s-BLOCK ELEMENTS

SHORT NOTES
SUNIL VODELA
 s - Block Element
The elements in which the last electron enters the outermost s-orbital are called s - block elements. The
group 1 and 2 of periodic table belong to the s-block.

Group - I Elements : (Alkali Metals)

(1) The Elements : are Li , Na, K, Rb, Cs, Fr (Radioactive : t1/2 of Fr233 = 21 minutes)
group - I elements are called alkali metals because they from hydroxides on reaction with water, which
are alkaline in nature.

(2) Outer Electronic configuration : ns1

(3) Atomic and Ionic radii

Li < Na < K < Rb < Cs.
Increase down the group, because value of n (principal quantum number) increases.

(4) Density
Li < K < Na < Rb < Cs.

(5) Ionization Energy

Li > Na > K > Rb > Cs.
As size increases, I.E. decreases down the group (so Cs have lowest I.P.)

(6) Hardness and melting points / boiling points

* These metals are very soft and can be cut with a knife. Lithium is harder than any other alkali metal.
The hardness depends upon cohesive energy
* Cohensive energy  Force of attraction between atoms.
M.P. Li > Na > K > Rb > Cs
B.P. Li > Na > K > Cs > Rb

(7) Electropositive character or metallic character

Alkali metals are strongly electropositive and metallic. Down the group electropositive nature increase
so metallic nature also increases.
i.e. M  M+ + e–
1
Metallic Nature : Electropositive character 
I.P.
Li < Na < K < Rb < Cs.

(8) Oxidation state

Show +1 oxidation state because by loosing one electron they get stable noble gas configuration.

(9) Photoelectric effect

The phenomenon of emission of electrons when electromagnetic rays strikes against them is called
photoelectric effect; Alkali metal have low I.P. so show photoelectric effect.
* Cs and K are used in Photoelectric cells.

s-Block Elements [2]

Chemical Properties
(1) Reactions with air
The alkali metals tarnish in dry air due to the formation of their oxides on their surface, which in turn react
with water to form hydroxides
4M + O2  2M2O
M2O + H2O  2MO
They react vigorously in oxygen forming following oxides.
4 Li + O2  2 Li2O (Monoxide)
2 Na + O2  Na2O2 (Peroxide)
M + O2  MO2 ( Superoxide) where M = K, Rb, Cs

(2) Solutions in liquid NH3

Alkali metals dissolve in liquid ammonia (high conc. 5 M) and give blue solution which is conducting,
reducing and paramagnetic in nature.

Reason
On dissolving Metal in NH3

M(s) NH 3
M+ + e–

M+ + x(NH3)  [M(NH3)X ]+ Ammoniated cation

e– + y(NH3)  [e(NH3)y ]– Ammoniated electron
The blue colour is due to  Ammoniated electron
The paramagnetic nature is due to  Ammoniated electron
The conducting nature is due to  Ammoniated M+ + Ammoniated electron

* On standing the colour fades due to formation of amide

1
M+ + e– + NH3  MNH2 (amide) + H
2 2 (g)
In the absence of impurities like. Fe, Pt, Zn etc, the solutions are stable.

* In concentrated solution, the blue colour changes to bronze colour and diamagnetic due to the formation
of metal clusters and ammoniated electrons also associate to form electron pairs
2 e– (NH3)y  [ e– (NH3)4]2
(3) Reducing Nature
* Reducing agent is electron donor.
Alkali metals are strong reducing agents with lithium being the strongest and sodium the least prowerful
reducing agent. Na < K < Rb < Cs < Li
Note : Lithium is expected to be least reducing agent due to it's very high IE. However it is strongest. (due to
high hydration energy).

(4) Reaction with H2O

The reaction with water to form the hydroxides having the formula MOH
2M + 2H2O  2MOH + H2
(Highly reactive)

(5) Reaction with H2

They react with H2 forming metal hydride with formula MH which are of ionic nature. Stability of hydride
decreases down the group.

s-Block Elements [3]

(6) Reaction with N2
Only Lithium reacts with N2 to form ionic lithium nitride Li3N.
3
3Li + N 2  Li3N
2
(7) Reaction with halogens X2
The alkali metals react vagariously with halogens to form ionic halides M+X–
2M + X2  2MX

(8) Sulphides
All metals react with S forming sulphides such as Na2S and Na2Sn (n = 2, 3, 4, 5 or 6). The polysulphide
ions are made from zig-zag chains of sulphur atoms.
S S S– S S

–S S– –S S –S S S–
(9) Crown Ethers and Cryptands:

O
O O O

M
+
O O N
N
O
O O O

O
Cryptand - 222
Dibenzo-18-Grown-6

[Na (Cryptand 222)]+ Na– [Contains Na– (sodide ion)]

[(s+(Cryptand - 222)] [(Cyrptand-222)e–] [electride]

Group II Elements (Alkaline Earth Metals)

(1) The Elements are Be, Mg, Ca, Sr, Ba Ra,

(2) Outermost Electronic configuration : - ns2

(3) Atomic and ionic sizes

* The atomic and ionic radii of the alkali earth metal are smaller than corresponding alkali metals
Reason : higher nuclear charge (Zeff)

* On moving down the group size increase, as value of n increases.

Be < Mg < Ca < Sr < Ba

(4) Ionization Enthalpy

Be > Mg > Ca > Sr > Ba
Down the group IE decreases due to increase in size

s-Block Elements [4]

Q. IE1 of AM < IE1 of AEM
IE2 of AM > IE2 of AEM
[where AM = Alkali metal, AEM = Alkaline earth metal]
Reason : IE1 of AEN is large due to increased nuclear charge in AEM as compared to AM but IE2 of
AM is large because second electron in AM is to be removed from cation which has
already acquired noble gas configuration.

(5) Melting and Boiling points

The have low m.p. and b.p. but are higher than corresponding value of group I.

Reason : They have two valency electrons which may participate in metallic bonding compared with
only one electron in AM. Consequently group II elements are harder and have higher cohesive energy
and  have much higher m.p./ b.p. than A.M.
M.P. Be > Ca > Sr >Ba > Mg
B.P. Be > Mg > Ca > Ba > Sr

(6) Electropositive and Metallic character

Due to low IE they are strong electropositive but not as strong as AM because of comparatively high IE.
The electropositive character increase down the group.
Be < Mg < Ca < Sr < Ba

(7) Oxidation State

Show + 2 oxidation state.

Chemical Properties
(1) Reactivity towards Air or Oxygen
* Be and Mg are kinetically inert towards oxygen becasue of formation of a film of oxide on their surface.
However powdered Be burn brilliantly.
2Be + O2 (air) 
 2BeO
3Be + N2 (air)  
 Be3N2
Only Mg give the following behaviour.
Mg + Air (N2 + O2)   MgO + Mg3N2
(Similar property with Li due to diagonal relation.)

* BeO, MgO are used as refractory, because these have high m.p.

* Other metals (Ba or Sr form peroxide)

M + O2 
 MO2

(2) Reaction with H2O

AEM have lesser tendency to react with water as compared to AM. They form hydroxides and liberate
H2 on reaction with H2O
M + 2H2O 
 M(OH)2+ H2

* Be is inert towards water.

* Magnesium react as
Mg + 2H2O  Mg(OH)2 + H2
or Mg + H2O  MgO + H2O
s-Block Elements [5]
 MgO forms protective layer, that is why it does not react readily unless layer is removed amalgamating
with Hg.
Other metals react quite readily (Ca, Sr, Ba).

Note: Be(OH)2 is amphoteric but other hydroxides are basic in nature.

(3) Reaction with Acids & Bases

AEM react with acids & liberate H2
Mg + 2HCl  MgCl2 + H2
Be is amphoteric as it also react with NaOH, other metals do not react as they are purely basic.
Be + 2NaOH  Be(OH)2 excess 2–
NaOH  [Be(OH)4]

(4) Tendency to form Complexes

AEM have tendency to form some stable complexes. Among these Be and Mg have maximum tendency
due to their small size and high charge density.
BeF2 + 2F–  [BeF4]–2
* Chlorophyll contains Mg2+ [Photosynthetic pigment in plants]
* Ca2+ and Mg2+ form complex with EDTA.

(5) Reactivity with NH3

Like AM, the AEM (only Ca, Sr, Ba) dissolve in by NH3 to give deep blue - black solutions having
ammoniated cations, and ammoniated electrons.

(6) Reaction with Carbon

AEM when heated with carbon form carbides
* Be form Be2C
* Mg, Ca, Sr, Ba form carbides of the formula MC2.

s-Block Elements [6]

 GROUP -I & II
OXIDES
Sodium Oxide (Na2O):
Preparation :
(i) It is obtained by burning sodium at 180°C in a limited supply of air or oxygen and distilling off the excess
of sodium in vacuum.
1
2Na + O 180
 Na2O
2 2
(ii) By heating sodium peroxide, nitrate or nitrite with sodium.
Na2O2 + 2Na  2Na2O
2NaNO3 + 10Na  6Na2O + N2
2NaNO2 + 6Na  4Na2O + N2

Properties :
(i) It is white amorphous mass.
(ii) It decomposes at 400°C into sodium peroxide and sodium
2Na2O 400  C
 Na2O2 + 2Na
(iii) It dissolve violently in water, yielding caustic soda.
Na2O + H2O  2NaOH
Sodium Peroxides (Na2O2):
Preparation: It is formed by heating the metal in excess of air or oxygen at 300°, which is free from moisture
and CO2.
2Na + O2  Na2O2
Properties:
(i) It is a pale yellow solid, becoming white in air from the formation of a film of NaOH and Na2CO3.
(ii) In cold water (~0°C) produces H2O2 but at room temperature produces O2. In ice-cold mineral acids
also produces H2O2.
~ 0C
Na2O2 + 2H2O  2NaOH + H2O2
2Na2O2 + 2H2O 25
C
 4NaOH + O2
Na2O2 + H2SO4 ~ 0C
 Na2SO4 + H2O2
(iii) It reacts with CO2, giving sodium carbonate and oxygen and hence its use for purifying air in a confined
space e.g. submarine, ill-ventilated room,
2Na2O2 + 2CO2  2Na2CO3 + O2
(iv) It is an oxidising agent and oxidises charcoal, CO, NH3, SO2.
3Na2O2 + 2C  2Na2CO3 + 2Na [deposition of metallic Na]
CO + Na2O2  Na2CO3
SO2 + Na2O2  Na2SO4
2NH3 + 3Na2O2  6NaOH + N2
(v) It contains peroxide ion [–O–O–]–2

Uses:
(i) For preparing H2O2, O2
(ii) Oxygenating the air in submarines
(iii) Oxidising agent in the laboratory.

s-Block Elements [7]

Oxides of Potassium:
K2O, K 2O 2 , K 2O 3 , KO 2 and KO 3

Colours: White White Red Bright Yellow Orange Solid

Preparation:
(i) 2KNO3 + 10K heating
  6K2O + N2
** K2O heating
 K2O
(White) (Yellow)
** K2O + H2O  2KOH
Controlled
(ii) 2K + O2    K2O2 [Props: Similar with Na2O2]
air at 300C
(iii) Passage of O2 through a blue solution of K in liquid NH3 yields oxides K2O2 (white), K2O3 (red) and
KO2 (deep yellow) i.e
O
K in liq. NH3 2 K2O2  K2O3  KO2
white red yellow
** KO2 reacts with H2O and produces H2O2 and O2 both
2KO2 + 2H2O ~
0C
 2KOH + H2O2 + O2
KO3 : KOH + O3 (ozonised oxygen)    KO 3
10 to 15C

(Dry powdered) (orange solid)

Magnesium Oxide (MgO):
It is also called magnesia and obtained by heating natural magnesite.
MgCO3  MgO + CO2
Properties:
(i) It is white powder.
(ii) It's m.p. is 2850°C. Hence used in manufacture of refractory bricks for furances.
(iii) It is very slightly soluble in water imparting alkaline reaction.

Calcium Oxide (CaO):

It is commonly called as quick lime or lime and made by decomposing lime stone at a high temperature
about 1000°C.
CaCO3  CaO + CO2 + 42000 cal

Properties:
(i) It is white amorphous powder of m.p. 2570°C.
(ii) It emits intense light (lime light), when heated in oxygen-hydrogen flame.
(iii) It is an basic oxide and combines with some acidic oxide e.g.
CaO + SiO2  CaSiO3
CaO + CO2  CaCO3
(iv) It combines with water to produce slaked lime.
CaO + H2O  Ca(OH)2

Magnesium Peroxide (MgO2) and Calcium Peroxide (CaO2):

These are obtained by passing H2O2 in a suspension of Mg(OH)2 and Ca(OH)2.

Uses: MgO2 is used as an antiseptic in tooth paste and as a bleaching agent.

s-Block Elements [8]

 HYDROXIDES
Sodium Hydroxides:
Preparation:
(i) Electrolysis of Brine :
NaCl  Na+ + Cl –
At anode : 2Cl–  Cl2 + 2e
At cathode : H+ + e–  H

(ii) Caustication of Na2CO3 (Gossage's method):

Na2CO3 + Ca(OH)2  2NaOH + CaCO3
(suspension)
Since the Ksp (CaCO3) < Ksp (Ca(OH)2), the reaction shifts towards right.

Properties:
(i) It is white crystalline, deliquescent, highly corrosive solid.
(ii) It is stable towards heat.
(iii) It's aqueous solution alkaline in nature and soapy in touch.
(iv) NH4Cl + NaOH  NaCl + NH3 + H2O
FeCl3 + 3NaOH  Fe(OH)3  + 3NaCl
Brown ppt

ZnCl2 + 2NaOH  Zn(OH)2  + 2NaCl

Zn(OH)2 + 2NaOH Excess  Na2ZnO2 + 2H2O [Same with AlCl3, SnCl2, PbCl2]
soluble
(v) Acidic and amphoteric oxides gets dissolved easily e.g.
CO2 + 2NaOH  Na2CO3 + H2O
Al2O3 + 2NaOH  2NaAlO2 + H2O
(vi) Aluminium and Zn metal gives H2 from NaOH
2Al + 2NaOH + 2H2O  3H2 + 2NaAlO2
(vii) Several non metals such as P, S, Cl etc. yield a hydride instead of hydrogen.e.g.
4P + 3NaOH + 3H2O  PH3 + 3NaH2PO2 (Disproportionation reaction)

Potassium Hydroxide:
Preparation: Electrolysis of KCl aqueous solution.
Properties: Same as NaOH
**(a) It is stronger base compared to NaOH.
(b) Solubility in water is more compared to NaOH.
(c) In alcohol, NaOH is sparingly soluble but KOH is highly soluble.
(d) As a reagent KOH is less frequently used but in absorption of CO2, KOH is preferably used compared
to NaOH. Because KHCO3 formed is soluble whereas NaHCO3 is insoluble and may therefore choke
the tubes of apparatus used.

Magnesium Hydroxide: It occurs in nature as the mineral brucite.

Preparation: It can be prepared by adding caustic soda solution to a solution of Mg-sulphate or chloride
solution.
Mg+2 + 2NaOH  Na2SO4 + Mg(OH)2

s-Block Elements [9]

Properties:
(i) It can be dried at temperature upto 100°C only otherwise it breaks into its oxide at higher temperature.
Mg(OH)2  MgO + H2O
(ii) It is slightly soluble in water imparting alkalinity.
(iii) It dissolves in NH4Cl solution
Mg(OH)2 + 2NH4Cl  MgCl2 + 2NH4OH
** Thus, Mg(OH)2 is not therefore precipitated from a solution of Mg+2 ions by NH4OH in presence of
excess of NH4Cl.

Calcium Hydroxide:
Preparation: By spraying water on quicklime
CaO + H2O  Ca(OH)2
Properties:
(i) It is sparingly soluble in water.
(ii) It's solubility in hot water is less than that of cold water. Hence solubility decreases with increase in
temperature.
(iii) It readily absorbs CO2 as used as a test for the gas.
(iv) It is used as a mortar.
[Mortar is a mixture of slaked lime (1 Part) and sand (3 Parts) made into paste with water.]

CARBONATES
Sodium Carbonate:
Preparation:
(i) Leblanc Process:
mild heating
NaCl + H2SO4 (conc.)    NaHSO4 + HCl
NaCl + NaHSO4 Strongly
  Na2SO4 + HCl
heated
(Salt Cake)
Na2SO4 + 4C  Na2S + 4CO
Na2S + CaCO3  Na2CO3 + CaS

(ii) Solvay Process:

NH3 + H2O + CO2  NH4HCO3
NaCl + NH4HCO3  NaHCO3 + NH4Cl
2NaHCO3 150  C
 Na2CO3 + H2O + CO2
Properties:
(i) Anhydrous Na2CO3 is called as soda ash, which does not decompose on heating but melts at 852°C.
(ii) It forms number of hydrates.
Na2CO3. H2O  Crystal carbonate  Na2CO3 + moisture in air
Na2CO3. 7H2O  –––––
Na2CO3.10H2O  Washing soda
(iii) Na2CO3 absorbs CO2 yielding sparingly soluble sodium bicarbonate which can be calcined at 250° to
get pure sodium carbonate.
Na2CO3 + H2O + CO2 2NaHCO3
(iv) It dissolved in acid with effervescence of CO2 and causticised by lime to give caustic soda.
Na2CO3 + HCl  2NaCl + H2O + CO2
Na2CO3 + Ca(OH)2  2NaOH + CaCO3
Uses: It is widely used in glass making as smelter.

s-Block Elements [10]

Potassium Carbonate:
By leblance process, it can be prepared but by solvay process it cannot be prepared because KHCO3
is soluble in water.
Properties: It resembles with Na2CO3, m.p. is 900°C but a mixture of Na2CO3 and K2CO3 melts at 712°C.

Uses: It is used in glass manufacturing.

Calcium Carbonate:
It occurs in nature as marble, limestone, chalk, coral, calcite etc. It is prepared by dissolving marble or
limestone in HCl and removing iron and aluminium present, by precipitating with NH3 and then adding
(NH4)2CO3 to the solution.
CaCl2 + (NH4)2CO3  CaCO3 + 2NH4Cl
Properties:
(i) It dissociates above 1000°C as follows:
CaCO3  CaO + CO2
(ii) It dissolves in water containing CO2 forming Ca(HCO3)2 but is precipitated from the solution by boiling.
CaCO3 + H2O + CO2 Ca(HCO3)2

Magnesium Carbonate:
It occurs in nature as magnesite, isomorphous with calcite. It is obtained as a white precipitated by
adding sodium bicarbonate to a solution of a magnesium salt; but only basic carbonate, called magnesia
alba, having the approximate composition MgCO3, Mg(OH)2, 3H2O is precipitated.
Properties: Same with CaCO3.

BICARBONATES
Sodium bicarbonates:
Preparation: By absorption of CO2 in Na2CO3 solution.
Na2CO3 + H2O + CO2 2NaHCO3
> 100°C sparingly soluble
Uses: It is used in medicine and as baking powder.
Potassium bicarbonates:
Preparation: Same as NaHCO3
Properties: Same with NaHCO3
But It is more alkaline and more soluble in water compared to NaHCO3.

Magnesium bicarbonate:
MgCO3 + CO2 + H2O Mg(HCO3)2

Calcium bicarbonate:
CaCO3 + CO2 + H2O  Ca(HCO3)2

CHLORIDES

Sodium Chloride: Prepared from brine containing 25% NaCl.

Properties:
(i) It is nonhygroscopic but the presence of MgCl2 in common salt renders it hygroscopic.
(ii) It is used to prepare freezing mixture in laboratory [Ice-common salt mixture is called freezing mixture
and temperature goes down to –23°C.]
(iii) For melting ice and snow on road.

s-Block Elements [11]

Potassium Chloride: It is also occurs in nature as sylvyne (KCl) or carnalite (2KCl · MgCl2 · 6H2O)
Uses: It is used as fertiliser.

Magnesium Chloride:
Preparation: By dissolving MgCO3 in dil. HCl
MgCO3 + 2HCl  MgCl2 + H2O + CO2
Properties:
(i) It crystallises as hexahydrate. MgCl2. 6H2O
(ii) It is deliquescent solid.
(iii) This hydrate undergoes hydrolysis as follows:
MgCl2·6H2O  Mg(OH)Cl + HCl + 5H2O
Mg(OH)Cl  MgO + HCl
** Hence, Anh. MgCl2 cannot be prepared by heating this hydrate.
** Because of this formation of HCl. Sea water cannot be used in marine boilers which corrodes the iron
body.
(iv) Anhydrous MgCl2 can be prepared by heating a double salt like. MgCl2 . NH4Cl . 6H2O as follows:
 H 2O strong
MgCl2 . NH4Cl . 6H2O   MgCl2 . NH4Cl  MgCl2 + NH3 + HCl
 
Sorel Cement: It is a mixture of MgO and MgCl2 (paste like) which set to hard mass on standing. This is used
in dental filling, flooring etc.

Calcium Chloride:
(i) It is the by-product in solvay process.
(ii) It may also be prepared by dissolving the carbonate in HCl
CaCO3 + 2HCl  CaCl2 + H2O + CO2
Properties:
(i) It is deliquescent crystals.
(ii) It gets hydrolysed like MgCl2 hence anhydrous CaCl2 cannot be prepared.
CaCl2 + H2O  CaO + 2HCl
Hence, anh CaCl2 is prepared by heating CaCl2. 6H2O in a current of HCl (dry)
(iii) Anh. CaCl2 is used in drying gases and organic compounds but not NH3 or alcohol due to the formation
of CaCl2 . 8NH3 and CaCl2 . 4C2H5OH.

SULPHATES
Sodium Sulphate:
Preparation:
It is formed in the 1st step of leblanc process by heating common salt with sulphuric acid.
2NaCl + H2SO4  Na2SO4 + 2HCl
Thus the salt cake formed is crystallised out from its aqueous solution as Na2SO4 . 10H2O. This
called as Glauber's salt.
** One interesting feature of the solubility of glauber's salt is; when crystallised at below 32.4°C, then
Na2SO4. 10H2O is obtained but above 32.4°C, Na2SO4 (anh.) comes out.

Properties: It is reduced to Na2S when fused with carbon.

Na2SO4 + 4C  Na2S + 4CO
Uses: It is used in medicine.

s-Block Elements [12]

Potassium Sulphate:
It occurs in stassfurt potash beds as schonite K 2 SO 4 · MgSO 4 · 6H 2 O and Kainite,
KCl · MgSO4 · 3H2O from which it is obtained by solution in water and crystallisation. It separates from
the solution as anh, crystals whereas Na2SO4 comes as decahydrate.

Uses: It is used to prepare alumn.

Magnesium Sulphate:
Preparation:
(i) It is obtained by dissolving kieserite. MgSO4. H2O in boiling water and then crystallising the solution as
a hepta hydrate. i.e. MgSO4. 7H2O. It is called as Epsom salt.
(ii) It is also obtained by dissolving magnesite in hot dil. H2SO4.
MgCO3 + H2SO4  MgSO4 + H2O + CO2
(iii) or by dissolving dolomite (CaCO3, MgCO3) in hot dil. H2SO4 and removing the insoluble CaSO4 by
filtration.
(iv) It is isomorphous with FeSO4. 7H2O, ZnSO4.7H2O

Calcium Sulphate: It occurs as anhydrite CaSO4 and as the dihydrate CaSO4. 2H2O, gypsum, alabaster or
satin-spar.
Properties:
(i) Gypsum (CaSO4. 2H2O) 2CaSO4. H2O (Plaster of paris)

(anhydrous)CaSO4.
Dead burnt. plaster
(ii) Solubility of CaSO4 at first increases upto a certain point and then decreases with rise of temperature.
(iii) Plaster paris is used in mould making due to its porous body.

s-Block Elements [13]

 Question Bank on s-block elements
Q.1 Cs+ ions impart violet colour to Bunsen flame. This is due to the fact that the emitted radiations are of
(A) high energy (B) lower frequencies
(C) longer wave-lengths (D) zero wave number
Q.2 The compound(s) of alkaline earth metals, which are amphoteric in nature is/are
(A) BeO (B) MgO (C) Be(OH)2 (D) Mg(OH)2
Q.3 An alkaline earth metal (M) gives a salt with chlorine, which is soluble in water at room temperature. It
also forms an insoluble sulphate whose mixture with a sulphide of a transition metal is called ‘lithopone’
-a white pigment. Metal M is
(A) Ca (B) Mg (C) Ba (D) Sr
Q.4 The reaction of an element A with water produces combustible gas B and an aqueous solution of C.
When another substance D reacts with this solution C also produces the same gas B. D also produces
the same gas even on reaction with dilute H2SO4 at room temperature. Element A imparts golden yellow
colour to Bunsen flame. Then, A, B, C and D may be identified as
(A) Na, H2, NaOH and Zn (B) K, H2, KOH and Zn
(C) K, H2, NaOH and Zn (D) Ca, H2, CaCOH2 and Zn
Q.5 The hydroxide of alkaline earth metal, which has the lowest value of solubility product (Ksp) at normal
temperature (25°C) is
(A) Ca(OH)2 (B) Mg(OH)2 (C) Sr(OH)2 (D) Be(OH)2
Q.6 The correct statement is/are
(A) BeCl2 is a covalent compound (B) BeCl2 is an electron deficient molecule
(C) BeCl2 can form dimer (D) the hybrid state of Be in BeCl2 is sp2

Q.7 K CrO / H 
(Yellow ppt) T 2  
4
 X dil
. HCl
 Y(Yellow ppt)  Z  (pungent smelling gas)

If X gives green flame test. Then, X is
(A) MgSO4 (B) BaS2O3 (C) CuSO4 (D) PbS2O3
Q.8 Which of the following carbonate of alkali metals has the least thermal stability?
(A) Li2CO3 (B) K2CO3 (C) Cs2CO3 (D) Na2CO3
Q.9 The ‘milk of magnesia’ used as an antacid is chemically
(A) Mg(OH)2 (B) MgO (C) MgCl2 (D) MgO + MgCl2
Q.10 The alkali metals which form normal oxide, peroxide as well as super oxides are
(A) Na, Li (B) K, Li (C) Li, Cs (D) K, Rb
Q.11 Mg2C3 + H2O  X (organic compound). Compound X is
(A) C2H2 (B) CH4 (C) propyne (D) ethene
Q.12 The hydration energy of Mg2+ is
(A) more than that of Mg3+ ion (B) more than that of Na+ ion
(C) more than that of Al3+ ion (D) more than that of Be2+ ion
Q.13 The golden yellow colour associated with NaCl to Bunsen flame can be explained on the basis of
(A) low ionisation potential of sodium (B) emission spectrum
(C) photosensitivity of sodium (D) sublimation of metallic sodium of yellow vapours

s-Block Elements [14]

Q.14 Solution of sodium metal in liquid ammonia is a strong reducing agent due to presence of
(A) solvated sodium ions (B) solvated hydrogen ions
(C) sodium atoms or sodium hydroxide (D) solvated electrons
Q.15 The order of solubility of lithium halides in non-polar solvents follows the order
(A) LiI > LiBr > LiCl > LiF (B) LiF > LiI > LiBr > LiCl
(C) LiCl > LiF > LiI > LiBr (D) LiBr > LiCl > LiF > LiI
Q.16 The salt which finds uses in qualitative inorganic analysis is
(A) CuSO4·5H2O or ZnSO4·5H2O (B) K2SO4·Al2(SO4)3·24H2O
(C) Na(NH4)HPO4·4H2O (D) FeSO4·(NH4)2SO4·6H2O
Q.17 Fire extinguishers contain
(A) conc. H2SO4 solution (B) H2SO4 and NaHCO3 solutions
(C) NaHCO3 solution (D) CaCO3 solution
Q.18 CsBr3 contains
(A) Cs–Br covalent bonds (B) Cs3+ and Br– ions
(C) Cs+ and Br3– ions (D) Cs3+ and Br33– ions
Q.19 KO2 finds use in oxygen cylinders used for space and submarines. The fact(s) related to such use of
KO2 is/are
(A) it produces O2 (B) it produces O3
(C) it absorbs CO2 (D) it absorbs both CO and CO2
Q.20 The compound(s) which have –O–O– bond(s) is/are
(A) BaO2 (B) Na2O2 (C) CrO5 (D) Fe2O3

High temperature CO in
Q.21 Na + Al2O3     X 2 Y; compound Y is
water
(A) NaAlO2 (B) NaHCO3 (C) Na2CO3 (D) Na2O2
Q.22 The correct order of second ionisation potentials (IP) of Ca, Ba and K is
(A) K > Ca > Ba (B) Ba > Ca > K (C) K > Ba > Ca (D) K = Ba = Ca
Q.23 EDTA is used in the estimation of
(A) Mg2+ ions (B) Ca2+ ions
(C) both Ca2+ and Mg2+ ions (D) Mg2+ ions but not Ca2+ ions
Q.24 Highly pure dilute solution of sodium in ammonia
(A) shows blue colouration due to solvated electrons
(B) shows electrical conductivity due to both solvated electrons as well as solvated sodium ions
(C) shows red colouration due to solvated electrons but a bad conductor of electricity
(D) produces hydrogen gas or carbonate
Q.25 aq. NaOH + P4 (white)  PH3 + X; compound X is
(A) NaH2PO2 (B) NaHPO4 (C) Na2CO3 (D) NaHCO3
Q.26 The correct order of solubility is
(A) CaCO3 < KHCO3 < NaHCO3 (B) KHCO3 < CaCO3 < NaHCO3
(C) NaHCO3 < CaCO3 < KHCO3 (D) CaCO3 < NaHCO3 < KHCO3
Q.27 The complex formation tendency of alkaline earth metals decreases down the group because
(A) atomic size increases (B) availability of empty d and f-orbitals increases
(C) nuclear charge to volume ratio increases (D) all the above

s-Block Elements [15]

Q.28 The alkaline earth metals, which do not impart any colour to Bunsen flame are
(A) Be and Mg (B) Mg and Ca (C) Be and Ca (D) Be and Ba

Q.29 Y   CaSO4·2H2O 

 , 205C
 X. X and Y are respectively
,120C

(A) plaster of paris, dead burnt plaster (B) dead burnt plaster, plaster of paris
(C) CaO and plaster of paris (D) plaster of paris, mixture of gases
Q.30 A metal M readily forms water soluble sulphate, and water insoluble hydroxide M(OH)2. Its oxide MO
is amphoteric, hard and having high melting point. The alkaline earth metal M must be
(A) Mg (B) Be (C) Ca (D) Sr
Q.31 When K2O is added to water, the solution becomes basic in nature because it contains a significant
concentration of
(A) K+ (B) O2– (C) OH– (D) O22–

Na CO K CrO
Q.32 ( White ppt ) D 23 A 2 
4  B(Yellow ppt )
(in acetic acid )
dil. H 2SO 4 
C( White ppt )

If A is the metallic salt, then the white ppt. of D must be of

(A) stronsium carbonate (B) red lead (C) barium carbonate (D) calcium carbonate
CO
Q.33 (Milky Cloud) C  2 A + Na2CO3 —C
The chemical formulae of A and B are
(A) NaOH and Ca(OH)2 (B) Ca(OH)2 and NaOH
(C) NaOH and CaO (D) CaO and Ca(OH)2
Q.34 An aqueous solution of an halogen salt of potassium reacts with same halogen X2 to give KX3, a brown
coloured solution, in which halogen exists as X3– ion, X2 as a Lewis acid and X– as a Lewis base,
halogen X is
(A) chlorine (B) bromine (C) iodine (D) fluorine
Q.35 The correct order of basic-strength of oxides of alkaline earth metals is
(A) BeO > MgO > CaO > SrO (B) SrO > CaO > MgO > BeO
(C) BeO > CaO > MgO > SrO (D) SrO > MgO > CaO > BeO
Q.36 Which of the following compounds are paramagnetic in nature?
(A) KO2 (B) K2O2 (C) Na2O2 (D) RbO2
Q.37 The order of melting point of chlorides of alkali metals is
(A) LiCl > NaCl > KCl < CsCl (B) LiCl > NaCl > KCl > CsCl
(C) NaCl > KCl > CsCl > LiCl (D) LiCl > NaCl > CsCl > KCl

Q.38 NaOH(Solid) + CO 200

 C
 X; product X is
(A) NaHCO3 (B) Na2CO3 (C) HCOONa (D) H2CO3
N , H O
Q.39 X 2 Y 
2
 Z(colourless gas) CuSO
  T (blue colour)
4

Then, substances Y and T are

(A) Y = Mg3N2 and T = CuSO4·5H2O (B) Y = Mg3N2 and T = CuSO4·4NH3
(C) Y = Mg(NO3)2 and T = CuO (D) Y = MgO and T = CuSO4·4NH3

s-Block Elements [16]

Q.40 Weakest base among KOH, NaOH, Ca(OH)2 and Zn(OH)2 is
(A) Ca(OH)2 (B) KOH (C) NaOH (D) Zn(OH)2
Q.41 If X and Y are the second ionisation potentials of alkali and alkaline earth metals of same period, then
(A) X > Y (B) X < Y (C) X = Y (D) X << Y
Q.42 The aqueous solutions of lithium salts are poor conductor of electricity rather than other alkali metals
because of
(A) high ionisation energy (B) high electronegativity
(C) lower ability of Li ions to polarize water molecules (D) higher degree of hydration of Li+ ions
+

Q.43 Sodium metal is highly reactive and cannot be stored under

(A) toluene (B) kerosene oil (C) alcohol (D) benzene
Q.44 Which of the following substance(s) is/are used in laboratory for drying purposes?
(A) anhydrous P2O5 (B) graphite (C) anhydrous CaCl2 (D) Na3PO4
Q.45 Nitrogen dioxide cannot be prepared by heating
(A) KNO3 (B) AgNO3 (C) Pb(NO3)2 (D) Cu(NO3)2
Q.46 In LiAlH4, metal Al is present in
(A) anionic part (B) cationic part
(C) in both anionic and cationic part (D) neither in cationic nor in anionic part
CoCl
Q.47 X 2  CaCl2 + Y ; the effective ingredient of X is
(A) OCl– (B) Cl– (C) OCl+ (D) OCl2–
Q.48 Which one of the following fluoride of alkali metals has the highest lattice energy?
(A) LiF (B) CsF (C) NaF (D) KF
Q.49 Crown ethers and cryptands form
(A) complexes with alkali metals
(B) salts of alkali metals
(C) hydroxides of alkali metals used for inorganic quantitative analysis
(D) organic salts of alkali metals
Q.50 White heavy precipitates are formed when BaCl2 is added to a clear solution of compound A. Precipitates
are insoluble in dilute HCl. Then, the compound A is
(A) a bicarbonate (B) a carbonate (C) a sulphate (D) a chloride
Q.51 Among MgCl2, RbCl, BeCl2 and LiCl, the compouds with the highest and the lowest % of ionic characters
are
(A) MgCl2 and BeCl2 (B) RbCl and BeCl2 (C) BeCl2 and MgCl2 (D) RbCl and LiCl

Q.52 X  C  Cl 2 High
 temperatur e
  Y  CO ; Y  2 H 2 O  Z  2 HCl
of about 1000 K

Compound Y is found in polymeric chain structure and is an electron deficient molecule. Y must be
(A) BeO (B) BeCl2 (C) BeH2 (D) AlCl3
Q.53 The correct order of degree of hydration of M+ ions of alkali metals is
(A) Li+ < K+ < Na+ < Rb+ < Cs+ (B) Li+ < Na+ < K+ < Rb+ < Cs+
(C) Cs+ < Rb+ < K+ < Na+ < Li+ (D) Cs+ < Rb+ < Na+ < K+ < Li+
Q.54 BeCl2 + LiAlH4  X + LiCl + AlCl3
(A) X is LiH (B) X is BeH2 (C) X is BeCl2·2H2O (D) None

s-Block Elements [17]

Q.55 The order of thermal stability of carbonates of IIA group is
(A) BaCO3 > SrCO3 > CaCO3 > MgCO3 (B) MgCO3 > CaCO3 > SrCO3 > BaCO3
(C) CaCO3 > SrCO3 > BaCO3 > MgCO3 (D) MgCO3 = CaCO3 > SrCO3 = BaCO3
Q.56 A pair of substances which gives the same products on reaction with water is
(A) Mg and MgO (B) Sr and SrO (C) Ca and CaH2 (D) Be and BeO
Q.57 Na2SO4 is water soluble but BaSO4 is insoluble because
(A) the hydration energy of Na2SO4 is higher than that of its lattice energy
(B) the hydration energy of Na2SO4 is less than that of its lattice energy
(C) the hydration energy of BaSO4 is less than that of its lattice energy
(D) the hydration energy of BaSO4 is higher than that of its lattice energy
Q.58 Which of the following is not a anomalous property of lithium?
(A) Hydrated lithium ion is the largest among alkali metals
(B) The melting and boiling points of lithium are comparatively high
(C) Lithium is softer than that of other alkali metals
(D) The ionisation potential and electronegativity of lithium are higher than those of other alkali metals
Q.59 The incorrect statement(s) is/are
(A) Mg cannot form complexes
(B) Be can form complexes due to a very small atomic size
(C) the first ionisation potential of Be is higher than that of Mg
(D) Mg forms an alkaline hydroxide while Be forms amphoteric oxides
Q.60 The commercial method of preparation of potassium by reduction of molten KCl with metallic sodium at
850°C is based on the fact that
(A) potassium is solid and sodium distils off at 850 °C
(B) potassium being more volatile and distils off thus shifting the reaction forward
(C) sodium is more reactive than potassium at 850 °C
(D) sodium has less affinity to chloride ions in the presence of potassium ion
Q.61 Be2C + H2O  BeO + X
CaC2 + H2O  Ca(OH)2 + Y; then X and Y are respectively
(A) CH4, CH4 (B) CH4, C2H6 (C) CH4, C2H2 (D) C2H2, CH4
Q.62 Which of the following statements are false?
(A) BeCl2 is a linear molecule in the vapour state but it is polymeric form in the solid state
(B) Calcium hydride is called hydrolith.
(C) Carbides of both Be and Ca react with water to form acetylene
(D) Oxides of both Be and Ca are amphoteric.
Q.63 Which of the following are ionic carbides?
(A) CaC2 (B) Al4C3 (C) SiC (D) Be2C
Q.64 Which of the following groups of elements have chemical properties that are most similar
(A) Na, K, Ca (B) Mg, Sr, Ba (C) Be, Al, Ca (D) Be, Ra, Cs
Q.65 MgBr2 and MgI2 are soluble in acetone because of
(A) Their ionic nature (B) Their coordinate nature
(C) Their metallic nature (D) Their covalent nature

s-Block Elements [18]

Q.66 Which of the following is not the characteristic of barium?
(A) It emits electrons on exposure to light
(B) It is a silvery white metal
(C) It forms Ba(NO3)2 which is used in preparation of green fire
(D) Its ionization potential is lower than radium.
Question No. 67 to 74
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.67 Assertion : Beryllium does not impart any characteristic colour to the bunsen flame.
Reason : Due to its very high ionization energy, beryllium requires a large amount of energy for
exciation of the electrons.
Q.68 Assertion : In fused state, calcium chloride cannot be used to dry alcohol or NH3.
Reason : Anhy. CaCl2 is not a good desiccant.
Q.69 Assertion : Diagonal relationship is shown between Be and Al.
Reason : Ionization potential of Be is almost the same as that of Al.
Q.70 Assertion : Beryllium halides dissolve in organic solvents.
Reason : Beryllium halides are ionic in character.
Q.71 Assertion : BeCl2 fumes in moist air.
Reason : BeCl2 reacts with moisture to form HCl gas.
Q.72 Assertion : Calcium carbide on hydrolysis gives methane.
Reason : Calcium carbide contains C22– anion.
Q.73 Assertion : When CO2 is passed through lime water, it first turns milky and then the solution becomes
clear when the passage of CO2 is continued.
Reason : The milkiness is due to the formation of insoluble CaCO3 which then changes to soluble
Ca(HCO3)2 when excess of CO2 is present.
Q.74 Assertion : MgCO3 is soluble in water when a current of CO2 is passed.
Reason : The solubility of MgCO3 is due to the formation of Mg(HCO3)2.

IIT JEE ASKED QUESTION

Q.75 The compound(s) formed upon combustion of sodium metal in excess air is (are) [JEE 2009]
(A) Na2O2 (B) Na2O (C) NaO2 (D) NaOH

Q.76 Amongst the following, the total number of compounds whose aqueous solution turns red litmus paper
blue is [JEE 2010]
KCN K2 SO 4 (NH4)2C2O4 NaCl Zn(NO3)2
FeCl3 K2 CO 3 NH4NO3 LiCN

s-Block Elements [19]

 ANSWER KEY
Q.1 A Q.2 A Q.3 C Q.4 A Q.5 D Q.6 A,B,C

Q.7 B Q.8 A Q.9 A Q.10 D Q.11 C Q.12 B Q.13 A

Q.14 D Q.15 A Q.16 C Q.17 B Q.18 C Q.19 A,C

Q.20 A,B,C Q.21 C Q.22 A Q.23 C Q.24 A,B Q.25 A Q.26 D

Q.27 A Q.28 A Q.29 A Q.30 B Q.31 C Q.32 C Q.33 B

Q.34 C Q.35 B Q.36 A,D Q.37 C Q.38 C Q.39 B Q.40 D

Q.41 A Q.42 D Q.43 C Q.44 A,C Q.45 A Q.46 A Q.47 A

Q.48 A Q.49 A Q.50 C Q.51 B Q.52 B Q.53 C Q.54 B

Q.55 A Q.56 C Q.57 A,C Q.58 C Q.59 A Q.60 B Q.61 C

Q.62 C,D Q.63 A,B,D Q.64 B Q.65 D Q.66 A Q.67 A Q.68 C

Q.69 A Q.70 C Q.71 A Q.72 D Q.73 A Q.74 A Q.75 A,B

Q.76 3

s-Block Elements [20]

p-BLOCK ELEMENTS
SHORT NOTES
SUNIL VODELA
 The p - Block Elements
The elements in which the last electron enters the other most p orbital are called p- block elements. As
the maximum number of electrons that can be accommodated in a set of p-orbitals is six, therefore there
are six groups of p - blocks in the periodic table.

Group 13 Elements : Boron Family

The Elements are B (Non metal), Al, Ga, In, T (Metals)

General electronic configuration [Noble gas] ns2 np1
Atomic and Physical properties.
(1) Atomic and Ionic radii
Atomic radii : B > Ga < Al < In < T

(2) Ionization Enthalpies.

B > T > Ga > Al > In (Sum of three IE values)

(3) Melting and Boiling points

M.P. B > Al > Tl > In > Ga
B.P. B > Al > Ga > In > Tl

(4) Electropositive Character

Due to high IE they are less electropositive on moving down the group metallic character increases due
to decrease in IE [  B is nonmetals and other elements are metals.]
B  Al  Ga  In  Tl
Non Metals
metal

Note : Boron exists in many allotropic forms. All the allotropes have basic building B12 icosahedral units made
up of polyhedron having 20 faces and 12 corners.For example one is the simplest form :  - rhombohedral
boron.

But Al , In & T all have close packed metal structure.

Chemical Properties :
B already discussed.
(1) Reaction with Air at Water
Al should react air to form a very thin oxide film (10–4 to 10–6 mm thick) on the surface and protects the
metal from further attack
3
2 Al(s) + O (g)  Al2O3(s) H° = – 1670 kJ/mole (Thermal reaction)
2 2
Ga and In are attacked neither by cold water nor hot water unless oxygen is present. T form an oxide
on surface.
p-Block elements [2]
(2) Reaction with Oxides and Bases
Al dissolve in dilute mineral acids liberating H2
2Al + 6HCl  2AlCl3 + 3H2
Al also dissolves in aqueous NaOH ( amphoteric) liberating H2 and forming aluminates
2Al + 2NaOH + 6H2O  2 Na[Al(OH)4] + H2
or
2NaAlO2 + 2H2O
Ga, In, T dissolve in dilute acids liberating H2 Ga is amphoteric like Al and it dissolves in aq. NaOH
liberating H2 and forming gallates.

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  B H + H + higher borane
2 6 2
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)
p-Block elements [3]
 Reaction of B2H6 :

(i) B2H6 + O2  burns

 in B2O3 + H2O
air spontaneo usly
(ii) B2H6 + H2O (Cold is enough)  H3BO3 + 6H2

anh .
(iii) B2H6 + HCl (dry)  B2H5Cl + H2
AlCl3

Orthoboric Acid
H3BO3 is soluble in water and behaves as weak monobasic acid. It does not donate protons like most
the acids, but rather it accepts OH– . It is therefore is Lewis acid (B(OH)3)
B(OH)3 + 2H2O H3O+ + [B(OH)4]–
or
H3BO3
Since B(OH)3 only partially reacts with water to form H3O+ and [B(OH)4]– it behaves as a weak acid.
Thus it cannot be titrated satisfactorily with NaOH as a sharp end point is not obtained. If certain
polyhydroxy compounds such as glycerol, mannitol or sugar are added to the titration mixture then
B(OH)3 behaves as a strong monobasic acid. and hence can now be titrated with NaOH and end point
is diluted using phenolphthalein as indicator.
B(OH)3 + NaOH Na[B(OH)4]
NaBO2 + 2H2O
The added compound must be a as diol to enhance the acidic proprieties in this way the cis-diol forms
very stable complexes with [B(OH)4]– formed in forward direction above, thus effectively removing it
from solution. Hence reaction proceeds in forward direction (Le-Chatelier principle.)

C OH HO OH C O OH
+ B B
–2H2O
C OH HO OH C O OH

C O O C HO C
B
C O O C –2H2O HO C

* Heating of boric acid :

H3BO3 100
 C
 HBO2 140
 C
 H2B4O7 
 B2 O 3
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 brightener

p-Block elements [4]

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

NaBO2 +  Na2B4O7·10H2O  Concentrated

   Na 2 B4O 7  NaBO 2
  
in Filtrate  as residue  crystallise out
and allowed to
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 :

(i) 2Al(OH)3 300

 C
 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
3
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.

p-Block elements [5]

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 14 Elements (Carbon Family)

The Elements are C [Non metals] ,
Si, Ge [Metalloids],
Sn, Pb, [Metals]

General electronic configuration [ noble gas] ns2 np2

(I) Atomic and Physical properties
(1) Atomic Radii
Covalent radii : C < Si < Ge < Sn < Pb

(2) Ionizations Enthalpies

C > Si > Ge > Pb > Sn (IE1 values)
(3) Melting and Boiling Points
M.P. C > Si > Ge > Pb > Sn
B.P. Si > Ge > Sn > Pb
(4) Metallic Character
C < Si < Ge < Sn < Pb (Metallic character)
C, Si [Non metal]
Ge [ Metal ]
Sn, Pb [Metal]
(II)
* Unique Character of C

* Catenation
The property of forming bonds with atoms of the same element or tendency to self linking called catenation.
Carbon shows maximum catenation. On moving down the group catenation tendency decreases. This
because the strength of C – C bond is very high and in case of other elements, strength of M – M (where
M = Si, Ge, Sn, Pb) bond is decreases down the group.

p-Block elements [6]

 Bond Bond Energy (kJmol–1)
C–C 348
Si – Si 297
Ge – Ge 260
Sn – Sn 240
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
(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
p-Block elements [7]
(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
Impure Ni + CO  Ni(CO)4 150
 C
 Ni + 4CO

recycled
Producer gas: CO + N2 + H2
Water gas: CO + H2
Water gas is having higher calorific value than producer gas.  in water gas, both CO & H2 burns while
in producer gas N2 doesn't burn.
Teflon —(CF2  CF2—
)n
heated with heated Polymerisation at
CHCl3 + HF     CF2HCl  CF2=CF2     —(CF2  CF2—
)n
SbFCl4 again 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.
p-Block elements [8]
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.
(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 ­ electro-ve than H
Si less electro-ve than H
So bond polarity is reversed when Nu– attacks, it faces repulsion in C but not in Si
(ii) Silicon is having vacant d orbital which is not in case of carbon
(iii) Silicon is larger in size compared to C. By which the incoming Nu– doesn't face any steric hindrance to
attack at Si whereas CH4 is tightly held from all sides.

p-Block elements [9]

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 R2Si(OH)2   O  Si  O  Si  O  Si O
H 2O | | |
R R R
Linear silicone
O
H O
R2CCl2 + H2O   R2C(OH)2 
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
R R
| |
R  Si  O  Si  R
| |
O O
| |
R  Si  O  Si  R
| |
R R
cyclic silicone
not planar
H 2O H O
R3SiCl  R3SiOH 2
 R3Si-O-SiR3

Silanol
R R
H 2O  H 2O | |
R2SiCl2 + R3SiCl      Si  O  Si    
hydrolysis heating
condensation | |
R R
This end of the chain can't be extended hence
R3SiCl is called as chain stopping unit
* Using R3SiCl in a certain proportion we can control the chain length of the polymer

| |
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
p-Block elements [10]
 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)
(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
  Na2SiO3(s) + CO2(g)
temp.

SiO2(s) + Na2SO4(s) high

  Na2SiO3(s) + SO3(g)
temp.

3SiO2(s) + Ca3(PO4)2(s) high

  3CaSiO3(s) + P2O5(g)
temp.

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.

p-Block elements [11]

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

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

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}
p-Block elements [12]
(2) A piece of Sn is always added to preserve a solution of SnCl2. Explain.
6SnCl2 + 2H2O + O2  2SnCl4 + 4Sn(OH)Cl (white ppt)
SnCl4 + Sn  2SnCl2
SnCl4 + 4H2O  Sn(OH)4 (white ppt.) + 4HCl
(3) SnCl2 + HCl  HSnCl3 HCl
 H2SnCl4

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

SnCl4+ 2NH4Cl  (NH4)2 SnCl6 (colourless crystalline compound known as " pink salt ")
(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
PbO2     PbO , hot oxide
above 600C

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.
p-Block elements [13]
(2) Pb3O4 : 6PbO + O2 2Pb3O4 {In the same way, prove that its formula is 2PbO. PbO2}
Pb3O4 + 4HNO3 (cold.conc) or (hot dil.)  2Pb(NO3)2 + PbO2 + 2H2O
But 2Pb3O4 + 6H2SO4   6PbSO4 + 6H2O + O2
Pb3O4 + 8HCl  3PbCl2 + 4H2O + Cl2
(3) PbO2 : Insoluble in water. HNO3, But reacts with HCl + H2SO4(hot conc.) and in hot NaOH / KOH.
(i) Pb3O4 + 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 15 Elements (Nitrogen Family)

The elements are N,P [ Non metal]
As [ Matalloid]
Sb, Bi [Metal]
The General electronic configuration is [noble gas] ns2 np3

(I) Atomic and Physical properties

(1) Atomic and Ionic radii
Covalent radius : N < P < As < Sb < Bi

(2) Ionization enthalpies

N > P > As > Sb > Bi (IE1 values)

(3) Electronegativity N > P > As > Sb = Bi

(4) Metallic Character

N  P As  Sb  Bi
Non Metalloid Metals
metal

p-Block elements [14]

(5) Catenation
* The group 15 elements also show catenation property but to much smaller extent than carbon. For
example hydrazine (H2NNH2) has two N atoms bonded together HN3 has three N atoms.
HN3 +
H–N=N=N
* Among group 15 elements P has the maximum tendency for catenation forming cyclic as well as open
chain compounds consisting of many phosphorous atoms.
P2H4 has tow P atoms bonded together the lesser tendency of elements of group 15 to show catenation
in compression to carbon is their low dissociation enthalpies.
C–C 353.3 kJ /mole
N–N 16.8 kJ / mole
P–P 201.6 kJ / mole
As – As 147.4 kJ / mole
(6) Allotropy
Except N and Bi all other elements of this group show allotropy.
Phosphorous : White, Black and Red
Arsenic : Yellow or Grey
Antimony : Yellow or Silvery grey.
Preparation of N2 :
(i) NH4NO2   N2 + 2H2O
(ii) (NH4)2 Cr2O7  N2 + 4H2O + Cr2O3
(iii) Ba(N3)2 
 Ba + 3N2 Purest N 2 obtained

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

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
p-Block elements [15]
(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) Interstitial : MN (
M  Sc, Ti, Zr, Hf , La )
  
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–
(iii) Haber's process : N2 + 3H2 450
 C
 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
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

p-Block elements [16]

(ii) A g ( N O

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

Cl– + [Ag(NH3)2]+

BaCl2 +[Ag(NH3)2]+ + NO3

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

OXIDES OF NITROGEN
Oxides of nitrogen Structure Physical state Colour of gas
— 
N2O NNO Gas Colourless
NO Gas Colourless
N 2O 3 ;O  N O N Blue liquid (–30°C)
||
O

NO 2  Gas Brown

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

p-Block elements [17]

 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 O 3
(i) HNO3 + As2O3  H3AsO4 + N2O3

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

  2
4. NO2 | Cool( 30C)

Blueliq ( N2O3 )
 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 O 5
(i) 2HNO3 + P2O5  2HPO3 + N2O5
(ii) 4AgNO3 + 2Cl2(dry gas)  4AgCl + 2N2O5 + O2

Properties:
(I) Decoposition Behaviour
(i) N2O 500 C 900C
  2N2 + O2
(ii) 2NO 800
 C
 N2 + O2
(iii) N2O3 Room . NO2 + NO
 temp

(Blue liq.) at (–30°C)

(iv) 2NO2 620

 C
 2NO + O2
N 2O 4 11C
  2 NO 2
( white solid) Brown gas
at (11C)
1
(v) N 2O5 30
C
 N 2O5 40
C
 2NO2 + 2 O2
colourless yellow
solid liq.
p-Block elements [18]
(II) Reaction with H2O & NaOH
H2O 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 NaNO 2
(iv) NO2: HNO2 + HNO3
called as mixed anhydride NaNO2 + NaNO3
(v) N2O5: 2HNO3
called as anhydride of NaNO 3
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.
(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
p-Block elements [19]
 NO not formed : 2KI + 2NO2 I2 + 2KNO2
(2) Reducing property of NO2.
KMnO4 + NO2 + H2SO4  K2SO4 + MnSO4 + HNO3 + H2O
4 5
O 30  2 NO 2  O 02  N 2 O 5

not the reduction product of O3

N2O5 :
I2 + 5N2O5  I2O5 + 10NO2
I2O5 is used for the estimation of CO
I2O5 + 5CO  I2 + 5CO2
I2 + 2S2O32  2I– + S4O 62
N2O5 + NaCl  NaNO3 + NO2Cl
This likes proves that N2O5 is consisting of ion pair of NO 2 & NO3
Oxyacids of N :
HNO2 :
Preparation
(i) dil. acid
M-nitrite   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
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–

p-Block elements [20]

 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

R .T.( 25C )
step 2 NO + O2 Air   NO2
step 3 NO2 + H2O  HNO2 + HNO3
step 4 HNO2  HNO3 + NO + H2O

PROPERTIES
Physical
Nitric acid usually acquires yellow colour due to its decomposition by sunlight into NO2.
4HNO3 Sunlight
 4NO2 + 2H2O + O2
The yellow colour of the acid can be removed by warming it to 60-80oC 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

(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

p-Block elements [21]

(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 sulphiode is oxidised to sulphur
H2S + 2HNO3  2NO2 + 2H2O + S
(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 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 hydro-
gen 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
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.

p-Block elements [22]

--------------------------------------------------------------------------------------------------------
Concentration of Metal Main Products
nitric acid
--------------------------------------------------------------------------------------------------------
Mg, Mn H2 + Metal nitrate
Very dilute HNO3 (6%) ----------------------------------------------------------
Fe, Zn, Sn NH4NO3 + metal nitrate + H 2O
--------------------------------------------------------------------------------------------------------
Pb, Cu, Ag, Hg NO + metal nitrate + H 2O
----------------------------------------------------------
Dilute HNO3 (20%) Fe, Zn N2O + metal nitrate + H 2O
----------------------------------------------------------
Sn NH4NO3 + Sn(NO3)2
--------------------------------------------------------------------------------------------------------
Zn, Fe, Pb, Cu, Ag NO2 + metal nitrate + H 2O
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:

p-Block elements [23]

 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

heated to 550C
Red 'P'     White 'P'
in an inert atm. and then
rapid cooling to room temp.

PREPRATION OFWHITE 'P'

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

12C + 4HPO3 1000

 C
 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

p-Block elements [24]
 (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
electrical
(iii) PH3 + 4N2O   H3PO4 + 4N2
sparking
(iv) 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 16 Elements (Oxygen family)

The Elements are O, S, Se, Te, Po
(Chalcogens)
Atomic and Physical Properties

(1) Atomic radii and Ionic radii

Covalent radius : O < S < Se < Te

(2) Ionization Enthalpies

O > S > Se > Te > Po (IE1 values)

(3) Melting and Boiling points

M.P. : Te > Po > Se > S > O
B.P. Te > Po > Se > S > O

(4) Electronegativity
O > S > Se > Te

(5) Metallic Character

O < S < Se < Te < Po

p-Block elements [25]

(6) Elemental State
Oxygen exist as diatomic molecular gas in this case there is p – p overlap thus tow O atoms form
double bond O = O. The intermolecular forces in O2 are weak VB forces.  O2 exist as gas . On the
other bond, other elements of family do not form stable p – p bonds and do not exist as M2
molecules. Other atoms are linked by single bonds and form poly atomic complex molecules for
eg. S – S8, Se – S8

(7) Allotropy
All element exhibit allotropy for e.g.
Oxygen – O2 and O3
Liquid O2 - pale base
Solid O2 - blue
Sulphur -
The main allotropic forms are
(i) Rhombic sulphur ( sulphur) (ii) Monoclinic ( sulphur) (iii) Plastic sulphur ( sulphur)

(i) Rhombic Sulphur ( sulphur)

This allotrope is yellow in colour (m.p. 385.8 K).
It is insoluble in water but readily soluble in CS2.

(ii) Monoclinic Sulphur ( sulphur)

It is soluble in CS2
>95.5°C
S() S()
<95.5°C

(iii) Plastic Sulphur ( sulphur) It is insoluble in CS2.

(8) Catenation
In this group only S has a strong tendency for catenation oxygen has this tendency to a limited extent.
H2 O 2 H–O–O–H (Poly oxides)
H2S2 H–S–S–H (Polysulphides or polysulphones)
H2S3 H–S–S–S–H
H2S4 H–S–S–S–S–H

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.

p-Block elements [26]

(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
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
p-Block elements [27]
 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

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

p-Block elements [28]

 Properties of H2SO4 :
(a) Dissociation : At 444°C. H2SO4  H2O + SO3
(b) Acidic nature : NaOH + H2SO4  NaHSO4 + H2O Na2SO4 + H2O
(c) CO 32 + H2SO4  SO 24 + H2O + CO2
Carbonates or bicarbonat es

HCO 3 + H2SO4  H 2SO 4 +
H2O + CO2  are getting decomposed
(d) Zn / Fe + H2SO4ZnSO4 & FeSO4+ H2
where as
Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
2Ag + 2H2SO4  Ag2SO4 + SO2 + 2H2O
Hg + 2H2SO4  HgSO4 + SO2 + 2H2O
(e) NaCl HCl
Ca3(PO4)2  H3PO4

FeS  H2S
CH3CO2Na   H SO  AcOH
2 4 
NaNO 3  HNO3
CaF2  HF
NaNO 2  HNO2
(f) Oxidising Prop.:
HBr / HI + H2SO4  I2/Cl2 + SO2 + H2O
C + 2H2SO4  CO2 + 2SO2 + 2H2O
S + 2H2SO4  3SO2 + 2H2O
2P + 5H2SO4  H3PO4 + 5SO2
(g) Dehydrating agent:
H SO
C12H22O11 2 
4  12 C
11 H 2O

H SO
C6H12O6  
4  6C
2
6H O 2

H 2SO 4
(COOH)2  
 CO + CO H SO
H O 2 PhH 2 
4  Ph–SO3H
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]
p-Block elements [29]
 
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
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 + 2S2O32  S4O 62 + 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

p-Block elements [30]

(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.
H2O2
Method of 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+ + 2H 2SO 4
2 H 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–  2CrO24 + 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

p-Block elements [31]

 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 + 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 + 2H2SO4
Yellow or orange
Pertitanic acid

Group -17 Elements (Halogens Family)

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
 2 H (at cathode) + F 2 (at anode)

Cl2 : (i) By electrolysis of aq. NaCl :

2NaCl + 2H2O  2 NaOH  H 2 + Cl 2

   ( anode )
at cathode
(ii) 2 NaCl Electrolys
 is
 2 Na + Cl 2
( 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

p-Block elements [32]

 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 HSO 3  2I– + 6SO 24 + 6H+

6H
5I– + IO3  3I2 + 3H2O
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 = Cl2 , 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.
Ans. NaCl + H2SO4 150
 C
 NaHSO 4 + HCl
Insoluble

NaCl + NaHSO4  Na 2SO 4 + HCl

550C
( 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 2 O  O 2  Na2SO4 + 2HCl
  2
gaseous mixture

Q. In the similar type of preparation of HBr and HI from bromide to 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

p-Block elements [33]

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

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

X = Cl, Br, I

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

p-Block elements [34]

 Similarly electrolysis of hot halide solution with severe stirring gives the same product.
2Cl– + 2H2O  Cl2 + 2OH– + H2  NaClO  KCl  KClO   NaCl [KClO3 prep.n ]
3 3
Cl2+6NaOH5NaCl+NaClO3+3H2O  on cooling
(recycled) 
 NaClO3  BaCl 2  Ba (ClO3 ) 2  NaCl 
 first
Properties : 
Ba (ClO3 ) 2  H 2SO 4  BaSO 4  HClO3
* 3HClO3 evaporatio
  n
 2ClO2 + H2O + HClO4
* IO3 + 5I– + 6H+  3I2 + 3H2O
 Oxidising property

ClO 3 + 3SO32  Cl– + 3SO 24 

* Disproportionation: 4KClO3 low

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

2KClO3 400
 500C
 2KCl + 3O2
MnO2 ( 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 2 O ClO 2 Cl 2 O 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 : Prepn.:
(i) 3KClO3 + 3H 2SO 4  3KHSO4 + HClO4 + 2ClO 2  + H2O
( powder ) conc. Pale yellow gas
(ii) 2HClO3 + H2C2O4 60
C
 2H2O + 2ClO2 + 2CO2
(iii) 2AgClO3 + Cl2 90
C
 2AgCl + 2ClO2 + O2 [By this reaction pure ClO2 obtained]

p-Block elements [35]

 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)
* 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  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 :

p-Block elements [36]

 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 type 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
 4H 2O  HIO4  7HF
(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

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 : 3ICl  [I2Cl]+ + [ICl2]–

* ICl3 does not exist

but its dimer exist.  2ICl3  I2Cl6
Structure is planar.

(Bright yellow solid)

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]–
p-Block elements [37]
(iv) IF5 + CsF  Cs+[IF6]–
(v) ICl + KBr  K+[BrICl]–

Rb[ICl2]  RbCl + ICl [not RbI + Cl2]
Here the products on heating depends on the lattice energy of the product halide. The lattice energy of
alkali halide with smaller halogen is highest since the interatomic distance is least.
Structure of I5 , I7 , I82

 
in NCH3   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–.
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)
NCN2–(Bivalent) H2NCN (cyanamide)
ONC – HONC (Fulminic acid)
N 3 HN3 (Hydrazoic acid)
CNshows maximum similarites with Cl–, Br–, I–
(i) froms HCN
(ii) forms(CN)2
(iii) AgCN, Pb(CN)2, are insoluble
(iv) Interpseudo halogen compounds ClCN, BrCN, ICN can be formed
(v) AgCN is insoluble in H2O but soluble in NH3
(vi) forms large no.of complex.e.g. [Cu(CN)4]3– & [CuCl4]–3
[Co(CN)6]–3 & [CoCl6]–3

p-Block elements [38]

 Group -18 Elements (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 order
* Atomic radius order : Same order
* Density order : Same order
* 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

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)

p-Block elements [39]

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

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

perxenate ion
(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)

p-Block elements [40]

 Question Bank on p-Block elements
ONLY ONE OPTION IS CORRECT
Q.1 Which is incorrectly matched?
(A) CsBr3  Cs+ + Br3 (B) I4O9 I3+ + ( IO3 ) 3

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

220°C
Q.2 H3PO4 (X)
32
0° 320°C
C

(Y)
(A) (X) = Phosphorous acid , (Y) = Metaphosphoric acid
(B) (X) = Pyrophosphoric acid , (Y) = Metaphosphoric acid
(C) (X) = Metaphosphoric acid , (Y) = Pyrophosphoric acid
(D) (X) = Metaphosphoric acid , (Y) = Phosphene gas

Q.3 H3PO3  (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
Q.9 When PH3 absorbed in HgCl2 solution the corresponding phosphide is obtained
(A) Hg2P3 (B) Hg3P2 (C) Hg3(PO4)2 (D) None of these
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

p-Block elements [41]

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 acid (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
Q.20 H3BO3  T1 X T
2 Y red
  B2O3
hot

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

p-Block elements [42]

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 conc. 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
cu powder
Q.30 RCl   R SiCl H
2 2
2O
 R2Si(OH)2    A
condensation
Si
Compound (A) is
(A) a linear silicone (B) a chlorosilane (C) a linear silane (D) a network silane
Q.31 When oxalic acid reacts with conc. 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   X
P4 O10 , 150 C

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

p-Block elements [43]

Q.36 Match List-I with List-II
List-I Chemical reaction List-II Name of process
I. 4NH3 + 5O2 800
  4NO + 6H2O
C / Pt (a) Contact process
3230C / CuCl
II. 4HCl + O2 450
 2  2Cl + 2H O
500 / V O 2 2 (b) Ostwald's process
2 5

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

IV. 2N2 + 3H2 Fe  2NH3
Mo
 (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
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 conc. HNO3 gives a compound (Y). (Y) with HCl ,
produces a chloride compound (Z) which can also be produced by treating (X) with conc. 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

p-Block elements [44]

Q.49 NaH2PO4 230  C
 Na3(P3O9) 638 C
 (D)
Compound (D) contains 200 (PO4) units
(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 phosphorous in the following change are respectively
513 K 823 K
A 1200 atm
B C
In an inert atm. and
then rapid cooling
to room temp.

(A) white, red, white (B) black, white, red (C) red, black, white (D) red, violet, black
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 3O72 (B) SiO 44 8

Si 3O10

(C) SiO 24 Si 3O92 (D) SiO 34 Si 3O87

Q.54 Si 3O96 (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 SiO 4 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

p-Block elements [45]

 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 1s , 2s2, 2p6, 3s1
2

Z 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s2, 4p5

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 H2 O 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
| | |
Me2SiCl2  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

p-Block elements [46]

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) N2O
(C) catalyst high pressure NO 2
(D) high pressure catalyst N 2O 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  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
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.

p-Block elements [47]

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  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
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.75 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

p-Block elements [48]

Q.76 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.77 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.78 2NO2  N2O4The dimerisation of NO2 is accompanied with
(A) decrease in paramagnetism (B) change in colour
(C) increase in temperature’ (D) increase in paramagnetism
Q.79 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.80 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
Q.81 When an inorganic compound (X) having 3c-2e as well as 2c-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.82 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.83 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.84 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.85 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–

p-Block elements [49]

Q.86 The species that undergo(es) disproportionation in an alkaline medium is/are
(A) Cl2 (B) MnO42– (C) NO2 (D) CIO4–
Q.87 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.88 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
Q.89 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.90 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

IIT JEE ASKED QUESTIONS

Q.91 The reaction of P4 with X leads selectively to P4O6. The X is [JEE 2009]
(A) Dry O2 (B) A mixture of O2 and N2
(C) Moist O2 (D) O2 in the presence of aqueous NaOH
Q.92 The nitrogen oxide(s) that contain(s) N–N bond(s) is (are) [JEE 2009]
(A) N2O (B) N2O3 (C) N2O4 (D) N2O5
Q.93 In the reaction [JEE 2009]
2X + B2H6  [BH2(X)2]+ [BH4]¯
the amine(s) X is (are)
(A) NH3 (B) CH3NH2 (C) (CH3)2NH (D) (CH3)3N

p-Block elements [50]

 ANSWER KEY
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 B 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 Q.75 A,B Q.76 A,B,C

Q.77 B,C Q.78 A,B Q.79 A,D Q.80 A,C Q.81 A,B,C Q.82 A,B,D

Q.83 A,B Q.84 A,B,C Q.85 A,D Q.86 A,B,C Q.87 A,B,C,D

Q.88 B,C Q.89 A,C,D Q.90 (A) Q,S (B) R (C) P (D) Q,R

Q.91 B Q.92 A,B Q.93 B,C

p-Block elements [51]