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P-BLOCK
ELEMENT
 QUIZRR 3

P-BLOCK ELEMENTS
Int rodu
ducctio n :

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 groupsÊ elements occupies the position in p-sub shell that
is why they are called as p-block elements. Their general configuration is ns2np1-6.

So
Somme Impo
porr tant P
Prrop
opee rtie s of P-
P-BBlock

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
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
The metallic character is governed by
(i) Size of atoms and
(ii) Ionization energy.
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
are located in left corner of p-block and strong non-metallic elements are located at right corner
and a diagonal strip of elements thus two, having in between properties are called as metalloids.

3. Oxidation state
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 ă pair effect, where the lower oxidation
state is more predominant.

4. 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 QUIZRR
(a) Small size
(b) Absence of vacant d-orbital
(c) High IP

Some Important Characteristics of PăBlock 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. Electro negativity Increases Decreases
5. Metallic character Decreases Increases
6. Oxidizing property Increases Decreases
7. Reducing property Decreases Increases

GROUP 13 EL
ELEEM ENTS

Elements : B, Al, Ga, In, TI.

Group 13 elements are boron (B), aluminium (Al), Gallium (Ga), Indium (In) and thallium (TI).
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 ns2np1.

Gener al Tr
Tree nd
ndss in Physic al Pr
Prop
op
opeert ies

Sr.No. Property Boron Aluminium Gallium Indium Thallium

1. Configuration [He]2s22p1 [Ne]3s23p1 [Ar]4s24p1 [Kr]5s25p2 [Xe]6s26p1

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
 QUIZRR 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. (29.8ĈC) 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
Generally IE decreases down the group but Ga has higher IE than Al exceptionally due to smaller
in size as compared to Al.

5. Metallic character
Electropositive character increases down the group hence metalic character also increase down the
group but aluminium is having high metallic character than Gallium due to low IE than Ga.

6. Inter Pair Effect

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
4d series element. This result into increase in effective nuclear charge and greater hold on valence
S electrons by nucleus. These s electrons canÊt 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. Oxidation states and nature of bond

The group ă 13 elements show variable oxidation states of + 3 and + 1. For lighter members +
3 state is more stable than + 1. Thus for Tl, + 1 state is more stable than + 3. It is due to inert
pair effect. The 6s2 pair does not prefer to form bonds and is called inert pair. The basic reason
for such an effect is bond energy. The MăCl bond energy in MCl3 compounds are as follows :
MCl3 MăCl, energy (KJ molă1)
Ga 242
In 206
TI 153
The ionisation energies of B is very high. It is, therefore, covalent in its compounds, always
tricovalent (2s22p1 electrons).

P-BLOCK ELEMENTS
6 QUIZRR
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. AlCl3 ) becomes ionic due
to high hydration energy of Al+3 (4665 KJ molă1) [Al(OH 2) 6] 3+.3Clă. The soluble compounds are
quite acidic due to hydrolysis (high charge to radius ratio of Al +3).

[Al(OH 2) 6] +3 + H 2O  H3O + + [Al(H 2O) 5OH]+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 ă 1 hydroxides. Tricovalent compounds, MX3 , are electron deficient as octet
around the central atom is not complete.

F Cl

Al
B
F F Cl Cl

(Six electrons around B or Al)

Such compounds remove their electron deficiency by :

(i) Back ă bonding
In BX3, B is sp2 and has a vacant p-orbital perpendicular at the triangular plane. X-atom
has filled p-orbital. The overlap resulting into ăbonding.

F
F
B Resonance
B
F F
F F

(ii) Coordination with Lewis bases

B has vacant orbital which accepts electron pair from F ă.
F
ă ă
B +F BF4
F F

Al(OH) 3 + HOă  Al(OH) 4

(iii) Polymerisation
AlCl3 removes electron deficiency by dimerisation.

2AlCl  Al2Cl6

P-BLOCK ELEMENTS
 QUIZRR 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 păp overlap is not effective.

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

BX3 can not stabilize by dimerisation. B is small in size. The dimer will have small ring.

X X X
B B
X X X

So, it is not stable.

REAC TIO NS OF EL
ELEEMEN TS

Pure crystalline boron is very unreactive. However, it is attacked at high temperatures by strong
oxidising agents such as a mixture of hot concentrated H2SO4 and HNO3 or Na 2O2.

2B(s) + 6HNO3 (aq)  2H3BO3 (aq) + 6NO2 (g)

In contrast, finely divided amorphous boron (containing about 2ă5% impurities) is more reactive.
Reactions are summarised in Table below
Reactions of Group 13 (IIIA) Elements
Reaction Comment
Ć 4M + 3O2  2M2 O3 Reaction at high temperature; with Al exotohermic, a
protective oxide layer is formed and TI also forms TI2O.
Ć 2M + N2  2MN Only Al and (B) form nitrides BN, a slippery white solid
with layer structure similar to graphite.
Ć 2M + 3X2  2MX 3 All form MX3, Tl also form TlX. Iodide of Tl3+ (TlI 3) is not
formed; but TlI reacts with I2 forming TlI 3 (Tl +, I3ă)
Ć 2M + 2NaOH + 2H2O  B, Al and Ga only form NaMO2
2NaMO 2 + 3H2

Ć 2M + 6NH3  2M(NH2 )3+ 3H2 All form amides except B which forms BN.
2B + 2NH 3  2BN + 3H2

Ć 2M + 6H+  2M3+ 3H2 Metals liberate H 2, but HNO3 makes Al passive.

P-BLOCK ELEMENTS
 8 QUIZRR
Ć Boron reacts directly with elements forming borides which are hard and refractory.

3Mg + 2B  Mg 3B2

Borides are decomposed by acids forming boranes

Mg 3B 2 + 6HCl  3MgCl2 + B2H6

diborane

Ć Aluminium is far more reactive than boron but in air and water it is stable. It is due to the
formation of aluminium oxide, Al2O3 layer, that makes it passive for further attack. HNO3
also makes Al passive by oxide layer formation.
Ć Reaction of Al with O2 is exothermic and is called thermite reaction.

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

The thermite reaction involves so much energy that it can be dangerous. The Al becomes
white hot and often causes fires. For this precise reason, mixture of Al and an oxide such
as Fe2O3 or SiO2 (a source of oxygen) were used to make incendiary bombs during World
War II.

BX3

H3BO3 + NO2
MxB y
X2
HNO3 a lM
et
m

N2 O2
BN BORON B 2O 3

NaOH
NH3 base
S
BN + H 2 Na 3BO 3 + H 2

B2S3

Bo
Borr on : Ex
Extt ract ion

acid 
Ć Na2 B4O7.10H2O   H3BO3  H 2O + B 2O3
orthoboric acid

B2O3 + 6Na 

 2B + 3Na 2O

B2O3 + 3Mg 

 2B + 3MgO

P-BLOCK ELEMENTS
 QUIZRR 9

red hot
Ć 2BCl3 + 3H2 
filament
 2B + 6HCl

Ć Pyrolysis of BI 3

red hot
2BI 3 
filament
 2B + 3I2

Ć thermal decomposition of B2 H6

B2H6 

 2B + 3H2

Com po
poun
un
unds
ds of Bo ro n

1. Borax (Na2B4 O7 .10H2 O)

Ć The actual formula is Na2 [B 4O5(OH)4].8H2O
OH

O Bă O

Na2 HO · B O B · OH
ă
O B O

OH
Ć Action of heat

Heat 740C
Na2 B4 O7 .10H2 O 
 Na2 B4 O7 
 2NaBO2  B2 O3
 10H 2O
sodium Boric
metaborate
anhydrid

Glassy mass

Ć Various reactions of borax

Na2 CO3 + H3 BO3

NaOH Na2B4O 7

NaBO2 NaBO2 + B2O 3
4 C i th

Sodium H2O
NH e d w
l

metaborate
HCl
at

H3BO3 + NaOH
He

CuO 
Heated
BN strongly NaCl + H 3BO3
(also called 100Ĉ C Cu(BO2)2
inorgonic graphite) (Blue)
B2O3
HBO 2 Boric anhydride

P-BLOCK ELEMENTS
 10 QUIZRR
Ć Solution of Borax is alkaline in nature. This is due to hydrolysis

Na2 B4 O7  7H2 O 

 2NaOH + 4H3 BO3


Strong Weak
alkali acid

2. Boric acids and oxides

(i) H3BO3 or B(OH) 3 orthoboric acid
(ii) HBO2 metaboric acid
(iii) H2B4O7 pyroboric acid

100Ĉ C 140Ĉ C
H3BO3 HBO2 H2B4O7

red hot

B 2O 3
3. Boron Trioxide, B2O 3

Ć 2H3BO3  B 2 O3 + 3H2 O

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

B2O3 + H2O  2HBO 2

HBO2 + H 2O  H3BO 3

Ć 2B2 O3 + P 4O10  4BPO4

Ć It is reduced by magnesium

Heated
B2O3 + 3Mg   2B + 3MgO

4. Boron halide

CaF2 + H2 SO4 + H3 BO3 (or B2 O3 )


H2 O ă
BF3 H3 BO3 + BF4

180Ĉ C NaH

B2H6

P-BLOCK ELEMENTS
 QUIZRR 11

5. Boron Hydrides

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

excess NH 3
B2H6 + NH3 (BN) x
high temp. boron nitride

ratio : 2NH3 : 1B2 H6

B 3N 3H 6
high temp. borazine

Ć B2H6 . 2NH3 is ionic and forms borazine on heating. Borazine is called inorganic benzene.

H N H

B B

N N
B
H H

Similarity between Boron and Silicon (Diagonal Relationship)

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

BCl 3 + 3H2O  H 3BO3 + 3HCl

SiCl 4 + 4H2O  H 4SiO 4 + 4HCl

Ć Boron forms binary compounds with several metalsăthese are called borides. Silicon form
silicides. Borides and silicides are hydrolysed by H 2O forming boranes and silanes :

Mg3 B2 + 6H 2O  3Mg(OH)2 + B2H 6

Al4Si3 + 12H2O  4Al(OH)3 + 3SiH4

Ć B2O3 and SiO2 are acidic in nature and are important constituents of glass. Borate and
silicates have tetrahedral BO4 and SiO4 structural units, respectively.
Ć Both are semi-conductors.

P-BLOCK ELEMENTS
 12 QUIZRR
Ć Boric acid (H3BO 3) and silicic acids (H4 SiO 4) are weak crystalline.
Ć They do not dissolve in cold dilute acids but do so in alkaliesăboron only in fused alkalies
and silicon in both fused and aqueous alkalies.

2B + 2NaOH + 2H2O  2NaBO2 + 3H2

Si + 2NaOH + H2O  Na2SiO 3 + 2H 2

Com pou nds of Al umi n ium

1. Aluminium oxide or Alumina, Al 2O3

2Al(OH)3  Al2O 3 + 3H 2O

Al 2(SO4) 3  Al 2O3 + 3SO 3

(NH 4)2SO 4 . Al 2(SO4 )3 . 24H2O  Al 2O 3 + 2NH 3 + 4SO3 + 25H2O

2. Aluminium Chloride
AlCl 3 exists as a dimer, thus attaining an octet of elections.

Cl Cl Cl

Al Al

Cl Cl Cl

However, when the halides dissolve in H 2O, the high enthalpy of hydration is sufficient to break
the covalent dimer into [M(H2O)6 ]3+ and 3Xă ions.

AlCl3 + 3H2O  Al(OH) 3 + 3HCl

3. Alums
Alums have general formula
M2 SO 4 . M´ 2(SO 4) 3 . 24H2 O
where M stands for monovalent basic radicals such as Na+ , K+, Rb+, Cs +, Ag+ etc. and M´ for
trivalent basic radicals such as Al3+, Cr3+ , Fe3+ , Mn 3+, Co 3+
Some examples of alums are :

Potash Alum K2SO4 . Al2 (SO4)3 .24H2O

Ferric alum (NH4) 2SO 4.Fe2(SO 4) 3

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

and the crystals of alums consists of [M(H2 O) 6]+, [M´(H 2O)6 ]3+ and SO 24 ions.

P-BLOCK ELEMENTS
 QUIZRR 13

G R O UP
UP––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
tó = 5770 yrs

Physical properties of groupă14 elements

Property C Si Ge Sn Pb

Atomic no. 6 14 32 50 82
Electronic ă 2s2 2p2 ă 3s23p 2 3d 104s 24p 2 4d105s25p2 4f 145d106s2 6p 2
structure
Atomic radius
(A) [covalent radius] 0.77 1.17 1.22 1.40 1.44
Ionic radius (A) 0.15 0.41 0.53 0.71 0.84
Metallic radius (Å) -- -- 1.37 1.62 1.75
Ionisation
energy (ev) [I] 11.3 8.2 7.8 7.3 7.4
[II] 24.4 16.3 15.9 14.6 15.0
Electronegativity 2.5 1.9 1.8 1.7 1.7
mp (ĈC) > 3550 1410 937 232 327
bp (ĈC) 4827 2355 2830 2260 1744

{The values are not to be remembered, these are given to show the variations}
Note :
(i) 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 ă orbital is least shielding.

P-BLOCK ELEMENTS
14 QUIZRR
Oxi dation stat e s and Bond
ndiing

Groupă14 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.
Tin and Pb form ionic compounds having appreciable covalent nature. It is because Sn and Pb
are not very large and have 18e core.
Carbon and Si differ widely in their bonding pattern. It is because of the following reasons :

Property C Si

Valence orbitals and 2s2 2p2 3s23p2 (3d0)

electrons

Number of bonds or
coordination number 4 only More than 4 (5 or 6)

-bonding Very effective No (p-p)  bonding but

(păp)  bonding (p ă d)  bonding. Using
vacant 3d orbitals

CăC bond energy 356 KJ molă1 226 KJ mol ă1

Low, however,
heterocatenation is
Catenation property Very high pronounced due to strong
Si ă O bond (368 KJ molă1)

The features of certain Si compounds having Si ă O and Si ă N bonds are explained by (d ă p)

bonding. For example,

(CH3) 3N triangular Pyramidal

(SiH3)3N triangular Planar
(SiH3)2 O < (Si ă O ă Si)  144Ĉ

Trisilylamine, (SiH3) 3N, is trogonal planar due to (d ă p)  bonding involving filled N 2pz orbital
and vacant Si 3dxy orbitals.

P-BLOCK ELEMENTS
 QUIZRR 15

Si · N Si N

The large angles at O of disilyl ethers (R3Si) 2O, is due both to electronic and steric factors.

Ca t e n a t io n

The property of self-linking is known as catenation. It depends mainly on bond energy. The
CăC 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.

C >> Si > Ge  Sn >> Pb

Bond Bond Energy (KJ molă1)

C ă C 356
Si ă Si 210 ă 250
Ge ă Ge 190 ă 210
Sn ă Sn 105 ă 145

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

Bond Bond Energy (KJ molă1)

S ă S 226
B ă O 560 ă 790
Si ă O 368
P ă O ~ 340

Al
Allo
lo
lottr op
opyy an d st ruc ture

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 QUIZRR
Tin is found as  ă Sn, and  ă Sn.

Element Allotrope Structure

Graphite Layer structure
C Diamond Cubic structure
Fullerence Carbon cluster

Si -- Diamond structure

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

Pb -- ccp

(a) G r a ph it e

It is soft dull looking greasy substance and is electrical conductor. Graphite has two-dimensional
layer structure.
Layers are made up of sp2 hybridized C atoms. Each C is joined with three other C atoms through
 ă bonds forming hexagonal rings. Each C is left with its fourth valence electron in a p-orbital.
They overlap and form  bonds. These  bonds are delocalized. Therefore, all C ă C bond distances
in graphite are equal (1.415 Å). Sheet to sheet distance in graphite is 3.35Å. It is known as C
ă dimension. Layers are joined by weak Van der waals force.
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.

C
C C

C C C

C C C C

C C C C

C C C

C C C

C C

P-BLOCK ELEMENTS
 QUIZRR 17

(b) D i a m on d

It is colourless transparent hardest substance known and is insulator. Cut diamond is sparkling
solid (due to refraction). Diamond has cubic unit cell. Each C is sp3 hybridised and is joined with
four other C atoms through  ă bonds.

C
C
C

As C ă C bond energy (356 KJ mol ă1) is very high and diamond has a giant structure, it is very
hard. This structure is responsible for its insulator property.

Density of diamond (3.51 g/cc) is greater than graphite (2.22g/cc). This shows that to convert
graphite into diamond, pressure must be applied. There is the equilibrium.

15000 atm
Graphite 
  diamond

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
(c)) F ul l e r e ne s

Fullerenes are carbon clusters having cage like structures.

Fullerenes C 60 and C70 can be separated by chromatogrphic method over alumina. Many other
fullerenes also exist such as C32 , C50, C76, C84 etc.

The fullerenes C60 is well known. It has a soccer ball structure which contains 12 five ă membered
and 20 six membered rings. The rings are unsaturated. The C60 fullerene is called Buckminster
fullerene in honour of American architect Robert Buckminster Fuller.

P-BLOCK ELEMENTS
 18 QUIZRR
St ruc
ucttur
uree 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 ă p) bond.

Tin exists in three forms,  ă Sn,  ă Sn and  ă Sn.

 · Sn  · Sn  · Sn
(Grey) (White) (Brittle)
(Non ă metallic (Metallic distorted (Rhombic)
diamond structure) close packed)

Se
Semi
mi
micc on
ondu
du
ducct or pr
prop
op
opeer ty of Si and Ge

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 ă 13 or group ă 15 elements,
they become semiconductor.

(i) Ge dopped with In

Ge ă 4s2 4sp2
In ă 5s2 5p1
When Ge is dopped with In, there is one electron less at In site. There develops a positive
hole in the lattice which makes Ge conducting. Such a semiconductor is called p ă type
(positive ă type) semiconductor.

(ii) Ge dopped with As

Ge ă 4s2 4p2
As ă 4s 24p3
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 ă type (negative type).

P-BLOCK ELEMENTS
 QUIZRR 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
Ge Ge As Ge

Ge Ge Ge Ge

Ge Ge Ge Ge

M ul
ultt i pl e Bo
Bonnd ing
In Group 14, carbon is the only element capable of forming comparatively stable multiple bonds
with another C atom and also with N, O etc. Examples are alkenes (> C = C <), alkynes (ă C 
C ă), imines (> C = N ă), nitriles (ă C  N ă), ketones (> C = O), etc. None of the other elements
of the group forms stable compounds containing multiple bonds. Recently, some
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
analogues like SiO2, SnO2 and (Me 2SiO)n are known which are giant macromolecules
containing MăOăM linkages.
The tendency of formation of multiple bonds easily, in case of carbon, is because of
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 or N atom for an effective overlap essential for -bond formation. p-orbitals
Ć Silicon also uses d-orbitals in multiple bonding, In case of N(CH3) 3 , geometry is
pyramidal, but in case of N(SiH3 ) 3 it is planar. It is due to the fact that in the
 ăd
latter, the lone pair of N-atom is transferred to empty d-orbitals of silicon (p 
overlapping) :

N N
CH3 CH3 SiH3 SiH3
CH3 SiH3
pyramidal planar
(no  bonding) (păd bonding)

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20 QUIZRR
Ć 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
availability of d-orbitals (empty but electrons of ns2 and np2 can be excited into this) is
responsible for the ability of the elements, except carbon, to make complex ions such as
SiF 62ă.

Energy
3d

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

silicon
Fig. Energy difference between 2p and 3d energy levels in
carbon and between 3p and 3d energy levels in silicon.
Ć The main chemical differences between silicon and carbon are :
ă Si does not form stable double bonds
ă Si does not form very stable Si ă Si bonds.
ă Si has vacant 3d-orbitals in its valence shell into which it can accept electrons from
donor atoms.
Ć Some carbon compound are less reactive than the corresponding compounds of the other
members of the group. CCl4 has no interaction with H 2O (hydrolysis) whereas SiCl4 does by
use of empty 3d-orbitals.
Ć All the elements give hydrides. Carbon, of course gives an immense number, but silicon and
germanium also show a wide variety.

CH 4 methane (alkane)
SnH 4 Stannane
SiH 4 silane
PbH4 plumbane
GeH 4 germane
Carbon hydrides will not ignite in air unless a flame is put to them. Apart from silane, SiH4 ,
the silicon hydrides are less well behaved. Si3H8 is spontaneously flammable in air :

Si 3H 8(l) + 5O2(g)  3SiO 2 (s) + 4H2O(l)

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

Oxides Nature Oxides Nature

CO, CO2 acidic SnO, SnO 2 amphoteric

SiO2 acidic PbO, PbO2 basic
GeO, GeO2 amphoteric Pb3O 4 amphoteric

Si, Ge, Sn and Pb form oxides MO2 . SiO2 is infinite three-dimensional network solid of
silicon and oxygen atoms connected by single covalent bonds. GeO 2, SnO2 and PbO2 are all
solids and exist in several modifications.

Exa mple 1

Why is graphite a better electrical conductor than diamond and why does the conductivity
of graphite depend on direction ?
Solution :
Graphite has a two-dimensional sheet like structure in which each carbon atom uses sp2 hybrid
orbitals to form trigonal planar  bonds to three neighbouring carbon atoms. In addition, each
carbon atom uses its remaining p-orbital, perpendicular to the plane of the sheet, to form a  bond.
Because each carbon atom must share its  bond with its three neighbours, the  electrons are
delocalised and are free to move in the plane of the sheet. As a result, the electrical conductivity
of graphite in a direction parallel to to the sheet is about 1020 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
different properties in different directions is called anisotropic.

Ex
Exaa mple 2

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

Comp ou
ounnds of C arb on a nd Si
Silli c on

1. Carbides : Binary compounds of carbon are called carbides, SiC, CaC2, Al4C 3 etc. Three types are
found :
(i) Ionic or salt like carbides,

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 22 QUIZRR
(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.

(a) Methanides : (Că4 unit)

Those carbides which are hydrolysed to give CH4 are called methanide. They are supposed
to contain Că4 unit.

Be2 C + 4H2O  2Be(OH) 2 + CH4

Al4C3 + 12H 2O  4Al (OH)3 + 3CH 4

(b) Acetylides : (C2 ă2 unit)

Those which are hydrolysed to C2H 2 are called acetylides. They are common and formed by
Group ă 1, Group ă 2, Mg, Ca, Sr, Ba, Zn, Cd, Cu, Ag, Al and La metals.
Gr ă 1
M2 C 2
Cu, Ag
Gr ă 2
MC2
Zn, Cd
Al, La M2 (C2)3

CaC2 + 2H 2O  Ca(OH)2 + C2H2

Al 2(C2) 3 + 6H2O  2Al(OH) 3 + 3C 2 H2

(c) Propynide : (C3 4ă unit)

Such carbides hydrolyse to propyne

Mg2C 3 + H 2 O  2Mg(OH)2 + CH 3 ă 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.

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 QUIZRR 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 2O3 + C   B 4C

B4C is a also very hard, infusible and inert. It is used to make bulletproof clothing.
These covalent carbides (or  ă Al2 O3) are comparable in hardness to diamond (MohÊs scale).

Hardness  Diamond > B 4C > SiC >  ă Al2O 3

(iii) Interstitial carbides

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. O x i de s

Electrons of this form oxides of the type MO and MO2. Carbon forms suboxides also, e.g., C3O2 .

Oxides C Si Ge Sn Pb

CO
GeO SnO PbO
MO (neutral) X  
ampoteric
GeO 2 SnO 2 PbO 2
MO 2 CO SiO 2  
ampoteric

 acidic 

(a) Carbon monoxide (CO)

It forms many important gaseous mixtures of industrial use
(i) Water gas or synthesis gas CO + H2
(ii) Producer gas CO + N2
(iii) Coal gas CO + H2 + CH4 + 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.

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24 QUIZRR
 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 (CO2)

 CO2 is acidic oxide
 CO2 is biologically important
(i) Maintains pH of blood, due to the equilibrium

CO2 + H2O  HCO3 + H+

(ii) Main components of photo synthesis

Chlorophyll
6CO2  6H2 O   C6 H12 O6  6O2
Sun light
 Glucose

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

C6H12O 6 + 6O2  6CO2 + 6H 2O + Energy

 CO2 is used in the synthesis of urea

NH2

CO2 + 2NH3 H2NCO2NH4 O C + H2 O
Ammonium
Carbamate NH2
Urea

 CO2 is gas at NTP and has the structure O == C == O. The (p ă p) bonding is very
effective. Therefore, even in solid state discrete CO2 molecules exist. The intermolecular
forces are weak Van der WaalsÊ force.
 Solid CO2 is called Âdry iceÊ or ÂcardiceÊ.

Silicon dioxide, SiO2 , unlike CO2 is a solid. The (p ă p)  bonding is not effective in SiO2 like CO2 .
It is due to larger size of Si and more core electrons (8e) in Si. Therefore, to stabilize; SiO 2 contains
a continuous lattice of Si and oxygen atoms joined by covalent bonds. Each Si is sp3 and is joined
with 4 O + atoms and each O ă atom with two Si ă atoms. A macromolecule is formed, hence SiO2
is a solid.
O O

O Si O Si O

O O

O Si O Si O

O O

P-BLOCK ELEMENTS
 QUIZRR 25

Ha lide
dess M X2 a
and
nd M X 4

Group ă 14 elements form tetrahalides of the type MX4 (X = F, Cl, Br, I) except PbI4.
PbI4 does not exist due to strong oxidizing power of Pb+4 and reducing nature of I ă ion. The Pb+4
is strong oxidizing agent due to greater stability of Pb+2 (inert pair effect).
Thus, MX4, [M = C, Si, Ge, Sn, X = F, Cl, Br, I]
Germanium, Sn and Pb also for MX2. The stability of MX 2 is maximum for Pb+2 .
SnF2 is sparingly soluble in water and is used in fluoride containing tooth pastes.
The MX4 halides are all colourless except GeI 4 and SnI4 which are bright orange solids. Colour
in these halides is due to charge transfer.
+4 ă +4 ă
Sn I Ge I
e e

All tetrachlorides except CCl4 are hydrolysed by water.

Carbon tetrachloride is not hydrolysed because :

(a) carbon in CCl 4 is coordinatively saturated

(b) C ă Cl bond is less polar
X C = 2.5, XCl = 3.0,  = 0.5

Silicon tetra chloride (SiCl4 ) is extensively hydrolysed. It is because :

(a) Si ă Cl bond is more polar

X Si = 1.8, XCl = 3.0,  = 1.2
(b) Si in SiCl4 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
and can form haloanions.

SiF 4 + 2Fă  SiF62

SnCl 4 + 2Cl ă  SnCl6

The hexacoordinated halo anions are octahedral having sp 3d2 hybridised central atom (Si).

Ex
Exaa mple 3

CCl4 can not be hydrolysed but SiCl4 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.

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 26 QUIZRR
Exa mple 4

SiCl2 is solid while SiCl4 is liquid at room temperature. Why ?

Solution :
SiCl 2 is more ionic than SiCl 4 by FajanÊs rule. Therefore it has greater m.p. so it is solid at room
temperature while SiCl4 is liquid.

Hy
Hydr
dr
drii des :
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 CnH 2n+2
Alkenes CnH 2n
Alkynes CnH 2nă2
Cyclo alkanes and cycloalkynes
Aromatic hydrocarbons (C6H6 )
Silicon (others also) form saturated hydrides only which are called silanes, SinH2n+2 (Si ~ 8).

SiCl 4 + LiAlH4  SiH4 + AlCl 3 + LiCl

Si
Silli co ns :
They are organosilicon polymers having empirical formula approximately R2SiO. Polymers are
very stable due to strong Si ă O and Si ă C bonds. Silicones can be prepared as oils, resins, plastics
etc. They are :

 Inert
 Water repellent
 Heat resistant
 Electrical insulator
All these properties make silicones very useful.
Hydrolysis of alkyl chlorosilanes produces products having Si ă OH bonds. They do not dehydrate
like gem diols (of C).

R Cl R OH R
Si + H2 O Si Si O
R Cl (ă2HCl) R OH R
Si l ic a t e s

Silicates are solids having Si ă 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
Na2 CO3 + SiO2   Na4SiO 4, (Na2SiO 3) n etc. + CO 2

P-BLOCK ELEMENTS
 QUIZRR 27

They are used in detergents. The concentrated aq. solution of Na 4SiO 4 is solid like and as known
as water glass. Variety of silicates are found but in all the basic unit is the SiO4 tetrahedron.

ă
O

Si or

Oă Oă
Oă

Each O ă atom carries one unit negative charge. In polymeric silicates SiO4 units share
O ă atoms(s). It provides a way of classification.

Or thos ilic ate s (M ono

nonn uc
uclle a r sili c at
atee s)

These are silicates having discrete SiO 44 ions. Metal ions are surrounded by Oăatoms.

Si 2O7–6 ) :
Pyrosili cates ((Si

When two SiO4 units share only one O ă atom pyrosilicates, Si2O76 , are formed. These are also
discrete units.

Oă O Oă
Si Si
O ă Oă
O
ă
Oă

Glas s

Solids are most stable in crystalline form. However, if a solid is formed rapidly (for example, when
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
1500ĈC, 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 ăcalled 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.

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28 QUIZRR

Na2CO 3 + SiO2   Na2SiO3 + CO2



CaCO3 + SiO2  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 :

Ć Calcium-alkali silicate glass ă normal domestic glass for windows

Sodium silicate ă soda glass used in cheap laboratory glassware
Ć Fining agents such as NaNO3 or As2O 3 are added to remove bubbles.
Ć Decolorising agents may be added to eliminate impurities and to obtain colourless glass.
CaF2 is sometimes added to make opal glass.

Glass is attacked by HF and this property is used to make marking on the glass (etching)

Na2SiO3 + 6HF  Na2SiF 6 + 3H 2O

(in glass)

CaSiO3 + 6HF  CaSiF6 + 3H2 O

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

Exa mple 5

The standard free energies of formation of B2O3 and MgO are ă 1194 kJ molă1 and ă 569 kJ
molă1 respectively. Should it be possible to prepare boron by reacting B 2O3 with magnesium ?
Solution :

B2O3 + Mg  2B + 3MgO

G Ĉ = Gproduct ă GĈ reactant

= 3GĈf (MgO) ă GĈf (B2 O3)
= 3(ă 569) ă (ă 1194)
= ă 513 kJ molă1 [GĈf (element) = 0]
The negative sign of GĈ shows that the reaction should be spontaneous. (However, the reaction
is initially endothermic when two reactants are heated.)

P-BLOCK ELEMENTS
 QUIZRR 29

Exa mple 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) They are anisotropic.

Ex
Exaa mple 7

If you had a mixture of CO and CO 2, how would you find out relative proportions of the
two gases in the mixture ?
Solution :
Method I : Mixture of CO2 is run into Ca(OH) 2 solution. CO2 is absorbed by Ca(OH)2 and thus
residual volume will be that of CO.

Ca(OH)2 + CO2  CaCO 3 + H 2O

Method II : Mixture of CO and CO2 is passed over heated charcoal :

CO2 + C  2CO

Increase in volume will be due to CO2. By measuring total volume after passing over heated
charcoal, composition of mixture of CO and CO2 can be determined.

Ex
Exaa mple 8

CO and CNă ions are highly poisonous. A sign that some one has been poisoned by either
of these two chemicals is that the personÊs 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 CNă 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 QUIZRR
Exa mple 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 ClCH2 SiCl3 react with 3 mol of LiAlH4 in diethyl ether solution ?
Solution :

(a) Sn + 2OHă + 4H2 O  [Sn(OH)6 ]2ă + 2H2

(b) PbO2 + SO 2  PbSO4

(c) CS2 + Na2 S  Na2 CS3

sodium thiocarbonate

H OH
(d) SiH2Cl2 + 2H2O  Si +2HCI
H OH
H
Si=O + H2 O
H

(e) 4ClCH2SiCl3 + 3LiAlH4  4ClCH2SiH 3 + 3LiCl + 3AlCl3

Ex
Exaa mple 1 0

Suggest syntheses (starting from deuterium oxide as the only source of deuterium) for:
(a) B2D6 (b) B(OD)3 (c) B 3N3 D6 (d) B (CH 2CH 2 D)3.
Solution :

(a) P2O5 + 3D2 O  2D3PO4

Mg3B 2 + 2D 3 PO4  Mg3 (PO4) 2 + B 2D6

(b) B2O3 + 3D2O  2B(OD) 3

(c) Mg3N2 + D2 O  ND3 + Mg(OD)2

2ND3 + B2D 6  [D 2B(ND 3)2)][BD4 ] 


 B 3N3 D6

(d) 6CH2 = CH2 + B2 D6  2B(CH2CH2D)3

P-BLOCK ELEMENTS
 QUIZRR 31

Exa mple 1 1

Explain the following :

(a) Boron does not usually form a cation :
B has
(IE)1 = 801 kJ mol ă1, (IE)2 = 2427 kJ molă1,
(IE)3 = 3659 kJ mol ă1
 Thus, the total energy required to give B 3+ ions is far more than that which would be
compensated by lattice energies of ionic compounds or hydration of such ions in solution.
Thus formation of cation (like B3+ ) is not possible.

(b) The polarity of BăX bonds is in the order : BăF > BăCl > BăBr but Lewis acidicity shows
the sequence : BF3 < BCl 3 < BBr3.
 With increase in polarity of BăX bond, acidity also increases and should be thus in the
order :
BF3 > BCl3 > BBr3
But Lewis acidity is in reverse order :
BF3 < BCl3 < BBr3
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 BăF 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.
This p-p bonding decreases going from BF 3 to BBr3 and thus Lewis acidic nature increases in
the order :

BF3 < BCI3 < BBr3

excite
B
ground state 2p1 2p2
1 1
2s 2s
excited state

F F
B F B F
F F

(c) Al and Ga are trivalent in their compounds but in case of Tl, monovalent compounds
are the most stable. Why ?
 It is due to Âinert pairÊ 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)

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3+ 3+ 3+ 3+
Al > Ga > In > TI
(most stable)

Al+ < Ga+ < In + < TI+

(most stable)

(d) CO2 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 CO2 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
CătoăO double bonds and a very stable triatomic molecule.
O=C=O
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
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
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 ăSiăOăSiăbonds and thus a hard (giant)
solid :

O O

O
O S O S O

Si
O O
O O
O
O S O S O

O O
(e) SiCl4 is hydrolysed but CCl4 is inert to hydrolysis :
 SiCl4 and CCl 4 are covalent compounds. Carbon has maximum covalency of four while
silicon has six. Thus CCl4 is inert towards water and is not hydrolysed but SiCl4 can
coordinate with 2 mol of H2 O molecules and is thus readily hydrolysed :

SiCl4 + 2H2O  Si(OH)4 + 2HCl

Cl Cl
H Cl Cl H

H2 O + Si + OH2 O Si O

H Cl Cl H
Cl Cl
Silicon with covalency six

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 QUIZRR 33

ă2HCl

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
|
OH

(f) (SiH3) 3N is planar while (CH3) 3 N is pyramidal :

 In case of (CH3) 3N, lone pair on N and three covalent bonds with CH3 groups results in sp 3
hybridisation but lone pair-bond pair repulsion causes distortion hence gives pyramidal
structure :

N
CH3 CH3
CH3

But in case of (SiH3)3N, lone pair on the nitrogen is transferred to the empty d-orbitals of
silicon (p  ă d overlap) thereby causing planarity of unit.

Exa mple 1 2

AlF3 is insoluble in anhydrous HF but when little KF is added to the compound it becomes
soluble. On addition of BF3, AlF3 is precipitated. Write the balanced chemical equations.
Solution :

3KF + AlF3  K 3AlF6

K3AlF6 + 3BF3  AlF3 + 3KBF4

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Exa mple 1 3

(SiH 3)3 N is a weaker base than (CH3) 3N. Explain.

Solution :
In (SiH3) 3N, the lone pair of electrons on nitrogen is involved in păd 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 (CH3) 3N is available for donation to Lewis acids, exactly acting as
stronger base.

Ex
Exaa mple 1 4

(i) A white precipitate (B) is formed when a mineral (A) is boiled with Na2CO3 solution.
(ii) The precipitate is filtered and the filtrate contains two compounds (C) and (D). The
compound (C) is removed by crystallisation and when CO2 is passed through the
mother liquor left, (D) changes to (C).
(iii) The compound (C) on strong heating gives two compounds (D) and (E).
(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 :
(i) The mineral (A) is colemanite, Ca2B6O11 . 5H2O

boiled
Ca2B6 O11 + 2Na2CO3(aq)   2CaCO3 + Na 2B4 O7 + 2NaBO2

(B) Insoluble (C) (D)

Soluble

(ii) (C), the borax is crystallized. The mother liquor consisting sodium metaborate is treated with
CO2.

4NaBO 2 + CO2  Na2B 4O7 + Na 2CO3

heated
(iii) Na2B4O 7.10H 2O   Na2B 4O7 + 10H2 O
Anhydrous

strongly
Na2B4O 7 
heated
 2NaBO 2 + B2O3

heat
(iv) CaO + B 2O3   CO(BO2) 2
cobalt meta borate
(blue coloured)

P-BLOCK ELEMENTS
 QUIZRR 35

Exa mple 1 5

PbCl4 is less stable than SiCl4. 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 1 5 ELEM EN
ENTTS

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 ns2np3 .

Tre nd
ndss i n Ch
Cheemic al R eact iv
iviity

Most common oxidation states shown by group 15 elements are ă 3, + 3 and + 5. The stability
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
> Sb > Bi. This is due to increasing size of atom which refers to FajanÊs rules.
Sb and Bi are the heavier elements of the group and form M3+ cations due to decrease in
ionization enthalpy.
In contrast to nitrogen, the phosphorus atom forms p=p bonding and forms both cyclic and open
chain compounds. Hence, it shows catenation.
As we move down the group there is a decrease is covalent character.
N > P > As > Sb > Bi
Nitrogen is chemically less reactive, due to high stability of its molecule. N2 in which two nitrogen
atoms are combined through a triple covalent bond (N  N) of which one is sigma () and two
are pie () bonds, thus posses high bond strength (941.4 KJ molă1)
Nitrogen has one special feature that it can form p-p multiple bonds with itself, carbon and
oxygen due to its small size. In phosphorus rather p-p, d-p is found as in POX3.

Gener al Tre nd
ndss in P hysica l Prop ert ies

Sr.No. Property Nitrogen Phosphorus Arsenic Antimony Bismuth

1. Configuration [He]2s 2p 3 [Ne]3s23p3 [Ar]4s2 4p3 [Kr]5s2 5p3 [Xe]6s 2 6p3
2. Common oxidation state ă 3, + 3, + 5 ă 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 QUIZRR
Since, it is not easy from energy consideration to gain three electrons to achieve stable noble gas
configuration, the formation of the tri-negative ion (M3ă) 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 3N,
Be3N 2, Mg3 N 2, Ca 3N 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
availability of d-orbitals in P, As, Sb and Bi, using which these elements can attain sp3d and sp3d 2
hybridisation, e.g. in PCl5 and PCl6ă, respectively. Thus, nitrogen does not function as a Lewis
acid whereas phosporus, arsenic antimony and bismuth do so. The hybrides of this group and
their alkyl derivatives act as Lewis bases, forming a number of addition complexes, e.g., NH 3 .
BF3 , CaCl2 . 4NH2, etc.
Ć Stability of + 3 state increases and that of + 5 state decreases going down the group due
to „inert pair effect‰, thus
Bi3+ > Sb3+ > As 3+
Bi5+ < Sb5+ < As 5+
Bi5+ salts are very rare and are good oxidising agents :

Bi5+ + 2eă  Bi 3+

As3+ salts are good reducing agents :

As3+  As 5+ + 2e ă

Ć They form trihalide and penthalide (except N, which does not form NCl5 etc.) As we go down
the group, covalent nature decrease and ionic nature increases; thus NCl3 and PCl3 are
covalent while BiCl 3 is ionic. This is also in accordance with FajanÊs rule : Smaller the size
of cation, larger the size of anion, greater the charge then greater the polarising power and
hence greater the covlalent nature. Halides are hydrolysed in water forming oxyacids or
oxychlorides :

PCl3 + 3H 2 O  H 3PO 3 + 3HCl

SbCl3 + H2O  SbOCl  + 2HCl

(orange ppt)

BiCl3 + H2O  BiOCl + 2HCl

(white ppt)

P-BLOCK ELEMENTS
 QUIZRR 37

Comp ou
ounnds of N itr og en

Oxides of N
(i) Dinitrogen oxide (or nitrous oxide) N2O


NH 4 NO3  N2O + 2H 2O

Structure : It is isoelectronic to CO2 and has linear structure. But unlike CO2 it has dipole
moment (0.16 D). It shows resonance

ă + + ă
N == N == O N N·O

(2) Nitric oxide (NO)

 Copper reacts with dil HNO3 (8M) to form NO. It is reduction of NO3

8HNO3 + 3Cu  3Cu(NO 3)2 + 4H2O + 2NO

 Commercially, NO is obtained by catalytic oxidation of NH3 (ostwald process for HNO 3)

Pt catalyst
4NH3  5O2   4NO + 6H2 O



Nitric oxide is a good ligand and form variety of complexes with transition metals which are
known as nitrosyls, Na2[Fe(CN) 5NO]

(3) Dinitrogen trioxide N2O3

It can be obtained by mixing NO and NO2 in equimolar quantities at low temperature.

Low
NO + NO2   N2 O3
Temp.
( 30F) (blue liq.)

In gaseous state it has the structure

The N ă N distance is very large, 1.864Å

(4) Nitrogen dioxide NO 2 (N 2O4 )

(i) Cu + conc. HNO3 


 NO 2

Cu + 4HNO 3 

 Cu(NO3 )2 + 2H 2O + 2NO2

P-BLOCK ELEMENTS
 38 QUIZRR
(ii) Di or trivalent metal nitrate decomposes on heating to NO2

Pb (NO 3)2 

 PbO + 2NO 2 + óO2
Structure : NO2 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 N2O 4
(dinitrogen tetraoxide).

2NO2  N 2O4

N2O 4 is planar

(5) Nitrogen pentaoxide N2O5

It is obtained by dehydration of HNO3 by P2O5

2HNO3 + P2O5 

 2HPO3 + N 2O5

Structure : N2O5 is solid and in this state it is NO2+ . NO3 i.e. nitronium nitrate. In gaseous state
it has the structure

O O

N O N

O O

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

NH 4 Cl + NaOH 

 NH3 + NaCl + H2O

2NH 4 OOCCH3 + Ca(OH) 2  NH 3 + Ca(CH3COO)2 + 2H 2O

P-BLOCK ELEMENTS
 QUIZRR 39

(ii) Ionic nitrides are hydrolysed by water to produce NH3 .

Mg 3N 2 + 3H 2O  2NH 3 + 3MgO

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

NH 4Cl 

 NH3 + H2Cl

Non-oxidizing anions are Clă, SO24 , CO23 , CH3 COO , PO43 etc.

However NH +4 salts which contain oxidizing anions forms N2 or N 2O on heating.

NH 4 NO3(l)  N2 O + 2H 2O

NH4 NO2  N 2 + 2H2 O

(NH4 ) 2 Cr2 O7  N2 + Cr2O3 + 4H2O

(iv) NH3 is manufactured by :

High pressure
~ 450 C
(a) HaberÊs process N2  3H2 
  2NH3 (g) + Q


Fe (Fe2 O3 ) catalyst
MO Promoter 

(b) Cyanamide process

Electric
CaC2  N2 
 CaCN2  C
furnace
(~ 1100 C) (Nitrolum)


CaCN2 + 3H2O   CaCO 3   2NH 3

Nitrous acid (HNO 2)

Ć It disproportionates to HNO3 (oxidation) and NO (reduction)

3HNO2 2NO + HNO 3 + H2O

+3 +2 +5
reduction

oxidation

P-BLOCK ELEMENTS
40 QUIZRR

HNO2

r e ag e
en g
ag izin

du nt
t

ci
id

ng
ox
Iă MnOă4 /H+
I2 Mn2+
S Fe2+ +
H2 Cr2O 72ă/H
H2O2
SO2
S Fe3+
2ă 3+
SO4 H2O Cr

Structure : H

O N
O

NO2 has planar triangular structure

N
ă
O O
Nitric acid (HNO3 )
HNO3 can act as an oxidizing agent.

SO42ă S
SO2
H 2S
2+
Fe
Fe3+
S
HNO3 H2SO4
C I2
P

H2CO3 HIO3
H2CO3

Aqua r egia

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 2O

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

Au + 3Cl  AuCl3

P-BLOCK ELEMENTS
 QUIZRR 41

AuCl3 + Clă  AuCl 4 (or HAuCl 4, chloroauric acid)

Pt + 4Clă  PtCl4

PtCl4 + 2Cl ă  PtCl 26 (or H 2PtCl6, Chloroplatinic acid)

Note : Au is not oxidized by HNO3 alone but by aquaregia.

R e d Phos ph or u s

Red phosporus is prepared by heating white phosphorus in the absence of air at 250ĈC 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
to eliminate any unchanged white phosphorus. It is finally washed with hot water and dried by
heating with steam.
Another allotrope of phosphorus is black phosphorus and is obtained by heating white phosphorus
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
neighbours by single covalent bonds. Thermodynamically, black phosphorus is the most stable
form.
White phosphorus, the form produced in the industrial synthesis, is a toxic, waxy, white solid that
contains discrete tetrahedral P4 molecules. Red phosphorus, by contrast, is essentially nontoxic
and has a polymeric structure :

P P P P

P P·P P·P P·
P ·P
P P P P
White phosphorus Red phosphorus

As expected for a molecular solid that contains small, non-polar molecules, white phosphorus has
a low melting point, (44ĈC) and is soluble in non-polar solvent such as CS2 . It is highly reactive,
bursting into flames when exposed to air, and is thus stored under water.

Phos ph
phii ne (P H3 )

(i) When a mixture of white P (P4 ) and NaOH soln. is heated, PH3 is formed.

P4 + 2NaOH + 3H 2O 

 3NaH 2PO2 + PH3

In this reaction some P2H 4 is also formed as side product. It is inflammable in air.
(ii) Ionic phosphides react with water to form PH3.

Ca3 P2 + 6H2O  3Ca(OH)2 + 2PH3

P-BLOCK ELEMENTS
 42 QUIZRR
NH3 is highly soluble in water by PH3 is insoluble in water. NH3 dissolves due to H-bonding.

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

PH3 cannot form H-bond, so it is insoluble in water.

Ox ide s of Ph
Phos
os
osph
ph
phor
or
orus
us

P ă oxides P4O6 and P4O 10

Stream of air
 P4 X  P4O6

600 C

Excess of air
P4   P4 O10


These oxides are solids.

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

P 4O6 and P4O10 both have cage structure. The structures are based upon P4 tetrahedra.

P4O6
In this oxide P ă atoms form a regular tetrahedron and O ă atoms are present at six edges of the
tetrahedron and bridge P ă atoms.
P
O O
O
P
O P

O P O

P4O10
In this oxide P4 tetrahedron has six edgeăbridging Oăatoms and four terminal Oăatoms. The
terminal P ă O bonds have (d ă p) bonding. Therefore, there are two types of P ă O distances
in P 4O 10 large bridging P ă O and small terminal P ă O distances.

P-BLOCK ELEMENTS
 QUIZRR 43

P
O O
O O
O P O P O
P
P
O O
O (d ă p) bonding in P 4O10

Oxy ac
aciids of P

The common oxy acids of P are :

Oxidation
State of P Name Formula Proticity Structure
+ 1 Hydrophosphorous
acid (phosphinic acid) H3PO 2 1 Td

+ 3 Phosphorous acid H3PO 3 2 Td.

Td. Polymeric
+ 5 Metaphosphoric acid (HPO3)n 1 and contain PO4
Td units

Td
+ 5 Orthophosphoric acid H3PO 4 3 Highly hydrogen
bonded

Td. (two
+ 5 Pyrophosphoric acid H4P2O 7 4 tetrahedra
joined through O
ă atom)

220 C
H3 PO4  320C
 H4P 2O7   (HPO3)

P ho sp ho r u s H al i d e s

P4 + 6X2  4PX3 (in limited supply of X 2)

P4 + 10X2  4PX 5 (in excess amount of X 2)

P-BLOCK ELEMENTS
44 QUIZRR

Ć SO 3 + PCl 3  POCl 3 + SO2

Ć PCl 3 + H2O  H 3 PO3 + 3H 2O

Ć PCl 3 + HI  PI3 + 3HCl

Ć 3ROH + PCl  3RCl + H3PO3

Ć ROH + PCl 5  RCl + POCl3 + HCl

Exa mple 1 6
Pb(NO3 )2

F2 H2 O
F A B C + HNO3

HCI
CO 

G+H
D+E A+D+H2O

Solution :
A = NO2, N 2O4, C = HNO2, D = NO, E = CO2, F = NO2F, G = NOCl, H = Cl 2.

Group 16 (VIA–The Cha

halc
lc
lcog
og
ogee ns
ns))

Ć The first four elements are called chalcogens meaning ore forming (oxides, sulphides, selenides,
tellurides).
Ć 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
and tellurium though essentially non-metallic, assume increasing metallic character and are
termed as metalloids. Polonium is most metallic in the group.
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., S8, Se8 ,
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
energy of the oxygen-oxygen double bond. O=O, is 498 kJ molă1. This makes the O=O bond
more than three times as strong as the OăO bond (bond energy for OăO is 142 kJ molă1). By
comparison the S=S bond is less than twice as strong as the SăS single bond (bond energy for

P-BLOCK ELEMENTS
 QUIZRR 45

S=S, 431 kJ molă1; SăS, 265 kJ molă1). This results in catenated ăOăOăOă chains begining
unstable relative to O=O, but catenated ăSăSăSă 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
to accept two electrons and give O2ă ion. Thus, almost all metal oxides are ionic and contain O2ă
ions. Usually oxygen exhibits an oxidation state ă 2 in its other compounds also. It exhibits
positive oxidation states only in a few compounds formed with fluorine, i.e., OF2 and O2F2. 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
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.
Ć Selenium has unique property of photoconductivity and is used in photocopying (xerox)
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
(Cu2Se, Cu 2Te). The colour of the red glass in the traffic signals is due to CdSe.
Ć With valence electronic configuration ns2 np 4 the group 16 (VI A) elements are just two
electrons short of an octet configuration, and ă 2 oxidation state is therefore, a common one.
The stability of 2 state decreases with increasing metallic character as indicated by EĈ
(redox) values. This oxygen is powerful oxidising agent and H2Se and H2 Te are reducing
agent (EĈ 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
SF4, SO2 and H2 SO3 , and + 6 in SF6, SO3 , H2 SO 4 .
Ć H2Se and H2 Te are unpleasant gaseous hydrides like H 2S but less stable than H2 S, order
being H2O > H 2S > H 2Se H2 Te > H2Po.
Ć Oxoacids of S, Se and Te exist and H2SO 4 and H2 SeO4 and considered as strong acids.
Ć The tendency for catenation decreases markedly as we go down the group. This property is
prominently displayed by sulphur (S8). The SăS 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 :

HăOăOăH, HăSăSăH, HăSăSăSăH,

HăSăSăSăS ăH.
Ć 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 QUIZRR
Ć 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 :
Se4+ < Te4+ < Po 4+
Se6+ > Te6+ > Po 6+
Ć 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.
Ć Thermal stability of the hyrdies decreases as we go down the group :
H2 O > H2S > H 2Se > H 2Te > H2 Po
Ć They form halides of different oxidation number + 1, + 2, + 4 and + 6.
Halides X Oxidation number
S2X 2 F, Cl, Br, 1 + 1
SX 2 F, Cl + 2
SX 4 F + 4
SX 6 F + 6
Se2X2 Cl, Br + 1
SeX2, TeX 2 Cl, Br + 2
SeX4, TeX 4 F, Cl, Br + 4
TeX4 I + 4
SeX6, TeX 6 F + 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 4) is formed.
SF6 is thermodynamically inert, non-toxic gas. Inertness of SF 6 is due to the presence of
sterically protected sulplhur atom. SF6 is used as a gaseous insulator in high voltage generators.
SF4 and SeF4 are good fluorinating agents and ăCOOH group can be converted into CF 3
and > C=O and ăP=O into CF 2 and ăPF 2 groups.
Ć Oxides of sulphur are more stable than the corresponding oxides of other elements.

Ozone ( O3 )

Ć In the laboratory, O3 can be made by passing oxygen through a strong electric field. An
equilibrium is set up :
3O2(s)  2O3 (g)
Ć Some 30 km above the earthÊs 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
 QUIZRR 47

O2(g) + O(g)  O3(g)

Ć O3 is an unstable, dark blue diamagnetic gas, b.p. ă 112ĈC. The colour is due to intense
absorption of red light.

NO + O3  NO2 + O 2

O3 + h  O2 + O

NO2 + O  NO + O2

Net reaction : 2O3 + h  3O2

ă based on reactive chlorine species from CFC

Cl + O3  ClO + O2

O 3 + hv  O + O2

ClO + O  Cl + O2

Net reaction : 2O3 + hv  3O2

Ć O3 is thermodynamically unstable, and decomposes to O2 :

2O 3  3O2 G = ă 163 kJ molă1

Ć O3 is an extremely powerful oxidising agent :
O3 + 2H+ + 2e ă  O 2 + H2 O

O3 + H2O + 2e ă  O 2 + 2OH ă

3PbS + 4O3  3PbSO4

6NO2 + O3  3N2O5

S + H2O + O 3  H2 SO 4

2KOH + 5O3  2KO3 + 5O2 + H2 O

O3 + 2KI + H2O  I2 + 2KOH + O2

3SnCl2 + 6HCl + O3  3SnCl4 + 3H 2O

2[Fe(CN)6 ]4ă + H2O + O3  2[Fe(CN)6] 3ă + O 2 + 2OHă

P-BLOCK ELEMENTS
48 QUIZRR

Potassium ozonide KO3 is an orange coloured solid and contains the paramagnetic O 3 ion.

Ć The amount of O3 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 + 2Iă + H2O  I 2 + 2OH ă + O2
2
I 2 + 2S 2O3   2I ă + S4 O62

Ć O3 also adds to unsaturated organic compounds at room temperature forming ozonides

which can be cleaved to aldehydes and ketones in solution :
O

CH2 CH2
H2O/Zn
CH2 CH 2 + O3 2HCHO
O O

Ć O3 is used as a disinfectant; it is used to purify drinking water since, it can destroy bacteria
and viruses. It is better than Cl 2 since, it (O3) avoids the unpleasant smell and taste of Cl 2
and any excess O3 soon decomposes to O2.

H2 O/ Zn  2CH CHO
CH · CH = CH · CH3  O3  3

KCl O3

 MnO2
electrolysis
Air O2 H 2O

strong
electric field
CH2=CH 2 Iă
HCHO O3 I2
H2 O/Zn (H Cl+S
n Cl )
4ă NO 2
]
( C N) 6 d es t oz on e la SnCl4
[ Fe ă PbS roy in ye
3ă OH S H 2O g rea r O2 +NO2
[Fe(CN)6 ] c ti on
H2

NO 2 s
KO
S

PbSO 4 H 2SO4 N2O5 H2SO4 KO3

The molecules O3 is bent with an OOO angle 116.8Ĉ and equal OăO distance of 128 pm and
may be described 90Ĉ canonical forms.

O O+ O+
O 116.8Ĉ O O O O O
218pm

P-BLOCK ELEMENTS
 QUIZRR 49

Al lo tr opy a nd Po lymor phi sm o f S ul

ulph
ph
phur
ur

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 :

Ć rhombic sulphur (S ) which has sixteen S8 rings in a unit cell

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

Ć liquid sulphur (S ) comprised of S8 molecules. This is yellow, transparent, mobile liquid.
At 160ĈC, a remarkable transformation occurs. The S8 rings open up and join together into
long spiral-chain molecules, resulting in :

Ć liquid sulphur (Sø) which is dark in colour and very thick and viscous. The chain
length and viscosity of the liquid reach a maximum at about 180Ĉ C. At higher
temperatures the chains break up and viscosity decreases again. At 445ĈC, this liquid boils,
producing :

Ć sulphur vapours, which consists of molecules ranging from S2 to S10, but predominantly
S8. At higher temperatures, S2 predominates. S2 is paramagnetic.

Ć Plastic sulphur forms if liquid sulphur (ø) is poured into cold water. It consists of chain-
like molecules and has rubber-like properties when first formed. On standing, it becomes
brittle and finally converts to rhombic sulphur. Above transformations can be written
as :

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

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

Ć If rhombic sulphur is heated rapidly, it fails to convert into monoclinic sulphur and melts
at 113ĈC.

Ć In cyclo-S6, the the ring adopts the chair form chain polymers, catena-S n are also
known.

P-BLOCK ELEMENTS
 50 QUIZRR
Co mpo und of Su l ph
phuur

Oxide :
Sulphur forms several oxides of which sulphur dioxide (SO2 ) and sulphur trioxide (SO 3) are
important.

Su l p hu r di
diooxide

Preparation :
4FeS2 + 11O2  2Fe2 O3 + 8SO 2

Propert ies :

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

SO 2 + Cl 2 + 2H2 O  H 2SO4 + 2HCl

(ii) Action on FeCl 3

2FeCl3 + SO 2 + 2H2O  H 2SO 4 + 2FeCl2 + 2HCl

2. Reaction with acidified KMnO4

2KMnO4 + 5SO2 + 2H2O  K2SO4 + 2MnSO 4 + 2H 2 SO4

3. Reaction with acidified K2 Cr2O7

K2Cr 2O7 + 3SO2 + H2 SO4  K2SO 4 + Cr2(SO4) 3 + H2O

4. Oxidising property

(i) 2H 2S + SO2  2H 2O + S 

(ii) SO 2 + 2Mg  2MgO + S 

Su l ph
phuur t r i ox i de

Preparation :
By dehydration of H2SO 4

P2O5
H 2SO 4   SO 3  H 2O
heat

Reaction : H2SO 4 + SO3  H 2S2O7

H2SO 4 saturated with SO3 is called oleum.

P-BLOCK ELEMENTS
 QUIZRR 51

Oxyacids of sulphur :
Based on the structural similarities, oxoacids or (oxyacids) of sulphur may be classified as :
1. Sulphoxylic acid, H 2SO 2
2. Sulphurous acid series
(a) Sulphurous acid, H2 SO3
(b) Thiosulphurous acid, H 2S2O2
(c) Dithionus acid, H2 S2 O 4
(d) Di or pyrosulphurous acid H2S2 O5
3. Sulphuric acid series
(a) Sulphuric acid, H2 SO 4
(b) Thiosulphuric acid, H2 S2O 3
(c) Di or pyrosulphuric acid, H2S2O 7
4. Peroxo-acid series
Peroxomonosulphuric acid (also called CaroÊs acid, H2SO5 )
Perdisulphuric acid (also called MarshallÊs acid, H2S2 O8)

O HO O
S
HO HO
HO S
S O S S S OH HO S O

HO HO
O O
Sulphurous acid Thiosulphurous acid Dithionous acid Pyrosulphurous acid

HO O
HO O HO S
S
S S
O O
O OH O OH
Sulphuric acid Thiosulphuric acid O S O

OH
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 QUIZRR
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)

Su l ph
phur
ur
urii c Ac
Acii d ( H 2SO4)

Ć As an oxidizing agent

2HBr + H2SO 4  Br2 + SO2 + 2H2O

K4[Fe(CN)6] + 6H 2SO4 + 6H2O  2K2SO4 + FeSO4 + 3(NH 4) 2SO 4 + 6CO

8HI + H2SO 4  H2S + 4I2 + 4H 2O

Ć As a dehydrating agent
Conc. H2SO4
CH3CH 2OH   CH 2 = CH2 + H2O

Ć HO ă SO2 ă OH + 2PCl 5  SO2Cl2 + 2POCl3 + 2HCl

Sulphuryl Chloride

O O

O S OH S
ă
O O
ă
OH O

S-atom is sp3 hybridised. SO24  ion is tetrahedral.

Ex
Exaa mp
mpll e 1 7

H2SO4 cannot be used to obtain HBr from KBr. Why ?

Solution :
H2SO4 oxidises HBr.

Sodium thiosulphate (Na2S2O 3.5H2O) :

If one of the oxygen atoms in the sulplhate ion is replaced by sulphur, the resulting ion (S2O32ă) is
known as thiosulphate.

P-BLOCK ELEMENTS
 QUIZRR 53

P r e p a r a t i on :

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

1 373K
Na 2 S O3  S8  Na 2S 2O3
8 H 2O

Hydrated sodium thioosulphate Na2S2 O3.5H 2O is known as HYPO.

(ii) SpringÊs 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 2 S + Na 2SO3  I2  Na 2 S2 O3  2NaI

P r op
opee r t ie
iess :

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

Na2S2O 3 + 2HCl  2NaCl + H 2O + S + SO2

(ii) Reaction with BaCl2 : It gives white ppt. of barium thiosulphate.

S2 O23  Ba2  BaS2 O3 

White

(iii) Reaction with silver nitrate solution : Gives white ppt. which quickly changes to yellow,
brown and finally black due to the formation of silver sulphide.

S2 O32  2Ag  Ag2 S2 O3 

White ppt.

Ag2S2O 3 + H2 O  Ag 2 S + H2SO 4

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

AgBr + 2Na2 S2O3  Na3 [Ag(S 2O3) 2] + NaBr

Sodium argento
thiosulphate complex

(v)  2
Thiosulphate S 2O 3  ion is oxidized by iodine I2 to tetrathionate S4 O62

2Na2S2O3 + I2  Na 2S4 O6 + 2NaI

P-BLOCK ELEMENTS
 54 QUIZRR
Ex a mp
mpll e 1 8
Why sodium thiosulphate is used in photography ?
Solution :
It can remove the undecomposed AgBr as soluble thiosulphate complex.

2Na 2S 2O3 + AgBr  Na3 [Ag(S2 O 3) 2 ] + NaBr

H y dr
droog e n sul phide
Preparation :
Prepared by the action of dil. HCl or H2SO 4 on iron sulphide

FeS + 2HCl (dil)  FeCl2 + H 2S 

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

H2S + Cl 2  2HCl + S 

(ii) Action on FeCl3

2FeCl3 + H2 S  2FeCl2 + 2HCl + S 

2. Reaction with acidified KMnO4

2KMnO4 + 3H2SO 4 + 5H2 S  K2SO 4 + 2MnSO4 + 8H2O + S 

3. Reaction with acidified K 2Cr2O7

K2Cr2O7 + 4H2 SO4 + 3H 2S  K2SO 4 + Cr2(SO4) 3 + 7H2O + S 

Ex
Exaa mp
mpll e 1 9
The two atoms of sulphur in Na2 S2 O3 have
(A) + 2 and + 4 oxidation state (B) ă 2 and + 6 oxidation state
(C) + 4 and + 6 oxidation state (D) same oxidation states
Solution : (B)

Ex
Exaa mp
mpll e 2 0
Bleaching action of SO 2 is due to
(A) reduction (B) oxidation
(C) hydrolysis (D) its acidic nature
Solution : (A)

P-BLOCK ELEMENTS
 QUIZRR 55

Ex a mp
mpll e 2 1

When sulphur is boiled with Na2 SO3 solution, the compound formed is
(A) sodium sulphide (B) sodium sulphate
(C) sodium persulphate (D) sodium thiosulphate
Solution : (D)

Ex
Exaa mp
mpll e 2 2

The structure of dithionate ion is

2ă 2ă
O O O O

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

2ă 2ă
O S

O S S O
S
(C) O O S O (D)
O O
O O

Solution : (B)

Ex
Exaa mp
mpll e 2 3

When SO2 gas is passed into an acidified solution of K2 Cr 2O7 , the oxidation state of
chromium changes
(A) from + 12 to + 6 (B) from + 3 to + 6
(C) from + 6 to + 3 (D) from + 6 to + 4
Solution : (C)

Ex
Exaa mp
mpll e 2 4

The stability of the hydrides of oxygen, sulphur, selenium and tellurium decreases in
the order

(A) H2 Te > H2Se > H2S > H 2O (B) H2 O > H2S > H 2Se > H2Te

(C) H2 O > H 2S > H2Se > H2 Te (D) H2 O  H2S > H 2Te > H 2Se

Solution : (B)

P-BLOCK ELEMENTS
 56 QUIZRR
Ex a mp
mpll e 2 5

Which of the following reaction does produce SO2 ?

(A) Ag + H2SO 4 (conc.) 


 (B) CaSO4 + C 



(C) FeS2 + O 2 

 (D) Zn + H2SO 4 



Solution : (D)

Ex
Exaa mp
mpll e 2 6
In preparing a standard aqueous solution of MohrÊ salt, [FeSO4.(NH 4) 2SO4. 6H2O] a few millitres
of H2 SO4 is added to the solution. The added H2SO4
(A) prevents reduction of the salt
(B) prevents oxidation of the salt
(C) makes the solution homogeneous by converting insoluble Fe(OH) 2, which is formed by
hydrolysis, into soluble FeSO4
(D) neutralizes the ammonia formed by hydrolysis
Solution : (C)

G r ou
oupp 1 7 ( H a lo
logg e ns
ns))

Halogens (X2 )
Ć F2 is extremely reactive, and this causes great difficulties in the preparation and handling of the
element.
ă Moissan (1886) prepared it from CaF2 :

CaF2 + H 2SO 4  CaSO4 + 2HF

KF + HF  KHF2

electrolysis
KHF2 
 H2  F2
at cathode at anode

ă Modern method uses graphite anode and steel cathode in a steam heated steel tank.
ă If F2 were formed by the electrolysis of aqueous fluoride solution, it would immediately
oxidise water to O 2

F2 + 2H2 O  4HF + O 2

Ć The commercial production of Cl2 is by electrolysis, either of concentrated aqueous NaCl or of

molten salt such as NaCl(l) or MgCl 2(l) :

electrolysis
2NaCl + 2H2 O 
 2NaOH + H2  Cl2
 
at cathode at anode

P-BLOCK ELEMENTS
 QUIZRR 57

Ć Br 2 is obtained from sea water and brine lakes. Sea water contains about 65 ppm Br. Br2 is
isolated in following which oxidises Bră to Br 2.

Cl 2 + 2Bră  Br2 + 2Cl ă

ă Br2 is quite volatile hence is removed by a stream of air.
ă Br2 is absorbed into aq Na 2CO3 solution when NaBr and NaBO 3 are formed :

3Na 2CO 3 + 3Br2  5NaBr + NaBrO3 + 3CO 2

or 3Br2 + 6OHă  5Br ă + BrO 3ă + 3H2O

Ć I2 is obtainable in small quantities from dried seaweed, since certain marine plants absorb and
concentrate Iă selectively in presence of Cl ă and Br ă. Low concentration of I ă are also found in
some natural brines (salt solutions) associated with oil fields.
Chile saltpetre is mainly NaNO3 but it contains traces of sodium iodate NaIO 3 and sodium
periodate NaIO 4.I2 is recovered by reducing IO3 to Iă by NaHSO3 and then oxidation of Iă to I2
by IO3 itself :
+
IO3 + 3HSO3  I + 3SO24  + 3H
ă

5Iă + IO 3 + 6H+  3I2 + 3H2O

Natural brine is treated with Cl2 water to oxidise Iă to I2 and the solution is passed through an
ion-exchange resin which absorbs I 2 as I3 .I3 is removed from the resin by treatment with alkali.

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

F2 > Cl2 > Br2 > I 2
Greater the BE, smaller the reactivity
MnO2
conc. HCl

KMnO4 conc. HCl Cl 2 electrolysis NaCl (aqueous or molten)

Bră
ă
OH ă ă
Br 2 Br + BrO3

Iă

I2

lOă3

Iă IO3ă
in chile salt petre

P-BLOCK ELEMENTS
58 QUIZRR
Ć Oxidising power is in order :
F2 > Cl2 > Br2 > I2 .

1
X 2 solid, liquid, gas   X   hydrated 
2

F2 has the most negative GĈ value, hence is strongest oxidising agent and can oxidise Clă, Br ă
and Iă to respectively Cl2, Br2 and I 2. F 2 can also oxidise H2O to O2 .

1
F 2 + H2O  2HF + O2
2

Similarly Cl2 will oxidise Bră and Iă, and Br2 will oxidise Iă. In general any halogen (X 2) of lower
atomic number will oxidise halide ions (Xă) of higher atomic number.
The ionic character of the MăX bond decreases in the order MăF > M ă Cl > M ă Br > M ă I.
Reaction Comment
Ć With H 2O

2F2 + 2H 2O  4H+ + 4Fă + O 2 Vigorous reaction with F2; atmospheric O2 can
oxidise Iă to I2 hence reverse reaction
2X2 + 2H 2O  4H + + 4X ă + O2 Cl2 > Br2 > I 2 (F2 does not disproportionate).

disproportionate +
X2 + H2O   X + HOX + H
ă

Ć With H 2

H2 + X2  2HX All the halogoens with Br2 photochemical reaction,

with I2 very slow even at high temperature
Ć With metals

2M + nX2  2MNn Most metals form halides.

Ć With CO

CO + X2  COX2 Only Cl2 , Br2 from carbonyl halide

Ć With P

2P + 3X2  2PX3 For F, Cl, Br, I

2P + 5X2  2PX5 For F, Cl, Br

Ć With S

2S + X2  S 2X2 Cl, Br

S + 2Cl2  SCl 4

S + 3F2  SF6

P-BLOCK ELEMENTS
 QUIZRR 59

Ć With H 2S

H2S + X 2  2HX + S All the halogens oxidise H 2S (S 2ă) to S

Ć With SO 2

SO2 + X2  SO 2X 2 F and Cl

Ć With NH3

8NH3 + 3X2  N2 + 6NH4X F, Cl, Br

Ć With halogens

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

Ć With cold NaOH

2NaOH + 2F2  2NaF + OF2 + H 2O

2NaOH + X2  NaX + NaOX + H2O (X = Cl, Br) I 2 does not react under the same
Cl2 reacts with dry slaked lime forming condition
bleaching powder

Ca(OH)2 + Cl 2  CaCl(OCl) + H 2O

Ć With hot NaOH

6NaOH + 3X2  5NaX + NaXO3 + 3H 2 O (X = Cl, Br, I)

Cl2 is used as a bleach or as a disinfectant (as in public water supplies). It reacts slowly with H 2O
to form HCl and HOCl. The hypochlorous acid then decomposes into HCl and O radicals, which
kill bacteria.
Cl2 + H2 O  HCl + HOCl

HOCl  HCl + O

These oxygen radicals are very strong oxidising as well as effective bleaching and disinfecting
agent in aqueous solution of Cl2 or hypochlorite salts.
Ć The halogens react with each other to form interhalogen compounds of the type AX, AX3, AX5 and
AX7 of which A is of higher atomic number as shown :
AX AX3 AX5 AX7
CIF CIF3 CIF 5
BrF BrF3 BrF 5
IC l ICl 3 (I2Cl 6) IF 5 IF7
IBr
BrCl

P-BLOCK ELEMENTS
 60 QUIZRR
Ć 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.,
IBrClă)
ă The electrical conductance of molten I2 is ascribed to self-ionisation

3I2  I+3  I3

ă The interhalogens are generally more reactive than the halogens (except F2 ). This is because
the AăX bond in interhalogens is weaker than the XăX bond in the halogens.
ă Hydrolysis of interhalogens gives halide and oxohalide Oxohalide is always formed from
larger halogens present.

H O
2
BrF5  5F  BrO3
bromate ion

H2 O
HCl Clă + IO ă3
iodate ion

H 2O
Clă + IOă
hypoiodite ion

An om
omaa l o u s B e h a v i o u r o f F l uo
uorr i n e

Fluorine differs from other elements of the group because of its exceptionally small atomic and
ionic size and low fluorineăfluorine 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 :
Ć It is more reactive than other halogens because of low FăF bond energy, also due to its high
electronegativity the bond between fluorine and other elements is very strong so its compounds
are more stable. Some of them are inert. e.g. SF6.
Ć Fluorine is almost invariably monocoordinate (coordination number = 1) and is never more
than mono covalent.
Ć Fluorides are more ionic.
Ć Fluorine forms strong hydrogen bonds resulting in the properties of hydrogen fluoride being
anomalous.
Ć Fluorine is the strongest oxidising agent and oxidises the elements to their highest oxidation
state, for example in IF7, iodine has oxidation number seven.
Ć 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
 QUIZRR 61

2F 2 + 2H2O  4HF + O2

X2 + H 2O  HOX + HX
Fluorine reacts with alkalies to yield the oxide, F2O :

2F2 + 2NaOH  OF2 + 2NaF + H 2O

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 2O

Ha l og
ogeen Acids

Ć 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

HI > HBr > HCl  HF

  weak acid
strong acids

Ć HX can be prepared by direct combination of H2 and X2

H2 (g) + X 2(g)  2HX (g)

ă reaction between H2 and F 2 is very fast,

ă reaction between H2 and Cl2 is also rapid,
ă but reaction between H2 and Br 2 or I2 is very slow.

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

H2 + X2  2HX

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

2HI(g)  H 2 (g) + I2 (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).

Ć CaF2 + H2 SO4 

 CaSO4 + 2HF

P-BLOCK ELEMENTS
62 QUIZRR
Ć CaF2 has also SiO2 as impurity otherwise. HF formed would react with SiO 2 forming SiF4
and H2 SiF 6.

SiO 2 + 4HF  SiF 4 + 2H2O

SiF4 + 2HF  H2 [SiF6]

150 C
Ć NaCl + H2 SO4 
 HCl + NaHSO4
conc. salt cake

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

This method is called Âsalt-cakeÊ method involves formation of NaHSO4 (salt cake)
Ć 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
halogen acids due to their smaller electronegativity values.
HCl < HBr < HI < HF
Some H-bonding also occurs in the gas, which consists of a mixture of cyclic (HF)6 polymers,
dimeric (HF)2 and the monomeric HF.
ă

+
+ F  +
 H 
H
ă
134Ĉ  H
Fă F


Because of the tendency to form hydrogen bond, metal fluorides are solvated by HF giving

species of the type HF2 etc. KHF2 (KF. HF), KH2F3 (KF.2HF) and KH3 F4 (KF.3HF) are

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

Na2SiO 3 + 6HF  Na2SiF 6 + 3H 2O

CaSiO 3 + 6HF  CaSiF6 + 3H2O

Hence HF canÊt 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
permanent marking eg. glass-wares.
Ć In the gaseous state, HX are essentially covalent. In aqueous solution, they ionise to form
H2O+ and Xă but not H + and Xă.

H2O  HX  H 3O +  X 
base acid acid base

P-BLOCK ELEMENTS
 QUIZRR 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) + Xă (hydrated)

Ć Dipole moment of HF is maximum and is in order

HF > HCl > HBr > HI

1.19D 1.05D 0.80D 0.420D

P r e pa
parr a t io
ions
ns o f o x o a c id
idss

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 :

X2 + H 2O  H + + Xă + HOX

X2  2NaOH  NaX + NaOX + H2 O

(cold dil.)

3X 2  6NaOH  5NaX + NaOXO 2  3H 2O

(conc. hot)

(X = Cl, Br, I)
All the above reactions are rapid disproportionation of halogens.
Note :
(i) Reaction of X2 and water can produce HOX only.
(ii) There is appreciable concentration of HOCl.
(iii) The HOI is negligible in a saturated solution of iodine.

Ha
Hall i c a c i ds H O XO2 (X = Cl
Cl,, B r , I )
All the three halic acids are known. The acids HOClO2 and HOBrO 2 are known only in solution
and as salts. Only iodic acid (HOIO2) is stable out of aq. solution. It is a white solid. It can be
prepared by oxidizing I2 with conc. HNO3 or O3.

I2 + 10HNO3  2HIO 3 + 10NO 2 + 4H 2O

HO
HOCC l O 2 a nd HO
HOBr
Br
BrOO2
They can be made by treating barium halates with H2 SO4
Ba(Cl O3 )2 + H 2SO4  2HClO3 + BaSO 4 

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Ba(ClO3) 2 can be prepared by passing Cl 2 in Ba(OH) 2 solution

6Ba(OH)2 + 6Cl2  Ba(ClO3 )2 + 5BaCl2 + 6H 2O

They can also be produced by reactions of X2 with hot aq. base (NaOH)

3X2 + 6HOă  XO 3 + 5Xă + 3H2 O

KClO3 decomposes on heating, the product depends on temperature

400 ă 500Ĉ C
(i) 2KClO 3 2KCl + 3O 2
[MnO 2]

150Ĉ C

Lower
(ii) 4KClO3 
Temp.
 3KClO4  KCl


Zn(ClO 3 ) 2  2ZnO + 2Cl 2  5O 2

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

Perbromic acid HOBrO 3

It is best prepared by oxidation of BrO 3 by F2 in 5M NaOH solution.

BrO 3  F2  2HO   BrO 4  2F   H 2O

Solution of HBrO4 can be concentrated upto 55% (6 M), without decomposition. The hydrate
HBrO4.2H2 O can be crystallized.

Periodic acid HO IO3

The common form in aq. solution of this acid is HIO4 and also H5 IO6. H5IO 6 is called paraperiodic
acid (or orthoperiodic acid). It is a white crystal. It is decomposes on heating as

100 C ~ 200 C
2H5IO6   2HIO4 
 I 2O5 + O2 + H2 O
 4H2 O

The IO 4 ion is tetrahedral while (OH)5IO is octahedral. Periodates can be made by oxiding iodate
with Cl2 in alkaline solution.

IO3  Cl2  6HO  IO65  2Cl  3H2 O

C ă OH HIO4
·C=O
+ HIO 3
· C ă OH ·C=O

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 QUIZRR 65

St r u c t ur
uree o f ox
oxoo a n io
ions
ns

Anions XOă 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 ă 8)/2 = 3 (20 ă 16)/2 = 2 (26 ă 24)/2 = 1 0
Total electrons pairs 1+ 3= 4 2+ 2= 4 3+ 1= 4 4ă 0 = 4
Structure Td Td Td Td
Shape Linear Angular  pyramidal Td

XO ă XO 2ă XO3ă XO4ă
O

X X X X
O O O O
O O

O O O
(Linear) (Angular) (Pyramid) (Tetrahedral)

St
Strr u c t ur
uree an
andd s h ap
apee
Total
Molecules Bond Lone electron Structure Shape
pairs pairs pairs
X´

X
XX´3 3 2 5 X´ T ă shaped
(tbp) X´
X´
X´ X´
X
XX´5 5 1 6 Square
X´ X´ pyramid
(Oh)

X´ X´
X´
XX´7 7 0 7 X Pentagonal
X´
bipyramid
X´
(pbp)
X´

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 66 QUIZRR
P s e u d o h a l o g e n s a n d P s e u do
dohh al id es

Many substances have properties either like X2 or Xă (X = halogen). They are called pseudohalogens
and pseudohalides. They contain two or more atoms in which one at least is N ă atom, such as
(CN)2, CNă , SCNă etc.
Some pseudohalogens and pseudohalides

Pseudohalogens Pseudohalides

Cyanide ion CN ă

Cyanamide ion CN 22

Cyanogen gas (CN)2 Azid ion N3

Thiocyanogen (SCN)2 Thiocyanate ion SCNă
Cyanate ion OCNă
Fulminate ion ONCă

The cyanogen gas and CNă ion are best-known pseudohalogen and pseudohalide. They behave
like X2 and Xă , e.g.,

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

(CN)2 + H 2O  HCN + HOCN
Cl2 + H2 O  HCl + HOCl

(b) CNă behaves similar to Iă

2Cu2+ 
(aq)  4CN(aq)  2CuCN +  CN 2

2+
2Cu(aq)  4I  2CuI + I2

Both the above reactions are reduction of Cu2+ to Cu+ by CNă and Iă ions.

(c) The solubility of metal halides and metal cyanides are very similar,
NaX and NaCN  Water-soluble
AgX and AgCN  Water-insoluble
(X = Cl, Br, I)
PbCl2 and Pb(CN) 2  Water insoluble

(d) Like halides pseudohalides (CNă , SCNă etc.) are good ligands CuCl24  , ZnCl24  , Cu(CN)24  .
{Please note, the word ligands will be dealt in chapter co-ordination complexes}
(i) CN ă complexes with transition metals and Zn, Cd and Hg.
(ii) Most of the CNă complexes are ionic [Fe(CN)6] 4ă, [Ni(CN)4] 2ă, [Mn(CN)6 ]4ă etc.
(iii) CN ă can stabilize low oxidation states also, e.g [Ni(CN) 4] 4ă.

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Bl e a c h i n g P o w d e r

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, Cl2 .Ca(OH)2 .H2O

Pr e pa r at io n

It is prepared by passing chlorine over slaked lime

Ca(OCl) 2  CaCl 2.Ca(OH) 2 . H 2O + H 2O

3Ca(OH)2 + 2Cl2    
Bleaching Powder

P r op
opee r t ie
iess :

1. Reaction with dilute acids : With dilute acids, it gives chlorine which is known as
available chlorine.

CaOCl2 + 2HCl  CaCl 2 + H2 O + Cl 2 

CaOCl2 + H2 SO4  CaSO4 + H 2O + Cl2 

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

2CaOCl2 + H2O  CaCl2 + Ca(OCl) 2 + H2 O

3. Bleaching powder reacts with CO2 (atmospheric) and gives chlorine which accounts for its
oxidising and bleaching actions.

CaOCl 2 + CO2  CaCO3 + Cl2 

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


6CaOCl2  Ca(ClO3 ) 2  5CaCl2

G r ou
oupp 1 8 ((T
The N
Nooble G
Gaa s e s)

Ć Because of highest ionisation energy of group 18 elements in their respective periods, they
were given the name Ânoble gasesÊ and thus inert. However, at least in the case of xenon,
it is not so; it forms series of compounds.
Ć 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.

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 68 QUIZRR
Ć 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.

X e on f l u o r i d e s

Xenon reacts directly with fluorine (only). The products depend on respective amounts of Xe and
F2 and temperature also. The reactions are generally carried out in seal tubes.

2:1
XeF2
/P
1:5
Xe + F2 XeF4
/P
1 : 20 XeF6
/P

  heart
P  Pressure
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.

XeF2 + 2HCl  Xe + Cl2 + 2HF

XeF4 + 4KI  Xe + 2I2 + 4KF

XeF2 + Ce2(SO 4)3 + SO24   Xe + 2Ce (SO4) 2 + F 2

They are good fluorinating agents also.

2SF4 + XeF4  2SF6 + Xe

Pt + XeF 4  Pt F4 + Xe

+ XeF 2 + Xe + HF

Their reaction with water is different

(a) XeF2 is water soluble and undergoes slow oxidative hydrolysis.

2XeF2 + 2H2O  2Xe + O2 + 4HF

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(b) XeF4 reacts with water violently to give XeO 3

3
3XeF4 + 6H2 O  2Xe + XeO 3 + O + 12HF
2 2

In this reaction XeF4 disproportionates and H2O is parthy oxidized.

(c) XeF6 also reacts violently to give XeO 3

XeF 6 + 6H2O  XeO 4 + 12HF

With small amount of water

XeF6 + H 2O  XeOF 4 + 2HF

Ex a mp l e

Xe cannot form XeF3 , XeF 5 type of compound.

Solution :
The electronic configuration of Xe is 5S2 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
of unpaired electrons in its outer most shell. For this reason it cannot form XeF3 or XeF 5 type of
compound.

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