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 How to use your
Tatva Practice Book
2. Hexagonal Packing
Hexagonal packing is more
efficient. Its coordination
number is 6 and voids in the
packing are smaller than square
packing. If we place another
layer on square packing then
there are the following
SCAN CODE
Solid State
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CHAPTER-1: SOLID STATE
Exercise-1: Basic Objective
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(NEET 2019)
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(c) 4.25 g/cm3 (d) 8.5 g/cm3
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6

TABLE OF CONTENTS

p -Block Elements (group 15-18)

Theory........................................................................................................................................................ 8

Solved Examples......................................................................................................................................... 42

Exercise - 1 : Basic Objective Questions....................................................................................................... 45

Exercise - 2 : Previous Year Questions......................................................................................................... 54

Exercise - 3 : Achiever’s Section ................................................................................................................. 58

Answer Key .............................................................................................................................................. 215

Metallurgy

Theory........................................................................................................................................................ 62

Solved Examples......................................................................................................................................... 80

Exercise - 1 : Basic Objective Questions....................................................................................................... 86

Exercise - 2 : Previous Year Questions......................................................................................................... 95

Exercise - 3 : Achiever’s Section ................................................................................................................. 99

Answer Key .............................................................................................................................................. 217

 7

d and f Block Elements

Theory...................................................................................................................................................... 103

Solved Examples....................................................................................................................................... 123

Exercise - 1 : Basic Objective Questions..................................................................................................... 131

Exercise - 2 : Previous Year Questions....................................................................................................... 141

Exercise - 3 : Achiever’s Section................................................................................................................ 145

Answer Key ............................................................................................................................................. 219

Chemistry in Everyday life

Theory....................................................................................................................................................... 149

Solved Examples........................................................................................................................................ 160

Exercise - 1 : Basic Objective Questions...................................................................................................... 164

Exercise - 2 : Previous Year Questions........................................................................................................ 172

Exercise - 3 : Achiever’s Section ................................................................................................................ 175

Answer Key ............................................................................................................................................. 221

Practical Organic Chemistry

Theory....................................................................................................................................................... 178

Solved Examples........................................................................................................................................ 197

Exercise - 1 : Basic Objective Questions...................................................................................................... 202

Exercise - 2 : Previous Year Questions........................................................................................................ 206

Exercise - 3 : Achiever’s Section ................................................................................................................ 210

Answer Key ............................................................................................................................................. 223

 11
p-
-BLOCK ELEMENTS
(GROUP 15-18)
Chapter 11

p-Block Elements (Group 15 -18)

1. Introduction 1.3 Ionisation Enthalpy

Group 15 includes nitrogen phosphorus, arsenic, antimony and
bismuth. As we go down the group, there is a shift from non-
metallic to metallic through metalloidic character. Nitrogen and
phosphorus are non-metal, arsenic and antimony metalloid and
bismuth is a typical metal.
1.1 Electronic Configuration
The valence shell electronic configuration of these element is
ns2 np3. The s orbital in these element is completely filled and p
orbitals are half- filled, making their electronic configuration extra
stable.
1.2 Atomic and Ionic Radii
Covalent and ionic radii increase down the group. There is a
considerable increase in covalent radius from N to P. However,
from As to Bi only a small increase in covalent radius is observed.
This is due to the presence of completely filled d and f orbitals in
heavier members.
Ionisation enthalpy decreases down the group due to gradual
increase in atomic size. Because of the extra stable half- filled p-
orbital electronic configuration and smaller size, the ionisation
enthaply of the group 15 element is much greater than of group
14 elements in the corresponding periods. The order of successive
ionisation enthalpies, as expected is iH1 < iH2 < iH3
2. Physical Properties of Group
15 Elements
All the elements of this group are polyatomic. Dinitrogen is a
diatomic gas while all others are solids. Metallic character
increases down the group. Nitrogen and phosphours are non-
metals, arsenic and antimony metalloids and bismuth is a metal.

Table 11.1 : Atomic & Physical Properties of Group 15 Elements

Element N P As Sb Bi
Atomic Number 7 15 33 51 83
Atomic Mass 14.01 30.97 74.92 121.76 208.98
Electronic configuration [He]2s22p3 [Ne]3s23p3 [Ar]3d104s24p3 [Kr]4d105s25p3 [Xe]4f145d106s26p3
Covalent Radius/pm 70 110 120 140 150
Ionic Radius/pm 171a 212a 222a 76b 103b
a=M ,b=M
3– +3

Ionization enthalpy I 1402 1012 947 834 703

/(kJ mol ) –1
II 2856 1903 1798 1595 1610
III 4577 2910 2736 2443 2466
Electronegativity 3.0 2.1 2.0 1.9 1.9

3. Chemical Properties of Group
15 Elements
Chemical Properties: Oxidation States and trends in a chemical
reactivity:
The common oxidation states of these elements are – 3 , + 3 and
+ 5. The tendency to exhibit – 3 oxidation state decreases down
the group, bismuth hardly forms any compound in –3 oxidation
state. The stability of + 5 oxidation state decreases down the
group. The only well characterised Bi (V) compound is BiF5. The
stability of + 5 oxidation state decreases and that of +3 state
increases (due to inert pair effect) down the group. Nitrogen
exhibits +1, + 2, + 4 oxidation states also when it reacts with
oxygen. Phosphours also shows + 1 and + 4 oxidation states in
some oxoacids.

SCAN CODE
p-Block Elements (Group 15-18)
10 p-BLOCK ELEMENTS (GROUP 15-18)

In the case of nitrogen , all oxidation states from +1 to +4 tend to Table 11.2 : Properties of Hydrides of Group 15
disproportionate in acid solution. For example, Elements
3 HNO2  HNO3 + H2O + 2 NO
Property NH3 PH3 AsH 3 SbH 3 BiH3
Similarly , in case of phosphorus nearly all intermediate oxidation
states disproportionate into +5 and –3. Melting point/K 195.2 139.5 156.7 185 –
Nitrogen is restricted to a maximum covalency of 4 since only Boiling point/K 238.5 185.5 210.6 254.6 290
four (one s and three p) orbitals are available for bonding. The (E-H) Distance/ 101.7 141.9 151.9 170.7 –
heavier elements have vacant d orbitals in the outermost shell pm
which can be used for bonding (covalency) and hence , expand
HEH angle 107.8 93.6 91.8 91.3 –
their covalence as in PF6– .
fH–/kJ mol–1 –46.1 13.4 66.4 145.1 278
Anomalous properties of nitrogen: Nitrogen differs from the rest
of the members of this group due to its smaller size, high dissH–(E–H)/ –46.1 13.4 66.4 145.1 278
electronegativity , high ionisation enthalpy and non – availability kJ/mol–1 389 322 297 255 –
of d orbitals. Nitrogen has unique ability to form p – p multiple
bonds with itself and with other elements having small size and 3.2 Reactivity Towards Oxygen
high electronegativity (e.g., C ,O). Heavier elements of this group All these elements form two types of oxides: E2O3 and E2O5. The
do not form p – p bonds as their atomic orbitals are so large oxide in the higher oxidation state of the element is more acidic
and diffuse that they cannot have effective overlapping. Thus, than that of lower oxidation state. Their acidic character decreases
nitrogen exists as a diatomic molecule with a triple bond (one s down the group. The oxides of the type E2O3 of nitrogen and
phosphours are purely acidic, that of arsenic and antimony
and two p) between the two atoms. Consequently , its bond amphoteric and those of bismuth is predominantly basic.
enthalpy (941.1 kJ mol –1) is very high. On the contrary,
phosphorus, arsenic and antimony form single bond (P - P, As- 3.3 Reactivity Towards Halogens
As, Sb-Sb) while Bi forms metallic bonds in elemental state. These elements react to form two series of halides: EX3 and EX5.
However , the single N – N bond is weaker than the single P – P Nitrogen does not form pentahalide due to non– availability of
bond because of high interelectronic repulsion of the non – the d– orbitals in its valence shell. Pentahalides are more covalent
bonding electrons, owing to the small bond length. As a result than trihalides. All the trihalides of these elements except those
of nitrogen are stable. In case of nitrogen , only NF3 is known to
the catenation tendency is weaker in nitrogen. Another factor be stable. Trihalides except BiF3 are predominantly covalent in
which affects the chemistry of nitrogen is the absence of d orbitals nature.
in its valence shell. Besides restricting its covalency to four ,
nitrogen cannot form d – p bonds as the heavier elements can 3.4 Reactivity Towards Metals
e.g., R3P = O or R3P = CH2 (R = alkyl group). Phosphours and These elements react with metals to form their binary compounds
arsenic can form d – p bond also with transition metals when exhibiting –3 oxidation state, such as, Ca3N2 (calcium nitride)
their compounds like P(C2H5)3 and As(C6H5)3 act as ligands. Ca3P2 (calcium phosphide), Na3As2 (sodium arsenide), Zn3Sb2
(zinc antimonide) and Mg3Bi2 (magnesium bismuthide).
3.1 Reactivity Towards Hydrogen
All the elements of Group 15 form hydrides of the type EH3 where 4. General Properties and
E = N , P, As, Sb or Bi. Some of the properties of these hydrides
are shown in Table. The hydrides show regular gradation in their Componds of Nitrogen
properties. The stability of hydrides decreases from NH3 to BiH3 4.1 Nitrogen (N2)
which can be observed from their bond dissociation enthalpy.
Consequently, the reducing character of the hydrides increases. Preparation:
Ammonia is only a mild reducing agent while BiH3 is the strongest (i) By treating an aqueous solution of ammonium chloride with
reducing agent amongst all the hydrides. Basicity also decreases sodium nitrate. It is laboratory method of preparation.
in the order
NH4Cl(aq) + NaNO2(aq)  N2(g) + H2O () + NaCl(aq)
NH3 > PH3 > AsH3 > SbH3  BiH3.
(ii) By heating ammonium dichromate:

(NH4)2Cr2O7  N2  + 4H2O + Cr2O3
(iii) By oxidation of ammonia

(iv) 2NH3 + 3NaOCl  N2 + 3NaCl + 3H2O

SCAN CODE
p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18)
(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)
Industrial Methods of Preparation:
(i) From liquefied air by fractional distillation: The bp of N2 is –
196oC and that of oxygen is –183oC and hence they can be
separated.
(ii) From producer gas from furnaces: Producer gas is a mixture
of CO and N2. When the mixture of CO and N2 is passed over
heated CuO, the CO gas is oxidized to CO2 which is absorbed
in alkalies & N2 remains which is collected in gas cylinders.
Properties:
(i) N2 is a colourless, odourless gas insoluble in water.
(ii) It is non-polar covalent and neutral molecule.
(iii) It is neither combustible nor a supporter of combustion.
(iv) It is absorbed by heated Mg and Al. The nitrides formed
thus react with water to form NH3.
3Mg + N2  Mg3N2 (+ 6H2O)  3Mg(OH)3 + 2NH3
2Al + N2  2AlN (+ 6H2O)  2Al(OH)3 + 2NH3
(v) Reaction with H2: At 200 atm and 500oC, and in the presence
of iron catalyst and molybdenum promoter, N2 combines with
H2 reversibly to form ammonia. The process is called Haber’s
Process and is the industrial method of manufacturing
ammonia. The reaction is exothermic.
N2 + 3H2  2NH3
(vi) Reaction with oxygen: When air free from CO2 and moisture
is passed over an electric arc at about 2000 K, nitric oxide is
formed. This reaction is endothermic.
N2 + O2  2NO
(vii) Reaction with CaC2 and BaC2: At 1100oC, these carbides react
with N2 forming CaCN2 and Ba(CN)2 respectively.
 Iron oxide  K O &Al O
CaC2 + N2 +  CaCN2 + C (nitrolim, a fertilizer)
 (ii) From destructive distillation of coal: When coal is heated at
BaC2 + N2 +  Ba(CN)2
CaCN2 reacts with H2O in the soil to produce NH3 gas. NH3
gas is converted by the nitrating bacteria present in soil into
nitrates. (The nitrates are readily absorbed by the plants and
meet their requirement of the element nitrogen.)
11
Uses
(i) for providing an inert atmosphere during many industrial
processes where presence of air or O2 is to be avoided.
(ii) for manufacture of NH3 by the Haber’s process.
(iii) for manufacture of HNO3 by the Birkeland-Eyde process.
(iv) for manufacture of nitrolim.
4.2 Compounds of Nitrogen
4.2.1 Ammonia:
Preparation:
(i) By the action of any base or alkali on any ammonium salt :

NH4Cl + NaOH  NH3 + NaCl + H2O

(NH4)2SO4 + 2NaOH  2NH3 + Na2SO4 + 2H2O

NH4NO3 + NaOH  NH3 + NaNO3 + H2O

(NH4)3PO4 + 3NaOH  3NH3 + Na3PO4 + 3H2O

(NH4)2SO4 + CaO  2NH3 + CaSO4 + H2O
This is a general method and is used as a test for ammonium
salts.
(ii) By the hydrolsis of metal nitrides like AlN or Mg3N2.
AlN + NaOH + H2O  NaAlO2 + NH3
(iii) From oxides of nitrogen: When oxides of nitrogen are mixed
with H2 and the mixture is passed over heated platinum
catalyst, NH3 gas is evolved.
2NO + 5H2  2NH3 + 2H2O
2NO2 + 7H2  2NH3 + 4H2O
(iv) From organic amides: When an organic amide is heated with
NaOH solution ammonia is evolved.

CH3CONH2 + NaOH  CH3COONa + NH3
(v) From nitrates and nitrites: When a metal nitrate or nitrite is
heated with zinc powder and concentrated NaOH solution
ammonia is obtained. The reactions are
NaNO3 + 7NaOH + 4Zn  4Na2ZnO2 + NH3 + 2H2O
NaNO2 + 3Zn + 5NaOH  3Na2ZnO2 + H2O + NH3
Industrial Methods of Preparation:
(i) Haber’s process:
500 C, 200atm
N2 + 3H2            2NH3
2 2 3
a high temperature in an iron retort and the distillate is bubbles
in water, three substances are obtained:
(a) Tarry black pitch, (b) Liquor ammonia & (c) Coal gas
The liquor ammonia is a concentrated solution of ammonia and
ammonium salts. When heated it gives out ammonia. When all
the free NH3 is obtained, the residual liquid is heated with Ca(OH)2
SCAN CODE
p-Block Elements (Group 15-18)
12 p-BLOCK ELEMENTS (GROUP 15-18)
when ammonium salts get decomposed to liberate further quantity MCl 2  2NH 4 OH  M  OH  2  2NH 4 Cl
of ammonia.  white 
 
 
(iii) Cyanamide process:
(M = Mg, Ca, Sr, Ba, Ra, Sn, Pb)
CaO + 2C + N2 2000ºC CaCN + CO (viii) When NH4OH solution is added to AgNO3 solution, a brown
2
CaCN2 + 3H2O  CaCO3 + 2NH3 ppt. is obtained
Properties: 2AgNO3  2NH 4 OH  Ag 2 O  2NH 4 NO 3  H 2 O
(i) Colourless gas lighter than air. Being basic in nature turns  brown 
 
 
red litmus blue. It acts as a Lewis base
Brown ppt of silver oxide formed dissolves in excess ammo-
(ii) Highly soluble in water. The solution is called ammonium nium hydroxide forming a soluble complex
hydroxide solution.
Ag2O + 2NH4OH  [Ag(NH3)2]OH + 2H2O

(iii) Na + NH3  NaNH2 + 1/2 H2
(ix) 2NH3 + CO2 + H2O  (NH4)2CO3
Amides decompose back with water to form NH3 and NaOH.
high pressure
Pt ,550ºC 4NO + 6H O 2NH3 + CO2   NH CONH (urea) + H O
(iv) 4NH3 + 5O2   2
 2 2 2

(Ostwald’s process of manufacturing HNO3) Uses:

(v) When Cl2 is bubbled in liquor ammonia, nitrogen gas is (i) Used as a refrigeration fluid.
formed. (ii) For the production of ammonium fertilizers such as ammonium
sulphate, ammonium phosphate, ammonium nitrate, urea etc.
8NH3 + 3Cl2  6NH4Cl + N2
(iii) For removing grease because NH4OH dissolves grease.
With excess of Cl2 it is converted to an explosive substance,
(iv) For manufacture of HNO3 by the Ostwald process.
nitrogen trichloride.
(v) As a laboratory reagent.
NH3 + 3Cl2  NCl3 +3HCl
(vi) In the production of artificial rayon, silk, nylon etc.
(vi) Cupric oxide and PbO are reduced to metal when NH3 is 4.2.2 Oxides of Nitrogen:
passed over heated CuO and PbO.
Nitrogen forms a number of oxides, N2O, NO, N2O3, NO2 or N2O4
3CuO + 2NH3  3Cu + 3H2O + N2 and N2O5, and also very unstable NO3 and N2O6. All these oxides
3PbO + 2NH3  3Pb + 3H2O + N2 of nitrogen exhibit p-p multiple bonding between nitrogen and
oxygen.
M  NO3  2  2NH 4 OH  M  OH  2  2NH 4 NO3
(vii)
 white 
 
 

Table 11.3 : Oxides of Nitrogen

Name Formula Colour Remarks

Nitrous oxide N2O Colourless (g) Neutral ,+ 1 oxidation state
Nitric oxide NO Colourless (g) Neutral ,+ 2 oxidation state
Dinitrogen trioxide N2O3 Dark blue (s) Acidic ,+ 3 oxidation state
Nitrogen dioxide NO2 Brown (g) Acidic , + 4 oxidation state
Dinitrogen tetroxide N2O4 Colourless (s) Extensively dissociated to NO2 as gas and partly
dissociated as liquid, acidic, + 4 oxidation state
Dinitrogen pentoxide N2O5 Colourless (s) Unstable as gas; ionic solid NO+2,
NO3– , acidic, +5 oxidation state

Preparation: On warming, its colour fades due to its dissociation into

(i) N2O is obtained generally by heating NH4NO3 with caution.
NH4NO3  N2O + 2H2O
(ii) N2O3 is obtained as an intense blue liquid or a pale blue solid
on cooling an equimolar mixture of NO and NO2 to 250 K.
NO + NO2  N2O3
these two oxides.
(iii) NO2 can be prepared by reduction of concentrated HNO3
with Cu or by heating heavy metal nitrates.
Cu + 4HNO3  Cu(NO3)2 + 2NO2 + 2H2O ;
673 K
2Pb(NO3)2  2PbO + 4NO2 + O2

SCAN CODE
p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18)
(iv) N2O5 is an anhydride of HNO3. It is best prepared by
dehydrating HNO3 by P4O10 at low temperatures.
250K  2N O + 4HPO
4HNO3 + P4O10  2 5 3
Properties:
Oxides of nitrogen are all oxidizing agents, N2O even supporting
the combustion of S and P. NO which is thermally more stable,
supports the combustion of Mg and P but not of S. Sulphur flame
is not hot enough to decompose it.
N2O is isoelectronic with CO2 and also has a linear structure.
However, unlike CO2, N2O has a small dipole moment.
NO has a total of 15 electrons. It is impossible for all of them to be
paired and hence this is an odd electron molecule. In the gaseous
state, it is paramagnetic. However, the liquid and the solid states
are diamagnetic because loose dimmers are formed canceling out
the magnetic effects of unpaired electrons.
• N2O :
(a) Reduction : Cu(hot) + N2O  CuO + N2
(b) Oxidation: 2KMnO4 + 3H2SO4 + 5N2O  K2SO4 +
2MnSO4 + 3H2O + 10NO
(c) Supporter of combustion : Mg + N2O  MgO + N2
• NO :
(a) Supporter of combustion : S + 2NO  SO2 + N2
(b) Oxidising properties (Reduction of NO) :
Pt  black 2NH + 2H O
5H2 + 2NO   3 2
(c) Reducing properties (oxidation of NO) :
2NO + X2  2NOX
N2O3 : It is anhydride of HNO2 : 2HNO2  N2O3 + H2O
NO2 : It behaves both like HNO2 and HNO3. It behaves like
HNO2 as a reducing agent and like HNO3 as an oxidising
agent according to following reactions respectively.
2KMnO4 + 3H2SO4 + 10NO2 + 2H2O  K2SO4 + 2MnSO4
+ 10HNO3
SO2 + H2O + NO2  H2SO4 + NO

N2O5 : 2N2O5  2N2O4 + O2
4.2.3 Oxyacids of Nitrogen:
4.2.3.1 Nitrous Acid (HNO2):
Preparation:
(i) By acidifying an aqueous solution of a nitrite
Ba(NO3)2 + H2SO4  2HNO2 + BaSO4
(ii) By passing an equimolar mixture of NO and NO2 into water:
NO + NO2 + H2O  2HNO2
13
Properties:
(i) It is an unstable, weak acid which is known only in aqueous
solution.
(ii) On trying to concentrate, the acid decomposes as given
below.
3HNO2  HNO3 + 2NO + H2O
(iii) Nitrous acid and nitrites are good oxidizing agents and
convert iodides to iodine, ferrous salts to ferric, stannous to
stannic and sulphites to sulphates eg.
2KI + 2HNO2 + 2HCl  2H2O + 2NO + 2KCl + I2
(iv) With strong oxidizing agents like KMnO4 nitrous acid and
nitrites function as reducing agents and get oxidized to
NO3- ions:
2KMnO4 + 5KNO2 + 6HCl2MnCl2 + 5KNO3 + 3H2O + 2KCl
(v) Nitrite ion is a good coordinating agent. Both nitrogen and
oxygen have lone pairs capable of forming coordinate bond
with metal ions. Nitrite ion can coordinate either through N
or through O.(It is an ambidentate ligand) This generates
linkage isomerism. Analogous organic derivatives are also
known, the nitrites, RONO and the nitro compounds RNO2
where R is any alkyl or aryl group.
4.2.3.2 Nitric Acid (HNO3):
Preparation:
(i) Laboratory method:
NaNO3 + H2SO4  NaHSO4 + HNO3
(ii) HNO 3 is now almost exclusively manufactured by the
Ostwald process. In this process NH3 is catalytically oxidized
to NO over a Pt-Rh catalyst at 1200K.
4NH3 + 5O2  4NO + 6H2O H = –904 kJ
About 96 to 98 % of NH3 is converted into NO. The mixture
is then diluted with air. NO combines with O2 to give NO2
which is absorbed in water to give HNO3 and NO, which is
then recycled.
2NO + O2  2NO2
3NO2 + H2O  2HNO3 + NO
Nitric acid can be concentrated to 68 % by distillation, when
a constant boiling mixture is formed. More concentrated
acid can be made by distilling the mixture with concentrated
sulphuric acid.
Properties:
(i) Pure nitric acid is colourless liquid (bp 359oC). It is a strong
acid and is almost completely dissociated into ions in
solution.
(ii) Thermal stability

4HNO3  2H2O + 4NO2 + O2
SCAN CODE
p-Block Elements (Group 15-18)
14
(iii) Oxidising properties
2HNO3 (conc.)  H2O + 2NO2 + [O]
2HNO3 (dilute)  H2O + 2NO + 3[O]
(a) Oxidises H2S to sulphur
H2S + 2HNO3 (conc.)  2H2O + 2NO2 + S 
3H2S + 2HNO3 (dilute)  4H2O + 2NO + 3S
(b) Oxidises SO2 to H2SO4
SO2 + 2HNO3 (conc.)  H2SO4 + 2NO2 
3SO2 + 2H2O + 2HNO3 (dilute)  3H2SO4 + 2NO
Similarly oxidises ferrous salts to ferric salts, halogen acids
to respective halogens.
(iv) Reaction with non-metals.
C + 4HNO3  H2CO3 + H2O + 4NO2
S + 6HNO3  H2SO4 + 2H2O + 6NO2
2 + 10HNO3  2HO3 + 4H2O + 10NO2 ;
P + 5HNO3  H3PO4 + H2O + 5NO2
These reactions are given with conc. HNO3 .
(v) Reaction with metals: Metals that are more electropositive
than hydrogen
(a) Action on zinc or Fe :
Zn + 4HNO3 (conc.)  Zn(NO3)2 + 2H2O + 2NO2
4Zn + 10HNO3 (dil.)  4Zn(NO3)2 + 5H2O + N2O
4Zn + 10HNO3 (v.dil.)  4Zn(NO3)2 + NH4NO3 + 3H2O
4Mg + 10HNO3 (v.dil.)  4Mg(NO3)2 + NH4NO3 + 3H2O
(b) Action on tin :
Sn + 4HNO3 (conc.)  H2SnO3 + 4NO2 + H2O
4Sn + 10HNO3 (dil.)  4Sn(NO3)2 + NH4NO3 + 3H2O
(c) Action on lead :
Pb + 4HNO3 (conc.)  Pb(NO3)2 + 2NO2 + 2H2O
3Pb + 8HNO3 (dil.)  3Pb(NO3)2 + 2NO + 4H2O
Metals which are less electropositive than hydrogen.
(i) Action on copper
Cu + 4HNO3 (conc.)  Cu(NO3)2 + 2NO2 + 2H2O
3Cu + 8HNO3 (v.dil)  3Cu(NO3)2 + NO + 4H2O
SCAN CODE
p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18)
Mg + 2HNO3  Mg(NO3)2 + H2
Mn + 2HNO3  Mn(NO3)2 + H2
• As concentrated nitric acid (80%) behaves as an oxidizing
agent and metals such as Al, Fe, Cr etc are rendered passive
due to the formation of a tenacious layer of insoluble oxide
on the metal surface.
• Noble metals such as Au, Pt, Rh, and Ir are not attacked by
nitric acid. However a 1:3 mixture of conc.
HNO3 and conc. HCl known as aqua regia dissolves Au and
Pt as it contains free(atomic) chlorine:
HNO3 + 3HCl  2H2O + 2Cl + NOCl
Au + 3Cl + HCl  HAuCl4
Pt + 4Cl + 2HCl  H2PtCl6
Brown Ring Test:
2HNO3 + 3H2SO4 + 6FeSO4  3Fe2(SO4)3 + 2NO + 4H2O
FeSO4 + NO + 5H2O  [Fe(H2O)5 NO]SO4
5. General Properties and
Compounds of Phosphorus
It is a very reactive non-metal. It catches fire in air. It occurs in
nature in the form of stable phosphates. (Animal bones also
contain calcium phosphate (58 %)).
Allotropic forms of Phosphorus:
(i) White or yellow phosphorus (P4):
Preparation:
2Ca3(PO4)2 + 10C + 6SiO2  6CaSiO3 + 10CO + P4(s)
Properties: It is white-to-transparent and soft waxy solid. Its mp
and bp are 44°C and 287°C respectively. It is soluble in CS2 but
insoluble in water. It glows in dark due to slow oxidation
producing
yellowish-green light.
P4 + 5O2 P4O10
White phosphorus is poisonous. It turns yellow after some time;it
is called yellow phosphorus. It undergoes oxidation in the
presence of air which slowly raises its temperature and due to its
low ignition temperature (~ 30ºC) after a few moments it catches
fire spontaneously.
Fig 11.1: Structure of white phosphorus
p-BLOCK ELEMENTS (GROUP 15-18)
(ii) Red phosphorus:
Preparation: When white phosphorus is heated in the atmosphere
of CO2 or coal gas at 573 K red phosphorus is prodouced. This
red phosphorus may still contain some white phosphours which
is removed by boiling the mixture with NaOH where white
phosphorus is converted into PH3 gas but red phosphorus remains
inert.
P4 + 3NaOH + 3H2O  PH3(g) + 3NaH2PO2
It is also prepared by heating white phosphorus with a few
crystals of iodine catalyst at 250oC under high pressure in
absence of air.
Properties : It is a red crystalline solid. It is less reactive than
white phosphorus and does not dissolve in liquid CS2. It does not
catch fire at room temperature because its ignition temperature is
260oC.
It is a polymeric substance forming linear chains like this.
Fig 11.2: Structure of Red phosphorus
(iii) Black phosphorus: It has two forms -black phosphorus
and -black phosphorous
(a) -black phosphorous
insulated 
P(red) 
tube803K P(-black)
-black phosphorous structure is not definite and is non
conductor of electricity.
(b) -black phosphorous
473 K

P(white) High  Heat above 250°C in presence of inert gas and condense in water
pressure P(-black)
-black phosphorous is an electrical conductor resembling
graphite in this respect and also in its flakiness and luster. It
is insoluble in CS2. It has a layered structure like graphite.
Fig 11.3: Structure of Black phosphorus
Chemical Properties of Phosphorus:
(i) Action of air: White phosphorus burns in air to form
phosphorus trioxide and pentoxide.
15
P4 + 5O2  2P2O5
P4 + 3O2  2P2O3
Red and other forms of phosphorus also burn in air or oxygen
but on heating.
(ii) Action of non-metals: When heated with non-metals
phosphorus forms compounds PX3, PX5, P2S3 and P2S5.
2P + 3X2  2PX3
2P + 5X2  2PX5 (where X = Cl, Br, and I.)
(iii) Action with metals: Alkali metals when heated with white
phosphorus in vacuum produce alkali metal phosphide, which
react with water to form phosphine gas.

3M + P  M3P

M3P + 3H2O  3MOH + PH3 {where M = Na, K etc.}
(iv) Action of NaOH: When white phosphorus is heated with
NaOH solution, phosphine gas is evolved.
P4 + 3NaOH + 3H2O  3NaH2PO2 + PH3
(v) Action of conc. HNO3 : When heated with conc. HNO3,
phosphorus is oxidized to H3PO4.
P + 5NHO3  H3PO4 + 5NO2 + H2O
(vi) Action of conc. H2SO4: When heated with conc. H2SO4
phosphorus is oxidized to H3PO4.

2P + 5H2SO4  2H3PO4 + 5SO2 + 2H2O
Conversion of white phosphorus to red phosphorus and red phos-
phorus to white phosphorus.
Heat in presence of 2 catalyst at 250oC and high pressure in ab-
sence of air
White phosphorus  Red phosphorus
5.1 Compounds of Phosphorus
5.1.1 Phosphine:
Preparation:
(i) By heating white phosphorus with NaOH solution in
presence of coal gas. Phosphine gas is collected by the
downward displacement of water.

P4 + 3NaOH + 3H2O  3NaH2PO2 + PH3
Coal gas is used to prevent oxidation of phosphine. The phsophine
gas is contaminated with a combustible gas P2H4. It is separated
from PH3 by passing the gaseous mixture through a freezing mixture
whereupon P2H4 condenses to a liquid and PH3 is collected by the
downward displacement of air. Pure PH3 does not burn in air.
SCAN CODE
p-Block Elements (Group 15-18)
16 p-BLOCK ELEMENTS (GROUP 15-18)

(ii) By the action of alkalies on phosphonium salts:

PH4I + NaOH  NaI + PH3 + H2O
(iii) By the action of dil. HCl or dil. H2SO4 on metal phosphides.
Na3P + 3HCl  3NaCl + PH3
AlP + 3HCl  AlCl3 + PH3
2Na3P + 3H2SO4  3Na2SO4 + 2PH3
Properties:
(i) It is a colourless gas with a smell of rotten fish and is neutral
to litmus paper, It is heavier than air and only slightly soluble
in water, It is a poisonous gas and acts as a Lewis base.
(ii) Action of chlorine: It reacts with Cl2 to form PCl5.
PH3 + 4Cl2  PCl5 + 3HCl
Similar reaction occurs between heated phosphine and Br2
and I2 vapours.
(iii) Reaction with hydrogen halides: When PH3 is bubbled in
solution of HX, phosphonium halides are formed.
PH3 + HX  PH4X
(iv) Action on CuSO4 solution: When PH3 is bubbled in acidic
solution of copper sulphate, a black precipitate of copper
phosphide is formed.
3CuSO4+2PH3 Cu3P2 {black} + 3H2SO4
(v) Reaction with AgNO3 solution: When PH3 gas is bubbled in
a solution of AgNO3, a yellow precipitate of silver phosphide,
Ag3P, is first formed which later decomposes to black Ag.
3AgNO3 + PH3  Ag3P (yellow) + 3HNO3
Ag3P + 3AgNO3 + 3H2O  6Ag + 3HNO3 + H3PO3
gaseous form whereas P4O10 condenses as a solid which is stopped
by glasswool. On passing the remaining gaseous mixture through
freezing mixture, it converts into colourless crystals of P 4O6.
Properties:
(i) It is colourless crystalline solid having mp 23.8oC and bp
178oC.
(ii) It dissolves in cold water to form phosphorus acid. It is thus
the anhydride of phosphorus acid.
P2O3 + 3H2O  2H3PO3
(iii) It dissolves in hot water liberating PH3
2P2O3 + 6H2O  3H3PO4 + PH3
(iv) It slowly gets oxidized in air to form P2O5
P2O3 + O2  P2O5
5.1.2.2 Phosphorus Pentoxide (P2O5) :
Preparation : It is obtained by burning phosphorus in air.
P4 + 5O2  P4O10
Properties:
(i) It is a white powder acidic in nature and is the anhydride of
orthophosphoric acid. Its empirical formula is P2O5 and its
molecular formula is P4O10.
(ii) It sublimes on heating at 250oC.
(iii) Action of water: It dissolves in water with hissing sound
forming metaphosphoric acid and finally orthophosphoric
acid.
P4O10 + 2H2O  4HPO3 , HPO3 + H2O  H3PO4
(iv) Dehydrating power: It dehydrates conc. H2SO4 and conc.
HNO3 to SO3 and N2O5 respectively.
distillation  2HPO + N O
2HNO3 + P2O5  3 2 5

(vi) Reaction with mercuric chloride solution: When mercuric

chloride solution is treated with PH3 gas, a brownish black distillation  2HPO + SO
H2SO4 + P2O5  3 3
precipitate of mercuric phosphide is formed.
Uses:
3HgCl2 + 2PH3  Hg3P2(brownish-black) + 6HCl (i) For drying acidic gases
Samples of PH3 can be dried using quick lime, or NaOH sticks. (ii) As a dehydrating agent
It cannot be dried by conc. H2SO4 because of its reaction (iii) For the preparation of SO3 and N2O5
with it.
(iv) For the preparation of phosphoric acid
Uses:
5.1.3 Oxy-Acids of Phosphorus
It is used in making smoke signals and producing smoke
screens in battle-fields. 5.1.3.1 Phosphorus Acid (H3PO3)
Preparation:
5.1.2 Oxides of Phosphorus
(i) By dissolving P2O3 in water:
5.1.2.1 Phosphorus Trioxide (P2O3)
Preparation: It is prepared by burning phosphorus in a limited P2O3 + 3H2O  2H3PO3
supply of oxygen when gaseous P4O10 and P4O6 are formed. On (ii) By hydrolysis of PCl3 with water:
lowering the temperature using a condenser, P4O6 remains in

SCAN CODE
p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18)
PCl3 + 3H2O  H3PO3 + 3HCl
The solution containing H3PO3 and HCl is heated to 180oC
and HCl gas is driven out. The resulting solution on
crystallization gives white crystals of H3PO3.
Properties:
(i) It is a white crystalline solid, soluble in water and having
melting point of 74oC.
(ii) It is a weak acid and a reducing agent
(iii) When neutralized with bases or alkalies, it forms neutral salts
called phosphites which are unstable.
H3PO3 + 3NaOH  Na3PO3 + 3H2O
Its basicity is 2 because it has only two replaceable H atoms.
The third H atom is not replaceable because it is not
connected to oxygen.

(iv) 4H3PO3  3H3PO4 + PH3 (Disproportionation)
(v) H3PO3 + 3PCl5  PCl3 + 3POCl3 + 3HCl
(vi) It is a strong reducing agent:
17
CaSO4 is insoluble. Solution of H3PO4 is separated from
CaSO4. It is then concentrated by evaporating it at 180oC
and dehydrated by conc. H 2SO 4 placed in a vacuum
dessicator cooled by freezing mixture. White crystals of
H3PO4 are thus formed.
(ii) By hydrolysis of PCl5:
PCl5 + 4H2O  H3PO4 + 5HCl
(iii) By heating white phosphorus with conc. HNO3:
P + 5HNO3  H3PO4 + 5NO2 + H2O
Properties:
(i) Pure orthophosphoric acid is a white crystalline solid highly
soluble in water having melting point of 42oC. It is a weak
acid. It forms two acid salts and one normal salt.NaH2PO4 is
sodium dihydrogen phosphate,Na 2HPO 4 is disodium
hydrogen phosphate & Na3PO4 is sodium orthophosphate.
(ii) Action of heat:
220ºC  H P O (pyrophosphoric acid)
H3PO4  4 2 7

2AgNO3 + H3PO3 + H2O  2Ag + 2HNO3 + H3PO4 316ºC HPO (metaphosphoric acid)
H4P2O7  3

2HgCl2 + H3PO3 + H2O  Hg2Cl2 + 2HCl + H3PO4 (iii) Neutralization with alkalies or bases:
5.1.3.2 Orthophosphoric Acid (H3PO4) NaOH  NaOH 
H3PO4  
H O NaH2PO4 (pri. phosphate) H O
Preparation: 2 2
(i) By heating calcium phosphate with conc. H2SO4 NaOH 

NaHPO4 (sec. phosphate) H O Na3PO4
2
Ca3(PO4)2 + 3H2SO4  2CaSO4 + 2H3PO4 (tert. phosphate)

•   NaPO + H O
NaH2PO4  3 2

Table 11.4 Oxoacids of Phosphorus

Name Formula Oxidation Characteristic Preparation

State of Bonds and their
Phosphorus Number
Hypophosphorous H3PO2 +1 One P–OH, Two P – H, One P =O White P4 + alkali
(Phosphinic)

Orthophosphorous H3PO3 +3 Two P – OH, One P – H, One P = O P 2O 3 + H 2O

(Phosphonic)

Pyrophosphorous H4P2O5 +3 Two P – OH, Two P – H, Two P = O PCl3 + H3PO3

Hypophosphoric H4P2O6 +4 Four P – OH, Two P = O, One P – P Red P4 + alkali

Orthophosphoric H3PO4 +5 Three P – OH, One P = O P4O10 + H2O

SCAN CODE
p-Block Elements (Group 15-18)
18 p-BLOCK ELEMENTS (GROUP 15-18)

Name Formula Oxidation Characteristic Preparation

State of Bonds and their
Phosphorus Number
Pyrophosphoric H4P2O7 +5 Four P – OH heat phosphoric acid
Two P = O
One P – O – P
Metaphosphoric (HPO3)n +5 Three P – OH Phosphorous acid + Br2, heart in
Three P = O a scaled cube
Three P – O – P

Fig 11.4: Oxoacids of Phosphorus

6.Uses of Group 15 Elements 7. Introduction of Group 16

(i) The main use of dinitrogen is in the manufacture of ammonia Elements (Oxygen Family)
and other industrial chemicals containing nitrogen, (e.g.,
Oxygen, sulphur, selenium, tellurium and polonium constitute
calcium cyanamide). It also finds use where an inert
group 16 of the periodic table. This is sometimes known as group
atmosphere is required (e.g., in iron and steel industry, inert
of chalcogens. The name is derived from the greek word for brass
diluent for reactive chemicals). Liquid dinitrogen is used as
and points to the association of sulphur and its congeners with
a refrigerant to preserve biological materials, food items and
copper. Most copper minerals contain either oxygen or sulphur
in cryosurgery.
and frequently the other members of the group.
(ii) Ammonia is used to produce various nitrogenous fertilisers
Occurrence :Oxygen is the most abundant of all the elements on
(ammonium nitrate, urea, ammonium phosphate and
the earth. Oxygen forms about 46.6% by mass of earth’s crust .
ammonium sulphate) and in the manufacture of some
Dry air contains 20.946% oxygen by volume.
inorganic nitrogen compounds, the most important one being
nitric acid. Liquid ammonia is also used as a refrigerant. However, the abundance of sulphur in the earth’s crust is only
0.03-0.1%. Combined sulphur exists primarily as sulphates such
as gypsum CaSO4.2H2O, epsom salt MgSO4 .7H2O, baryta BaSO4

SCAN CODE
p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18) 19

and sulphides such as galena PbS, zinc blende ZnS, copper pyrites
CuFeS2 . Traces of sulphur occur as hydrogen sulphide in
volcanoes.
7.4 Electron Gain Enthalpy
Because of the compact nature of oxygen atom, it has less negative
electron gain enthalpy than sulphur.

7.1 Electronic Configuration

The elements of group 16 have six electrons in the outermost
shell and have ns2 np4 general electronic configuration.
7.2 Atomic and Ionic Radii
Due to increase in the number of shells , atomic and ionic radii
increase from top to bottom in the group. The size of oxygen
atoms is however, exceptionally small.
7.3 Ionisation Enthalpy
Ionisation enthalpy decrease down the group. It is due to increase
in size. However, the element of this group have lower ionisation
enthalpy values compared to those of group 15 in the
corresponding periods. This is due to the fact that group 15 element
have extra stable half-filled p orbitals elelctronic configurations.
7.5 Electronegativity
Next to fluorine, oxygen has the highest electronegativity value
amongst the elements. Within the group, electronegativity
decrease with an increase in atomic number. This implies that the
metallic character increase from oxygen to polonium.
8.Physical Properties of Group 16
Elements
Oxygen and sulphur are non-metal, selenium and tellurium
metalloids, whereas polonium is a metal. Polonium is radioactive
and is short lived (Half-life 13.8 days). All these element exhibit
allotropy. The melting and boiling points increase with an increase
in atomic number down the group. The larger difference between
the melting and boiling points of oxygen and sulphur may be
explained on the basis of their atomicity.

Table 11.5 : Physical Properties of Group 16

Element Oxygen (O) Sulphur (S) Selenium (Se) Teryllium (Te)

Atomic Number 8 16 34 52
Atomic Mass 16 32.06 78.96 127.6
Electronic configuration [He]2s22p4 [Ne]3s23p4 [Ar]3d104s24p4 [Kr]4d105s25p4
Covalent Radius/pm 74 103 119 142
Ionic Radius X /pm
–2
140 184 198 221
Ionization enthalpy (KJ mol–1) I 1314 1000 941 869
Ionization enthalpy (KJ mol–1) II 3388 2251 2045 1790
Electronegativity 3.5 2.44 2.48 2.01
Density/[g cm (293 K)]
–3
1.32 2.06 4.19 6.25
Melting point/K 54 393 490 725
Boiling point/K 90 718 958 1260

SCAN CODE
p-Block Elements (Group 15-18)
20 p-BLOCK ELEMENTS (GROUP 15-18)

9. Chemical Properties of Group 9.1 Reactivity with Hydrogen

16 Elements All the elements of group 16 form hydrides of the type H E (E = S,
Se., Te, Po). Some properties of hydrides are given in Table. Their
2

The elements of group 16 exhibit a number of oxidation states.
The stability of -2 oxidation state decreases down the group.
Polonium hardly shows -2 oxidation states. Since electronegativity
of oxygen is very high, it shows only negative oxidation states as
-2 except in the case of OF2 where its oxidation states is + 2. Other
elements of the group exhibit + 2 + 4 + 6 oxidation states but + 4
and + 6 are more common. Sulphur, selenium and tellurium usually
show + 4 oxidation in their compounds with oxygen and +6
oxidations state with fluorine. The stability of +6 oxidation state
decreases down the group and stability of + 4 oxidation state
increases (inert pair effect). Bonding in + 4 and + 6 oxidation
states are primarily covalent.
Anomalous behaviour of oxygen: The anomalous behaviour of
oxygen, like other member of p-block present in second period is
due to its small size and high electronegativity. One typical example
of effects of small size and high electronegativity is the presence
of strong hydrogen bonding in H2O which is not found in H2S.
The absence of d orbitals in oxygen limits its covalency to four
and in practice, rarely exceeds two. On the other hand, in case of
other elements of the group, the valence shell can be expanded
and covalence exceeds four.
Table 11.6 : Properties of Hydrides of Group 16 Elements
acidic character increases from H2O to H2Te. The increase in
acidic character can be explained in terms of decrease in bond (H-
E) dissociation enthalpy down the group. Owing to the decrease
in bond (H-E) dissociation enthalpy down the group, the thermal
stability of hydrides also decreases from H2O to H2Po. All the
hydrides except water possess reducing property and this
character increases from H2S to H2Te.
9.2 Reactivity with Oxygen
All these elements form oxides of the EO2 and EO3 types where E
= S, Se, Te or Po. Ozone (O3) and sulphur dioxide (SO2) are gases
while selenium dioxide (SeO2) is solid. Reducing property of dioxide
decreases from SO2 to TeO2 ; SO2 is reducing while TeO2 is an
oxidising agent. Besides EO2 type sulphur, selenium and tellurium
also form EO3 type oxide (SO3, SeO3, TeO3). Both types of oxides
are acidic in nature.

Property H 2O H2S H 2 Se H2Te

m.p./K 273 188 208 222
b.p./K 373 213 232 269
H-E distance/pm 96 134 146 169
HEH angle (°) 104 92 91 90
fH/kJ mol–1 –286 –20 73 100
diss H(H–E)/kJ mol –1
463 347 276 238
Dissociation constanta 1.8×10–16 1.3×10–7 1.3×10–4 2.3×10–3

9.3 Reactivity Toward Halogens
Elements of group 16 form a larger number of halides of the type
EX6, EX4 and EX2 where E is an element of the group and X is an
halogen. The stabilities of the halides decrease in the order F > Cl
> Br > l. Amongst hexahalides, hexafluorides are the only stable
halides. All hexafluorides are gaseous in nature. They have
octahedral structure. Shulphur hexafluoride SF\6 is exceptionally
stable for steric reasons.
Amongst terrafluorides, SF4 is a gas , SeF4 liquid and TeF4 a solid
These fluorides have sp3d hybridisation and thus, have trigonal
bipyramidal structure in which one of the equatorial position is
occupied by a lone pair of electrons. This geometry is also regarded
as see - saw geometry.
All elements except selenium form dichlorides and dibromides.
These dihalides are formed by sp3 hybridisation and thus have
tetrahedral structure. The well known monohalides are dimeric in
nature, Examples are S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2. These
dimeric halides undergo disproportionation as given below:
2Se2Cl2  SeCl4 + 3Se.

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p-BLOCK ELEMENTS (GROUP 15-18) 21

16 17 18
8O , 8O and 8O . Oxygen does not burn but is a strong
10. General Properties and supporter of combustion.
Compounds of Oxygen Uses:
Oxygen mixed with helium or CO2 is used for artificial respiration,
10.1 Dioxygen (O2) Liquid oxygen is used as oxidising agent in rocket fuels and Oxy-
It differs from the remaining elements of the VIth group because of gen is used for production of oxy-hydrogen or oxy-acetylene
the following properties. flames employed for cutting and welding.
(i) small size
(ii) high electronegativity and
10.2 Oxides
(iii) non-availability of d-orbitals. 10.2.1 Acidic Oxides
Preparation: They dissolve in water forming oxyacids , e.g., CO2, SO2 , SO3,
(a) Dioxygen N2O5 , N2O3 , P4O6 , P4O10, Cl2O7, CrO3 , Mn2O7 , V2O5.
(i) By thermal decomposition of oxides of metals. Cl2O7 + H2O  2 HClO4
450 C  2 Hg + O
2 HgO  Mn2O7 + H2O  2 HMnO4
2

350 C  4 Ag + O
2 Ag2O 
10.2.2 Basic Oxides
2

  Mn O + O They either dissolve in water to form alkalies or combine with

3 MnO2  3 4 2 acids to form salts and water or combine with acidic oxides to
2 Pb3O4   6 PbO + O form salts; e.g., Na2O, CaO. CuO, FeO, BaO etc.
2

(ii) By thermal decomposition of oxygen rich compounds. Na2O + H2O  2 NaOH
  2NaNO + O
2 NaNO3  CaO + H2O  Ca(OH)2
2 2

  2 KCl + 3O (laboratory method)

2 KClO3  CuO + H2SO4  CuSO4 + H2O
2

  4 K CrO + 2 Cr O + 3O
4 K2Cr2O7  10.2.3 Neutral Oxides
2 4 2 3 2
They neither combine with acids nor with the bases to form salts
2 KMnO4    K MnO + MnO + O
2 4 2 2 e.g., CO, N2O, NO etc.
(iii) By the action of conc. H2SO4 on MnO2. 10.2.4 Amphoteric Oxides
2 MnO2 + 2H2SO4  2 MnSO4 + 2H2O + O2 These can combine with acids as well as bases e.g., ZnO, Al2O3,
(iv) By the action of water on Na2O2. BeO, Sb2O3, Cr2O3, PbO etc.

2 Na2O2 + 2 H2O  4 NaOH + O2 PbO + 2 NaOH  Na2 PbO2 + H2O
(v) By the action of conc. H2SO4 on KMnO4 or K2Cr2O7. PbO + H2SO4  PbSO4 + H2O
4 KMnO4 + 6 H2SO4  2 K2SO4 + 4MnSO4 + 6H2O + 5O2 Cr2O3 + 2 NaOH  Na2Cr2O4 + H2O
2 K2Cr2O7 + 8H2SO4  2 K2SO4 + 2Cr2(SO4)3 + 8H2O + Cr2O3 + 3 H2SO4  Cr2(SO4)3 + 3 H2O
3O2
(vi) By Brins process:
10.2.4 Mixed Oxides
They behave as mixture of two simple oxides, e.g., Pb3O4
500 C  2BaO
2 BaO + O2(air)  2 (2PbO + PbO2), Fe3O4 (FeO + Fe2O3), Mn3O4 (2 MnO + MnO2)
800 C  2 BaO + O
2 BaO2  10.2.5 Peroxides
2

(vii) From air: Oxygen is obtained by liquification of air and then They react with dilute acids and form H2O2, e.g., Na2O2, K2O2,
its fractional distillation. BaO2 etc.
Properties: Colourless , odourless and tasteless gas. It is para- Na2O2 + H2SO4  Na2SO4 + H2O2
magnetic and exhibits allotropy. Three isotopes of oxygen are

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22 p-BLOCK ELEMENTS (GROUP 15-18)

They react with water forming O2 . (b) It oxidises moist S, P, As into their oxy acids.
Na2O2 + H2O  2NaOH + 1/2O2 O3  O2 + [O] × 3
10.2.6 Dioxides
S + 3 [O]  SO3
Like peroxide, they contain excess of oxygen but do not yield
H2O2 with dil. acids e.g. PbO2, MnO2 etc. SO3  H 2 O  H 2SO 4
They evolve Cl2 with conc. HCl and O2 with conc. H2SO4. S  3O3  H 2 O  H 2SO 4  3O 2
MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O; (c) It oxidises H2S to S
2MnO2 + 2H2SO4  2MnSO4 + O2 + 2H2O H2S + O3  H2O + S  (yellow)
10.2.7 Super Oxides (iii) Reaction with Silver:
They contain O2– ion, e.g., KO2 , RbO2 and CsO2. These oxides Silver articles become black in contact with ozone.
react with water forming H2O2 and O2
Ag + O3  Ag2O  (black) + O2
10.2.8 Sub Oxides (iv) Reaction with H2O2 :
They contain less oxygen than expected from the normal valency
O3  H 2 O 2  2O 2  H 2 O
of the elements e.g., C3O2, N2O, Pb2O, Hg2O etc. Oxidising Reducing
agent agent
C3O2  O  C
sp
CCO
sp sp
It is supported by the fact that SRP of ozone is higher (+2.07)
10.3 Ozone (O3) than SRP of hydrogen peroxide (+1.77). Therefore , ozone is
stronger oxidising agent than hydrogen peroxide.
Preparation:It is prepared by passing silent electric discharge
(v) Bleaching Action:
through pure and dry oxygen
O3 also bleaches coloured substances through oxidation
3O2 2O3 H = + 142 kJ/mole
(vi) Ozonolysis:
Mixture obtained contains 5-10% ozone by volume and this mix-
Alkenes, alkynes react with ozone forming ozonides.
ture is called ozonised oxygen. The apparatus used for this is
called as ozoniser.
Zn  H O
Properties : CH2 = CH2 + O3   2  2HCHO
(i) Pale blue gas which forms a blue liquid on cooling and on  ZnO
solidification forms violet black crystals. It has a strong fish- Tests for Ozone
like smell and is slightly soluble in water but more in turpen- (i) A filter paper soaked in a alcoholic benzidine
tine oil, glacial acetic acid or CCl4. O3 molecule is diamag-
netic but O3– is paramagnetic.
(ii) Oxidising agent :

O3 + 2H+ + 2e-  O2 + H2O ; SRP = + 2.07 v becomes brown when brought in contact with O3 (this is not
(In acidic medium) shown by H2O2)
O3 + H2O + 2e-  O2 + 2OH– ; SRP = + 1.24 v (ii) Tailing of mercury
(In alkaline medium) Pure mercury is a mobile liquid but when brought in contact
Therefore, ozone is a strong oxidising agent in acidic me- with O3 its mobility decreases and it starts sticking to glass
dium. surface forming a type of tail due to the dissolution of Hg2O
(mercury sub-oxide) in Hg.
(a) It oxidises – to I2 (from neutral solution of K)
2 Hg + O3  Hg2O + O2
O3  O2   O
Uses:
2Kl  H 2 O   O   2KOH  l 2 (i) As a germicide and disinfectant for sterilising water and im-
2Kl  H 2 O   2KOH  O 2  l2 proving the atmosphere of crowded places.
• Alkaline K is oxidised to potassium iodate & periodate. (ii) For detecting the position of double bond in the unsatur-
ated organic compounds.
K + 3O3  KO3 + 3O2 (iii) In mfg. of artificial silk, synthetic camphor, KMnO4 etc.
K + 4O3  KO4 + 4O2

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p-BLOCK ELEMENTS (GROUP 15-18)
11. General Properties and 11.1 Compounds of Sulphur
Compounds of Sulphur 11.1.1 Sodium Thiosulphate (Na2S2O3 .5H2O)
Sulphur Allotropic Froms: Sulphur forms numerous allotropes
of which the yellow rhombic ( - sulphur) and monoclinic ( -
sulphur) forms are the most important. The stable forms at room
temperature is rhombic sulphur, which transfroms to monoclinic
sulphur when heated above 369 K.
Rhombic Sulphur (- sulphur): This allotrope is yellow in colour
, m.p. 385.8 K and specific gravity 2.06. Rhombic sulphur crystals
are formed on evaporating the solution of roll sulphur in CS2. It is
insoluble in water but dissolved to some extent in benzene, alcohol
and ether. It is readily soluble in CS2 .
Monoclinic Sulphur ( - sulphur): Its m.p. is 393 K and specific
gravity 1.98. It is soluble in CS2. This form of sulphur is prepared
by melting rhombic sulphur in a dish and cooling till crust is
formed. Two holes are made in the crust and the remaining liquid
poured out. On removing the crust, colourless needle shaped
crystals of  - sulphur are formed. It is stable above 369 K and
transforms into  - sulphur below it . Conversely, - sulphur is
stable below 369 K and transfroms into  - sulphur above this. At
369 K both the forms are stable. This temperature is called transition
temperature.
Both rhombic and monoclinic sulphur have S8 molecules these S8
molecules are packed to give different crystal structures. The S8
ring in both the forms is puckered and has a crown shape. The
molecular dimensions are given in figure.
Fig 11.5: (a) S8 ring in rhombic sulphur and (b) S6 form
Several other modifications of sulphur containing 6-20 sulphur
atoms per ring have been synthesised in the last two decades. In
cyclo- S6, the ring adopts the chair form and the moleculatr
dimension are as shown in fig. (b) At elevated temperatures
(~ 1000 K ), S2 is the dominant species and is paramagnetic like O2.
23
Preparation:
boiled
(i) Na2SO3 + S in absence of air Na2S2O3
(ii) Na2CO3 + 2SO2 (excess) + H2O  2NaHSO3 + CO2
2NaHSO3 + Na2CO3  2Na2S2O3 + H2O + CO2
(iii) Na2S + Na2SO3 + I2  Na2S2O3 + 2 NaI
Properties:
(i) It is a colourless crystalline substance soluble in water which
loses water of crystallisation on strong heating
(ii) As antichlor: It removes the chlorine from the surface of
fibres (while dyeing) according to following reaction.
Na2S2O3 + Cl2 + H2O  Na2SO4 + 2HCl + S
Therefore, it is known as antichlor
(iii) Reaction with HCl :
Na2S2O3 + HCl  2NaCl + SO2 + S + H2O
This test is used for distinction between S2O32- and SO32-
ions as SO32- ions give only SO2 with HCl.
(iv) Complex formation reactions :
(a) Reaction with silver salts (AgNO3 , AgCl, AgBr or AgI):
Na2S2O3 + 2AgNO3  Ag2S2O3  (white) + 2 NaNO3
Ag2S2O3 + H2O  Ag2S  (Black) + H2SO4
If hypo is in excess, then soluble complex is formed.
2Na2S2O3 + AgNO3  Na3[Ag(S2O3)2] + NaNO3
This reaction is utilized in photography where hypo is used
as fixer.
(b) Reaction with FeCl3: It develops a pink or violet colour which
soon vanishes according to following reaction.
Fe3+ + 2S2O32–  [Fe(S2O3)2]– (Pink or violet)
[Fe(S2O3)2]– + Fe3+  2Fe2+ + S4O62–
(c) Reaction with AuCl3 (Soluble in water):
AuCl3 + Na2S2O3  AuCl  + Na2S4O6 + 2HCl
AuCl + Na2S2O3  Na3 [Au(S2O3)2] + NaCl
(d) Reaction with CuCl2 :
2 CuCl2 + 2Na2S2O3  2CuCl  + Na2S4O6 + 2 NaCl
CuCl + Na2S2O3  Cu2S2O3  + 2 NaCl
3 Cu2S2O3 + 2 Na2S2O3  Na4 [Cu6(S2O3)5]
Uses:
(i) As an ‘antichlor’ to remove excess of chlorine from
bleached fabrics.
(ii) In photography as fixer.
(iii) As a reagent in iodometric and iodiometric titrations.
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24 p-BLOCK ELEMENTS (GROUP 15-18)

11.1.2 Hydrogen Sulphide (H2S) Similarly bisulphites also give SO2 with dil. HCl
Preparation: NaHSO3 + HCl  NaCl + SO2 + H2O
(i) FeS + H2SO4  FeSO4 + H2S (v) By heating sulphides in excess of air
It is prepared in kipp’s apparatus 2 ZnS + 3O2  2ZnO + 2SO2
(ii) Preparation of pure H2S gas 
(vi) CaSO4 (gypsum) + C 
1000C 2 CaO + SO2 + CO2
Sb2S3 (pure) + 6 HCl (pure)  2 SbCl3 + 3 H2S
Properties: By this method SO2 is obtained in large scale
(i) Colourless gas with rotten egg smell Properties:
(ii) Moderately soluble in water but solubility decreases with (i) Colourless gas with burning sulphur smell.
increasing temperature. (ii) It is heavier than air and is highly soluble in water
(iii) Reducing Agent: (iii) Neither burns nor helps in burning but burning magnesium
Acts as a strong reducing agent as it decomposes evolv- and potassium continue to burn in its atmosphere.
ing hydrogen. 3Mg + SO2  2 MgO + MgS
(a) H2S + X2  2 HX + S 4K + 3SO2  K2SO3 + K2S2O3
(iv) Acidic Nature : Acidic oxide and thus dissolve in water form-
(b) moisture  H O + S
H2S + SO2  2 ing sulphurous acid.
(c) It also reduces KMnO4  Mn2+ SO2 + H2O  H2SO3
H2SO4  SO2 & K2Cr2O7  Cr3+ (v) Addition Reaction:
(iv) Acidic Nature: Its aquesous solution acts as a weak
Sun light SO Cl (sulphuryl chloride)
SO2 + Cl2 
dibasic acid according to following reaction  2 2

H 2S HS + H+ S2- + 2H+ platinised

 SO
SO2 + O2 
Therefore, It forms two series of salts as given below Asbests 3

NaOH + H2S  NaHS + H2O PbO2 + SO2  PbSO4

NaOH + NaHS  Na2S + 2H2O (vi) Reducing Nature :
(v) Formation of Polysulphides: They are obtained by H2O + SO2  H2SO3
passing H2S gas through metal hydroxides.
H2SO3 + H2O  H2SO4 + 2H
Ca(OH)2 + H2S  CaS + 2H2O
Reducing character is due to the liberation of nascent hy-
CaS + 4 H2S  CaS5 + 4H2 drogen
Tests for H2S: (a) Reduces halogens to corresponding halides
(i) Turns acidified lead acetate paper black SO2 + 2H2O  H2SO4 + 2H
(ii) Gives violet or purple colouration with sodium nitropruside
2H + Cl2  2HCl
solution.
––––––––––––––––––––––––––––––––
Uses:
(i) As a loboratory reagent for the detection of basic radicals in SO2 + 2H2O + Cl2  H2SO4 + 2HCl
qualitative analysis. (b) Reduces acidified iodates to iodine
(ii) As reducing agnet. 2KIO3 + 5SO2 + 4H2O  K2SO4 + 4H2SO4 + I2

11.1.3 Sulphur Dioxide It also reduces acidified KMnO4  Mn2+ (decolourises),
Preparation: Acidified K2Cr2O7  Cr3+ (green coloured solution) &
Ferric Sulphate  Ferrous sulphate
(i) Burn
S + O2 or air   SO2 (vii) Oxidising nature: Acts as oxidising agent with strong
  3SO + 2H O reducing agent
(ii) S + 2H2SO4 (conc.)  2 2
moisture  2H O + 3S
(a) 2H2S + SO2 
(iii) By heating Cu or Ag with conc. H2SO4 2

Cu + H2SO4  CuSO4 + 2H2O + SO2 (b) 2SnCl2 + SO2 + 4HCl  2SnCl4 + 2H2O + S
(iv) By reaction of metal sulphites with dil.HCl (c) 2Hg2Cl2 + SO2 + 4HCl  2HgCl2 + 2H2O + S
Na2SO3 + 2HCl  2NaCl + SO2 + H2O

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p-BLOCK ELEMENTS (GROUP 15-18) 25

(d) 2CO + SO2  2CO2 + S (iii) Contact process (Industrial method) :
(e) 2 Fe + SO2  2FeO + FeS catalyst
 2SO3
O2 + 2SO2 
(viii) Bleaching Action:
SO2 + 2H2O  H2SO4 + 2H The commonly used catalysts are platinum, ferric oxide or
vanadium pentoxide. V2O5 is preferred as it is cheaper and is
This is due to the reducing nature of SO2 not poisoned by impurities

Coloured matter + H   colourless matter.. H2SO4 (58%) + SO3  H2S2O7 (oleum)
Air oxidation
Sulphuric acid of any desired concentration can be obtained
Therefore, bleaching is temporary
from oleum by dilution with water.
Uses:
H2S2O7 + H2O  2H2SO4
(i) Used in manufacture of H2SO4 & paper from wood pulp.
Oxidation of sulphur dioxide is reversible and exothermic.
(ii) As a bleaching agent for delicate articles like wool, silk and According to Le-chatelier principle, the favourable condi-
straw. tions for the greater yield of sulphur trioxide are.
(iii) Used in refining of petroleum and sugar. (a) An excess of air- SO2 and oxygen are taken in 2:3 molecular
11.1.4 Sulphur Trioxide (SO3) proportion
Preparation: (b) Low tempt-optimum tempt. 450°C
(i) 6H2SO4 + P4O10  6SO3 + 4H3PO4 (c) Higher pressure-one atmosphere
P4O10 is dehydrating agent Properties :
(i) A colourless syrupy liquid (it is H-bonded)
  Fe O + 3SO
(ii) Fe2(SO4)3  2 3 3 (ii) It fumes strongly in moist air and is highly corrosive in
pt nature.
 2SO
(iii) 2SO2 + O2  3 440C  H O + SO

(iii) Thermal decomposition : H2SO4 
Properties:  2 3

(i) Acidic Nature: Dissolves in water forming sulphuric acid (iv) Acidic Nature: It is a strong dibasic acid and ionises as
SO3 + H2O  H2SO4 H2SO4 H+ + HSO4– 2H+ + SO42–
(ii) H2SO4 + SO3  H2S2O7 (oleum) (a) Forms two series of salts
(iii) SO3 + HCl  SO2(OH) Cl (chlorosulphuric acid) NaOH + H2SO4  NaHSO4 (sodium bisulphate) + H2O
(iv) Oxidising Nature : NaHSO4 + NaOH  Na2SO4 (sodium sulphate) + H2O
(b) Decomposes carbonates and bicarbonates into carbon
100C
(a) 2SO3 + S  3SO2 dioxide
(b) 5SO3 + 2P  5SO2 + P2O5 Na2CO3 + H2SO4  Na2SO4 + H2O + CO2
(c) SO3 + PCl5  POCl3 + SO2 + Cl2 NaHCO3 + H2SO4  NaHSO4 + H2O + CO2
(d) SO3 + 2HBr  H2O + Br2 + SO2 (c) Displaces more volatile acids from their metal salts.
Uses: 2NaCl + H2SO4  Na2SO4 + HCl
(i) Used in manufacture of H2SO4 and oleum. 2NaNO3 + H2SO4  Na2SO4 + 2HNO3
(ii) Used as a drying agent for gases. CaF2 + H2SO4  CaSO4 + 2HF
11.1.5 Sulphuric Acid (H2SO4) (v) Oxidising Nature: H2SO4 acts as a strong oxidising agent
Preparation: H2SO4  H2O + SO2 + [O]
(a) Non-metals (carbon, sulphur etc) are oxidised to their oxides.
(i) dist. Fe O + H SO + SO + 13H O
2FeSO4 . 7H2O  2 3 2 4 2 2
H2SO4  H2O + SO2 + O] × 2
(ii) Lead Chamber Process (Industrial method) :
C + 2[O]  CO2
2SO2 + O2 (air) + 2H2O + [NO] (catalyst)  2H2SO4 +
––––––––––––––––––––––––––––––––––––
[NO] (catalyst)
C + 2H2SO4  CO2 + 2SO2 + 2H2O
Acid obtained is 80% pure and is known as brown oil of
––––––––––––––––––––––––––––––––––––
vitriol
2P + 5H2SO4  2H3PO4 + 5SO2 + 2H2O

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p-Block Elements (Group 15-18)
26 p-BLOCK ELEMENTS (GROUP 15-18)
(b) Metals (copper, silver, mercury etc.) are oxidised to their (e) H2SO4 + P2O5  2HPO3 + SO3
oxides which then combine with acid to form corresponding Uses :
sulphates. (i) For the manufacture of fertilizer such as ammonium sulphate
H2SO4  H2O + SO2 + [O] and super phosphate of lime.
Cu + [O]  CuO (ii) As an important laboratory reagent.
CuO + H2SO4  CuSO4 + H2O (iii) In storage batteries.
––––––––––––––––––––––––––––––––– (iv) In leather, textile, paper and dyeing industries.
Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
(c) Iodine is liberated from KI
12. Uses of Group 16 Elements
2 KI + H2SO4  K2SO4 + 2HI Sulphur dioxide is used (i) in refining petroleum ans sugar (ii) in
bleaching wool and silk and (iii) as an anti-chlor, disinfectant and
H2SO4  H2O + SO2 + [O]
preservative. Sulphuric acid, sodium hydrogen sulphite and
2 HI + [O]  I2 + H2O calcium hydrogen sulphite (industrial chemicals) are manufactured
––––––––––––––––––––––––––––––––––––– from sulphur dioxide. Liquid SO2 is used as a solvent to dissolve
2 KI + 2H2SO4  K2SO4 + SO2 + I2 + 2H2O a number of organic and inorganic chemicals.
Here HI is oxidised to I2. Similarly bromine is liberated from
KBr 13. Introduction of Group 17
(vi) Dehydrating agent: Sulphuric acid acts as a powerful Elements: The Halogen Family
dehydrating agent because it has a great affinity for water
Fluorine, chlorine, bromine, iodine and astatine are members of
H SO Group 17. These are collectively known as the halogens (Greek
2 4
(a) C12H22O11 (cane sugar) 
–11H O 12C
2 halo means salt and genes born i.e., salt producers). The halogens
are highly reactive non-metallic elements.
COOH H SO
(b) | 2 4
 CO + CO2 + H2O
COOH 
(vii) Miscellaneous reactions: 13.1 Electronic Configuration
(a) Sulphonation of aromatic compounds All these elements have seven electrons in their outermost shell
(ns2 np5) which is one electron short of the next noble gas.

13.2 Atomic and Ionic Radii

The halogens have the smallest atomic radii in their respective
Benzene Benzene sulphonic acid periods due to maximum effective nuclear charge . Atomic and
ionic radii increase from fluorine to iodine due to increasing number
(b) Reaction with PCl5:
of quantum shells.

+ POCl3 + HCl 13.3 Ionisation Enthalpy

They have little tendency to lose electron. Thus they have very
Chlorosulphonic acid high ionisation enthalpy. Due to increase in atomic size, ionisation
enthalpy dereases down the group.

+ 2 POCl3 + 2HCl 13.4 Electron Gain Enthalpy

Halogen have maximum negative electrons gain enthalpy in the
Sulphury chloride corresponding period. This is due to the fact that the atoms of
(c) K4[Fe(CN)6] + 6H2SO4 + 6H2O  2K2SO4 + FeSO4 + these elements have only one electron less than stable noble gas
3(NH4)2SO4 + 6CO configurations. Electron gain enthalpy of the elements of the group

(d) 3KClO3 + 3H2SO4  3 KHSO4 + HClO4 + 2ClO2 + H2O becomes less negative down the group. However, the negative

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p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18) 27
electron gain enthalpy of fluorine is less than that of chlorine. It is
13.5 Electronegativity
due to small size of fluorine atom. As a result, there are strong
interelectronic repulsions in the relatively small 2p orbitals of They have very high electronegativity. The electronegativity
fluorine and thus, the incoming electron does not experience much decreases down the group. Fluorine is the most electronegative
attraction. element in the periodic table.

Table 11.7 : Physical Properties of Halogens

Element F Cl Br I
Atomic Number 9 17 35 53
Atomic Mass 19 35.45 79.90 126.90
Electronic configuration [He]2s22p5 [Ne]3s23p5 [Ar]3d104s24p5 [Kr]4d105s25p5
Covalent Radius/pm 64 99 114 133
Ionic Radius X /pm
–
133 184 196 220
Ionization enthalpy /(kJ mol ) –1
1680 1256 1142 1008
Electronegain enthalpy/(kJ/mol–1) –333 –349 –325 –296
Distance X-X/pm 143 199 229 266
Enthalpy of dissociation 158.8 242.6 192.8 151.1
(X2)/kJ mol –1

Electronegativity 4 3.2 3.0 2.7

Melting point/K 54.4 172 265.8 386.6
Boiling point/K 84.9 239.0 335.5 458.2

14. Physical Properties of Group 15. Chemical Properties of Group

17 Elements 17 Elements
Fluorine and chlorine are gases, bromine is a liquid and iodine is
a solid. Their melting and boiling points steadily increase with
atomic number. All halogen are coloured. This is due to absorp-
tion of radiations in visible region which results in the excitation
of outer electrons to higher energy level. By absorbing different
quanta of radiation, they display different colours. For example,
F2, has yellow, Cl2, greenish yellow, Br2, red and I2, violet colour.
Fluorine and chlorine react with water. Bromine and iodine are
only sparingly soluble in water. But are soluble in organic sol-
vents such as chloroform, carbon tetrachloride, carbon disulphide
and hydrocarbons to give coloured solutions.Except the smaller
enthalpy of dissociation of F2 compared to that of Cl2 whereas X-
X bond dissocitation enthalpies from chlorine onwards show the
expected trend: Cl – Cl > Br – Br > I – I . A reason for this anomaly
is the relatively larger electrons- electron repulsion among the
lone pairs in F2 molecule where they are much closer to each other
than in case of Cl2.
Oxidation states and trends in chemical reactivity: All the halo-
gens exhibit –1 oxidation state. However, chlorine, bromine and
iodine exhibit + 1, + 3, + 5 and + 7 oxidation states also. The higher
oxidation states of chlorine, bromine and iodine are realised mainly
when the halogens are in combination with the small and highly
electronegative fluorine and oxygen atoms e.g., in interhalogens,
oxides and oxoacids.
The fluorine atom has no d orbitals in its valence shell and there-
fore cannot expand its octet. Being the most electronegative, it
exhibits only – 1 oxidation state.
All the halogens are highly reactive. They react with metals and
non-metals to form halides. The reactivity of the halogens de-
creases down the group.
The ready acceptance of an electron is the reason for the strong
oxidising nature of halogens. F2 is the strongest oxidising halo-
gen and it oxidises other halide ions in solution or even in the
solid phase. The decreasing oxidising ability of the halogen in
aqueous solution down the group is evident from their standard
electrode potentials. Fluorine oxidises water to oxygen whereas

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p-Block Elements (Group 15-18)
28
chlorine and bromine react with water to form corresponding
hydrohalic and hypohalous acids. The reactions of iodine with
water is non- spontaneous . I– can be oxidised by oxygen in acidic
medium; just the reverse of the reaction observed with fluorine.
2F2(g) + 2H2O()  4H+ (aq) + 4F– (aq) + O2(g)
X2(g) + H2O ()  HX(aq) + HOX (aq)
(where X = Cl or Br)
4I– (aq) + 4H+ (aq) + O2(g)  2 I2 (s) + 2H2O ()
Standard Reduction Potential (SRP)
X2 + 2e–  2X–
F2 + 2e–  2F– ° = + 2.87 V ;
Cl2 + 2e–  2Cl– ° = + 1.36 V
Br2 + 2e –  2Br – ° = + 1.09 V;;
2 + 2e–  2– ° = + 0.54 V
 More the value of the SRP, more powerful is the (algebraically)
oxidising agent. Hence the order of oxidising power is
F2 > Cl2 > Br2 > 2
Since SRP is the highest for F2 (among all elements of P.T.),
it is a strogenst oxidising agent.
 F2 is more powerful oxidising agent than O3 [Inspite of 3 ‘O’s
in O3 ]
NOTE:
Electrode potential values would be the monitoring parameter
in solution phase because they are experimental (based on the
correct situation).
Hydration energy of X–
Smaller the ion, higher is the hydration energy
F– Cl – Br – –
515 kJ/mol 381 347 305
Anomalous behaviour of fluorine: The anomalous behviour of
fluorine is due to its small size, highest electronegativity, low F- F
bond dissociation enthalpy, and non availability of d orbitals in
valence shell. Most of the reactions of fluorine are exothermic
(due to the small and strong bond formed by it with other elements).
It forms only one oxoacid while other halogen form a number of
oxoacids. Hydrogen fluoride is liquid (b.p. 293 K) due to strong
hydrogen bonding. Other hydrogen halides are gases.
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p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18)
15.1 Reactivity Towards Hydrogen
They all react with hydrogen to give hydrogen halides but affinity
for hydrogen decreases from fluorine to iodine. They dissolve in
water to form hydrohalic acids. The acidic strength of these acids
varies in the order : HF < HCl < HBr < HI. The stability of these
halides dereases down the group due to decrease in bond (H–X)
dissociation enthalpy in the order :
H – F > H – Cl > H –Br > H – I .
15.2 Reactivity Towards Oxygen
Halogens form many oxides with oxygen but most of them are
unstable. Fluorine forms two oxides OF2 and O2F2. However, only
OF2 is the thermally stable at 298 K. These oxide are essentially
oxygen fluorides because of the higher electronegativity of
flurorine than oxygen . Both are strong fluorinating agents. O2F2
oxidises plutonium to PuF6 and the reactions is used in removing
plutonium as PuF6 from spent nuclear fuel.
Chlorine, bromine and iodine form oxides in which the oxidation
states of these halogen range from + 1 to + 7. A combination of
kinetic and thermodynamic factors lead to the generally decreas-
ing order of stability oxides formed by halogens, I > Cl > Br. The
higher oxides of halogens tend to be more stable than the lower
ones.
Chlorine oxides, Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive
oxidising agents and tend to explode. ClO2 is used as a bleaching
agent for paper pulp and textiles and in water treatment.
The bromine oxides, Br2O, BrO2, BrO3 are the least stable halogen
oxides and exist only at low temperature. They are very powerful
oxidising agents.
The iodine oxides, I2O4, I2O5, I2O7 are insoluble solids and de-
compose on heating. I2O5 is very good oxidising agent and is
used in the estimation of carbon monoxide.
15.3 Reactivity Towards Metals
Halogen react with metals to form metal halides. For e.g., bromine
reacts with magnesium to give magnesium bromide.
15.4 Reactivity of Halogen Towards other
Halogens
Halogens combine amongst themselves to form a number of com-
pounds known as interhalogen of the types AB, AB3, AB5 and
AB7 where A is a larger size halogen and and B is smaller size
halogen.
p-BLOCK ELEMENTS (GROUP 15-18) 29

16. General Properties and F2 + ClO3– + H2O  2F– + ClO4– + 2H+
(iii) Reaction with NaOH Solution : With dilute alkali forms
Compounds of Halogens oxygen difluoride and with concentrated alkali O2.
16.1 Fluorine (F2) 2F2 + 2 NaOH (dil)  OF2 (g) + 2 NaF + H2O
Preparation
2F2 + 4 NaOH (conc.)  O2 (g) + 4 NaF + 2H2O
(i) Electrolytic method: Electrolyte : Molten KHF2 (1 part) +
HF (5 part) (iv) Reaction with NH3 : (Distinction from other halogens)
Anode : Carbon 2NH3 + 3F2  N2 + 6 HF
Cathode : Steel
Other halogens form explosive NX3. with conc. NH3 (liquor
Vessel : Metal ammonia)
On Electrolysis (v) Reaction with H2S :
Cathode : 2H + 2e  H2(g)
+ –
H2S + F2  SF6 + 2 HF
Anode : 2F–  F2 + 2e– (vi) Reaction with SiO2 : It attacks glass at about 1000C.
The F2 gas thus evolved must be free from HF which is more SiO2 (s) + 2F2 (g)  SiF4 (g) + O2 (g)
corrosive than fluorine.
The reaction is slow with dry F2 .
In order to make flourine free from HF, the gas is passed
through NaF which absorbs HF. (vii) Reaction with H2O :

 Anode of carbon should be free from gaaphite because F2 2H2O + 2F2  4 HF + O2
reacts with graphite easily to form a polymeric susbstance sometime a little amount of O3 also forms
known as graphite fluoride.
3H2O + 3F2  6HF + O3
There should be no moisture present in the vessel otherewise
fluorine will react with water. (viii) Reaction with Xe:

3H2O + 3F2  6HF + O3 , 2F2 + 2H2O  4HF + O2

 It is not possible to prepare fluorine by electrolysis of aq.
solution of NaF or KF. It is because when aq. solution of KF
is subjected to electrolysis, there will be following two
oxidation in competition at anode,
(ix) Reaction with H2 :
H2O  1/2O2 + 2H+ + 2e– SOP = – 1.23 v
and H2 + F2  2 HF or H2 F2
F  1/2F + e
–  –
2
SOP = – 2.87v This reactions occurs even in dark
As a matter of rule that substance will be oxidise whose SOP
16.2 Chlorine (Cl2)
is higher therefore water gets oxidise at anode and not F–.
Preparation:
Properties:
(i) Common Method (Cl2 , Br2 , 2) :
(i) Diatomic, Pale green-yellow gas which appears to be almost
colourless. 
2 NaX + 3H2SO4 (conc.) + MnO2 (oxidising agent) 
(ii) Oxidising Character: It is the most powerful oxidising agent.
X2 + MnSO4 + 2NaHSO4 + 2H2O
F2 + 2NaX  2NaF + X2
4H+ + MnO2 + 2X–  X2 + Mn+2 + 2H2O
(X = Cl, Br, )
(a) It can oxidise all other halide ions into halogen molecules
5 7
(b) It can oxidise Cl O 3 into Cl O 4 and IO3– to IO4–

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p-Block Elements (Group 15-18)
30 p-BLOCK ELEMENTS (GROUP 15-18)

(ii) Only for Cl2 : (iv) Reaction with NH3 (common for Cl2 & Br2) :

(a) NaCl + HNO3  NaNO3 + HCl × 3 (a) 8 NH3 + 3 Cl2  N2 + 6 NH4 Cl

HNO3 + 3HCl  NOCl + Cl2 + 2H2O (b) NH3 + 3Cl2  NCl3 + 3 HCl
–––––––––––––––––––––––––––––––––––– (excess)
3NaCl + 4 HNO3  3 NaNO3 + NOCl (nitrosyl chloride) (v) Reaction with Alkali Metal Halides (KX) :
2 KBr + Cl2  2KCl + Br2
2NOCl + O2  2NO2 + Cl2 ;
2K + Cl2  2 KCl + 2
NO2 + H2O  HNO3 (to be recycled)
 Cl2 can oxidise both Br– & – but Br2 can oxidise – only.
(b) When Cl2 is used for the chlorination of hydrocarbon the
byproduct is HCl. The HCl is catalytically oxidised into H2O  F2 is not used in aqueous reaction since it itself reacts with
water.
& Cl2 using copper powder mixed with rare earth chlorides.
(vi) Oxidising & Bleaching Properties: Chlorine water on
Cu powder  rare earth standing loses its yellow colour due to the formation of HCl
4 HCl + O2 
Chloride
 2H O + 2Cl
2 2 and HOCl. Hypochlorous acid (HOCl) so formed, gives
nascent oxygen which is responsible for oxidising and
OCl
(c) Ca / + 2HCl  CaCl2 + Cl2 + H2O
bleaching properties of chlorine.
\
Cl (a) It oxidises ferrous to ferric, sulphite to sulphate, sulphur
(iii) Manufacture of Chlorine : dioxide to sulphuric acid and iodine to iodic acid.
(a) Deacon’s Process: By oxidation of hydrogen chloride gas 2 FeSO4 + H2SO4 + Cl2  Fe2(SO4)3 + 2 HCl
by atmoshperic oxygen in the presence of CuCl2 (catalyst) Na2SO3 + Cl2 + H2O  Na2SO4 + 2 HCl
at 723 K. SO2 + 2 H2O + Cl2  H2SO4 + 2 HCl
CuCl
4 HCl + O2  I2 + 6 H2O + 5 Cl2  2 HIO3 + 10 HCl
2  2 Cl2 + 2 H2O
(b) It is a powerful bleaching agent ; Bleaching action is due to
(b) Electrolytic Process : Chlorine is obtained by the electrolysis
oxidation.
of brine (concentrated NaCl solution). Chlorine is liberated
at anode. It is also obtained as a by–product in many Cl2 + H2O  2 HCl + O
chemical industries. Coloured substance + O  Colourless substance
NaX (aq)  Na+ (aq) + X– (aq) It bleaches vegetable or organic matter in the presence of
moisture. Bleaching effect of chloride is permanent.
Anode : 2X–  X2 + 2e–  But the bleching action of SO2 is temporary because it takes
Properties: place through reduction.
(i) It is a greenish–yellow gas with pungent and suffocating SO2 + 2 H2O  H2 SO4 + 2 H
odour. It is about 2–5 times heavier than air. It can be liquefied
SO32– + Coloured material  SO42– + Reduced coloured
into greenish–yellow liquid which boils at 239 K. It is soluble
in water. material (colourless)
(ii) At low temperature it forms a hydrate with water having O of air
Reduced Coloured material (colourless) 
2 
formula Cl2 . 8H2O which is infact a clathrate compound.
Coloured material
(iii) H2 + Cl2 
(a zero order reaction) 2HCl (g) , (vii) Reaction with NaOH:
Common to Br2 , 2 & Cl2 (but with F2 it is different, OF2 or O2
[H2 + Br2  2HBr is not a zero order reaction] is obtained)

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p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18) 31

(a) 2 NaOH (cold & dilute) + Cl2  NaCl + NaClO + H2O
(b) 6 NaOH (hot & concentrated) + 3 Cl2  5 NaCl +
NaClO3 + 3 H2O
(viii) Reaction with Hypo Solution:
This reaction is common with Cl2 & Br2 but with 2 it is
different.
 0
Na 2S2 O3  H 2 O  Cl2  Na 2SO 4  2HCl   S
 colloidal 
 
 
In this reaction thiosulphate ions undergo
disproportionation into SO42– and S. Cl2 is reduced to Cl– .
(ix) Reaction with dry Slaked Lime, Ca(OH)2: It gives bleaching
powder.
2 Ca(OH)2 + 2 Cl2  Ca(OCl)2 + CaCl2 + 2 H2O
(x) Reaction with Metals & non–Metals : Forms corresponding
chlorides.
2 Al + 3 Cl2  2 AlCl3
2 Na + Cl2  2 NaCl
P4 + 6 Cl2  4 PCl3
S8 + 4 Cl2  4 S2Cl2
 It has great affinity for hydrogen. It reacts with compounds
containing hydrogen to form HCl.
H2 + Cl2  2 HCl
H2S + Cl2  2 HCl + S
Uses : Cl2 is used
(i) for bleaching woodpulp (required for the manufacture of
paper and rayon). bleaching cotton and textiles,
(ii) in the manufacture of dyes, drugs and organic compounds
such as CCl4 , CHCl3 , DDT, refrigerants, etc.
(iii) in the extraction of gold and platinum.
(iv) in sterilising drinking water and
(ii) From Sea-Water: NaCl is main component but NaBr is also
present in some quantity in sea water. Cl2 gas is passed
through sea water when vapours of bromine are evolved.
2 Br– (aq) + Cl2  2Cl– (aq.) + Br2
Properties:
(i) Reddish brown liquid, fairly soluble in water. It also forms
hydrate like Cl2
(Br2 . 8H2O)  Clathrate compound
(ii) Rest reactions are same as with Cl2
16.4 Iodine (I2)
Preparation:
(i) Common Method :

2Na + 3H2SO4 (conc.) + MnO2  2 + MnSO4 +
2NaHSO4 + 2H2O
(ii) From Caliche or Crude Chile Salt Petre : The main source
of iodine is NaO3 (sodium iodate) which is found in nature
with NaNO3 (chile saltpetre). NaO3 is present in small
amount. After crystallisation of NaNO3 , the mother liquor
left contains NaO3 (soluble). To this solution NaHSO3 is
added where upon 2 is precipitated.
(iii) From Sea-Weeds : Sea-weeds are dried and burnt in shallow
pits, ash left is called kelp. Ash on extraction with hot water
dissolves out chlorides, carbonates, sulphates and iodides
of sodium and potassium. The solution on concentration
seperates out all leaving behind iodide in the solution.
Solution is mixed with MnO2 and concentrated H2SO4 in
iron retorts. Liberated iodine is condensed in series of
earthen-ware known as aludels.
2Na+ MnO2 + 3H2SO4 2NaHSO4 + MnSO4 + 2 + 2H2O
(iv) 2K+ Cl2  2KCl + 2
(v) 2K+ H2O2  2KOH + 2

(v) preparation of poisonous gases such as phosgene (COCl2), (vi) CuSO4 + 2K  K2SO4 + Cu2 ;
tear gas (CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl). This 2 gets dissolved into K forming 3 , since 3– ions are
yellow, therefore solution develops yellow colour.
16.3 Bromine (Br2) Properties :
Preparation: (i) It is a dark violet solid, undergoes sublimation, least soluble
(i) Common Method: (among halogens) in water but much more soluble in K(aq.)
 Br + MnSO + due to formation of K3
2 NaBr + 3H2SO4 (conc.) + MnO2  2 4
KF3 cannot be formed similarly since F does not have ‘d’ orbitals. So
2NaHSO4 + 2H2O
sp3d hybridisation is not possible with F.

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p-Block Elements (Group 15-18)
32 p-BLOCK ELEMENTS (GROUP 15-18)

(ii) It is soluble in organic solvents like CHCl3, CCl4 etc. to get agents and reduce H2SO4 to SO2 and get themselves oxidised
violet solutions. to bromine and iodine respectively.
(iii) Reaction with Hypo: iodometric titrations KX + H2SO4  KHSO4 + HX
2.5
S2 O32– (thiosulphate ions) + 2  S4 O 62  H2SO4 + 2HX  SO2 + X2 + 2H2O (X = Br or )
–
(tetrathionate ions) + 2 Hence, HBr and H are prepared by heating bromides and
This reaction is the basis of iodometric (direct 2 titration) iodides respectively with conc. H3PO4 .
titration, which is carried out for the estimation of iodine 3KBr(K) + H3PO4  K3PO4 + 3HBr (H)
using starch indicator.
Properties:
(iv) Reaction with KClO3 or KBrO3:
(i) These are colourless, pungent smelling gases with acidic

2 KClO3 + 2  2 KIO3 + Cl2 tastes.
(ii) It is heavier than air, can be liquified to colourless liquids.

2 KBrO3 + 2  2KIO3 + Br2 (iii) These are neither combustible nor supporter of combustion.
(v) Reaction with Ozone (dry) : (iv) When perfectly dry, they have no action on litmus, but in
22 (s) + 3O3 (g)  4O9 (s) presence of moisture, they turn blue litumus red, showing
acidic nature. Among HX, H is the strongest and HF is the
4O9 is an ionic compound consisting of 3+ & O3–)3 weakest acid.
indicative of metallic character of  (low .E, low E.N.) (v) These are quite soluble in water.
With NaOH there is common reaction as with Cl2 and Br2 . With HCl ionises as below.
H2 there is reversible reaction. HCl(g) + H2O ()  H3O+ (aq) + Cl– (aq) Ka = 107
16.5 Hydra Acids (Halogen Acids) It aqueous solution is called hydrochloric acid. High value
HCl, HBr & HI : of dissociation constant (Ka) indicates that it is a strong acid
Preparation: in water.
(i) By direct combination of elements: When three parts of concentrated HCl and one part of
concentrated HNO3 are mixed, aqua regia is formed which is
H2 + Cl2  2HCl
used for dissolving noble metals, e.g., gold, platinum.
Pt 2HBr
H2 + Br2 
Au + 4 H+ + NO3– + 4 Cl–  AuCl4– + NO + 2 H2O
Pt , 450 C 2H
H2 + 2  3 Pt + 16 H+ + 4 NO3– + 18 Cl–  3 PtCl62– + 4 NO + 8 H2O

(ii) By heating a halide with acid : (v) Reaction with metals oxides, hydroxides and bicarbonates

NaCl + H2SO4  NaHSO4 + HCl Zn + 2HCl  ZnCl2 + H2

NaHSO4 + NaCl  Na2SO4 + HCl MgO + 2HCl  MgCl2 + H2O

For HCl we use H2SO4 as an acid, while for HBr and H we NaOH + HCl  NaCl + H2O
use H3PO4.
CaCO3 + 2HCl  CaCl2 + H2O + CO2
(a) HCl cannot be dried over P2O5 (P4O10) or quick lime since
(vi) Reaction with salts, HCl decomposes salts of weaker acids.
they react with gas chemically.
NaHCO3 + HCl  NaCl + CO2 + H2O
CaO + 2HCl  CaCl2 + H2O
Na2S + 2HCl  2NaCl + H2S
P4O10 + 3HCl  POCl3 + 3HPO3

HCl is, hence dried by passing through conc. H2SO4 . Na2SO3 + 2HCl  2NaCl + SO2 + H2O

(b) HBr (or H) cannot be prepared by heating bromide (iodide) Na2S2O3 + HCl  2NaCl + SO2 + H2O + S
with conc. H2SO4 because HBr and H are strong reducing

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p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18)
2NaNO2 + 2HCl  2NaCl + NO + NO2 + H2O
(vii) Reducing Property and Stability of Hydracids:
HCl: It is quite stable and hence is oxidised by strong
oxidising agents like MnO2, KMnO4, K2Cr2O7, PbO2, Pb3O4.
(i) MnO2 + 4HCl  MnCl2 + 2H2O + Cl2
(ii) 2KMnO4 + 16HCl  2KCl + 2MnCl2 + 8H2O + 5Cl2
(iii) K2Cr2O7 + 14HCl  2KCl + 2CrCl3 + 7H2O + 3Cl2
(iv) PbO2 + 4HCl  PbCl2 + 2H2O + Cl2 ; (v) Pb3 O4
+ 8HCl  3PbCl2 + 4H2O + Cl2
Therefore, HCl is a weak reducing agent.
HBr : It is not very stable and hence more easily oxidised or
acts as a strong reducing agents. In addition to above
reducing properties of HCl, it also reduces H2SO4 to SO2
which is not done by HCl.
H2SO4 + HBr  SO2 + Br2 + 2H2O
Aqueous HBr on exposure to atmospheric oxygen is oxidised
to bromine (yellow)
4HBr + O2  2 Br2 + 2H2O
H : It is least stable hydrogen halide. It is readily oxidised
and thus acts as a powerful reducing agent.
In addition to reaction shown by HCl, it shows following
reactions also.
(a) H2SO4 + 2H  SO2 + 2 + H2O ;
H2SO4 + 6H  S + 32 + 4H2O;
H SO + 8H  H S + 4 + 4H O ;
2 4 2 2 2
(b) 2HNO3 + 2H  2NO2 + 2 + 2H2O
(c) 2HNO2 + 2H  2NO + 2 + 2H2O
(d) HO3 + 5H  32 + 2H2O
(e) K2S2O8 + 2H  K2SO4 + 2 + H2SO4
(f) 2FeCl3 + 2H  2FeCl2 + 2 + 2HCl
(g) Aqueous solution of acid, if exposed to O2 is oxidised to
iodine.
4H + O2  22 + 2H2O
(viii) Reaction with Ammonia:
NH3 + HX  NH4X (white fumes) (where X = Cl, Br, )
33
(ix) Action of Halogens:
(a) Cl2 is liberated from HCl by F2 alone.
F2 + HCl  2HF + Cl2
(b) Br2 is liberated from HBr by F2 and Cl2 (not by 2)
2HBr + F2 / Cl2  2HF (2HCl) + Br2
(c) 2 is liberated from H by F2, Cl2 and Br2
2H + F2 (Cl2, Br2)  2HF (HCl, HBr) + 2
(x) Detection of Cation:
HCl : AgNO3 + HCl  AgCl (white) + HNO3
(CH3COO)2 Pb + 2HCl  PbCl2(white) + 2CH3COOH
HBr : AgNO3 + HBr  AgBr (pale yellow) + HNO3
(CH3COO)2 Pb + 2HBr  PbBr2  (white) + 2CH3COOH
H: AgNO3 + H  Ag (bright yellow) + HNO3
(CH3COO)2 Pb + 2H  Pb2 (yellow) + 2CH3COOH
(xi) Formation of Aqua-regia : 3 parts of conc. HCl and 1 part of
conc. HNO3 is known as aqua-regia. This is used for
dissolving noble metals like Au (Gold) and Pt (Platinum).
3HCl + HNO3  NOCl + 2H2O + 2Cl (reactive) ;
Au + 3Cl  AuCl3
Uses:
(i) HCl is used in preparation of Cl2, chlorides, aqua regia,
glucose, (from corn starch), medicines, laboratory reagents,
cleaning metal surfaces before soldering or electroplating. It
is also used for extracting glue from bones and purifying
bone black.
(ii) HBr is used as laboratory reagent for preparing bromo
derivatives like sodium bromides and potassium bromide.
These are used in medicines as sedatives.
(iii) H is used as reducing agent in organic chemistry.
16.6 Hydrofluoric Acid [H2 F2, HF]
Preparation : H2 and F2 combine with each other very violently
(even in dark) to form HF. So simple reaction cannot be used for
its preparation, special methods are employed for its preparation.
(i) Laboratory Method: Anhydrous HF is obtained by heating
dry potassium hydrogen fluoride in a copper retort con-
nected with copper condenser.

KHF2  KF + HF
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p-Block Elements (Group 15-18)
34
(ii) Industrial Method : HF is prepared by heating fluorspar
(CaF2) with conc H2SO4.
CaF2 + H2SO4  CaSO4 + 2HF
 Aqueous HF being corrosive to glass, is stored in wax lined
bottles or vessel made of copper or monel.
In glass or silica bottles, it attacks them as follows:
Na2SiO3 + 6HF  Na2 SiF6 + 3H2O;
CaSiO3 + 6HF  CaSiF6 + 3H2O
SiO2 + 4HF  SiF4 + 2H2O
SiF4 + 2HF  H2 SiF6
This action of HF on silica (silicates) is used for etching
glass. The glass surface to be etched is coated with wax, the
design, is scratched on glass through wax coating this is
then treated with 40% solution.
Properties:
(i) It is colourless, corrosive liquid with pungent smell with
high boiling point due to hydrogen bonding.
(ii) Dry HF does not attack metals under ordinary conditions
(except K), but in presence of water, it dissolves metals with
liberation of hydrogen gas.
16.7 Oxy-Acids of Chlorine
16.7.1 Hypo-Chlorous Acid [HClO]
Preparation:
(i) The acid is known only in solution, It is obtained by shaking
precipitate of HgO with chlorine water.
2HgO + 2Cl2 + H2O  Hg2OCl2 + 2HClO
(ii) Commercially, it is obtained by passing CO 2 through
suspension of bleaching powder and then distilling.
2CaOCl2 + H2O + CO2  CaCl2 + CaCO3 + 2HClO
Properties:
(i) It is a weak acid. Its concentrated solution is yellow in colour
while dilute solution is colourless. It is unstable and
decomposes.
2HClO  2HCl + O2
(ii) It dissolves magnesium with evolution of hydrogen.
Mg + 3HClO  Mg(ClO)2 + H2
(iii) With alkalies, it forms salts called hypochlorites.
(iv) It acts as a powerful oxidising and bleaching agent. This is
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p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18)
due to release of nascent oxygen easily.
HClO  HCl + O
16.7.2 Chlorous Acid [HClO2]
Preparation:It is obtained in aqueous solution when barium
chlorite suspension in water is treated with H2SO4 . The insoluble
barium sulphate is filtered off.
Ba(ClO2)2 + H2SO4  BaSO4 + 2HClO2
Properties:
(i) The freshly prepared solution is colourless but it soon
decomposes to ClO2 which makes the solution yellow.
5 HClO2  4 ClO2 + HCl + 2H2O
(ii) The acid undergoes auto-oxidation.
2HClO2  HClO + HClO3
(iii) The acid liberates iodine from K
4K + HClO2 + 2H2O  4KOH + HCl + 22
16.7.3 Chloric Acid [HClO3]
Preparation: This acid is only known in solutuion. The acid is
preapred by the action of the dilute H2SO4 on barium chlorate.
Ba (ClO3)2 + H2SO4  BaSO4+ 2HClO3.
Properties: Concentrated acid is colourless and pungent smelling
liquid. It decomposes in light. However, it is stable in dark. It acts
as a strong oxidising and bleaching agent in light. Organic
substances like paper, cotton, wool, etc., catch fire in contact with
the acid.
16.7.4 Per-Chloric Acid [HCIO4]
Preparation: It is the most stable oxy-acid of chlorine. Anhydrous
HClO4 is obtained by doing distillation of KCIO4 (potassium
perchlorate), with 96-97.5% H2SO4 under low pressure at 90-160°C.
KCIO4 + H2SO4  KHSO4 + HCIO4
An aqueous solution of the acid is obtained by reacting barium
perchlorate with calculated quantity of dilute H 2SO 4. The
insoluble barium sulphate is removed by filtration.
Ba(CIO4)2 + H2SO4  BaSO4  + 2HClO4
Properties:
(i) Anhydrous HClO4 is a colourless liquid which turns dark on
keeping. It fumes in moist air.
(ii) It is one of the strongest acid and ionises as follows :
HClO4  H+ + ClO4–
p-BLOCK ELEMENTS (GROUP 15-18) 35

(iii) It dissolves most of the metals.

CaOCl2 + CO2  CaCO3 + Cl2
Zn + 2HClO4  Zn(ClO4)2 + H2
 HNO3 is a strong oxidising acid to be avoided, here.
(iv) It is an oxidising agent and explodes in contact with organic
matter.
Some Important order
(a) Acid strength:
(v) 2HClO4 + P2O5  2HPO3 + Cl2O7
(i) H > HBr > HCl > HF
16.8 Bleaching Powder (CaOCl2.H2O) (ii) HOCl > HOBr > HO
Bleaching powder is also called calcium chlorohypochlorite (iii) HClO4 > HClO3 >HClO2 > HClO
because it is considered as a mixed salt of hydrochloric acid and (b) Oxidising power :
hypochlorous acid. (i) F2 > Cl2 > Br2 > 2 (According to electrode potential)
Ca(OCl)Cl (ii) BrO4– > IO4– > ClO4–
Preparation: (iii) HClO4 < HClO3 < HClO2  HClO
(c) Order of disproportionation:
40C
Ca(OH)2 + Cl2   Ca(OCl)Cl + H2O 3 XO–  2X– + XO3– (hypohalite ion)
Properties
O– > BrO– > ClO–
(i) It is a pale yellow powder. It has a strong smell of chlorine. It
is soluble in water but a clear solution is never formed due
to the presence of impurities.
17. Interhalogen Compounds
(ii) On long standing, it undergoes auto–oxidation into calcium We know that halogen atoms have different electronegativity.
chlorate and calcium chloride. Due to this difference in electronegativity the halogen atoms
combine with each other and give rise to the formation of binary
6 CaOCl2  Ca(CIO3)2 + 5 CaCl2
covalent compounds, which are called interhalogen
CoCl compounds.These are of four types.
(iii) 2 CaOCl2  2  2 CaCl + O
2 2
AB AB3 AB5 AB7
(iv) In presence of a little amount of a dilute acid, it loses oxygen.
ClF ClF3 ClF5 lF7
2 CaOCl2 + H2SO4  CaCl2 + CaSO4 + 2 HClO BrF BrF3 BrF5
ICl ICl3 IF5
HClO  HCl + O
IF IF3
On account of the liberation of nascent oxygen, it shows
Preparation:
oxidising and bleaching properties.
(i) By the direct combination of halogens :
(a) Oxidising properties
473 K
Cl2 + F2 (equal volumes)   2ClF
CaOCl2 + H2S  CaCl2 + H2O + S
573K
CaOCl2 + 2 KI + 2 HCl  CaCl2 + 2 KCl + H2O + I2 Cl2 + 3F2 (excess)   2ClF3

3 CaOCl2 + 2 NH3  3 CaCl2 + 3 H2O + N2 I2 + Cl2  2ICl

It oxidises NO2– to NO3– , AsO33– to AsO43– and Fe2+ to Fe3+ (equimolar)
(in acidic medium) (ii) Diluted with water.
(b) Bleaching action
Br2 (g) + 3F2  2BrF3
Coloured matter + [O]  colourless product. (iii) F2 is diluted with N2
(v) When bleaching powder reacts with dilute acids or CO2 it
78ºC 2IF
I2 + 3F2 
liberates chlorine which is known as available chlorine. 3

(iv) F2 is taken in excess.

CaOCl2 + 2 HCl  CaCl2 + H2O + Cl2
Br2 + 5F2 (excess)  2BrF5
CaOCl2 + H2SO4  CaSO4 + H2O + Cl2
IF7 can not be prepared by direct combination of I2 & F2 .

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p-Block Elements (Group 15-18)
36 p-BLOCK ELEMENTS (GROUP 15-18)
(ii) From lower Interhalogens: IF7 + 6H2O  7HF + H5IO6
ClF + F2  ClF3
BrF5 + 3H2O  5HF + HBrO3
350ºC ClF
ClF3 + F2 (excess)  5  Hydrolysis products are halogen acid and oxy-halogen acid.
Oxy-halogen acid is of larger central halogen atom.
200ºC BrF
BrF3 + F2 (excess)  5
 Oxidation state of A atom does not change during hydrolysis.
270ºC IF (viii) Reaction with non-metallic and metallic oxides :
IF5 + F2  7

This method is generally applied for the preparation of halogen
fluorides.
Properties:
(i) These compounds may be gases, liquids or solids.
Gases : ClF, BrF, ClF3 , IF7
Liquids : BrF3, BrF5
Solids : ICl, IBr, IF3, ICl3.
(ii) Interhalogens containing fluorine are colourless but inter
halogens consisting of heavier halogens are coloured. The
intensity of colour increases with increase in the molecular
weight of the compounds.
(iii) All interhalogens are covalent molecules and are diamagnetic
in nature since all the valence electrons present as bonding
or non-bonding electrons are paired.
(iv) The boiling points increases with the increase in the
electronegativity difference between A and B atoms.
(v) Thermal stability of AB type interhalogen compounds
decreases with the decrease in electronegativity difference
between A and B atoms. IF > BrF > ClF > ICl > IBr > BrCl.
More polar is the A – B bond more is the stability of interhalogen.
(vi) Interhalogen compounds are more reactive than the parent
halogens but less reactive than F2.
ICl + 2Na  NaI + NaCl
The order of reactivity of some interhalogens is as follows :
ClF3 > BrF3 > IF7 > BrF5 > BrF.
(vii) Hydrolysis : All these undergo hydrolysis giving halide ion
derived from the smaller halogen and a hypohalite (when
AB), halite (when AB3), halate (when AB5), and perhalate
(when AB7) anion derived from the larger halogen.
AB + H2O  HB + HOA
BrCl + H2O  HCl + HOBr
ICl + H2O  HCl + HIO
ICl3 + 2H2O  3HCl + HIO2
IF5 + 3H2O  5HF + HIO3
4BrF3 + 3SiO2  3SiF4 + 2Br2 + 3O2
4BrF3 + 3WO3  2WF6 + 2Br2 + 3O2
(ix) Addition reaction (of AB type compounds):
– CH = CH – + ICI  – CHI – CHCl –
CH2 = CH2 + BrCI  CH2Br – CH2Cl
(x) Reaction with alkali metal halides :
IBr + NaBr  NaIBr2 ICl3 + KCl  KICl4
Uses
These compounds can be used as non aqueous solvents.
Interhalogen compounds are very useful fluorinating agents. ClF3
and BrF3 are used for the production of UF6 in the enrichment of
235
U.
U(s) + 3 ClF3 (l)  UF6 (g) + 3 ClF (g)
18. Pseudo Halogens & Pseudo
Halides
Some inorganic compounds like (CN) 2 cyanogen, (SCN) 2
thiocyanogen, (SeCN) 2 selenocyanogen, (SCSN 3 ) 2
azidocarbondisulphide have been found to behave like halogens
& they are known as pseudo halogen solids. Similarly few ions
are known, consisting of two or more atoms of which at least one
is N, that have properties similar to those of the halide ions. They
are therefore called pseudohalide ions, e.g. (CN–) cyanide ion,
(SCN–) thiocyanate ion, (SeCN–) selenocyanate ion, (OCN–)
cyanate ion, (NCN2–) cyanamide ion, (N3–) azide ion etc.
19. Uses of Group 17 Element (Cl2)
It is used (i) for bleaching woodpulp (required) for the manufacture
of paper and rayon), bleaching cotton and textiles, (ii) in the
extraction of gold and platinum (iii) in the manufacture of dyes,
drugs and organic compounds such as CCl4, CHCl3, DDT,
refrigerants, etc. (iv) in sterilising drinking water and (v) preparation
of poisonous gases such as phosge (COCl2), tear gas (CCl3NO2),
mustard gas (ClCH2CH2SCH2CH2Cl).

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p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18) 37

20.Introduction of Group 18 20.1 Electronic Configuration

Elements: (The Zero Group All noble gases have general electronic configuration ns np ex- 2 6

cept helium which has 1s . Many of the properties of noble gases 2

Family) including their inactive nature are ascribed to their closed shell
structures.
Group 18 Consists of six elements: helium, neon, argon, krypton,
xenon and radon . All these are gases and chemically unreactive. 20.2 Ionisation Enthalpy
They form very few compounds . Because of this they are termed Due to stable electronic configuration these gases exhibit very
noble gases. high ionisation enthalpy . However, it decreases down the group
Occurrence: All the noble gases except radon occur in the atmo- with increases in atomic size.
sphere. Their atmospheric abundabce in dry air is ~ 1% by
volume of which argon is the major constituent. Helium and some-
20.3 Atomic Radii
times neon are found in minerals of radioactive origin e.g., pitch- Atomic radii increase down the group with increase in atomic
blende, monazite, cleveite. The main commercial source of helium number.
is natural gas. Xenon and radon are the rarest elements of the 20.4 Electron Gain Enthalpy
group. Radon is obtained as a decay product of 226Ra.
Since noble gases have stable electronic configurations, they
226 Ra  222 Rn  4 He have no tendency to accept the electron and therefore, have larger
88 86 2
positive values of electron gain enthalpy.
Most abundant element in air is Ar. Order of abundance in the air
is Ar > Ne > Kr > He > Xe.
Table 11.8 : Physical Properties of Group 18

Element He Ne Ar Kr Xe
Atomic Number 2 10 18 36 54
Atomic Mass 4 20.18 39.10 83.80 131.30
Electronic configuration 1s 2
[He]2s 2p2 6
[Ne]3s 3p2 6
[Ar]3d 4s 4p
10 2 6
[Kr]4d105s25p6
Covalent Radius/pm 120 160 190 200 220
Ionization enthalpy /(kJ mol–1) 2372 2080 1520 1351 1170
Density (at STP)/g cm –3
1.8 ×10 –4
9.0×10 –4
1.8×10 –3
3.7×10 –3
5.9×10–3
Melting point/K – 24.6 83.8 115.9 161.3
Boiling point/K 4.2 27.1 87.2 119.7 165.0

21. Physical Properties of Group
18 Elements
All the noble gases are monoatomic. They are colourless, and
tasteless. They are sparingly soluble in water. They have very
low melting and boiling points because the only type of inter-
atomic interaction in these elements is weak dispersion forces,.
Helium has the lowest boiling point (4.2K) of any known sub-
stance. It has a unusual property of diffusing through most com-
monly used laboratory materials such as rubber, glass or plastics.
22. Chemical Properties of Group
18 Elements
In general, noble gases are least reactive. Their inertness to chemi-
cal reactivity is attributed to the following reasons:
(i) The noble gases expect helium (1S2) have completely filled
ns2 np6 electronic configuration in their valence shell.
(ii) They have high ionisation enthalpy and more positive elec-
tron gain enthalpy.
The reactivity of noble gases has been investigated occa-
sionally ever since their discovery, but all attempt to force
them to react to form the compounds were unsuccessful for
quite a few years. In March 1962, Neil Bartlett, then at the
University of British Columbia, observed the reaction of a
noble gas. First , he prepared a red compound which is
formulated as O2+ PtF6–. He , then realised that the first
ionisation enthalpy of molecular oxygen (1175 kj mol –1) was
almost identical with that xenon (1170 kJ mol –1). He made
efforts to prepare same type of compound with Xe+ PtF6 – by
mixing Pt F6 and Xenon. After this discovery, a number of

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p-Block Elements (Group 15-18)
38 p-BLOCK ELEMENTS (GROUP 15-18)

xenon compounds mainly with most electronegative ele- 118C XeF + O

ments like fluorine and oxygen, have been synthesised.
The compounds of krypton are fewer. Only the difluoride
(KrF2) has been studied in detail. Compounds of radon have
not been isolated but only identified (e.g., RnF2) by radiotracer
technique. No true compounds of Ar, Ne or He are yet known.
 If Helium is compressed and liquified it forms He() liquid at
4.2 K. This liquid is a normal liquid like any other liquid. But
if it is further cooled then He() is obtained at 2.2 K, which is
known as super fluid, because it is a liquid with properties of
gases. It climbs through the walls of the container & comes
out. It has very high thermal conductivity & very low
viscosity.
Compounds of inert gases are of following two types.
(i) Physical compounds (possess no proper bonding)
Physical compounds may be (A) compounds whose
existence is on the basis of spectroscopic studies (temporary
phase not isolated) and (B) clatherate compounds.
Clatherate compounds : Inert gas molecules get trapped in
the cages formed by the crystal structure of water.
During the formation of ice Xe atoms will be trapped in the
cavities (or cages) formed by the water molecules in the
crystal structure of ice. Compounds thus obtained are called
clatherate compounds.
There are no chemical bonds. They do not possess an exact
chemical formula but approx it is 6 water molecules : 1 inert
gas molecule. The cavity size is just smaller than the atom of
the noble gas. Such compounds are also formed by the other
organic liquids like dihydroxybenzene (for example quinol).
Fig 11.6: Clatherate compound
(ii) True chemical compounds (posses proper bonding).
23. Compounds of Xenon
23.1 Xenon Difluoride (XeF2)
Preparation:
873K ,1bar
(i) Xe + F2 Ni 
Tube or monel metal (alloy of Ni) XeF2
Volume ratio should be 2:1 otherwise other higher fluorides
tend to form.
(ii) Xe + O2 F2  2 2
Hg (arc)
(iii) Xe + F2   XeF2
(iv) Recently discovered method :
K+ [AgF4]– [potassium tetrafluoroargentate ()] is first
prepared and this is reacted with BF3 .
BF3 AgF (red solid) + KBF
K+ [AgF4]–   3 4
2 AgF3 + Xe  2 AgF2 (Brown solid) + XeF2
Properties:
(i) Colorless crystalline solid and sublimes at 298 K.
(ii) Dissolves in water to give a solution with a pungent odour.
Much soluble in HF liquid.
(iii) This is stored in a vessel made up of monel metal which is a
alloy of nickel.
(iv) Reaction with H2: It reacts with hydrogen gas at 400°C
XeF2 + H2  Xe + 2HF
(v) Hydrolysis:
(a) 2XeF2 + 2H2O  2Xe + 4HF + O2 (slow)
The above is neither a cationic hydrolysis nor an anionic
hydrolysis as seen in ionic equilibrium. It is a covalent
compound and hydrolysis is like that of PCl5 .
(b) Hydrolysis is more rapid with alkali.
1
XeF2 + 2 NaOH  Xe + O + 2NaF + H2O (fast)
2 2
The reaction (a) is slower probably due to dissolution of
XeF2 in HF.
(vi) Oxidising Properties: Higher the value of SRP better is the
oxidising property of the species.
The standard reduction potential for XeF2 is measured to be
+ 2.64 V. Therfore it acts as a strong oxidising agent.
2e– + 2H+ + XeF2  Xe + 2HF SRP = + 2.64 V
This oxidises halides to their respective halogens.
XeF2 + 2 HCl  Xe + 2 HF + Cl2
It oxidises 2Br –  Br2 + 2e– & 2–  2 + 2e–
In this manner XeF2 will oxidise halide ions (except F–) into
free halogens.
Similarly it can oxidise BrO3– (bromate) which are themselves
good oxidising agents to BrO4– (perbromate ions) and Ce+3
to Ce+4 ion.
(vii) Oxidising as well as Fluorinating Properties: It can act as
strong oxidising agent as well as fluorinating agent.

SCAN CODE
p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18) 39

C6 H5  + XeF2  C6 H5 F2 + Xe 23.2 Xenon Tetrafluoride (XeF4)

CH3+XeF2  CH3 F2 + Xe Preparation:

 CH3 F2 exists as CH3+F2– ,F2– is analogous to 3– 873K,  XeF

Xe  2F 
2 7bar 4
1 : 5 Ni tube

Properties:
(i) It is a colorless crystalline solid and sublimes at 298 K.
Hybridisation = sp d 3 (ii) It undergoes sublimation, soluble in CF3 COOH.
It undergoes hydrolysis violently hence no moisture
must be present during it’s preparation.
Fig 11.7 Structure of IF2- (iii) Reaction with H2O :
 F3 cannot be formed as it has no d-orbitals to attain sp d
– 3
6 XeF4 + 12 H2O  4 Xe + 2XeO3 + 24 HF + 3O2
hybridisation.
XeO3 is white solid and explosive compound (dry), soluble in
(viii) Reactions of XeF2 + HF (anhydrous):
water (well behaved in water)
HF
Pt + 3XeF2  PtF6 + 3Xe XeO3 reacts with NaOH forming sodium xenate
S8 + 24 XeF2  8SF6 + 24 Xe XeO3 + NaOH  Na+ [HXeO4]– (sodium xenate)
2CrF2 + XeF2  2CrF3 + Xe  It disproportionates into perxenate ion in basic medium.
2MoO3 + 6XeF2  2MoF6 + 6Xe + 3O2 2 [HXeO4]– + 2OH– [XeO6]4– + Xe + O2 + 2H2O
Xenic acid (H2XeO4) is a very weak acid.
Mo (CO)6 + 3 XeF2  Mo F6 + 3 Xe + 6CO
HF H 
 XeO6 
4–
2 C6H6 + XeF2  2 C6H5F + Xe water  XeO3  O 2
(i)
8 NH3 + 3 XeF2  N2 + 6 NH4 F + 3 Xe
 slow decomposition 

 XeO 6 
4–
2NO2 + XeF2  2 NO2 F + Xe (ii)  Mn 2  MnO 4–  XeO3
(nitronium fluoride) [XeO6]4– is obtainable as Na4 XeO6.8H2O
(ix) Formation of Addition Compounds: XeF2 reacts with fluoride (sodium perxenate)
ion acceptors to form cataionic species and fluoride ion (iv) Oxidising properties of XeF4
donors to form fluoroanions.
XeF4 + 2 H2  Xe + 4HF
XeF2 + PF5  [XeF]+ [PF6]–
F5 (lewis acid) + XeF2  [XeF]+ [F6]– XeF4 + 2 Hg  Xe + 2HgF2

2SbF5 (lewis acid) + XeF2  [XeF]+ [SbF6]– (v) Addition Reactions: XeF4 reacts with fluoride ion acceptors
to form cataionic species and fluoride ion donors to form
Similar behaviour is shown by PF5 and AsF5
fluoroanions.
Structure: Shape linear and geometry trigonal bipyramidal.
XeF4 + SbF5  [XeF3]+ [SbF6]–
(vi) Fluorinating Agents:
XeF4 + Pt  PtF4 + Xe

Hybridisation = sp3d XeF4 + 4NO  Xe + 4NOF (nitrosyl Fluoride)

XeF4 + 4 NO2  Xe + 4 NO2 F (nitronium fluoride)

Fig 11.8 Structure of XeF2 XeF4 + 2C6 H6  C6H5F + 2HF + Xe

SCAN CODE
p-Block Elements (Group 15-18)
40 p-BLOCK ELEMENTS (GROUP 15-18)
Structure : Shape square planar & geometry octahedral XeF6 + MF  M+ [XeF7]– (M = Na, K, Rb or Cs)

donation { XeF6 + PtF5  (XeF5+) (PtF6–)

 CsF  XeF6  CsXeF7

  alkali metal   caesium heptafluoroxenate 
 

acceptance   fluride
  

2CsXeF7 XeF6  Cs2 XeF8
  caesium octafluoraxenate 
 
  
Fig 11.8: Structure of XeF4
Order of Oxidising Power:
23.3 Xenon Hexafluoride (XeF6) XeF2 > XeF4 > XeF6
Preparation: Structure: Shape caped octahedral (distorted oactahedral)
Xe  3F2 573K,60–70 bar
  XeF
23.4 Xenon–Oxygen Compounds
(i) 1 : 20 Ni  tube 6
Hydrolysis of XeF4 and XeF6 with water gives XeO3.

6 XeF4 + 12 H2O  4 Xe + 2 XeO3 + 24 HF + 3 O2

(ii) XeF4 + O2 F2  XeF6 + O2
Properties: XeF6 + 3 H2O  XeO3 + 6 HF
(i) Colourless crystalline solid and sublimes at 298 K. Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2
(ii) It gives yellow liquid on melting where as other form white XeF6 + H2O  XeOF4 + 2 HF
liquids on melting (a point of difference)
XeF6 + 2 H2O  XeO2F2 + 4 HF
(iii) HF is a good solvent for all three fluorides.
XeO3 is a colourless explosive solid and has a pyramidal molecu-
(iv) Hydrolysis: lar structure. XeOF4 is a colourless volatile liquid and has a square
(a) Complete hydrolysis: pyramidal molecular structure.
XeF6  3H 2 O  XeO3  2HF

 whitesolid 
24.Uses of Group 18 Elements


XeF6  H 2 O  XeOF4  2HF

(b) Partial hydrolysis:  colourless  Helium is a non–inflammable and light gas. Hence, it is used in
 
 
filling ballons for meterological observations. It is also used in
(v) Reaction with Silica (SiO2): gas–cooled nuclear reactors. Liquid helium (b.p.4.2 K) finds use
as cryogenic agent for carrying out various experiments at low
2XeF6 + SiO2  2XeOF4 + SiF4
temperatures. It is used to produce and sustain powerful
(vi) Thermal Decomposition (effect of heat): superconducting magnets which form an essential part of modern
 NMR spectrometers and Magnetic Resonance Imaging (MRI)
2XeF6  XeF2 + XeF4 + 3 F2
systems for clinical diagnosis. It is used as a diluent for oxygen in
XeF2 & XeF4 do not undergo decomposition modern diving apparatus because of its very low solubility in
(vii) Formation of Addition Compounds: blood.
XeF6 + SbF5  [XeF5]+ [SbF6] Neon is used in discharge tubes and fluorescent bulbs for
advertisement display purposes. Neon bulbs are used in botanical
XeF6 + BF3  [XeF5]+ [BF4]– gardens and in green houses.
(viii) Reaction with H2 : Argon is used mainly to provide an inert atmosphere in high
XeF6 + 3H2  6HF + Xe temperature metallurgical process (arc welding of metals or alloys)
and for filling electric bulbs. It is also used in the laboratory for
(ix) Reaction of XeF6 with XeO3 : handing substances that are air–sensitive.
XeO3 + 2 XeF6  3 XeOF4 Xenon and Krypton are used in light bulbs designed for special
purposes.
(x) F– donating/F accepting properties: XeF6 reacts with fluoride
ion acceptors to form cataionic species and fluoride ion
donors to form fluoroanions.

SCAN CODE
p-Block Elements (Group 15-18)
p-BLOCK ELEMENTS (GROUP 15-18)
Summary
Group-15 Elements
 General Electron Configuration : ns2np3, extra stable
electronic configuration due to half filled p-orbital.
 Atomic and Ionic Radii : Increase down the group due to
increase in the number of inner shells.
 Ionisation Enthalpy(IE) : Decreases down the group due to
increase in atomic size.
 Electronegativity : Decreases down the group.
 Melting & Boiling Point : Boiling points increase from top
to bottom and Melting points increase upto Arsenic & then
decrease upto Bismuth.
 Oxidation State : The tendency to exhibit -3 oxidation state
decreases down the group due to increase in size and metallic
character (i.e electronegativity). +3 and +5 are generally the
covalency and the tendency to show (+3) O.S. in comparison
to (+5) O.S. increases down the group due to the inert pair
effect.
Group-16 Elements
 General Electron Configuration: ns2np4
 Atomic and Ionic Radii : Increase down the group due to
increase in the number of shells.
 Ionisation Enthalpy(IE) : Decreases down the group due to
increase in size.
 Electron Gain Enthalpy (EGE) : Becomes less negative down
the group (S < Se < Te < Po < O) due to increase in size. O is
an exception due to interionic repulsion in its small size
 Electronegativity : Decreases down the group.
 Melting & Boiling Point : Increase down the group as the
strength of van der waals force increases with increase in
molar mass & size.
 Oxidation State : The stability of -2 oxidation state decreases
down the group because of decrease in electronegativity.
The tendency or stability of +4 oxidation state in comparison
to +6 oxidation state increases down the group due to inert
pair effect.
41
Group-17 Elements
 General Electron Configuration : ns2np5
 Atomic & Ionic Radii : F < Cl < Br < I due to increasing
number of shells down the group.
 Ionisation Enthalpy(IE) : F > Cl > Br > I due to increase in
size down the group.
 Electron Gain Enthalpy (EGE) : I > Br > F > Cl as size increases
down the group. F is an exception because the incoming
electron faces greater interelectronic repulsions in the small-
sized 2p orbital of fluorine(F).
 Electronegativity: Fluorine is the most electronegative
element.
 Melting & Boiling Point : Their melting and boiling points
increase down the group with atomic number. Because the
strength of van der Waal force increases with increase in
mass.
 Order of Bond Dissociation Energy is Cl2 > Br2 > F2 > I2.
Group-18 Elements
 General Electron Configuration : ns2np6 except helium which
has 1s2.
 Ionisation Enthalpy : Decreases down the group, Due to
stable electronic configuration these gases exhibit very
high ionisation enthalpy.
 Atomic Radius : Increases down the group.
 Electron Gain Enthalpy (EGE) : They have no tendency to
accept the electron & therefore, have large +ve values of
EGE.
 Melting & Boiling Point : They have low melting point and
boiling point. Boiling point increases down the group with
increase in strength of dispersion forces.
 All noble gases are monatomic, colourless, they are
sparingly soluble in water.
SCAN CODE
p-Block Elements (Group 15-18)
42 p-BLOCK ELEMENTS (GROUP 15-18)

Solved Examples
Example-1 Example-6
Why does NH3 form hydrogen bond but PH3 does not? In the reaction
Sol. Hydrogen bond is always formed between highly burnt in
electronegative atoms and H atoms. Nitrogen is highly NH 3  A
air at 750 C (gas)
electronegative compared to phosphorus as Pt catalyst and 6 atm
electronegativity decreases sown the group.
Passed into
Hence, the extent of hydrogen bonding in PH3 is very less A  B
(gas) SnCl solution
as compared to NH3 2
in presence of HCI
Example-2
Why does R3P = O exist but R3N = O does not (R = alkyl The compound B is:
group) (a) NH2OH (b) NH3
Sol. N (unlike P) lacks the d-orbital. This restricts nitrogen to (c) N2O (d) NH2– NH2
expand its coordination number beyond four. Hence, Ans. (a)
R3N = O does not exist.
gauze
Example-3 Sol. 4NH3  5O2   4NO 6H2 O
750C,6 atm (A)
How is nitrogen prepared in the laboratory? Write the
chemical equations of the reactions involved. 3SnCl2  6HCl  2NO  3SnCl 4  2NH 2 OH
Sol. An aqueous solution of ammonium chloride is treated with Example-7
sodium nitrite.
Mg (NH4) PO4 and Na(NH4) HPO4 are heated separately.
NH4Cl(aq) + NaNO2(aq)  N2(g) + 2H2O(l) + NaCl(aq)
Which of the following statements is/are completely
NO and HNO3 are produced in small amounts. These are incorrect regarding the product obtained in the above
impurities that can be removed on passing nitrogen gas process?
through aqueous sulphuric acid, containing potassium
(I) Same gas is evolved
dichromate.
(II) Same type of phosphate is formed
Example-4
(III) Different types of gases are formed
What is the covalence of nitrogen in N2O5?
(IV) Different types of phosphates are formed
Sol.
(a) I and II (b) II and IV
(c) I and IV (d) II and III
Ans. (d)
Sol. 3Mg  NH 4  PO4  Mg 2 P2 O7  MgHPO 4  3NH3 
Na  NH 4  HPO 4 

 NaPO3  NH3  H 2 O
From the structure of N2O5, it is evident that the covalency
of nitrogen is 4. Same gas, different phosphates
Example-5 Example-8
NH3 burns in air under suitable conditions to produce Phosphorescence shown by P is due to
(a) N2 (b) NO (a) oxidation of P into P2O3.
(c) N2O (d) N9O3 (b) oxidation of P into P2O5.
Ans. (b) (c) oxidation of luciferin by luciferage enzyme.

Pt
(d) reduction of P into phosphide ions.
Sol. 4NH 3 + 5O 2  4NO + 6H 2 O .
700º 800º C Ans. (a)
Sol. P4  3O 2  2P2 O3  hv
p-BLOCK ELEMENTS (GROUP 15-18) 43

Example-9 Example-13
Can PCl5 act as an oxidizing as well as a reducing agent? In the separation of noble gas mixture from air by Ramsay
Justify. and Rayleigh’s first method, the substances used for the
Sol. PCl5 can only act as an oxidizing agent. The highest oxidation removal of N2 and O2 respectively, are:
state that P can show is +5. (a) Cu and Mg (b) Mg and Cu
In PCl5, phosphorus is in its highest oxidation state (+5). (c) C and CaC2 (d) KOH solution
Thus, it can only decrease its oxidation state and act as an Ans. (b)
oxidizing agent. Sol. N2 + 3Mg  Mg3N2
Example-10 2Cu + O2  2CuO
Why are pentahalides more covalent than trihalides? Example-14
Sol. In pentahalides, the oxidation state is +5 and +3 oxidation Which aerosols deplete ozone?
state in trihalides. Since the metal ion with a high charge has
Sol. Freon's or chlorofluorocarbons (CFCs) are aerosols that
more polarizing power, pentahalides are more covalent than
accelerate the depletion of ozone. In the presence of
trihalides.
ultraviolet radiation, molecules of CFCs break down to form
Example-11
chorine-free radicals that combine with ozone to form oxygen.
Give the disproportionation reaction of H3PO3
Example-15
Sol. On heating, orthophosphorus acid (H3PO3)disproportionate
to give orthophosphoric acid (H3PO4) and phosphine (PH3). Which of the following solutions does not change its colour
on passing ozone through it?
The oxidation states of P in various species involved in the
reaction are mentioned below. (a) Starch iodide solution
3 5 –3 (b) Alcoholic solution of benzidine
4H 3 P O3  3H3 P O 4  P H 3 (c) Acidic solution of K2Cr2O7
Example-12 (d) Acidified solution of FeSO4
Ans. (c)
Sol.
O3  Turns benzidine solution brown
O3  Turns starch iodide solution Violet (l2 formn)

X, Y and Z are O3  2FeSO 4  H 2SO4  O3

green
(a) H4P2O7, HPO3 and P4O10 
(b) HPO3, H4P2O7 and P4O10 Fe 2  SO 4 3  H 2 O  O 2
(c) H4P2O6, H3PO3 and P4O6 Yellowish 




(d) H4P2O6 , HPO3 and P4O6

Example-16
Ans. (a)
Concentrated H2SO4 can be used to dry the gas:
250ºC  H P O  H O
Sol. 2H 3 PO 4  4 2 7
X
2 (a) H2S (b) CO2
(c) NH3 (d) all
600ºC  2HPO  H O
H 4 P2 O7  3 2 Ans. (b)
X  Y
Sol. H2SO4 will oxidize NH3 & H2S or form salts.
600ºC HPO  H O
H 3 PO 4  3 2
Y

4HPO3  P4 O10  2H 2 O
(Y)  Z
44 p-BLOCK ELEMENTS (GROUP 15-18)

Example-17 Example-21
Which of the following has the maximum vapour pressure? Why do noble gases have comparatively large atomic sizes?
(a) HCl (b) HBr Sol. Noble gases do not form molecules. In case of noble gases,
(c) HF (d) HI the atomic radii correspond to van der waals radii. On the
Ans. (a) other hand, the atomic radii of other elements correspond to
their covalent radii. By definition, van der waals radii are
Sol. Due to lowest B.P. (high volatility) it has the highest vapour
larger than covalent radii. It is for this reason that noble
pressure
gases area very large in size as compared to other atoms
HF > Hl > HBr > HCl (Boiling point)
belonging to the same period.
Example-18
Example-22
Explain why fluorine forms only one oxoacid, HOF.
The shape of XeO2F2 molecule is:
Sol. Fluorine forms only one oxoacid i.e., HOF because of its
(a) trigonal bipyramidal (b) square planar
high electronegativity, small size and non-availability of d-
(c) tetrahedral (d) see-saw
orbitals.
Ans. (d)
Example-19
Sol.
Which is incorrectly matched?

(a) CsBr3  Cs+ + Br 3  Cs+ + Br- + Br2

(b) I4O9  I3+ + 3(IO3)-

(c) AgBrO3  Ag+ + BrO 3

 
(d) I2O4  IO 2 + IO 2
Ans. (d) Example-23
XeF2 reacts with SbF5 to form:
Sol. I 2 O 4  IO   IO3
(a) [XeF]+ [SbF6]– (b) [XeF3] [SbF4]
Example-20 (c) XeSbF6 (d) XeF4
Ans. (a)
Sol. XeF2  SbF5  XeF2 .SbF5   XeF SbF6 
 

Example-24
Compounds (A) and (B) are: What are the products formed in the reaction of xenon
hexafluoride with silica?
(a) NaClO3, NaClO (b) NaOCl2, NaOCl
(a) XeSiO4 + HF (b) XeF2 + SiF4
(c) NaClO4, NaClO3 (d) NaOCl, NaClO3
(c) XeOF4 + SiF2 (d) XeO3 + SiF4
Ans. (d)
Ans. (d)
Sol. Cl 2  2NaOH
 Cold & dil 
 NaCl  NaClO  H 2 O Sol. 2XeF6 + 3SiO2  2XeO3 + 3SiF4
Example-25
3Cl2  6NaOH  5NaCl  NaClO 3  3H 2 O
 hot & conc. XeF6 on reaction with CsF gives:
(a) [XeF5] [CsF2] (b) XeF8
(c) [XeF4] [CsF3] (d) Cs [XeF7]
Ans. (d)
Sol. XeF6 + CsF  Cs+[XeF7]–
p-BLOCK ELEMENTS (GROUP 15-18) 45

EXERCISE – 1: Basic Objective Questions

Introduction and Physical Properties of Group
15 Elements

1. The most stable oxidation states of nitrogen are 11. Which of the following gases is the least reactive?
(a) O2 (b) N2
(a) –3, +3 and +5 (b) –3, 0 and –1
(c) –3, +3 and 0 (d) –3, +3 and –5 (c) H2 (d) O3
2. The element which forms oxides in all oxidation states 12. Which of the following forms strong p - p bonding
+I to + V is : (a) P4 (b) As4
(a) N (b) P (c) N2 (d) Sb4
(c) As (d) Sb
3. Among the following, the element that does not show 13. N2 is commercially prepared by
allotropy is (a) fractional distillation of liquefied air
(a) N (b) P (b) heating sodium nitrite
(c) As (d) Bi (c) heating sodium azide
4. Which of the following halides of nitrogen is stable? (d) heating a mixture of ammonium chloride
(a) NF3 (b) NCl3 sodium nitrite

(c) NBr3 (d) NI3

Chemical Properties of Group 15 Elements
5. The tendency of nitrogen halides to act as Lewis bases
decreases in the order 14. Which of the following reactions is used in the
(a) NF3> NCl3> NBr3> NI3 preparation of N2?
(b) NI3> NBr3> NCl3> NF3 heat 
(a) NH Cl + NaNO 
4 2
(c) NF3 NCl3> NBr3> NI3 heat 
(b) Ca(OCl)2 + NH3 
(d) NF3> NCl3> NBr3 NI3 heat 
(c) (NH ) Cr O 
4 2 2 7
6. Which one of the following compounds is most (d) All of these
explosive? 15. Small quantities of very pure N2 is obtained by
(a) NCl3 (b) PCl3 carefully warming
(c) AsCl3 (d) NF3 (a) sodium azide (NaN3)
7. Which of the following is the increasing order of (b) a mixture of CuO and NH 3
enthalpy of vaporization? (c) a mixture of NH3 and Br2
(a) NH3, PH3, AsH3 (b) AsH3, PH3, NH3
(d) a mixture of Zn, NaNO3 and NaOH
(c) NH3, AsH3, PH3 (d) PH3, AsH3, NH3
16. Which of the following compounds does not give N2
8. Among the following compounds of nitrogen and on heating?
hydrogen, the most acidic compound is (a) KNO3 (b) NH4NO2
(a) NH3 (b) N2H4
(c) (NH4)2 Cr2O7 (d) NaN3
(c) N2H2 (d) HN3
17. The reaction between urea and nitrous acid produces
9. Which of the following oxides is the most acidic? (a) NH3 (b) NO2
(a) N2O5 (b) P2O5
(c) N2O (d) N2
(c) As2O5 (d) Sb2O5
18. Which of the following fertilizers on repeated
10. An aqueous solution of ammonia consists of application would increase the acidity of the soil?
(a) H+ (b) OH– (a) Urea (b) Potassium nitrate
(c) NH3 and OH– (d) NH4+ and OH– (c) Superphosphate of lime (d) Ammonium sulphate
46 p-BLOCK ELEMENTS (GROUP 15-18)

19. Mg (NH4)PO4 and Na(NH4) HPO4 are heated 29. N2O3 is

separately. Which of the following statements is/are (a) an acidic oxide and the anhydride of HNO2
completely incorrect regarding the product obtained in
(b) an acidic oxide and the anhydride of H2N2O2
the above process?
(I) Same gas is evolved (c) a neutral oxide and the anhydride of HNO3
(II) Same type of phosphate is formed (d) a basic oxide and the anhydride of HNO2
(III) Different types of gases are formed 30. Which of the following oxides of nitrogen is a mixed
(IV) Different types of phosphates are formed anhydride of two acids?
(a) I and II (b) II and IV (a) N2O3 (b) N2O4
(c) I and IV (d) II and III
(c) N2O5 (d) NO2
20. Ammonia gas can be dried by
(a) conc. H2SO4 (b) P4O10 31. Liquid N2O4 self-ionizes as
(c) anhydrous CaCl2 (d) none of these (a) N2O4 (l) ⇌ 𝑁𝑂2+ + 𝑁𝑂2−
21. Ammonia, on reaction with excess of chlorine, gives: (b) 2N2O4 (l) ⇌ 𝑁𝑂3− + 2𝑁𝑂2+ + 𝑁𝑂
(a) NCl3 and HCl (b) N4 and NH4Cl (c) N2O4 (l)⇌ 𝑁𝑂+ + 2𝑁𝑂3−
(c) NCl3 and NH4Cl (d) N2 and HCl (d) N2O4 (l) ⇌2NO2
22. A solution of sodium in liquid ammonia is blue due to 32. Which of the following reactions gives reasonably
the presence of pure NO?
(a) solvated electrons (b) ammonium ions (a) 2NaNO2 + 2NaI + 4H2SO4
(c) solvated sodium ions (d) sodium atoms  I2+ 4NaHSO4+ 2H2O +2NO
23. The bond order in the NO molecule is
(b) 2NaNO2 + 2FeSO4 + 3H2SO4
(a) 3 (b) 1.5
(c) 2.5 (d) 2.0  Fe2(SO4)3+ 2NaHSO4+ 2H2O +2NO
 (c) 3KNO2(1) + KNO3(1) + Cr2O3(s)
24. In NO3 ion, the number of bond pairs and lone pair
of electrons on nitrogen atom are  2K2CrO4 +4NO
(a) 2, 2 (b) 3, 1 (d) All of these
(c) 1, 3 (d) 4, 0 33. At present, HNO3 is industrially prepared by the
25. Which of the following oxides of nitrogen is solid? (a) contact process
(a) NO2 (b) N2O (b) Birkeland-Eyde process
(c) N2O3 (d) N2O5 (c) Ostwald process
(d) Haber process
26. Which statement is wrong for NO?
34. Phosphorus reacts with concentrated HNO3 to produce
(a) It is anhydride of nitrous acid
(a) hypophosphoric acid
(b) It dipole moment is 0.22 D
(b)orthophosphorus acid
(c) It form dimer
(c) pyrophosphoric acid
(d) It is paramagnetic
(d) orthophosphoric acid
27. FeSO4 is a very good absorber for NO. The number of
35. Iodine reacts with concentrated HNO3 to produce
unpaired electrons in the new compound formed by
(a) H5IO6 (b) HIO4
this process is.
(a) 4 (b) 5 (c) HIO3 (d) HIO
(c) 3 (d) 6 36. Gold reacts with aqua regia forming
28. Which of the following complexes is responsible for (a) auric chloride (AuCl3)
the brown colour of the ring formed in the ring test for (b) chloroauric acid (HAuCl4)
the nitrates?
(c) chloroaurous acid (HAuCl3)
(a)[Fe(CN)5NO]3+ (b)[Fe(H2O)4NO]2+NO+
(d) purple of Cassius
(c) [Fe (CN)5NO]2+ (d) [Fe (H2O)5NO]2+
p-BLOCK ELEMENTS (GROUP 15-18) 47

37. Platinum reacts with aqua regia to produce 46. The reaction of P4 with X leads selectively to P4O6.
chloroplatinic acid represented by the formula The X is:
(a) H4 [PtCl6] (b) H [PtCl4] (a) a dry O2
(c) H2 [PtCl6] (d) H2 [PtCl4] (b) a mixture of O2 and N2
38. Which one of the following is not an ore of (c) moist O2
phosphorus?
(a) Malachite (b) Fluorapatite (d) O2 in presence of aqueous NaOH
(c) Chlorapatite (d) Phosphorite 47. On boiling phosphorus with KOH solution, product
39. Which of the following statements is correct? formed is
(a) Phosphorus does not form p-p multiple bonds in (a) Potassium sulphate (b) Phosphorus pentoxide
its compounds. (c) Phosphorus hydroxide (d) Phosphine
(b) Phosphorus forms weak to moderate d- 48. White phosphorus reacts with NaOH to give PH3 and
pmultiple bonds in some of its compounds. NaH2PO2. This reaction involves
(c) Phosphorus can expand its valence shell by (a) oxidation (b) reduction
utilizing inner 3d orbitals. (c) disproportionation (d) neutralization
(d) All of these 49. PCl5 on hydrolysis gives
40. White phosphorus is kept under
(a) H3PO2 (b) H3PO3
(a) kerosene oil
(b) water (c) H3PO4 (d) H5P3O10
(c) concentrated HNO3 50. PH3 and NH3 on separate reaction with bleaching
(d) ethanol powder produce respectively
41. White phosphorus is more reactive than N2 because (a) P and N2 (b) PCl3 and NCl3
(a) electronegativity of phosphorus is low (c) PCl3 and N2 (d) PCl5 and NCl3
(b) ionization energy of phosphorus is low
51. Solid PCl5 exists as
(c) P—P bond is weaker than NN bond
(d) P—P bond is polymeric (a) [PCl4]+ and [PCl6]- ions
42. The most stable allotropic form of phosphorus is
(b) [PCl4]- and [PCl6]+ ions
(a) yellow P (b) red P
(c) scarlet P (d) black P (c) covalent PCl5 molecules only
43. Red phosphorus is less reactive than white phosphorus (d) [PCl4]2+ and [PCl6]2- ions
because
52. White phosphorus reacts with concentrated HNO3 to
(a)the P—P bond length is greater in red phosphorus
give
(b) red P has a polymeric structure
(a) orthophosphoric acid (b) pyrophosphoric acid
(c) red P is held by weak van der Waals forces
(c) phosphorus acid (d) metaphosphoric acid
(d) red P has greater tendency to act as a donor
53. Syrupy H3PO4 is viscous due to
44. Which of the following statements is correct regarding
the behaviour of white phosphorus? (a) intermolecular hydrogen bonding
(a) It is soft, waxy and reactive (b) van der Waals forces among the H3PO4 molecules
(b) It reacts with moist air to emit a light called (c) covalent bonding in P—O linkage
chemiluminescence. (d) low activation energy in H3PO4
(c) It exists as tetrahedral P4 molecules both in the 54. The reaction of white phosphorus with aqueous NaOH
liquid and gaseous states. gives phosphine and another phosphorus containing
(d) All the above compound. The reaction type, the oxidation states of
45. The percentage of p-character in the orbitals forming phosphorus in phosphine and other product are
P–P bonds in P4 is: respectively:
(a) 25 (b) 33 (a) redox reaction, -3 and -5
(c) 50 (d) 75 (b) redox reaction, +3 and +5
(c) disproportionation reaction, -3 and +1
(d) disproportionation reaction, -3 and +3
48 p-BLOCK ELEMENTS (GROUP 15-18)

55. Which of the following statements is true for the Physical Properties of Group 16 Elements
H3PO3 molecule?
(a) It contains two acidic H atoms 62. Group 16 elements (except polonium) are called
(b) It contains one reducing H atom chalcogens because
(c) It can form two series of salts (a) these elements, particularly sulphur and oxygen,
(d) All of these are present in many metallic ores mainly as oxides
56. Which of the following structures represents and sulphides
hypophosphoric acid? (b) a large number of acids contain these elements,
H H H particularly sulphur and oxygen
(a) (b) (c) these elements mainly form anions
H P OH HO P O P OH (d) these elements exist in different allotropic forms
63. In which of the following species, S-atom assumes sp3
O O O
OH OH OH hybrid state?
(I) SO3 (II) SO2
O P P O H O P O (III) H2S (IV) S8

(c) OH OH (d) OH (a) I, II (b) II, III

57. The true statement for the acids of phosphorus, (c) II, IV (d) III, IV
H3PO2, H3PO3 and H3PO4 is 64. Oxygen is more electronegative than sulphur, yet H2S is
acidic in nature while H2O is neutral because:
(a) The order of their acidity is (a) water molecules are associated due to inter-
H3PO4> H3PO3> H3PO2 molecular hydrogen bonding
(b) All of them are reducing in nature (b) water has higher boiling point than H2S
(c) All of them are tribasic acids (c) H—S is weaker than O—H bond
(d) The geometry of phosphorus is tetrahedral in all (d) H2S is a gas at ordinary temperature while H2O is a
the three liquid
58. Which of the following oxoacids of phosphorus is a 65. The stability of the hydrides of oxygen, sulphur,
reducing agent and a monobasic acid as well? selenium and tellurium decreases in the order
(a) Orthophosphorus acid (H3PO3) (a) H2Te > H2Se >H2S > H2O
(b) Hypophosphorus acid (H3PO2) (b) H2O > H2S >H2Se > H2Te
(c) Pyrophosphorus acid (H4P2O5) (c) H2O > H2S < H2Se > H2Te
(d) Metaphosphorus acid (HPO3) (d) H2O > H2S > H2Te > H2Se
59. Which of the following compounds consists of a P–P 66. Which of the following statements regarding sulphur is
linkage? incorrect?
(a) hypophosphoric acid (a) S2 molecule is paramagnetic
(b) pyrophosphorous acid (b) The vapour at 200°C consists mostly S8 rings
(c) dipolyphosphoric acid (c) At 600°C, the gas mainly consists of S2 molecules
(d) metaphosphoric acid (d) The oxidation state of sulphur is never less than +4
60. The number of P–O–P bonds in the structure of in its compounds
phosphorus pentoxide and phosphorus trioxide are 67. The number of lone pairs and the number of S—S
respectively bonds in S8 molecules are respectively:
(a) 6, 6 (b) 5, 5 (a) 8, 8 (b) 16, 8
(c) 5, 6 (d) 6, 5 (c) 8, 16 (d) 8, 4
61. The number of P—O—P bonds in cyclic 68. Which of the following has pπ – dπ bonding?
metaphosphoric acid is – 2–
(a) NO 3 (b) SO3
(a) zero (b) two 3– 2–
(c) three (d) four (c) BO 3 (d) CO3
p-BLOCK ELEMENTS (GROUP 15-18) 49

69. O3 is 78. A green coloured solution of a salt changes its colour to

(a) an allotrope of oxygen light pink on passing ozone through it. Which of the
(b) an isomer of oxygen following species represent pink and green colour
(c) an isotone of oxygen respectively ?
(a) Mn2+ and MnO2
- 2-
(d) isostructuralwith O2 (b) MnO 4 and MnO 4
70. In ozone, the central oxygen atom uses
(c) Co2+ and Co3+
2- -
(d) MnO and MnO
(a) roughly sp2 orbitals for  bonding
4 4

79. O3 cannot oxidise:

(b) sp orbitals for  bonding only
(a) KI (b) FeSO4
(c) sp3 orbitals for  bonding
(d) pdbonding for both  and  bonding (c) KMnO4 (d) K2MnO4
80. Which of the following is/are correct?
Chemical Properties of Group 16 Elements (a) O3 + moist iodine  HIO3
(b) FeCl3 + H2S  colloidal sulphur
71. Ozone is prepared by the action of silent electric
discharge upon oxygen in an apparatus called ozonizer. (c) O3 + Ag  black silver
The reaction (d) All
(a) is exothermic 81. In the cyclo-S8 molecule of rhombic sulphur, all the
(b) is endothermic S—S bond lengths and all the S—S—S bond angles are
(c) leads to the dissociation of the O2 molecule respectively (approximate values)

(d) leads to the formation of O 2 (a) 204 pm and 105° (b) 102 pm and 120°
72. Ozonized oxygen is a mixture of (c) 204 pm and 180° (d) 102 pm and 60°
(a) O3 and N2 (b) O3 and O 82. Which of the following statements is correct for
(c) O3 and O2 (d) O3 and Cl2 sulphur?
73. Which of the following statements is correct? (a) In sulphur, stronger p-d overlap takes place
(a) Ozone decomposes to give oxygen because the size of the d orbitals is similar to that
(b) Ozone is thermodynamically unstable. of the p orbitals.
(c) The decomposition of ozone is exothermic. (b) The size of the atom and the size of the 3d orbitals
(d) All of these decrease from S to Cl because on crossing a period
74. Ozone is an extremely powerful oxidizing agent. It is in the periodic table, the nuclear charge is
(a) second only to F2 in oxidizing power increased and s and p electrons shield the nuclear
charge incompletely
(b) second only to O2 in oxidizing power
(c) Due to stronger p-d overlap, only a few sulphur
(c) second only to Cl2 in oxidizing power compounds polymerize.

(d) second only to MnO4 in oxidizing power (d) All of these
75. At room temperature, O3 is absorbed by 83. H2S turns an acidified K2Cr2O7 solution

(a) water (b) palladium (a) violet (b) orange

(c) acetic acid (d) turpentine oil (c) green (d) colourless
76. The gases absorbed by alkaline pyrogallol and oil of 84. H2S turns an acidified KMnO4 solution
cinnamon are respectively (a) green (b) pink
(a) O3 and CH4 (b) O2 and O3 (c) blue-black (d) colourless
(c) SO2 and CH4 (d) N2O and O3 85. Which of the following compounds is thermo-
dynamically unstable?
77. In the presence of water, sulphur is oxidized by ozone (a) H2O (b) H2Se
to give
(a) H2SO3 (b) SO2 (c) H2S (d) NH3

(c) H2SO4 (d) SO3

50 p-BLOCK ELEMENTS (GROUP 15-18)

86. H2S is less stable than H2O because 94. A gas that cannot be collected over water is
(a) the bonding orbitals of sulphur are larger and more (a) N2 (b) O2
diffuse than those of oxygen, and hence they overlap (c) SO2 (d) PH3
less effectively with the 1s orbital of the hydrogen
atom
(b) the bonding orbitals of sulphur are smaller and more Physical and chemical Properties of Group 17
diffuse than those of oxygen, and hence they overlap Elements
less effectively with the 1s orbital of the hydrogen
atom 95. Which of the following elements can have both positive
(c) the bonding orbitals of sulphur are smaller and less and negative oxidation states?
diffuse than those of oxygen, and hence they overlap (a) Fluorine (b) Iodine
less effectively with the 1s orbital of the hydrogen (c) Lithium (d) Helium
atom 96. Which of the following halogens has only one oxidation
(d) H2O molecules form H bonds but H2S molecules state of –1 in an aqueous solution?
(a) Iodine (b) Chlorine
do not
87. Sulphur dioxide reacts with chlorine in the presence of (c) Bromine (d) Fluorine
97. Which one among the following is the most powerful
charcoal (which acts as a catalyst) to give
(a) sulphuryl chloride oxidizing agent?
(b) thionyl chloride (a) Cl2 (b) Br2
(c) sulphur dichloride and oxygen (c) F2 (d) I2
(d) chlorine monoxide and sulphur 98. All the halogens are coloured. The colours arise due to
88. Which of the following gases may act both as an (a) weak van der Waals forces between the halogen
oxidizing and a reducing agent? molecules
(a) H2S (b) SO3 (b) strong oxidizing power of the halogens
(c) SO2 (d) O2 (c) absorption of light which causes an electron to
89. Dehydration of concentrated H2SO4 in the presence of jump from the ground state to a higher state
P4O10 produces (d) emission of light due to transfer of an electron from
(a) SO2 (b) H2S a higher state to the ground state
99. Which of the following statements is correct for the
(c) O2 (d) SO3
iodine molecule?
90. H2SO4 is manufactured from SO2(g) by the (a) In liquid state it conducts electricity, though very
(a) Hall process (b) contact process slightly, due to self-ionization: 3I 2 I3   I3 
(c) Raschig process (d) Haber process
(b) Its conductivity increases with the rise in
91. Which of the following ions does not have an S—S
temperature.
linkage?
(c) It behaves like an intrinsic semiconductor
(a) S2O 82 (b) S2O 62 (d) All the above
(c) S2O 52 (d) S2O 32 100. Which of the following is arranged in order of
increasing bond energy?
92. When SO2 gas is passed into an acidified solution of
K2Cr2O7, the oxidation state of chromium changes (a) I2< Br2< Cl2< F2 (b) I2< F2< Br2< Cl2
(a) from +12 to +6 (b) from +3 to +6 (c) I2< Br2< F2< Cl2 (d) Cl2< Br2< F2 < I2
(c) from +6 to +3 (d) from +6 to +4 101. Which of the following are not correctly matched?
93. Standard sodium thiosulphate solution is used in the (a) A halogen which is a liquid at room temperature 
estimation of iodine present in a solution. The bromine
equivalent weight of sodium thiosulphate which is
(b) The most electronegative element  fluorine
required to make the standard solution is
(a) (molecular weight)/2 (c) The strongest oxidizing halogen  iodine
(b) (molecular weight)/3 (d) The most reactive halogen  fluorine
(c) the same as the molecular weight
(d) (molecular weight)/4
p-BLOCK ELEMENTS (GROUP 15-18) 51

102. Which of the following halide ions the most basic? 110. The halogen which has zero standard enthalpy of
(a) F– (b) Cl– formation is
(a) Cl2(g) (b) Br2(g)
(c) Br– (d) I–
103. One of the reasons why the F—F bond is weak is that (c) Br2(l) (d) F2(s)
(a) the repulsion between the nonbonding pairs of 111. The property of halogen acids, that indicated incorrect
electrons of the two fluorine atoms is high is:
(b) the ionization energy of the fluorine atom is very (a) HF > HCl > HBr > HI ....... acidic strength
high (b) HI > HBr > HCl > HF ........ reducing strength
(c) the F—F bond distance is large (c) HI > HBr > HCl > HF ......... bond length
(d) the F—F bond distance is small and hence (d) HF > HCl > HBr > HI ........ thermal stability
internuclear repulsion is small 112. Which has maximum pH in aqueous solution?
104. In spite of having lower dissociation energies, bromine (a) NaClO (b) NaClO2
and iodine are weaker oxidizing agents than chlorine (c) NaClO3 (d) NaClO4
due to their
113. What products are expected from disproportionation
(a) smaller electron affinities and greater hydration
reaction of hypochlorous acid?
energies
(a) HClO3 and Cl2O (b) HClO2 and HClO4
(b) smaller electron affinities and smaller hydration
energies (c) HCl and Cl2O (d) HCl and HClO3
(c) greater electron affinities and greater hydration 114. Which one of the following oxides is expected to
energies exhibit paramagnetic behaviour?
(d) greater electron affinities and smaller hydration (a) CO2 (b) ClO2
energies
(c) SO2 (d) SiO2
105. Which of the following statements is not appropriate
regarding the characteristics of interhalogen 115. In the following statements which combination of true
compounds? (T) and false (F)options is correct?
(a) They are usually less reactive than halogens (except (I) Ionic mobility is the highest for I– in water as
fluorine). compared to other halides.
(b) They are not so stable, but none of them is explosive - - -
(II) Stability order is: Cl3 > Br3 > I3
(c) They are covalent in nature
(III) Reactivity order is F < Cl < Br < I
(d) They have low boiling points and are highly volatile
(IV) Oxidizing power order is : F2< Cl2< Br2< I2
106. Which one of the following molecules will form a
linear polymeric structure due to hydrogen bonding? (a) TFTF (b) TFFF
(a) HCl (b) HF (c) TFFT (d) FTFT
(c) H2O (d) NH3 116. Fluorine was first prepared by
(a) electrolysis of hydrogen fluoride
107. Which of the following is not true?
(b) electrolysis of fused KF
(a) Among halide ions, iodide ion is the most powerful
(c) electrolysis of a solution of KHF2 in HF
reducing agent
(d) electrolysis of molten cryolite
(b) Fluorine is the only halogen which does not show a
117. Pyrolusite on heating with concentrated HCl produces
variable oxidation state
Cl2 (g). This process is known as
(c) HOCl is a stronger acid than HOBr
(d) HF is a stronger acid than HCl (a) Weldon process
108. Which of the following halides forms salt like KHX2 (b) Deacon process
(where X is a halogen atom)? (c) Beckmann process
(a) HF (b) HCl (d) Mond process
(c) HBr (d) HI 118. Chlorine is manufactured by oxidizing HCl (g) with O2
109. The correct order of thermal stability of hydrogen at 400°C in the presence of CuCl catalyst. This process
halides (H—X) is: is known as
(a) HI > HBr > HCl > HF (b) HF > HCl > HBr > HI (a) Leblanc process (b) Solvay process
(c) HCl > HF > HBr > HI (d) HI > HCl > HF > HBr (c) Dennis process (d) Deacon process
52 p-BLOCK ELEMENTS (GROUP 15-18)

119. PtF6 converts O2 to 129. In BrF3 molecule, the lone pairs occupy equatorial
    positions to minimise
(a) O PtF
2 6 (b) O PtF
2 6
(a) lone pair-bond pair repulsions only
(c) F2+PtO2 (d) F2O + Pt (b) bond pair-bond pair repulsion only
120. Which of the following reactions may be used for the (c) lone pair-lone pair and lone pair-bond pair
preparation of chlorine? repulsions
(a) KMnO4+HCl (conc.) → (d) lone pair-lone pair repulsions only
(b) NaCl + MnO2 + H2SO4 (conc.) → 130. Bromine can be liberated from KBr by the action of
(a) iodine solution (b) chlorine water
(c) Ca(OCl)Cl + H2O → (d) All of these (c) sodium chloride (d) potassium iodide
121. Fluorine react with water to produce 131. Which of the following products is formed when a
(a) HF, O2 and O3 (b) HF and O2 mixture of solid NaCl and solid K2Cr2O7 (in excess) is
(c) HF and OF2 (d) HF and O3 heated with concentrated H2SO4?
122. Which one of the following represents the reaction (a) H2CrO4 (b) Cr2(SO4)3
between fluorine and cold NaOH (dil.)? (c) CrCl3 (d) CrO2Cl2
(a) 2F2 + 4 NaOH  4NaF + 2H2O + O2
132. Sodium thiosulphate reacts with iodine to give
(b) 3F2 + 6 NaOH  5NaF + NaFO3 + 3H2O 2-
(a) SO 4
2-
(b) SO 3
(c) F2 + 2NaOH  NaF + NaOF + H2O 2- 2
(c) S4 O 6 (d) S2 O 3
(d) 2F2 + 2NaOH  2NaF + OF2 + H2O 133. Concentrated HNO3 reacts with iodine to give
123. Chlorine reacts with dilute NaOH under ordinary (a) HI (b) HOIO2
conditions to give (c) HOI (d) HOIO3
(a) NaCl and NaClO3 (b) NaCl and ClO2
134. Which of the following processes is not feasible
(c) NaCl and NaClO (d) NaCl and Cl2O spontaneously?
124. Chlorine on reaction with hot and concentrated NaOH (a) H2O + F2  HF + HOF
produces (b) H2O + Cl2  HCl + HOCl
(a) NaClO3 and NaClO (b) NaCl and NaClO3
(c) H2O + Br2  2HBr + [O]
(c) NaCl and NaClO4 (d)NaClO3and NaClO4
(d) H2O + I2  2HI + [O]
125. Dry SO2 reacts with Cl2 to produce
135. Tincture iodine is:
(a) S2Cl2 (b) SOCl2
(a) aqueous solution of I2
(c) S(OCl)2 (d) SO2Cl2 (b) solution of iodine in aqueous KI
126. When SO2 gas is passed into chlorine water, the (c) alcoholic solution of I2
products formed are (d) aqueous solution of KI
(a) SCl2 and S2Cl2 (b) H2SO4 and HCl 136. The shape of O2F2 is similar to that of :
(c) SO2Cl2 (d) SOCl2 and HCl (a) C2F2 (b) H2O2
127. Chlorine shows bleaching action in: (c) H2F2 (d) C2H2
(a) dry conditions 137. SiO2 reacts with HF to produce
(b) presence of HCl only (a) SiF4 and H2O (b) Si and HFO2
(c) moist conditions
(c) SiF6 and H2O (d) H2[SiF6] and H2O
(d) none of these
128. The products of the chemical reaction between 138. The etching action of HF does not involve
Na2S2O3, Cl2 and H2O are: (a) formation of SiF4
(b) corrosion of vessel wall
(a) S, HCl, Na2SO4 (b) S, HCl, Na2S
(c) formation of H2SiF6
(c) S, HCl, Na2SO3 (d) S, NaClO3 (d) white marking on laboratory ware.
p-BLOCK ELEMENTS (GROUP 15-18) 53

Physical Properties and Compounds of Xenon of 145. What is the correct order of occurrence (% by weight)
Group 18 Elements in air of Ne, Ar and Kr?
(a) Ne > Ar > Kr (b) Ne > Kr > Ar
(c) Ar > Kr > Ne (d) Ar > Ne > Kr
139. The element which has the highest first ionization
energy is 146. The structure of XeO3F2 is
(a) hydrogen (b) xenon (a) square pyramidal (b) pentagonal bipyramidal
(c) trigonal bipyramidal (d) octahedral
(c) fluorine (d) helium
140. Which of the following forms the least number of 147. Which of the following is planar?
(a) XeO4 (b) XeO3F
compounds?
(a) Helium (b) Argon (c) XeO2F2 (d) XeF4
(c) Krypton (d) Xenon 148. Which of the following compounds is explosive?
141. Which of the following noble gases is used for (a) XeF2 (b) XeF4
cryogenic works?
(c) XeO3 (d) XeF3
(a) Neon (b) Krypton
(c) Helium (d) Argon 149. Among the following molecules, (i) XeO3 (ii) XeOF4
142. Noble gases are difficult to liquefy because their (iii) XeF6 those having same number of lone pairs on
(a) dispersion forces are large Xe are
(b) dispersion forces are small (a) (i) and (ii) only (b) (i) and (iii) only
(c) ionization energies are low (c) (ii) and (iii) only (d) (i), (ii) and (iii)
(d) electron affinities are high 150. Which of the following reactions of xenon compounds
143. Xenon trioxide (XeO3) has a shape of a is not feasible?
(a) XeO3 + 6HF → XeF6 + 3H2O
(a) trigonal bipyramid (b) octahedron
(c) pyramid (d) tetrahedron (b) 3XeF4 + 6H2O → 2Xe + XeO3+12HF + 1.5 O2
144. Which of the following noble gases is the least (c) 2XeF2 + 2H2O → 2Xe + 4HF + O2
polarizable? (d) XeF6 + RbF → Rb [XeF7]
(a) He (b) Ar
(c) Ne (d) Xe
54 p-BLOCK ELEMENTS (GROUP 15-18)

EXERCISE – 2: Previous Years Questions

1. When conc. H2SO4 is heated with P2O5 the acid is (d) HClO3 > HClO2 > HClO4 > HClO
converted to (UP CPMT 2012) 9. Aqueous solutions of hydrogen sulphide and sulphur-
(a) sulphur trioxide dioxide when mixed together, yield (KCET 2013)
(b) sulphur dioxide (a) Sulphur trioxide and water
(c) sulphur (b) hydrogen and sulphurous acid
(d) a mixture of sulphur dioxide and sulphur trioxide (c) sulphur and water
2. Which one of the following statements is not valid for (d) hydrogen peroxide and sulphur
oxoacids of phosphorous? (Manipal 2012) 10. The increases order of reducing power of halogen acid
(a) Orthophosphoric acid is used in the manufacture of is (Manipal 2013)
triple super phosphate (a) HCl < HBr < HF < HI (b) HF < HCl < HBr < HI
(b) Hypophosphorous acid is a diprotic acid (c) HI < HBr < HCl < HF (d) HBr < HCl < HF < HI
(c) All oxoacids contain tetrahedral four coordinated 11. The compound represents phosgene is
phosphorus (Manipal 2013)
(d) All oxo-acids contain at least one P = O unit and (a) phosphine (b) phosphorus trichloride
one P–OH group (c) carbonyl chloride (d)phosphorus oxychloride
3. When Cl2 gas reacts with hot and concentrated sodium
12. Bleaching powder loses its power on keeping for a long
hydroxide solution, the oxidation number of chlorine
time because (KCET 2013)
changes from (CBSE AIPMT 2012)
(a) it changes into calcium hypochlorate
(a) zero to +1 and zero to –5 (b) it changes into calcium chloride and calcium
(b) zero to –1 and zero to +5 hydroxide
(c) zero to –1 and zero to +3 (c) it absorbs moisture
(d) zero to +1 and zero to –3 (d) it changes into calcium chloride and calcium
4. When a colorless gas is passed through bromine water, chlorate
only decolourisation takes places. The gas is 13. The statement that is not correct is (KCET 2014)
(AFMC 2012) (a) hypophosphorus acid reduces silver nitrate to silver
(a) SO2 (b) HBr (b) in solid state PCl5 exists as [PCl4]+ [PCl6]–
(c) HCl (d) H2S (c) pure phosphine in non-inflammable
5. Which of the following is not a peroxyl acid? (d) phosphorous acid on heating disproportionates to
(Manipal 2012) give metaphosphoric acid and phosphine
(a) Per phosphoric acid (b) Per nitric acid 14. The species that is not hydrolysed in water is
(c) Persulphuric acid (d) Perchloric acid (KCET 2014)
6. The mixture of concentrated HCl and HNO3 made in 3 : (a) P4O10 (b) BaO2
1 ratio contains (AIIMS 2013) (c) CaC2 (d) Mg3N2
(a) ClO2 (b) NOCl 15. The correct arrangement of following acids of
(c) NCl3 (d) N2O4 phosphorus in the increasing order of oxidation state of
7. In pyrophosphoric acid the number of hydroxyl groups phosphorus is (Guj CET 2014)
are (UP CMT 2013) (a) hypophosphorus acid (<) orthophosphorus acid <
(a) 2 (b) 3 pyrophosphoric acid
(c) 4 (d) 5 (b) hypophosphorus acid (<) pyrophosphoric acid =
8. The correct order of relative acidity is orthophosphorus acid
(UP CPMT 2013) (c) pyrophosphoric acid (<) hypophosphorus acid <
orthophosphorus acid
(a) HClO > HClO2 > HClO3 > HClO4
(d) pyrophosphoric acid (<) orthophosphorus acid <
(b) HClO4 > HClO3 > HClO2 > HClO
hypophosphorus acid
(c) HClO > HClO4 > HClO2 > HClO3
.
p-BLOCK ELEMENTS (GROUP 15-18) 55

16. Acidity of diprotic acids in aqueous solutions increases 25. Xenon hexafluoride reacts with silica to form a xenon
in the order (CBSE AIPMT 2014) compound X. The oxidation state of xenon in X is
(a) H2S < H2Se < H2Te (b) H2Se < H2S < H2Te (JIPMER 2018)
(c) H2Te < H2S < H2Se (d) H2Se < H2Te < H2S (a) +2 (b) +4
17. Which among the following group 16 elements exists in (c) +6 (d) 0
more than two allotropic states? (JCECE 2014) 26. In which of the following arrangements, the order is not
(a) Polonium (b) Tellurium strictly according to the property written against it?
(c) Selenium (d) Oxygen (AIIMS 2018)
18. The gaseous product formed when HOCl reacts with (a) CO2 < SiO2 < SnO2 < PbO2 (oxidising power)
H2O2 in acidic medium is (Kerala CEE 2014) (b) HF < HCl < HBr < Hl (acidic strength)
(a) H2 (b) Cl2 (c) NH3 > PH3 < AsH3 < SbH3 (basic strength)
(c) O2 (d) HCOl2 (d) B < C < O < N (first ionization enthalpy)
19. Nitrogen dioxide and sulphur dioxide have some 27. Which of the following products will be obtained when
properties in common. Which property is shown by one copper metal is reacted with HNO3? (AIIMS 2018)
of these compounds, but not by the other? (a) NO and N2O5 (b) NO and NO2
(CBSE AIPMT 2015) (c) NO2 and N2O5 (d) HNO2 and N2
(a) Forms acid-rain 28. Which of the following oxyacid does not contain P–O–
(b) Is a reducing agent P bond? (AIIMS 2018)
(c) Is soluble in water (a) Isohypophosphoric acid
(d) Is used as a food-preservative (b) Pyrophosphorus acid
20. Which of the following oxide is most acidic? (c) Diphosphoric acid
(JIPMER 2017) (d) Hypophosphoric acid
(a) As2O3 (b) P2O5 29. The correct order of N-compounds in its decreasing
(c) Sb2O3 (d) Bi2O3 order of oxidation states is (NEET 2018)
21. Among the following compounds, which will produce (a) HNO3, NH4Cl, NO, N2 (b) HNO3, NO, NH4Cl, N2
POCl3 with PCl5? (JIPMER 2017) (c) HNO3, NO, N2, NH4Cl (d) NH4Cl, N2, NO, HNO3
(a) Only O2 30. Which of the following chemicals are used to
(b) O2 and CO2 manufacture methyl isocyanate that caused “Bhopal
(c) CO2, O2 and P4O10 Gas Tragedy” ? (JIPMER 2018)
(d) SO2, H2O, H2SO4,P4O10 (i) Methylamine (ii) Phosgene
22. In which of the following compounds, sulphur show (iii) Phosphine (iv) Dimethylamine
maximum oxidation number? (JIPMER 2017) (a) (i) and (ii) (b) (iii) and (iv)
(a) H2SO4 (c) (i) and (iii) (d) (ii) and (iv)
(b) SO3 31. Which of the following pair behaves as strong and
(c) H2S2O7 weak base hydride respectively? (JIPMER 2018)
(d) All have same oxidation number for sulphur (a) NH3, PH3 (b) NH3, BiH3
23. Name the gas that can readily decolourise acidified (c) PH3, BiH3 (d) BiH3, AsH3
KMnO4 solution. (NEET 2017) 32. Conversion of oxygen into ozone is non-spontaneous at
(a) CO2 (b) SO2 (AIIPMT 2018)
(c) NO2 (d) P2O5 (a) low temperature
24. A gas ‘X’ is used in filling balloons for meteorological (b) all temperature
observations. It is also used in gas-cooled nuclear (c) high temperature
reactors. Here, the gas X is (AIIMS 2018) (d) room temperature
(a) neon (b) argon 33. Among the following, the correct formula of Marshall’s
(c) krypton (d) helium acid is (JIPMER 2018)
(a) H2S2O6 (b) H2S2O8
(c) H2SO4 (d) H2SO5
56 p-BLOCK ELEMENTS (GROUP 15-18)

34. Which is the correct order of thermal stability for H 2E 41. Which of the following statements is not true for
(E = O, S, Se, Te and Po)? (NEET 2019) halogens? (NEET 2019)
(a) H2O  H2S  H2Se  H2Te  H2 Po (a) All but fluorine show positive oxidation states
(b) All are oxidizing agents
(b) H2 Po  H2Te  H2Se  H2S  H2O
(c) All form monobasic oxyacids
(c) H2Se  H2Te  H2 Po  H2O  H 2S (d) Chlorine has the highest electron-gain enthalpy
(d) H2S  H2O  H2Se  H 2Te  H2 Po 42. Which of the following inert gas participate in
35. Which of the following statement is correct for oleum? chemicals reaction? (AIIMS 2019)
(AIIMS 2019) (a) Xe (b) He
(a) It is prepared by absorption of SO3 in conc. H2SO4 (c) Ne (d) None of the above
(b) It contains O–O groups 43. In how many of the following number of lone at central
(c) It has six OH groups atom is zero
(d) None of the above XeO3, XeO2F2, XeO4, XeO3F2, XeO3F6 ?
36. Correct order of bond dissociation energy is (AIIMS2019)
(a) 2 (b) 3
(AIIMS 2019)
(c) 4 (d) Zero
(a) Br2 > Cl2 (b) F2 > Cl2
(c) l2 > F2 (d) F2 > l2 44. Which of the following rare gas is the abundant in air?
37. Yellow colour of chlorine water fades because of (JIPMER 2019)
(a) He (b) Ne
(AIIMS 2019)
(c) Ar (d) Kr
(a) Form action of chlorine HCl and HOCl
45. Identify the incorrect statement related to PCl5 from the
(b) Chlorine gas escapes
(c) ClO2 + H2 following: (NEET 2019)
(d) Cl2O (a) Two axial P-Cl bonds make an angle of 180º with
each other
38. Affinity for hydrogen decreases in the group from
(b) Axial P-Cl bonds are longer than equatorial P-Cl
fluorine to iodine. Which of the halogen acids should
bonds.
have highest bond dissociation enthalpy?
(c) PCl5 molecule is non-reactive.
(AIIMS 2019)
(a) HF (b) HCl (d) Three equatorial P-Cl bonds make an angle of 120º
with each other.
(c) HBr (d) HI
46. A compound ‘X’ upon reaction with H2O produced a
39. What is X and Y in the below reaction? (AIIMS 2019)
colourless gas ‘Y’ with rotten fish smell. Gas ‘Y’ is
8NH3  3Cl2  X
(Excess) absorbed in a solution of CuSO4 to give Cu3P2 as one of
the products. Predict the compound ‘X’
NH3 3Cl2  Y
(Excess) (NEET (Odisha)2019)
(a) X = 6NH4 Cl + N 2 ; Y = NCl3 + 3HCl (a) Ca3P2 (b) NH4Cl
(b) X = NCl3+ 3HCL; Y = 6NH4 Cl + N2 (c) As2O3 (d) Ca3(PO4)2
(c) X = NCl3 + N2 ; Y 6 NH4 Cl + 3HCL 47. Which of the following oxoacids of phosphorus has
(d) X = 6NH4 Cl + 3HCl; Y = NCl3 + N2 strongest reducing property? (NEET (Odisha)2019)
40. A green yellow gas reacts with an alkali metal (a) H4P2O7 (b) H3PO3
hydroxide to form a halite which can be used in (c) H3PO2 (d) H3PO4
fireworks and safety matches. The gas and halite are, 48. In which of the following, oxidation state of
respectively (AIIMS 2019) phosphorus is +3? (JIPMER 2019)
(a) Br2 , KBrO3 (a) Orthophosphoric acid (b) Pyrophosphoric acid
(b) Cl2, KClO3 (c) Orthophosphrous acid (d) Meta Phosphoric acid
(c) I2 , NaIO3
(d) Cl2 , NaClO3
p-BLOCK ELEMENTS (GROUP 15-18) 57

49. Urea reacts with water to form A which will 50. In which on of the following arrangements the given
decomposes to form B. B when passed through Cu2+ sequence is not strictly according to the properties
(aq), deep blue color solution C is formed. What is the Indicated against it? (NEET 2021)
formula of C from the following. (NEET 2020) (a) CO2<SIO2<SnO2<PbO2 : Increasing oxidizing power
(a) Cu(OH)2 (b) CuCO3. Cu(OH)2 (b) HF<HCl<HBr<HI : Increasing acidic strength
(c) CuSO4 (d) [Cu(NH3)4]+2 (c) H2O<H2S<H2Se<H2Te : Increasing pKa values
(d) NH3<PH3<AsH3<SbH3 : Increasing acidic character
58 p-BLOCK ELEMENTS (GROUP 15-18)

EXERCISE – 3: Achiever’s Section

Single Answer Type Questions
1. The best reducing agent among the following is (c) 2.5 and 3.0 (d) 3 in both
(a) NH3 (b) SbH3 8. NH4NO2 NH4NO2 on heating gives
(c) PH3 (d) AsH3 (a) N2O (b) HNO3
2. Which of the following compounds does not form (c) N2 (d) N2H4
ammonia on heating? 9. Phosphorus is obtained by
(a) (NH4)2 SO4 (b) NH4Cl (a) reducing phosphate rock with coke at a high
(c) (NH4)2 CO3 (d) NH4NO2 temperature in the presence of silica in an electric
3. N2 is passed through overheated CaC2. Which of the furnace
following options is correct for the product formed? (b) reducing phosphate rock with sulphur and alumina
(I) State of hybridization of C is sp. (c) reducing phosphate rock with silica and iron oxide
(II) Urea is an intermediate formed during hydrolysis in an electric furnace
of the above product. (d) reducing phosphatic fertilizers with boron and
(III) Anion present in the product is not a pseudo alumina in an electric furnace
halide ion. 10. White phosphorus on reaction with limewater gives
(IV) Hydrolysis of the product gives rise to NH3 gas calcium salt of an acid (A) along with a gas (X). Which
slowly. of the following is correct?
(a) I, II and III (b) III and IV (a) (A) on heating gives (X) and O2
(c) I, II and IV (d) None of the above (b) The bond angle in (X) is less than that in case of
4. Which of the following compounds give NH3 on ammonia
heating? (c) (A) is a dibasic acid
(d) (X) is more basic than ammonia
(I) NH4NO3 (II) NH4NO2
11. White phosphorus reacts with calcium to give a certain
(III) (NH4)2 Cr2O7 (IV)(NH4)2CO3 compound. This compound on hydrolysis produces
(V) Mg (NH4) PO4 (a) P2H4 (b) PH3
(a) I, IV (b) II, V (c) P2 (d) P4O10
(c) IV only (d) IV, V 12. Which is not correct regarding the Holme’s signal?
5. Pure nitric acid is a colourless liquid, but on exposure to (a) PH3 catches fire in contact of air spontaneously.
light it turns brownish due to (b) P2H4 catches fire in contact of air spontaneously.
(a) slight decomposition of HNO3 into O2 (c) PH3, C2H2 and P2H4 are formed together
(b) slight decomposition of HNO3 into NO2 and O2 (d) All the gases burn together
(c) the formation of N2O 13. Which of the following does not have S—S linkage?
(d) the formation of H3O+ and NO
(a) S2 O82  (b) S2 O 62 
6. When AgNO3 is heated strongly above 800°C, it
produces (c) S2 O 52  (d) S2 O 32 
(a) Ag2O, NO and NO2 14. The number of S—S bonds in sulphur trioxide trimer
(b) Ag, NO2 and O2 S3O9 is:
(c) Ag2O, NO2 and O2 (a) three (b) two
(d) Ag, NO and O2 (c) one (d) zero
15. Na2SO3 on being heated with sulphur produces
7. In the cationic parts of solid N2O5 and solid N2O4, the
(a) Na2S2O3 (b) Na2S4O6
bond order of N–O are, respectively,
(c) Na2SO4 (d) Na2S5
(a) 3.0 and 2 (b) 2 and 3
p-BLOCK ELEMENTS (GROUP 15-18) 59

16. When H2S gas is passed into aqueous sulphur dioxide 23. Dry Cl2 reacts with dry SO2 to form:
(a) a clear solution of H2SO4 is formed (a) thionyl chloride
(b) SO2 is converted into a yellow precipitate of (b) sulphuryl chloride
sulphur (c) sulphur dichloride
(c) H2S is converted into a yellow precipitate of (d) sulphur monochloride
sulphur 24. When F2 reacts with hot and conc. alkali, then
(d) both SO2 and H2S are converted into a yellow
following will be obtained:
precipitate of sulphur
(i) OF2 (ii) O2
17. NH4Cl is preferred to NaCl for the preparation of HCl
by the action of concentrated H2SO4 because (iii) H2O (iv) NaF
(a) NH4Cl is not expensive (a) (i), (iii) and (iv)
(b) NH4Cl is very volatile (b) (ii) and (iii) only
(c) NH4HSO4 formed during the reaction is insoluble (c) (ii), (iii) and (iv)
but NaHSO4 is soluble (d) all of these
(d) NH4HSO4 formed during the reaction is soluble but 
25. The oxidation state of xenon atom in XeF4, HXeO 4
NaHSO4 is insoluble
and Na4XeO6 are respectively:
18. The property of halogens, that indicated incorrect is:
(a) F > Cl > Br > I ........ ionisation energy (a) + 4, + 6, + 6 (b) + 4, + 6, + 7
(b) F > Cl > Br > I ......... electron affinity (c) + 4, + 6, + 8 (d) + 4, + 5, + 8
(c) F > Cl > Br > I ........ electronegativity 26. The shape of XeO2F2 molecule is:
(d) I > Br > Cl > F ........ density in liquid state (a) trigonal bipyramidal
19. Liquid I2 Cl6 has the structure (b) square planar
(c) tetrahedral
(d) see-saw
(a)

Assertion and Reason Types questions

(b) [ICl2]+[ICl4]–
(c) monometric (A) If both assertion and reason are true and
(d) None of these reason is the correct explanation of the assertion.
20. When iodine is treated with a mixture of NaF, NaBr (B) If both assertion and reason are true but reason is not the
and NaCl in water, it gives correct explanation of the assertion.
(a) a mixture of F2, Cl2 and Br2 (C) If assertion is true but reason is false.
(D) If assertion is false but reason is true.
(b) Cl2
(c) Br2 27. Assertion: HNO3 is a stronger acid than HNO2.
(d) no reaction
Reason: In HNO3 there are two nitrogen to oxygen
21. HClO4 + P2O5  (A) + (B)
bonds whereas in HNO2 there is only one.
(A) and (B) are:
(a) A (b) B
(a) HClO3, H3PO4 (b) Cl2O6, HPO3
(c) C (d) D
(c) ClO2, H3PO4 (d) Cl2O7 , HPO3 28. Assertion: Although PF5, PCl5 and PBr5 are known, the
22. Which of the following oxides of chlorine is obtained pentahalides of nitrogen have not been observed.
by passing dry chlorine over silver chlorate at 90 0C? Reason: Phosphorous has a lower electronegativity
(a) Cl2O (b) ClO3 than nitrogen.
(a) A (b) B
(c) ClO2 (d) ClO4
(c) C (d) D
60 p-BLOCK ELEMENTS (GROUP 15-18)

29. Assertion: O3 has a fishy smell.

Reason: It absorbs red part of the visible light.
(a) A (b) B
(c) C (d) D
30. Assertion: The electronic structure of O3 is

Reason: The following structure is not allowed because

the octet around O cannot be expanded.

(a) A (b) B
(c) C (d) D
p-BLOCK ELEMENTS (GROUP 15-18) 61

Notes:

Find Answer Key and Detailed Solutions at the end of this book
:

p-BLOCK ELEMENTS (GROUP 15-18)

 12
METALLURGY
Chapter 12

Metallurgy

1. Introduction extracted are called ores. An ore is usually contaminated with

The compound of a metal found in nature is called a mineral. The earthy or undesired materials known as gangue. So all minerals
minerals from which metal can be economically and conveniently are not ores but all ores are minerals.

Table 12.1 : Some Important Ores of Metals

Metal Ores Composition
Aluminium Bauxite Al2O3 .2H2O
Diaspore Al2O3.H2O
Corundum Al2O3
Iron Haematite Fe2O3
Magnetitie Fe3O4
Siderite FeCO3
Iron pyrite FeS2
Limonite Fe2O3.3H2O
Copper Copper pyrite CuFeS2
Copper glance Cu2S
Cuprite Cu2O
Malachite CuCO3.Cu(OH)2
Azurite 2CuCO3.Cu(OH)2
Zinc Zinc blende or Sphalerite ZnS
Calamine ZnCO3
Zincite ZnO
Lead Galena PbS
Anglesite PbSO4
Cerussite PbCO3
Magnesium Carnallite KCl.MgCl2 6H2O (K2MgCl4.6H2O)
Magnesite MgCO3
Dolomite MgCO3 CaCO3
Epsomsalt (Epsomite) MgSO4 7H2O
Langbeinite K2Mg2(SO4)3
Tin Cassiterite (Tin Stone) SnO2
Silver Silver glance (Argentite) Ag 2 S
Pyrargyrite (Ruby Silver) Ag3SbS3
Chlorargyrite (Horn silver) AgCl
Stephanite Ag5SbS4
Proustite Ag 3 AsS 3

SCAN CODE
Metallurgy
64 METALLURGY

2. Metallurgy 2.2.2 Electromagnetic Separation

The scientific and technological process used for extraction/
isolation of the metal from its ore is called as metallury.
The isolation and extraction of metals from their ores involve the
following major steps :
It is based on differences in magnetic properties of the ore and the
gangue. It is used when either the ore or the impurities associated
with it are magnetic in nature.
A magnetic separator consists of a belt (of leather or brass) moving
over two rollers, one of which is magnetic. When the powdered
ore is dropped on the belt at the other end, magnetic component
of the ore is attracted by the magnetic roller and falls nearer to the
roller while the non-magnetic impurities fall away from it.

Fig. 12.1 : Steps in metallurgical process

2.1 Crushing and Grinding of Ores

The ore is first crushed by jaw crushers and ground to a powder
(pulverisation of the ore) in equipments like ball mills and stamp
mills.
2.2 Concentration of Ores
The removal of unwanted impurities like sand, clay etc., from
the ore is called dressing, concentration or benefaction of ore.
There are several methods avalible for concentration of ores. The
selection of the method depends upon the physical properties of
metal and the gangue.
Fig. 12.3 : Electromagnetic separation
Chromite ore (FeO.Cr2O3) is separated from non-magnetic sillicious
impurities and cassiterite ore (SnO2) is separated from magnetic
Wolframite (FeWO4 + MnWO4).
2.2.3 Froth Floatation Process
This method is commonly used for the concentration of the low
grade sulphide ores like galena, PbS (ore of Pb), copper iron pyrites
Cu2S.Fe2S3 or CuFeS2 (ore of copper), zinc blende, ZnS (ore of
zinc) etc.

2.2.1 Hydraulic Washing or Gravity Separation

It is based on the difference in the densities of the gangue and
ore particles. In this, the powdered ore is agitated with water or
washed with a upward stream of running water, the lighter
particles of sand, clay etc are washed away leaving behind
heavier ore particles.

Fig. 12.2 : Hydraulic washing

Fig. 12.4 : Froth floatation method

SCAN CODE
Metallurgy
METALLURGY 65
This method is based on the fact that gangue and ore particles (ii) Extraction of Gold and Silver :
have different degree of wetability with water and pine oil. The In the metallurgy of silver and gold, the respective metal/ore is
gangue particles are preferentially wetted by water while the ore leached with a dilute solution of NaCN or KCN in the presence of
particles are wetted by oil. air (or O2) form which the metal is obtained later by displacement
The ore is powder and converted into a suspension by dissolving with zinc scrap.
in water. To this suspension, collectors and froth stabilisers are

added. Collectors (e. g., pine oils, fatty acids, xanthates, etc.)  4  Ag  CN 2   4OH 
4Ag  8CN   2H 2 O  O 2 
enhance non-wettability of the mineral particles and froth
stabilisers (e. g., cresols, aniline) stabilise the froth.  2
2  Ag  CN 2   Zn 
  Zn  CN 4   2Ag
The ore particles become wet by oils while the gangue particles
by water. A rotating paddle agitates the mixture and froth is formed This is also known as Mac-Arthur Forest Cyanide process.
which carries the ore particles. The froth is skimmed off, then
dried for recovery of the ore particles.
When a mineral contains other minerals as impurities. The addition 2.3 Extraction of Crude Metal from
of these agents activates or depresses the flotation property of Concentrated Ore
other minerals present as impurities and thus helps in separating
Before reduction, the concentrated ore must be converted into a
the impurities. For example galena (PbS) usually contains the
form which is more suitable for reduction. Usually the sulphide
minerals namely zinc blende (ZnS) and pyrites (FeS2) as impurities. ore is converted to the metal oxide before reduction, because
Flotation is carried out by using potassium ethyl xanthate (used metal oxides are easier to reduce. Thus isolation of metals from
as a collector) along with NaCN and Na2CO3 (used as depressing concentrated ore involves two major steps as given below:
agent). It selectively prevents ZnS from coming to the froth but (i) Conversion to metal oxide
allows PbS to come with the froth.
(ii) Reduction of the metal oxide to metal.
2.2.4 Leaching 2.3.1 Conversion to Metal Oxide
Leaching is used if the ore is soluble in some suitable solvent. Conversion of ore into metal oxide is carried out in two ways
(i) Alumina from Bauxite : depending upon the nature of ore.
The principal ore of aluminium, bauxite, usually contains SiO2, 2.3.1.1 Calcination
iron oxides and titanium oxide (TiO2) as impurities. Concentration It is a process of heating the concertrated ore strongly in a limited
is carried out by digesting the powdered ore with a concentrated supply of air or in the absence of air. The process of calcination
solution of NaOH at 473-523 K and 35 - 36 bar pressure. This way, brings about the following changes :
Al2O3 is leached out as sodium aluminate (and also SiO2 as sodium (a) The carbonate ore gets decomposed to form the oxide of the
silicate) leaving behind the impurities, iron oxide and titanium metal, e.g.,
oxide.
FeCO3 (siderite) FeO + CO2;
Al2O3(s) + 2NaOH (aq) + 3H2O (l) 2Na [Al(OH)4] (aq)
PbCO3 (cerrusite)) PbO + CO2
The aluminate in solution is neutralised by passing CO2 gas and
hydrated Al2O3 is precipitated. At this stage, the solution is seeded CaCO3 (calcite ore/lime stone) CaO + CO2
with freshly prepared samples of hydrated Al2O3 which induces
ZnCO3 (calamine) ZnO + CO2
the precipitation of Al(OH)3.
(b) Water of crystallisation present in the hydrated oxide ore
2Na[Al(OH)4] (aq) + CO2(g) Al2O3.xH2O(s) + 2NaHCO3 (aq) gets lost as moisture, e.g.,
The sodium silicate remains in the solution and hydrated alumina
2Fe2O3.3H2O (limonite) 2Fe2O3 (s) + 3H2O(g)-
is filtered, dried and heated to give back pure Al2O3 :
Al2O3.2H2O (bauxite) Al2O3 (s) + 2H2O(g)-
1470 K/calcination
Al2O3.xH2O(s)   Al2O3 (s) + xH2O(g) (c) Organic matter, if present in the ore, gets expelled and the ore
or1200o C becomes porous. Volatile impurities are removed.
These steps comprises the Bayer’s process.

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2.3.1.2 Roasting 2.3.3 Pyrometallurgy

It is a process of heating the concentratd ore (generally sulphide The oxides of less electropositive metals like Pb, Zn, Fe, Sn, Cu
ore) strongly in the excess of air or O2 below its melting point. etc. are reduced by strongly heating them with coal or coke, in the
Roasting is an exothermic process, once started it does not require blast furnace.
additional heating. “The process of expracting the metal by heating the metal oxide
Some of the reactions involving sulphide ores during roasting : with a suitable reducing agent is called pyrometallurgy.”

Flux : The substance used for remove impurities from the ore to
2PbS + 3O2   2PbO + 2SO2 ; from fusible material (slag) is called flux.
 Acidic flux : Borax, SiO2 (remove basic impurity)
2ZnS + 3O2  2ZnO + 2SO2

Basic impurity + Flux  slag
2Cu2S + 3O2  2Cu2O + 2SO2
(a) MgCO3 + SiO2  MgSiO3 + CO3 ¯
Some times roasting may not bring about complete oxidation.
(b) FeO + SiO2  FeSiO3
2 CuFeS2 (copper pyrite) + 4O2 Cu2S + 2FeO + 3SO2
Basic flux : MgO, MgCO2, CaCO3 (remove acidic impurity)
The reduction of the sulphide ore directly into metal by heating it
Slag : Fusible material formed during reduction process.
in air or O2 is called by various names like self-reduction, auto-
(gangue) Acidic impurity + flux  slag
reduction, air-reduction etc. The SO2 produced is utilised for
manufacturing of H2SO4. (a) SiO2 + CaCO3  CaSiO3 + CO2 ¯
(b) P2O5 + 3CaO  Ca3(PO4)2

3. Thermodynamic Principles
of Metallurgy
The basic concepts of thermodynamics are quite helpful in
selecting which element will be the most suitable reducing agent
for a particular oxide during a metallurgical operation. It can also
predict the optimum temperature at which the reduction can occur
smoothly.
For any reaction or process, Gibb’s Helmholtz free energy change
 G  is given by the equation,

G  H  TS ....... (i)

Fig. 12.5 : Reverberatory furnace
Roasting is done in reverberatory furnace with air vents open
while calcination is done in reverberatory furnace with air vents
closed or some times partially closed.
2.3.2 Reduction of Metal Oxide to the Metal :
Reduction of the metal oxide usually done by heating it with
reducing agent like C, CO or even another metal. The reducing
agent (e.g., carbon) combines with the oxygen of the metal oxide
and reduce metal oxide to metal.
When reduction is done with carbon or carbon monoxide, it is
known as smelting.
M x O y  yC 
 xM  y CO
where H is the enthalpy change and S is the entropy change
and T is the absolute temperature at which the reaction is carried
out. For the feasibility of any reaction at any temperature the
value of G must be negative at the temperature. The free energy
change is also related to the equilibrium constant ‘K’ of the reaction
at temperature T by the following equation,
G = – RT ln K ........ (ii)
A negative G implies a + ve K in the equation. This can happen
only if the reaction proceeds towards the products.
The following conclusions can be drawn :
(i) Greater the negative value of free energy change  G  , more
spontaneous is the reaction.

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Table 12.2 : Condition for Spontaneous Process Consider the formation of a metal oxide (MxO).
2xM (s) + O2(g)  2 MxO(s)
Favourable conditions In this reaction, there is decrease in the value of Sº as MxO is
ΔG TΔS
solid and O2 is a gas, i.e., S is negative. Thus, if temperature is
– ve + ve Any temperature increased, TSº becomes more negative.
– ve – ve H  T S As in the equation
(Temp. should be low) Gº = Hº – TSº
+ ve + ve TS  H TSº is subtracted, therefore, Gº becomes less negative, i.e., Gº
(Temp. should be high) is likely to increase with rise in temperature and this trend is
confirmed from the curves.
(i) The slope of the curves of the formation of metal oxides is
(ii) If two reactions are put together in a system and the net G
+ve because Gº becomes less negative or increases with
of both the reactions is –ve, the overall reaction will occur,
the rise in temperature.
i.e., a reaction with G positive can be made to occur if it is
(ii) Each curve is a straight line except when some change takes
coupled with another reaction having a large negative G place in phase (s  l or l  g). The temperature at which
so that the net G of both the reactions is negative. such a change occurs is indicated by an increase in the slope
Such coupling reactions can be easily understood through on the +ve side. For example, in the Zn–ZnO curve, the melting
Ellingham diagram. of zinc is indicated by an abrupt increase in the +ve slope at
temperature 692 K.
(iii) In the case of less reactive metals like silver and mercury, Gº
3.1 Ellingham Diagram becomes positive at high temperatures. It indicates that both
Ellingham diagram consists of graphs which represent the silver oxide (Ag2O) and mercury oxide (HgO) are unstable
variation of standard free energy with temperature of the formation and decompose at high temperature.
of oxides of various elements, i.e., of f G vs T. Similar plots can
2Ag 2 O Heat
 4Ag  O 2
also be plotted for sulphides and halides.
These were first plotted by H.J.T. Ellingham. These diagrams help 2HgO Heat
 2Hg  O 2
us in predicting the feasibility of thermal reduction of an ore. (iv) In the curve of CO, Gº decreases as Sº increases. This is
indicated by the downward trend.
(v) Any metal oxide with lower value of Gº is more stable than
a metal oxide with higher Gº. This implies that the metal
oxide placed higher in the diagram can be reduced by the
metal involved in the formation of the oxide placed lower in
the diagram. For example, Cr2O3 can be reduced by Al metal
but Al2O3 cannot be reduced by Cr.
Cr2O3 + 2Al  Al2O3 + 2Cr
Thus, the relative tendency of the various metals to act as
reducing agents is :
Ca > Mg > Al > Cr > Zn > Fe > Ni
3.2 Applications of Pyrometallurgy
3.2.1 Reducing Nature of Carbon
Carbon in the form of coke, charcoal or carbon monoxide is used
as a reducing agent in pyrometalurgical operations. Such a
reduction process used in the extraction of a metal is termed
Fig. 12.6 : Ellingham diagram for formation of some oxides smelting.
When carbon is to act as a reducing agent, the following three
reactions are possible :

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C(s) + O2(g)  CO2(g) ...... (i)
2C(s) + O2(g)  2CO(g) ...... (ii)
2CO(g) + O2(g)  2CO2(g) ...... (iii)
In the first reaction (formation of CO2) there is hardly any change
in entropy, i.e., Sº  0 and therefore, Gº remains nearly the same
with rise in temperature, i.e., Gº is independent of temperature.
Fig. 12.7 : Ellingham diagram for the reducing nature of carbon
In the second reaction (formation of CO), there is increase in
entropy (Sº is positive) and therefore, Gº becomes more negative
with increase in temperature.
However, in third reaction, there is decrease in entropy
(Sº is negative) and therefore, Gº becomes less negative with
increase in temperature.
The above observations can be seen in Fig. The three curves
have been found to intersect at 983 K. It implies that above this
temperature, the reaction (ii) is most suitable. It means that carbon
can reduce any metal oxide at very high temperatures and is then
itself oxidised to CO. However, the reduction with carbon at high
temperatures is not preferred in all cases due to the following
reasons :
(a) It involves high cost.
(b) Some metals react with carbon at high temperatures and form
carbides.
(c) There are many practical difficulties in the maintenance of
high temperature.
3.2.2 Extraction of Iron from its Oxides
Oxide ores of iron, after concentration through calcination/roasting
are mixed with limestone and coke and added into a Blast furnace
from its top. Here, the oxide is reduced to the metal.
Thermodynamics helps us to understand how coke reduces the
oxide and why this furnace is chosen.
In the Ellingham diagram, there are three curves which illustrate
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the formation of ferric oxide from Iron, formation of CO from carbon
and formation of CO2 from CO. The curves cross each other at
1073 K.
Fig. 12.8 : Ellingham diagram for the reduction of haematite
Above 1073 K, Gº for the formation of Fe2O3 is less negative
than Gº for the formation of carbon monoxide from carbon. Thus,
above 1073 K, carbon (coke) can reduce Fe2O3, i.e., rGº for the
reaction,
 1073 K
Fe2O3 (s) + 3C(s)  2Fe(s) + 3CO(g)
is negative.
Below 1073 K, Gº for formation of CO from carbon is less negative
than Gº for the formation of Fe2O3. rGº for the reduction of
Fe2O3 with carbon will be positive and hence, reduction is not
possible. However, it is observed from the diagram that Gº of
formation of CO2 from CO is more negative than Gº of formation
of Fe2O3. This means that Fe2O3 can be reduced by CO below
1073 K, i.e., rGº is negative for the following reaction.
 1073 K
Fe2O3 (s) + 3CO(g)  2Fe(s) + 3CO2(g)
Thus, in the blast furnace, reduction of Fe2O3 occurs in different
temperature ranges either below 1073 K by carbon monoxide or
above 1073 K by carbon (coke).
In the Blast furnace, reduction of iron oxides takes place in different
temperature ranges. Hot air is blown from the bottom of the furnace
and coke is burnt to give temperature upto about 2200K in the
lower portion itself. The burning of coke therefore supplies most
of the heat required in the process. The CO and heat moves to
upper part of the furnace. In upper part, the temperature is lower
and the iron oxides (Fe2O3 and Fe3O4) coming from the top are
reduced in steps to FeO. Thus, the reduction reactions taking
place in the lower temperature range and in the higher temperature
range, depend on the points of corresponding intersections in
METALLURGY 69
content (about 3%) and is extremely hard and brittle.
the  r G o vs T plots.
3.2.3 Theory of Reduction of ZnO
Ellingham diagram reveals that the curves involving the formation
of ZnO and carbon monoxide cross each other at about 1270 K.

Fig. 12.10 : Ellingham diagram for the reduction of ZnO

There is sudden increase in the value of Gº for the formation of

ZnO above 1180 K. This is due to the fact that zinc begins to boil
at this temperature. Above 1270 K, rGº of the following equation,
 1270 K
ZnO(s) + C(s)  Zn(g) + CO(g)
is considerable negative and thus, reduction of ZnO with coke
occurs easily.

Fig. 12.9 : Blast furnace 4. Electrochemical Principles

of Metallurgy
At 500 – 800 K temperature range in the blast furnace: Just like principles of thermodyamics are applied to pyrometallurgy,
3Fe2 CO3  CO 
 2Fe3O3  CO2 the electrochemical principles are applied in the electrolytic
reduction of a molten metal salt. This could be understood through
Fe3CO4  4CO 
 2FeO  4CO2 the equation,

Fe 2CO3  CO 
 2FeO  CO2 G o   nFE o
here n is the number of electrons and EO is the electrode potential
At 900 – 1500 K temperature range in the blast furnace:
of the redox couple formed in the system.
C  CO2 
 2CO More reactive metals have large negative values of the electrode
potential. So their reduction is difficult.
FeO  CO 
 Fe  CO2
In simple electrolysis, the Mn+ ions are discharged at negative
Limestone removes silicate impurity of the ore as slag. The slag is electrodes (cathodes) and deposited there. Sometimes a flux is
in molten state and separates out from iron. added for making the molten mass more conducting.
The iron obtained from Blast furnace contains about 4% carbon
and many impurities in smaller amount (e.g., S, P, Si, Mn). This is
known as pig iron and cast into variety of shapes. Cast iron is
different from pig iron and is made by melting pig iron with scrap
iron and coke using hot air blast. It has slightly lower carbon

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The electrolysis of the molten mass is carried out in an electrolytic
cell using carbon electrodes. The oxygen liberated at anode reacts
4.1 Application of Electrolysis with the carbon of anode producing CO and CO2. This way for
Electrolytic reduction is mainly used for the extraction of highly each kg of aluminium produced, about 0.5 kg of carbon anode is
electropositive metals. burnt away. The electrolytic reactions are :
Electrolysis is carried out in a large cells and a small amount of Cathode : Al3+ (melt) + 3e– Al (l)
another suitable electrolyte is added which :
Anode : C(s) + O2– (melt) CO (g) + 2e–
(a) Lowers the melting point of the main electrolyte
C(s) + 2O2– (melt) CO2(g) + 4e–
(b) Enhances its conductivity
(c) Reduces corrosion troubles
4.1.1 Manufacture of Metallic Sodium 5. Purification or Refining of
(Down’s Process) Metals
Molten NaCl containing a little CaCl2 is electrolyzed between Metals obtained by reducing processes still contains some
graphite anode and iron cathode. The various reactions that take objectionable impurities and have to be refined. Refining
place are : techniques vary widely from metal to metal and also depend on
the use to which a metal has to be put.

On Fusion : NaCl  Na   Cl
(Ions become mobile)
5.1 Liquation Process
On Electrolysis : At Cathode : Na   e  
 Na
This process is used for the purification of the metal, which itself
At Anode : 2Cl– 
 Cl2 (g) + 2e– is readily fusible, but the impurities present in it are not, i.e., the
impurities are infusible. In other words, we can say that the melting
4.1.2 Electrolytic Reduction of Alumina
point of the metal to be purified should be lower than than of each
(Hall-Heroult process) of the impurities associated with the metal. This process is used
The purified Al2O3 is mixed with Na3AlF6 (cryolite) or CaF2 for the purification of Sn and Zn, and for removing Pb from Zn-Ag
(fluorspar) which lowers the melting point of the mixture and alloy, which is obtained at the end of Parke’s process and contains
increases conductivity. The fused matrix is electrolysed. Steel Pb as impurity.
cathode and graphite anode are used. The graphite anode is useful
for reduction to the metal. The overall reaction may be taken as : 5.2 Distillation Process
2Al2O3 + 3C 4Al + 3CO2
This process is used to purify those metals which themselves are
volatile and the impurities in them are nonvolatile and vice-versa.
Zn, Cd and Hg are purified by this process.

5.3 Zone Refining Method

This process is used when metals are required in very high purity,
for specific application.

Fig. 12.11 : Electrolytic cell for extraction of aluminium

Fig. 12.12 : Zone refining method

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For example pure Si and Ge are used in semiconductors and hence ion (Al3+), and at the cathode (top layer), these ions are reduced
are purified by this method. Zone refining method is based on the to the pure metal. In operation, molten metal is added to the bottom
principle that an impure molten metal on gradual cooling will of the cell and pure aluminum is drawn off the top. Aluminium
deposit crystals of the pure metal, while the impurities will be left obtained is 99.98% pure.
in the remaining part of the molten metal. At anode : Al Al3+ + 3e–
At cathode : Al3+ + 3e– Al
5.4 Chromatographic Methods
This method is based on the principle that different components 5.6 Vapour Phase Refining
of a mixture are differently adsorbed on an adsorbent. The mixture
is put in a liquid or gaseous medium which is moved through the In this method, the metal is converted into its volatile compound
adsorbent. Different components are adsorbed at different levels and then collected. It is then heated so that it gets decomposed to
give pure metal. So, following two requirements are essential for
on the column. Later the adsorbed components are removed
(eluted) by using suitable solvent (eluant). vapour phase refinning.
(i) The metal should form a volatile compound with an available
reagent.
(ii) The volatile compound should be easily decomposable, so
that the recovery is easy.
5.6.1 Refining of Nickel - Mond Process
In this process, nickel is heated in a stream of carbon monoxide
forming a volatile complex named as nickel tetracarbonyl. This
complex is decomposed at higher temperature to obtain pure metal.
330 350 K
 Ni  CO 4
Ni  4CO 

450 470K
Ni  CO 4 
 Ni  4CO

5.6.2 Refining of Zr and Ti - Van Arkel Method

This method is very useful for removing all the oxygen and nitro-
gen present in the form of impurity in certain metals like Zr and Ti.
The crude metal is heated in an evacuated vessel with iodine.
The metal iodide being more covalent, volatilises:
Zr  2I2  ZrI 4
The metal iodide is decomposed on a tungsten filament, electri-
cally heated to about 1800K. The pure metal deposits on the
filament.
Fig. 12.13 : Chromatography method
ZrI 4  Zr  2I2

5.5 Electrolytic Refining

Some metals such as Cu, Ni, and Al are refined electrolytically. The
Hoope’s process is a process for the electrolytic refining of
aluminum. Impure Al forms the anode and pure Al forms the
cathode of the Hooper’s cell which contains three liquid layers.
The bottom layer is molten impure Al, the middle is a fused salt
layer containing aluminum fluoride, and the top layer is pure Al.
At the anode (bottom layer), Al passes with solution as aluminum

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6. Extraction of Some Metals

6.1 Aluminium (Al)
Extraction : Aluminium is mainly isolated from bauxite ore which
is generally contaminated with ferric oxide and silica. The removal
of ferric oxide and silica from bauxite ore is essential before it is
subjected to electrolysis. Thus, the extraction of aluminium from
bauxite ore involves the following three steps.
(i) Purification of bauxite ore, i.e., removal of ferric oxide and
silica.
(a) Baeyer’s process : This process is mainly applied to bauxite
ore containing ferric oxide as chief impurity.
(b) Hall’s process : This process is applied to bauxite ore
containing both ferric oxide and silica as impurity.
(c) Serpeck’s process : This process is mainly applied to bauxite
ore containing silica as a chief impurity.

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Fig. 12.14 Extraction of Aluminium

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6.2 Iron (Fe)

Extraction : Iron is extracted from its oxide ores especially from the magnetite, haematite and limonite ores. The extraction involve the
following steps given in flow sheet :

Fig. 12.15 Extraction of Iron

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6.2.1 Various Forms of Iron Varieties of Steel :

When the molten pig iron is cooled at once, the iron is called
white cast iron, which contains carbon in the form of cementite,
Fe3C and when the molten pig iron is cooled slowly and slowly,
the iron is called as grey cast iron, which contains carbon in the
form of graphite.
(i) Cast Iron or Pig Iron :
This is the least pure form of commercial iron and contains the
highest percentage of carbon viz., 2.5 to 4.5% and traces of
impurities like S, P, Mn and Si. The average composition of cast
iron is : Fe = 93 – 95%, C = 2.5 – 4.5%, Si = 0.6 – 2.8%, P = 0.4 –
1.0%, S = 0.1 – 0.3%, Mn = 0.3 – 1.2%.
(ii) Wrought Iron :
It is the purest form of commercial iron and contains the lowest
percentage of carbon viz. 0.12 to 0.25% and 0.3% of impurities like
S, P, Si and Mn.
There are many varieties of steel depending on the amount of
carbon present in it.
(a) Mild and Quenched Steels :
Mild steel is a variety which contains lower percentage of
carbon. It possesses the properties of wrought iorn along with
elasticity and hardness of steel. If mild steel is heated to a high
temperature (i.e., to bright redness) and then suddenly cooled
by plunging in oil or water, it becomes as hard and brittle as
glass. This is called quenched steel and process is called
quenching or hardening.
steels or alloy steels and find extensive use in industry.
(b) Hard Steel :
This variety contains higher percentage of carbon. It is hard
and brittle like glass.

6.2.2 Steel
Composition of Steel :
Steel is an alloy of iron (as ferrite) containing 0.25 to 2.5% of
carbon (as cementite, Fe3C) and traces of S, P, Si and Mn. The
percentage of S and P are usually below 0.05%, depending on the
method used for the manufacture of steel. Si is usually between
0.15 to 0.35% and is present as iron silicide, FeSi which is soluble
in ferrite. High content of Si gives a fibrous structure to steel. Mn
is added to steel during is manufacture to serve as a deoxidiser
and to neutralise the harmful effect of sulphur by forming MnS
which is inert, while FeS makes steel brittle in hot working.
(c) Special Steels or Alloy Steels
Addition of small amounts of nickel, cobalt, chromium, tungsten,
molybdenum, manganese and silicon confer special properties
on steel considerably altering its hardness, tenacity, resistance
to corrosion and coefficient of expansion. Such products are
called special
(d) Steel Containing S and P :
Iron or steel containing excess of S is brittle when hot (hot short)
and that containing excess of P is also brittle when cold (cold
short).

Table 12.3 : Comparison between Cast Iron, Wrought Iron and Steel

Property Cast iron Wrought iron Steel

Chemical Iron 93–95%, Iron 99.5–99.8%, Iron 99.5–98.0%,

composition Carbon 2.5–5% Carbon 0.1–0.25% Carbon 0.25 to 2.0%

Impurities about 2% Impurities about 0.3%

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6.3 Copper (Cu)

Extraction : Copper is extracted mainly from copper pyrites (Cu Fe S2). The extraction involve the following steps given in flow sheet.

Fig. 12.16 Extraction of Copper

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6.4 Silver (Ag)

Silver is also associated in the form of Ag2S in the lead ore, galena (PbS). The lead extracted usually contains silver and called
argentiferous lead. Silver is recovered before lead is put into use.

Fig. 12.17 Extraction of Silver

NOTE:
Same process is employed for the extraction of gold (Au).

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Some Important Compounds, Minerals,

Mixtures and their Formulas

1. Epsom salt MgSO4. 7H2O 25. Nitrolium CaCN2

2. Gypsum salt CaSO4.2H2O 26. Hydrolith CaH2

3. Glauber’s salt Na2SO4. 10H2O 27. Fusion mixture Na2CO3+K2CO3

4. Lime water Ca(OH)2 (slaked lime) 28. Gun powder KNO3 + K2CO3

5. Quick lime CaO 29. Pink salt (NH4)2SnCl6

6. Washing Soda Na2CO3.10H2O 30. Laughing gas N2O (nitrous oxide)

7. Crystal carbonate Na2CO3.H2O 31. Red Lead Pb3O4
8. Soda ash Na2CO3 32. Blue vitriol CuSO4.5H2O
9. Baking Soda NaHCO3 33. Green vitriol FeSO4.7H2O
10. Turnbull’s blue Fe3[Fe(CN)6]2 34. Chiense white ZnO
11. Chile salt petre NaNO3 35. Philospher’s wool ZnO

12. Indian salt petre KNO3 36. Potash alum K2SO4.Al2(SO4)3.24H2O

13. Brine or Table salt 37. Chrome alum K2SO4.Cr2(SO4)3.24H2O

or Rock salt NaCl 38. Ferric alum Fe2(SO4)3. (NH4)2SO4. 24H2O
14. Potash ash or Pearl ash K2CO3 39. Chrome lemon (or)
15. Nitre or Indian salt petre Yellow chrome PbCrO4
or Chemical refrigerant KNO3 40. Pyrolusite MnO2
16. Norwegian salt petre Ca(NO3)2 41. Rochelle salt CH(OH)COONa
17. Salt Cake K2SO4
CH(OH)COOK
18. Carnallite KCl.MgCl2.6H2O
42. Sorel’s cement MgCl2.5HgO,H2O
19. Hypo Na2S2O3.5H2O
43. Lithopone BaSO4 + ZnS
20. Borax or Tincal Na2B4O7.10H2O
44. Aqua regia Conc. HnO3 + Conc. HCl (1 : 3)
21. Barytes of Heavy spar
45. Ammonium alum (NH4)2SO4.Al2(SO4)3.24H2O
or Barium meal BaSO4
46. Sodium Alum Na2SO4.Al2(SO4)3.24H2O
22. Baryta water Ba(OH)2
47. Killed salt (or Butter of Zinc) ZnCl2.2H2O
23. Magnesia MgO
48. Oxymuriate (or) Butter of Tin SnCl4.5H2O
24. Microcosmic salt NaNH4HPO4.4H2O

SCAN CODE
Metallurgy
METALLURGY 79

Summary

SCAN CODE
Metallurgy
80 METALLURGY

Solved Examples
Example-1 Example-4
High purity copper is obtained by- Write the overall reaction taking place in the process used
(a) Zone refining (b) Poling for the electrolysis of Alumina by Hall-Heroult process.
(c) Electrolytic refining (d) Cupelling Sol. The reaction taking place in process used for the electrolysis
of Alumina by Hall-Heroult process is
Ans. (c)
Sol. After electrolytic refining. Purity of copper is 99.99% which 2Al 2O 3  3C 
 4Al  3CO 2
( Carbon )
is enough for electrical applications. ( Alumina ) ( Aluminium )

Example-2 Example-5
A metal is extracted from its sulphide ore and (a) Extraction of Au by leaching with NaCN involves both
the process of extraction involves the following steps. oxidation and reduction. Justify by giving equations for
Metal sulphide 
(A) Concentrated ore 
(B) Matte the reactions involved.
(b) Why is the froth flotation method selected for the

(C) Impure metal  (D) Pure metal. Identity the
concentration of sulphide ores ?
steps (A), (B), (C) and (D).
Sol. (a) Oxidation of Au to Au+
Sol. (A)Froth floatation process. Sulphide ores are

concentrated by froth-floatation process. 4Au(s) + 8 CN– (aq) + 2H2(aq)O + O2(g)  4[Au(CN)2(aq)]– 4OH  aq 
(B) Roasting Metal sulphides are roasted to convert into
Reduction of Au+ to Au
metal oxide and to remove impurities.
In roasting; 2CuFeS2 + O2  Cu2S + 2FeS + SO2. 2  Au  CN 2 
 2
 Zn  s    Zn  CN 4   2Au s 
 aq   aq 
2FeS + 3O2  2FeO + 2SO2.
2Cu2S + 3O2  2Cu2O + 2SO2. (b) Because sulphide ores are preferentially wetted by oil
and impurities by water.
FeO + SiO2  FeSiO3
Example-6
(C) Bessemerisation/self reduction. Reduction of metal
What is a flux ? What is the role of flux in the metallurgy of
oxide by its sulphide takes place in Bessemer converter.
Iron and Copper ?
(D) Electro-refining. Pure metal is obtained at cathode.
Sol. Flux : Flux is a substance that combines with gangue to form
Mn+ + n e–  M slag. The gangue may be present in roasted or the calcined
Example-3 ore.
Write chemical equations for metallurgical processes to In metallurgy of Cu
represent :
FeO  SiO 2  Fe SiO3
(i) roasting of galena (PbS) in limited supply of air at (Slag)
moderate temperature.
In the blast furnace, CaO (flux) removes silica present in the
(ii) reduction of Cu2O using coke as a reducing agent.
ore
(iii)deposition of pure silver from an aqueous solution
In metallurgy of iron
of Ag+.
Sol. (i) 2PbS + 3O2  2PbO + 2SO2 ; CaO  SiO 2  Ca SiO3
(Slag)
PbS + 2O2  PbSO4
(ii) Cu2O + C  2Cu + CO

(iii)Ag+ + e– (   Ag  (at cathode)

Electrolys is )
METALLURGY 81
Example-7 A circular mobile heater is fixed at one end of the rod of
the impure metal. The molten zone moves along with the
(a)What is the role of depressant in froth floatation process
heater which is moved forward. As the heater moves
?
forward, the pure metal crystalises out of melt and the
(b) Out of C and CO which is a better reducing agent for impurities pass on into the adjacent molten zone. This
FeO process is repeated several times and the heater is moved
(i) In the lower part of blast furnace in the same direction. At one end, impurities get
(Higher temperature) concentrated.
(ii) In the upper part of blast furnace
(Lower temperature)
Sol. (a) Depressant is used in the froth floatation process for
preventing the specific sulphide ore from forming in a
mixture of sulphides.
(b) C is better reducing agent at higher temperature.
CO is better reducing agent at lower temperature.
Example-8
What are chief ores of Zinc ? Write chemical reactions taking
place in the extraction of zinc from zinc blende. This method is very useful for producing semiconductor
and other metals of very high purity like germanium,
Sol. The chief ores of zinc are :
silicon, boron etc.
(i) Zinc blende, ZnS
(ii) Electrolytic refining : In this method, the impure metal is
(ii) Calamine, ZnCO3 made to act as anode. A strip of the same metal in pure
(iii)Zincite, ZnO form is used as Cathode. They are put in a suitable
Extraction of zinc : The zinc from zinc blende is extracted by electrolyte both containing soluble salt of the same metal.
roasting followed by reduction with coke. The more basic metal remains in the solution and the
less basic ones go to the anode mud. The reactions are
(a) Roasting : The concentrated ore is heated with oxygen
at 900°C in reverberatory furnace to convert zinc sulphide Anode : M  Mn+ + ne–
to zinc oxide. Cathode : Mn+ + ne–  M
Copper and zinc are refined by this method.
2 ZnS  3O 2  2 ZnO  2SO 2
( Zinc blende ) ( Zinc oxide ) (iii)Distillation : In this method, the impure metal is evaporated
to obtain the pure metal as distillate. This method is very
(b) Reduction : The reduction of zinc oxide is done using
useful for low boiling metals like zinc and mercury.
coke.
Example-10
ZnO  C 673
 K
 Zn  CO Explain the vapour phase refining method for extraction of
The metal is distilled off and collected by rapid chilling. metal. Give example.
Example-9 Sol. Vapour phase refining : In this method, the metal is
Outline the principles of refining of metals by the following converted into its volatile compound and collected
methods : elsewhere. It is then decomposed to give pure metal. There
are two requirements :
(i) Zone refining
(i) the metal should form a volatile compound with an
(ii) Electrolytic refining
available reagent.
(iii)Distillation
(ii) the volatile compound should be easily decomposable,
Sol. (i) Zone refining : This method is based on the principle so that recovery is easy.
that the impurities are more soluble in the melt than in
the solid state of the metal.
82 METALLURGY
Example-11 Cathode : 2Al3+ (melt) + 6e–  2Al ()
Name the principal ore of aluminium and describe how Anode : C(s) + O2– (melt)  CO (g) + 2e–
aluminium metal is extracted from this ore. C(s) + 2O2–  CO2 (g) + 4e–
Sol. Extraction of Aluminium : The anodes burn away. Therefore, they must be replaced
Principal (main) ore of aluminium = Bauxite (Al2 O3× H2O) from time to time.
Other ores :
(i) cryolite - Na3 Al F6
(ii) Orthoclase - K Al Si3O8
Aluminium metal is extracted from bauxite in two stage
process.
(i) pure alumina (Al2O3) is obtained from bauxite.
(ii) Electrolysis of Al2O3 in molten cryolite : Na3AlF6 to
obtained aluminium metal.
Stage-I : (Leaching) : The bauxite ore contains the impurities
like silica (SiO2), ironoxide and titanium (IV) oxide.
The ore is treated with sodium hydroxide solution. Aluminium
oxide and silica dissolve to form sodium aluminate and
sodium silicate respectively. Iron oxide and TiO2 is filtered
off.
Electrolytic reduction of alumina
Al2O3 + 2NaOH + 3H2O  2Na[Al(OH)4]
Example-12
Or
Explain the Froth Floatation Method.
Al2O3 (s) + 2NaOH (aq) + 3H2O ()  2Na[Al(OH)4] (aq)
Sol. Froth Floatation Method :
The filtrate sodium aluminate and sodium silicate is diluted
with aluminium hydroxide which precipitates the aluminium
hydroxide leaving behind sodium silicate in solution.

Na[Al(OH) 4 ] H
2O
 Al(OH)3  NaOH
Or

Na[Al(OH ) 4 ] (aq) H

2O
 Al(OH ) 3 (s)  NaOH (aq)
The aluminium hydroxide is filtered, dried and calcined
(heated) at 1473 K to get pure alumina. This process is known
as Hall-Heroult process.

2Al(OH) 3 
 Al 2 O 3  3H 2 O
aluminium hydroxide pure alumina

Stage-II : The alumina is dissolved in molten cryolite

Na3AlF6 and then electrolysed in a large steel tank lined
with graphite which acts as Cathode. The anodes are made
of carbon (graphite). On passing current, molten aluminium
is produced at Cathode and oxygen gas is evolved at the
anode reacts with carbon of anode producing CO and CO2.
The molten aluminium is drawn from the bottom of the tank.
The overall reactions may be written as
The method has been in use for removing gangue from
sulphide ores. In this process, a suspension of the powdered
ore is made with water. To it, collectors and froth stabilisers
are added. Collectors (e.g., pine oils, fatty acids, xanthates,
etc.) enhance non-wettability of the mineral particles and
froth stabilisers (e.g., Cresols, aniline) stabilise the froth.
METALLURGY
The mineral particles become wet by oils while the gangue
particles by water. A rotating paddle agitates the mixture
and draws air in it. As a result, froth is formed which carries
the mineral particles. The froth is light and is skimmed off. It
is then dried for recovery of the ore particles.
Example-13
Explain the magnetic separation process.
Sol. Magnetic separation process : This process is based on
differences in magnetic properties of the ore components. If
either the ore or the gangue (one of these two) is capable of
being attracted by a magnetic field, then such separations
are carried out (e.g., in case of iron ores). The ground ore is
carried on a conveyer belt which passes over a magnetic
roller.
Example-14
Write down the reactions taking place in different zones in
the blast furnace during the extraction of iron.
Sol. Extraction of iron : In the Blast furnace, reduction of iron
oxides takes place in different temperature. Hot air is blown
from the bottom of the furnace and coke is burnt to give
temperature upto 2200 K in the lower portion itself. The
burning of coke supplies most of the heat required in this
process. The CO (Carbon monoxide) and heat moves to
upper part of the furnace. The temperature is lower in upper
part.
The reduction of Fe2O3 takes place at about 500-800 K
3Fe 2 O 3  CO  2Fe 3O 4  CO 2
( Iron ore )
Fe3O4 + CO  3FeO + CO2
At 900-1500 K, the carbon-dioxide reacts with coke to give
CO which combine FeO to give Iron.
C + CO2  2 CO
FeO + CO  Fe + CO2
Limestone is decomposed to CaO which removes silicate
83
impurity of the ore as slag
CaCO 3  CaO  CO 2
( Limestone )
CaO  SiO 2  CaSiO 3
Slag
The slag is in molten state and separated out from iron.
Example-15
Give reasons for the following :
(i) Alumina is dissolved in cryolite for electrolysis instead
of being electrolysed directly.
(ii) Zinc oxide can be reduced to the metal by heating with
carbon but not Cr2O3.
(iii)Extraction of copper directly from sulphide ores is less
favourable than that from its oxide ore through reduction.
Sol. (i) Cryolite lowers the melting point of the mixture and
improves the electrical conductivity of the cell.
(ii) Since carbon is better reducing agent for reduction of
zinc oxide (ZnO).
(iii)It is quite easy to reduce oxide ore (Cu2O) directly to
metal by heating with coke. However, most of the ores of
copper are sulphide ores. These sulphide ores are
roasted/smelted to obtain oxide ores.
Example-16
Describe the role of the following :
(i) NaCN in the extraction of silver from a silver ore
(ii) Iodine in the refining of titanium
(iii)Cryolite in the metallurgy of aluminium
Sol. (i) Role of NaCN in the extraction of silver is to do the
leaching of silver ore in the presence of air from which
the silver is obtained later by replacement
4 Ag(s) + 8CN– (aq) + 2 H2O (aq) + O2 (g) 
4 [Ag(CN)2]– (aq) + 4 OH– (aq)
2 [Ag(CN)2]– (aq) + Zn (s)  2 Ag (s) + [Zn(CN)4]2– (aq)
(ii) Iodine is heated with Titanium to form a volatile
compound which on further heating decompose to give
pure titanium
Ti (impure) + 2I2  TiI4TiI4  Ti (Pure) + 2I2
(iii)Cryolite lowers the melting point of the mixture and
improves the electrical conductivity of the cell.
84
Example-17
Describe the principle behind each of the following
processes
(i) Vapour phase refining of a metal.
(ii) Recovery of silver after silver ore was leached with NaCN.
Sol. (i) In this method crude metal is freed from impurities by
first converting it into a suitable volatile compound by
heating it with a specific reagent at a lower temperature
and then decomposing the volatile compound at some
higher temperature to give the pure metal. Thus, the two
requirements are :
- the metal should from a volatile compound with a
suitable reagent.
- the volatile compound should be easily decomposable
so that the recovery is easy.
(ii) Role of NaCN in the extraction of silver is to do the
Leaching of silver ore in the presence of air from which
the silver is obtained Later by replacement
4Ag(s) + 8 CN– (aq) + 2H2O (aq) + O2 (g) 
4[Ag(CN)2]– (aq) + 4 OH– (aq)
2[Ag(CN)2]– (aq) + Zn (s)  2Ag(s) + [Zn(CN4)]2– (aq)
Example-18
Explain the role of each of the following in the extraction of
metals from their ores :
(i) CO in the extraction of nickel.
(ii) Zinc in the extraction of silver.
(iii)Silica in the extraction of copper.
Sol. (i) CO in the extraction of nickel : The Cu2O line is almost at
the top. So it is quite easy to reduce oxide ores of copper
directly to the metal by heating with coke (both the lines
of C, CO and C, CO2 are at much lower positions in the
particularly, after 500-600 K). However most of the ores
are sulphide and some may also contains iron. The
sulphide ores are smelted to give oxides.
2 Cu2S + 3O2  2Cu2O + 2SO2
The oxides can then be easily reduced to metallic copper
using coke.
Cu2O + C  2Cu + CO
(ii) Zinc in the extraction of silver : The reduction of zinc
oxide is done using coke. The temperature in this case is
higher than that in case of copper. For the purpose of
heating, the oxide is made into brickettes with coke and
clay.
METALLURGY
ZnO  C Coke
 , 673 K
 Zn  CO
The metal is distilled off and collected by rapid chilling.
(iii)The ore is heated in a reverberatory furnance after mixing
with silica. In the furnance, iron oxide slags of as iron
silicate and copper is produced in the form of copper
matte. This contains Cu2S and FeS.
FeO  SiO 2 
 Fe SiO 3
(Slag )
Copper matte is then charged into silica lined convertor.
Some silica is also added and hot air blast is blow to
convert the remaining FeS2, FeO and Cu2S/Cu2O to
metallic copper. Following reactions take place :
2FeS + 3O2  2FeO + 2SO2
FeO + SiO2  FeSiO3
2Cu2S + 3O2  2Cu2O + 2SO2
2Cu2O + Cu2S  6Cu + SO2
The solidified copper obtained has blistered appearance
due to the evolution of SO2 and so it is called blister
copper.
Example-19
Differentiate between a mineral and an ore.
Sol. Minerals : Which are naturally occuring chemical substances
in the earth’s crust obtainable by mining.
Ores : Only a few are viable to be used as sources of that
metal. Such minerals are known as ores. The mineral from
which metals can be entracted profitasty are ores.
Example-20
How can you obtain pure alumina from a bauxite ore
associated with silica ? Write the reactions involved in this
process.
Sol. “Al” is extracted from bauxite Al2O3. 2H2O.
(i) concentration of bauxite is done by leaching Process.
(ii) Electrolytic reduction is that the purified bauxite ore mixed
with cryolite or CaF2 which lowers its melting point and
increases electrical conductivity. Molten mixture is
electrolysed using number of graphite rods as anode
and carbon lining as cathode.
The graphite anode is useful for reduction of metal oxide
to metal.
2Al2O3 + 3C  4Al + 3CO2
Al 2 O3 electrolys
 is
 2Al3  3O 2
At cathode : Al3+ (melt) + 3e–  Al ()
METALLURGY
At anode : O2– – 2e–  O
O + O  O2
C + O2  CO2
Graphite rods get burnt forming CO and CO2. The
aluminium thus obtained is refined electrolytically using
impure Al as anode, pure Al as cathode and mother
cryolite as electrolyte.
At anode : Al  Al3+ + 3e–
(impure)
At cathode : Al3+ + 3e–  Al (pure)
Example-21
Why is the extraction of copper from pyrites more difficult
than that from its oxide ore through reduction ?
Sol. The standard Gibbs energy of formation of Cu2S is more
negative than that of CS2 and H2S. Therefore, neither carbon
nor hydrogen can reduce Cu2S to Cu metal. In contrast, G°
of Cu2S is less negative than that of CO, and hence carbon
can easily reduce Cu2O to Cu.
Example-22
Out of C and CO, which is a better reducing agent at 673 K ?
Sol. From Ellingham diagram (refer to), it is clear that below 673
K, both C and CO can be used as reducing agent but since
CO can be more easily oxidized to CO2 than C to CO2;
therefore below 673 K, CO is more stable and hence its
oxidation to CO2 is less rapid than that of C to CO2. Therefore,
above 673 K, C is a better reducing agent than CO.
85
Example-23
How is “cast iron” different from “pig iron” ?
Sol. Pig iron contains 4% carbon and impurities such as P, S, Si,
Mn in small amounts, while cast iron is obtained by melting
pig iron. It has lesser carbon content (3%) and is more hard
and brittle than pig iron.
electricity.
Example-24
Why copper matte is put in silica-lined converter ?
Sol. Copper matte is put in silica-lined converter to remove the
remaining FeO and FeS present in the matte as slag (FeSiO3).
Example-25
Why is zinc not extracted from zinc oxide through reduction
using CO ?
Sol. Zinc is not extracted from zinc oxide through reduction using
CO because the standard Gibbs energy of formation of ZnO
from Zn is lower than that of CO 2 from CO. So,
thermodynamically it is not favorable.
86 METALLURGY

EXERCISE – 1: Basic Objective Questions

Occurrence of Elements in Nature 11. In the froth-floatation process, the ore particles float
because
1. An element whose electronic configuration is 4s13d10. (a) they are light
The possibility of element is (b) their surface is not easily wetted by water
(a) A metal (b) A non-metal (c) they bear electrostatic charge
(c) Element of 10th gp (d) Liquid at 2981ºC (d) they are insoluble
2. Which of the following statements is correct? 12. In the froth-floatation process, the sulphide ores are
(a) All ores are minerals. concentrated by mixing the ore with
(b) All minerals are ores. (a) water, pine oil and sodium ethyl xanthate
(c) A mineral cannot be an ore. (b) water, wax and benzene
(d) An ore is always obtained in a pure form. (c) water, benzene and sodium ethyl xanthate
3. The impurities present in a mineral are called (d) water, matrix and air
(a) gangue (b) flux 13. Wolframite (FeWO4), present as an impurity in
(c) froth (d) nuggets cassiterite (SnO2), can be removed by the process of
4. Among the following, the most abundant metal in the (a) froth floatation
earth’s crust is (b) gravity separation
(a) Fe (b) Al (c) electromagnetic separation
(c) Cu (d) Na (d) zone refining
5. The metal which mainly occurs as oxide ore in nature 14. Chemical leaching is useful in the concentration of:
is: (a) Copper pyrite (b) Bauxite
(a) Silver (b) Lead (c) Cassiterite (d) Cinnabar
(c) Aluminium (d) Copper 15. Which of the following benefaction processes is used
6. The ore of calcium which contains phosphorus is for the mineral, Al2O3.2H2O?
(a) gypsum (b) talc (a) Forth floatation (b) Leaching
(c) fluorapatite (d) asbestos (c) Liquation (d) Magnetic separation
7. Rocky impurities present in a mineral are known as: 16. In the froth floatation process for benefaction of the
(a) flux (b) gangue ores, the ore particles float because
(c) matte (d) slag (a) they are light
8. Silicon is the main constituent of (b) their surface is not easily wetted by water
(a) rocks (b) alloys (c) they bear electrostatic charge
(c) animals (d) plants (d) they are insoluble.
17. Which one of the following ores is best concentrated by
Concentration of Ore froth floatation method?
(a) Siderite (b) Galena
9. Concentration of ores is not done by the (c) Malachite (d) Magnetite
(a) gravity separation process
(b) electromagnetic separation process Extraction of Crude Metal from Concentrated
(c) froth-floatation process Ore
(d) roasting process
10. Sulphide ores are generally concentrated by the 18. Flux is used to remove:
(a) gravity separation process (a) basic impurities
(b) calcination process (b) acidic impurities
(c) froth-floatation process (c) all type of impurities
(d) carbon-reduction process (d) acidic and basic both impurities
METALLURGY 87

19. Which one of the following is not a basic flux? 28. The metal which is extracted by electrolytic reduction is
(a) CaCO3 (b) SiO2 (a) Sn (b) Pb
(c) CaO (d) MgO (c) Zn (d) Ca
20. A flux is often added to remove impurities from an ore 29. Which of the following metals is obtained by
in a blast furnace. In the reaction electrolytic reduction process:
CaO + SiO2 CaSiO3 (a) Fe (b) Cu
the slag and the flux are (c) Ag (d) Al
(a) CaSiO3 and SiO2 (b) CaSiO3 and CaO 30. Heating with carbon in absence of air is known as :
(c) CaO and SiO2 (d) SiO2 and CaSiO3 (a) reduction (b) carbon-reduction
21. By which of the following processes is an oxide ore (c) smelting (d) roasting
reduced to the free metal? 31. Which of the following metals cannot be extracted by
(a) Leaching (b) Smelting the carbon reduction process?
(c) Roasting (d) Calcination (a) Zn (b) Fe
22. Calcination of ores involves heating the ore below its (c) Al (d) Sn
fusion temperature 32. Heating pyrites to remove sulphur is called
(a) in presence of air (a) Smelting (b) Calcination
(b) in an atmosphere of nitrogen (c) Liquation (d) Roasting
(c) in absence of air 33. Out of the following metals that cannot be obtained by
(d) in presence of superheated steam electrolysis of the aqueous solution of their salts is
23. Which one of the following reactions represents a (a) Ag (b) Cr
calcination reaction? (c) Cu (d) Mg
(a) HgS + O2  Hg + SO2 34. Which of the following reactions represents the self-
reduction process?
(b) Ag2S + NaCl  AgCl + Na2S
(c) CuCO3. Cu(OH)2  CuO + CO2 + H2O HgS  O2  HgO  SO 2

HgO  HgS  Hg  SO2
(d) Al2O3 + NaOH  NaAlO2 + H2O (a) 
24. Roasting or ores is done Cu 2S  O2  Cu 2 O  SO2
(a) in absence of air 
Cu S  Cu 2 O  Cu  SO2
(b) in presence of a limited supply of air (b)  2
(c) in presence of superheated steam PbS  O2  PbO  SO2
(d) in presence of an excess of oxygen 
(c) PbO  PbS  Pb  SO2
25. Which of the following changes take place during
roasting? (d) All of these
(a) Oxidation-reduction 35. Thomas slag is
(b) Only oxidation (a) Calcium silicate (b) Calcium phosphate
(c) Neither oxidation nor reduction (c) barium phosphate (d) Strontium silicate
(d) Expulsion of metals 36. Which of the following reactions represents the self-
26. The main function of roasting is reduction process?
(a) to remove the volatile impurities HgS  O2  HgO  SO 2

(b) to oxidize the metal HgO  HgS  Hg  SO2
(c) to reduce the metal oxide (a) 
(d) to make a slag Cu 2S  O2  Cu 2 O  SO2

27. Process of heating ore in air to remove sulphur is:
(b) Cu 2S  Cu 2 O  Cu  SO2
(a) Calcination (b) Roasting
(c) Smelting (d) None PbS  O2  PbO  SO2

PbO  PbS  Pb  SO2
(c) 
(d) All of these
88 METALLURGY

Thermodynamic Principles of Metallurgy 45. Certain metals can be obtained in the ultrapure state by
heating with iodine and then decomposing the metal
37. Hydrogen gas will not reduce iodide at a much higher temperature. This method is
(a) heated cupric oxide known as
(b) heated ferric oxide (a) the van Arkel process
(c) heated stannic oxide (b) the Mond process
(d) heated aluminium oxide (c) the liquation process
38. Calcium is obtained by: (d) the zone-refining process
(a) Roasting of lime stone 46. Which of the following metals is refined by the van
(b) Electrolysis of calcium chloride in H2O Arkel process?
(c) Electrolysis of molten anhydrous calcium chloride (a) Au (b) Cu
(d) Reduction of calcium chloride with carbon (c) Ni (d) Ti
47. The van Arkel method for purification of metals
Refining involves the conversion of the metal into a
(a) volatile stable compound
39. Which of the following pair is incorrectly matched? (b) volatile unstable compound
(a) van Arkel method — Zirconium (c) nonvolatile stable compound
(b) Kroll’s process — Titanium (d) metal carbonyl
(c) Froth Floatation — Cerussite 48. Which method of purification is represented by the
(d) Distillation — Zinc following equation?
40. The zone-refining process for purification of metals is Ti+2I 2 
773 K
 TiI 4 
1675 K
 Ti+2I 2
based on
(a) Cupellation (b) Poling
(a) the difference in volatilities of the metal and the
(c) Van Arkel method (d)Zone-refining process
impurities
49. Impure nickel is purified by
(b) the difference in fusibilities of the metal and the
(a) the distillation process
impurities
(b) the Mond process
(d) the difference in solubilities of the impurities in the
(c) liquation
molten and solid states of the metal
(d) the zone-refining process
(d) the difference in the oxidizing abilities of the metal
50. Ultrapure silicon, used to make semiconductors, is
and the impurities
obtained by the
41. The liquation process is used for the purification of
(a) cupellation process (b) Mond process
(a) Sn (b) Al
(c) zone-refining process (d) cyanide process
(c) Zn (d) Hg
–
42. In electrorefining of metals, the anode is made of 51. In the equation, 4M+8CN + 2H2O + O2 
(a) the impure metal concerned – –
4 [M(CN)2] + 4OH , the metal M is
(b) the pure metal concerned
(c) graphite (a) Copper (b) Iron
(d) silica (c) Gold (d) Zinc
43. The anode mud in the electrolytic refining of silver
contains: Extraction of Iron and Copper
(a) Zn, Cu, Ag, Au (b) Zn, Ag, Au
(c) Cu, Ag, Au (d) Au only 52. Which ore contains both iron and copper?
44. The distillation process (under reduced pressure) is used (a) Cuprite (b) Chalcocite
for the purification of (c) Chalcopyrite (d) Malachite
(a) Pb (b) Hg 53. Which of the following is also known as “Fools gold”?
(c) Sn (d) Cs (a) Wurtzite (b) Iron pyrites
(c) Chalcocite (d) Silver glance
METALLURGY 89

54. In the extraction of iron, Fe2O3 is reduced by 65. In the extraction of Fe from Fe2O3, the reducing agent is
(a) carbon dioxide (a) CO (b) Al
(b) aluminium (c) electrolytic reduction (d) Cu
(c) carbon and carbon monoxide 66. Blister copper is refined by stirring molten impure
(d) electrolytic reduction metal with green logs of wood because such a wood
55. Blister copper is obtained in liberates hydrocarbon gases (like CH4). This Process X
(a) Bessemer converter (b) blast furnace
is called .......... and the metal contains impurities of Y
(c) muffle furnace (d) reverberatory furnace
is ...........
56. Which of the following mixtures is called matte?
(a) X = cupellation, Y = CuO2
(a) CuO + Cu2S (b) PbS + PbSO4
(c) Cu2S + FeO (d) Cu2S + FeS (b) X = polling, Y = Cu2O
57. The extraction of which of the following metals (c) X = polling, Y = CuO
involves bessemerisation? (d) X = cupellation, Y = CuO
(a) Fe (b) Ag
(c) Al (d) Cu Extraction of Gold and Silver
58. Which one is the ore of iron:
(a) Cuprite (b) Magnetite 67. Which of the following is a sulphide ore?
(c) Bauxite (d) None of these (a) Argentite (b) Cuprite
59. During the extraction of iron, slag produced is (c) Azurite (d) Cerussite
(a) CO (b) FeSiO3 68. Native silver metal forms a water-soluble complex
with a dilute aqueous solution of NaCN in the presence
(c) MgSiO3 (d)CaSiO3
of
60. In metallurgy of iron, when lime stone is added to the (a) nitrogen (b) oxygen
blast furnace, the calcium ion ends up in (c) carbon dioxide (d) argon
(a) slag (b) gangue 69. The cyanide process is used for the extraction of
(c) metallic calcium (d) calcium carbonate (a) Cu (b) Ag
61. Which of the following minerals does not contain iron? (c) Zn (d) Al
(a) Magnetite (b) Magnesite 70. Cyanide process is used for the extraction of
(c) Haematite (d) Limonite (a) barium (b) silver
62. In the extraction of copper from its sulphide ore, the (c) boron (d) zinc
metal is formed by reduction of Cu2O with 71. Which of the following ligands is used to form the
(a) FeS (b) CO complex from which silver is extracted?
(c) Cu2S (d) SO2 (a) NaCNS (b) NH3
63. Copper is extracted from sulphide ore using the (c) NaCN (d) NaCNO
method: 72. In the process of extraction of gold,
Roasted gold ore + CN + H2O  [X] + HO
– –
(a) carbon reduction
(b) carbon monoxide reduction [X] + Zn  [Y] + Au
(c) auto reduction Identify the complexes [X] and [Y]
–
(d) none of these (a) X = [Au(CN)2] , Y = Zn(CN)4]
2–

64. Which of the following reactions taking place in the 3– 2–

(b) X = [Au(CN)4] , Y = [Zn(CN)4]
blast furnace during extraction of iron is endothermic? – 4–
(a) CaCO3 CaO + CO2 (c) X = [Au(CN)2] , Y = [Zn(CN)6]
– 2–
(d) X = [Au(CN)4] , Y = [Zn(CN)4]
(b) 2C + O2 2CO
73. Silver is obtained from Na [Ag(CN)2] by reaction with:
(c) C + O2 CO2
(a) Fe (b) Na
(d) Fe2O3 + 3CO  2Fe + 3CO/2
(c) Zn (d) Au
90 METALLURGY

Extraction of Lead and Tin Extraction of Zinc, Chromium, Manganese

74. Cassiterite is an ore of 84. Extraction for zinc from zinc blende is achieved by
(a) manganese (b) tin (a) electrolytic reduction
(c) silicon (d) zinc (b) roasting followed by reduction with carbon
75. Copper and lead are mainly extracted by (c) roasting followed by reduction with another metal
(a) electrolysis (d) roasting followed by self-reduction
(b) the carbon reduction process 85. In extractive metallurgy of zinc, partial fusion of ZnO
(c) the self-reduction process with coke is called
(d) the thermite process (a) smelting (b) calcination
76. Silver can be separated from lead by: (c) roasting (d) sintering
(a) fractional crystallisation (b) amalgamation 86. In extractive metallurgy of zinc, partial fusion of ZnO
(c) cupellation (d) Hall Heroult Process with coke is called
77. The methods chiefly used for the extraction of lead and (a) smelting (b) calcination
tin from their ores are respective (c) roasting (d) sintering
(a) self reduction and carbon reduction
(b) self reduction and electrolytic reduction Extraction of Aluminium
(c) carbon reduction and self reduction
(d) cyanide process and carbon reduction 87. Aluminium is not present in which of the following
78. Silver containing lead as an impurity is purified by mineral?
(a) Poling (b) Cupellation (a) Cryolite (b) Feldspar
(c) Levigation (d) distillation (c) Fluorspar (d) Mica
88. Which of the following is a fluoride ore?
Extraction of Sodium and Magnesium (a) Cryolite (b) Carnallite
(c) Feldspar (d) Ilmenite
79. The mineral carnallite contains 89. During the electrolytic reduction of aluminium, the
(a) Ca and Na (b) Ca and Mg carbon anodes are replaced from time to time because
(c) Mg and K (d) Al and K (a) the carbon anodes get decayed
80. Which of the following minerals contains calcium as (b) the carbon prevents atmospheric oxygen from
well as magnesium? coming in contact with aluminium
(a) Tridymite (b) Aragonite (c) oxygen liberated at the carbon anodes reacts with
(c) Dolomite (d) Carnallite anodes to form CO2
81. Of the following metals, the one which cannot be obtained (d) carbon converts Al2O3 to Al
by the electrolysis of the aqueous solution of its salt is 90. The major role of fluorspar (CaF2) which is added in
(a) Ag (b) Mg small quantities in the electrolytic reduction of alumina
(c) Cu (d) Hg dissolved in fused cryolite (Na3AlF6) is
82. The electrometallurgical process (electrolysis of fused
(a) as a catalyst
salts) is employed to extract
(b) to make the fused mixture very conducting
(a) lead (b) silver
(c) to increase the temperature of the melt
(c) sodium (d) copper
(d) to decrease the rate of oxidation of carbon at the
83. Which of the following is not an ore of magnesium?
anode
(a) Carnallite (b) Magnesite
(c) Dolomite (d) Gypsum
METALLURGY 91

91. Electrolytic reduction of alumina to aluminium by the 98. Fused cryolite is used in the electrolytic extraction of
Hall-Heroult process is carried out aluminium:
(a) in the presence of NaCl (a) To decomposes alumina
(b) in the presence of fluorite (b) To oxidise alumina
(c) in the presence of cryolite which forms a melt at (c) To protect anode
lower temperature and increases the electrical (d) To protect cathode
conductivity 99. The major role of fluorspar (CaF2) which is added in
(d) in the presence of cryolite which forms a melt at small quantities in the electrolytic reduction of alumina
higher temperature and increases the electrical dissolved in fused cryolite (Na3AlF6) is
conductivity (a) as a catalyst
92. Cryolite is the ore of: (b) to make the fused mixture very conducting
(a) Al (b) Cu (c) to increase the temperature of the melt
(c) Ag (d) Fe (d) to decrease the rate of oxidation of carbon at the
93. The metal which cannot be obtained by electrolysis of anode
aqueous solution of its salt is 100. In the commercial electrochemical process for
(a) Ag (b) Zn aluminium extraction, the electrolyte used as
(c) Cu (d) Al (a) Al(OH)3 in NaOH solution
94. The chief impurity present in red bauxite is:
(b) an aqueous solution of Al2 (SO4)3
(a) SiO2 (b) Fe2O3
(c) a molten mixture of Al2O3 and Na3AlF6
(c) K2SO4 (d) NaF
(d) a molten mixture of AlO (OH) and Al (OH) 3
95. Cryolite is:
101. Electrolytic reduction of alumina to aluminium by Hall-
(a) Na3AlF6 and is used in the electrolysis of
Heroult process is carried out
alumina for decreasing electrical conductivity. (a) in the presence of NaCl
(b) Na3AlF6 and is used in the electrolysis (b) in the presence of fluorite
of alumina for lowering the melting point of (c) in the presence of cryolite which forms a melt with
alumina. lower melting temperature
(c) Na3AlF6 and is used in the electrolytic (d) in the presence of cryolite which forms a melt
with higher melting temperature
purification of alumina.
(d) Na3AlF6 and is used in the electrolysis of
Uses of Metals
alumina.
96. In the context of the Hall - Heroult process for the 102. Which of the following is used in electro plating:
extraction of Al, which of the following statements is (a) AgCl (b) AgNO3
false? (c) Sodium argentocyanide (d) None
(a) Al3+ is reduced at the cathode to form Al 103. In the aluminothermic process, aluminium acts as
(b) Na3AlF6 serves as the electrolyte (a) an oxidizing agent (b) a reducing agent
(c) CO and CO2 are produced in this process (c) a flux (d) a solder
(d) Al2O3 is mixed with CaF2 which lowers the 104. Which of the following represents the thermite
melting point of the mixture and brings conductivity. reaction?
97. Aluminium is extracted by the electrolysis of (a) Mn3O4 + Al  Mn + Al2O3
(a) alumina (b) MgCO3 + SiO2 MgSiO3 + CO2
(b) bauxite (c) Cu2S + Cu2O  Cu + SO2
(c) molten cryolite (d) Fe2O3 + CO  Fe + CO2
(d) alumina mixed with molten cryolite
92 METALLURGY

105. Which of the following reaction forms the basis of 116. Percentage of gold in 20 Carat gold-
Goldschmidt alumino-thermite process? (a) 80% (b) 83.33%
(a) 2Al + N2  2AlN (c) 86.66% (d) 96%
(b) 2Al + 3Cl2  2AlCl3 117. Which is a non-exothermic reaction taking place in the
(c) 2Al + 6HCl  2AlCl3 + 3H2 blast furnace during extraction of iron?
(d) 2Al + Fe2O3  Al2O3 + 2Fe (a) CaCO3  CaO  CO2
106. In the alumino-thermite process, aluminium acts as (b) Fe2 O3  3CO  2Fe  3CO2
(a) an oxidizing agent (b) a flux
(c) FeO  CO  Fe  CO2
(c) a reducing agent (d) a solder
107. In which of the following maximum percentage of (d) All
carbon: 118. Why can’t aluminium be reduced by carbon ?
(a) Electrolysis copper (b) Cast iron (a) Carbon is more reactive than aluminium.
(c) Steel (d) Stainless steel (b) Carbon is stronger reducing agent than aluminium.
108. German silver is: (c) Aluminium is stronger reducing agent than carbon.
(a) silver made in Germany (b) an alloy of silver (d) The react to form aluminium carbide.
(c) an alloy of copper (d) a silver white paint 119. Which is the chief ore of aluminium?
109. One of the constituents of the German silver is: (a) Bauxite (b) Cryolite
(a) Ag (b) Cu (c) Feldspar (d) None of these
(c) Mg (d) Al 120. Which is not an ore of copper?
110. Which of the following properties of pure metal makes (a) Copper pyrites (b) Copper glance
them more useful than alloys: (c) Malachite (d) Carnallite
(a) They are harder than alloys 121. Which is the principal ore of zinc?
(b) They have high density (a) Zinc blende (b) Calamine
(c) Can be extracted very easily (c) Zincite (d) Franklinite
(d) Conduct heat and electricity very easily 122. Which is not an ore of iron?
111. Thermite is a mixture of iron oxide and: (a) Haematite (b) Magnetite
(a) aluminium powder (b) zinc powder (c) Dolomite (d) Limonite
(c) potassium metal (d) sodium metal 123. Why is the froth flotation method selected for the
112. Several blocks of magnesium are fixed to the bottom of concentration of Sulphide ores ?
a ship to (a) Sulphide ores react with oil
(a) prevent puncturing by under-sea rocks (b) Sulphide ores react with water
(b) keep away the sharks (c) Impurities are selectively wetted by oil
(c) make the ship lighter (d) Sulphide ores are selectively wetted by oil
(d) prevent action of water and salt 124. What type of ores can be concentrated by magnetic
113. The chemical process in the production of steel from separation method?
haematite ore involve (a) Sulphide ores (b) Oxide ores
(a) reduction (c) Carbonate ores (d) Magnetic ores
(b) oxidation 125. Which metals are generally extracted by the electrolytic
(c) reduction followed by oxidation processes?
(d) oxidation followed by reduction (a) Highly reactive metals
114. In blast furnace, iron oxide is reduced by- (b) Moderately reactive metals
(a) Silica (b) CO (c) Less reactive metals
(c) C (d) lime stone (d) Noble metals
115. Purple of Cassius is – 126. Which one of the following ores is best concentrated by
(a) Pure gold (b) Solid solution of gold froth-flotation method?
(c) Gold (I) hydroxide (d) Gold (III) chloride (a) Magnetite (b) Malachite
(c) Galena (d) Cassiterite
METALLURGY 93

127. Which method is commonly used to extract copper? 138. The cup and cone arrangement is used in blast furnace
(a) Electrolytic reduction (b) Reduction with carbon (a) to heat the charge with the gases
(c) Self reduction method (d) None of these (b) to escape the gases during charging
128. In froth floatation method, the role of collectors is (c) not to allow the escape of the gases
(a) to enhance non-wettability of the mineral particles (d) None of the above
(b) to enhance wettability of the mineral particles 139. Electrolytic extraction of Al is widely known as
(c) Both (a) and (b) (a) Half-Heroult process (b) vapour phase refining
(d) None of the above (c) van-Arkel method (d) None of these
129. Which of the following act as froth stabilisers? 140. In the electrolysis of alumina, cryolite is added to
(a) Cresols (b) Aniline (a) minimize the anode effect
(c) Both (a) and (b) (d) Neither (a) nor (b) (b) remove impurities from alumina
130. Gravity separation method is based upon (c) lower the melting point of alumina and to increase the
(a) difference in densities of ore particles and impurities electrical conductivity
(b) difference in chemical properties of the particles and (d) None of the above
impurities 141. Siag is a product of
(c) preferential washing of ores and gangue particles (a) coke and metal oxide (b) flux and impurities
(d) None of the above (c) metal and flux (d) flux and coke
131. The concentrated ore must be converted into a form 142. The process of bringing the metal or its ore into
which is suitable for …A… Here, A refers to solution by the action of a suitable chemical reagent
(a) reduction (b) oxidation followed by extraction of the metal either by
(c) Either (a) or (b) (d) None of the above electrolysis or by a suitable precipitating agent is
132. In roasting, the ores are usually converted into known as
(a) hydrated metal oxides (b) metals (a) zona refining (b) electrometallurgy
(c) metal oxides (d) None of these (c) electrorefining (d) hydrometallurgy
133. Roasting and calcination are 143. In the extraction of chlorine by electrolysis of brine
(a) used for the purification of metals (a) oxidation of Cl– ion to chlorine gas occurs
(b) usually carried out in reverberatory furnace (b) reduction of Cl– ion to chlorine gas occurs
(c) employed for the concentration of the ore (c) Go has negative value for overall reaction
(d) different names of the same operation (d) a displacement reaction takes place
134. Iron oxides is reduced in 144. In electrolytic refining method
(a) reverberatory furnace (b) blast furnace (a) the impure metal is made to act as anode
(c) Both (a) and (b) (d) None of these (b) a strip of the pure metal is used as cathode
135. Roasting and calcination are usually carried out in (c) they are kept in a suitable electrolytic bath containing
(a) muffle furnace (b) reverberatory furnace soluble salt of the same metal
(c) open hearth furnace (d) blast furnace (d) All the above are true
136. Usually, refractory metals are used in the construction 145. Zone refining method of the metals is based on the
of furnaces because principle that the
(a) they are chemically inert (a) impurities are more soluble in the melt than in the
(b) their melting point is high solid state of the metal
(c) they can withstand high temperature (b) impurities are less soluble in the melt than in the solid
(d) None of the above state of the metal
137. Fig iron is converted into steel by lowering the amount (c) Both (a) and (b)
of carbon contained in it, in a (d) None of the above
(a) pyrite burner (b) Bessemer converter
(c) blast furnace (d) None of the above
94 METALLURGY

146. Zone refining method is very useful for producing 148. van-Arkel method is useful in the removal of all
(a) semiconductors impurities of …I… and …II… present in the metals
(b) other metals of very high purity, ,e.g., Ge, Si, B, Ga, like Zn and Ti. Here, I and II refer to
etc. (a) oxygen and nitrogen (b) oxygen and carbon
(c) Both (a) and (b) (c) carbon and nitrogen (d) carbon and silicon
(d) None of the above 149. Usually copper is added to gold and silver to be used in
330350K
147.  Ni  CO4
Ni  4CO  jewellery to
(a) increase the hardness (b) increase malleability
450470K
Ni  CO4 
 Ni  4CO (c) increase the shine (d) lower the cost
The above reactions are of the purification of Ni by 150. Specific gravity of slag is
(a) Mond’s process (b) van-Arkel method (a) always less than molten metal
(c) Hall-Heroult process (d) None of these (b) always higher than molten metal
(c) same as that of molten metal
(d) None of the above
METALLURGY 95

EXERCISE – 2: Previous Year Questions

1. The ore having two different metal atoms is 7. The magnetite ore is (AIPMT 2007)
(AIPMT 2006) (a) ferrous oxide (b) Ferric oxide
(a) haematite (b) galena (c) Ferric hydroxide (d) Ferroso-ferric oxide
(c) magnetite (d) copper pyrites 8. Among the metals Cr, Fe, Mn, Ti, Ba and Mg, the one
2. Consider the following reaction at 1000ºC. that cannot be obtained by reduction of metal oxide
(AIPMT 2006) by aluminium is (RPMT 2007)
1 (a) Cr (b) Fe
I. Zn(s)+ O2 (g)  ZnO(s);ΔG°=-360KJmol-
2 (c) Mn (d) Mg
1 9. Which of the following statements, about the advantage
II. C(gr)+ O2 (g)  CO(g);ΔG°=-460KJmol- of roasting of sulphide ore before reduction is not true?
2
Choose the correct statement at 1000ºC (RPMT 2007)
(a) zinc can be oxidised by carbon monooxide. (a) The Gf° of the sulphide is greater than those for
(b) zinc oxide can be reduced by graphite. CS2 and H2S.
(c) both statements (a) and (b) are true. (b) TheGf° is negative for roasting of sulphide ore to
(d) both statements (a) and (b) are false. oxide.
3. Which of the following reactions taking place in the (c) Roasting of the sulphide to the oxide is
blast furnace during extraction of iron is endothermic? thermodynamically feasible.
(RPMT 2006) (d) Carbon and hydrogen are suitable reducing agents
(a) CaCO3  CaO + CO2 for metal sulphides.
10. Identify the reaction that does not take place in a blast
(b) 2C + O2  2CO
furnace. (AIPMT 2008)
(c) C + O2  CO2 (a) 2Fe2O3 + 3C  4Fe + 3CO2
(d) Fe2O3 + 3CO  2Fe + 3CO/2 (b) CO2 + C  2CO
4. Gº vs T plot in the Ellingham’s diagram slopes (c) CaCO3  CaO + CO2
downwards for the reaction. (RPMT 2006)
(d) FeO + SiO2  FeSiO3
1 1
(a) Mg+ O2  MgO (b) 2Ag+ O2  Ag 2 O 11. Which metal has a greater tendency to form metal
2 2
oxide? (RPMT 2008)
1 1
(c) C  O2  CO (d) CO  O2  CO2 (a) Al (b) Ca
2 2 (c) Cr (d) Fe
5. Sulphide ores of metals are usually concentrated by
12. When compared, the Gº for the formation of Al2O3,
Froth floatation process. Which one of the following
sulphide ores offers an exception and is concentrated by the Gº for the formation of Cr2O3 is (AIPMT 2008)
chemical leaching? (AIPMT 2007) (a) same (b) unpredicted
(a) Sphalerite (b) Argentite (c) higher (d) lower
(c) Galena (d) Copper pyrite Ans. (c)
6. Blister copper is: (AIPMT 2007) 13. In the extraction of silver, Ag2S is dissolved in:
(a) Impure Cu (AIPMT 2009)
(b) Cu Alloy (a) HCl (b) HNO3
(c) Pure Cu (c) KCN (d) H2SO4
(d) Copper having 1% impurity
96 METALLURGY

14. The process of extracting Ti from TiCl4 in presence of 24. Which of the following elements is present as the
Mg is called: (RPMT 2009) impurity to the maximum extent in the pig iron?
(a) 1MI method (b) Haber process (AIPMT 2011)
(c) Kroll collen process (d) None (a) Manganese (b) Carbon
15. In the cryolite CaCl2 is added to: (AIPMT 2009) (c) Silicon (d) Phosphorus
(a) Reduce emf of the cell (b) Increase emf of the cell 25. The following reactions take place in the blast furnace
(c) Decrease melting point (d) (b) and (c) both in the preparation of impure iron. Identify the reaction
16. The minimum voltage required to electrolyse alumina pertaining to the formation of the slag. (AIPMT 2011)
in the Hall-Heroult process is (a) Fe2O3(s) + 3CO(g) → 2Fe(l) + 3CO2(g)
(b) CaCO3(s) → CaO(s) + CO2(g)
(Given, Gf  Al2 O3   1520kJ mol ;
o 1
(c) CaO(s) + SiO2(s) → CaSiO3(s)
Gof  CO2   394kJ mol1 ) (AIIMS 2009) (d) 2C(s) + O2(g) → 2CO(g)
(a) 1.575 V (b) 1.60 V 26. Which of the following pairs of metals is purified by
(b) 1.312 V (d) – 2.62 V van Arkel method? (AIPMT 2011)
17. Which of the following diagram explain extraction of (a) Ga and In (b) Zr and Ti
metal from metal oxide: (RPMT 2010) (c) Ag and Au (d) Ni and Fe
(a) Free energy V/s temp. 27. The correct order of the abundance of the elements in
(b) Free energy V/s concentration earth’s crust is (AIMPT 2011)
(c) Free energy V/s pressure (a) O > Si > Al > Fe (b) Fe > Al > Si > O
(d) Free energy V/s volume (c) Si > Fe > Al > O (d) Al > Fe > O > Si
18. Mond’s process is used for: (AIPMT 2010) 28. Which one of the following is a mineral of iron?
(a) Ni (b) Al (AIPMT 2012)
(c) Fe (d) Cu (a) Malachite (b) Cassiterite
19. Which of the following is not a mineral of iron? (c) Pyrolusite (d) Magnetite
(AIPMT 2010) 29. In the extraction of copper from its sulphide ore, the
(a) Magnetite (b) Siderite metal is finally obtained by the reduction of cuprous
(c) Smithsonite (d) Limonite oxide with? (AIPMT 2012)
20. Which of the following sulphides when heated strongly (a) Copper (1) sulphide (Cu2S)
in air gives the corresponding metal? (b) sulphur dioxide (SO2)
(AIPMT 2011) (c) iron sulphide (FeS)
(a) Cu2S (b) CuS (d) carbon monoxide (CO).
(c) Fe2S3 (d) HgS 30. Aluminium is extracted from alumina (Al2O3) by
21. Heating pyrite ores to remove sulphur is known as: electrolysis of a molten mixture of
(AIPMT 2011) (AIPMT 2012)
(a) Liquation (b) Smelting (a) Al2O3 + HF + NaAlF4
(c) Calcination (d) Roasting (b) Al2O3 + CaF2 + NaAlF4
22. Cupellation process is used in the metallurgy of: (c) Al2O3 + Na3AlF6 + CaF2
(AIPMT 2011) (d) Al2O3 + KF + Na3AlF6
(a) Copper (b) Silver 31. Identify the ore not containing iron. (UP CPMT 2012)
(c) Iron (d) Aluminium (a) Limonite (b) Siderite
(c) Carnallite (d) Chalcopyrite
23. Park’s process is used:
(AIPMT 2011)
(a) to extract silver using NaCN
(b) to extract copper using CuFeS2
(c) to extract silver from argentiferrous lead
(d) to extract silver by forming amalgam
METALLURGY 97

32. Roasting of sulphides give the gas X as a by- 39. In the extraction of copper from its sulphide ore, the
product. This is a colourless gas with choking smell of metal is finally obtained by the reduction of cuprous
burnt sulphur and causes great damage to respiratory oxide with (NEET 2016)
organs as a result of acid rain. Its aqueous solution is (a) copper(I) sulphide (b) sulphur dioxide
acidic acts as a reducing agent and its acid has never (c) iron(II) sulphide (d) carbon monoxide.
been isolated. The gas X is 40. Match items of Column I with the items of Column II
(NEET 2013) and assign the correct code: (NEET-I 2016)
(a) H2S (b) SO2 Column I Column II
(c) CO2 (d) SO3 (A) Cyanide process (i) Ultrapure Ge
(B) Froth floatation process (ii) Dressing of ZnS
33. The metal oxide which cannot be reduced to metal by
(C) Electrolytic reduction (iii) Extraction of Al
carbon is (Karnataka NEET 2013)
(D) Zone refining (iv) Extraction of Au
(a) Al2O3 (b) PbO
(v) Purification of Ni
(c) ZnO (d) Fe2O3
Code: A B C D
34. The process of converting hydrated alumina into
(a) (i) (ii) (iii) (iv)
anhydrous alumina is called (AIPMT 2013)
(b) (iii) (iv) (v) (i)
(a) roasting (b) smelting
(c) (iv) (ii) (iii) (i)
(c) dressing (d) calcination
(d) (ii) (iii) (i) (v)
35. The ore of aluminium is (UP CPMT 2013)
(a) carnallite (b) malachite 41. Extraction of gold and silver involves leaching with CN –
ion. Silver is later recovered by (NEET 2017)
(c) galena (d) bauxite
(a) distillation (b) zone refining
36. Metals are usually not found as nitrates in their ores’.
(c) displacement with Zn (d) liquation
Out of the following two (a and b) reasons which is/are
42. In Cyanide extraction process of silver from argentite
true for the above observation? (NEET 2015) .
(1) Metal nitrates are highly unstable. ore, the oxidizing and reducing agents are respectively.
(2) Metal nitrates are highly soluble in water. (JIPMER 2017)
(a) O2 and CO2 (b) O2 and Zn dust
(a) (1) and (2) are false
(c) HNO3 and Zn dust (d) HNO3 and CO
(b) (1) is false but (2) is true
43. Considering Ellingham diagram, which of the
(c) (1) is true but (2) is false
(d) (1) and (2) are true following metals can be used to reduce alumina?
37. Identify the incorrect statement. (NEET 2018)
(a) Zn (b) Mg
(NEET Odisha 2015)
(c) Fe (d) Cu
(a) The scientific and technological process used for
44. In the extraction of copper from its sulphide ore, the
isolation of the metal from its ore known as
metallurgy metal is formed by the reduction of Cu2O
with
(b) Minerals are naturally occurring chemical substance
in the earth’s crust. (JIPMER 2018)
(a) FeS (b) CO
(c) Ores are minerals that may contain a metal
(c) Cu2S (d) SO2
(d) Gangue is an ore contaminated with undesired
45. Which one is malachite from the following?
materials
38. Which one is malachite from the following? (NEET 2019)
(a) CuCO3.Cu(OH)2 (b) CuFeS2
(NEET 2015)
(c) Cu(OH)2 (d) Fe3O4
(a) Cu  OH 2 (b) Fe3O4
(c) CuCO3 .Cu  OH 2 (d) CuFeS2
98 METALLURGY

46. Identify the incorrect statement. 48. Identify the correct statement from the following:
(Odisha NEET 2019) (NEET 2020)
(a) The scientific and technological process used for (a) Wrought iron is impure iron with 4% carbon.
isolation of the metal from its ore is known as (b) Blister copper has blistered appearance due to
metallurgy. evolution of CO2.
(b) Minerals are naturally occurring chemical substances (c) Vapour phase refining is carried out for Nickel by
in the earth’s crust. van Arkel method.
(c) Ores are minerals that may contain a metal. (d) Pig iron can be moulded into a variety of shapes.
(d) Gangue is an ore contaminated with undesired 49. Which one of the following methods can be used to
materials. obtain highly pure metal which is liquid at room
47. Which of the following has maximum iron content? temperature? (NEET 2021)
(AIIMS 2019) (a) Electrolysis (b) Chromatography
(a) Cast iron (b) Wrought iron (c) Distillation (d) Zone refining
(c) Pig iron (d) Stainless steel 50. The maximum temperature that can be achieved in blast
furnace is: (NEET 2021)
(a) Up to 1900 K (b) Up to 5000 K
(c) Up to 1200 K (d) Up to 2200 K
METALLURGY 99

EXERCISE – 3: Achiever’s Section

Single Choice Questions 8. Formation of metallic copper from the sulphide ore in
the commercial metallurgical process involves.
1. The two most abundant metals in the earth crust are: 3
(a) Cu 2S+ O2  Cu 2 O+SO2 ; Cu 2 O+C  2Cu+CO
(a) Al, Zn (b) Ag, Au 2
(c) Fe, Cu (d) Fe, Al 3
2. The chemical composition of ‘slag’ formed during the (b) Cu 2S  O2  Cu 2 O  SO2 ; 2Cu 2 O  Cu 2S  6Cu  SO2
2
smelting process in the extraction of copper is
(c) Cu 2S  2O2  CuSO4 ; CuSO4  Cu 2S  3Cu  2SO2
(a) Cu2O + FeS (b) FeSiO3
3
(c) CuFeS2 (d) Cu2S + FeO (d) Cu 2S  O2  Cu 2O  SO2 ; Cu 2 O  CO  2Cu  CO2
2
3. Carbonate of which of the following metal does not
9. Which of the following pair of ores cannot be converted
liberate carbon dioxide on heating:
into corresponding metals by pyrometallurgy?
(a) Li (b) Mg
(a) Ag2S, ZnS (b) Cu2S, HgS
(c) Na (d) Ca
4. Among the following statements, the incorrect one is: (c) MnO2, SnO2 (d) None of these
(a) Calamine and siderite are carbonates 10. Consider the following metallurgical processes:
(b) Argentite and cuprite are oxides (I) Heating impure metal with CO and distilling the
(c) Zinc blende and pyrites are sulphides resulting volatile carbonyl (b.p. 430C) and finally
(d) Malachite and azurite are ores of copper
decomposition at 1500-2000C to get the pure
5. Boron can be obtained by various methods but not by:
metal
(a) thermal decomposition of B2H6
(II) Heating the sulphide ore in air until a part is
(b) pyrolysis of BI3 (van Arkel) converted to oxide and then further heating in the
(c) reducing BCl3 with H2 absence of air to let the oxide react with
(d) electrolysis of fused BCl3 unchanged metal sulphide
(III) Electrolysis of the molten electrolyte containing
6. Select correct statement:
approximately equal amounts of the metal
(a) The decomposition of an oxide into oxygen and metal
chloride and NaCl to obtained the metal
vapour entropy increases
The processes used for obtaining magnesium nickel and
(b) Decomposition of an oxide is an endothermic change
copper are respectively:
(c) To make  G0 negative, temperature should be high (a) I, II and III (b) II, III and I
enough so that T  S0 >  H0 (c) III, I and II (d) II, I and III
(d) All are correct statement: 11. The methods chiefly used for the extraction of lead
7. Which of the following factors is of no significance for and tin from their ores are respective
roasting sulphide ores to the oxides and not subjecting (a) self-reduction and carbon reduction
the sulphide ores to carbon reduction directly (b) self-reduction and electrolytic reduction
(a) Metal sulphides are thermodynamically more stable (c) carbon reduction and self-reduction
than CS2 (d) cyanide process and carbon reduction
(b) CO2 is thermodynamically more stable than CS2 12. Refining of impure copper with zinc impurity is to be
(c) Metal sulphides are less stable than the done by electrolysis using electrodes as
corresponding oxides. Cathode Anode
(d) CO2 is more volatile than CS2 (a) pure copper pure zinc
(b) pure zinc pure copper
(c) pure copper impure copper
(d) pure zinc impure zinc
100
13. During the process of electrolytic refining of copper,
some metals present as impurity settle as ‘anode mud’.
These are
(a) Fe and Ni (b) Ag and Au
(c) Pb and Zn (d) Sn and Ag
Comprehension
Minerals from which metals can be extracted economically
and easily are called ores. The extraction of metals from their
ores involves the following processes.
(i) Concentration.
(ii) Calcination | roasting | leaching.
(iii) Reduction.
It is carried out by one of the following methods.
(A) Carbon | carbon monoxide reduction
(B) Self reduction
(C) Electrolytic reduction
(D) Reduction by more electropositive metal (i.e.
displacement method)
14. Which of the following reactions does not occur in
Bessemer converter in the extraction of copper from
chalcopyrites?
(a) 2 Cu FeS2 + 4O2  Cu2S + 2FeO + 3SO2
(b) FeO + SiO2  FeSiO3
(c) 2FeS + 3O2  2FeO + 2SO2
(d) Cu2S + 2Cu2O  6 Cu + SO2
15. Silver is extracted from its native ore by:
(a) Formation of soluble complex by dilute solution of
NaCN in presence of air followed by the reduction
with zinc.
(b) Formation of soluble complex by dilute solution of
NaCN in absence of air followed by the reduction
with zinc.
(c) Roasting followed by the self reduction
(d) Roasting followed by electrolytic reduction
16. Which of the following is not correctly matched?
(a) Red bauxite – Purification by Serpeck’s method
(b) Iron from haematite – Carbon monoxide reduction
(c) Calamine – Carbonate ore
(d) FeSiO2 – Slag obtained in the extraction of copper.
METALLURGY
Comprehension
Amongst the various ores of a metal (M) (sulphide,
carbonates, oxides, hydrated or hydroxides) two ores [X] and
[Y] show the following reactivity.
(i) [X] on calcination gives a black solid (S), carbon dioxide
and water.
(ii) [X] Dissolved in dilute HCl, on reaction with Kl gives a
white precipitate (P) and iodine.
(iii) [Y] on roasting gives metal (M) and a gas (G1) which
turns acidified K2Cr2O7 solution green.
(iv) [Y] on reaction with dil. HCl gives a white precipitate
(Q) and another gas (G2) which turns lead acetate solution
black. and also reacts with gas (G1) to precipitate colloidal
sulphur in presence of moisture.
17. The metal ores [X] and [Y] are respectively:
(a) Carbonate and sulphide ores
(b) Sulphide and carbonate ores
(c) Carbonate and hydroxide ores
(d) Carbonate and oxide ores
18. Which of the following statements is correct about [Y]?
(a) [Y] is converted to metal (M) by self reduction
(b) Carbonate extract of [Y] gives yellow precipitate
with suspension of CdCO3.
(c) [Y] is chalcocites or chalcopyrites
(d) All of these
Assertion-Reason Type Questions
While answering these questions, you are required to choose
any one of the following four responses.
(A) If both Assertion and Reason are correct and the
Reason is a correct explanation of the Assertion.
(B) If both Assertion and Reason are correct but Reason is not a
correct explanation of the Assertion.
(C) If the Assertion is correct but Reason is incorrect.
(D) If the Reason is correct but Assertion is incorrect.
19. Assertion: Extraction of iron metal from iron oxide
ore is carried out by heating with coke.
3
Reason: The reaction, Fe2 O3 (s)  Fe(s)+ O2 (g)
2
is a spontaneous process.
(a) A (b) B
(c) C (d) D
METALLURGY 101

20. Assertion: Ores are generally converted into oxides, 26. Assertion: In the electrolytic reduction of Al2O3,
prior to reduction. cryolite is used.
Reason: Metal oxides can be easily reduced. Reason: Cryolite is an ore of aluminium.
(a) A (b) B (a) A (b) B
(c) C (d) D (c) C (d) D
21. Assertion: In the extraction of Ag, complex Na [Ag 27. Assertion: Wrought iron is more malleable and ductile
(CN)2] is reacted with Zn. than steel.
Reason: Zn is d-block transition metal. Reson: It contains slightly less percentage of carbon.
(a) A (b) B (a) A (b) B
(c) C (d) D (c) C (d) D
22. Assertion: Thermite mixture Fe2O3+ Al (powder) is 28. Assertion: Lead, tin and bismuth are purified by
liquation method.
used in the welding.
Reason: Lead, tin and bismuth have low m.p. as
Reason: Al is a good reductant.
compared to impurities.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
23. Assertion: In froth flotation process sodium ethyl
29. Assertion: Al2O3 is converted into Al by reduction
xanthate is used as collector.
Reason: Sulphide ores are water soluble. with carbon at high temp.
(a) A (b) B Reason: Carbon has greater affinity for oxygen than
(c) C (d) D aluminium.
24. Assertion: Cryolite is used in electrolytic extraction of (a) A (b) B
Al from alumina. (c) C (d) D
Reason: It dissolves alumina. 30. Assertion: All the ores are mineral.
(a) A (b) B Reason: Ores contains metals in combined state
(c) C (d) D (a) A (b) B
25. Assertion: CuFeS2 is concentrated by froth floatation (c) C (d) D
method.
Reason: CuFeS2 is main ore of copper.
(a) A (b) B
(c) C (d) D
102 METALLURGY

Notes:

Find Answer Key and Detailed Solutions at the end of this book
:

METLLURGY
 13
d AND f BLOCK ELEMENTS
Chapter 13
d and f Block Elements
1. The d-Block Elements
1.1 Introduction
“The elements in which the last differentiating electron enters into
the d-orbitals of the penultimate shell are called d-block elements”.
The properties of these elements are intermediate between the
properties of s-block and p-block elements.
These elements represent a change or transition in properties
from more electropositive elements (s-block) to less electropositive
elements (p-block). Therefore these elements are called transition
elements.
A transition element may also be defined as the element which
has partially filled d-orbital in their ground state or most stable
oxidation state.
Fig. 13.1: Blocks in periodic table
SCAN CODE
d and f Block Elements
Cu (Z = 29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1
Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9 (Cupric ion)
1.2 Position of d-Block Elements in
Periodic Table
In modern periodic table, d-block elements are placed in between
s-block and p-block elements. There are total 10 groups of d-
block elements placed in the middle of periodic table. These are
from group-3 to group-12. d-block elements are further classified
into four series.
4th period (21Sc to 30Zn, 10 elements) 1st Transition series.
5th period (39Y to 48Cd, 10 elements) 2nd Transition series.
6th period (51La, 72Hf to 80Hg, 10 elements) 3rd Transition series.
7th period (89Ac, 104Rf to 112Cn, 10 elements) 4th Transition series.
d AND f BLOCK ELEMENTS 105
Thus, the electronic configuration of chromium (Z = 24) and copper
1.3 Electronic Configuration (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2 2s2 2p6 3s6 3p6 3d10 4s1
In d-block elements with increase in atomic number, the d-orbitals respectively.
of penultimate shell i.e. (n-1) d are gradually filled by electrons.
The general electronic configuration of d-block element is, (n-1)
d1-10, ns0-2. 1.4 General Properties of Transition
Depending upon the d-orbitals of which penultimate shell (i.e. n = Elements
4, 5, 6, 7) are filled, four rows (called series) of ten elements each
1.4.1 Physical Properties
obtained. They correspond to 3d, 4d, 5d and 6d subshells.
All the transition elements show typical metallic properties like
Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’ subshell,
high tensile strength, ductility, malleability, high thermal and
hence ns orbital is filled first then (n – 1) d orbitals.
electrical conductivity and metallic lustre. With the exceptions of
The electronic configuration of d-block elements of four series is
Zn, Cd, Hg and Mn, they have one or more typical metallic
shown as follows : structures at normal temperatures.
Table 13.1 : First (3d) Transition Series (Sc–Zn)
At. No. 21 22 23 24 25 26 27 28 29 30 Table 13.5 : Lattice Structures of d-Block Elements
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
4s 2 2 2 1 2 2 2 2 1 2 Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d 1 2 3 5 5 6 7 8 10 10 hcp hcp bcc bcc X bcc ccp ccp ccp X
(bcc) (bcc) (bcc, (hcp) (hcp) (hcp)
ccp)
Table 13.2 : Second (4d) Transition Series (Y-Cd) Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
hcp hcp bcc bcc hcp hcp ccp ccp ccp X
At. No. 39 40 41 42 43 44 45 46 47 48
(bcc) (bcc) (hcp)
Element Y Zr Nb Mo Tc Ru Rh Pd Au Cd
5s 2 2 1 1 1 1 1 0 1 2 La Hf Ta W Re Os Ir Pt Au Hg
4d 1 2 4 5 6 7 8 10 10 10 hcp hcp bcc bcc hcp hcp ccp ccp ccp X
(ccp, (bcc)
bcc)
Table 13.3 : Third (5d) Transition Series (La-Hg)
At. No. 57 72 73 74 75 76 77 78 79 80 The melting and boiling points of transition metals are very high.
Element La Hf Ta W Re Os Ir Pt Au Hg The high melting points of these metals are attributed to the
6s 2 2 2 2 2 2 2 1 1 2 involvement of greater number of electrons from (n-1)d in addition
5d 1 2 3 4 5 6 7 9 10 10
to the ns electrons.

Table 13.4 : Fourth (6d) Transition Series (Ac-Cn)

At. No. 89 104 105 106 107 108 109 110 111 112
Element Ac Rf Db Sg Bh Hs Mt Ds Rg Cn
7s 2 2 2 2 2 2 2 2 1 2
6d 1 2 3 4 5 6 7 8 10 10

Exceptional Configuration of Cr and Cu:

The exceptions observed in the first series are in case of electronic
configurations of chromium (Z = 24) and copper (Z = 29). It may be
noted that unlike other elements, chromium and copper have a
single electron in the 4s-orbital. This is due to the gain of additonal
stability by the atom by either having half-filled configuration
(i.e., containing 5 electrons in the d-sublevel) or completely filled
configuration, (i.e., containing 10 electrons in the d-sublevel). The
3d-level in case of chromium gets excatly half-filled with
configuration 3d5 4s1 and that in case of copper, it gets completely
filled with configuration 3d10 4s1. This can be explained on the Fig 13.2 : Melting points of transition elements
basis of exchange energy.

SCAN CODE
d and f Block Elements
106
In any series of transition elements the melting points rise to a
maximum at d5 except for anomalous values of Mn and Tc and fall
regularly as the atomic number increases. Mn has stable electronic
configuration (3d5 half filled, 4s2 fully filled). As a result 3d electrons
are more tightly held by the nucleus and this reduces the
delocalisation of electrons resulting in weaker metallic bonding.
Transition elements have high enthalpies of atomisation. The
maxima at about the middle of each series indicate that one
unpaired electron per d orbital is particularly favourable for strong
interatomic interaction. In general, greater the number of valence
electrons, stronger is the resultant bonding. Metals with very
high enthalpy of atomisation tend to be noble in their reactions.
The transition metals of the second and third series have greater
enthalpies of atomisation than the corresponding elements of the
first series.
Fig 13.3 : Enthalpies of atomisation of transition elements
1.4.2 Atomic Radii
(i) The atomic radii of the transition metals lie in-between those
of s- and p-block elements.
(ii) Generally the atomic radii of d-block elements in a series
decrease with increase in atomic number but the decrease in
atomic size is small after midway.
Explanation
The atomic radius decreases with the increase in atomic
number as the nuclear charge increases whereas the shielding
effect of d-electron is small. After midway, as the electrons
enter the last but one (penultimate) shell, the added d-electron
shields (screens) the outermost electron. Hence, with the
increase in the d-electrons, screening effect increases. This
counterbalances the increased nuclear charge due to increase
in atomic number. As a result, the atomic radii remain practically
same after chromium. For example in Fe, the two opposing
tendencies almost counterbalance and there is no change in
the size from Mn to Fe.
SCAN CODE
d and f Block Elements
d AND f BLOCK ELEMENTS
(iii) At the end of the period, there is a slight increase in the
atomic radii.
Explanation
Near the end of series, the increased electron-electron
repulsions between added electrons in the same orbitals are
greater than the attractive forces due to the increased nuclear
charge. This results in the expansion of the electron cloud
and thus the atomic radius increases.
(iv) The atomic radii increase down the group. This means that
the atomic radii of second series are larger than those of first
transition series. But the atomic radii of the second and third
transition series are almost the same.
The atomic radii of the elements of the second and third
transition metals are nearly same due to lanthanide contraction
(or also called lanthanoid contraction) discussed later.)
Fig 13.4 : Atomic radii of transition elements
1.4.3 Ionic Radii
(i) The trend followed by the ionic radii is the same as that
followed by atomic radii.
(ii) Ionic radii of transition metals are different in different
oxidation states.
(iii) The ionic radii of the transition metals are smaller than those
of the representative elements belonging to the same period.
1.4.4 Ionisation Enthalpies
(i) The first ionisation enthalpies of d-block elements lie between s-
block and p-block elements. They are higher than those of s-
block elements and are lesser than those of p-block elements.
The ionisation enthalpy gradually increases with increase in
atomic number along a given transition series though some
irregularities are observed.
d AND f BLOCK ELEMENTS 107
Table 13.6 : Ionisation Enthalpies of 3d Series of Transition Elements
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Δi H o in kJ mol-1
IE1 I 631 656 650 653 717 762 758 736 745 906
IE 2 II 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734
IE 3 III 2393 2657 2833 2990 3260 2962 3243 3402 3556 3837
Standard
Electrode M2+/M  -1.63 -1.18 -0.90 -1.18 -0.44 0.28 -0.25 +0.34 -0.76
Potential Eo/V M3+/M2+  -0.37 -0.26 -0.41 +1.57 +0.77 +1.97   

Explanation 1.4.5 Oxidation State

The increasing ionization enthalpies are due to increased nuclear
charge with increase in atomic number which reduces the size of
the atom making the removal of outer electron difficult.
(ii) In a given series, the difference in the ionisation enthalpies
between any two successive d-block elements is very much
less than the difference in case of successive s-block or p-
block elements.
Explanation
The addition of d electrons in penultimate shell with increase
in atomic number provides a screening effect and thus shields
the outer s electrons from inward nuclear pull. Thus, the
effects of increased nuclear charge and addition of d electrons
tend to oppose each other.
(iii) The first ionization enthalpy of Zn, Cd and Hg are, however,
very high because of the fully filled (n-1) d10 ns2 configuration.
(iv) Although second and third ionization enthalpies also, in
general, increase along a period, but the magnitude of increase
for the successive elements is much higher.
(v) The high values of 3rd ionization enthalpies for Cu, Ni and
Zn explain why they show a maximum oxidation state of +2.
(i) With the exception of few elements, most of the d-block
elements show more than one oxidation state.
(ii) The elements show variable oxidation state because ‘(n-1) d’
and ‘ns’ orbitals in the atoms of d-block elements have almost
same energies and therefore electron can be removed from
‘(n-1)d’ orbitals as easily as ‘ns’ orbitals electrons.
(iii) Minimum oxidation state = Total number of 4s electrons lost.
Maximum oxidation state = (Total number of 4s electrons lost
+ 3d electrons lost).
(iv) The elements which give the greatest number of oxidation
states occur near the middle of the series. For example, Mn
exhibits all the oxidation states from +2 to +7.
(v) The extreme ends of a series show less number of oxidation
states. For example, Sc shows only +3 and Zn shows only +2.
(vi) Transition metals also show zero oxidation states in metal
carbonyl complex. For example : Ni in [Ni(CO)4] (Nickel
tetracarbonyl) has zero oxidation state.
(vii) In groups 4 to 10, the lower oxidation states are more stable in
3d series. For example, in group 6, Mo(VI) and W(VI) are
more stable than Cr(VI). Thus Cr(VI) in dichromate is a stronger
oxidising agent then MoO3 and WO3 in acidic medium.

Table 13.7 : Oxidation States in 3d Series of Transition Elements

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1 +2
Oxidation states

+3 +3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7

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108 d AND f BLOCK ELEMENTS

1.4.6 Standard Electrode Potentials (E o) Table 13.8 : Eo ( M 2+  M o ) Values for Ti to Zn

In solution, the stability of the compounds of transition metals
depends upon electrode potentials. Electrode potential values M a Ho  i H1o  i H o2  Hyd H o  M 2   Eo/V
depend upon factors such as enthalpy of sublimation (or
Ti 469 656 1309 –1866 –1.63
atomisation) of the metal, the ionisation enthalpy and the hydration
V 515 650 1414 –1895 –1.18
enthalpy, i.e.,
Cr 398 653 1592 –1925 –0.90
 sub H
M  s   M  g  , (  sub H is enthalpy of sublimation) Mn 279 717 1509 –1862 –1.18
Fe 418 762 1561 –1998 –0.44
 iH
M  g    M  g   e , (  i H is ionisation enthalpy)
 
Co 427 758 1644 –2079 –0.28
Cu 339 745 1958 –2121 0.34
 H
M   g   aq 
hyd
M   aq  , (  hyd H is enthalpy of hydration) Zn 130 906 1734 –2059 –0.76

The total energy, T H , for the process involving sublimation,

(iv) The values of Eo for Mn, Ni and Zn are more negative than
ionisation and hydration simultaneously, i.e., for the process, expected from the general trend. This is due to greater stability
M  s  
 M   aq   e  , will be the sum of the three types of of half-filled d-subshell (d5) in Mn2+, and completely filled d-
subshell (d10) in Zn2+. The exceptional behaviour of Ni towards
enthalpies, i.e.,
Eo value from the regular trend is due to its high negative
 T H   sub H   i H   hyd H enthalpy of hydration.

Thus, T H , is the total enthalpy change when solid metal, M is

brought in the aqueous medium in the form of monovalent ion,
M+ (aq).

Trends in the M2+/M Standard Electrode Potentials:

(i) There is no regular trend in the Eo (M2+/M) values. This is
because their ionization enthalpies (IE1 + IE2) and sublimation
enthalpies do not show any regular trend.
(ii) The general trend towards less negative Eo values along the
series is due to the general increase in the sum of first and
second ionization enthalpies.
(iii) Copper shows a unique behaviour in the series as it is the
only metal having positive value for Eo. This explains why is
does not liberate H2 gas from acids. It reacts only with the
oxidizing acids (HNO3 and H2SO4) which are reduced. The
reason for positive Eo value for copper is that the sum of
enthalpies of sublimation and ionization is not balanced by
hydration enthalpy.
2
Fig 13.5 : Eo ( M  Mo ) values for Ti to Zn
Trends in the M3+/M2+ Standard Electrode Potentials:
(i) A very low value for Eo (Sc3+/Sc2+) reflects the stability of
Sc3+ ion which has a noble gas configuration.
(ii) The highest value for Zn is on account of very high stability
of Zn2+ ion with d10 configuration. It is difficult to remove an
electron from it to change it into +3 state.
(iii) The comparatively high value of Eo (Mn3+/Mn2+) shows that
Mn 2+ is very stable which is on account of stable d 5
configuration of Mn2+.

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d AND f BLOCK ELEMENTS
(iv) The comparatively low value of Eo (Fe3+/Fe2+) is on account
of extra stability of Fe3+ (d5), i.e., low third ionization enthalpy
of Fe.
Chemical Reactivity and Eo Values:
The transition metals vary widely in their chemical reactivity. Some
of them are highly electropositive and dissolve in mineral acids
whereas a few of them are ‘noble’, i.e., they do not react with simple
acids. Some results of chemical reactivity of transition metals as
related to their Eo values are given below :
(i) The metals of the first transition series (except copper) are
relatively more reactive than the other series. Thus, they are
oxidized by H+ ions though the actual rate is slow, e.g., Ti and
V are passive to dilute non-oxidizing acids at room
temperature.
(ii) As already explained, less negative Eo values for M2+/M along
the series indicate a decreasing tendency to form divalent
cations.
(iii) More negative Eo values than expected for Mn, Ni and Zn
show greater stability for Mn2+, Ni2+ and Zn2+.
(iv) Eo values for the redox couple M3+/M2+ indicate that Mn3+
and Co3+ ions ar the strongest oxidizing agents in aqueous
solution whereas Ti2+, V2+ and Cr2+ are strongest reducing
agents and can liberate hydrogen from a dilute acid, e.g.,
2 Cr2+ (aq) + 2 H+ (aq) 
 2 Cr3+ (aq) + H2 (g)
109
Diamagnetic substances are repelled by the applied field while
the paramagnetic substances are attracted. Most of the transition
metal ions are paramagnetic due to the presence of unpaired
electrons. Each such electron having a magnetic moment
associated with its spin angular momentum and orbital angular
momentum.
In first transition elements series the orbital angular magnetic
moment is insignificant the orbital contribution is quenched by
the electric fields of the surrounding atoms so magnetic moment
is equal to the spin magnetic moment only.
It can be calculated by using the formula:
 eff  n (n  2) BM
n  no. of unpaired electron.
The magnetic moment increases with the increasing number of
unpaired electrons. Thus, the observed magnetic moment is
directly related to the number of unpaired electrons present in the
atom, molecule or ion.
1.4.8 Catalytic Properties
Most transition elements and their compounds have good catalytic
properties because
(a) They possess variable oxidation state.
(b) They provide a large surface area for the reactant to be
absorbed.

Table 13.10 : Some Common Catalysts

1.4.7 Magnetic Behaviour
When a magnetic field is applied to substances, mainly two types
Catalysts Uses
of magnetic behaviour are observed: diamagnetism and
paramagnetism. TiCl4 + Al (C2H5)3 Ziegler-Natta catalyst, used in
polymerisation of ethylene
Table 13.9 : Magnetic Moments of 3d Series Ions V2O5 Contact process SO2  SO3
Fe Haber Bosch process
Ion Unpaired Magnetic moment PdCl2 Wacker’s process for CH3CHO
electron(s) Calculated Observed
manufacturing
Sc3+ 3d0 0 0 0
Ti3+ 3d1 1 1.73 1.75 Pd Hydrogenation of alkene, alkyne
Tl2+ 3d2 2 2.84 2.76 Pt/PtO Adam’s catalyst for selective
V2+ 3d3 3 3.87 3.86 reduction
Cr2+ 3d4 4 4.90 4.80
Pt Catalytic convertor, for
Mn2+ 3d5 5 5.92 5.96
Fe2+ 3d6 4 4.90 5.3 – 5.5 cleaning car exhaust fumes
Co2+ 3d7 3 3.87 4.4 – 5.2 Pt/Rh Ostwald’s process :
Ni2+ 3d8 2 2.84 2.9 – 3, 4 NH3  NO
Cu2+ 3d9 1 1.73 1.8 – 2.2
Zn2+ 3d10 0 0 Cu Oxidation of alcohols

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110 d AND f BLOCK ELEMENTS

1.4.9 Complex Formation 1.4.11 Interstitital Compounds

Transition metal ions form a large number of complex compounds. The transition metals form a large number of interstitial compounds
Complex compounds are those which have a metal ion linked to a in which small atoms such as hydrogen, carbon, boron and
number of negative ions (anions) or neutral molecules having nitrogen occupy the empty spaces (interstitial sites) in their
lone pairs of electrons. These ions or molecules are called ligands. lattices.
They donate lone pairs of electrons to the central transition metal They are represented by formulae like TiC, TiH2, Mn4N, Fe3H,
ion forming coordinate bonds. Fe3C etc. However, actually they are non-stoichiometric materials,
A few examples are given below : e.g., TiH1.7, VH0.56 etc. and the bonds present in them are neither
[Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+, [Zn(NH3)4]2+, [Ni(CN)4]2– typically ionic nor covalent. Some of their important characteristics
and [PtCl4]2– are as follows:
Such complex compounds are not formed by s - and p - block (i) They are very hard and rigid, e.g., steel which is an interstitial
elements. compound of Fe and C is quite hard. Similarly, some borides
Explanation. The transition elements form complexes because of are as hard as diamond.
the following reasons : (ii) They have high melting points which are higher than those
(i) Comparatively smaller size of their metal ions. of the pure metals.
(ii) Their high ionic charges and high charge/size ratio. (iii) They show conductivity like that of the pure metal.
(iii) Availability of vacant d-orbitals so that these orbitals can (iv) They acquire chemical inertness.
accept lone pairs of electrons donated by the ligands.
1.4.10 Formation of Coloured Compounds 1.4.12 Alloy Formation
Transition elements form coloured ions due to presence of Alloys are homogeneous solid solutions of two or more metals
incompletely filled d-orbitals and unpaired electrons. They can obtained by melting the components and then cooling the melt.
undergo d-d transition by absorbing colour from visible region These are formed by metals whose atomic radii differ by not more
and radiating complementary colour, e.g. Cu2+ (blue), V2+(violet), than 15% so that the atoms of one metal can easily take up the
Cr3+(green). Cu+(3d10), Zn2+(3d10), Cd2+(4d10), Sc3+(3d0 ) are white positions in the crystal lattice of the other.
due to presence of no unpaired electrons and cannot undergo d- As transition metals have similar atomic radii and other
d transition. characteristics, hence they form alloys very readily.
Alloys are generally harder, have higher melting points and more
Table 13.11 : Colour of Ions of 3d Series
resistant to corrosion than the individiual metals.
The most commonly used are the ferrous alloys the metals
Configuration Example Colour chromium, vanadium, molybdenum, tungsten and manganese are
3d0 Sc3+ colourless used in the formation of alloy steels and stainless steels. Some
3d0 Ti4+ colourless alloys of transition metals with non-transition metals are also very
common. e.g., brass (Cu + Zn) and bronze (Cu + Sn)
3d1 Ti3+ purple
3d1 V4+ blue
3d2 V3+ green
3d3 V2+ violet
3d3 Cr3+ violet
3d4 Mn3+ violet
3d4 Cr2+ blue
3d5 Mn2+ pink
3d5 Fe3+ yellow
3d6 Fe2+ green
Fig 13.6 : Alloy Formation
3d63d7 Co3+Co2+ bluepink
3d8 Ni2+ green
3d9 Cu2+ blue
3d10 Zn2+ colourless

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d AND f BLOCK ELEMENTS 111

2. Important Compounds of After the reaction, the roasted mass is extracted with water
when sodium chromate is completely dissolved while ferric
Transition Elements oxide is left behind. Ferric oxide is separated out by filtration.
(ii) Conversion of Sodium Chromate into Sodium Dichromate:
2.1 Oxides and Oxocations The filtrate containing sodium chromate solution is treated
(i) The metals of the first transition series form oxides with oxygen with concentrated sulphuric acid when sodium chromate is
at high temperature. converted into sodium dichromate.
(ii) The oxides are formed in the oxidation, states +1 to +7.
(iii) The highest oxidation state in the oxides of any transition 2Na 2 CrO 4  H 2SO 4  Na 2 Cr2 O7  Na 2SO 4  H 2 O
Sod.chromate  Conc. Sod. dichromate
metal is equal to its group number, e.g., 7 in Mn2O7. Beyond
group 7, no higher oxides of iron above Fe2O are known. Sodium sulphate being less soluble crystallizes out as
Some metals in higher oxidation state stabilize by forming decahydrate, Na2SO4. 10H2O and is removed. The clear
solution is then evaporated in iron pans to a specific gravity
oxocations, e.g., VV as VO2 , VIV as VO2+ and TiIV as TiO2+.
of 1.7 when a further crop of sodium sulphate is formed. It is
(iv) All the metals except scandium form the oxides with the removed and the solution is cooled when orange crystals of
formula MO which are ionic in nature. As the oxidation number sodium dichromate, Na2Cr2O7. 2H2O separate on standing.
of the metal increases, ionic character decreases, e.g., Mn2O7 (iii) Conversion of Na2Cr2O7 into K2Cr2O7 :
is a covalent green oil. Even CrO3 and V2O5 have low melting Hot concentrated solution of sodium dichromate is treated
points. with calculated amount of potassium chloride when potassium
2 8/3 3 4 7 dichromate, being much less soluble than sodium salt,
MnO Mn 3O4 Mn 2 O3 MnO2 Mn 2 O7 crystallizes out on cooling as orange crystals.
(v) In general, the oxides in the lower oxidation states of the
Na 2 Cr2 O7  2KCl 
 K 2 Cr2 O7  2NaCl
metals are basic and in their higher oxidation states, they are
Sodium dichromate Potassium dichromate
acidic whereas in the intermediate oxidation state, the oxides
are amphoteric. 2.2.2 Structures of Chromate and Dichromate Ions
For example, the behaviour of the oxides of manganese may The chromate ion, CrO42– is tetrahedral and the dichromate ion,
be represented as follows : Cr2O72– is made up of two tetrahedra sharing one corner with Cr–
2 8/3 3 4 7
O–Cr bond angle of 126°.
MnO Mn 3O 4 Mn 2 O3 MnO 2 Mn 2 O 7
Basic Amphoteric Amphoteric Amphoteric Acidic

Thus, Mn2O7 dissolves in water to give the acid HMnO4.

2.2 Potassium Dichromate, K2Cr2O7

2.2.1 Preparation Process
It is prepared from the ore called chromite or ferrochrome or chrome
iron, FeO.Cr2O3. The various steps involved are as follows :
(i) Preparation of Sodium Chromate:
The ore is finely powdered, mixed with sodium carbonate and
quick lime and then roasted, i.e., heated to redness in a
reverberatory furnace with free exposure to air when sodium
chromate (yellow in colour) is formed and carbon dioxide is
evolved. Quick lime keeps the mass porous and thus facilitates
oxidation.
Fig 13.7 : Structure of chromate and dichromate ions
2.2.3 Properties of Potassium Dichromate
(a) Colour and Melting Point: It forms orange crystals which
melt at 669 K.
(b) Solubility: It is moderately soluble in cold water but freely
soluble in hot water.
(c) Action of Heat: When heated to a white heat, it
decomposes with the evolution of oxygen.

4FeCr2O4 + 8Na2CO3+ 7O2 

 8Na2CrO4 + 2Fe2O3 + 8CO2 4K 2 Cr2 O7 
 4K 2 CrO4  2Cr2 O3  3O2
Chromite ore Sod. chromate Ferric oxide

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112 d AND f BLOCK ELEMENTS
(d) Action of Alkalies: When an alkali is added to an orange (ii) It oxidises ferrous salts to ferric salts
red solution of dichromate, a yellow solution results due to  K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  7H 2 SO 4  6FeSO 4 
the formation of chromate.
3Fe2  SO4 3  2H 2 O
K 2 Cr2 O7  KOH 
 2K 2 CrO 4  H 2 O
Pot. dichromate Pot.chromate (iii) It oxidises H2S to sulphur

or Cr2 O72   2 OH  
 2 CrO42   H 2 O  K 2 SO 4  Cr2 SO 4 3
K 2 Cr2 O7  4H 2SO 4  3H 2S 

On acidifying, the colour again changes to orange red due to + 7H2O + 3S

the reformation of dichromate. (iv) It oxidises sulphites to sulphates and thiosulphates to
sulphates and sulphur
2 K 2 CrO 4  H 2SO4 
 K 2 Cr2 O7  K 2SO4  H 2 O
 K 2SO4  Cr2  SO 4 3
K 2 Cr2 O7  4H 2SO 4  3Na 2SO3 
or 2 CrO 24   2 H  
 Cr2 O72   H 2 O
+ 4H2O + 3Na2SO4
This interconversion is explained by the fact that in dichromate (v) It oxidises nitrites to nitrates
solution, the Cr2 O72 ions are invariably in equilibrium with  K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  4 H 2SO 4  3NaNO 2 
2
CrO 4
ions at pH = 4, i.e., + 3 NaNO3 + 4 H2O
(vi) It oxidises halogen acids to halogen
pH  4
Cr2 O 2
7

 H 2 O  2CrO 42   2H 
Orange red Yellow K 2 Cr2 O7  14 HCl 
 2KCl  2CrCl3  7H 2 O  3Cl2
 dichromate   chromate 
(vii) It oxidises SO2 to sulphuric acid
(e) Action of Concentrated Sulphuric Acid :
K 2 Cr2 O7  H 2SO4  3SO2  K 2SO4 Cr2  SO 4 3 3H 2 O
(i) In cold, red crystals of chromic anhydride (chromium trioxide)
are formed. (viii) It oxidises stannous salts to stannic salts

K 2 Cr2 O7  2H 2SO 4 
 2CrO3  2KHSO4  H 2 O Cr2 O72   14 H   3Sn 2  
 2 Cr 3  3 Sn 4   7 H 2 O

(ii) On heating the mixture, oxygen is evolved. (ix) It oxidises ethyl alcohol to acetaldehyde and acetic acid.

K 2 Cr2 O7  4H 2SO4  K 2SO4  Cr2  SO4 3  4H 2 O  3  O

2K 2 Cr2 O7 8H 2SO4 2K 2SO4 2Cr2  SO 4 3  8H 2 O  3O2
(f) Oxidising Properties: It is a powerful oxidising agent. In CH2 CH2 OH  O 
 CH3CHO  H2 O
the presence of dilute sulphuric acid, one molecule of Ethyl alcohol
potassium dichromate furnishes 3 atoms of available oxygen
as indicated by the equation : CH3CHO   O 
 CH3COOH
Acetaldehyde Acetic acid
K 2 Cr2 O7  4H 2SO4  K 2SO4 Cr2  SO 4 3 4H 2 O  3 O 
Test for a drunken driver : The above reaction helps to test
2   3 whether a driver has consumed alcohol or not. He is asked to
or Cr2 O  14H  6e 
7  2Cr  7H 2 O
breathe into the acidified K2Cr2O7 solution taken in a test tube. If
Mol. wt. 294 the orange colour of the solution changes into green colour (due
 Eq. wt. of K 2 Cr2 O 7    49
6 6 to Cr2(SO4)3 formed in the reaction), the driver is drunk, otherwise
not.
(i) It liberates I2 from KI
(g) Chromyl Chloride test : (Reaction with a chloride and
 4K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  7H 2SO 4  6KI  conc. sulphuric acid). When heated with concentrated
hydrochloric acid or with a chloride and strong sulphuric
3I2  7H 2 O
acid, reddish brown vapours of chromyl chloride are obtained.

K 2 Cr2 O7  4KCl  6H 2SO 4 

 2CrO 2 Cl 2  6KHSO 4
Chromyl chloride
 Re d vapour   3H 2 O

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d AND f BLOCK ELEMENTS 113
(h) Reaction with Hydrogen Peroxide : Acidified K2Cr2O7 MnO2 + 2KOH + KNO3 
 K2MnO4 + KNO2 + H2O
solution reacts with H2O2 to give a deep blue solution due to
the formation of peroxo compound, CrO (O2)2. 3MnO2 +6KOH+KClO3 
 3K2MnO4 +KCl+2H2O
(ii) Oxidation of Potassium Manganate to Potassium
Cr2 O72   2 H   4 H 2 O2 
 2 CrO5  5 H 2 O
Permanganate:
The blue colour fades away gradually due to the Potassium manganate thus formed undergoes
decomposition of CrO5 into Cr3+ ions and oxygen. disproportionation in the neutral or acidic solution as follows,
if allowed to stand for some time :
The structure of CrO5 is in which Cr is in +6 VI VII IV
3MnO24   4 H   2MnO4  MnO2  2 H 2 O
Manganate ion Permanganate ion
oxidation state.
2.2.4 Uses of Potassium Dichromate The fused mass is extracted with water and the solution after
filtration is converted into potassium permanganate by
(i) In volumetric analysis, it is used as a primary standard for the
bubbling carbon dioxide, chlorine or ozonised oxygen through
estimation of Fe2+ (ferrous ions) and I– (iodides) in redox
the green solution.
titrations.
(ii) In industry, it is used 3K 2 MnO4  2CO2 
 2KMnO 4  MnO 2  2K 2 CO3
(a) In chrome tanning in leather industry. 2K 2 MnO4  Cl2 
 2KMnO4  2KCl
(b) In the preparation of chrome alum K2SO4.Cr2(SO4)3. 24H2O 2K 2 MnO4  H 2 O  O3   2KMnO4  2KOH  O2
and other industrially important compounds such as Cr2O3, The carbon dioxide process is uneconomical as one third of the
CrO3, CrO2Cl2, K2CrO4, CrCl3 etc. original manganate is reconverted to manganese dioxide. However,
(c) In calico printing and dyeing. this process has the advantage that the potassium carbonate
(d) In photography and in hardening gelatine film. formed as a by-product can be used for the oxidative fusion of
(iii) In organic chemistry, it is used as an oxidising agent. manganese dioxide. In the chlorine process, potassium chloride
obtained as a by-product is lost.

NOTE : 2.3.2 Structure of Manganate and Permanganate ions

Unlike K2Cr2O7, Na2Cr2O7 is not used in volumetric analysis
because it is deliquescent.
2.3 Potassium Permanganate (KMnO4)
2.3.1 Preparation Methods
On a large scale, it is prepared from the mineral, pyrolusite, MnO2.
The preparation involves the following two stesp:
(i) Conversion of MnO2 into Potassium Manganate:
Both manganate  MnO 4  and permanganate  MnO 4  ions are
2 
tetrahedral. Here the  -bonding takes place by overlap of p
orbitals of oxygen with d orbitals of manganese. The green
manganate ion is paramagnetic because of one unpaired electron
but the permanganate ion is diamagnetic due to the absence of
any unpaired electron.
Its intense colour and diamagnetism along with temperature-
dependent weak paramagnetism can be explained by molecular
orbital theory.

The finely powdered pyrolusite mineral is fused with

potassium hydroxide or potassium carbonate in the presence
of air or oxidising agent such as potassium nitrate or
potassium chlorate when green coloured potassium
manganate is formed.

2MnO2 + 4KOH + O2 
 2K2MnO4 + 2H2 O
Potassium manganate
Fig 13.8 : Structure of manganate and permanganate ions
2MnO2 + 2K2CO3 + O2 
 2K2MnO4 + 2 CO2

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2.3.3 Properties of Potassium Permanganate (iii) It oxidises nitrites  NO 


2 to nitrates  NO  , arsenites

3

(a) Colour : Potassium permanganate exists as deep purple black

prisms with a greenish lustre which become dull in air due to  AsO 
3
3 to arsentates  AsO 
3
4 and sulphites and
superficial reduction. thiosulphates to sulphates.
(b) Solubility : It is moderately soluble in water at room
2KMnO 4  3H 2SO4  5KNO 2 
 K 2SO4  2MnSO4 
temperature and it is more soluble in hot water.
(c) Action of Heat : When heated to 513 K, it readily decomposes 3H 2 O  5KNO3
giving oxygen. (iv) It oxidises oxalates or oxalic acid to CO2
2KMnO 4 
 K 2 MnO 4  MnO 2  O 2 2KMnO4  3H 2SO4  5C2 H 2 O4 
 K 2SO4  2MnSO4 
Pot. manganate
8H 2 O  10 CO2
At red heat, potassium manganate formed decomposes into
potassium manganite (K2MnO3) and oxygen. (v) It oxidises ferrous sulphate to ferric sulphate (i.e., ferrous salt
2K 2 MnO4   2K 2 MnO3  O 2 to ferric salt).
(d) Action of heat in current of hydrogen : When heated in a 2KMnO4  8H 2SO4  10FeSO4 
 K 2SO 4  2MnSO 4 
current of H2, solid KMnO4 gives KOH, MnO and water
vapours. 5Fe2  SO4 3  8H 2 O
 (vi) It oxidises H2O2 to H2O and O2. This is because acidified
2KMnO 4  5H 2 
 2KOH  2MnO  4H 2 O
KMnO4 is a stronger oxidising agent than H2O2.
(e) Oxidising Property. Potassium permanganate is powerful
oxidising agent. The actual course of reaction depends on 2KMnO4  3H 2SO4  5H 2 O 2 
 K 2SO4  2MnSO4 
the use of the permanganate in (a) acidic medium (b) neutral
8H 2 O  5O 2
medium or (c) alkaline medium.
In acidic medium : Potassium permanganate in the presence of (vii) It oxidises potassium iodide to iodine
dil. sulphuric acid, i.e., in acidic medium, acts as a strong oxidising 2KMnO 4  3H 2SO 4  10KI 
 K 2SO 4  2MnSO 4 
agent because of the reaction
8H 2 O  5I 2
 K 2 SO 4  2MnSO 4  3H 2 O  5  O 
2KMnO 4  3H 2 SO 4 
(viii) It oxidises HX (where X = Cl, Br, I) to X2
or MnO4  8H   5 e  
 Mn 2   4H 2 O.
2KMnO4  3H 2SO 4  10 HX 
 K 2SO 4  2MnSO 4 

Since in the above reaction, MnO ion gains 5 electrons of five
4 8H 2 O  5X 2
atoms of oxygen are available from two molecules of KMnO4.
(ix) It oxidises ethyl alcohol to acetaldehyde
Hence.
2KMnO 4  3H 2SO 4  5C 2 H 5 OH  K 2SO 4
Mol. wt. 158
Eq. wt. of KMnO 4    31.6  2MnSO 4  5CH 3 CHO  8H 2 O
5 5
Some oxidizing properties of KMnO4 in the acidic medium: In neutral solution :
These are given below : Potassium permanganate acts as a moderate oxidising agent in
(i) It oxidises H2S to S. neutral aqueous solution because of the reaction :
 2KOH  2MnO 2  3 O 
2KMnO 4  H 2 O 
2KMnO 4  3H 2SO 4  5H 2S 
 K 2SO 4  2MnSO 4
or
8H2O 5S
MnO 4  2H 2 O  3 e  
 MnO2  4OH 
(ii) It oxidises sulphur dioxide to sulphuric acid.
2KMnO4  5 SO2  2H 2 O 
 K 2SO4  2MnSO 4  2H 2SO4

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d AND f BLOCK ELEMENTS 115
or
Thus, MnO4 ion gains 3 electrons. Also, according to the above  
I  6OH   IO3  3H 2 O  6 e
equation, in neutral medium, from two moles of permanganate,
In this case, iodine is not liberated unlike the case of acidic
three oxygen atoms are available. In fact, during the course of
medium.
reaction, the alkali generated renders the medium alkaline even
when we start with neutral solutions. Hence, Eq. wt. of KMnO4 in Similar reaction takes place with KBr.
(ii) It oxidises olefinic compounds to glycols, i.e., when an olefinic
neutral or weakly alkaline medium
compound is shaken with alkaline KMnO4, pink colour of
Mol. wt. 158 KMnO4 is discharged.
   52.67
3 3 CH 2 CH OH
Some oxidizing properties of KMnO4 in the neutral medium. These Alkaline  | 2
||  H 2 O   O  
are given below : CH 2 KMnO4 CH OH
2
(i) It oxidises hot manganous sulphate to manganese dioxide. Ethylene Ethylene glycol

2KMnO4  3MnSO4  2H 2 O 
 K 2SO 4  2H 2SO 4  5MnO2 Alkaline KMnO4 used for this test is known as Baeyer’s
Presence of ZnSO4 or ZnO catalyses the oxidation. reagent. It is used for oxidation of a number of organic
compounds.
(ii) It oxidises sodium thiosulphate to sodium sulphate.
8KMnO 4  3Na 2S2 O3  H 2 O 
 3K 2SO4  8MnO 2 
2.3.4 Uses of Potassium Permanganate
3Na 2SO 4  2KOH
(i) It is often used in volumetric analysis for the estimation of
(iii) It oxidises hydrogen sulphide to sulphur. ferrous salts, oxalates, iodides and hydrogen peroxide.
2KMnO4  4H 2S 
 2MnS  S  K 2SO4  4H 2 O However, it is not a primary standard because it is difficult to
obtain it in the pure state and free from traces of MnO2. It is,
In alkaline solution : In strongly alkaline solution, MnO 24 
therefore, always first standardised with a standard solution
(manganate) ion is produced. of oxalic acid.
 2K 2 MnO 4  H 2 O   O 
2KMnO 4  2KOH  (ii) Volumetric titrations inolving KMnO4 are carried out only in
or presence of dilute H2SO4 but not in the presene of HCl or
  HNO3. This is because oxygen produced from KMnO4 + dill.
 MnO 24 
MnO  e 
4
H2SO4 is used only for oxidizing the reducing agent. Moreover,
Mol. wt. 158 H2SO4 does not give any oxygen of its own to oxidize the
 Eq. wt. of KMnO 4    158
1 1 reducing agent. In case HCl is used, the oxygen produced
from KMnO4 + HCl is partly used up to oxidize HCl to chlorine
Potassium manganate is also further reduced to MnO2 when a
and in case HNO3 is used, it itself acts as oxidizing agent and
reducing agent is present. partly oxidizes the reducing agent.
 MnO 2  2KOH  O 
K 2 MnO 4  H 2 O  (iii) It is used as a strong oxidising agent in the laboratory as well
as in industry. Alkaline potassium permanganate is used for
or MnO24   2H 2 O  2 e  
 MnO2  4OH  testing unsaturation in organic chemistry and is known as
So the complete reaction is : Baeyer’s reagent.
 2MnO 2  2 KOH  3  O 
2KMnO 4  H 2 O  (iv) Potassium permanganate is also widely used as a disinfectant
or and germicide. A very dilute solution of permanganate is used
for washing wounds and gargling for mouth sore. It is also
MnO  2H 2 O  3 e  

4  MnO2  4OH 
used for purifying water of stinking wells.
which is the same as that for neutral medium. Hence, equivalent
(v) Because of its strong oxidizing power, it is also used for
weight of KMnO4 in weakly alkaline medium is same as that in the
bleaching of wool, cotton, silk and other textile fibres and
neutral medium, viz., 52.67
also for decolourisation of oils.
Some oxidizing properties of KMnO4 in the alkaline medium:
These are given below :
(i) It oxidises potassium iodide to potassium iodate.

2KMnO 4  H 2 O  KI 
 2MnO 2  2KOH  KIO3
Pot. iodate

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116 d AND f BLOCK ELEMENTS

THE f-BLOCK ELEMENTS

1. Introduction 2.2 Oxidation State
The innter transition elements are also known as f-block elements. The sum of the first three ionization energies for each element are
There are two f-block series, lanthanoids (the fourteen elements low. Thus the oxidation state (+III) is ionic and Ln3+ dominates
following lanthanum) and actinoids (the fourteen elements the chemistry of these elements. The Ln2+ and Ln4+ ions that do
following actinium). The lanthanoids resemble each other closely. occur are always less stable than Ln3+.
They have only one stable oxidation state and their chemistry
Oxidation numbers (+II) and (+IV) do occur, particularly when
resembles largely with each other. On the other hand, the chemistry
they lead to :
of the actinoids is much more complicated due to the occurrence
of a wide range of oxidation states and radioactive nature. 1. a noble gas configuration e.g. Ce4+ (f 0)
2. a half filled f shell, e.g. Eu2+ and Tb4+ (f7)
2. The Lanthanide Series 3. a completely filled f level, e.g. Yb2+ (f14).
The 14 elements after La-57 are collectively called lanthanoides or
NOTE :
lanthanide series or 4f series. Some times, lanthanoides are
collectively represented by symbol Ln. The 4f electrons in the antipenultimate shell are very effectively
shielded from their chemical environment outside the atom by
the 5s and 5p electrons. Consequently the 4f electrons do not
2.1 Electronic Confignration take part in bonding. Whether the f orbitals are filled or empty
These elements have electronic configration [Xe]4f1-14 5d0-1 6s2. has little effect on the normal chemical properties. However, it
They have 6s2 common but with variable occpancy of 4f and 5d does affect their spectra and their magnetic properties.
level. The electronic conigurations of all tripostive ions are of the
form 4f1-14.
Table 13.12 : Electronic Configuration and Oxidation States of Lanthanoides
Element Electronic Electronic Oxidation States
Configuration Configuration of M3+
Lanthanum La [Xe] 5d1 6s2 [Xe] +3
Cerium Ce [Xe] 4f 5d 6s
1 1 2
[Xe] 4f 1
+3 (+ 4)
Praseodymium Pr [Xe] 4f 3 6s2 [Xe] 4f 2 +3 (+ 4)
Neodymium Nd [Xe] 4f 4
6s 2
[Xe] 4f 3
(+2) +3
Promethium Pm [Xe] 4f 5
6s 2
[Xe] 4f 4
(+2) +3
Samarium Sm [Xe] 4f 6 6s2 [Xe] 4f 5 (+2) +3
Europium Eu [Xe] 4f 7 6s2 [Xe] 4f 6 (+ 2) +3
Gadolinium Gd [Xe] 4f 5d7 1
6s 2
[Xe] 4f 7
+3
Terbium Tb [Xe] 4f 9
6s 2
[Xe] 4f 8
+3 (+ 4)
Dysprosium Dy [Xe] 4f 10 6s2 [Xe] 4f 9 +3 (+ 4)
Holmium Ho [Xe] 4f 11 6s2 [Xe] 4f 10 +3
Erbium Er [Xe] 4f 12
6s 2
[Xe] 4f 11
+3
Thulium Tm [Xe] 4f 13
6s 2
[Xe] 4f 12
(+ 2) +3
Ytterbium Yb [Xe] 4f 14 6s2 [Xe] 4f 13 (+ 2) +3
Lutetium Lu [Xe] 4f 5d14 1
6s 2
[Xe] 4f 14
+3

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2.3 Atomic and Ionic Radii of the third transition series to be very similar to those of the
corresponding members of the second series. The almost identical
(Lanthanide Contraction) radii of Zr (160 pm) and Hf (159 pm), a consequence of the
In lanthanide series, with increasing atomic number, there is a lanthanoid contraction, account for their occurrence together in
progressive decrease in the atomic as well as ionic radii of trivalent nature and for the difficulty faced in their separation.
ions from La3+ to Lu3+. This regular decrease in the atomic and
ionic radii with increasing atomic number is known as lanthanide
contraction.
As we move along the lanthanide series, the nuclear charge
increases by one unit at each successive element. The new
electron is added into the same subshell (4f subshell). As a result,
the attraction on the electrons by the nucleus increases and this
tends to decrease the size. Further, as the new electron is added
into the f-subshell, there is imperfect shielding of one electron by
another in this subshell due to the shapes of these f-orbitals. This
imperfect shielding is unable to counterbalance the effect of the
increased nuclear charge. Hence, the net result is a contraction in
the size though the decrease is very small.
It is interesting to note that in lanthanides, the decrease in the
atomic radius for 14 elements [Ce (58) to Lu (71)] is only 11pm
(from 183 to 172 pm). Similarly, decrease in ionic radii from Ce3+ to
Lu3+ is only 17 pm (103 to 86 pm).
The cumulative effect of the contraction of the lanthanoid series,
known as lanthanoid contraction, causes the radii of the members

Fig 13.9 : Trends in ionic radii of lanthanoids

Table 13.13 : Atomic and Ionic Radii of Lanthanoides

Atomic Electronic configurations Radii/pm
Name Symbol
Number Ln Ln2+ Ln3+ Ln 4+
Ln Ln3+
57 Lanthanum La 5d16s2 5d1 4f0 187 106
58 Cerium Ce 4f15d16s2 4f2 4f1 4f0
183 103
59 Praseodymium Pr 4f36s2 4f3 4f2 4f1 182 101
60 Neodymium Nd 4f46s2 4f4 4f3 4f2 181 99
61 Promethium Pm 4f56s2 4f5 4f4 181 98
62 Samarium Sm 4f66s2 4f6 4f5 180 96
63 Europium Eu 4f76s2 4f7 4f6 199 95
64 Gadolinium Gd 4f75d16s2 4f75d1 4f7 180 94
65 Terbium Tb 4f96s2 4f9 4f8 4f7 178 92
66 Dysprosium Dy 4f106s2 4f10 4f9 4f8 177 91
67 Holmium Ho 4f116s2 4f11 4f10 176 89
68 Erbium Er 4f126s2 4f12 4f11 175 88
69 Thulium Tm 4f136s2 4f13 4f12 174 87
70 Ytterbium Yb 4f146s2 4f14 4f13 173 86
71 Lutetium Lu 4f145d16s2 4f145d1 4f14 – –

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2.4 Magnetic Behaviour They form oxides M2O3 and hydroxides M(OH)3. The oxides and
hydroxides are basic like alkaline earth metal oxides and hydroxides.
Paramagnetism is shown by the positive ions of lanthanides except
La3+ (lanthanum ion, f0) and Lu3+ (lutetium ion, f14). This property
of the lanthanides is due to presence of unpaired electrons in the
incomplete 4f subshell.
Lanthanides differ from transition elements in the fact that their
magnetic moments do not obey ‘spin only’ formula, viz.,

 eff  n ( n  2) B.M. where n is the number of unpaired

electrons. This because in case of transition elements, the orbital
contribution is quenched by the electric field of the environment
but in case of lanthanides, 4f orbitals lie to deep to be quenched.
Hence, their magnetic moment is calculated by considering spin
as well as orbital contribution, i.e,

 eff  4 S (S  1)  L ( L  1) B.M.
where S is spin quantum number and L is orbital quantum number.
Fig 13.10 : Chemical reactions of the lanthanoids
NOTE :
Separation of the Lanthanide Elements
The hydroxides Ln(OH) 3 are precipitated as gelationous
Since the change in ionic radius is very small, the chemical
precipitates by the addition of NH4OH to aqueous solutions. These
properties are similar. This makes the separation of the element in
hydroxides are ionic and basic. They are less basic than Ca(OH)2
pure state difficult. Separation is done by Ion Exchange methods
which is based on the ionic size. but more basic than Al(OH)3 which is amphoteric. The metals,
oxides and hydroxides all dissolve in dilute acids, forming salts.
2.5 Colour Ln(OH)3 are sufficiently basic to absorb CO2 from the air and form
carbonates. The basicity decreases as the ionic radius decreases
The lanthanides are silvery white metals. However, most of the
trivalent metal ions are coloured, both in the solid state and in from Ce to Lu. Thus Ce(OH)3 is the most basic, and Lu(OH3),
aqueous solution. This is due to the partly filled-f-orbitals which which is the least basic, is intermediate between Scandium and
permit f-f transition. Yttrium in basic strength. The decrease in basic properties is
illustrated by the hydroxides of the later elements dissolving in
NOTE :
hot concentrated NaOH, forming complexes.
Lanthanides ions with x f electrons have a similar colour to those
Yb(OH)3 + 3NaOH  3Na+ + [Yb(OH)6]3–
with (14–x) f electrons e.g., La3+ and Lu3+ are colourless, Sm3+
Lu(OH)3 + 3NaOH  3Na+ + [Lu(OH)6]3–
and Dy3+ are yellow and Eu3+ and Tb3+ are pink.

2.7 Uses of Lanthanides

2.6 Chemical Reactivity
Chemically the earlier members of the lanthanide series are quite
similar to calcium but, with increasing atomic number, they behave
more like aluminium.
These metals combine with hydrogen when gently heated in
hydrogen gas to from hydrides (LnH3).
When these metals are heated with carbon, they give carbides,
Ln3C, Ln2C3 and LnC2.
They liberate hydrogen from dilute acids and burn in halogens to
form halides (LnX3).
The lanthanoids are mainly used for :
(i) Production of alloy steels for plates and pipes
(ii) Production of Mischmetall, it is an alloy containing (95%)
lanthanoid metals + (5%) iron + traces of S, C, Ca and Al.
(iii) Mischmetall is used as Mg based alloy to produce bullets
shell and lighter flints.
(iv) Mixed oxides of lanthanoids are used as catalyst in petroleum
cracking.
(v) Some lanthanide oxides are used as phosphors in television
screens and similar fluorescing surfaces.

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3. The Actinides Series 3.2 Atomic and Ionic Radii

The actinoids include the fourteen elements from Th to Lr. The actinides show actinide contraction (very much like lanthanide
contraction) due to poor shielding effect of the 5f-electrons. As a
The actinoids are radioactive elements and the earlier members
result, the radii of the atoms or ions of these metals decrease
have relatively long half-lives, the latter ones have half-life values
regularly across the series. The contraction is greater from element
ranging from a day to 3 minutes for lawrencium (Z =103). The
to element in this series due to poorer shielding by 5f electrons
latter members could be prepared only in nanogram quantities.
compared to 4f electrons in lanthanoides. This is because 5f orbitals
extend in space beyond 6s and 6p orbitals whereas 4f orbitals are
3.1. Electronic Configuration buried deep inside the atom.
All the actinoids have the electronic configuration of 7s2 and
variable occupancy of the 5f and 6d subshells. The fourteen 3.3 Oxidation State
electrons are formally added to 5f, though not in thorium (Z = 90)
Unlike lanthanides, actinides show a large number of oxidation
but from Pa onwards the 5f orbitals are complete at element 103.
states. This is because of very small energy gap between 5f, 6d
The irregularities in the electronic configurations of the actinoids,
and 7s subshells. Hence, all their electrons can take part in bond
like those in the lanthanoids are related to the stabilities of the f0,
formation. The dominant oxidation state of these element is +3
f7 and f14 occupancies of the 5f orbitals. Thus, the configurations
(similar to Lanthanides). Besides +3 state, Actinides also exhibit
of Am and Cm are [Rn] 5f7 7s2 and [Rn] 5f76d17s2. Although the 5f
an oxidation state of +4. Some Actinides show still higher oxidation
orbitals resemble the 4f orbitals in their angular part of the wave-
states. The maximum oxidation state first increases upto the middle
function, they are not as buried as 4f orbitals and hence 5f electrons
of the series and then decreases, e.g., it increases from + 4 from Th
can participate in bonding to a far greater extent than 4f orbitals in
to +5, +6, and +7 for Pa, U and Np but decreases in the succeeding
case of lanthanoides.
elements.
The actinides resemble lanthanides in having more compounds in
+3 state than in the +4 state. However, the compounds in the +3
and +4 state tend to undergo hydrolysis.

Table 13.14 : General Characteristics of Actinoids

Atomic Electronic Configurations Radii/pm Oxidation

Name Symbol
Number M M3+ M4+ M3+ M4+ States
89 Actinium Ac 6d17s2 5f0 111 3
90 Thorium Th 6d27s2 5f1 5f 0
99 4
91 Protactinium Pa 5f26d17s2 5f2 5f1 96 3, 4, 5
92 Uranium U 5f36d17s2 5f3 5f2 103 93 3, 4, 5, 6
93 Neptunium Np 5f46d17s2 5f4 5f3 101 92 3, 4, 5, 6, 7
94 Plutonium Pu 5f67s2 5f5 5f4 100 90 3, 4, 5, 6, 7
95 Americium Am 5f77s2 5f6 5f5 99 89 3, 4, 5, 6
96 Curium Cm 5f76d17s2 5f7 5f6 99 88 3, 4
97 Berkelium Bk 5f97s2 5f8 5f7 98 87 3, 4
98 Callifornium Cf 5f107s2 5f9 5f8 98 86 3
99 Einstenium Es 5f117s2 5f10 5f9 – – 3
100 Fermium Fm 5f127s2 5f11 5f10 – – 3
101 Mendelevium Md 5f137s2 5f12 5f11 – – 3
102 Nobelium No 5f147s2 5f13 5f12 – – 3
103 Lawrencium Lr 5f146d17s2 5f14 5f13 – – 3

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3.4 Magnetic Behaviour 4. Comparison of Lanthanides

Like lanthanides, the actinides are strongly paramagnetic. The
variation in magnetic susceptibility of actinides with the increasing
and Actinides
number of unpaired electrons is similar to that of lanthanides but Similarities :
the values are higher for the actinides than the lanthanides. As both lanthanides and actinides involve filling of f-orbitals,
they show similarities in many respects as follows :
3.5 Colour (i) Both show mainly oxidation state of +3.
These metals are silvery white. However, actinide cations are (ii) Both are electropositive and very reactive.
generally coloured. The colour of the cation depends upon the (iii) Both exhibit magnetic and spectral properties.
number of 5f-electrons. The cations containing no 5f-electron or (iv) Actinides exhibit actinide contraction like lanthanide
having seven 5f-electrons (i.e., exactly half-filled f-subshell) are contraction shown by lanthanides.
colourless. The cations containing 2 to 6 electrons in the 5f- Differences :
subshell are coloured both in the crystalline state as well as in
The show differences in some of their characteristics as follows :
aqueous solution. The colour arises due to f–f transition e.g. Ac3+
(5f 0) = colourless, U3+ (5f 3) = Red, Np3+ (5f 4) = Blue, Pu3+ (5f 5) =
Table 13.15 : Difference between Lanthanides and
Voilet, Am3+ (5f 6) = Pink, Cm3+ (5f 7) = Colourless, Th3+ (5f 0) =
Colourless as so on.
Actinides
Lanthanides Actinides
3.6 Chemical Reactivity (i) Besides + 3 oxidation (i) Besides +3 oxidation
state they show + 2 and +4 state, they show higher
Actinides show almost similar chemical behaviour to lanthanides.
oxidation states only in few oxidation states of +4, +5,
cases. +6, + 7.
(ii) Most of their ions are (ii) Most of their ions are
colourless. coloured.
(iii)They have less tendency (iii) They have greater
towards complex formation. tendency towards complex
formation.
(iv) Lanthanides compounds (iv) Actinides compounds
are less basic. are more basic.
(v) They do not form (v) They from oxocations.
oxocation. e.g. UO 22  , PuO 22  and UO  .
(vi) Except promethium, (vi) They are radioactive.
they are non-radioactive.
(vii) Their magnetic (vii) Their magnetic
Fig 13.11 : Chemical reactions of the actinides properties can be explained properties cannot be
easily. explained easily.

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d AND f BLOCK ELEMENTS
Summary
d-Block Elements
 d-block elements are those in which the last electron goes to
(n-1) d-orbitals.
 General electronic configurations of d-block elements is :
ns1-2, (n-1)d1-10
 Transition metals have high values of melting and boiling
points which are due to the presence of strong metallic
bonding in these metals.
 Due to lanthanide contraction, atomic radii for the elements
of 3rd transition series are almost equal to those for the
elements of 2nd transition series.
 The values of ionisation energies increase as we move from
left to right in each series.
 Except for Cu, E°red values for other metals of Ist transition
series are negative.
 Excepting a few metals, most of the metals show several
oxidation states. This is due to the fact that (n-1)d and ns
orbitals have almost the same energy.
 Transition metal ions which contain partially filled d-orbitals
are usually coloured. The colour arises because of d-d
transition. Transition metal ions with d0 or d10 configuration
are colourless because d-d transition is not possible in such
ions.
 Transition metals form interstitial compounds.
 Many transition metals and their alloys and compounds act
as catalysts in many chemical reactions.
121
f-Block Elements
 The elements in which the last electron enters f-orbital of (n-
2)th shell are called f-block elements. f-block elements are of
two types lanthanides and actinides.
 General electronic configuration of f-block elements is ns2,
(n-1)d0-1, (n-2)f1-14
 + 3 oxidation state (O.S.) is the most stable O.S. of
lanthanides.
 There is a steady decrease in atomic and ionic (M³+ ions)
radii of lanthanides. This steady decrease in atomic and ionic
radii is called lanthanide contraction.
 Magnetic moment value of lanthanides and actinides is
calculated by considering both orbital spin contribution. µeff
value is given by µeff = 4S (S+1)+L(L+1) B.M, here S spin
quantum number and L= orbital quantum number
 Mischmetal is an important alloy of lanthanides. It contains
90% lanthanides (La= 40%, Ce and other lanthanides= 50%)
, Fe = 5% and traces of other elements like C, S, Al, Ca.
 The actinide elements lying beyond U (Np-93 to Lw-103) are
called trans-uranic or trans-uranium elements.
 Unlike lanthanides, actinides show a large number of
oxidation states.
 Actinides have lower values of ionisation energies.
 Most of actinide halides form complex compounds with alkali
metal halides. The degree of complex formation for the ions
decreases as : M4+ > MO22+ > M3+ > MO2+.
 Thorium is used in atomic reactors and in the treatment of
cancer. Uranium is used as a nuclear fuel. Plutonium is used
as a fuel for atomic reactors as well as for making atomic
bombs.
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Solved Examples
Example-1
Why Cr and Cu show exceptional configuration ?
Sol. By deviating from normal configuration, Cr and Cu acquires
half-filled and fully filled configurations which gives them
extra stability. Hence they show exceptional configuration.
Cr [Ar] 3d5 4s1 and Cu [Ar] 3d10 4s1
Example-2
In what way is the electronic configuration of the transition
elements different from that of the non-transition
elements?
Sol. Transition elements have incomplete penultimate d-orbitals
while penultimate orbitals of representative elements (s -
and p - block elements) are completely filled up. The general
valence shell configuration of s-block (group 1 and 2)
elements is ns1–2 and for p-block elements (group 13 to 18)
is ns2 np1–6. The valence shell configuration of transition
elements can be written as (n – 1) d1–9 ns1–2 .
Example-3
What are the characteristics of the transition elements and
why are they called transition elements ? Which of the d-
block elements may not be regarded as the transition
elements?
Sol. The important characteristics of transition metals are:
(i) All transition elements are metallic in nature, e.g., all
are metals.
(ii) These metals exhibit variable oxidation states.
(iii) Transition metal atoms or ions generally form the
complexes with neutral, negative and positive
ligands.
(iv) Compounds of transition metals are usually coloured.
(v) The compounds of these metals are usually
paramagnetic in nature.
(vi) Transition metals and their compounds act as good
catalysts, i.e., they show catalytic activities.
(vii) These metals form various alloys with other metals of
the series.
(viii) These metals form interstitial compounds with C, N,
B and H.
The presence of partially filled d-orbitals in the electronic
configuration of atomic and ionic species of these elements
is responsible for the characteristic properties of transition
elements. They are called transition elements because of
123
their position in the periodic table. These elements lie in the
middle of periodic table between s and p-block (i.e., between
group 2 and group 13). A transition element may be defined
as a element whose atom or at least one of its simple ions
contain partially filled d-orbitals, e.g., iron, copper,
chromium, nickel etc.
The general characteristic electronic configuration may be
written as (n – 1) d1–10ns1–2.
The elements of group 12 i.e., Zinc, Cadmium, and Mercury
are generally not regarded as transition elements as their
atoms and all ions formed have completely filled d-orbitals
i.e., these do not have partially filled d-orbitals in atomic
state or common oxidation state (Zn2+, Cd2+, Hg2+)
Zn (30) = [Ar] 4s23d10 Zn2+ = [Ar] 3d10 4s0
Cd (48) = [Kr] 5s2 4d10 Cd2+ = [Kr] 4d10 5s0
Hg (80) = [Xe] 6s2 5d10 Hg2+ = [Xe] 5d10 6s0
Example-4
Explain giving reason
(i) Transition metals and many of their compounds show
paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals
are high.
(iii) The transition metals generally form coloured
compounds.
(iv) Transition metals and their many compounds act as
good catalyst.
Sol. (i) Due to presence of unpaired electrons
(ii) The metallic bonds in transition elements are very
strong due to participation of (n 1) d electrons along
with valence s-electrons in the bond formation.
Therefore, the cleavage of these bonds is extremely
difficult and consequently, enthalpies of atomization
are high.
(iii) Due to d-d transitions
(iv) They exhibit variable oxidation states and have large
surface area, hence acts as good catalysts
124 d AND f BLOCK ELEMENTS
Example-5 provide a new path with lower activation energy for
the reaction.
How would you account for the following :
(ii) In some cases, the transition metal provides a suitable
(a) Of the d4 species Cr2+ is strongly reducing while
large surface area with free valencies on which
manganese(III) is strongly oxidising.
reactants are adsorbed.
(b) Cobalt(II) is stable in aqueous solution but in the
(b) Because they have strong metallic bonds due to greater
presence of complexing reagents it is easily oxidized.
number of unpaired d electrons.
(c) The d1 configuration is very unstable in ions?
(c) this is due to d-d transition.
Sol. (a) Of d4 species, Cr2+ has 3d4 configuration and tends to
Example-7
loose one electron to acquire d3 configuration as it is
highly stable and best metallic specie available for Describe the trends in the following properties of the first
complex formation. Cr3+ can accommodate six lone pair series of the transition elements:
of electrons from ligands due to sp3d2 hybridisation (i) Oxidation states
e.g. [Cr(NH3)6]3+ Mn3+ although have d4 configuration
(ii) Atomic sizes
but tends to become Mn2+ stable specie by acquiring
one electron to attain d5 configuration. It becomes (iii) Magnetic behaviour of dipositive gaseous ions (M2+).
exactly half filled on one hand and more energy is Sol. (i) As there is very little energy difference between 4s and
released in gain of electron due to higher nuclear 3d orbitals, electrons from both energy levels can be
charge. used for chemical bond formation. Therefore all elements
except Sc and Zn, of the first transition series show a
(b) Co2+ is stable in aqueous solution because it get
number of oxidation states as shown in table.
surrounded and weakly bonded to water molecules. In
presence of strong ligands and air it gets oxidised tc Sc Ti V Cr Mn Fe Co Ni Cu Zn
Co(III) as strong ligands get co-ordinated more 2 2 2 2 2 2 2 1
strongly with Co(III). The electronic configuration of 3 3 3 3 3 3 3 3 2 2
Co(II) and Co(III) are : 4 4 4 4 4 4 4
Co(II) = [Ar]18 4s03d7 and Co(III) = [Ar]18 4s03d6 5 5 5
In Co(III) specie, 6 lone pairs of electrons from ligands 6 6 6
are accommodated by sp3d2 hybridisation which is not 7
possible in Co(II). (ii) Atomic radii of the first transition series decreases
(c) Some species with d1 configuration are reducing and from Sc to Cr, then reamins almost constant till Ni and
tends to loose one electron to acquire d4 stable then increases from Cu to Zn.
configuration. Some other species with d1 The reason of this variation in atomic radii has been
configuration like Cr(V) and Mn(VI) undergo attributed to the increase in nuclear charge in the
disproportionation. beginning of the series. But as the electrons continue
Example-6 to be filled in d-orbitals, they screen the outer 4s
Explain the following facts electrons from the influence of nuclear charge. When
the increased nuclear charge. When the increased
(a) transition metals act as catalysts.
nuclear charge and the increased screening effect
(b) chromium group elements have the highest melting balance each other in the middle of transition series,
points in their respective series. the atomic radii becomes almost constant (Mn to Fe).
(c) transition metals form coloured complexes. Towards the end of the series, the repulsive interaction
Sol. (a) The catalytic activity of transition metals is attributed between electrons in d orbitals become very dominant.
to the following reasons : As a result there is an expansion of the electron cloud;
consequently, the atomic size increases.
(i) Because of their variable oxidation states transition
metals form unstable intermediate compounds and (iii) Except Zn2+, all other divalent gaseous ions of the first
series of the transition elements contain unpaired
electrons in their 3d subshell and are therefore
paramagnetic in nature.
d AND f BLOCK ELEMENTS 125
The magnetic moment () of the elements of the first Because of the presence of three unpaired electrons
transition series can be calculated with the unpaired in the 3d subshell Cr3+ is paramagnetic. Sc3+ is
electrons (n) by the spin-only formula diamagnetic as it does not have any unpaired
electrons.
 n  n  2  B.M.
(ii) The electronic configurations of V and Mn are given
below:
Ion Configuration Unpaired Magnetic moment
electrons  μ  calculated 23 V :  Ar  3d3 4s 2 25 Mn :  Ar  3d 5 4s 2
Mn2+ 3d54s0 5 5  5  2   5.92 B.M. Mn exhibits more number of oxidation states than V
because of the greater number of electrons in its
Cu2+ 3d94s0 1 11  2   1.73 B.M. valence shell.
Zn2+ 3d104s0 0 Example-10
0 0  2  0
Explain:
(i) CrO42– is a strong oxidizing agent while MnO42– is not.
Example-8
(ii) Zr and Hf have identical sizes.
How would you account for the following :
(iii) The lowest oxidation state of manganese is basic while
(i) Many of the transition elements and their compounds
the highest is acidic.
can act as good catalysts.
(iv) Mn (II) shows maximum paramagnetic character
(ii) The metallic radii of the third (5d) series of transition
amongst the divalent ions of the first transition series.
elements are virtually the same as those of the
corresponding members of the second series. Sol. (i) CuF2 and CCl2 compounds will be coloured because
they incompletely filled d-orbitals and unpaired
(iii) There is a greater range of oxidation states among the
electrons, they can undergo d-d transition by
actinoids than among the lanthanoids.
absorbing colour from visible region and radiating
Sol. (i) The catalytic activity of transition metals is attributed complementary colour.
to the following reasons:
(ii) Zr and Hf have identical sizes because paring of
(a) Because of their variable oxidation states transition electrons takes place in d-orbitals causing repulsion
metals form unstable intermediate compounds and and effective nuclear charge does not increase
provide a new path with lower activation energy for apprecialby. or becaule of canthanoide contraction.
the reaction.
(iii) Manganese (Z = 25) exhibits the largest number of
(b) In some cases, the transition metal provides a suitable oxidation states because its atoms has the maximum
large surface area with free vacancies on which number of unpaired electrons. The lowest oxidation
reactants are adsorbed. state of manganese is basic while the highest is acidic.
(ii) This due to filling of 4f orbitals which have poor (iv) Mn(II) shows maximm paramagnetic character amongst
shielding effect or due to lanthanoid contraction. the divalent ions of the first transition series because
(iii) This is due to comparable energies of 5f, 6d and 7s it has the largest number of unpaired electrons.
orbital in actinoids. Example-11
Example-9 In transition series, with an increase in atomic number, the
Decide giving reasons which one of the following pairs atomic radius does not change very much. Why is it so ?
exhibits the property indicated: Sol. With the increase in atomic number along a transition series
(i) Sc3+ or Cr3+ exhibits paramagnetism. the nuclear charge increases which tends to decrease the
(ii) V or Mn exhibits more number of oxidation states. size of the atom. But the addition of electrons in the d
subshell increases the screening effect which
(Atomic Numbers: Sc = 21; Cr = 24; V = 23; Mn = 25)
counterbalances the increased nuclear charge. Hence, along
Sol. (i) The electronic configurations of Sc3+ and Cr3+ are a transition series the atomic radius does not change very
given below.
much.
Sc3 :  Ar  3d 0 4s0 Cr 3 :  Ar  3d3 4s0
126
Example-12
Explain why Cu+ ion is not stable in aqueous solutions ?
Sol. Cu+ in aqueous solution undergoes disproportionation i.e.,
2Cu   aq  
 Cu 2   aq   Cu  s 
The Eo, value for this is favourable.
Example-13
On what ground can you say that scandium (Z = 21) is a
transition element but zinc (Z = 30) is not ?
Sol. On the basis of incompletely filled 3d orbitals in case of
scandium atom is its ground state (3d1), it is regarded as a
transition element. On the other hand, zinc atom has
completely filled d orbitals (3d10) in its ground state as well
as in its oxidised state, hence it is not regarded as a transition
elements.
Example-14
What are interstitial compounds ? Why are such compounds
well known for transition metals ?
Sol. Interstitial compounds are those which are formed when
small atoms like H, C, N, B etc. are trapped inside the crystal
lattices of metals. They are generally non-stoichiometric
and neither typically ionic nor covalent.
Most of transition metals form interstitial compounds with
small non-metal atoms such as hydrogen, boron, carbon
and nitrogen. These small atoms enter into the void sites
between the packed atoms of crystalline transition metals.
For Example, steel and cast iron become hard by forming
interstitial compound with carbon.
The existence of vacant (n – 1) d orbitals in transition
elements and their ability to make bonds with trapped small
atoms in the main cause of interstitial compound formation.
Other examples are : VH0.56, TiH1.7. Some main characteristics
of these compounds are :
(i) They have high melting and boiling points, higher than
those of pure metals.
(ii) They are very hard. Some borides of transition elements
approach diamond in hardness.
(iii)They are chemically inert but retain metallic
conductivity.
Example-15
Explain giving reasons :
(i) Transition metals and their compounds generally exhibit
a paramagnetic behaviour.
(ii) The Chemistry of actinoids is not so smooth as that of
lanthanoids.
d AND f BLOCK ELEMENTS
Sol. (i) Paramagnetism is a property due to presence of
unpaired electrons. In case of transition metals, as they
contain unpaired electrons in (n – 1) d orbitals, most of
the transition metal ions and their compounds are
paramagnetic.
(ii) The general electronic configuration of lanthanoids is
[Xe]54 4f0–4 5d0–1 6s2 and that of actinoids is [Rn]86 5f1–14
6d0–1 7s2. Unlike 4f orbitals, 5f orbitals are not deeply
burried and participate in bonding to a greater extent.
In actinoids due to poor shielding effect of 5f orbitals,
the effective nuclear charge experienced by valence
shell electrons is more than those in lanthanoids. As a
result the Chemistry of actinoids is not so smooth as
that of lanthanoids.
Example-16
How is the variability in oxidation states of transition metals
different from that of the non-transition metals ? Illustrate
with examples
Sol. The variability in oxidation states is a fundamental
characteristic of transition elements and it arises due to
incomplete filling of d-orbitals in such a way that their
oxidation states differ from each other by unity. For
example, vanadium, V show the oxidation states of +2, +3,
+4 and +5. Similarly, Cr shows oxidation states of +2, +3, +4,
+5 and +6; Mn shows all oxidation states from +2 to +7.
This is contrasted with variability of oxidation states of
non-transition element where oxidation states generally
differ by units of two. For example, S shows oxidation states
of –2, +2, +4, +6 while P shows +3 and +5 oxidation states.
Halogenes like Cl, Br and I show oxidation states of –1, +1,
+3, +5 and +7 states. In non-transition elements variability
of oxidation states is caused due to unpairing of electrons
in ns or np orbitals and their promotion to np or nd vacant
orbitals.
Example-17
Describe the preparation of potassium dichromate from iron
chromite one. What is the effect of increasing pH on a
solution of potassium dichromate ?
Sol. The following steps are involved in preparation of K2Cr2O7
from iron chromite (FeCr2O4) ore :
(i) Preparation of sodium chromate : The chromite ore
(FeO.Cr2O3) is finely powdered and mixed with sodium
carbonate and quick lime and then heated to redness
in a reverberatory furnace with free supply of air.
d AND f BLOCK ELEMENTS
4FeO.Cr2O3 + O2  2Fe2O3 + 4Cr2O3
[4Na2CO3 + 2Cr2O3 + 3O2  4Na2CrO4 + 4CO2] × 2
4FeO.Cr2O3 + 8Na2CO3 + 7O2  8Na2CrO4 + 2Fe2O3 +
8CO2
The mass is then extracted with water, when sodium
chromate is completely dissolved while Fe2O3 is left
behind.
(ii) Conversion of sodium chromate into sodium
dichromate (NaCr2O7) : The sodium chromate extracted
with water in previous step is acidified.
3Na2CrO4 + H2SO4  Na2Cr2O7 + Na2SO4 + H2O
On cooling Na2SO4 separates out as Na2SO4. 10H2O
and Na2Cr2O7 is remains in solution.
(iii) Conversion of Na2Cr2O7 into K2Cr2O7 : The solution
containing Na2Cr2O is treated with KCl
Na2Cr2O7 + KCl  K2Cr2O7 + 2NaCl
Sodium chloride (NaCl) being less soluble separates
out on cooling. On crystallising the remaining solution,
orange coloured crystals of K2Cr2O7 separate out.
Effect of Change of pH : When pH of solution of
K2Cr2O7 is increased slowly the medium changes from
acidic to basic. The chromates and dichromates are
interconvertible in aqueous solution depending upon
pH of solution.
Cr2 O 72   H 2 O
Alkali
  2CrO 2   2H 
 
Acid Chromate ion4 at high pH
Dichromate ion at low pH
(Orangein acidic medium) (Yellow in alkaline medium)
At low pH (acidic medium), K2Cr2O7 solution is oranged
coloured while at higher pH (alkaline medium) it changes
to yellow due to formation of chromate ions.
Example-18
Describe the preparation of potassium permanganate. How
does the acidified permanganate solution reacts with (a)
iron(II) ions (b) SO2 and (c) oxalic acid ? Write the ionic
equations for the reactions.
Sol. Preparation of KMnO4 from pyrolusite ore (MnO2) involves
the following steps :
(i) Fusion of ore with alkali in presence of air : Pyrolusite
ore is fused with alkali in the presence of air when
potassium manganate is obtained as green mass.
2MnO2 + 4KOH + O2  2K2MnO4 + 2H2O
(green mass)
127
The green mass is dissolved in water to obtain aqueous
solution of potassium manganate. The insoluble
impurities of sand and other metal oxides are removed
by filtration.
(ii) Oxidation of manganate into permanganate : The
aqueous solution of K2MnO4 is oxidised
electrolytically or by using ozone or Cl2 to obtain
potassium permanganate. The process is carried out
till green colour disappear and solution acquires distinct
pink colour.

MnO 4 2  
 MnO 4  e 
 at anode  (oxidation at anode)
green colour
pink
H2O + e–  1/2H2 + (OH)– (reduction at cathodes)
(at cathode)
or 2K 2 MnO 4  Cl 2  2KMnO 4  2KCl
 green colour   pink colour 
Potassium permanganate is crystallised out from the
solution.
Oxidising Properties : It acts as a powerful oxidising agent
in different media differentily. In acidic medium, it oxidises
iron(II) salts to iron(III) salts, SO2 to H2SO4 and oxalic acid
to CO2 and H2O.
(a) It oxidises iron(II) salt to iron(III) salts.
2MnO42- + 16+ + 10Fe2+  2Mn2+ + 8H2O + 10Fe3+
(b) It oxidise sulphur dioxide to sulphuric acid.
2MnO4– + 5SO2 + 2H2O  5SO42– + 2Mn2+ 4H+
(c) It oxidises oxalic acid to CO2 and H2O
2MnO4– + 16H+ + 5C2O42–  2Mn2+ + 8H2O + 10CO2
Example-19
Write complete chemical equations for :
(i) Oxidation of Fe2+ by Cr2O72– in acid medium.
(ii) Oxidation of S2O32– by MnO4 in neutral aqueous
solution.
Sol. (i) 6Fe2+ + Cr2O72– + 14 H+ 
 6Fe3+ + 2Cr3+ + 7H2O
(ii) 2MnO4– + 3S2O32– + H2O 
 2MnO2 + 3SO42– +
3S + 2OH–.
128 d AND f BLOCK ELEMENTS

Example-20
(i) A black mineral (A) on treatment with dilute sodium
cyanide solution in presence of air gives a clear solution
of (B) and (C).
(ii) The solution (B) on reaction with zinc gives precipitate
of a metal (D).
(iii) (D) is dissolved in dilute HNO3 and the resulting
solution gives a white precipitate (E) with dilute HCl.
(iv) (E) on fusion with sodium carbonate gives (D).
(v) (E) dissolves in ammonia solution giving a colourless
solution of (F). Identify (A) to (F) and give chemical
equations for reactions at steps (i) to (v).
Sol. On the basis of the given data, the black mineral (A) is silver
glance, Ag2S. It is confirmed by the following :
(i) It dissolves in sodium cyanide solution in presence of
air.
Ag2S + 4NaCN + 2O2  2[NaAg(CN) 2 ]  Na 2SO 4
Sodium Sodium
argento cyanide sulphate
(B) (C)
(ii) 2[NaAg(CN) 2 ]  Zn  Na 2 Zn(CN) 4  2Ag
(B) (D)
(iii) 3Ag  4HNO 3  3AgNO3  NO  2H 2 O
(D)
Example-21
Explain the following :
(i) Acidified K 2Cr 2O 7 solution turns green when
sodium sulphite is added to it.
(ii) Zinc becomes dull in moist air.
(iii) A little acid is always added in the preparation
of aqueous ferrous sulphate solution.
(iv) The addition of NaOH solution to a solution of zinc
chloride produces a white precipitate which
dissolves on further addition of NaOH.
(v) The addition of NH 4 OH to ZnSO 4 solution
produces white precipitate but no
precipitate is formed if it contains NH4Cl.
(vi) Zinc and not copper is used for the recovery of silver
from complex [Ag(CN)2]–.
(vii) Copper sulphate dissolves in NH 4OH solution
but FeSO4 does not.
(viii) Copper hydroxide is soluble in ammonium
hydroxide but not in sodium hydroxide.
Sol. (i) Na2SO3 is a reducing agent. It reduces acidified K2CrO7
to chromic sulphate which is green in colour.
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2(SO4)3 + 4H2O + 3 [O]
[Na2SO3 + [O]  Na2SO4] × 3

K2Cr2O7 + 3Na2SO3 + 4H2SO4  K2SO4 + Cr2(SO4)3

AgNO3  HCl  AgCl  HNO3 Green
(E)

+ 3Na2SO4 + 4H2O
1 (ii) When zinc is exposed to moist air, the surface is af
(iv) 2AgCl Na 2 CO 3  2Ag  2NaCl  CO 2  O 2
(E ) (D) 2 fected with the formation of a film of basic zinc car
bonate on it. Due to this zinc becomes dull.
(v) AgCl  2NH 4 OH  Ag(NH 3 ) 2 Cl  2H 2 O
(E) (F) [2Zn + 2H2O + O2  2Zn (OH)2] × 2
Colourless solution
Zn(OH)2 + CO2  ZnCO3 + H2O
(A) = Silver glance, Ag2S ZnCO3 + 3Zn(OH)2  ZnCO3.3Zn (OH)2
(B) = Sodium argentocyanide, NaAg(CN)2 4Zn + 3H2O + CO2 + 2O2  ZnCO3.3Zn(OH)2
(C) = Sodium sulphate, Na2SO4 Basic zinc carbonate
(D) = Silver metal, Ag (iii) Ferrous sulphate is a salt of a weak base and a strong
(E) = Silver chloride, AgCl acid. Thus, its hydrolysis occurs when it is dissolved
in water and solution becomes turbid due to
(F) = Diamminsilver (I) chloride, Ag (NH3)2Cl
formation of ferrous hydroxide.
FeSO4 + 2H2O Fe(OH)2 + H2SO4
Addition of a small amount of acid shifts the equilib
rium towards left and thus prevents hydrolysis.
d AND f BLOCK ELEMENTS
(iv) On addition of NaOH, a white precipitate of Zn (OH)2
is formed which dissolves in excess of NaOH forming
sodium zincate.
ZnCl2 + 2NaOH  Zn(OH)2 + 2NaCl
Zn (OH)2 + 2NaOH  Na2ZnO2 + 2H2O
Soluble
(v) NH4OH is a weak hydroxide. It ionises slightly
furnishing OH– ions. However, the OH– ions are
sufficient to cause the precipitation of Zn(OH)2 as its
solubility product is exceeded.
ZnSO4 + 2NH4OH  Zn(OH)2 + (NH4)2SO4
white ppt.
In presence of NH4Cl, the ionisation of NH4OH is
further suppressed and sufficient OH– ions are not
available to cause precipitation as the solubility
product is not exceeded.
(vi) Zinc is cheaper as well as stronger reducing agent in
comparison to copper.
Zn + 2[Ag(CN)2]  2Ag + [Zn(CN)4]
– 2–
(vii) Copper sulphate dissolves in the ammonium
hydroxide due to formation of a copper complex.
Ferrous sulphate reacts with NH4OH to form insoluble
Fe(OH)2. It does not form any complex with NH4OH.
CuSO4 + 4NH4OH  [Cu(NH3)4]SO4 + 4H2O
Deep blue solution
FeSO4 + 2NH4OH  Fe(OH)2 + (NH4)2SO4
Insoluble
(viii) Cu(OH)2 dissolves in NH4OH by forming a complex.
Cu(OH)2 + 4NH4OH  [Cu(NH3)4] (OH)2 + 4H2O
Cu(OH)2 is insoluble in NaOH as no such complex is
formed.
Example-22
Describe the oxidising action of potassium dichromate and
write the ionic equations for its reaction with :
(a) iodide (b) iron (II) solution and (c) H2S.
Sol. Potassium dichromate, K2Cr2O7 is a strong oxidising agent
and is used as a primary standard in volumetric analysis
involving oxidation of iodides, ferrous ion and S2– ions etc.
In acidic solution, its oxidising action can be represented
as follows :
Cr2O72– + 14H+ + 6e–  2Cr3+ + 7H2O; (E+ = 1.33 V)
129
(a) It oxidises potassium iodide to iodine.
Cr2O72– + 14H+ 6I–  2Cr3 + 7H2O + 3I2
(b) It oxidises iron(II) salt to iron (III) salt
Cr2O72– + 14H+ + 6Fe2+  2Cr3+ + 6Fe3+ + 7H2O
(c) It oxidises H2S to S
Cr2O72– + 8H+ + 3H2S  2Cr3+ + 7H2O + 3S
Example-23
Use Hund’s rule to derive the electronic configuration of
Ce3+ ion, and calculate its magnetic moment on the basis of
‘spin only’ formula.
Sol. The electronic configuratio of Ce and Ce3+ ion is :
Ce(Z = 58) = 54[Xe] 4f15d16s2
Ce3+ = 54[Xe] 4f1
The no. of unpaired electron = 1
‘Spin only’ formula for magnetic moment of a specie,
  n  n  2  B.M.
 Magnetic moment of Ce3+
  11  2  B.M.
 3 B.M.  1.732 B.M.
Example-24
What is lanthanoid contraction ? What are the consequences
of lanthanoid contraction ?
Sol. A group of fourteen elements following lanthanum i.e. from
58
Ce to71 Lu placed in 6th period of long form of periodic
talbe are known as lanthanoids (or lanthanide series). These
fourteen elements are represented by common general
symbol ‘Ln’. In these elements, the last electron enters the 4f-
subshells (pre penultimate shell). It may be noted that atoms
of these elements have electronic configuration with 6s2
common but with variable occupancy of 4f level. However, the
electronic configuration of all the tripositive ions (the most
stable oxidation state of all lanthanoids) are of the form 4f n(n
= 1 to 14) with increasing atomic number). These elements
constitute one of the two series of inner transition elements or
f-block.
Lanthanoid contraction : In the lanthanoide series with the
increase in atomic number, atomic radii and ionic radii
decrease from one elements to the other, but this decrease
is very small. the regular small decrease in atomic radii and
ionic radii of lanthanides with increasing atomic number
along the series is called lanthanoid contraction.
130 d AND f BLOCK ELEMENTS
Cause of lanthanoid contraction: When one moves from Sol. Cerium (Ce) and Terbium (Tb) show +4 oxidation state.
58
Ce to 71Lu along the lanthanide series nuclear charge goes Their electronic configurations are given below :
on increasing by one unit every time. Simultaneously an Ce = [Xn] 4f1 5d1 6s2
electron is also added which enters to the inner f subshell.
Tb = [Xn] 4f0 6s2
The shielding effect of f-orbitals in very poor due to their
diffused shape. It results in the stronger force of nuclear It is clear from the configuration of Ce that Ce+4 is favoured
attraction of the 4f electrons and the outer electrons causing by its noble gas configuration i.e., [Xn] 4f0 5d0 5s0, but can
decrease in size. be easily converted into Ce3+ ([Xn]) 4f1 5d0 6s0). Due to
this reason Ce+4 is an oxidising agent. Tb4+ ion is stabilized
Consequences of lanthanoid contraction:
due to half filled f-subshell i.e., [Xn] 4f7. It also acts as an
(i) Similarly in the properties of elements of second and oxidant.
third transition series e.g. Zr and Hf; Nb and Ta; Mo
Europium (63) and ytterbium (70) show +2 oxidation state,
and W. This resemblance is due to the similarity in size
this acts as reducing agents because they can be converted
due to the presence of lanthanoids in between.
into common oxidation state +3. The electronic
(ii) Similarity among lanthanoids : Due to the very small configuration of Eu and Y are as follows :
change in sizes, all the lanthanoids resemble one
Eu = [Xn] 4f7 6s2
another in chemical properties.
Y = [Xn] 4f14 6s2
(iii) Decrease in basicity : With the decrease in ionic radii,
covalent character of their hydroxides goes on Formation of Eu2+ ion leaves 4f7 configuration and Y2+ ion
increasing from Ce(OH)3 to Lu(OH)3 and so base leaves 4f14 configuration. These configurations can stable
strength goes on decreasing. due to half filled and full filled f-subshell. Samarium, Sm
(62) 4f6 6s2 also shows both +2 and +3 oxidation states like
Example-25
europium.
Name the members of the lanthanoid series which exhibit +4
oxidation states and those which exhibit +2 oxidation state.
Try to correlate this type of behaviour with the electronic
configurations of these elements.
d AND f BLOCK ELEMENTS 131

EXERCISE – 1: Basic Objective Questions

General Introduction of d Block Elements 9. Transition elements
(a) exhibit inert-pair effect
1. Transition elements have (b) show nonmetallic character
(a) completely filled ‘d’ levels (c) do not form complex compounds
(b) completely filled ‘s’ levels and d levels (d) exhibit variable oxidation states
(c) incompletely filled ‘s’ levels and completely filled ‘d’ 10. The electronic configuration of chromium is actually
levels [Ar]3d54s1 instead of normally expected [Ar]3d44s2. This
(d) incompletely filled ‘d’ levels is because
2. The general electronic configuration of the transition (a) an exactly half-filled d level gives additional
elements is stability, according to the Hund’s rule of maximum
(a) (n – 1)d10 (n + 1)s2 multiplicity
(b) (n – 1)d1–10 (n + 1)s1–2 (b) the 4s orbital has higher energy than the 3d orbitals
(c) (n – 1)d1–10 np6 ns2 (c) the 4s orbitals has lower energy than the 3d orbitals
(d) (n – 1)d1–10 ns0–2 (d) the 3d and 4s orbitals have equal energies and
3. Which of the following elements has completely filled d hence electron migration occurs readily
orbitals (the d10 configuration) ? 11. The last electron of a d-block element occupies the
(a) Co (b) Cr orbital
(c) Hg (d) Ni (a) (n – 1)d (b) nd
4. In which of the following transition elements are the (c) np (d) (n – 1)s
d orbitals not completely filled ? 12. Transition metals
(a) Zn (b) Hg (a) form only ionic compounds
(c) Cd (d) Ag (b) form exclusively covalent compounds
5. The electronic configurations of the first four members (c) may form either ionic or covalent compounds
of the actinide series cannot be written accurately in a depending on the condition
regular manner because of (d) exclusively form coordination compounds but no
(a) small difference in energy between 5f and 6d orbitals. simple compounds
(b) large difference in energy between 5f and 6d
Classification of d Block Elements
orbitals.
(c) small difference in energy between 5f and 6s orbitals 13. Among the transition metals, the melting points of Zn,
(d) violation of the Pauli exclusion principle Cd and Hg are relatively low because
6. The electronic configuration of silver is (a) their d shells are not completely filled
(a) [Ar]3d10 4s1 (b) [Ar]4d10 4s1 (b) their d electrons do not participate in metallic
(c) [Kr]4d10 5s1 (d) [Kr]4d8 5s2 bonding
7. The electronic configuration of palladium is (c) their densities are higher
(a) [Ar]3d84s2 (b) [Kr]4d85s2 (d) of all the above
8 2
(c) [Kr]5d 6s (d) [Kr]4d105s0 14. The noble character of platinum and gold is favoured by
8. The electronic configuration of platinum is (a) high enthalpies of sublimation, high ionization
(a) [Xe] 4f145d96s1 (b) [Xe] 4f145d106s2 energies and low enthalpies of solvation
14 10 2 (b) high enthalpies of sublimation, low ionization
(c) [Rn] 5f 6d 7s (d) [Rn] 5f146d97s1
energies and low enthalpies of solvation
(c) low enthalpies of sublimation, high ionization
energies and low enthalpies of solvation
(d) high enthalpies of sublimation, high ionization
energies and high enthalpies of salvation
132 d AND f BLOCK ELEMENTS

15. Which one of the following is a d-block element ? 24. The atom of which one of the following elements has
(a) Gd (b) Hs the highest number of unpaired electrons ?
(a) 25 Mn (b) 24 Cr
(c) Es (d) Cs
(c) 96 cm (d) 26 Fe
16. Which of the following statements is correct ?
25. Which one of the following ions is colourless ?
(a) The second-row elements have smaller radii than the
corresponding third-row ones. + 2+
(a) Cu (b) Co
(b) Because of lanthanide contraction, the radii of the
2+ 3+
third-row elements are almost the same as those (c) Ni (d) Fe
of the first-row elements. 26. Which of the following species is/are paramagnetic ?
(c) Because of lanthanide contraction, the radii of the
2+ 0 2+ 4+
third-row elements are almost the same as those of Fe , Zn , Hg , Ti
the second-row elements. 2+ 0 4+
(d) Because of lanthanide contraction, the separation (a) Fe only (b) Zn and Ti
of second-row elements from one another is 2+ 2+ 0 2+
easier. (c) Fe and Hg (d) Zn and Hg
27. Which of the following metals does not show variable
Physical Properties of d Block Elements oxidation states ?
(a) Mercury (b) Zinc
17. The highest possible oxidation state shown by osmium (c) Gold (d) Silver
in its compounds is 28. The covalent radii of transition metals decrease from left
(a) +4 (b) +8 to right in a period because
(c) +6 (d) +10 (a) the densities of the metals decrease with increasing
18. Which of the following ions is paramagnetic ? atomic number due to poor shielding of electrons
(a) Zn2+ (b) N3– (b) the screening of nuclear charge by d electrons is poor
4+
(c) Mn (d) Cu+ and hence the nuclear charge attracts all the electrons
19. Which of the following ions is diamagnetic ? strongly, causing a decrease in size
(a) Ni2+ (b) Ti4+
(c) the ionization energies also decrease
(c) Cr3+ (d) Co3+
correspondingly
3+
20. Number of unpaired electrons in Mn is (d) the metallic character decreases as the atomic
(a) 2 (b) 3 number increases
(c) 4 (d) 5 29. For a given ion, the magnetic moment is 2.83 BM. The
total spin (s) of all the unpaired electrons is
21. Which one of the following statements is not true
with regard to transition elements ? (a) 2 (b) 1
(a) They readily form complex compounds (c) 3/2 (d) ½
30. Among the following series of transition metal ions, the
(b) They show variable oxidation states
2
(c) All their ions are colourless one in which all metal ions have 3d , electronic
configuration is (At. no. Ti = 22 ; V = 23 ; Cr = 24, Mn
(d) Their ions contain partially filled d-electrons
= 25)
22. Which of the following ions has the least magnetic
3+ 2+ 3+ 4+
moment? (a) Ti ,V , Cr , Mn
2+ 2+ + 4+ 6+ 7+
(a) Cu (b) Ni (b) Ti , V , Cr , Mn
3+ 2+
(c) Co (d) Fe 4+ 3+ 2+ 3+
(c) Ti ,V , Cr , Mn
23. The ion of least magnetic moment among the
following is 2+ 3+ 4+ 5+
(d) Ti ,V , Cr , Mn
3+ 2+
(a) Ti (b) Ni
2+ 2+
(c) Co (d) Mn
d AND f BLOCK ELEMENTS 133

31. Which of the following statements concerning (a) Ti, TiSO4, KI and TiI2
transition elements is false ?
(b) Zn, ZnSO4, KI and Zn2I2
(a) They are all metals
(c) Cu, CuSO4, KI and Cu2I2
(b) They easily form complex coordination compounds
(c) They form compounds containing unpaired electrons (d) Cu, CuSO4, Cu2I2 and CuI2
and their ions are mostly coloured 37. Which one of the following sets correctly represent
(d) They show multiple oxidation states always differing the increase in the paramagnetic property of the ions?
by units of two 2+ 2+ 2+ 2+
(a) Cu < V < Cr < Mn
32. Mercury is a liquid metal because
2+ 2+ 2+ 2+
(a) it has a completely filled s-orbital (b) Cu < Cr < V < Mn
2+ 2+ 2+ 2+
(b) it has a small atomic size (c) Cu > V > Cr > Mn
(c) it has a completely filled d-orbital that prevents 2+ 2+ 2+ 2+
(d) V < Cu < Cr < Mn
d-d overlapping of orbitals
(d) it has a completely filled d-orbital that causes d-d Chemical Properties of d Block Elements
overlapping
3+ 38. The oxidation states shown by transition elements is
33. The spin only magnetic moment of Fe ion (in BM) is related to their
approximately
(a) electropositive characters
(a) 4 (b) 7
(b) electronic configurations
(c) 5 (d) 6 (c) atomic weights
2+ (d) atomic sizes
34. Experimental value of magnetic moment of Mn
complex is 5.96 BM. This indicates 39. Which of the following is not true about the transition
(a) axial and orbital motion of electron in same elements ?
direction (a) They show variable oxidation states
(b) axial and orbital motion of electron in opposite (b) Their ions have a strong tendency to form complexes
direction (c) Their compounds usually do not absorb ultraviolet
and visible lights
(c) electron does not exhibit orbital motion, it only
(d) Their ions and complex ions usually possess
exhibits axial motion
magnetic moments.
(d) electron does not axial motion, it only exhibits orbital 40. Which of the following ions is colourless in solution ?
motion
(a) V3+ (b) Cr3+
35. The magnetic moment of a transition metal ion is 15 (c) Co2+ (d) Sc3+
BM. Therefore, the number of unpaired electrons present 41. Which of the following ions has the maximum number
in it is of unpaired d electrons ?
(a) 4 (b) 1 (a) Fe3+ (b) V3+
(c) 2 (d) 3 (c) Ti 3+
(d) Mg2+
36. A transition metal ‘A’ has ‘spin-only’ magnetic moment 42. Which of the following ions possesses the maximum
value of 1.8 BM. When it is reacted with dilute sulphuric number of unpaired electrons ?
acid in the presence of air, a compound ‘B’ is formed. (a) Ni2+ (b) Fe2+
‘B’ reacts with compound ‘C’ to give compound ‘D’ (c) Cu +
(d) Zn2+
with liberation of iodine. Then, the metal A and
43. Which of the following does not possess unpaired
compounds B, C and D are respectively
electrons ?
(a) Co3+ (b) Cu2+
(c) Ti2+ (d) Hg2+
134 d AND f BLOCK ELEMENTS

44. Which of the following electronic configurations 53. The formula of mercurous ion is
represents Fe3+ ? +
(a) [Ar]3d64s2 (b) [Ar]3d54s1 (a) Hg (b) Hg 2
5 2
(c) [Ar]3d 4s (d) [Ar]3d54s0 (c) Hg 22  (d) None of these
45. Which of the following ions is expected to the coloured 54. Which of the following is an incorrect statement?
in solution ?
(a) The lowest oxide of a transition metal is acidic
(a) Cu+ (b) Cu2+ whereas the highest one is usually basic.
(c) Ti4+ (d) Sc3+ (b) A transition metal usually exhibits higher oxidation
46. The transition elements are states in its fluorides than in its iodides.
(a) more reactive than group 1 elements
(c) Transition metal halides become more covalent with
(b) more reactive than group 2 elements
the increasing oxidation state of the transition metal
(c) less reactive than group 1 elements but more
and are more susceptible to hydrolysis.
reactive than group 2 elements
(d) less reactive than group 1 and 2 elements (d) The highest oxide of a transition metal is acidic
whereas the lowest one is usually basic.
47. The transition metals sometimes form
nonstoichiometric compounds. These compounds have 55. Which one of the following ionic species will impart
(a) definite structures and definite proportions colour to an aqueous solution ?
(b) indefinite structures and definite proportions (a) Ti4+ (b) Cu+
(c) definite structures and indefinite proportions (c) Zn 2+
(d) Cr3+
(d) indefinite structures and indefinite proportions
56. Which of the following oxides of chromium is
48. The maximum number of unpaired electrons is amphoteric in nature ?
present in
(a) CrO (b) CrO 3
(a) Fe (b) Cu
(c) Cr2O3 (d) CrO5
(c) Co (d) Ni
57. Which of the following statements is incorrect ?
49. The stability of ferric ion is due to
(a) The compounds formed by the 3d transition metals
(a) half-filled f-orbitals in lower valence states are ionic but those in higher
(b) half-filled d-orbitals valence states are covalent.
(c) completely filled f-orbitals (b) The 4d and 5d transition metals form less ionic
(d) completely filled d-orbitals compounds than do the 3d transition metals.
50. The maximum oxidation state shown by Mn in its (c) The compounds formed by the 3d transition metals
are less ionic than the corresponding compounds
compounds is
formed by the 4d and 5d transition metals.
(a) +4 (b) +5 (d) The ionization energies of 3d, 4d and 5d transition
(c) +6 (d) +7 metals are greater than those of group 1 and 2 metals.
51. The highest oxidation state exhibited by transition 58. Ammonia will not form complex with
metals is 2+ 2+
(a) Ag (b) Pb
(a) +7 (b) +8
2+ 2+
(c) +6 (d) +5 (c) Cu (d) Cd
52. A transition metal ion exists in its highest oxidation 59. Which of the following pairs of transition metal ions are
state. It is expected to behave as the stronger oxidising agents in aqueous solutions ?
(a) a chelating agent (a) V2 and Cr 2 (b) Ti 2  and Cr 2 
(b) a central metal in a coordination compound (c) Mn3 and Co3 (d) V 2  and Fe2 
(c) an oxidising agent 60. The coordination number in an ....... complex may
(d) a reducing agent increase to 8.
(a) cobalt (b) osmium
(c) nickel (d) iron
d AND f BLOCK ELEMENTS 135

61. The titanium (atomic number 22) compound that 69. The pair, that referred as ‘chemical twins’ is
does not exist is (a) Ac, Cf (b) Hg, Ta
(a) TiO (b) TiO2 (c) Tc, Re (d) La, Ac
(c) K2TiF6 (d) K2TiO4
Potassium Permanganate
62. The acidic, basic or amphoteric nature of Mn2O7,
V2O5 and CrO are respectively, 70. Which of the following compounds is green in colour ?
(a) acidic, acidic and basic (a) KMnO4 (b) (NH4)2Cr2O7
(b) basic, amphoteric and acidic (c) MnO2 (d) K2MnO4
(c) acidic, amphoteric and basic 71. KMnO4 is manufactured on a large scale by
(d) acidic, basic and amphoteric (a) fusing MnO2 with KOH and then oxidizing the fused
63. In which of the following ions, d–d transition is not mixture with KNO3
possible?
(b) fusing MnO2 with Na2CO3 in the presence of O2
3+ 4+
(a) Cr (b) Ti (c) fusing MnO2 with KOH and KNO3 to form K2MnO4
2+ 2+ which is then electrolytically oxidized in an alkaline
(c) Cu (d) Mn
solution
64. Copper exhibits only +2 oxidation state in its stable
(d) fusing MnO2 with KNO3 and then acidifying the
compounds. Why ?
fused mixture
(a) Copper is transition metal in +2 state.
72. MnO 4 is prepared by treating a solution containing
(b) +2 state compounds of copper are formed by
Mn2+ ions with a very strong oxidizing agent such as
exothermic reactions.
(c) Electron configuration of copper in +2 state is (a) PbO2 (b) C2 O 24 
9 0 (c) I2 (d) Fe3+
[Ar]3d 4s .
(d) Copper gives coloured compounds in +2 state. 73. KMnO4 in an acidic medium will not oxidize
4 (a) NO 2 (b) SO 24 
65. A transition element X has the configuration [Ar]d in
its +3 oxidation state. Its atomic number is (c) HN3 (d) H2O2
(a) 25 (b) 26 74. Which of the following is an incorrect statement ?
(c) 22 (d) 19 (a) In a redox reaction in acidic medium, KMnO4
66. Among K, Ca, Fe and Zn, the element which can form produces Mn2+ ions.
more than one binary compound with chlorine (b) In a redox reaction in strongly alkaline medium,
is KMnO4 produces MnO 24  ions.
(a) Fe (b) Zn (c) In a redox reaction in neutral medium, KMnO4
(c) K (d) Ca produces MnO2.
67. Which of the following metals form amphoteric (d) In a redox reaction in alkaline medium, KMnO4
oxide ? produces Mn2O7.
(a) Fe (b) Cu
75. KMnO4 in an acidic medium oxidizes
(c) Zn (d) Ca
2
68. When Zn is treated with excess of NaOH, the product (a) C 2 O 4 to CO2 (b) N2H4 to N2
obtained is (c) HSO3 to SO 4 2  (d) all of these
(a) Zn(OH)2 (b) ZnOH
(c) Na2ZnO2 (d) None of these
136 d AND f BLOCK ELEMENTS

Potassium Dichromate 84. Chromyl chloride, CrO2Cl2, is prepared by heating a

mixture of
76. CrO 24  reacts with H+ as (a) NaCl, K2Cr2O7 and NaOH
(b) NaCl, K2Cr2O7 and concentrated H2SO4
2CrO 24   2H   Cr2 O72   H 2 O
(c) NaCl, K2Cr2O7 and MnO2
The change in oxidation number of Cr is
(a) +5 (b) +7 (d) CrO3 and NaCl
(c) +6 (d) zero 85. Which is the correct statement about Cr2O72  structure?
77. When hydrogen peroxide is added to an acidic solution (a) It has neither Cr – Cr bonds nor O–O bonds
of a dichromate, the most probable product is
(b) It has one Cr – Cr bond and six O – O bonds
(a) K2CrO4 (b) CrO3
(c) It has no Cr – Cr bond and has six O – O bonds
(c) Cr2O3 (d) CrO(O2)2
(d) It has one Cr – Cr bond and seven Cr – O bonds
78. Acidified K2Cr2O7 on treatment with KI produces 86. Assertion : Solution of Na2CrO4 in water is intensely
(a) KIO3 (b) I2 coloured.
(c) KIO4 (d) I3 Reason : Oxidation state of Cr in Na2CrO4 is +VI.
79. Na2CrO4 on treatment with lead acetate gives a (a) Both Assertion and Reason are true and Reason is the
precipitate. This precipitate is dried and the solid is used correct explanation of Assertion.
as a pigment for road signs and markings. The solid is
(b) Both Assertion and Reason are true but Reason is not
known as
the correct explanation of Assertion.
(a) white lead (b) chrome green
(c) Assertion is true but Reason is false.
(c) chrome yellow (d) red lead
(d) Both Assertion and Reason are false.
80. Potassium dichromate is used
Heat
87. 4K 2Cr2O7 
 4K 2CrO4  3O2  X . In the above
(a) in electroplating
reaction X is
(b) as a reducing agent
(a) CrO3 (b) Cr2O7
(c) oxidise ferrous ions into ferric ions in acidic media as
an oxidising agent (c) Cr2O3 (d) CrO5
(d) as an insecticide 88. When dil. H2SO4 is added to aqueous solution of
81. CrO3 dissolves in aqueous NaOH to give potassium chromate, yellow colour of solution turns
(a) CrO 24  (b) Cr(OH)2 to orange colour. It indicates
(a) chromate ions are reduced
(c) Cr2 O72  (d) Cr(OH)3
(b) chromate ions are oxidised
82. Cr2 O72  reacts with OH– as
(c) mono centric complex is converted into dicentric
Cr2 O  2  OH
2
7

  2CrO 2
4  H2 O complex
(d) oxygen gets removed from chromate ions
The change in oxidation number of Cr is
(a) +6 (b) +3
(c) zero (d) +4 Other Compounds of d-Block Elements
83. Sodium chromate is prepared by
(a) fusing chromite (FeCr2O4) with NaCl in air 89. Identify the species having an atom in +6 oxidation state.
(a) MnO 4 (b) [Cr(CN)6 ]3
(b) fusing chromite (FeCr2O4) with NaOH in air
(c) fusing (NH4)2Cr2O7 with sodium hydrogen sulphate (c) NiF63 (d) CrO2Cl2
in nitrogen
(d) fusing sodium dichromate with carbon
d AND f BLOCK ELEMENTS 137

90. Which of the following compounds is expected to be 98. Which of the following oxides of manganese is
coloured ? amphoteric ?
(a) Ag2SO4 (b) CuF2 (a) MnO (b) Mn 2O3
(c) MgF2 (d) CuCl (c) Mn2O7 (d) MnO2
91. Which of the following compounds is colourless? 99. Which of the following oxides of manganese is stable as
(a) K2MnO4 (b) HgI2 well as strongly acidic ?
(a) MnO2 (b) Mn2O7
(c) ZnSO4 (d) FeSO4
(c) MnO3 (d) Mn2O3
92. The compound ZnSO4 is white because
100. The colourless species is
(a) charge is transferred from the metal to the oxygen
atoms (a) VCl3 (b) VOSO4
(b) electron transfer to d level does not occur as the level (c) Na3VO4 (d) [V(H2O)6]SO4 . H2O
is already filled to capacity in zinc
101. An aqueous solution of CoCl2 on addition of excess
(c) Zn2+ has d10 configuration and d–d transition occurs
easily of conc. HCl turns blue due to the formation
of
(d) Zn2+ ions absorb light of the visible range
93. Which one of the following oxides of chromium is 2–
(a) [Co(H2O)]Cl2 (b) [Co(H2O)2Cl4]
amphoteric in nature ?
2–
(a) CrO (b) Cr 2O3 (c) [CoCl4] (d) [Co(H2O)2Cl2]
(c) CrO3 (d) CrO5 102. The amphoteric oxide among the following is
94. The colour of zinc sulphide is (a) Cr2O3 (b) Mn2O7

(a) white (b) black (c) V2O3 (d) CrO

(c) brown (d) red 103. The solid product formed on heating AgNO3 strongly
95. The value of magnetic moment ( spin only) for Cu2+ in to 980 K is
CuSO4.5H2O is (a) silver carbonate (b) silver nitride
(a) 5.92 BM (b) 4.92 BM (c) silver oxide (d) silver metal
(c) 2.83 BM (d) 1.73 BM 104. CuSO4 when reacts with KCN forms CuCN which is
96. Which of the following statements is incorrect for CrO3? insoluble in water. It is soluble in excess of KCN, due to
(a) It is a bright orange solid. formation of the following complex
(b) It is commonly called chromic acid. (a) K2[Cu(CN)4] (b) K3[Cu(CN)4]
(c) It is prepared by adding concentrated H2SO4 to a (c) CuCN2 (d) Cu[K Cu(CN)4]
saturated solution of sodium dichromate.
105. The dark blue colour of the solution formed when
(d) The colour arises due to d–d transition.
excess of ammonia is added to a solution of
97. Deep red-yellow vapour of CrO2Cl2 is passed into an copper(II) sulphate is due to the presence of the ion
aqueous solution of NaOH. The solution turns
2–
(a) yellow due to the formation of Na2Cr2O7 (a) [Cu(OH)4 (H2O)2]
(b) yellow due to the formation of Na2CrO4 2+
(b) [Cu(H2O)6]
(c) green due to the formation of CrCl3
4+
(d) red due to the formation of Na2CrO4 (c) [Cu(NH3)2 (H2O)4]
2+
(d) [Cu(NH3)4 (H2O)2]
138 d AND f BLOCK ELEMENTS

106. Choose the correct reaction to prepare mercurous 115. Silver nitrate solution is kept in brown bottles in
chloride (calomel). laboratory because :
 (a) it reacts with ordinary white bottles
(a) HgCl2  Hg   (b) Hg  Cl 2 

(b) brown bottles cut the passage of light through
(c) HgCl2  SnCl 2 
 (d) Both options (a) and (c) (c) brown bottles do not react with it
107. Calomel on reaction with ammonium hydroxide gives (d) ordinary bottles catalyse its decomposition
(a) HgO (b) Hg 2O 116. A white precipitate of AgCl dissolves in excess of :
(I) NH3 (aq) (II) Na 2S2O3
(c) NH2 – Hg – Hg – Cl (d) HgNH2Cl
(III) NaCN
108. The following is known as “bordeaux mixture” (a) III only (b) I, II, III
(a) Borax and copper sulphate (c) I, II (d) I only
(b) Orthoboric acid and ferrous sulphate 117. Boiling CuCl2 with Cu in conc. HCl gives :
(c) Sodium borate and zinc sulphate (a) CuCl (b) CuCl2
(d) Copper sulphate and lime (c) H[CuCl2] (d) Cu2Cl
109. Which of the following is red in colour ?
118. Zinc (II) ion on reaction with NaOH first give a white
(a) Cu2O (b) CuF precipitate which dissolves in excess of NaOH due to
(c) ZnF2 (d) ZnCl2 the formation of :
(a) ZnO (b) Zn(OH) 2
110. Formula of ammonium manganate is
(c) [Zn(OH)4]2– (d) [Zn(H2O)4]2+
(a) NH4MnO4 (b) (NH4)2MnO4
(c) NH4(MnO4)2 (d) NH4Mn2O4 Uses of d Block Elements
111. Chemically philosopher of wool is :
119. Permanent magnets are generally made from the alloy of
(a) ZnO (b) BaO (a) Co (b) Zn
(c) HgCl (d) Hg2Cl2 (c) Al (d) Pb
120. In haemoglobin, the metal ion present is
112. Malachite and azurite are used respectively are : 2+ 2+
(a) Blue and green pigment (a) Fe (b) Zn
2+ 2+
(b) Red and green pigment (c) Co (d) Cu
(c) Green and blue pigment 121. German silver alloy contains
(a) zinc, silver and copper
(d) Green and red pigment
(b) nickel, silver and copper
113. HgCl2 is a covalent compound, sparingly soluble in (c) germanium, silver and copper
water, the solubility increases by the addition of (d) zinc, nickel and copper
chloride ions due to :
122. Which of the following is used as purgative ?
(a) common ion effect
(a) HgS (b) Hg 2Cl2
(b) formation of complex [HgCl4]2–
(c) HgCl2 (d) ZnSO4
(c) weakening of Hg – Cl bonds
(d) strong ion-dipole forces 123. Which of the following is used as indelible ink ?
114. Mercury is the only metal that is liquid at 0ºC. This is (a) Aqueous CuSO4 solution
due to its :
(b) Aqueous AgNO3 solution
(a) Very high ionisation energy and weak metallic
bond (c) Aqueous NaCl solution
(b) Low ionisation potential (d) Aqueous NaOH solution
(c) High atomic weight
(d) High vapour pressure
d AND f BLOCK ELEMENTS 139

f-Block Elements 131. The point of dissimilarity between lanthanides and

actinides is
(a) three outermost shells are partially filled.
124. Lanthanide elements have (b) they show oxidation state of +3 (common).
(a) similar lattice energies but widely different solvation (c) they are called inner-transition elements.
and ionization energies (d) they are radioactive in nature.
(b) similar lattice and solvation energies but widely
different ionization energies General Characteristics of f-Block Elements
(c) similar lattice and ionization energies but widely
different hydration energies 132. The electronic configuration of f-block elements is
(d) similar lattice energies, solvation energies and represented by
ionization energies (a) (n – 2)f1–14 (n – 1)d0–1ns2
125. The electronic configuration of cerium is (b) (n – 2)f1–14 (n – 1)d0–5ns0–2
(a) [Xe]4f15d16s2 (b) [Xe]4f25d06s1 (c) (n – 2)f1–14 (n – 1)d0–10ns1–2
1 2 2
(c) [Xe]4f 5d 6s (d) [Xe]4f25d06s2 (d) (n – 2)f1–14 (n – 1)d0–2 (n – 1)s2
126. Lanthanides are 133. Lanthanides are characterized by the filling of the
(a) 14 elements in the sixth period (atomic no. = 90 to (a) penultimate 4f energy level
103) that are filling 4f sub-level.
(b) antepenultimate 4f energy level
(b) 14 elements in the seventh period (atomic no. = 90 to (c) penultimate 3f energy level
103) that are filling 5f sub-level. (d) antepenultimate 3f energy level
(c) 14 elements in the sixth period (atomic no. = 58 to 134. Which of the following statements is correct for the
71) that are filling 4f sub-level. lanthanoids ?
(d) 14 elements in the seventh period (atomic no. = 58 to (a) The 4f electrons do not take part in bonding.
71) that are filling 4f sub-level. (b) The 4f electrons can neither be removed to produce
127. Which of the following is not an actinide ? ions nor be made to take part in crystal field
(a) Curium (b) Californium stabilization of complexes.
(c) The 4f electrons in the antepenultimate shell are very
(c) Uranium (d) Terbium
effectively shielded by the 5s and 5p electrons.
128. Which of the following is not an actinoid ?
(d) All of these
(a) Am (b) Cm
135. The most common and stable oxidation state of a
(c) Fm (d) Tm lanthanide is
129. Differentiating electron in inner-transition elements (a) +II (b) +IV
enters in the ........ orbital. (c) +VII (d) +III
(a) s (b) p 136. The atomic and ionic radii (M3+ ions) of lanthanide
(c) d (d) f elements decrease with increasing atomic number. This
130. Identify the incorrect statement among the following. effect is called
(a) lanthanide contraction
(a) d-block elements show irregular and erratic chemical
properties among themselves. (b) lanthanide expansion
(b) La and Lu have partially filled d-orbitals and no other (c) actinide contraction
partially filled orbitals. (d) none of these
(c) The chemistry of various lanthanoids is very 137. The lanthanoid contraction relates to
similar. (a) atomic radii
(d) 4f- and 5f - orbitals are equally shielded. 3+
(b) atomic as well as M radii
(c) valence electrons
(d) oxidation states
140 d AND f BLOCK ELEMENTS

138. On which factors, the stability of an oxidation state of 144. General electronic configuration of lanthanides are
lanthanoide elements depends ? 1–14 0–1 2
(a) (n – 2) f (n – 1) d ns
(a) Enthalpy
10–14 0–1 2
(b) Internal energy (b) (n – 2) f (n – 1) d ns
(c) Combined effect of hydration energy and ionisation 0–14 10 2
(c) (n – 2) f (n – 1) d ns
energy
0–1 1–14 2
(d) Electronic configuration (d) (n – 2) d (n – 1) f ns
139. Lanthanide for which +II and +III oxidation states are 145. Across the lanthanide series, the basicity of the
common is lanthanide hydroxides
(a) La (b) Nd (a) increases
(c) Ce (d) Eu (b) decreases
140. Which of the following elements shows the maximum (c) first increases and then decreases
number of different oxidation states in its compounds ?
(d) first decreases and then increases
(a) Eu (b) La
146. Most basic hydroxide among the following is
(c) Gd (d) Am
(a) Lu(OH)3 (b) Eu(OH)3
141. Lanthanide contraction occurs because
(a) the 4f electrons, which are gradually added, create a (c) Yb(OH)3 (d) Ce(OH)3
strong shielding effect 147. The lanthanoid contraction is responsible for the fact
(b) the 4f orbitals are greater in size than the 3d and 3f that
orbitals
(a) Zr and Y have about the same radius
(c) the 5f orbitals strongly penetrate into the 4f orbitals
(b) Zr and Nb have similar oxidation state
(d) the poor shielding effect of 4f electrons is coupled
with increased attraction between the nucleus and the (c) Zr and Hf have about the same radius
added electrons (d) Zr and Zn have the same oxidation state
142. The hardness, melting point and boiling point of 148. More number of oxidation state are exhibited by the
elements increase from Ce to Lu because actinoids than by the lanthanoids. The main reason
(a) the attraction between the atoms increases as the size for this is
increases (a) lesser energy difference between 5f- and 6d-orbitals
(b) the attraction between the atoms decreases as the size than that between 4f- and 5d-orbitals.
increases (b) greater metallic character of the lanthanoids than that
(c) the attraction between the atoms increases as the size of the corresponding actionoids.
decreases
(c) more active nature of the actinoids.
(d) the attraction between the atoms remains the same as
the size increases. (d) more energy difference between 5f and 6d-orbitals
than that between 4f and 5d-orbitals.
3+ 3+ 3+
143. The correct order of ionic radii of Y , La , Eu and 4+
3+ 149. Ce in stable. This is because of
Lu is
(a) half-filled d-orbitals
3+ 3+ 3+ 3+
(a) Y < La < Eu < Lu (b) all paired electrons in d-orbitals
3+ 3+ 3+ 3+ (c) empty orbitals
(b) Lu < Eu < La < Y
(d) fully filled d-orbitals
3+ 3+ 3+ 3+
(c) La < Eu < Lu < Y 150. Most common oxidation states of Ce (cerium) are
3+ 3+ 3+ 3+ (a) +3, +4 (b) +2, +3
(d) Y < Lu < Eu < La
(c) +2, +4 (d) +3, +5
d AND f BLOCK ELEMENTS 141

EXERCISE – 2: Previous Year Questions

1. Which one of the following ions is the most stable in 9. Out of and (Z of Ti = 22, Co = 27, Cu = 29, Ni = 28), the
aqueous solution ? (At. no. Ti = 22, V = 23, Cr = 24, colourless species are
Mn = 25) (CBSE AIPMT 2007)
(CBSE AIPMT, AMU 2009)
3+ 3+
(a) Cr (b) V (a) TiF62  and CoF63 (b) Cu 2Cl2 and NiCl24
3+ 3+ (c) TiF62  and Cu 2Cl2 (d) CoF63 and NiCl42 
(c) Ti (d) Mn
2. Acidified potassium permanganate solution is 10. Transition metals show paramagnetic behaviour. This is
decolourised by (AFMC 2007) because of their (AFMC 2009)
(a) bleaching powder (b) white vitriol (a) high lattice energy
(c) Mohr’s salt (d) microcosmic salt (b) variable oxidation state
3. Reason of passivity of iron is (RPMT 2007) (c) characteristic configuration
(a) Fe2O3 (b) Fe3O4 (d) unpaired electrons
(c) FeO (d) Fe2O4 . 3H2O 11. For which of the following pairs, magnetic moment is
4. Essential component of amalgam is (RPMT 2007) same? (AIIMS 2009)
(a) Fe (b) Pb (a) MnCl2, CuSO4 (b) CuCl2, TiCl3
(c) Hg (d) Cr (c) TiO2, CuSO4 (d) TiCl3, NiCl2
5. Identify the incorrect statement among the following 12. Which compound is expected to be coloured ?
(CBSE AIPMT 2007) (CPMT 2009)
(a) There is a decrease in the radii of the atoms or ions (a) CuCl (b) CuF2
as one proceeds from La to Lu.
(c) Ag2SO4 (d) MgF2
(b) Lanthanoid contraction is the accumulation of
successive shrinkages. 13. Which of the following is man-made element ?
(c) As a result of lanthanoid contraction, the properties (AFMC 2009)
of 4d-series of the transition elements have no (a) Ra (b) U
similarities with the 5d-series of elements.
(c) Np (d) C
(d) Shielding power of 4f electrons is quite weak.
14. Which of the following pairs has the same size ?
6. What is the correct order of spin only magnetic moment
2+ 2+ 2+ (CBSE AIPMT 2010)
(in BM) of Mn , Cr and Ti ? 2+ 4+ 2+ 2+
(AFMC 2008) (a) Zn , Hf (b) Fe , Ni
2+ 2+ 2+ 2+ 2+ 2+ 4+ 4+ 4+ 4+
(a) Mn > Ti > Cr (b) Ti > Cr > Mn (c) Zr , Ti (d) Zr , Hf
2+ 2+ 2+ 2+ 2+ 2+ 15. Which of the following ions will exhibit colour in
(c) Mn > Cr > Ti (d) Cr > Ti > Mn aqueous solutions ? (CBSE AIPMT 2010)
7. Which of the following compounds is coloured ? 3+ 3+
(a) Sc (Z = 21) (b) La (Z = 57)
(AIIMS 2008)
3+ 3+
(a) TiCl3 (b) FeCl3 (c) Ti (Z = 22) (d) Lu (Z = 71)
(c) CoCl2 (d) All of these 16. Which of the following transition metal ions is not
coloured? (AFMC 2010)
8. Which of the following group of transition metals is + 3+
called coinage metals? (RPMT 2008) (a) Cu (b) V
(a) Cu, Ag, Au (b) Ru, Rh, Pd 2+ 2+
(c) Co (d) Ni
(c) Fe, Co, Ni (d) Os, Ir, Pt
142 d AND f BLOCK ELEMENTS

17. Maximum number of unpaired electrons are present 24. The catalytic activity of transition metals and their
in (CPMT 2010) compounds is ascribed mainly to (Mains 2012)
2+ 2+ (a) their magnetic behaviour
(a) Fe (b) Mn
+ 2+ (b) their unfilled d-orbitals
(c) Cu (d) Cr (c) their ability to adopt variable oxidation states
18. Which of the following has maximum unpaired d- (d) their chemical reactivity.
electrons? (RPMT 2010)
25. Which of the following lanthanoid ions is diamagnetic?
2+ 2+ (Atoms, Ce = 58, Sm = 62, Yb = 70)
(a) Zn (b) Fe
2+ + (CBSE AIPMT 2013)
(c) Ni (d) Cu
2+ 2+
19. In Cu (at. no. 29) (RPMT 2010) (a) Yb (b) Ce
(a) 13 electrons have spin in one direction and 16 2+ 2+
(c) Sm (d) Eu
electrons in other direction 26. KMnO4 can be prepared from K2MnO4 as per the
(b) 14 electrons have spin in one direction and 15 reaction :
electrons in other direction
(c) one electron can have spin only in the clockwise 3MnO24  2H2O 2MnO4  MnO2  4OH
direction –
The reaction can go to completion by removing OH ions
(d) None of the above is correct
by adding :- (CBSE AIPMT 2013)
20. For the four successive transition elements (Cr, Mn,
(a) SO2 (b) HCl
Fe and Co), the stability of +2 oxidation state will be
there in which of the following order ? (c) KOH (d) CO 2
(CBSE AIPMT 2011) 27. Sc (Z = 21) is a transition element but Zn (Z = 30) is
(At. no. Cr = 24, Mn = 25, Fe = 26, Co = 27) not because (NEET 2013)
(a) Cr > Mn > Co > Fe (b) Mn > Fe > Cr > Co 3+ 2+
(a) both Sc and Zn ions are colourless and form
(c) Fe > Mn > Co > Cr (d) Co > Mn > Fe > Cr white compounds
21. Acidified K2Cr2O7 solution turns green when (b) in case of Sc, 3d orbitals are partially filled but in Zn
Na2SO3 is added to it. This is due to the formation of these are filled
(c) last electron is assumed to be added to 4s level in case
(CBSE AIPMT 2011)
of Zn
(a) CrSO4 (b) Cr2(SO4)3
(d) both Sc and Zn do not exhibit variable oxidation
(c) CrO 24  (d) Cr2(SO3)3 states
28. Which of the following statements about the interstitial
22. Which of the statements is not true ?
compounds is incorrect? (NEET 2013)
(CBSE AIPMT 2012)
(a) They are much harder than the pure metal.
(a) K2Cr2O7 solution becomes yellow on increasing the
(b) They have higher melting points than the pure
pH beyond 7 metal.
(b) On passing H2S through acidified K2Cr2O7 (c) They retain metallic conductivity.
solution, a milky colour is observed (d) They are chemically reactive.
(c) Na2Cr2O7 is preferred over K2Cr2O7 in volumetric 29. Magnetic moment 2.83 BM is given by which of the
analysis following ions ? (At. No. Ti = 22, Cr = 24, Mn = 25, Ni
(d) K2Cr2O7 solution in acidic medium is orange = 28) (AIPMT 2014)
3+ 2+
23. Identify the alloy containing a non-metal as a (a) Ti (b) Ni
constituent in it. (AIPMT-2012) 3+ 2+
(c) Cr (d) Mn
(a) Invar (b) Steel
(c) Bell metal (d) Bronze
d AND f BLOCK ELEMENTS 143

30. Reason of lanthanide contraction is (AIPMT 2014) 37. The electronic configurations of Eu (Atomic No. 63), Gd
(a) negligible screening effect of ‘f’ orbitals (Atomic No. 64) and Tb (Atomic No. 65) are
(b) increasing nuclear charge (NEET-I 2016)
(c) decreasing nuclear charge (a) [Xe]4f 5d 6s , [Xe]4f 5d 6s and [Xe]4f85d16s2
6 1 2 7 1 2

(d) decreasing screening effect. (b) [Xe]4f76s2, [Xe]4f75d1 6s2 and [Xe]4f96s2
31. Magnetic moment 2.84 BM is given by (c) [Xe]4f76s2, [Xe]4f86s2 and [Xe]4f85d1 6s2
(At. no. Ni = 28, Ti = 22, Cr = 24, Co = 27) (d) [Xe]4f65d16s2, [Xe]4f75d16s2 and [Xe]4f96s2
(AIPMT 2015) 38. Which one of the following statements related to
lanthanons is incorrect? (NEET 2016)
3+ 2+
(a) Ti (b) Cr (a) The basicity decreases as the ionic radius decreases
2+ 2+ from Pr to Lu.
(c) Co (d) Ni
(b) All the lanthanons are much more reactive than
32. Because of lanthanoid contraction, which of the
aluminium.
following pairs of elements have nearly same atomic
radii ? (Numbers in the parenthesis are atomic (c) Ce (+4) solutions are widely used as oxidizing agent
numbers.) (AIPMT 2015) in volumetric analysis.
(a) Zr (40) and Nb (41) (b) Zr (40) and Hf (72) (d) Europium shows +2 oxidation state.
(c) Zr (40) and Ta (73) (d) Ti (22) and Zr (40) 39. The reason for greater range of oxidation states in
actinoids is attributed to (NEET 2017)
33. The angular momentum of electron in ‘d’ orbital is equal
to (AIPMT 2015) (a) actinoid contraction.
(b) 5f, 6d and 7s levels having comparable energies.
(a) 2 h (b) 2 3h (c) 4f and 5d levels being close in energies.
(c) 0 h (d) 6 h (d) the radioactive nature of actinoids.
34. Which of the following processes does not involve 40. HgCl2 and I2 both when dissolved in water containing
oxidation of iron? (NEET 2015) ions the pair of species formed is (NEET 2017)
(a) Formation of Fe(CO)5 from Fe. (a) HgI2, (b) HgI24 ,I3
(b) Liberation of H2 from steam by iron at high  
temperature. (c) Hg2 I2 ,I (d) HgI2 ,I3
(c) Rusting of iron sheets. 41. Name the gas that can readily decolourise acidified
(d) Decolourisation of blue CuSO4 solution by iron. KMnO4 solution. (NEET 2017)
35. Which one of the following statements is correct when (a) SO2 (b) NO2
SO2 is passed through acidified K2Cr2O7solution ? (c) P2O5 (d) CO2
(NEET 2016) 42. Match the metal ions given in Column I with the spin
magnetic moments of the ions given in Column II and
(a) The solution turns blue.
assign the correct code (NEET 2018)
(b) The solution is decolorized.
Column I Column II
(c) SO2 is reduced.
A. Co3+ i. 8 B.M.
(d) Green Cr2(SO4)3 is formed.
B. Cr3+ ii. 35 B.M.
36. When copper is heated with conc. HNO3 it produces
C. Fe3+ iii. 3 B.M.
(NEET 2016)
(a) Cu(NO3)2 and NO2. D. Ni2+ iv. 24 B.M.

(b) Cu(NO3)2 and NO. v. 15 B.M.

(c) Cu(NO3)2, NO and NO2.
(d) Cu(NO3)2 and N2O
144 d AND f BLOCK ELEMENTS

A B C D 48. Identify the incorrect statement. (NEET 2020)

(a) i ii iii iv (a) Cr2+ (d4) is a stronger reducing agent than Fe2+ (d6)
in water.
(b) iv i ii iii
(b) The transition metals and their compounds are
(c) iv v ii i
known for their catalytic activity due to their ability
(d) ii iv i ii to adopt multiple oxidation states and to form
43. Which one of the following ions exhibits d-d transition complexes.
and paramagnetic as well? (NEET 2018) (c) Interstitial compounds are those that are formed
(a) CrO42– (b) Cr2O72– when small atoms like H, C or N are trapped inside
(c) MnO4– (d) MnO42– the crystal lattices of metals.
44. The manganate and permanganate ions are tetrahedral, (d) The oxidation states of chromium in CrO42– and
due to: (NEET 2019) Cr2O72– are not the same.
(a) There is no -bonding 49. Zr (Z = 40) and Hf (Z = 72) have similar atomic and
ionic radii because of: (NEET 2021)
(b) The -bonding involves overlap of p-orbitals of
oxygen with p-orbitals of manganese (a) lanthanoid contraction
(b) having similar chemical properties
(c) The -bonding involves overlap of d-orbitals of
oxygen with d-orbitals of manganese (c) Belonging to same group
(d) The -bonding involves overlap of p-orbitals of (d) diagonal relationship
oxygen with d-orbitals of manganese 50. The incorrect statement among the following is:
45. When neutral or faintly alkaline KMnO4 is treated (NEET 2021)
with potassium iodide, iodide ion is converted into (a) Lanthanoids are good conductors of heat and
‘X’. ‘X’ is (Odisha NEET 2019) electricity
(a) I2 (b) IO4– (b) Actinoids are highly reactive metals, especially
(c) IO3– (d) IO– when finely divided.
46. The calculated spin only magnetic moment of Cr 2+ (c) Actinoid contraction is greater for element to
ion is : (NEET 2020) element than Lanthanoid contraction
(a) 5.92 BM (b) 2.84 BM (d) Most of the trivalent ions are colorless in the solid
(c) 3.87 BM (d) 4.90 BM state.
47. Identify the incorrect statement. (NEET 2020)
(a) Interstitial compounds are those that are formed
when small atoms like H, C or N are trapped
inside the crystal lattices of metals.
(b) The oxidation state of chromium in CrO 24 and
Cr2 O72 are not the same.
(c) Cr 2+ (d 4 ) is a stronger reducing agent than
Fe2+ (d 6 ) in water.
(d) The transition metals and their compounds are
known for their catalytic activity due to their
ability to adopt multiple oxidation states and to
form complexes.
d AND f BLOCK ELEMENTS 145

EXERCISE – 3: Achiever’s Section

Single Choice Questions 9. Sodium thiosulphate, Na2S2O3. 5H2O is used in
photography to :
1. Give the correct order of initials T or F for the (a) Reduce the silver bromide to metallic silver
following statements. Use T if the statement is true and (b) Convert the metallic silver to silver salt
F if it is false. (c) remove undecomposed AgBr as soluble silver
(I) Sulphide ions reacts with Na2 [Fe(CN)5(NO)] to thiosulphate complex
form a purple-coloured compound Na4 [Fe(CN)5 (d) remove reduced silver
(NOS)]. In the reaction, the oxidation state of 10. When AgNO3 comes in contact with skin, it leaves a
iron changes. black stain. This is because of :
(II) Pt (IV) compounds are relatively more stable (a) HNO3 produced by hydrolysis of AgNO3
than Ni (IV) compounds.
(b) AgOH produced by hydrolysis of AgNO3
(III) The welding of magnesium can be done in the
atmosphere of Helium. (c) Its reduction of silver
(IV) LiAlH4 on hydrolysis will give H2 (d) Its oxidation to silver oxide
(a) FFTT (b) FTTT 11. The oxidation state of copper changes when aqueous
(c) TFTF (d) TFTT copper (II) ions react with :
2. Philosopher’s wool when heated with BaO at 1100ºC (I) NaOH (aq) (II) Fe(s)
gives the compound : (III) KI (aq)
(a) BaCdO2 (b) Ba + ZnO2 (a) I, II, III (b) II only
(c) BaO2 + Zn (d) BaZnO 2 (c) II, III (d) I only
3. Spiegeleisen is an alloy of : 12. Fe(OH)2 is precipitated from Fe(II) solutions as a
(a) Cu + Zn + Ni (b) Ni + Cr white solid but turns dark green and then brown due
(c) Mn + Fe + C (d) Fe + Cr + Ni to the formation of :
4. Chloroplatinic acid is : (a) Fe(OH)2 and Fe(OH)3 (b) only Fe(OH)3
(a) monobasic (b) dibasic (c) Fe2O3 . (H2O)n (d) Fe2O3 . 2H2O
(c) tribasic (d) tetrabasic
13. The false statement about iron (III) hydroxide is that :
5. Which of the following is the correct formula for a
(a) it is a weaker base than Fe(OH)2
compound of scandium and oxygen?
(b) with concentrated KOH, it forms a complex
(a) Sc2O (b) ScO
K3[Fe(OH)6]
(c) Sc3O2 (d) Sc2O3 (c) it gradually loses water and transforms into Fe2O3
6. Oxide of metal cation which is not amphoteric? (d) it exhibits amphoteric properties with acid ones
(a) Al3+ (b) Cr3+ predominating
3+
(c) Fe (d) Zn2+ 14. Mercury on heating with aqua-regia gives :
7. Gold dissolves in aqua-regia forming :
(a) Hg(NO3)2 (b) HgCl2
(a) Auric chloride (b) Aurous chloride
(c) Chloroauric acid (d)Aurous nitrate (c) Hg(NO2)2 (d) Hg2Cl2
8. The solubility of silver bromide in hypo solution is
due to the formation of :
(a) Ag2SO3 (b) Ag2S2O3
(c) [Ag(S2O3)]– (d) [Ag(S2O3)2]3–
146 d AND f BLOCK ELEMENTS

15. Which of the following statements regarding copper 21. Assertion : KMnO4 is purple in colour to charge
salts is not true? transfer.
(a) Copper (I) disproportionates to copper and copper Reason : There is no electron present in d-orbitals of
(II) ion in aqueous solution manganese in KMnO4.
(b) Copper (I) can be stablished by the formation of (a) A (b) B
insoluble complex compounds such as CuCl 2 (c) C (d) D
and Cu  CN 2
 22. Assertion : KMnO4 has different equivalent weights
(c) Copper (II) oxide is red powder in acid, neutral or alkaline medium.
(d) The water of crystallization of copper sulphate is Reason : In different medium, change in oxidation
five number shown by manganese is altogether different.
16. Ferrous sulphate on heating gives : (a) A (b) B
(a) SO2 and SO3 (b) SO2 only (c) C (d) D

(c) SO3 only (d) H 2S only 23. Assertion : AgNO3 reacts with KCN to form white
17. Mercury is transported in containers made of : ppt. of AgCN. This white ppt. disappears when
excess KCN is added.
(a) Ag (b) Pb
Reason : AgCN decomposes to form silver-carbide
(c) Al (d) Fe and evolve N2 gas.
(a) A (b) B
Assertion-Reason Type Questions (c) C (d) D
24. Assertion : CrO3 reacts with HCl to form chromyl
While answering these questions, you are required to choose
any one of the following four responses. chloride gas.
(A) If both Assertion and Reason are correct and the Reason : Chromyl chloride (CrO2Cl2) has tetrahedral
Reason is a correct explanation of the Assertion. shape.
(B) If both Assertion and Reason are correct but Reason is not (a) A (b) B
a correct explanation of the Assertion. (c) C (d) D
(C) If the Assertion is correct but Reason is incorrect. 25. Assertion : Zn(OH)2 is dissolved in both NH4OH
(D) If the Reason is correct but Assertion is incorrect. and NaOH solution.
Reason : Both NaOH and NH4OH being basic can
18. Assertion : The melting point of Mn is more than dissolve amphoteric Zn(OH)2.
that of Fe. (a) A (b) B
Reason : Mn has higher number of unpaired e– than (c) C (d) D
Fe in atomic state.
26. Assertion : CuSO4. 5H2O and FeSO4. 7H2O are blue
(a) A (b) B
(c) C (d) D and green colour compounds respectively.
19. Assertion : Hg is the only metal that is liquid at Reason : Both compounds have their specific colour
due to the phenomenon of polarisation of the anion.
0ºC.
(a) A (b) B
Reason : It has a very high I.P. and weak metallic
bond. (c) C (d) D
(a) A (b) B
(c) C (d) D Comprehension
20. Assertion : Cu2+ is more stable than Cu+. A certain metal (X) is boiled in dilute HNO3 to give a salt (Y)
Reason : Electrode potential is more important in
and an oxide of nitrogen (Z). An aqueous solution of (Y) with
determining stable oxidation state than electronic
configuration. brine solution gives a white precipitate (P). When (Y) was
(a) A (b) B treated with Na2S2O3 solution a white precipitate (Q) was
(c) C (d) D obtained which on standing turns to a black compound (R).
d AND f BLOCK ELEMENTS 147

27. Salt (Y) and the oxide of nitrogen (Z) is 29. ‘Y’ and ‘Z’ are respectively
(a) AgNO3 + NO2 (b) AgNO3 + NO (a) ZnO, ZnSO4 (b) ZnS, ZnCl2
(c) AgNO3 + N2 (d) AgNO3 + NH3 (c) ZnCl2 Zn(OH)2 (d) ZnO, ZnS
28. ‘X’ is 30. Bluish white precipitate formed is
(a) ZnO (b) ZnSO 4 . 7H2O (a) Zn2[Fe(CN)6] (b) K2[Zn(CN)4]
(c) Cu2Cl2 (d) ZnCO3 (c) Zn3[Fe(CN)6]2 (d) None of these
148 d AND f BLOCK ELEMENTS

Notes:

Find Answer Key and Detailed Solutions at the end of this book
:

d AND f BLOCK ELEMENTS

 14
CHEMISTRY IN
EVERYDAY LIFE
Chapter 14
Chemistry in Everyday Life
1. Introduction
Chemical substances helping to a human body or an animal either
for treatment of diseases or to reduce suffering from pain are
called medicine or drug.
The treatment of disease by chemical compound which destroy
the micro organism without attacking the tissue of the human
body is known as chemotherapy, and the compounds used are
called chemotherapeutic agent.
1.1 Classfication of Drugs
(a) On the basis of pharmalogical effect : This classification is
useful for doctors because it provides them the whole range
of drugs available for the treatment of a particular type of
problem.e.g., Aangesics have pain killing effect, antiseptics
kill or arrest the growth of microorganisms.
(b) On the basis of drug action : It is based on the action of a
drug on a particular biochemical process.e.g., All anti
histamines inhibit the action of the compound histamine
which causes inflamation in the body.
(c) On the basis of chemical structure : Drugs classified in
this way share common structural features and often have
similar pharmacological activity. Sulphonamides have
coomon structural feacture.
(d) On the basis of molecules targets : Drugs usually interact
with biomolecules such as carbohydrates, lipids, proteins
and nucleic acids. These are called taget molecules or drug
targets.
2. Drug-Target Interaction
In the body, proteins act as enzymes in biological reactions and
also act as receptors in the body's communication system. In
biological reactions, proteins as enzymes facilitate the reaction of
the substrate with the reagent.
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2.1 Enzymes as Drug Targets
Enzymes hold the substrate molecule in a suitable position, so
that it can be attacked by the reagent effectively. Substrates bind
to the active site of the enzyme through a variety of interactions
such as ionic bonding, hydrogen bonding, van der Waals
interaction or dipole-dipole interaction.
2.2 Drug-Enzyme Interaction
When the substrate comes closer to the enzyme then it binds to
the enzyme and then with the help of reagent, chemical reaction
happen and then the product is formed.Now, drugs inhibit this
activity of the enzyme. Drugs itself bind to the active site of the
enzyme and lock the space for the substrate to bind and thus the
chemical reaction does not proceed. This inhibition by drugs is
done in two different ways:
(i) When the drug binds to the enzyme at the active site and
thus no space available for the substrate and thus no
chemical reaction proceeds.
(ii) When the drug binds to the enzyme at some different site
also known as allosteric site, but due to this binding, the
shape of the enzyme changes and thus substrate is not able
to bind with the enzyme and thus no chemical reaction
proceeds.
Fig. 14. 1:Competitive Inhibition
CHEMISTRY IN EVERYDAY LIFE 151

Terfenadine (Seldane)

Fig. 14. 2: Non-competitive Inhibition 3.3 Neurologicaly Active Drugs

3.3.1 Tranquilizers
The chemical substances which act on the central nervous system
3. Therapeaction of Different and has a calming effect. Since these are used for mental diseases
Classes of Drug so are known as psycotherapeutic drugs.
They are of two types :
(a) Sedative or hypnotics (b) Mood elevators
3.1 Antacids (a) Sedative : Reduce nervous tension and promote relaxation.
e.g. Reserpine, barbituric acid and its derivatives as luminal
Antacid is a base which neutralizes excess of acid secreted in the
& seconal.
stomach during digestion of food.Histamine stimulate the
secretion of pepsin and HCl in stomach.e.g. Histamine and (b) Mood elevators or Antidepressants : A drug used for
ranitidine. treatment of highly depressed patient, who has lost his
confidence.e.g., Benzedrine (amphetamine).
Some tranquilizers namely, chlordiazepoxide and meprobamate,
are relatively mild tranquilizers suitable for relieving tension.
Equanil is used in controlling depression and hypertension.

Histamine

Equanil

Ranitidine

3.2 Antihistamine
Antihistamine prevent the interaction between histamine and
receptors in the stomach wall.Hence decrease the secretion of
acid.e.g., brompheniramine (Dimetapp) and terfenadine (Seldane).
They interfere with the natural action of histamine by competing
with histamine for binding sites of receptor where histamine exerts
its effect. Chlordiazepoxide

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Meprobamate
3.3.2 Analgesics
The substances which are used to get relief from pain. These are
of two types :
(a) Narcotics or habit forming drugs
(b) Non-narcotics (non-addictive)
(a) Narcotics : These are alkaloids and mostly opium products,
causes sleep and unconciousness when taken in higher
doses. These analgesics are chiefly used for the relief of
postoperative pain, cardiac pain and pains of terminal cancer,
and in child birth.e.g., Morphine, codeine, heroine.
Morphine Codeine
Heroin
(b) Non-narcotics : Analgesics belonging to this category are
effective antipyretics also.These drugs are effective in
relieving skeletal pain such as that due to arthritis.Aspirin
is an non-narcotics and act as a anti blood clotting agent,
so find use in prevention of heart attacks. e.g., Aspirin &
novalgin, Ibuprofen, Naproxen.
3.4 Antimicrobials
They tend to prevent/destroy or inhibit the pathogenic action of
microbes as bacteria, virus, fungi etc. They are classified as :
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CHEMISTRY IN EVERYDAY LIFE
3.4.1 Antibiotics
These are the substances (produced wholly or partially by chemical
synthesis) which in low concentrations to inhibit the growth of
microorganisms or destroy them by intervening in their metabolic
processes.e.g., Penicillin.
Penicillin
Classification of Antibiotics Based on Spectrum :
(i) Broad spectrum antibiotics : Antibiotics which kill or inhibit
a wide range of Gram-positive and Gram negative bacteria
are known as broad spectrum antibiotic. eg.,
Chloromphenicol, Ampicillin, ofloxacin etc.
Chloromphenicol
(ii) Narrow spectrum antibiotics : The antibiotics which are
effective against either gram positive or gram negative
bacteria are known as narrow spectrum antibiotics. eg.,
Penicillin-G has a narrow spectrum.
(iii) Limited spectrum antibiotics : Antibiotics which are
effcetive against a single organism single disease known as
limited spectrum antibiotics. eg., Dysidazirine.
3.4.2 Antiseptics
Substance prevent or destroy the growth of the harmful micro
organism, common antiseptics are - Dettol, Savlon, Cetavlon,
acriflavin, iodine, methylene blue, mercurochrome & KMnO4.
Dettol is a mixture of chloroxylenol and terpineol. Its dilute solution
is used to clean wounds.
Bithional - It is added to soap to impart antiseptic properties.
Tincture of iodine is a 2-3% solution of iodine in alcohol, which is
a powerful antiseptic for wounds. Iodoform (CHI3) is also used as
an antiseptic for wounds.
CHEMISTRY IN EVERYDAY LIFE 153
3.7 Antifertility Drugs
These are the chemical substances used to control the pregnancy.
These are also called oral contraceptives. They belong to the
class of natural products, known as steroids. Birth control pills
essentially contain a mixture of synthetic estrogen and
progesterone derivatives. Norethindrone is widely used as
antifertility drug.

Chloroxylenol Terpineol
3.4.3 Disinfectants
The chemical compounds capable of completely destroying the
micro organism are termed as disinfectants. These are toxic to
living tissues. These are utilized for sterilization of floor, toilets
instruments & cloths. eg., 1% solution of phenol is disinfectant
while 0.2% solution of phenol is antiseptic.
Chlorine in the concentration of 0.2 to 0.4 ppm in aqueous solution Norethindrone
and sulphur dioxide in very low concentrations, are disinfectants.

3.5 Antipyretics
To bring down the body temp. in high fever are called antipyretics.

Noverstrol (Ethynylestradiol)

4. Chemicals in Food
Chemicals are added to food for (i) their preservation, (ii) enhancing
their appeal, and (iii) adding nutritive value in them. Some important
Aspirin Paracetamol food additives are as follows:
3.6 Anaesthetics
These are chemical substances helping for producing general or 4.1 Artificial Sweetening Agents
local insensibility to pain and other sensation. These are of two
Sucrose and fructose are the most widely used natural sweetners.
types: (a) General (b) Local
Since they add to our calorie-intake and promote tooth decay,
(a) General : Produce unconciousness and are given at the
therefore, many people use artificial sweeteners. For example,
time of major surgical operations.e.g. Gaseous form – Nitrous
saccharin, aspartame, alitame, sucralose, cyclamate and L-glucose.
oxide, ethylene, cyclopropane etc.
(i) Saccharin : It is used in form of its sodium or calcium salt
Liquid form – Chloroform, divinyl ether and sodium pentothal etc.
which is highly soluble in water. It is not biodegradable and
(b) Local anaesthetics: Produce loss of sensation on a small hence does not have calorific value of food. It is primarily
portion of the body. It is used for minor operations.e.g. Jelly used as a sweetening agent by diabetic patients and by
form – Oxylocain those who need to control intake of calories.
Spray form – Ethyl chloride (ii) Aspartame : It is the methyl ester of the dipeptide derived
Injection form – Procain from phenylalanine and aspartic acid. It is roughly 100 times
as sweet as cane sugar. Therefore, it is used as a sugar
substitute in cold foods and soft drinks.

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(iii) Alitame : Although it is similar to aspartame but is more stable
than aspartame.
(iv) Sucralose : It is trichloro derivative of sucrose. It is stable at
cooking temperature. It neither provides calories nor causes
tooth decay.
(v) Cyclamate : It is N-cyclohexylsulphamate. Cyclamate is an
artificial sweetener. It is 30–50 times sweeter than sucrose
(table sugar), making it the least potent of the commercially
used artificial sweeteners.
(vi) L-Glucose : Like D-sugars, L-sugars are also sweet in taste
but do not provide any energy since our body does not
have the enzymes for their metabolism.
4.2 Preservatives
Chemical substances which are used to protect food against
bacteria, yeasts and moulds are called preservatives. The most
CHEMISTRY IN EVERYDAY LIFE
commonly used preservative is sodium benzoate. Another well
known preservative is sodium or potassium metabisulphite which
is used in jams, squashes, pickles etc. Its preservative action is
due to SO2 which dissolves in water to form sulphurous acid
which inhibits the growth of yeasts, moulds and bacteria. Salts of
propionic acid and sorbic acid are also used as preservatives.
4.3 Antioxidants
Chemicals which are used to prevent oxidation of fats in processed
foods such as potato chips, biscuits, breakfast cereals, crackers
etc. are called antioxidants. In fact, they are more reactive towards
oxygen than the material they are protecting. They also reduce
the rate of involvement of free radicals in the ageing process. The
two most familiar antioxidants used are butylated hydroxytoluene
(BHT) and butylated hydroxyanisole (BHA).

Table 14.1: Artificial Sweetning Agent

Artificial Sweetener Structural Formula Sweetness Value

Comparison to Cane Sugar

Aspartame 100

Saccharin 550

Sucralose 600

Altrame 2000

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CHEMISTRY IN EVERYDAY LIFE
4.4 Edible Colours
Colours are added to thousands of food items to improve their
appearance although they do not have any nutritive or food value.
These are essentially dyes which may be either synthetic or
natural. The synthetic edible colours are azo dyes which are
harmful for young children and asthma patients. The most
important synthetic dye is tetrazine which is shown to be harmful.
Natural edible colours such as annatto, caramel, carotene and
saffron are, however, safe. Some inorganic salts have also been
used. For example, iron oxide is used to impart red colour and
titanium dioxide is used to intensify whiteness.
5. Cleansing Agent
The word detergent means cleansing agent. Actually detergent
word is derived from Latin word „detergere" means “to wipe off”,
Cleansing agents are the substance which remove dirt and have
cleansing action in water. These are also called surfactants.“
5.1 Soaps
Soaps are sodium or potassium salts of higher fatty acids such as
lauric acid, (C11H23COOH), myristic acid (C13H27COOH), palmitic
acid (C15H31COOH), stearic acid (C17H35COOH), oleic acid
(C17H33COOH), linoleic acid (C17H31COOH) and linolenic acid
(C17H29COOH).
Soaps containing sodium salts are formed by heating fat (i.e.,
glyceryl ester of fatty acid) with aqueous sodium hydroxide
solution. This reaction is known as saponification.
Soaps are 100% biodegradable, i.e., microorganisms present in
sewage water completely oxidise them to CO2. As a result, soaps
do not create any water pollution problem.
155
However, they have two disadvantages :
(i) Soaps cannot be used in hard water since calcium and
magnesium ions present in hard water produce curdy white
precipitates of calcium and magnesium soaps.
(ii) Soaps cannot be used in acidic solutions since acids
precipitate the insoluble free fatty acids which adhere to the
fabrics and hence prevent the process of dyeing.
Different kind of soaps are made by using different raw materials:
(i) Toilet soaps : These are prepared by using better grade of
fat or oil and care is taken to remove excess alkali. Colour
and perfumes are added to make these more attractive.
(ii) Floating soaps : These can be prepared by beating tiny
bubbles into the product before it hardens.
(iii) Transparent soaps : These are made by dissolving the soap
in ethanol and then evaporating the excess solvent.
(iv) Medicated soaps : Medicated soaps are prepared by some
antiseptics like dettol or bithional.
(v) Shaving soaps : These contain glycerol to prevent drying.
A gum called rosin is added while making them. It forms
sodium rosinate which lather well
(vi) Laundry soaps : Contain fillers like Sodium Rosinate, Sodium
Silicate, Borax, and Sodium Carbonate.
(vii) Soap Chips : These are made by running a thin sheet of
melted soap on a cool cylinder and scraping off the soaps in
small broken pieces.
(viii) Soap grannules : These are dried miniature soap bubbles.
(ix) Soap powder and scouring soaps : These contain a scouring
agent (abrasive) such as powdered pumice or finely divided
sand and builders like sodium carbonate and trisodium
phosphate. Builders make the soaps act more quickly.
NOTE:
Hard water contains calcium and magnesium ions. These ions
form insoluble calcium and magnesium soaps respectively when
sodium or potassium soaps are dissolved in hard water. These
insoluble soaps separate as scum in water and are useless as
cleansing agent.
5.2 Synthetic Detergents
Synthetic detergents, on the other hand, are generally sodium salts
of alkyl hydrogen sulphates of long chain alcohols or alkylbenzene
sulphonates. Unlike soaps, detergents can be used even in hard
water since like sodium or potassium salts, their calcium and
magnesium salts are soluble in water. However, unlike soaps,
synthetic detergents are not completely biodegradable and hence
cause water-pollution.
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Synthetic detergents are of the following three types :
(a) Anionic detergents : These are so named because a large
part of their molecules are anions. These are of two types :
(i) Sodium alkyl sulphate : These are obtained from long chain
alcohols by treatment with conc. H2SO 4 followed by
neutralization with NaOH. For example,
CHEMISTRY IN EVERYDAY LIFE
extensively as germicides, e.g., cetyltrimethylammonium

  –
chloride CH 3  CH 2 15 N  CH 3 3  Cl .
 
(c) Non-ionic detergents : These are esters of high molecular
mass obtained by reaction between polyethylene glycol and
stearic acid.
These may also be obtained from long chain alcohols by treatment
with excess of ethylene oxide in presence of a base.

These sodium alkyl sulphates are 100% biodegradable.

(ii) Alkylbenzene sulphonates (ABS) : These are obtained by 5.3 Detergent Pollution
F.C. alkylation of benzene with long chain alkyl halide or an
Detergents having branched hydrocarbon chains cause pollution
alkene or an alcohol followed by sulphonation and
in rivers and other waterways. The reason being that side chains
neutralization with NaOH. The most widely used domestic
stop bacteria from attacking and breaking the chains. This results
detergent is the sodium dodecylbenzenesulphonate (SDS).
in slow degradation of detergent molecule leading to their
Another important example is sodium
accummulation.
2-dodecylbenzenesulphonate :

6. Rocket Propellants
In order to provide sufficient push to the rocket satellites to enter
into the space, some chemical fuels are used, which are termed as
rocket propellants.A propellant is a combination of two
compounds i.e.
(a) An explosive compound called fuel
(b) Oxidiser
A chemical compound should satisfy the following conditions to
function as propellant :
(i) The burning of fuel should not leave any ash.
(ii) The burning of fuel should produce a large volume of gases/g
of fuel.
These detergents are also effective in slightly acidic solutions since
they form the corresponding alkyl hydrogen sulphates which are (iii) The combustion should proceed at a fast rate.
soluble materials whereas soaps react with acidic solutions to
form insoluble fatty acids.
(b) Cationic detergents : These are quaternary ammonium salts
6.1 Classification of Propellant
(chlorides, bromides, acetates etc.) containing one or more Depending upon physical state of fuel and oxidiser, the propellants
long chain alkyl groups. Being more expensive than the anionic are of three types :
detergents, they find limited use. Such detergents, however, (a) Solid propellants
possess germicidal properties and hence are used quite (b) Liquid propellants
(c) Hybrid propellants

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CHEMISTRY IN EVERYDAY LIFE 157

6.1.1 Solid Propellants 7. Dyes

In which fuel and oxidiser both are solid. These are of two types:
Dyes are coloured substances which can be applied in solution
(i) Composite propellant : It contains polymeric binder as fuel or dispersion to a substrate such as textile fibres (cotton, wool,
and ammonium perchlorate as oxidiser. silk, polyester, nylon), paper, leather, hair, fur, plastic material etc.
Fuel - Polyurethane or polybutadiene, giving it a coloured appearance.
Oxidiser - Ammonium perchlorate If a compound absorbs light in the visible region, its colour will be
(ii) Double base propellant : It consists of nitro cellulose and that of the reflected light, i.e. complementary to that absorbed.
nitroglycerine For example, if a dye absorbs blue colour, it will appear yellow
Disadvantage of solid propellant : which is the complementary colour of blue.
Once they ignite, they burn with a predetermined rate. Auxochromes are groups which themselves do not absorb light
These do not have the start and stop capability. (i.e. are not chromophores) but deepen the colour when introduced
into the coloured compounds, i.e., OH, NH2, Cl, CO2H etc.
6.1.2 Liquid Propellants
These are of two types :
(i) Monoliquid propellant : When a single liquid acts as fuel 7.1 Classification of Dyes
and oxidiser. eg. Nitromethane, Methyl nitrate, H2O2 etc. A large number of dyes are used for various purposes. These are
(ii) Biliquid propellant : It comprises a liquid fuel and a liquid classified on the basis of their
oxidiser e.g. Fuel – Kerosene, alcohol, hydrazine, (i) Sources, (ii) constitution, (iii) and Application
monomethyl hydrazine (MMH) or liquid hydrogen.
7.1.1 Source
Oxidiser : Liquid oxygen, dinitrogen tetraoxide (N2O4) or
(i) Natural dyes are obtained from plants. For example, alizarin,
nitrous acid. indigo etc.
Advantages : (ii) Synthetic dyes are prepared in the laboratory. For example,
(i) These provide higher thrust than solid propellants. martius yellow, malachite green, orange-I, orange-II, congo
(ii) The thrust can be controlled by switching on and off the red, aniline yellow etc.
flow of liquid propellant. 7.1.2 Constitution
6.1.3 Hybrid Propellants (i) Nitro dyes : martius yellow
These consist of a solid fuel and a liquid oxidizer. e.g. (ii) Azo dyes : aniline yellow, methyl orange, orange-I, congo
Fuel – Acrylic rubber red etc.
Oxidiser – Liquid N2O4 (iii) Triphenylmethane dyes : malachite green, magneta
(iv) Indigoid dyes : Indigo, indigosol
(v) Anthraquinone dyes : alizarin
6.2 Specific Impulse (Is) (vi) Phthalein dyes : phenolphthalein
The superiority and performance of a propellant is expressed in 7.1.3 Application
terms of specific impulse (Is).
(i) Acid Dyes are sodium salts of azo dyes containing sulphonic
acid or carboxylic acid groups, e.g. orange-I, orange-II,
T
Is  congo red, methyl orange and methyl red. These dyes do
M
not have any affinity for cotton but are used to dye wool,
Where T = Flame temperature, M = average molecular mass. silk, polyurethane fibres. The affinity of acid dyes for nylon
Thus the performance of rocket propellant will be better if flame is higher than that for other types because polycaprolactam
temperature is higher and the average mass of the product gas is fibres contain a higher proportion of free amino groups.
lower.

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(ii) Basic Dyes are the salts of azo and triphenylmethane dyes
containing amino groups as auxochromes, e.g., aniline
yellow, butter yellow, malachite green and chrysoidine G.
These dyes are applied in their soluble acid solutions and
get attached to the anionic sites present on the fabrics.
Such dyes are used to dye polyesters and reinforced nylons.
(iii) Direct Dyes are water soluble dyes which are directly applied
to the fabric from an aqueous solution. These dyes are most
useful for fabrics which can form H-bonds such as cotton,
wool, silk, rayon and nylon. Some example of direct dyes are :
congo red and martius yellow.
(iv) Fibre Reactive dyes attach themselves to the fibre by an
irreversible chemical reaction. Therefore, their dyeing is fast
and colour is retained for a longtime. These dyes contain a
reactive group which combines directly with the hydroxyl
or amino group of the fibre (cotton, wool, silk). Dyes which
are derivatives of 2, 4-dichloro-1, 3, 5-triazine are important
examples of fibre reactive dyes.
(iv) Insoluble Azo Dyes constitute about 60% of the total dyes
used. These are obtained by coupling of phenols, naphthols,
aminophenols adsorbed on the surface of a fabric with a
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polyurethanes, polyacrylonitriles and leather. Azo dyes can
also be used to dye foodstuffs, cosmetics, drugs, biological
strains such as indicators etc. However, because of their toxic
nature, these dyes are no longer permitted to dye foodstuffs.
(v) Ingrain Dyes are water insoluble azo dyes which are
produced in situ on the surface of the fabric by means of
coupling reactions. e.g. para red.
(vi) Vat Dyes are insoluble dyes which are first reduced to
colourless soluble form (leuco compound) in large vats with
a reducing agent such as alkaline sodium hydrosulphite
and applied to the fabric and then oxidised to the insoluble
coloured form by exposure to air or some oxidising agent
such as chromic acid or perboric acid, e.g., indigo. Indigosol
O, on the other hand, is readily fibre with formation of indigo.
It is especially suitable for wool.
(viii) Mordant Dyes are applied to the fabric after treating them
with a metal ion (mordant) which acts as a binding agent
between the dye and the fabric. Depending upon the metal
ion used, the same dye can give different colours. Thus,
alizarin gives a rose red (turkey red) colour with Al+3 ions
and blue colour with Ba2+ ions. These dyes are especially
used for dyeing wool.
CHEMISTRY IN EVERYDAY LIFE 159

Summary
Drugs Description Examples
Analgesics Relieve or decreases the pain without causing unconsciousness. These Asprin, Analgin, seridon etc.
are also known as “Pain Killers”.

Tranquizers / These are used for treatment of mental diseases. Equanil, Calmpose, Tofranil,
Antidepressants Barbituric Acid, Cocaine and
Iproniazids etc..

Antiseptics They are applied on living tissues to kill or prevent the growth of micro- Dettol, Savlon and Acriflavin
organisms. etc.

Disinfectants These are applied on floor, instruments or wall etc. to kill microorgan- Phenol
isms but are not safe for application on living tissues.

Antimicrobial These are use to either kill (bactericidal) or stop the growth of diseases Salvarsan, Prontosil,
causing microorganisms. (bacteriostatic). Sulphanilamide, Bacteriostatic
Drugs: Erythromycin,
Tetracycline, Chloramphenicol
Bactericidal Drugs: Ofloxacin,
Aminoglycosides.

Antipyretics These drugs bring down the body temperature during fever. Paracetamol, Analgin and
Novalgin.

Antifertility Drugs Prevent pregnancy in women by controlling menstrual cycle and Norethindrone & Mestranol
ovulation.

Antacids Used for the treatment of acidity. Eno, & Milk of magnesia
Metal hydroxides are generally used as antacids. [Mg(OH)2]

Antibiotics These are the chemical substances which are produced by micro – Penicillin, Amoxicillin and
organisms like bacteria and fungi and are able to kill or stop the growth Ampicillin.
of pathogenic microorganisms.

Antihistamins These drugs compete with histamine for finding sites of receptors and Brompheniramine &
thus interfere with the natural action of histamine. Terfenadine.

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Solved Examples
Example-1
t Define the term chemotherapy.
Sol. The use of chemicals for therapeutic effect is called
chemotherapy. For example: the use of chemicals in the
diagnosis, prevention, and treatment of diseases like cancer.
Example-2
Explain the term target molecules or drug targets as used in
medicinal
Sol. In medicinal chemistry, drug targets refer to the key
molecules involved in certain metabolic pathways that
result in specific diseases. Carbohydrates. proteins, lipids,
and nucleic acids are examples of drug targets. Drugs are
chemical agents designed to inhibit these target molecules
by binding with the active sites of the key molecules.
Example-3
Name the macromolecules that are chosen as drug targets.
Sol. The macromolecules chosen as drug targets are carbohydrates,
lipids, proteins. and nucleic acids.
Example-4
Why should not medicines be taken without consulting
doctors?
Sol. A medicine can bind to more than one receptor site. Thus,
a medicine may be toxic for some receptor sites. Further, in
most cases, medicines can cause harmful effects when taken
in higher doses than recommended. As a result, the intake
of medicines may be poisonous and can cause abnormalities.
Hence, medicines should not be taken without consulting
the doctors.
Example-5
Which forces are involved in holding the drugs to the active
site of enzymes?
Sol. Either of the following forces can be involved in holding
drugs to the active sites of enzymes.
1. Ionic bonding
2. Hydrogen bonding
3. Dipole - dipole interaction 4. van der Waals forces
Example-6
Antacids include
(a) Omeprazole (b) Lansoprazole
(c) Sodium bicarbonate (d) All of these
Ans. (d)
Sol. All are antacids
CHEMISTRY IN EVERYDAY LIFE
Example-7
While antacids and anti-allergic drugs interfere with the
function of histamines, why do these not interfere with the
function of each other?
Sol. Specific drugs affect only particular receptors. Antacids
and anti-allergic drugs work on different receptors. This is
the reason why antacids cure acidity caused by histamine
and anti-allergic drugs cure allergy due to histamines and
they do not interfere with each other's functions, but
interfere with the functions of histamines.
Example-8
Why are cimetidine and ranitidine better antacids than
sodium hydrogen carbonate or magnesium or aluminium
hydroxide?
Sol. Antacids such as sodium hydrogen carbonate, magnesium
hydroxide, and aluminium hydroxide work by neutralising
the excess hydrochloric acid present in the stomach. But
they are not effective in treating the actual cause of excess
of acid in the stomach. Cimetidine and ranitidine are better
antacids as they work on the root cause of acidity. These
drugs prevent the interaction of histamine with the
receptors present in the stomach walls that results in the
decrease in the amount of acid released by the stomach.
This is why cimetidine and ranitidine are better antacids
than sodium hydrogen carbonate, magnesium hydroxide,
and aluminium hydroxide.
Example-9
Drawback of excess of hydrogen carbonate taking as antacid
is
(a) It is insoluble
(b) It can make stomach alkaline and trigger the production
of even more acid
(c) It causes ulcer
(d) It causes pain and irritation
Ans. (b)
Sol. NaHCO3 as antacid has a drawback that its consumption
trigger the production of more acid.
CHEMISTRY IN EVERYDAY LIFE 161

Example-10 Example-14
Important function of the drug with the following structure The correct structure of Bithional is

(a) (b)

(a) Reducing fever (b) Relieving pain

(c) Anti blood clotting action (d) All of these
Ans. (d)
Sol.
(c) (d)

Ans. (d)
This is Aspirin Sol. The correct structure of Bithional is
• Reduce fever
• Reduce pain
• Anti flood cloting agent
Example-11
Non-narcotics includes all, except Example-15
(a) Ibuprofen (b) Paracetamol Which is mismatched regarding the structure?
(c) Opiate (d) Diclofenac sodium
Ans. (c) (a)
Sol. Opiate is Narcotic drug.
Example-12
Antibiotics which do not have bactericidal action among
the following is
(b)
(a) Penicillin (b) Tetracycline
(c) Ofloxacin (d) Streptomycin
Ans. (b)
Sol. Antibiotics which do not have bactericidal action among
the following is Tetracycline.
Example-13 (c)
Antiseptic which is a mixture of chloroxylenol and -
terpineol is.
(d) Both (b) & (c)
(a) Savlon (b) Dettol
Ans. (b)
(c) Bithinal (d) Salol
Sol. Choice (b) is incorrect because the correct structure of
Ans. (b) Aspirin is
Sol. Dettol  Chloroxylenol + Terpineol
162 CHEMISTRY IN EVERYDAY LIFE

Example-16 Example-20
How do antiseptics differ from disinfectants? Give one Drugs which contain mixture of norethindrone and
example of each. ethynylestradiol are
Sol. Antiseptics and disinfectants are effective against (a) Antibiotics (b) Antifertility
microorganisms. They differ in the function that antiseptics (c) Antiseptic (d) Antacid
are applied to the living tissues such as wounds, cuts, Ans. (b)
ulcers, and diseased skin surfaces, while disinfectants are
Sol.
useful upon inanimate objects such as cleaning floors,
Norethindrone  ethynylestradiol
drainage system, instruments, etc. Disinfectants are harmful
  
to the living tissues. Antifertility Drugs
Iodine is an example of a strong antiseptic. Tincture of Example-21
iodine (2 - 3 percent of solution of iodine in alcohol - water
Birth control pills essentially contains
mixture) is applied to wounds. one percent solution of
phenol is used as a disinfectant. (a) Synthetic estrogen
(b) Synthetic progesterone
Example-17
(c) Both (a) & (b)
Name a substance which can be used as an antiseptic as
(d) Neither (a) nor (b)
well as disinfectant.
Ans. (c)
Sol. Phenol can be used as an antiseptic as well as a disinfectant.
Sol. Birth control pills essentially contains
0.2 percent solution of phenol is used as an antiseptic,
(a) Synthetic estrogen
while one percent of its solution is used as a disinfectant.
(b) Synthetic progesterone
Example-18 Example-22
0.2% of solution of phenol and 0.2-0.4 ppm chlorine in Which is mismatched, regarding the examples?
aqueous solution respectively behave as
(a) Broad spectrum Antibiotic – Chloramphenicol
(a) Antiseptic, Disinfectant
(b) Narrow spectrum antibiotic – Ampicillin
(b) Disinfectant, Antiseptic
(c) Antiseptic – Furacine
(c) Disinfectant, Disinfectant
(d) Antifertility – Novestrol
(d) Antiseptic, Antiseptic
Ans. (b)
Ans. (a)
Sol. Ampicillin is categorised in Broad-spectrum antibiotics.
Sol. 0.2% solution of phenol  Antiseptic
Example-23
0.2-0.4 ppm chlorine in aq. solution  Disinfectant
Chemicals are added to food for
Example-19
(a) Preservation
Salvarsan is an antimicrobial agent which is used for curing (b) Enhancing the appeal
(a) Malaria (b) Allergy (c) Adding nutritive value
(c) Syphilis (d) Depression (d) All of these
Ans. (c) Ans. (d)
Sol. Salvarsan is an antimicrobial agent used to cure syphilis. Sol. Chemicals are added to food for
(a) Preservation (b) Enhancing the appeal (c) Adding
nutritive value
CHEMISTRY IN EVERYDAY LIFE 163
Example-24 Example-25
The first popular artificial sweetening agent is What are food preservatives?
(a) Saccharin (b) Aspartame Sol. Food preservatives are chemicals that are used to prevent
(c) Alitame (d) Both (b) & (c) food from spoilage due to microbial growth. Table salt,
Ans. (a) sugar, vegetable oil, sodium benzoate(C6H5COONa) and
salts of propanoic acid are some examples of food
Sol. The first popular artificial agent is Saccharin
preservatives.
164 CHEMISTRY IN EVERYDAY LIFE

EXERCISE- 1: Basic Objective Questions

Therapeutic Action of Different Classes of Drugs
(c) If assertion is true but reason is false.
1. Chemotherapy is (d) If the assertion and reason both are false.
(a) Use of heat for therapeutic effect 10. Tranquilizers are prescribed for curing
(b) Use of chemical for therapeutic effect (a) Anxiety, stress, irritability
(c) Use of natural reagent for therapeutic effect (b) The growth of microorganism
(d) All of these (c) Pain, Fever
2. Drugs can be classified on the basis of (d) All of these
(a) Pharmocological effect 11. Assertion: Sedatives are given to patients who are
(b) Drug action mentally agitated and violent.
(c) Chemical structure Reason: Sedatives are used to suppress the activities
(d) All of these central nervous system.
3. Find the incorrect statement. (a) If both assertion and reason are true and the reason
(a) Drugs which produce sleep and unconsciousness is the correct explanation of the assertion.
are called narcotics (b) If both assertion and reason are true but reason is
(b) 4-Acetamidophenol is antipyretic not the correct explanation of the assertion.
(c) All tranquilizers work by same mechanism (c) If assertion is true but reason is false.
(d) The substance which kills micro-organisms called (d) If the assertion and reason both are false.
antimicrobial 12. Acetoxy benzoic acid is
4. Veronal, a barbiturate drug is used as (a) Antiseptic (b) Aspirin
(a) Anaesthetic (b) Sedative (c) Antibiotic (d) Mordant dye
(c) Antiseptic (d) None of these 13. Antiseptic chloroxylenol is
5. The substances which effect the central nervous system (a) 4-chloro-3, 5-dimethylphenol
and induce sleep are called (b) 3-chloro-4, 5-dimethylphenol
(a) Tranquillizers (b) Antipyretics (c) 4-chloro-2, 5-dimethylphenol
(c) Analgesics (d) None of these (d) 5-chloro-3, 4-dimethylphenol
6. Further growth of cancerous cells in the body is 14. Which of the following is an insecticide ?
arrested by (a) Bakelite (b) TNT
(a) Physiotherapy (b) Chemotherapy (c) BHC (d) Aspirin
(c) Electrotherapy (d) Psychotherapy 15. Which of the following drugs is an analgesic ?
7. Tranquilisers are substances used for the treatment of (a) Sulphaguanidine (b) Paludrin
(a) Cancer (b) AIDS (c) Analgin (d) Iodex
(c) Mental diseases (d) Physical disorders 16. Aspirin is
8. Which of the following is not used as an (a) Antibiotic (b) Antipyretic
antidepressant? (c) Sedative (d) Psychedelic
(a) Iproniazid (b) Phenelzine 17. Which one is a broad spectrum antibiotic?
(c) Salvarsan (d) Nardil (a) Chloroamphenicol (b) Penicillin
9. Assertion: Equanil is a tranquilizer. (c) Paracetamol (d) Ampicillin
Reason: Equanil is used to cure depression and
hypertension.
(a) If both assertion and reason are true and the reason
is the correct explanation of the assertion.
(b) If both assertion and reason are true but reason is
not the correct explanation of the assertion.
CHEMISTRY IN EVERYDAY LIFE 165

18. Antipyretics are medicinal compounds which 31. Which of the following is a hypnotic drug?
(a) Relieve pain (a) Catechol (b) Luminal
(b) Lower the body temperature (d) chemisol (d) Salol
(c) Kill other organisms 32. Streptomycin is an example of
(d) Control maleria (a) Antibiotic (b) Analgesic
19. The compounds which have general depressant action (c) Antipyretic (d) Anaesthetic
on the central nervous system are called 33. Chloroxylenol is an important component of
(a) Sedatives (b) Tranquilizers (a) Soap (b) Antibiotics
(c) Narcotics (d) Anaesthetics (c) Dettol (d) Pain Killing ointments.
20. Compounds used to produce unconsciousness and 34. Which of the following is not a narcotic?
muscular relaxation, sufficient to carry out surgical (a) Codeine (b)Pethidine hydrochloride
operations are called (c) Novalgin (d) Methadon
(a) Sedatives (b) Tranquilizers 35. Which of the following drugs is a tranquilizer and
(c) Anaesthetics (d) Antibiotics sedative ?
21. When a mixture of salicylic acid, acetic anhydride and (a) Sulphadiazine (b) Papaverine
acetic acid is refluxed, the product obtained is (c) Equanil (d) Mescaline
(a) Aspirin (b) Acetophenone 36. Which one of the following is employed as a
(c) p−Acetamidophenol (d) Chloroxylenol Tranquilizer drug?
22. Which of the following is not a Narcotics? (a) Promethazine (b) Valium
(a) Opium (b) Heroin (c) Naproxen (d) Mifepristone
(c) Pethidine (d) Bithional 37. Which one of the following is employed as a
23. Ampicillin is also called tranquilizer?
(a) Penicillin G (b) Penicillin V (a) Naproxen (b) Tetracycline
(c) Penicillin K (d) None of these (c) Chlorpheninamine (d) Equanil
24. Phenylbutazone is another name for 38. The compound is used as
(a) Brufen (b) Phenacetin
(c) Butazolidine (d) None of these
25. The drug used for treatment of typhoid is
(a) Chloromycetin (b) Novalgin
(c) Paracetamol (d) Quinine
(a) An anti-inflammatory compound
26. One of the most widely used drug in medicine iodex is
(b) Analgesic
(a) Methyl salicylate
(c) Hypnotic
(b) Ethyl salicyate
(d) Antiseptic
(c) Acetylsalicylic acid
39. Which one of the following statements is not true?
(d) o-Hydroxybenzoic acid
(a) Ampicillin is a natural antibiotic
27. Which of the following term means pain killing?
(b) Aspirin is both analgesic and antipyretic
(a) Antibiotic (b) Analgesic
(c) Sulphadiazine is a synthetic antibacterial drug
(c) Antipyretic (d) Penicllin
(d) Some disinfectants can be used as antiseptics
28. Which of the following is a sedative?
40. Which of the following can possibly be used as
(a) Barbiturates (b) Bithional
analgesic without causing addiction and mood
(c) Penicillin (d) Benzyl penicillin.
modification?
29. Which of the following is an antibiotic?
(a) Drazepom
(a) Chloroxylenol (b) Bithional
(b) Tetrahydrocatinol
(c) Penicillin (d) Benzyl penicillin.
(c) Morphine
30. Which of the following is an analgesic?
(d) N-acetyl-para-aminophenol
(a) Paracetamol (b) Penicillin
(c) Chloromphenicol (d) Streptomycin
166 CHEMISTRY IN EVERYDAY LIFE

41. An antipyretic is (c) Chloroquin

(a) Quinine (b) Paracetamol (d) Penicillin
(c) Luminal (d) Piperazine 52. Which of the following is used as an antipyretic drug?
42. The drug used as an antidepressant is (a) Aspirin (b) Paracetamol
(a) Luminol (b) Tofranil (c) Phenacetin (d) All of these
(c) Mescaline (d) Sulphadiazine 53. Bacteriostatic drugs work by
43. Chloramine-T is a (a) Arresting the growth of organisms
(a) Disinfectant (b) Antiseptic (b) By increasing immunity and resistance of body to
(c) Analgesic (d) Antipyretic infection
44. Streptomycin is effective in the treatment of (c) By killing the organism in the body
(a) Tuberculosis (b) Malaria (d) Both (a) & (c)
(c) Typhoid (d) Cholera 54. Which of the following is not an antiseptic drug
45. The first antibiotic was ______ and was discovered by (a) Iodoform (b) Dettol
______. (c) Gammexane (d) Genatian violet
(a) Ofloxacin – Ehrlich 55. A drug effective in the treatment of pneumonia,
(b) Streptomycin – Alexander Fleming bronchitis, etc, is
(c) Streptomycin – Ehrlich (a) Streptomycin (b) Chloramphenicol
(d) Penicillin – Alexander Fleming (c) Penicillin (d) Sulphaguanidine
46. Which of the following drugs combination is not 56. Aspirin is obtained by the reaction of CH3COCl with
correct? (a) Phenol (b) Benzoic acid
(a) Biothional – Tranquilizer (c) Salicylic acid (d) Benzaldehyde
(b) Chloramphenicol – Broad spectrum antibiotics 57. Salol can be used as
(c) Equanil – Sedative (a) Antiseptic (b) Antipyretic
(d) Phenacetin – Antipyretic (c) Analgesic (d) None of these
47. The following compound is used as: 58. The drug which is effective in curing malaria is
(a) Quinine (b) Aspirin
(c) Analgin (d) Equanil
59. Morphine is
(a) Anaesthetic (b) Analgesic
(c) Antiseptic (d) Antibiotics
(a) An anti-inflammatory compound 60. Which of the following is a hallucinogenic drug
(b) Analgesic (a) Methedrine (b) Calmpose
(c) Hypnotic (c) LSD (d) Seconal
(d) Antiseptic 61. Which of following antibiotic consist of arsenic ?
48. Paracetamol is: (a) Salvarsan (b) Sulphanilamide
(a) Both antipyretic and analgesic (c) Both a and b (d) none of these
(b) Analgesic 62. Heroin is a derivative of
(c) Antipyretic (a) Cocaine (b) Morphine
(d) Antimalaricl (c) Caffeine (d) Nicotine
49. Brufen is used to relieve 63. Which of following is antiseptic?
(a) Pain (b) Constipation (a) Terpineol (b) Morphine
(c) Fungi infection (d) Bacterial infection (c) Norethindrone (d) none of these
50. Which of the following is used as anaesthesia? 64. The formulation of dettol contains
(a) CH4 (b) CO2 (a) Chloroxylenol (b) Terpineol
(c) N2O (d) N2 (c) Alcohol (d) All of these
51. A drug that is antipyretic as well as analgesic is 65. Which are insecticides
(a) Chloropromazine hydrochloride (a) Baygon (b) Savine
(b) para-Acetamidophenol (c) Methoxy chlor (d) All of these
CHEMISTRY IN EVERYDAY LIFE 167

66. Which one is a bacterial disease ? (d) Stopping the growth of bacteria
(a) Amoebic dysentery (b) Gonorrhoea 80. Various phenol derivatives, tincture of iodine (2– 3% I2
(c) Cholera (d) Mumps in water / alcohol) and some dyes like methylene blue
67. Which of the following is not antibiotic? are
(a) Tetracyclin (b) Neomycin (a) Antiseptics (b) Disinfectants
(c) Carbomycin (d) Cyclohexane (c) Analgesics (d) Antipyretics
68. Morphine is 81. The correct structure of the drug paracetamol is
(a) An alkaloid (b) An enzyme (a)
(c) A carbohydrate (d) A protein
69. Substance used for bringing down temperature in high
fever are called
(a) Pyretic (b) Antipyretics
(c) Antibiotics (d) Antiseptics
70. A large number of antibiotics have been isolated from
(a) Bacteria actinomycetes (b) Acids (b)
(c) Alkanals (d) Bacteria rhizobium
71. Which of the following is not an antipyretic ?
(a) Aspirin (b) Paracetamol
(c) Barbituric acid (d) Phenacetin
72. Arsenic drugs are mainly used in the treatment of
(a) Jaundice (b) Typhoid
(c) Syphilis (d) Cholera
(c)
73. An antibiotic contains nitro group attached to aromatic
nucleus. It is
(a) Penicillin (b) Streptomycin
(c) Tetracycline (d) Chloramphenicol
74. An antibiotic with a broad spectrum
(a) Kills the antibodies
(b) Acts on a specific antigen
(d)
(c) Acts on different antigens
(d) Acts on both the antigens and antibodies
75. Penicillin was first discovered by
(a) A. Fleming (b) Tence and Salke
(c) S.A. Waksna (d) Lewis Pasteur
76. A medicine which promotes the secretion of urine is
called
(a) Uretic (b) Monouretic 82. An ester used as medicine is
(c) Diuretic (d) Triuretic (a) Ethyl acetate (b) Methyl acetate
77. An example of a psychedelic agent is (c) Methyl salicylate (d) Ethyl benzoate
(a) DNA (b) LSD 83. The use of chemicals for treatment of diseases is called
(c) DDT (d) TNT as
78. 2, 4-dichloro phenoxyacetic acid is used as a (a) Homoeotherapy (b) Isothermotherapy
(a) Fungicide (b) Insecticide (c) Angiotherapy (d) Chemotherapy
(c) Herbicide (d) Moth repellent 84. Amoxillin is semi-synthetic modification of
79. Sulpha drugs are used for (a) Penicillin
(a) Precipitating bacteria (b) Streptomycin
(b) Removing bacteria (c) Tetracycline
(c) Decreasing the size of bacteria (d) Chloroampheniol
168 CHEMISTRY IN EVERYDAY LIFE

85. Which of the following is an antidiabatic drug ? (c) Acetyl salicylic acid
(a) Insulin (b) Penicillin (d) o-hydroxy benzoic acid
(c) Chloroquine (d) Aspirin 97. Which of the following can possibly be used as
86. Which of these is a hypnotic ? analgesic without causing addiction and any
(a) Metaldehyde (b) Acetaldehyde modification ?
(c) Paraldehyde (d) None of these (a) Morphine
87. Which one is an antibiotic ? (b) N-acetylparaaminophenol
(a) Aspirin (b) Chloromycetin (c) Diazepam
(c) Chloroquin (d) Madribon (d) Tetra hydrocatenol
88. Which of the following term means pain killing ? 98. Which one of the following is known as broad spectrum
(a) Antibiotic (b) Analgesic antibiotics ?
(c) Antipyretic (d) Penicillin (a) Streptomycine (b) Ampicillin
89. The compound is (c) Chloramphenicol (d) Penicillin G
99. Medicine which is antibiotic is
(a) Ampicillin (b) Phenacetin
(c) Calmpose (d) Chloroquine.
100. Which of the following is a local anaesthetic ?
(a) Antipyretic (b) Antihistamin (a) Diazepam (b) Procaine
(c) Tranquilizers (d) Antiseptic (c) Mescaline (d) None of the above
90. 2-Acetoxy benzoic acid is used as an 101. Bithional is an example of
(a) Antimalarial (b) Antidepressant (a) Disinfectant (b) Antiseptic
(c) Antiseptic (d) Antipyretic (c) Antibiotic (d) Analgesic
91. Which of the following is used as an antibiotic ? 102. Which statement is false ?
(a) Ciprofloxacin (b) Paracetamol (a) Some disinfectants can be used antiseptics at low
(c) Ibuprofen (d) Tocopherol concentration
92. When salicyclic acid is treated with acetic anhydride we (b) Sulphadiazine is a synthetic antibacterial
get (c) Ampicillin is a natural antibiotic
(a) Aspirin (b) Paracetamol (d) Aspirin is analgesic and antipyratic both
(c) Salol (d) None of these 103. Assertion: The drugs which act on the central nervous
93. Which of the following is not an antibiotic ? system and help in reducing anxiety are called
(a) Penicillin (b) Sulphaguanidine antibiotics.
(c) Chloramphenical (d) None of these Reason: Pencillin is an antibiotic.
94. Which of the following is not a broad spectrum (a) If both assertion and reason are true and the reason
antibiotic ? is the correct explanation of the assertion.
(a) Tetracycline (b) Chloromycetin (b) If both assertion and reason are true but reason is
(c) Penicillin (d) None of these not the correct explanation of the assertion.
95. The structure given below is known as (c) If assertion is true but reason is false.
(d) If assertion is false but reason is true.
104. Antiseptics and disinfectants either kill or prevent
growth of microorganisms. Identify which of the
following statements is not true ?
(a) Chlorine and Iodine are used as strong disinfectants
(b) Dilute solutions of Boric acid and Hydrogen,
(a) Penicilline F (b) Penicillin G Peroxide are strong antiseptics
(c) Penicillin K (d) Ampicillin (c) Disinfectants harm the living tissues
96. Aspirin is chemically (d) A 0.2% solution of phenol is an antiseptic while
(a) Methyl salicylate 1% solution acts as a disinfectant
(b) Ethyl salicylate
CHEMISTRY IN EVERYDAY LIFE 169

105. Chloroamphenicol is an (c) Penicillin (d) Sulphaguanidine

(a) Antifertility drug 115. Major point of difference between antiseptic and
(b) Antihistaminic disinfectant is
(c) Antiseptic and disinfectant (a) Antiseptic prevents growth of micro organism
(d) Antibiotic-broad spectrum (b) Disinfectant kills micro-organism
106. Which one of the following is employed as (c) Disinfectant are not safe to be applied to living
Antihistamine? tissues
(a) Omeprazole (d) Both (a) & (b)
(b) Chloramphenicol 116. Which of the following is not correctly match?
(c) Diphenyl hydramine Column-I Column-II
(d) Norothindrone (a) Iodoform – Antiseptic powder
107. Assertion: Tetracyclin is a broad spectrum antibiotic. (b) Barbiturates – Hypnotic drug
Reason: Tetracyclin is effective against a number of (c) Hydrogen peroxide – Strong antiseptic
types of bacteria, large viruses and typhus fever. (d) Boric acid – Antimicrobial
(a) If both assertion and reason are true and the reason
is the correct explanation of the assertion. Cleansing Agents
(b) If both assertion and reason are true but reason is
not the correct explanation of the assertion. 117. Soaps are sodium or potassium salt of long chain fatty
(c) If assertion is true but reason is false. acids like
(d) If the assertion and reason both are false. (a) Palmitic acid (b) Oleic acid
108. Assertion: Antiseptics are applied to living tissues. (c) Stearic acid (d) All of these
Reason: Iodine is a powerful antiseptic. 118. Product ‘A’ in the below reaction is
(a) If both assertion and reason are true and the reason Glycerylester of + NaOH → Sodium + 'A '
is the correct explanation of the assertion. Stearic Acid Stearate
(b) If both assertion and reason are true but reason is (a) Acetone (b) Glycol
not the correct explanation of the assertion. (c) Methanol (d) Glycerol
(c) If assertion is true but reason is false. 119. Soaps which are made by dissolving the soap in ethanol
(d) If the assertion and reason both are false. and then evaporating the excess solvent
109. 1% phenol acts as (a) Transparent soap (b) Shaving soap
(a) Disinfectant (b) Antiseptic (c) Medicated soap (d) Toilet soap
(c) Analgesic (d) Both (a) & (b) 120. The fillers that can be present in laundary soap is/are
110. Chemical compounds used for releasing stress are (a) Sodium rosinate (b) Borax
(a) Analgesic (b) Tranquilizer (c) Sodium silicate (d) All of these
(c) Antiseptic (d) Antimicrobials 121. Soap powders and scouring soap contains builders like
111. Which of the following is not a constituent of talcum (a) Trisodium phosphate
powder? (b) Finely divided sand
(a) Talc (b) Zinc sulphide (c) Powdered pumice
(c) Zinc stearate (d) Perfume (d) All of these
112. Which of the following is not a tranquilizer? 122. Soaps on reaction with hard water forms insoluble scum
(a) Morphine (b) Nembutal due to the formation of
(c) Veronol (d) Amytal (a) NaCl
113. Bithional is generally added to the soaps as an additive (b) CaCl2
to function as a/an (c) C17H35COONa
(a) Antiseptic (b) Softener (d) (C17H35COO)2Ca
(c) Dryer (d) Buffering agent
114. A drug effective in the treatment of pneumonia,
bronchitis, etc., is:
(a) Streptomycin (b) Chloramphenicol
170 CHEMISTRY IN EVERYDAY LIFE

123. Which of the following represents a synthetic 132. Which is correctly matched regarding the use?
detergent? (a) Anionic detergent – Hair conditioners
(a) C15 H 31COOK (b) Cationic detergent –Household work and in
(b) CH3 CH2 16 COONa
toothpaste
(c) Non-ionic detergent–Liquid diswashing
(d) All of these
133. Detergents obtained from LAB are biodegradable.
(c)
LAB stand for
(d) None of these
(a) laboratory tested raw material
124. Which of the following represents soap
(b) low anionic balance
(a) C17 H 35COOK (b) C17 H 35COOH
(c) linear alkyl benzene
(c) C15 H 31COOH (d) ( C17 H35COO)2 Ca (d) none of these.
125. Which type of detergents are preferably used in liquid 134. Biodegradable detergent should have
dish washing? (a) Phenyl side chain
(a) Cationic detergent (b) Anionic detergent (b) Aromatic side chain
(c) Non-ionic detergent (d) All of these (c) Normal unbranched side chain
126. Which of the following is an anionic detergent? (d) Branched side chain
(a) CH3(CH2)15(CH3)3N+Br– 135. Which of the following soap/detergents is least
(b) CH3(CH2)16CH2OSO3–Na+ biodegradable?
(c) CH3(CH2)16COO(CH2CH2O) nCH2CH2OH (a) C17H35 − Coonan
(d) CH3(CH2)16COO–Na+ (b) CH3 – (CH2)11 – OSO2Na
127. Non-ionic detergents are
(a) Salts of sulphonic acid (c)
(b) Quaternary ammonium salts
(c) Esters (d)
(d) All of these
128. Which of the following is incorrect?
(a) In anionic detergent, anionic part of the molecule is
involved in cleansing action
(b) Alkyl benzene sulphonate can be formed by
neutralising alkyl benzene sulphonic acid with
alkali
(c) Branched chain detergents are more easily 136. Structurally biodegradable detergent should contain
biodegradable (a) Normal alkyl chain (b) Branched alkyl chain
(d) All of these (c) Phenyl side chain (d) Cyclohexyl side chain
129. Glyceryl oleate can be represented by the formula
(a) (C15H31COO)3C3H (b) (C17H33COO)3C3H5 Chemicals in Food
(c) (C17H35COO)3C3H5 (d) Both (b) & (c)
130. Which of the following enhances lathering property of 137. Which is correct about saccharin?
soap?
(a) Sodium carbonate (b) Sodium rosinate
(c) Sodium stearate (d) Trisodium phosphate
131. Which is not true for a detergent molecule?
(a) It has non-polar organic part and a polar group (a) It is
(b) It is not easily biodegraded (b) It is 600 times sweeter than sugar
(c) It is sodium salt of a fatty acid (c) It is used as sweetening agent
(d) It is a surface active reagent (d) All of these
CHEMISTRY IN EVERYDAY LIFE 171

138. The main disadvantage associated with use of 145. Nitrogen dioxide and sulphur dioxide have some
aspartame is properties in common. Which property is shown by one
(a) Its sweetening power is less of these compounds, but not by the other?
(b) It is unstable at cooking temperature (a) Is used as a food-preservative
(c) It provide calories (b) Forms 'acid-rain'
(d) It is difficult to control its sweetness (c) Is a reducing agent
139. Among the following, the maximum high potency sugar (d) Is soluble in water
is 146. Which of the following can be used as food
(a) Saccharin (b) Alitame preservative?
(c) Sucralose (d) Aspartame (a) Vegetable oil (b) Table salt
140. Which of the following will not enhance nutritional (c) Sodium benzoate (d) All of these
value of food? 147. Which is incorrect regarding antioxidants?
(a) Minerals (b) Artificial sweeteners (a) They retard the action of oxygen on food
(c) Vitamins (d) Amino acids (b) Helps in food preservation for long time
141. Artificial sweetner which is stable under cold (c) Butylated hydroxy toluene and Butylated hydroxy
conditions only is anisole are important antioxidant
(a) Saccharine (b) Sucralose (d) They are flavouring agent
(c) Aspartame (d) Alitame 148. Which of the following acts as an antioxidant in edible
142. The compound with structure oils?
(a) Vitamin B (b) Vitamin C
(c) Vitamin D (d) Vitamin E
149. Which is correct about vanillin?
is used as
(a) A flavouring agent having vanila flavour
(a) Food preservative (b) Artificial sweetener
(b) o-hydroxy-m-methoxy benzaldehyde
(c) Medicine (d) Edible colour
(c) A food additive
143. Artificial sweetener used in soft drinks is :
(d) All of these
(a) lactose (b) aspartame
150. Substance used for the preservation of coloured fruit
(c) glycerol (d) fructose.
juices is
144. Sweetest artificial sweetener
(a) Benzene (b) Benzoic acid
(a) Saccharine (b) Aspartame
(c) Phenol (d) Sodium meta bisulphite
(c) Sucralose (d) Alitame
172 CHEMISTRY IN EVERYDAY LIFE

EXERCISE- 2: Previous Year Questions

1. Which of the following is not true for antibiotics? 9. The bacteriostatic antibiotic among the following is
(BHU 2008) (J&K CET 2009)
(a) Tetracycline is one of the broad spectrum (a) erythromycin (b) penicillin
antibiotics which is effective against a large (c) aminoglycoside (d) ofloxacin
number of harmful microorganisms 10. The oxidant which is used as an antiseptic is
(b) Streptomycin is highly effective against (WB JEE 2009)
microorganisms which cause tuberculosis. (a) KBrO3 (b) KMnO4
(c) Penicillin has a narrow spectrum and certain (c) CrO3 (d) KNO3
persons patients for sensitivity to it. 11. Assertion (A) Sodium-2-dodecylbenzene sulphonate is
(d) Penicillin may be administered without testing the a biodegradable detergent.
patients for sensitivity to it. Reason (R) Detergent having highly branched chains
2. Tranquilizers are also know as (MHT CET 2008) are biodegradable. (AIIMS 2009)
(a) psychosomatic drugs (a) Both A and R are correct and R is the correct
(b) psychotherapeutic drugs explanation of A
(c) psychosystolic drugs (b) Both A and R are correct and R is not the correct
(d) None of these explanation of A
3. The environmental friendly method of killing harmful (c) A is correct but R is incorrect
insects is through the use of (Kerala CEE 2008) (d) Both A and R incorrect
(a) insecticides (b) sex attractants 12. The role of phosphate in detergent powder is to
(c) sex normones (d) pesticides (UP CMT 2009)
4. The fuctional groups presents in ‘salol’ are (a) control pH level of the detergent water mixture.
(Punjab PMET 2008) (b) remove Ca2+ and Mg2+ ions from the water that
(a) –NH2 and –OR (b) –OH and –COR cause that hardness of water.
(c) –NH2 and –COOH (d) –OH and –COOR (c) provide whiteness to the fabrics.
5. Which of the following is a local anaesthetic? (d) form solid detergents as phosphateless detergents
(AMU 2008) are liquid in nature.
(a) Diazepam (b) Procaine 13. Which one of the following is employed as a
(c) Chlorophenicol (d) Penicillin-G tranquilizer drug? (CBSE AIPMT 2010)
6. Which of the following is used as an antibiotic? (a) Mifepristone (b) Promethanzine
(DUMET 2008) (c) Valium (d) Naproxen
(a) Ciprofloxacin (b) Paracetamol 14. The chemical name of aspirin is
(c) Ibuprofen (d) Tocopherol (UP CPMT, WB JEE 2010)
7. Which of the following statement is not true? (a) methylbenzoate
(Kerala CEE 2008) (b) hydroxybenzoic acid
(a) some disinfectants can be used as antiseptic at low (c) acetyl salicylic acid
concentration (d) ethylsalicylate
(b) sulphadiazine is a synthetic antibacterial 15. Arsenic drugs are mainly used in the treatment of
(c) pheromones provide chemical means of (BVP 2010)
establishing communication (a) jaundicc (b) typhoid
(d) norethindrone is a pheromone (c) syphilis (d) cholera
8. Which one of the following is employed as a
tranquilizer? (CBSE AIPMT 2009)
(a) Equanil (b) Naproxan
(c) Tetracycline (d) Chlorpheniramine
CHEMISTRY IN EVERYDAY LIFE 173

16. The following compound is used as (RPMT 2010) (d) broad spectrum antibiotic
27. The antiseptic present in Dettol is (AIIMS 2012)
(a) quinoline (b) chloroxylenol
(c) bithional (d) None of these
28. Parkinson’s disease is linked to abnormal in the level of
dopamine in the body. The structure of dopamine is
(a) an anti-inflammatory compound (Manipal 2012)
(b) analgesic
(c) hypnotic
(d) antiseptic
17. Which one of the following types of drugs reduces
fever? (RPMT 2010)
(a) Analgesics (b) Antipyretics (a) (b)
(c) Aspirin (d) Tranquilizers
18. Potassium metabisulphite is a (an) (MHT CET 2010)
(a) preservative (b) antioxidant
(c) artificial sweetener (d) Both (a) and (b)
19. The sweetest artificial sugar among the following is
(AIIMS 2010)
(a) aspartame (b) sucralose (c) (d)
(c) alitame (d) sucrose 29. Which of the following antibiotics was first discovered?
20. Which type of dyes are not used to dye nylon and (OJEE 2012)
polyester fibers? (Guj CET 2010) (a) Ampicillin (b) Amoxycillin
(a) Vat dyes (b) Basic dyes (c) Penicillin (d) Chloramphenicol
(c) Disperse dyes (d) Insoluble azo dyes 30. Which of the following sweeteners is limited to cold
21. In the following which is soap? (MP PMT 2010) foods and soft drinks? (KCET 2012)
(a) CH3COONa (b) CH3ONa (a) Aspartame (b) Sucralose
(c) C17H35COONa (d) C17H35SO3Na (c) Alitame (d) None of these
22. Which one of the following is employed as 31. Antiseptics and disinfectants either kill or prevent
antihistamine? (CBSE AIPMT 2011) growth of microorganisms. Identify which of the
(a) Omeprazole (b) Chloramphenicol following is not true? (NEET 2013)
(c) Diphenyl hydramine (d) Norethindrone (a) A 0.2% solution of phenol is an antiseptic while
23. Terfenadine is commonly used as a/an 1% solution acts as a disinfectant
(Kerala CEE 2011) (b) Chlorine and iodine are used as strong disinfectants
(a) tranquilizer (b) antihistamine (c) Dilute solutions of boric acid and hydrogen
(c) antifertility drug (d) antibiotic peroxide are strong antiseptics
24. Which one of the following has antiseptic property? (d) Disinfectants harm the living tissue
(Kerala CEE 2011) 32. Salol is (AIIMS 2013)
(a) Dichloromethane (b) Trifluoromethane (a) acetylsalicylic acid
(c) Triiodomethane (d) Tetrachloromethane (b) phenylsalicylate
25. Which of the following is pheromone? (c) methyl salicylate
(Guj CET 2011) (d) None of these
(a) Linalool (b) Disparlure 33. Paracetamol is used as an (Manipal 2013)
(c) BHA (d) Alitame (a) antibiotic (b) antimalarial
26. Chloramphenicol is an (CBSE AIPMT 2012) (c) antipyretic (d) arsenical
(a) antifertility drug 34. Which of the following antigens? (Manipal 2013)
(b) antihistamine (a) Insulin (b) Antibodies
(c) antiseptic and disinfectant (c) Chromoprotein (d) Phosphoprotein
174 CHEMISTRY IN EVERYDAY LIFE

35. Hydrolytic reaction of fats with caustic soda is know as (b) table salt, sugar
(KCET 2013) (c) vegetable oils and sodium benzoate
(a) acetylation (b) carboxylation (d) All of the above
(c) esterification (d) saponification 44. Which one among the following is added to soap to
36. Butylated hydroxyl toluene as a food additive acts as impart antiseptic property? (JIPMER 2018)
(KCET 2014) (a) Sodium lauryl sulphate
(a) antioxidant (b) flavoring agent (b) Sodium dodecyl benzene sulphonates
(c) colouring agent (d) emulsifier (c) Rosin
37. Which of the following is a bacteriostatic drug? (d) Bithional
(Kerala CEE 2014) 45. Among the following, the narrow spectrum antibiotic is
(a) Aminoglycosides (b) Penicillin-G (NEET 2019)
(c) Ofloxacin (d) Tetracycline (a) ampicillin (b) amoxycillin
38. Match the following Column I with Column II. (c) chloramphenicol (d) penicillin G
46. The artificial sweetener stable at cooking temperature
Column I Column II and does not provide calories is (NEET 2019)
A. Sucralose 1. Antioxidant (a) saccharin (b) aspartame
B. Iodine 2. Artificial sweetener (c) sucralose (d) alitame
C. Sodium benzoate 3. Antacid 47. Saccharin an artificial sweetener is manufactured from
D. Ranitidine 4. Food preservative (JIPMER 2019)
5. Food preservative (a) toluene (b) cyclohexane
The correct answer is (EAMCET 2014) (c) starch (d) cellulose
A B C D 48. Assertion (A) For liquid dishwashing non-ionic type of
(a) 2 4 1 3 detergent are used.
(b) 2 4 5 3 Reason (R) Remove grease and oil by micelle
(c) 2 3 5 1 formation. (AIIMS 2019)
(d) 2 1 3 4 (a) Both A and R are correct and R is the correct
39. Bithional is generally added to the soap as an additive explanation of A
to function as a/an (CBSE AIPMT 2015) (b) Both A and R are correct but R is not the correct
(a) softener (b) dryer explanation of A
(c) buffering agent (d) antiseptic (c) A is correct but R is incorrect
40. Which of the following is an analgesic? (NEET 2016) (d) Both A and R incorrect
(a) Penicillin (b) Streptomycin 49. Which of the following is cationic detergent?
(c) Chloromycetin (d) Novalgin (NEET 2020)
41. Mixture of chloroxylenol and terpineol acts as (a) Sodium dodecylbenzene sulphonate
(NEET 2017) (b) Sodium lauryl sulphate
(a) analgesic (b) antiseptic (c) Sodium stearate
(c) antipyretic (d) antibiotic (d) Cetryltrimethyl ammonium bromide
42. Which type of drugs come under anti-microbial drugs? 50. Given below are two statements:
(JIPMER 2018) (I) Aspirin and Paracetamol belong to the class of
(a) Antiseptics, antacids, antihistamines narcotic analgesics.
(b) Tranquilizers, antiseptics ,antifertility (II) Morphine and Heroin are non-narcotic analgesics.
(c) Tranquilizers, analgesics, antiseptics In the light of the above statements, choose the correct
(d) Antiseptics, antibiotics, disinfectants answer from the options given below. (NEET 2021)
43. Food preservatives prevent spoilage of food due to (a) Statement I is incorrect but Statement II is true.
microbial growth. The most commonly used (b) Both Statements I and Statement II are true.
preservatives are (AIIMS 2018) (c) Both Statement I and Statement II are false.
(a) C6H5COONa (d) Statement I is correct but Statement II is false.
CHEMISTRY IN EVERYDAY LIFE 175

EXERCISE- 3: Achiever’s Section

Single Answer Type Questions
10. Which of the following can possibly be used as
analgesic without causing addiction and modification?
1. How do enzyme catalyse the reaction?
(a) morphine
(a) By holding the substrate molecule for chemical
(b) N-acetyl-para-aminophenol
reaction
(c) diazepam
(b) By providing functional groups which will attack
(d) tetrahydrocatenol
the substrate to carry out chemical reaction
11. The antibiotic used for the treatment of typhoid is
(c) Both (a) & (b)
(a) penicillin
(d) Neither (a) nor (b)
(b) chloramphenicol
2. Drugs which compete with natural substrate for their
(c) terramycin
attachment on the active sites of enzymes are called
(d) sulphadiazine
(a) Enzyme Inhibitors
12. Which of the following is used as antipyretic?
(b) Competitive Inhibitors
(a) Paracetamol (b) Chloroquine
(c) Non-competitive Inhibitors
(c) Chloramphenicol (d) LSD
(d) Drug targets
13. Which is not antipyretic?
3. Antacids include
(a) novalgin (b) aspirin
(a) Omeprazole
(c) paracetamol (d) irgapyrin
(b) Lansoprazole
14. Aspirin is a/an
(c) Sodium bicarbonate
(a) narcotic (b) antipyretic
(d) All of these
(c) tranquillizer (d) anaesthetic
4. Drugs which interfere with natural action of histamine
15. Sulpha drugs are used for
by competing with histamine are called
(a) removing bacteria
(a) Antidepressant (b) Antihistamines
(b) precipitating bacteria
(c) Antimicrobial (d) Antipyretic
(c) stopping the growth of bacteria
5. Barbituric acid and its derivatives constitutes an
(d) decreasing the size of bacteria
important class of
16. Which of the following gives paracetamol on
(a) Narcotic analgesic (b) Antiallergic
acetylation?
(c) Tranquilizers (d) Antimicrobial
6. The use of chemicals for the treatment of diseases is
called as
(a) homeotherapy (b) isothermtherapy
(c) chemotherapy (d) physiotherapy
7. The substances which relieve anxiety, reduce mental (a) (b)
tension and induce sleep are called
(a) analgesics (b) antipyretics
(c) tranquilizer (d) anaesthetics
8. Which one of the following is employed as a
tranquilizer ?
(a) Equanil (b) Naproxen
(c) Tetracycline (d) Chlorpheninamine (c) (d)
9. Which one of the following is employed as a 17. Which of the following is used as a ‘morning after
tranquilizer drug ? pill’.
(a) Promethazine (b) Valium (a) Norethindrone (b) Ethynylestradiol
(c) Naproxen (d) Mifepristone (c) Promethazine (d) Bithional
176 CHEMISTRY IN EVERYDAY LIFE

18. A drug that is antipyretic as well as analgesic is Codes:

(a) chloropromazine hydrochloride (a) I-B, II-E, III-C, IV-D (b) I-D, II-B, III-A, IV-C
(b) para- acetamidophenol (c) I-B, II-E, III-A, IV-C (d) I-C, II-A, III-D, IV-B
(c) chloroquine 26. Synthetic detergents are more effective in hard water
(d) penicillin than soaps because
19. Aspirin is an acetylation product of (a) they are non-ionic
(a) o-hydroxybenzoic acid (b) their Ca+2 and Mg+2 salts are insoluble in water
(b) o-hydroxybenzene (c) their Ca+2 and Mg+2 salts are water soluble
(c) m-hydroxybenzoic acid (d) they are highly soluble in water
(d) p-dihydroxybenzene 27. Detergents are prepared by the action of H2SO4
20. Which of the following is an antibiotic? followed by neutralization by starting with
(a) Terramycin (b) Aspirin (a) cholesterol (b) lauryl alcohol
(c) Paracetamol (d) Chloroquine (b) cyclohexanol (d) p- nitrophenol
21. Which one of the following is not a broad spectrum
antibiotic? Assertion Reason Type Questions
(a) Tetracycline
(b) Chloromycetin (A) If both Assertion and reason are true and reason is
(c) Penicillin the correct explanation of the assertion.
(d) None of these (B) If both assertion and reason are true but reason is
22. Tincture of iodine is not the correct explanation of the assertion.
(a) aqueous solution of I2 (C) If assertion is true but reason is false.
(b) alcoholic solution of I2 (D) If assertion is false but reason is true.
(c) solution of I2 in aqueous KI 28. Assertion: Phenyl is used as a household germicide.
(d) aqueous solution of KI Reason: Phenyl is phenol derivative and phenol is an
23. Commonly used antiseptic ‘Dettol’ is a mixture of effective germicide.
(a) o-chlorophenoxylenol + terpineol (a) A (b) B
(b) o-cresol + terpineol (c) C (d) D
(c) phenol + terpineol 29. Assertion: Benzene removes a butter stain from a
(d) chloroxylenol + terpineol table cloth.
24. A substance which can act both as an antiseptic and Reason: Butter has an affinity towards benzene.
disinfectant is (a) A (b) B
(a) aspirin (b) phenol (c) C (d) D
(c) analgin (d) sodium pentothal 30. Assertion: The drugs which act on the central
25. Match List I with List II and select the correct answer nervous system and help in reducing anxiety are
using the codes given below the list. called antibiotics.
List I List II Reason: Penicillin is an antibiotic.
I. Iodoform A. Anaesthetic (a) A (b) B
II. Methyl salicylate B. Antiseptic (c) C (d) D
III. Diethyl ether C. Insecticide
IV. Hexaxchlorocyclohexane D. Detergent
E. Pain Balm
CHEMISTRY IN EVERYDAY LIFE 177

Notes:

Find Answer Key and Detailed Solutions at the end of this book

CHEMISTRY IN EVERYDAY LIFE

 15
PRACTICAL ORGANIC
CHEMISTRY
Chapter 15

Practical Organic Chemistry

1. Functional Group Detection
(i) All organic compound are grouped into smaller number, each
group exhibits similar chemical properties.
(ii) This means that all the compounds of the group must have
something common, this common feature is known as
functional group or reactive functional group.
(iii) It is defined as the group which largely determine the
properties of a compound e.g., CH3OH, C2H5OH, C3H7OH are
all collectively called alcohol as the common reactive group
in all is – OH.
For example, homologous series of alcohol like CH3OH,
CH3CH2OH, CH3CH2OH etc.
(iii) The chemical properties of compound containing same
functional group are similar.
For example methyl alcohol (CH3OH) & ethyl alcohol
(C2H5OH) have similar chemical properties. Therefore,
(iv) Chemical identification of a class of compounds involues
the same type of tests.
1.3 Identification Tests

1.1 Some Common Functional Groups 1.3.1 Test for Unsaturation

Name of the Functional group Example (i) Unsaturation in an organic is indicated by or
family or group
–C  C – bonds in its structure.
Alkene CH2 = CH2 (ii) Because of the presence of this -bonds these compounds
are bound to undergo addition reaction & therefore,
Alkyne –CC– HC  CH
unsaturation in the organic compound (aliphatic) can be
Alcohol –OH, (Alcoholic) CH3OH detect by exporting their this addition reaction.
Phenol Ar–OH (Phenolic) C6H5OH (iii) Two methods used for detecting unsaturation in organic
(–OH group attached compounds are-
to aromatic ring) (a) Bromine test :
Aldehyde –CHO, Aldehydic CH3CHO (i) Discharge bromine solution to colourless without evolving
HBr.
Ketone CH3COCH3

Carboxylic –COOH, Carboxylic CH3COOH

acid
Amine – NH2, amino CH3NH2
(b) Baeyer’s test or Permanganate test:
Nitro alkane – NO2 – Nitro CH 3 – NO2
(i) When alkaline solution of potassium permanganate (2%) is
Cyanide – CN – Cyano CH3 – CN added, decolourization of pink colour of kMnO4 indicates
unsaturation. A brown ppt. of MnO2 is also observed.

1.2 Characteristic of Functional Group CH 3 – CH  CH 2  2KMnO 4  4H 2 O 

(i) The physical and chemical properties of compound 2KOH + MnO 2  3CH 3  CH  CH 2
Brown | |
containing different functional groups are different. ppt OH OH
(ii) There exists a homologous series of compound containing 
Colourless 
each type of functional group.

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Practical Organic Chemistry
180 PRACTICAL ORGANIC CHEMISTRY

CH  CH  KMnO 4  H 2 O  R – OH  l   Na  s   R – ONa 
1
H 2 g 
Sodium Alkoxide 2
 COOH 2  MnO2  KOH
Oxalicacid Brown NOTE:
ppt
Test tube & alcohol should not contain even trace of moisture
NOTE: as water also reacts with sodium metal to evolve hydrogen
(i) Apply both tests, since some compounds react slowly gas.
with bromine. (b) Cerric ammonium nitrate test: To about 1 ml. of the
(ii) Enols (–OH group containing compounds) are also found substance in test tube add a few drops of cerric ammonium
to decolourise bromine as well as permanganate solution. nitrate solution. Appearance of red colour indicate the
but the type of reaction which takes place with bromine is presence of alcohols.
somewhat different in this case than with unsaturated
compounds. Enols are substituted by bromine and an CH 3 OH   NH 4  2 Ce  NO3 6 

 Colourless  Cerric ammonium nitrate
equivalent of HBr is evolved. So during the reaction white 
 Yellow 
fumes will come, when a glass rod moistened with
 CH 3OH 2 Ce  NO3 4  2NH 4 NO3
concentrated ammonia solution is held near the mouth of  Red   Colourless 
the test tube.
(c) Ester test:
HBr  NH 3 
 NH 4 Br
(i) When alcohol is treated with acetic acid in the presence of
conc. H2SO4, a characteristic fruity smell due to the formation
1.3.2 Test for Terminal Alkyne of ester indicates the presence of alcohol.
Acetylene and other terminal alkyne (1 – alkyne) are weakly acidic Conc. H SO
2 4
in character. They react with ammonical solution of cuprous C2 H 5 OH  CH3 COOH   CH3 COOC 2 H 5  H 2 O
chloride and silver nitrate to form the corresponding copper and (ii) When a compound is treated with acetyl chloride and a rod
silver alkynide. dipped in NH4OH is brought in contact with gas. If the white
H  C  C  H  2[Cu(NH3 ) 2 ] OH – 
 fume are produced, indicate the presence of alcohol.

Cu C  C Cu  2H 2 O  4NH3 ROH  CH COCl  CH3 COOR  HCl

3
Alcohol Acetylchloride Ester
Dicopper ethynide
 Red ppt 
HCl  NH 4 OH  NH 4 Cl  H 2 O
H  C  C  H  2[Ag(NH 3 ) 2 ]+ OH – 
  white fumes 
Tollens'reagent
AgC  CAg  2H 2 O  4NH 3
Disilver acetylide 1.3.4. Test for Phenolic Group
 white ppt 
 Non terminal Alkynes will not give this test Compound containing one or more hydroxyl group attached to a
aromatic ring are called phenols e.g.,

1.3.3 Test for Alcoholic (–OH) Group

(i) –OH group is called alcoholic or hydroxy group, but it is
different from the hydroxy group of inorganic compounds.
(ii) For example, – OH group of sodium hydroxide and methanol
have entirely different properties. Sodium hydroxide is a base
and turns red litmus blue but methanol does not give this Phenolic group in organic compound can be detected by following
test. test:
(a) Sodium metal test or Xanthate test :- (a) Ferric chloride test:
(i) Take compound in an absolutely, dry test tube. Add a small
(i) Take about 5 ml of ferric chloride solution (neutral) in test
quantity of anhydrous calcium chloride to absorb moisture,
tube.
decant it into another test tube.
(ii) Add a small piece of dry sodium metal to it. Effervescence (ii) Add into it 2-3 drops or pitch of compound.
with the evolution of hydrogen gas indicate the presence of (iii) Appearance of dark green, red or violet colour indicate the
alcoholic group in the compounds. presence of phenolic group in the compound.

SCAN CODE
Practical Organic Chemistry
PRACTICAL ORGANIC CHEMISTRY
(b) Litmus test
(i) Take about 1 ml of blue litmus solution in test tube. Add into
it small amount of the compound.
(ii) If the litmus turn red, then Phenolic group may be present in
compound. Phenol behave like weak acid.
(c) With Phthalic anhydride: Phenol when heated with phthalic
anhydride in the presence of concentrated H2SO4 given
phenolphthalein, a colourless compound which produce
beautiful pink colour with alkali solution due to the formation
of coloured sodium salt.
181
(d) Cerric Ammonium nitrate test : To Cerric Ammonium nitrate
add a pinch of given compound. Appearance of green or
brown precipitates indicate the presence of phenolic group
in the given compound.
(e) Liebermann’s reaction: To a small amount of substance in a
test tube add few crystals of solid sodium nitrite and then
few drops of conc. H2SO4.
A green or blue colour is obtained which change to red on
dilution and again turn blue or green an making the solution
alkaline with NaOH.
NOTE:
(i) Nitrophenols and p-substituted phenol do not give this
test.
(ii) This test is also shown by o-cresol.
1.3.5. Test for Carboxylic Group
Compound containing this group behave like acid and almost all
the tests meant for acids can be applied for testing this group.
(a) Litmus test :-
(i) Place a small quantity of the organic substance an a piece of
moist blue litmus paper, or in a blue litmus solution.
(ii) If the colour change to red, carboxylic group may be present.
(b) Sodium bicarbonate test : Take 5 ml of dilute solution of
sodium bicarbonate in a test tube and add a small quantity
of substance to it strong effervescence with the evolution
of carbon dioxide gas indicate the presence of carboxylic
acid.
R – COOH  NaHCO 3  RCOONa  CO 2   H 2 O
(c) Ester test: To a small quantity of substance add 5 drops of
ethyl alcohol and two drops of conc. H2SO4. warm the tube
an water both. A fruity small of ester indicate the presence of
– COOH group.
Conc. H SO
2 4  CH COOC H  H O
CH 3 COOH  C 2 H 5 OH  3 2 5 2
Ethyl acetate
(d) To a mixture of about 3 ml 0.1% acriflavine solution and 3 ml
1% potassium chromate solution add a few drops of aqueous
solution of substance (if it is liquid then it may be added as
such). Appearance of a yellow or brown-yellow precipitate
confirms the presence of carboxylic acid.
1.3.6. Test for Aldehydes
(a) Schiff test: To 2 ml of substance, if it is liquid or to its 2 mol
cold aqueous solution add 2ml Schiff’s reagent* (Rosaniline
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decolourised with SO2) and shake for 2 minutes. Do not heat
or warm. A deep violet-red or red colour indicates the
presence of aldehydic group.
(b) Fehling’s test: In a test tube mix 1 ml each of Fehling A
(CuSO4 in water with few drops of acetic acid) and Fehling B
(Rochelle salt and NaOH solution) solutions when a deep
blue colour appears. To this add 0.1gm or 2-3 drops of
substance and boil for 5 minutes. The blue colour of Fehling’s
solution slowly fades away and a reddish-brown precipitate
of Cu2O is obtained indicating the presence of aldehydic
group.
Tartrato-cuprate anion (blue)
(Fehling’s solution
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NOTE:
Aromatic aldehydes not give Fehling’s test.
(c) Tollen’s test: To 2 ml Tollen’s reagent in a test tube (To 1 ml
AgNO3 solution) add few drops of NaOH solution and
dissolve the precipitate of silver oxide by adding excess
NH4OH add 2-3 drops or 0.1 gm of substance. Keep the test
tube in boiling water without disturbing for 5 minutes when
a shining silver mirror deposits on the walls of test tube
indicating the presence of aldehydic group.

2  Ag  NH 3 2  OH –  RCHO  H 2 O 

Tollen 's reagent
RCOONH 4  NH 3  2NH 4 OH  2Ag 
1.3.7. Test for Ketones
If the tests for aldehydes are negative perform following tests for
ketones.
(i) To a solution of 0.5 gm or 0.5 ml substance in 5 ml dilute HCl
add 2 ml of solution of 2, 4-dinitrophenylhydrazine in dilute
HCl. Cool and allow to stand for 2 minutes when a yellow,
orange or red coloured crystalline precipitate (in case Schiff’s
test is negative) indicates the presence of kentonic group.
(ii) To 2-3 drops of substances add 1 ml freshly prepared sodium
nitroprusside solution and then NaOH solution drop by drop.
A wine red or orange red colour confirms the presence of
ketonic group.
1.3.8. Test for Ethers
(a) Zeisel’s method: A method of determining the number of
methoxy (–OCH3) groups in an organic compound. The
compound is heated wih excess hydriodic acid, forming an
alcohol and iodomethane.
R–O–CH3 + HI  ROH + CH3I
The iodomethane is distilled off and led into an alcoholic
solution of silver nitrate, where it precipitates silver iodide.
The weight of this AgI precipitate which gives us the number
of methoxy groups present. In other words, the number of
moles of AgI will be equal to the number of
(–OCH3) groups.
(b) Iodine test: Ethers may be distinguished from hydrocarbons
by iodine test.
PRACTICAL ORGANIC CHEMISTRY 183
Dissolve 2-3 drops of substance in 5ml benzene and to this
add 5 ml of very dilute solution of iodine in benzene and
shake when the solution acquires a brown tint.

1.3.9. Test for Esters and Lactones

Dissolve about 0.5 gm or 0.5 ml substance in 10 ml alcohol, add a
drop of phenolphthalein and few drops of NaOH solution. A pink
colour is produced by phenolphthalein in alkaline medium. Heat
the reaction mixture for 5 minutes when NaOH solution is used
up in the hydrolysis of ester or lactone and the pink colour of
phenolphthalein disappears.
R.COOR’ + NaOH  R.COONa + R’OH

1.3.10. Test for Primary Amines

Whether aliphatic or aromatic, all primary amines respond to
carbylamine test. (c) Reaction with carbon di-sulphide: Primary amines react with
(a) Carbylamine test: To a small amount of substance add 2ml carbon disulfide to form dithioalkyl carbamic acids which
alcoholic KOH solution, 3-4 drops of chloroform and heat decompose on heating with mercuric chloride to give alkyl
the mixture. Highly offensive odour of carbylamine or isothiocyanates.
isocyanide is produced. These have a characteristic smell like mustard oil. This
R N H 2  C H C l 3  3K O H  
 RNC  3 K C l  3H 2 O reaction is called the Hoffmann mustard oil reaction and is
alk yl iso cyan id e
u n p leasan t sm ell used as a test for primary amines.
Some derivatives of amines such as acetyl derivatives which S
||
get hydrolysed under the conditions of the reaction, may HgCl2
RNH 2  S  C  S  RNH – C – SH   
also respond to this test.
RN  C  S  HgS  2HCl
(b) Dye test: In addition, aromatic primary amines respond to Alkyl isothiocynate

dye test. Dissolve a small amount of substance in 2 ml dil. 1.3.11. Test for Secondary Amines
HCl. If the substance is insoluble add 3-4 ml water and cool
Dissolve a small amount of substance in 2 ml HCl, dilute it with 3-
the mixture to 0°. To this then add precooled 2 ml 2% NaNO2
4 ml water and add 2 ml of 2% NaNO2 solution. If white or yellow
solution in such small amounts that no brown fumes escape
oily emulsion is obtained or a low melting solid separates the
from the solution. If light turbidity is obtained, ignore it.
compound is a secondary amine.
Add 1 ml of this solution to a solution of -naphthol in alkali
when an orange-red coloured dye is obtained. Ar–NHR  HNO 2 
 Ar– NR  H 2 O
|
NO

1.3.12. Test for Tertiary Amines

Most of the aromatic tertiary amines respond to following test :
On adding 2 ml of 2% NaNO2 solution to a solution of substance
in dilute HCI, if a yellow or yellow-green colour is produced
which turns dark greenish on making the solution alkaline then
the compound may be an aromatic tertiary amine.

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1.3.13. Test for Nitro Compound
(a) Mulliken’s test: To a small amount of substance add 2 ml
alcohol, 1 ml CaCl2 solution and a pinch of zinc dust or 1-2
small tin pieces. Boil the mixture for 5 minutes, cool and filter.
To the filtrate add Tollen’s reagent (ammoniacal AgNO3) when
a white precipitate, turning grey and finally black, is produced
(b) On reduction of nitro compound a hydroxylamine derivative
is formed which reduces Tollen’s reagent.
RNO2  4  H  
 RNHOH  H 2 O
Hydroxylamine
derivative
NOTE:
If the amino group is absent then these nitro compounds
may be reduced to amino compounds which can be tested
either by carbylamine test or dye test.
1.3.14. Test of Carbohydrates
(a) Molish test: Molish test is used for detection of all types of
carbohydrates, i.e. monosaccharides, disaccharides and
polysaccharides.
Molisch reagent (1% alcoholic solution of -naphthol) is
added to the aqueous solution of a carbohydrate followed
by conc. H2SO4 along the sides of the test tube. A violet ring
is formed at the junction of the two layers.
(b) Barfoed test: This test is used for distinguishing
monosaccharides from reducing disaccharides.
Monosaccharides usually react in about 1 - 2 min while the
reducing disaccharides take much longer time between 7 - 12
min to get hydrolysed and then react with the reagent.
Brick red color is obtained in this test which is due to the
formation of cuprous oxide.
(c) Seliwanoff’s test: This test is used to distinguish aldoses
from ketoses. Ketoses undergo dehydration to give furfural
derivatives, which then condense with resorcinol to form a red
complex. Prolonged heating will hydrolyze disaccharides and
other monosaccharides will also eventually give color.
(d) Iodine test: Iodine forms colored adsorption complexes with
polysacchaides. Starch gives blue color with iodine, while
glycogen reacts to form reddish brown complex. Hence it is
useful, convenient and rapid test for detection of amylase,
amylopectin and glycogen.
(e) All Monosaccharides give Tollens’ test, Fehling’s test,
Benedict’s test and Picric acid test (given by reducing sugar).
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1.3.15. Test for Proteins
(a) Biuret test: An alkaline solution of a protein when treated
with a few drops of 1% CuSO4 solution, produces a violet
colouration. The colour is due to the formation of a
coordination complex of Cu+2 with and –NH– groups
of the peptide linkages.
(b) Xanthoproteic test: When a protein is treated with conc.
HNO3 a yellow colour is produced. This test is given by a
protein which consists of -amino acids containing a benzene
ring such as tyrosine, phenylalanine etc. and the yellow
colour is due to the nitration of the benzene ring. An important
example of this test is that when conc. HNO3 is spilled on
your hands, the skin turns yellow due to nitration of benzene
ring of the amino acids of the proteins present in your skin.
(c) Millon’s test: Millon’s reagent is a solution of mercurous
nitrate and mercuric nitrate in nitric acid containing little
nitrous acid. When Millon’s reagent is added to aqueous
solution of protein, a white ppt. is formed. This test is given
by all proteins containing phenolic -amino acids i.e. tyrosine.
As such gelatin which does not contain phenolic -amino
acids does not give this test.
(d) Ninhydrin test: When proteins are boiled with a dilute
aqueous solution of ninhydrin (2, 2-dihydroxyindane-1,3-
dione), a blue-violet colour is produced. This test is actually
given by all -amino acids. Since proteins on hydrolysis give
-amino acids, therefore, proteins and peptides also give
this test.
2. Distinction and Separate
Organic Compounds
The compounds belonging to a group have similar chemical
properties. In some cases the properties of the two compounds
are so similar that sometimes these created great confusion.
Therefore, a knowledge of the tests to distinguish between such
pairs of organic compounds is of vital significance. Here below,
some such pairs have been dealt.
2.1 Distinction between Methanol and
Ethanol
Methanol, CH3OH, and ethanol, C2H5OH, both contain the same
functional group – OH. Therefore most of their chemical properties
are similar. However, the alkyl group in the two are different. In
methanol, alkyl group is CH3 whereas in ethanol it is C2H5. This
PRACTICAL ORGANIC CHEMISTRY 185
difference in alkyl group makes some of the properties of the two Some physical properties, like odour and boiling point, of the
different. two are also different. Benzaldehyde possesses smell of bitter
(i) Boiling point of ethanol is 78C whereas that of methanol is almonds whereas acetone has a pleasant smell.
60C. This is because of the high molecular weight of ethanol
as compared to methanol. 2.3 Distinction between Ethanol and Phenol
(ii) Both get oxidised by mild oxidising agent, but the products
Ethanol, C2H5OH and phenol, C6H5OH, both contain – OH group.
formed in the two are different
But in ethanol this – OH group is attached an alkyl group whereas
Oxidation
CH 3 OH   HCHO in phenol, it is attached to a aromatic benzene ring. This different
Methanol Formaldehyde in the two makes the following properties different.
Oxidation (i) Phenol is acidic in nature while ethanol is not.
CH3 CH 2 OH   CH 3CHO
Ethanol Acetaldehyde
(ii) Phenol gives characteristic colour with ferric chloride
As acetaldehyde forms iodoform with I2 and alkali, therefore, solution while ethanol does not give any.
iodoform test can be employed to distinguish ethanol from
(iii) Ethanol undergoes iodoform reaction i.e. it gives yellow
methanol.
precipitates with I2/NaOH. Phenol does not exhibit this
2 I / NaOH reaction.
CH 3 CH 2 OH 
 CHI3
Iodoform (iv) Being aromatic, Phenol burns with a sooty flame. Ethanol
I2 / NaOH burns with a blue flame.
CH 3 OH 
 No Iodoform
(v) Viscosity and boiling points of the two are also different.
Phenol is more viscous and has high boiling point as
2.2 Distinction between Benzaldehyde and compared to ethanol.

Acetone
2.4 Distinction between Phenol and Benzoic
Benzaldehyde, C 6H 5CHO, both contain carbonyl group,
> C = O. Both are liquids and colourless. The two can be
Acid
distinguished by exploting the reducing nature of aldehyde. That Phenol, C6H5OH and benzoic acid, C6H5COOH, both are aromatic
is, aldehydes are reducing in nature, whereas ketones are not. So in nature and turn blue litmus red. Thus, both exhibit acidic
aldehydes respond to Schiff’s reagent, Fehling’s solution and character also. But with sodium bicarbonate only benzoic acid
Tollen’s reagent, whereas ketones do not. gives effervescence. Phenol, being a very weak acid, does not
 evolve carbon dioxide with sodium bicarbonate.
C6 H5 CHO   Ag  NH3 2   3OH – 

Benzaldehyde Tollen 's reagent C6 H 5 COOH  NaHCO 3 
 C6 H 5 COONa  H 2 O  CO 2
Benzoic acid Sod. bicarbonate Carbon dioxide
C6 H5 OCOO  –
2Ag
Benzoate ion Metallic silver C6 H 5 OH  NaHCO 3 
 No reaction
CH 3 COCH 3  Tollen 's reagent 
 No Silver Mirror Phenol gives violet colour with neutral ferric chloride solution
On the other hand, acetone undergoes iodoform test whereas whereas benzoic acid does not give any.
benzaldehyde does not, because iodoform test given by aldehydes
 
  2.5 Distinction between Aniline and Phenol
CH3 – C – 
or ketones containing acetyl group  || . Aniline C6H5NH2 and phenol, C6H5OH, both are aromatic. Both
 O 
 have almost same boiling point. Except these two similarities, the
CH 3 COCH 3  3I 2  4NaOH 
 two compounds differ widely.
Acetone
(i) Aniline is basic in nature whereas phenol is acidic.
CHI3  CH 3 COONa  3NaI  3H 2 O
Iodoform (ii) Aniline contains amino, –NH 2, group whereas phenol
C6 H 5 CHO  I 2  NaOH 
 No reaction. contains –OH group. Therefore, aniline respond to
carbylamine test whereas phenol does not.

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(iii) Phenol gives violet colour with ferric chloride solution

whereas aniline does not.
(iv) Aniline also gives dye test whereas phenol does not.
2.6 Distinction between 1°, 2° and 3° Amine
3. Qualitative Estimation of
Elements
The qualitative analysis of an organic compound involves the
detection of all the elements present in it.

(a) Hinsberg test: Benzenesulphonyl chloride (C6H5SO2Cl),

which is also known as Hinsberg’s reagent, reacts with
primary and secondary amines to form sulphonamides.
3.1. Detection of Carbon and Hydrogen
A small amount of the dry and powdered substance is mixed with
about double the amount of pure and dry copper oxide. The
mixture is heated in a well dried hard glass tube (fig) delivery
tube is packed with glass wool containing anhydrous copper
sulphate (white) . When the mixture is heated , the carbon present
in the compound is oxidised to carbon dioxide which turns lime
water milky. The hydrogen present in the organic compound is
oxidised to water which turns anhydrous copper sulphate in the
bulb to blue.

Fig. 15.1: Detection of carbon and hydrogen in an organic

compound
CuSO 4  5H 2 O 
 CuSO 4  5H 2 O
anhydrous hydrated copper sulphate
copper sulphate (blue)
Heat
C  2CuO   CO 2  2Cu
from organic
compound
CO 2  Ca(OH) 2 
 CaCO3  H 2 O
lime water milky
(white)
Heat
2H  CuO   H 2 O  Cu
from organic
compound
This method is known as copper oxide test.
Tertiary amines do not react with benzenesulphonyl chloride.

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3.2 Detection of Other Element red colouration by reaction with ferric ions.

Nitrogen, sulphur and halogens in an organic compound are 3 NaSCN  Fe 3 

detected by Lassaigne’s test through Lassaigne’s extract. Organic
compounds contain these elements mostly linked through
covalent bonds. In order to make them free, we convert them into
ionic form by treating the compound with sodium. The ionic
compound formed are water soluble and releases the element in
ionic form, which is easy to detect.
Preparation of Lassaigne’s Extract:A small piece of dry sodium
metal is heated gently in a fusion tube till it melts to a shining
globule. Then, a small amount of organic substance is added and
the tube is heated strongly till it becomes red hot, The red hot
tube is plunged into distilled water contained in a china dish. The
fusion tube should break into pieces on adding to water. If it is
not broken, it is broken using a glass rod. Then the solution is
boiled for some time. It is then cooled and filtered. The
filtrate is known as sodium extract or Lassaigne’s extract.
Sodium reacts with elements of the organic compound to give
following reactions.
C  N  Na 
 NaCN
S  2Na 
 Na 2S
X  Na 
 NaX (Where X  Cl, Br or I)
When nitrogen and sulphur both are present in the organic com-
pound, then sodium thiocynate is formed.
Na C N S NaSCN
All the sodium salts being soluble in water, can be easily de-
tected.
3.2.1 Detection of Nitrogen
If the organic compound contains nitrogen, the sodium fusion
extract will contain sodium cyanide (NaCN). A small portion of
the extract is boiled with ferrous sulphate solution and acidified
with dilute sulphuric acid. A blue precipitate of prussian blue
(ferric ferrocyanide) confirms the presence of nitrogen.
2NaCN  FeSO 4  Fe(CN) 2  Na 2SO 4
Fe(CN) 2  4 NaCN  Na 4 [Fe(CN) 6 ]
excess
Oxidised by
FeSO 4 
H SO
 Fe 2 (SO 4 )3
2 4
3Na 4 [Fe(CN) 6 ]  2Fe 2 (SO 4 ) 3 
 Fe 4 [Fe(CN) 6 ]3  6Na 2SO 4
Prussian blue
If the organic compound contains sulphur along with nitrogen
and the sodium, present is in insufficient amount then sodium
thiocyanate is formed, which gives blood
[Fe(SCN)3 ]  3Na 
Blood red colour
However, the absence of blood red colouration does not neces-
sarily mean that sulphur is absent in the organic compound be-
cause NaCNS combines with Na to give NaCN and Na2S.

2Na  NaSCN   Na 2S  NaCN
3.2.2 Detection of Sulphur
The test of sulphur from sodium extract many be done in three
ways
(i) Sodium nitroprusside test : Only a little reagent is added to
sodium extract,
Na 2 [Fe(NO)(CN)5 ]  Na 2S  Na 4 [Fe(NOS)(CN)5 ]
Sodium nitroprusside Voilet complex
(ii) Lead acetate test : Add a few drops of lead acetate solution
to sodium extract, appearance of a black ppt. shows the
presence of sulphur.
(CH 3 COO) 2 Pb  Na 2S  2 CH 3 COONa  PbS 
(Black)
(iii) Silver coin test: On adding a silver coin to the sodium ex-
tract, the coin turns black.
(iv) Oxidation test of sulphur : The unknown compound is
heated with fusion mixture (Na2CO3+KNO3) in an ignition
tube when sulphur is oxidized to sulphate.
Na 2 CO 3  S  3[O]  Na 2 SO 4   CO 2 
The fused mass is extracted with hot water, filtered and a few
drops of barium chloride solution are added. The appear-
ance of a white precipitate which is insoluble in conc. HCl or
HNO3, confirms the presence of sulphur.
Na 2 SO4  BaCl2  BaSO4   2NaCl
(white)
BaSO 4  HNO3  Insoluble
(Conc.)
3.2.3 Detection of Halogens
(i) Lassaigne test : The extract is boiled with conc. HNO3 to
expel nitrogen and sulphur, because NaCN and Na2S react
with AgNO3 to give white and black precipitates, respec-
tively

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NaCN  AgNO3  AgCN   NaNO3 C6 H 5 N 2 Br  AgNO3  C 6 H 5 N 2 NO 3  AgBr 

NaS  2AgNO3  Ag 2S   2NaNO3
C 6 H 5 NH 3 Cl  AgNO 3  C 6 H 5 NH 3  NO 3  AgCl 
Boiling with conc. HNO3 evolves HCN and H2S as volatile 3.2.4 Detection of Phosphorus
gases.
The organic compound containing phosphorus is fused with

NaCN  HNO3   NaNO3  HCN  sodium peroxide and extracted with water. The aqueous solution
 is boiled with concentrated nitric acid and ammonium molybdate
Na 2S  2HNO3   2NaNO3  H 2S 
is added. A canary yellow precipitate indicates the presence of
Now add AgNO3 solution phosphorus.
(a) Formation of a curdy precipitate which is soluble in Na 3 PO 4  3HNO 3 
 H 3 PO 4  3NaNO3
NH4OH solution shows the presence of chlorine. H 3 PO 4  12  NH 4 2 MoO4  21HNO3
Ammonium
NaCl  AgNO3  AgCl   NaNO3 molybdate
(white) 

(b) Formation of a light yellow ppt, which is sparingly  NH 4 3 PO4 12MoO3  21NH 4 NO3  12H 2 O
Ammonium
soluble in NH4OH shows the presence of iodine. Phosphomolybdate
(yellow ppt)
NaI  AgNO3  AgI   NaNO3
(Light
yellow) 4. Quantitative Estimation of
(c) Formation of a lemon yellow ppt. insoluble in NH4OH Elements
shows the presence of bromine.
4.1 Estimation of Carbon and Hydrogen
NaBr  AgNO3  AgBr   NaNO3
(Lemon
yellow)
4.1.1 Liebig Combustion Method
(ii) Layer test for bromine and iodine : The presence of nitro- Principle: A known weight of the given dry organic
gen and sulphur does not interfere in this test. In this test compound is heated strongly with dry cupric oxide in an atmo-
acidify a little sodium extract with dil. HNO3 or dil. H2SO4 and sphere of air or oxygen free from CO2. The carbon and hydrogen of
add CHCl3 or CCl4 and excess of chlorine water. If organic the organic compound are oxidised to The CO2 and water vapour as :
layer becomes yellow or brown, bromine is present and if
violet, iodine is present. C  2CuO 
 CO 2  2Cu
2NaBr + Cl2  2NaCl + Br2. (from compound)
CHCl3 + Br2  Yellow brown layer 2H  CuO 
 H 2 O  Cu
2NaI + Cl2  2NaCl + I2 (from compound)
CHCl3 + I2  Violet layer
(iii) Beilstein’s test : Many organic compounds containing halo-
gens impart a green colour to the Bunsen flame when heated
on a copper wire. The green colour is developed
due to the formation of volatile halides of copper.
However, nitrogen compound urea also imparts green colour
to the flame.
(iv) Test of halogen present in the ionic form : Benzene diazo-
nium halides and halide salts of aliphatic and aromatic amines
contain halide ion. If the aqueous solution of any compound
gives a white or yellow ppt. on addition of AgNO3, halide
ions are present. Fig. 15.2 : Apparatus for estimation of Hydrogen and Carbon
Procedure : Let the mass of organic compound taken = w g
C 6 H 5 N 2  Cl   AgNO 3  C 6 H 5 N 2  NO 3   AgCl 
Benzene diazonium
chloride

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Mass of water formed = x g (increase in CaCl2 U-tube) passing over a heated copper gauze. The gaseous mixture is
Mass of carbon dioxide formed = y g (increase in potash tubes) collected over an aqueous solution of KOH when all the gases
except nitrogen are absorbed. The volume of nitrogen produced
(a) Percentage of Carbon: We know that 1 mole of carbondioxide
is measured at room temperature and atmospheric pressure. From
(44 g) contains
the volume of N2 produced, percentage of nitrogen in the sample
1 gram atom of carbon (12g) can be calculated.
CO 2  C
C  2CuO 
 CO 2  2Cu
44 g of CO2 contain C = 12 g
2H  CuO 
 H 2 O  Cu
12
Y g of CO2 contains C   yg
44 2N  CuO 
 N 2  oxide of nirogen

12y Oxides of nitrogen + Cu  CuO + N2

Hence, Percentage of carbon   100
44  w Calculation:

(b) Percentage of Hydrogen: We know that one mole of water  Y

C x H Y N Z   2x   CuO 
(18 g) contains 2 gram atom of hydrogen (2g)  2
H2O  2H Y Z  Y
x CO 2    H 2 O    N 2   2x   Cu
18 g of H2O contain H = 2 g 2 2  2
Let the mass of organic compound = w g
2
 x g of H2O contains H  xg The volume of nitrogen collected = Vcm3
18
Atmospheric pressure (from barometer) = P mm of Hg
2x Room temperature = t0C
Percentage of hydrogen  100
18  w
Aqueous tension at t0C = a mm of Hg
Percentage of C Pressure of dry nitrogen = (P - a) mm of Hg

12 Mass of CO 2 formed Let us first convert the volume of nitrogen to volume at

   100 S.T.P.
44 Mass of compound taken
Experimental conditions S.T.P. conditions
Percentage of H
P1 = (P - a) mm Hg P2 = 760 mm
2 Mass of H 2 O formed T1 = (273 + t) K T2 = 273
   100
18 Mass of compound taken V1 = V cm3 V2 = ?

P1V1 P2 V2
4.2 Estimation of Nitrogen Applying gas equation T  T
1 2
There are two methods for the estimation of nitrogen
(i) Duma’s Method P1V1T1 (P  a)  V  273
 V2    x cm3 (say)
(ii) Kjeldahl’s Method P2 T2 760(273  t)

Now 22400 cm3 of N2 at S.T.P. weight = 28 g

4.2.1 Duma’s Method
x cm3 of N2 at S.T.P. will weigh
Principle of the method: A known mass of an organic compound
28
is heated with dry cupric oxide in an atmosphere of carbon diox-  xg
ide. The carbon and hydrogen are oxidised to carbon dioxide and 22400
water respectively while nitrogen is set free. If any oxide of nitro-
gen is produced during this process, it is reduced to nitrogen by

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Mass of nitrogen  Ammonia liberated = (V - v) cm3 of N1 solution

Percentage of nitrogen =  100
Mass of organic compound Now, 1000 cm3 of 1N NH3 solution contains nitrogen = 14 g
28x  100 (V - v) cm3 of N1 NH3 solution contains nitrogen

22400  w
14(V  v)  N1
4.2.2 Kjeldahl’s Method  g
1000
This method cannot be used for Mass of nitrogen
Percentage of nitrogen   100
(i) Organic compounds containing nitrogen in the ring such as Mass of organic compound
pyridine, quinoline, etc. 1.4(V  v)  N1 100 1.4(V  v)  N1
N%   
(ii) Organic compounds containing nitrogen (-NO2) and diazo 1000 w w
(-N = N-) groups.
Principle: A known weight of the organic compound is heated 4.3 Estimation of Halogens
with conc. H2SO4 so that nitrogen is quantitatively converted
into ammonium sulphate. The solution is then heated with excess 4.3.1 Carius Method
of sodium hydroxide. The ammonia gas evolved is passed into a
known but excess volume of standard acid (HCl or H2SO4). The Principle: A known mass of the organic substance is heated
acid left unused is estimated by titrating the solution with with fuming HNO3 in a Carius tube. The silver halide so obtained
standard alkali. From the amount of acid left unused the amount is separated, washed, dried and weighed. From the weight of
of acid used for neutralisation of ammonia can be calculated. silver halide formed, the percentage of halogen can be calculated.
From this percentage of nitrogen can be calculated. X  AgNO 3 
 AgX
Conc. H2SO4
C, H, S 
 CO 2  H 2 O  SO 2 Halogen, Carbon, hydrogen or sulphur present in the compound
(from organic will be oxidised to CO2, H2O and H2SO4 respectively.
compound) 3 HNO
C  2O   CO 2
Conc. H SO
2 4  (NH ) SO
N  4 2 4 HNO
3H O
2H  O 
(from organic ammonium sulphate 2

compound) HNO
3
S  H 2 O  3O   H 2SO 4
Heat
(NH 4 )2 SO 4  2NaOH   Na 2SO4  2NH3  2H 2 O
Calculations
2NH3 + H2SO4  (NH4)2SO4 Let the mass of organic compound be w g
NH3 + HCl  NH4Cl Mass of silver halide formed = a g
Calculations Now, AgX = X
Let the mass of organic compound = w g 108 + X parts by weight of silver halide contains X parts by
Volume of standard acid taken = V cm 3
weight of halogen
Normality of acid = N1 (X is its atomic mass)
Let vol. of standard alkali used for neutralisation of unused (108 + X) g of silver halide give halogen = X
acid = V2 cm3
X
Normality of standard alkali = N2 a g of silver halide will give halogen  (108  X)  a g
N1V1  N 2 V2  Percentage of halogen
 
alkali acid
Mass of halogen Xa 100
Let this volume of v cm3  100  
Mass of organic compound (108  X) w
 Vol. of acid used for neutralisation of ammonia Here X is the atomic mass of halogen, e.g.
= (V - v) cm3 of N1 normality Cl = 35.5, Br = 80 (79.9 exact), I = 127

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(126.9 exact)
31 m1  100
Percentage of P = %
Percentage of halogen = 1877  m
Atomic mass of halogen  Mass of silver halide If phosphorus is estimated as Mg2P 2O7,
 100
(108  At.mass of halogen)  Mass of org. substance
62  m1 100
Percentage of P = %
222  m
4.4 Estimation of Sulphur 4.6 Estimation of Oxygen
Sulphur is estimated by Carius method.
Percentage of oxygen in an organic compound
Principle: A known mass of the organic compound is heated
= 100 – percentage of other elements
with fuming HNO3 in a sealed tube when sulphur is quantitatively
converted into sulphuric acid. It is then precipitated with barium A definite mass of an organic compound is decomposed by
chloride as barium sulphate. The precipitate is filtered, washed, heating in a stream of nitrogen gas. The mixture of gaseous
dried and weighed. From the weight of BaSO4 formed, the products containing oxygen is passed over red-hot coke when
percentage of sulphur can be calculated. The main reactions are: all the oxygen is converted to carbon monoxide. This mixture
is passed through warm iodine pentoxide (I2O5) when carbon
HNO
3  H SO
S  H 2 O  3O  monoxide is oxidised to carbon dioxide producing iodine.
2 4
heat
Compound 
 O 2  other gaseous products
H 2SO 4  BaCl 2 
 BaSO 4 ppt.
1373K
2C  O 2   2CO
Calculations
I 2 O5  5CO  I2  5CO2
Let the mass of organic compound = w g
Mass of BaSO4 formed = a g
5. General Separation Techniques
BaSO4  S
137 + 32 + 64 = 32 = 233
5.1 Sublimation
233 g of BaSO4 contain sulphur = 32 g
• Some solid substances change from solid to vapour state
32  a without passing through liquid state.
a g of BaSO4 will contain sulphur  g
233
• The purification technique is used to separate sublimable
Percentage of sulphur compounds from nonsublimable impurities.

Mass of sulphur
 100  32a  100
Mass of organic compound 233 w
4.5 Estimation of Phosphorus
A known mass of an organic compound is heated with fuming
nitric acid whereupon phosphorus present in the compound
is oxidised to phosphoric acid. It is precipitated as ammonium
phosphomolybdate, (NH4)3PO4.12MoO3, by adding ammonia
and ammonium molybdate. Alternatively, phosphoric acid may
be precipitated as Mg(NH4)PO 4 by adding magnesia mixture
which on ignition yields Mg2P 2O7.
Mass of organic compound taken = m g
Mass of ammonium phosphomolydate = m1 g
Molar mass of (NH4)3PO4.12MoO3 = 1877 g
5.2 Crystallization
• It is based on the difference in the solubility of the
compound and the impurities in a suitable solvent.
• The impure compound is dissolved in a solvent in which it is
sparingly soluble at room temperature but appreciably
soluble at higher temperature.
• The solution is concentrated to get a nearly saturated
solution. On cooling the solution, pure compound
crystallises out and is removed by filtration.The filtrate
(mother liquor) contains impurities and small quantity of the
compound.
• The process of inducing crystallization by adding a crystal
of pure substance into its saturated solution is
called seeding.

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• Impurities, which impart colour to the solution, are removed
by adsorbing over activated charcoal.
• Repeated crystallisation becomes necessary for the
purification of compounds containing impurities of
comparable solubility
• Sugar and benzoic acid are separated by this process.
5.3 Distillation
5.3.1 Distillation
This important method is used to separate.
• Volatile liquids from non-volatile impurities
• Liquids having sufficient difference in their boiling points.
• Liquids having different boiling points vaporise at
different temperatures. The vapours are cooled and the
liquids so formed are collected separately.
Example
Chloroform (b.p. 334 K) and Aniline (b.p. 457 K)
Mechanism
• On boiling, the vapours of lower boiling component are
formed first. The vapours are condensed by using a
condenser and the liquid is collected in a receiver.
• The vapours of higher boiling component form later and
the liquid can be collected separately.
Fig. 15.3 : Appratus for Simple Distillation
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5.3.2 Fractional Distillation
Fractional distillation is required if the difference in boiling points
of two liquids is not much or less than 25ºC. The vapours of
such liquids are formed within the same temperature range and
are condensed simultaneously.
Mechanism
• Vapours of a liquid mixture are passed through a fractionating
column before condensation.
• Vapours of the liquid with higher boiling point condense
before the vapours of the liquid with lower boiling point.
• The vapours rising up in the fractionating column become
richer in more volatile component.
• By the time the vapours reach to the top of the fractionating
column, these are rich in the more volatile component.
Fig.15.4 : Apparatus for Fractional Distillation
Fractionating columns
• A fractionating column provides many surfaces for heat
exchange between the ascending vapours and the
descending condensed liquid.
• The vapours thus become richer in low boiling component.
The vapours of low boiling component ascend to the top of
the column.
• On reaching the top, the vapours become pure in low boiling
component and pass through the condenser and the pure
liquid is collected in a receiver.
PRACTICAL ORGANIC CHEMISTRY 193

• After a series of successive distillations, the remaining liquid

in the distillation flask gets enriched in high boiling
component.
• Each successive condensation and vaporisation unit in the
fractionating column is called a theoretical plate.
Example:
Crude oil in petroleum industry.
Types of Fractionating Columns

Fig.15.6 : Distillation under Reduced Pressure

5.3.4 Steam Distillation

• It is used to separate substances which are steam
volatile and are immiscible with water.
• In steam distillation, steam from a steam generator is
passed through a heated flask containing the liquid to be
distilled. The mixture of steam and the volatile organic
compound is condensed and collected.
• In steam distillation, the liquid boils when the sum of
vapour pressures due to the organic liquid (p 1) and that
due to water (p 2) becomes equal to the atmospheric
pressure (p), i.e. p =p 1 + p 2. Since p 1 is lower than (p 2) ,
the organic liquid vaporises at lower temperature than its
boiling point.
• Thus, if one of the substances in the mixture is water and
the other, a water insoluble substance, then the mixture
will boil close to but below, 373K.
Fig:15.5 Various type of Fractionating columns
• A mixture of water and the substance is obtained which
can be separated by using a separating funnel.
5.3.3 Distillation under Reduced Pressure
Example: Aniline–Water Mixture
• This method is used to purify liquids having very high
boiling points and those, which decompose at or below
their boiling points.
• Such liquids are made to boil at a temperature lower than
their normal boiling points by reducing the pressure on
their surface. A liquid boils at a temperature at which its
vapour pressure is equal to the external pressure. The
pressure is reduced with the help of a water pump or
vacuum pump.
Example:
Glycerol can be separated from spent-lye in soap industry.

Fig.15.7 : Apparatus for Steam Distillation

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5.4 Differential Extraction
• When an organic compound is present in an aqueous
medium, it is separated by shaking it with an organic
solvent in which it is more soluble than in water.
• The organic solvent and the aqueous solution should be
immiscible with each other so that they form two distinct
layers which can be separated by separatory funnel. The
organic solvent is later removed by distillation or by
evaporation to get back the compound.
• If the organic compound is less soluble in the organic
solvent, a very large quantity of solvent would be required
to extra ct eve n a very small q uantity o f t he
compound. Continuous extraction is employed in such
cases. In this technique same solvent is repeatedly used
for extraction of the compound.
Differential Extraction Apparatus
Fig.15.8 : Differential Extraction Apparatus
5.5 Chromatography
Chromatography is used to separate mixtures into their
components, purify compounds and also to test the purity of
compounds. It is based on adsorption.
Greek word chroma - colour.
5.5.1 Column Chromatography
Mechanism
• The mixture of substances is applied onto a stationary phase,
which may be a solid or a liquid. A pure solvent, a mixture of
solvents, or a gas is allowed to move slowly over the
stationary phase.
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• The components of the adsorbent are placed on the top of
the adsorbent column packed in a glass tube. An appropriate
eluant, which is a liquid or a mixture of liquids is allowed to
flow down the column slowly.
• Depending upon the degree to which the compounds are
adsorbed, complete separation takes place. The most readily
adsorbed substances are retained near the top and others
come down to various distances in the column.
Fig.15.9 : Column Chromatography different stages
represent the progressive separation of the mixture into
three bands.
5.5.2 Thin Layer Chromatography
It involves separation of substances of a mixture over a thin
layer of an adsorbent coated on glass plate. A thin layer of an
adsorbent (silica gel or alumina) is spread over a glass plate
of suitable size. The plate is known as thin layer
chromatography plate or chromaplate.
Mechanism
• The solution of the mixture to be separated is applied as a
small spot about 2 cm above one end of the TLC plate. The
glass plate is then placed in a closed jar containing the
eluant.
• As the eluant rises up the plate, the components of the
mixture move up along with the eluant to different distances
depending on their degree of adsorption and separation
takes place.
• The relative adsorption of each component of the mixture
is expressed in terms of its retardation factor i.e. Rf value.
PRACTICAL ORGANIC CHEMISTRY 195

TLC Apparatus
Fig.15.10 : TLC chromatograph being developed
Fig.15.11 : Developed chromatogram measurement of Rf
value
Distance travelled by substance from the baseline (x)
Rf =
Distance travelled by solvent from the baseline (y)
Detection of Movement
The spots of coloured compounds are visible on TLC plate
due to their original colour.
• Place the plate in a covered jar containing a few crystals
of iodine. Spots of compounds, which adsorb iodine, will
show up as brown spots.
• Spraying Agents - Amino acids may be detected by
spraying the plate with ninhydrin solution.
5.5.3 Partition Chromatography
It is based on continuous differential partitioning of
components of a mixture between stationary and mobile
phases.
Paper Chromatography
It is a type of partition chromatography. A special quality paper
known as chromatography paper is used.
Mechanism
• Chromatography paper contains water trapped in it, which
acts as the stationary phase. A strip of chromatography
paper spotted at the base with the solution of the mixture
is suspended in a suitable solvent or a mixture of solvents.
This solvent acts as the mobile phase.
• The solvent rises up the paper by capillary action and
flows over the spot. The paper selectively retains different
components according to their differing partition in the
two phases. The paper strip so developed is known as
a chromatogram.

Other Detection Techniques

• Colourless compounds can be detected by putting the
plate under ultraviolet light.

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Summary

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PRACTICAL ORGANIC CHEMISTRY 197

Solved Examples
Example-1 (c) Both (d) None
In Lassaigne’s test for nitrogen, the blue colour is due to Sol. Ethanol (C2H5OH) and dimethyl ether (CH3OCH3) have same
the formation of– molecular formula (C2H6O), hence % of each element (C, H
(a) Ferric ferrocyanide and O) in the two must be same.

(b) Potassium ferrocyanide Example-5

(c) Sodium ferrocyanide Liebig method is used for the estimation of–

(d) Sodium cyanide (a) Nitrogen

Sol. In Lassaigne’s test substance is heated strongly with (b) Sulphur

sodium metal then water extract is boiled with alkaline FeSO4 (c) Carbons and Hydrogen
solution and after cooling FeCl3 solution and excess of HCl (d) Halogens
is added in it. If prussian blue or green ppt. is obtained then
Sol. Liebig method is used for the estimation of carbon and
Nitrogen is confirmed –
hydrogen.
Na  C  N 
 NaCN Example-6
FeSO 4  2NaOH 
 Fe(OH) 2  Na 2SO 4 An organic compound has the % composition as follows C
= 40%, H = 6.67%. Its vapour density is 45. The molecular
6NaCN  Fe(OH) 2 
 Na 4 [Fe(CN)6 ]  2NaOH formula of the compound is–
(a) CH2O (b) C2H4O2
Fe 4 [Fe(CN) 6 ]3  12NaCl (c) C3H6O3 (d) C2H6O
prussian blue or green Sol.
.
(ferric ferrocyanide)- Element % Atomic Relative Simple Ratio
amout weight Number
Example-2
of atom
In sodium fusion test of organic compounds, the nitrogen
of an organic compound is converted to– 40 3.33
C 40 12  3.33
(a) Sodamide (b) Sodium cyanide 12 3.33

(c) Sodium nitrite (d) Sodium nitrate 6.67 6.67

H 6.67 1  6.67 2
Sol. Na  C  N 
fusion
 NaCN 1 3.33

Example-3 53.33 3.33

O 53.33 16  3.33 1
A compound which give a positive test in the Lassaigne’s 16 3.33
test for ‘N’ is–
Therefore the empirical formula of molecule is CH2 and the
(a) Phenyl hydrazine (b) Urea empirical formula weight is 30
(c) Azobenzene (d) All of these Molecular weight = 45 × 2 = 90
Sol. Lassaigne’s test is given by the compound which contain C
Molecula weight 90
atom bonded N atom. n   3
empirical formula weight 30
Hence all the given compound gives Lassaigne’s test for
‘N’. and molecular formula is C3H6O3
Example-4 Example-7
An organic compound contains about 52% carbon. It could An organic compound has C and H percentage in the ratio
be– 6:1 and C and O percentage in the ratio 3:4. The compound
(a) Only ethanol (b) Only dimethyl ether is–
198 PRACTICAL ORGANIC CHEMISTRY

(a) HCHO (b) CH3OH substituting the various values in the above equation,
(c) CH3CH2OH (d) (COOH)2 31.7(758  12) 273
V   29.6 ml
Sol. % ratio of C : H : : 6 : 1 and C : O : : 3 : 4 14  273 760
 % ratio of C : H : O : : 6 : 1 : 8 % at. wt. 28
Weight of 29.6 ml of nitrogen =  29.6 g
6 40 22400
% C   100  40,  3.33
15 12
28  29.6 100
1 6.66  Percentage of nitrogen    19.72
% H   100  6.66,  6.6 22400 0.1877
15 1
Example-10
8 53.3
%O  100  53.3,  3.33 In the estimation of nitrogen present in an organic
15 16
compound by Dumas method, 0.200 g yielded 20.7 ml of
 Simplest ratio of C : H : O : : 1 : 2 : 1 i.e., CH2O
nitrogen at 15C and 760 mm pressure. Calculate the
Example-8 percentage of nitrogen in the compound.
0.2475 g of an organic substance gave on combustion
v  P 273
0.4950 g of carbon dioxide and 0.2025 g of water. Calculate Sol. Volume of N2 at NTP   V ml
the percentage of carbon and hydrogen in it.
t  273 760

Sol. Weight of the substance taken = 0.2475 g Substituting the various values in the above equation,
Weight of CO2 formed = 0.4950 g 20.7  760 273
V   19.63 ml
Weight of H2O formed = 0.2025 g 288 760
Now, we know CO2 = C and H2O = 2H 28
Weight of 19.63 ml of Nitrogen =  19.63 g
44 12 18 2 22400
Weight of C in 0.4950 g of CO2  Percentage of Nitrogen
28 100
0.4950  12   19.63   12.27
 g 22400 0.2
44
Example-11
Weight of H in 0.2025 g of H2O
0.257 g of an organic substance was heated with conc.
0.2025  2 sulphuric acid and then distilled with excess of strong alkali.
 g
18 The ammonia gas evoled was absorbed in 50 ml of N/10
hydrochloric acid which required 23.2 ml of
Hence, percentage of C
N/10 NaOH for neutralisation at the end of the operation.
0.4950  12 100 Determine the percentage of nitrogen in the substance.
   54.54
44 0.2475 Sol. Volume of N/10 HCl neutralised by ammoina
and percentage of H = 50 – 23.2 = 26.8 ml
0.2025  2 100 Now,
   9.09 26.8 ml of N/10 HCl = 26.8 ml of N/10 NH3
18 0.2475
Example-9 = 26.8 ml of N/10 N (combined)

0.1877 g of an organic substance when analysed by the 26.8 ml of N/10 N solution contains
Dumas method yield 31.7 ml of moist nitrogen measured at 14 26.8
 g of nitrogen
14C and 758 mm mercury pressure. Determine the 10 1000
percentage of nitrogen in the substance. (Aqueous tension This weight of Nitrogen was originally present in 0.257 g
at 14C = 12 mm). of the organic substance.

v(P  a) 273 14  26.8 100

Sol. Volume of N2 at NTP    Percentage of Nitrogen    14.6
10  1000 0.257
t  273 760
= V ml
PRACTICAL ORGANIC CHEMISTRY 199

Example-12 31
V  150   2  23  25 m1  46.8%
0.4 g of an organic compound was kjeldahlised and ammonia 400
evolved was absorbed into 50 ml of semi-normal solution
Example-13
of sulphuric acid. The residual acid solution was diluted
with distilled water and the volume was made up to 150 ml. 0.197 g of an organic substance when heated with excess
20 ml of this diluted solution required 31ml of N/20 NaOH of strong nitric acid and silver nitrate gave 0.3525 g of silver
solution for complete neutralisation. Calculate the iodide. Find the percentage of iodine in the compound.
percentage of nitrogen in the compound. Sol. 1 mol AgI  1 mol I
Sol. Given, mass of organic compound  0.4g 234.77 g AgI  127 g I
M N 127
50 ml H 2 SO 4  50 ml H 2 SO 4 1 g AgI  g of I
4 2 234.77
N 127
Let us assume that V ml of H 2SO 4 is unused. 0.3525 g AgI  0.3525  g
2 234.77
N  0.19068 g of I
V ml of H 2SO 4 is diluted to 150 ml & 20 ml of this
2 Now,
M mass of I
solution is titrated against 30 ml NaOH solution. %I   100
20 mass of substance
Now,
0.19068
M N   100  96.7%
For NaOH solution = 0.197
20 20
Example-14
Now, V1S1  V2S2
0.395 g of an organic compound by Carius method of the
N 1 1 31 estimation of sulphur gas afforded 0.582 g of BaSO4. Find
20ml  s1 31  S1  31     N the percentage of sulphur in the compound.
20 20 20 400
Sol. Mass of BasSO4 = 0.582g
N
23.25ml   H 2 SO 4 is unused used amount of 233g of BaSO4 Contains sulphur = 32g
2
32
H 2SO 4   20  23.25  0.582g of BaSO4 Contains sulphur   0.582 g
233
N N Now,
26.75 ml H 2 SO 4  26.75 ml NH 3
2 2 wt. of sulphur
N % of Sulphur  wt. of compound  100
So, the amount of N is 26.75 ml NH 3
2 32  0.582
  100 = 20.24%
 14 26.75  233  0.395
   g  0.18725 g
 2 1000  Example-15
Now,
Dil. H2SO 4
0.18725 O P1 + P2
% of N in 0.4 g   100  46.8%
0.4
P1 and P2 product are identify by
N 31
 Vml H 2SO 4  150 ml of  N  H 2 SO 4 (a) Tollen’s reagent
2 400 (b) Iodoform test
(c) Br2 + H2O test
(d) 1 per cent alkaline KMnO4
200 PRACTICAL ORGANIC CHEMISTRY

Sol. Example-18
In Lassaigne’s test, the organic compound is first fused
with sodium metal. The sodium metal is used because
(a) The melting point of sodium metal is low.
(b) Sodium metal reacts with elements present in organic
compounds to form inorganic compounds.
(c) All sodium salts are soluble in water.
(d) All sodium salts are not soluble in water.
Sol. (a) and (b) and (c) are true because sodium has weak metallic
P2 gives Tollen's test while P1 gives iodoform test bond due to larger size, as well as ionisation enery. Sodium
Example-16 salts are soluble in water because hydration energy
Which of the following compound can liberate CO2 when dominates over lattic energy. It follows that (d) is incorrect.
treated with NaHCO3? Example-19
Ethanol and Ethanal are distinguished by
(a) Fehling’s solution test
(b) Tollen’s reagent test
(a) (b) CH3CO2H
(c) Iodoform test
(d) Cerric ammonium nitrate
Sol. (a) Fehling solution
Ethanal + Fehling solution  Brick Red ppt
(c) HCO2H (d) Ethanal + Fehling solution No reaction
(b) Ethanal gives silver mirror test with Tollen's reagent
Sol. Those acids which are stronger then H2CO3 liberates CO2 where as Ethanol does not react
gas. Here Option a b & c are correct. (c) Iodoform can't be used because both respond to
Example-17 iodotorm test
(d) Ethanol gives wine red colouration with CAN while
Among the following, which will respond to iodoform test?
Ethanal does not react.
(a) (b) Example-20
Which of the following statements are correct?
(a) An organic compound is pure if mixed melting point

(c) (d) is same.

(b) Ethanol and water can be separated by azeotropic
Sol. Iodoform test is given by Carbonyl compounds having distillation because it forms azeotrope.
 O  (c) Impure aniline is purified by steam distillation as it is
 || 
 R  C   group. steam volatile.
  (d) Glycerol is purified by vacuum distillation because it
 
decomposes at its normal boiling point.
Alcohol having (R–CH2– OH) group and secondary alk– 2 –
Sol. All statments are self explanatory.
ol and 1, 3-dicarbonyl.
Example-21
Hence, all gives iodoform.
Which of the following will respond to iodoform test?
O OH
|| |
(a) CH 3  C  COOH (b) CH 3  CH  COOH
PRACTICAL ORGANIC CHEMISTRY 201

OH Sol. Anhydrous CaCl2 and Mg(CIO4)2 are used as desiccants

|
(c) CH 3  CH  CH 3 (d) CH3CH2OH because they are different absorbent of water.

Sol. Iodoform test is given by Carbonyl compounds having Example-25

Column I Column II
 O 
 ||  (Reagents) (Compound)
 R  C   group. (a) Tollen’s reagent (p) Me - CH = CH - Me
 
  give white ppt. with
(b) Br2 + H2O test (q) Me - C  C - H
Alcohol having  R  CH 2  OH  group and secondary given by
alk– 2 – ol  
(c) Product of reaction (r) Cl NH 3  NH 2
Hence, all gives iodoform.
Example-22 of acetylene with
Which of the following will not show iodoform test? 1 percent HgSO4 and
Dil. H2SO4
O O O
|| || ||
(a) CH 3  C  CH 3 (b) CH3  C  Cl (d) Pd/H2 reacts with (s) Me  C  H
O
O ||
|| (t) Me  C  Me
(c) CH 3  C  NH 2 (d) CH3 - COOH
Sol. (a) Tollen's reagent gives white ppt with terminal alkynes
Sol. Iodoform test is given by aldehyde & Ketone having
 
& Cl NH  NH
O 3 2
||
R  C  group. T.R R – C  CAg 
R – C  CH 
So, b, c, d can’t show iodoform test.
 white ppt 
Example-23 (b) Br2  H 2 O test : – Bromine water test is used for
HCOOH and CH3COOH can be distinguished by alkenes & alkynes.
(a) Tollen’s reagent (b) Fehling’s solution Me – CH = CH – Me + Br2 + H2O 
(c) KMnO4 (d) NaHCO3 CH 3  CH CH  CH 3  HBr
Sol. (a) Tollen's test is used to distinguish HCOOH & CH3COOH | |
OH Br
HCOOH gives silver mirror test where as acetic acid do
not give O
||
(b) Formic acid reduces fehling solution while acetic acid 1% HgSO4
(c) HC  CH   CH3  C  H
does not react with Fehling Solution. DilH2SO4
(c) KMnO4 reacts with formic acid to give red-brown
(d) Pd/H2 is a strong reducing agent & reduces carbonyl
coloured compound.
compounds and - bond containing species (Alkenes
Example-24 & alkynes).
The desiccants used for absorbing water during Liebig’s
method for estiamtion of carbon and hydrogen are
(a) anhydrous CaCl2 (b) anhydrous Na2SO4
(c) Mg(ClO4)2 (d) MgSO4.7H2O
202 PRACTICAL ORGANIC CHEMISTRY

EXERCISE - 1 : Basic Objective Questions

Functional Group Detection

10. KOH can be used as a drying agent for

1. Which of the following test is not used for protein/amino
(a) Amines (b) Phenols
acids–
(c) Acids (d) Esters
(a) Biuret test (b) Ninhydrin test
11. Which of the following observations is correct and is used
(c) Xanthoproteic test: (d) Iodine test
in the identification of carboxylic acids?
2. Which of the following is the test of primary amine?
(a) Carboxylic acids liberate CO2 gas from NaHCO3
(a) Carbylamine test solution.
(b) Reaction with carbon di-sulphide (b) They produce fruity smell of esters when heated with
(c) Heinsberg test alcohol in presence of Conc. H2SO4
(d) All of these (c) Both (a) and (b)
3. Which of the following is the test of carbohydrates? (d) Iodoform test
(a) Molish test (b) Biuret test 12. An organic compound is heated with HNO2 at 0oC and
then the resulting solution is added to a solution -napthol
(c) Ninhydrin test (d) None of these
whereby a brilliant red dye is produced. The observations
4. Zeisel’s method is use for the determination of indicate that the compound possesses.
(a) Ether (b) Alcohol (a) -NO2 group (b) -CONH2 group
(c) Phenol (d) Carboxylic acid (c) aromatic NH2 group (d) aliphatic NH2 group
5. Schiff test is used for the identification:
(a) Ketones (b) Aldehydes Distinguish and Separate Organic Compounds
(c) Phenol (d) Alcohols
6. Which of the following will give Tollen’s test? 13. Barfoed test is used for the distinguish:

(a) Acetone (b) But-2-one (a) Phenol from carboxylic acid

(c) Benzaldehyde (d) Cyclohexanone (b) Amino acids

7. Which of the following compound Discharge bromine (c) Monosaccharides from reducing disaccharides
solution to colourless without evolving HBr? (d) Peptide linkage
(a) Alkene (b) Alkane 14. Seliwanoff’s test is used for the distinguish:
(c) Cyclo alkane (d) Benzene (a) Aldoses from ketoses
8. Which of the following is the test of alcohol? (b) Primary and secondary structure of proteins
(a) Sodium metal test (c) Polysaccharides
(b) Cerric ammonium nitrate test (d) Amino acids.
(c) Ester test 15. Which of the following test can use for separation of
(d) All of these alcohol and phenol?
9. Silver salt method is used to determine molecular weight (a) Tollen’s test
of (b) Sodium bicarbonate test
(a) Organic acids (b) Organic bases (c) Reaction with neutral FeCl3 solution
(c) Both acids and bases (d) None of these. (d) Fehling’s test
PRACTICAL ORGANIC CHEMISTRY 203
16. Phenol and benzoic acid can be separated by (b) Using Beilstein’s test the presence of halogen in a
(a) NaHCO3 (b) NaOH solution compound can be tested
(c) FeCl3 solution (d) All of these. (c) In Lassaigne’s filtrate, the nitrogen present in the
17. Among the following which compound gives precipitate organic compound is converted into NaCN
with AgNO3 solution? (d) In the estimation of carbon, an organic compound
is heated with CaO in a combustion tube
25. Sulphur is estimated by Carius method in the form of
(a) (b) (a) Ba(OH)2 (b) BaSO4
(c) BaCO3 (d) None of these
26. Compounds which do not contain halogen but give
positive Beilstein test?
(c) (d) None of these.
(a) Urea (b) Thiourea
(c) CH3COOH (d) Both (a & b)
27. Which Metal cyanide give a positive Lassaigne’s test for
Qualitative Estimation of Elements
nitrogen?
(a) NaCN (b) KCN
18. Which of the following compounds will answer
(c) CuCN (d) None of these
Lassaigne’s test for nitrogen
28. Lassaigne’s test is not shown by diazonium salts. Why?
(a) NH2NH (b) NH4Cl
(a) Diazonium salts usually lose N2 on heating
(c) NaCN (d) NaNO3
(b) Diazonium salts usually does not lose N2 on heating
19. Which of following will give Lassaigne’s test for nitrogen
(c) Diazonium salts react with fused sodium metal
(a) NH4NO3 (b) NH2NH2
(d) None of these
(c) KNO3 (d) Cyanogen
20. The oxygen is estimated in the organic compound by 29. What conclusion would you draw if during Lassaigne‘s
test, a blood red colouration is obtained?
(a) Aluise’s method (b) Victor-Meyer method
(a) Only N is present
(c) Carius method (d) There is no direct method
(b) Both N and S is present
21. In Lassaigne’s test when both N and S are present, blood
red colour obtained is due to the formation of– (c) Both P and S is present
(a) Ferric ferrocyanide (b) Ferric sulpocyanide (d) Only S is present
(c) Ferric cyanide (d) None 30. What type of organic compounds cannot be Kjeldahlised?
22. Kjeldahl’s method is used in the estimation of– (a) Nitro compound (b) Azo compound
(a) Nitrogen (b) Halogens (c) Both (a) and (b) (d) None of these
(c) Sulphur (d) Oxygen 31. How is phosphorus estimated in an organic compound?
23. Dumas method involves the determination of nitrogen (a) Ammonium Phosphomolybdate
content in the organic compound in form of– (b) Magnesium Pyrophosphate
(a) NH3 (b) N2 (c) Both (a) and (b)
(c) NaCN (d) (NH4)2SO4 (d) Ammonium Pyrophosphate
24. Which of the following statements is wrong?
(a) Using Lassaigne’s test nitrogen and sulphur present
in an organic compound can be tested
204 PRACTICAL ORGANIC CHEMISTRY
32. Will you get any precipitate if you add silver nitrate 38. The molecular mass of a organic compound which
solution to chloromethane? If not, why? contains only one nitrogen atom can be
(a) Chloromethane is a covalent compound (a) 73 (b) 76
(b) Chloromethane is a ionic compound (c) 146 (d) 152
(c) Both (a) and (b) 39. When 0.32g of a compound is heated with conc. HNO3
and BaCl2, 0.932g BaSO4 is obtained. The percentage of
(d) None of these
sulphur in the compound is
33. Sodium nitrorusside Na2[Fe(CN)5NO] is used as reagent
(a) 20 (b) 40
for detection of ______ and the compound formed is
____. (c) 60 (d) 80
(a) Sulphur, Na4[Fe(CN)5NOS] 40. 0.2475g of an organic compound gave on combustion
0.4950g of carbon dioxide and 0.2025g of water. The
(b) Nitrogen, Na4[Fe(CN)6]
percentage of carbon and hydrogen are:
(c) Sulphur, Na2[Fe(CN)4NOS]
(a) 54.54, 9.09 (b) 52.54,8.09
(d) Sulphur, Na2[Fe(CN)5NOS]
(c) 120, 5.8 (d) None
34. The prussian blue colouration obtained in the test for
41. 0.15 g of an organic compound gave 0.12 g of AgBr by
nitrogen in the organic compound is
Carius method. The percentage of bromine in the
(a) K4[Fe(CN)]6 (b) Fe4[Fe(CN)6]3 compound is
(c) Fe[Fe(CN)6] (d) Fe3[Fe(CN)6]2 (a) 43 (b) 54
35. If N and S both are present in an organic compound during (c) 34 (d) 66
Lassaigne’s test, both will change into
42. 0.395 g of an organic compound by Carius method for the
(a) Na2S and NaCN (b) NaSCN
estimiation of sulphur gave 0.582 g of BaSO 4. The
(c) Na2SO3 and NaCN (d) Na2S and NaCNO percentage of sulphur in the compound is–
36. An organic compound contains C, H, N, S and Cl. For the (a) 20.24 (b) 35
detection of chlorine, the sodium extract of the compound
(c) 40 (d) 45
is first heated with a few drops of concentrated HNO3 and
then AgNO3 is added to get a white ppt. of AgCl. The 43. Find out the percentage of carbon in acetic acid.
digestion with HNO3 before the addition of AgNO3 is (a) 40 (b) 45
(a) to prevent the formation of NO2 (c) 70 (d) 50
(b) to create a common ion effect 44. Which of the following test is used for quantitative
(c) to convert CN- and S2- to volatile HCN and H2S, or estimation of N
else they will interfere with the test forming AgCN or
(a) Duma’s Method (b) Kjeldahl’s Method
Ag2S
(c) Carius Method (d) Both (a) and (b)
(d) to prevent the hydrolysis of NaCN and Na2S
45. An organic compound having carbon, hydrogen and
37. Which of the following will not give test for ‘N’ in sodium
sulphur contains 4% of sulphur. The minimum molecular
extract?
weight of the compound is
(a) C6H5NHNH2 (b) NH2CONH2
(a) 200 (b) 400
NH2
(c) 600 (d) 800
46. In a Dumas nitrogen estimation 0.3 g of an organic
(c) NH2 - NH2 (d) compound gave 50 cm3 of nitrogen collected at 300 K and
715 mm pressure. The percentage of nitrogen in the
SO3H compound (vapour pressure of water at 300K is 15 mm) is
(a) 15.46 (b) 17.46
(c) 50 (d) 70
PRACTICAL ORGANIC CHEMISTRY 205
General Separation Techniques 52. The best method for the sepration of naphthalene and
benzoic acid from their mixture is
47. A mixture of benzene and chloroform is separated by– (a) sublimation (b) chromatography
(a) Sublimation (b) Separating funnel (c) crystallisation (d) distillation
(c) Crystallization (d) Distillation 53. The separation of the constituents of a mixture by column
48. How will you purify a liquid having non-volatile impurities? chromatography depends upon their
(a) Sublimation (b) Crystallization (a) different solubilities
(c) Simple Distillation (d) Chromatography (b) different boiling points
49. Which of the following compound is/are purified by (c) different refractive indices
sublimation? (d) differential adsorption
(a) Naphthalene (b) Benzoic acid 54. A mixture of acetone and CCl4 can be separated by
(c) Camphor (d) All of these (a) Azeotropic distillation
50. How will you separate iodine from sodium chloride? (b) Fractional distillation
(a) Sublimation (b) Distillation (c) Steam distillation
(c) Both (a) and (b) (d) Crystalisation (d) vacuum distillation
51. An organic liquid decomposes below its boiling point. 55. Anthracene can be purified by
How will you purify it? (a) Distillation (b) Sublimation
(a) Chromatography (c) Filtration (d) Fractional distillation
(b) Crystallization
(c) Sublimation
(d) Distillation under reduced pressure
206 PRACTICAL ORGANIC CHEMISTRY

EXERCISE - 2 : Previous Year Questions

1. Assertion (A): During test for nitrogen with Lassaigne’s 5. In an organic compound, C  68.5% and H  4.91% .
extract on adding FeCl3 solution sometimes a red precipitate Which empirical formula is correct for it?
is obtained. (CPMT 2009)
Reason (R): Sulphur is also present (a) C6 H10 (b) C7 H 6 O 2
(AIIMS2007)
(a) Both Assertion and Reason are true and Reason is (c) C5 H 8 O (d) C9 H 3 O
the correct explanation of Assertion. 6. In the Duma's method of estimation of nitrogen, the
(b) Both Assertion and Reason are true but Reason is nitrogen in the organic compound is finally converted
not the correct explanation of Assertion. into (Kerala CEE 2009)
(c) Assertion is true but Reason is false. (a) NO2 (b) N 2
(d) Both Assertion and Reason are false.
(c) NH3 (d)  NH 4  2 SO4
2. Assertion (A): Oils are purified by steam distillation.
Reason (R): The compounds which decompose at their (e) HNO 3
boiling points can be purified by steam distillation. 7. The masses of carbon, hydrogen and oxygen in an organic
(AIIMS 2008) compound are in the ratio 6: 1: 8 respectively. Which of
(a) Both Assertion and Reason are true and Reason is the following pairs of formulae correspond to the above
the correct explanation of Assertion. information? (Kerala CEE 2009)
(b) Both Assertion and Reason are true but Reason is (a) CH 2 O and CH 3 CHO
not the correct explanation of Assertion.
(b) CH 2 O and C3 H 6 O
(c) Assertion is true but Reason is false.
(d) Both Assertion and Reason are false. (c) C3 H 6 O and C2 H 6 O2

S (d) C3 H 6 O3 and HCHO

||
3. Assertion (A): NH 2 – C– NH 2 gives red color in (e) C 2 H 4 O and C 4 H8 O 2
Lassaigne’s test 8. 1 percent composition of an organic compound A is
Reason (R): Compounds having N along with C give red carbon: 85.71% and hydrogen 14.20% . Its vapour density
colour in Lassaigne’s test. is 14. Consider the following reaction sequence
(AIIMS 2009) Cl /H O (i) KCN/EtOH
A 
2 2  B 
(ii) H O
C
(a) Both Assertion and Reason are true and Reason is 3
the correct explanation of Assertion. Identify C (EAMCET 2009)
(b) Both Assertion and Reason are true but Reason is
CH 3  CH  CO 2 H
not the correct explanation of Assertion. (a) |
(c) Assertion is true but Reason is false.
OH

(d) Both Assertion and Reason are false. (b) HO  CH 2  CH 2  CO 2 H

4. A hydrocarbon has carbon and hydrogen. Its molecular (c) HO  CH 2  CO 2 H
weight is 28. Its possible formula would be
(AFMC 2009) (d) CH 3  CH 2  CO 2 H

(a) C3 H 6 (b) C2 H 4 9. A hydrocarbon contains 80% carbon. What is the

empirical formula of the compound? (KCET 2009)
(c) CH 4 (d) C4 H8
(a) CH2 (b) CH3
(c) CH4 (d) CH
(e) C2H3
PRACTICAL ORGANIC CHEMISTRY 207

10. Which of the following compounds gives blood red 18. In Carius method of estimation of halogens, 0.099 g
coloration when it Lassaigne’s extract is treated with alkali organic compound gave 0.287. The
and ferric chloride? (DPMT 2009) percentage of chlorine in the compound will be
(a) thiourea (b) diphenyl sulphide (Haryana PMT 2010)
(c) phenylhydrazine (d) benzamide (a) 28.6 (b) 71.7
11. Sublimation is a process in which a solid (c) 35.4 (d) 64.2
(KCET 2010) 19. Which of the following compounds will not give answer
(a) changes into vapour form. Lassaigne’s test for nitrogen (DPMT 2010)
(b) changes into another allotropic form. (a) NH2NH2 (b) C6H5NHNH2
(c) changes into liquid form. (c) PhN=NPh (d) NH2CONH2
(d) None of the above 20. The Lassaigne's extract is boiled with conc. HNO3 while
12. Violet coloured complex obtained in the detection of
testing for halogens. By doing so it
sulphur is (AFMC 2010)
(CBSE AIPMT 2011)
(a) Na 2  Fe(NO)(CN)5 
(a) increase the concentration of NO 3 ions
(b) Na 3  Fe(ONS)(CN)5 
(b) decomposes Na 2 S and NaCN , if formed
(c) Na 4  Fe(CN)5 NOS
(c) helps in the precipitation of AgCl
(d) Both (b) and (c)
13. Chemical formula of Prussian blue is (AFMC 2010) (d) increases the solubility product of AgCl

(a) Na 4  Fe(CN)6  (b) K 4  Fe(CN) 6  21. In Duma's method of estimation of nitrogen 0.35 g of an
organic compound gave 55 mL of nitrogen collected at
(c) Fe4  Fe(CN)6 3 (d) None of these 300K temperature and 715 mm pressure. The percentage
composition of nitrogen in the compound would be
14. The compound formed in the positive test for nitrogen
(Aqueous tension at 300 K = 15 mm)
with the Lassaigne solution of an organic compound is
(RPMT 2010) (CBSE AIPMT 2011)
(a) Fe4(CN)6]3 (b) Na3[Fe(CN)6] (a) 14.5% (b) 15.45%
(c) Fe(CN)3 (d) Na4[Fe(CN)5COS] (c) 16.45 (d) 17.45%
15. In an organic compound, phosphorus is estimated as 22. 1.2g of organic compound on Kjeldahlisation liberates
(AFMC 2010) ammonia which consumes 30 cm3 of 1N HCl. The
percentage of nitrogen in the organic compound is
(a) Mg 2 P2 O 7 (b) Mg3  PO4 2 (KCET 2011)
(c) H 3 PO 4 (d) P2 O5 (a) 30% (b) 35%
(c) 46.67% (d) 20.8%
16. In Kjeldahl's method, ammonia from 5g of food neutralizes
23. The Lassaigne's extract is boiled with conc. HNO3 while
30 cm 3 of 0.1 N acid. The percentage of nitrogen in the testing for halogens. By doing so it
food is (KCET 2010) (CBSE AIPMT 2011)
(a) 0.84 (b) 8.4
(a) increase the concentration of NO3 ions.
(c) 16.8 (d) 1.68
17. 0.765 g of an acid gives 0.535 g of CO2 and 0.138 g of H2O. (b) decomposes Na2S and NaCN, if formed.
Then, the ratio of the percentage of carbon and hydrogen (c) helps in the precipitation of AgCl.
is (JCECE 2010) (d) increases the solubility product of AgCl.
(a) 19: 2 (b) 18: 11
(c) 20: 17 (d) 1: 7
208 PRACTICAL ORGANIC CHEMISTRY

24. In Duma's method of estimation of nitrogen 0.35 g of an 31. Correct pair of compounds, which gives blue colouration/
organic compound gave 55 mL of nitrogen collected at precipitate and white precipitate, respectively, when their
300 K temperature and 715 mm pressure. The percentage Lassaigne’s test is separately done is
composition of nitrogen in the compound would be
(West Bengal JEE 2013)
(Aqueous tension at 300 K = 15 mm)
(a) NH2NH2.HCl and ClCH2COOH
(CBSE AIPMT 2011)
(b) NH2CSNH2 and PhCH2Cl
(a) 14.45 (b) 15.45
(c) NH2CH2COOH and NH2CONH2
(c) 16.45 (d) 17.45
25. 1.2 g of organic compound of Kjeldalization liberaze
ammonia which consumes 30 cm3 of 1N HCl. The
percentage of nitrogen in the organic compound is
(KCBT 2011) (d)
(a) 30 (b) 35
(c) 46.67 (d) 20.8
32. A liquid which decomposes at its boiling point can be
26. The Lassiaigne’s extract is boiled with conc. HNO3 while purified by (Manipal 2014)
testing for halogens. By doing so it
(a) distillation at atmospheric pressure
(AIPMT Prelim 2011) (b) distillation under reduced pressure
(a) decomposes Na2S and NaCN, if formed (c) fractional distillation
(b) helps in the precipitation of AgCl (d) steam distillation
(c) increases the solubility product of AgCl 33. Which one of the following methods can be used to
(d) increases the concentration of NO3 ions
– separate a mixture of ortho and para-nitrophenols?
(EAMCET 2014)
27. Presence of halogen in organic compounds can be
(a) Crystallisation
detected by using (UP CPMT 2012)
(b) Solubility
(a) Leibig's test (b) Duma's test
(c) Sublimation
(c) Kjeldahl's test (d) Beilstein test
(d) Steam distillation
28. In the estimation of sulphur by Carius method 0.480 g of 34. In which among the following compounds presence of
an organic compound given 0.699g of barium sulphide. nitrogen cannot be detected by Lassaigne's method?
The percentage of sulphur in this compound is (atomic (MHT CET 2014)
masses : Ba = 137.5 = 32 and O = 16) (Kerala PET 2012) (a) Hydrazine (b) Aniline
(a) C7H8 (b) C2H4
(c) p-toluidine (d) Picric acid
(c) C3H4 (d) C6H5 35. Lassaigne's test is used in qualitative analysis to detect
29. Kjeldahl's method cannot be used for the estimation of (UK PMT 2014)
nitrogen in (AFMC 2013) (a) nitrogen (b) sulphur
(a) pyridine (b) nitro compounds (c) chlorine (d) All of the above
(c) azo compounds (d) All of the above 36. In the Kjeldahl's method for estimation of nitrogen present
30. The colour of the solution/precipitate obtained in the in a soil sample, ammonia evolved from 0.75g of sample
elemental analysis of an organic compound and the neutralised 10 mL of 1M H 2SO 4 . The percentage of
molecule/ion responsible for the colour are given below.
nitrogen in the soil is (CBSE AIPMT 2014)
Choose the incorrectly matched pair:
(a) 37.33 (b) 45,33
(Kerala PET 2013 )
(c) 35.33 (d) 45.33
(a) Prussian blue–Fe4[Fe(CN)6]3.xH2O
37. Camphor is purified by (Kerala PMT 2014)
(b) Black – PbS
(a) distillation (b) vacuum distillation
(c) Violet colour – [Fe(CN)5NOS]4–
(c) sublimation (d) steam distillation
(d) Yellow – (NH4)2MoO4
PRACTICAL ORGANIC CHEMISTRY 209
38. An organic compound which produces a bluish green 43. Assertion (A): A mixture of o-nitrophenol and p-
coloured flame on heating in presence of copper is nitrophenol can be separated by steam distillation
(AIIMS 2014) Reason (R): p-Nitrophenol is steam volatile while o-
(a) chlorobenzene (b) benzaldehyde nitrophenol is not steam volatile. (AIIMS2015)
(c) aniline (d) benzoic acid (a) Both Assertion and Reason are true and Reason is
the correct explanation of Assertion.
39. Paper chromatography has following mobile and stationary
phases respectively (Bihar CECE 2015) (b) Both Assertion and Reason are true but Reason is
(a) liquid, solid (b) solid, solid not the correct explanation of Assertion.
(c) gas, liquid (d) liquid, liquid (c) Assertion is true but Reason is false.
40. In sodium fusion test of organic compounds N is converted (d) Both Assertion and Reason are false.
to (Bihar CECE 2015) 44. The most suitable method of separation of 1: 1 mixture of
(a) NaNH2 (b) NaCN ortho and para-nitrophenols is (NEET 2017)
(c) NaNO2 (d) NaNO3 (a) Crystallisation (b) Steam distillation
41. In the Lassaigne’s test for the detection of nitrogen in the
(c) Sublimation (d) Chromatography
organic compound, the appearance of blue coloured
compound is (West Bengal PMT 2015) 45. Paper chromatography is an example of : (NEET 2020)
(a) ferric ferricyanide (b) ferrous ferricyanide (a) Thin layer chromatography
(c) ferric ferrocyanide (d) ferrous ferrocyanide (b) Column chromatography
(c) Adsorption chromatography
42. 0.30 g of an organic compound containing C, H and O on
(d) Partition chromatography
combustion yields 0.44 g CO2 and 0.18 g H2O. If one mole
of compound weighs 60, then molecular formula of the
compound is (Karnataka CET 2015)
(a) C3H8O (b) C2H4O2
(c) CH2O (d) C4H6O
210 PRACTICAL ORGANIC CHEMISTRY

EXERCISE - 3: Achiever’s Section

Single Choice Questions
6. Which of the following organic compounds will give white
Conc.H SO
precipitate with AgNO3?
1. Phenol + Phthalic anhydride  2 4  B. B gives
fusion (a) C6H5NH3+Cl-
which of the following colour in alkaline medium?
(b) NaCl
(a) Yellow (b) Colourless
(c) 2,4,6-trinitro chlorobenzene
(c) Pink (d) Violet
(d) All of these
2. Among the following, which statement is not correct?
7. Which of the following reactions occur during the detection
O of nitrogen in organic substances by Lassaigne’s test?
||
(a) H 3C  C  OH will not respond to haloform test (a) Na + C + N 
 NaCN

(b) FeSO4 + 6NaCN 

 Na4[Fe(CN)6] + Na2SO4
(b) Schiff ’s regent and Schiff ’s base are different
compounds (c) 3Na4[Fe(CN)6] + 2Fe(SO4)3 
 Fe4[Fe(CN)6]3 +
(c) Fehling’s solution is a good ragent to detect aromatic 6Na2SO4
aldehydes (d) All of these
(d) Both aldehyde and ketone can react with 2, 8. Compound A reacts with CHCl3 and KOH and gives an
4- dinitrophenylhydrazine reagent offesnive smelling compound. A can be
3. To separate a mixture of amines from each other, one should (a) Primary aliphatic amine
follow: (b) Primary aromatic amine
(a) Beckmann’s method (c) both (a) and (b)
(b) Hinsberg’s method (d) Tertiary amine
(c) Zeisel’s method 9. HCOOH and HCHO may be distinguished by
(d) Victor Merye’s Method (a) Tollen’s test (b) Sodium bicarbonate test
4. Phenol can be distinguished from ethanol by (c) 2, 4-DNP test (d) Benedict’s test
(a) Tollen’s reagent (b) Benedict’s reagent
CHO
(c) FeCl3 (d) Schiff’s base
10. and CH3CHO can be distinguished by
Multiple Choice Questions
(a) Tollen’s test
5. An organic compound has the structure
(b) sodium by carbonate test
(c) Iodoform test
(d) 2, 4-DNP test
11. Acetic acid and CH3COCl can be distinguished by
(a) NaHCO3 test (b) Na metal test
(b) Ester formation test (d) both (a) and (b)
It will give
(a) Cerric ammonium nitrate test
(b) Brick effervescene with sodium bicarbonate
(c) A characteristic colouration with neutral ferric chloride
after decarboxylation and reduction by Clemenson’s
method
(d) All of these
PRACTICAL ORGANIC CHEMISTRY 211
Comprehension Based Question (sodium carbonate + potassium nitrate) or Na2O2, followed by
Passage-1 extraction, followed by addition of Conc. HNO3 and ammonium
Steam distillation is used to purify a compound which is steam molybdate gave a yellow precipitate.
volatile and insoluble in water. The impurities should not be steam
volatile. It is based on the principle that liquid will boil when 17. Compound X contains
partial vapour pressure of liquid and partial vapour pressure of (a) N (b) S
steam both become equal to atmospheric pressure, P = p1 + p2. It
(c) N + S (d) P
reduces the boiling point of a liquid.
18. Compound X
Wt. of water distilled M.Wt. of water × VP of steam (a) will contain halogens

Wt. of substance distilled M.Wt. of substance × VP of aniline
(b) may contain halogens
(c) may contain only sulphur
12. Isolation of essential oils from flowers, etc. is done by (d) will contain only nitrogen
(a) Steam distillation 19. Compound Y contain
(b) Distillation (a) N (b) S
(c) Fractional distillation (c) X (d) P
(d) Distillation under reduced pressure 20. The chemical reaction taking place in Y, when it is fused
13. Which of the following is steam volatile? with fusion mixture is
(a) o-nitrophenol
(a) 3Na + P + 4O 
 Na3PO4
(b) p-nitrophenol
(c) p-hydroxy benzaldehyde (b) 3Na2CO3 + 2P + [O] 
 2Na3PO4 + 3CO2
(d) Ethanol (c) KNO3 + P + 30 
 K3PO4 + 3NO2 + O2
14. Calculate weight of aniline distilled if weight of water distilled (d) None of these
is 100g when Porganic compound =100 mm and PH 2O = 200 mm. 21. The formula of yellow precipitate is
(a) (NH4)3PO4 (b) Mo(PO4)
(a) 250 g (b) 258 g
(c) (NH4)3PO4. 12MoO3 (d) Mo(PO4)2
(c) 100 g (d) 25.8 g
15. Steam distillation is based on
Passage-3
(a) Dalton’s law of partial pressures
The 0.2 g of anhydrous organic acid gave on combustion 0.04 g
(b) Graham’s law of diffusion
of water and 0.195 g of CO2. The acid is a dibasic acid and 0.5 g of
(c) Raoult’s law of non-volatile solute
its silver salt leaves on ignition 0.355 g of silver.
(d) None of these
16. Which of the following cannot be separated by steam
22. The percentage of carbon in the compound is
distillation?
(a) 50 (b) 52
(a) Nitrobenzene (b) Essential oil
(c) 26.6 (d) 90
(c) Aniline (d) Glycerol
23. The percentage of hydrogen in the compound is
(a) 5.6 (b) 2.22
Passage-2
(c) 4.44 (d) 10
Test (Q). A compound X was fused with Na metal and the extract
24. The empirical weight of the compound is
gave a white precipitate with AgNO3. The Lassaigne’s extract
gave a red colouration with neutral FeCl3. (a) 90 (b) 100
Test (R). While compound Y when fused with Na metal and (c) 10 (d) 45
subsequent analysis on its Lassaigne’s extract did not give any 25. The molecular weight of the compound is
characteristic test. (a) 90 (b) 100
Test (S). While compound Y on fusion with fusion mixture (c) 10 (d) 45
212 PRACTICAL ORGANIC CHEMISTRY

26. The molecular formula of the compound is (a) (a-rs) (b-q) (c-p) (d-pt)
(a) CHO (b) CHO2 (b) (a-q) (b-rs) (c-p) (d-pt)
(c) C2H2O4 (d) C3H6O2 (c) (a-q) (b-p) (c-rs) (d-pt)
(d) (a-q) (b-pt) (c-p) (d-rs)
Matrix Match Type Question 29. Column I Column II
(reagents) (Product/ compound)
27. Column I Column II (a) Product of reaction (p) Me - CH = CH - Me
(pair of compounds) (test to distinguish) of propyne with 1
percent HgSO4 and
Dil. H2SO4
(a) (p) Liebermann’s (b) Br2 water test (q) Me - C  C - H
given by
nitroso test

(c) Additioin of HBr (r)

can be with
(d) Tollen’s reagent (s) Me - CH = CH2
(b) (q)
give white ppt. with
O
||
(t) Me  C  Me
(a) (a-t) (b-pqrs) (c-pqrs) (d-q)
(c) (r) Iodoform test
(b) (a-t) (b-q) (c-pqrs) (d-pqrs)

(d) CH3– CH2 – CHO (s) Lucas test (c) (a-q) (b-pqrs) (c-pqrs) (d-t)
and CH3– CHO (d) (a-t) (b-pqrs) (c-q) (d-pqrs)
(t) NaHSO3
(a) (a-rs) (b-pq) (c-p) (d-r)
(b) (a-pq) (b-rs) (c-p) (d-r)
(c) (a-rs) (b-r) (c-p) (d-pq)
(d) (a-rs) (b-p) (c-pq) (d-r)
28. Column I Column II
(pair of compounds) (identification test)

(a) and (p) Tollen’s reagent

test
OH OH

(b) and (q) Bromine water test

O
||
(c) H  C  OH and (r) Lucas test
O
||
CH 3  C  OH

(d) and (s) Iodoform test

(t) Ammonical Cu2Cl2
test
PRACTICAL ORGANIC CHEMISTRY 213
30. Column I Column II
(compound) (tests)

(a) (p) 2,4-DNP test

(b) (q) Yellow ppt. with NaOH

+ I2
O
||
(c) CH 3  C  H (r) Red ppt. with Fehling’s
solution

(d) (s) Silver mirror with

Tollen’s reagent
(a) (a-pq) (b-ps) (c-pqrs) (d-pq)
(b) (a-pqrs) (b-pq) (c-ps) (d-pq)
(c) (a-ps) (b-pq) (c-pq) (d-pqrs)
(d) (a-ps) (b-pq) (c-pqrs) (d-pq)
214 PRACTICAL ORGANIC CHEMISTRY

Notes:

Find Answer Key and Detailed Solutions at the end of this book

PRACTICAL ORGANIC CHEMISTRY

ANSWER KEY 215

Answer Key
CHAPTER - 11: p-BLOCK ELEMENTS (GROUP 15-18)
Exercise - 1: Basic Objective Questions

DIRECTIONS FOR USE-

Scan the QR code and check detailed solutions.

1. (a) 2. (a) 3. (d) 4. (a) 77. (c) 78. (d) 79. (c) 80. (d)
5. (b) 6. (a) 7. (d) 8. (d) 81. (a) 82. (d) 83. (c) 84. (d)
9. (a) 10. (d) 11. (b) 12. (c) 85. (b) 86. (a) 87. (a) 88. (c)
13. (a) 14. (d) 15. (a) 16. (a) 89. (d) 90. (b) 91. (a) 92. (c)
17. (d) 18. (d) 19. (d) 20. (d) 93. (c) 94. (c) 95. (b) 96. (d)
21. (a) 22. (a) 23. (c) 24. (d) 97. (c) 98. (c) 99. (d) 100. (b)
25. (d) 26. (a) 27. (c) 28. (d) 101. (c) 102. (a) 103. (a) 104. (b)
29. (a) 30. (b) 31. (c) 32. (d) 105. (a) 106. (b) 107. (d) 108. (a)
33. (c) 34. (d) 35. (c) 36. (b) 109. (b) 110. (c) 111. (a) 112. (a)
37. (c) 38. (a) 39. (d) 40. (b) 113. (d) 114. (b) 115. (b) 116. (c)
41. (c) 42. (d) 43. (b) 44. (d) 117. (a) 118. (d) 119. (b) 120. (d)
45. (d) 46. (b) 47. (d) 48. (c) 121. (a) 122. (d) 123. (c) 124. (b)
49. (c) 50. (c) 51. (a) 52. (a) 125. (d) 126. (b) 127. (c) 128. (a)
53. (a) 54. (c) 55. (d) 56. (c) 129. (d) 130. (b) 131. (a) 132. (c)
57. (a) 58. (b) 59. (a) 60. (a) 133. (b) 134. (d) 135. (b) 136. (b)
61. (c) 62. (a) 63. (d) 64. (c) 137. (d) 138. (d) 139. (d) 140. (a)
65. (b) 66. (d) 67. (b) 68. (b) 141. (c) 142. (b) 143. (c) 144. (a)
69. (a) 70. (a) 71. (b) 72. (c) 145. (d) 146. (c) 147. (d) 148. (c)
73. (d) 74. (a) 75. (d) 76. (b) 149. (d) 150. (a)
216 ANSWER KEY
Exercise- 2: Previous Year Questions Exercise - 3: Achiever’s Section

DIRECTIONS FOR USE- DIRECTIONS FOR USE-

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1. (a) 2. (b) 3. (b) 4. (a) 1. (b) 2. (d) 3. (c) 4. (d)

5. (d) 6. (b) 7. (c) 8. (b) 5. (b) 6. (b) 7. (b) 8. (c)
9. (c) 10. (b) 11. (c) 12. (d) 9. (a) 10. (b) 11. (b) 12. (a)
13. (c) 14. (a) 15. (a) 16. (a) 13. (a) 14. (d) 15. (a) 16. (d)
17. (c) 18. (c) 19. (d) 20. (b) 17. (d) 18. (b) 19. (b) 20. (d)
21. (d) 22. (d) 23. (b) 24. (d) 21. (d) 22. (c) 23. (b) 24. (c)
25. (c) 26. (c) 27. (b) 28. (d) 25. (c) 26. (d) 27. (a) 28. (b)
29. (c) 30. (a) 31. (b) 32. (c) 29. (b) 30. (b)
33. (b) 34. (b) 35. (a) 36. (d)
37. (a) 38. (a) 39. (a) 40. (b)
41. (a) 42. (a) 43. (a) 44. (c)
45. (c) 46. (a) 47. (c) 48. (c)
49. (d) 50. (c)
ANSWER KEY 217

CHAPTER - 12: METALLURGY

Exercise - 1: Basic Objective Questions

DIRECTIONS FOR USE-

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1. (a) 2.(a) 3. (a) 4. (b) 77. (a) 78. (b) 79. (c) 80. (c)
5. (c) 6. (c) 7. (b) 8. (a) 81. (b) 82. (c) 83. (d) 84. (b)
9. (d) 10. (c) 11. (b) 12. (a) 85. (d) 86. (d) 87. (c) 88. (a)
13. (c) 14. (b) 15. (b) 16. (b) 89. (c) 90. (b) 91. (c) 92. (a)
17. (b) 18. (d) 19. (b) 20. (b) 93. (d) 94. (b) 95. (b) 96. (b)
21. (b) 22. (c) 23. (d) 24. (d) 97. (d) 98. (a) 99. (b) 100. (c)
25. (a) 26. (a) 27. (b) 28. (d) 101. (c) 102. (c) 103. (b) 104. (a)
29. (d) 30. (b) 31. (c) 32. (d) 105. (d) 106. (c) 107. (b) 108. (c)
33. (d) 34. (d) 35. (b) 36. (d) 109. (b) 110. (d) 111. (a) 112. (c)
37. (d) 38. (c) 39. (c) 40. (c) 113. (d) 114. (b) 115. (b) 116. (b)
41. (a) 42. (a) 43. (d) 44. (a) 117. (a) 118. (c) 119. (a) 120. (d)
45. (a) 46. (d) 47. (a) 48. (c) 121. (a) 122. (c) 123. (d) 124. (d)
49. (b) 50. (c) 51. (c) 52. (c) 125. (a) 126. (c) 127. (c) 128. (a)
53. (b) 54. (c) 55. (a) 56. (d) 129. (c) 130. (a) 131. (a) 132. (c)
57. (d) 58. (b) 59. (d) 60. (a) 133. (b) 134. (b) 135. (b) 136. (c)
61. (b) 62. (c) 63. (c) 64. (a) 137. (b) 138. (a) 139. (a) 140. (c)
65. (a) 66. (b) 67. (a) 68. (b) 141. (b) 142. (d) 143. (a) 144. (d)
69. (b) 70. (b) 71. (c) 72. (a) 145. (a) 146. (c) 147. (a) 148. (a)
73. (c) 74. (b) 75. (c) 76. (c) 149. (a) 150. (a)
218 ANSWER KEY

Exercise - 2: Previous Year Questions Exercise - 3: Achiever’s Section

DIRECTIONS FOR USE- DIRECTIONS FOR USE-

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1. (d) 2.(b) 3. (a) 4. (c) 1. (d) 2. (b) 3. (c) 4. (b)

5. (b) 6. (d) 7. (d) 8. (d) 5. (d) 6. (d) 7. (c) 8. (b)
9. (d) 10. (d) 11. (b) 12. (c) 9. (a) 10. (c) 11. (a) 12. (c)
13. (c) 14. (c) 15. (c) 16. (b) 13. (b) 14. (a) 15. (a) 16. (a)
17. (a) 18. (a) 19. (c) 20. (d) 17. (a) 18. (d) 19. (c) 20. (c)
21. (d) 22. (b) 23. (c) 24. (b) 21. (c) 22. (b) 23. (c) 24. (a)
25. (c) 26. (b) 27. (a) 28. (d) 25. (b) 26. (b) 27. (a) 28. (a)
29. (a) 30. (c) 31. (c) 32. (b) 29. (c) 30. (b)
33. (a) 34. (d) 35. (d) 36. (b)
37. (d) 38. (c) 39. (a) 40. (c)
41. (c) 42. (b) 43. (b) 44. (c)
45. (a) 46. (d) 47. (b) 48. (d)
49. (c) 50. (d)
ANSWER KEY 219

CHAPTER - 13: d AND f BLOCK ELEMENTS

Exercise- 1: Basic Objective Questions

DIRECTIONS FOR USE-

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1. (d) 2.(d) 3. (c) 4. (d) 77. (d) 78. (b) 79. (c) 80. (c)
5. (a) 6. (c) 7. (d) 8. (a) 81. (a) 82. (c) 83. (b) 84. (b)
9. (d) 10. (a) 11. (a) 12. (c) 85. (a) 86. (b) 87. (c) 88. (c)
13. (b) 14. (a) 15. (b) 16. (c) 89. (d) 90. (b) 91. (c) 92. (b)
17. (b) 18. (c) 19. (b) 20. (c) 93. (b) 94. (a) 95. (d) 96. (d)
21. (c) 22. (a) 23. (a) 24. (c) 97. (b) 98. (d) 99. (b) 100. (c)
25. (a) 26. (a) 27. (b) 28. (b) 101. (c) 102. (a) 103. (d) 104. (b)
29. (b) 30. (d) 31. (d) 32. (c) 105. (d) 106. (d) 107. (d) 108. (d)
33. (d) 34. (a) 35. (d) 36. (c) 109. (a) 110. (b) 111. (a) 112. (c)
37. (a) 38. (b) 39. (c) 40. (d) 113. (b) 114. (a) 115. (b) 116. (b)
41. (a) 42. (b) 43. (d) 44. (d) 117. (c) 118. (c) 119. (a) 120. (a)
45. (b) 46. (d) 47. (d) 48. (a) 121. (d) 122. (b) 123. (b) 124. (d)
49. (b) 50. (d) 51. (b) 52. (c) 125. (a) 126. (c) 127. (d) 128. (d)
53. (c) 54. (a) 55. (d) 56. (c) 129. (d) 130. (d) 131. (d) 132. (a)
57. (c) 58. (b) 59. (c) 60. (b) 133. (b) 134. (d) 135. (d) 136. (a)
61. (d) 62. (c) 63. (b) 64. (b) 137. (b) 138. (c) 139. (d) 140. (d)
65. (a) 66. (a) 67. (c) 68. (c) 141. (d) 142. (c) 143. (d) 144. (a)
69. (c) 70. (d) 71. (c) 72. (a) 145. (b) 146. (d) 147. (c) 148. (a)
73. (b) 74. (d) 75. (d) 76. (d) 149. (c) 150. (a)
220 ANSWER KEY

Exercise - 2: Previous Year Questions EXERCISE - 3: Achiever’s Section

DIRECTIONS FOR USE- DIRECTIONS FOR USE-

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1. (a) 2.(c) 3. (b) 4. (c) 1. (b) 2. (d) 3. (c) 4. (b)

5. (c) 6. (c) 7. (d) 8. (a) 5. (d) 6. (c) 7. (c) 8. (d)
9. (c) 10. (d) 11. (b) 12. (b) 9. (c) 10. (c) 11. (c) 12. (c)
13. (c) 14. (d) 15. (c) 16. (a) 13. (d) 14. (b) 15. (c) 16. (a)
17. (b) 18. (b) 19. (b) 20. (b) 17. (d) 18. (d) 19. (a) 20. (a)
21. (b) 22. (c) 23. (c) 24. (c) 21. (b) 22. (a) 23. (c) 24. (b)
25. (a) 26. (d) 27. (b) 28. (d) 25. (c) 26. (c) 27. (b) 28. (d)
29. (b) 30. (a) 31. (d) 32. (b) 29. (b) 30. (a)
33. (d) 34. (a) 35. (d) 36. (a)
37. (b) 38. (b) 39. (b) 40. (b)
41. (a) 42. (c) 43. (d) 44. (d)
45. (c) 46. (d) 47. (b) 48. (d)
49. (a) 50. (d)
ANSWER KEY 221

CHAPTER - 14: CHEMISTRY IN EVERYDAY LIFE

Exercise - 1: Basic Objective Questions

DIRECTIONS FOR USE-

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1. (b) 2. (d) 3. (c) 4. (b) 77. (b) 78. (c) 79. (d) 80. (a)
5. (a) 6. (b) 7. (c) 8. (d) 81. (b) 82. (c) 83. (d) 84. (a)
9. (a) 10. (a) 11. (a) 12. (b) 85. (a) 86. (c) 87. (b) 88. (b)
13. (a) 14. (c) 15. (c) 16. (b) 89. (d) 90. (d) 91. (a) 92. (a)
17. (a) 18. (b) 19. (b) 20. (c) 93. (b) 94. (c) 95. (b) 96. (c)
21. (a) 22. (d) 23. (d) 24. (c) 97. (c) 98. (c) 99. (a) 100. (b)
25. (a) 26. (a) 27. (b) 28. (a) 101. (a) 102. (c) 103. (d) 104. (b)
29. (c) 30. (a) 31. (b) 32. (c) 105. (d) 106. (c) 107. (a) 108. (b)
33. (c) 34. (c) 35. (c) 36. (b) 109. (a) 110. (b) 111. (b) 112. (a)
37. (d) 38. (b) 39. (a) 40. (d) 113. (a) 114. (c) 115. (c) 116. (d)
41. (b) 42. (b) 43. (b) 44. (a) 117. (d) 118. (d) 119. (a) 120. (d)
45. (d) 46. (a) 47. (b) 48. (a) 121. (a) 122. (d) 123. (c) 124. (b)
49. (a) 50. (a) 51. (b) 52. (d) 125. (c) 126. (b) 127. (c) 128. (c)
53. (a) 54. (c) 55. (c) 56. (a) 129. (b) 130. (b) 131. (c) 132. (c)
57. (a) 58. (a) 59. (b) 60. (c) 133. (c) 134. (c) 135. (d) 136. (c)
61.(a) 62. (b) 63. (a) 64. (d) 137. (d) 138. (b) 139. (b) 140. (b)
65. (d) 66. (c) 67. (d) 68. (a) 141. (c) 142. (b) 143. (b) 144. (d)
69. (b) 70. (a) 71. (c) 72. (c) 145. (a) 146. (d) 147. (d) 148. (d)
73. (d) 74. (c) 75. (a) 76. (c) 149. (d) 150. (b)
222 ANSWER KEY

Exercise - 2: Previous Year Questions Exercise - 3: Achiever’s Section

DIRECTIONS FOR USE- DIRECTIONS FOR USE-

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.

1. (d) 2. (b) 3. (b) 4. (d) 1. (c) 2. (b) 3. (d) 4. (b)

5. (b) 6. (a) 7. (d) 8. (a) 5. (c) 6. (c) 7. (c) 8. (a)
9. (a) 10. (b) 11. (d) 12. (b) 9. (b) 10. (b) 11. (b) 12. (a)
13. (c) 14. (c) 15. (c) 16. (b) 13. (d) 14. (b) 15. (c) 16. (d)
17. (b) 18. (d) 19. (c) 20. (a) 17. (c) 18. (b) 19. (a) 20. (a)
21. (c) 22. (c) 23. (b) 24. (c) 21. (c) 22. (b) 23. (d) 24. (b)
25. (b) 26. (d) 27. (b) 28. (d)
25. (c) 26. (c) 27. (b) 28. (a)
29. (c) 30. (a) 31. (c) 32. (b)
29. (b) 30. (d)
33. (c) 34. (b) 35. (d) 36. (a)
37. (d) 38. (b) 39. (d) 40. (d)
41. (b) 42. (b) 43. (d) 44. (d)
45. (d) 46. (c) 47. (a) 48. (a)
49. (d) 50. (c)
ANSWER KEY 223

CHAPTER - 15: PRACTICAL ORGANIC CHEMISTRY

Exercise- 1: Basic Objective Questions Exercise - 2: Previous Year Questions

DIRECTIONS FOR USE-

DIRECTIONS FOR USE- Scan the QR code and check detailed solutions.
Scan the QR code and check detailed solutions.

1. (d) 2.(d) 3. (a) 4. (a) 1. (a) 2. (d) 3. (c) 4. (b)

5. (b) 6. (c) 7. (a) 8. (d) 5. (b) 6. (b) 7. (d) 8. (b)
9. (a) 10. (a) 11. (c) 12. (c) 9. (b) 10. (a) 11. (a) 12. (c)
13. (c) 14. (a) 15. (c) 16. (a) 13. (c) 14. (a) 15. (a) 16. (a)
17. (b) 18. (c) 19. (d) 20. (d) 17. (a) 18. (b) 19. (c) 20. (b)
21. (b) 22. (a) 23. (b) 24. (d) 21. (c) 22. (b) 23. (a) 24. (c)
25. (b) 26. (d) 27. (a) 28. (a) 25. (b) 26. (c) 27. (d) 28. (b)
29. (b) 30. (c) 31. (c) 32. (a) 29. (d) 30. (d) 31. (d) 32. (b)
33. (a) 34. (b) 35. (b) 36. (c) 33. (d) 34. (a) 35. (d) 36. (a)
37. (c) 38. (a) 39. (b) 40. (a) 37. (c) 38. (a) 39. (d) 40. (b)
41. (c) 42. (a) 43. (a) 44. (b) 41. (c) 42. (b) 43. (c) 44. (b)
45. (d) 46. (b) 47. (d) 48. (c) 45. (d)
49. (d) 50. (a) 51. (d) 52. (c)
53. (d) 54. (b) 55. (b)
224 ANSWER KEY

Exercise- 3: Achiever’s Section

DIRECTIONS FOR USE-

Scan the QR code and check detailed solutions.

1. (c) 2. (c) 3. (b) 4. (c)

5. (d) 6. (d) 7. (d) 8. (c)
9. (d) 10. (c) 11. (d) 12. (a)
13. (a) 14. (b) 15. (a) 16. (d)
17. (c) 18. (b) 19. (d) 20. (b)
21. (c) 22. (c) 23. (b) 24. (d)
25. (a) 26. (c) 27. (a) 28. (b)
29. (a) 30. (d)
MASTER INDEX
VOLUME 1:
Solutions
Solid State
General Organic Chemistry (Revision) & Isomerism
Alkyl and Aryl Halides
Alcohols, Phenols and Ethers

VOLUME 2:
Aldehydes and Ketones
Biomolecules
Carboxylic Acids and Its Derivatives
Amines
Polymers

VOLUME 3:
p -Block Elements (group 15-18)
Metallurgy
d and f Block Elements
Chemistry in Everyday Life
Practical Organic Chemistry

VOLUME 4:
Coordination Compounds
Chemical Kinetics
Electrochemistry
Surface Chemistry
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