P Block II PDF

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GURU
Vidyamandir Classes p-Block Elements - II
p-Block Elements - II
Group 15 Section - 1
The elements of group 15 have ns2 np3 as their valence shell electronic configuration. They can complete
their octets in two different ways :
(a) Electron Transfer : The atoms of the elements of this group may accept three electrons from more
metallic elements to form triply charged negative ions such as nitride, N3– ion and phosphide, P3– ion
and thereby attain noble gas configuration. Only small atoms can form highly charged negative ions
because of their greater electronegativities. Obviously nitrogen with greater electronegativity and smaller
size, has a stronger tendency to form N3– ion as compared to phosphours to form P3–. The other
members of the family show little tendency to form triply charged negative ions and this tendency
decreases down the group because of increase of size and decrease of electronegativity.
The elements of this group also exhibit oxidation states of +3 and +5 ions are generally not known
because their ionization enthalpy will be very high. As we go down the group, the stability of +3
oxidation state increases while that of +5 decreases.
(b) Electron Sharing : Since the atoms of these elements contain three unpaired p-electrons so these
can pair with unpaired p-electrons in another atom or atoms to form three covalent bonds, e.g. , NH3,
PH3, AsH3, BiH3.
Hydrides :
Stability order : NH3 > PH3 > As H3 > SbH3 > BiH3
Basicity : NH3 > PH3 > As H3 > SbH3 > BiH3
H - E - H bond angle : NH3 > PH3 > As H3 > SbH3
Boiling point : SbH3 > NH3 > As H3 > PH3
Reducing character : BiH3 > SbH3 > As H3 > PH3 > NH3
The bond angle in PH3, As H3 and SbH3 is close to 92° which suggests the orbitals used for bonding
are close to pure p-orbitals.
Oxides :
Oxides with higher oxidation state are more acidic :

I II III IV V
N 2O  NO  N 2O3  NO 2  N 2 O5
 
neutral acidic
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p-Block Elements - II Vidyamandir Classes
Moreover, acidity decreases down the group :
N 2O3  P4O6  As 4O6  Sb 4O6  Bi 2O3

   
acidic Amphoteric basic
Halides : NX3 are unstable except NF3.

Ammonia forms NCl3, NBr3.6NH3 and NI3. 6NH3 (used as explosives) with Cl2, Br2 and I2 respectively.
NCl3 was formerly used to bleach flour to make white bread but it was banned when it was suspected that
this bread sent dogs mad !!
Penta halides are more covalent than trihalides because higher oxidation state leads to high polarising power.
Nitrogen and its Compounds :

Nitrogen is present in air to the extent of 78.06 % by volume. N2 is colourless, tasteless, odorless and
diamagnetic. It is lighter than air, sparingly soluble in water and a non-supporter of combustion.
Preparation :
1. In laboratory, nitrogen samples are obtained by warming ammonium nitrite or by oxidising ammonia
by bromine water, sodium hypochlorite (NaOCl) or CuO
NH3  CuO 
 N 2  Cu  H 2O
 NaOCl 
 N2  NaCl  H2O
 Br2 
 N2  NH4 Br.
2. Small quantities of very pure N2 is obtained by carefully warming sodium azide.
300°C
NaN3 
 N 2  Na
3. Heating ammonium salts with more oxidizing anion (Cr2O 72  , NO 2 , NO 3 , ClO 4 )
 
(NH 4 ) 2 Cr2O7  N 2  Cr2O3  4N 2O ; NH4 NO2 
 N 2  2H 2O
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Chemical Properties :
(i) It is used to prepare NO in the ‘Birkeland and Eyde process’.
Electric arc
N 2  O 2  2NO
3500°C
(ii) It is used to prepare ammonia by ‘Habers Process’.

Fe/ Mo
N 2  H 2   NH3
500°C
250 atm
(iii) Reaction with metals :
[a] Ammonia NH3

Ammonia is a colourless gas having characteristic pungent smell. It is quite poisonous and brings tears
in eyes. NH3 is highly soluble in water due to extensive hydrogen bonding.
 NH 4 (aq)  OH  (aq)
NH3  H 2O 
Preparation :
1. In laboratory :
NH 4Cl  NaOH 
 NaCl  NH3  H 2O
ammonium
salt
NH3 produced is dried with quick lime CaO. Note that it cannot be dried with H2SO4, CaCl2 or
P4O10 as they react with the gas instead of drying it.
NH3  H2SO4 
 (NH 4 )2 SO4
 CaCl2 
 CaCl2 . 8NH3
 P4O10 
 (NH4 )3 PO4
2. Haber - Bosch Process :
Finely divided Fe + Mo

N 2  H 2   NH3  HΘ   46.1kJ / mol
high pressure (200 atm)
low temp. (500°C)

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3. NH3 is prepared by the Cynamide process :
4. Serpeck’s Process :
Al2O2  3C  N2 
 2AlN  3CO
AlN  3H 2O 
 Al(OH)3  NH3 
1. Ammonia is a non supporter of combustion but burns in oxygen with a pale yellow flame if continuous
heat is supplied.
4NH3  3O2 
 2N 2  3H 2O
Also, it undergoes catalytic oxidation.
Pt gauze
4NH3  5O2   4NO  6H 2O
800°C
2. Formation of complex ions used in qualitative analysis :
NH 4OH  AgCl 
 Ag(NH3 )2 Cl  H 2O
excess white colourless
 CuSO 4 
 Cu(OH)2   (NH 4 )2 SO 4 ; 4NH 3  CuSO4 
 [Cu(NH 3 )]4 SO 4
Blue Deep Blue
 ZnSO4 
 Zn(OH)2 
white
3. Reaction with Nessler’s Reagent is used as a test to detect ammonia :

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4. Reaction with chlorine :
NH3 (excess)  Cl2 

 NH 4Cl  N 2 . This is also used as a test to detect NH3.
white fumes
NH3  Cl2 (excess) 

 NCl3  HCl
[b] Ammonium Salt (NH4)x B :

All ammonium salts are very soluble in water. They are usually slightly acidic and decompose readily
on heating producing NH3, N2 or N2O.
 If the anion (Bx –) is not particularly oxidising (eg. Cl , CO32  or SO 24  ) then ammonia is
evolved.

NH 4Cl 
 NH3  HCl

(NH 4 )2 SO4 
 2NH3  N 2SO4
 If the anion is more oxidising (e.g. NO 2 , NO 3 , ClO 4 , Cr2O 72  ) then NH 4 is oxidised to

N2 or N2O.

NH 4 NO2 
 N2  2H 2O

NH 4 NO3 
 N 2 O  2H 2O

(NH 4 )2 Cr2O7 
 N 2  4H 2O  Cr2O3
Orange Green
[c] Oxides of Nitrogen :

1. Nitrous oxide N2O [Laughing gas] :
It is colourless, non-combustible gas with a sweatish odour and taste. It is a neutral oxide, and is
dimagnetic.
Preparation :
1. It is prepared by careful thermal decomposition of molten ammonium nitrate at about 280°C

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2. 10 HNO3  4Zn 
 4Zn(NO3 )2  N 2O  5H 2O
dil.
HSO3 NH 2  HNO3 
 N 2 O  H 2SO 4  H 2O
sulphamic acid conc.
3. 2 NO  SO 2  H 2O 
 H 2SO 4  N 2O
moist
900°C
(i) 2N2O 
 2N 2  O 2
(ii) Reduction of N2O to N2 :
N 2O  Cu 
 CuO  N 2
hot
 Mg 
 MgO  N2
 C 
 CO 2  N 2
 P4 
 P4O10  N 2
(iii) Oxidation : 5N2O  2KMnO4  3H2SO4 

 K 2SO4  MnSO4  3H 2O  10NO
Uses : It is used an on anaesthetic by dentists and a propellant for whipped ice - cream.
2. Nitric oxide NO/N2O2 :

It is a colourless, neutral gas which is paramagnetic due to the presence of odd electrons. It is sparingly
soluble in water.
Preparation :
1. NO is prepared in the laboratory by the reduction of dilute HNO3 with Cu.
8HNO3  3Cu 
 2NO  3Cu(NO3 )2  4H 2O.
2. Commercial Method :
electric
N 2  O2  2NO (in Birkeland and Eyde Process)
arc
Pt gauze
Or NH3  5O2 
 4NO  6H 2O (Catalytic Oxidation of ammonia)

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(i) It is sparingly soluble in water and its solid state forms diamagnetic dimer O = N – N – O.
(ii)  NO2 (brown fumes) Thus it is not possible to detect its smell.
NO  O2 
[This reaction is also used to detect O2]
900C
(iii) Action of heat : NO   N 2  O2
(iv) Reduction (to N2) : NO  S 

 SO2  N 2
1
 Cu 
 CuO  N 2
2
(v) Oxidising / Reducing properties
10NO  6KMnO4  9H 2SO4 

 3K 2SO4  6MnSO4  4H 2O  10HNO3
2NO  Cl2 
 2NOCl
NO  2HNO3 
 3NO2  H2O
(vi) NO is used in Ostwad’s Process (to make HNO3) and Lead Chamber Process (to make H2SO4)
Note : No is colourless gas is readily soluble in cold FeSO 4 solution forming dard-brown colourtion due to formation
of complex [Fe(H 2O)5 NO]SO 4 .
3. Dinitrogen Trioxide N2O3 :

It exists only in solid state at low temperature which is pale blue in colour. N2O3 is an acidic anhydride
of nitrous acid (HNO2). It is diamagnetic.
Preparation :
1. It can be made by condensing equimolar amounts of NO and NO2 together at 253 K.
NO  NO2 
 N 2 O3
2. 2Cu  6HNO3 
 2Cu(NO3 ) 2  NO 2  NO  3H 2O
(5N)

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3. As 2O3  2HNO3  2H 2O 
 NO  NO 2  2H 3AsO 4
(50%)

(i) N 2O3 (s) 
 NO 2  NO

(liquid)
(ii) It being the anhydride of nitrous acid forms nitrites with alkalies.
(NO  NO2 )  2KOH 

 2KNO2  H 2O
nitrites
(iii) It forms brown coloured FeSO4.NO with FeSO4. This is used as a test for nitrates called Brown Ring
Test.
IV. Nitrogen Dioxide NO2 :

It is a reddish brown gas and exists at the room temperature. Being an odd electron molecule it is paramagnetic
and dimerises into N2O4 at low temperature. It is acidic.
10C 20C 140C 620C

N 2O 4 
 N 2O 4 
 N 2 O4 
 2NO 2 
 2NO  O 2
solid solid vapour Dark Colour
colourless yellow Reddish Brown less
Brown
Structure :
Preparation :
1. In the laboratory it is prepared by heating dried lead nitrate :
2. It is produced on a large scale by oxidizing NO in the Ostwald’s Process for the manufacture of nitric
acid.
2NO  O2 
 2NO2

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(i) NO2  H 2O 
 HNO2  HNO3
Thus NO2 is called as mixed anhydride of nitrous acid and nitric acid. The reaction of NO2 with
aqueous alkalies is similar to that of a mixture of HNO2 and HNO3.
NO2  2NaOH 
 NaNO2  NaNO3  H2O
(ii) Oxidation :
10NO2  3H2SO4  2KMnO4  H 2O 

 K 2SO4  2MnSO4  10 HNO3
NO 2  H 2SO 4 
 HNO3  NO2 .SO2 (OH)
nitrosulphuric acid
(iii) Reduction :
NO 2  SO 2  H 2O 
 H 2SO 4  NO
(here NO2 behaves likeHNO3 )
NO2  H2S 
 N 2O  NO  S
V. Dititrogen Pentoxide N2O5 :

It is a colourless crystalline solid which sublimes readily and is acidic.
The solid form consists of (NO2+ + NO3–) which is ionic and called as nitronium while in solution it is
covalent.
Preparation :
P O
2 5  N O  H O (Dehydration)
1. 2HNO3 
1000 temp. 2 5 2 . Thus N2O5 is the anhydride nitric acid.
60  90C
2. AgNO3  Cl2   AgCl  N 2O5  O 2
3. 4NO2  O2 
 2N 2O5

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(i) It dissolves in water with a hissing sound.
N 2O5  H 2O 
 2HNO3
Thus it is called as nitric anhydride and neutralisation reactions similar to HNO3 :
N 2O5  NaOH 
 NaNO3  H2O

(ii) Since N 2O5  NO2  NO  O2 it is a very powerful oxidising agent. It destroys all organic
substances.
5N2O5  I2 
 10NO2  I2O5
[d] Oxoacids of Nitrogen :

Nitrous acid HNO2 :
Nitrous acid is unstable except in dilute aqueous solution. It is considered to be a tautomeric mixture of two
forms :
Preparation :
1. It is easily made by acidifying a solution of a nitrite
Ba(NO2 )2  H 2SO 4 
 2HNO2  BaSO4 
filteredoff
2. Dissolving nitrous anhydride(N2O3) in water of course forms nitrous acid :
N 2O3  H 2O 
 2HNO2
Oxidising Properties :
NO 2 ion is a weak oxidising agent and gets reduced to NO which forms a red complex with haemoglobin
and improves the look of meat.
NO 2  Fe2   2H  
 Fe3 NO  H 2O
2NO2  2I  4H  
 I2  2NO  2H 2O

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However it is oxidised by KMnO4, Cl2 forming NO3 (but to NO2 by H2SO4) :
HNO2  Cl2  H 2O 
 HNO3  2HCl
5NO2  2MnO4  3bH  

 2Mn 2   5NO3  3H 2O
2HNO2  H 2SO4 
 SO2  2NO2  2H2O
Reactions with Amines :

HNO 2  NH3 
 [NH 4 NO 2 ] 
 N 2  2H 2O
ammonia unstable
HNO2  EtNH 2 
 EtOH  N 2  H 2O
1° amine
Secondary and tertiary aliphatic amines form nitrosamines with nitrites :
HNO 2  Et 2 NH 
 Et 2  N  O  H 2O
2° amine

HNO2  Et 3 N 
 [Et 3 NH][NO 2 ] 
 Et 2  N  N  O  EtOH
3° amine
Nitrites are used to make diazo compounds used in azo dyes :


 Ph  N  N Cl  2H 2O
PhNH 2  HNO 2 
aniline
Other Reactions :
On standing HNO2 decomposes into NO and NO2 :
2HNO 2 
 NO  NO2  H 2O
While on boiling it disproportionates :
III V II

3 HNO 2 
 HNO3  2 NO   H 2O
Nitric acid HNO3 :

Also called as Aqua fortis, it is colourless fuming liquid with a pungent smell. Yellow colour occurs on
standing due to decomposition into NO2.

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Preparation :
1. In laboratory :
distilling in
2NaNO3  H 2SO4  Na 2SO 4  2HNO3 
glass retort
nitrates conc.
HNO3 vapours are then condensed in a water cooled receiver.
2. Birkeland and Eyde Process :
3. Ostwald Process :
Pt gauze
Step (a) : 4NH3 (g)  5O2   4NO  6H 2O (Catalytic Oxidation)
300C
2O 2H 2 O  O 2
Step (b) : 
2
4NO 
 4NO 2 
distillation
4HNO3  4HNO3
50C
(60%) (68%)
azeotrope
Due to the formation of azeotrope, HNO3 cannot be further concentrated by distillation and other methods
are used like dehydrating using sulphuric acid vapours.
dehydration with
HNO3   HNO3 (conc.)
H SO 2 4
68% 98%
Oxidising Properties :
V
N O3 is a very powerful oxidising agent in acidic solution. Cu, Ag which are insoluble in HCl dissolve in
HNO3. Concentrated HNO3 froms NO2 with a reducing agent although. Fe, CO, Al, Ni, Cr and B are
rendered passive by concentrated HNO3 due to the formation of a protective oxide layer (like Fe3O4 with
iron).
Dilute HNO3 forms NO with a poor reducing agent (Cu, Hg) ; N2O with a good reducing agent in hot
3 5
conditions and N H 4 N O3 with a good reducing agent in cold conditions.

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Some reactions with non-metals are :
HNO3  N 2 
 no reaction
dil. or conc.

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 Only Mg and Mn react with 2% dil. HNO3.

 Mg(NO3)2 + H2
HNO3 (dil.2 %) + Mg (or Mn) 
 Solution of 75% HCl and 25% HNO3 is called Aqua Regia which contains NO+ Cl– ions. Aqua Regia
is capable of dissolving Gold and Platinum by forming soluble HAuCl4 and H2PtCl6 respectively.
Other Oxoacids :
HOONO Pernitrous acid
H2NO2 Hydronitrous acid
HNO4 Pernitric acid
H2N2O2 Hyponitrous acid
Remember that N2O is NOT an anhydride of Hyponitrous acid (H2N2O2)
Phosphorous and its Compounds :

Allotropy :
It exists in many allotropic forms, the important ones being white, red and black phosphorous
300C 
White P 
inert atmosphere
 Re d P 
 Black P
for several days thermodynamically
most stable allotrope

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Only white phosphorous reacts with caustic alkalies to undergoe a disproportion reaction.
P4  3NaOH  3H 2O 
 3NaH 2 PO4  PH3 
sodium hypophosphite Phosphine
Uses :
Red phosphorus is used in Match - Industry and white phosphorus as a rat poison.
Preparation :
Phosphorous is obtained by the reduction of calcium phosphate with C in an electric furance. Sand (SiO2)
is added to remove the calcium as a fluid slag.
Ca 3 (PO4 )  SiO 2 
 CaSiO3  P4O10
slag
P4O10  C 
 P4  CO 

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Other oxides like P4O8 and P4O9 are intermediate between

P4O6 and P4O10 and form a mixture of phosphoric acid P(+V)
and phosphorous acid P(+III) on hydrolysis.

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Oxo Acids of Phosphorous

All oxo acids of phosphosphorous can be categorized into two main acid series namely, phsphorous acid
series and phosphoric acid series.
The Phosphorous acid series :
They contain P(+III) and are generally reducing agents due to the presence of P – H bonds which are
reducing (as they break down easily to loose H+).
[I] Orthophosphorous acid H3PO3 :
H3PO3 is a dibasic acid formed by hydrolysis of P4O6 .
P4O6  6H 2O 
 4H3PO3
1. H3PO3 forms phosphites on hydrolysis which are very strong

reducing agents in basic solutions.
 H   H 2 PO3
H3PO3  Ka1 = 1.6 × 10–2
 H   HPO32 
H 2 PO3  Ka2 = 7 × 10–7
2. On heating orthophosphorous acid disproportionates :

3 5 3

4H3 P O3 
 3H3 P O4  P H3
3. It is a moderotely strong reducing agent and reduces Ag+ to Ag, Au3+ to Au, Cu2+ to Cu and
itself gets oxidised to H3PO4 :
2AgNO3  H3PO3  H 2O 
 2Ag   3HNO3  H3PO4
[II] Hypophosphorous Acid H3PO2 :

It is prepared by alkaline hydrolysis of (white) phosphorous.
P4  3OH   3H 2O 
 PH3   3H 2PO2
Hypophosphite Ion

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It is a monobasic acid and a very strong reducing agent.
4Ag   H3PO2  2H2O 

 4Ag  H3PO4  4H 
[III] Pyrophosphorous Acid H4P2O5 :
While reaction with PCl5 is :
H3PO3  3PCl5 
 PCl3  3POCl3  3HCl
Trichloride Oxychloride
The Phosphoric Acid Series :

They usually cortain P(+V) and have oxidising properties. The simplest phosphoric acid is orthophosphoric
acid.
[I] Orthosphoric acid H3PO4 :
Preparation :
1. It is formed by hydrolysis of phosphorous pentaoxide (P2O5 or P4O10). The scheme for its
hydrolysis is :

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2. In laboratory
2 I
P4  20 HNO3  4H3PO 4  20NO 2  4H 2O
Catalyst
conc.
3. Impure H3PO4 is prepared in large amounts by ‘Wet Process’.
Ca 3 (PO4 )2  3H 2SO 4 
 2H3PO4  3CaSO 4
Phosphate Rock
CaSO4 is hydrated to gypsum CaSO4.2 H2O and filtered off. H3PO4 thus produced is used to
make fertilizers.
Properties :
1. H3PO4 is hydrogen bonded in aqueous solution and thus the ‘concentrated acid’ is syrupy and
viscous.
2. It forms meta phosphates on heating:
220 320C
H3PO 4 
 H 4P2O7 
8r
  HPO3 n
pyrophosphoric 2
metaphosphoric
acid acid
(Na PO3)n or sodium metaphosphate is called Graham’s salt or Calgon (Commercial name). It is
soluble in water and precipitates Pb2+ , Ag+ but not Ca2+, Mg2+. Thus it is used for softening water.
3. It forms 3 series of salts :
 H   H 2 PO 4
(a) H3PO 4  Ka1 = 7.5 × 10–3
Dihydrogen phosphates are slightly acidic in water.
 H   HPO 42 
(b) H 2 PO 4  Ka2 = 6.2 × 10–8
Monohydrogen phosphates are slightly basic in water.
 H   PO34
(c) HPO24   Ka3 = 1 × 10–12
Normal phosphates are appreciably basic in water.

4 Phosphates are estimated quantitatively by adding a solution containing NH4OH solution of the
phosphate and Mg2+. Magnesium ammonium phosphate precipitated is ignited and weighed as
Mg2P2O7.

2NH4  2Mg 2   2PO34 
 2MgNH4PO4 
 Mg2P2O7  2NH3  H2O

JEEMAIN.GURU
[II] Hypophosphoric acid H4P2O6 :

It contains P(+ IV) and is prepared by hydrolysis and oxidation of red phosphorous by NaOCl.
On hydrolysis it forms both H3PO3 and H3PO4
Phosphine [PH3]
It is a colourless, extremely toxic gas which smells of garlic or rotten fish. It is highly reactive and not very
soluble in water. It’s aqueous solutions are neutral.
The H – P – H bond angle is 93.5° which suggests the presence of almost pure p orbitals.
Preparation :
It can be formed by hydrolysing metal phosphides or hydrolysing white phosphorous in basic media.
Ca 3P2  6H2O 
 2PH3   3Ca(OH)2
 PH3   3NaH2 PO2 (disproportionation)

P4  3NaOH  3H 2O 
The second method also produces small amounts of highly inflammable P2H4 . Thus PH3 is removed in the
following manner:
 KOH
PH3  HI 
 PH 4 I  KI  H 2O  PH3 
Phosphonium (Pure)
Iodide

JEEMAIN.GURU
Properties :
1. PH3 is stable in air but catches fire at 150°C.
150C
PH3  2O2  H3PO4
2. It explodes in contact with traces of oxidising agents like HNO3, Cl2 and Br2.
2PH3  16HNO3 
 P2O5  16NO2  11H2O
3. Solution of PH3 in water decomposes in presence of light giving red phosphorous and H2.
4. Formation of metallic phosphides :
3CuSO 4  2PH3 
 Cu 3P2   3H 2SO4
Black
3AgNO3  PH3 
 Ag3P   3HNO3
Black
5. Phosphine is weakly basic and forms phosphonium salts with anhydrous acids while NH3 readily forms
NH4X in aqueous solutions of the acids.
PH3  HX 
 PH4 X (X = Cl, Br, I)
Uses :
It is used for making ‘Holme’s signals’. Containers containing CaC2 and Ca3P2 are pierced and thrown in
sea when gases evolved, burn and serve as a signal.
Halides :
1. PCl3 is a colourless oily liquid and is widely used in organic chemistry while PCl5 is a yellowish white
powder.

P4  6Cl2 
 4PCl3
White Dry
P4  8SOCl2 
 4PCl3  4SO2
Thionyl
Chloride
P4  10Cl2 
 4PCl5
White Dry, excess
P4  10SO 2Cl2 
 4PCl5  10SO 2
Sulphuryl
Chloride

JEEMAIN.GURU
PCl3  Cl2 (or S2Cl2 ) 

 PCl5
2. PCl3 fumes in moisture.
PCl 3  3H2O 
 H3PO3   3HCl 
While, PCl5  H 2O 
 POCl3  2HCl
Moist Air
 H3PO4  3HCl .
POCl3  3H 2O 
3. In liquid and gaseous state PCl5 is trigonal bipyramidal. While in solid state it is ionic and hence
conducts electricity
 [PCl4 ]  [PCl6 ]

2PCl5 
Tetrahedral Octahedral
4. PF5 forms an unusual trigonal bipyramid where axial and equatorial bonds interchange their positions
in short time. This is called pseudo rotation.
Fertilizers :
Fertilizers are compounds of nitrogen, phosphorus and potassium which are soluble in water and easily
assimilated by plants without being injurious to them.
I. Nitrogenous Fertilizers :
(i) Ammonium sulphate (NH4)2SO4 :
It is made by passing NH3 and CO2 gases into a slurry of CaSO4 in water :
4 CaCO  (NH ) SO  CaSO
2NH3  CO2  H 2O 
 (NH 4 )2 CO3  3 4 2 4
In soil, the action is :

soil nitrifying
(NH 4 ) 2 SO 4  NH3   Nitrates (easily taken up by plants)
bacteria
Excess of this fertilizer makes the soil acidic.
(ii) Calcium Ammonium Nitrate (CAN) :

Ostwalds 3  Ca(NO ) CaCO
NH3   HNO3  3 2
Pr ocess
NH3  HNO3 
 NH 4 NO3
NH4NO3 alone is explosive and is mixed with calcium nitrate to form Ca(NO3)2.NH4NO3
known as Calcium Ammonium Nitrate (CAN). It is more soluble in water and does not make
soil acid.

JEEMAIN.GURU
(iii) Nitrolim Ca NCN

Preparation :
It is a slow fertilizer and produces more permanant effect.
(iv) Urea (NH 2CO NH2) :

It has high nitrogen content (46%) and is very soluble in water. Thus it is quick acting but is easily
washed away.
180  200
2NH3  CO 2   NH 2COONH 4 
 NH 4CONH 2  H 2O
high pressure
Ammonium Urea
Carbamate
In soil, urea slowly hydrolyses to ammonium carbonate :
NH 4CONH 4  2H2O 
 (NH 4 )2 CO3
II. Phosphatic Fertilizers :

Phosphate rocks like fluorapetite [3Ca3(PO4)2.CaF2] are very insoluble and of no use to plants. Thus they
are processed to form useful fertilizers.
Note : Superphosphate consists of the insoluble waste CaSO4 which is of no use to plants being in soluble while
triple phosphate doesnot contain it.

JEEMAIN.GURU
III. Potash Fertilizers KNO3, KCl and K2SO4 are some examples.
IV. NPK Fertilizers They contain N, P and K in suitable proportions. Example is 4 – 8 – 2 mixed
fertilizers which contain 4% N2, 8% P2O5 and 2% K2O.
IN-CHAPTER EXERCISE - A
1. Give balanced equations involved :
(a) effect of heat on
(i) NaNO3 (ii) NH4NO3 (iii) Mixture of NH4Cl and NaNO2
(b) effect of water on
(i) Li3N (ii) AlN (iii) NCl3
(iv) NO2 (v) PCl3 (vi) PCl5
(c) preparation of
(i) nitric oxide from nitric acid (ii) NH3 commercially
(iii) HNO3 commercially
2. Give reasons for the following :
(i) NF3 is not hydrolysed but NCl3 is readily hydrolysed.
(ii) Ammonia has a higher boiling point than phosphine.
(iii) Concentrated nitric acid turns yellow in sunlight.
(iv) (CH3)3N is pyramidal in shape while (SiH3)3 N is planar.
(v) PF5 is known but NF5 is not
(vi) NH3 gas is dried by CaO and not by P2O5 and H2SO4.
(vii) H3PO3 is a dibasic acid
3. Identify the unknown compounds A, B, C, . . . in the following reactions :
(a) P + conc. HNO3 
 A+B
(b) PCl5 + SO2 
 A+B
PCl5 + P4O10 
B
A is a colourless fuming liquid which on reaction with P4 gives SO2(g) and C.
Pt O
2 B (brown fumes ) 
2 C  D H O
(c) NH 3  O2  A( g ) 
(oxo acids)
–
C + I   E (violet vapours)

(d) Colourless salt (A) + NaOH 
 B (g) + C (alkaline solution)
B + HCl 
 white fumes.

JEEMAIN.GURU
 D  g   E l 
A 
  
both triatomic
NaOH , Δ
2  A  H O Al , Δ Δ
(e) 
 C   E ( g ) 
 A or B E is used as an anaesthetic.
 O2  O2  H 2O P4 O10
(f) A  P4 
 P4O10  B  C   D (brown fumes )   F  G
electric arc
cool
C  D  E (blue)
A, B, C, D, E, F are all compounds of nitrogen while A, B, C and D are gases.
4. Give structural formula for the following :
(a) H3PO3 (b) H3PO2 (c) H4P2O5 (d) H3PO4
(e) H4P2O6 (f) H4P2O7 (g) P4 O10
5. (a) Reaction of phosphoric acid with Ca3(PO4)2 yields a fertilizer “triple phosphate”. Represent the
same through balanced chemical equation.
(b) Give reason(s) why elemental nitrogen exists as a diatomic molecules while elemental phosphorus
is a tetratomic molecule.
NOW ATTEMPT IN-CHAPTER EXERCISE-A REMAINING QUESTIONS IN THIS EBOOK

JEEMAIN.GURU
CHALCOGENS Section - 2
Group 16
Ionization Enthalpy
The first ionization enthalpies of the elements of group 16 are unexpectedly lower than those of correspond-
ing elements of group 15 despite their smaller atomic radii and higher nuclear charge.
Normally as the atomic radii decreases or nuclear charge increases along a period, the ionization enthalpy is
expected to increase. But the ionization enthalpy of these elements is smaller than those of group 15 ele-
ments. This is due to the relatively symmetrical and stable electronic configuration of the elements of group
15 as compared to the elements of group 16 (oxygen family). e.g.
Group 15 element
N(Z = 7)1s2 2s2 2 p1x 2 p1y 2 p1z (more symmetrical, stable)

Group 16 element
O(Z = 18)1s2 2s 2 2 p 2x 2 p1y 2 p1z (less symmetrical, less stable)
Therefore, first ionization enthalpy values of elements of oxygen family are smaller.
Metallic Character
Because of high ionization enthalpy values, the elements of group 16 are less metallic. However, as we
move down the group, the ionization enthalpy decreases and hence the metallic character increases.
Electronegativity
The elements of group 16 have higher values of electronegativity than the corresponding elements of group
15. Oxygen is the second most electronegative element, the first being fluorine.
Bonding
Oxygen can form strong p  p double bonds. The double bonds formed by other elements becomes
weaker as the atomic number increases. Thus CO 2 is stable, CS2 is less stable, CSe 2 polymerises and
CTe2 is unknown.
S, Se, Te, Po can even form 4 or 6 bonds unlike oxygen due to the presence of d-orbitals. S forms strong
d  p bond with O due to its small sized d-orbital which is similar to the p-orbital of O in size.
Hydrogen bonding is important for oxygen compounds.
Hydrides
H 2O , H 2S, H 2Se, H 2Te, H 2 Po
   
liquid colourless toxic gases with foulsmell.

JEEMAIN.GURU
As we go down the group, f H of hydrides becomes more positive and bonding orbitals diffuse on becoming
larger. This decreases stability and thus increases acidity down the goup.
H 2S, H 2Se, H 2Te use almost pure p-orbitals for bonding as is indicated by their H-E-H bond angles
which are close to 90. The boiling points usually increase as the atoms become larger and heavier but
boiling point of H 2O is abnormally high due to extensive hydrogen bonding in solid and liquid state. Thus
the order is :
H 2O >> H 2Te > H 2S > H 2S.
Halides
Elements of this group form dihalides, tetrahalides and hexahalides. Among hexahalids only hexafluoride
are stable.
SF4 is a powerful fluorinating agent.
SCl2 is a foul smelling red liquid. It forms poisonous ‘mustard gas’ which is NOT a gas but a volatile
liquid.
2CH 2 = CH 2 + SCl2 
 S(CH 2CH 2Cl)2
ethene Bis(2-Chloroethyl)sulphide
(Mustard gas)
Oxygen and its Compounds

Preparation :
O2 is a colourless, odourless and tasteless gas which is partially soluble in water. Liquid dioxygen is pale
blue in colour and the solid is also blue. It is paramagnetic due to presence of unpaired electrons.
1. It is prepared industrially by the electrolysis of acidic or alkaline H 2O or by Claud’s Process
(fractional distillation of liquid air)
2. In laboratory it is prepared from thermal decomposition of
MnO
2  2 KCl+ 3O + traces of Cl , ClO
2 KClO3  2 2 2
heat

Pb(NO3 )2   PbO + NO 2 + O2
3. It can also be made by catalytic decomposition of hypochlorites :
Co2
2 HOCl  HCl + O2 
catalyst

CaOCl2  CaCl2 + O2 
bleaching powder

JEEMAIN.GURU
Uses :
Most of the O2 is used in the steel making industry. Some of it is used in oxy-acetylene welding and as an
oxidant in rockets. It is an essential constituent of life.
[a] Oxides and their general properties
Dioxygen reacts with practically all elements to form oxides. The reactions are usually exothermic and
once started often continue spontaneously.
 If an element exists in several oxidation states then generally lower ones are basic and higher ones are
acidic
N 2O, NO , N 2O3 , NO 2 , N 2O5
    
neutral acidic
CrO
 , Cr2O , CrO
 3 3
basic amphoteric acidic

JEEMAIN.GURU
PbO
 , PbO 2
more basic less basic
 The order of acidic strength of oxides can be obtained as follows :
The further apart two oxides are in the series, the more stable the compound formed when they react
together.
Example : CaO + H 2O + SO3 
 more stable CaSO4 (CaO.SO3 )
[b] Ozone O3
O3 is an unstable, dark blue diamagnetic toxic gas. The colour is due to intense absorption of red light, It
also absorbs strongly in the UV region.
2
For each O atom, of the three sp orbitals two are occupied by two lone pairs and one forms   bond.
The remaining 4 electrons form   bonds. The  system is thus 4e 3 centre bond.
Preparation :
O3 is prepared by the action of a silent electric discharge upon dioxygen in an ozoniser..
Bond order = 1.5 for O – O bonds.
Preparation :
O3 is prepared by the action of a silent electric discharge upon dioxygen in an ozoniser..
Silent electric discharge is used because sparking can generate heat and decompose O3 .

JEEMAIN.GURU
1. O3 turns starch iodide paper blue.
2. The amounts of O3 in a gas mixture is determined by passing gas into KI solution buffered with a
borate buffer (pH 9.2)
Iodine liberated is titrated with sodium thiosulphate.
O3 + 2 K + + 2 I  + H 2O   I 2 + KOH + O 2
Alternatively, it is decomposed catalytically and the change in volume measured.
2 O3 
 3O 2
2 volumes 3 volumes
3. Hg in the presence of ozone is oxidized to sub-oxide and starts sticking to glass and loses its meniscus.
This is used as a test for ozone called ‘Tailing of Mecury’
4. O3 is an extremely powerful oxidising agent, second only to F2 .
3PbS + 4O3 
 3PbSO4
2 NO 2 + O3 
 N 2O5 + O 2
2 KOH + 5O3 
 2 KO3 + 5O2 + H 2
Potassium
ozonide
(Orange solid)
5. O3 reduces peroxides
O3 + BaO 2 
 BaO + 2 O2
O3 + H 2O 2 
 H 2O + 2 O2
Uses :
It is used as a disinfectant for water. Its advantage over chlorine is that it avoids unpleasant smell and
taste of chlorine, since any excess O3 decomposes to O2 .
[C] Hydrogen Peroxide H 2O2 :

Pure H 2O2 is a colourless liquid (like water), more hydrogen bonded than water (and thus has highest
boiling point)
Preparation :
1. At one time H 2O2 was obtained by electrolysis of H 2SO4 or (NH 4 )2 SO4 using high current density..
electrolysis
2SO24   S2O82  + 2 e

JEEMAIN.GURU
H 2S2O8 + 2 H 2O 
 2 H 2SO 4 + H 2 O2
Peroxodisulphuric
acid
2. Now, it is produced industrially by a cyclic process.
H 2O2 is extracted with water as 1% solution which is concentrated to 30% solution.

3. In laboratory :
cool
Na 2O 2 + H 2SO 4 
 Na 2SO 4 + H 2O 2 
 Na 2SO4 . 10 H 2O 2 crystals
(dil, cold)
OR BaO2 + CO2 + H2O 

 BaCO3  + H2O2 (Merck's Process)
1. H 2O2 decomposes in presence of impurities like Fe2+ , Fe3+ , Ni 2+ , Pt . to undergoes a
disproportionation reaction :
2 H 2O 2   2 H 2O + O 2
Glycerol or acetanilide is added to check its decomposition.
2. In most of its reactions H 2O2 acts as a strong oxidising agent (slow in acidic medium while fast in
alkaline).
H 2O 2 + 2 Fe2+ 
 2 Fe3+ + 2 H 2O
H 2O 2 + 2[Fe(CN)6 ]4  
 2[Fe(CN) 6 ]3 + 2 OH 
Ferrocyanide Ferricyanide
H2O2 + SO32  
 SO 42  + H 2O

JEEMAIN.GURU
 4 H O + Cr O 2  + 2 H + 
 2 CrO5 + 5 H 2O
 2 2 2 7
Chromium peroxide
 (blue)

 4 CrO5 +12 H +   4 Cr 3+ + 6 H 2O+ 7 O2 

3. H 2O 2 is forced to act as a reducing agent with stronger oxidising agents and O2 is evolved.
5H 2O2 + 2 MnO4 + 6 H + 
 2 Mn 2+ + 8H 2O + 5O 2 
H 2O 2 + KIO 4 
 KIO3 + H 2O + O 2 
H 2O2 is useful to counteract chlorine:
H2O2 + Cl2 
 2 HCl + O2
4. H 2O2 is a mild bleaching agent for hair feathers due to the oxidation reaction :
H 2O 2 
 H 2O [O]
5. Qualitative Analysis : It is detected qualitatively by its action on KI.
H O starch
2 2  I  blue
KI  2
It also forms blue CrO5 with Cr2 O 72  / H + and decolourises KMnO 4 .
Structure :
It is proposed H 2O2 is a tautomeric mixture of two forms :
It shows restricted rotation about O O bond due to repulsion between

two H’s. The structure is same in liquid and gaseous forms but angles
and bond lengths change due to hydrogen bonding.

JEEMAIN.GURU
Sulphur and its Compounds

Allotropy :
Sulphur has the maximum number of allotropic structures. The two common crystalline forms are :
(i)   Rhombic Sulphur :
It is a yellow solid stable at room temperature, m.p. 11.8C and specific gravity 2.06 g/cc.
(ii)   Monoclinic Sulphur :
It is a colourless solid stable above 95.5C , mp 120C and specific gravity 1.98g/cc.
heat
Note :   sulphure    Sulphur..
cool
At 95.5C (transition temperature both forms are stable).

Both  and  forms contain puckered S8 rings in crown
conformation.
Other allotropic forms are :
(iii) Engels Sulphur (  sulphur) :
It is unstable and has S6 rings in chair conformation.
Toluene
Na 2S2O3 + conc.HCl  S
(iv) Plastic Sulphur (  - sulphur) :
It is elastic, dark coloured and obtained liquid sulphure into water. It can be moulded with fingers.
(v) Colloidal Sulphur :
It is prepared by passing H 2S gas into an oxidising solution like HNO3 , FeCl3 ....
2 HNO3 + H 2S 
 S  2 NO 2  H 2O
Note :  ,  ,  - sulphur are soluble in CS2 and insoluble in water while  - sulphur is insoluble in both CS2 and
water.
Extraction :
Sulphur is obtained from natural gas plants (which contain ) and from metal sulphide ores (especially iron
pyrites ) which produce SO 2 .
2 H2S + O 2 
 2SO 2 + 2 H 2O
SO2 + 2 H 2S 
 2 H 2O + 3S

JEEMAIN.GURU
Uses :
Almost 90% of S produced is used to manufacture H 2SO 4 . The rest is used in vulcanizing of rubber,,
making fungicides, gunpowder etc.
[a] Hydrogen sulphide H 2S (Sulphuretted Hydrogen)

It is a colourless, poisonous gas, soluble in H 2O and smells of rotten eggs.
Preparation :
It is easier to make H 2S by the action of mineral acids on metal sulphides.
FeS + H2SO4 
 FeSO4 + H 2S 
Sb 2S3 + 6 HCl 
 2SbCl3 + 3H 2S 
pure
1. It burns with blue flame.
2 H 2S + O2 
 2 H 2O + 2SO2
excess
A saturated solution of H 2S is slowly oxidized by air and Sulphur is deposited.
2 H 2S + O2 (limited) 
 2 H 2O + 2S
2. It is a very weak dibasic acid.
H2S + NaOH 
 NaHS + H2O ; NaHS + NaOH 
 Na 2S + H 2O
The two salts NaHS, Na 2S are basic and soluble in water..
3. H 2S + NH3   (NH 4 ) HS (not ( NH 4 )2 S )

dil solution
Yellow ammonium sulphide is a mixture of ammonium polysulphide and is made by dissolving
sulphur in colourless (NH 4 ) HS/ NH3 solution. This solution is used to precipitate metal sulphides
in qualitative analysis.
4. H 2S is a reducing agent and reduces Cl2 to Cl , H 2SO4 to SO 2 , FeCl3 to FeCl2 and itself gets
oxidized to S.
H 2S + Cl2 
 2 HCl + S
H 2S + H 2SO 4 
 SO 2 + 2 H 2O + S
H 2S + 2 FeCl3 
 2 FeCl2 + 2 HCl + S

JEEMAIN.GURU
[b] Sulphur Dioxide SO 2

It is a colourless poisonous gas with a choking smell. It is highly soluble in water and almost completely
present as SO 2  6 H 2O in water and only 1% as H 2SO3 . Liquid SO 2 has also been used as a non-
aqueous solvent.
Preparation :
1. It is prepared by burning S or H 2S in air..
S + O 2 
 SO 2
2 H 2S + 3O2 
 2SO2 + 2 H 2O
excess
2. It is also prepared by roasting various metal sulphides in smelters.
2 ZnS + O 2 
 2 ZnO + 2SO2
4 FeS2 +11O 2 
 2 Fe2O3 +8SO 2
1. Most of SO 2 is oxidized to SO3 by the contact process and used to manufacture H 2SO 4 .
 r H   196.6 kJ/ mol

2 5 V O
2SO2 + O2  2SO3
2. Bleaching action :
SO 2 + H 2O 
 H 2SO 4 +[H]
Bleaching by SO 2 is temporary as reduced colour is reoxidised by air to give black coloured matter..
Also, H 2SO 4 produced during bleaching may be harmful to fibres.
2  XOH HCl H O
X  OH+ SO2 
 XHSO3 
 XCl 
coloured colourless  HCl coloured
Cl2 although has a permanent effect as it produces [O].

3. It shows reducing properties in presence of moisture.
SO 2 + Cl2 + 2 H 2O 
 H 2SO4 + 2 HCl
5SO 2 + 2 KIO3 + 4 H 2O   K 2SO4 + 4 H 2SO 4 + I2

Although with stronger reducing agents it acts as an oxidising agent.
2 H 2S + SO 2 
 2 H 2O + 3S 
3Fe + SO2 
 2 FeO + FeS

JEEMAIN.GURU
Detection of SO 2 :
It may be detected in three ways in the laboratory :
1. By its choking smell
2. It turns filter paper moistened with K 2Cr2O7 / H + green.
K 2Cr2O7 + 3SO2 + H 2SO4 

 Cr2 (SO 4 )3 + K 2SO4 + H 2O
orange green
3. It turns starch iodate paper blue.
2 KIO3 + 5SO 2 + H 2O 
 I 2 + 2 KHSO 4 + 3 H 2SO4
turns starch
blue
Quantitative Analysis :
SO 2 is determined quantitatively by first converting to H 2SO 4 and then determining H 2SO 4 by titration
or conductimetric titration.
SO 2 + H 2O2 
 H 2SO4
Structure :
3d orbital of S cannot be used to form  bond as its symmetry is
z2
wrong. Instead 3d xz orbital on S is used to make the second  bond
with 2 p z orbital on the second O atom. Although, it is surprising that
both  bonds have the same energy..
[C] Sulphur Trioxide SO3

It is the anhydride of H 2SO 4 and is solid at room temperature. It has three forms :
2
In gaseous state, SO3 has a planar triangular structure involving sp hybrid sulphur atom. The lone pair
of Sulphur atom forms coordinate bond ( ). Therefore, bond angle is exactly 120. Solid SO3 possesses
either cyclic trimer (  form) or infinite helical chains (   form).

JEEMAIN.GURU
Note : Of the three forms :   SO3 is most stable.

 25C dry
  SO3 
   SO3 
   SO3
Preparation :
1. It is manufactured on a huge scale by the Contact Process. Practically all of it is converted to H 2SO 4 in
the same process :
2 5 Pt/V O
2SO2 + O2  2SO3
2. 
Fe2 (SO4 )3 
 Fe2O3 + 3SO3
1. 1000°C
2SO3 
 2SO 2 + O2
2. SO3 + H 2O 
 H 2SO 4
vapour dense mist
It is used to prepare oleum (mainly pyrosulphuric acid H 2S2O7 )
SO3 (g) + H 2SO 4 

 H 2S2O7
98% oleum/fuming sulphuric acid
3. SO3 is used to make sulphamic acid NH 2SO3H (the only strong acid that can exist as a solid at
room temperature).
NH 2CONH 2 + SO3 + H 2SO4 

 2 NH 2SO3H + CO 2
Urea Sulpharic acid
[d] Oxo Acids of Sulphur :

Oxo - acid of Sulphur ending in – ous have S in the oxidation state (+IV) and form salts ending in –ite.
Acid ending in –ic have S in the oxidation state (+VI) and form salts ending in –ate. Four main series
exist which are :
I Sulphurous Acid Series :
The most important acid in this series is sulphurous acid (H 2SO3 ) :

JEEMAIN.GURU
Preparation :
It is only known in solution (like carbonic acid) and as discussed SO 2 solution in water gives 1%
H 2SO3 .
SO 2 + H 2O  H 2SO3
Chemical Properties of SO32  ion.

 
1. H 2SO3 being dibasic forms salt of bisulphites (HSO3 ) and sulphites (SO3 ).HSO3 however
undergoes internal dehydration to form S2O52  ion.

heat
2 HSO3  S2O52   H 2O
disulphite
 
2. S( + IV) in SO3 and HSO3 is a moderately strong reducing agent and forms sulphates on oxidation.
SO32  + H 2O 2 
 SO 42  + H 2O
H 2SO3 + H 2O + 2 FeCl3 
 H 2SO4 + 2 FeCl2 + 2 KCl
while with sulphur, sulphites form thiosulphates :
OH 
SO32  + S  S2O32 
thiousulphate
Sulphites and hydrogen sulphites liberates SO 2 on treatment with dilute acids
H + (dil)
SO32  (or HSO32  ) 
 SO2 
3. SO32  acts as an oxidising agent with a strong RA like H 2S.
SO32  + 2S2  + 6 H + 
 3S  +3H 2O
II Sulphuric Acid Series :

JEEMAIN.GURU
(i) Sulphuric acid [oil of Vitriol] H 2SO 4 :

H 2SO 4 is the most important acid used in the chemical industry. It is a colourless syrupy liquid with
boiling point 338C and freezes into crystals at 10.5C . It is strongly hydrogen bonded.
Preparation
1. In ancient days it was prepared from ferrous sulphate (Green vitriol) and hence called Oil of Vitriol.
heat
2(FeSO 4 .7 H 2O) 
 Fe2O3 + SO 2 + 13 H 2O + H 2SO4
green vitriol (oil of vitriol)
2. Lead Chamber Process
Was used to manufacture H 2SO 4 industrially but the process is now obsolete as it only produced
78% H 2SO 4 . NO 2 is used as a homogeneous catalyst to oxidise SO 2 in the presence of water..
NO produced combines with air to produce NO 2 which is reused. Thus, NO and NO 2 act as
oxygen carriers
3. Contact Process :
It is the most important and widely used commercial process for the manufacture of H 2SO4 .

JEEMAIN.GURU
(i) SO 2 is first collected from burning of Sulphur or sulphide ores.

(ii) SO 2 is then oxidized.
2SO2 (g) + O 2 (g)  2SO3 (g)
The forward reaction is exothermic and is favoured by low temperature, high pressure and
excess of oxygen. A catalyst (activated V2O5 ) is used to obtain a reasonable conversion.
Earlier Pt gauze was used but due to high costs and its susceptibility to poisoning it has been
replaced by V2O5 .
(iii) SO3 is then passed into 98% H 2SO 4 forming pyrosulphuric acid (H 2S2O7 ) called oleum.
Dilution of oleum with water gives concentrated H 2SO 4(98%).
1. H 2SO 4 due to its low volatility is used to manufacture more volatile acids.
2 MX + H 2SO 4 
 2 HX + H 2SO 4
(M=metal; X=F, Cl, NO3 )
2. H 2SO 4 is a powerful dehydrating agent especially for gases.
It dehydrates HNO3 forming NO 2 +
2 H 2SO 4 + HNO3 
 NO 2+ + H 3O + + 2 HSO 4
Nitronium ion
It removes elements of water from organic compounds.
2 EtOH + H2SO4 
 Et  O  Et + H 2SO 4 . H 2O
(COOH)2 + H 2SO 4 
 CO + CO 2 + H 2SO4 . H 2O
Note : H 2SO 4 mixes with water to evolve large amount of heat. If water is poured into concentrated acid, the heat
evolved causes violent splashing. Thus to dilute strong acids like H 2SO 4 , acid is poured into water while
stirring (not water into acid).
3. H 2SO 4 is a quite strong oxidising agent.
conc. H2SO4 + Br  
 SO2 + Br2 + H2O
2conc. H 2SO4 + Cu 
 CuSO4 + SO 2 + 2 H 2O
2conc. H 2SO4 + C 
 CO 2 + 2SO 2 + 2 H 2O

JEEMAIN.GURU
4. Pure H 2SO 4 is a non-aqueous solvent and a sulphonating agent.
C6 H 6 + HO . SO3H 
 C6 H 5SO 2 OH + H 2O
Benzene sulphonic acid
Uses :
1. The largest used is in making superphosphate fertilizer.
2. It is used in Pickling (removal of oxides from the surfaces of metals like Fe, Cu before electroplating
or galvanizing.
3. It is used as a dehydrating agent. O.A. and as strong acid.
(ii) Thiosulphuric acid H 2S2O3 :

The free acid is unstable and decomposes in water into a mixture of S, H 2S, SO 2 and H 2SO4 while
the salts (thiosulphates) are stable. It forms large colourless hexagonal crystals, highly soluble in water.
The most important thiosulphate is sodium thiosulphate (Na 2S2O3 . 5 H 2O) also called hypo.
Preparation :
boiling
SO32  +  S2O32 
S 
Neutral/alkaline
1. Hypo solutions are used for iodine titrations in volumetric analysis.
2 Na 2S2O3 + I2 
 Na 2S4O6 + 2 NaI
Sodium tetrathionate
In iodometric estimation O.A.’s like CuSO4 , K 2Cr2O7 are treated with KI which liberates
I2 which is determined by hypo as above.
2CuSO4 + 4 KI 
 2 K 2SO4 + Cu 2 I2 + I 2
2. Na 2S2O3 is used to destroy excess Cl2 on fabrics after they have been bleached and called as
antichlor.
Na 2S2O3 + 4 Cl2 + 5 H 2O 
 2 NaHSO 4 + 8 HCl
This is also used to remove the taste from heavily chlorinated drinking water.
3. Hypo is used in photography for ‘fixing’ films and prints. It dissolves unreacted
AgNO3 , AgBr salts.
 Na 2S2O3
Na 2S2O3 + AgBr 
 Ag 2S2O3    soluble complexes Na 3[Ag(S2O3 )2 ]

JEEMAIN.GURU
Note :
(iii) Thionic Acid Series :
(iv) Peroxo Acid Series

They contain the peroxo linkage  O O .

JEEMAIN.GURU
IN - CHAPTER EXERCISE - B
1. Write equations for :
(a) preparation of oxygen from (i) KClO3 (ii) Ozoe (iii) Pb( NO3 )2
(b) reaction of H 2O2 with (i) acidified solution of KMnO4 (ii) aqueous HI.
2. State reasons for the following statements

(a) Statues coated with white lead on long exposure to atmosphere turn black and the original
colour can be restored on treatment with H 2O2 .
(b) Presence of water is avoided in the preparation of H 2O2 from Na2O2 .
(c) Hydrogen peroxide acts as an oxidizing as well as a reducing agent.
(d) Ozone destroys mercury meniscus.
(e) A white turbidity is obtained by passing H 2 S in aqueous solution of SO2 .
(f) Conc. H 2 SO4 can’t be used for drying up H 2 S and NH 3.
(g) Liquid oxygen sticks to the poles of a magnet but liquid nitrogen does not.
(h) SF6  is known but OF6 is not.
3. Describe the differences in structure between gaseous and solid SO3.
4. Which of nitric acid and sulphuric acid is the stronger Bronsted acid, i.e., which donates proton to the
other?
5. How are the following gases detected ?
(a) O2 (b) O3 (c) H 2S (d) SO2
NOW ATTEMPT IN-CHAPTER EXERCISE-B REMAINING QUESTIONS IN THIS EBOOK

JEEMAIN.GURU
THE HALOGENS Section - 3
Group – 17
Ionisation Energy
The ionization energies of halogens are very high, next only to the noble gases in each group. On moving
down the group, the ionization enthalpies progressively decrease as the size of halogen increases from
F to I
Electronegativity
Due to small size and higher nuclear charge, each halogen has the highest electronegativity in their respec-
tive periods. F is the most electronegative element (electronegativity of 4.0).
The electronegativity decreases down the group.
Electron Affinity
Halogens have large negative electron gain enthalpies. Down the group, electron affinity decreases as the
size increases.
F < Cl > Br > I > At.
However, Cl is more electronegative than F due to extremely small size of F as a result of which strong
electron repulsions are present in the relatively compact 2p – orbitals of fluorine and thus its tendency to
accept an electron decreases.
Oxidation States
F shows O.S of only – 1 (being most electronegative) often halogens show oxidation states of
1,  5 and  7.
Bond Dissociation Enthalpy

All elements form diatomic molecules. The bond dissociation energy decreases down the group since the
atoms become larger which results in less effective overlap of orbitals.
F2 << Cl2 > Br2 > I2 .
However bond energy of F2 is abnormally low due its very high reactivity. The small size of F atoms
induces e  e repulsion between the lone pairs of electrons on the two fluorine atoms.

JEEMAIN.GURU
Note : I2 is tested by starch indicator which turns blue. The bluish colour produced disappears on titration with
S2 O32  . This colour reappears after 2 – 3 minutes due to atmospheric oxidation.
I2 + 2S2O32 
 2 I + S4O62 
1
2 I + O2 + 2 H + 
 I 2 + H 2O
2

JEEMAIN.GURU
Hydra – Acids
I Hydrofluoric acid [H 2F2 or HF]
1. HF is a colourless, corrosive liquid with pungent smell. It attacks glass and is thus stored in wax
bottles or gutta percha bottles.
 [SiF6 ]2  + 2 H+ + 2 H 2O
SiO2 + 6 HF  (This is also used for etching glass.)
HF is kept in laboratory in KF giving K + [F H  F] ions.

2. H 2 and F2 combine with each other very violently even in dark to form HF. Thus special methods
are employed in its preparation.
Industrially it is made by heating CaF2 with strong H 2SO 4 .The reaction is endothermic : hence the
need for heating. SiO 2 impurities are removed from CaF2 otherwise they consume much of HF
produced.
CaF2 + H 2SO4 
 CaSO4 + 2 HF
SiO 2 + 4 HF 
 SiF4 + 2 H 2O
SiF4 + 2 HF(aq) 
 H 2 [SiF6 ]
3. Two thirds of HF produced are used to make chlorofluoro charbons (Freons) used as refrigerating
fluids.
anhydrous conditions
CCl4 + 2 HF  CCl2 F2 + 2 HCl
SbCl5 freon
4. In liquid form HF is used as a non - aquous solvent.
2 HF()  [H 2 F]+ + F
II. Hydrochloric acid [HCl]

1. At one time HCl was made exclusively by ‘salt cake’ method.

NaCl + conc.H 2SO4  HCl(g) + NaHSO 4
Rock salt
NaHSO 4 + NaCl 
 HCl(g) + Na 2SO 4
2. Highly pure HCl is made by bringing H 2 and Cl2 in a special combustion chamber. (Direct combination
is explosive)
Cl2 + H 2 
 2 HCl

JEEMAIN.GURU
3. In laboratory :
2 NH 4Cl + H 2SO4 
 2 HCl + (NH 4 ) 2 SO 4
conc.
4. HCl cannot be dried over P2O5 or quick lime because it reacts with them :
CaO + HCl 
 CaCl2 + H 2O
P4O10 + 3HCl 
 POCl3 + 3HPO3
Hence it is dried by passing through conc. H 2SO 4
5. HCl(g) is colourless, weak reducing agent (is oxidized by strong oxidising agents like
MnO 2 , KMnO 4 , K 2Cr2O7 ) and highly soluble in water..
6. Aqua Regia :
It is a fuming mixture of HCl and HNO3 in the ratio 3 : 1. It can dissolve both gold and platimum
while no other acid has that capability.
Au + NO3 + 4Cl + 4 H + 
 AuCl4 + NO  + 2 H 2O
Pt + NO3 + 6Cl + 2 H + 
 PtCl62  + NO  + 2 H 2O
3Pt + 4 NO3 + 18Cl + 16 H + 

 3PtCl62  + 4 NO + 8H 2O
III HBr and HI

1. They are prepared by reaction of phosphoric acid on metal bromides or iodides (similar to salt cake
process)
NaI + H3PO 4 
 HI + NaH 2 PO4
NaBr + H3PO4   HBr + NaH 2 PO 4

2. The usual laboratory process is :
+6 H O
2  6 HBr + 2 H PO
2 P + 3Br2 
 2 PBr3  3 3
Red
+6 H O
2  6 HI + 2 H PO
2 P + 3I2 
 2 PI3  3 3
Red
3. HBr is not very stable and acts as a strong reducing agent while HI is least stable and thus a more
powerful reducing agent.
2 HNO3 + 2 HI 
 2 NO 2 + I2 + 2 H 2O
2 HNO3 + 2 HI 
 2 NO + I 2 + 2 H 2O
HIO3 + 5HI 
 3I2 + 3H 2O
H 2SO4 + 2 HI 
 SO 2 + I2 + 2 H 2O

JEEMAIN.GURU
Oxides
There is only a small difference in electronegativity between the halogens and oxygen and thus the bonds in
oxides are largely covalent. Most halogen oxides are unstable and tend to explode when subjected to shock.
Stability of oxides increases down the group and higher oxidation states are more stable than lower oxidation
states.
I Dichloro oxide [Cl2O]
Cl2O is a yellow – brown gas which condenses to an orange liquid (bp = 2°C). It is the anhydride of
hypochlorous acid (HClO).
1. It is prepared by passing dry chlorine over freshly precipitated mercuric oxide.
HgO + 2 Cl2 
 HgCl2 + Cl2O.
dry
2. It is solube in water Cl2O + H 2O  2 HOCl(aq)

Golden solution
3. It explodes in presence of NH3 or a reducing agent or on heating.
3Cl2O + 10 NH3 
 2 N 2 + 6 NH 4Cl + 3H 2O
4. It is a strong oxidising agent.
Cl2O + 2 HCl 
 2Cl2 + H 2O
II Chlorine Dioxide [ClO2 ]

It is a yellow gas, condenses to deep red liquid, explodes above 40° C and in
presence of reducing agents. It is paramagnetic being an odd electron molecule
but DOESNOT dimerises as the odd electron is delocalised.
1. It explodes when mixed with reducing agents. The safest laboratory preparation is form sodium
chlorate and oxalic acid as this automatically dilutes the gas with CO 2 .
2 NaClO3 + 2(COOH)2 
 2ClO 2 + 2CO2 + (COONa) 2 + 2 H 2O
2. ClO2 + H 2O 
 HClO3 + HClO 2 + heat

dark green solution
3. It is used to manufacture NaClO2 which is used for bleaching paper textile.
2ClO 2 + 2 NaOH + H 2O2 

 2 NaClO 2 + O 2 + 2 H 2O
2ClO2 + 2 NaOH 
 NaClO2 + NaClO3 + H 2O
Chlorite Chlorate
4. ClO2 is a powerful oxidising about and a bleaching agent and is used to purify water..

JEEMAIN.GURU
III Dichlorine Hexoxide [Cl2O6 ]

It is a dark red liquid which freeze at 180° C to a yellow solid. It is diamagnetic
in nature due to absence of unpaired electrons and exists as a dimer. The structure
is guessed to be as shown but the exact structure is unknown.
1. It is obtained from ClO2 and O3 .
ClO2 + O3 
 ClO3 + O2
2ClO3  Cl2O6
2. Hydrolysis with water or alkali gives chlorate and perchlorate
Cl2O6 + H 2O 
 HClO3 + HClO 4
Cl2O6 + 2 NaOH 
 NaClO3 + NaClO 4 + H 2O
Chlorate per chlorate
3. It is a strong oxidising agent which explodes on contact with grease.
4. Reaction with anhydrous HF is reversible :
Cl2O6 + HF  FClO 2 + HClO 4
IV Dichlorine Heptoxide [Cl2O7 ]

It is a colourless oily liquid which is moderately stable and less reactive than
others. It is the only exothermic oxide of Cl and the anhydride of perchloric
acid HClO 4 . It is anhydride of perchloric acid and made by dehydrating
perchloric acid with P2O5 or H3PO 4 .
PO
4 10  Cl O
2 HClO 4  2 7
Oxo Acids
Four series of oxo acids are known (HOX, HOX 2 , HOX3 and HOX4 ). The structure of the ions formed from
these oxoacids are :

JEEMAIN.GURU
 In general, for any series of oxoacids, the acid with most oxygen (i.e. highest oxidation state) is most
dissociated. This is because, the most oxygen atoms are bonded, the more the electrons will be pulled

away from the O H bond and thus weaking the bond. [Note that plainly ClO4 ion is larger than

OCl ion and so hydration energy of ClO4 is less than that of OCl . This suggests HOCl to be a
stronger acid but the reverse in true. The reason is the bond energies discussed above]
Thus the acidic character follows the trend :
HClO 4 > HClO3 >> HClO2 > HClO
Similarly,
H 2SO4 > H 2SO3 ; HNO3 > HNO2
 The thermal stability of the oxyhalide ion increase from  OCl to ClO4 .
ClO4 > ClO3 > ClO2 > ClO

This is due to the increase in the number of oxygen atoms.
 Among the hypohalous acids (HXO) stability order is :
HClO > HBrO > HIO >> HFO.
Oxoacids of F are exceptionally unstable because all the oxoacid ions except those of F are stabilised
by p  d  bonding between full 2p orbitals on O and empty d orbitals on the halogen atoms.

JEEMAIN.GURU
Bleaching Powder :
Bleaching powder is actually written as Ca(OCl)2 .Ca(OH)2 .CaCl2 .2 H2 O. It is a pale yellow powder having
a strong smell of chlorine and sobuble in water. However, a clear solution in never formed due to the presence of
impurities.
Preparation :
It is made by passing Cl2 into slaked lime.
3Ca(OH)2 + 2 Cl2 
 Ca(OCl) Cl + H 2O

JEEMAIN.GURU
1. Bleaching action
Coloured matter + [O] 

 Colourless product.
While,
2. Oxidising action
CaOCl2 + H 2S 
 CaCl2 + H 2O+ S
CaOCl2 + Pb(NO3 )2 + 2 NaOH 

 CaCl2 + PbO 2 + 2 NaNO3 + H 2O.
3. It converts acetone into chloroform.
Halogen Halides
I. Inter Halides
A + X 
 AX, AX 3 , AX5 , AX 7 (inter halides) where X is smaller than A.
halogen halogen
Interhalogen compounds are covalent and have physical properties intermediate of A and X. They are
more reactive than halogens (except F2 ) as A – X bond is weaker than X – X bond.
[Draw the structures of all four king of interhalides]
1. ICl(l) is conducting as it ionizes :
3 IC l  [I 2Cl]+ + [IC l 2 ]
Addition of AlCl3 in molten ICI greatly increases conductivity as it increases the ionisation by forming
[AlCl4 ] and [I2Cl]+ ions.
[I2Cl]+ [AlCl4 ]
AlCl3 + 2 ICl 
2. ICl3 exists as dimer I2Cl6 with two Cl bridges
[I2Cl6 ]  [ICl2 ]+ + [ICl4 ]

and is thus conductive.
Square planar

JEEMAIN.GURU
3. Hydrolysis of interhalides :
AX n + H 2O 
 HA + HXO n+1 (n = 1,3,5, 7)
2
II. Poly Halides

The most important polyhalide is I3 . It has very long, weak bonds with bond
order 0.5 and is linear in shape. I2 is only slightly in water. Its solubility is
greatly increased if some iodide ions are present. This is due to the formation
of the polyhalide
I2 + I   I3
III. Pseudo Halides

These are univalent ions with at least one N atom, that have properties similar to those of the halide ions.
   
Example are CN ,SCN , N 3 , OCN .

CN  resemble Cl closely in the following ways :
1. It forms an acid HCN and the dimer (CN)2 just like HCl and Cl2
2. It forms insoluble salts with Ag + , Pb 2+ , Hg 2+ and soluble salts with Na + .
OH _
3. (CN)2  CN  + OCN  .
H+
and 3 ICN  [I2CN]+ +[I(CN) 2 ]
(Replace CN  by Cl  and compare the above reactions with those of Cl  ).

JEEMAIN.GURU
IN - CHAPTER EXERCISE - C
1. Give reason for the following :

(a) HF exists as dimeric molecule i.e. H 2 F2 or HF has higher viscosity or high boiling point.
(b) When blue limus is dipped into a solution of hypochlorous acid, it first turns red and then later
gets decolourised.
(c) In preparation of HI from alkali iodide, H 3 PO4 is preferred in place of H 2 SO4 .
(d) Fluorine is better oxidant than chlorine.
(e) The brown colour of an acidified dilute solution of iodine in aqueous KI is intensified by the
addition of nitrite but it is discharged by the addition of a sulphite.
(f) It is not possible to obtain F2 by electrolysis of acqueous HF, aqueous NaF or anhydrous HF..
(g) A mixture of KF and HF is electrolyzed to increase the conductivity of anhydrous HF.
2. Write balanced equations for :

(a) reaction between HF and (i) CCl4 (ii) SiO2 (iii) KF
(b) reaction between Cl2 and (i) SO2 (ii) H 2 (iii) NaOH
3. Find A, B, C, . . . . in the following reactions :

(a) hot NaOH
MnO2  HCl 
 A( g ) 
BC;
OH 
B  C  D( g ). D is a yellow triatomic gas.

(b) excess CN 
HCN  CuSO4 
 A( g )  B  complex C
Br2 H 2O conc.H 2 SO4
(c) Red phosphorus   A   B( g )   Br2
(d) CH 3  CH  CH 2  ICI 

4. H 2 SO4 is a weaker acid than HCl, yet HCl is evolved when conc H 2 SO4 is added to NaCl. Explain.
5. HF can be prepared by the action of H 2 SO4 on NaF. Explain why HBr cannot be prepared by the
action of the same acid on NaBr.
NOW ATTEMPT IN-CHAPTER EXERCISE-C REMAINING QUESTIONS IN THIS EBOOK

JEEMAIN.GURU
NOBLE GASES Section - 4
Group 18
Physical Properties of Noble Gases
1. They are monoatomic, colourless, odourless, tasteless and sparingly soluble in water.
2. They have very low m.p. and b.p due to weak dispersion forces. Helium has the lowest known b.p.
(4K) and shows superfluidity.
3. All noble gases can diffuse through glass, rubber, plastic and some metals making them difficult to
handle in the laboratory.
Clathrate Compounds
In the clathrates atoms or molecules of the appropriate size trapped in cavities in the crystal lattice of other
compounds. These atoms donot form any bond. Clathrates provide a convenient means of storing radioac
-tive isotopes of Kr and Xe produced in nuclear reactors.
Chemistry of Xenon
Xe reacts directly only with F2 .Oxygen compounds can be obtained from the fluoride.
1. Xenon fluorides are white solide which are extremely powerful oxidising and fluorinating agents. They
sublime readily at room temperature and are hydrolyzed even by traces of water. Thus they are stored
in Ni or Monel containers.

JEEMAIN.GURU
XeO3 is a hygroscopic white explosive solid. XeOF4 is a colourless volatile liquid.

OH 
 Na + [HXeO4 ]
XeO3 + NaOH   Na 4 XeO6 + Xe + O2 + H2O
Sod.xenate Disproportionate Sod.perxenate
2. All xenon fluorides react with hydrogen and oxidise Cl  to Cl2 . I  to I 2 and Ce(III) to Ce(IV)
3. Xenon fluorides reacts with fluoride ion acceptors to form cationic species and fluoride ion donors
to form fluoro anions.
[XeF]+ [PF6 ]
XeF2 + PF5 
[XeF3 ]+ + [SbF6 ]
XeF4 + SbF5 
 M + [XeF7 ]
XeF4 + MF 
(M = Na, K, Rb, Cs)
4. Xe compounds show a variety of shapes :
XeF2 is linear, XeF4 is square planar,, XeF6 is a capped octahedron, XeO3 is pyramidal, XeOF4 is
square pyramidal, XeO 2 F2 is see saw shaped, XeOF2 is bent T – shaped, XeO 4 is tetrahedral,
XeO3F2 is trigonal bipyramidal and [XeO6 ]4  ion is octahedral. [Draw geometries of all these
compounds].
IN - CHAPTER EXERCISE - D
1. Why xenon does not form fluorides XeF , XeF3 or XeF5 ?
NOW ATTEMPT IN-CHAPTER EXERCISE-D REMAINING QUESTIONS IN THIS EBOOK

JEEMAIN.GURU
SOLUBILITY OF SALTS Section - 5
[A] In Aqueous Solvent :

A solvent may be polar (having high dielectric constant such as water or mineral acids) or non-polar (having
low dielectric constant such as benzene and tetrachloromethane). Ionic compounds are usually soluble in
polar solvents while covalent compounds usually dissolve in covalent solvents. This rule may be stated as
‘like dissolves like’.
For a substance to dissolve in an aqueous solvent (water) the energy evolved when the ions are hydrated
(hydration energy) must be larger than the energy required to break the crystal lattice (lattice enthalpy). Thus
solubility in principle depends upon two major factors.
(i) Lattice Enthalpy : The lattice enthalpy is inversely proportional to the distance between the cation
and the anion (i.e. r+ + r–). Thus the lattice enthalpy decreases as we go down the group due to the
increase in size of cation if the anion being considered is came.
(ii) Hydration Enthalpy : Hydration enthalpy usually varies as the inverse of radius of cation (r+). This
is because as the size of cation increases, the polarising power of cation decreases and thus the
tendency to attract water molecules decreases. (also known as Dehydrating Capacity). This decrease
in dehydrating capacity decreases the hydration energy that is released when a molecule is hydrated.
The General Solubility Rules in Water are as follows :

1. All nitrates (NO3–) and chlorates (ClO3– ) are soluble. All sulphates (SO42–) are soluble except
those of [Sr2+, Ba2+ and Pb2+] which are sparingly soluble and hence are used in qualitative analysis.
2. All the carbonates (CO32–), suphites (SO32–), phosphates (PO43–) and dichromates (Cr2O72–) are
insoluble except of Group I, Na+, K+ and NH4+ . Practically almost all salts of Group I, Na+, K+ and
NH4+ are soluble in water.
3. All simple salts of Group I metals dissolve in water producing ions. The solubility of most salts
(NO3–, CO32–, HCO3–) decreases down the group. This is because the decrease in hydration
energy of metal ions is much more than the decrease in the lattice energy given.
Exception : The solubility of alkali metal fluorides, hydroxides and carbonates increases rapidly
down the group. The reason is L.E. is proportional to 1/(r+ + r–) and thus the lattice energy will
vary most when r– is small (as in fluorides) and least when r+ is longer(with I–). Thus the change in
lattice enthalpy exceeds the change in hydration enthalpy in this case.
4. The solubility of most salts of Group II also decreases down the group.
For example, BeSO4 > MgSO4 >> CaSO4 > SrSO4 > BaSO4. (As has been stated, all sulphates
except these of Ca, Sr, Ba, Pb, Ag are very soluble).
Exception : The fluorides and hydroxide of Group II metals show an increase in solubility down the
group. The reason in same as that for Group I salts.
5. All hydroxides are insoluble except those of alkali metals (Group I) leaving LiOH. Those of Ca2+,
Sr2+ and Ba2+ are moderately soluble.

JEEMAIN.GURU
6. All sulphides (S2–) are insoluble except those of alkali metals, alkali earth metals and the ammonium
(NH4+) ion.
7. All chlorides, bromides and iodides are soluble except those of Ag+, Hg22+ and Pb2+ which are used
in qualitative analysis.
8. It has been noticed that compounds with large difference in radii of ions are generally soluble while the
least soluble salts are those of ions with similar radii. Thus :
L iOH < NaOH < K OH < RbOH < CsOH
L iF < NaF < K F < RbF < CsF
[Here the difference in size between the cation and anion increases down the group].
while, L iBr > NaBr > K Br > RbBr > CsBr.
BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4
[Here the difference in size between the cation and anion decreases down the group].
[B] In Non-aqueous Solvents :

Important non-aqueous solvents include liquid hydrofluoric acid(HF), liquid NO2 and liquid ammonia
(NH3).
Liquid ammonia is the most studied non aqueous solvent and it resembles the aqueous system quite
closely.
 NH 4  NH 2
2NH3 () 
Thus substances producing NH4+ are acids (like NH4Cl) in liquid ammonia and those producing NH2– are
bases (like NaNH2)
Similarly,
 NO  NO  NO3
N 2O4 
(liquid)
Thus in N2O4 substances containing NO+ are acid (like NOCl) and those containing NO3– are bases (like
NH4N3).
For HF we have :
 [H 2 F]  F
2HF 
Like in water, acid-base neutralisation and precipitation reactions also occur in liquid ammonia. Liquid
ammonia is an extremely good solvent for the alkali metals and the heavier Group II metals Ca, Sr and Ba.
The metals are very soluble and solutions in liquid ammonia have a conductivity comparable to that of pure
metals. Thus solutions are very good reducing agents because of the presence of free electrons.
Liquid ammonia
Na   [Na(NH3 )n ]  e

JEEMAIN.GURU
NOW ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK
SOLUTIONS TO IN-CHAPTER EXERCISE - A

1. (a) (i) 2NaNO3  (ii) 
 2NaNO2  O2 NH4 NO3 
 N2O  2H2O

(iii) NH4Cl  NaNO2   N2  2H 2O  NaCl
(b) (i) Li3 N  H2O 
 Li (ii) AlN  3H 2O 
 Al(OH)3  NH3 
(iii) NCl3  4H 2 O 
 NH 4OH  3HOCl (iv) 2NO2  H2O 
 HNO3  HNO2
(c) (i) 8HNO3  3Cu   2NO  3Cu(NO3 )2  4H 2O
(Laboratory preparation)
(ii) Serpeck’s process :
Al2O3  3C  N 2 
 2AlN  CO
AlN  3H2O   Al(OH)3  NH3 

(iii) Using Ostwalds Process :
Pt 2O
2H 2O  O 2
(a) 4NH3 (g)  5O 2  2
 4NO  6H 2O (b) 4NO  4NO2   4HNO3
50C
(60%)
2. (i) NF3 is more stable than NCl3 due to higher bond dissociation enthalpy. Thus it is not readily hydrolysed.
(ii) NH3 has higher b.p. than PH3 molecules due to hydrogen bonding present among NH3 molecules. This
makes it difficult to evaporate solid NH3 than solid PH3.
light
(iii) conc. HNO3   NO2  O2  H2O
The brown colour of NO2 produced makes it look yellow in solution.
(iv) (CH3)3N is pyramidal while (SiH3)3N is planar because in (SiH3)3N[trisilyamine] there sp2 orbitals are used
for  - bonding. The lp of e– occupy a p orbital at right angles to the plane triangle. This overlaps with empty
d orbitals on each of the three silicon atoms resulting in p – d bonding. This is impossible in (CH3)3N
because C does not passes d orbitals.
(v) NF5 cannot exist because there are no d-orbitals to accomodate the 5 electrons coming from five fluorine
atoms. This however can occur in PF5.
(vi) NH3 cannot be dried with H2SO4 for else they will nautralise each other. Similarly P2O5 will react with CaO.
(vii) H3PO3 has the structure :
OH
|
OPH
|
OH
Which shows that it is dibasic due to only 2 OH groups.
Self Study Course for IITJEE with Online Support Solutions INE 59
JEEMAIN.GURU
3. (a) P4  conc. HNO3 

 H3PO4  NO2
(b) PCl5  SO 2 
 POCl3  SOCl2
(A)
6PCl5  P4O10 
 10POCl3
(B)
SOCl2  P4 
 SO 2  PCl3
(A) (C)
Pt
(c) NH3  O2  H2O O2
 NO(g) 
 NO 2   HNO 2  HNO3
(A) (B) (C) (D)
HNO 2  I 
 I2
(C) (E)

(d) NH 4 NO3  NaOH   NH3 (g)  NaNO3
(A) (B) (C)
NH3  HCl 
 NH 4Cl (white fumes)

 N 2O(g)  H 2O()
NH 4 NO3 
(D) (E)
(f) N 2O  P4  O2 O2 H 2O P4O10
 P4O10  N 2   NO   NO2   HNO3   H3PO 4
electric arc (C)
(A) (B) (D) (F) (G)
cool
NO  NO 2 
 N 2O3 (blue)
(C) (D) (E)
4. (a) (b) (c)
(d) (e) (f)
60 Solutions INE Self Study Course for IITJEE with Online Support
JEEMAIN.GURU
(g)
5. (a) 3Ca 3 (PO 4 ).CaF2  14H 3PO 4 

 10Ca(HPO4 )2  2HF
triple phasphate
(b) This is because N2 can form much stabler triple bond than an unstable tetrahedral structure.
SOLUTIONS TO IN-CHAPTER EXERCISE - B
1. (a) (i) Heat KClO3 in the presence of manganese dioxide.

MnO
2  2KCl  3O
2KClO3  2
(ii) Passing carbon dioxide through oxone releases O2.
1
Na 2O 2  CO2 
 Na 2CO3  O2
2

(iii) Pb(NO3 )2   PbO  NO2  O2
(b) (i) 5H2O2  2MnO4  6H  

 2Mn 2   8H2O  5O2
(ii) H2O2  2I   2H    2H 2O  I2
2. (a) White lead on exposure to atmosphere oxidises to block plumbous oxide. This can be removed by a treatment
with hydrogen peroxide.
 2PbO (black) ;
2Pb  O2  PbO  H 2O 2 
 PbO2  H 2O
(soluble)
(b) Na2O2 gives H2O2 with dilute acids.

Na 2O2  H 2SO4   Na 2SO4  H 2O2
However if water is used (or present), the NaOH formed being basic catalyses decomposition of H2O2 :
JEEMAIN.GURU
(c) In most reactions H2O2 acts as a strong oxidising agent (like with Fe2+, SO32–, Cr2O72–) but however with
sronger oxidising agents it is forced to act as a reducing agent (like with MnO4–, IO4–).
(d) Hg in the presence of ozone is oxidied to suboxide and starts sticking to glass and loses its meniscus.
(e) Passing H2S in aqueous solution of SO2 precipitates sulphur which produces turbidity in the solution.
2H 2 S  SO 2 
 2H 2 O  3S 
(f) NH3 cannot be dried with H2SO4 as they nutralise each other. NH3  H 2SO 4   (NH 4 )SO 4 . Ammonia is
thus best dried with quick lime (CaO).
(g) Liquid oxygen is paramagnetic due to presence of unpaired electrons which liquid nitrogen being diamagnetic
doesnot stick to a magnet.
(h) OF6 cannot exist because their are no d orbital in an oxygen atom to accomodate incoming electrons from
fluorine atoms.
3. Gaseous SO3 has a planar triangular strucure with sp2 hybridised s atom while solid SO3 exists in a cyclic
trimer form (or hetical chains)
4. H2SO4  HNO3   HSO4  H 2 NO3
Thus H2SO4 is the stronger Bronsted acid.
5. (a) O2 burns with a blue flame which serves as a test for it. (b) O3 turns starch iodide paper blue.
(c) H2S can be detected by its small of rotten eggs.
(d) SO2 can be detected by its choking small. It also turns filter paper moistened with K2Cr2O7/H+ green.
JEEMAIN.GURU
IN - CHAPTER EXERCISE - C
1. (a) There is hydrogen bonding among HF molecules which increases its viscosity and boiling point. Its existence
as a dimer is also due to very strong hydrogen bond between two HF molecules (which is due to the larger
electronegativity difference).
(b) HOCl is an acid [H+ + OCl–] which turns blue litmus red. HOCl is also an oxidising agen [HCl + O] and thus
bleaches the colour of litmus solution. Thus this involves acidic as well as bleaching action of HOCl.
(c) NaI  H2SO4 
 NaHSO4  HI
HI thus formed being a strong reducing agent reduces H2SO4 to SO2.
2HI  H2SO4  H 2SO4 
 SO2  I2  2H2O
H3PO4 is not reduced by HI.
(d) F2 is better O.A. than Cl2 because it has a very low value of bond dissociation energy (though its electron
affinity is lower than Cl–)
 NO
2  I  I  KI
(e) I  2 3 will lead to intensification of colour while,
SO 2
3  2I  will not.
I2 
(f) Water must be excluded otherwise F2 produced will oxidize it to dioxygen and itself will get reduced to F–.
While anhydrous HF is only slightly ionized and therefore a poor conductor of electricity.
(g) A mixture of KF and HF is used to increase conductivity and lower the m.p.. The mixture exists in the ionic
form K+[F – H – F]–
2. (a) (i) 2HF  CCl4 

 CC2 F2  2HCl (ii) 4HF  SiO2 
 SiF4  2H2O
(freon)
 K  [F  H  F]
(iii) HF  KF 
(b) (i) Cl2  SO2 

 SO2Cl2 (ii) Cl2  H 2 
 2HCl
(iii) Cl2  2NaOH 

 NaOCl  NaCl  H2O
hot NaOH
3. (a) MnO 2  HCl 
 Cl2 (g)   NaClO3  NaCl
(A) (B) (C)
OH 
NaClO3  NaCl  O 2
 (C)
(B) (D)
(b) HCN  CuSO 4 

 Cu 2 (CN)2  (CN)2 (g)
(B) (A)
excess CN 
Cu 2 (CN)2  [(Cu(CN) 4 ]3
(C)
JEEMAIN.GURU
3Br
2  2PBr 
2  6H O
(c) 2P(red)  3  6HBr(g)  2H3PO3
(A) (B)
conc. H SO
2 4  Br
HBr  2
(d) CH 3  CH  CH 2  ICl 
 CH 3  C H  C H 2
| |
Cl I
 I   Cl )
(Iodination occurs : ICl 
4. NaCl  H 2SO4 
 NaHSO4  HCl(g)
(Weaker acid) (Stronger acid)
This occurs because HCl gas escapes taking equilibrium tothe right.
5. H2SO4 oxidises HBr formed to Br2 while this is not the case with HF.
SOLUTIONS TO IN-CHAPTER EXERCISE - D
1. By unpairing of one paired orbital,two singly occupied orbitals come into existence. Thus either two or four or
six singly occupied orbitals can be formed instead of one or three or five singly occupied orbitals.
JEEMAIN.GURU
Vidyamandir Classes
My Chapter Notes
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Vidyamandir Classes
Illustration - 1

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Vidyamandir Classes

JEEMAIN.GURU
Vidyamandir Classes

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JEEMAIN.

Vidyamandir Classes p-Block Elements - II

Oxides with higher oxidation state are more acidic :

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p-Block Elements - II Vidyamandir Classes

Moreover, acidity decreases down the group :

N 2O3  P4O6  As 4O6  Sb 4O6  Bi 2O3

Halides : NX3 are unstable except NF3.

Nitrogen and its Compounds :

3. Heating ammonium salts with more oxidizing anion (Cr2O 72  , NO 2 , NO 3 , ClO 4 )

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Vidyamandir Classes p-Block Elements - II

(ii) It is used to prepare ammonia by ‘Habers Process’.

(iii) Reaction with metals :

[a] Ammonia NH3

2. Haber - Bosch Process :

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p-Block Elements - II Vidyamandir Classes

3. NH3 is prepared by the Cynamide process :

3. Reaction with Nessler’s Reagent is used as a test to detect ammonia :

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Vidyamandir Classes p-Block Elements - II

4. Reaction with chlorine :

NH3 (excess)  Cl2 

NH3  Cl2 (excess) 

[b] Ammonium Salt (NH4)x B :

 If the anion is more oxidising (e.g. NO 2 , NO 3 , ClO 4 , Cr2O 72  ) then NH 4 is oxidised to

[c] Oxides of Nitrogen :

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p-Block Elements - II Vidyamandir Classes

(ii) Reduction of N2O to N2 :

(iii) Oxidation : 5N2O  2KMnO4  3H2SO4 

2. Nitric oxide NO/N2O2 :

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Vidyamandir Classes p-Block Elements - II

(iv) Reduction (to N2) : NO  S 

10NO  6KMnO4  9H 2SO4 

3. Dinitrogen Trioxide N2O3 :

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p-Block Elements - II Vidyamandir Classes

(NO  NO2 )  2KOH 

IV. Nitrogen Dioxide NO2 :

10C 20C 140C 620C

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Vidyamandir Classes p-Block Elements - II

10NO2  3H2SO4  2KMnO4  H 2O 

V. Dititrogen Pentoxide N2O5 :

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p-Block Elements - II Vidyamandir Classes

[d] Oxoacids of Nitrogen :

2. Dissolving nitrous anhydride(N2O3) in water of course forms nitrous acid :

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Vidyamandir Classes p-Block Elements - II

However it is oxidised by KMnO4, Cl2 forming NO3 (but to NO2 by H2SO4) :

5NO2  2MnO4  3bH  

Reactions with Amines :

Secondary and tertiary aliphatic amines form nitrosamines with nitrites :

Nitrites are used to make diazo compounds used in azo dyes :

Nitric acid HNO3 :