Shubhang Garodia

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)
3
Al + 3H2O  Al(OH)3 + H
2 2
(iii) B + HCl  no reaction
B + H2SO4 (dil) no reaction
2B + 3H2SO4 (conc.)  2H3BO3 + 3SO2
B + 3HNO3  H3BO3 + 3NO2
2Al + 6H2SO4  Al2(SO4)3 + 3SO2 + 6H2O
Al + HNO3(80%)  Al2O3 (passive layer) and does not react further.
(iv) 2B + 2NaOH + 2H2O  2NaBO2 + 3H2
2Al + 2NaOH + 2H2O  2NaAlO2 + 3H2
(v) 2B + N2  2BN 2Al + N2  2AlN
4B + C  B4C 4Al + 3C  Al4C3
(vi) 3Mg + 2B  Mg3B2

Preparation of B2H6 :
(i) Mg3B2 + HCl  B2H6 + B4H10 + B5H9 etc.
(10%)

(ii) B4H10 
 B2H6 + H2 + higher borane
100C
Electric
(iii) BCl3 (or B Br3) + 6H2      B2H6 + 6HCl
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 spontaneously

(ii) B2H6 + H2O (Cold is enough)  H3BO3 + 6H2

 Shubhang Garodia
(iii)

*
anh .
B2H6 + HCl (dry)  B2H5Cl + H2

Heating of boric acid :

AlCl3

C C
H3BO3 100
  HBO2 140
  H2B4O7 

B2O3
red hot

Metaboric acid tetraboric acid Glassy mass

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

 Na2 · 6H2O

Sodium peroxy borate used in washing powder

as whitener
Preparation of Borax :
2CaO · 3B2O3 + 2Na2CO3  2CaCO3 +Na2B4O7 + 2NaBO2
Colemanite

NaBO2 +  Na2B4O7·10H2O  Concentrated Na 2 B 4O 7  NaBO 2

   
in Filtrate  
as residue  and allowed to
crystallise out in solution
and filtered

[4NaBO2 + CO2  Na2B4O7 + Na2CO3]

Na2B4O7 ·10H2O 
as 2nd Crop. of the
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 300
  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

AlCl3 preparation:

(i) 2Al + 6HCl (vap.)  2AlCl3 + 3H2

(over heated) dry
 Shubhang Garodia
(ii) Al2O3 + 3C + 3Cl2 

 2AlCl3 (vap.) + 3CO
1000C

Solid anh. AlCl3

Props:
(i) Its anhydrous formed 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

(ii) Dyeing, drug. & perfumes etc.

Alumns: M2SO4, M '2 (SO4)3 ·24 H2O Props: Swelling characteristics

where M = Na+, K+, Rb+, Cs+, As+, Tl+, NH 4

M' = Al+3, Cr+3, Fe+3, Mn+3, Co+3
K2SO4·Al2(SO4)3·24H2O Potash alum
(NH4)2SO4·Al2(SO4)3·24H2O Ammonium alum
K2SO4·Cr2(SO4)3 ·24H2O Chrome alum
(NH4)2SO4·Fe2(SO4)3·24H2O Ferric alum

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

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

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

C2 unit: CaC2, BaC2

CaC2 + 12H2O — Ca(OH)2 + CH  CH

C3 unit: Mg2C3
Mg2C3 + H2O — 2Mg(OH)2 + CH3–C  CH : Propyne
 Shubhang Garodia
(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
2000 to
SiO2 + 2C(coke)   Si + 2CO
2500C
2000 to
Si + C   SiC diamond like structure colourless to yellow solid in room temp.
2500C

when impurity is present
Properties
(i) It is very hard and is used in cutting tools and abrassive powder(polishing material)
(ii) It is very much inert
(iii) It is not being affected by any acid except H3PO4

CO
— 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 + S2O32  2I– + S4O 62
(iii) What are its absorbers
(a) Cu2Cl2 : CuCl + CO + 2H2O — [CuCl(CO)(H2O)2]

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.
 Shubhang Garodia
Teflon —(CF2  CF2—

CHCl3 + HF   
)n
heated with heated Polymerisa tion at
 CF2HCl  CF2=CF2     —(CF2  CF2—
SbFCl 4 again
)n
high temp. and press
catalyst HCl

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

SILICON (Si)
Occurrence
Silicon is the second most abundant (27.2%) element after oxygen (45.5%) in the earth's crust. It does
not occur free in nature but in the combined state, it occurs widely in form of silica and silicates. All
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.
Silica is found in the free state in sand, flint and quartz and in the combined state as silicates like
(i) Feldspar – K2O. Al2O3. 6SiO2
(ii) Kaolinite – Al2O3. 2SiO2. 2H2O
(iii) Asbestos – CaO. 3MgO. 4SiO2
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) high temperature
  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.
(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.
 Shubhang Garodia
(iv) Reaction with carbon : Silicon combines with carbon at 2500 °C forming silicon carbide (SiC) known
as carborundum.
Si(s) + C(s) 2500C
  SiC(s)
Carborundum is an extremely hard substance next only to diamond. It is mainly used as an abrasive and
as a refractory material.
USES:

(i) Silicon is added to steel as such or more usually in form of ferrosilicon (an alloy of Fe and Si) to make it
acid-resistant.
(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.
COMPOUNDS OF SILICON:
What is silane. SinH2n+2 SiH4 & Si2H6
Only these two are found
Higher molecules are not formed.  Si can't show catanetion property
dil. H SO
Hot Mg + Si–vap  Mg2Si   2
4  MgSO4 + SiH4 + Si2H6 + ...
Ques. SiH4 is more reactive than CH4. Explain
Reasons
(i) Si   H in C  H 
C ­ electro­ve 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.

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(3-D silicate)

R R R

| | |
R2SiCl2 + H2O  
2 HCl
 R2 Si(OH) 
2 H O  O  Si  O  Si  O  Si O
2 | | |
R R R
Linear silicone
O
H O
R2CCl2 + H2O  2
 R2C(OH)2   ||
2 HCl
looses H 2O R CR
readily
Silicones may have the cyclic structure also having 3, 4, 5 and 6 nos. of silicon atoms within the ring.
Alcohol analogue of silicon is known as silanol
 Shubhang Garodia R
|
|
R
|
R  Si  O  Si  R
|
O O
| |
R  Si  O  Si  R
| |
R R

cyclic silicone
not planar
H 2O 2 H O
R3SiCl  R3SiOH   R3Si-O-SiR3

Silanol
R R
H O 2 H O | |
R2SiCl2 + R3SiCl   2
     Si  O  Si    
hydrolysis heating
condensati on | |
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

| |
O R O
| | |

RSiCl3 + H2O  R-Si(OH)3  R  Si  O  Si  O  Si  O 
| | |
O O R
| |
cross linked silicone
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.
(4) As a lubricant in the gear boxes.
SILICA (SiO2)
Occurrence:
Silica or silicon dioxide occurs in nature in the free state as sand, quartz and flint and in the combined
state as silicates like, Feldspar : K2O.Al2O3.6SiO2, Kaolinite : Al2O3. 2SiO2. 2H2O etc.
PROPERTIES:
(i) Pure silica is colourless, but sand is usually coloured yellow or brown due to the presence of ferric oxide
as an impurity.
(ii) Silicon dioxide is insoluble in water and all acids except hydrofluoric acid.
SiO2(s) + 4HF(l)  SiF4(l) + 2H2O(l)
 Shubhang Garodia
(iii) It also combines with metallic oxides at high temperature giving silicates e.g.

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) high temp.
 Na2SiO3(s) + CO2(g)
SiO2(s) + Na2SO4(s) high temp.
 Na2SiO3(s) + SO3(g)
3SiO2(s) + Ca3(PO4)2(s) high temp.
 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.
| | |
— 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.
(iv) Silica gel (SiO2.xH2O) is used as a desiccant (for absorbing moisture) and as an adsorbent in
chromatography.

TIN & ITS COMPOUND

1500C
(i) Sn  
 SnO2 [Burns with a bright flame]
O2

(ii) Sn + 2H2O
(iii) Reaction with acid.
 Shubhang Garodia
Sn

(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
strongly
Oxides:  
 Sn + O2
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
But conc. hot alkali behaves differently.
2SnO + 2KOH or NaOH  K2SnO3 or Na2SnO3 + Sn + H2O
* Bi(OH)3 + [Sn(OH)4]2–  Bi  + [Sn(OH)6]2–
(black)
SnO2 + 2H2SO4   Sn(SO4)2 + 2H2O

(Soluble only in hot conc. H2SO4)
SnO2+ 2NaOH  Na2SnO3 + H2O

SnCl2 & SnCl4 :

(1) Sn + 2HCl (hot conc.) SnCl2 + H2
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
 Shubhang Garodia
SnCl4 + 2HCl  H2SnCl6(Hexachloro stannic (IV) acid)
SnCl4+ 2NH4Cl  (NH4)2 SnCl6 (colourless crystalline compound known as " pink salt ")
(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 + SnCl2  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.

Mosaic gold : SnS2 yellow crystalline substance :

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

* Distinction of Sn+2 / Sn+4 :

2
(i) H2S (ii) Hg+2 (iii) Fe+3 + K3[Fe(CN)6] Sn
 Blue ppt.

COMPOUNDS OF LEAD
Oxides of lead :
(i) PbO (ii) Pb3O4 (Red) (iii) Pb2O3(reddish yellow) (Sesquioxide)
(iv) PbO2 (dark brown)

(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.

(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
 Shubhang Garodia
(3) PbO2 : Insoluble in water. HNO3, But reacts with HCl + H2SO4(hot conc.) and in hot NaOH / KOH.
(i) Pb3O4 + 4HNO3 2Pb(NO3)2 + PbO2 + 2H2O
(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
PbO2 + 2NaOH  Na2PbO3 + H2O
PbO2 : Powerful oxidising agent :
(i) PbO2 + SO2  PbSO4 [spontaneously]
(ii) PbO2 + 2HNO3 + (COOH)2  Pb(NO3)2+ 2CO2 + 2H2O
(iii) 2Mn(NO3)2 + 5PbO2 + 6HNO3  3Pb(NO3)2 + 2PbSO4 + 2HMnO4 + 2H2O

PbCl4 : Exists as H2[PbCl6]

PbO2 + 4HCl  PbCl4 + 2H2O
{ice cold conc. saturated with Cl2}
PbCl4 + 2HCl  H2PbCl6

TetraEthyl lead :
4Na–Pb(alloy 10%–Na.) + 4C2H5Cl(vap.)  3Pb + Pb(Et)4 + 4NaCl
It is antiknocking agent.
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
2NaN3  2Na + 3N2  by this method
(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
-------------------------------
3Cl2 + 8NH3  N2 + 6NH4Cl
In this method NH3 conc. should not be lowered down beyond a particular limit.
3Cl2 + NH3  NCl3 + 3HCl
(Trimendously explosive)
Properties of N2 :
(i) It is inert due to high bond energy.
(ii) It is absorbed by hot metal like Ca, Mg, Al etc.
3Ca + N2  Ca3N2
Bright hot 2Al + N2  2AlN
 Shubhang Garodia 
Al2O3 + 3C + N2  2AlN + 3CO
(BN)x : Inorganic graphile
White slippery solid having 2D-sheet structure.
3000C
(BN)x    (BN)x
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
CaC2 + N2 1000C
   CaNCN
 C
cyanamide ion nitro lim
It is a very good fertiliser.
Cyanamide ion

(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
NH3 preparation :
(i) Nitrate or nitrite reduction : NO3 / NO 2 +Zn or Al + NaOH  NH3 + [Zn(OH)4]2– or [Al(OH)4]–
(ii) Metal nitride hydrolysis : N3– + 3H2O  NH3 3OH–
C
(iii) Haber's process : N2 + 3H2 450
  2NH3
2001000 atm

catalyst Fe / Mo
Q.1 NH3 can't be dried by H2SO4, P2O5 and anh.CaCl2 because:
2NH3 + H2SO4  (NH4)2 SO4
H2O + NH3 + P2O5  (NH4)3 PO4
CaCl2 + 8NH3  CaCl2 . 8NH3
forms adduct
Quick lime is used for this purpose
CaO + H2O  Ca(OH)2 (base)  Hence no
NH3 (base)  interaction
 Shubhang Garodia
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

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

(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
more solvation of H+ in NH3.
(iv) Hydrolysis and Ammonolysis occurs is a same way.

SiCl4 + 4H2O  4HCl + Si(OH)4  SiO2 + 2H2O
SiCl4 + 8NH3  4NH4Cl + Si(NH2)4   Si3N4 + NH3
Rate of hydrolysis and Ammonolysis will be affected by the presence of HCl vapour & NH4Cl vapour
respectively.
NH 4  Salts Pr eparation
 Shubhang Garodia
OXIDES OF NITROGEN
Oxides of nitrogen Structure Physical state Colour of gas
— 
N2 O NNO Gas Colourless
NO Gas Colourless
N2 O 3 ;O  N O  N Blue liquid (–30°C)
||
O

NO 2 l Gas Brown

N2 O 5 Colourless solid – (no existance in gas phase)

Preparations:
1. N2 O
(i) NH4NO3  N2O + H2O
(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
(ii) KNO3 + FeSO4 + H2SO4  Fe2(SO4)3 + K2SO4 + NO + H2O
FeSO4 + NO  FeSO4 . NO   FeSO4 + NO
(iii) Oswald process–Restricted oxidation of NH3.
Industrial process.
6 atm
4NH3 + 5O2    4NO + 6H2O
750C, Pt Cat

3. N2 O3
(i) HNO3 + As2O3  H3AsO4 + N2O3
(ii) NO  NO2 )
Cu + HNO3(6M)  Cu(NO3)2 + (
 
| Cool(30C)

Blue liq ( N2O3 )

4. NO2
 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. N2 O5
(i) 2HNO3 + P2O5  2HPO3 + N2O5
(ii) 4AgNO3 + 2Cl2(dry gas)  4AgCl + 2N2O5 + O2
 Shubhang Garodia
Properties:
(I) Decoposition Behaviour
 C 900C
(i) N2O 500   2N2 + O2
(ii) 2NO 800 C
  N2 + O2
(iii) N2O3 Room
 temp
. NO2 + NO

(Blue liq.) at (–30°C)

(iv) 2NO2 620C

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

C C
1
(v) N 2O 5 30
  N 2O5 40   2NO2 + 2 O2
colourless yellow
solid liq .
(II) Reaction with H2O & NaOH
H2 O NaOH
(i) N2O : Fairly soluble in water and
produces neutral solution -------
(ii) NO : Sparingly soluble in water
and produces neutral soln. -------
(iii) N2O3: 2HNO2
Hence it is known as
anhydride of HNO2 NaNO2
(iv) NO2: HNO2 + HNO3
called as mixed anhydride NaNO2 + NaNO3
(v) N2O5: 2HNO3
called as anhydride of NaNO3
HNO3
Other properties:
N2O : 2N2O  2N2 + O2 mixture contains
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
(iii) It is being absorbed by FeSO4 solution.
 Shubhang Garodia
(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
N2O3 : No more properties.
NO2 : (1) It is having oxidising property.
S + NO2  SO2 + NO
P + NO2 P2O5 + NO
C + NO2  CO2 + NO
SO2 + NO2 + H2O  H2SO4 + NO
H2S + NO2  H2O + S + NO
CO + NO2  CO2 + NO
NO not formed : 2KI + 2NO2 I2 + 2KNO2
(2) Reducing property of NO2.
KMnO4 + NO2 + H2SO4  K2SO4 + MnSO4 + HNO3 + H2O
4 5
O30  2 NO 2  O 02  N 2 O5

not the reduction product of O3

N2O5 :
I2 + 5N2O5  I2O5 + 10NO2
I2O5 is used for the estimation of CO
I2O5 + 5CO  I2 + 5CO2
I2 + 2S2O 32  2I– + S4O62
N2O5 + NaCl  NaNO3 + NO2Cl
This likes proves that N2O5 is consisting of ion pair of NO 2 & NO 3
Oxyacids of N :
HNO2 :
Preparation
(i) M-nitrite 
dil. acid
 HNO2
HCl or H 2SO 4

(ii) N2O3 + H2O  2HNO2

Properties
(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
 Shubhang Garodia
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–
Nitric acid (HNO3)
It was named aqua fortis (means strong water) by alchemists.
Preparation
(i) Laboratory Method
KNO3 + conc. H2SO4  KHSO4 + HNO3(vap)
vapours of nitric acid evolved are condensed in a glass receiver.
(ii) Industrial Preparation
(A) Birkeland Eyde Process or arc process
0
3000 C
step 1 N2 + O2   2NO - heat
Electric Arc

step 2 NO + O2  NO2
step 3 NO2 + H2O  HNO2 + HNO3
step 4 HNO2  HNO3 + NO + H2O
(B) Ostwald’s Process
Pt . gauze
step 1 NH3 + O2 700  NO + H O + heat
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.
 4NO2 + 2H2O + O2
4HNO3 Sunlight
The yellow colour of the acid can be removed by warming it to 60-80oC and bubbling dry air through it.
It has extremely corrosive action on the skin and causes painful sores.
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
 Shubhang Garodia
(2) Carbon is oxidised to carbonic acid
C + 4HNO 3  H 2CO 3 + 4NO 2 + 2H 2O
(3) Phosphorus is oxidised to orthophosphoric acid.
2P + 10HNO 3  2H 3PO 4 + 10NO 2 + 2H 2O
conc. and hot
(4) Iodine is oxidised to iodic acid
I 2 + 10HNO 3  2HIO 3 + 10NO 2 + 4H 2O
conc. and hot
(ii) Oxidation of metalloids
Metalloids like non-metals also form highest oxyacids
(1) Arsenic is oxidised to arsenic acid
2As + 10HNO 3  2H 3AsO 4 + 10NO 2 + 2H 2O
or As + 5HNO 3  H 3AsO 4 + 5NO 2 + H 2O
conc. and hot
(2) Antimony is oxidised to antimonic acid
Sb + 5HNO 3  H 3SbO 4 + 5NO 2 + H 2O
conc. and hot
(3) Tin is oxidised to meta-stannic acid.
Sn + 2HNO 3  H 2SnO3 + 4NO 2 + H 2O
(iii) Oxidation of Compounds:
(1) Sulphur dioxide is oxidised to sulphuric acid
SO 2 + 2HNO 3  H 2SO 4 + 2NO 2
(2) Hydrogen sulphiode is oxidised to sulphur
H 2S + 2HNO 3  2NO 2 + 2H 2O + S
(3) Ferrous sulphate is oxidised to ferric sulphate in presence of H2SO 4
6FeSO 4 + 3H 2SO 4 + 2HNO 3  3Fe 2(SO 4) 3 + 2NO + 4H 2O
(4) Iodine is liberated from KI.
6KI + 8HNO 3  6KNO 3 + 2NO + 3I 2 + 4H 2O
(5) HBr, HI are oxidised to Br 2 and I 2, respectively.
2HBr + 2HNO 3  Br 2 + 2NO 2 + 2H 2O
Similarly, 2HI + 2HNO 3  I 2 + 2NO 2 + 2H 2O
(6) Ferrous sulphide is oxidised to ferrous sulphate
FeS + HNO 3  Fe 2(SO 4) 3 + 8NO 2 + 4H 2O
(7) Stannous chloride is oxidised to stannic chloride is presence of HCl.
2HNO 3 + 14H  NH 2OH + NH 3 + 5H 2O
Hydroxylamine
NH 3 + HNO 3  NH 4NO 3
------------------------------------------------------------------------------
7SnCl2 + 14HCl + 3HNO 3  7SnCl4 + NH 2OH + NH 4NO 3 + 5H 2O
(8) Cane sugar is oxidised to oxalic acid.
C 12 H 22 O 11 + 36HNO 3  6(COOH) 2 + 36NO 2 + 23H 2O
(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
nascent form. Before this hydrogen is allowed to escape, it reduces the nitric acid into number of products
like NO2, NO, N2O, N2 or NH3 according to the following reactions:
Metal + HNO3  Nitrate + H
2HNO3 + 2H  2NO + 2H2O
2HNO3 + 6H 2NO + 4H2O
2HNO3 + 10H  N2 + 6H2O
2HNO3 + 16 H  2NH3 + 6H2O
 Shubhang Garodia
The progress of the reaction is controlled by a number of factors:
(a) the nature of the metal,
(b) the concentration of the acid,
(c) the temperature of the reaction,
(d) the presence of other impurities.
--------------------------------------------------------------------------------------------------------
Concentration of Metal Main Products
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
--------------------------------------------------------------------------------------------------------
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:

PHOSPHOROUS

INTERCONVERSION OF WHITE 'P' & RED 'P'

240 250C
White 'P'     Red 'P'
in an inert atm. like
N 2 or CO 2
I 2 : catalyst

550C
Red 'P' heated
 to  White 'P'
in an inert atom and then
rapid cooling to room temp.
Shubhang Garodia
PREPRATION OF WHITE '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
– H2O
meta phosphoric acid

C
12C + 4HPO3 1000
   2H2 + 12CO + P4
Coke white 'P'
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
(ii) PH4I + KOH  KI + PH3 + H2O 

(PH3 + HI)
 Purest PH 3
(iii) 2AlP + 3H2SO4  Al2(SO4)3 + PH3 
PHYSICAL PROPERITIES
(i) It is having 'rotten fish' smell
(ii) It is soluble in CS2 and insoluble in water.
(NH3 is soluble in water)
NH 4 + OH–

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
 Shubhang Garodia
(iv)
electrical
(iii) PH3 + 4N2O   H3PO4 + 4N2
sparking
2PH3 + 3CuSO4  Cu3P2 + 3H2SO4
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

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

(ii) Monoclinic or -sulphur.
(iii) -Sulphur
Amorphous forms are
(i) Plastic sulphur
(ii) Milk of sulphur
(iii) Colloidal sulphur
* Viscosity of 'S' with temperature:
m.p. of 'S' 112.8°C.
(i) > 112.8°C to 160°C  slow decreases due to
S8 rings slip and roll over one another easily.
(ii) > 160°C, increases sharply due to breaking of
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
 Shubhang Garodia
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
With metal (hot)
2Na + H2S Na2S + H2
Cu + H2S CuS + H2
Pb + H2S PbS + H2
With metal oxide (hot)
CaO + H2S CaS + H2O
ZnO + H2S ZnS + H2O
Metal ion + H2S M-Sulphides
** (i) Alkali-sulphide  water soluble
(ii) Alkaline earth–sulphide  sparingly soluble
(iii) Al2S3 & Cr2S3 + 6H2O  Al(OH)3 or Cr(OH)3 + 3H2S
Test :
(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
Props: (i) Incombustible gas, but heated K burns in SO2
4K + 3SO2  K2SO3 + K2S2O3
 Shubhang Garodia
Na2SO3 + SO2

Na2S + 3Na 2SO 4

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

4FeCl2 + SO2 + 4HCl  4FeCl3 + H2O + S

6SnCl2 + 2SO2 + 8HCl  5SnCl4 + 4H2O + SnS2 (Yellow solid)
150C
(ii) SO2 + 2H2SO3   2H SO + S
sealed tube 2 4

* FeSO4  Fe2O3 + SO2 + SO3

Fe2(SO4)3  Fe2O3 + 3SO3

H2SO4 & SO3 :

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 bicarbonates

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
2Ag + 2H2SO4  Ag2SO4 + SO2 + 2H2O
Hg + 2H2SO4  HgSO4 + SO2 + 2H2O
 Shubhang Garodia
(e) NaCl HCl
Ca3(PO4)2  H3PO4

FeS  H2S
CH3 CO2 Na   H SO   AcOH
2 4
NaNO3  HNO3
CaF2  HF
NaNO2 
 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

2 H SO
C6H12O6  4  6C

6H O 2

2 H SO
(COOH)2  4  CO + CO
 H SO
PhH 2 
4  Ph–SO3H
H O 2
2
HCO2H  CO
H O 2
SODIUM THIOSULPHATE
Prepn.:
(i) Na2SO3 soln. + S (powder) boiling
  Na2S2O3 eavporatio
 n  Na2S2O3.5H2O, monoclinic crystal

 Na 2 CO 3  2SO 2  H 2 O  2 NaHSO 3  CO 2
2 NaHSO  Na CO  Na SO  H O  CO
 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)
Reaction: (i) Na2S2O3 + I2  S4O 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
 Shubhang Garodia
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.
 [b.p. of O –183°C ; b.p. of liq. air is –190°C]
2
 Oxidising property of O3
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
It is next to F2. [above 2.07 V, only F2, F2O are there]
(i) Metal Sulphides to Sulphates.
MS + 4O3  MSO4 + 4O2 [M = Pb, Cu, Zn, Cd]
(ii) 2HX + O3  X2 + H2O + O2 [X = Cl, Br, I]
(iii) NaNO2 + O3 NaNO3 + O2
Na2SO3 + O3 Na2SO4 + O2
Na2AsO3 + O3  Na2AsO4 + O2
(iv) Moist S, P, As + O3 
S + H2O + 3O3  H2SO4 + 3O2
2P + 3H2O + 5O3  2H3PO4 + 5O2
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 

alk . KI + 3O3  KIO3 + 3O2 
(c)  KI + 4O  KIO + 4O 
 3 4 2
(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
Uses: (i) Sterilising water
(ii) Detection of position of the double bond in the unsaturated compound.
 Shubhang Garodia
Method of preparation:
(i)
H2 O 2
Na2O2 + H2O (ice cold water)  2NaOH + H2O2
(ii) BaO2 + H2SO4  BaSO4 + H2O2
Instead of H2SO4, H3PO4 is added now-a-days because H2SO4 catalyses the decomposition of H2O2
whereas H3PO4 favours to restore it.
3BaO2+2H3PO4  Ba3(PO4)2+3H2O2 and Ba3(PO4)2+3H2SO43BaSO4+ 2H3PO4 (reused again)
(iii) Electrolysis of 50% H2SO4 using high current density.
2H2SO4 l 2H+ + 2H 2SO 4
2H 2SO 4  H2S2O8 + 2e. [At anode] [At cathode 2H+ + 2e  H2]
H2S2O8 + 2H2O  2H2SO4 + H2O2

H / Pd O
(iv) 2 
 2
 + H2O2

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
(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–  2CrO 24 + 8H2O
CrO 24 + 2H+ + 2H2O2  CrO5(Blue)  + 3H2O
4CrO5 + 12H+  4Cr+3 + 7O2 + 6H2O
Mn+2 + OH– + H2O2  MnO2 + 2H2O  This reaction can be utilised to detect NH3
Reducing properties:
(a) Ag2O + H2O2  2Ag + H2O + O2
(b) O3 + H2O2 H2O + 2O2
(c) MnO2 + H2O2 + H2SO4  MnSO4 + 2H2O + O2
(d) PbO2 + H2O2  PbO + H2O + O2
(e) Pb3O4 + 4HNO3  2Pb(NO3)2 + PbO2 + 2H2O
PbO2 + H2O2  PbO + H2O + O2
PbO + 2HNO3  Pb(NO3)2 + H2O
Pb3O4 + H2O2 + 6HNO3  3Pb(NO3)2 + 4H2O + O2
(f) X2 + H2O2  2HX + O2 [X = Cl, Br]
 Shubhang Garodia
2KMnO4 + 3H2O2  2KOH + 2MnO2 + 2H2O + 3O2
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 + 2H2 SO4
Yellow or orange
Pertitanic acid

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
Electrolys is
 2 Na + Cl 2
(ii) 2 NaCl   
( Molten ) ( cathode ) ( anode )
(iii) In laboratory : Oxidising HCl by KMnO4 or MnO2
2KMnO4 + 16HCl 2KCl + 2MnCl2 + 5Cl2 + 8H2O
MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O
Br2 : From Brine water (contains 65 ppm of Br–)
Cl2 + 2Br–  2Cl– + Br2 (Br2 is volalite in nature)
Hence it is collected by
(i) removal of Br2 vapour by stream of air.
(ii) absorbing it into Na2CO3 solution.
Br2 + 6OH–  Br– + BrO3 + 3H2O
Then acidified to get pure Br2
5Br– + BrO3 + 6H+  3Br2 + 3H2O
I2 : Chille salt petre contains traces of NaIO3 which is reduced to I– by NaHSO3, then
oxidation of I– to I2 by IO3 .
2IO3 +6 HSO3  2I– + 6SO 24 + 6H+

6H
5I– + IO3  3I2 + 3H2O
 Shubhang Garodia
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– + XO3 + H2O back the same element.
X2 = Cl3 Br2 . I2 . But For F2 i.e. X– + OX– + 2H+  X2 + H2O
5X– + XO3 + 6H+  3X2 + 3H2O
2F2 + 2NaOH  2NaF + F2O + H2O [X = Cl, Br, I ]
F2O + 2NaOH  2NaF + O2 + H2O
----------------------------------------
2F2 + 4NaOH  4NaF + O2 + 2H2O

HALOGEN ACID:
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.
Ans. CaF2 + H2SO4  CaSO4 + HF
If SiO2 present as impurity
4HF + SiO2  SiF4 + 2H2O Hence presence of one molecule SiO2
SiF4 + 2HF  H2[SiF6] consumes 6 molecule of HF
Q. HF can not be stored in glass vessel. Explain– same reason.
Q. In the salt-cake method of prepn. of HCl, NH4Cl is being used instead of NaCl. Explain.
C
Ans. NaCl + H2SO4 150
  NaHSO 4 + HCl
Insoluble

NaCl + NaHSO4 550C

  Na 2SO 4 + HCl
(Salt Cake )

2NH4Cl + H2SO4  2HCl + (NH4)2SO4

[NH4HSO4 intermediate is water soluble and easy to handle]
** Another alternative process to avoid the formation of NaHSO4
1
NaCl + SO 2  H 2O  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
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
 Shubhang Garodia
OXOACIDS :
HOF : H2O + F2 HOF + HF
HO X: very unstable because
it reacts with both H2O
and F2 as follows :
HOCl  HOF + F2  F2O + HF
HOBr X 2  H 2O  HOX  HX HOF + H2O  H2O2 + HF
HOI 
OX– disproportionates in hot solution eg. 3OCl–  2Cl– + ClO 3
X = Cl, Br, I

Bleaching Powder :

Prepn.: Cl2(g) + Ca (OH) 2 40C

  Ca(OCl)Cl + H2O
Slaked lime
(a) On long standing it undergoes
(i) auto oxiation 6Ca(OCl)Cl  Ca(ClO3)2 + 5CaCl2
CoCl
(ii) 2Ca(OCl)Cl 2  2CaCl2 + O2
Cat .
(iii) Ca(OCl)Cl + H2O  Ca(OH)2 + Cl2
Oxidising Prop.:
CaOCl2 + H2S  S + CaCl2+ H2O
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.
H
5HClO2  4ClO2 + HCl + 2H2O
HXO3 : HClO3 > HBrO3 > HIO3 are known and acidic order is as shown
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 3  KCl  KClO 3   NaCl [KClO 3 prep.n ]
Cl2+6NaOH5NaCl+NaClO3+3H2O  on cooling
(recycled) 
NaClO 3  BaCl 2  Ba (ClO 3 ) 2  NaCl 
 first
Properties : 
Ba (ClO 3 ) 2  H 2SO 4  BaSO 4  HClO 3
* 3HClO3 evaporatio
 n  2ClO2 + H2O + HClO4
* IO3 + 5I– + 6H+  3I2 + 3H2O
 Oxidising property

ClO 3 + 3SO32  Cl– + 3SO 24 
*
Shubhang Garodia
Disproportionation: 4KClO3 low
 temp
 KCl + 3KClO4
absence of catalyst


2KClO3 400 500C
 2KCl + 3O2
MnO 2 ( Cat .)

HXO4 : NaClO3 + H2O Electrolys

  is
 NaClO4 + H2
KClO4 + H2SO4(conc.)  HClO4 + KHSO4
A : ClO 3 + H2O  ClO 4 + 2H+ + 2e
Electrode reaction 
 C : 2H+ + 2e  H2 KClO4 H2SO
4  HClO4

Props: K+ + HClO4  KClO4 + H+
Zn + 2HClO4  Zn(ClO4)2 + H2
Fe + 2HClO4  Fe(ClO4)2 + H2 
Acidity order : HOX < HXO2 < HXO3 < HXO4
Oxidising power : HOX > HXO2>HXO3 > HXO4
Thermal stability: HOX < HXO2 < HXO3 < HXO4

OXIDES OF CHLORINE
(I) +1 +4 +6 +7
Cl 2O ClO 2 Cl 2O 6 Cl 2O 7
( Brownish yellow ) ( Pale Yellow ) colourless
( liq .  dark red
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
(iii) It is oxidising agent
Cl2O + 2HCl  2Cl2 + H2O

(iv) Structures. Back bonding

(II) ClO2 : Prep .: n

(i) 3KClO 3 + 3H 2SO 4  3KHSO4 + HClO4 + 2ClO 2  + H2O

( powder ) conc . Pale yellow gas
60C
(ii) 2HClO3 + H2C2O4  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
used in bleaching
textles and paper.
* ClO2 does not dimerise because odd e' undergoes delocalisation (in its own vaccant 3d-orbital)
 Shubhang Garodia
* Cl2O4 (Cl.ClO4) is not the dimer of ClO2. Actually it is Cl-perchlorate.
CsClO4 + ClOSO2F  Cs(SO3)F + ClOClO3
Cl2O6 : Possible structures are:

ClO 2 ClO 4

liq  dark red

Solid  Yellow
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 :

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.
Reactions : ICl + H2O  HCl + HOI Oxohalide is always formedwith larger
 halogen present during hydrolysis of
BrF5  3H 2O  HBrO3  5HF 
 interhalogen compounds
IF5  3H 2O  HIO3  5HF
IF  H O  IOF  2HF less
 7 2 5
 4 H 2 O  HIO 4  7 HF
(i) ClF is highly reactive and as a fluorinating agent.
6ClF + 2Al  2AlF3 + 3Cl2
6ClF + U  UF6 + 3Cl2
6ClF + S  SF6 + 3Cl2
ClF + SF4  SF5Cl
 Shubhang Garodia
One pecularity with ICl :

In IInd case, the attacking species is I+ which has been supporetd by the formation of I+ in fused state
as follows : 3I Cl  [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]–

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 , I 7 , I82

 
in NCH 3   I7
4
in Cs2I8

** Only F3 not known [due to absence of d-orbital] [i.e. Cs2 I3 – I2– I3]
I3 , Br3 , Cl 3 are known Cl 3 compounds are very less.
Stability order : I3  Br3  Cl 3 : depends upon the donating ability of X–.
 Shubhang Garodia
PSEUDO HALOGEN
There are univalent ion consisting of two or more atoms of which at least one is N, that have properties
similar to those of the halide ions. E.g.
(i) Na-salts are soluble in water but Ag-salts are insoluble in water.
(ii) H-compounds are acids like HX.
(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)
2–
NCN (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

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.
* Noble gases are all able to diffuse through glass, rubber, plastics and same metals.
* He liquid can exist in two forms. I-form when changes to II-form at -point temperature many
physical properties change abruptly.
e.g.
(i) Sp. heat changes by a factor of 10
(ii) Thermal conductivity increases by 106 and it becomes 800 times faster than Cu
(iii) It shows zero resistance
(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.
What is noble gas hydrate?
eg. Xe • 6H2O  formed only when
Ar • 6H2O  water freezes at high
Kr • 6H2O  pressure together with noble gas
Shubhang Garodia
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
3
3XeF4 + 6H2O  2Xe + XeO3 + 12HF + O2
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–  XeO64 –  + Xe + 2H2O + O2

(7) They are used as fluorinating agent
2SF4 + XeF4  2SF6 + Xe
Pt + XeF4  PtF4 + Xe
(8) Act as a fluoride donor
XeF2 + MF5  [XeF]+ [MF6]– (M = As, Sb, P)
XeF6 + BF3  [XeF5]+ [BF4– ]
XeF6 + HF  [XeF5]+ [HF2]–
(9) Act as Fluoride acceptor also:
XeF6 + RbF/CsF  Rb+/Cs+ [XeF7]–

2Cs+[XeF7]– 
 XeF6 + Cs2[XeF8]
50C

XeF4 + MF  M+ + XeF5

(alkali metals fluoride)
 Shubhang Garodia
Q.1
Question Bank on p-Block elements
ONLY ONE OPTION IS CORRECT
Which is incorrectly matched?
(A) CsBr3 l Cs+ + Br3 (B) I4 O9 l I3+ + (IO3 )3

(C) AgBrO3 l Ag+ + BrO3 (D) I2O4 l IO2 + IO2

Q.2

(A) (X) = Pyrophosphoric acid (liquid), (Y) = Metaphosphoric acid (liquid)

(B) (X) = Pyrophosphoric acid (liquid), (Y) = Metaphosphoric acid (solid)
(C) (X) = Pyrophosphoric acid (solid), (Y) = Metaphosphoric acid (solid)
(D) (X) = Pyrophosphoric acid (solid), (Y) = Metaphosphoric acid (liquid)


Q.3 H3PO2  (X) + PH3 ; is
(A) Dehydration reaction (B) Oxidation reaction
(C) Disproportionation reaction (D) Dephosphorelation reaction

Q.4 Which of the following species is not a pseudohalide?

(A) CNO– (B) RCOO– (C) OCN– (D) N 3

Q.5 An orange solid (X) on heating, gives a colourless gas (Y) and a only green residue (Z). Gas (Y) on
treatement with Mg, produces a white solid substance .................
(A) Mg3N2 (B) MgO (C) Mg2O3 (D) MgCl2

Q.6 Conc. HNO3 is yellow coloured liquid due to

(A) dissolution of NO in conc. HNO3 (B) dissolution of NO2 in conc. HNO3
(C) dissolution of N2O in conc. HNO3 (D) dissolution of N2O3 in conc. HNO3

Q.7 A gas at low temperature does not react with the most of compounds. It is almost inert and is used to
create inert atmosphere in bulbs. The combustion of this gas is exceptionally an endothermic reaction.
Based on the given information, we can conclude that the gas is
(A) oxygen (B) nitrogen
(C) carbon mono-oxide (D) hydrogen

Q.8 When chlorine gas is passed through an aqueous solution of a potassium halide in the presence of chloroform,
a voilet colouration is obtained. On passing more of chlorine water, the voilet colour is disappeared and
solution becomes colourless. This test confirms the presence of ........... in aqueous solution.
(A) chlorine (B) fluorine (C) bromine (D) iodine

C 250C 316C
Q.9 H3PO2 140
  A   B   C
Compound (C) is
(A) H2PO3 (B) H3PO3 (C) HPO3 (D) H4P2O7
 Shubhang Garodia
Q.10 An explosive compound (A) reacts with water to produce NH4OH and HOCl. Then, the compound (A), is
(A) TNG (B) NCl3 (C) PCl3 (D) HNO3

Q.11 An inorganic salt (A) is decomposed at about 523 K to give products (B) and (C). Compound (C) is a
liquid at room temperature and is neutral to litmus paper while oxide (B) on burning with white phosphorous,
given a dehydrating agent (D). Compounds (A), (B), (C) and (D) will be identified as
(A) NH4NO3, N2O, H2O, P2O5 (B) NH4NO2, K2O, H2O, P2O5
(C) CaCO3 , CaO, H2O, CaCl2 (D) CaCO3 , CaO, H2O, Ca(OH)2

Q.12 An inorganic compound (A) made of two most occuring elements into the earth crust, having a polymeric
tetra-headral network structure. With carbon, compound (A) produces a poisonous gas (B) which is the
most stable diatomic molecule. Compounds (A) and (B) will be
(A) SiO2’ CO2 (B) SiO2’ CO (C) SiC,CO (D) SiO2’ N2

Q.13 A sulphate of a metal (A) on heating evolves two gases (B) and (C) and an oxide (D). Gas (B) turns
K2Cr2O7 paper green while gas (C) forms a trimer in which there is no S–S bond. Compound (D) with
HCI, forms a Lewis base (E) which exists as a dimer. Compounds (A), (B), (C), (D) and (E) are respectively
(A) FeSO4, SO2, SO3, Fe2O3, FeCl3 (B) Al2(SO4)3, SO2, SO3, Al2O3, FeCl3
(C) FeS, SO2, SO3, FeSO4, FeCl3 (D) FeS, SO2, SO3 , Fe2(PO4)3, FeCl2

Q.14 A tetra-atomic molecule (A) on reaction with nitrogen(I)oxide, produces two substances (B) and (C).
(B) is a dehydrating agent in its monomeric form while substance (C) is a diatomic gas which shows
almost inert behaviour. The substances (A) and (B) and (C) respectively will be
(A) P4, P4O10, N2 (B) P4, N2O5’ N2 (C) P4, P2O3, Ar (D) P4, P2O3, H2

Q.15 First compound of inert gases was prepared by scientist Neil Barthlete in 1962. This compound is
(A) XePtF6 (B) XeO3 (C) XeF6 (D) XeOF4

Q.16 Carbongene has X% of CO2 and is used as an antidote for poisoning of Y . Then, X and Y are
(A) X = 95% and Y = lead poisoning (B) X = 5% and Y = CO poisoning
(C) X = 30% and Y = CO2 poisoning (D) X = 45% and Y = CO poisoning

Q.17 The correct order of acidic strength of oxides of nitrogen is

(A) NO < NO2 < N2O < N2O3 < N2O5
(B) N2O < NO < N2O3 < N2O4 < N2O5
(C) NO < N2O < N2O3 < N2O5 < N2O4
(D) NO < N2O < N2O5 < N2O3 < N2O4

Q.18 Nitrogen dioxide is dissolved in water to produce

(A) HNO3 and HNO2 (B) only HNO3
(C) only HNO2 (D) HNO2 and N2

Q.19 Consider two reactions

I. Zn + conc. HNO3 (hot)  Zn(NO3)2 + X + H2O
II. Zn + dil. HNO3 (cold)  Zn(NO3)2 + Y + H2O
Compounds X and Y are respectively
(A) N2O, NO (B) NO2, N2O (C) N2, N2O (D) NO2, NO
 Shubhang Garodia
Q.20 H3BO3  T1 X T2 Y red

hot
 B2O3
if T1 < T2 then X and Y respectively are
(A) X = Metaboric acid and Y = Tetraboric acid
(B) X = Tetraboric acid and Y = Metaboric acid
(C) X = Borax and Y = Metaboric acid
(D) X = Tetraboric acid and Y = Borax

Q.21 Boron forms BX3 type of halides. The correct increasing order of Lewis-acid strength of these halides is
(A) BF3 > BCl3 > BBr3 > BI3 (B) BI3 > BBr3 > BCl3 > BF3
(C) BF3 > BI3 > BCl3 > BBr3 (D) BF3 > BCl3 > BI3 > BBr3

Q.22 Which one of the following compounds on strong heating evolves ammonia gas?
(A) (NH4)2SO4 (B) HNO3 (C) (NH4)2Cr2O7 (D) NH3NO3

Q.23 The compound (SiH3)3N is

(A) pyramidal and more basic than (CH3)3N (B) planar and less basic than (CH3)3N
(C) pyramidal and less basic than (CH3)3N (D) planar and more basic than (CH3)3N

Q.24 The correct order of acidic strength of oxy-acids of chlorine is

(A) HCIO < HCIO2 < HCIO3 < HCIO4 (B) HCIO4 < HCIO3 < HCIO2 < HCIO
(C) HCIO > HCIO4 > HCIO3 > HCIO2 (D) HCIO4 < HCIO2 > HCIO3 > HCIO

Q.25 In a molecule of phosphorus (V)oxide, there are

(A) 4P–P, 10P–O and 4P=O bonds (B) 12P–O and 4P=O bonds
(C) 2P–O and 4P=P bonds (D) 6P–P, 12P–O and 4P=P bonds

Q.26 The structures of O3 and N3– are

(A) linear and bent, respectively (B) both linear
(C) both bent (D) bent and linear, respectively

Q.27 When conc. H2SO4 was treated with K4[Fe(CN )6], CO gas was evolved. By mistake, somebody
used dilute H2SO4 instead of conc. H2SO4 then the gas evolved was
(A) CO (B) HCN (C) N2 (D) CO2

Q.28 A  O 2  X  Y  Z
( organic Compound )
Compound (A) in pure form does not give ppt. with AgNO3 solution. A mixture cootaining 70% of (A)
and 30% of ether is used as an anaesthetic. Compound (X) and (Y) are oxides while (Z) is a pungent
smelling gas. (X) is a neutral oxide which turns cobalt chloride paper pink. Compound (Y) turns lime
water milky and produces an acidic solution with water. Compounds (A), (X), (y) and (Z) respectively
will be
(A) CH4, H2O, CO2’ Cl2 (B) CHCl3 , H2O, CO2, Cl2
(C) CH3OH, H2O, CO2, N2 (D) NH2CONH2, H2O, N2O, CO2

Q.29 An inorganic white crystalline compound (A) has a rock salt structure. (A) on reaction with cone. H2SO4
and MnO2, evolves a pungent smelling, greenish-yellow gas (B). Compound (A) gives white ppt. of (C)
with AgNO3 solution. Compounds (A), (B) and (C) will be respectively
(A) NaCl, Cl2, AgCl (B) NaBr, Br2, NaBr
(C) NaCl, Cl2, Ag2SO4 (D) NazCO3 , CO2, Ag2CO3
 Shubhang Garodia
cu powder
Q.30 RCl   
Si
Compound (A) is
 R SiCl H

(A) a linear silicone

2 2
2O


(B) a chlorosilane
condensation
 R2Si(OH)2    A

(C) a linear silane (D) a network silane

Q.31 When oxalic acid reacts with cone. H2SO4 , two gases produced are of neutral and acidic in nature
respectively. Potassium hydroxide absorbs one of the two gases. The product formed during this absorption
and the gas which gets absorbed are respectively
(A) K2CO3 and CO2 (B) KHCO3 and CO2 (C) K2CO3 and CO (D) KHCO3 and CO

Q.32 Concentrated HNO3 reacts with iodine to give

(A) HI (B) HOI (C) HOIO2 (D) HOIO3

Q.33 Conc. H2SO4 cannot be used to prepare HBr from NaBr because it
(A) reacts slowly with NaBr (B) oxidises HBr
(C) reduces HBr (D) disproportionates HBr

COOH
Q.34 CH2 P4O10 , 150C
   X
COOH
Compound (X) is
(A) malonic acid (B) carbon suboxide (C) tartaric acid (D) acetic acid

Q.35 Molecular shapes of SF4, CF4 and XeF4 are

(A) the same, with 2, 0 and 1 lone pairs of electrons respectively
(B) the same, with 2, 0 and 1 lone pairs of electrons respectively
(C) the different, with 0, 1 and 2 lone pairs of electrons respectively
(D) the different, with 1, 0 and 2 lone pairs of electrons respectively

Q.36 Match List-I with List-II

List-I Chemical reaction List-II Name of process

4NH3 + 5O2 800
I. C / Pt
 4NO + 6H2O (a) Contact process
3230C / CuCl
II. 4HCl + O2 450
  2  2Cl + 2H O (b) Ostwald's process
500 / V O2 5
2 2

III. 2SO2 + O2  2SO3 (c) Deacon's process

IV. 2N2 + 3H2 Fe Mo
 2NH3
 (d) Haber's proces
(A) I-a, II-b, III-d, IV-c (B) I-b, II-c, III-a, IV-d
(C) I-a, II-d, III-c, IV-b (D) I-a, II-c, III-b, IV-d

Q.37 Ammonia can be dried by

(A) conc. H2SO4 (B) P4O10 (C) CaO (D) anhydrous CaCl2

Q.38 When chlorine reacts with a gas X, an explosive inorganic compound Y is formed. Then X and Y will be
(A) X = O2 and Y = NCl3 (B) X = NH3 and Y=NCl3
(C) X = O2 and Y = NH4Cl (D) X = NH3 and Y = NH4Cl

Q.39 The solubility of anhydrous AlCl3 and hydrous AlCl3 in diethyl ether are S1 and S2 respectively. Then
(A) S1 = S2 (B) S1 > S2 (C) S1 < S2 (D) S1 < S1 but not S1 = S2
 Shubhang Garodia
Q.40 Which one of the following statements is not true regarding diborane?
(A) It has two bridging hydrogens and four perpendicular to the rest.
(B) When methylated, the product is Me4B2H2.
(C) The bridging hydrogens are in a plane perpendicular to the rest.
(D) All the B–H bond distances are equal.

Q.41 When AgNO3 is heated strongly, the products formed are

(A) NO and NO2 (B) NO2 and O2 (C) NO2 and N2O (D) NO and O2

Q.42 HNO3 + P4O10  HPO3 + A ; the product A is

(A) N2O (B) N2O3 (C) NO2 (D) N2O5

Q.43 Which of the following is the correct order of acidic strength?

(A) Cl2O7 > SO2 > P4O10 (B) CO2 > N2O5 > SO3
(C) Na2O > MgO > Al2O3 (D) K2O > CaO > MgO

Q.44 Ca + C2 CaC2 N 2 A

Compound (A) is used as a/an
(A) fertilizer (B) dehydrating agent (C) oxidising agent (D) reducing agent

Q.45 A gas which exists in three allotropic forms ,  and  is

(A) SO2 (B) SO3 (C) CO2 (D) NH3

Q.46 A red coloured mixed oxide (X) on treatment with cone. HNO3 gives a compound (Y). (Y) with HCl ,
produces a chloride compound (Z) which can also be produced by treating (X) with cone. HCl.
Compounds (X) , (Y), and (Z) will be
(A) Mn3O4, MnO2, MnCl2 (B) Pb3O4, PbO2, PbCl2
(C) Fe3O4, Fe2O3, FeCl2 (D) Fe3O4, Fe2O3, FeCl3

Q.47 There is no S–S bond in

(A) S2O42– (B) S2O52– (C) S2O32– (D) S2O72–

Q.48 One mole of calcium phosphide on reaction with excess of water gives
(A) one mole of phosphine (B) two moles of phosphoric acid
(C) two moles of phosphine (D) one mole of phosphorus penta-oxide

C
Q.49 NaH2PO4 230   Na3(P3O9) 638
 C
 (NaPO3)n  D (glossy solid)
Compound (D) is sodium hexametaphosphate which is known as
(A) Bunsen’s salt (B) Graham’s salt (C) Reimann’s salt (D) Werner’s salt

Q.50 Three allotropes (A), (B) and (C) of phoiphorous in the following change are respectively

(A) white, black, red (B) black, white, red (C) red, black, white (D) red, violet, black
 Shubhang Garodia
Q.51 When an inorganic compound reacts with SO2 in aqueous medium, produces (A). (A) on reaction with
Na2CO3, gives compound (B) which with sulphur, gives a substance (C) used in photography. Compound
(C) is
(A) Na2S (B) Na2S2O7 (C) Na2SO4 (D) Na2S2O3

Q.52 Borax is actually made of two tetrahedra and two triangular units joined together and should be written
as: Na2[B4O5(OH)4]·8H2O
Consider the following statements about borax:
a. Each boron atom has four B–O bonds
b. Each boron atom has three B–O bonds
c. Two boron atoms have four B–O bonds while other two have three B–O bonds
d. Each boron atom has one –OH groups
Select correct statement(s):
(A) a, b (B) b, c (C) c, d (D) a, c

Question No. 53 to 55 (3 questions)

Read the following short write-up and answer the questions at the end of it
The name 'silica' covers an entire group of minerals, which have the general formula SiO2, the most
common of which is quartz. Quartz is a framework silicate with SiO4 tetrahedra arranged in spirals. The
spirals can turn in a clockwise or anticlockwise direction – a feature that results in there being two mirror
images, optically active, varieties of quartz.
Q.53 The following pictures represent various silicate anions. Their formulae are respectively:

(A) SiO 32 Si 3O 72 (B) SiO 44 8

Si 3O10

(C) SiO 24 Si 3O 92 (D) SiO 34 Si 3O87

Q.54 Si 3O 69 (having three tetrahedral) is represented as:

(A) (B)

(C) both (D) none

Q.55 The silicate anion in the mineral kinoite is a chain of three SiO4 tetrahedra that share corners with
adjacent tetrahedra. The mineral also contains Ca2+ ions, Cu2+ ions, and water molecules in a 1:1:1 ratio
mineral is represented as:
(A) CaCuSi3O10·H2O (B) CaCuSi3O10·2H2O
(C) Ca2Cu2Si3O10·2H2O (D) none of these
 Shubhang Garodia
Question No. 56 to 57 (2 questions)
Questions given below are based on electronic configurations of the elements. The three elements X, Y
and Z with the electronic configurations shown below all form hydrides:
Element Electronic configuration
X 1s2, 2s2, 2p2
Y 1s2, 2s2, 2p6, 3s1
Z 1s , 2s , 2p6, 3s2, 3p6, 3d10, 4s2, 4p5
2 2

Q.56 Which line of properties (A, B, C, or D) correctly lists properties of the hydrides of these elements?
Hydride of X Hydride of Y Hydride of Z
(A) Colourless gas Silver/grey solid, reacts Colourless gas form a
insoluble in H2O with H2O to form an strong acid in H2O
alkaline solution
(B) Colourless liquid, no Silver/grey solid, forms Ionic solid with formula
reaction with H2O H2O ZH
(C) Colourless gas found Does not conduct Colourless gas, reacts
naturally electricity in the molten with Cl2
state
(D) Non-polar compound Silver/grey ionic solid Forms when water is
reacts with Cl2 in light with formula YH2 added to phosphorus
and element Z

Q.57 Which of the following exists as gas?

(A) X2 (B) Y2 (C) Z2 (D) all of the above

Question No. 58 to 59 (2 questions)

Read the following write-ups and answer the questions at the end of it.
Silicons are synthetic polymers containing repreated R2SiO units. Since, the empirical formula is that of
a ketone (R2CO), the name silicone has been given to these materials. Silicones can be made into oils,
rubbery elastomers and resins. They find a variety of applications because of their chemical inertness,
water repelling nature, heat-resistance and good electrical insulating property.
Commercial silicon polymers are usually methyl derivatives and to a lesser extent phenyl derivatives and
are synthesised by the hydrolysis of
R2SiCl2[R=methyl (Me) or phenyl ()]
Me Me Me
H 2O
| | |
Me 2SiCl 2  O  Si  O  Si  O  Si  O 
| | |
Me Me Me
Q.58 If we mix Me3SiCl with Me2SiCl2, we get silicones of the type:

Me Me
| |
Me Me Me Me  O  Si  O  Si  O 
| | | | | |
(A) Me  Si  O  Si  O  Si  O  Si  Me (B) O O
| | | | | |
Me Me Me Me  O  Si  O  Si  O 
| |
Me Me
(C) both of the above (D) none of the above
 Shubhang Garodia
Q.59 If we start with MeSiCl3 as the starting material, silicones formed is:
Me Me
| |
Me Me Me Me  O  Si  O  Si  O 
| | | | | |
(A) Me  Si  O  Si  O  Si  O  Si  Me (B) O O
| | | | | |
Me Me Me Me  O  Si  O  Si  O 
| |
Me Me
(C) Both of the above (D) None of the above

Q.60 The molecular shapes of diborane is shown:

Consider the following statements for diborane:
1. Boron is approximately sp3 hybridised
2. B–H–B angle is 180°
3. There are two terminal B–H bonds for each boron atom
4. There are only 12 bonding electrons available
Of these statements:
(A) 1, 3 and 4 are correct (B) 1, 2 and 3 are correct
(C) 2, 3 and 4 are correct (D) 1, 2 and 4 are correct

Question No. 61 to 62 (2 questions)

The following flow diagram represents the industrial preparation of nitric acid from ammonia:
(A)
 NO (
NH3 + O2 
B)
 (C) water
 HNO + NO
900C air 3
(excess air)

Answer the questions given below:

Q.61 Which line of entry describes the undefined reagents, products and reaction conditions?
A B C
(A) catalyst R.T. (25°C) NO 2
(B) catalyst R.T. (25°C) N2 O
(C) catalyst high pressure NO 2
(D) high pressure catalyst N2 O 3

Q.62 Formation of HNO3 when (C) is dissolved in H2O takes place through various reactions. Select the
reaction not observed in this step.
(A) NO2 + H2O  HNO3 + HNO2 (B) HNO2  H2O + NO + NO2
(C) NO2 + H2O  HNO3 + NO (D) none of these

Q.63 B(OH)3 + NaOH l NaBO2 + Na[B(OH)4] + H2O

How can this reaction is made to proceed in forward direction?
(A) addition of cis 1,2 diol (B) addititon of borax
(C) addition of trans 1,2 diol (D) addition of Na2HPO4
 Shubhang Garodia
Question No. 64 to 71 (8 questions)
Questions given below consist of two statements each printed as Assertion (A) and Reason (R); while
answering these questions you are required to choose any one of the following four responses:
(A) if both (A) and (R) are true and (R) is the correct explanation of (A)
(B) if both (A) and (R) are true but (R) is not correct explanation of (A)
(C) if (A) is true but (R) is false
(D) if (A) is false and (R) is true
Q.64 Assertion : Borax bead test is applicable only to coloured salt.
Reason : In borax bead test, coloured salts are decomposed to give coloured metal meta
borates.

Q.65 Assertion : Aluminium and zinc metal evolve H2 gas from NaOH solution
Reason : Several non-metals such as P, S, Cl, etc. yield a hydride instead of H2 gas from
NaOH

Q.66 Assertion : Conc. H2SO4 can not be used to prepare pure HBr from NaBr
Reason : It reacts slowly with NaBr.

Q.67 Assertion : Oxygen is more electronegative than sulphur, yet H2S is acidic, while H2O is neutral.
Reason : H–S bond is weaker than O–H bond.

Q.68 Assertion : Al(OH)3 is amphoteric in nature.

Reason : It can not be used as an antacid.

Q.69 Assertion : Chlorine gas disproportionates in hot & conc. NaOH solution.
Reason : NaCl and NaOCl are formed in the above reaction.

Q.70 Assertion : Silicones are very inert polymers.

Reason : Both Si–O and Si–C bond energies are very high.

Q.71 Assertion : Liquid IF5 conducts electricity.

Reason : Liquid IF5 self ionizes as, 2IF5 l IF4  IF6

Paragraph for Question No. 72 to 74

There are some deposits of nitrates and phosphates in earth’s crust. Nitrates are more soluble in water.
Nitrates are difficult to reduce under the laboratory conditions but microbes do it easily. Ammonia forms
large number of complexes with transition metal ions. Hybridization easily explains the ease of sigma
donation capability of NH3 and PH3. Phosphine is a flammable gas and is prepared from white
phosphorous.

Q.72 Among the following, the correct statement is

(A) Phosphates have no biological significance in humans
(B) Between nitrates and phosphates, phosphates are less abundant in earth’s crust
(C) Between nitrates and phosphates, nitrates are less abundant in earth’s crust
(D) Oxidation of nitrates is possible in soil
 Shubhang Garodia
Q.73 Among the following, the correct statement is :
(A) Between NH3 and PH3, NH3 is a better electron donor because the lone pair of electrons occupies
spherical ‘s’ orbital and is less directional
(B) Between NH3 and PH3, PH3 is a better electron donor because the lone pair of electrons occupies
sp3 orbital and is more directional
(C) Between NH3 and PH3, NH3 is a better electron donor because the lone pair of electrons occupies
sp3 orbital and is more directional
(D) Between NH3 and PH3, PH3 is a better electron donor because the lone pair of electrons occupies
spherical ‘s’ orbital and is less directional

Q.74 White phosphorus on reaction with NaOH gives PH3 as one of the products. This is a
(A) dimerization reaction (B) disproportionation reaction
(C) condensation reaction (D) precipitation reaction

ONE OR MORE THAN ONE OPTION MAY BE CORRECT

Q.1 When a compound X reacts with ozone in aqueous medium, a compound Y is produced. Ozone also
reacts with Y and produces compound Z. Z acts as an oxidising agent, then X, Y and Z will be
(A) X = HI, Y = I2 and Z = HIO3 (B) X = KI, Y = I2 and Z = HIO3
(C) X = KI, Y = I2 and Z = HIO4 (D) X = HI, Y = I2 and Z = HIO4

Q.2 Which of the following statements is/are correct regarding B2H6?

(A) banana bonds are longer but stronger than normal B–H bonds
(B) B2H6 is also known as 3c–2e compound
(C) the hybrid state of B in B2H6 is sp3 while that of sp2 in BH3
(D) it cannot be prepared by reacting BF3 with LiBH3 in the presence of dry ether

Q.3 Which of the following pairs of nitrates gives the same gaseous products on thermal decomposition?
(A) KNO3 and Pb(NO3)2 (B) KNO3 and NaNO3
(C) Pb(NO3)2 and Cu(NO3)2 (D) NaNO3 and Ca(NO3)2

Q.4 2NO2 l N2O4The dimerisation of NO2 is accompanied with

(A) decrease in paramagnetism (B) change in colour
(C) increase in temperature’ (D) increase in paramagnetism

Q.5 C(OH)4 is unstable because a carbon atom cannot hold more than one –OH groups but Si(OH)4 is a
stable compound because
(A) C–O bond energy is low (B) C–O bond energy is high
(C) Si-O bond energy is low (D) Si-O bond energy is high

Q.6 Which of the following statements is/are correct regarding inter-halogen compounds of ABx types?
(A) x may be 1,3,5 and 7
(B) A is a more electronegative halogen than B
(C) FBr3 cannot exit
(D) the structures of ClF3 and IF7 show deviation from normal structures and could be explained on the
basis of VSEPR theory
 Shubhang Garodia
Q.7 When an inorganic compound (X) having 3e-2e as well as 2e-2e bonds reacts with ammonia gas at a
certain temperature, gives a compound (Y) iso-structural with benzene. Compound (X) with ammonia
at a high temperature, produces a hard substance (Z). Then
(A) (X) is B2H6 (B) (Z) is known as inorganic graphite
(C) (Z) having structure similar to graphite (D) (Z) having structure similar to (X)

Q.8 Boric acid

(A) exists in polymeric form due to inter-molecular hydrogen bonding.
(B) is used in manufacturing of optical glasses.
(C) is a tri-basic acid
(D) with borax, it is used in the preparation of a buffer solution.

Q.9 The correct statement(s) related to allotropes of carbon is/are

(A) graphite is the most stable allotropes of carbon and having a two dimensional sheet like structure of
hexagonal rings of carbon (sp2)
(B) diamond is the hardest allotrope of carbon and having a three dimensional network structure of
C(sp3)
(C) fullerene (C60) is recently discovered non-crystalline allotrope of carbon having a football-like structure.
(D) Vander Waal's force of attraction acts between the layers of graphite 6.14 Å away from each other

Q.10 Al2(SO4)3 + NH4OH  X, then

(A) X is a white coloured compound (B) X is insoluble in excess of NH4OH
(C) X is soluble in NaOH (D) X cannot be used as an antacid

Q.11 The hybrid states of phosphorous atoms in each PCl5 and PBr3 in gaseous phase are sp3d. But, in solid
PCl5, phosphorous shows sp3d2 and sp3 hybrid states. While, P in PBr5 is in Sp3 hybrid state. This is
because
(A) PCl5 in solid form exists as [ PCl4]+[PCI6]–
(B) PBr5 in solid form exists as [PCI4]+[ PBr6]–
(C) PCl5 in solid form exists as [PCI4]+Cl–
(D) PBr5 in solid form exists as [PBr4]+Br–

Q.12 The species that undergo(es) disproportionation in an alkaline medium is/are

(A) Cl2 (B) MnO42– (C) NO2 (D) CIO4–

Q.13 Select correct statement(s):

(A) Borax is used as a buffer
(B) 1 M borax solution reacts with equal volumes of 2 M HCl solution
(C) Titration of borax can be made using methyl orange as the indicator
(D) Coloured bead obtained in borax-bead test contains metaborate

Q.14 Select correct statement about B2H6

(A) Bridging groups are electron-deficient with 12 valence electrons
(B) It has 2c - 2e B–H bonds
(C) It has 3c - 2e B–H–B bonds
(D) All of above are correct statements
 Shubhang Garodia
Q.15 Which of the following is / are correct for group 14 elements?
(A) The stability of dihalides are in the order CX2 < SiX2 < GeX2 < SnX2 < PbX2
(B) The ability to form p–p multiple bonds among themselves increases down the group
(C) The tendency for catenation decreases down the group
(D) They all form oxides with the formula MO2.

Q.16 Match the following:

Column I Column II
(A) Bi3+  (BiO)+ (P) Heat
(B) [AlO2]–  Al(OH)3 (Q) Hydrolysis
(C) SiO 44  Si 2O67 (R) Acidification

(D) (B4O 72 )  [B(OH)3] (S) Dilution by water

 Shubhang Garodia ANSWER KEY

ONLY ONE OPTION IS CORRECT

Q.1 D Q.2 B Q.3 C Q.4 B Q.5 A Q.6 B Q.7 B

Q.8 D Q.9 C Q.10 B Q.11 A Q.12 B Q.13 A Q.14 A

Q.15 A Q.16 B Q.17 B Q.18 A Q.19 B Q.20 A Q.21 B

Q.22 A Q.23 B Q.24 A Q.25 B Q.26 D Q.27 B Q.28 B

Q.29 A Q.30 A Q.31 A Q.32 C Q.33 B Q.34 B Q.35 D

Q.36 B Q.37 C Q.38 B Q.39 B Q.40 D Q.41 B Q.42 D

Q.43 A Q.44 A Q.45 B Q.46 B Q.47 D Q.48 C Q.49 B

Q.50 A Q.51 D Q.52 C Q.53 B Q.54 B Q.55 C Q.56 A

Q.57 C Q.58 A Q.59 B Q.60 A Q.61 A Q.62 D Q.63 A

Q.64 A Q.65 B Q.66 C Q.67 A Q.68 C Q.69 C Q.70 A

Q.71 A Q.72 C Q.73 C Q.74 B

ONE OR MORE THAN ONE OPTION MAY BE CORRECT

Q.1 A,B Q.2 A,B,C Q.3 B,C Q.4 A,B

Q.5 A,D Q.6 A,C Q.7 A,B,C Q.8 A,B,D

Q.9 A,B Q.10 A,B,C Q.11 A,D Q.12 A,B,C

Q.13 A,B,C,D Q.14 B,C Q.15 A,C,D

Q.16 A – Q,S; B – R; C – P; D – Q,R