INORGANIC CHEMISTRY

P-BLOCK ELEMENTS
JEE (ADVANCED) SYLLABUS 2019

Isolation/preparation and properties of the following non-metals

Boron, silicon, nitrogen, phosphorus, oxygen, sulphur and halogens; )
AI
Properties of allotropes of carbon (only diamond and graphite), phosphorus and sulphur.
IL
BH

Preparation and properties of the following compounds

I(

13th Group : Boron: diborane, boric acid and borax; Aluminium: alumina, aluminium chloride and alums;
TH

14th Group : Carbon: oxides and oxyacid (carbonic acid); Silicon: silicones, silicates and silicon carbide;
A
IP
TR

15th Group : Nitrogen: oxides, oxyacids and ammonia; Phosphorus: oxides, oxyacids (phosphorus acid, phosphoric acid)
and phosphine;
H
D

16th group : Oxygen: ozone and hydrogen peroxide; Sulphur: hydrogen sulphide, oxides, sulphurous acid, sulphuric acid
D

and sodium thiosulphate;

U
IR

17th Group: Halogens: hydrohalic acids, oxides and oxyacids of chlorine, bleaching powder;
AN

18th Group: Xenon fluorides.

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 GROUP-III

Isolation of "B":
(i) Preparation of B2O3 from Borax or Colemanite
Na2B4O7 + HCl/H2SO4  NaX + H2B4O7
H2B4O7 + 5H2O  4H3BO3   B2O3 + H2O
(ii) Reduction of B2O3
B2O3 + Na/K/Mg/Al  B + Na2O/K2O/MgO/Al2O3

Chemical Props.:
(i) Burning in air : 4 B + 3O2  2B2O3
4Al + 3O2  2Al2O3
(ii) Reaction with water
B + H2O (Cold & hot)  no reaction
2B + 3H2O  B2O3 + H2

)
(red hot)

AI
IL
3
Al + 3H2O  Al(OH)3 + H

BH
2 2
(iii) B + HCl  no reaction I(
B + H2SO4 (dil) no reaction
H
2B + 3H2SO4 (conc.)  2H3BO3 + 3SO2
AT

B + 3HNO3  H3BO3 + 3NO2

IP

2Al + 6H2SO4  Al2(SO4)3 + 3SO2 + 6H2O

TR

Al + HNO3  Al2O3 (passive layer) and does not react further.

2B + 2NaOH + 2H2O  2NaBO2 + 3H2
H

(iv)
D

2Al + 2NaOH + 2H2O  2NaAlO2 + 3H2

D

(v) 2B + N2  2BN 2Al + N2  2AlN

U

4B + C  B4C 4Al + 3C  Al4C3

IR

3Mg + 2B  Mg3B2
AN

(vi)

Preparation of B2H6 :
(i) Mg3B2 + HCl  B2H6 + B4H10 + B5H9 etc.
(10%)

(ii) B4H10  B H + H + higher borane
2 6 2
100C

BCl3 (or B Br3) + 6H2      B2H6 + 6HCl

Electric
(iii)
discharge at low pressure
(iv) 3LiAlH4 + 4BF3  3LiF + 3AlF3 + 2B2H6
or LiBH4 or 3(BF3)

Reaction of B2H6 :

(i) B2H6 + O2  burns

 in B2O3 + H2O
air spontaneo usly

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 (ii) B2H6 + H2O (Cold is enough)  H3BO3 + 6H2
(iii) B2H6 + 2KOH  2KOBH2 + 2H2
B2H6 + HCl (dry)  B2H5Cl + H2
anh .
(iv)
AlCl3

* Heating of boric acid :

C C 
H3BO3 100
  HBO2 140
  H2B4O7  B2 O 3
red hot
Metaboric acid Pyroboric acid Glassy mass

* H3BO3 + H2O2(H2O)+ (HO)2B–O–O–H NaOH

 Na2 · 6H2O

Sodium peroxy borate used in washing powder

as whitener

)
AI
Preparation of Borax :

IL
2CaO · 3B2O3 + 2Na2CO3  2CaCO3 +Na2B4O7 + 2NaBO2

BH
Colemanite I(
H
AT

NaBO2 +  Na2B4O7·10H2O   Na 2 B4 O 7  NaBO 2

IP

  
Concentrated


 

TR

in Filtrate as residue and allowed to

crystallise out in solution
and filtered
H

[4NaBO2 + CO2  Na2B4O7 + Na2CO3]

D
D
U

Na2B4O7 ·10H2O 
IR

as 2nd Crop. of the

AN

reaction.

Uses of borax:(i) In making glass, enamel and glaze of pottery.

(ii) As antiseptic in medicinal soaps preparation.

Al2O3 preparation :

C
(i) 2Al(OH)3 1100
   Al2O3 + 3H2O

(ii) Al2(SO4)3  Al2O3 + 3SO3

(iii) (NH4)2SO4· Al2(SO4)3 ·24H2O  Al2O3 + 2NH3 + 4SO3 + 25H2O

Uses: (i) In making refractory brick

(ii) as abrasive
(iii) To make high alumina cement

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 AlCl3 preparation:

(i) 2Al + 6HCl (vap.)  2AlCl3 + 3H2

(over heated) dry

(ii) Al2O3 + 3C + 3Cl2  2AlCl (vap.) + 3CO
3
1000C

Solid anh. AlCl3

Props:
(i) It is deliquescent and fumes in air.
(ii) It sublimes at 180°C.
(iii) It is covalent and exists in the form of dimer even if in non polar solvents e.g.
alc., ether, benzene, where it is soluble in fair extent.

Uses: (i) Friedel-Craft reaction

)
AI
(ii) Dyeing, drug. & perfumes etc.

IL
BH
Alumns: M2SO4, M '2 (SO4)3 ·24 H2O Props: Swelling characteristics
I(
where M = Na+, K+, Rb+, Cs+, As+, Tl+, NH 4
H
AT

M' = Al+3, Cr+3, Fe+3, Mn+3, Co+3

IP

K2SO4·Al2(SO4)3·24H2O Potash alum

TR

(NH4)2SO4·Al2(SO4)3·24H2O Ammonium alum

K2SO4·Cr2(SO4)3 ·24H2O Chrome alum
H

(NH4)2SO4·Fe2(SO4)3·24H2O Ferric alum

D
D

Preparation: Al2O3 + 3H2SO4  Al2(SO4)3 + 3H2O

U
IR

Al2(SO4)3 + K2SO4 + aq. soln  crystallise

AN

Uses: (i) Act as coagnlant

(ii) Purification of water
(iii) Tanning of leather
(iv) Mordant in dying
(v) Antiseptic
GROUP -IV
Types of Carbide
(i) Ionic and salt like:
Classification on basis of (a) C1 unit
no. of carbon atoms  (b) C2 unit

present in hydrocarbon  (c) C3 unit
found on their hydrolysis

C1 unit: Al4C3, Be2C

Be2C + H2O — Be(OH)2 + CH4
Al4C3 + 12H2O — 4Al(OH)3 + 3CH4

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 C2 unit: CaC2, BaC2
CaC2 + 12H2O — Ca(OH)2 + CH  CH

C3 unit: Mg2C3
Mg2C3 + H2O — 2Mg(OH)2 + CH3–C  CH : Propyne
(ii) Covalent carbide : SiC & B4C
(iii) Interstitial carbide : MC (Transition element or inner transitional elements forms this kind of carbide)

Interstitial carbide formation doesn't affect the metalic lusture and electrical conductivity.( no chemical
bond is present, no change in property)

SiC

Preparation

SiO2 + 2C(coke)   Si + 2CO

2000 to

)
AI
2500C

IL
Si + C   SiC
2000 to

BH
diamond like structure colourless to yellow solid in room temp.
2500C
I( 
H
when impurity is present
AT

Properties
IP

(i) It is very hard and is used in cutting tools and abrassive powder(polishing material)
TR

(ii) It is very much inert

(iii) It is not being affected by any acid except H3PO4
H

(iv) It reacts with NaOH in presence of air

D

SiC + 2NaOH + O2  Na2SiO3 + CO2 + H2O

D
U
IR

CO
AN

— How to detect
— How to estimate
— What are its absorbers

(i) How to detect

(a) burns with blue flame
(b) CO is passed through PdCl2 solution giving rise to black ppt.
CO + PdCl2 + H2O  CO2 + Pd + 2HCl
Black metallic
deposition
(ii) How to estimate
I2O5 + 5CO  I2 + 5CO2
I2 + S2O 32  2I– + S4O 62
(iii) What are its absorbers
(a) Cu2Cl2 : CuCl + CO + 2H2O — [CuCl(CO)(H2O)2]

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 Uses:
In the Mond's process of Ni - extraction
CO is the purifying agent for Ni
50C C
Impure Ni + CO  Ni(CO)4 150
  Ni + 4CO

recycled
Producer gas: CO + N2 + H2
Water gas: CO + H2
Water gas is having higher calorific value than producer gas.  in water gas, both CO & H2 burns while
in producer gas N2 doesn't burn.

Teflon —(CF2  CF2—

)n

 CF2HCl  CF2=CF2     —(CF2  CF2—

heated Polymerisation at
CHCl3 + HF   
heated with
)n
SbFCl4 again high temp. and press
catalyst  HCl

)
AI
Purpose

IL
Temp. withstanding capacity upto 500–550°C (1st organic compound withstand this kind of high temp.)

BH
I(
SILICON (Si)
H
Occurrence
AT

Silicon is the second most abundant (27.2%) element after oxygen (45.5%) in the earth's crust. It does
IP

not occur free in nature but in the combined state, it occurs widely in form of silica and silicates. All
TR

mineral rocks, clays and soils are built of silicates of magnesium, aluminium, potassium or iron. Aluminium
silicate is however the most common constituent of rocks and clays.
H

Silica is found in the free state in sand, flint and quartz and in the combined state as silicates like
D

(i) Feldspar – K2O. Al2O3. 6SiO2

D
U

(ii) Kaolinite – Al2O3. 2SiO2. 2H2O

IR

(iii) Asbestos – CaO. 3MgO. 4SiO2

AN

Preparation
(i) From silica (sand): Elemental silicon is obtained by the reduction of silica (SiO2) with high purity coke in
an electric furnace.
SiO2(s) + 2C(s)  Si(s) + 2CO(g)
(ii) From silicon tetrachloride (SiCl4) or silicon chloroform (SiHCl3) : Silicon of very high purity required for
making semiconductors is obtained by reduction of highly purified silicon tetrachloride or silicon chloroform
with dihydrogen followed by purification by zone refining.
SiCl4(l) + 2H2(g)  Si(s) + 4HCl(g)
SiHCl3(s) + H2(g)  Si(s) + 3HCl (g)
PHYSICAL PROPERTIES :
(i) Elemental silicon is very hard having diamond like structure.
(ii) It has shining luster with a melting point of 1793 K and boiling point of about 3550 K.
28 29 30 28
(iii) Silicon exists in three isotopes, i.e. 14 Si , 14 Si and 14 Si but 14 Si is the most common isotope.
CHEMICAL PROPERTIES:
Silicon is particularly unreactive at room temperature towards most of the elements except fluorine.
Some important chemical reactions of silicon are discussed below.
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 (i) Action of air : Silicon reacts with oxygen of air at 1173 K to form silicon dioxide and with nitrogen of
air at 1673 K to form silicon nitride,.
Si(s) + O2(g) 1173
 K
 SiO2(s)
Silicon dioxide
3Si(s) + 2N2(g) 1673
 K
 Si3N4(s)
Silicon nitride
(ii) Action of steam : It is slowly attacked by steam when heated to redness liberating dihydrogen gas.
Si(s) + 2H2O(g) redness
  SiO2(s) + 2H2(g)
(iii) Reaction with halogens: It burns spontaneously in fluorine gas at room temperature to form silicon
tetrafluoride (SiF4).
Si(s) + 2F2(g) Room
 Temperatur
 e  SiF4(l)
However, with other halogens, it combines at high temperatures forming tetrahalides.
(iv) Reaction with carbon : Silicon combines with carbon at 2500 K forming silicon carbide (SiC) known
as carborundum.

)
AI
Si(s) + C(s) 2500
 K
 SiC(s)

IL
Carborundum is an extremely hard substance next only to diamond. It is mainly used as an abrasive and

BH
as a refractory material.
USES:
I(
H
AT

(i) Silicon is added to steel as such or more usually in form of ferrosilicon (an alloy of Fe and Si) to make it
IP

acid-resistant.
TR

(ii) High purity silicon is used as semiconductors in electronic devices such as transistors.
(iii) It is used in the preparation of alloys such as silicon-bronze, magnesium silicon bronze and ferrosilicon.
H

COMPOUNDS OF SILICON:
D
D

Silicates: Details about silicates are given in the topic " Solid State".
U

What is silane. SinH2n+2 (SiH4) & Si2H6

IR

Only these two are found

AN

Higher molecules are not formed.  Si can't show catanetion property

Hot Mg + Si–vap  Mg2Si  
dil . H SO
2
4  MgSO4 + SiH4 + Si2H6 + ...
Ques. SiH4 is more reactive than CH4. Explain
Reasons
(i) Si  H  in C  H
C - electro-ve than H
Si less electro-ve than H
So bond polarity is reversed when Nu– attacks, it faces repulsion in C but not in Si
(ii) Silicon is having vacant d orbital which is not in case of carbon
(iii) Silicon is larger in size compared to C. By which the incoming Nu– doesn't face any steric hindrance to
attack at Si whereas CH4 is tightly held from all sides.

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 Silicones
It is organo silicon polymer
CCl4 + H2O  no hydrolysis
but CCl4 + H2O  COCl2 + 2HCl
super heated
steam
SiCl4 + H2O  Si(OH)4 + 4HCl
SiO2

R R R

| | |
R2SiCl2 + H2O  
2 HCl
 R 2 Si(OH) 
2 H O
 O  Si  O  Si  O  Si O
2 | | |
R R R

)
silicone

AI
IL
O
H O
R2CCl2 + H2O   R2C(OH)2  

BH
2 ||
2 HCl
looses H 2O R CR
readily
I(
H
Silicones may have the cyclic structure also having 3, 4, 5 and 6 nos. of silicon atoms within the ring.
AT

Alcohol analogue of silicon is known as silanol

IP
TR

R R
| |
R  Si  O  Si  R
H

| |
D

O O
D

| |
R  Si  O  Si  R
U
IR

| |
R R
AN

not planar
H O
 R3SiOH   R3Si-O-SiR3
H 2O
R3SiCl  2

Silanol
R R
H 2O  H 2O | |
R2SiCl2 + R3SiCl      Si  O  Si    
hydrolysis heating
condensation | |
R R
This end of the chain can't be extended hence
R3SiCl is called as chain stopping unit
* Using R3SiCl in a certain proportion we can control the chain length of the polymer

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 | |
O R O
| | |

RSiCl3 + H2O  R-Si(OH)3  R  Si  O  Si  O  Si  O 
| | |
O O R
| |
3 dimensional network
It provides the crosslinking among the chain making the polymer more hard and hence controling the
proportion of RSiCl3 we can control the hardness of polymer.
Uses
(1) It can be used as electrical insulator (due to inertness of Si–O–Si bonds)
(2) It is used as water repellant ( surface is covered) eg. car polish, shoe polish, massonary works in
buildings
(3) It is used as antifoaming agent in sewage disposal, beer making and in cooking oil used to prepare potato
chips.

)
AI
(4) As a lubricant in the gear boxes.

IL
BH
SILICA (SiO2)
Occurrence: I(
H
Silica or silicon dioxide occurs in nature in the free state as sand, quartz and flint and in the combined
AT

state as silicates like, Feldspar : K2O.Al2O3.6SiO2, Kaolinite : Al2O3. 2SiO2. 2H2O etc.
IP

PROPERTIES:
TR

(i) Pure silica is colourless, but sand is usually coloured yellow or brown due to the presence of ferric oxide
H

as an impurity.
D

(ii) Silicon dioxide is insoluble in water and all acids except hydrofluoric acid.
D

SiO2(s) + 4HF(l)  SiF4(l) + 2H2O(l)

U

(iii) It also combines with metallic oxides at high temperature giving silicates e.g.
IR


AN

SiO2(s) + CaO(s)  CaSiO3(s)

(iv) When silica is heated strongly with metallic salts, silicates are formed and the volatile oxides are driven
off as vapours.
SiO2(s) + Na2CO3(s)  Na2SiO3(s) + CO2(g)
SiO2(s) + Na2SO4(s)  Na2SiO3(s) + SO3(g)
3SiO2(s) + Ca3(PO4)2(s)  3CaSiO3(s) + P2O5(g)
The first two examples quoted here are important in glass making.
STRUCTURES OF SILICA :
Silica has a three-dimensional network structure. In silica, silicon is sp3-hybridized and is thus linked to
four oxygen atoms and each oxygen atom is linked to two silicon atoms forming a three-dimensional
giant molecule as shown in figure. This three-dimensional network structure imparts stability to SiO2
crystal and hence a large amount of energy is required to break the crystal resulting in high melting point.

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 | | |
— Si — O — Si — O — Si —
| | |
O O O
| | |
— Si — O — Si — O — Si —
| | |
O O O
| | |
— Si — O — Si — O — Si —
| | |

USES:
(i) Sand is used in large quantities to make mortar and cement.
(ii) Being transparent to ultraviolet light, large crystal of quartz are used for making lenses for optical instruments
and for controlling the frequency of radio-transmitters.
(iii) Powdered quartz is used for making silica bricks.

)
AI
(iv) Silica gel (SiO2.xH2O) is used as a desiccant (for absorbing moisture) and as an adsorbent in

IL
chromatography.

BH
TIN & ITS COMPOUND I(
H
C
(i) Sn 1500
   SnO2 [Burns with a bright flame]
AT

O2
IP
TR
H
D
D

(ii) Sn + 2H2O
U
IR

(iii) Reaction with acid.

AN

Sn

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 (iv) Sn + 2NaOH + H2O  Na2SnO3 + 2H2.
or
KOH [In absence of air Na2SnO2 forms and in contact with air it readity converts into Na2SnO3]
1500  C
Oxides:  
  Sn + O2
strongly
heated
SnO (grey)
& SnO2 (white) 
SnC2O4  SnO (grey) + CO + CO2
out of
contact of
air

SnCl2 KOH
 Sn(OH)2
Both are amphoteric in nature :
SnO + H2SO4  SnSO4 + H2O
SnO + 2HCl  SnCl2 + H2O
SnO + 2NaOH or KOH cold  Na2SnO2 or K2SnO2 +H2O

)
AI
But conc. hot alkali behaves differently.

IL
2SnO + 2KOH or NaOH  K2SnO3 or Na2SnO3 + Sn + H2O

BH
* Bi(OH)3 + [Sn(OH)4]2–  Bi  + [Sn(OH)6]2–
I(
(black)
H
SnO2 + 2H2SO4 Sn(SO4)2 + 2H2O
AT

(Soluble only in hot conc. H2SO4)

IP

SnO2+ 2NaOH  Na2SnO3 + H2O

TR

SnO2 + 4S + 2Na2CO3  Na2SnS3 + Na2SO4 + 2CO2

H

(Insoluble in all acids even if in aq. rigia)

D
D

SnCl2 & SnCl4 :

U
IR

Sn + 2HCl (hot conc.) SnCl2 + H2

AN

(1)
SnCl2.2H2O   Sn(OH)Cl + HCl  + H2O Hence anh. SnCl2 cannot be obtained.

SnO + HCl 
{SnCl4 + 4H2O  Sn(OH)4 + 4HClfumes comes out}
(2) A piece of Sn is always added to preserve a solution of SnCl2. Explain.
6SnCl2 + 2H2O + O2  2SnCl4 + 4Sn(OH)Cl (white ppt)
SnCl4 + Sn  2SnCl2

SnCl4 + 4H2O  Sn(OH)4 (white ppt.) + 4HCl

(3) SnCl2 + HCl  HSnCl3 HCl

 H2SnCl4

SnCl4 + 2HCl  H2SnCl6(Hexachloro stannic (IV) acid)

SnCl4+ 2NH4Cl  (NH4)2 SnCl6 (colourless crystalline compound known as " pink salt ")

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 (4) Red Prop. of SnCl2 :
Sn+2 + 2Fe+3  2Fe+2 + Sn+4
2Cu+2 + Sn+2 2Cu+ + Sn+4
Hg+2 + Sn+2 Hg  +Sn+4
PhNO2 + SnCl2 / HCl  PhNH2 + Sn+4
K2Cr2O7 + SnCl2 + HCl  Cr+3 + Sn+4 + KCl + H2O

(5) Readily combines with I2  SnCl2I2  This reaction is used to estimate tin.

Formation of SnCl4 :
(i) Sn + Cl 2 (Excess)  SnCl4 (ii) 2HgCl2 + Sn  2Hg  + SnCl4
( molten ) (dry)
(iii) Sn + Aq. rigia  SnCl4 + NO + H2O
* SnCl4. 5H2O is known as butter of tin  used as mordant.
(NH4)2 SnCl6 is known as 'pink salt'  used as calico printing.

)
AI
IL
Mosaic gold : SnS2 yellow crystalline substance :

BH
Sn + 4NH4Cl  (NH4)2 SnCl4 + 2NH3 + H2
2(NH4)2 SnCl4 + 2S  SnS2 + 2NH4Cl + (NH4)2SnCl6
I(
H
AT

* Distinction of Sn+2 / Sn+4 :

IP

2
(i) H2S (ii) Hg+2 (iii) Fe+3 + [K3Fe(CN)6] Sn
 Blue ppt.
TR

COMPOUNDS OF LEAD
H
D

Oxides of lead :
D

(i) PbO (ii) Pb3O4 (Red) (iii) Pb2O3(reddish yellow) (Sesquioxide)

U

(iv) PbO2 (dark brown)

IR
AN

(1) PbO

Laboratory Prepn. :
Pb(NO3)2  2PbO + 4NO2 + O2
above 600C
PbO2     PbO , hot oxide
Pb3O4   easily reduced to Pb by
 H 2 or C.
Pb2O3  

Preparation of Pb2O3 :
2PbO + NaOCl  Pb2O3 + NaCl
n Limited
hot sol . amount
of it in NaOH

Pb2O3 + 2HNO3  PbO2  + Pb(NO3)2 + H2O

This reaction suggests that Pb2O3 contains PbO2.
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 (2) Pb3O4 : 6PbO + O2 2Pb3O4 {In the same way, prove that its formula is 2PbO. PbO2}
Pb3O4 + 4HNO3 (cold.conc) or (hot dil.)  2Pb(NO3)2 + PbO2 + 2H2O
But 2Pb3O4 + 6H2SO4  6PbSO4 + 6H2O + O2
Pb3O4 + 8HCl  3PbCl2 + 4H2O + Cl2

(3) PbO2 : Insoluble in water. HNO3, But reacts with HCl + H2SO4(hot conc.) and in hot NaOH / KOH.
(i) Pb3O4 + HNO3 
(ii) Pb(OAc)2 + Ca(OCl)Cl + H2O  PbO2[Brown(dark)] + CaCl2 + 2CH3CO2H

Excess bleaching powder
is being removed by stirring with
HNO3
Reaction : PbO2 + 4HCl  PbCl2 + Cl2 + 2H2O
2PbO2 + 2H2SO4  2PbSO4 + 2H2O + O2

)
AI
PbO2 + 2NaOH  Na2PbO3 + H2O

IL
BH
PbO2 : Powerful oxidising agent :
(i)
I(
PbO2 + SO2  PbSO4 [spontaneously]  PbS + O3  PbSO4 + 4O2
 PbS + 4H O  PbSO + 4H O
H

AT

2 2 4 2
(ii) PbO2 + 2HNO3 + (COOH)2  Pb(NO3)2+ 2CO2 + 2H2O
IP

(iii) 2 M

4 + 5PbO2 + 6HNO3  3Pb(NO3)2 + 2PbSO4 + 2HMnO4 + 2H2O

n S O
TR

PbCl4 : Exists as H2[PbCl6]

H

PbO2 + 4HCl  PbCl4 + 2H2O

D
D

{ice cold conc. saturated with Cl2}

U

PbCl4 + 2HCl  H2PbCl6

IR
AN

Lead Tetraacetate :
Pb3O4 + 8AcOH(hot glacial)  Pb(OAc)4 + 2Pb(OAc)2 + 4H2O
Pb(OAc)2 is also converted into Pb(OAc)4 by passing into Cl2
2Pb(OAc)2 + Cl2  Pb(OAc)4 + PbCl2 
It is used as oxidising agent in org. chemistry to oxidise 1,2-diol to aldehydes and ketones.
RCH (OH)
| [
O]
2RCHO + H2O
RCH (OH)
TetraEthyl lead :
4Na–Pb(alloy 10%–Na.) + 4C2H5Cl(vap.)  3Pb + Pb(Et)4 + 4NaCl
It is antiknocking agent.
Lead storage cell :
Pb + PbO2 + 2H2SO4 2PbSO4 + 2H2O

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 GROUP -V

Preparation of N2 :
(i) 
NH4NO2  N2 + 2H2O
(ii) 
(NH4)2 Cr2O7  N2 + 4H2O + Cr2O3
(iii) 
Ba(N3)2  Ba + 3N2 Purest N obtained
 2
2NaN 
3
 2Na + 3N  by this method
2
(iv) 2NH3 + 3NaOCl  N2 + 3NaCl + 3H2O
(v) 2NO + 2Cu  2CuO + N2
(red,overheated) (Black)
(vi) Cl2 passed into liquor NH3
3Cl2 + 2NH3  N2 + 6HCl
6NH3 + 6HCl 6NH4Cl
-------------------------------

)
AI
3Cl2 + 8NH3  N2 + 6NH4Cl

IL
In this method NH3 conc. should not be lowered down beyond a particular limit.

BH
3Cl2 + NH3  NCl3 + 3HCl
(Trimendously explosive) I(
H
Properties of N2 :
AT

(i) It is inert due to high bond energy.

(ii) It is absorbed by hot metal like Ca, Mg, Al etc.
IP

3Ca + N2  Ca3N2
TR

Bright hot 2Al + N2  2AlN

H


Al2O3 + 3C + N2  2AlN + 3CO
D
D

(BN)x : Inorganic graphile

U

White slippery solid having 2D-sheet structure.

IR

3000C
(BN)x    (BN)x
AN

3–D network structure similar to diamond (Borazon) which is harder than diamond and used for dimond
cutting.

Na2B4O7 + 2NH4Cl  2NaCl + 2NH3 + 2B2O3 + H2O
B2O3 + 2NH3  2BN + 3H2O
(iii) N2 can be absorbed by calcium carbide at the temp around 1000°C CaC2
C
CaC2 + N2 1000
   CaNCN
 C
cyanamide ion nitro lim
It is a very good fertiliser.
Cyanamide ion

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 (iv)

TYPES OF NITRIDE :

(i) Salt like or ionic : Li3N, Na3N, K3N (?), Ca3N2, Mg3N2, Be3N2
(ii) Covalent : AlN, BN, Si3N4, Ge3N4, Sn3N4
(iii) M  Sc, Ti, Zr, Hf , La )
Interstitial : MN (  
HCP or FCC

No of metal atom per unit cell is equal to no of octahedral voids per unit cell.
All the octahedral voids are occupied by nitrogen atoms. Hence the fornmula is MN.
HCP : Hexagonal closed pack
FCC : Face centred cubic

)
AI
NH3 preparation :

IL
(i) Nitrate or nitrite reduction : NO3 / NO 2 +Zn or Al + NaOH  NH3 + [Zn(OH)4]2– or [Al(OH)4]–

BH
(ii) Metal nitride hydrolysis : N3– + 3H2O  NH3 3OH–
C
I(
Haber's process : N2 + 3H2 450
  2NH3
H
(iii)
200 1000 atm
AT

catalyst Fe / Mo
IP
TR

Q.1 NH3 can't be dried by H2SO4, P2O5 and anh.CaCl2 because:

2NH3 + H2SO4  (NH4)2 SO4
H

H2O + NH3 + P2O5  (NH4)3 PO4

D
D

CaCl2 + 8NH3  CaCl2 . 8NH3

U

forms adduct
IR

Quick lime is used for this purpose

AN

CaO + H2O  Ca(OH)2 (base)  Hence no


NH3 (base)  interaction
Properties :
(i) It dissolves several electropositive metals like Li, Na, K, Rb, Cs, Sr, Ba etc.
Eg. : K in liq NH3  (i) Blue in colour
(ii) Conducts electricity
(iii) having reducing property

K2[Ni(CN)4]   K4[Ni(CN)4]
K in liq
NH3
Square planar Tetrahedral
complex complex

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 (ii) Ag(NO3)(aq) + BaCl2(aq)  AgCl  + Ba(NO3)2

Cl– + [Ag(NH3)2]+

BaCl2 +[Ag(NH3)2]+ + NO 3
(iii) CH3COOH is strong acid in liq. NH3 while in water is weak acid.
—
AcOH l Ac O + H+
NH3 + H+  NH 4 H2O + H+  H3O+
Basisity order NH3 > H2O

)
AI
more solvation of H+ in NH3.

IL
(iv) Hydrolysis and Ammonolysis occurs is a same way.

BH

SiCl4 + 4H2O  4HCl + Si(OH)4  SiO2 + 2H2O
I(
SiCl4 + 8NH3  4NH4Cl + Si(NH2)4   Si3N4 + NH3
H
AT

Rate of hydrolysis and Ammonolysis will be affected by the presence of HCl vapour & NH4Cl vapour
IP

respectively.
TR

NH 4  Salts Pr eparation
H
D
D
U
IR
AN

OXIDES OF NITROGEN

Oxides of nitrogen Structure Physical state Colour of gas

— 
N2O NNO Gas Colourless
NO Gas Colourless
N 2O 3 ;O  N O N Blue liquid (–30°C)
||
O

NO 2 l Gas Brown

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 N 2O 5 Colourless solid – (no existance in gas phase)

Preparations:
1. N2O
(i) N

4NO3  N2O + H2O

H

(ii) (NH4)2SO4 + NaNO3  NH4NO3 + Na2SO4

N2O + 2H2O
(iii) Zn + HNO3  Zn(NO3)2 + N2O + H2O
(dil.& cold)

2. NO
(i) Cu + HNO3 (1 : 1)  Cu(NO3)2 + NO + H2O
hot

)
AI
(ii) KNO3 + FeSO4 + H2SO4  Fe2(SO4)3 + K2SO4 + NO + H2O

IL
FeSO4 + NO  FeSO4 . NO   FeSO4 + NO

BH
(iii) Oswald process–Restricted oxidation of NH3. I(
Industrial process.
H
AT

4NH3 + 5O2    4NO + 6H2O

6 atm
750C , Pt  Cat
IP

3. N 2O 3
TR

(i) HNO3 + As2O3  H3AsO4 + N2O3

H

(ii) NO  NO2 )
Cu + HNO3(6M)  Cu(NO3)2 + (
D


 
D

| Cool( 30C)
U


IR

Blueliq ( N 2O3 )
AN

4. NO 2
 1
(i) M(NO3)2  MO + 2NO2 + O
2 2
M = Pb, Cu, Ba, Ca
(ii) (Cu, Pb, Ag) + HNO3  M-nitrate + NO2 + H2O
(hot & conc.)
5. N 2O 5
(i) 2HNO3 + P2O5  2HPO3 + N2O5
(ii) 4AgNO3 + 2Cl2(dry gas)  4AgCl + 2N2O5 + O2

Properties:
(I) Decoposition Behaviour
(i) 
N2O 500 C 900C
  2N2 + O2
2NO 800 C
(ii)   N 2 + O2

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 (iii) N2O3 Room
 temp

. NO2 + NO
(Blue liq.) at (–30°C)

2NO2 620 C
(iv)   2NO + O2
N 2O 4 
11C
 2 NO 2
( white solid ) Brown gas
at (11C)

C C
1
(v) N 2O5 30
  N 2O5 40
  2NO2 + 2 O2
colourless yellow
solid liq.

(II) Reaction with H2O & NaOH

H2O NaOH
(i) N2O : Fairly soluble in water and
produces neutral solution -------

)
AI
(ii) NO : Sparingly soluble in water

IL
and produces neutral soln. -------

BH
(iii) N2O3: 2HNO2
Hence it is known as I(
anhydride of HNO2 NaNO 2
H
AT

(iv) NO2: HNO2 + HNO3

called as mixed anhydride NaNO2 + NaNO3
IP

(v) N2O5: 2HNO3

TR

called as anhydride of NaNO 3

H

HNO3
D
D

Other properties:
U
IR

N2O : 2N2O  2N2 + O2 mixture contains

AN

Hence it is better supporter 33% O 2 compared

for combustion to 20% in air
S + N2O  SO2 + N2
P + N2O P2O5 + N2
Mg + N2O  MgO + N2
Na + N2O  Na2O + N2
Cu + N2O  CuO + N2
H2 + N2O  H2O + N2

1
NO : (i) It burns : NO + O  NO2
2 2
(ii) It supports combustion also for molten sulphur and hot phosphorous.
S + 2NO  SO2 + N2
5
2P + 5NO  P2O5 + N
2 2

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 (iii) It is being absorbed by FeSO4 solution.
(iv) It is having reducing property.
KMnO4 + NO + H2SO4  K2SO4 + MnSO4 + HNO3 + H2O
HOCl + NO + H2O  HNO3 + HCl
(v) NO shows oxidising property also.
SO2 + 2NO + H2O  H2SO4 + N2O
H2S + 2NO  H2O + S + N2O
3SnCl2 + 2NO + 6HCl  3SnCl4 + 2NH2OH
(Used for NH2OH preparation)
(vi) NO combines with X2 (X2= Cl2Br2F2) to produce NO X
2NO + X2  2NOX
N2 O3 : No more properties.

NO2 : (1) It is having oxidising property.

S + NO2  SO2 + NO
P + NO2 P2O5 + NO
C + NO2  CO2 + NO

)
AI
SO2 + NO2 + H2O  H2SO4 + NO

IL
H2S + NO2  H2O + S + NO

BH
CO + NO2  CO2 + NO
I(
H
NO not formed : 2KI + 2NO2 I2 + 2KNO2
AT
IP

(2) Reducing property of NO2.

KMnO4 + NO2 + H2SO4  K2SO4 + MnSO4 + HNO3 + H2O
TR

4 5
H

O 30  2 NO 2  O 02  N 2 O 5
D


D

not the reduction product of O3

U
IR

N2 O5 :
I2 + 5N2O5  I2O5 + 10NO2
AN

I2O5 is used for the estimation of CO

I2O5 + 5CO  I2 + 5CO2
I2 + 2S2O 32  2I– + S4O 62
N2O5 + NaCl  NaNO3 + NO2Cl
This likes proves that N2O5 is consisting of ion pair of NO 2 & NO3
Oxyacids of N :

HNO2 :
Preparation
(i) M-nitrite   HNO2
dil. acid
HCl or H 2SO 4

(ii) N2O3 + H2O  2HNO2

Properties

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 (i) Oxidising property of HNO2
KI + HNO2 + HCl  KCl + H2O + NO + I2
SnCl2 + HNO2 + HCl  SnCl4 + NO + H2O
SO2 + HNO2 + H2O  H2SO4 + NO
H2S + HNO2  H2O + S + NO
FeSO4 + HNO2 + H2SO4  Fe2(SO4)3 + NO + H2O
Na3AsO3 + HNO2  Na3AsO4 + NO + H2O
(ii) Reducing property of HNO2
KMnO4 + HNO2 + H2SO4  K2SO4 + MnSO4 + HNO3 + H2O
K2Cr2O7 + HNO2 + H2SO4 K2SO4 + Cr2(SO4)3 + HNO3 + H2O
H2O2 + HNO2 H2O + HNO3
HNO2 + urea 
+ thiourea 
+ sulphamic acid 
+ NH3  NH4NO2
+ C2H5NH2  C2H5OH + N2
 5 C

)
+ Ph–NH2  PhN2+X–

AI
IL
BH
Nitric acid (HNO3)
It was named aqua fortis (means strong water) by alchemists.
I(
Preparation
H
AT

(i) Laboratory Method

KNO3 + conc. H2SO4  KHSO4 + HNO3(vap)
IP

vapours of nitric acid evolved are condensed in a glass receiver.

TR

(ii) Industrial Preparation

H

(A) Birkeland Eyde Process or arc process

D
D

N2 + O2   2NO - heat

3000 C
step 1
U

Electric Arc
IR

step 2 NO + O2  NO2
AN

step 3 NO2 + H2O  HNO2 + HNO3

step 4 HNO2  HNO3 + NO + H2O
(B) Ostwald’s Process
NH3 + O2 700  NO + H O + heat
Pt . gauze
step 1 8000 C 2

step 2 NO + O2  NO2
step 3 NO2 + H2O  HNO2 + HNO3
step 4 HNO2  HNO3 + NO + H2O
PROPERTIES
Physical
Nitric acid usually acquires yellow colour due to its decomposition by sunlight into NO2.
4HNO3 Sunlight
 4NO2 + 2H2O + O2
The yellow colour of the acid can be removed by warming it to 60-80 oC and bubbling dry air through it.
It has extremely corrosive action on the skin and causes painful sores.

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Phone :- 9929617387 Fax :- 0744 - 2405300
 Chemical
(a) It is very strong acid. It exhibits usual properties of acids. It reacts with basic oxides, carbonates,
bicarbonates and hydroxides forming corresponding salts.
CaO + 2HNO3  Ca(NO3)2 + H2O
Na2CO3 + 2HNO3  2NaNO3 + H2O + CO2
NaOH + HNO3  NaNO3 + H2O
(b)Oxidising nature: Nitric acid acts as a strong oxidising agent as it decomposes to give nascent oxygen easily.
2HNO3  H2O + 2NO2 + O
or 2HNO3  H2O + 2NO + 3O
(i) Oxidation of non-metals: The nascent oxygen oxidises various non-metals to their corresponding
highest oxyacids.
(1) Sulphur is oxides to sulphuric acid
S  6HNO 3  H SO + 6NO + 2H O
conc . and hot 2 4 2 2

(2) Carbon is oxidised to carbonic acid

C + 4HNO 3  H 2 CO 3 + 4NO 2 + 2H 2 O

)
AI
IL
(3) Phosphorus is oxidised to orthophosphoric acid.

BH
2P + 10HNO 3  2H 3 PO 4 + 10NO 2 + 2H 2 O
conc. and hot I(
H
(4) Iodine is oxidised to iodic acid
AT

I2 + 10HNO 3  2HIO 3 + 10NO 2 + 4H 2 O

IP

conc. and hot

TR

(ii) Oxidation of metalloids

Metalloids like non-metals also form highest oxyacids
H
D

(1) Arsenic is oxidised to arsenic acid

D

2As + 10HNO 3  2H 3 AsO 4 + 10NO 2 + 2H 2 O

U

or As + 5HNO 3  H 3 AsO 4 + 5NO 2 + H 2 O

IR

conc. and hot

AN

(2) Antimony is oxidised to antimonic acid

Sb + 5HNO 3  H 3 SbO 4 + 5NO 2 + H 2 O
conc. and hot
(3) Tin is oxidised to meta-stannic acid.
Sn + 2HNO 3  H 2 SnO3 + 4NO 2 + H 2 O
(iii) Oxidation of Compounds:
(1) Sulphur dioxide is oxidised to sulphuric acid
SO 2 + 2HNO 3  H 2 SO 4 + 2NO 2
(2) Hydrogen sulphiode is oxidised to sulphur
H 2 S + 2HNO 3  2NO 2 + 2H 2 O + S
(3) Ferrous sulphate is oxidised to ferric sulphate in presence of H 2SO 4
6FeSO 4 + 3H 2 SO 4 + 2HNO 3  3Fe 2 (SO 4 ) 3 + 2NO + 4H 2 O
(4) Iodine is liberated from KI.
6KI + 8HNO 3  6KNO 3 + 2NO + 3I 2 + 4H 2 O

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Phone :- 9929617387 Fax :- 0744 - 2405300
 (5) HBr, HI are oxidised to Br 2 and I2 , respectively.
2HBr + 2HNO 3  Br 2 + 2NO 2 + 2H 2 O
Similarly, 2HI + 2HNO 3  I2 + 2NO 2 + 2H 2 O
(6) Ferrous sulphide is oxidised to ferrous sulphate
FeS + HNO 3  FeSO 4 + 8NO 2 + 4H 2 O
(7) Stannous chloride is oxidised to stannic chloride is presence of HCl.
2HNO 3 + 14H  NH 2 OH + NH 3 + 5H 2 O
Hydroxylamine
NH 3 + HNO 3  NH 4 NO 3
------------------------------------------------------------------------------
7SnCl 2 + 14HCl + 3HNO 3  7SnCl 4 + NH 2 OH + NH 4 NO 3 + 5H 2 O
(8) Cane sugar is oxidised to oxalic acid.
C 12 H 22 O 11 + 36HNO 3  6(COOH) 2 + 36NO 2 + 23H 2 O
(c) Action on Metals: Most of the metals will the exveption of noble metals like gold and platinum are
attacked by Nitric acid plays a double role in the action of metals, i,e, it acts as an acid as well as an
oxidising agent. ARmstrong postulated that primary action of nitric acid is to produce hydrogen in the

)
AI
nascent form. Before this hydrogen is allowed to escape, it reduces the nitric acid into number of products

IL
like NO2, NO, N2O, N2 or NH3 according to the following reactions:

BH
Metal + HNO3  Nitrate + H
2HNO3 + 2H  2NO + 2H2O I(
2HNO3 + 6H 2NO + 4H2O
H
2HNO3 + 10H  N2 + 6H2O
AT

2HNO3 + 16 H  2NH3 + 6H2O

IP

The progress of the reaction is controlled by a number of factors:

TR

(a) the nature of the metal,

(b) the concentration of the acid,
H

(c) the temperature of the reaction,

D
D

(d) the presence of other impurities.

U

--------------------------------------------------------------------------------------------------------
IR

Concentration of Metal Main Products

AN

nitric acid
--------------------------------------------------------------------------------------------------------
Mg, Mn H2 + Metal nitrate
Very dilute HNO3 (6%) ----------------------------------------------------------
Fe, Zn, Sn NH4NO3 + metal nitrate + H2O
--------------------------------------------------------------------------------------------------------
Pb, Cu, Ag, Hg NO + metal nitrate + H2O
----------------------------------------------------------
Dilute HNO3 (20%) Fe, Zn N2O + metal nitrate + H2O
----------------------------------------------------------
Sn NH4NO3 + Sn(NO3)2
--------------------------------------------------------------------------------------------------------
Zn, Fe, Pb, Cu, Ag NO2 + metal nitrate + H2O
Conc. HNO3(70%) ----------------------------------------------------------
Sn NO2 + H2SnO3
Metastannic acid
--------------------------------------------------------------------------------------------------------

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Phone :- 9929617387 Fax :- 0744 - 2405300
 Action on Proteins
(i) Nitric acid attacks proteins forming a yellow nitro compound called xanthoprotein. It, therefore, stains
skin and renders wool yellow. This property is utilized for the test of proteins.
(ii) Oxidation A number of organic compounds are oxidised.
Sawdust catches fire when nitric acid is poured on it. Turpentine oil bursts into flames when treated with fuming
nitric acid. Cane sugar is oxidised to oxalic acid. Toluene is oxidised to benzoic acid with dil. HNO3.
Structure
Nitric acid is a monobasic acid, i.e., the molecule consist of one hydroxyl group as it is formed by the hydrolysis
of nitryl chloride, NO2Cl. It may be structurally represented as below:

Gaseous nitric aicd is a planar molecule. The bond lengths and bond angles as present in the molecule are
represented in the figure:

)
AI
IL
BH
PHOSPHOROUS I(
H
AT

INTERCONVERSION OF WHITE 'P' & RED 'P'

IP

240  250C
White 'P'     Red 'P'
TR

in an inert atm. like

N 2 or CO 2
H

I 2 : catalyst
D
D

heated to 550  C
Red 'P'      White 'P'
U

in an inert atom and then

IR

rapid cooling to room temp .

AN

PREPRATION OFWHITE 'P'

(i) Bone ash orApatite rock  Ca3(PO4)2 + 3SiO2 1200 C
    3CaSiO3 + P2O5
 C
both have same formula  2P2O5 + 10C 1500
   P4 + 10CO 
(Coke) white 'P'
(ii) Ca3(PO4)2 + 3H2SO4 (conc.)  3CaSO4 + 2H3PO4
320C
H3PO4  HPO3
– H 2O
meta phosphoric acid

C
12C + 4HPO3 1000
   2H2 + 12CO + P4
Coke white 'P'

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Phone :- 9929617387 Fax :- 0744 - 2405300
 REACTIONS OF 'P'
* P + H2SO4 (hot & conc.)  H3PO4 + SO2 + H2O
P + KIO3 + H2SO4  H3PO4 + I2 + K2SO4

* Reaction with hot metal —

3Na + P  Na3P
3Mg + 2P  Mg3P2
3Ca + 2P  Ca3P2
2Cu + 2P  Cu3P2
Al + P  AlP

Ca3P2 + H2O  M(OH)n + PH3

or Mg3P2
or AlP

PREPARATION OF PH3 (PHOSPHINE GAS)



)
(i) 4H3PO3  PH3 + 3H3PO4

AI
(ii) PH4I + KOH  KI + PH3 + H2O 

IL


BH
(PH3 + HI)
 Purest PH 3
(iii) 2AlP + 3H2SO4  Al2(SO4)3 + PH3  I(
H
PHYSICAL PROPERITIES
AT

(i) It is having 'rotten fish' smell

IP

(ii) It is soluble in CS2 and insoluble in water.

TR

(NH3 is soluble in water)

NH 4 + OH–
H
D
D
U
IR
AN

PH 4 is formed with acids

(iii) Like NH3, PH3 also can form addition product.
 
CaCl2 • 8NH3 Cu2Cl2 • 2PH3, AlCl3 • 2PH3, SnCl4 • 2PH3
PH3 can be absorbed by Ca(OCl)Cl.
PH3 + 3Ca(OCl)Cl + 3H2O  PCl3 + 3HCl + 3Ca(OH)2
2NH3 + 3Ca(OCl)Cl  N2 + 3CaCl2 + 3H2O

OTHER REACTIONS OF PH3

(i) PH3 + O2 150
 P2O5 + H2O
(ii) PH3 + 3Cl2  PCl3 + 3HCl

(iii) PH3 + 4N2O   H3PO4 + 4N2

electrical
sparking
(iv) 2PH3 + 3CuSO4  Cu3P2 + 3H2SO4

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Phone :- 9929617387 Fax :- 0744 - 2405300
 Detection of PH3 Black ppt.
(v) PH3 + 6AgNO3  [Ag3P • 3AgNO3] + 3HNO3
yellow ppt.
Ag3P • 3AgNO3 + 3H2O  6Ag + 3HNO3 + H3PO3
Black ppt.
(vi) PH3 + 4HCHO + HCl  [P(CH2OH)4]+Cl–
white/colourless solid
which is used for making
fire-proof cotton fabrics

EXAMPLE OF DEHYDRATING REACTION OF P2O5

HClO3 + P2O5  2HPO3 + Cl2O7
H2SO4 + P2O5  2HPO3 + SO3
HNO3 + P2O5  2HPO3 + N2O5
GROUP VI

SULPHUR CHEMISTRY

)
AI
IL
* Allotropes: (i) Rhombic or -sulphur.

BH
(ii) Monoclinic or -sulphur.
(iii) -Sulphur I(
H
Amorphous forms are
AT

(i) Plastic sulphur

(ii) Milk of sulphur
IP

(iii) Colloidal sulphur

TR

* Viscosity of 'S' with temperature:

m.p. of 'S' 112.8°C.
H
D

(i) > 112.8°C to 160°C  slow decreases due to

D

S8 rings slip and roll over one another easily.

U
IR

(ii) > 160°C, increases sharply due to breaking of

AN

S8 rings into chains and polymerses into large size chain.

(iii) 190°C, again large chains are being broken into small chain.
* Milk of sulphur :
Powdered 'S' + Ca(OH)2 suspension  Solution Acidified
  Milk of 'S'
12 S + 3Ca(OH)2  2CaS5 + CaS2O3 + 3H2O
2CaS5 + CaS2O3 + 6HCl  3CaCl2 + 12 S + 3H2O
* Colloidal Sulphur : Na2S2O3 + 2HCl  2NaCl + H2O + SO2 + S 
2H2S + SO2  3  + 2H2O
Props. of 'S' : (a) Thin Cu-strip catches fire in sulphur vapour.
Cu + S  CuS.
(b) 'S' burns spontaneously in fluorine. S + 3F2  SF6
Cl2 passed into liq. sulphur  2 S + Cl2  S2Cl2
(c) S + 2H2SO4  3SO2 + 2H2O
S + 2HNO3  H2SO4 + 2NO
(d) 4 S + 6 KOH  2K2S + K2S2O3 + 3H2O
(e) Burns in air : S + O2  SO2

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Phone :- 9929617387 Fax :- 0744 - 2405300
 H2S :
Prepn.: FeS + dil. H2SO4  FeSO4 + H2S
FeS + dil. HCl  FeCl2 + H2S
Sb2S3 + (conc.)6HCl  2SbCl3 + 3H2S
* Drying agent for this gas : fused CaCl2, Al2O3 (dehydrated)
P2O5 etc. But not H2SO4, because
H2SO4 + H2S  2H2O + SO2 + S
Reducing property of H2S :
Cl2 + H2S  2HCl + S
I2 + H2S 2HI + S
H2O2 + H2S 2H2O + S
SO2 + 2H2S 2H2O + 3 S
2FeCl3 + H2S 2FeCl2 + 2HCl + S
** 4H2O + 4Cl2 + H2S H2SO4 + 8HCl
KMnO4 + H2S + H2SO4 S + Mn2+
H2Cr2O7 + H2S + H2SO4 Cr3+ + S +

)
HNO3 + H2S S + NO2 + H2O

AI
With metal (hot)

IL
2Na + H2S Na2S + H2

BH
Cu + H2S CuS + H2 I(
Pb + H2S PbS + H2
H
With metal oxide (hot)
AT

CaO + H2S CaS + H2O

IP

ZnO + H2S ZnS + H2O

TR

Metal ion + H2S M-Sulphides

H

** (i) Alkali-sulphide  water soluble

D

(ii) Alkaline earth–sulphide  sparingly soluble

D

Al2S3 & Cr2S3 + 6H2O  Al(OH)3 or Cr(OH)3 + 3H2S

U

(iii)
IR

Test :
AN

(i) Smell  rotten egg.

(ii) Pb– Acetate paper–black
(iii) Purple colour when alk. Nitropruside + H2S
Absorbent : NaOH, KOH, PbNO3 solution
Pb(NO3)2 + H2S  2HNO3 + PbS (Black)
SO2
Prepn.:
Industrial : 4FeS2 + 11O2  2Fe2O3 + 8SO2
2ZnS + 3O2  2ZnO + 2SO2
Lab prepn.: Cu + 2H2SO4 (conc.)  CuSO4 + 2H2O + SO2
Hg + H2SO4  HgSO4 + H2O + SO2
2Ag + H2SO4  Ag2SO4 + H2O + SO2
S + 2H2SO4  3SO2 + 2H2O
(Charcoal)C + 2H2SO4  CO2 + 2SO2 + 2H2O
NaHSO3+ H2SO4  NaHSO4 + H2O + SO2

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Phone :- 9929617387 Fax :- 0744 - 2405300
 Props: (i) Incombustible gas, but heated K burns in SO2
4K + 3SO2  K2SO3 + K2S2O3

Na2SO3 + SO2

Na2S + 3Na 2SO 4

Reducing Prop.: (Revise from acid radical)
(i) FeCl3 + SO2  FeCl2 + H2SO4

)
AI
IL
BH
4FeCl2 + SO2 + 4HCl  4FeCl3 + H2O + S
I(
H
6SnCl2 + 2SO2 + 8HCl  5SnCl4 + 4H2O + SnS2 (Yellow solid)
AT

150C
SO2 + 2H2SO3   2H SO + S
IP

(ii) sealed tube 2 4

TR

* FeSO4  Fe2O3 + SO2 + SO3

Fe2(SO4)3  Fe2O3 + 3SO3
H
D
D

H2SO4 & SO3 :

U
IR
AN

Both gas
 
SO 2  Cl 2  SO2Cl2
H2SO4 + 2PCl5  ..........SO2Cl2 + 2POCl3 + 2HCl
Use of H2SO4 as nitrating mixture: 
good chlorinating agent
** P2O5 is stronger dehydrating agent than H2SO4 : H2SO4 + P2O5  2HPO3 + SO3

Properties of H2SO4 :
(a) Dissociation : At 444°C. H2SO4 l H2O + SO3
(b) Acidic nature : NaOH + H2SO4 l NaHSO4 + H2O Na2SO4 + H2O
(c) CO 32 + H2SO4  SO 24 + H2O + CO2
Carbonates or bicarbonat es

HCO 3 + H2SO4  H 2SO 4 +
H2O + CO2  are getting decomposed
(d) Zn / Fe + H2SO4ZnSO4 & FeSO4+ H2
where as
Cu + 2H2SO4  CuSO4 + SO2 + 2H2O

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Phone :- 9929617387 Fax :- 0744 - 2405300
 2Ag + 2H2SO4  Ag2SO4 + SO2 + 2H2O
Hg + 2H2SO4  HgSO4 + SO2 + 2H2O
(e) NaCl HCl
Ca3(PO4)2  H3PO4

FeS  H2 S
CH3CO2Na   H SO 
4 
AcOH
2
NaNO 3  HNO3
CaF2  HF
NaNO 2 
 HNO2
(f) Oxidising Prop.:
HBr / HI + H2SO4  I2/Cl2 + SO2 + H2O
C + 2H2SO4  CO2 + 2SO2 + 2H2O
S + 2H2SO4  3SO2 + 2H2O
2P + 5H2SO4  H3PO4 + 5SO2
(g) Dehydrating agent:
H SO
C12H22O11 2 
4  12 C

)
11 H 2O

AI
IL
H SO
C6H12O6  
4  6C
2

BH
6H O 2

H SO
I(
(COOH)2  
4  CO + CO
2 H SO
PhH 2 
4  Ph–SO3H
H
H O 2
AT

HCO2H  CO
IP

H O 2
TR

SODIUM THIOSULPHATE
Prepn.:
H

(i) Na2SO3 soln. + S (powder) boiling

  Na2S2O3 eavporatio
  n
 Na2S2O3.5H2O, monoclinic crystal
D
D
U

 Na 2 CO 3  2SO 2  H 2 O  2 NaHSO 3  CO 2
IR

2 NaHSO  Na CO  Na SO  H O  CO

AN

3 2 3 2 3 2 2

(ii) Na 2SO 4 + 4C roasting

  Na2S + 4CO
Salt cake Coke

Na2S2O3 [3SO2 + 2Na2S  2Na2S2O3 + S ]

(iii) 2Na2S + Na2CO3 + 4SO2  3Na2S2O3 + CO2
(iv) 6NaOH + 4S  Na2S2O3 + 2Na2S + 3H2O
3Ca(OH)2 + 12 S  CaS2O3 + 2CaS5 + 3H2O
(v) Na2SO3 + Na2S + I2  Na2S2O3 + 2NaI
(vi) 2Na2S + 2O2 + H2O  Na2S2O3 + 2NaOH [Na2S is readily oxidised in air giving rise to Na2S2O3]

Props : (i) 4Na2S2O3  Na2S5 + 3Na2SO4

(ii) Na2S2O3 + 2H+  H2S2O3  H2O + SO2 + S  (White turbidity)

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Phone :- 9929617387 Fax :- 0744 - 2405300
 Reaction: (i) Na2S2O3 + I2  S4 O 62 + 2I–

+ Cl2 – water  SO 24 + S + 2HCl

+ Br2 – water  SO 24 + S + 2HBr

+ 4OI– + 2OH–  2 SO 24 + 4I– + H2O

+ 4Cl2 + 5H2O  Na2SO4 + 8HCl + H2SO4
excess

OZONE
 Unstable deep blue, diamagnetic gas, with fishy smell. Toxic enough (more toxic than KCN). It's intense
blue colour is due to the absorption of red light.

 2F2 + 2H2O  4HF + O2  Ozonised is separated by passing into spiral tube cooled by liq.

F2 + 3H2O  6HF + O3  oxygen  air. Ozone condenses at –112.4°C.


)
AI
[b.p. of O2 –183°C ; b.p. of liq. air is –190°C]


IL
Oxidising property of O3

BH
It is one of best oxidising agent, in acid solution, its standard, reduction potential value is 2.07 V.
O3 + 2H+ + 2e  O2 + H2O E° = +2.07 V
I(
It is next to F2. [above 2.07 V, only F2, F2O are there]
H
(i) Metal Sulphides to Sulphates.
AT

MS + 4O3  MSO4 + 4O2 [M = Pb, Cu, Zn, Cd]

IP

(ii) 2HX + O3  X2 + H2O + O2 [X = Cl, Br, I]

TR

(iii) NaNO2 + O3 NaNO3 + O2

Na2SO3 + O3 Na2SO4 + O2
H

Na2AsO3 + O3  Na2AsO4 + O2
D
D

(iv) Moist S, P, As + O3 
U

S + H2O + 3O3  H2SO4 + 3O2

IR

2P + 3H2O + 5O3  2H3PO4 + 5O2

AN

2As + 3H2O + 5O3  2H3AsO4 + 5O2

(v) Moist I2 HIO3 whereas dry iodine  I4O9 (yellow)
I2 + 5O3 + H2O  2HIO3 + 5O2
2I2 + 9O3  I4O9 + 9O2
(vi) 2K2MnO4 + O3 + H2O  2KMnO4 + 2KOH + O2
2K4[Fe(CN)6] + O3 + H2O  2K3[Fe(CN)6] + 2KOH + O2
2FeSO4 + O3 + H2SO4  Fe2(SO4)3 + O2 + H2O

(vii)(a) 2KI (acidified) + O3 + 2HCl  I2 + 2KCl + H2O + O2

(b) 2KI (neutral) + O3 + H2O  I 2  2KOH + O2 
 
KI KOI

KI + KOI + 2HCl  2KCl + I2 + H2O  O3 estimated by this reaction

I2 + 2S2O 32  S4O 62 + 2I 

KI + 3O3  KIO3 + 3O2 
(c) alk . 
 KI + 4O3  KIO4 + 4O2 
CHEMISTRYDigital Chemistry labs
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TRIPATHI
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Phone :- 9929617387 Fax :- 0744 - 2405300
 (viii) Hg loses its fluidity (tailing of Hg)
2Hg + O3 Hg2O + O2
similarly 2Ag + O3  Ag2O + O2
Brown
(ix) BaO2 + O3  BaO + 2O2
H2O2 + O3  H2O + 2O2
Na2O2 + O3 + H2O  2NaOH + 2O2

(x) 2KOH + 5O3  2KO3 + 5O2 + H2O

In all above reaction O3 gives up O2 but some reactions are there which consumes all O-atom.
(i) 3SO2 + O3  3SO3
(ii) 3SnCl2 + 6HCl + O3  3SnCl4 + 3H2O
Absorbent : (i) Turpentine oil
(ii) Oil of cinnamon

)
AI
Uses: (i) Sterilising water

IL
(ii) Detection of position of the double bond in the unsaturated compound.

BH
H2O2 H
I(
AT

Method of preparation:
(i) Na2O2 + H2O (ice cold water)  2NaOH + H2O2
IP
TR

(ii) BaO2 + H2SO4  BaSO4 + H2O2

H

Instead of H2SO4, H3PO4 is added now-a-days because H2SO4 catalyses the decomposition of H2O2
D

whereas H3PO4 favours to restore it.

D

3BaO2+2H3PO4  Ba3(PO4)2+3H2O2 and Ba3(PO4)2+3H2SO43BaSO4+ 2H3PO4 (reused again)

U
IR

(iii) Electrolysis of 50% H2SO4 using high current density.

2H2SO4 --> 2H+ + 2H SO 4
AN

2HSO 4  H2S2O8 + 2e. [At anode] [At cathode 2H+ + 2e  H2]

H2S2O8 + 2H2O  2H2SO4 + H2O2

O
(iv) H / Pd
2 
 
2 + H2 O2

Properties:
(i) Colourless, odourless liquid (b.p.152°)

(ii) Acidic nature: H2O2 + 2NaOH  Na2O2 + H2O

H2O2 + Ba(OH)2  BaO2 + 2H2O
H2O2 + Na2CO3 Na2O2 + CO2 + H2O

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Phone :- 9929617387 Fax :- 0744 - 2405300
 (iii) It is oxidant as well as reductant.
H2O2 + 2H+ + 2e  2H2O [reaction in acidic medium]
H2O2 + 2e  2OH– [rxnn in alkali medium]
Oxidising Properties:

(i) PbS + 4H2O2 + PbSO4 + 4H2O (Used in washing of oil painting)

(ii) NaNO2 + H2O2  NaNO3 + H2O

Na2SO3 + H2O2  Na2SO4 + H2O
Na3AsO3 + H2O2 Na3AsO4 + H2O
2KI + H2O2  2KOH + I2  X2 + H2O2  2HX + O2 X = Cl, Br.. 
H2S + H2O2  S  + 2H2O  S.R.P order of Cl > Br > H O > I 
2 2 2 2 2
H2SO4 + 2FeSO4 + H2O2  Fe2(SO4)3 + 2H2O
2 K4[Fe(CN)6] + H2O2 + H2SO4 2K3[Fe(CN)6] + K2SO4 + 2H2O
2[Cr(OH)4]– + 3H2O2 + 2OH–  2CrO24 + 8H2O
CrO 24  + 2H+ + 2H2O2  CrO5(Blue)  + 3H2O

)
4CrO5 + 12H+  4Cr+3 + 7O2 + 6H2O

AI
Mn+2 + OH– + H2O2  MnO2 + 2H2O  This reaction can be utilised to detect NH3

IL
BH
Reducing properties:
(a) Ag2O + H2O2  2Ag + H2O + O2 I(
H
(b) O3 + H2O2 H2O + 2O2
AT

(c) MnO2 + H2O2 + H2SO4  MnSO4 + 2H2O + O2

PbO2 + H2O2  PbO + H2O + O2
IP

(d)
Pb3O4 + 4HNO3  2Pb(NO3)2 + PbO2 + 2H2O
TR

(e)
PbO2 + H2O2  PbO + H2O + O2
H

PbO + 2HNO3  Pb(NO3)2 + H2O

D

Pb3O4 + H2O2 + 6HNO3  3Pb(NO3)2 + 4H2O + O2

D

X2 + H2O2  2HX + O2 [X = Cl, Br]

U

(f)
IR

2KMnO4 + 3H2O2  2KOH + 2MnO2 + 2H2O + 3O2

AN

2MnO 4 + 2OH–  2MnO 24 + H2O + O

2MnO24 + 2H2O 2MnO2 + 4OH– + 2O
2MnO4 + H2O 2MnO2 + 2OH– + 3O
(g) 2KMnO4 + 5H2O2 + 3H2SO4 2MnSO4 + K2SO4 + 5O2 + 8H2O
(h) 2[Fe(CN)6]3– + 2OH– + H2O2 2[Fe(CN)6]4– + 2H2O + O2
(i) NaOCl + H2O2 NaCl + H2O + O2
(j) NaIO4 + H2O2 NaIO3 + H2O + O2

Uses: (i) As a rocket propellant:

NH2.NH2 + 2H2O2 N2 + 4H2O [highly exothermic and large increase in volume]
(ii) In detection of Cr+3, Ti+4 etc.
Ti(SO4)2 + H2O2 + 2H2O H2TiO4 + 2H2SO4
Yellow or orange
Pertitanic acid

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Phone :- 9929617387 Fax :- 0744 - 2405300
 GROUP -VII
HALOGENS
Method of Prepn :
F2 : By electrolysis of KHF2 (which is obtained from CaF2)
CaF2 + H2SO4  CaSO4 + 2HF  KF decreases the m.p. of 
HF + KF  KHF2  the mix. depending upon 
 the composition. 
KHF2 Electrolys
 is
 H2 (at cathode) + F2 (at anode)
Cl2 : (i) By electrolysis of aq. NaCl :

2NaCl + 2H2O  2 NaOH  H 2 + Cl 2

   ( anode )
at cathode
(ii) 2 NaCl   
 2 Na + Cl 2
Electrolysis
( Molten ) ( cathode ) ( anode )
(iii) In laboratory : Oxidising HCl by KMnO4 or MnO2
2KMnO4 + 16HCl 2KCl + 2MnCl2 + 5Cl2 + 8H2O
MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O
From Brine water (contains 65 ppm of Br–)

)
Br2 :

AI
Cl2 + 2Br–  2Cl– + Br2 (Br2 is volalite in nature)

IL
Hence it is collected by

BH
(i) removal of Br2 vapour by stream of air.
(ii) absorbing it into Na2CO3 solution. I(
H
Br2 + 6OH–  Br– + BrO3 + 3H2O
AT

Then acidified to get pure Br2

IP

5Br– + BrO3 + 6H+  3Br2 + 3H2O

TR

I2 : Chille salt petre contains traces of NaIO3 which is reduced to I– by NaHSO3, then
H

oxidation of I– to I2 by IO3 .
D
D

2IO3 +6 HSO 3  2I– + 6SO 24 + 6H+

U
IR


5I– + IO3  3I2 + 3H2O
6H
AN

Physical Prop.:
(i) Electronic configuration : ns2 np5
(ii) Electronegativity order : F > Cl > Br > I
(iii)I.E. order : F > Cl > Br > I
(iv) E.A. order : Cl > F > Br > I
(v) Hydration energy order : F– > Cl– > Br– > I–
(vi) At. radius / ionic : F < Cl < Br < I
(vii)S.R.P. value order: F2 > Cl2 > Br2 > I2 [X2 + 2e  2X–]
(viii)
Bond energy : Cl2 > Br2 > F2 > I2
210 158 126 118 kJ/mol
(ix) m.p. or b.p. order : F2 < Cl2 < Br2 < I2
(x) Oxidising power : F2 > Cl2 > Br2 > I2
(xi) Common ox. state: –1, {–1, +1, +3, +5, +7}
(xii) Physical state: F2  Pale yellow gas
Cl2  greenish yellow gas  HOMO  LUMO
Br2  Dark red liquid  transition is the cause
for the colour
I2  Volatile black solid
CHEMISTRYDigital Chemistry labs
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Phone :- 9929617387 Fax :- 0744 - 2405300
 Q. Liquid I2 conducts electricity. Explain
Ans. Due to its self ionisation 3I2  I3 + I3
Q. X2 + OH–  X– + OX– + H2O but on acidification the disproportionated product gives
 X– + XO 3 + H2O back the same element.
X2 = Cl3 Br2 . I2 . But For F2 i.e. X– + OX– + 2H+  X2 + H2O
5X– + XO 3 + 6H+  3X2 + 3H2O
2F2 + 2NaOH  2NaF + F2O + H2O [X = Cl, Br, I ]
F2O + 2NaOH  2NaF + O2 + H2O
----------------------------------------
2F2 + 4NaOH  4NaF + O2 + 2H2O

HALOGENACID:
Acidity order: HI > HBr > HCl >> HF.(due to hydrogen bonding & less effective overlap with
H atom)
Q. CaF2 used in HF prepn. must be free from SiO2. Explain.

)
AI
Ans. CaF2 + H2SO4  CaSO4 + HF

IL
If SiO2 present as impurity

BH
4HF + SiO2  SiF4 + 2H2O Hence presence of one molecule SiO2
SiF4 + 2HF  H2[SiF6] I(
consumes 6 molecule of HF
H
Q. HF can not be stored in glass vessel. Explain– same reason.
AT

Q. In the salt-cake method of prepn. of HCl, NH4Cl is being used instead of NaCl. Explain.
IP

C
Ans. NaCl + H2SO4 150
  NaHSO 4 + HCl
TR

Insoluble
550C
NaCl + NaHSO4  Na 2SO 4 + HCl
H
D

( Salt Cake )
D

2NH4Cl + H2SO4  2HCl + (NH4)2SO4

U

[NH4HSO4 intermediate is water soluble and easy to handle]

IR

** Another alternative process to avoid the formation of NaHSO4

AN

1
NaCl + SO 2  H 2 O  O 2  Na2SO4 + 2HCl
  2
gaseous mixture

Q. In the similar type of preparation of HBr and HI from bromide ot iodide, H2SO4 can not be used and
H3PO4 is used. Explaain.
Ans. Since H2SO4 is an oxidising agent it oxidises HBr & HI to Br2 and I2 respectively.
2HBr + H2SO4  Br2 + SO2 + 2H2O
Hence. NaBr + H3PO4  NaH2PO4 + HBr
Another process: PBr3 + 3H2O  H3PO4 + 3HBr
Q. Boiling point order of HX : HF > HI > HBr > HCl

Due to H-bonding

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Phone :- 9929617387 Fax :- 0744 - 2405300
 Q. HCl, H2SO4, HNO3 are bases in liquid HF where HClO4 is acid. Comment.
Ans. HCl + HF  H2Cl+ + F– ; H2SO4 + HF  H 3SO 4 + F– ; HNO3 + HF  H 2 NO 3 + P–

But HClO4 + HF  H2F+ + ClO 4

* HF is weak acid but addition of BF3, AsF5, PF5, SbF5 makes it strongly acidic. Explain

OXOACIDS :
HOF : H2O + F2 HOF + HF
HO X: very unstable because
it reacts with both H2O
and F2 as follows :
HOCl  HOF + F  F O + HF
HOBr X 2  H 2O  HOX  HX HOF + H2 O 2H O + HF
HOI  2 2 2

OX– disproportionates in hot solution eg. 3OCl–  2Cl– + ClO 3

)
X = Cl, Br, I

AI
IL
BH
Bleaching Powder :
I(
H
Prepn.: Cl2(g) + Ca (OH) 2 40C
  Ca(OCl)Cl + H2O
AT

Slaked lime
IP

(a) On long standing it undergoes

(i) auto oxiation 6Ca(OCl)Cl  Ca(ClO3)2 + 5CaCl2
TR

CoCl
(ii) 2Ca(OCl)Cl 2  2CaCl2 + O2
H

Cat .
D

(iii) Ca(OCl)Cl + H2O  Ca(OH)2 + Cl2

D
U

Oxidising Prop.:
IR

CaOCl2 + H2S  S + CaCl2+ H2O

AN

CaOCl2 + 2FeSO4 + H2SO4  Fe2(SO4)3 + CaCl2 + H2O

CaOCl2 + KNO2  CaCl2 + KNO3
3CaOCl2 + 2NH3  3CaCl2 + 3H2O + N2
CaOCl2 + 2KI + 2HCl  CaCl2 + 2KCl + H2O + I2
CaOCl2 + 2KI + 2AcOH  CaCl2 + 2KOAc + H2O + I2
CaOCl2 + Na3AsO3  Na3AsO4 + CaCl2
Reaction with acid:
CaOCl2 + 2HCl  CaCl2 + H2O + Cl2 ; Ca(OCl)Cl + H2SO4  CaSO4 + H2O + Cl2
Ca(OCl)Cl + CO2  CaCO3 + Cl2
HXO2 :
BaO2 + 2ClO2  Ba(ClO2)2 + O2 / Ba(ClO2)2 + H 2SO 4  BaSO4 + HClO2
( dil )

Only Known HClO2. It is stable in alkaline solution but disproportionates in acid solution.

5HClO2  4ClO2 + HCl + 2H2O
H

HXO3 : HClO3 > HBrO3 > HIO3 are known and acidic order is as shown

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Phone :- 9929617387 Fax :- 0744 - 2405300
 Prepn:
HClO3 : Cl2 + 6NaOH hot  5NaCl + NaClO3 + 3H2O
Similarly electrolysis of hot halide solution with severe stirring gives the same product.
2Cl– + 2H2O  Cl2 + 2OH– + H2  NaClO  KCl  KClO   NaCl [KClO 3 prep.n ]
Cl2+6NaOH5NaCl+NaClO3+3H2O 
3 3
on cooling

(recycled)  NaClO3  BaCl 2  Ba (ClO 3 ) 2  NaCl 
 first
Properties : Ba (ClO )  H SO  BaSO  HClO
 3 2 2 4 4 3
* 3HClO3 evaporatio
  n
 2ClO2 + H2O + HClO4
* IO3 + 5I– + 6H+  3I2 + 3H2O
 Oxidising property

ClO 3 + 3SO32  Cl– + 3SO 24 

* Disproportionation: 4KClO3 low

  KCl + 3KClO4
temp
absence of catalyst


2KClO3 400 500C
 2KCl + 3O2

)
AI
MnO2 ( Cat.)

IL
BH
HXO4 : NaClO3 + H2O Electrolys
 is
 NaClO4 + H2
KClO4 + H2SO4(conc.)  HClO4 + KHSO4 I(
A : ClO 3 + H2O  ClO 4 + 2H+ + 2e
H

Electrode reaction 
AT

 C : 2H+ + 2e  H2 KClO4 H2SO


4  HClO4
IP

Props: K+ + HClO4  KClO4 + H+

TR

Zn + 2HClO4  Zn(ClO4)2 + H2
Fe + 2HClO4  Fe(ClO4)2 + H2 
H
D

Acidity order : HOX < HXO2 < HXO3 < HXO4

D

Oxidising powder : HOX > HXO2>HXO3 > HXO4

U
IR

Thermal stability: HOX < HXO2 < HXO3 < HXO4

AN

OXIDES OF CHLORINE
(I) +1 +4 +6 +7
Cl 2 O ClO 2 Cl 2 O 6 Cl 2O 7
( Brownish yellow ) ( Pale Yellow )
( liq .  dark red colourless
solid  yellow ) solid

Prepn.: Cl2 does not combine directly to produce its oxides but indirect methods are there.
Cl2O : 2Cl 2 + 2HgO(s)  HgO.HgCl 2 + Cl2O (Brownish yellow gas)
dry in cooled tube Basic Hg ( II ) chloride |

Condensed to orange liq.
Props.:
(i) It dissolves in water : Cl2O + H2O  2HClO
(ii) Explodes violently with NH3.
3Cl2O + 10 NH3  2N2 + 6NH4Cl + 3H2O

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Phone :- 9929617387 Fax :- 0744 - 2405300
 (iii) It is oxidising agent
Cl2O + 2HCl  2Cl2 + H2O

(iv) Structures. Back bonding

(II) ClO2 : Prepn.:
(i) 3KClO3 + 3H 2SO 4  3KHSO4 + HClO4 + 2ClO 2  + H 2O
( powder ) conc. Pale yellow gas
C
(ii) 2HClO3 + H2C2O4 60
  2H2O + 2ClO2 + 2CO2
C
(iii) 2AgClO3 + Cl2 90
  2AgCl + 2ClO2 + O2 [By this reaction pure ClO2 obtained]
ClO2 dissolves in water ClO2  ClO + O
producting dark green 2ClO + H2O  HCl + HClO3
solution which decomposes
in presence of light.
But in alkali gives a mixture of chlorite and chlorate.
2ClO2 + 2NaOH  NaClO2 + NaClO3 + H2O

)
where 2ClO2 + 2NaOH + H2O2  2NaClO2 + O2 + 2H2O

AI
IL
used in bleaching

BH
textles and paper.
* I(
ClO2 does not dimerise because odd e' undergoes delocalisation (in its own vaccant 3d-orbital)
H
* Cl2O4 (Cl.ClO4) is not the dimer of ClO2. Actually it is Cl-perchlorate.
AT

CsClO4 + ClOSO2F  Cs(SO3)F + ClOClO3

IP

Cl2O6 : Possible structures are:

TR
H

ClO 2 ClO 4
D
D
U

liq  dark red

IR

Solid  Yellow
AN

Q. Prove that Cl2O6 is consisting of ClO 2 and ClO 4 .

0C
Prepn.: 2ClO2 + 2O3   Cl2O6 + 2O2
Cl2O6 l 2ClO3 (monomer is paramagnetic)
Reactions : Cl2O6 + H2O  HClO3 + HClO4
Cl2O6 + NaOH  NaClO3 + NaClO4 + H2O
Cl2O6 + HF  ClO2F + HClO4
Cl2O6 + NO2  ClO2 + [NO2]+ [ClO4]–
Cl2O7 (colourless solid): It is the anhydriide of HClO4 and prepared from it by the action of P2O5.
2HClO4 + P2O5  2HPO3 + Cl2O7

Structure :

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 INTER HALOGEN
Types : AX AX3 AX5 AX7
ClF ClF3 ClF5 IF7
BrF BrF3 BrF5
BrCl (ICl3)2 IF5
ICl IF3(unstable)
IBr
IF(unstable)
* 5IF  IF5 + 2I2 [The overall system gains B.E. by 250 kJ/mol ]
* There are never more than two halogens in a molecule.
* Bonds are essentially covalent and b.p. increases as the E.N. difference increases.
* AX5 & AX7 type formed by large atoms like Br & I to accommodate more atoms around it.
* The interhalogens are generally more reactive than the halogens (except F2) due to weaker A–X bonds
compared toX–X bond. Oxohalide is always formedwith larger
Reactions : ICl + H2O  HCl + HOI   halogen present during hydrolysis of
 interhalogen compounds
BrF5  3H 2O  HBrO3  5HF
IF5  3H 2O  HIO3  5HF

)
AI
IF  H O  IOF  2HF less
 7

IL
2 5
 4H 2O  HIO4  7HF

BH
(i) ClF is highly reactive and as a fluorinating agent. I(
6ClF + 2Al  2AlF3 + 3Cl2
H
6ClF + U  UF6 + 3Cl2
AT

6ClF + S  SF6 + 3Cl2

IP

ClF + SF4  SF5Cl

TR

One pecularity with ICl :

H
D
D
U
IR
AN

In IInd case, the attacking species is I+ which has been supporetd by the formation of I+ in fused state
as follows : 3ICl  [I2Cl]+ + [ICl2]–
* ICl3 does not exist
but its dimer exist.  2ICl3 l I2Cl6
Structure is planar.

(Bright yellow solid)

I2Cl6 : liq. has appreciable electrical conductivity like other interhalogens.

I2Cl6 l [ICl2]+ + [ICl4]–
BrF3 l [BrF2]+ + [BrF4]–
IF5 l [IF4]+ + [IF6]–
3ICl l [I2Cl]+ + [ICl2]–
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 Polyhalides :
(i) KI + I2  KI3
(ii) ICl + KCl  K+ [ICl2]–
(iii) ICl3 + KCl  K+[ICl4]–
(iv) IF5 + CsF  Cs+[IF6]–
(v) ICl + KBr  K+[BrICl]–

Rb[ICl2]  RbCl + ICl [not RbI + Cl2]
Here the products on heating depends on the lattice energy of the product halide. The lattice energy of
alkali halide with smaller halogen is highest since the interatomic distance is least.
Structure of I5 , I7 , I82

)
AI
IL
 
in NCH3   I7

BH
in Cs2I8
4

**
I(
Only F3 not known [due to absence of d-orbital] [i.e. Cs2 I3 – I2– I3]
H
AT

I3 , Br3 , Cl 3 are known Cl 3 compounds are very less.

Stability order : I 3  Br3  Cl 3 : depends upon the donating ability of X–.
IP
TR

PSEUDO HALOGEN
There are univalent ion consisting of two or more atoms of which at least one is N, that have properties
H
D

similar to those of the halide ions.

D

e.g.
U

(i) Na-salts are soluble in water but Ag-salts are insoluble in water.
IR

(ii) H-compounds are acids like HX.

AN

(iii) Some anions can be oxidised to give molecules X2.

Anions : Acids Dimer
CN – HCN (CN)2
SCN – HSCN(thiocyanic acid) (SCN)2
SeCN– (SeCN)2
OCN – HOCN (cyanic acid)
NCN2–(Bivalent) H2NCN (cyanamide)
ONC – HONC (Fulminic acid)
N 3 HN3 (Hydrazoic acid)

CN shows maximum similarites with Cl–, Br–, I–
(i) froms HCN
(ii) forms(CN)2
(iii) AgCN, Pb(CN)2, are insoluble
(iv) Interpseudo halogen compounds ClCN, BrCN, ICN can be formed
(v) AgCN is insoluble in H2O but soluble in NH3
(vi) forms large no.of complex.e.g. [Cu(CN)4]3– & [CuCl4]–3
[Co(CN)6]–3 & [CoCl6]–3
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 NOBLE GASES
* I.E. order : He > Ne > Ar > Kr > Xe > Rn
* M.P. order : He < Ne < Ar < Kr < Xe < Rn

* B.P. order : (–269°C) same
* Atomic radius order : Same
* Density order : Same
* Relative abundance : Ar is highest (Ne, Kr, He, Rn)
* "He" (helium) has the lowest b.p (–269°C) of any liquid (lowest of any substance)
(i) It is used in cryoscopy to obtain the very low temperature required for superconductor and
laser.
(ii) It is used in airships though H2 is cheaper and has lower density compared to He because H2
is highly inflammable.
(iii) He is used in preference to N2 to dil. O2 in the gas cylinders used by divers. This is because
N2 is quite soluble in blood, so a sudden change in pressure causes degassing and gives
bubbles of N2 in the blood. This causes the painful condition called bends.
He is slightly soluble so the risk of bends is reduced.

)
AI
* Noble gases are all able to diffuse through glass, rubber, plastics and same metals.

IL
* He liquid can exist in two forms. I-form when changes to II-form at -point temperature many

BH
physical properties change abruptly.
e.g. I(
H
(i) Sp. heat changes by a factor of 10
AT

(ii) Thermal conductivity increases by 106 and it becomes 800 times faster than Cu
IP

(iii) It shows zero resistance

TR

(iv) It can flow up the sides of the vessel

* Ar, Kr, Xe can form clathrate compounds but He, Ne cannot due to their smaller size.
H

What is noble gas hydrate?

D

eg. Xe • 6H2O  formed only when

D


U

Ar • 6H2O  water freezes at high

Kr • 6H2O  pressure together with noble gas
IR
AN

Xe – COMPOUNDS
Xenon Fluorides:–

(1) Xe + F2

(2) H2 reduces Xe – fluorides to Xe

XeF2 + H2  Xe + 2HF and so on
(3) Xe - fluorides oxidise Cl– to Cl2 and I– to I2
XeF2 + 2HCl  2HF + Xe + Cl2
XeF4 + 4KI  4KF + Xe + 2I2
(4) Hydrolysis
XeF2 reacts slowly with water
2XeF2 + 2H2O  2Xe + 4HF + O2
XeF4 and XeF6 react violently with water giving XeO3

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 3
3XeF4 + 6H2O  2Xe + XeO3 + 12HF + O
2 2
XeF6 + 3H2O  XeO3 + 6HF

(explosive, white hygroscopic solid)

(5) SiO2 also converts XeF6 into XeOF4

2XeF6 + SiO2  SiF4 + 2XeOF4
violet
Similarly, XeO3 + XeOF4  2XeO2F2 | XeO3 + 2XeF6  3XeOF4
(6) Xe-fluorides are also hydrolysed in alkaline medium
2XeF2 + 4OH–  2Xe + 4F– + 2H2O + O2
XeF6 + 7OH–  HXeO 4– + 3H2O + 6F–
Xenate ion

2HXeO 4– + 2OH–  XeO 64 –  + Xe + 2H2O + O2

)
(7) They are used as fluorinating agent

AI
2SF4 + XeF4  2SF6 + Xe

IL
Pt + XeF4  PtF4 + Xe

BH
(8) Act as a fluoride donor
XeF2 + MF5  [XeF]+ [MF6]– I(
(M = As, Sb, P)
H
BF3  [XeF5]+ [ BF4– ]
AT

XeF6 +
XeF6 + HF  [XeF5]+ [HF2]–
IP

(9) Act as Fluoride acceptor also:

TR

XeF6 + RbF/CsF  Rb+/Cs+ [XeF7]–

H


2Cs+[XeF7]–  XeF6 + Cs2[XeF8]
D
D

50C
U

XeF4 + MF  M+ + XeF5

IR
AN

(alkali metals fluoride)

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