Boron

Extraction :
Boron is mainly extracted from Borax(Na2B4O7.10H2O)

Na2B4O7.10H2O heat H3BO3 heat B2O3

This B2O3 on reduction with Mg gives amorphous boron

B2O3 + 3Mg 2B(amorphous) + 3MgO

The reactions involved are –

Na2B4O7 + 2HCl 2NaCl + H2B4O7(tetraboric acid)

H2B4O7 + 5H2O 4H3BO3 B2O3 + 3H2O

High Purity crystalline Boron is obtained by following reaction
2BBr3 (g) + 3H2(g) Ta or W wire 2B(s) + 6HBr(g)
1200 C

Compounds of Boron
Borax or Tincal or Suhaga (Na2B4O7.10H2O )
•It is a white crystalline solid which contains tetranuclear
units [B4O5(OH)4]2- and its correct formula is
Na2[B4O5(OH)4].8H2O
•
Borax dissolves in water to give an alkaline solution
Na2B4O7 + 7H2O 2NaOH + 4H3BO3

Borax bead Test

When borax is heated, it swells and then is converted to
transparent glassy bead of composition 2NaBO2 + B2O3.
Na2B4O7. 10H2O  Na2B4O7 + 10H2O
Na2B4O7  2NaBO2 + B2O3
glassy bead

this glassy bead combines with transition metal oxides to

form characteristic coloured beads.
CuO + B2O3  Cu(BO2)2 Blue
The color of bead is different in oxidizing and reducing flame
Metal Oxidising Flame Reducing Flame
Cold Hot Cold Hot
Cu Blue Green Red brown Colorless
Co Blue Blue Blue Blue
Fe Yellow Green Green Green
Ni Brown Violet Green Green
 Ortho Boric Acid (H3BO3)
It is prepared by the acidification of aq. Borax solution
Na2B4O7 + 2HCl + 5H2O → 2NaCl + 4 H3BO3
It is also obtained by the hydrolysis of most boron
compounds like halides and hydrides.
Properties
It is a weak monobasic acid and act as a lewis acid by
accepting lone pair from water molecule
B(OH)3 + 2H2O → *B(OH)4]– + H+

STRUCTURE
It has a layer structure in which planar BO3 units are
joined by H- bonds.
 Heating Effect
On heating at 1000C it gives metaboric acid
which converts into tetra boric acid on heating at 1600C
and on further heating boric oxide(boric Anhydride) is formed.
H3BO3 → HBO2 → H2B4O7 → B2O3
 BORON HYDRIDES
Boron forms a large number of volatile covalent hydrides
known as Boranes. There are two series of boranes
(i) BnHn+4 (more stable) (ii) BnHn+6
Diborane (B2H6) is the most important .

DIBORANE (B2H6)
It is prepared by the reduction of Boron trichloride
4BCl3 + 3 LiAlH4 → 2B2H6 + 3AlCl3 + 3LiCl
In Laboratory it is prepared by the oxidation of NaBH4 by I2
2NaBH4 + I2 → B2H6 + 2NaI + H2
On Industrial scale it is prepared by the reduction of BF3 by
NaH
2BF3 + 6NaH → B2H6 + 6NaF
 Properties
1. Combustion: Diborane is a colorless toxic gas and
spontaneously catches fire on exposure to air.
B2H6 + 3O2 → B2O3 + 3H2O DH = -1976 kJmol-1
2. Hydrolysis : Diborane is easily hydrolyzed and forms
boric acid
B2H6(g) + 6H2O(l) → 2B(OH)3(aq) + 6H2(g)

3. Reaction with NH3 : First an addition product is formed at

lower temperature B2H6 + 2NH3 → B2H6.2NH3 or
[BH2(NH3)2]+[BH4]-
This addition compound on heating at around 450 K gives
Borazole which is known as Inorganic Benzene or Borazine.
B2H6 + 6NH3 → 2B3N3H6 + 12H2
 Structure of Diborane
The four terminal hydrogen atoms and the two boron
atoms lie in one plane . Above and below this plane, there
are two bridging hydrogen atoms. The four terminal
B-H bonds are regular two centre-two electron bonds
(normal covalent bonds) while the two bridge (B-H-B)
bonds are different. Each bridge hydrogen is bonded to
the two boron atoms by sharing of only two electrons and
there fore is called 2 centre 3 electron (2c-3e) bond.
Note : The hybridised orbitals used in diborane are
Sp3.
 Aluminium And It’s Compounds
Chemical Properties
1. Action Of Air : Al is unaffected by dry air whereas in moist
air oxide layer is formed on its surface .In presence of oxygen
it burns producing high amount of energy
4Al + 3O2 → Al2O3

2. Reaction with acid and alkali : Al giving off hydrogen with

both acids and alkalis .
2Al + 6HCl → 2AlCl3 + 3H2
2Al + 2NaOH + 2H2O → 2NaAlO2 + 3H2
3. Reducing Agent :
Due to its high electropositive character it is a strong reducing
agent and is used to reduce Cr, Mn ,Fe oxides .
2Al + Cr2O3 → Al2O3 + 2Cr DH = -ive

Compounds Of Aluminium
Al2O3
Al2O3 is very hard and resistant to chemicals. It’s m.p. is 20500C
It is an amphoteric oxide and reacts with both acids and bases.
Al2O3 + 6HCl → 2AlCl3 + 3H2O
Al2O3 + 2NaOH → 2NaAlO2 + H2O
 Al2Cl3
It is a white deliquescent solid and fumes in air due to
hydrolysis. It sublimes at 1800C and exists in the form of dimer.
AlCl3 + 6H2O → 2Al(OH)3 + 6HCl
Group 14 Elements (Carbon Family)
C Si Ge Sn Pb
Electronic Configuration – ns2 np2

Atomic size
it increases from C to Si and than after there is
slight increase in atomic size from Si to Pb due to poor
shielding by d and f electrons.

Ionisation Energy
I.E. decreases down the group but the decrease is slight after
Si due to poor shielding by d and f orbitals.
 Chemical Properties
Oxidation state
These elements have 4 electrons in their outermost shell
these elements do not form M4+ ions due to high value of
(IE1 +IE2+IE3+IE4). Generally they form covalent
compounds by sharing of electrons.

The common oxidation state shown by these elements is

+4 and +2 .The tendency to show +2 state increases down
the group due to inert pair effect .
1. Reaction with oxygen
All elements combine with oxygen to form two types
of oxides MO and MO2.
Oxides in higher state are more acidic.
The acidic character decreases down the group .
CO2 SiO2 GeO2 SnO2 PbO2

acidic amphoteric
CO GeO SnO PbO

Neutral acidic amphoteric

 2. Rxn with water
C, Si and Ge are unaffected by water but Tin decomposes
steam
Sn + 2H2O → SnO + 2H2
 Chemical Properties Of CO2
(i) Acidic nature :
It is an acidic oxide and its solution in water
contains unstable carbonic acid. H2CO3 is not isolated
in solid state but its salt NaHCO3 and Na2CO3 are
known in solid state.

(ii) Reaction with alkalis :

CO2 combines with alkalis to form carbonates.
CO2 + 2KOH  K2CO3 + H2O
Excess of CO2, converts carbonates into bicarbonates
CO2 + K2CO3 + H2O  2KHCO3
Lime water Ca(OH)2, turns milky when CO2 is passed
through due to formation of insoluble calcium carbonate.
Ca(OH)2 + CO2 CaCO3 + H2O

However, the milkiness disappears on passing more of

CO2 due to formation of soluble calcium bicarbonate.
CaCO3 + H2O + CO2 Ca(HCO3)2
soluble

(iii) Photosynthesis : O2 is evolved and glucose is

synthesized.
6CO2 + 6H2O C6H12O6 + 6O2
 Allotropes Of Carbon
Diamond
It has a crystalline lattice. In diamond each carbon atom
undergoes sp3 hybridisation and is linked to four other
carbon atoms by using sp3 hybridised orbitals in
tetrahedral fashion.
In this way it makes a large 3D network of covalent bonds
making it so hard .
 Graphite

In graphite each carbon atom is sp2 hybridised and is

attached to 3 other carbon atoms to form hexagonal rings

This bonding results in a layered structure in which two

layers are held together by weak Vander Waal forces.

Due to presence of one free electrons graphite can

conduct electricity along its layers.
 FULLERENE(BUCKY BALLS)
Fullerenes are made by the heating of graphite in an
electric arc in the presence of inert gases such as
helium or argon.
Fullerenes are the purest form of Carbon.
There are two types: (i) C60 (ii) C70
C60 Molecule contains 12 Five member rings and 20 six
member rings .
A five member ring can only fuse with a six member ring
whereas a six member ring can fuse with both 6 & 5.
All the C atoms undergo sp2 hybridisation.
Graphite is the most stable allotrope of carbon and
therefore its enthalpy of formation is taken as zero.
The enthalpy of formation of fullerene(C60) and
Diamond is 38.1 and 1.9 kJmol-1respectively.

This ball shaped molecule has 60 vertices and each

one is occupied by one carbon atom and it also
contains both single and double bonds
 Silica (SiO2)
Silicon dioxide is a covalent, three-dimensional network
solid in which each silicon atom is covalently bonded in a
tetrahedral manner to four oxygen atoms.

The entire crystal may be considered as giant molecule

in which eight membered rings are formed with alternate
silicon and oxygen atoms.
 Chemical Properties of SiO2
Silica is almost unreactive due to high SiO bond enthalpy.
It is unaffected by most of the acids but is attacked by HF
and NaOH.
SiO2 + NaOH Na2SiO3 + H2O
SiO2 + HF SiF4 + 2H2O
 Silicones
They are a group of organosilicon polymers, which have
(R2SiO) as a repeating unit.
The starting materials for the manufacture of silicones are
alkyl or aryl substituted Chlorosilanes , RnSiCl(4–n), where R
is alkyl or aryl group.
These chlorosilanes on hydrolysis and condensation
produces silicones.
2CH3Cl + Si Cu Powder (CH3)2SiCl2 Hydrolysis (CH3)2Si(OH)2
They have in general high thermal stability, high dielectric
strength and resistance to oxidation and chemicals.

Silicones being surrounded by non-polar alkyl groups are

water repelling in nature.
 Silicates
Silicates are the compounds which contains tetrahedral
SiO44- as their structural unit.
 Types Of Silicates
(1) Orthosilicates
They contain single discrete unit of tetrahedral SiO44-
units and some examples are as given below :
ZrSiO4 (Zircon) Mg2SiO2 (Forestrite or Olivine)
Be2SiO4 (Phenacite) Zn2SiO4 (Willemite)

(2) Pyrosilicates
They contain two units of joined along a corner
containing O-atom. They are called as Island silicate also.

They contain Si2O76- units .

 (3) Cyclic or Ring structure silicates
Their general formula is(SiO32-) or (SiO3)n2n-
 (4) Chain silicates
In chain silicates two O– atoms of each tetrahedra
[SiO4]2– unit share with another [SiO4]2– unit.
 NITROGEN FAMILY (15th Group)
General properties:-
1.Electronic configuration:- The elements of group 15
have electronic configuration ns2np3. These elements
have stable half filled configuration and are not so
reactive. Nitrogen behaves as noble element under
ordinary conditions.

2. Atomic and ionic radii:- Radii increases from top to

bottom. From As to Bi there is small decrease becauseof
presence completely filled d and f orbitals.
 3. Ionisation enthalpy:-
Ionisation enthalpy decreases on moving down the
group.

The I.E. of Nitrogen is very high due to its small size.the

difference between N and P is comparatively high.

But the difference afterwards between two members is

small. This is due to the less shielding effect of d and f
electrons in As, Sb and Bi respectively .
 4. Electronegativity
Electronegativity decreases down the group and N is
the most electronegative among these.

5. Allotropy
All the elements except N & Bi show allotropy.

Phosphorus exist in a number of allotropic forms such

as white, red, scarlet, black, a-black, b-black and violet.

Arsenic exist in three forms grey, yellow and black.

Antimony exist in three forms yellow, black and

explosive.
 6. Atomicity
Nitrogen is diatomic molecule at room temperature.
Two N atoms are bonded through a triple bond.

P, As and Sb all exist as discrete tetratomic molecules ,

viz., P4, As4,Sb4. The pp – pp bonding is not possible in
these elements.
 Chemical properties
1.Oxidation states
Elements of this group can exhibit a maximum
oxidation state +5.
Due to inert pair effect the tendancy to show +3 state
increases.
N and P generally exhibit -3 oxidation state due to small
size and high electronegativity .
The tendency to show -3 state decreases on moving
down.
Nitrogen besides -3, +3 and +5 exihibits a large nuber of
O.S.
-3 in (NH3, Li3N, Ca3N2, AlN),
-2 in (NH2NH2),
-1 in NH2OH,
0 in N2,
+1 in N2O, The maximum covalency of nitrogen is 4
since it doesnot posses d-orbitals in the
+2 in NO,
valence shell .
+3 in N2O3,
+4 in NO2 and
+5 in HNO3and N2O5.
 DINITROGEN (N2)
Commercially it is produced by the liquification and
fractional distillation of air Liquid N2(b.p. 77.2K) distils
out first leaving behind O2(90K).

In laboratory Nitrogen is prepared by treating

aqueous NH4Cl with sodium nitrite.
NH4Cl(aq.) + NaNO3(aq.)  N2(g) + 2H2O(l) + NaCl(aq)
Nitrogen can also be obtained by thermal decomposition
of ammonium dichromate or ammonium nitrate .

NH4NO2  N2 + 2H2O
(NH4)2Cr2O7  N2 + 4H2O + Cr2O3
Very pure nitrogen can be obtained in small amounts by
thermal decomposition of sodium or barium azide.

Ba(N3)2  Ba + 3N2
Properties
It is a colourless, tasteless , odourless and non-toxic gas.
Because of high bond enthalpy it is chemically inert at
room temperature and reactive at high temperature.

Only at very high temperature(2000K ) it combines

with Oxygen to form Nitric oxide.
N2 + O2(g)  2NO(g)
 B. N2 combines with metals at high temperature to
form nitrides
6Li + N2  2Li3N

3Mg + N2  Mg3N2

 AMMONIA(NH3)
In atmosphere it is formed by the decay of urea
NH2CONH2 + 2H2O  (NH4)2CO3  2NH3 + H2O
+ CO2
On a small scale it is obtained by decomposition of
ammonium salts
NH4Cl + Ca(OH)2  2NH3 + 2H2O + CaCl2

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

High pressure(200 × 105Pa) and high temperature(700K

On a large scale it is prepared by haber’s process.
and use
N2of
(g)a+catalyst
3H2(g) like
2NHiron
(g) oxide
, DH =with
- small
46.1 kJ mol-1
3
Amounts of K2O and Al2O3 favours the formation of NH3
By the Hydrolysis of cyanamide
CaCN2 + 3H2O  2NH3 + CaCO3

Physical Properties
It is a colorless gas with characteristic pungent odour.
It is highly soluble in water. One volume of water
dissolves 1300 volumes of NH3 at 00C and 1 atm pressure.
The high solubility is due to hydrogen bonding.
 Its aqueous solution is basic in nature.
Structure of Ammonia
N atom is in sp3 hybridization state in NH3 but due to
presence of lone pair on N atom its structure is Pyramidal
With a bond angle of 107.80.
NH3 can not be dried using Conc. H2SO4, P2O5 CaCl2
because it react with them
2NH3 + H2SO4  (NH4)2 SO4
H2O + NH3 + P2O5  (NH4)3 PO4
CaCl2 + 8NH3  CaCl2 . 8NH3 adduct

There for Quick lime Ca(OH)2 is used to dry it

because both are bases and can’t react.
 Chemical Properties
1. Combustion
It burns in oxygen with yellow flame.
4NH3 + 3O2  2N2 + 6H2O
When a mixture of NH3 and air is passed over platinum
at 1123K NO is formed. This reaction is used in ostwald’s
Process of HNO3 formation.
4NH3 + 5O2  4NO + 6H2O

2. Reaction With Chlorine

(i) Chlorine in excess :
NH3 + 3Cl2  NCl3 + 3HCl
(ii) Ammonia in excess : N2 is formed
8NH3 + 3Cl2  N2 + 6NH4Cl
 3. Reactions of aqueous ammonia
Aqueous ammonia reacts with metals to precipitate
their hydroxides first, some of which are soluble in excess.
(i) Metals which form ppt. which is not soluble
CrCl3 + 3NH4OH  Cr(OH)3 + 3NH4Cl
Green ppt.

AlCl3 + 3NH4OH  Al(OH)3 + 3NH4Cl

White ppt.

FeCl3 + 3NH4OH  Fe(OH)3 + 3NH4Cl

Red ppt.

(ii) Metal whose ppts are soluble

CuSO4 + NH4OH  Cu(OH)2 + (NH4)2SO4
Cu(OH)2 + NH4OH [Cu(NH3)4]2+
deep blue solution
AgNO3 + NH4OH AgOH + NH4NO3
AgOH + NH4OH [Ag(NH3)2]+

CdSO4 + NH4OH [Cd(NH3)4]SO4

4. Reaction with Hg2Cl2

A grey ppt. is formed .
Hg2Cl2 + 2NH4OH  Hg + HgNH2Cl + NH4Cl + 2H2
Grey

On reaction with Nessler’s reagent a brown ppt is formed

2K2HgI4 + NH3 + 3KOH H2NHgOHgI + 7KI + 2H2O
Brown(Iodide of million’s base )
 Oxyacids of nitrogen
Nitric Acid (HNO3)
Preparation : Ostwald’s process : On passing a
mixture f ammonia and oxygen over a platinum gauge
wire at Hook forms nitric oxide (NO)
4NH3 + 5O2  4NO + 6H2O

This NO is cooled and oxidized in air to form NO2.

2NO + O2  2NO2
This NO2 is converted to 60% HNO3 when water is
sprayed over it in adsorption tower.

The obtained HNO3 is further concentrated by

dehydrating it with Conc. H2SO4.
 Fuming nitric acid
It contains dissolved NO2 in conc. HNO3 and is obtained
by the distillation of conc. HNO3 with starch. It gives
brown fumes and hence called fuming.
Properties
* It is a colorless liquid having pungent smell.
* It’s color changes to brown when it has some
NO2 dissolved in it.
* It is soluble in water in all proportions.
* It becomes yellow in presence of sunlight due
to it’s decomposition into NO2.

* It has extremely corrosive action on skin

•Acidic Nature : It is a very strong acid and reacts with
basic compounds to form their corresponding nitrates
which are soluble in water.

Structure
 Oxides of Nitrogen
Formula Name Oxidation State Strutre

N2O Nitrous Oxide +1

Or
Laughing gas

No Nitric Oxide +2

N2O3 Di-nitrogen trioxide +3

NO2 Nitrogen dioxide +4

N2O4 Dinitrogen tetraoxide +4

N2O5 Dinitrogne pentaoxide +8

N2O
* Laughing gas

* It supports combustion but it self is not

combustile

* Isoelectronic with CO2

NO :

* It is an odd e– molecule

* Paramagnetic in nature.

* It gives brown ning with FeSO4 due to

formation of FeSO4.NO (nitroso ferrous
sulphate)
[Fe(H2O)5 NO]SO4 (brown complex)
N2O3 :

* It is a mix of NO and NO2.

* At 30°C it liquifies to a blue liquid which is

unstable at room temp.

* N2O3 on dissolving in water gives HNO2 nitrous

and therefore it is also known as anhydride to
HNO2.
 NO2 :

* It is a paramagnetic gas which is brown in

color.

*It exists as a dimer in the form of a pale yellow

liquid.

* It also gives brown ring test with acidic ferrous

sulphate solution.
 Nitrate Salts
* All nitrate salts are water soluble.
(i) Action of heat

* Alkali metal nitrates on heating liberates

oxygen with corresponding nitrite salts.
* Moderately reactive metals like alkaline earth
metals Cu, Fe etc gives metal oxide + NO2 + O2

* Lees reactive metals like Ag , Hg gives metal

along with NO2 and O2 on heating
 Phosphorus
Allotropic forms
Phosphorus exists in three allotropic forms
white, red and black phosphorous

White Phosphorus
 Red Phosphorus

* Black phosphorus is the most stable allotrope

of phosphorus.
 White Phosphorus
* It has a characteristic garlic smell and is
poisonous in nature.
Persons working with phosphorus develops a
disease phosphy Jaw.

* Action of air : It’s ignition temp is low (30°C). It

readily catches five giving dense fumes of P2O5
or P4O10
* Reaction with NaOH : On boiling with NaOH,
Phosphine is formed.

* White phosphorus contains discrete units of P4

atoms lying at the corners of regular
tetrahedron with bond angle 60°. The bond
angle indicates the ring is under strain and that
is why white phosphorus is heat unstable
and most reactive allotrope of Phosphorus.

* It is insoluble in water but soluble in carbon

disulphide.
Red Phosphorus :
* It is obtained by heating white phosphorus on
at around 500 k in inert atmosphere.

* It is a dark red powder and is odorless

nonpoisonous and insoluble in water.

* It’s ignition temp. is hinh and is less reactive

then white phosphorus.
* It has a polymeric structure with chains of P4
tetrahedral units linked with each other.
Black Phosphorus :
* It exists in two allotropic forms : a-black and
b-black
White P  b-black
Red P  a-black
Compounds of Phosphorus :
(i) Phosphine (PH3) sp3 hybridisation (Pyramidal)
Preparation
* By boiling white phosphorous in NaOH in inert
atmosphere of CO2.

* By hydrolysis of Calcium phosphide :

Note : PH3 is non-inflammable but becomes
inflammable in presence of P2H4. P2H4 can be
removed by paving it through HI, where PH3 gets
absorbed.
Properties :
* It is a colorless, poisonous gas with rotten fish
smell.

* It decomposes in presence of electric spark

giving red phosphorous and hydrogen
* Basic nature : Due to presence of cone pari on
phosphorus atom it can at as a weak base. It’s
basic strength is greater then NH3 due to less E.N.
* It is used in making Holme’s signal and smoke
screens. (containers containing calcium carbide
and calcium phosphide are pierced and thrown
into the sea where calcium phosphide reacts with
water to form PH3 which burns giving dense
fumes of P2O5 and making a signal.
Some metal salts on reaction with PH3 precipitates their
phosphides.
Halides of Phosphorus :

(PX3 – trihalide PX5 – Pentahalide)

(i) PCl3 : SP3 pyramidal

Preparation
* From Thionyl chloride (SOCl2) : When white
phosphorus reacts with SOCl2, PCl3 is formed.

* From Lab : By heating P4 in current of dry

chlorine.
Properties :
* Reaction with water Phosphorus acid is
formed on hydrolysis

* Reaction with compounds containing OH

group. The OH group of organic compounds get
replaced by Cl on reaction wtih PCl3.
(ii) PCl5 : sp3 d

Preparation :
* From thionyl chloricle (SO2Cl2)

* Lab method :

In solid state, PCl5 exists in ionic form.

Properties :
* Hydrolysis :

* Replacement of OH group : PCl5 also replaces

on group present in organic molecules
* Replacement with metals : Finely divided
metals on heating with PCl5 forms their
corresponding chlorides.

* Heating effect : PCl5 sublimes on heating but

get decomposed if heated strongly.
Q PCl3 gives fumes in moisture why ?
Ans. HCl gas is released which gives white fumes.
Oxyacids Of Phosphorous
Phosphorous acid(H3PO3)
Phosphoric acid(H3PO4)
HPO3 exists in two polymeric structures.
Imp. Points :
* The acid of phosphorous in +3 state have a
tendency to disproportionate into higher and
lower oxidation state.

* The oxyacids of phosphorous which contains

P–H bonds can at as a good reducing agent.
* Action of heat on phosphoric acid.

* H3PO3 and H3PO2 disproportionate on heating

 * Only oxyacids containing P-H bond will
undergo disproportionation.

Q A gas X shows following reaction

(i) It turns red litmus blue
(ii) When added in excess to CuSO4 solution a
deep blue color is obtained.
(iii) When paved in excess through FeCl3 solution
a brownish ppt is obtained Identfy the gas and
write the reaction.
Ans.
Oxygen Family : (Basics from NCERT)
Acidic Character : H2O < H2S < H2Se < H2Te < H2Po

Thermal Stability : H2O > H2S > H2Se > H2Te > H2PO

Reducing Character : H2O < H2S < H2Se < H2Te < H2Po

* All elements except selenium (Se) Forms

monohalides (Ex) which exists in the form of
dimers ie. E2X2.
Ex. S2Cl2 , S2Br2, S2F2 etc.
 * Selenium dichloride (SeCl2) undergoes
disproportion ation.

Q. 5F6 is formed but oF6 does not or oxygen only

form diflouride and not hexathoride Why?
Ans. Due to non-availability of vacant d-orbitals.
Q. SF4 is hydrolysed but SF6 is not or SF6 is
chemically inert as compared to SF4. Justify?
Ans. In SF4, sulphur has vacant d-orbitals whereas in
SF6 it doesn’t have SF6 is sterically more
hindered then SF4. Hence it is more inert.
Compounds of Oxygen :
(i) Dioxygen (O2) :
 * As oxidation state of central atom increases
the acidic character increases.

* some metallic oxides with metal in highest

oxides states are acidic. like Mn2O7 , CrO3

(iii) Ozone :
It is prepared by paying silent electric dis charge
through oxygen.
Properties :
* Oxidizing nature : Due to formation of nascent
oxygen o zone outs as strong oxidzing agent.

\ Ozone when reacts with iodide ions, it

produces iodine which when pared through
starch solution, turns it blue due to formation of
starch iodide complex. Non- metals are oxidized
to their corresponding oxy-acids.
It oxidizes nitric oxide to convert it into nitogen
dioxide
NO + O3  NO2 + O2
This reaction is the main reason for ozone
depletion from the exhaust of supersonic jet
planes.
* Formation of ozonides when ozone reacts with
unsaturated systems, ozonides are formed
when forms different product after hydrolysis
Q How is O3 estimated quantitatively ?
Ans

by the amount of hypo used we can calculate amount of

O3 used

Sulphur
Rhombic sulphur Monoclinic sulphur
(a – sulphur) (b – sulphur)
* At room temp, a-sulphur is more stable
* Both are soluble in CS2
* a-sulphur transform to b- sulphur when heated
above 369k
At 369 k both forms are stable and both exist
(transition temp)

* Below 369k, a is stable and above 369 k b is

more stable.

* Sulphur can also exist in cyclo S6 form in chair

shape.
* At high temp it can exist as a diatomic
molecule S2 which is paramagnetic.
Compounds of Sulphur
(i) Hydrogen Suphide (H2S)

* By reaction of FeS with H2SO4 :

Properties :
* It is a colorless poisonous gas with rolten egg
smell.

* It burns in air with blue came.

* Reducing nature : H2S on decomposition gives

hydrogen and \ it can act as a reducing agent
on reaction with an oxidizing agent it itself gets
oxide to colloidal sulphur
*It reduces Fe+3 ® Fe+2

It reduces H2O2 to H2O

It reduces KMnO4 to Mn+2 is acidic medium

It reduces HNO3 to NO2
*Acidic nature : It is a weak dibasic acid

k1 >> k2

* Action on salts : When H2S is paused through salt

solution of metals, sulphides are ppted depending on the
medium of solution.
(i) Sulphides which are precipitated in acidic
medium
Hg  HgS Cd  CdS
Pb  PbS Sn  SnS and SnS2
Cu  CuS Sb  Sb2S3
Bi  Bi2S3 As  As2S3
Rest all are soluble in YAS.
(ii) Sulphides which are pptd in basic (alkaline
medium)
Black Co  CoS
Ni  NiS
Fe  FeS
White Zn  ZnS
Pink Mn  MnS
Stuture : H2S  sp3 hydridisation 92.5° bond ® Bent
shape
(ii) Sulphur dioxide (SO2) :
* Burning sulphur in air :

* By reaction of dilute acids on sulphides and

bisulphides
 By roasting of sulphide ores

Properties :
* It is a colorless, pungent, smelling, suffocating gas.
* It is highly soluble in water and its aqueous solution is
acidic in nature.

* It reacts with alkalies to form two types of salts :

sulphites and bisulphites
 * It SO2 gas is passed through lime water, the
solution turns milky.
* It SO2 gas is paced through lime water, the
solution turns milky.

The milkiness disappears when SO2 is passed in excess

due to formation of calcium bisulphite.
* Reducing with chlorine : It gives sulphur
chloride or phosgene.
* Reducing nature : It can act as reducing agent
and itself get converted to H2SO4. It can reduce.
Structure : sp2  angular shape  119.5°
(iii) Sulphur trioxide (SO3)
When SO2 reacts with O2 in presence of V2O5
catalyst, SO3 is formed.
Structure : In the given structure there is one
pp-pp and twp pp-dp bonds.(make coorections.)
* In gaseous state, it exists as a planar SO3
molecule while it exist as a trimer in solid state.
Oxyacids of sulphur
H2SO4

H2S2O7
H2SO5

P  Peroxy Linkage in
S  Sulphur acids
M  Marshall acid (H2S2O8)
C  Caro's acid (H2SO5)
P  Pyro sulphuorous acid (H2S2O5)
H  Hypo sulphorous (H2S2O4)
 H2SO4
*Solubility in water : It is easily soluble in water
due to H-bonding.
It dissolves in water with liberation of heat i.e.
exothermic dissolution.

Q. When H2SO4 is diluted it is added to water

instead of adding water to it why ?
 Chemical Properties
* It's a strong dibasic acid.

* Dehydrating nature : It is a very strong

dehydrating agent and absorbs water from
almost all organic compounds.
* Oxidizing nature : H2SO4 can act as a
moderately strong oxidizing agent and it oxidizes
(i) Metals to metal sulphates :

(ii) Carbon to CO2 :

(iii) I– to I2

(iv) Br– to Br2

Q.

Identify A,B,C,D ?
A  conc. H2SO4
B  Br2
C  NO2+
D  TNT (Trinitro Toulene)
 Halogen Family
F Cl Br I At
Electron Affinity : I < Br < F < Cl
( due to small size the interelectronic repulsion are
large)
* They act as oxidizing agent due to high
tendency to accept electrons . They have high
E.N. and E.A.
Oxidizing nature : I2 < Br2 < Cl2 < F2
Oxidizing nature of halogen depends on
(i) X2 bond dissociation energy
I2 < Br2 < Cl2 < F2
(due to more repulsion between e– on F-atoms)

(ii) Electron affinity

F < Cl
(iii) Hydration energy :
due to small size of Fluorine it has very high
DHhydration .
So the overall DH becomes –ve for F then Cl, so
F2 is better oxidizing agent then Cl.
 Chlorine(Cl2)
Preparation
(i) From MnO2
By heatingMnO2 with conc. HCl
MnO2 + 4HCl → MnCl2 + Cl2 + 2H2O
A Mixture of NaCl and H2SO4 can be used
4NaCl + MnO2 + 4H2SO4 → MnCl2 + 4NaHSO4 + 2H2O + Cl2
By the action of HCl on potassium permanganate.
2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2O + 5Cl2
(ii) Deacon’s Process:
By oxidation of hydrogen chloride gas by atmospheric oxygen
in the presence of CuCl2 (catalyst) at 723 K.
4HCl +O2 ⎯⎯⎯⎯→ 2Cl2 + 2H2 O
 Physical &Chemical Properties
It is a greenish yellow gas with pungent and suffocating
smell.
Chlorine reacts with a number of metals and non-metals
to form chlorides.
2Al + 3Cl2 → 2AlCl3 P4 + 6Cl2 → 4PCl3

It has great affinity for hydrogen. It reacts with compounds

containing hydrogen to form HCl.
H2S + Cl2 → S + 2HCl
With dry slaked lime it gives bleaching powder.
2Ca(OH)2 + 2Cl2 → CaOCl2 + CaCl2 + 2H2O
The composition of bleaching powder is
CaOCl2.CaCl2.Ca(OH)2.2H2O.
 Reaction with NH3
(i) NH3 is in excess :
8NH3 + 3Cl2  6NH4Cl + N2
(ii) Cl2 is in excess.
NH3 + 3Cl2  NCl3 + 3HCl
Chlorine water on standing loses its yellow colour due to the
formation of HCl and HOCl.
It is a powerful bleaching agent, bleaching action is due to
oxidation.
Cl2 + H2O → 2HCl + O
Coloured substance + O → Colourless substance
 Reaction with alkalies :
(i) cold and dilute :
Halide and hypohalite are formed.

(ii) Hot and conc : Halide and Halate are formed

•All halides show the same reaction except fluorine

With dilute alkali F2 gives OF2
2NaOH + F2 2NaF + OF2 + H2O
and with concentrated alkali oxygen gas is evolved
4NaOH + 2F2 2NaF + O2 + 2H2O
 Reaction of halogen acids with AgNO3 :

HCl can react with F2 but not with Br2 and I2

 Aqua Regia(3 part HCl + 1 part HNO3)
It is used for dissolving noble metals like gold, Pt
Au + 4H+ + NO3- +4Cl- → AuCl4- + NO + 2H2O
3Pt + 16H+ + 4NO3- +18Cl- → 3PtCl62- + 4NO + 8H2O

Reaction of HCl with Fe

HCl when reacts with iron ferrous chloride is formed.

Ferric chloride is not formed due to formation of Hydrogen
Which prevents further oxidation
Fe + 2HCl → FeCl2 + H2
Oxyacids of halogen
 Interhalogen compounds

XX bond is stronger then XX' bond

ClF3 is T shaped
Hydrolysis of interhalogen compounds :
 Noble Gases
In general, noble gases are least reactive. Due to –
(i) Fulfilled cinfiguration ns2 np6
(ii) High I.E. and +ive E.A.
Xenon-fluorine compounds
Xe + F2 → XeF2(s)
( 1 : 2) (673K, 1 bar)
Xe + 2F2 → XeF4(s)
( 1 : 5) (873K, 7bar)
Xe +3F2 → XeF6(s)
( 1 : 20) (573K, 60-70 bar)
XeF6 can also be prepared by the interaction of XeF4 and
O2F2 at 143K.
XeF4 + O2 F2 → XeF6 + O2

XeF2, XeF4 and XeF6 are colourless crystalline solids

and sublime readily at 298 K. They are powerful
fluorinating agents.

XeF2 + PF5 → *XeF]+ [PF6]–

XeF4 + SbF5 → *XeF3]+ [SbF6]–
 Hydrolysis of Xenon-Fluorides :
*XeF2
2XeF2 (s) + 2H2O(l) → 2Xe (g) + 4 HF(aq) + O2(g)
•XeF4
(i) Complete Hydrolysis : XeF4 disproportionate on
hydrolysis forming Xe and XeO3.
6XeF4 + 12 H2O → 4Xe + 2XeO3 + 24 HF + 3 O2
XeO3 is an explosive and its structure is :
(ii) partial Hydrolysis

* XeF6

(i) Complete Hydrolysis

XeF6 + 3 H2O → XeO3 + 6 HF
(ii) Partial Hydrolysis :
XeF6 + H2O → XeOF4 + 2 HF
XeF6 + 2 H2O → XeO2F2 + 4HF