51. Predict the product of the following reaction:
(1) CO (2) (CN)2 2Au + 3HNO3 + 11HCl 
(3) C3O2 (4) SO2 (1) HAuCl4 (2) AuCl3
44. Which one of the following compounds on heating (3) NO2 (4) All of these
evolves ammonia gas?
52. Graphite is a good conductor of electricity. Its electrical
(1) (NH4)2Cr2O7 (2) NH4NO2 conductivity is due to the fact that
(3) NH4NO3 (4) (NH4)2SO4 (1) It is an allotrope of carbon
45. Which of the following complex is known as (2) It has C-atoms arranged in large plates of rings
Nessler’s reagent? of strongly bound C-atoms
(1) K4[Fe(CN)6] (2) H2[PtCl6] (3) In it C-atoms are sp2 hybridised
(3) K2[HgI4] (4) [Fe(H2O)5NO]SO4 (4) It is a non-crystalline substance
46. Which of the following is/are correct about the 53. Borax is used as a cleansing agent because on
reaction? dissolving in water, it gives
Hot (1) Alkaline solution
Cl2 + NaOH 
Conc.
 NaCl + NaClO3 + H2O
(2) Acidic solution
(1) It is a disproportionation reaction
(3) Bleaching solution
(2) Oxidation number of chlorine decreases as well
as increases in this reaction (4) Amphoteric solution

(3) n-factor of chlorine is equal to 5/3 54. TII3 (ionic solid) dissociate as

(4) All of these (1) Tl+ + I3– (2) Tl3+ + 3I–

47. Which of the following statements is wrong? (3) Tl+ + 3I– (4) Tl3+ + I3–

(1) The maximum covalency of sulphur is 6 55. The lead of the lead pencils melts at

(2) O3 molecule is angular in shape (1) 2000°C (2) 350°C

(3) 3170°C (4) 75°C
(3) The most stable allotropic form of sulphur is
rhombic sulphur 56. Darkling of surface painted with white lead is due to

(4) When PCl5 reacts with H2SO4, thionyl chloride (1) H2S (2) CO2
is formed (3) Cu (4) O2
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180 The p-Block Elements NEET

57. The main reason that SiCl4 is easily hydrolysed as 66. Which of the following is not correct?
compared to CCl4 is that
(1) Al reacts with NaOH and liberate H2
(1) Si — Si bond is weaker
(2) AlCl3 is a Lewis acid
(2) SiCl4 can form hydrogen bonds
(3) SiCl4 is covalent (3) Al is used in the manufacture of electrical cables
(4) Si can extend its coordination number beyond four (4) NaOH is used during Hall's process of
58. SiCl4 on hydrolysis forms 'X' and HCl. Compound 'X' purification of bauxite
loses water at 1000°C and gives 'Y'. Compounds 'X' 67. X reacts with aqueous NaOH solution to form Y and
and 'Y' respectively are H2. Aqueous solution of Y is heated to 323-333 K
(1) H2SiCl6, SiO2 (2) H4SiO4,Si and on passing CO2 into it, Na2CO3 and Z were
formed. When Z is heated to 1200°C, Al2O3 is
(3) SiO2,Si (4) H4SiO4, SiO2
formed. X, Y and Z respectively are
59. Inorganic graphite is
(1) Al, AlCl3, NaAlO2
(1) B3N3H6 (2) BN
(2) Zn, Na2ZnO2, Al(OH)3
(3) SiC (4) Fe(CO)5
(3) Al, Al(OH)3, AlCl3
60. A fibrous mineral which can withstand red hot flames
without any damage is (4) Al, NaAlO2, Al(OH)3

(1) Talc (2) Glass wool 68. Sindoor is represented by

(3) Soap stone (4) Asbestos (1) Pb(NO3)2 (2) PbCO3Pb(OH)2

61. Product of the following reaction is (3) Pb(OH)24PbCO3 (4) Pb3O4

Al4C3 + D2O  69. Which one of the following statements about the
(1) Al(OD)3 + CD4 (2) Al(OD)2 + CD4 zeolites is false?

(3) Al(OD)4 + CD4 (4) Al(OD)3 + CD (1) They are used as cation exchangers

62. A when added to silicon will give B. A and B are (2) They have open structure which enables them
to take up small molecules
(1) HF, H2SiF4 (2) HF, H2SiF6
(3) Zeolites are aluminosilicates have three
(3) HCl, H2SiCl6 (4) Hl, H2Sil6
dimensional network
63. Monosilane on coming in contact with air burns with
a luminous flame producing vortex rings. These rings (4) Some of the SiO 44– units are replaced by
are of AlO45– and AlO69– ions in zeolites.

(1) SiO2 (2) SiO 70. Gas A is bubbled through slaked lime when a white
precipitate is formed. On prolonged bubbling, the
(3) Si (4) H2SiO3 precipitate is dissolved. On heating the resultant
64. For prevention of rusting to iron, which paint is used? solution, the white precipitate reappears with the
evolution of gas B. The gases A and B respectively
(1) PbO (2) PbO2
are
(3) Pb3O4 (4) PbSO4
(1) CO2 and CO
65. The number of isomers possible for disubstituted
borazine, B3N3H4X2 is (2) CO and CO2

(1) 3 (2) 4 (3) CO and CO

(3) 6 (4) 2 (4) CO2 and CO2

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NEET The p-Block Elements 181
Which of the following is the correct option?
SECTION - C
(a) (b) (c) (d)
Previous Years Questions
(1) (i) (ii) (iii) (iv)
1. Aluminium chloride in acidified aqueous solution
forms a complex 'A', in which hybridisation state of (2) (ii) (iv) (i) (iii)
Al is 'B'. What are 'A' and 'B', respectively? (3) (iii) (iv) (ii) (i)
[NEET-2019 (Odisha)] (4) (iv) (iii) (ii) (i)
(1) [Al(H2O)6]3+ , d2sp3 7. Identify the incorrect statement related to PCl5
from the following: [NEET-2019]
(2) [Al(H2O)6]3+, sp3d2
(1) Three equatorial P–Cl bonds make an angle of
(3) [Al(H2O)4]3+, sp3
120° with each other
(4) [Al(H2O)4]3+, dsp2
(2) Two axial P–Cl bonds make an angle of 180°
2. Which of the following compounds is used in with each other
cosmetic surgery? [NEET-2019 (Odisha)]
(3) Axial P–Cl bonds are longer than equatorial P–
(1) Zeolites (2) Silica Cl bonds
(3) Silicates (4) Silicones (4) PCl5 molecule is non-reactive
3. Which of the following is incorrect statement? 8. The correct order of atomic radii in group 13
elements is [NEET-2018]
[NEET-2019]
(1) B < Al < In < Ga < Tl
(1) PbF4 is covalent in nature
(2) B < Al < Ga < In < Tl
(2) SiCl4 is easily hydrolysed
(3) B < Ga < Al < In < Tl
(3) GeX4 (X = F, Cl, Br, I) is more stable than
GeX2 (4) B < Ga < Al < Tl < In

(4) SnF4 is ionic in nature 9. Which one of the following elements is unable to
form MF63– ion? [NEET-2018]
4. Which of the following species is not stable?
(1) Ga (2) Al
[NEET-2019]
(3) In (4) B
(1) [SiF6]2– (2) [GeCl6]2–
10. Name the gas that can readily decolourises
(3) [Sn(OH)6]2– (4) [SiCl6]2– acidified KMnO4 solution [NEET-2017]
5. Which is the correct thermal stability order for (1) CO2 (2) SO2
H2E (E = O, S, Se, Te and Po)? [NEET-2019]
(3) NO2 (4) P2O5
(1) H2S < H2O < H2Se < H2Te < H2Po
11. In which pair of ions both the species contain
(2) H2O < H2S < H2Se < H2Te < H2Po S–S bond? [NEET-2017]
(3) H2Po < H2Te < H2Se < H2S < H2O (1) S2O72–, S2O32– (2) S4O62–, S2O32–
(4) H2Se < H2Te < H2Po < H2O < H2S (3) S2O72–, S2O82– (4) S4O62–, S2O72–
6. Match the following : [NEET-2019] 12. It is because of inability of ns2 electrons of the
valence shell to participate in bonding that
(a) Pure nitrogen (i) Chlorine
[NEET-2017]
(b) Haber process (ii) Sulphuric acid
(1) Sn2+ is reducing while Pb4+ is oxidising
(c) Contact process (iii) Ammonia
(2) Sn2+ is oxidising while Pb4+ is reducing
(d) Deacon’s process (iv) Sodium azide or
(3) Sn2+ and Pb2+ are both oxidising and reducing
Barium azide
(4) Sn4+ is reducing while Pb4+ is oxidising
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182 The p-Block Elements NEET

13. Match the interhalogen compounds of column I 19. Which one of the following orders is correct for the
with the geometry in column II and assign the bond dissociation enthalpy of halogen molecules?
correct code [NEET-2017]
[NEET-2016]
Column I Column II
(1) F2 > Cl2 > Br2 > I2
(a) XX (i) T-shape
(2) I2 > Br2 > Cl2 > F2
(b) XX3 (ii) Pentagonal bipyramidal (3) Cl2 > Br2 > F2 > I2

(c) XX5 (iii) Linear (4) Br2 > I2 > F2 > Cl2
20. Match the compounds given in Column-I with the
(d) XX7 (iv) Square-pyramidal hybridisation and shape given in Column-II and
mark the corect option. [NEET-2016]
(v) Tetrahedral
Column-I Column-II
(1) a(iii), b(iv), c(i), d(ii) (2) a(iii), b(i), c(iv), d(ii)
(a) X3F6 (i) Distorted octahedral
(3) a(v), b(iv), c(iii), d(ii) (4) a(iv), b(iii), c(ii), d(i)
14. AIF3 is soluble in HF only in presence of KF. It is (b) XeO3 (ii) Square planar
due to the formation of [NEET-(Phase-2)-2016] (c) XeOF4 (iii) Pyramidal
(1) K3[AIF3H3] (2) K3[AIF6] (d) XeF4 (iv) Square pyramidal
(3) AIH3 (4) K[AIF3H]
(a) (b) (c) (d)
15. When copper is heated with conc. HNO 3 , it
(1) (iv) (i) (ii) (iii)
produces [NEET-2016]
(1) Cu(NO3)2 and N2O (2) (i) (iii) (iv) (ii)

(2) Cu(NO3)2 and NO2 (3) (i) (ii) (iv) (iii)

(3) Cu(NO3)2 and NO (4) (iv) (iii) (i) (ii)

(4) Cu(NO3)2, NO and NO2 21. The stability of +1 oxidation state among Al, Ga,
16. Which is the correct statement for the given In and Tl increases in the sequence
acids? [NEET-2016] [Re-AIPMT-2015]
(1) Phosphinic acid is a diprotic acid while (1) TI < In < Ga < Al
phosphonic acid is a monoprotic acid
(2) In < Tl < Ga < Al
(2) Phosphinic acid is a monoprotic acid while
phosphonic acid is a diprotic acid (3) Ga < In < Al < Tl

(3) Both are diprotic acids (4) Al < Ga < In < Tl

(4) Both are triprotic acids 22. The variation of the boiling points of the hydrogen
17. Among the following, the correct order of acidity is halides is in the order HF > HI > HBr > HCl.

[NEET-2016] What explains the higher boiling point of hydrogen

fluoride? [Re-AIPMT-2015]
(1) HCIO4 < HCIO2 < HCIO < HCIO3
(1) The bond energy of HF molecules is greater
(2) HCIO3 < HCIO4 < HCIO2 < HCIO
than in other hydrogen halides
(3) HCIO < HCIO2 < HCIO3 < HCIO4
(2) The effect of nuclear shielding is much reduced
(4) HCIO2 < HCIO < HCIO3 < HCIO4 in fluorine which polarises the HF molecule
18. The product obtained as a result of a reaction of (3) The electronegativity of fluorine is much higher
nitrogen with CaC2 is [NEET-2016] than for other elements in the group
(1) Ca2CN (2) Ca(CN)2 (4) There is strong hydrogen bonding between HF
(3) CaCN (4) CaCN3 molecules

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NEET The p-Block Elements 183
23. Which of the statements given below is incorrect? 30. Which of the following is electron-deficient?
[Re-AIPMT-2015] [NEET-2013]
(1) ONF is isoelectronic with O2N– (1) (SiH3)2 (2) (BH3)2
(2) OF2 is an oxide of fluorine (3) PH3 (4) (CH3)2
(3) Cl2O7 is an anhydride of perchloric acid 31. Which is the strongest acid in the following?
(4) O3 molecule is bent [NEET-2013]
24. Strong reducing behaviour of H3PO2 is due to (1) HClO3
[Re-AIPMT-2015] (2) HClO4
(1) High oxidation state of phosphorus (3) H2SO3
(2) Presence of two –OH groups and one P – H (4) H2SO4
bond
32. Roasting of sulphides give the gas X as by product.
(3) Presence of one –OH group and two P – H This is a colourless gas with choking smell of burnt
bonds sulphur and causes great damage to respiratory
(4) High electron gain enthalpy of phosphorus organs as a result of acid rain. Its aqueous solution
is acidic, acts as a reducing agent and its acid has
25. Acidity of diprotic acids in aqueous solutions never been isolated. The gas X is [NEET-2013]
increases in the order [AIPMT-2014]
(1) SO2 (2) CO2
(1) H2S < H2Se < H2Te
(3) SO3 (4) H2S
(2) H2Se < H2S < H2Te
33. XeF2 is isostructural with [NEET-2013]
(3) H2Te < H2S < H2Se
(1) ICI2– (2) SbCl3
(4) H2Se < H2Te < H2S
(3) BaCl2 (4) TeF2
26. Which of the following structure is similar to
34. Which of the following does not give oxygen on
graphite? [NEET-2013]
heating? [NEET-2013]
(1) B (2) B4C
(1) Zn(ClO3)2
(3) B2H6 (4) BN
(2) K2Cr2O7
27. Which of these is not a monomer for a high molecular
(3) (NH4)2Cr2O7
mass silicone polymer? [NEET-2013]
(4) KClO3
(1) Me2SiCl2
35. Which of the following species contains three bond
(2) Me3SiCl pairs and one lone pair around the central atom ?
(3) PhSiCl3 [AIPMT (Prelims)-2012]
(4) MeSiCl3 (1) NH2– (2) PCl3
28. Which of these is least likely to act as a Lewis (3) H2O (4) BF3
base ? [NEET-2013]
36. When Cl2 gas reacts with hot and concentrated
(1) F– (2) BF3 sodium hydroxide solution, the oxidation number of
(3) PF3 (4) CO chlorine changes from [AIPMT (Prelims)-2012]
(1) Zero to –1 and zero to +3
29. The basic structural unit of silicates is [NEET-2013]
(2) Zero to +1 and zero to –3
(1) SiO44  (2) SiO32 
(3) Zero to +1 and zero to –5

(3) SiO24 (4) SiO– (4) Zero to –1 and zero to +5

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184 The p-Block Elements NEET

37. A mixture of potassium chlorate, oxalic acid and (1) Three dimensional (2) Linear chain silicate
sulphuric acid is heated. During the reaction which
(3) Sheet silicate (4) Pyrosilicate
element undergoes maximum change in the
oxidation number? [AIPMT (Prelims)-2012] 43. Which of the following oxide is amphoteric ?
(1) Cl (2) C [AIPMT (Mains)-2011]
(3) S (4) H (1) SiO2 (2) CO2
38. Sulphur trioxide can be obtained by which of the (3) SnO2 (4) CaO
following reaction [AIPMT (Prelims)-2012]
44. Which one of the following molecular hydrides acts
 as a Lewis acid ? [AIPMT (Prelims)-2010]
(1) S + H2SO4 
(1) NH3 (2) H2O

(2) H2SO4 + PCl5 
(3) B2H6 (4) CH4BF3

(3) CaSO4 + C  45. The tendency of BF3, BCl3 and BBr3 to behave as
Lewis acid decreases in the sequence

(4) Fe2(SO4)3 
[AIPMT (Prelims)-2010]
39. Which of the following statements is not valid for
(1) BCl3 > BF3 > BBr3 (2) BBr3 > BCl3 > BF3
oxoacids of phosphorus? [AIPMT (Prelims)-2012]
(3) BBr3 > BF3 > BCl3 (4) BF3 > BCl3 > BBr3
(1) All oxoacids contain tetrahedral four
coordinated phosphorus 46. The correct order of increasing bond angles in the
following species are [AIPMT (Prelims)-2010]
(2) All oxoacids contain atleast one P = O unit and
one P–OH group (1) Cl2O < ClO2 < ClO2–

(3) Orthophosphoric acid is used in the (2) ClO2 < Cl2O < ClO2–
manufacture of triple superphosphate (3) Cl2O < ClO2– < ClO2
(4) Hypophosphorous acid is a diprotic acid (4) ClO2– < Cl2O < ClO2
40. In which of the following arrangements the given 47. How many bridging oxygen atoms are present in
sequence is not strictly according to the property P4O10? [AIPMT (Mains)-2010]
indicated against it? [AIPMT (Mains)-2012]
(1) 6 (2) 4
(1) HF < HCl < HBr < HI : increasing acidic
(3) 2 (4) 5
strength
48. Which of the following molecules acts as a Lewis
(2) H2O < H2S < H2Se < H2Te : increasing pKa acid? [AIPMT (Prelims)-2009]
values
(1) (CH3)2O (2) (CH3)3P
(3) NH3 < PH3 < AsH3 < SbH3 : increasing acidic
character (3) (CH3)3N (4) (CH3)3B

(4) CO 2 < SiO 2 < SnO 2 < PbO 2 : increasing 49. Among the following which is the strongest oxidising
agent? [AIPMT (Prelims)-2009]
oxidising power
(1) Br2 (2) I2
41. Which of the following is least likely to behave as
Lewis base? [AIPMT (Prelims)-2011] (3) Cl2 (4) F2
(1) OH– (2) H2O 50. Which one of the following anions is present in the
chain structure of silicates? [AIPMT (Prelims)-2007]
(3) NH3 (4) BF3
42. Name the type of the structure of silicate in which (1) SiO44  (2) Si2O76 
one oxygen atom of [SiO4]4– is shared?
[AIPMT (Prelims)-2011] (3)  SiO 
2
3
n
(4)  Si O 
2
2
5
n

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NEET The p-Block Elements 185
51. Which of the following oxidation states are the most 58. Which of the following is the electron deficient
characteristic for lead and tin respectively ? molecule? [AIPMT (Prelims)-2005]
[AIPMT (Prelims)-2007] (1) B2H6 (2) C2H6
(1) +2, +2 (2) +4, +2 (3) PH3 (4) SiH4
(3) +2, +4 (4) +4, +4 Questions asked Prior to Medical Ent. Exams. 2005
52. Which one of the following orders correctly represents 59. Which statement is wrong?
the increasing acid strengths of the given acids ?
(1) Feldspars are not aluminosilicates
[AIPMT (Prelims)-2007]
(2) Beryl is an example of cyclic silicate
(1) HOClO3 < HOClO2 < HOClO < HOCl
(3) Mg2SiO4 is orthosilicate
(2) HOCl < HOClO < HOClO2 < HOClO3
(3) HOClO3 < HOCl < HOClO3 < HOClO2 (4) Basic structural unit in silicates SiO44  is the
(4) HOClO2 < HOClO3 < HOClO < HOCl tetrahedron

53. Al2O3 can be converted to anhydrous AlCl3 by heating 60. Carbon and silicon belong to (IV) group. The
maximum coordination number of carbon in
[AIPMT (Prelims)-2006]
commonly occurring compounds is 4, whereas that
(1) Al2O3 with HCl gas of silicon is 6. This is due to
(2) Al2O3 with NaCl in solid state (1) Availability of low lying d-orbitals in silicon
(3) A mixture of Al2O3 and carbon in dry Cl2 gas (2) Large size of silicon

(4) Al2O3 with Cl2 gas (3) More electropositive nature of silicon

54. Which of the following is the most basic oxide ? (4) Both (2) & (3)

[AIPMT (Prelims)-2006] 61. Which of the following statements about H3BO3 is

not correct?
(1) Al2O3 (2) Sb2O3
(1) It has a layer structure in which planar BO3
(3) Bi2O3 (4) SeO2 units are joined by hydrogen bonds
55. Which of the following is not isostructural with (2) It does not act as proton donor but acts as a
SiCl4 ? [AIPMT (Prelims)-2006] Lewis acid by accepting hydroxyl ion
(3) It is a strong tribasic acid
(1) SCl4 (2) SO24
(4) It is prepared by acidifying an aqueous solution
of borax
(3) PO34 (4) NH4
62. Aluminium (III) chloride forms a dimer because
56. In which of the following molecules are all the bonds aluminium
not equal? [AIPMT (Prelims)-2006]
(1) Belongs to 3rd group
(1) ClF3 (2) BF3 (2) Can have higher coordination number
(3) AlF3 (4) NF3 (3) Cannot form a trimer
57. Which one of the following orders is not in accordance (4) Has high ionization energy
with the property stated against it?
63. Boron compounds behave as Lewis acids, because
[AIPMT (Prelims)-2006]
of their
(1) F2 > Cl2 > Br2 > I2 : Oxidising power (1) Ionisation property
(2) HI > HBr > HCl > HF : Acidic property in water (2) Electron deficient nature
(3) F2 > Cl2 > Br2 > I2 : Electronegativity (3) Acidic nature
(4) F2 > Cl2 > Br2 > I2 : Bond dissociation energy (4) Covalent nature

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186 The p-Block Elements NEET

64. In graphite, electrons are 72. Which of the following displaces Br 2 from an
aqueous solution containing bromide ions?
(1) Localised on each C-atom
(1) I2 (2) I3–
(2) Localised on every third C-atom
(3) Cl2 (4) Cl–
(3) Delocalised within the layer
73. Repeated use of which one of the following
(4) Present in anti-bonding orbital fertilizers would increase the acidity of the soil?
65. In borax bead test which compound is formed? (1) Ammonium sulphate
(1) Orthoborate (2) Metaborate (2) Superphosphate of lime
(3) Double oxide (4) Tetraborate (3) Urea
66. Which one of the following statements about the (4) Potassium nitrate
zeolite is false?
74. Which of the following oxides is most acidic?
(1) They are used as cation exchangers (1) As2O5 (2) P2O5
(2) They have open structure which enables them (3) N2O5 (4) Sb2O5
to take up small molecules
75. Which of the following phosphorus is the most
(3) Zeolites are aluminosilicates having three reactive?
dimensional network
(1) Scarlet phosphorus (2) White phosphorus
(4) Some of the SiO 44– units are replaced by
(3) Red phosphorus (4) Violet phosphorus
AlO45– and AlO69– ions in zeolites
76. The decomposition of organic compounds, in the
67. The straight chain polymer is formed by
presence of oxygen and without the development of
(1) Hydrolysis of (CH 3 ) 2 SiCl 2 followed by odoriferous substances, is called
condensation polymerisation
(1) Nitrification (2) N2-fixation
(2) Hydrolysis of (CH 3 ) 3 SiCl followed by (3) Decay (4) Denitrification
condensation polymerisation
77. Nitrogen forms N2, but phosphorus does not form
(3) Hydrolysis of CH 3 SiCl 3 followed by P2, however, it forms P4, reason is
condensation polymerisation
(1) Triple bond present between phosphorus atom
(4) Hydrolysis of (CH3)4 Si by addition polymerisation
(2) p – p bonding is weak
68. The metal oxide which cannot be reduced to metal
(3) p – p bonding is strong
by carbon is
(4) Multiple bonds form easily
(1) Fe2O3 (2) Al2O3
78. Which reaction is not feasible?
(3) PbO (4) ZnO
(1) 2KI + Br2  2KBr + I2
69. Oxalic acid on heating with conc. H2SO4 gives
(2) 2KBr + I2  2KI + Br2
(1) CO only (2) CO2 only
(3) 2KBr + Cl2  2KCl + Br2
(3) CO2 + H2O (4) CO + CO2 + H2O
(4) 2H2O + 2F2  4HF + O2
70. Chemical formula of phosgene is
79. Which one of the following statements is not true?
(1) COCl2 (2) CaOCl2
(1) Among halide ions, iodide is the most powerful
(3) CaCO3 (4) COCl reducing agent
71. In which of the following compounds, nitrogen (2) Fluorine is the only halogen that does not show
exhibits highest oxidation state? a variable oxidation state
(1) N3H (2) NH2OH (3) HOCl is a stronger acid than HOBr
(3) N2H4 (4) NH3 (4) HF is a stronger acid than HCl

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NEET The p-Block Elements 187
80. Oxidation states of P in H4P2O5, H4P2O6, H4P2O7,
SECTION - D
are respectively
NEET Booster Questions
(1) + 3, + 4, + 5
1. Tendency to form puckered ring structure of eight
(2) + 3, + 5, + 4
atoms follows the order
(3) + 5, + 3, + 4
(1) S > Se > Te (2) Se > S > Te
(4) + 5, + 4, + 3
(3) Te > Se > S (4) Te > S > Se
81. In which one of the following species the central
2. Aluminium chloride exists as dimer Al2Cl6, when
atom has the type of hybridisation which is not the
dissolved in water forms
same as that present in the other three?
(1) [Al(H2O)6]3+ + 3Cl– (2) [Al(OH)6]3– + 3HCl
(1) PCl5 (2) SF4
(3) I3– (4) SbCl52– (3) Al+3 + 3Cl– (4) Al2O3 + 6HCl

82. Least volatile hydrogen halide is 3. Inorganic graphite is

(1) HF (2) HCl (1) B3N3H6 (2) C

(3) HBr (4) HI (3) (BN)x (4) SiC

83. Pb + conc. HNO3 gives 4. Orthoboric acid

(1) Pb(NO3)2 + NO2 (1) Is a Lewis acid
(2) PbNO3 + N2O (2) Forms a layer structure due to hydrogen bonds
(3) Pb(NO3)2 + N2O3 among BO33  units
(4) Pb(NO3)2 + N2O (3) Burns with ethyl alcohol to give green edged
84. Which has ability to release bromine from KBr? flame due to formation of volatile B(OC2H5)3

(1) I2 (2) Br2 (4) All of these

(3) F2 (4) SO2 5. Repeating unit of organosilicon polymers is

85. Which of the following has P-P linkage? (1) ( R2Si )n (2) ( R2Si – O2 )n
(1) H4P2O6 (2) H4P2O7 (3) ( R2SiO )n (4) All of these
(3) HPO3 (4) H3PO4 6. What is not correct about P4O10?
86. Bonds present in N2O5 are (1) It is anhydride of H3PO4
(1) Only covalent (2) It contains 16 sigma bonds
(2) Only ionic (3) It is anhydride of H4P2O7
(3) Covalent and coordinate
(4) It contains 4  bonds
(4) Covalent and ionic
7. Which is not formed?
87. Which of the following dissolves in water but does
(1) PCl5 (2) AsF5
not gives any oxyacid solution?
(3) SbF5 (4) BiCl5
(1) SO2 (2) OF2
8. CaC2, Be2C and Mg2C3 are known as respectively
(3) SCl4 (4) SO3
(1) Acetylide, methanide and acetylide
88. Which of the following is used during the
preparation of fluorine by Whytlaw Gray method? (2) Acetylide, methanide and allylide
(1) KF(aq) (2) HF(aq) (3) Allylic, methanide and acetylide
(3) Molten KHF2 (4) NH4F (4) Acetylide, methanide and methanide

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188 The p-Block Elements NEET

9. Oxide of phosphorus reacts with water to produce 16. Consider the following statements
an acid. Acid is dibasic and can form two types of
I. PCl3 hydrolyses in the presence of moisture
salts with NaOH. Salts will be
giving fumes of HCl.
(1) NaH2PO3 and Na2HPO3
II. PCl5 exists as [PCl4]– [PCl6]+ in solid state.
(2) NaH2PO4 and Na2HPO4
III. All the five bonds in PCl 5 molecule are
(3) NaH2PO2 and Na2HPO2 equivalent.
(4) NaHPO3 and NaHPO4 Choose the correct statement(s) :
10. Two gases ‘X’ and ‘Y’ act as bleaching agents, ‘X’ (1) Only I (2) I & II
is due to its reducing character and ‘Y’ is due to
(3) II & III (4) I, II & III
its oxidising character. Identify ‘X’ and ‘Y’.
(1) X = SO2, Y = Cl2 (2) X = Cl2, Y = SO2 17. Correct order of acidic strength is

(3) X = NH3, Y = SO2 (4) X = Cl2, Y = NH3 (1) HClO4 > HClO3 > HClO2 > HClO

11. How many B atoms are sp2 hybridised in borax (2) H3PO2 > H3PO3 > H3PO4
structure? (3) HI > HBr > HCl > HF
(1) 1 (2) 2 (4) All of these
(3) 3 (4) 4 18. Give the correct order of stability of trivalent cations
12. Which of the following is responsible factor for of group 13.
weak acidic nature of BF3? (1) In+3 > Tl3+ > Ga3+ (2) Ga+3 > In3+ > Tl3+
(1) p – p back bonding (3) Ga3+ > Tl3+ > In3+ (4) In3+ > Ga3+ > Tl3+
(2) p – d back bonding 19. Borax on strong heating produces
(3) High electronegativity of fluorine (1) Na2B4O7 (2) NaBO2
(4) sp2 hybridisation of boron (3) B2O3 (4) Both (2) & (3)
13. The valency and oxidation number of sulphur in S8
573 K, 60  70 bar
are 20. Xe + F2   A . What is A?
(1 : 20)
(1) 2 and 2 respectively
(2) 0 and 0 respectively (1) XeF2 (2) XeF4

(3) 2 and 0 respectively (3) XeF6 (4) XeF5

(4) 0 and 2 respectively 21. Boron compounds behave as Lewis acids because
of their
14. Which of the following is sesquioxide?
(1) Acidic nature
(1) NO2
(2) Covalent nature
(2) N2O3
(3) Ionisation energy
(3) N2O5
(4) Electron deficient nature
(4) N2O
22. The compound that can act as Lewis base is
15. What is not correct regarding N(CH 3 ) 3 and
N(SiH3)3? (1) BF3 (2) AlCl3
(1) N(CH3)3 is more basic than N(SiH3)3 (3) PCl3 (4) SnCl4
(2) N(CH3)3 is pyramidal in shape 23. In which of the following reaction boron does not
act as reducing agent?
(3) N(SiH3)3 is planar
(4) Central atom is sp 3 hybrid in both the (1) B + CO2  (2) B + Mg 
compounds (3) B + SiO2  (4) B + HNO3 

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NEET The p-Block Elements 189
24. Which of the following statement is correct? 30. Diborane can't be obtained from
(1) Boron and aluminium halides behave as Lewis (1) Na2B4O7 + HCl (2) NaBH4 + I2
acids
(3) BF3 + LiAlH4 (4) BF3 + NaH
(2) Al forms [AlF 6] 3– ion but B does not form
31. Number of hydroxyl group attached to Boron in
[BF6]3– ion
Borax are
(3) The p – p back bonding occurs in the halides
(1) Four (2) Five
of boron and not in those of aluminium
(3) Six (4) Ten
(4) All of these
32. In Diborane, the incorrect statement is
25. White fumes appear around the bottle of anhydrous
AlCl3 due to (1) All 6 B–H bond are on same plane
(1) Decomposition of AlCl3 (2) 4 B–H bonds are on the plane and two B–H
(2) Hydrolysis of AlCl3 liberating H2 gas bonds above and below the plane

(3) Hydrolysis of AlCl3 liberating Cl2 gas (3) It is the 12 valance e– species

(4) Hydrolysis of AlCl3 liberating HCl gas (4) Two BH3 are attached with three centre electron
pair bond
26. Borax is
33. On strong heating, boric acid yields
(1) Na2[B4O5(OH)4].8H2O
(1) B (2) B2H6
(2) Na2[B4O5(OH)6].7H2O
(3) Na2[B4O3(OH)8].6H2O (3) B2O3 (4) BO2

(4) Na2[B4O2(OH)10].5H2O 34. The correct match is

27. Aluminium chloride in acidified aqueous solution (1) C60 – Buckminster fullerene
forms (2) Na2B4O7.4H2O – Kernite
(1) Tetrahedral [Al(H2O)4]+3 ion (3) Borazole – B3N3H6
(2) Octahedral [Al(H2O)4]+3 ion (4) All of these
(3) Tetrahedral [Al(H2O)6]+3 ion 35. The correct match is
(4) Octahedral [Al(H2O)6]+3 ion
(1) B(OH)3 – basic
740°C
28. Na2B4O7 2NaBO2 + B2O3 (2) SnO, PbO – amphoteric
 X + Y
(3) GeO2 – basic
Transparent
(4) PbO2 – only acidic
Z + CuO(s)  Cu(BO2)2
36. C – O bond length is maximum in
Blue Bead
The 'Z' will be (1) CH3CHO (2) CO2
(1) X
(3) CO (4) CO32
(2) Y
37. Dry ice is composed of
(3) Mixture of X & Y in 2 : 1 ratio
(1) Solid He (2) Solid CO2
(4) Mixture of X & Y in 1 : 2 ratio
(3) Solid SO2 (4) Solid C6H6
29. Reaction of ammonia with diborane gives initially
B2H6.2NH3 which can also be written as 38. The metallic character of group 14
(1) [BH2(NH3)2]+[BH4]– (1) Decreases from top to bottom
(2) [BH4]+[BH2(NH3)2]– (2) Increases from top to bottom
(3) [BH3NH3]+[BH4]– (3) Does not change gradually
(4) [B2N2H6]+[H3]– (4) Metallic character is not seen

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190 The p-Block Elements NEET

39. In carbon family the tendency to show +2 45. Catalyst used in Deacon's process is
oxidation state increases in order of
(1) CuCl2 (2) MnO2
(1) Ge < Sn < Pb (3) Fe (4) NO
(2) Pb < Sn < Ge 46. The geometry of SiCl4 is
(3) Sn < Ge < Pb (1) Tetrahedral (2) Square planar

(4) Sn < Pb < Ge (3) Octahedral (4) Planar triangular

47. The correct statement is
40. Which one of the following is correct statement of
fullerenes –C60? (1) Diamond is covalent yet it has high melting
point
(1) Fullerenes are made by heating of graphite in
an electric arc in the presence of Hydrogen (2) [SiF6]2– is known whereas [SiCl6]2– is not
(3) SiO only exist at high temp.
(2) Fullerenes are the only impure form of carbon
due to presence of dangling bonds (4) All of these

(3) Both (1) & (2) 48. The silicates which contain discrete tetrahedral
units are
(4) It contains twenty six-membered rings and
(1) Sheet silicates
twelve five membered rings
(2) Orthosilicates
41. The mixture of CO & H2 is known as
(3) Three dimensional silicates
(1) Water gas or producer gas
(4) Pyrosilicate
(2) Water gas or synthesis gas
Cu Powder 2H2O
49. CH3Cl  Si   x  y
(3) Synthesis gas or producer gas 570 K

(4) Producer gas y & x respectively are

42. When SiCl4 is allowed to undergo hydrolysis it gives
(1) (CH3)2SiCl2, (CH3)2Si(OH)2
(1) SiO2 – Silicic acid (2) (CH3)2Si(OH)2, (CH3)2SiCl2
(2) Si(OH)4 – Silicic acid (3) SiCl4, Si(OH)4
(3) Si(OH)Cl3 – Silicic acid (4) Si(OH)4, SiCl4
(4) SiCl4 do not undergo hydrolysis 50. Hydrolysis of dimethyldichloro silane; (CH3)2SiCl2
followed by condensation polymerisation yields
43. Which statement is correct for carbon family? straight chain polymer of
(1) Tin mainly occurs as Cassiterite, SnO2
O O
(2) Silicon is the third most abundant element on
earth's crust (1) O Si Si O

(3) Only two isotopes of carbon are present C12 O O

and C13
(2) Si O O Si
(4) Germanium is most abundant than other
members of carbon family CH3 CH3

44. p–p multiple bond is seen in (3) O Si O Si O

(1) Mostly carbon CH3 CH3

(2) All carbon family member CH3 CH3

(3) Sn but not in carbon (4) O Si Si O
(4) Boron family and not in carbon family CH3 CH3
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NEET The p-Block Elements 191
51. Silicons are 59. In P4O10 the number co-ordinate bonds is
(1) Water repelling in nature (1) 1 (2) 8
(2) With high thermal stability (3) 3 (4) 4
(3) With high dielectric strength 60. Calomel (Hg2Cl2) on reaction with NH4OH gives
(4) All of these (1) Hg2O (2) HgO
52. Which one is correct statement for zeolite? (3) HgNH2Cl (4) NH2Hg2Cl
(1) They are alumino silicates 61. Nitrogen is obtained when NaNO2 reacts with
(2) Hydrated zeolites are used as ion exchangers (1) NH4Cl (2) NH4NO3
in hardening of soft water
(3) (NH4)2CO3 (4) NH4OH
(3) ZSM-5 is used to convert gasoline to alcohol
62. Oxide which has ‘N – O – N’ bond is
(4) All of these
(1) N2O4 (2) N2O5
53. (i) SiO2 + NaOH ?
(3) N2O (4) N2O3
(ii) SiO2 + HF ?
63. HNO3 + HCl A + NOCl + H2O
The products of (ii) & (i) respectively are
Pt/HCl
(1) H2SiF6, SiO44– (2) SiF4, Na2SiO3
‘P’
(3) Na2SiO3, SiF4 (4) Na2SiO4, H2SiF6
The product ‘P’ will be
54. Calcium carbide on hydrolysis gives
(1) H2PtCl4 (2) H2PtCl6
(1) Ethylene (2) Acetylene
(3) H2PtCl2 (4) H3PtCl3
(3) Methane (4) Propyne
64. What is the product formed when NH3 reacts with
55. Carbon suboxide has the formula
excess of Cl2?
(1) H2CO3 (2) C2O3
(1) NH4Cl & HCl (2) NH4Cl & N2
(3) C3O2 (4) CO
(3) NCl3 & HCl (4) NH4Cl & NCl3
56. NH3  O2  A  H2O
Pt
 65. Hybridisation of central ‘N’-atom in N2O is

A + O2  B (1) sp (2) sp2

B + H2O  C + D (3) sp3 (4) sp & sp2

A, B, C and D respectively are 66. In solid state PBr5 exist as

(1) NO, NO2, HNO3 and HNO2 (1) [PBr4]+ [PBr6]– (2) [PBr5]+ [PBr5]–

(2) NO2, HNO2, NO and HNO3 (3) [PBr4]+ [Br–] (4) PBr5
(3) HNO2, NO2, HNO3 and N2O 67. Which of the following metal gives NH4NO3 with very
dilute HNO3?
(4) HNO2, N2O, NO and HNO3
(1) Fe (2) Ti
57. Which of the following can be hydrolysed?
(3) Cu (4) Hg
(1) TeF6 (2) NF3
68. In iodide of Millon’s base formed by the reaction of
(3) SF6 (4) All of these
Nessler’s reagent with NH3, the coordination number
58. Phosphine on reaction with hydrobromic acid gives of Hg will be
(1) PBr3 (2) P2H4Br2 (1) 2 (2) 3
(3) PBr5 (4) PH4Br (3) 4 (4) 6

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192 The p-Block Elements NEET

69. The compound insoluble in aqueous NH3 is 77. Which of the following is most basic?
(1) AgI (2) AgCl (1) Cl– (2) F–
(3) ZnSO4 (4) HgCl2 (3) I– (4) Br–
70. Which of the following is called mixed anhydride? 78. The final product formed, when alkaline KI solution
reacts with ozone, is
(1) NO2 (2) N2O3
(1) I2
(3) N2O5 (4) All of these
(2) KIO3
71. Which of the following do not exist?
(3) HI
(1) NCl5 (2) PH5
(4) Reaction will not occur
(3) [BCl6]3– (4) All of these
79. The shape of ClF2–, is
72. PCl3 + H2O  A + B. What are A and B
(1) Linear (2) Trigonal bipyramidal
(1) H3PO2 + HCl (2) H3PO4 + HCl
(3) Square pyramidal (4) T-shape
(3) H3PO3 + HCl (4) HPO3 + HClO3
80. Reaction of Cl2 with hot and conc. NaOH produces
73. Which of the following is correct?
(1) NaClO (2) NaClO3
(1) In PF 5 , axial and equatorial bonds are
interchanged, known as pseudo rotation (3) NaClO4 (4) NaClO2
(2) In solid state PF5 remains covalent 81. Hydrolysis of ICI3 forms
(3) PH5 cannot be obtained, because H is not (1) HOI (2) HIO2
sufficiently electronegative to make the
(3) HIO3 (4) HIO4
d-orbitals contact sufficiently
82. Which one of the following does not form during
(4) All of these
the hydrolysis of XeF6?
74. When Cu is reacted with hot concentrated solution
(1) XeO3
of H2SO4 then the gas obtained is
(2) XeOF4
(1) O2 (2) H2
(3) XeO2F2
(3) SO2 (4) SO3
(4) XeOF3
75. A metal X when burnt in air, X-forms oxide and nitride
both, X can be 83. In xenon fluorides most reactive in XeF6, XeF4 and
XeF2 is
(1) Rb (2) Mg
(1) XeF6
(3) Na (4) K
(2) XeF2
76. The most acidic oxide among the following is
(1) SO3 (2) P2O5 (3) XeF4

(3) Cl2O7 (4) SiO2 (4) All are equally reactive

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