P-BLOCK

ELEMENT
 ZION TUTORIALS 3

P-BLOCK ELEMENTS
Introduction :

The right side of the periodic table having group number 13, 14, 15, 16, 17 and 18 are known
as p-block elements. These elements have 3, 4, 5, 6, 7 and 8 electrons in their outer most shell,
respectively. The last electron of these groups’ elements occupies the position in p-sub shell that
2
is why they are called as p-block elements. Their general configuration is ns np 1-6 .

Some Important Properties of P-Block

1. Electron affinity :
Electron affinity increase from left to right along the period amongst the p-block elements and it
decreases from top to bottom. But group 15 is having exceptionally low values of electron affinity

LS
and is due to extra stability because of the presence of exactly half filled orbital in their valence
shell. Similarly, elements of group 18 (noble gases) have zero affinities due to presence of complete
octet which provides them stability.

2. Metallic Character
IA
The metallic character is governed by
(i) Size of atoms and
R
(ii) Ionization energy.

TO
The elements having bigger size and low ionization energy has a greater metallic character. After
combining both above mentioned factors we observe that the elements with above two properties

3.
U
are located in left corner of p-block and strong non-metallic elements are located at right corner

T
and a diagonal strip of elements thus two, having in between properties are called as metalloids.

Oxidation state

N
The p-block elements shows variety of oxidation states both positive and negative. Some of the
p-block elements show different oxidation state due to inert – pair effect, where the lower oxidation

IO
state is more predominant.

4.

Z
Diagonal relationship
On moving diagonally across the periodic table the element show certain simplarities.
Li Be B C

Na Mg Al St
Note : Elements of 2nd period differ from their own group elements in some of the properties. This
is due to the following reasons :

P-BLOCK ELEMENTS
 4 ZION TUTORIALS
(a) Small size
(b) Absence of vacant d-orbital
(c) High IP

Some Important Characteristics of P–Block In Tabular Form

Sr. No. Property Along period Along group

(left to right) (top to bottom)

1. Atomic radii Decreases Increases

2. Ionization potential Increases Decreases
3. Electron affinity Increases Decreases
4.
5.
Electro negativity
Metallic character
LS
Increases
Decreases
Decreases
Increases
6.
7.
Oxidizing property
Reducing property
IA
Increases
Decreases
Decreases
Increases

GROUP 13 ELEMENTS R
Elements : B, Al, Ga, In, TI.

TO
Group 13 elements are boron (B), aluminium (Al), Gallium (Ga), Indium (In) and thallium (TI).

T U
Boron is the only non-metal in this group others are metal. Non-metallic character of boron is due
to its small size and high ionization energy. The general valence shell electronic configuration of
these elements is ns 2 np 1 .

N
General Trends in Physical Properties

Sr.No. Property Boron Aluminium Gallium Indium Thallium

1.

IO
Configuration [He]2s 2
2p 1 [Ne]3s 2 3p 1 [Ar]4s 2 4p 1 [Kr]5s 2 5p 2 [Xe]6s 2 6p 1

Z
2. Common +3 +3 +3 +3 + 3, + 1
oxidation state
3. Atomic radius 83 143 135 167 170
(pm)
4. First ionization 801 578 579 558 589
energy (KJ/mol)
5. Electro negativity 2.0 1.5 1.6 1.7 1.8

P-BLOCK ELEMENTS
 ZION TUTORIALS 5

1. Density
Generally increases down the group but aluminium has an exceptionally low density.

2. Melting point and Boiling point

B to Ga decrease then Ga to TI increase Ga has lowest M.P. (29.8°C) and therefore liquid at room
temperature.

3. Atomic radii and ionic radii

On moving from B to TI the size increases due to addition of new energy shells at each step down
the group but Ga is smaller than Al.

4. Ionization energy

in size as compared to Al.

LS
Generally IE decreases down the group but Ga has higher IE than Al exceptionally due to smaller

5. Metallic character

IA
Electropositive character increases down the group hence metalic character also increase down the

R
group but aluminium is having high metallic character than Gallium due to low IE than Ga.

6. Inter Pair Effect

TO
When we go down the group in p block element, stable positive valency decreases by a factor of
2. This effect is known as inert pair effect. It arises mainly due to poor shielding effect 3d and

T U
4d series element. This result into increase in effective nuclear charge and greater hold on valence
S electrons by nucleus. These s electrons can’t be pulled easily out which decreases the valency
by a factor of 2.
e.g. In 14th group while carbon & silicon show + 4 valency, while Pb is mostly stable in +2 state.

7. N
Oxidation states and nature of bond

IO
The group – 13 elements show variable oxidation states of + 3 and + 1. For lighter members +
3 state is more stable than + 1. Thus for T l, + 1 state is more stable than + 3. It is due to inert

Z
pair effect. The 6s 2
pair does not prefer to form bonds and is called inert pair. The basic reason
for such an effect is bond energy. The M–Cl bond energy in MCl
MCl 3 M–Cl, energy (KJ mol –1
)
3
compounds are as follows :

Ga 242
In 206
TI 153
The ionisation energies of B is very high. It is, therefore, covalent in its compounds, always
tricovalent (2s 2 2p 1 electrons).

P-BLOCK ELEMENTS
6 ZION TUTORIALS
In + 3 oxidation state Al has very high charge to radius ratio (~ 6.0). So, it is also covalent in
its anhydrous compounds. However, in aq. solution tricovalent Al (e.g. AlCl 3
) becomes ionic due
+3 –1 3+ –
to high hydration energy of Al (4665 KJ mol ) [Al(OH 2 )6 ] .3Cl . The soluble compounds are
+3
quite acidic due to hydrolysis (high charge to radius ratio of Al ).

[Al(OH 2 )6 ]+3 + H 2 O  H 3 O + + [Al(H 2 O) 5 OH] +2

+
TI is ionic in + 1 oxidation state, TICl ionic. The TI ion resembles K + and Rb + . It is because radii
+
of the ions are comparable (K ~ 1.38 Å, TI ~ 1.5 Å, Rb ~ 1.52 Å). Therefore, TIOH is a strong
base like group – 1 hydroxides. Tricovalent compounds, MX 3
, are electron deficient as octet
around the central atom is not complete.

F Cl

F
B
F
LS Cl
Al

Cl

IA
(Six electrons around B or Al)

Such compounds remove their electron deficiency by :

(i) Back – bonding
R
has filled p-orbital. The overlap resulting into

TO
In BX 3 , B is sp 2 and has a vacant p-orbital perpendicular at the triangular plane. X-atom
–bonding.

U
F
F

F
B
F
T F
B
F
Resonance

(ii) N
Coordination with Lewis bases

IO
B has vacant orbital which accepts electron pair from F –
.

Z F
F

B
F
+F
–
BF 4
–


Al(OH) 3 + HO –  Al(OH) 4

(iii) Polymerisation
AlCl 3 removes electron deficiency by dimerisation.

2AlCl  Al 2 Cl 6
P-BLOCK ELEMENTS
 ZION TUTORIALS 7

Dimer is made easily because Cl has lp and Al has vacant orbital.

Cl Cl Cl
Al Al
Cl Cl Cl

AlCl 3 is not stabilized by back bonding. It is due to the following facts :

(i) p-orbital of Al is large, so p–p overlap is not effective.

(ii) 8 electron core in Al causes larger repulsion (8e – 8e) destabilizing back bonding effective.

BX 3 can not stabilize by dimerisation. B is small in size. The dimer will have small ring.

X X X
B B

So, it is not stable.

X X

LS X

REACTIONS OF ELEMENTS

IA
R
Pure crystalline boron is very unreactive. However, it is attacked at high temperatures by strong
oxidising agents such as a mixture of hot concentrated H 2
SO 4 and HNO 3
or Na 2 O 2 .

2B(s) + 6HNO 3

TO
(aq)  2H 3 BO 3 (aq) + 6NO 2 (g)

In contrast, finely divided amorphous boron (containing about 2–5% impurities) is more reactive.
Reactions are summarised in Table below

Reaction
T U
Reactions of Group 13 (IIIA) Elements
Comment

• 4M + 3O  2M 2 O 3 Reaction at high temperature; with A l exotohermic, a

N
2
protective oxide layer is formed and TI also forms TI 2
O.
•

IO
2M + N 2  2MN Only Al and (B) form nitrides BN, a slippery white solid
with layer structure similar to graphite.
•

•
Z
2M + 3X 2

2M + 2NaOH + 2H
 2MX 3

2
O 
All form MX 3 , Tl also form T lX. Iodide of T l 3+ (TlI 3 ) is not
formed; but T lI reacts with I
B, Al and Ga only form NaMO
2
forming T lI 3 (Tl + , I 3 – )

2
2NaMO 2
+ 3H 2

• 2M + 6NH 3
 2M(NH 2 )3 + 3H 2 All form amides except B which forms BN.
2B + 2NH 3  2BN + 3H 2
+ 3+
• 2M + 6H  2M 3H 2 Metals liberate H 2
, but HNO 3
makes Al passive.

P-BLOCK ELEMENTS
 8 ZION TUTORIALS
• Boron reacts directly with elements forming borides which are hard and refractory.

3Mg + 2B  Mg 3 B 2
Borides are decomposed by acids forming boranes

Mg 3 B 2 + 6HCl  3MgCl 2 + B 2 H 6

diborane

• Aluminium is far more reactive than boron but in air and water it is stable. It is due to the
formation of aluminium oxide, Al O layer, that makes it passive for further attack. HNO
2 3 3
also makes Al passive by oxide layer formation.
• Reaction of Al with O 2
is exothermic and is called thermite reaction.

2Al(s) +
3
2 2

LS
O (g)  Al 2 O 3 (s), H = – 1670 kJ

The thermite reaction involves so much energy that it can be dangerous. The Al becomes

IA
white hot and often causes fires. For this precise reason, mixture of Al and an oxide such
as Fe 2 O 3 or SiO 2 (a source of oxygen) were used to make incendiary bombs during World
War II.

R
O
BX3

H 3BO 3 + NO 2

U T
HNO 3
X2

m
et
al
M
M xB y

BN
N2
T BORON
O2
B 2O 3

N NH 3
NaOH
base

IO BN + H 2
S
Na 3BO 3+ H

Z
2

B 2S 3

Boron : Extraction

acid
• Na 2
B 4 O 7 .10H 2 O   H 3 BO 3 

 H 2O + B 2O 3
orthoboric acid

B 2 O 3 + 6Na 

 2B + 3Na 2 O

B 2 O 3 + 3Mg 

 2B + 3MgO

P-BLOCK ELEMENTS
 ZION TUTORIALS 9

red hot
• 2BCl 3
+ 3H 2 
filament
 2B + 6HCl

• Pyrolysis of BI 3

red hot
2BI 3 
filament
 2B + 3I 2

• thermal decomposition of B 2
H6

B 2 H 6 

 2B + 3H 2

Compounds of Boron

1. Borax (Na 2
B 4 O 7 .10H 2 O)
• The actual formula is Na 2
OH
S
[B 4 O 5 (OH) 4 ].8H 2 O

L
A
–
O B O

Na 2 HO — B

O B–
O

R IB — OH

• Action of heat

Heat
OH

TO 740 C

U
Na 2 B 4O 7.10H O
2 Na B2 O
 4 7 
2NaBO 2 B
 O2 3
 10H 2O
sodium Boric
metaborate anhydrid

T

Glassy mass

• Various reactions of borax

N Na 2CO 3+ H BO
3 3

IO NaOH Na 2B 4O 7

Z

NaBO 2 NaBO 2+ B O
4 Cl i t h

Sodium 2 3
H 2O
N H ed w

metaborate
HCl
at

H 3BO 3 + NaOH
He

CuO 
Heated
BN strongly NaCl + H BO
3 3
(also called 100°C Cu(BO 2) 2
inorgonic graphite) (Blue)
B 2O 3
HBO 2 Boric anhydride

P-BLOCK ELEMENTS
 10 ZION TUTORIALS
• Solution of Borax is alkaline in nature. This is due to hydrolysis

Na 2 B 4O 7 7H 2O 2 NaOH + 4H BO
3 3
Strong Weak
alkali acid

2. Boric acids and oxides

(i) H 3 BO 3 or B(OH) 3
orthoboric acid
(ii) HBO 2 metaboric acid
(iii) H 2 B 4 O 7 pyroboric acid

100°C 140°C
H 3BO 3 HBO 2 H 2B 4O 7

LS red hot

3. Boron Trioxide, B 2
O3
IA B 2O 3

• 2H 3 BO 3  B 2 O 3 + 3H 2 O

R
B 2 O 3 + H 2 O  2HBO 2

TO
It is a white hygroscopic solid. It absorbs moisture and converted into boric acid.

•
HBO 2 + H 2 O  H 3 BO 3

2B 2 O 3 + P 4 O 10  4BPO

It is reduced by magnesium T 4
U
N Heated
B 2 O 3 + 3Mg   2B + 3MgO

4. Boron halide

IO
Z CaF 2+ H SO
2 4+ H BO
3 (or
3 B O2 ) 3


H 2O –
BF 3 H 3BO 3 + BF 4

180°C NaH

B 2H 6

P-BLOCK ELEMENTS
 ZION TUTORIALS 11

5. Boron Hydrides

excess NH 3
B 2H 6.2NH 3
low temp.

excess NH 3
B 2H 6 + NH 3 (BN) x
high temp. boron nitride

ratio : 2NH :3 1B H2 6
B 3N 3H 6
high temp. borazine

• B 2 H 6 . 2NH 3
is ionic and forms borazine on heating. Borazine is called inorganic benzene.

H
H

N
LS H

IAB

R N

O
B
H H

U
H

Similarity between Boron and Silicon (Diagonal Relationship)T

T
• Both form volatile hydrides (called boranes and silanes) which spontaneously catch fire on
exposure to air and are easily hydrolysed.
• Halides of both (except BF 3
) are easily hydrolysed :

N BCl 3 + 3H 2 O  H 3 BO 3 + 3HCl

IO SiCl 4 + 4H 2 O  H 4 SiO 4 + 4HCl

Z
Boron forms binary compounds with several metals–these are called borides. Silicon form
silicides. Borides and silicides are hydrolysed by H 2

Mg 3 B 2 + 6H 2 O  3Mg(OH)
O forming boranes and silanes :

2
+ B 2H 6

Al 4 Si 3 + 12H 2 O  4Al(OH) 3

+ 3SiH 4

• B 2 O 3 and SiO 2 are acidic in nature and are important constituents of glass. Borate and
silicates have tetrahedral BO 4
and SiO 4 structural units, respectively.
• Both are semi-conductors.

P-BLOCK ELEMENTS
 12 ZION TUTORIALS
• Boric acid (H 3
BO 3 ) and silicic acids (H 4
SiO 4 ) are weak crystalline.
• They do not dissolve in cold dilute acids but do so in alkalies–boron only in fused alkalies
and silicon in both fused and aqueous alkalies.

2B + 2NaOH + 2H 2
O  2NaBO 2
+ 3H 2

Si + 2NaOH + H 2
O  Na 2 SiO 3 + 2H 2

Compounds of Aluminium

1. Aluminium oxide or Alumina, Al 2

O3

2Al(OH) 3  Al 2 O 3 + 3H 2 O

LS
Al 2 (SO 4 )3  Al 2 O 3 + 3SO 3

(NH 4 )2 SO 4 . Al 2 (SO 4 )3 . 24H 2 O  Al 2 O 3 + 2NH + 4SO 3 + 25H 2 O

A
3

2. Aluminium Chloride

R I
AlCl 3 exists as a dimer, thus attaining an octet of elections.

Cl

Cl
Al

TO Cl

Cl
Al
Cl

Cl

However, when the halides dissolve in H

the covalent dimer into [M(H 2
3+
2

T
O) 6 ] and 3X – ions.
U
O, the high enthalpy of hydration is sufficient to break

N
AlCl 3 + 3H 2 O  Al(OH) 3 + 3HCl
3. Alums

IO
Alums have general formula
M 2 SO 4 . M´ 2 (SO 4 )3 . 24H 2 O

Z
where M stands for monovalent basic radicals such as Na
trivalent basic radicals such as Al
Some examples of alums are :
3+
+

, Cr 3+ , Fe 3+ , Mn 3+ , Co 3+
, K + , Rb + , Cs + , Ag + etc. and M´ for

Potash Alum K 2
SO 4 . Al 2 (SO 4 )3 .24H 2 O
Ferric alum (NH ) SO 4 .Fe 2 (SO 4 ) 3
4 2

Alums are crystalline compounds. In alums each metal ion is surrounded by six water molecules

and the crystals of alums consists of [M(H 2

O) 6 ]+ , [M´(H 2 O) 6 ]3+ and SO 24  ions.

P-BLOCK ELEMENTS
 ZION TUTORIALS 13

GROUP–14

Elements of this group are p-block element. Carbon and Si are non-metals (Si slightly metallic),
Ge is metalloid, Sn and Pb are metals.
Carbon has three isotopes, they are :

Isotope No. of neutron Abundance Nature

12
C 6 98.9%
Stable isotopes
13
C 7 1.1%
Radioactive
14
C 8 Trace
t ½ = 5770 yrs

Physical properties of group–14 elements

Property C Si
LS Ge Sn Pb

Atomic no.
Electronic – 2s
6
2
2p 2
14

I
– 3s 2 3p 2A 32
3d 10 4s 2 4p 2
50
4d 10 5s 2 5p 2
82
4f 14 5d 10 6s 2 6p 2
structure
R
Atomic radius
(A) [covalent radius]
Ionic radius (A)
0.77
0.15
1.17
0.41
TO 1.22
0.53
1.40
0.71
1.44
0.84
Metallic radius (Å)
Ionisation
energy (ev) [I]
--

11.3
T U
--

8.2
1.37

7.8
1.62

7.3
1.75

7.4
[II] 24.4 16.3 15.9 14.6 15.0

N
Electronegativity 2.5 1.9 1.8 1.7 1.7
mp (°C)
bp (°C)
IO > 3550
4827
1410
2355
937
2830
232
2260
327
1744

Note :
(i)
Z
{The values are not to be remembered, these are given to show the variations}

The radii of Si and Ge are very similar due to d-block contraction. Also Sn and Pb have
almost similar radii due to lanthanide contraction.
(ii) Ionisation energy vary as C > Si ~ Ge > Sn < Pb. Silicon and Ge have comparable IE due
to similarity in their radii.
The radius of Sn is smaller than Pb but Pb has higher IE than Sn. It is due to higher Z* for Pb
as F – orbital is least shielding.

P-BLOCK ELEMENTS
14 ZION TUTORIALS
Oxidation states and Bonding

Group–14 elements show variable oxidation states of + 2 and + 4. The stability of + 2 state is very
stable for Pb. It is due to inert pair effect.

C +4 +2
Si
Ge
Sn
Pb
Stability decreases Stability increases

Carbon and Si have high ionisation energy. Therefore, they are covalent in their compounds.

are not very large and have 18e core.

LS
Tin and Pb form ionic compounds having appreciable covalent nature. It is because Sn and Pb

Carbon and Si differ widely in their bonding pattern. It is because of the following reasons :

Property C
2
2p 2 IA Si

3s 2 3p 2 (3d 0 )

R
Valence orbitals and 2s
electrons

Number of bonds or
coordination number 4 only

Very effective
TO More than 4 (5 or 6)

No (p-p)  bonding but

U
-bonding
(p–p)  bonding (p – d)  bonding. Using

C–C bond energy T

356 KJ mol –1
vacant 3d orbitals

226 KJ mol –1

N Low, however,
heterocatenation is

IO
Catenation property Very high pronounced due to strong
Si – O bond (368 KJ mol –1
)

Z
The features of certain Si compounds having Si – O and Si – N bonds are explained by (d – p)
 bonding. For example,

(CH 3 )3 N triangular Pyramidal

(SiH 3 )3 N triangular Planar
(SiH 3 )2 O < (Si – O – Si)  144°

Trisilylamine, (SiH ) N, is trogonal planar due to (d – p)

3 3
 bonding involving filled N 2p z
orbital
and vacant Si 3d xy
orbitals.

P-BLOCK ELEMENTS
 ZION TUTORIALS 15

Si — N Si N

The large angles at O of disilyl ethers (R 3

Si) 2 O, is due both to electronic and steric factors.

Catenation

The property of self-linking is known as catenation. It depends mainly on bond energy. The
C–C bond energy is very high. Therefore, C has maximum catenation property. The bond energy
decreases down the group and so also the catenation property, i.e.

Bond S
C >> Si > Ge  Sn >> Pb

L
Bond Energy (KJ mol –1
)

C–C
Si – Si
IA 356
210 – 250
Ge – Ge

R 190 – 210

O
Sn – Sn 105 – 145

T
Sulphur also shows catenation because S – S bond energy is relatively high. Boron, Si, P shows
heterocatenation as B – O, Si – O and P – O bond energies are high.

Bond

S – S
T UBond Energy (KJ mol

226
–1
)

B –O 560 – 790

N Si – O 368

IO P–O ~ 340

Z
Allotropy and structure

All the elements are solid. Carbon and Sn only show allotropy.

Carbon has three crystalline allotropes :

(a) Graphite
(b) Diamond and
(c) Fullerene.

P-BLOCK ELEMENTS
16 ZION TUTORIALS
Tin is found as  – Sn, and  – Sn.

Element Allotrope Structure

Graphite Layer structure
C Diamond Cubic structure
Fullerence Carbon cluster

Si -- Diamond structure

Ge -- Diamond structure
 – Sn Diamond structure
Sn  – Sn Cubic structure
 – Sn Simple cubic structure

Pb -- ccp

LS
(a) Graphite

IA
It is soft dull looking greasy substance and is electrical conductor. Graphite has two-dimensional
layer structure.
Layers are made up of sp 2
R
hybridized C atoms. Each C is joined with three other C atoms through

They overlap and form O

 – bonds forming hexagonal rings. Each C is left with its fourth valence electron in a p-orbital.

T
 bonds. These  bonds are delocalized. Therefore, all C – C bond distances
in graphite are equal (1.415 Å). Sheet to sheet distance in graphite is 3.35Å. It is known as C

U
– dimension. Layers are joined by weak Van der waals force.

T
The weak force between layers allows one layer to slide over the other. It imparts softness to
graphite. It is, therefore, used in pencils for writing. Due to delocalized  electrons graphite is a
conductor (though along the sheet not perpendicular to it). Hence, it is used as electrode.

N
O
C

Z I C
C

C
C

C
C

C C C C

C C C

C C C

C C

P-BLOCK ELEMENTS
 ZION TUTORIALS 17

(b) Diamond

It is colourless transparent hardest substance known and is insulator. Cut diamond is sparkling
3
solid (due to refraction). Diamond has cubic unit cell. Each C is sp hybridised and is joined with
four other C atoms through  – bonds.

C
C
C

LS
As C – C bond energy (356 KJ mol –1

IA
) is very high and diamond has a giant structure, it is very
hard. This structure is responsible for its insulator property.

R
Density of diamond (3.51 g/cc) is greater than graphite (2.22g/cc). This shows that to convert

Graphite
O
graphite into diamond, pressure must be applied. There is the equilibrium.

T 15000 atm
diamond

T U 300 k

Graphite can be transformed into diamond at a reasonable rate at high pressure and ~ 300 K in
the presence of a transition metal (Fe, Cr, Pt) catalyst.

(c) Fullerenes
N
IO
Fullerenes are carbon clusters having cage like structures.

Z
Fullerenes C 60

The fullerenes C
and C

60
70
fullerenes also exist such as C
can be separated by chromatogrphic method over alumina. Many other

32
, C 50 , C 76 , C 84 etc.

is well known. It has a soccer ball structure which contains 12 five – membered
and 20 six membered rings. The rings are unsaturated. The C fullerene is called Buckminster
60
fullerene in honour of American architect Robert Buckminster Fuller.

P-BLOCK ELEMENTS
18 ZION TUTORIALS
Structure of C 60

Silicon exists only in diamond structure. A graphite like structure for Si is not possible because
it has no propensity to form (p – p)  bond.

Tin exists in three forms,  – Sn,  – Sn and

LS  – Sn.

 — Sn
(Grey)
(Non – metallic
IA  — Sn
(White)
(Metallic distorted
 — Sn
(Brittle)
(Rhombic)

R
diamond structure) close packed)

Semiconductor property of Si and Ge

TO
Silicon and to a less extent Ge are important semiconductor materials. Pure Si and Ge are non-
conductor of electricity. However, when they are droped with group – 13 or group – 15 elements,
they become semiconductor.

(i) Ge dopped with In

Ge – 4s 2 4sp 2 T U
N
In – 5s 2 5p 1
When Ge is dopped with In, there is one electron less at In site. There develops a positive

IO
hole in the lattice which makes Ge conducting. Such a semiconductor is called p – type
(positive – type) semiconductor.

(ii)
Z
Ge dopped with As
Ge – 4s 2 4p 2
As – 4s 2 4p 3
When As is dopped in Ge, there is one electron excess at As site. Due to this excess electron
Ge conducts electricity. Such a semiconductor is called n – type (negative type).

P-BLOCK ELEMENTS
 ZION TUTORIALS 19

Ge Ge Ge Ge

Ge Ge In Ge

Ge Ge Ge Ge
+In
Ge Ge Ge Ge
Ge Ge Ge Ge
Ge Ge Ge Ge

Ge Ge Ge Ge
Ge Ge Ge Ge
Ge Ge Ge Ge
+As

LS Ge

Ge
Ge

Ge
As

Ge
Ge

Ge

IA Ge Ge Ge Ge

R
Multiple Bonding
In Group 14, carbon i s the only element capable of forming comparatively stable multiple bonds

C –), imines (> C = N –), nitriles (– C

O
with another C atom and also with N, O etc. Examples are alkenes (> C = C <), alkynes (– C
 N –), ketones (> C = O), etc. None of the other elements

T
of the group forms stable compounds containing multiple bonds. Recently, some


U
success has been achieved in synthesising compounds with > Si = Si < and Si = C
< double bonds, but their details are beyond the scope of this course. Stoichiometric

containing M–O–M linkages.

T
analogues like SiO 2 , SnO 2 and (Me 2 SiO) n are known which are giant macromolecules

The tendency of formation of multiple bonds easily, in case of carbon, is because of

N
the high bond energy and a small atomic radius of carbon is compared to other
elements of the group. So its p-orbitals can approach the p-orbitals of the other C,

•
O
O or N atom for an effective overlap essential for

I
Silicon also uses d-orbitals in m
-bond formation.
ultiple bonding, In case of N(CH
p-orbitals
) , geometry is
3 3

Z
pyramidal, but in case of N(SiH

overlapping) :
) it is planar. It is due to the fact that in the
3 3
latter, the lone pair of N-atom is transferred to empty d-orbitals of silicon (p –d 

N N
CH 3 CH 3 SiH 3 SiH 3
CH 3 SiH 3
pyramidal planar
(no  bonding) (p –d bonding)

P-BLOCK ELEMENTS
20 ZION TUTORIALS
• The normal valency of the elements is four, but apart from carbon, the elements can make
more than four bonds. This is because they make use of a set of d-orbitals in bonding. Thus
2
availability of d-orbitals (empty but electrons of ns and np 2 can be excited into this) is
responsible for the ability of the elements, except carbon, to make complex ions such as
SiF 6 2– .

Energy
3d

very large
energy gap,
can not 3d
use 3 d orbitals
relatively small
in bonding
2p

Carbon
LS 3p
energy gap, can
use 3 dorbitals
in bonding

IA silicon

R
Fig. Energy difference between 2p and 3d energy levels in
carbon and between 3p and 3d energy levels in silicon.
•
– Si does not form stable double bonds
TO
The main chemical differences between silicon and carbon are :

•
–
–
U
Si does not form very stable Si – Si bonds.
Si has vacant 3d-orbitals in its valence shell into which it can accept electrons from
donor atoms.
T
Some carbon compound are less reactive than the corresponding compounds of the other

N
members of the group. CCl 4 has no interaction with H
use of empty 3d-orbitals.
2
O (hydrolysis) whereas SiCl 4
does by

O
All the elements give hydrides. Carbon, of course gives an immense number, but silicon and

I
germanium also show a wide variety.

Z CH 4
SnH
SiH 4
PbH 4
4
methane (alkane)
Stannane
silane
plumbane
GeH 4 germane
Carbon hydrides will not ignite in air unless a flame is put to them. Apart from silane, SiH 4
,
the silicon hydrides are less well behaved. Si H is spontaneously flammable in air :
3 8

Si 3 H 8 (l) + 5O 2 (g)  3SiO 2 (s) + 4H 2 O(l)

P-BLOCK ELEMENTS
 ZION TUTORIALS 21

Alkanes as well as silane are not hydrolysed however, traces of alkali converts silane into
hydrated silica SiO 2
. nH 2 O.
• As we descend the group, acidic nature of the oxides decreases and basic nature of the oxides
increases.

Oxides Nature Oxides Nature

CO, CO 2
acidic SnO, SnO 2
amphoteric
SiO 2 acidic PbO, PbO 2
basic
GeO, GeO 2
amphoteric Pb 3
O4 amphoteric

Si, Ge, Sn and Pb form oxides MO 2

. SiO 2 is infinite three-dimensional network solid of
silicon and oxygen atoms connected by single covalent bonds. GeO , SnO 2 and PbO 2 are all

S
2
solids and exist in several modifications.

Example 1

AL
Solution :

R I
Why is graphite a better electrical conductor than diamond and why does the conductivity
of graphite depend on direction ?

O
Graphite has a two-dimensional sheet like structure in which each carbon atom uses sp hybrid
orbitals to form trigonal planar  bonds to three neighbouring carbon atoms. In addition, each

Because each carbon atom must share its

U T
carbon atom uses its remaining p-orbital, perpendicular to the plane of the sheet, to form a
 bond with its three neighbours, the
 bond.
 electrons are
delocalised and are free to move in the plane of the sheet. As a result, the electrical conductivity

T
20
of graphite in a direction parallel to to the sheet is about 10 times greater than the conductivity
of diamond. The conductivity of graphite perpendicular to the sheets of carbon atoms is lower
because electrons must hop from one sheet to the next. The substance or crystal that show

N
different properties in different directions is called anisotropic.

Example 2

IO
Why elemental silicon does not form graphite like structure as carbon does ? Explain.
Solution :
Z
This is due to the reluctance of silicon to form p
atom. Hence Si exists only in diamond form.
-p multiple bonds because of large size of silicon

Compounds of Carbon and Silicon

1. Carbides : Binary compounds of carbon are called carbides, SiC, CaC 2

, Al 4 C 3 etc. Three types are
found :
(i) Ionic or salt like carbides,

P-BLOCK ELEMENTS
 22 ZION TUTORIALS
(ii) Covalent carbides,
(iii) Interstitial carbides.

(i) Ionic carbides

Three types of ionic carbides are found :
(a) Methanides,
(b) Acetylides,
(c) Propynide.
Ionic carbides are decomposed by water (or dil. Acid) at room temperature. The liberated anions
are also immediately hydrolysed. It affords a method of classification.
–4
(a) Methanides : (C unit)
Those carbides which are hydrolysed to give CH
to contain C –4
unit.

LS 4
are called methanide. They are supposed

Be 2 C + 4H 2 O  2Be(OH)

Al 4 C 3 + 12H 2 O  4Al (OH)

IA 2
+ CH 4

+ 3CH

R
3 4

–2
(b) Acetylides : (C unit)

O
2
Those which are hydrolysed to C H are called acetylides. They are common and formed by

T
2 2
Group – 1, Group – 2, Mg, Ca, Sr, Ba, Zn, Cd, Cu, Ag, Al and La metals.
Gr – 1
Cu, Ag
Gr – 2
Zn, Cd
M 2C2

T
MC 2
U
N Al, La M 2 (C 2 ) 3

IO CaC 2 + 2H 2 O  Ca(OH) 2

+ C 2H 2

(c) Z
Propynide : (C 3
Al 2 (C 2 )3 + 6H 2 O  2Al(OH)
4–

Such carbides hydrolyse to propyne

unit)
3
+ 3C 2 H 2

Mg 2 C 3 + H 2 O  2Mg(OH) 2
+ CH 3 – C  CH

(ii) Covalent carbides

Elements which compares with C in size and electronegativity form such carbides, Be, B, Si etc.
Boron and Si carbides are more important.

P-BLOCK ELEMENTS
 ZION TUTORIALS 23

SiO 2 + 2C 

 Si + 2CO

High temp
Si + C   SiC

Silicon carbide (SiC) is called carborundum. It is very inert and extremely hard.
High temp
B 2 O 3 + C   B 4C

B 4 C is a also very hard, infusible and inert. It is used to make bulletproof clothing.
These covalent carbides (or  – Al 2 O 3 ) are comparable in hardness to diamond (Moh’s scale).

Hardness  Diamond > B 4

C > SiC >  – Al 2 O 3

(iii) Interstitial carbides

LS
Transition metals form such carbides, in which C atoms occupy octahedral voids. Such materials
are very hard, electrically conducting and have very high mp. For example : TiC, ZrC, MoC, WC
etc.

2. Oxides
IA
Electrons of this form oxides of the type MO and MO

R 2
. Carbon forms suboxides also, e.g., C 3
O 2.

Oxides

MO
C

CO
(neutral) X
Si

TO Ge

GeO SnO

Sn

PbO


Pb

U
ampoteric

T
GeO 2 SnO 2 PbO 2
MO 2 CO SiO 2  

ampoteric

 acidic 

(a)
N
Carbon monoxide (CO)

(i)
IO
It forms many important gaseous mixtures of industrial use
Water gas or synthesis gas CO + H

Z
2
(ii) Producer gas CO + N 2
(iii) Coal gas CO + H 2
+ CH 4 + C O 2
 CO is a neutral oxide.
 Carbon monoxide has a triple bonded C atom, one s and two p bonds (best explained
by MO model).
 CO, however, is a strong ligand towards transition metals and form variety of complexes
known as carbonyls, Ni (CO) 4 , Fe(CO) 5 etc. They are stable due to synergic bonding.

P-BLOCK ELEMENTS
24 ZION TUTORIALS
 CO is very toxic and rapidly forms a bright red complex with haemoglobin of blood.
Thus preventing haemoglobin to carry oxygen to cells, using oxygen deficiency to
unconsciousness and then death.

(b) Carbon dioxide (CO 2

)
 CO 2 is acidic oxide
 CO 2 is biologically important
(i) Maintains pH of blood, due to the equilibrium
+
CO 2 + H 2 O HCO 3 + H

(ii) Main components of photo synthesis

S
Chlorophyll
6CO 2  6H 2O  C 6H 12O 6 6O 2
Sun light

L
 Glucose 

(iii) The reverse process of the above takes place in the process of respiration.

C 6 H 12 O 6 + 6O 2  6CO 2 + 6H 2 O + Energy

IA
 CO 2 is used in the synthesis of urea

R NH 2

CO 2 + 2NH 3 H 2NCO 2NH

T
Ammonium
O
Carbamate
4

O C
NH 2
Urea
+ H 2O


T
forces are weak Van der Waals’ force.
Solid CO
U
CO 2 is gas at NTP and has the structure O == C == O. The (p – p)
effective. Therefore, even in solid state discrete CO

is called ‘dry ice’ or ‘cardice’.

2
 bonding is very
molecules exist. The intermolecular

N
2

Silicon dioxide, SiO 2

, unlike CO 2 is a solid. The (p – p)  bonding is not effective in SiO 2
like CO 2 .

IO
It is due to larger size of Si and more core electrons (8e) in Si. Therefore, to stabilize; SiO
a continuous lattice of Si and oxygen atoms joined by covalent bonds. Each Si is sp 3
2
contains
and is joined

Z
with 4 O + atoms and each O – atom with two Si – atoms. A macromolecule is formed, hence SiO 2
is a solid.
O O

O Si O Si O

O O

O Si O Si O

O O

P-BLOCK ELEMENTS
 ZION TUTORIALS 25

Halides MX 2
and MX 4

Group – 14 elements form tetrahalides of the type MX 4

(X = F, Cl, Br, I) except PbI 4
.
+4 – +4
PbI 4 does not exist due to strong oxidizing power of Pb and reducing nature of I ion. The Pb
+2
is strong oxidizing agent due to greater stability of Pb (inert pair effect).
Thus, MX 4 , [M = C, Si, Ge, Sn, X = F, Cl, Br, I]
+2
Germanium, Sn and Pb also for MX 2
. The stability of MX 2
is maximum for Pb .
SnF 2 is sparingly soluble in water and is used in fluoride containing tooth pastes.
The MX 4 halides are all colourless except GeI 4
and SnI 4
which are bright orange solids. Colour
in these halides is due to charge transfer.

Sn +4 I – Ge +4 I –

All tetrachlorides except CCl

e

4
LS
are hydrolysed by water.
e

Carbon tetrachloride is not hydrolysed because :

(a) carbon in CCl is coordinatively saturated

IA
R
4
(b) C – Cl bond is less polar

(a)
XC = 2.5, X Cl = 3.0,  = 0.5

Silicon tetra chloride (SiCl

Si – Cl bond is more polar

4

TO
) is extensively hydrolysed. It is because :

(b)
XSi = 1.8,  XCl = 3.0,  = 1.2
Si in SiCl 4
T U
can increase its coordination number by using 3d orbitals

The tetra halides of Si, Ge, Sn and Pb can increase their coordination numbers by using d orbitals

N
and can form haloanions.

IO SiF 4 + 2F –  SiF 62 

SnCl 4 + 2Cl –  SnCl 6

Z
The hexacoordinated halo anions are octahedral having sp

Example 3
3 2
d hybridised central atom (Si).

CCl 4 can not be hydrolysed but SiCl 4

can be. Why ?
Solution :
Vacant d orbital is not present in carbon so it can not extend its configuration like Si. Therefore
it can not be hydrolysed.

P-BLOCK ELEMENTS
 26 ZION TUTORIALS
Example 4

SiCl 2
is solid while SiCl 4
is liquid at room temperature. Why ?
Solution :
SiCl 2 is more ionic than SiCl 4 by Fajan’s rule. Therefore it has greater m.p. so it is solid at room
temperature while SiCl 4
is liquid.

Hydrides :
All element of this group form hydrides.
Carbon forms a large number of chain and ring compounds due to high catenation property. They
are :
Alkanes C n
H 2n+2
Alkenes
Alkynes
Cyclo alkanes and cycloalkynes
C n H 2n
C n H 2n–2

LS
Aromatic hydrocarbons (C 6
H 6)

IA
Silicon (others also) form saturated hydrides only which are called silanes, Si n
H 2n+2 (Si ~ 8).

SiCl 4 + LiAlH 4
R
 SiH 4 + AlCl 3 + LiCl

Silicons :

TO
They are organosilicon polymers having empirical formula approximately R 2
SiO. Polymers are

U
very stable due to strong Si – O and Si – C bonds. Silicones can be prepared as oils, resins, plastics
etc. They are :



Inert
Water repellent T


N
Heat resistant
Electrical insulator

IO
All these properties make silicones very useful.
Hydrolysis of alkyl chlorosilanes produces products having Si – OH bonds. They do not dehydrate

Z
like gem diols (of C).

R
Si
Cl

Cl
+ H 2O
(–2HCl)
R

R
Si
OH

OH
R

R
Si O

Silicates

Silicates are solids having Si – O bonds. Most of the rocks and even soil contain silicates. Alkali
metal silicates are water soluble. They are made on a large scale as

~ 1500 C
Na 2 CO 3 + SiO 2   Na 4 SiO 4 , (Na 2 SiO 3 )n etc. + CO 2 

P-BLOCK ELEMENTS
 ZION TUTORIALS 27

They are used in detergents. The concentrated aq. solution of Na 4

SiO 4 is solid like and as known
as water glass. Variety of silicates are found but in all the basic unit is the SiO 4
tetrahedron.

O–

Si or

O– O–
O–

Each O – atom carries one unit negative charge. In polymeric silicates SiO 4
units share
O – atoms(s). It provides a way of classification.

Orthosilicates (Mononuclear silicates)

These are silicates having discrete

LS
SiO 44  ions. Metal ions are surrounded by O–atoms.

IA
R
Pyrosilicates (Si

When two SiO 4

2
O 7 –6 ) :

TO
units share only one O – atom pyrosilicates, Si 2O 76 , are formed. These are also
discrete units.

O–
T
Si
U O
Si
O–

O – O–

N O
–
O–

Glass

IO
Solids are most stable in crystalline form. However, if a solid is formed rapidly (for example, when

Z
a liquid is cooled quickly), its atoms or molecules do not have time to align themselves and may
become locked in positions other than those of a regular crystal.
If we mix sodium carbonate and calcium carbonate with sand and fuse the mixture at about
1500°C, we get a liquid mixture of sodium and calcium silicates. When this mixture is cooled, it
becomes viscous and eventually ceases to flow; it becomes solid –called glass. Glass is thus super-
cooled liquid (solid solution). Amorphous solids, such as glass, lack regular three dimensional
arrangement of atoms. Glass thus refers to an optically transparent fusion product of inorganic
materials that has cooled to a rigid state without crystallising.

P-BLOCK ELEMENTS
 28 ZION TUTORIALS

Na 2 CO 3 + SiO 2 

 Na 2 SiO 3 + CO 2

CaCO 3 + SiO 2  CaSiO 3

+ CO 2

By varying the proportions of the three basic ingredients, and by adding other substances, we can
alter the properties of the glass as given :

• Calcium-alkali silicate glass – normal domestic glass for windows

Sodium silicate – soda glass used in cheap laboratory glassware
• Fining agents such as NaNO 3
or As 2 O 3 are added to remove bubbles.
• Decolorising agents may be added to eliminate impurities and to obtain colourless glass.
CaF 2 is sometimes added to make opal glass.

Na 2 SiO 3 + 6HF
LS
Glass is attacked by HF and this property is used to make marking on the glass (etching)

 Na 2 SiF 6 + 3H 2 O
(in glass)

IA
R
CaSiO 3
+ 6HF  CaSiF 6
+ 3H 2 O

HF, however does not attack wax. The portion of the glass on which etching is to be done is

TO
covered with wax layer. Markings are carved on the wax layer with a pin and HF is poured on
the carved parts and left for sometime. After washing with water, wax is removed and permanent
marking is obtained.

Example 5

The standard free energies of formation of B

–1 T U
O and MgO are – 1194 kJ mol
2 3
mol respectively. Should it be possible to prepare boron by reacting B
–1
and – 569 kJ
O with magnesium ?

N
2 3
Solution :

IO
B 2 O 3 + Mg  2B + 3MgO

G° = G product – G°reactant

Z
= 3 G°f (MgO) – G°f (B 2 O 3 )
= 3(– 569) – (– 1194)
= – 513 kJ mol –1
[G°f (element) = 0]
The negative sign of G° shows that the reaction should be spontaneous. (However, the reaction
is initially endothermic when two reactants are heated.)

P-BLOCK ELEMENTS
 ZION TUTORIALS 29

Example 6

(i) What type of bonding holds the layer in graphite ?

(ii) Why will graphite conduct electricity well in a direction parallel to the planes of
hexagons, but not at all well in a direction perpendicular to the planes ?
(iii) What is the name we give to crystal or substances, that show different properties in
different directions ?
Solution :
(i) Van der Waals bonding
(ii) The delocalised orbitals in graphite lie parallel to the planes and electrons can move along
the planes making use of these orbitals; conduction is good parallel to the planes. There is
no overlap of orbitals perpendicular to the planes, so conduction is poor in this direction.
(iii)

Example 7
They are anisotropic.

LS
If you had a mixture of CO and CO
two gases in the mixture ?
2

IA
, how would you find out relative proportions of the

Solution :
R
Method I : Mixture of CO 2 is run into Ca(OH)
residual volume will be that of CO.

Ca(OH)
TO
+ CO 2  CaCO
2
solution. CO 2

+ H 2O
is absorbed by Ca(OH) 2
and thus

U
2 3

Method II : Mixture of CO and CO is passed over heated charcoal :

T
2

CO 2 + C  2CO

Increase in volume will be due to CO . By measuring total volume after passing over heated

N
2
charcoal, composition of mixture of CO and CO 2
can be determined.

Example 8

IO
Z
CO and CN – ions are highly poisonous. A sign that some one has been poisoned by either
of these two chemicals is that the person’s blood changes colour. They both have the effect
of preventing oxygen being taken up by the blood stream. What might happen to
haemoglobin to stop oxygen being taken up ?
Solution :
CO and CN – ions are able to bond more strongly to the iron atom in haemoglobin than can
oxygen. If you were to breathe in CO for any length of time, your haemoglobin would become
saturated with CO molecules rather than oxygen. As a result, all the body processes that rely on
a supply of oxygen gradually cease. Death is the result.

P-BLOCK ELEMENTS
 30 ZION TUTORIALS
Example 9

What would you expect to happen when :

(a) Tin is heated with a concentrated aqueous solution of sodium hydroxide
(b) Sulphur dioxide is passed over lead dioxide
(c) Carbon disulphide is shaken with aqueous sodium sulphide
(d) Dichlorosilane is hydrolysed by water
(e) 4 mol of ClCH 2
SiCl 3
react with 3 mol of LiAlH 4
in diethyl ether solution ?
Solution :
–
(a) Sn + 2OH + 4H 2 O  [Sn(OH) 6 ]2– + 2H 2

(b)

(c)
PbO 2 + SO 2  PbSO

CS 2 + Na 2 S  Na 2 CS 3
4

LS
sodium thiocarbonate

H OH
IA
R
(d) SiH 2 Cl 2 + 2H 2 O  Si +2HCI
H OH
H

H
TO Si=O + H 2O

(e)

Example 10
4ClCH 2 SiCl 3 + 3LiAlH 4

T U
 4ClCH 2 SiH 3 + 3LiCl + 3AlCl 3

N
Suggest syntheses (starting from deuterium oxide as the only source of deuterium) for:

O
(a) B 2 D 6 (b) B(OD) 3
(c) B 3 N 3 D 6 (d) B (CH 2
CH 2 D) 3 .
Solution :

(a)

Z I
P 2 O 5 + 3D 2 O  2D 3 PO 4

Mg 3 B 2 + 2D 3 PO 4  Mg 3 (PO 4 )2 + B 2 D 6

(b) B 2 O 3 + 3D 2 O  2B(OD) 3

(c) Mg 3 N 2 + D 2 O  ND 3 + Mg(OD) 2

2ND 3 + B 2 D 6  [D 2 B(ND 3 )2 )][BD 4 ] 


 B 3N 3D 6

(d) 6CH 2 = CH 2 + B 2 D 6  2B(CH 2 CH 2 D) 3

P-BLOCK ELEMENTS
 ZION TUTORIALS 31

Example 11

Explain the following :

(a) Boron does not usually form a cation :
B has
–1 –1
(IE) 1 = 801 kJ mol , (IE) 2 = 2427 kJ mol ,
–1
(IE) 3 = 3659 kJ mol
3+
 Thus, the total energy required to give B ions is far more than that which would be
compensated by lattice energies of ionic compounds or hydration of such ions in solution.
3+
Thus formation of cation (like B ) is not possible.

(b) The polarity of B–X bonds is in the order : B–F > B–Cl > B–Br but Lewis acidicity shows
the sequence : BF

order :
3
< BCl 3 < BBr 3 .

LS
With increase in polarity of B–X bond, acidity also increases and should be thus in the

But Lewis acidity is in reverse order :

IA
BF 3 > BCl 3 > BBr 3

R
BF 3 < BCl 3 < BBr 3

TO
There is lateral overlap of the vacant 2p orbital of B with one completely filled orbital of F leading
to p -p bonds between B and F. This B–F bond thus acquires double bond character. This also
leads to compensate electron deficiency of boron and thus Lewis acid character of BF 3
is reduced.

U
This p -p bonding decreases going from BF 3
to BBr 3
and thus Lewis acidic nature increases in
the order :

T
BF 3 < BCI 3< BBr 3
excite

N
B
ground state 2p 1 2p 2
2s 1 2s 1

IO excited state

Z F

F
B F
F

F
B F

(c) Al and Ga are trivalent in their compounds but in case of T l , monovalent compounds
are the most stable. Why ?
 It is due to ‘inert pair’ effect due to which stability of + 3 state decreases and that of + 1
state increases while going down the group (in this case Group 13)

P-BLOCK ELEMENTS
 32 ZION TUTORIALS
3+ 3+ 3+
Al > Ga > In > TI 3+
(most stable)

Al + < Ga + < In + < TI +

(most stable)

(d) CO 2
is a gas but SiO 2
is a solid :
 Carbon and silicon (Group 14, IVA) have four valence electrons. We might expect carbon
and silicon to form oxides with similar properties. In CO 2
the ability of C and O atoms to
form  bonds through the side-wise overlap of their 2p orbitals is strong. The result is strong
C–to–O double bonds and a very stable triatomic molecule.
O=C=O

S
Silicon, being in third period, would have to use 3 p orbitals to form double bonds with
oxygen. The side-wise overlap of these orbitals with the 2p orbitals of oxygen is too limited

AL
for  bond formation. From an energy stand point, a stronger bonding arrangement results
if the Si atoms from four single bonds with O atoms (bond energy : 464 kJ/mol) rather than

I
two double bonds (bond energy : 640 kJ/mol) since each O atom must be simultaneously
bonded to two Si atoms, the result in a network of –Si–O–Si–bonds and thus a hard (giant)
solid :

R
O

TO O
O

S O
O

S O

O
Si

O
O

T U O
O

S O
O

S O

(e) SiCl
N
is hydrolysed but CCl is inert to hydrolysis :
O O

O
4 4


Z I
SiCl 4 and CCl 4 are covalent compounds. Carbon has maximum covalency of four while
silicon has six. Thus CCl 4 is inert towards water and is not hydrolysed but SiCl
coordinate with 2 mol of H 2 O molecules and is thus readily hydrolysed :

SiCl 4 + 2H 2 O  Si(OH) 4 + 2HCl

4
can

Cl Cl
H Cl Cl H

H 2O + Si + OH 2 O Si O

H Cl Cl H
Cl Cl
Silicon with covalency six

P-BLOCK ELEMENTS
 ZION TUTORIALS 33

–2HC l

Cl
H Cl Cl H
2H 2O
O Si O OH S OH

H Cl Cl H
Cl
Silicon with covalency six

OH
|
 2HCl
 HO  Si OH
|

S
OH

(f) (SiH


) N is planar while (CH
3 3

In case of (CH
) N is pyramidal :
3 3

AL
) N, lone pair on N and three covalent bonds with CH groups results in sp 3

I
3 3 3
hybridisation but lone pair-bond pair repulsion causes distortion hence gives pyramidal

R
structure :

TO N

But in case of (SiH T U

CH 3
CH 3
CH 3

) N, lone pair on the nitrogen is transferred to the empty d-orbitals of

3 3

N
silicon (p 
– d  overlap) thereby causing planarity of unit.

Example 12

IO
Solution :
Z
AlF 3 is insoluble in anhydrous HF but when little KF is added to the compound it becomes
soluble. On addition of BF 3
, AlF 3 is precipitated. Write the balanced chemical equations.

3KF + AlF 3  K 3 AlF 6

K 3 AlF 6 + 3BF 3  AlF 3 + 3KBF 4

P-BLOCK ELEMENTS
 34 ZION TUTORIALS
Example 13

(SiH 3 ) 3 N is a weaker base than (CH 3 3

) N. Explain.
Solution :
In (SiH 3 )3 N, the lone pair of electrons on nitrogen is involved in p –d  back bonding, while such
bonding is not possible (CH 3 )3 N as d-orbitals are not present in carbon. Hence, the lone pair of
electrons on nitrogen in (CH ) N is available for donation to Lewis acids, exactly acting as
3 3
stronger base.

Example 14

(i) A white precipitate (B) is formed when a mineral (A) is boiled with Na 2
CO 3 solution.
(ii) The precipitate is filtered and the filtrate contains two compounds (C) and (D). The
compound (C) is removed by crystallisation and when CO
mother liquor left, (D) changes to (C).

LS
(iii) The compound (C) on strong heating gives two compounds (D) and (E).
2
is passed through the

IA
(iv) (E) on heating with cobalt oxide produces blue coloured substance (F). Identify (A) to
(F) and give chemical reactions for the reactions at step (i) to (iv).
Solution :
R
O
(i) The mineral (A) is colemanite, Ca 2
B 6 O 11 . 5H 2 O

T
boiled
Ca 2 B 6 O 11 + 2Na 2 CO 3(aq)   2CaCO 3
+ Na 2 B 4 O 7 + 2NaBO 2

(B) Insoluble (C) (D)

(ii)
T U Soluble

(C), the borax is crystallized. The mother liquor consisting sodium metaborate is treated with
CO 2 .

N 4NaBO 2
+ CO 2  Na 2 B 4 O 7 + Na 2 CO 3

(iii)

IO heated
Na 2 B 4 O 7 .10H 2 O   Na 2 B 4 O 7 + 10H 2 O
Anhydrous

(iv)
Z strongly
Na 2 B 4 O 7 
heated

heat
CaO + B 2 O 3 
 2NaBO

 CO(BO 2 )2
2
+ B 2O 3

cobalt meta borate

(blue coloured)

P-BLOCK ELEMENTS
 ZION TUTORIALS 35

Example 15

PbCl 4
is less stable than SiCl 4
. Why ?
Solution :
Pb is more stable in + 2 stable due to inert pair effect while Sn is more stable in + 4 state as
compared to Pb +4 .

GROUP 15 ELEMENTS

Elements : N, P, As, Sb, Bi

Nitrogen and phosphorus are non-metals. The metallic character increases down the group due
to lower I.E. and larger size. Hence, bismuth shows metallic character. The group state electronic
configuration is ns 2 np 3 .

Trends in Chemical Reactivity

LS
A
Most common oxidation states shown by group 15 elements are – 3, + 3 and + 5. The stability

I
of highest oxidation state (+ 5) decreases down the group.
The covalent character goes on decreasing as we move down the group in the sequence, P > As

R
> Sb > Bi. This is due to increasing size of atom which refers to Fajan’s rules.

O
3+
Sb and Bi are the heavier elements of the group and form M cations due to decrease in
ionization enthalpy.
In contrast to nitrogen, the phosphorus atom forms p
chain compounds. Hence, it shows catenation.

U T =p  bonding and forms both cyclic and open

As we move down the group there is a decrease is covalent character.

T N > P > As > Sb > Bi

Nitrogen is chemically less reactive, due to high stability of its molecule. N 2
in which two nitrogen

N
atoms are combined through a triple covalent bond (N
are pie ( ) bonds, thus posses high bond strength (941.4 KJ mol
 N) of which one is sigma ( ) and two
–1
)

IO
Nitrogen has one special feature that it can form p
oxygen due to its small size. In phosphorus rather p
-p multiple bonds with itself, carbon and
-p, d -p is found as in POX 3 .

Z
General Trends in Physical Properties

Sr.No. Property Nitrogen Phosphorus Arsenic

3 2 3
Antimony
2 3
Bismuth
1. Configuration [He]2s 2p [Ne]3s 3p [Ar]4s 4p [Kr]5s 2 5p 3 [Xe]6s 2 6p 3
2. Common oxidation state – 3, + 3, + 5 – 3, + 5, + 5 + 3, + 5 + 3, + 5 +3
3. Atomic radius (pm) 70 110 120 140 150
4. First ionization 1403 1012 947 834 703
5. Electronegativity 3.0 2.1 2.0 1.9 1.9

P-BLOCK ELEMENTS
36 ZION TUTORIALS
Since, it is not easy from energy consideration to gain three electrons to achieve stable noble gas
3–
configuration, the formation of the tri-negative ion (M ) is rare. But, nitrogen being the smallest
and the most electronegative of all the members of the group, forms trivalent anion with reactive
metals which have low ionisation energies. Thus, nitrogen forms ionic nitrides such as Li 3
N,
Be 3 N 2 , Mg 3 N 2 , Ca 3 N 2 . As the electronegativity of the other elements of the group, i.e., P, As, Sb
and Bi, is low, most of their compounds are covalent in nature.
Nitrogen is not able to extend its coordination number beyond four, the other elements have
coordination numbers of five as well as six. The extension of coordination number is due to the
3
availability of d-orbitals in P, As, Sb and Bi, using which these elements can attain sp d and sp 3 d 2
–
hybridisation, e.g. in PCl 5
and PCl 6
, respectively. Thus, nitrogen does not function as a Lewis
acid whereas phosporus, arsenic antimony and bismuth do so. The hybrides of this group and

BF 3 , CaCl 2
. 4NH 2 , etc.

LS
their alkyl derivatives act as Lewis bases, forming a number of addition complexes, e.g., NH 3
.

A
• Stability of + 3 state increases and that of + 5 state decreases going down the group due
to “inert pair effect”, thus
Bi 3+ > Sb 3+ > As 3+
Bi 5+ < Sb 5+ < As 5+
R I
Bi 5+ + 2e –  Bi 3+

As 3+ salts are good reducing agents : TO

Bi 5+ salts are very rare and are good oxidising agents :

•
As 3+  As 5+ + 2e –

T U
They form trihalide and penthalide (except N, which does not form NCl 5
etc.) As we go down
the group, covalent nature decrease and ionic nature increases; thus NCl and PCl 3 are

N
3
covalent while BiCl 3 is ionic. This is also in accordance with Fajan’s rule : Smaller the size
of cation, larger the size of anion, greater the charge then greater the polarising power and

IO
hence greater the covlalent nature. Halides are hydrolysed in water forming oxyacids or
oxychlorides :

Z PCl 3 + 3H 2 O  H 3 PO 3 + 3HCl

SbCl 3 + H 2 O  SbOCl  + 2HCl

(orange ppt)

BiCl 3 + H 2 O  BiOCl + 2HCl

(white ppt)

P-BLOCK ELEMENTS
 ZION TUTORIALS 37

Compounds of Nitrogen

Oxides of N
(i) Dinitrogen oxide (or nitrous oxide) N 2
O


NH 4NO 3 N 2O + 2H O
2

Structure : It is isoelectronic to CO 2
and has linear structure. But unlike CO 2
it has dipole
moment (0.16 D). It shows resonance

– + + –
N == N == O N N—O

(2) Nitric oxide (NO)

 Copper reacts with dil HNO

8HNO + 3Cu  3Cu(NO 3 )2 + 4H 2 O + 2NO

3

LS
(8M) to form NO. It is reduction of NO 3

A
3

 Commercially, NO is obtained by catalytic oxidation of NH

4NH 3  5O 2
Pt catalyst
4NO + 6H O2



R I 3
(ostwald process for HNO 3
)

(3) Dinitrogen trioxide N O3

TO
Nitric oxide is a good ligand and form variety of complexes with transition metals which are
known as nitrosyls, Na 2 [Fe(CN) 5 NO]

It can be obtained by mixing NO and NO

2

T
NO + NO
U2
2
in equimolar quantities at low temperature.

Low
 N 2O

Temp. 3
(blue liq.)
( 30 F)

N
In gaseous state it has the structure

IO
Z
The N – N distance is very large, 1.864Å

(4) Nitrogen dioxide NO 2

(N 2 O 4 )

(i) Cu + conc. HNO 3  NO 2



Cu + 4HNO 3  Cu(NO 3 )2 + 2H 2 O + 2NO


2

P-BLOCK ELEMENTS
 38 ZION TUTORIALS
(ii) Di or trivalent metal nitrate decomposes on heating to NO 2

Pb (NO 3 )2 

 PbO + 2NO 2
+ ½O 2

Structure : NO 2 is an odd electron (17 electrons) molecule and is paramagnetic. It has the
structure

The unpaired electron ensures ready dimerisation to a diamagnetic colourless species N 2

O4
(dinitrogen tetraoxide).

S
2NO 2 N 2O 4

L
N 2 O 4 is planar

IA
R
(5) Nitrogen pentaoxide N 2
O5
TO
It is obtained by dehydration of HNO

Structure : T
2HNO 3

N 2 O 5 is solid and in this state it is

U
3
by P 2 O 5

+ P 2 O 5 

 2HPO 3
+ N 2O 5

NO +2.NO 3 i.e. nitronium nitrate. In gaseous state

N
it has the structure

O
O O

Z I O
N O N

AMMONIA – NH 3
It can be prepared in many ways :
(i) Any ammonium salt on heating with alkali forms ammonia.

NH 4 Cl + NaOH  NH 3 + NaCl + H


2
O

2NH 4 OOCCH 3
+ Ca(OH) 2  NH 3 + Ca(CH 3 COO) 2 + 2H 2 O

P-BLOCK ELEMENTS
 ZION TUTORIALS 39

(ii) Ionic nitrides are hydrolysed by water to produce NH 3

.

Mg 3 N 2 + 3H 2 O  2NH 3 + 3MgO

(iii) NH +4 salts which contain non-oxidizing anions, on heating given NH 3

.

NH 4 Cl 

 NH 3 + H 2 Cl

–
Non-oxidizing anions are Cl , SO 24 , CO 23 , CH 3COO ,PO 3
4 etc.

However NH +4 salts which contain oxidizing anions forms N 2

or N 2 O on heating.

NH 4 NO 3 (l)  N 2 O + 2H 2 O

LS
NH 4 NO 2  N 2 + 2H 2 O

(NH 4 )2 Cr 2 O 7  N 2 + Cr 2 O 3 + 4H 2 O

(iv) NH 3 is manufactured by :
IA
R
High pressure

O
~ 450 C
(a) Haber’s process N 2  3H 2 2NH 3(g) + Q
Fe (Fe 2O 3) catalyst

T
MO Promoter 

U
(b) Cyanamide process

CaC 2  N 2 
CaCN
Electric
furnace
(~ 1100 C)
T 2 C
(Nitrolum)

CaCN
N 2
+ 3H 2 O 

 CaCO 3   2NH 3

Nitrous acid (HNO

IO 2
)

•
Z
It disproportionates to HNO

3HNO
+3
2
3
(oxidation) and NO (reduction)

2NO + HNO 3+ H O2
+2 +5
reduction

oxidation

P-BLOCK ELEMENTS
 40 ZION TUTORIALS

HNO 2

r e a ge
en n g

du n t
a g iz i

ci
t
id

ng
ox
I– MnO 4– /H +
I2 Mn 2+
S Fe 2+ +
H2 Cr 2 O 72– /H
H 2O 2
SO 2
S Fe 3+
2– 3+
SO 4 H 2O Cr

Structure : H

S
O N
O

NO 2 has planar triangular structure

AL
N
R I
O
–
O O

Nitric acid (HNO 3

)
HNO 3 can act as an oxidizing agent.

U T
Fe 3+
SO 42–

Fe
T
2+
SO 2
H 2S
S

N
S
HNO 3 H 2SO 4
C I2
P

IO H 2CO 3
H 2CO 3
HIO 3

Aqua regia Z
A mixture of conc. HCl and HNO 3
in the ratio 3 : 1 is called aquaregia. This is a powerful
oxidizing agent and dissolves metals like Au and Pt. The two acids on mixing react as

3HCl + HNO 3 NOCl + 2Cl + H O2

The presence of NOCl and Cl makes aquaregia a powerful oxidizing agent.

Au + 3Cl  AuCl 3

P-BLOCK ELEMENTS
 ZION TUTORIALS 41

AuCl 3 + Cl –  AuCl 4 (or HAuCl 4 , chloroauric acid)

–
Pt + 4Cl  PtCl 4

PtCl 4
+ 2Cl –  PtCl 2
6 (or H 2 PtCl 6 , Chloroplatinic acid)

Note : Au is not oxidized by HNO 3

alone but by aquaregia.

Red Phosphorus

Red phosporus is prepared by heating white phosphorus in the absence of air at 250°C for a few
hours with a trace of iodine as catalyst in a closed iron vessel fitted with a safety valve. At the
end of conversion, the product is ground under water and treated with hot caustic soda solution

heating with steam.

LS
to eliminate any unchanged white phosphorus. It is finally washed with hot water and dried by

Another allotrope of phosphorus is black phosphorus and is obtained by heating white phosphorus

IA
at 470 K under high pressure. A series of phases of black phosphorus are formed and one of these
phases consists of an extended layer structure in which each phosphorus is bonded to three

R
neighbours by single covalent bonds. Thermodynamically, black phosphorus is the most stable
form.

contains discrete tetrahedral P

and has a polymeric structure :
4
O
White phosphorus, the form produced in the industrial synthesis, is a toxic, waxy, white solid that

T
molecules. Red phosphorus, by contrast, is essentially nontoxic

P
P
P
P —P

T
P
U P
P—P
P

P
P—P
P

P
P—

White phosphorus

N
Red phosphorus

As expected for a molecular solid that contains small, non-polar molecules, white phosphorus has

IO
a low melting point, (44°C) and is soluble in non-polar solvent such as CS
bursting into flames when exposed to air, and is thus stored under water.
2
. It is highly reactive,

Phosphine (PH

(i)
Z 3
)

When a mixture of white P (P 4

) and NaOH soln. is heated, PH 3
is formed.

P 4 + 2NaOH + 3H 2
O 

 3NaH 2 PO 2 + PH 3

In this reaction some P 2

H 4 is also formed as side product. It is inflammable in air.
(ii) Ionic phosphides react with water to form PH 3
.

Ca 3 P 2 + 6H 2 O  3Ca(OH) 2
+ 2PH 3

P-BLOCK ELEMENTS
42 ZION TUTORIALS
NH 3 is highly soluble in water by PH 3
is insoluble in water. NH 3
dissolves due to H-bonding.

H
H O H
H
O H N H O H
H
H H O H

PH 3 cannot form H-bond, so it is insoluble in water.

Oxides of Phosphorus

P – oxides P 4
O 6 and P 4
O 10

 P4  X
LS
Stream of air
 P 4O 6

600 C

IA
Excess of air
P 4  P 4O 10


These oxides are solids.

R
O
They differ from N oxides in stoichiometry and structure. It is due to inbality of P to form
(p – p)  bonds.

P 4O 6
U T
P 4 O 6 and P 4 O 10 both have cage structure. The structures are based upon P 4
tetrahedra.

T
In this oxide P – atoms form a regular tetrahedron and O – atoms are present at six edges of the
tetrahedron and bridge P – atoms.

N O
P
O

IO P
O

Z
O P

O P O

P 4 O 10
In this oxide P 4 tetrahedron has six edge–bridging O–atoms and four terminal O–atoms. The
terminal P – O bonds have (d – p)  bonding. Therefore, there are two types of P – O distances
in P 4 O 10 large bridging P – O and small terminal P – O distances.

P-BLOCK ELEMENTS
 ZION TUTORIALS 43

P
O O
O O
O P P O
O P
P
O O
O (d – p)  bonding in P 4
O 10

Oxy acids of P

S
The common oxy acids of P are :

L
Oxidation
State of P Name Formula Proticity Structure
+1 Hydrophosphorous
acid (phosphinic acid)
I
HA PO 2 1 Td

R
3

+3 Phosphorous acid H 3
PO 3 2 Td.

+5 Metaphosphoric acid

TO (HPO 3
)n 1
Td. Polymeric
and contain PO
Td units
4

+5

T
Orthophosphoric acid
U H 3
PO 4 3
Td
Highly hydrogen
bonded

Td. (two
+5
N Pyrophosphoric acid H P O7
4 2
4 tetrahedra

O
joined through O

Z I 220 C
H 3 PO 4  320 C
 H 4 P 2 O 7   (HPO 3 )
– atom)

Phosphorus Halides

P 4 + 6X 2  4PX 3 (in limited supply of X 2

)

P 4 + 10X 2  4PX 5 (in excess amount of X 2

)

P-BLOCK ELEMENTS
 44 ZION TUTORIALS

• SO 3
+ PCl 3  POCl 3 + SO 2

• PCl 3
+ H 2 O  H 3 PO 3 + 3H 2 O

• PCl 3
+ HI  PI 3 + 3HCl

• 3ROH + PCl  3RCl + H 3 PO 3

• ROH + PCl 5  RCl + POCl 3

+ HCl

Example 16
Pb(NO 3) 2

LS
A
F2 H 2O
F A B C + HNO

I
3

HCI
CO

R


G+H
D+E A+D+H 2O

Solution :
A = NO 2 , N 2 O 4 , C = HNO 2 , D = NO, E = CO
TO 2
, F = NO 2 F, G = NOCl, H = Cl 2
.

Group 16 (VIA–The Chalcogens)

•
T U
The first four elements are called chalcogens meaning ore forming (oxides, sulphides, selenides,
tellurides).
•

N
Similar to the groups discussed earlier, the metallic character in Group 16 increases with increasing
atomic number. Oxygen and sulphur are entirely non-metallic in their chemical behaviour. Selenium

IO
and tellurium though essentially non-metallic, assume increasing metallic character and are
termed as metalloids. Polonium is most metallic in the group.

Z
Density, melting and boiling points covalent and ionic radii, show a regular increase from oxygen
to polonium. The large difference in melting and boiling points between oxygen and sulphur can
be explained on the basis of their structure. Oxygen exists mostly as a diatomic molecule held
together by weak van der Waals forces while others exist as polyatomic molecules, e.g., S , Se 8 ,
8
etc., where the atoms are bonded by covalent bonds associated with high dissociation energy.
Their existence as diatomic and polyatomic molecules can be explained as follows. The bond
–1
energy of the oxygen-oxygen double bond. O=O, is 498 kJ mol . This makes the O=O bond
–1
more than three times as strong as the O–O bond (bond energy for O–O is 142 kJ mol ). By
comparison the S=S bond is less than twice as strong as the S–S single bond (bond energy for

P-BLOCK ELEMENTS
 ZION TUTORIALS 45
–1 –1
S=S, 431 kJ mol ; S–S, 265 kJ mol ). This results in catenated –O–O–O– chains begining
unstable relative to O=O, but catenated –S–S–S– chains being stable relative to the molecule S=S.

The elements of Group 16 are characterised by high ionisation energies. Their electronegativities
decrease with increasing atomic number. Thus, in view of the fall in electronegativity, metallic
character within the group increases with increasing atomic size.

Oxygen, the second most electronegative element, fluorine being the first, has a strong tendency
2– 2–
to accept two electrons and give O ion. Thus, almost all metal oxides are ionic and contain O
ions. Usually oxygen exhibits an oxidation state – 2 in its other compounds also. It exhibits
positive oxidation states only in a few compounds formed with fluorine, i.e., OF 2
and O 2 F 2 . The
tendency for the formation of divalent anions decreases from sulphur downwards because of the
increasing size and decreasing electronegativity of the elements. Sulphur, selenium an tellurium

LS
show a tendency for covalent with formal oxidation states + 2, + 4 and + 6 in compounds in which
they are combined with more electronegative elements such as oxygen and halogens. In the
higher oxidation states of + 4 and + 6 of these elements electrons are unpaired and promoted to
vacant d orbitals.
•
IA
Selenium has unique property of photoconductivity and is used in photocopying (xerox)

R
machines and also a decoloriser of glass. Te and Po are highly toxic. Po is higher due to its
intense radioactivity. Se and Te are found as selemides and tellurides in sulphide ores

• With valence electronic configuration ns

TO
(Cu 2 Se, Cu 2 Te). The colour of the red glass in the traffic signals is due to CdSe.
2
np 4 the group 16 (VI A) elements are just two
electrons short of an octet configuration, and – 2 oxidation state is therefore, a common one.

U
The stability of 2 state decreases with increasing metallic character as indicated by E°
(redox) values. This oxygen is powerful oxidising agent and H Se and H Te are reducing

T
2 2
agent (E° values of Se and Te are negative). Because S, Se, and Te are much less
electronegative than oxygen, they are commonly found in positive oxidation states as + 4 in
SF 4 , SO 2 and H 2 SO 3 , and + 6 in SF , SO 3 , H 2 SO 4 .

N
6
• H 2 Se and H 2 Te are unpleasant gaseous hydrides like H 2
S but less stable than H 2
S, order

O
being H 2 O > H 2 S > H 2 Se H 2 Te > H 2 Po.
•
•

Z I
Oxoacids of S, Se and Te exist and H 2
SO 4 and H 2 SeO 4 and considered as strong acids.
The tendency for catenation decreases markedly as we go down the group. This property is
prominently displayed by sulphur (S 8
). The S–S bond is important in biological system and
is found in compounds such as cysteine, some proteins and enzymes. Stable polyoxides and
polysulphides are known. Examples are :

H–O–O–H, H–S–S–H, H–S–S–S–H,

H–S–S–S–S–H.
• The metallic character increases as we descend the group. S is non-metal and insulator. Se
and Te are metalloids and are semiconductors. Po is a metal.

P-BLOCK ELEMENTS
46 ZION TUTORIALS
• Unlike oxygen, the maximum coordination number of sulphur and other elements can
exceed four and valency is not limited to two because of available d-orbitals for bonding.
Stability of + 6 state decreases and that of + 4 state increases going down the group due
to inert-pair effect. It is :
Se 4+ < Te 4+ < Po 4+
Se 6+ > Te 6+ > Po 6+
• The tendency to form multiple bonds to C, N and O decreases as we descend the group from
Se to Te. Thus S=C=S is moderately stable; Se=C=Se decomposes readily whereas Te=C=Te
does not exist.
• Thermal stability of the hyrdies decreases as we go down the group :
H 2 O > H 2 S > H 2 Se > H 2 Te > H 2 Po
•

S 2 X2
X
F, Cl, Br, 1
S
They form halides of different oxidation number + 1, + 2, + 4 and + 6.
Halides

L Oxidation number
+1
SX 2
SX 4
F, Cl
F
IA +2
+4
SX 6 F
R +6
Se 2 X2
SeX 2 , TeX 2
SeX 4 , TeX 4
Cl, Br
Cl, Br
F, Cl, Br
TO +1
+2
+4
TeX 4
SeX 6 , TeX 6
I
F

T U +4
+6
The stability of the halides decreases in the order F > Cl > Br > I. + 6 oxidation is observed
in fluroide, while iodide of Te(TeI ) is formed.

N
4
SF 6 is thermodynamically inert, non-toxic gas. Inertness of SF 6
is due to the presence of

O
sterically protected sulplhur atom. SF 6
is used as a gaseous insulator in high voltage generators.

•
Z I
SF 4 and SeF 4 are good fluorinating agents and –COOH group can be converted into CF
and > C=O and –P=O into CF 2
and –PF 2 groups.
Oxides of sulphur are more stable than the corresponding oxides of other elements.
3

Ozone (O 3
)

• In the laboratory, O 3
can be made by passing oxygen through a strong electric field. An
equilibrium is set up :
3O 2 (s) 2O 3 (g)
• Some 30 km above the earth’s surface oxygen molecules can be split apart by UV light from
the sun. Some of the atoms join with other oxygen molecules to make ozone :

P-BLOCK ELEMENTS
 ZION TUTORIALS 47

O 2 (g) + O(g)  O 3 (g)

• O 3
is an unstable, dark blue diamagnetic gas, b.p. – 112°C. The colour is due to intense
absorption of red light.

NO + O 3  NO 2 + O 2

O 3 + h   O 2 + O

NO 2 + O  NO + O
2

Net reaction : 2O 3
+ h   3O 2
– based on reactive chlorine species from CFC

LS
Cl + O 3  ClO + O 2

O 3 + hv

ClO + O
IA  O + O 2

 Cl + O

R
2

Net reaction : 2O + hv  3O 2

O
3

• O 3
is thermodynamically unstable, and decomposes to O 2
:

• O 3

U T2O 3  3O 2
is an extremely powerful oxidising agent :
G = – 163 kJ mol –1

T
O 3 + 2H + + 2e –

O 3 + H 2 O + 2e –
O 2 + H 2O

O 2 + 2OH –

N 3PbS + 4O 3
 3PbSO 4

IO 6NO 2 + O 3  3N 2 O 5

Z S + H 2 O + O 3  H 2 SO 4

2KOH + 5O 3
 2KO + 5O + H O
3 2 2

O 3 + 2KI + H 2 O  I 2 + 2KOH + O 2

3SnCl 2
+ 6HCl + O 3  3SnCl 4
+ 3H 2 O

2[Fe(CN) 6 ]4– + H 2 O + O 3  2[Fe(CN) 6 ]3– + O 2 + 2OH –

P-BLOCK ELEMENTS
48 ZION TUTORIALS

Potassium ozonide KO 3
is an orange coloured solid and contains the paramagnetic O 3 ion.

• The amount of O 3 in a gas mixture can be determined by passing the gas into a KI solution
(at a constant pH 9.2 using borate buffer). The iodine that is liberated is titrated with
sodium thiosulphate solution.
O 3 + 2I – + H 2 O  I 2 + 2OH –
+ O2
2 – 2
I 2 + 2S 2O 3  2I + S 4O 6
• O 3
also adds to unsaturated organic compounds at room temperature forming ozonides
which can be cleaved to aldehydes and ketones in solution :
O

CH 2 CH 2 + O 3
CH 2

LS CH 2

O
H 2O/Zn
2HCHO

•
and viruses. It is better than Cl 2
A
O 3 is used as a disinfectant; it is used to purify drinking water since, it can destroy bacteria

I
since, it (O 3 ) avoids the unpleasant smell and taste of Cl 2

R
and any excess O 3 soon decomposes to O 2 .

H 2O /Zn
CH — CH = CH — CH O 2CH CHO

O
3 3  3

T
KC lO 3

 MnO 2

Air

T U O2

strong
electrolysis

electric field
H 2O

N HCHO
CH 2 =CH 2
H 2 O/Zn
O3
I–
I2

O
(H Cl+
S n Cl )
4–

I
NO 2
]
(C N) 6 d est
oz on SnCl 4
[F e – PbS r oyi e l a ye r
S H 2O ng r

Z
[Fe(CN) 6] 3– OH ea ct O 2+NO 2
H2

NO 2 i on s
KO
S

PbSO 4 H 2 SO 4 N 2 O 5 H 2SO 4 KO 3

The molecules O 3 is bent with an OOO angle 116.8° and equal O–O distance of 128 pm and
may be described 90° canonical forms.

O O+ O+
O 116.8° O O O O O
218pm

P-BLOCK ELEMENTS
 ZION TUTORIALS 49

Allotropy and Polymorphism of Sulphur

Many different molecular species are possible for the elemental sulphur, and this accounts for the
existence of the large number of physical forms in which the element may appear. Allotropy is
more complex for the element sulphur than for any other element of group 16 (VI). Sulplhur may
exist as :

• rhombic sulphur (S 
) which has sixteen S 8
rings in a unit cell

• monoclinic sulphur (S 
) which has six S 8
rings in its unit cell.

• liquid sulphur (S 
) comprised of S 8
molecules. This is yellow, transparent, mobile liquid.
At 160°C, a remarkable transformation occurs. The S rings open up and join together into

S
8
long spiral-chain molecules, resulting in :

• liquid sulphur (S µ
L
) which is dark in colour and very thick and viscous. The chain

A
I
length and viscosity of the liquid reach a maximum at about 180°C. At higher
temperatures the chains break up and viscosity decreases again. At 445°C, this liquid boils,
producing :

R
• sulphur vapours,
S 8 . At higher temperatures, S 2

TO
which consists of molecules ranging from S
predominates. S 2
is paramagnetic.
2
to S 10 , but predominantly

U
Plastic sulphur forms if liquid sulphur (µ) is poured into cold water. It consists of chain-
like molecules and has rubber-like properties when first formed. On standing, it becomes

T
brittle and finally converts to rhombic sulphur. Above transformations can be written
as :

N 95.5 C
S   S  
 S  
S 8 g
160 C
 445 C


IO 2000 C
S  S 2  S 4 S 6
1000 C


•
Z
If rhombic sulphur is heated rapidly, it fails to convert into monoclinic sulphur and melts
at 113°C.

• In cyclo-S 6
, the the ring adopts the chair form chain polymers, catena-S n
are also
known.

P-BLOCK ELEMENTS
 50 ZION TUTORIALS
Compound of Sulphur

Oxide :
Sulphur forms several oxides of which sulphur dioxide (SO 2
) and sulphur trioxide (SO 3
) are
important.

Sulphur dioxide

Preparation :
4FeS 2
+ 11O 2  2Fe 2 O 3 + 8SO 2

Properties :

1. As reducing agent
(i) Action on halogens :

SO 2 + Cl 2 + 2H 2 O  H 2 SO 4 + 2HCl
LS
(ii) Action on FeCl 3

IA
2.
2FeCl 3
+ SO 2 + 2H 2 O  H 2 SO 4 + 2FeCl

Reaction with acidified KMnO

R 2
+ 2HCl

O
4

2KMnO + 5SO 2 + 2H 2 O  K 2 SO 4 + 2MnSO + 2H 2 SO 4

T
4 4

3. Reaction with acidified K Cr 2 O 7

U
2

K 2 Cr 2 O 7 + 3SO 2 + H 2 SO 4  K 2 SO 4 + Cr 2 (SO 4 )3 + H 2 O

4. Oxidising property

(i) 2H 2 S + SO
T
 2H 2 O + S 

N
2

(ii) SO 2 + 2Mg  2MgO + S 

Sulphur trioxide
IO
Z
Preparation :
By dehydration of H

P O
2
SO 4

2 5  SO
H 2SO 4 
heat 3 H 2O

Reaction : H 2
SO 4 + SO 3  H 2 S 2 O 7

H 2 SO 4 saturated with SO 3
is called oleum.

P-BLOCK ELEMENTS
 ZION TUTORIALS 51

Oxyacids of sulphur :
Based on the structural similarities, oxoacids or (oxyacids) of sulphur may be classified as :
1. Sulphoxylic acid, H 2 SO 2
2. Sulphurous acid series
(a) Sulphurous acid, H 2
SO 3
(b) Thiosulphurous acid, H 2 2
S O2
(c) Dithionus acid, H 2 2
S O4
(d) Di or pyrosulphurous acid H 2 2
S O5
3. Sulphuric acid series
(a) Sulphuric acid, H 2
SO 4

4.
(b)
(c)
Thiosulphuric acid, H
Di or pyrosulphuric acid, H
Peroxo-acid series
S O3
2 2
S O7
2 2

LS
Peroxomonosulphuric acid (also called Caro’s acid, H
Perdisulphuric acid (also called Marshall’s acid, H
IA 2
S O 8)
SO 5 )

R
2 2

O HO O

O
S
HO HO
HO S

HO
S O

HO
S

U T S S

O
OH HO

O
S O

Sulphurous acid

T
Thiosulphurous acid Dithionous acid

HO
Pyrosulphurous acid

N HO O HO S
S
S S

O
O O

Z I O
Sulphuric acid
OH O OH
Thiosulphuric acid O S

OH
O

Pyrosulphuric acid

O O O O

HO S S OH HO S (S)n S OH

O O O O
Dithionic acid Polythionic acid

P-BLOCK ELEMENTS
 52 ZION TUTORIALS
O O O

HO O S OH HO S O O S OH

O O O
Peroxomonosulphuric acid Peroxodisulphuric acid

(Structure of oxoacids of sulphur)

Sulphuric Acid (H 2
SO 4 )

• As an oxidizing agent

S
2HBr + H 2 SO 4  Br 2 + SO 2 + 2H 2 O

AL
K 4 [Fe(CN) 6 ] + 6H 2 SO 4 + 6H 2 O  2K 2 SO 4 + FeSO 4
+ 3(NH 4 )2 SO 4 + 6CO

I
8HI + H 2 SO 4  H 2 S + 4I 2 + 4H 2 O

• As a dehydrating agent
Conc. H 2SO 4
CH 3 CH 2 OH   CH 2 = CH 2 + H 2 O R
O


• HO – SO 2
– OH + 2PCl 5

U T
 SO 2 Cl 2 + 2POCl
Sulphuryl Chloride
3
+ 2HCl

O
O

S OH
T O

N OH
O
O
–
O
–

IO
S-atom is sp 3
hybridised. SO 24  ion is tetrahedral.

Example 17
Z
H 2 SO 4 cannot be used to obtain HBr from KBr. Why ?
Solution :
H 2 SO 4 oxidises HBr.

Sodium thiosulphate (Na S O 3 .5H 2 O) :

2 2
If one of the oxygen atoms in the sulplhate ion is replaced by sulphur, the resulting ion (S 2
O32– ) is
known as thiosulphate.

P-BLOCK ELEMENTS
 ZION TUTORIALS 53

Preparation :

(i) Sodium thiosulphate is prepared by boiling aq. solution of metal sulplhites with elemental
sulphur.

1 373K
Na 2SO 3  S 8 Na S2 O
2 3
8 H 2O

Hydrated sodium thioosulphate Na S O 3 .5H 2 O is known as HYPO.

2 2
(ii) Spring’s reaction may be used for the preparation of sodium thiosulphate. It consists in
treating a mixture of sodium sulphide and sodium sulphite with calculate quantity of iodine.

Na 2S + Na 2SO 3 I 2 Na S2 O2 3 2NaI



Properties :

(i)
LS
Reaction with dilute acids : It reacts with dilute acids to liberate sulphur dioxide gas along
with precipitate of sulphur.

I
Na 2 S 2 O 3 + 2HCl  2NaCl + HA 2
O + S  + SO 2

(ii) Reaction with BaCl 2

R
: It gives white ppt. of barium thiosulphate.

(iii)
TO
S 2O 32   Ba 2
 BaS 2O
White
3 

Reaction with silver nitrate solution : Gives white ppt. which quickly changes to yellow,

T U
brown and finally black due to the formation of silver sulphide.

S 2O 32   2Ag   Ag 2S 2O 3 
White ppt.

N Ag 2 S 2 O 3 + H 2 O  Ag 2 S + H 2 SO 4

(iv)
IO
With conc. solution of sodium thiosulphate, silver nitrate gives no ppt.
It reacts with silver salts to form sodium argento thiosulphate complex

Z AgBr + 2Na 2 S 2 O 3  Na 3 [Ag(S 2 O 3 )2 ] + NaBr

Sodium argento
thiosulphate complex

2
(v) Thiosulphate S O 
2 3 ion is oxidized by iodine I 2
to tetrathionate S 4O 62 

2Na 2 S 2 O 3 + I 2  Na 2 S 4 O 6 + 2NaI

P-BLOCK ELEMENTS
 54 ZION TUTORIALS
Example 18
Why sodium thiosulphate is used in photography ?
Solution :
It can remove the undecomposed AgBr as soluble thiosulphate complex.

2Na 2 S 2 O 3 + AgBr  Na 3 [Ag(S 2 O 3 )2 ] + NaBr

Hydrogen sulphide
Preparation :
Prepared by the action of dil. HCl or H 2
SO 4 on iron sulphide

FeS + 2HCl (dil)  FeCl 2 + H 2 S 

Properties :

LS
It is a colourless, poisonous gas having the smell of rotten eggs.
1. As reducing agent
(i) Action on halogens

IA
(ii)
H 2 S + Cl 2  2HCl + S 

Action on FeCl
R
O
3

2FeCl + H 2 S  2FeCl + 2HCl + S 

T
3 2

2. Reaction with acidified KMnO 4

3.
2KMnO 4

Reaction with acidified K

T 2
U
+ 3H 2 SO 4 + 5H 2 S  K 2 SO 4 + 2MnSO

Cr 2 O 7
4

K 2 Cr 2 O 7 + 4H 2 SO 4 + 3H 2 S  K 2 SO 4 + Cr 2 (SO 4 )3 + 7H 2 O + S 
+ 8H 2 O + S 

Example 19
N
IO
The two atoms of sulphur in Na S O 3 have
2 2

Z
(A) + 2 and + 4 oxidation state (B) – 2 and + 6 oxidation state
(C) + 4 and + 6 oxidation state (D) same oxidation states
Solution : (B)

Example 20
Bleaching action of SO 2
is due to
(A) reduction (B) oxidation
(C) hydrolysis (D) its acidic nature
Solution : (A)

P-BLOCK ELEMENTS
 ZION TUTORIALS 55

Example 21

When sulphur is boiled with Na 2

SO 3 solution, the compound formed is
(A) sodium sulphide (B) sodium sulphate
(C) sodium persulphate (D) sodium thiosulphate
Solution : (D)

Example 22

The structure of dithionate ion is

2– 2–
O O O O
O S S O O S S O

S
(A) (B)
O O O O O

O
2–

AL S 2–

(C)
O
O
S
O
S
S
O

O
O

R I (D)
O
S

O
O

Solution :

Example 23
(B)

TO
When SO
chromium changes
(A)
2

from + 12 to + 6
U
gas is passed into an acidified solution of K

T (B) from + 3 to + 6
2
Cr 2 O 7 , the oxidation state of

(C)
Solution : (C)
N
from + 6 to + 3 (D) from + 6 to + 4

Example 24
IO
(A)
Z
The stability of the hydrides of oxygen, sulphur, selenium and tellurium decreases in
the order

H 2 Te > H 2 Se > H 2 S > H 2 O (B) H 2 O > H 2 S > H 2 Se > H 2 Te

(C) H 2 O > H 2 S > H 2 Se > H 2 Te (D) H 2

O  H 2 S > H 2 Te > H 2 Se

Solution : (B)

P-BLOCK ELEMENTS
 56 ZION TUTORIALS
Example 25

Which of the following reaction does produce SO 2

?

(A) Ag + H 2 SO 4 (conc.) 

 (B) CaSO 4
+ C 



(C) FeS 2 + O 2 

 (D) Zn + H 2 SO 4 


Solution : (D)

Example 26
In preparing a standard aqueous solution of Mohr’ salt, [FeSO 4
.(NH 4 )2 SO 4 . 6H 2 O] a few millitres
of H 2 SO 4 is added to the solution. The added H 2
SO 4

S
(A) prevents reduction of the salt
(B) prevents oxidation of the salt
(C)
hydrolysis, into soluble FeSO

AL
makes the solution homogeneous by converting insoluble Fe(OH) 2
, which is formed by

I
4
(D) neutralizes the ammonia formed by hydrolysis

R
Solution : (C)

O
Group 17 (Halogens)

T
Halogens (X 2
)
• F 2 is extremely reactive, and this causes great difficulties in the preparation and handling of the
element.
–

T
Moissan (1886) prepared it from CaF
U
CaF 2 + H 2 SO 4  CaSO
2
:

4
+ 2HF

N KF + HF  KHF 2

O
electrolysis
KHF 2  H2 F2

I
 
at cathode at anode

–
–
Z
Modern method uses graphite anode and steel cathode in a steam heated steel tank.
If F 2 were formed by the electrolysis of aqueous fluoride solution, it would immediately
oxidise water to O 2

F 2 + 2H 2 O  4HF + O 2

• The commercial production of Cl 2

is by electrolysis, either of concentrated aqueous NaCl or of
molten salt such as NaCl( l) or MgCl 2 (l) :

electrolysis
2NaCl + 2H O
2 2NaOH + H 2 Cl 
 2

at cathode at anode

P-BLOCK ELEMENTS
 ZION TUTORIALS 57

• Br 2 is obtained from sea water and brine lakes. Sea water contains about 65 ppm Br. Br 2
is
–
isolated in following which oxidises Br to Br 2 .
– –
Cl 2 + 2Br  Br 2 + 2Cl
– Br 2 is quite volatile hence is removed by a stream of air.
– Br 2 is absorbed into aq Na 2
CO 3 solution when NaBr and NaBO 3
are formed :

3Na 2 CO 3 + 3Br 2  5NaBr + NaBrO 3

+ 3CO 2

– – –
or 3Br 2
+ 6OH  5Br + BrO 3
+ 3H 2 O

• I 2 is obtainable in small quantities from dried seaweed, since certain marine plants absorb and
concentrate I – selectively in presence of Cl – and Br – . Low concentration of I – are also found in
some natural brines (salt solutions) associated with oil fields.
Chile saltpetre is mainly NaNO 3
periodate NaIO 4 .I 2 is recovered by reducing
by IO 3 itself :
–

S
but it contains traces of sodium iodate NaIO 3
and sodium
IO 3 to I by NaHSO 3 and then oxidation of I


L
–
to I 2

IA
IO 3 + 3HSO 3  I + 3SO 24  + 3H

5I – + IO 3 + 6H +  3I 2 + 3H 2 O
+

Natural brine is treated with Cl 2

R
water to oxidise I –
to I 2 and the solution is passed through an
ion-exchange resin which absorbs I

–
2

TO
as I 3.I 3 is removed from the resin by treatment with alkali.

Reactivity of halogens is based on bond-energy (BE) value.

F 2 > Cl 2 > Br 2 > I 2
Greater the BE, smaller the reactivity

T MnO 2 U
conc. HCl

N
KMnO 4 conc. HCl Cl 2 electrolysis NaCl (aqueous or molten)

IO Br –
OH
–

Z
Br 2 Br – + BrO –
3

I–

I2

lO3–
– –
I IO 3
in chile salt petre

P-BLOCK ELEMENTS
 58 ZION TUTORIALS
• Oxidising power is in order :
F 2 > Cl 2 > Br 2 > I 2 .

1 
X 2  solid, liquid, gas  X hydrated
 
2
–
F 2 has the most negative G° value, hence is strongest oxidising agent and can oxidise Cl , Br –
–
and I to respectively Cl 2
, Br 2 and I 2 . F 2 can also oxidise H 2
O to O 2 .

1
F 2 + H 2 O  2HF + O2
2

Similarly Cl 2 will oxidise Br – and I – , and Br 2 will oxidise I – . In general any halogen (X 2
) of lower
–
atomic number will oxidise halide ions (X ) of higher atomic number.

Reaction

LS
The ionic character of the M–X bond decreases in the order M–F > M – Cl > M – Br > M – I.
Comment

A
• With H 2
O

2F 2 + 2H 2 O  4H + + 4F – + O 2

2X2 + 2H 2 O  4H + + 4X – + O 2
R I Vigorous reaction with F
oxidise I –
2
; atmospheric O
to I 2 hence reverse reaction
Cl 2 > Br 2 > I 2 (F 2 does not disproportionate).
2
can

• With H
disproportionate
X2 + H 2 O 

2
–
 X + HOX + H


TO +

•
H 2 + X 2  2HX

With metals
T U All the halogoens with Br
with I 2
2
photochemical reaction,
very slow even at high temperature

2M + nX  2MN n Most metals form halides.

N
2

• With CO

• With P
IO
CO + X 2  COX 2 Only Cl 2 , Br 2 from carbonyl halide

Z
2P + 3X 2  2PX 3

2P + 5X 2  2PX 5
For F, Cl, Br, I

For F, Cl, Br
• With S

2S + X 2  S 2 X2 Cl, Br

S + 2Cl 2  SCl 4

S + 3F 2  SF 6

P-BLOCK ELEMENTS
 ZION TUTORIALS 59

• With H 2
S

H 2 S + X 2  2HX + S All the halogens oxidise H 2

S (S 2– ) to S
• With SO 2

SO 2 + X 2  SO 2 X2 F and Cl
• With NH 3

8NH 3 + 3X 2  N 2 + 6NH 4 X F, Cl, Br

• With halogens

X2 + X´ 2  2XX´ Interhalogen compounds

• With cold NaOH

2NaOH + 2F 2  2NaF + OF

2NaOH + X 2  NaX + NaOX + H

2
S
+ H 2O

L O (X = Cl, Br) I does not react under the same

A
2 2
Cl 2 reacts with dry slaked lime forming condition

•
bleaching powder

Ca(OH) 2
With hot NaOH
+ Cl 2  CaCl(OCl) + H

R I
2
O

6NaOH + 3X 2
 5NaX + NaXO
3

TO+ 3H 2 O (X = Cl, Br, I)

Cl 2 is used as a bleach or as a disinfectant (as in public water supplies). It reacts slowly with H O

U
2
to form HCl and HOCl. The hypochlorous acid then decomposes into HCl and O radicals, which
kill bacteria.

T
Cl 2 + H 2 O HCl + HOCl

N HOC l  HCl + O

O
These oxygen radicals are very strong oxidising as well as effective bleaching and disinfecting

Z I
agent in aqueous solution of Cl 2
or hypochlorite salts.
The halogens react with each other to form interhalogen compounds of the type AX, AX
AX7 of which A is of higher atomic number as shown :
AX AX 3 AX 5 AX 7
3
, AX 5 and

CIF CIF 3
CIF 5
BrF BrF 3
BrF 5
IC l ICl 3 (I 2 Cl 6 ) IF 5 IF 7
IBr
BrC l

P-BLOCK ELEMENTS
 60 ZION TUTORIALS
• There are never more than two different halogens in a molecule. The bonds are covalent because
of the small electronegativity difference. Ternary combinations occur in polyhalide ions (e.g.,
IBrCl –)
– The electrical conductance of molten I 2
is ascribed to self-ionisation

3I 2 I +3  I 3

– The interhalogens are generally more reactive than the halogens (except F 2
). This is because
the A–X bond in interhalogens is weaker than the X–X bond in the halogens.
– Hydrolysis of interhalogens gives halide and oxohalide Oxohalide is always formed from
larger halogens present.

2 H O  
BrF 5 5F  BrO

S
3
bromate ion

HCl
H 2O

AL Cl – + IO 3–
iodate ion

H 2O

R ICl – + IO –

hypoiodite ion

Anomalous Behaviour of Fluorine

TO
Fluorine differs from other elements of the group because of its exceptionally small atomic and

• T U
ionic size and low fluorine–fluorine bond dissociation energy. The result of these differences is
that fluorine is the most electronegative element in the periodic table and is a powerful oxidant.
Some differences between flourine and other halogens are :
It is more reactive than other halogens because of low F–F bond energy, also due to its high

N
electronegativity the bond between fluorine and other elements is very strong so its compounds
are more stable. Some of them are inert. e.g. SF 6
.
•

O
Fluorine is almost invariably monocoordinate (coordination number = 1) and is never more

I
than mono covalent.
•
•

•
Z
Fluorides are more ionic.
Fluorine forms strong hydrogen bonds resulting in the properties of hydrogen fluoride being
anomalous.
Fluorine is the strongest oxidising agent and oxidises the elements to their highest oxidation
state, for example in IF 7
, iodine has oxidation number seven.
• The reactions of fluorine are also different from other halogens. Fluorine fumes in moist air
and decomposes water to give oxygen, whereas other halogens are sparingly soluble in
water and react partly to give hydrohalic and hypohalous acids.

P-BLOCK ELEMENTS
 ZION TUTORIALS 61

2F 2 + 2H 2 O  4HF + O 2

X2 + H 2 O HOX + HX
Fluorine reacts with alkalies to yield the oxide, F 2
O:

2F 2 + 2NaOH  OF 2 + 2NaF + H 2

O

The other halogens react with alkalies to yield a solution of hypohalite ions, which may
disproportionate. The oxoacid of fluorine, HOF, prepared recently is very unstable. The oxides of
fluorine are not acidic.

Cl 2 + 2NaOH  NaClO + NaCl + H 2

O

Halogen Acids

LS
All the halogens acids (HF, HCl, HBr, HI) are known. In aqueous solution, they are typical
mineral acids whose acid strengths decrease in the direction of increasing bond energy, that
is

IA
R
HI > HBr > HCl  HF
  weak acid
strong acids

• HX can be prepared by direct combination of H

H 2 (g) + X 2 (g)  2HX (g)

TO 2
and X 2

–
–
–
reaction between H
reaction between H
2

2
but reaction between H
and F

T
and Cl

2
U
2

2
and Br
is very fast,
is also rapid,

2
or I 2 is very slow.

N
G f of HF, HCl and HBr are large and negative suggesting that for them reaction

O
H 2 + X 2  2HX

Z I
goes to completion. For HI(g), G f is small and positive suggesting that HI should dissociate

2HI(g)  H 2 (g) + I 2 (g)

to some extent. However, because of the high activation energy the dissociation occurs only
very slowly in the absence of a catalyst. As a result, HI(g) is quite stable at room temperature.
Thus, at room temperature decomposition of HI(g) is kinetically controlled (rather than
thermodynamically controlled).

• CaF 2
+ H 2 SO 4 

 CaSO 4 + 2HF

P-BLOCK ELEMENTS
62 ZION TUTORIALS
• CaF 2
has also SiO 2
as impurity otherwise. HF formed would react with SiO 2
forming SiF 4
and H 2 SiF 6 .

SiO 2 + 4HF  SiF 4 + 2H 2 O

SiF 4 + 2HF  H 2 [SiF 6 ]

150 C
• NaCl + H 2SO 4 HCl + NaHSO
 4
conc. salt cake

550 C
NaHSO 4 NaCl HCl + Na SO
 2 4

This method is called ‘salt-cake’ method involves formation of NaHSO 4

(salt cake)

S
• HF is only just liquid at room temperature and HCl, HBr and HI are gases. HF has
abnormally high boiling point due to intermolecular H-bonding which is not possible in other

AL
halogen acids due to their smaller electronegativity values.
HCl < HBr < HI < HF

dimeric (HF) 2 and the monomeric HF.

R

I
Some H-bonding also occurs in the gas, which consists of a mixture of cyclic (HF)

–
6
polymers,

O
+
+ F  +
 H –

H H

T

134°
F– F


species of the type

known examples.
HF 2 etc. KHF U
Because of the tendency to form hydrogen bond, metal fluorides are solvated by HF giving

T 2
(KF. HF), KH F (KF.2HF) and KH
2 3
F (KF.3HF) are
3 4

N
HF attacks glass, other halogen acids do not. Glass is silicates of sodium and calcium and
are converted into complex fluorides :

IO Na 2 SiO 3 + 6HF  Na 2 SiF 6 + 3H 2 O

Z CaSiO 3
+ 6HF  CaSiF 6

Hence HF can’t be stored in a glass vessel. Instead, it is stored in a wax-vessel which does
not react with HF. This unique property of HF of attacking glass is used for making
+ 3H 2 O

permanent marking eg. glass-wares.

• In the gaseous state, HX are essentially covalent. In aqueous solution, they ionise to form
H 2 O + and X – but not H + and X – .

+ 
H 2O  HX H 3O X
base acid acid base

P-BLOCK ELEMENTS
 ZION TUTORIALS 63

HF has more ionic character (due to greater electronegativity difference) than HCl, HBr and

HF  HCl < HBr < HI

HI but acid strength varies as : weak  
strong

Acid strength is dependent not on the electronegativity difference of H and X but on the
tendency of the hydrated molecule to form hydrogen ions :
+ –
HX (hydrated)  H (hydrated) + X (hydrated)

• Dipole moment of HF is maximum and is in order

HF > HCl > HBr > HI

1.19D 1.05D 0.80D 0.420D

Preparations of oxo acids

LS
Most of the oxo acids and acid anions of halogens are known only in solution. They can be
obtained by reaction of the free halogens with (i) water or (ii) aq. bases :

IA
X2 + H 2 O  H + + X – + HOX

R
X2  2NaOH NaX + NaOX + H O2
(cold dil.)

(conc. hot)

TO
3X 2  6NaOH 5NaX + NaOXO

(X = Cl, Br, I)
2 3H
 O2

Note :
(i) Reaction of X 2 T U
All the above reactions are rapid disproportionation of halogens.

and water can produce HOX only.

N
(ii) There is appreciable concentration of HOCl.
(iii) The HOI is negligible in a saturated solution of iodine.

Halic acids HOXO

IO 2
(X = Cl, Br, I)

Z
All the three halic acids are known. The acids HOClO
and as salts. Only iodic acid (HOIO 2
prepared by oxidizing I 2 with conc. HNO 3 or O 3 .

I 2 + 10HNO  2HIO

2
and HOBrO 2 are known only in solution
) is stable out of aq. solution. It is a white solid. It can be

+ 10NO + 4H 2 O
3 3 2

HOClO 2 and HOBrO 2

They can be made by treating barium halates with H 2

SO 4
Ba(C lO 3 )2 + H 2 SO 4  2HClO 3
+ BaSO 4


P-BLOCK ELEMENTS
64 ZION TUTORIALS
Ba(ClO 3 )2 can be prepared by passing Cl 2
in Ba(OH) 2
solution

6Ba(OH) 2
+ 6Cl 2  Ba(ClO 3 )2 + 5BaCl 2
+ 6H 2 O

They can also be produced by reactions of X 2

with hot aq. base (NaOH)
– –
3X2 + 6HO  XO 3 + 5X + 3H 2 O


KClO 3 decomposes on heating, the product depends on temperature

400 – 500°C
(i) 2KClO 3 2KCl + 3O 2
[MnO 2]

150°C

S
Lower
(ii) 4KClO 3 
3KClO 4 KCl
Temp.


Zn(ClO 3) 2 2ZnO + 2Cl 2 5O 2

AL
Perbromic acid HOBrO 3

R I
Chlorates are used in matches and fireworks. Sodium chlorate is used as a powerful weed killer.

It is best prepared by oxidation of

BrO 3  F 2  2HO
TO
BrO 3 by F 2 in 5M NaOH solution.


BrO 
4 2F
 
H O2


Solution of HBrO 4
HBrO 4 .2H 2 O can be crystallized.

Periodic acid HO IO 3
T U
can be concentrated upto 55% (6 M), without decomposition. The hydrate

N
The common form in aq. solution of this acid is HIO 4
and also H 5 IO 6 . H 5 IO 6 is called paraperiodic
acid (or orthoperiodic acid). It is a white crystal. It is decomposes on heating as

IO 2H 5IO 6 
  4H 2O 
100 C
2HIO 4
~ 200 C
I O


2 5+ O 2+ H O
2

with Cl
Z
The IO 4 ion is tetrahedral while (OH)

2
in alkaline solution.
5
IO is octahedral. Periodates can be made by oxiding iodate

5
IO 3  Cl 2  6HO 
IO 6 2Cl 
3H O2

C – OH —C=O
HIO 4
+ HIO 3
— C – OH —C=O

P-BLOCK ELEMENTS
 ZION TUTORIALS 65

Structure of oxo anions

–
Anions XO XO 2 XO 3 XO 4

Total valence electrons 14 20 26 32

No. of bonds (= no. of bps) 1 2 3 4
Electrons for bonds 8 16 24 32
Lone pairs (14 – 8)/2 = 3 (20 – 16)/2 = 2 (26 – 24)/2 = 1 0
Total electrons pairs 1+ 3= 4 2+ 2= 4 3+ 1= 4 4–0 = 4
Structure Td Td Td Td
Shape Linear Angular  pyramidal Td

XO– XO2–

LS XO3– XO4–
O

X X
IA X X
O

RO
O
O
O
O

(Linear)
O
(Angular)

TO O
(Pyramid)
O
(Tetrahedral)

U
Structure and shape
Total
Molecules Bond
pairs
Lone
pairs
T
electron
pairs
Structure

X´
Shape

XX´3 N 3 2 5 X´
X
T – shaped

IO (tbp) X´
X´

XX´5 Z 5 1 6
X´

X´
(Oh)
X
X´

X´
Square
pyramid

X´ X´
X´
XX´7 7 0 7 X Pentagonal
X´
bipyramid
X´
(pbp)
X´
P-BLOCK ELEMENTS
66 ZION TUTORIALS
Pseudohalogens and Pseudohalides

Many substances have properties either like X 2

or X – (X = halogen). They are called pseudohalogens
and pseudohalides. They contain two or more atoms in which one at least is N – atom, such as
(CN) 2 , CN – , SCN – etc.
Some pseudohalogens and pseudohalides

Pseudohalogens Pseudohalides
–
Cyanide ion CN

Cyanamide ion CN 22 

Cyanogen gas (CN) 2

Azid ion N 3

S
–
Thiocyanogen (SCN) 2
Thiocyanate ion SCN
–

L
Cyanate ion OCN
–
Fulminate ion ONC

The cyanogen gas and CN

–
like X 2 and X , e.g.,
–

IA
ion are best-known pseudohalogen and pseudohalide. They behave

(a) (CN) 2 disproportionate in water like X

R 2

(b)
(CN) 2 + H 2 O  HCN + HOCN
Cl 2 + H 2 O  HCl + HOCl

CN – behaves similar to I –
TO
2Cu 2+
(aq)  4CN

2Cu 2+
(aq)  4I


(aq) 2CuCN + CN

2CuI + I


2
T U 2

N
2+ + – –
Both the above reactions are reduction of Cu to Cu by CN and I ions.

(c) The solubility of metal halides and metal cyanides are very similar,

IO
NaX and NaCN  Water-soluble

Z
AgX and AgCN  Water-insoluble
(X = Cl, Br, I)
PbCl 2 and Pb(CN) 2
 Water insoluble
–
(d) Like halides pseudohalides (CN , SCN – etc.) are good ligands CuCl 24  , ZnCl 24  , Cu(CN) 2 .
4

{Please note, the word ligands will be dealt in chapter co-ordination complexes}
(i) CN – complexes with transition metals and Zn, Cd and Hg.
–
(ii) Most of the CN complexes are ionic [Fe(CN) 6
]4– , [Ni(CN) 4 ]2– , [Mn(CN) 6 ]4– etc.
(iii) CN – can stabilize low oxidation states also, e.g [Ni(CN) 4
]4– .

P-BLOCK ELEMENTS
 ZION TUTORIALS 67

Bleaching Powder

The exact chemical composition of bleaching powder is not yet known but it behaves as if it
contains calcium hypochlorite Ca(OCl) 2
and basic calcium chloride, C l 2 .Ca(OH) 2 .H 2 O

Preparation

It is prepared by passing chlorine over slaked lime

3Ca(OH) 2
+ 2Cl 2  Ca(OCl) 2 CaCl .Ca(OH)

.H
2 O2 + H O2
2 
Bleaching Powder

Properties :

1. Reaction with dilute acids :

available chlorine. S
With dilute acids, it gives chlorine which is known as

L
CaOCl

CaOCl
2

+ H 2 SO 4  CaSO
IA
+ 2HCl  CaCl 2 + H 2 O + Cl 2 

+ H 2 O + Cl 2 

R
2 4

2. When treated with water it decomposes into calcium chloride and calcium hypochlorite.

3.
2CaOCl 2

Bleaching powder reacts with CO 2

TO
+ H 2 O  CaCl 2 + Ca(OCl) 2
+ H 2O

(atmospheric) and gives chlorine which accounts for its

U
oxidising and bleaching actions.

T
CaOCl 2
+ CO 2  CaCO 3
+ Cl 2 

4. Action of heat : On heating bleaching powder gives a mixture of chlorate and chloride.

N 6CaOCl 2

Ca(ClO )3 2 5CaCl 2

IO
Group 18 (The Noble Gases)

Z
• Because of highest ionisation energy of group 18 elements in their respective periods, they
were given the name ‘noble gases’ and thus inert. However, at least in the case of xenon,
it is not so; it forms series of compounds.
• The noble gases are colourless, tasteless and odourless. In the liquid and solid states the only
forces of attraction among the atoms are very weak London or van der Waals forces.
Polarisability and interatomic interactions increase with increasing atomic number. The
attractive forces among the atoms are so small that they remain liquid at 1 atmospheric
pressure even at a temperature of 0.001 K.

P-BLOCK ELEMENTS
68 ZION TUTORIALS
• Helium has the lowest boiling point of any element, and its behaviour as a liquid is most
unusual. It will creep up the walls of the container in which it is placed and thus it exists
in two phases in liquid helium, one of which has an extremely low viscosity.

Xeon fluorides

Xenon reacts directly with fluorine (only). The products depend on respective amounts of Xe and
F 2 and temperature also. The reactions are generally carried out in seal tubes.

2:1
XeF 2
/P
1:5
Xe + F 2 XeF 4
/P

LS
1 : 20
/P
XeF 6

A
  heart
P  Pressure

R I
These three fluorides are crystalline volatile substances which sublime at room temperature but
can be kept in nickel containers.
The fluorides are strong oxidising agents.

TO
XeF 2 + 2HCl  Xe + Cl 2 + 2HF

T U
XeF 4 + 4KI  Xe + 2I 2 + 4KF

XeF 2 + Ce 2 (SO 4 )3 + SO 24   Xe + 2Ce (SO 4 )2 + F 2

They are good fluorinating agents also.

N 2SF 4 + XeF 4  2SF 6 + Xe

IO Pt + XeF 4
 Pt F 4
+ Xe

Z + XeF 2
F

+ Xe + HF

Their reaction with water is different

(a) XeF 2 is water soluble and undergoes slow oxidative hydrolysis.

2XeF 2 + 2H 2 O  2Xe + O 2 + 4HF

P-BLOCK ELEMENTS
 ZION TUTORIALS 69

(b) XeF 4 reacts with water violently to give XeO 3

3
3XeF 4 + 6H 2 O  2Xe + XeO + O 2 + 12HF
3 2

In this reaction XeF 4

disproportionates and H 2
O is parthy oxidized.
(c) XeF 6 also reacts violently to give XeO 3

XeF 6 + 6H 2 O  XeO 4 + 12HF

With small amount of water

XeF 6 + H 2 O  XeOF 4 + 2HF

Example

Xe cannot form XeF 3

, XeF 5
type of compound.

LS
A
Solution :
The electronic configuration of Xe is 5S 2

I
5p 6 . So, all the electrons are paired up and when it is
excited, then either 2 or 4 or 6 etc. electrons will be unpaired. There is no scope to get odd number

R
of unpaired electrons in its outer most shell. For this reason it cannot form XeF
compound.
3
or XeF 5
type of

TO
T U
N
IO
Z

P-BLOCK ELEMENTS
 70 ZION TUTORIALS
LEVEL–I
MCQ with only ONE Correct Alternate
1. The decrease stability of higher oxidation state in p-block with increasing atomic number is due
to :
(a) decrease in bond energy as going down the group
(b) energy required to unpair ns 2 -electrons is not compensated by the energy released in forming
the two additional bonds.
(c) both are correct
(d) none is correct
3+
2. Boron does not form B cation easily. It is due to :

S
3+
(a) energy required to form B ion is far more than that which would be compensated by lattice
energies or hydration energies of such ion :
(b)
(c)
boron is non-metal
boron is semiconductor

AL
3.
(c) none of the above
N 2 gas is passed over heated Mg and B. Products formed are :
(a) Mg 3 N 2 ,BN
R I (b) Mg 3 N 2 , BN and Mg B2

O
3
(c) MgN, BN (d) no reaction
4. Pure boron is best prepared by :
(a)
(c)
heating B
heating KBF
2
O 3 with H
with Na or K
2

U T (b)
(d)
heating B
heating BBr
2
O 3 with Na or K
with H in presence of catalyst

T
4 3 2
5. The borax bead test can be used to detect the presence of :
(a) Al 3+ (b) Mg 2+

6.
(c) Fe 3+

N
Which of the following statements regarding ortho boric acid (H
(d) Na +
BO 3 ) is false ?

O
3

7.
(a)
(c)

Z I
It acts as a weak monobasic acid
It has a planar structure
Orthoboric acid H 3
(b)
(d)
It is soluble in hot water
It acts as a tribasic acid
BO 3 behaves as weak monobasic acid giving H 3
O + and :

(a) H 2BO 2+ (b) H 2BO 2–

(c) [B(OH) 4 ] – (d) [B(OH) 4 ] +

8. The structure of BF 3
is :
(a) terahedral (b) pyramidal
(c) planar triangular (d) T-shaped

P-BLOCK ELEMENTS
 ZION TUTORIALS 71

9. In BF 3
:
(a) all the B—F bond are single covalents in a nature
(b) boron-fluorine bond has some double bond character and this bond is delocalised.
(c) bond energy and bond length of B—F bond indicate its single bond character
(d) all the bonds are ionic
10. BF 3 behaves as a :
(a) Lewis acid and lone pair from the Lewis base is filled into empty 2 p z orbital
(b) Lewis base and lone pair on B is donated to empty orbital of the Lewis acid
(c) amphoteric pieces due to interaction with acid and base both
(d) polymeric substance
11. BF 3 on hydrolysis forms :
(a)
(c)
H 3 BO 3
both (a) and (b) (d)
LS(b) HBF 4
none of these
12. In B 2 H 6 :
(a) there is direct boron-boron bond
IA
(b) the B—H bonds are ionic

R
O
(c) it is isostructural to C 2
H6
(d) boron atoms are linked through hydrogen bridges
13. From B 2 H 6 all the following can be prepared except :
(a) H 3 BO 3

U T (b) NaBH 4

T
(c) B 2 (CH 3 ) 6 (d) B 2O 3
14. The solubility of Al(OH) 3
in strong NaOH solution is best explained by the formation of :

Al O 3– ion

N
(a) (b) double salt

(c) a peptised colloidal sol (d) a complex hydroxyl aluminate ion

15.
(a)
IO
Buckminster fullerene is :
pure graphite (b) C-60

16.
(c)
Z
diamond
Stable oxides of carbon are :
(a) CO, CO 2 , C 3 O 2
(d)

(b)
C-90

CO 2 , C 3 O 2 , C 2 O
(c) CO, CO 2 (d) C 2 O, C 3 O 2
17. Silicon reacts with hot solution of NaOH forming :
(a) Si(OH) 4
(b) Si(OH) 2
(c) SiO 2 (d) Na 4 SiO 4

P-BLOCK ELEMENTS
 72 ZION TUTORIALS
18. Select correct statement(s) :

2–
(a) Cyanamide ion  CN  is isoelectronic with CO
2 2
and has the same linear structure

(b) Mg 2 C 3 reacts with water to form propyne

(c) CaC 2 has NaCl type of lattice
(d) All are correct statements
19. Silicones are :
(a) synthetic polymers containing repeated R 2
SiO units
(b) silicates with common SiO 4
unit
(c) ketones with silyl group (SiH 3
) similar to alkyl, (SiH ) CO
3 2

20.
(d)

(a)
Zircon (neso silicates)
SnCl 2 can be used as :
reducing agent (b)
LS oxidising agent

21.
(c) catalyst in Friedel-Craft’s reaction
Both NF and NCl
(d)

IA a base
are covalent but they differ in the extent of hydrolysis because :

R
3 3
(a) NF 3
is more stable than NCl 3
and hydrolysis product of NF 3
, that is HFO, does not exist

O
(b) dipole moment of NF 3
is greater than that of NCl 3
(c) electronegativity of F is greater than that of Cl

22.
(d) Cl can expand its outer by using
Nitric oxide is paramagnetic in :

U T
d -orbitals

T
(a) gaseous state (b) liquid state
(c) solid state (d) polymeric state
23. The dipole moment of NF is less than that of NH because :

N
3 3
(a) F is more reactive than H

O
(b) NH3 forms associated molecules

24.
(c)
(d) I
the resultant of the individual bond polarities is less

Z
the resultant of the individual bond polarities is opposed by the polarity of lone pair
A gaseous substance dissolves in water giving a pale blue solution which decolourises KMnO 4
and
oxidises KI to I 2 . Gaseous substance is :
(a) N 2O 5 (b) NH 3
(c) N 2O 3 (d) HNO 3
25. p-p multiple bonding between nitrogen atoms is present in :
(a) hyponitrous acid (b) nitrous acid
(c) nitric acid (d) in all

P-BLOCK ELEMENTS
 ZION TUTORIALS 73

26. MnO 4–/H + oxidises NO 2– to :

(a) N2 (b) NH 3

(c) NO 3– (d) N 2O

27. Compound A undergoes hydrolysis to produce a colourless gas with rotten fish smell. The gas
gives a vortex ring. The gas is :
(a) PH 3
(b) P 2O 3
(c) P 2O 5 (d) P 2S 5
28. Stability of pentahalides is in order :
(a) P > Sb > As > Bi for given X (b) F > Cl > Br for given element

29.
(c) both are correct

In SO 32– :
(d)

LS none is correct

(a)
(b)
d -p bond between S and O is delocalised
bonds between S and O are equivalents
IA
(c)
(d)
there is sp 3 hybridised sulphur atom
all the facts given above are true
R
30. S 2O 32– has :

(a) S—S linkage

TO (b) S—Olinkage

31.
(c) both (a) and (b)

T U (d)
The tetrahedral arrangement of perchlorate ion is due to :
(a) presence of a lone pair of electrons (b)
none of these

trigonal bipyramidal shape of the ion

(c) sp 3 hybridisation (d) sp 2
hybridisation
32.
N
Acid strength of oxoacids of chlorine is in order :
(a)
(c)
IO
HOCl < HClO
HClO 3 < HClO
2
< HClO

4
3
< HClO
< HClO

2
4
< HOCl
(b)
(d) HClO
HClO 4

2
< HClO
< HClO
3

3
< HClO 2
< HOCl < HClO
< HOCl

4
33.

(c)
Z
Acid strength of oxoacids halogen is in order :
(a) HOF > HOCl > HOBr > HOI
HOI > HOCl > HOBr > HOF
(b)
(d)
HOI > HOBr > HOCl > HOF
HOCl > HOBr > HOI > HOF
34. SO 2 can reduce :

(a) HC lO 3 to HCl (b) Cr 2O 72–/H + to Cr 3+

(c) M n O 4– /H + to M n 2+ (d) all of these

P-BLOCK ELEMENTS
 74 ZION TUTORIALS
35. The thermal stability of hydrides of oxygen family is in order :
(a) H 2 Po < H 2 Te < H 2 Se < H 2 S < H 2 O
(b) H 2 Po < H 2 O < H 2 Te < H 2 Se < H 2 S
(c) H 2 S < H 2 O < H 2 Te < H 2 Se < H 2 Po
(d) H 2 O < H 2 S < H 2 Te < H 2 Se < H 2 Po
36. When boron is fused with NaOH, products formed are :
(a) Na 2 B 4 O 7 and H 2
(b) NaBO 2
and H 2
(c) Na 3 BO 3 and H 2
(d) B 2 O 3 and H 2

SECTION–B

S
ONE OR MORE THAN ONE MAY BE CORRECT
1. Be and Al show diagonal relationship and thus :
(a)
L
their oxides are soluble in alkali solution forming [Be(OH)

A
4
]2– and [Al(OH) 6 ]3–

(b)

(c)
(d)
they form complex anion

BeCl 2 and AlCl

Oxides are basic
3
are Lewis acids

R I
BeF 42– and AlF 63–

2. Select correct statement :

(a) B 2 H 6 has all B—H bond equal

TO
(b)
(c)
(d)
LiAlH 4 is an ionic compound
U
AlH 3 is colourless solid and is polymeric containing Al—H—bridges

T
AlX 3 (X = Cl, Br I) have low m.p., are covalent and have the halogen-bridged dimeric
structure
3.

N
In the following statements, select the correct statement :

O
(a) N(CH 3 )3 has pyramidal structure
(b)
(c)
(d)
I
Ni(SiH 3 )3 shows planar arrangement

Z
SiC is highly highly volatile
SiO 2 is called silane
4. Which are correct statements ?
(a) All halogens form oxoacids
(b) All halogens show –1, + 1, +3, +5, +7 oxidation states
(c) Hydrofluoric acid is a dibasic acid and attacks glass
(d) Oxidising power is in order F 2
> Cl 2 > Br 2 > I 2

P-BLOCK ELEMENTS
 ZION TUTORIALS 75

5. Select correct statements :

(a) Hydrides of B and Si are volatile and catch fire on exposure to air
(b) Oxides of B and Si (B 2
O 3 and SiO 2 ) are acidic in nature
(c) Borates and silicates have tetrahedral BO 4
and SiO 4
structural units
(d) Carbon has pronounced ability to form p-p multiple bonds to itself and to other elements
like O and N.
6. Which is incorrect statement about silicones ?
(a) They are repeating units (SiO 4
) is silicates
(b) They are synthetic polymers containing repeated R 2
SiO 2 unites
(c) They are formed by hydrolysis of R SiCl 2

S
2
(d) All the incorrect statement
7. Select incorrect statement :
(a)

AL
ClO 2 and Cl 2 O are used as bleaching agents for paper pulp and textiles
(b)
(c)
OCl – (hypohalites) salts are used as detergent
OCl – disproportionates in alkaline medium

R I
O
–
(d) BrO 3– is oxidised to Br 2
by Br in acidic medium

8. Which of the following statements are true ?

(a)
(b)
Cold and very dilute HNO
Conc. HNO
3

forms NH 4 NO 3 with Sn
U T
forms NH 4 NO 3 with Zn or Sn

T
3

(c) Cold and more concentrated HNO 3

forms N 2
with Cu
(d) HNO can be stored in Al-vessel

N
3

9. Borax is not used :

(a)
(b)
IO
as a flux in brazing and in silver soldering
in making enamel and glass

10.
(c)
(d) Z
in leather tanning
as indicator
Na 3 AlF 6 is added to Al 2
O 3 to :
(a) improve the electrical conductivity of the cell
(b) increase rate of production
(c) increase the m.p.
(d) decrease the electrical conductivity

P-BLOCK ELEMENTS
 76 ZION TUTORIALS
SECTION–C

Comprehension Based MCQ

1. Question are based on following medical report.
In the first biological application of buckyball, chemists at the University of California at San
Francisco and Santa Barbara made a discovery in 1993 that could help in designing drugs to treat
AIDS. The human immunodeficiency virus (HIV) that causes AIDS reproduces by synthesising
a long protein chain, which is cut into smaller segments by an enzyme called HIV-protease. One
way to stop AIDS then might be to inactivate the enzyme. When the chemists reacted a water-
soluble derivative of buckyball with HIV-protease, they found that is binds to the portion of the
enzyme that would ordinarily cleave the reproductive protein, thereby preventing the HIV virus
from reproducing. Consequently, the virus could no longer infect the human cells they had grown

LS
in the laboratory. The buckyball compound itself is not a suitable drug fro use against AIDS
because of potential side effects and delivery difficulties, but it does provide a model for the
development of such drugs.
I. Buckyball is the allotrope of :
(a) phosphorus
IA
(b) sulphur
(c) carbon
R (d) titanium
II. What is the formula of the buckyball ?
(a)
(c)
P4
Ti 3
TO (b)
(d)
S8
C 60
III. In buckyball each atom is:
(a)
(b) T U
sp 2 hybridised element with extensive delocalised molecular orbital
sp 2 hybridised element with localised molecular orbital
(c)

N
sp 3 hybridised element with delocalised molecular orbital
sp 3 hybridised element with localised molecular orbital

O
(d)
IV.
A :
B :
I
Consider following statement about buckyball :

Z
It is also called fullerence
It is also called buckminster fullerence
C : Bucky tubes (made of fullerenes) are several times stronger than steel wires
D : Buckyball is a plastic polymer
Select correct statement (s) :
(a) A, C, D (b) A, B, C
(c) A, B, D (d) B, C, D

P-BLOCK ELEMENTS
 ZION TUTORIALS 77

2. Read the following structural aspects of borax and answer the questions given at the end.
‘‘Borax is actually made of two tetrahedra and two triangular units joined together and should
be written as’’ :
Na 2 [B 4 O 5 (OH) 4 ].8H 2 O
I. Consider following statements about borax :
A : Each boron atom has four B—O bonds
B : Each boron atom has three B—O bonds
C : Two boron atoms have four B—O bonds while other two have three B—O bonds
D : Each boron atom has one—OH group
Select correct statement(s):

S
(a) A, B (b) B, C
(c) C, D (d) A, C
II. Select correct statement(s) :
(a) Borax is used as a buffer

AL
(b)
(c)
(d)
I
1 M borax solution reacts with equal volumes of 2 M HCl solution

R
Titration of borax can be made using methyl orange as the indicator
Coloured bead obtained in borax-bead test contains metaborate

3.

TO
Based on following short report answer the questions given at the end.
In some foam-type fire extinguishers, the reactants are Al (SO 4 )3 (aq.) and NaHCO 3 (aq.). When

U
2
the extinguisher is activated, these reactants are allowed to mix producing Al(OH) 3
(s) and CO 3 (g).

I. CO 2 is formed as a result of :
T
The Al(OH) 3 —CO 2 foam extinguishes the fire.

N
3+
(a) reaction between Al and HCO 3–

O
3+
(b) reaction between hydrolysis product of Al and HCO 3–

II.
(c)
(d)

Z I
reaction between hydrolysis product of NaHCO
direct reaction between Al 2
(SO 4 )3 and NaHCO
Net reaction of the above chemical change is :
3
3
and Al 2 (SO 4 )3

(a) Al 3+ HCO 3– + H 2 O  Al(OH) 3 + CO 2

(b) Al 3+ + HCO 3– + OH –  Al(OH) 3 + CO 2 + H 2 O

(c) [Al(H 2O) 6 ]3+ + HCO 3–  Al(OH) 3 + CO 2 + H 2 O

(d) Al 2 (SO 4 )3 + NaHCO 3

 Na 2 SO 4 + Al(OH) 3
+ H 2O

P-BLOCK ELEMENTS
 78 ZION TUTORIALS
III. Addition of Na 2
CO 3 to a solution of an oxide in water produces CO 2
. This experiment indicates
that :
(a) the oxide is that of a non-metal (b) the oxide is basic
(c) the oxide is amphoteric (d) the oxide is neutral

SECTION–D
Codes
(a) Both A and R are true and R is the correct explanation of A.
(b) Both A and R are true but R is not the correct explanation of A.
(c) A is true but R is false.
(d) A is false but R is true.

1.
(e) A and R both are flase.

Assertion (A) : SiF 62– is known but

LS
SiCl 62– is not known.

Reasons( (R) :

IA
Interaction of F lone pair electrons with Si is stronger than that of chlorine and
due to smaller size of F steric repulsion will be less.
2. Assertion (A) :

R
Sulphur exhibits paramagnetic behaviour in vapour state.

O
Reason (R) : In vapour state sulphur partly exists as S 2
molecule which has two unpaired
electrons in antibonding * orbitals.
3. Assertion (A) :

Reason (R) :
U
SnCl 4 , PbCl 4 , SbCl 5 and UF
T
If a metal exhibits more than one oxidation state, the halide in the higher
oxidation state will be more covalent than the one in lower oxidation state.
are more covalent than SnCl , PbCl and UF 4 .

T
6 2 3
4. Assertion (A) : NaH 2 PO 2 is the acid salt.
Reason (R) : It contains two ionisable protons.

5. Assertion (A) :
N The bond lengths in BF 3

are 1.30 A and are shorter than the sum of the covalent
radii.
Reason (R) :
IO p-p interaction exists and all B—F bonds are equivalent and based on modern

6.
Z
explanation, the double bond is delocalised.
Assertion (A) :
Reason (R) :
3+
In aqueous solution AlCl 3
forms dimer Al 2
Cl 6 .
The high enthalpy of hydration is sufficient of break the covalent dimer into
[M(H 2 O) 6 ] and Cl ions.
7. Asssertion (A) : CO is toxic.
Reason (R) : CO forms complex with haemoglobin in the blood, and this complex is more stable
than oxy-haemoglobin.

P-BLOCK ELEMENTS
 ZION TUTORIALS 79

8. Assertion (A) : SiCl 4 is easily hydrolysed as compared to CCl 4

.
Reason (R) : Silicon can extend its coordination number beyond four.
9. Assertion : Although PF 5
, PCl 5 and PBr 6
are known, the pentahalides of nitrogen have not been
observed.
Reason (R) : Phosphorus has lower electronegativity than nitrogen.
10. Assertion : F atom has a less negative electron affinity than Cl atom.
Reason (R) : Additional electrons are repelled more effectively by 3p electrons in Cl atom than
by 2p electrons in F-atom.
11. Assertion : Hydrazine functions as a monodentate ligand.
Reason : There are lone pairs of electrons on N atoms in hydrazine.
12. Assertion : Ozone in the upper atmosphere (stratosphere) is beneficial but it is harmful in the
lower atmosphere.
Reason :

LS
Ozone absorbs UV light and is a strong oxidising agent.

IA
SECTION–E
Match the Following

R
I. Column I Column II
(A) BF 3 P. Colourless
(B)
(C)
BCl 3
BI 3

TO Q.
R.
S.
Solid
Liquid
Gas

II.

(A)
Column I

Na 2 B 4O 7 + NH 4 Cl 
T U P.
Column II

B 2O 3

(B)

N
NaH + B 2 O 3  Q. NaBO 2

(C)

IO
B + NaOH  R. Na 3 BO 3

Z
(D) Na 2 B 4 O 7 

 S. NaBH 4

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 80 ZION TUTORIALS
LEVEL-II
1. Give structural formula for the following :
(i) Phosphorous acid, H 3
PO 3 (1981, 1)
(ii) Pyrophosphoric acid, H P O7
4 2
(1981, 1)
2. Give reasons for the following :
(i) Carbon acts as an abrasive and also as a lubricant.
(ii) Solid carbon dioxide is known as dry ice. (1983, 1)
(iii) Orthophosphorus acid is not tribasic acid. (1987, 1)
(iv) The molecule of magnesium chloride is linear whereas that of stannous chloride is angular.
(1981, 1)
(v)
(vi)
H 3 PO 3 is a diabasic acid

LS
Sulphur dioxide is a more powerful reducing agent in an alkaline medium than in acidic
medium. (1992, 1)
(1989, 1)

(vii) The experimentally determined N–F bond–length in NF

single bond covalent radii of N and F.
IA 3
is greater than the sum of the
(1995, 2)
(viii) Mg 3 N 2 when reacted with water gives off NH
reaction with water at room temperature.
R 3
but HCl is not obtained from MgCl
(1995, 2)
2
on

3. State with balanced equations what happens when :

(i) White phosphorous (P
atmosphere.
4

TO
) is boiled with a strong solution of sodium hydroxide in an inert
(1982, 1987, 1)
(ii)
(iii)

T U
Dilute nitric acid is slowly reacted with metallic tin.
Phosphorus reacts with nitric acid to give equimolar ratio of nitric oxide and nitrogen
dioxide.
(1987, 1)

(1988, 1)

N
(iv) Elemental phosphorus reacts with conc. HNO 3
to give phosphoric acid. (1991, 1)

(v) P 4 O 10 + PC l 5 (1998, 1)

O

4.
(i)
(ii)
I
Arrange the following in :

Z
HOC l, HOC lO 2 , HOC lO 3 , HOC lO in increasing order of thermal stability.
Increasing order of extent of hydrolysis :
(1988, 1)
(1991, 1)
CC l 4 , MgC l 2 , AlCl 3 , PC l 5 , SiC l 4
5. Mention the products formed in the following : (1986, 1)
(i) Iodine is added to solution of stannous chloride.
(ii) Sulphur dioxide gas, water vapour and air are passed over heated sodium chloride.
6. Draw the structure of P 4
O 10 and identify the number of single and double P–O bonds.
(1996, 3)

P-BLOCK ELEMENTS
 ZION TUTORIALS 81

7. Complete the following chemical equations :

(A) KI + C l 2 

(B) KC lO 3 + I 2 

Justify the formation of the products in the above reactions. (1996, 2)

8. In contact process for industrial manufacture of sulphuric acid some amount of sulphuric acid is
used as a starting material. Explain briefly. What is the catalyst used in the oxidation of SO 2
?
(1994, 4)
9. Give an example of oxidation of one halide by another halogen. Explain the feasibility of the
reaction. (2000, 2)
10. Compound (X) on reaction with LiAlH gives a hydride (Y) containing 21.72% hydrogen along

S
4
with other products. The compound (Y) reacts with air explosively resulting in boron trioxide.

air. Draw the structure of (Y).

AL
Identify (X) and (Y). Give balanced reactions involved in the formation of (Y) and its reaction with
(2001, 5)
11.
(give reactions only) :
(i) Silicon (1)

R I
Starting from SiCl 4 , prepare the following in steps not exceeding the number given in parentheses
(2001, 5)

O
(ii) Linear silicone containing methyl groups only (4)
(iii) Na 2 SiO 3 (3)
12.
(i) Al 4 C 3 T
Write balanced equations for the reactions of the following compounds with water

U (ii) CaNCN

T
(iii) BF 3 (iv) NC l 3
(v) XeF 4
13. Identify the following :

Na 2 CO 3 
N
SO 2 Na 2CO 3
 A 
Elementnal S
 B 
2
 C 
 D
I

O


Z I
Also mention the oxidation state of S in all the compounds. (2003)

P-BLOCK ELEMENTS
82 ZION TUTORIALS

ANSWERS

LEVEL–I
Section–A Section–B
1. c 1. a, b, c
2. a 2. b, c, d
3. b 3. a, b
4. b 4. a, c, d
5. c 5. a, b, c, d
6. d 6. a
7. c 7. b
8. c 8. a, d
9.
10.
11.
b
a
c
LS 9.
10.
d
a
Section–C
12.
13.
14.
d
c
d
IA I. 1.
2.
3.
c
d
a
15. b
R 4. b

O
16. d II. 1. c
17. c 2. a, b, c, d
18.
19.
20.
d
a
a

U T III. 1.
2.
3.
b
c
a
21.
22.
23.
a
a
d T 1. a
5. a
2. a
6. d
Section–D
3. b
7. a
4. e
8. a
24.
25.
c
a
N 9. b 10. c 11. a
Section–E
12. a

26.
27.
c
a
IO I. A  p, s

Z
28. c B  p, r
29. d C  q
30. c II. A P
31. c
B  Q, S
32. a
33. b C R
34. d D  P, Q
35. a
36. c

P-BLOCK ELEMENTS
 ZION TUTORIALS 83

LEVEL–II

4. (i) HOCl < HOClO < HOClO 2

< HOClO 3

(ii) CCl 4 < MgCl 2 < AlCl 3 < SiCl 4

< PCl 5

6. 12, 4

8. Vanadium pentoxide

10. BCl 3
or BBr 3 , B 2 H 6

13. NaHSO 3
(O.S. = + 4), Na 2
CO 3 (O.S. = + 4),

Na 2 S 2 O 3 (O.S. = –2), Na 2 4
S O 6 (O.S. = + 2.5)

LS
IA
R
TO
T U
N
IO
Z

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 84 ZION TUTORIALS
NOTES

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LS
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IA
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R
....................................................................................................................................................................................

TO
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T U
....................................................................................................................................................................................

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N
....................................................................................................................................................................................

IO
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Z
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