CHEMISTRY p-BLOCK ELEMENTS

3
p-BLOCK ELEMENTS
Isolation of “B” :
(i) Preparation of B2O3 from Borax or Colemanite
Na2B4O7 + HCl / H2SO4  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 : 4B + 3O2  2B2O3
4Al + 3O2  2Al2O3
(ii) Reaction with water
B + H2O (Cold & Hot)  no reaction
2B + 3H2O  B2O3 + H2
(red hot)
Al + 3H2O  Al(OH)3 + 3/2 H2
(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 (10%)  B2H6 + B4H10 + B5H9 etc.

(ii) B4H10  B2H6 + H2 + higher borane
100 º C
Electric disch arg e
(iii) BCl3 (or BBr3) + 6H2     B2H6 + 6HCl
at low temperature
(iv) 3LiAlH4 or (LiBH4) + 4BF3  3LiF + 3AlF3 or 3(BF3) + 2B2H6
Reaction of B2H6 :
burns in air
(i) B2H6 + O2     B2O3 + H2O
spon tan eously
(ii) B2H6 + H2O (Cold is enough)  H3BO3 + 6H2
anh.
(iii) B2H6 + HCl (dyr)  B2H5Cl + H2
AlCl3

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• Heating of Boric Acid :

100 ºC 140 ºC 
H3BO3    H2B4O7  B2O3
 HBO2  
red hot
Metaboric acid Tetraboric acid Glassy mass
O–O
NaOH
• H3BO3 + H2O2  (H2O) + (HO)2B–O–O–H  
 Na2 (HO)2B B(OH)2 · 6H2O
O–O
Sodium peroxy borate used in washing
powder as whitener

Preparation of Borax :
2CaO·3B2O3 + 2Na2CO3  2CaCO3 + Na2B4O7 + 2NaBO2
Colemanite Filtered
–CaCO3 (as residue)

Concentrated
NaBO 2 + Na2B4 O7  10H2O    Na2B4O7  NaBO3
in Filtrate  as residue 
and allowed to 
crystallise out in solution
and filtered

CO2 passed and

cystallise out again [4NaBO2 + CO2  Na2B4O7 + Na2CO3
Na2B4O7·10H2O

Uses of Borax :
(i) In making glass, enamel and gaze or pottery.
(ii) As antiseptics in medicinal soaps preparation.

Al2O3 preparation :
300º C
(i) 2Al(OH)3 
 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)

(ii) Al2O3 + 3C + 3Cl2   2AlCl (vap.) + 3CO
1000ºC 3

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Cooled

Solid anh. AlCl3

Props :
(i) Its anhydrous formed is deliquescent and fumes in air.
(ii) It sublimes at 180ºC.
(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.

Cl Cl Cl
Al Al
Cl Cl Cl
Uses : (i) Friedel–Craft reaction
(ii) Dyeing, drug & perfumes etc.

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

where M = Na+, K+, Rb+, Cs+, As+, Tl+, NH4+
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. solution  crystallise
Uses : (i) Act as coagulant. (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

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p-BLOCK ELEMENTS CHEMISTRY

(ii) Covalent carbinde : SiC & B4C

(iii) Interstitial carbide : MC (Transition element or inner transitional elements forms this kind of
carbide)
Interstitial carbide formation doesn’t affect the metallic lusture and electrical conductivity. (  no
chemical bond is present, no change in property.)
SiC
2000 to
Preparation : SiO2 + 2C(coke) 
2500 ºC
Si + 2CO

2000 to
Si + C 
2500 ºC
SiC diamond like structure colourless to yellow solid in room temp.


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
2O5 + 5CO  2 + 5CO2
2 + S2O32–  2– + S4O62–

(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
50ºC 150ºC
Impure Ni + CO  Ni(CO)4  Ni + 4CO
recycled

Producer gas : CO + N2 + H2
Water gas : CO + H2
Water gas is higher calorific value than producer gas.

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CHEMISTRY p-BLOCK ELEMENTS

 in water gas, both CO & H2 burns while in producer gas N2 doesn’t burn.

Taflon —(CF2 – CF2)—

n

heated with heated

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

Purpose
Temp. withstanding capacity upto 500-550ºC (1st organic compound withstand this kind of high
temperature.)
SILICON (Si)
Occurence :
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 howeve the most common constituent of rocks and clays.
Silikca 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 (SiO 2) with high purity
coke in an electric furnace.
high temperature
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.
(iii) Silicon exists in three isotopes, i.e. 28 29 30 28
14Si , 14Si and 14Si but 14Si 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,
1173 K
Si(s) + O2(g)  SiO2(s)
Silicon dioxide
1673 K
3Si(s) + 2N2(g)  Si3N4(s)
Silicon nitride
(ii) Action of steam : It is slowly attacked by steam when heated to redness liberating dihydrogen
gas.
redness
Si(s) + 2H2O(g)  SiO2(s) + 2H2(g)
(iii) Reaction with halogens : It burns spontaneously in fluorine gas at room temperature to form
silicon tetrafluoride (SiF4).
Room temperature
Si(s) + 2F2  SiF4(l)
However, with other halogens, it combines at high temperature forming tetrahalides.
(iv) Reaction with carbon : Silicon combines with carbon at 2500ºC forming silicon carbide (SiC)
known as carborundum.
2500º C
Si(s) + C(s) 
 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 sually 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  MgSO + SiH + Si H + ......
4 4 2 6

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.

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CHEMISTRY p-BLOCK ELEMENTS

(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)
–2H2O

R R R
| | |

R2SiCl2 + H2O 
 R2Si(OH)2  O  Si O  Si O  Si O 
2HCl H2O | | |
R R R
Linear silicone

O
||
H2O
R2CCl2 + H2O   R2C(OH)2 
 R  C R
HCl
looses H2O
readify
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.
R R R R
| |
Si
O O R  Si  O  Si  R
R | |
sp3 R
Si Si O O
R O R | |
sp3 R  Si  O  Si  R
cyclic silicone | |
not planar O O
H O
2  R SiOH 
2  H O
R3SiCl  3 
R3Si–O–SiR3
Silanol

R R
H2O H2O
R2SiCl2 + R3SiCl    R3Si-O – 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
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 work
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)
(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.
high temp.
SiO2(s) + Na2CO3(s)   Na2SiO3(s) + CO2(g)

high temp.
SiO2(s) + Na2SO4(s)   Na2SiO3(s) + CO3(g)

high temp.
3SiO2(s) + Ca3(PO4)2(s)   3CaSiO3(s) + P2O5(g)
The first two examples quoted here are important in glass making.

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Structure of Silica :
Silica has a three-dimensional network structure. In silica, silicon is sp 3-hybridized and in 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 absorbent in
chromatography.

Tin & Its Compound

1500ºC
(i) Sn 
+O
SnO2 [Burns with a bright flame]
2
Cl2,
SnCl4
S,
SnS2
Room temp.
No reaction
(ii) Sn + 2H2O At high temp.
SnO2 + 2H2

(iii) Reaction with acid,

dil. HCl
reaction is very slow {Due to nonoxidising in nature}
hot conc. HCl
Sn + 2HCl  SnCl2 + H2
dil. H2SO4
dissolve Sn slowly forming SnSO4 + H2
Sn hot conc. H2SO4
Sn + 4H2SO4  Sn(SO4)2 + 2SO2 + 4H2O
cold dil. HNO3
4Sn + 10HNO3  4Sn(NO3)2 + NH4NO3 + 3H2O
hot conc. HNO3
5Sn + 20HNO3  H2Sn5O11.4H2O + 20NO2 + 5H2O
Metastannic acid

SnO2
(iv) Sn + 2NaOH + H2O  Na2SnO3 + 2H2.
or
KOH [In absence of air Na2SnO2 forms and in contact with air it readily converts into Na2SnO3.]

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Oxides : SnO(grey) & SnO2(white)

1500ºC
+1/2 O2 strongly
SnO2(White)  Sn + O2
heated

SnC2O4  SnO(grey) + CO + CO2 H2Sn5O11.4H2O
out of
contact of  (in absence of air)
air
KOH
SnCl2  Sn(OH)2

Both are amphoteric in nature :

SnO + H2SO4  SnSO4 + H2O
SnO + 2HCl  SnCl2 + H2O
cold
SnO + 2NaOH or KOH  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 preserved 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

HCl
(3) SnCl2 + HCl  HSnCl3  H2SnCl4
Chlorostannous acid
SnCl4 + 2HCl  H2SnCl6 (Hexachloro stannic (IV) acid)
SnCl4 + 2NH4Cl  (NH4)2SnCl6 (colourless crystalline compound known as “pink salt”)

(4) Red Prop. of SnCl2 :

Sn+2 + 2Fe+3  2Fe+2 + Sn+4
2Cu2+ + 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

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(5) Readily combines with 2  SnCl22  This reaction is used to estimate tin.
Formation of SnCl4 :
(i) Sn + Cl2(Excess)  SnCl4
(molten) (dry)
(ii) 2HgCl2 + SnCl2  2Hg + SnCl4
(iii) Sn + Aq. rigia  SnCl4 + NO + H2O
 SnCl4.5H2O is known as butter of tin  used as mordant.
(NH4)2SnCl6 is known as ‘pink salt’  used as calico printing.

Mosaic gold : SnS2 yellow crystalline substance :

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

 Distinction of Sn+2 / Sn+4 :

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

Compound of Lead
Oxides of Lead :.
(i) PbO (ii) Pb3O4 (Red) (iii) Pb2O3 (reddish yellow) (Sesquioxide)
(iv) PbO2 (dark brown)
fused, cooled
Yellow (Massicot) and powdered
Litharge
(1) PbO
Reddish yellow (litharge)
Laboratory Preparation :
Pb(NO3)2  2PbO + 4NO2 + O2
above 600ºC
PbO2    H2
PbO, hot oxide Pb + H2O
Pb3O4  easily reduced to Pb by
Pb2O3  H2 or C. Pb + CO
C

Preparation of Pb2O3 :
2PbO + NaOCl  Pb2O3 + NaCl
hot solution Limited
of it in NaOH amount
Pb2O3 + 2HNO3  PbO2 + Pb(NO3)2 + H2O
This reaction suggest that Pb2O3 contains PbO2.

340ºC
(2) Pb3O4 : 6PbO + O2 2Pb3O4 (In the same way, prove that its formula is 2PbO.PbO2)
>470ºC

Pb3O4 + 4HNO3 (cold. conc.) or (hot dil.)  2Pb(NO3)2 + PbO2 + 2H2O


But 2Pb3O4 + 6H2SO4  6PbSO4 + 6H2O + O2
Pb3O4 + 8HCl  3PbCl2 + 4H2O + Cl2

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p-BLOCK ELEMENTS CHEMISTRY

(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 HNO 3.
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)2Cr2O7  N2 + 4H2O + Cr2O3


(iii) Ba(N3)2  Ba + 3N2
Purest N2 obtained
 by this method
2NaN3  2Na + 3N2
(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

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CHEMISTRY p-BLOCK ELEMENTS

In this method NH3 conc. should not be lowered down beyond a particular limit.
3Cl2 + NH3  NCl3 + 3HCl
(Tremendously 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

Al2O3 + 3C + N2  2AlN + 3CO

(BN)x : Inorganic graphite

White slippery solid having 2D-sheet structure.
3000ºC
(BN)x   (BN)x
3–D network structure similar to diamond (Borazon) which is harder than diamond and used for
diamond cutting.

Na2B4O7 + 2NH4Cl  2NaCl + 2NH3 + 2B2O3 + H2O
B2O3 + 2NH3  2BN + 3H2O

(iii) N2 can be absorbed by calcium carbide at the temp around 1000ºC, CaC2

1000ºC
CaC2  N2   CaNCN

 C it is a very good fertiliser.
nitro lim
cyanamide ion

2
N–CN
Cyanamide ion :
N=C=N

(iv) (Ca(NCN) + C) + 3H2O  CaCO3 + 2NH3 + C

Slowly decomposes
NH2–CO–NH2
(Intermediate formed)

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

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p-BLOCK ELEMENTS CHEMISTRY

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 formula is MN.
HCP : Hexagonal closed pack FCC : Face centred cubic

NH3 preparation :
(i) Nitrate or nitrite reduction : NO3– / NO2– + Zn or Al + NaOH  NH3 + [Zn(OH)4]2– or [Al(OH)4]–
(ii) Metal nitride hydrolysis : N3– + 3H2O  NH3 3OH–
450ºC
(iii) Haber’s process : N2 + 3H2 
 2NH3
200 1000 atm
catalyst Fe / Mo

Q.1 NH3 can’t be dried by H2SO4, P2O5 and anh. CaCl2 because :
2NH3 + H2SO4  (NH4)2SO4
H2O + NH3 + P2O5  (NH4)3PO4
CaCl2 + 8NH3  CaCl2.8NH3
forms adduct
Quick lime is used for this purpose

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


NH3 (base) int eraction

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 K + e 
+ e(NH3)x It is the cause
K (NH3)n
solvated e– for above 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

Residue Filtrate
AgCl Ba(NO3)2
liq. NH3

Cl– + [Ag(NH3)2]+
Ba(NH3)2
crystal
+ –
BaCl2  +[Ag(NH3)2] + NO3

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CHEMISTRY p-BLOCK ELEMENTS

(iii) CH3COOH is strong acid in liq. NH3 while in water is weak acid.

AcOH  AcO  H
NH3 + H+  NH4+ 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 & NH 4Cl
vapour respectively.

NH4+ – Salts Preparation

Gypsum (NH4)2SO4 + CaCO3
Na
suspension NO
saturated NaCl 3

with NH3 NH4NO3

NH4Cl
and CO2
passed NaNO2
(NH4)2CO3
NH4(NO2)
Oxides of Nitrogen :
Oxides of Nitrogen Structure Physical state colour of gas


N2O NNO Gas Colourless

NO N = O or N O Gas Colourless
O O;O=N–O–N
N2O3 N—N Gas Blue liquid (–30ºC)
O
O
O O O
NO2 2N N—N Gas Brown
O O O
O O
N2O5 N N Colourless solid –(no existance in gas phase)
O O O

Preparations :
1. N2O :
(i) NH4NO3  N2O + H2O
(ii) (NH4)2SO4 + NaNO3  NH4NO3 + Na2SO4

N2O + 2H2O

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p-BLOCK ELEMENTS CHEMISTRY

(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) Ostwald process – Restricted oxidation of NH3.
Industrial process :
6 atm
4NH3 + 5O2 
750ºC, Pt Cat
 4NO + 6H2O

3. N2O3 :
(i) HNO3 + As2O3  H3AsO4 + N2O3
(ii) Cu + HNO3(6M)  Cu(NO3)2 + (NO + NO2)
Cool(–30ºC)
Blue liq.(N2O3)

4. NO2 :

(i) M(NO3)2  MO + 2NO2 + 1/2O2 [M = Pb, Cu, Ba, Ca]
(ii) (Cu, Pb, Ag) + HNO3  M–nitrate + NO2 + H2O
Hot & Conc.

5. N2O5 :
(i) 2HNO3 + P2O5  2HPO3 + N2O5
(ii) 4AgNO3 + 2Cl2(dry gas)  4AgCl + 2N2O5 + O2

Properties :
(I) Decomposition Behaviour :
500ºC900ºC
(i) N2O 
 2N2 + O2

800ºC
(ii) 2NO 
 N2 + O 2

Room temp.
(iii) N2O3 
 NO2 + NO
(Blue liq.) at (–30º C)
620ºC
(iv) 2NO2 
 2NO + O2

11ºC
N2O4 
 2NO2
(white solid) Brown gas
at (–11ºC)

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CHEMISTRY p-BLOCK ELEMENTS

30ºC 40ºC
(v) N2O4 
 N2O5 
 2NO2 + 1/2O2
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 solution ............
(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 HNO3 NaNO3

Other properties :
N2O : 2N2O  2N2 + O2 mixture contains
Hence it is better supporter 33% O2 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

NO : (i) It burns : NO + 1/2 O2  NO2

(ii) It supports combustion also for molten sulphur and hot phosphorous.
S + 2NO  SO2 + N2
2P + 5NO  P2O5 + 5/2 N2
(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

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(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  2 + 2KNO2
(2) Reducing property of NO2.
KMnO4 + NO2 + H2SO4  K2SO4 + MnSO4 + HNO3 + H2O
4 5
O03  2NO2  O02  N2O5

not the reduction product of O3

N2O5 :2 + 5N2O5  2O5 + 10NO2 (2O5 is used for the estimation of CO)
2O5 + 5CO  2 + 5CO2
2 + 2S2O32–  2– + S4O62–
N2O5 + NaCl  NaNO3 + NO2Cl
It proves that N2O5 is consisting of ion pair of NO2+ & NO3–.
Oxyacids of N :
HNO2 : Preparation
 dil. aicd
(i) M–nitrite 
HCl or H SO
 HNO
2
2 4

(ii) N2O3 + H2O  2HNO2

Properties :
(i) Oxidising property of HNO2
K + HNO2 + HCl  KCl + H2O + NO + 2
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  Na2AsO4 + NO + H2O
(ii) Reducing property of HNO2
KMnO4 + HNO2 + H2SO4  K2SO4 + MnSO4 + HNO3 + H2O

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CHEMISTRY p-BLOCK ELEMENTS

K2Cr2O7 + HNO2 + H2SO4  K2SO4 + Cr2(SO4)3 + HNO3 + H2O

H2O2 + HNO2  H2O + HNO3
HNO2 + urea 
+ thiourea 
+ sulphamic acid 
+ NH3  NH4NO2
+ C2H5NH2  C2H5OH + N2

 5ºC
 PhN2+ X–
+ Ph–NH2 

NITRIC ACID (HNO3)

1. It was named aqua forties (means strong water) by alchemists.

Preparation
(i) Laboratory Method
KNO3 + conc. H2SO4 KHSO4 + HNO3(vap)

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

(ii) Industrial Preparation

(A) Birkeland Eyde Process or arc process

3000ºC
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 NO + H2O + heat
700 - 800ºC
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 NO 2.
4HNO3 Sunlight 4 NO2 + 2H2O + O2
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.

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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 oxidised to sulphuric acid
S + 6HNO3 H2SO4 + 6NO2 + 2H2O
conc. and
hot
(2) Carbon is oxidised to carbonic acid
C + 4HNO3 H2CO3 + 4NO2 + 2H2O
(3) Phosphorus is oxidised to orthophosphoric acid.
2P + 10HNO3 2H3PO4 + 10NO2 + 2H2O
conc. and hot

(4) Iodine is oxidised to iodic acid

I2 + 10HNO3 2HIO3 + 10NO2 + 4H2O
conc. and hot

(ii) Oxidation of metalloids

Metalloids like non-metals also form highest oxyacids
(1) Arsenic is oxidised to arsenic acid
2As + 10HNO3 2H3AsO4 + 10NO2 + 2H2O

or As + 5HNO3 H3AsO4 + 5NO2 + H2O

conc. and hot

(2) Antimony is oxidised to antimonic acid

Sb + 5HNO3 H3SbO4 + 5NO2 + H2O
conc. and hot

(3) Tin is oxidised to meta - stannic acid.

Sn + 2HNO3 H2SnO3 + 4NO2 + H2O

(iii) Oxidation of compounds :

(1) Sulphur dioxide is oxidised to sulphuric acid

SO2 + 2HNO3 H2SO4 + 2NO2

(2) Hydrogen sulphide is oxidised to sulphur

H2S + 2HNO3 2NO2 + 2H2O + S

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(3) Ferrous sulphate is oxidised to ferric sulphate in presence of H2SO4

6FeSO4 + 3H2SO4 + 2HNO3 3Fe2(SO4)3 + 2NO + 4H2O

(4) Iodine is liberated from KI.

6KI + 8HNO3 6KNO3 + 2NO + 3I2 + 4H2O

(5) HBr, HI are oxidised to Br2 and I2, respectively.

2HBr + 2HNO3 Br2 + 2NO2 + 2H2O
Similarly, 2HI + 2HNO3 I2 + 2NO2 + 2H2O

(6) Ferrous sulphide is oxidised to ferrous sulphate

FeS + HNO3 Fe2(SO4)3 + 8NO2 + 4H2O

(7) Stannous chloride is oxidised to stannic chloride is presence of HCl.

2HNO3 + 14H NH2OH + NH3 + 5H2O
Hydroxylamine
NH3 + HNO3 NH4NO3
------------------------------------------------------------------------
7SnCl2 + 14HCl + 3HNO3 7SnCl4 + NH2OH + NH4NO3 + 5H2O

(8) Cane sugar is oxidised to oxalic acid.

C12H22O11 + 36HNO3 6(COOH)2 + 36NO2 + 23H2O
(c) Action on Metals : Most of the metals will the exception 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. Amstrong 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, H2O, 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 + 16H 2NH3 + 6H2O
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
------------------------------------------------------------------------------------------
Very dilute HNO3 (6%) Mg, Mn H2 + Metal nitrate
----------------------------------------------------------
Fe, Zn, Sn NH4NO3 + metal nitrate + H2O
------------------------------------------------------------------------------------------
Dilute HNO3 (20%) Pb, Cu, Ag, Hg NO + metal nitrate + H2O
----------------------------------------------------------
Fe, Zn N2O + metal nitrate + H2O
----------------------------------------------------------

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p-BLOCK ELEMENTS CHEMISTRY

Sn NH4NO3 + Sn(NO3)2
------------------------------------------------------------------------------------------
Conc. HNO3(70%) Zn, Fe, Pb, Cu, Ag NO2 + metal nitrate + H2O
----------------------------------------------------------
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 colour. 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 hdyroxyl group as it is formed by
the hdyrolysis of nitryl chloride, NO2Cl. It may be structurally represented as bellow :
O
HO – N
O
Gaseous nitric acid is a planar molecule. The bond lengths and bond angles as present in the
molecule are represented in the figure :

H O
Å
22

102º
0.

116º
1.
96

O N 130º
Å

1.41 Å
1.
22
Å

PHOSPHOROUS

INTERCONVERSION OF WHITE ‘P’ & RED ‘p’

240 - 250ºC
White 'P' Red 'P'
in an intert atm. like
N2 or CO2
I2 : catalyst

heated to 550ºC
Red 'P' White 'P'
in an intert atmosphere and
then rapid cooling to room temp.

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CHEMISTRY p-BLOCK ELEMENTS

PREPARATION OF WHITE ‘P’

1200ºC
Ca3(PO4)2 + 3SiO2 3CaSiO3 + P2O5
Bone ash or Apatite rock
(i)
both have same formula
1500ºC
2P2O 5 + 10C P4 + 10CO
(Coke) (white 'P')

(ii) Ca3(PO4)2 + 3H2SO4 (conc.) 3CaSO4 + 2H3PO4

320ºC
H3PO4 HPO3
–H2O
meta phosphoric acid

12C + 4HPO3 1000ºC 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 AIP
Ca3P2 + H2O M(OH)n + PH3
or Mg3P2
or AIP
PREPARATION OF PH3 (PHOSPHINE GAS)

(i) 4H3PO3 PH3 + 2H3PO4

(ii) PH4I + KOH KI + PH3 + H2O

(PH3 + HI)
Purest PH3
(iii) 2AlP + 3H2SO4 Al2(SO4)3 + PH3

PHYSICAL PROPERTIES
(i) It is having rotten fish smell
(ii) It is soluble in CS2 and insoluble in water.
(NH3 is soluble in water)
NH4  OH
:

PH3 + H2O +
PH4 + OH
–

in s-orbital, so donating capacity is less

PH4 is formed with acids

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p-BLOCK ELEMENTS CHEMISTRY

(iii) Like NH3, PH3 also can form addition product.

CaCl2 . 8NH3 CuCl2 . 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 150º P2O5 + H2O

(ii) PH3 + 3Cl2 PCl3 + 3HCl
electrical
(iii) PH3 + 4N2O H3PO4 + 4N2
sparking
(iv) 2PH3 + 3CuSO4 Cu3PO2  + 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 :
95.5ºC
R
below above
95.5ºC 95.5ºC
(iii) -Sulphur

Amorphous forms are

(i) Plastic sulphur
(ii) Milk of sulphur
(iii) Colloidal sulphur

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CHEMISTRY p-BLOCK ELEMENTS

n
190ºC

112ºC
Temp.
160ºC

Viscosity of ‘S’ with temperature

m.p. of ‘S’ 112.8ºC
(i) > 112.8ºC to 160ºC  slow decrease due to
S8 rings slip and roll over one another easily.
(ii) > 160ºC, increases sharply due to breaking of
S8 rings into chains and polymerises into large size chain.
(iii) 190ºC, 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 3S  + 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

H2 S :
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

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p-BLOCK ELEMENTS CHEMISTRY

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
Prep :
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

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CHEMISTRY p-BLOCK ELEMENTS

SO2
NaHSO3 + CO2
excess
evaporation
Na2S2O5.xH2O
Na2CO3 in excess SO2 pyrosulphite
solution or disulphite

SO2 Na2SO3 + SO2

in excess Na2SO3
Na2CO3

Na2S + 3Na2SO4

Reducing Prop.: (Revise from acid radical)

FeCl3 + SO2 FeCl2 + H2SO4

Add HCl
to make
strongly
acidic and
SO2
passed

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

6SnCl2 + 2SO2 + 8HCl 5SnCl4 + 4H2O + SnS2  (Yellow solid)

150ºC
(ii) SO2 + 2H2SO3 2H2SO4 + S
sealed tube
FeSO4 Fe2O3 + SO2 + SO3
Fe2(SO4)3 Fe2O3 + 3SO3

H2SO4 & SO3 :

Both gas

SO2 + Cl2 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 444ºC. H2SO4 H2O + SO3

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p-BLOCK ELEMENTS CHEMISTRY

(b) Acidic nature : NaOH + H2SO4 + H2O NaOH Na2SO4 + H2O

(c) CO32– + H2SO4 SO42– + H2O + CO2

Carbonates or bicarbonates
HCO3+ H2SO4 H3SO4– + 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

(e) NaCl HCl

Ca 3(PO 4)2 H3PO 4
FeS H2S
CH3CO 2Na + H2SO 4 AcOH
NaNO3 HNO 3
CaF2 HF
NaNO2 HNO 2

(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 :

140ºC
C2H5O–C2H5
H2SO4 H2SO4
C12H22O11 12 C C2H5OH
–11H2O
C2H4
180ºC

H2SO4
C6H12O6 6C
–6H2O

H2SO4
(COOH)2 CO + CO2 PhH H2SO4 Ph – SO3H
–H2O

HCO2H –H O CO
2

SODIUM THIOSULPHATE
Propn”. :
(i) Na2SO3soln + S (powder) boiling Na2S2O3 evaporation Na2S2O3.5H2O, monoclinic crystal

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CHEMISTRY p-BLOCK ELEMENTS

SO2 Na2CO3 + 2SO2 + H2O

passed 2NaHSO3 + Na2CO3 Na2SO3 + H2O + CO2

Na2CO3
excess

roasting
(ii) Na2SO4 + 4C Na2S + 4CO
Salt cake Coke SO2 passed into it

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

(iii) 2Na2S + Na2CO3 + 4SO2 3Na2S2O3 + CO2

(iv) 6NaOH + 4S Na2S2O3 + 2Na2S + 3H2O
3Ca(OH)2 + 12 S CaS2O3 + 3H2O + 2CaS5

(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 S4O62– + 2I–
+ Cl2 – water SO42– + S + 2HCl
+ Br2 – water SO42– + S + 2HBr
+ 4OI– + 2OH– 2SO42– + 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.

Ozonised
2F2 + 2H2O 4HF + O2 is separated by passing into spiral tube cooled by liq.
F2 + 3H2O 6HF + O3 air. Ozone condenses at – 112.4ºC.
oxygen
[b.p. of O2 – 183ºC ; b.p. of liq. air is –190ºC]
 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 Eº = +2.07 V
It is next to F2. [above 2.07 V, only F2, F2O are there ]

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p-BLOCK ELEMENTS CHEMISTRY

(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

I2 + 2KOH + O2

KI+KOI O3 estimated by this reaction

KI + KOI + 2HCl 2KCl + I2 + H2O

I2 + 2S2O3 2–
S4O62– + 2I–

KI + 3O3 KIO3 + 3O2

(c) alk.
KI + 4O3 KIO4 + 4O2

(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 + O2 3SO3

(ii) 3SnCl2 + 6HCl + O3 3SnCl4 + 3H2O

Absorbent :
(i) Turpentine oil
(ii) Oil of cinnamon

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CHEMISTRY p-BLOCK ELEMENTS

test :
(i) Sterilising water

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

H2O2

Method preparation :
(i) 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 2H+ + 2H2SO4–
2H2SO4– H2S2O8 + 2e. [At anode] [At cathode 2H+ + 2e H2]
H2S2O8 + 2H2O 2H2SO4 + H2O2

(iv)

O OH
C2H5 O
Et
H2 / Pd Et
O2
+ H2O2
O OH
O

Properties :
(i) Colourless, odourless liquid (b.p. 152º)
(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– [reaction 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
X2 + H2O2 2HX + O2X = Cl, Br.
2KI + H2O2 2KOH + I2
H2S + H2O2 S  + 2H2O S.R.P order of Cl2 > Br2 > H2O2 > I2
H2SO4 + 2FeSO4 + H2O2 Fe2(SO4)3 + 2H2O
2K4[Fe(CN)6] + H2O2 + H2SO4 2K3[Fe(CN)6] + K2SO4 + 2H2O
2[Cr(OH)4]– + 3H2O2 + 2OH– 2CrO42– + 8H2O

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p-BLOCK ELEMENTS CHEMISTRY

CrO42– + 2H+ + H2O2 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]

2KMnO4 + 3H2O 2KOH + 2MnO2 + 2H2O + 3O2
2MnO4– + 2OH– 2MnO42– + H2O + O
2MnO42– + 2H2O 2MnO2 + 4OH– + 2O
2MnO4– + 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 exothemic 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
GROUP - VII
HALOGENS
Method of Prep” :
F2 : By electrolysis of KHF2 (which is obtained from CaF2)
CaF2 + H2SO4 CaSO4 + 2HF KF decrease the m.p. of
HF + KF KHF2 the mix. depending upon
the composition.
KHF2 Electrolysis H2(at cathode) + F2 (at anode)

Cl2 :
(i) By electrolysis of aq. NaCl
2NaCl + 2H2O 2NaOH + H2 + Cl2
(anode)
at cathode
Electrolysis
(ii) 2NaCl 2Na + Cl2
(Molten) (cathode) (anode)

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CHEMISTRY p-BLOCK ELEMENTS

(iii) In laboratory : Oxidising HCl by KMnO4 or MnO2

2KMnO4 + 16HCl 2KCl + 2MnCl2 + 5Cl2 + 8H2O
MnO2 + 4HCl MnCl2 + Cl2 + 2H2O

Br2 : From Bromine water (contains 65 ppm of Br–)

Cl2 + 2Br– 2Cl– + Br2 (Br2 is volatite 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
5 Br– + BrO3– + 6H+ 3Br2 + 3H2O

I2 : Chille salt petre contains traces ofNaIO3 which is reduced to I– by NaHSO3, then oxidation
of I– to I2 by IO3– .
2IO3– + 6HSO3– 2I– + 6SO42– + 6H+
+
6H
5I– + IO3– 3I2 + 3H2O

Q. Liquid I2 conducts electricity. Explain

Ans. Due to its self ionisation 3I 2 I3+ + I3–

Q. X2 + OH– X– + OX– + H2O but on acidification the disproportionated product gives

X + XO3– + H2O
–
back the same element.
X2 = Cl2, Br2, I2 But For F2 i.e. X– + OX– + 2H+ X2 + H2O
5X– + XO–3 + 6H+ 3X2 + 2H2O
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 SiO 2

SiF4 + 2HF H2[SiF6] consumer 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.
150ºC
Ans. NaCl + H2SO4 NaHSO4 + HCl
Insoluble
550ºC
NaCl + NaHSO4 Na2SO4 + HCl
(Salt Cake)

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2NH4Cl + H2SO4 2HCl + (NH4)2SO4

[NH4HSO4 intermediate is water soluble and easy to handle]

** Another altermative process to avoid the formation of NaHSO4

1
NaCl + SO2 + H2O + O Na2SO4 + 2HCl
2 2
gaseous mixture

Q. In the similar type of preparation of HBr and HI from bromide and iodide, H 2SO4 can not be used
and H3PO4 is used. Explain.
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 + 3HBr
Another process ; PBr3 + 3H2O H3PO4 + 3HBr

Q. Boiling point order HX : HF > HI > HBr > HCl


Due to H-bonding

Q. HCl, H2SO4, HNO3 are bases in liquid HF where as HClO4 is acid. Comment.
Ans. HCl + HF H2Cl+ + F– ; H2SO4 + HF H3SO4+ + F–; HNO3 + HF H2NO3+ + P–
But HClO4 + HF H2F + ClO4
+ –

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

OXOACIDS :
HOF : H2O + F2 –40ºC HOF + HF
HOX : very unstable becuase
it reacts with both H2O
and F2 as follows :
HOCl HOF + F2 F2O + HF
HOBr X2 + H2O HOX + HX
HOI HOF + H2O2 H2O + HF
OX disproportionates in hot solution eg. 3OCl
– –
2Cl + ClO3–
–

X = Cl, Br, I
Cl
Bleaching Powder : Ca
OCl
Prepn. : Cl2(g) + Ca(OH)2 40ºC Ca(OCl)Cl + H2O
Slaked lime

(a) On long standing it undergoes

(i) auto oxiation 6Ca(OCl)Cl Ca(ClO3)2 + 5CaCl2
CoCl2
(ii) 2Ca(OCl)Cl 2CaCl2 + O2
Cat.
(iii) Ca(OCl)Cl + H2O Ca(OH)2 + Cl2

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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 + C
Ca(OCl)Cl + CO2 CaCO3 + Cl2
HXO2 :
BaO2 + 2ClO2 Ba(ClO2)2 + O2, Ba(ClO2)2 + H2SO4 BaSO4  + HClO2
(dil)
Only Known HClO2. It is stable in alkaline solution but disproportionates in acid solution.
5HClO2 H+ 4ClO2 + HCl + 2H2O
HXO3 : HClO3 > HBrO3 > HIO3 are known and acidic order is as shown
Prepn:

hot
HClO3 : Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O
Similarly electrolysis of hot halide solution with severe stirring gives the same product.
2Cl– + 2H2O Cl2 + 2OH– + H2

NaClO3 + KCl KClO3 + NaCl[KClO3 prep. ]

n

on cooling
Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O NaClO3 + BaCl2 Ba(ClO3)2 + NaCl
first
(recycled)
Ba(ClO3)2 + H2SO4 BaSO4 + HClO3

Properties :

* 3HClO3 evaporation 2ClO2 + H2O + HClO4

* IO3– + 5I– + 6H+ 3I2 + 3H2O
Oxidising property
ClO3– + 3SO32– Cl– + 3SO42–

low temp.
Disproportionation : 4KClO3 KCl + 3KClO4
absence of catalyst

400º-500ºC
2KClO3 2KCl + 3O2
MnO2(Cat.)

HXO4 : NaClO3 + H2O Electrolysis NaClO4 + H2

KClO4 + H2SO4 (conc.) HClO4 + KHSO4

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ClO4 + 2H + 2e
– +
A : ClO3– + H2O
Electrode reaction H2SO4
C : 2H + 2e
+
H2 KClO 4 HClO4
KCl
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 CHILORINE

+1 +4 +6 +7
Cl2O ClO2 Cl2O6 Cl2O7
(Brownish yellow) (Pale yelloow) (liq. – dark red colourless
solid – yellow) solid
Prepn :
Cl2 does not combine directly to produce its oxides but indirect methods are there.
Cl2O : 2Cl2 + 2HgO(s) HgO. HgCl 2
+Cl2O  (Brownish yellow gas)
dry in cooled tube Basic Hg(II) chloride

Condensed to oragne liq.
Props :
It dissolves in water : Cl2O + H2O 2HClO
Explodes violently with NH3.
3Cl2O + 10 NH3  2N2 + 6NH4Cl + 3H2O
It is oxidising agent
Cl2O + 2HCl 2Cl2 + H2O
O S
110º 102º
Structures :
Cl Cl Cl Cl Back bonding
ClO2 : Prepn :
3KClO3 + 3H2SO4 3KHSO4 + HClO4 + 2ClO2  + H2O
(powder) conc. Pale yellow gas

2HClO3 + H2C2O4 60ºC 2H2O + 2ClO2 + 2CO2

2AgClO3 + Cl2 90ºC 2AgCl + 2ClO2 + O2 [By this reaction pure ClO2 obtained]
ClO2 dissolves in water ClO2 ClO + O
producing dark green 2ClO + H2O HCl + HClO3
solution which decomposes
in presence of light.
but in alkali gives mixture of chlorite and chlorate.
2ClO2 + 2NaOH NaClO2 + H2O
where 2ClO2 + 2NaOH + H2O2 2NaClO2 + O2 + 2H2O
used in bleaching
textiles and paper.

ClO2 does not dimerise because odd e—s undergoes delocalisation (in its own vaccant 3d-orbital)

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Cl2O4 (Cl.ClO4) is not the dimer of ClO2. Actually it is Cl-perchlorate.

CsClO4 + ClOSO2F Cs(SO3)F + ClOClO3
Cl2O6 : Possible structures are :
O O O O O
O Cl – Cl O Cl Cl ClO2+ ClO 4
–

O O O O O
liq dark red
Solid Yellow

Q. Prove that Cl2O6 is consisting ClO2+ and ClO4–

Prepn : 2ClO2 + 2O3 0ºC Cl2O6 + 2O2
Cl2O6 2ClO3 (monomer is paramagnetic)
Reactions : Cl2O6 + H2O HClO3 + HClO
Cl2O6 NaOH NaClO3 + NaClO4 + H2O
Cl2O6 + HF ClO2F + HClO4
Cl2O6 + NO2 ClO2 + [NO2]+ [ClO4]–
Cl2O7 (colourless solid) : It is the anhydride of HClO4 and prepared from it by the action P2O5.
2HClO4 + P2O5  2HPO3 + Cl2O7
O O
Structure : O Cl 119ºC Cl O
O
O
O

INTER HALOGEN

Types : AX AX3 AX5 AX7

ClF ClF3 ClF5 IF7
BrF BrF3 BrF5
BrCl (lCl3)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 moelcule.
* 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 mroe atoms around it.
* The interhalogens are genrally more reactive than the halogens (except F2) due to weaker
A–X bonds compared to X – X bond.
Reactions : ICl + H2O HCl + HOI Oxohalide is always formed with larger
BrF5 + 3H2O HBrO3 + 5HF halogen present during hydrolysis of
IF5 + 3H2O HBrO3 + 5HF interhalogen compounds

IF7 + H2O IOF5 + 2HF (less)

Parallel reaction
4H2O HIO4 + 7HF

(i) ClF is hightly reactive and as a fluorinating agent.

6ClF + 2Al 2AlF3 + 3Cl2
6ClF + U UF6 + 3Cl2

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6ClF + S SF6 + 3Cl2

ClF + SF4 SF5Cl
One pecularity with Cl :
Cl CO2H
ICl vap. is chlorination (I)
CO2H
OH
OH ICl in
I CO2H
Nitrobenzene
is chlorination (II)
OH

In IInd case, the attacking species is I + which has been supported by the formation of I+ in fuse state
as follows :
3ICl [I2Cl]+ + [ICl2]–
* ICl3 does not exist
but its dimer exist. 2ICl3 I2Cl6
Structure is palnar.
Cl Cl Cl
I I (Bright yellow solid)
Cl Cl Cl
I2Cl6 : liq. has appreciable electrical conductivity like other interhalogens.
I2Cl6 [ICl2]+ + [ICl4]–
BrF3 [BrF2]+ + [BrF4]–
IF5 [IF4]+ + [IF6]–
3ICl [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

I
I
— — 2—
I – I ----- I I – I ----- I
I–I I – I – I---I

I I
I
I I
I

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in [N(CH3)4]+ I7– in Cs2I8

* Only F3– not known [due to absence of d-orbital] [i.e. Cs2I3 – I2 – I3]
I3–, Br3–, Cl3– are known Cl3– compounds are very less.
Stability order : I3– > Br3– > Cl3– : depends upon the donating ability of X–.

PSEUDO HALOGEN

There are univalent ion consisting of two or more atoms of which at least one is N, that have
property 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)
NCN2–(Bivalent) H2NCN(cyanamide)
ONC– HONC (Fulminic acid)
N3– HN3 (Hydrazoic acid)
CN shows maximum similarties with Cl–, Br–, I–
(i) froms HCN
(ii) forms (CN)2
(iii) AgCN, Pb(CN)2, are insoluble
(iv) Inter pseudo 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 : (–269ºC) same
* Atomic radius order : Same
* Density order : Same
* Relative abundance : Ar is highest (Ne, Kr, He, Rn)
“He” (helium) has the lowest b.p (–269ºC) 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 H 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

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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 some 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 ?
e.g. Xe . 6H2O formed only when
Ar . 6H2O water freezes at high
Kr. 6H2O pressure together with noble gas

Xenon Fluorides :–

400ºC, 1 atm
2:1 XeF 2

600ºC, 7 atm
(1) Xe + F2 1:5 XeF 4

1 : 20 XeF 6
300ºC, 60-70 atm

(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 + XeO2 + 12HF + O2
2
XeF6 + 2H2O XeO3 + 6HF

(explosive, white hygroscopic solid)

(5) SiO2 also converts XeF6 into XeOF4

2XeF6 + SiO2 SiF4 + 2XeOF4
violet
Similary, XeO3 + XeOF4 2XeO2F2 , XeO3 + 2XeF6 3XeOF4

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(6) Xe - fluorides are also hydrolysed in alkaline medium.

2XeF2 + 4OH– 2Xe + 4F– + 2H2O + O2
XeF6 + 7OH –
HXeO4– + 3H2O + 6F–
Xenate ion

2HXeO4– + 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 Flouride acceptor also :

XeF6 + RbF /CsF Rb+ /Cs+ [XeF7]–

2Cs+[XeF7]– XeF6 + Cs2[XeF8]

50ºC
XeF4 + MF M+ + XeF5–
(alkali metals fluoride)

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