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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
2
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CHAPTER-1: SOLID STATE
Exercise-1: Basic Objective
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(c) 4.25 g/cm3 (d) 8.5 g/cm3
3
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 TABLE OF CONTENTS

p -BLOCK ELEMENTS (GROUP 15-18)

Theory ................................................................................................................................................ 9
Solved Examples ............................................................................................................................... 43

Exercise - 1 : Basic Objective Questions........................................................................................... 48

Exercise - 2 : Previous Year JEE MAINS Questions .......................................................................... 56

Exercise - 3 : Advanced Objective Questions ................................................................................. 61
Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 64
Answer Key ........................................................................................................................................ 272

METALLURGY

Theory ................................................................................................................................................ 68

Solved Examples ............................................................................................................................... 85

Exercise - 1 : Basic Objective Questions........................................................................................... 93

Exercise - 2 : Previous Year JEE MAINS Questions .......................................................................... 98

Exercise - 3 : Advanced Objective Questions ................................................................................. 105

Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 111

Answer Key ........................................................................................................................................ 274

 d AND f BLOCK ELEMENTS

Theory ..................................................................................................................................................... 115

Solved Examples ..................................................................................................................................... 135

Exercise - 1 : Basic Objective Questions.................................................................................................. 152

Exercise - 2 : Previous Year JEE MAINS Questions ................................................................................. 159

Exercise - 3 : Advanced Objective Questions ....................................................................................... 163

Exercise - 4 : Previous Year JEE Advanced Questions ....................................................................... ... 168

Answer Key .............................................................................................................................................. 276

CHEMISTRY IN EVERYDAY LIFE

Theory ...................................................................................................................................................... 172

Solved Examples ..................................................................................................................................... 183

Exercise - 1 : Basic Objective Questions.................................................................................................. 186

Exercise - 2 : Previous Year JEE MAINS Questions.................................................................................. 192

Answer Key .............................................................................................................................................. 278
 PRACTICAL ORGANIC CHEMISTRY

Theory ...................................................................................................................................................... 198

Solved Examples ..................................................................................................................................... 216

Exercise - 1 : Basic Objective Questions.................................................................................................. 222

Exercise - 2 : Previous Year JEE MAINS Questions.................................................................................. 226

Exercise - 3 : Advanced Objective Questions ....................................................................................... 233

Answer Key .............................................................................................................................................. 279

QUALITATIVE ANALYSIS

Theory ...................................................................................................................................................... 238

Solved Examples ..................................................................................................................................... 256

Exercise - 1 : Basic Objective Questions.................................................................................................. 262

Exercise - 2 : Previous Year JEE MAINS/Advanced Questions............................................................... 266

Answer Key .............................................................................................................................................. 281
p-BLOCK ELEMENTS (GROUP 15 -18)
 Chapter 11 10

p-Block Elements (Group 15 -18)

1. INTRODUCTION 1.3 Ionisation Enthalpy

Group 15 includes nitrogen phosphorus, arsenic, antimony and Ionisation enthalpy decreases down the group due to gradual
bismuth. As we go down the group, there is a shift from non- increase in atomic size. Because of the extra stable half- filled p-
metallic to metallic through metalloidic character. Nitrogen and orbital electronic configuration and smaller size, the ionisation
phosphorus are non-metal, arsenic and antimony metalloid and enthalpy of the group 15 element is much greater than of group
bismuth is a typical metal. 14 elements in the corresponding periods. The order of successive
1.1 Electronic Configuration ionisation enthalpies, as expected is iH1 < iH2 < iH3
The valence shell electronic configuration of these element is
ns2 np3. The s orbital in these element is completely filled and p 2. PHYSICAL PROPERTIES OF GROUP 15
orbitals are half- filled, making their electronic configuration extra ELEMENTS
stable. All the elements of this group are polyatomic. Dinitrogen is a
1.2 Atomic and Ionic Radii diatomic gas while all others are solids. Metallic character
Covalent and ionic radii increase down the group. There is a increases down the group. Nitrogen and phosphours are non-
considerable increase in covalent radius from N to P. However, metals, arsenic and antimony metalloids and bismuth is a metal.
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.
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]2s 2p 2 3
[Ne]3s 3p 2 3
[Ar]3d 4s 4p
10 2 3
[Kr]4d 5s 5p
10 2 3
[Xe]4f145d106s26p3
Covalent Radius/pm 70 110 120 140 150
Ionic Radius/pm 171a 212a 222a 76b 103b
a = M3–, b = M+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.
In the case of nitrogen , all oxidation states from +1 to +4 tend to
disproportionate in acid solution. For example,
3 HNO2  HNO3 + H2O + 2 NO

SCAN CODE
p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18) 11
Similarly , in case of phosphorus nearly all intermediate oxidation
Properties of Hydrides of Group 15 Elements
states disproportionate into +5 and –3.
Nitrogen is restricted to a maximum covalency of 4 since only
four (one s and three p) orbitals are available for bonding. The Property NH3 PH3 AsH3 SbH3 BiH3
heavier elements have vacant d orbitals in the outermost shell Melting point/K 195.2 139.5 156.7 185 –
which can be used for bonding (covalency) and hence , expand Boiling point/K 238.5 185.5 210.6 254.6 290
their covalence as in PF6– . (E-H) Distance/ 101.7 141.9 151.9 170.7 –
Anomalous properties of nitrogen: Nitrogen differs from the rest pm
of the members of this group due to its smaller size, high HEH angle 107.8 93.6 91.8 91.3 –
electronegativity , high ionisation enthalpy and non – availability
fH–/kJ mol–1 –46.1 13.4 66.4 145.1 278
of d orbitals. Nitrogen has unique ability to form p – p multiple
dissH–(E–H)/ –46.1 13.4 66.4 145.1 278
bonds with itself and with other elements having small size and
high electronegativity (e.g., C ,O). Heavier elements of this group kJ/mol–1 389 322 297 255 –
do not form p – p bonds as their atomic orbitals are so large
3.2 Reactivity Towards Oxygen
and diffuse that they cannot have effective overlapping. Thus,
All these elements form two types of oxides: E2O3 and E2O5. The
nitrogen exists as a diatomic molecule with a triple bond (one s oxide in the higher oxidation state of the element is more acidic
and two p) between the two atoms. Consequently , its bond than that of lower oxidation state. Their acidic character decreases
enthalpy (941.1 kJ mol –1) is very high. On the contrary, down the group. The oxides of the type E2O3 of nitrogen and
phosphours are purely acidic, that of arsenic and antimony
phosphorus, arsenic and antimony form single bond (P - P, As- amphoteric and those of bismuth is predominantly basic.
As, Sb-Sb) while Bi forms metallic bonds in elemental state.
However , the single N – N bond is weaker than the single P – P 3.3 Reactivity Towards Halogens
bond because of high interelectronic repulsion of the non – These elements react to form two series of halides: EX3 and EX5.
Nitrogen does not form pentahalide due to non– availability of
bonding electrons, owing to the small bond length. As a result the d– orbitals in its valence shell. Pentahalides are more covalent
the catenation tendency is weaker in nitrogen. Another factor than trihalides. All the trihalides of these elements except those
which affects the chemistry of nitrogen is the absence of d orbitals of nitrogen are stable. In case of nitrogen , only NF3 is known to
be stable. Trihalides except BiF3 are predominantly covalent in
in its valence shell. Besides restricting its covalency to four , nature.
nitrogen cannot form d – p bonds as the heavier elements can
e.g., R3P = O or R3P = CH2 (R = alkyl group). Phosphours and 3.4 Reactivity Towards Metals
arsenic can form d – p bond also with transition metals when These elements react with metals to form their binary compounds
their compounds like P(C2H5)3 and As(C6H5)3 act as ligands. exhibiting –3 oxidation state, such as, Ca3N2 (calcium nitride)
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
E = N , P, As, Sb or Bi. Some of the properties of these hydrides 4. GENERAL PROPERTIES AND COMPONDS OF
are shown in Table. The hydrides show regular gradation in their NITROGEN
properties. The stability of hydrides decreases from NH3 to BiH3 4.1 Nitrogen (N2)
which can be observed from their bond dissociation enthalpy.
Preparation:
Consequently, the reducing character of the hydrides increases.
(i) By treating an aqueous solution of ammonium chloride with
Ammonia is only a mild reducing agent while BiH3 is the strongest
sodium nitrate. It is laboratory method of preparation.
reducing agent amongst all the hydrides. Basicity also decreases
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

(v) 2NO + 2Cu  2CuO + N2

(red, overheated) (Black)

SCAN CODE
p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18)
(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.

CaC2 + N2 +  CaCN2 + C (nitrolim, a fertilizer)
 a high temperature in an iron retort and the distillate is bubbles
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.)
Uses:
(i) for providing an inert atmosphere during many industrial
processes where presence of air or O2 is to be avoided.
12
(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 hydrolysis 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
Iron oxide  K O &Al O
2 2 3
(ii) From destructive distillation of coal: When coal is heated at
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
when ammonium salts get decomposed to liberate further quantity
of ammonia.
SCAN CODE
p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18) 13
(iii) Cyanamide process:
MCl 2  2NH 4 OH  M  OH  2  2NH 4 Cl
CaO + 2C + N2 2000ºC CaCN + CO  white 
 
2  
CaCN2 + 3H2O  CaCO3 + 2NH3 (M = Mg, Ca, Sr, Ba, Ra, Sn, Pb)
Properties: (viii) When NH4OH solution is added to AgNO3 solution, a brown
(i) Colourless gas lighter than air. Being basic in nature turns ppt. is obtained
red litmus blue. It acts as a Lewis base
2AgNO3  2NH 4 OH  Ag 2 O  2NH 4 NO 3  H 2 O
(ii) Highly soluble in water. The solution is called ammonium  brown 
 
hydroxide solution.  

Brown ppt of silver oxide formed dissolves in excess ammo-

(iii) Na + NH3 
 NaNH2 + 1/2 H2 nium hydroxide forming a soluble complex
Amides decompose back with water to form NH3 and NaOH. Ag2O + 2NH4OH  [Ag(NH3)2]OH + 2H2O
Pt ,550ºC 4NO + 6H O
(iv) 4NH3 + 5O2  (ix) 2NH3 + CO2 + H2O  (NH4)2CO3
 2

(Ostwald’s process of manufacturing HNO3) high pressure

2NH3 + CO2   NH2CONH2 (urea) + H2O
(v) When Cl2 is bubbled in liquor ammonia, nitrogen gas is 
formed. Uses:
8NH3 + 3Cl2  6NH4Cl + N2 (i) Used as a refrigeration fluid.
With excess of Cl2 it is converted to an explosive substance, (ii) For the production of ammonium fertilizers such as ammonium
nitrogen trichloride. sulphate, ammonium phosphate, ammonium nitrate, urea etc.
(iii) For removing grease because NH4OH dissolves grease.
NH3 + 3Cl2  NCl3 +3HCl
(iv) For manufacture of HNO3 by the Ostwald process.
(vi) Cupric oxide and PbO are reduced to metal when NH3 is
(v) As a laboratory reagent.
passed over heated CuO and PbO.
(vi) In the production of artificial rayon, silk, nylon etc.
3CuO + 2NH3  3Cu + 3H2O + N2
4.2.2 Oxides of Nitrogen:
3PbO + 2NH3  3Pb + 3H2O + N2 Nitrogen forms a number of oxides, N2O, NO, N2O3, NO2 or N2O4
M  NO3  2  2NH 4 OH  M  OH  2  2NH 4 NO3 and N2O5, and also very unstable NO3 and N2O6. All these oxides
(vii)  white  of nitrogen exhibit p-p multiple bonding between nitrogen and
 
 
oxygen.

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

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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
 Nitric acid can be concentrated to 68 % by distillation, when
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
14
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) HNO3 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
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
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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18)
(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
15
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.
Structure of white phosphorus
(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
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p-BLOCK ELEMENTS (GROUP 15 -18)
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 crys
tals 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.
16
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.
Structure of Red phosphorus
(iii) Black phosphorus: It has two forms -black phosphorus P + 5NHO3  H3PO4 + 5NO2 + H2O
and -black phosphorous (vi) Action of conc. H2SO4: When heated with conc. H2SO4
(a) -black phosphorous phosphorus is oxidized to H3PO4.

insulated  
2P + 5H2SO4  2H3PO4 + 5SO2 + 2H2O
P(red) 
tube803K P(-black)
Conversion of white phosphorus to red phosphorus and red
-black phosphorous structure is not definite and is non phos-phorus to white phosphorus.
conductor of electricity. Heat in presence of 2 catalyst at 250oC and high pressure in ab-
(b) -black phosphorous sence of air

473 K White phosphorus  Red phosphorus


P(white) High 
pressure P(-black) Heat above 250°C in presence of inert gas and condense in water
-black phosphorous is an electrical conductor resembling 5.1 Compounds of Phosphorus
graphite in this respect and also in its flakiness and luster. It 5.1.1 Phosphine
is insoluble in CS2. It has a layered structure like graphite.
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
Structure of Black phosphorus whereupon P2H4 condenses to a liquid and PH3 is collected by the
Chemical Properties of Phosphorus: downward displacement of air. Pure PH3 does not burn in air.
(i) Action of air: White phosphorus burns in air to form (ii) By the action of alkalies on phosphonium salts:
phosphorus trioxide and pentoxide.

P4 + 5O2  2P2O5 PH4I + NaOH  NaI + PH3 + H2O
P4 + 3O2  2P2O3 (iii) By the action of dil. HCl or dil. H2SO4 on metal phosphides.
Red and other forms of phosphorus also burn in air or oxygen Na3P + 3HCl  3NaCl + PH3

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p-BLOCK ELEMENTS (GROUP 15 -18) 17
(ii) It dissolves in cold water to form phosphorus acid. It is thus
AlP + 3HCl  AlCl3 + PH3 the anhydride of phosphorus acid.
2Na3P + 3H2SO4  3Na2SO4 + 2PH3 P2O3 + 3H2O  2H3PO3
Properties: (iii) It dissolves in hot water liberating PH3
(i) It is a colourless gas with a smell of rotten fish and is neutral 2P2O3 + 6H2O  3H3PO4 + PH3
to litmus paper, It is heavier than air and only slightly soluble (iv) It slowly gets oxidized in air to form P2O5
in water, It is a poisonous gas and acts as a Lewis base. P2O3 + O2  P2O5
(ii) Action of chlorine: It reacts with Cl2 to form PCl5. 5.1.2.2 Phosphorus Pentoxide (P2O5) :
PH3 + 4Cl2  PCl5 + 3HCl Preparation : It is obtained by burning phosphorus in air.
Similar reaction occurs between heated phosphine and Br2 P4 + 5O2  P4O10
and I2 vapours. Properties:
(iii) Reaction with hydrogen halides: When PH3 is bubbled in (i) It is a white powder acidic in nature and is the anhydride of
solution of HX, phosphonium halides are formed. orthophosphoric acid. Its empirical formula is P2O5 and its
PH3 + HX  PH4X molecular formula is P4O10.
(iv) Action on CuSO4 solution: When PH3 is bubbled in acidic (ii) It sublimes on heating at 250oC.
solution of copper sulphate, a black precipitate of copper (iii) Action of water: It dissolves in water with hissing sound
phosphide is formed. forming metaphosphoric acid and finally orthophosphoric
3CuSO4+2PH3 Cu3P2 {black} + 3H2SO4 acid.
(v) Reaction with AgNO3 solution: When PH3 gas is bubbled in
P4O10 + 2H2O  4HPO3 , HPO3 + H2O  H3PO4
a solution of AgNO3, a yellow precipitate of silver phosphide,
(iv) Dehydrating power: It dehydrates conc. H2SO4 and conc.
Ag3P, is first formed which later decomposes to black Ag.
HNO3 to SO3 and N2O5 respectively.
3AgNO3 + PH3  Ag3P (yellow) + 3HNO3
distillation  2HPO + N O
2HNO3 + P2O5  3 2 5
Ag3P + 3AgNO3 + 3H2O  6Ag + 3HNO3 + H3PO3
(vi) Reaction with mercuric chloride solution: When mercuric distillation  2HPO + SO
H2SO4 + P2O5  3 3
chloride solution is treated with PH3 gas, a brownish black
precipitate of mercuric phosphide is formed. Uses:
(i) For drying acidic gases
3HgCl2 + 2PH3  Hg3P2(brownish-black) + 6HCl
(ii) As a dehydrating agent
Samples of PH3 can be dried using quick lime, or NaOH sticks.
(iii) For the preparation of SO3 and N2O5
It cannot be dried by conc. H2SO4 because of its reaction
with it. (iv) For the preparation of phosphoric acid
Uses: 5.1.3 Oxy-Acids of Phosphorus
5.1.3.1 Phosphorus Acid (H3PO3):
It is used in making smoke signals and producing smoke
screens in battle-fields. Preparation:
5.1.2 Oxides of Phosphorus (i) By dissolving P2O3 in water:
5.1.2.1 Phosphorus Trioxide (P2O3): P2O3 + 3H2O  2H3PO3
Preparation: It is prepared by burning phosphorus in a limited (ii) By hydrolysis of PCl3 with water:
supply of oxygen when gaseous P4O10 and P4O6 are formed. On
lowering the temperature using a condenser, P4O6 remains in PCl3 + 3H2O  H3PO3 + 3HCl
gaseous form whereas P4O10 condenses as a solid which is stopped The solution containing H3PO3 and HCl is heated to 180oC
by glasswool. On passing the remaining gaseous mixture through and HCl gas is driven out. The resulting solution on
freezing mixture, it converts into colourless crystals of P 4O6. crystallization gives white crystals of H3PO3.
Properties: Properties:
(i) It is colourless crystalline solid having mp 23.8 C and bp
o (i) It is a white crystalline solid, soluble in water and having
178oC. melting point of 74oC.

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

(ii) It is a weak acid and a reducing agent

PCl5 + 4H2O  H3PO4 + 5HCl
(iii) When neutralized with bases or alkalies, it forms neutral salts
called phosphites which are unstable. (iii) By heating white phosphorus with conc. HNO3:

H3PO3 + 3NaOH  Na3PO3 + 3H2O P + 5HNO3  H3PO4 + 5NO2 + H2O
Its basicity is 2 because it has only two replaceable H atoms. Properties:
The third H atom is not replaceable because it is not (i) Pure orthophosphoric acid is a white crystalline solid highly
connected to oxygen. soluble in water having melting point of 42oC. It is a weak

(iv) 4H3PO3  3H3PO4 + PH3 (Disproportionation) acid. It forms two acid salts and one normal salt.NaH2PO4 is
sodium dihydrogen phosphate,Na 2HPO 4 is disodium
(v) H3PO3 + 3PCl5  PCl3 + 3POCl3 + 3HCl hydrogen phosphate & Na3PO4 is sodium orthophosphate.
(vi) It is a strong reducing agent: (ii) Action of heat:
2AgNO3 + H3PO3 + H2O  2Ag + 2HNO3 + H3PO4 220ºC H P O (pyrophosphoric acid)
H3PO4  4 2 7

2HgCl2 + H3PO3 + H2O  Hg2Cl2 + 2HCl + H3PO4 316ºC HPO (metaphosphoric acid)
H4P2O7  3
5.1.3.2 Orthophosphoric Acid (H3PO4):
(iii) Neutralization with alkalies or bases:
Preparation:
NaOH  NaOH 
(i) By heating calcium phosphate with conc. H2SO4 H3PO4  
H O NaH2PO4 (pri. phosphate) H O
2 2
Ca3(PO4)2 + 3H2SO4  2CaSO4 + 2H3PO4 NaOH 

CaSO4 is insoluble. Solution of H3PO4 is separated from NaHPO4 (sec. phosphate) H O Na3PO4
2
CaSO4. It is then concentrated by evaporating it at 180oC (tert. phosphate)
and dehydrated by conc. H 2SO 4 placed in a vacuum
•   NaPO + H O
NaH2PO4 
dessicator cooled by freezing mixture. White crystals of 3 2

H3PO4 are thus formed.

(ii) By hydrolysis of PCl5:

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

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

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

Oxoacids of Phosphorus

6. USES OF GROUP 15 ELEMENTS 7.INTRODUCTION OF GROUP 16 ELEMENTS

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

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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18)
and sulphides such as galena PbS, zinc blende ZnS, copper pyrites
CuFeS2 . Traces of sulphur occur as hydrogen sulphide in
volcanoes.
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.
20
7.4 Electron Gain Enthalpy
Because of the compact nature of oxygen atom, it has less negative
electron gain enthalpy than sulphur.
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.

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 ) I
–1
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

9. CHEMICAL PROPERTIES OF GROUP 16 ELEMENTS
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.
9.1 Reactivity with Hydrogen
All the elements of group 16 form hydrides of the type H2E (E = S,
Se., Te, Po). Some properties of hydrides are given in Table. Their
acidic character increases from H2O to H2Te. The increase in

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p-BLOCK ELEMENTS (GROUP 15 -18) 21

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.

Properties of Hydrides of Group 16 Elements

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

(ii) high electronegativity and
Elements of group 16 form a larger number of halides of the type
(iii) non-availability of d-orbitals.
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 Preparation:
> Br > l. Amongst hexahalides, hexafluorides are the only stable (a) Dioxygen
halides. All hexafluorides are gaseous in nature. They have (i) By thermal decomposition of oxides of metals.
octahedral structure. Shulphur hexafluoride SF\6 is exceptionally 450 C  2 Hg + O
2 HgO 
stable for steric reasons. 2

Amongst terrafluorides, SF4 is a gas , SeF4 liquid and TeF4 a solid 350 C  4 Ag + O
2 Ag2O  2
These fluorides have sp3d hybridisation and thus, have trigonal
bipyramidal structure in which one of the equatorial position is   Mn O + O
3 MnO2  3 4 2
occupied by a lone pair of electrons. This geometry is also regarded   6 PbO + O
2 Pb3O4 
as see - saw geometry. 2

All elements except selenium form dichlorides and dibromides. (ii) By thermal decomposition of oxygen rich compounds.
These dihalides are formed by sp3 hybridisation and thus have   2NaNO + O
2 NaNO3  2 2
tetrahedral structure. The well known monohalides are dimeric in
nature, Examples are S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2. These   2 KCl + 3O (laboratory method)
2 KClO3  2
dimeric halides undergo disproportionation as given below:
  4 K CrO + 2 Cr O + 3O
4 K2Cr2O7 
2Se2Cl2  SeCl4 + 3Se. 2 4 2 3 2

10. GENERAL PROPERTIES AND COMPOUNDS 2 KMnO4    K MnO + MnO + O

2 4 2 2

OF OXYGEN (iii) By the action of conc. H2SO4 on MnO2.

10.1 Dioxygen (O2)
2 MnO2 + 2H2SO4  2 MnSO4 + 2H2O + O2
It differs from the remaining elements of the VIth group because of
(iv) By the action of water on Na2O2.
the following properties.
(i) small size 2 Na2O2 + 2 H2O  4 NaOH + O2

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p-BLOCK ELEMENTS (GROUP 15 -18) 22

(v) By the action of conc. H2SO4 on KMnO4 or K2Cr2O7.

Cr2O3 + 2 NaOH  Na2Cr2O4 + H2O
4 KMnO4 + 6 H2SO4  2 K2SO4 + 4MnSO4 + 6H2O + 5O2
Cr2O3 + 3 H2SO4  Cr2(SO4)3 + 3 H2O
2 K2Cr2O7 + 8H2SO4  2 K2SO4 + 2Cr2(SO4)3 + 8H2O + 10.2.4 Mixed Oxides
3O2
They behave as mixture of two simple oxides, e.g., Pb3O4
(vi) By Brins process:
(2PbO + PbO2), Fe3O4 (FeO + Fe2O3), Mn3O4 (2 MnO + MnO2)
500 C  2BaO
2 BaO + O2(air)  2 10.2.5 Peroxides
They react with dilute acids and form H2O2, e.g., Na2O2, K2O2,
800 C  2 BaO + O
2 BaO2  2 BaO2 etc.
(vii) From air: Oxygen is obtained by liquification of air and then Na2O2 + H2SO4 Na2SO4 + H2O2
its fractional distillation.
They react with water forming O2 .
Properties: Colourless , odourless and tasteless gas. It is para-
magnetic and exhibits allotropy. Three isotopes of oxygen are Na2O2 + H2O 2NaOH + 1/2O2
16 17 18 10.2.6 Dioxides
8O , 8O and 8O . Oxygen does not burn but is a strong
supporter of combustion. Like peroxide, they contain excess of oxygen but do not yield
H2O2 with dil. acids e.g. PbO2, MnO2 etc.
Uses:
They evolve Cl2 with conc. HCl and O2 with conc. H2SO4.
Oxygen mixed with helium or CO2 is used for artificial respiration,
Liquid oxygen is used as oxidising agent in rocket fuels and Oxy- MnO2 + 4HCl MnCl2 + Cl2 + 2H2O;
gen is used for production of oxy-hydrogen or oxy-acetylene
2MnO2 + 2H2SO4 2MnSO4 + O2 + 2H2O
flames employed for cutting and welding.
10.2.7 Super Oxides
10.2 Oxides They contain O2– ion, e.g., KO2 , RbO2 and CsO2. These oxides
10.2.1 Acidic Oxides react with water forming H2O2 and O2
They dissolve in water forming oxyacids , e.g., CO2, SO2 , SO3, 10.2.8 Sub Oxides
N2O5 , N2O3 , P4O6 , P4O10, Cl2O7, CrO3 , Mn2O7 , V2O5.
They contain less oxygen than expected from the normal valency
Cl2O7 + H2O  2 HClO4 of the elements e.g., C3O2, N2O, Pb2O, Hg2O etc.
Mn2O7 + H2O  2 HMnO4
C3O2  O  C
sp
CCO
sp sp

10.2.2 Basic Oxides 10.3 Ozone (O3)

They either dissolve in water to form alkalies or combine with Preparation:It is prepared by passing silent electric discharge
acids to form salts and water or combine with acidic oxides to through pure and dry oxygen
form salts; e.g., Na2O, CaO. CuO, FeO, BaO etc. 3O2 2O3 H = + 142 kJ/mole
Mixture obtained contains 5-10% ozone by volume and this mix-
Na2O + H2O  2 NaOH
ture is called ozonised oxygen. The apparatus used for this is
CaO + H2O  Ca(OH)2 called as ozoniser.
Properties :
CuO + H2SO4  CuSO4 + H2O (i) Pale blue gas which forms a blue liquid on cooling and on
10.2.3 Neutral Oxides solidification forms violet black crystals. It has a strong fish-
They neither combine with acids nor with the bases to form salts like smell and is slightly soluble in water but more in turpen-
e.g., CO, N2O, NO etc. tine oil, glacial acetic acid or CCl4. O3 molecule is diamag-
netic but O3– is paramagnetic.
10.2.4 Amphoteric Oxides
(ii) Oxidising agent :
These can combine with acids as well as bases e.g., ZnO, Al2O3,
BeO, Sb2O3, Cr2O3, PbO etc. O3 + 2H+ + 2e-  O2 + H2O ; SRP = + 2.07 v
(In acidic medium)
PbO + 2 NaOH  Na2 PbO2 + H2O
O3 + H2O + 2e-  O2 + 2OH– ; SRP = + 1.24 v
PbO + H2SO4  PbSO4 + H2O
(In alkaline medium)

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p-BLOCK ELEMENTS (GROUP 15 -18) 23

Therefore, ozone is a strong oxidising agent in acidic me- (ii) Tailing of mercury
dium. Pure mercury is a mobile liquid but when brought in contact
(a) It oxidises – to I2 (from neutral solution of K) with O3 its mobility decreases and it starts sticking to glass
surface forming a type of tail due to the dissolution of Hg2O
O3  O2   O
(mercury sub-oxide) in Hg.
2Kl  H 2 O   O   2KOH  l 2 2 Hg + O3  Hg2O + O2
2Kl  H 2 O   2KOH  O 2  l2 Uses:
• Alkaline K is oxidised to potassium iodate & periodate. (i) As a germicide and disinfectant for sterilising water and im-
K + 3O3  KO3 + 3O2 proving the atmosphere of crowded places.
(ii) For detecting the position of double bond in the unsatur-
K + 4O3  KO4 + 4O2 ated organic compounds.
(b) It oxidises moist S, P, As into their oxy acids.
(iii) In mfg. of artificial silk, synthetic camphor, KMnO4 etc.
O3  O2 + [O] × 3 11. GENERAL PROPERTIES AND COMPOUNDS
S + 3 [O]  SO3 OF SULPHUR
Sulphur Allotropic Froms: Sulphur forms numerous allotropes
SO3  H 2 O  H 2SO 4
of which the yellow rhombic ( - sulphur) and monoclinic ( -
S  3O3  H 2 O  H 2SO 4  3O 2 sulphur) forms are the most important. The stable forms at room
(c) It oxidises H2S to S temperature is rhombic sulphur, which transfroms to monoclinic
sulphur when heated above 369 K.
H2S + O3  H2O + S  (yellow) Rhombic Sulphur (- sulphur): This allotrope is yellow in colour
(iii) Reaction with Silver: , m.p. 385.8 K and specific gravity 2.06. Rhombic sulphur crystals
Silver articles become black in contact with ozone. are formed on evaporating the solution of roll sulphur in CS2. It is
insoluble in water but dissolved to some extent in benzene, alcohol
Ag + O3  Ag2O  (black) + O2 and ether. It is readily soluble in CS2 .
(iv) Reaction with H2O2 : 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
O3  H 2 O 2  2O 2  H 2 O by melting rhombic sulphur in a dish and cooling till crust is
Oxidising Reducing formed. Two holes are made in the crust and the remaining liquid
agent agent
poured out. On removing the crust, colourless needle shaped
It is supported by the fact that SRP of ozone is higher (+2.07) crystals of  - sulphur are formed. It is stable above 369 K and
than SRP of hydrogen peroxide (+1.77). Therefore , ozone is transforms into  - sulphur below it . Conversely, - sulphur is
stronger oxidising agent than hydrogen peroxide. stable below 369 K and transfroms into  - sulphur above this. At
(v) Bleaching Action: 369 K both the forms are stable. This temperature is called transition
O3 also bleaches coloured substances through oxidation temperature.
(vi) Ozonolysis: Both rhombic and monoclinic sulphur have S8 molecules these S8
Alkenes, alkynes react with ozone forming ozonides. molecules are packed to give different crystal structures. The S8
ring in both the forms is puckered and has a crown shape. The
Zn  H O molecular dimensions are given in figure.
CH2 = CH2 + O3   2 2HCHO
 ZnO
Tests for Ozone
(i) A filter paper soaked in a alcoholic benzidine

becomes brown when brought in contact with O3 (this is not

shown by H2O2)

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p-BLOCK ELEMENTS (GROUP 15 -18) 24
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
(a) S8 ring in rhombic sulphur and (b) S6 form 3 Cu2S2O3 + 2 Na2S2O3  Na4 [Cu6(S2O3)5]
Uses:
Several other modifications of sulphur containing 6-20 sulphur
(i) As an ‘antichlor’ to remove excess of chlorine from
atoms per ring have been synthesised in the last two decades. In
bleached fabrics.
cyclo- S6, the ring adopts the chair form and the moleculatr
(ii) In photography as fixer.
dimension are as shown in fig. (b) At elevated temperatures
(iii) As a reagent in iodometric and iodiometric titrations.
(~ 1000 K ), S2 is the dominant species and is paramagnetic like O2.
11.1.2 Hydrogen Sulphide (H2S)
11.1 Compounds of Sulphur
Preparation:
11.1.1 Sodium Thiosulphate (Na2S2O3 .5H2O)
Preparation: (i) FeS + H2SO4  FeSO4 + H2S
It is prepared in kipp’s apparatus
boiled (ii) Preparation of pure H2S gas
(i) Na2SO3 + S in absence of air Na2S2O3
Sb2S3 (pure) + 6 HCl (pure)  2 SbCl3 + 3 H2S
(ii) Na2CO3 + 2SO2 (excess) + H2O  2NaHSO3 + CO2 Properties:
2NaHSO3 + Na2CO3  2Na2S2O3 + H2O + CO2 (i) Colourless gas with rotten egg smell
(iii) Na2S + Na2SO3 + I2  Na2S2O3 + 2 NaI (ii) Moderately soluble in water but solubility decreases with
Properties: increasing temperature.
(i) It is a colourless crystalline substance soluble in water which (iii) Reducing Agent:
loses water of crystallisation on strong heating Acts as a strong reducing agent as it decomposes evolv-
(ii) As antichlor: It removes the chlorine from the surface of ing hydrogen.
fibres (while dyeing) according to following reaction. (a) H2S + X2  2 HX + S
Na2S2O3 + Cl2 + H2O  Na2SO4 + 2HCl + S (b) moisture  H O + S
H2S + SO2  2
Therefore, it is known as antichlor
(c) It also reduces KMnO4  Mn2+
(iii) Reaction with HCl :
H2SO4  SO2 & K2Cr2O7  Cr3+
Na2S2O3 + HCl  2NaCl + SO2 + S + H2O (iv) Acidic Nature: Its aquesous solution acts as a weak
This test is used for distinction between S2O32- and SO32- dibasic acid according to following reaction
ions as SO32- ions give only SO2 with HCl.
H 2S HS + H+ S2- + 2H+
(iv) Complex formation reactions :
Therefore, It forms two series of salts as given below
(a) Reaction with silver salts (AgNO3 , AgCl, AgBr or AgI):
NaOH + H2S  NaHS + H2O
Na2S2O3 + 2AgNO3  Ag2S2O3  (white) + 2 NaNO3 NaOH + NaHS  Na2S + 2H2O

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p-BLOCK ELEMENTS (GROUP 15 -18) 25
(v) Formation of Polysulphides: They are obtained by (vi) Reducing Nature :
passing H2S gas through metal hydroxides. H2O + SO2  H2SO3
Ca(OH)2 + H2S  CaS + 2H2O H2SO3 + H2O  H2SO4 + 2H
CaS + 4 H2S  CaS5 + 4H2 Reducing character is due to the liberation of nascent hy-
Tests for H2S: drogen
(i) Turns acidified lead acetate paper black (a) Reduces halogens to corresponding halides
(ii) Gives violet or purple colouration with sodium nitropruside SO2 + 2H2O  H2SO4 + 2H
solution. 2H + Cl2  2HCl
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 agent.
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) &
(i) Burn
S + O2 or air   SO2 Ferric Sulphate  Ferrous sulphate
  3SO + 2H O (vii) Oxidising nature: Acts as oxidising agent with strong
(ii) S + 2H2SO4 (conc.)  2 2 reducing agent
(iii) By heating Cu or Ag with conc. H2SO4
moisture  2H O + 3S
(a) 2H2S + SO2 
Cu + H2SO4  CuSO4 + 2H2O + SO2 2

(iv) By reaction of metal sulphites with dil.HCl (b) 2SnCl2 + SO2 + 4HCl  2SnCl4 + 2H2O + S
Na2SO3 + 2HCl  2NaCl + SO2 + H2O (c) 2Hg2Cl2 + SO2 + 4HCl  2HgCl2 + 2H2O + S
Similarly bisulphites also give SO2 with dil. HCl (d) 2CO + SO2  2CO2 + S
NaHSO3 + HCl  NaCl + SO2 + H2O (e) 2 Fe + SO2  2FeO + FeS
(v) By heating sulphides in excess of air (viii) Bleaching Action:
2 ZnS + 3O2  2ZnO + 2SO2 SO2 + 2H2O  H2SO4 + 2H
 This is due to the reducing nature of SO2
(vi) CaSO4 (gypsum) + C 
1000C 2 CaO + SO2 + CO2 
Coloured matter + H   colourless matter..
Air oxidation
By this method SO2 is obtained in large scale
Properties: Therefore, bleaching is temporary
(i) Colourless gas with burning sulphur smell. Uses:
(ii) It is heavier than air and is highly soluble in water (i) Used in manufacture of H2SO4 & paper from wood pulp.
(iii) Neither burns nor helps in burning but burning magnesium (ii) As a bleaching agent for delicate articles like wool, silk and
and potassium continue to burn in its atmosphere. straw.
3Mg + SO2  2 MgO + MgS (iii) Used in refining of petroleum and sugar.
4K + 3SO2  K2SO3 + K2S2O3 11.1.4 Sulphur Trioxide (SO3)
(iv) Acidic Nature : Acidic oxide and thus dissolve in water form- Preparation:
ing sulphurous acid. (i) 6H2SO4 + P4O10  6SO3 + 4H3PO4
SO2 + H2O  H2SO3 P4O10 is dehydrating agent
(v) Addition Reaction:
  Fe O + 3SO
(ii) Fe2(SO4)3  2 3 3
Sun light SO Cl (sulphuryl chloride)
SO2 + Cl2   2 2
pt
 2SO
(iii) 2SO2 + O2 
platinised 3
 SO
SO2 + O2  Properties:
Asbests 3

(i) Acidic Nature: Dissolves in water forming sulphuric acid

PbO2 + SO2  PbSO4
SO3 + H2O  H2SO4

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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18) 26
(ii) H2SO4 + SO3  H2S2O7 (oleum) NaHSO4 + NaOH  Na2SO4 (sodium sulphate) + H2O
(iii) SO3 + HCl  SO2(OH) Cl (chlorosulphuric acid) (b) Decomposes carbonates and bicarbonates into carbon
(iv) Oxidising Nature : dioxide
Na2CO3 + H2SO4  Na2SO4 + H2O + CO2
100C
(a) 2SO3 + S  3SO2 NaHCO3 + H2SO4  NaHSO4 + H2O + CO2
(b) 5SO3 + 2P  5SO2 + P2O5 (c) Displaces more volatile acids from their metal salts.
(c) SO3 + PCl5  POCl3 + SO2 + Cl2 2NaCl + H2SO4  Na2SO4 + HCl
(d) SO3 + 2HBr  H2O + Br2 + SO2 2NaNO3 + H2SO4  Na2SO4 + 2HNO3
Uses: CaF2 + H2SO4  CaSO4 + 2HF
(i) Used in manufacture of H2SO4 and oleum. (v) Oxidising Nature: H2SO4 acts as a strong oxidising agent
(ii) Used as a drying agent for gases.
H2SO4  H2O + SO2 + [O]
11.1.5 Sulphuric Acid (H2SO4) (a) Non-metals (carbon, sulphur etc) are oxidised to their oxides.
Preparation: H2SO4  H2O + SO2 + O] × 2
(i) 2FeSO4 . 7H2O  dist. Fe O + H SO + SO + 13H O C + 2[O]  CO2
2 3 2 4 2 2

(ii) Lead Chamber Process (Industrial method) : ––––––––––––––––––––––––––––––––––––

2SO2 + O2 (air) + 2H2O + [NO] (catalyst)  2H2SO4 + C + 2H2SO4  CO2 + 2SO2 + 2H2O
[NO] (catalyst) ––––––––––––––––––––––––––––––––––––
Acid obtained is 80% pure and is known as brown oil of 2P + 5H2SO4  2H3PO4 + 5SO2 + 2H2O
vitriol (b) Metals (copper, silver, mercury etc.) are oxidised to their
(iii) Contact process (Industrial method) : oxides which then combine with acid to form corresponding
sulphates.
catalyst
 2SO3
O2 + 2SO2  H2SO4  H2O + SO2 + [O]
The commonly used catalysts are platinum, ferric oxide or Cu + [O]  CuO
vanadium pentoxide. V2O5 is preferred as it is cheaper and is CuO + H2SO4  CuSO4 + H2O
not poisoned by impurities –––––––––––––––––––––––––––––––––
H2SO4 (58%) + SO3  H2S2O7 (oleum) Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
Sulphuric acid of any desired concentration can be obtained (c) Iodine is liberated from KI
from oleum by dilution with water.
2 KI + H2SO4  K2SO4 + 2HI
H2S2O7 + H2O  2H2SO4
H2SO4  H2O + SO2 + [O]
Oxidation of sulphur dioxide is reversible and exothermic.
According to Le-chatelier principle, the favourable condi- 2 HI + [O]  I2 + H2O
tions for the greater yield of sulphur trioxide are. –––––––––––––––––––––––––––––––––––––
(a) An excess of air- SO2 and oxygen are taken in 2:3 molecular 2 KI + 2H2SO4  K2SO4 + SO2 + I2 + 2H2O
proportion Here HI is oxidised to I2. Similarly bromine is liberated from
(b) Low tempt-optimum tempt. 450°C KBr
(c) Higher pressure-one atmosphere (vi) Dehydrating agent: Sulphuric acid acts as a powerful
Properties : dehydrating agent because it has a great affinity for water
(i) A colourless syrupy liquid (it is H-bonded) H SO
2 4
(ii) It fumes strongly in moist air and is highly corrosive in (a) C12H22O11 (cane sugar)    
–11H O 12C
nature. 2

440C H O + SO

(iii) Thermal decomposition : H2SO4  COOH H SO
 2 3 (b) | 2 4
 CO + CO2 + H2O
COOH 
(iv) Acidic Nature: It is a strong dibasic acid and ionises as
H2SO4 H+ + HSO4– 2H+ + SO42–
(a) Forms two series of salts
NaOH + H2SO4  NaHSO4 (sodium bisulphate) + H2O

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p-BLOCK ELEMENTS (GROUP 15 -18) 27
(vii) Miscellaneous reactions:
(a) Sulphonation of aromatic compounds 13. INTRODUCTION OF GROUP 17 ELEMENTS:
THE HALOGEN FAMILY
Fluorine, chlorine, bromine, iodine and astatine are members of
Group 17. These are collectively known as the halogens (Greek
halo means salt and genes born i.e., salt producers). The halogens
are highly reactive non-metallic elements.
Benzene Benzene sulphonic acid
(b) Reaction with PCl5:
13.1 Electronic Configuration
All these elements have seven electrons in their outermost shell
(ns2 np5) which is one electron short of the next noble gas.
+ POCl3 + HCl 13.2 Atomic and Ionic Radii
The halogens have the smallest atomic radii in their respective
Chlorosulphonic acid periods due to maximum effective nuclear charge . Atomic and
ionic radii increase from fluorine to iodine due to increasing number
of quantum shells.
+ 2 POCl3 + 2HCl 13.3 Ionisation Enthalpy
They have little tendency to lose electron. Thus they have very
high ionisation enthalpy. Due to increase in atomic size, ionisation
Sulphury chloride
enthalpy decreases down the group.
(c) K4[Fe(CN)6] + 6H2SO4 + 6H2O  2K2SO4 + FeSO4 + 13.4 Electron Gain Enthalpy
3(NH4)2SO4 + 6CO
Halogen have maximum negative electrons gain enthalpy in the
(d) 3KClO3 + 3H2SO4   3 KHSO4 + HClO4 + 2ClO2 + H2O corresponding period. This is due to the fact that the atoms of
(e) H2SO4 + P2O5  2HPO3 + SO3 these elements have only one electron less than stable noble gas
Uses : configurations. Electron gain enthalpy of the elements of the group
(i) For the manufacture of fertilizer such as ammonium sulphate becomes less negative down the group. However, the negative
and super phosphate of lime. electron gain enthalpy of fluorine is less than that of chlorine. It is
(ii) As an important laboratory reagent. due to small size of fluorine atom. As a result, there are strong
(iii) In storage batteries. interelectronic repulsions in the relatively small 2p orbitals of
(iv) In leather, textile, paper and dyeing industries. fluorine and thus, the incoming electron does not experience much
attraction.
12. USES OF GROUP 16 ELEMENTS 13.5 Electronegativity
Sulphur dioxide is used (i) in refining petroleum ans sugar (ii) in They have very high electronegativity. The electronegativity
bleaching wool and silk and (iii) as an anti-chlor, disinfectant and decreases down the group. Fluorine is the most electronegative
preservative. Sulphuric acid, sodium hydrogen sulphite and element in the periodic table.
calcium hydrogen sulphite (industrial chemicals) are manufactured
from sulphur dioxide. Liquid SO2 is used as a solvent to dissolve
a number of organic and inorganic chemicals.

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p-BLOCK ELEMENTS (GROUP 15 -18) 28

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]2s 2p 2 5
[Ne]3s 3p 2 5
[Ar]3d 4s 4p
10 2 5
[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
Electron gain 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

exhibits only – 1 oxidation state.

14. PHYSICAL PROPERTIES OF GROUP 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 dissociation 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.
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
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 ()
+

15. CHEMICAL PROPERTIES OF GROUP 17 ELEMENTS Standard Reduction Potential (SRP)

Oxidation states and trends in chemical reactivity: All the halo-
gens exhibit –1 oxidation state. However, chlorine, bromine and X2 + 2e–  2X–
iodine exhibit + 1, + 3, + 5 and + 7 oxidation states also. The higher
F2 + 2e–  2F– ° = + 2.87 V ;
oxidation states of chlorine, bromine and iodine are realised mainly
when the halogens are in combination with the small and highly Cl2 + 2e–  2Cl– ° = + 1.36 V
electronegative fluorine and oxygen atoms e.g., in interhalogens,
oxides and oxoacids. Br2 + 2e –  2Br – ° = + 1.09 V;;
The fluorine atom has no d orbitals in its valence shell and there-
fore cannot expand its octet. Being the most electronegative, it

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2 + 2e–  2– ° = + 0.54 V ones.

 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.
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
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 decom-
pose 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.
16. GENERAL PROPERTIES AND COMPOUNDS OF
HALOGENS
16.1 Fluorine (F2)
Preparation
(i) Electrolytic method: Electrolyte : Molten KHF2 (1 part) + HF
(5 part)
Anode : Carbon
Cathode : Steel
Vessel : Metal
On Electrolysis
Cathode : 2H+ + 2e–  H2(g)
Anode : 2F–  F2 + 2e–
The F2 gas thus evolved must be free from HF which is more
corrosive than fluorine.
In order to make flourine free from HF, the gas is passed
through NaF which absorbs HF.
 Anode of carbon should be free from graphite because F2
reacts with graphite easily to form a polymeric substance
known as graphite fluoride.
There should be no moisture present in the vessel otherwise
fluorine will react with water.
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,

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p-BLOCK ELEMENTS (GROUP 15 -18) 30
H2O  1/2O2 + 2H+ + 2e– SOP = – 1.23 v (ix) Reaction with H2 :
and H2 + F2  2 HF or H2 F2
– 
F 1/2F2 + e –
SOP = – 2.87v
This reactions occurs even in dark
As a matter of rule that substance will be oxidise whose SOP
is higher therefore water gets oxidise at anode and not F–. 16.2 Chlorine (Cl2)
Properties: Preparation:
(i) Diatomic, Pale green-yellow gas which appears to be almost (i) Common Method (Cl2 , Br2 , 2) :
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, )
(ii) Only for Cl2 :
(a) It can oxidise all other halide ions into halogen molecules
(a) NaCl + HNO3  NaNO3 + HCl × 3
5 7
(b) It can oxidise Cl O 3 into Cl O 4 and IO3– to IO4–
HNO3 + 3HCl  NOCl + Cl2 + 2H2O
F2 + ClO + H2O  2F + ClO4 + 2H
3
– – – +
––––––––––––––––––––––––––––––––––––
(iii) Reaction with NaOH Solution : With dilute alkali forms
3NaCl + 4 HNO3  3 NaNO3 + NOCl (nitrosyl chloride)
oxygen difluoride and with concentrated alkali O2.
2F2 + 2 NaOH (dil)  OF2 (g) + 2 NaF + H2O 2NOCl + O2  2NO2 + Cl2 ;

2F2 + 4 NaOH (conc.)  O2 (g) + 4 NaF + 2H2O NO2 + H2O  HNO3 (to be recycled)

(iv) Reaction with NH3 : (Distinction from other halogens) (b) When Cl2 is used for the chlorination of hydrocarbon the
byproduct is HCl. The HCl is catalytically oxidised into H2O
2NH3 + 3F2  N2 + 6 HF & Cl2 using copper powder mixed with rare earth chlorides.
Other halogens form explosive NX3. with conc. NH3 (liquor Cu powder  rare earth
ammonia) 4 HCl + O2 
Chloride
 2H O + 2Cl
2 2

(v) Reaction with H2S :

OCl
H2S + F2  SF6 + 2 HF (c) Ca / + 2HCl  CaCl2 + Cl2 + H2O
\
Cl
(vi) Reaction with SiO2 : It attacks glass at about 100 C. 0

(iii) Manufacture of Chlorine :

SiO2 (s) + 2F2 (g)  SiF4 (g) + O2 (g)
(a) Deacon’s Process: By oxidation of hydrogen chloride gas
The reaction is slow with dry F2 . by atmospheric oxygen in the presence of CuCl2 (catalyst)
(vii) Reaction with H2O : at 723 K.

2H2O + 2F2  4 HF + O2 CuCl

4 HCl + O2  2  2 Cl2 + 2 H2O
sometime a little amount of O3 also forms
(b) Electrolytic Process : Chlorine is obtained by the electrolysis
3H2O + 3F2  6HF + O3 of brine (concentrated NaCl solution). Chlorine is liberated
(viii) Reaction with Xe: at anode. It is also obtained as a by–product in many
chemical industries.
NaX (aq)  Na+ (aq) + X– (aq)

Anode : 2X–  X2 + 2e–

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p-BLOCK ELEMENTS (GROUP 15 -18) 31
Properties: SO32– + Coloured material  SO42– + Reduced coloured
(i) It is a greenish–yellow gas with pungent and suffocating
material (colourless)
odour. It is about 2–5 times heavier than air. It can be liquefied
into greenish–yellow liquid which boils at 239 K. It is soluble O of air
Reduced Coloured material (colourless) 
2 
in water.
Coloured material
(ii) At low temperature it forms a hydrate with water having
formula Cl2 . 8H2O which is infact a clathrate compound. (vii) Reaction with NaOH:
Common to Br2 , 2 & Cl2 (but with F2 it is different, OF2 or O2
(iii) H2 + Cl2 
(a zero order reaction) 2HCl (g) , is obtained)
(a) 2 NaOH (cold & dilute) + Cl2  NaCl + NaClO + H2O
[H2 + Br2  2HBr is not a zero order reaction]
(b) 6 NaOH (hot & concentrated) + 3 Cl2  5 NaCl +
(iv) Reaction with NH3 (common for Cl2 & Br2) :
NaClO3 + 3 H2O
(a) 8 NH3 + 3 Cl2  N2 + 6 NH4 Cl (viii) Reaction with Hypo Solution:
(b) NH3 + 3Cl2  NCl3 + 3 HCl This reaction is common with Cl2 & Br2 but with 2 it is
different.
(excess)
(v) Reaction with Alkali Metal Halides (KX) :  0
Na 2S2 O3  H 2 O  Cl2  Na 2SO 4  2HCl   S
2 KBr + Cl2  2KCl + Br2  colloidal 
 
 

2K + Cl2  2 KCl + 2 In this reaction thiosulphate ions undergo

 Cl2 can oxidise both Br &  but Br2 can oxidise  only.
– – – disproportionation into SO42– and S. Cl2 is reduced to Cl– .
 F2 is not used in aqueous reaction since it itself reacts with
water.
(vi) Oxidising & Bleaching Properties: Chlorine water on
standing loses its yellow colour due to the formation of HCl
and HOCl. Hypochlorous acid (HOCl) so formed, gives
nascent oxygen which is responsible for oxidising and
bleaching properties of chlorine.
(a) It oxidises ferrous to ferric, sulphite to sulphate, sulphur
dioxide to sulphuric acid and iodine to iodic acid.
2 FeSO4 + H2SO4 + Cl2  Fe2(SO4)3 + 2 HCl
Na2SO3 + Cl2 + H2O  Na2SO4 + 2 HCl
SO2 + 2 H2O + Cl2  H2SO4 + 2 HCl
I2 + 6 H2O + 5 Cl2  2 HIO3 + 10 HCl
(b) It is a powerful bleaching agent ; Bleaching action is due to
oxidation.
Cl2 + H2O  2 HCl + O
Coloured substance + O  Colourless substance
It bleaches vegetable or organic matter in the presence of
moisture. Bleaching effect of chloride is permanent.
 But the bleaching action of SO2 is temporary because it takes
place through reduction.
SO2 + 2 H2O  H2 SO4 + 2 H
(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
(v) preparation of poisonous gases such as phosgene (COCl2),
tear gas (CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl).

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p-BLOCK ELEMENTS (GROUP 15 -18) 32

16.3 Bromine (Br2) KF3 cannot be formed similarly since F does not have ‘d’ orbitals. So
Preparation: sp3d hybridisation is not possible with F.
(i) Common Method: (ii) It is soluble in organic solvents like CHCl3, CCl4 etc. to get
violet solutions.
 Br + MnSO +
2 NaBr + 3H2SO4 (conc.) + MnO2  2 4 (iii) Reaction with Hypo: iodometric titrations
2NaHSO4 + 2H2O 2.5

(ii) From Sea-Water: NaCl is main component but NaBr is also S2 O32– (thiosulphate ions) + 2  S4 O 62 
present in some quantity in sea water. Cl2 gas is passed (tetrathionate ions) + 2–
through sea water when vapours of bromine are evolved. This reaction is the basis of iodometric (direct 2 titration)
2 Br (aq) + Cl2  2Cl (aq.) + Br2
– – titration, which is carried out for the estimation of iodine
using starch indicator.
Properties:
(iv) Reaction with KClO3 or KBrO3:
(i) Reddish brown liquid, fairly soluble in water. It also forms
hydrate like Cl2 
2 KClO3 + 2  2 KIO3 + Cl2
(Br2 . 8H2O)  Clathrate compound  2KIO + Br
2 KBrO3 + 2  3 2
(ii) Rest reactions are same as with Cl2 (v) Reaction with Ozone (dry) :
16.4 Iodine (I2) 22 (s) + 3O3 (g)  4O9 (s)
Preparation:
4O9 is an ionic compound consisting of 3+ & O3–)3 indicative
(i) Common Method : of metallic character of  (low .E, low E.N.)

2Na + 3H2SO4 (conc.) + MnO2  2 + MnSO4 + With NaOH there is common reaction as with Cl2 and Br2 . With H2
there is reversible reaction.
2NaHSO4 + 2H2O
16.5 Hydra Acids (Halogen Acids)
(ii) From Caliche or Crude Chile Salt Petre : The main source
of iodine is NaO3 (sodium iodate) which is found in nature HCl, HBr & HI :
with NaNO3 (chile saltpetre). NaO3 is present in small amount. Preparation:
After crystallisation of NaNO3 , the mother liquor left contains (i) By direct combination of elements:
NaO3 (soluble). To this solution NaHSO3 is added where
H2 + Cl2  2HCl
upon 2 is precipitated.
Pt 2HBr
H2 + Br2 
(iii) From Sea-Weeds : Sea-weeds are dried and burnt in shallow
pits, ash left is called kelp. Ash on extraction with hot water Pt , 450 C 2H
H2 + 2  
dissolves out chlorides, carbonates, sulphates and iodides
of sodium and potassium. The solution on concentration (ii) By heating a halide with acid :
seperates out all leaving behind iodide in the solution. NaCl + H2SO4  NaHSO4 + HCl
Solution is mixed with MnO2 and concentrated H2SO4 in iron
retorts. Liberated iodine is condensed in series of earthen- NaHSO4 + NaCl  Na2SO4 + HCl
ware known as aludels.
For HCl we use H2SO4 as an acid, while for HBr and H we
2Na+ MnO2 + 3H2SO4 2NaHSO4 + MnSO4 + 2 + 2H2O use H3PO4.
(iv) 2K+ Cl2  2KCl + 2 (a) HCl cannot be dried over P2O5 (P4O10) or quick lime since
(v) 2K+ H2O2  2KOH + 2 they react with gas chemically.
(vi) CuSO4 + 2K  K2SO4 + Cu2 ; CaO + 2HCl  CaCl2 + H2O
This 2 gets dissolved into K forming 3 , since 3– ions are yellow,
therefore solution develops yellow colour. P4O10 + 3HCl  POCl3 + 3HPO3
Properties : HCl is, hence dried by passing through conc. H2SO4 .
(i) It is a dark violet solid, undergoes sublimation, least soluble (b) HBr (or H) cannot be prepared by heating bromide (iodide)
(among halogens) in water but much more soluble in K(aq.) with conc. H2SO4 because HBr and H are strong reducing
due to formation of K3 agents and reduce H2SO4 to SO2 and get themselves oxidised

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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18) 33
to bromine and iodine respectively.
(vii) Reducing Property and Stability of Hydracids:
KX + H2SO4  KHSO4 + HX HCl: It is quite stable and hence is oxidised by strong
oxidising agents like MnO2, KMnO4, K2Cr2O7, PbO2, Pb3O4.
H2SO4 + 2HX  SO2 + X2 + 2H2O (X = Br or )
(i) MnO2 + 4HCl  MnCl2 + 2H2O + Cl2
Hence, HBr and H are prepared by heating bromides and
iodides respectively with conc. H3PO4 . (ii) 2KMnO4 + 16HCl  2KCl + 2MnCl2 + 8H2O + 5Cl2
3KBr(K) + H3PO4  K3PO4 + 3HBr (H)
(iii) K2Cr2O7 + 14HCl  2KCl + 2CrCl3 + 7H2O + 3Cl2
Properties:
(iv) PbO2 + 4HCl  PbCl2 + 2H2O + Cl2 ;
(i) These are colourless, pungent smelling gases with acidic
tastes. (v) Pb3 O4 + 8HCl  3PbCl2 + 4H2O + Cl2
(ii) It is heavier than air, can be liquified to colourless liquids.
Therefore, HCl is a weak reducing agent.
(iii) These are neither combustible nor supporter of combustion.
HBr : It is not very stable and hence more easily oxidised or
(iv) When perfectly dry, they have no action on litmus, but in
acts as a strong reducing agents. In addition to above
presence of moisture, they turn blue litmus red, showing
reducing properties of HCl, it also reduces H2SO4 to SO2
acidic nature. Among HX, H is the strongest and HF is the
which is not done by HCl.
weakest acid.
(v) These are quite soluble in water. H2SO4 + HBr  SO2 + Br2 + 2H2O
HCl ionises as below. Aqueous HBr on exposure to atmospheric oxygen is oxidised
HCl(g) + H2O ()  H3O (aq) + Cl (aq) Ka = 10
+ – 7 to bromine (yellow)
It aqueous solution is called hydrochloric acid. High value 4HBr + O2  2 Br2 + 2H2O
of dissociation constant (Ka) indicates that it is a strong acid
H : It is least stable hydrogen halide. It is readily oxidised
in water.
and thus acts as a powerful reducing agent.
When three parts of concentrated HCl and one part of
In addition to reaction shown by HCl, it shows following
concentrated HNO3 are mixed, aqua regia is formed which is
reactions also.
used for dissolving noble metals, e.g., gold, platinum.
(a) H2SO4 + 2H  SO2 + 2 + H2O ;
Au + 4 H+ + NO3– + 4 Cl–  AuCl4– + NO + 2 H2O
H2SO4 + 6H  S + 32 + 4H2O;
3 Pt + 16 H+ + 4 NO3– + 18 Cl–  3 PtCl62– + 4 NO + 8 H2O
H2SO4 + 8H  H2S + 42 + 4H2O ;
(v) Reaction with metals oxides, hydroxides and bicarbonates
(b) 2HNO3 + 2H  2NO2 + 2 + 2H2O
Zn + 2HCl  ZnCl2 + H2 (c) 2HNO2 + 2H  2NO + 2 + 2H2O
(d) HO3 + 5H  32 + 2H2O
MgO + 2HCl  MgCl2 + H2O
(e) K2S2O8 + 2H  K2SO4 + 2 + H2SO4
NaOH + HCl  NaCl + H2O (f) 2FeCl3 + 2H  2FeCl2 + 2 + 2HCl
(g) Aqueous solution of acid, if exposed to O2 is oxidised to
CaCO3 + 2HCl  CaCl2 + H2O + CO2
iodine.
(vi) Reaction with salts, HCl decomposes salts of weaker acids.
4H + O2  22 + 2H2O
NaHCO3 + HCl  NaCl + CO2 + H2O
(viii) Reaction with Ammonia:
Na2S + 2HCl  2NaCl + H2S
NH3 + HX  NH4X (white fumes) (where X = Cl, Br, )
Na2SO3 + 2HCl  2NaCl + SO2 + H2O (ix) Action of Halogens:
Na2S2O3 + HCl  2NaCl + SO2 + H2O + S (a) Cl2 is liberated from HCl by F2 alone.
F2 + HCl  2HF + Cl2
2NaNO2 + 2HCl  2NaCl + NO + NO2 + H2O
(b) Br2 is liberated from HBr by F2 and Cl2 (not by 2)

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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18)
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.
 16.7.2 Chlorous Acid [HClO2]
KHF2  KF + HF
(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:
34
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
due to release of nascent oxygen easily.
HClO  HCl + O
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.
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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18) 35

5 HClO2  4 ClO2 + HCl + 2H2O to the presence of impurities.

(ii) On long standing, it undergoes auto–oxidation into calcium
(ii) The acid undergoes auto-oxidation.
chlorate and calcium chloride.
2HClO2  HClO + HClO3 6 CaOCl2  Ca(CIO3)2 + 5 CaCl2
(iii) The acid liberates iodine from K CoCl
(iii) 2 CaOCl2  2  2 CaCl + O
4K + HClO2 + 2H2O  4KOH + HCl + 22
2 2

(iv) In presence of a little amount of a dilute acid, it loses oxygen.

16.7.3 Chloric Acid [HClO3]
Preparation: This acid is only known in solution. 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 H2SO4. The insoluble
barium sulphate is removed by filtration.
Ba(CIO4)2 + H2SO4  BaSO4  + 2HClO4
2 CaOCl2 + H2SO4  CaCl2 + CaSO4 + 2 HClO
HClO  HCl + O
On account of the liberation of nascent oxygen, it shows
oxidising and bleaching properties.
(a) Oxidising properties
CaOCl2 + H2S  CaCl2 + H2O + S
CaOCl2 + 2 KI + 2 HCl  CaCl2 + 2 KCl + H2O + I2
3 CaOCl2 + 2 NH3  3 CaCl2 + 3 H2O + N2
It oxidises NO2– to NO3– , AsO33– to AsO43– and Fe2+ to Fe3+
(in acidic medium)
(b) Bleaching action
Coloured matter + [O]  colourless product.
(v) When bleaching powder reacts with dilute acids or CO2 it
liberates chlorine which is known as available chlorine.

Properties: CaOCl2 + 2 HCl  CaCl2 + H2O + Cl2

(i) Anhydrous HClO4 is a colourless liquid which turns dark on
keeping. It fumes in moist air. CaOCl2 + H2SO4  CaSO4 + H2O + Cl2
(ii) It is one of the strongest acid and ionises as follows : CaOCl2 + CO2  CaCO3 + Cl2
HClO4  H+ + ClO4–  HNO3 is a strong oxidising acid to be avoided, here.
(iii) It dissolves most of the metals.
Some Important order
Zn + 2HClO4  Zn(ClO4)2 + H2 (a) Acid strength:
(iv) It is an oxidising agent and explodes in contact with organic
matter. (i) H > HBr > HCl > HF
(v) 2HClO4 + P2O5  2HPO3 + Cl2O7 (ii) HOCl > HOBr > HO
(iii) HClO4 > HClO3 >HClO2 > HClO
16.8 Bleaching Powder (CaOCl2.H2O)
(b) Oxidising power :
Bleaching powder is also called calcium chlorohypochlorite
because it is considered as a mixed salt of hydrochloric acid and (i) F2 > Cl2 > Br2 > 2 (According to electrode potential)
hypochlorous acid. (ii) BrO4– > IO4– > ClO4–
Ca(OCl)Cl (iii) HClO4 < HClO3 < HClO2  HClO
Preparation: (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

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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18) 36

17. INTERHALOGEN COMPOUNDS intensity of colour increases with increase in the molecular
We know that halogen atoms have different electronegativity. weight of the compounds.
Due to this difference in electronegativity the halogen atoms (iii) All interhalogens are covalent molecules and are diamagnetic
combine with each other and give rise to the formation of binary in nature since all the valence electrons present as bonding
covalent compounds, which are called interhalogen or non-bonding electrons are paired.
compounds.These are of four types. (iv) The boiling points increases with the increase in the
AB AB3 AB5 AB7 electronegativity difference between A and B atoms.
ClF ClF3 ClF5 lF7 (v) Thermal stability of AB type interhalogen compounds
BrF BrF3 BrF5 decreases with the decrease in electronegativity difference
between A and B atoms. IF > BrF > ClF > ICl > IBr > BrCl.
ICl ICl3 IF5
More polar is the A – B bond more is the stability of interhalogen.
IF IF3
(vi) Interhalogen compounds are more reactive than the parent
Preparation:
halogens but less reactive than F2.
(i) By the direct combination of halogens :
ICl + 2Na  NaI + NaCl
473 K
Cl2 + F2 (equal volumes)   2ClF The order of reactivity of some interhalogens is as follows :
573K ClF3 > BrF3 > IF7 > BrF5 > BrF.
Cl2 + 3F2 (excess)   2ClF3
(vii) Hydrolysis : All these undergo hydrolysis giving halide ion
I2 + Cl2  2ICl derived from the smaller halogen and a hypohalite (when
(equimolar) AB), halite (when AB3), halate (when AB5), and perhalate
(when AB7) anion derived from the larger halogen.
(ii) Diluted with water.
AB + H2O  HB + HOA
Br2 (g) + 3F2  2BrF3
(iii) F2 is diluted with N2 BrCl + H2O  HCl + HOBr
78ºC 2IF
I2 + 3F2  ICl + H2O  HCl + HIO
3

(iv) F2 is taken in excess. ICl3 + 2H2O  3HCl + HIO2

Br2 + 5F2 (excess)  2BrF5
IF5 + 3H2O  5HF + HIO3
IF7 can not be prepared by direct combination of I2 & F2 .
(ii) From lower Interhalogens: IF7 + 6H2O  7HF + H5IO6

ClF + F2  ClF3 BrF5 + 3H2O  5HF + HBrO3

350ºC ClF  Hydrolysis products are halogen acid and oxy-halogen acid.
ClF3 + F2 (excess)  5
Oxy-halogen acid is of larger central halogen atom.
200ºC BrF
BrF3 + F2 (excess)   Oxidation state of A atom does not change during hydrolysis.
5

(viii) Reaction with non-metallic and metallic oxides :

270ºC IF
IF5 + F2  7 4BrF3 + 3SiO2  3SiF4 + 2Br2 + 3O2
This method is generally applied for the preparation of halogen
fluorides. 4BrF3 + 3WO3  2WF6 + 2Br2 + 3O2
Properties: (ix) Addition reaction (of AB type compounds):
(i) These compounds may be gases, liquids or solids. – CH = CH – + ICI  – CHI – CHCl –
Gases : ClF, BrF, ClF3 , IF7
Liquids : BrF3, BrF5 CH2 = CH2 + BrCI  CH2Br – CH2Cl
Solids : ICl, IBr, IF3, ICl3. (x) Reaction with alkali metal halides :
(ii) Interhalogens containing fluorine are colourless but inter IBr + NaBr  NaIBr2 ICl3 + KCl  KICl4
halogens consisting of heavier halogens are coloured. The

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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18)
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
U.
235
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 ELEMENTS
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 sterlising drinking water and (v) preparation
of poisonous gases such as phosgene (COCl2), tear gas (CCl3NO2),
mustard gas (ClCH2CH2SCH2CH2Cl).
20. INTRODUCTION OF GROUP 18 ELEMENTS:
(THE ZERO GROUP FAMILY)
Group 18 Consists of six elements: helium, neon, argon, krypton,
xenon and radon . All these are gases and chemically unreactive.
They form very few compounds . Because of this they are termed
37
noble gases.
Occurrence: All the noble gases except radon occur in the atmo-
sphere. Their atmospheric abundabce in dry air is ~ 1% by
volume of which argon is the major constituent. Helium and some-
times neon are found in minerals of radioactive origin e.g., pitch-
blende, monazite, cleveite. The main commercial source of helium
is natural gas. Xenon and radon are the rarest elements of the
group. Radon is obtained as a decay product of 226Ra.
226 Ra  222 Rn  4 He
88 86 2
Most abundant element in air is Ar. Order of abundance in the air
is Ar > Ne > Kr > He > Xe.
20.1 Electronic Configuration
All noble gases have general electronic configuration ns2np6 ex-
cept helium which has 1s2 . Many of the properties of noble gases
including their inactive nature are ascribed to their closed shell
structures.
20.2 Ionisation Enthalpy
Due to stable electronic configuration these gases exhibit very
high ionisation enthalpy . However, it decreases down the group
with increases in atomic size.
20.3 Atomic Radii
Atomic radii increase down the group with increase in atomic
number.
20.4 Electron Gain Enthalpy
Since noble gases have stable electronic configurations, they
have no tendency to accept the electron and therefore, have larger
positive values of electron gain enthalpy.

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 1s2 [He]2s22p6 [Ne]3s23p6 [Ar]3d104s24p6 [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

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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18) 38
Clatherate compounds : Inert gas molecules get trapped in
21. PHYSICAL PROPERTIES OF GROUP 18 the cages formed by the crystal structure of water.
ELEMENTS During the formation of ice Xe atoms will be trapped in the
All the noble gases are monoatomic. They are colourless, and cavities (or cages) formed by the water molecules in the
tasteless. They are sparingly soluble in water. They have very crystal structure of ice. Compounds thus obtained are called
low melting and boiling points because the only type of inter- clatherate compounds.
atomic interaction in these elements is weak dispersion forces,. There are no chemical bonds. They do not possess an exact
Helium has the lowest boiling point (4.2K) of any known sub- chemical formula but approx it is 6 water molecules : 1 inert
stance. It has a unusual property of diffusing through most com- gas molecule. The cavity size is just smaller than the atom of
monly used laboratory materials such as rubber, glass or plastics. the noble gas. Such compounds are also formed by the other
22. CHEMICAL PROPERTIES OF GROUP 18 organic liquids like dihydroxybenzene (for example quinol).
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. Clatherate compound
The reactivity of noble gases has been investigated occa- (ii) True chemical compounds (posses proper bonding).
sionally ever since their discovery, but all attempt to force
them to react to form the compounds were unsuccessful for
23. COMPOUNDS OF XENON
quite a few years. In March 1962, Neil Bartlett, then at the
23.1 Xenon Difluoride (XeF2)
University of British Columbia, observed the reaction of a
noble gas. First , he prepared a red compound which is Preparation:
formulated as O2+ PtF6–. He , then realised that the first
873K ,1bar
ionisation enthalpy of molecular oxygen (1175 kj mol –1) was (i) Xe + F2 Ni 
Tube or monel metal (alloy of Ni) XeF2
almost identical with that xenon (1170 kJ mol –1). He made
efforts to prepare same type of compound with Xe+ PtF6 – by Volume ratio should be 2:1 otherwise other higher fluorides
mixing Pt F6 and Xenon. After this discovery, a number of tend to form.
xenon compounds mainly with most electronegative ele- 118C XeF + O
(ii) Xe + O2 F2  2 2
ments like fluorine and oxygen, have been synthesised.
The compounds of krypton are fewer. Only the difluoride Hg (arc)
(iii) Xe + F2   XeF2
(KrF2) has been studied in detail. Compounds of radon have
not been isolated but only identified (e.g., RnF2) by radiotracer (iv) Recently discovered method :
technique. No true compounds of Ar, Ne or He are yet known. K+ [AgF4]– [potassium tetrafluoroargentate ()] is first
 If Helium is compressed and liquified it forms He() liquid at prepared and this is reacted with BF3 .
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 BF3 AgF (red solid) + KBF
K+ [AgF4]–   3 4
known as super fluid, because it is a liquid with properties of
gases. It climbs through the walls of the container & comes 2 AgF3 + Xe  2 AgF2 (Brown solid) + XeF2
out. It has very high thermal conductivity & very low Properties:
viscosity. (i) Colorless crystalline solid and sublimes at 298 K.
Compounds of inert gases are of following two types. (ii) Dissolves in water to give a solution with a pungent odour.
(i) Physical compounds (possess no proper bonding) Much soluble in HF liquid.
Physical compounds may be (A) compounds whose (iii) This is stored in a vessel made up of monel metal which is a
existence is on the basis of spectroscopic studies (temporary alloy of nickel.
phase not isolated) and (B) clatherate compounds.

SCAN CODE
p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18) 39
(iv) Reaction with H2: It reacts with hydrogen gas at 400°C (viii) Reactions of XeF2 + HF (anhydrous):
HF
XeF2 + H2  Xe + 2HF Pt + 3XeF2  PtF6 + 3Xe
(v) Hydrolysis: S8 + 24 XeF2  8SF6 + 24 Xe
(a) 2XeF2 + 2H2O  2Xe + 4HF + O2 (slow) 2CrF2 + XeF2  2CrF3 + Xe
The above is neither a cationic hydrolysis nor an anionic 2MoO3 + 6XeF2  2MoF6 + 6Xe + 3O2
hydrolysis as seen in ionic equilibrium. It is a covalent
compound and hydrolysis is like that of PCl5 . Mo (CO)6 + 3 XeF2  Mo F6 + 3 Xe + 6CO
(b) Hydrolysis is more rapid with alkali. HF
2 C6H6 + XeF2  2 C6H5F + Xe
1
XeF2 + 2 NaOH  Xe + O + 2NaF + H2O (fast) 8 NH3 + 3 XeF2  N2 + 6 NH4 F + 3 Xe
2 2
The reaction (a) is slower probably due to dissolution of 2NO2 + XeF2  2 NO2 F + Xe
XeF2 in HF.
(nitronium fluoride)
(vi) Oxidising Properties: Higher the value of SRP better is the
oxidising property of the species. (ix) Formation of Addition Compounds: XeF2 reacts with fluoride
ion acceptors to form cataionic species and fluoride ion
The standard reduction potential for XeF2 is measured to be
donors to form fluoroanions.
+ 2.64 V. Therefore it acts as a strong oxidising agent.
2e– + 2H+ + XeF2  Xe + 2HF SRP = + 2.64 V XeF2 + PF5  [XeF]+ [PF6]–

This oxidises halides to their respective halogens. F5 (lewis acid) + XeF2  [XeF]+ [F6]–

XeF2 + 2 HCl  Xe + 2 HF + Cl2 2SbF5 (lewis acid) + XeF2  [XeF]+ [SbF6]–
Similar behaviour is shown by PF5 and AsF5
It oxidises 2Br –  Br2 + 2e– & 2–  2 + 2e–
Structure: Shape linear and geometry trigonal bipyramidal.
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 Hybridisation = sp3d
strong oxidising agent as well as fluorinating agent.
C6 H5  + XeF2  C6 H5 F2 + Xe Structure of XeF2
CH3+XeF2  CH3 F2 + Xe 23.2 Xenon Tetrafluoride (XeF4)
Preparation:
 CH3 F2 exists as CH3+F2– ,F2– is analogous to 3–
873K,  XeF
Xe  2F 
2 7bar 4
1 : 5 Ni tube

Properties:
Hybridisation = sp3d (i) It is a colorless crystalline solid and sublimes at 298 K.
(ii) It undergoes sublimation, soluble in CF3 COOH.
It undergoes hydrolysis violently hence no moisture
Structure of IF2- must be present during it’s preparation.
 F3– cannot be formed as it has no d-orbitals to attain sp3d (iii) Reaction with H2O :
hybridisation.
6 XeF4 + 12 H2O  4 Xe + 2XeO3 + 24 HF + 3O2
XeO3 is white solid and explosive compound (dry), soluble in
water (well behaved in water)

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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18) 40
XeO3 reacts with NaOH forming sodium xenate Properties:
XeO3 + NaOH  Na+ [HXeO4]– (sodium xenate) (i) Colourless crystalline solid and sublimes at 298 K.
(ii) It gives yellow liquid on melting where as other form white
 It disproportionates into perxenate ion in basic medium.
liquids on melting (a point of difference)
2 [HXeO4]– + 2OH– [XeO6]4– + Xe + O2 + 2H2O
(iii) HF is a good solvent for all three fluorides.
Xenic acid (H2XeO4) is a very weak acid.
(iv) Hydrolysis:
H (a) Complete hydrolysis:
 XeO6 
4–
water  XeO3  O 2
(i) XeF6  3H 2 O  XeO3  2HF
 slow decomposition  
 whitesolid 


 XeO 6 
4–
(ii)  Mn 2  MnO 4–  XeO3 XeF6  H 2 O  XeOF4  2HF
(b) Partial hydrolysis: 
 colourless 
[XeO6]4– is obtainable as Na4 XeO6.8H2O 

(sodium perxenate) (v) Reaction with Silica (SiO2):

(iv) Oxidising properties of XeF4
XeF4 + 2 H2  Xe + 4HF
XeF4 + 2 Hg  Xe + 2HgF2
(v) Addition Reactions: XeF4 reacts with fluoride ion acceptors
to form cataionic species and fluoride ion donors to form
fluoroanions.
XeF4 + SbF5  [XeF3]+ [SbF6]–
(vi) Fluorinating Agents:
XeF4 + Pt  PtF4 + Xe
XeF4 + 4NO  Xe + 4NOF (nitrosyl Fluoride)
XeF4 + 4 NO2  Xe + 4 NO2 F (nitronium fluoride)
XeF4 + 2C6 H6  C6H5F + 2HF + Xe
Structure : Shape square planar & geometry octahedral
2XeF6 + SiO2  2XeOF4 + SiF4
(vi) Thermal Decomposition (effect of heat):

2XeF6  XeF2 + XeF4 + 3 F2
XeF2 & XeF4 do not undergo decomposition
(vii) Formation of Addition Compounds:
XeF6 + SbF5  [XeF5]+ [SbF6]
XeF6 + BF3  [XeF5]+ [BF4]–
(viii) Reaction with H2 :
XeF6 + 3H2  6HF + Xe
(ix) Reaction of XeF6 with XeO3 :
XeO3 + 2 XeF6  3 XeOF4
(x) F– donating/F accepting properties: XeF6 reacts with fluoride
ion acceptors to form cataionic species and fluoride ion
donors to form fluoroanions.
XeF6 + MF  M+ [XeF7]– (M = Na, K, Rb or Cs)

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

 CsF  XeF6  CsXeF7

  alkali metal   caesium heptafluoroxenate 
 

acceptance   fluride
  

Structure of XeF4 2CsXeF7 XeF6  Cs 2XeF8
  caesium octafluoraxenate 
 
23.3 Xenon Hexafluoride (XeF6)   

Preparation: Order of Oxidising Power:

Xe  3F2 573K,60–70 bar XeF2 > XeF4 > XeF6
(i)   XeF Structure: Shape caped octahedral (distorted oactahedral)
1 : 20 Ni  tube 6

(ii) XeF4 + O2 F2  XeF6 + O2

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p-Block Elements (Group 15 -18)
p-BLOCK ELEMENTS (GROUP 15 -18)
23.4 Xenon–Oxygen Compounds
Hydrolysis of XeF4 and XeF6 with water gives XeO3.
6 XeF4 + 12 H2O  4 Xe + 2 XeO3 + 24 HF + 3 O2
XeF6 + 3 H2O  XeO3 + 6 HF
Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2
XeF6 + H2O  XeOF4 + 2 HF
XeF6 + 2 H2O  XeO2F2 + 4 HF
XeO3 is a colourless explosive solid and has a pyramidal molecu-
lar structure. XeOF4 is a colourless volatile liquid and has a square
pyramidal molecular structure.
24. USES OF GROUP 18 ELEMENTS
Helium is a non–inflammable and light gas. Hence, it is used in
filling balloons for meterological observations. It is also used in
gas–cooled nuclear reactors. Liquid helium (b.p.4.2 K) finds use
41
as cryogenic agent for carrying out various experiments at low
temperatures. It is used to produce and sustain powerful
superconducting magnets which form an essential part of modern
NMR spectrometers and Magnetic Resonance Imaging (MRI)
systems for clinical diagnosis. It is used as a diluent for oxygen in
modern diving apparatus because of its very low solubility in
blood.
Neon is used in discharge tubes and fluorescent bulbs for
advertisement display purposes. Neon bulbs are used in botanical
gardens and in green houses.
Argon is used mainly to provide an inert atmosphere in high
temperature metallurgical process (arc welding of metals or alloys)
and for filling electric bulbs. It is also used in the laboratory for
handing substances that are air–sensitive.
Xenon and Krypton are used in light bulbs designed for special
purposes.
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.
42
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)
p-BLOCK ELEMENTS (GROUP 15 -18) 43

SOLVED EXAMPLES

Example – 3
Example – 1
NH3 burns in air under suitable conditions to
In the reaction produce

NH 3 
burnt in
 A (gas) 
Passed int o
B (a) N2 (b) NO
o
air at 750 C SnCl solution 2
in presence of HCI
Pt catalyst and 6 atm (c) N2O (d) N9O3
The compound B is: Ans. (b)
(a) NH2OH (b) NH3 Pt
Sol. 4 NH 5  5O2  4 NO  6 H 2O .
700º 800ºC
(c) N2O (d) NH2 – NH2
Ans. (a)
gauze
Sol. 4 NH 3  5O2  4 NO  6 H 2O Example – 4
750ºC ,6atm ( A)
Phosphorescence shown by P is due to
3SnCl2  6 HCl  2 NO  3SnCl4  2 NH 2OH .
(a) oxidation of P into P2O3.
(b) oxidation of P into P2O5.
Example – 2
o
(c) oxidation of luciferin by luciferage enzyme.
250 C
H3PO4 (X)
60 (d) reduction of P into phosphide ions.
0 Co 600oC
Ans. (a)
(Y) strongly
heated
(Z)
Sol. P4  3O2  2 P2O3  hv
X, Y and Z are
(a) H4P2O7, HPO3 and P4O10 Example – 5
(b) HPO3, H4P2O7 and P4O10 Which of the following compounds give NH3 on
(c) H4P2O6, H3PO3 and P4O6 heating?

(d) H4P2O6 , HPO3 and P4O6 (I) NH4NO3 (II) NH4NO2

Ans. (a) (III) (NH4)2 Cr2O7 (IV) (NH4)2 CO3

250º C
(V) Mg (NH4) PO4
2 H 3 PO4 
 H 4 P2 O7  H 2 O
Sol. (a) I, IV (b) II, V
X 
(c) IV only (d) IV, V
600º C
H 4 P2 O7 
 2 HPO3  H 2O Ans. (d)
X Y  Sol.
600º C
H 3 PO4 
 HPO3  H 2 O 
NH 4 NO3  N 2 O  2 H 2 O 
Y  
 
NH 4 NO2  N 2  2 H 2 O 
4 HPO3  P4O10  2 H 2O  
(Y ) Z   NH 4 2 Cr2 O2  N 2  Cr2 O3  4 H 2 O 
p-BLOCK ELEMENTS (GROUP 15 -18) 44
Example – 9
 
 NH 4 2 CO3   2 NH 3  H 2 O  CO2  The best reducing agent among the following is


3Mg  NH 4  PO4  3 NH 3  MgHPO4  Mg 2 P2O3  (a) NH3 (b) SbH3
(c) PH3 (d) AsH3
Example – 6
Ans. (b)
Mg (NH 4) PO 4 and Na(NH 4) HPO 4 are heated
separately. Which of the following statements is/are Sol. Conceptual, as down the group, metallic character
completely incorrect regarding the product obtained increases, so reducing capacity increases.
in the above process? Example – 10
(I) Same gas is evolved The number of lone pairs and the number of S—S
(II) Same type of phosphate is formed bonds in S8 molecules are respectively:
(III) Different types of gases are formed (a) 8, 8 (b) 16, 8
(IV) Different types of phosphates are formed (c) 8, 16 (d) 8, 4
(a) I and II (b) II and IV Ans. (b)
(c) I and IV (d) II and III
Ans. (d)

Sol. 3Mg  NH 4  PO4  Mg 2 P2O7  MgHPO4  3NH 3 

Sol.

Na  NH 4  HPO4  NaPO3  NH 3  H 2O

Same gas, different phosphates

Example – 11

Example – 7 In which of the following species, S-atom assumes

sp3 hybrid state?
Solid PCl5 exists as:
(I) SO3 (II) SO2
(a) dimer P2Cl10 (b) [PCl4]+ [PCl6]-
(III) H2S (IV) S8
(c) (PCl3) (Cl2) (d) PCl5 as such
(a) I, II (b) II, III
Ans. (b)
(c) II, IV (d) III, IV
 
Sol. 2 PCl5   PCl4   PCl6  Ans. (d)

Example – 8 Sol. SO3 sp2

The percentage of p-character in the orbitals forming SO2 sp2

P–P bonds in P4 is: H2S sp3
(a) 25 (b) 33 S8 sp3

(c) 50 (d) 75
Ans. (d) Example – 12
Sol. Which of the following solutions does not change its
colour on passing ozone through it?
(a) Starch iodide solution
(b) Alcoholic solution of benzidine
(c) Acidic solution of K2Cr2O7
(d) Acidified solution of FeSO4
Ans. (c)
p-BLOCK ELEMENTS (GROUP 15 -18) 45
Sol. O3 Turns benzidine solution brown
Example – 16
O3  Turns starch iodide solution Violet (l2 formn)
Which is incorrectly matched?
O3  2 FeSO4  H 2 SO4  O3
green
(a) CsBr3  CS+ + Br 3  Cs+ + Br- + Br2

(b) I4O9  IO3+ + 3(IO3)-
Fe2  SO4 3  H 2 O  O2
Yellowish  (c) AgBrO3  Ag+ + BrO 3
 
(d) I2O4  IO 2 + IO 2
Example – 13
Ans. (d)
Concentrated H2SO4 can be used to dry the gas:
Sol. I 2O4  IO  IO3
(a) H2S (b) CO2
Example – 17
(c) NH3 (d) all
Ans. (b) Dry Cl2 reacts with dry SO2 to form:

Sol. CO2 only as H2SO4 will oxidize NH3 & H2S (a) thionyl chloride (b) sulphuryl chloride
(c) sulphur dichloride (d)sulphur monochloride
H 2 S  H 2 SO4  2 H 2 O  SO2  S  or form salts
Ans. (b)
2NH3 + H2SO4 (NH4)2 SO4
SO2  Cl2  SO2Cl2
Example – 14
Sol.  Dry   Dry  Sulphuryl .
chloride
When F 2 reacts with hot and conc. alkali, then
following will be obtained: Example – 18
(i) OF2 (ii) O2 Chlorine shows bleaching action in:
(iii) H2O (d) NaF (a) dry conditions (b) presence of HCl only

(a) (i), (iii) and (iv) (b) (ii) and (iii) only (c) moist conditions (d) none of these

(c) (ii), (iii) and (iv) (d) all of these Ans. (c)

Ans. (c) Sol. Cl2 + H2O HCl + HOCl+


4 NaOH  2 F2  4 NaF  O2  2 H 2O
Sol.  hot & conc. HCl + [O]  responsible for bleaching
Example – 19
Example – 15 PH3 and NH3 on separate reaction with bleaching
The property of halogens, that indicated incorrect is: powder produce respectively

(a) F > Cl > Br > I ........ ionisation energy (a) P and N2 (b) PCl3 and NCl3
(b) F > Cl > Br > I ......... electron affinity (c) PCl3 and N2 (d) PCl5 and NCl3
(c) F > Cl > Br > I ........ electronegativity Ans. (c)
(d) I > Br > Cl > F ........ density in liquid state Sol. 3CaOCl2  2 NH 3  3CaCl2  N 2  3H 2O
Ans. (b)
3CaOCl2  PH 3  PCl3  3CaO  3HCl .
Sol. Cl > F > Br > l ......(Electron affinity, as in F,
The lone pairs repel the incoming e- due to very small
size)
p-BLOCK ELEMENTS (GROUP 15 -18) 46
Example – 20 Example – 24
Chlorine reacts with dilute NaOH under ordinary Which of the following has the maximum vapour
conditions to give pressure?
(a) NaCl and NaClO3 (b) NaCl and ClO2 (a) HCl (b) HBr
(c) NaCl and NaClO (d) NaCl and Cl2O (c) HF (d) HI
Ans. (c) Ans. (a)
2 NaOH  Cl2  NaCl  NaClO  H 2O Sol. Due to lowest B.P. (high volatility) it has the highest
Sol. (Cold & dilute ) vapour pressure
Example – 21 HF > Hl > HBr > HCl (Boiling point)
Chlorine on reaction with hot and concentrated
NaOH produces Example – 25
(a) NaClO3 and NaClO (b) NaCl and NaClO3 In the separation of noble gas mixture from air by Ramsay
(c) NaCl and NaClO4 (d) NaClO 3 and and Rayleigh’s first method, the substances used for
NaClO4 the removal of N2 and O2 respectively, are:
Ans. (b) (a) Cu and Mg (b) Mg and Cu
6 NaOH  3Cl2  5 NaCl  NaClO3  3H 2O (c) C and CaC2 (d) KOH solution
Sol. ( Hot & conc.)
Ans. (b)
Example – 22
Sol. N2 + 3Mg Mg3N2
Dry SO2 reacts with Cl2 to produce 2Cu + O2  2CuO
(a) S2Cl2 (b) SOCl2 Example – 26
(c) S(OCl)2 (d) SO2Cl2
What is the correct order of occurrence (% by weight)
Ans. (d) in air of Ne, Ar and Kr?
dry (a) Ne > Ar > Kr (b) Ne > Kr > Ar
SO2  Cl2 
 SO2Cl2
Sol.
( dry ) (c) Ar > Kr > Ne (d) Ar > Ne > Kr

Example – 23 Ans. (d)

Cold and dilute NaOH
(A)+ NaCl +H2O
Sol. Ar 9.34 × 10-1 % of air

Cl2 Kr 1.45 × 10-3 % of air

Hot and conc. NaOH
(B)+ NaCl +H2O Ne 1.82 × 10-3 % of air
Ar > Ne > Kr
Compounds (A) and (B) are:
Example – 27
(a) NaClO3, NaClO (b) NaOCl2, NaOCl
The shape of XeO2F2 molecule is:
(c) NaClO4, NaClO3 (d) NaOCl, NaClO3
(a) trigonal bipyramidal (b) square planar
Ans. (d)
(c) tetrahedral (d) see-saw
Ans. (d)

Sol.

Sol.
p-BLOCK ELEMENTS (GROUP 15 -18) 47

Example – 28
XeF2 reacts with SbF5 to form:
(a) [XeF]+ [SbF6]- (b) [XeF3] [SbF4]
(c) XeSbF6 (d) XeF4
Ans. (a)

Sol. XeF2  SbF5  XeF2 .SbF5   XeF 


 SbF6  .
Example – 29
What are the products formed in the reaction of xenon
hexafluoride with silica?
(a) XeSiO4 + HF (b) XeF2 + SiF4
(c) XeOF4 + SiF2 (d) XeO3 + SiF4
Ans. (d)
Sol. 2XeF6 + 3SiO2 2XeO3 + 3SiF4
Example – 30
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) 48

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Introduction of Group 15 Elements 10. Which of the following statements is correct regarding the
1. Which of the following properties is not compatible with behaviour of white phosphorus?
nitrogen? (a) It is soft, waxy and reactive
(a) Hydrogen bonding (b) Catenation (b) It reacts with moist air to emit a light called
(c) Supporter of life (d) Low boiling point chemiluminescence.

2. N2 is commercially prepared by (c) It exists as tetrahedral P4 molecules both in the liquid

and gaseous states.
(a) fractional distillation of liquefied air
(d) All the above
(b) heating sodium nitrite
Chemical Properties of Group 15 Elements
(c) heating sodium azide
11. Which of the following halides is the most acidic?
(d) heating a mixture of ammonium chloride sodium nitrite
(a) PCl3 (b) SbCl3
3. Which of the following forms strong p - p bonding
(c) BiCl3 (d) CCl4
(a) P4 (b) As4
12. Which of the following halides of nitrogen is stable?
(c) N2 (d) Sb4
(a) NF3 (b) NCl3
4. Nitrogen is an essential constituent of
(c) NBr3 (d) NI3
(a) fats and carbohydrates
(b) carbohydrates and enzymes 13. PCl3 and PCl5 both exist; NCl3 exists but NCl5 does not exist.
It is due to
(c) Proteins and amino acids
(a) lower electronegativity of P than N
(d) vitamin A and vitamin B
(b) lower tendency of N to form covalent bond
5. White phosphorus is kept under
(c) availability of vacant d-orbital in P but not in N
(a) kerosene oil (b) water
(d) statement is itself incorrect
(c) concentrated HNO3 (d) ethanol
14. In which of the following arrangements, the sequence is not
6. Number of electrons shared in the formation of nitrogen
strictly according to the property written against it ?
molecule is
(a) CO2 < SiO2 < SnO2 < PbO2 : increasing oxidising power
(a) 6 (b) 10
(b) HF < HCl < HBr < HI : increasing acid strength
(c) 2 (d) 8
(c) NH3 > PH3 < AsH3 < SbH3 : increasing basic strength
Physical Properties of Group 15 Elements
(d) B < C < O < N : increasing first ionisation enthalpy
7. Among the following, the element that does not show
allotropy is 15. Which of the following gases is the least reactive?
(a) N (b) P (a) O2 (b) N2
(c) As (d) Bi (c) H2 (d) O3
8. Which of the following, exhibits a layered structure? 16. White phosphorus reacts with NaOH to give PH 3 and
NaH2PO2. This reaction involves
(a) BN (b) N2
(a) oxidation (b) reduction
(c) P4 (d) AsH3
(c) disproportionation (d) neutralization
9. The struture of boron nitride resembles that of
17. Which of the following oxides will be the least acidic?
(a) nickel arsenide (b) graphite
(a) As4O6 (b) As4O10
(c) rock salt (d) diamond
(c) P4O10 (d) P4O6
p -BLOCK ELEMENTS (GROUP 15-18) 49

18. White phosphorus is more reactive than N2 because 26. N2O3 is

(a) electronegativity of phosphorus is low (a) an acidic oxide and the anhydride of HNO2
(b) ionization energy of phosphorus is low (b) an acidic oxide and the anhydride of H2N2O2
(c) P—P bond is weaker than N  N bond (c) a neutral oxide and the anhydride of HNO3
(d) P—P bond is polymeric (d) a basic oxide and the anhydride of HNO2
General Properties and Compounds of Nitrogen 27. Which of the following oxides of nitrogen is a mixed
anhydride of two acids?
19. The bond order in the NO molecule is
(a) N2O3 (b) N2O4
(a) 3 (b) 1.5
(c) N2O5 (d) N2O
(c) 2.5 (d) 2.0
28. Which of the following oxides of nitrogen is paramagnetic?
20. Which of the following statements is true ?
(a) NO2 (b) N2O3
(a) H3PO3 is a stronger acid than H2SO3
(c) N2O (d) N2O5
(b) In aqueous medium HF is a stronger acid than HCl
29. Which of the following is a nitric acid anhydride?
(c) HClO4 is weaker acid than HClO3
(a) NO (b) NO2
(d) HNO3 is a stronger acid than HNO2 (c) N2O5 (d) N2O3
21. Which of the following statements is wrong ? 30. Ammonia gas can be dried by
(a) The stability of hydries increases from NH3 to BiH3 in (a) conc. H2SO4 (b) P4O10
group 15 of the Periodic Table (c) anhydrous CaCl2 (d) CaO
(b) Nitrogen can’t form d-p bond. 31. At present, HNO3 is industrially prepared by the
(c) Single N—N bond is weaker than the single P—P bond. (a) contact process
(d) N2O4 has two resonance structure (b) Birkeland-Eyde process
22. Which one of the following properties is not shown by (c) Ostwald process
NO ?
(d) Haber process
(a) It is a neutral oxide
32. Gold reacts with aqua regia forming
(b) It combines with oxygen to form nitrogen dioxide
(a) auric chloride (AuCl3)
(c) It’s bond order is 2.5
(b) chloroauric acid (HAuCl4)
(d) It is diamagnetic in gaseous state
(c) chloroaurous acid (HAuCl3)
23. Which one of the following molecules is paramagnetic ?
(d) purple of Cassius
(a) O3 (b) N2 33. Platinum reacts with aqua regia to produce chloroplatinic
(c) NO (d) CO acid represented by the formula
24. Aqueous solution of ammonia consists of (a) H4 [PtCl6] (b) H [PtCl4]
–
(a) H (b) OH (c) H2 [PtCl6] (d) H2 [PtCl4]
34. A solution of sodium in liquid ammonia is blue due to the
(d) NH4 and OH
–
(c) N 4
presence of
25. Iodine reacts with concentrated HNO3 to produce (a) solvated electrons (b) ammonium ions
(a) H5IO6 (b) HIO4 (c) solvated sodium ions (d) sodium atoms
(c) HIO3 (d) HIO
p -BLOCK ELEMENTS (GROUP 15-18) 50

35. Among the following compounds of nitrogen and hydrogen, 43. The number of hydrogen atom(s) attached to phosphorus
the most acidic compound is atom in hypophosphorous acid is
(a) NH3 (b) N2H4 (a) three (b) one
(c) N2H2 (d) HN3 (c) two (d) zero
36. Which one of the following compounds is most explosive? 44. Syrupy H3PO4 is viscous due to
(a) NCl3 (b) PCl3 (a) intermolecular hydrogen bonding
(c) AsCl3 (d) NF3 (b) van der Waals forces among the H3PO4 molecules
37. The most stable oxidation states of nitrogen are (c) covalent bonding in P—O linkage
(a) -3, +3 and +5 (b) -3, 0 and -1 (d) low activation energy in H3PO4
(c) -3, +3 and 0 (d) -3, +3 and -5 45. Which of the following statements is true for the H3PO3
molecule?
General Properties and Compounds of Phosphorus
(a) It contains two acidic H atoms
38. Phosphorus reacts with concentrated HNO3 to produce
(b) It contains one reducing H atom
(a) hypophosphoric acid (b) orthophosphorus acid
(c) It can form two series of salts
(c) pyrophosphoric acid (d) orthophosphoric acid
(d) All of these
39. White phosphorus reacts with concentrated HNO3 to give
46. PCl5 on hydrolysis gives
(a) orthophosphoric acid (b) pyrophosphoric acid
(a) H3PO2 (b) H3PO3
(c) phosphorus acid (d) metaphosphoric acid
(c) H3PO4 (d) H5P3O10
40. Which of the following structures represents
hypophosphoric acid? 47. Solid PCl5 exists as
(a) [PCl4]+ and [PCl6]- ions
H H H
(b) [PCl4]- and [PCl6]+ ions
(a) H P OH (b) HO P O P OH (c) covalent PCl5 molecules only
O O O (d) [PCl4]2+ and [PCl6]2- ions
48. Identify the incorrect statement related to PCl5 from the
OH OH OH following:

P P O (a) PCl5 molecule is non-reactive.

(c) O (d) H O P O
(b) Three equatorial P – Cl bonds make an angle of 120° with
OH OH OH each other.
41. Which of the following oxoacids of phosphorus is a reducing (c) Two axial P – Cl bond make an angle of 180° with each
agent and a monobasic acid as well? other.
(a) Orthophosphorus acid (H3PO3) (d) Axial P – Cl bonds are longer than equatorial P – Cl
(b) Hypophosphorus acid (H3PO2) bonds.

(c) Pyrophosphorus acid (H4P2O5)
(d) Metaphosphorus acid (HPO3)
42. The number of P—O—P bonds in cyclic metaphosphoric
acid is
49. Which one of the following substance is used in the
laboratory for fast drying of neutral gases?
(a) Phosphorus pentoxide
(b) Active charcoal

(a) zero (b) two (c) Anhydrous calcium chloride

(c) three (d) four (d) Na3PO4

p -BLOCK ELEMENTS (GROUP 15-18) 51

50. The structural formula of hypophosphorus acid is 55. Which of the following statements regarding sulphur is
incorrect ?
(a) (b) (a) S2 molecule is paramagnetic.
(b) The vapour at 200ºC consists mostly of S8 rings.
(c) At 600ºC the gas mainly consists of S2 molecules.
(c) (d) None of these (d) The oxidation state of sulphur is never less than +4 in its
compounds.
Chemical Properties of Group 16 Elements
51. Which of the following statements is correct? 56. H2S is less stable than H2O because
(a) Phosphorus does not form p-p multiple bonds in its (a) the bonding orbitals of sulphur are larger and more
compounds. diffuse than those of oxygen, and hence they overlap
(b) Phosphorus forms weak to moderate d- p multiple less effectively with the 1s orbital of the hydrogen atom
bonds in some of its compounds. (b) the bonding orbitals of sulphur are smaller and more
(c) Phosphorus can expand its valence shell by utilizing diffuse than those of oxygen, and hence they overlap
inner 3d orbitals. less effectively with the 1s orbital of the hydrogen atom
(d) All of these (c) the bonding orbitals of sulphur are smaller and less
diffuse than those of oxygen, and hence they overlap
Uses of Group 15 Elements less effectively with the is orbital of the hydrogen atom
52. Regular use of which of the following fertilizers increase the
(d) H2O molecules form H bonds but H2S molecules do not
acidity of soil ?
57. The stability of the hydrides of oxygen, sulphur, selenium
(a) Potassium nitrate and tellurium decreases in the order
(b) Urea
(a) H2Te > H2Se >H2S > H2O
(c) Superphosphate of lime
(b) H2O > H2S >H2Se > H2Te
(d) Ammonium sulphate (c) H2O > H2S < H2Se > H2Te
Introduction and Physical Properties of Group 16 (d) H2O  H2S > H2Tee > H2Se
Elements 58. Which of the following compounds is thermodynamically
53. Group 16 elements (except polonium) are called unstable?
chalcogens because (a) H2O (b) H2Se
(a) these elements, particularly sulphur and oxygen, are (c) H2S (d) NH3
present in many metallic ores mainly as oxides and 59. Which would quickly absorb oxygen?
sulphides
(a) Alkaline solution of pyrogallol
(b) a large number of acids contain these elements,
(b) Conc. H2SO4
particularly sulphur and oxygen
(c) Lime Water
(c) these elements mainly form anions
(d) Alkaline solution of CuSO4
(d) these elements exist in different allotropic forms
60. PtF6 converts O2 to
54. In the cyclo-S8 molecule of rhombic sulphur, all the S—S
bond lengths and all the S—S—S bond angles are (a) O 2 PtF 6 (b) O 2 PtF 6
respectively (approximate values)
(c) F2+PtO2 (d) F2O + Pt
(a) 204 pm and 1070 (b) 102 pm and 1200
(c) 204 pm and 1800 (d) 102 pm and 600
p -BLOCK ELEMENTS (GROUP 15-18) 52

General Properties and Compounds of Oxygen General Properties and Compounds of Sulphur
61. In ozone, the central oxygen atom uses 69. Which of the following statements is not correct for sulphur?
(a) roughly sp2 orbitals for  bonding (a) In sulphur, stronger p-d overlap takes place because
(b) sp orbitals for  bonding only the size of the d orbitals is similar to that of the p orbitals.

(c) sp3 orbitals for  bonding (b) The size of the atom and the size of the 3d orbitals
decrease from S to Cl because on crossing a period in
(d) pd 2z bonding for both  and  bonding the periodic table, the nuclear charge is increased and s
and p electrons shield the nuclear charge incompletely
62. Which of the following statements is correct?
(c) Due to stronger p-d overlap, only a few sulphur
(a) Ozone decomposes to give oxygen
compounds polymerize.
(b) Ozone is thermodynamically unstable.
(d) Sulphur belongs to 18th group.
(c) The decomposition of ozone is exothermic.
70. H2S turns an acidified K2Cr2O7 solution
(d) All of these
(a) violet (b) orange
63. Ozone is an extermely powerful oxidizing agent. It is
(c) green (d) colourless
(a) second only to F2 in oxidizing power
71. H2S turns an acidified KMnO4 solution
(b) second only to O2 in oxidizing power
(a) green (b) pink
(c) second only to Cl2 in oxidizing power
(c) blue-black (d) colourless

(d) second only to MnO in oxidizing power
4
72. Which of the following ions does not have an S—S linkage?

64. At room temperature, O3 is absorbed by (a) S2O 82  (b) S2O 26 

(a) water (b) palladium
(c) S2O 52  (d) S2O 32 
(c) acetic acid (d) turpentine oil
65. The gases absorbed by alkaline pyrogallol and oil of 73. Sulphur dioxide reacts with chlorine in the presence of
cinnamon are respectively charcoal (which acts as a catalyst) to give
(a) O3 and CH4 (b) O2 and O3 (a) sulphuryl chloride
(c) SO2 and CH4 (d) N2O and O3 (b) thionyl chloride
66. O3 is (c) sulphur dichloride and oxygen
(a) an allotrope of oxygen (b) an isomer of oxygen (d) chlorine monoxide and sulphur
(c) an isotone of oxygen (d) isostructural with O2 74. Which of the following gases may act both as an oxidizing
and a reducing agent?
67. Ozone is prepared by the action of silent electric discharge
upon oxygen in an apparatus called ozonizer. The reaction (a) H2S (b) SO3
(a) is exothermic (c) SO2 (d) O2
(b) is endothermic 75. When SO2 gas is passed into an acidified solution of K2Cr2O7,
the oxidation state of chromium changes
(c) leads to the dissociation of the O2 molecule
(a) from +12 to +6 (b) from +3 to +6
(d) leads to the formationi of O 2
(c) from +6 to +3 (d) from +6 to +4
68. Ozonized oxygen is a mixture of 76. A gas that cannot be collected over water is

(a) O3 and N2 (b) O3 and O 2 (a) N2 (b) O2

(c) SO2 (d) PH3
(c) O3 and O2 (d) O3 and Cl2
p -BLOCK ELEMENTS (GROUP 15-18) 53

77. Dehydration of concentrated H2SO4 in the presence of P4O10 85. All the halogens are coloured. The colours arise due to
produces (a) weak van der Waals forces between the halogen
(a) SO2 (b) H2S molecules
(c) O2 (d) SO3 (b) strong oxidizing power of the halogens
78. H2SO4 is manufactured from SO2(g) by the (c) absorption of light which causes an electron to jump
(a) Hall process (b) contact process form the ground state to a higher state

(c) Raschig process (d) Haber process (d) absorption of light due to transfer of an electron from a
higher state to the ground state
79. In the presence of water, sulphur is oxidized by ozone to
give Chemical Properties of Group 17 Elements
(a) H2SO3 (b) SO2 86. Standard sodium thiosulphate solution is used in the
(c) H2SO4 (d) SO3 estimation of iodine present in a solution. The equivalent
weight of sodium thiosulphate which is required to make
Introduction of Group 17 Elements the standard solution is
80. Which of the following are not correctly matched? (a) (molecular weight)/2
(a) A halogen which is a liquid at room temperature  (b) (molecular weight)/3
bromine
(c) the same as the molecular weight
(b) The most electronegative element  fluorine
(d) (molecular weight)/4
(c) The strongest oxidizing halogen  iodine
87. Sodium thiosulphate reacts with iodine to give
(d) The most reactive halogen  fluorine
(a) SO 24  (b) SO 32 
81. Which of the following elements can have both positive
and negative oxidation states?
(c) S4O 26  (d) S2-
(a) Fluorine (b) Iodine
(c) Lithium (d) Helium 88. Bromine can be liberated from KBr by the action of

82. Which of the following halogens has only one oxidation (a) iodine solution (b) chlorine water
state of –1 in an aqeous solution? (c) sodium chloride (d) potassium iodide
(a) Iodine (b) Chlorine 89. Identify the incorrect statement amont the following.
(c) Bromine (d) Fluorine (a) Ozone reacts with SO2 to give SO3
83. Which of the following reactions may be used for the (b) Silicon reacts with NaOH (aq) in the presence of air to
preparation of chlorine? give Na2SiO3 and H2O
(a) KMnO4+HCl (conc.)  (c) Cl2 reacts with excess of NH3 to give N2 and HCl
(b) NaCl + MnO2 + H2SO4 (conc.) 
(d) Br2 reacts with hot and strong NaOH solution to give
(c) Ca(OCl)Cl + H2O  NaBr, NaBrO4 and H2O
(d) All of these 90. Which of the following halide ions the most basic?
Physical Properties of Group 17 Elements
(a) F– (b) Cl–
84. Which of the following statements is correct for the iodine
(c) Br– (d) I–
molecule?
91. Which one among the following is the most powerful
(a) In liquid state it conducts electricity, though very slightly,
oxidizing agent?
due to self-ionization: 3I2  I 3 + I 3 (a) Cl2 (b) Br2
(b) Its conductivity increases with the rise in temperature. (c) F2 (d) I2
(c) It behaves like an intrinsic semiconductor
(d) All the above
p -BLOCK ELEMENTS (GROUP 15-18) 54

92. Which of the following is arranged in order of increasing General Properties and Compounds of Halogens
bond energy?
99. SiO2 reacts with HF to produce
(a) I2 < Br2 < Cl2 < F2 (b) I2 < F2 < Br2 < Cl2
(a) Si and H2O (b) Si and HFO2
(c) I2 < Br2 < F2 < Cl2 (d) Cl2 < Br2 < F2 < I2
(c) SiF6 and H2O (d) H2[SiF6] and H2O
93. One of the reasons why the F—F bond is weak is that
100. Concentrated hydrochloric acid when kept in open air
(a) the repulsion between the nonbonding pairs of electrons sometimes produces a cloud of white fumes. The explanation
of the two fluorine atoms is high for it is that
(b) the ionization energy of the fluorine atom is very high (a) concentrated hydrochloric acid emits strongly smelling
(c) the F—F bond distance is large HCl gas all the time
(d) the F—F bond distance is small and hence internuclear (b) oxygen in air reacts with the emitted HCl gas to form a
repulsion is small cloud of chlorine gas
94. In spite of having lower dissociation energies, bromine and (c) strong affinity of HCl gas for moisture in air results in
iodine are weaker oxidizing agents than chlorine due to their forming of droplets of liquid solution which appears like
(a) smaller electron affinities and greater hydration energies a cloudy smoke

(b) smaller electron affinities and smaller hydration energies (d) due to strong affinity for water, concentrated hydrochloric
acid pulls moisture of air towards itself. This moisture
(c) greater electron affinities and greater hydration energies forms droplets of water and hence, the cloud
(d) greater electron affinities and smaller hydration energies
Interhalogen Compounds and Uses of Group 17
95. Fluorine react with water to produce
Elements
(a) HF, O2 and O3 (b) HF and O2
101. Which of the following statements is not appropriate
(c) HF and OF2 (d) HF and O3 regarding the characteristics of interhalogen compounds?
96. When Cl2 gas reacts with hot and concentrated sodium (a) They are usually less reactive than halogens (except
hydroxide solution, the oxidation number of chlorine fluorine).
changes from
(b) They are not so stable, but none of them is explosive
(a) zero to +1 and zero to –5
(c) They are covalent in nature
(b) zero to –1 and zero to +5
(d) They have low boiling points and are highly volatile
(c) zero to –1 and zero to +3
102. The bleaching action of chlorine is due to
(d) zero to +1 and zero to –3
(a) reduction (b) hydrogenation
97. Which of the following is used in the preparation of chlorine?
(c) chlorination (d) oxidation
(a) Both MnO2 and KMnO4
Introduction and Physical Properties of Group 18
(b) Only KMnO4
Elements
(c) Only MnO2
103. Which of the following forms the least number of
(d) Either MnO2 or KMnO4 compounds?
98. When SO2 gas is passed into chlorine water, the products (a) Helium (b) Argon
formed are
(c) Krypton (d) Xenon
(a) SCl2 and S2Cl2 (b) H2SO4 and HCl
104. Which of the following noble gases is the least polarizable?
(c) SO2Cl2 (d) SOCl2 and HCl
(a) He (b) Ar
(c) Ne (d) Xe
105. The element which has the highest first ionization energy is
(a) hydrogen (b) xenon
(c) fluorine (d) helium
p -BLOCK ELEMENTS (GROUP 15-18) 55

106. Noble gases are difficult to liquefy because their 111. Which of the following xenon-OXO compounds may not
(a) dispersion forces are large be obtained by hydrolysis of xenon fluorides?

(b) dispersion forces are small (a) Xe O3 (b) Xe O4

(c) ionization energies are low (c) Xe O2F2 (d) Xe O F4
(d) electron affinities are high 112. XeF4 reacts violently with water to give
Compounds of Xenon (a) Xe and O2 (b) XeOF4
107. Indentify the incorrect statement, regarding the molecule (c) Xe, O3 and HF (d) XeO3, O2 and HF
XeO4. Uses of Group 18 Elements
(a) XeO4 molecule is square planar.
113. Which of the following noble gases is used for cryogenic
(b) There are four p-d bonds. works?

(c) There are four sp 3  p ,bonds. (a) Neon (b) Krypton

(c) Helium (d) Argon
(d) XeO4 molecule is tetrahedral.
114. For breathing, deep-sea divers use a mixture of
108. Which one of the following reaction of xenon compounds
is not feasible ? (a) O2 and H2 (b) O2 and N2

(a) XeO3 + 6HF  XeF6 + 3H2O (c) O2 and He (d) O2 and Ar

115. Which one of the following statements regarding helium is
(b) 3XeF4 + 6H2O  2Xe + XeO3 + 12HF + 1.5O2
incorrect ?
(c) 2XeF2 + 2H2O  2Xe + 4HF + O2
(a) It is used to fill gas balloons instead of hydrogen because
(d) XeF6 + RbF  Rb [XeF7] it is lighter and non-inflammable
109. Xenon trioxide (XeO3) has a shape of a (b) It is used as a cryogenic agent for carrying out
(a) trigonal bipyramid (b) octahedron experiments at low temperatures
(c) pyramid (d) tetrahedron (c) It is used to produce and sustain powerful
superconducting magnts
110. The structure of XeO3F2 is
(d) It is used in gas-cooled nuclear reactors
(a) square pyramidal (b) pentagonal bipyramidal
(c) trigonal bipyramidal (d) octahedral
p -BLOCK ELEMENTS (GROUP 15-18) 56

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS

Objective Questions I [Only one correct option] (d) Br2 reacts with hot and strong NaOH solution to give
1. The correct order of the thermal stability of hydrogen NaBr, NaBrO4 and H2O
halides (H—X) is (2005) 9. Among the following substituted silanes the one which
(a) HI > HCl > HF > HBr (b) HCl < HF > HBr < HI will give rise to cross linked silicone polymer on hydrolysis
(c) HF > HCl > HBr > HI (d) HI > HBr > HCl > HF is (2008)
2. The number of hydrogen atom(s) attached to phosphorus (a) R4Si (b) RSiCl3
atom in hypophosphorous acid is (2005) (c) R2SiCl2 (d) R3SiCl
(a) three (b) one 10. Graphite is a soft solid lubricant extermely difficult to melt.
(c) two (d) zero The reason for this anomalous behaviour is that graphite
3. Heating of an aqueous solution of aluminium, chloride to (2015)
dryness will give (2005) (a) is a non-crystalline substance
(a) Al(OH) Cl2 (b) Al2O3 (b) is an allotropic form of diamond
(c) Al2Cl6 (d) AlCl3 (c) has molecules of variable molecular masses like
polymers
4. The structure of diborane (B2H6) contains (2005)
– – (d) has carbon atoms arranged in large plates of rings of
(a) four 2c – 2e bonds and four 3c – 2e bonds strongly bound carbon atoms with weak interplate
– –
(b) two 2c – 2e bonds and two 3c – 3e bonds bonds
– – 11. The products obtained when chlorine gas reacts with
(c) two 2c – 2e bonds and four 3c – 2e bonds
– – cold and dilute aqueous NaOH are (2017)
(d) four 2c – 2e bonds and two 3c – 2e bonds
5. A metal, M forms chlorides in its +2 and +4 oxidation (a) ClO  and ClO 3 (b) ClO 2 and ClO 3
states. Which of the following statements about these (c) Cl  and ClO  (d) Cl  and ClO 2
chlorides is correct ? (2006)
12. The type of hybridisation and number of lone pair(s) of
(a) MCl2 is more volatile than MCl4
electrons of Xe in XeOF4 respectively are (2019)
(b) MCl2 is more soluble in anhydrous ethanol than MCl4
(c) MCl2 is more ionic than MCl4 (a) sp3 d 2 and 1 (b) sp 3 d and 2
(d) MCl2 is more easily hydrolysed than MCl4 (c) sp3 d 2 and 2 (d) sp 3 d and 1
6. Which of the following statements is true ? (2006)
13. The noble gas that does NOT occur in the atmosphere
(a) H3PO3 is a stronger acid than H2SO3
is: (2019)
(b) In aqueous medium HF is a stronger acid than HCl
(a) He (b) Kr
(c) HClO4 is weaker acid than HClO3 (c) Ne (d) Ra
(d) HNO3 is a stronger acid than HNO2 14. An organic compound ‘A’ is oxidized with Na2O2 followed
7. Regular use of which of the following fertilizers increases by boiling with HNO3. The resultant solution is then
the acidity of soil ? (2007) treated with ammonium molybdate to yield a yellow
(a) Potassium nitrate (b) Urea precipitate. Based on above observation, the element
(c) Superphosphate of lime (d) Ammonium sulphate present in the given compound is: (2019)
8. Identify the incorrect statement among the following. (2007) (a) Nitrogen (b) Phosphorus
(a) Ozone reacts with SO2 to give SO3 (c) Fluorine (d) Sulphur
(b) Silicon reacts with NaOH (aq) in the presence of air to
give Na2SiO3 and H2O
(c) Cl2 reacts with excess of NH3 to give N2 and HCl
p -BLOCK ELEMENTS (GROUP 15-18) 57
15. Good reducing nature of H3PO2 is attributed to the 22. The reaction in which the hybridisation of the
presence of: (2019) underlined atom is affected is: (2020)
(a) Two P - OH bonds (b) One P - H bond 420 K
(a) H 2 SO 4  NaCl 
(c) Two P - H bonds (d) One P - OH bond
16. Chlorine on reaction with hot and concentrated sodium (b) XeF4  SbF5 

hydroxide gives: (2019) H 
(c) NH 3 
(a) Cl and ClO3 (b) Cl and ClO
Disproportionation
(d) H 3 PO 2 
(c) H+ Only (d) Cl Only
23. The structure of PCl5 in the solid state is : (2020)
17. On heating compound (A) gives a gas (B) which is a
(a) Square planar [PCl4]+ and octahedral [PCl6]–
constituent of air. This gas when treated with H2 in the (b) Tetrahedral [PCl4]+ and octahedral [PCl6]–
presence of a catalyst gives another gas (C) which is (c) Trigonal bipyramidal
basic in nature. (A) should not be : (2020) (d) Square pyramidal
(a) (NH 4 ) 2 Cr2 O7 (b) NaN3 24. Reaction of ammonia with excess Cl2 gives : (2020)

(c) NH 4 NO 2 (d) Pb  NO3 2 (a) NH 4 Cl and N 2 (b) NH 4 Cl and HCl

18. The shape/structure of [XeF5]– and XeO3F2, (c) NCl3 and HCl (d) NCl3 and NH 4 Cl

respectively, are : (2020) 25. In the following reactions, product (A) and (B),
(a) Pentagonal planar and trigonal bipyramidal respectively, are:

(b) Trigonal bipyramidal and trigonal bipyramidal NaOH  Cl2  (A)  side products (hot & conc.)
(c) Octahedral and square pyramidal Ca(OH) 2  Cl2  (B)  side products (dry)
(d) Trigonal bipyramidal and pentagonal planar (2020)
19. Aqua regia is used for dissolving noble metals (Au, Pt, (a) NaClO3 and Ca(ClO3)2 (b) NaOCl and Ca(ClO3)2
etc.) The gas evolved in this process is : (2020)
(c) NaOCl and Ca(OCl)2 (d) NaClO3 and Ca(OCl)2
(a) N 2 O3 (b) N2 26. The number of bonds between sulphur and oxygen
(c) N 2 O5 (d) NO atoms in S2 O82 and number of bonds between
20. In a molecule of pyrophosphoric acid, the number of sulphur and sulphur atoms in rhombic sulphur,
P-OH, P = O and P – O – P bonds/moiety(ies) respectively, are: (2020)
respectively are : (2020) (a) 8 and 6 (b) 4 and 6
(a) 3, 3 and 3 (b) 4, 2 and 1 (c) 8 and 8 (d) 4 and 8
(c) 2, 4 and 1 (d) 4, 2 and 0 27. White phosphorus on reaction with concentrated
21. On heating, lead(II) nitrate gives a brown gas(A). The NaOH solution in an inert atmosphere of CO2 gives
gas(A) on cooling changes to a colourless solid/liquid phosphine and compound (X). (X) on acidification with
(B). (B) on heating with NO changes to a blue solid(C). HCl gives compound (Y). The basicity of compound
The oxidation number of nitrogen in solid (C) is:
(Y) is: (2020)
(2020)
(a) +3 (b) +4 (a) 4 (b) 2
(c) +2 (d) +5 (c) 3 (d) 1
p -BLOCK ELEMENTS (GROUP 15-18) 58
28. Which of the following oxides are acidic, basic and 35. Fex2 and Fey3 are known when x and y are :
amphoteric, respectively? (2020) (2020)
(a) MgO,Cl2O, Al2O3 (b) N2O3,Li2O,Al2O3 (a) x = F, Cl, Br, I and y = F, Cl, Br, I
(c) SO3,Al2O3,Na2O (d) P4O10,Cl2O,CaO (b) x = F, Cl, Br, I and y = F, Cl, Br
(c) x = F, Cl, Br and y = F, Cl, Br, I
(d) x = Cl, Br, I and y = F, Cl, Br, I
29. The correct statement with respect to dinitrogen is?
(2020) 36. Chemical nature of the nitrogen oxide compound obtained
(a) Liquid dinitrogen is not used in cryosurgery from a reaction of concentrated nitric acid and P4 O10
(b) N2 is paramagnetic in nature (in 4 : 1 ratio) is: (2021)
(c) It can combine with dioxygen at 25°C (a) acidic (b) basic
(d) It can be used as an inert diluent for reactive (c) amphoteric (d) neutral
chemicals 37. Which one of the following gases is reported to retard
30. Reaction of an inorganic sulphite X with dilute H2SO4 photosynthesis (2021)
generates compound Y. Reaction of Y with NaOH gives (a) CO (b) CFCs
(c) CO2 (d) NO2
X. Further, the reaction of X with Y and water affords
38. Which one of the following group-15 hydrides is least
compound Z. Y and Z, respectively, are : (2020) stable? (2021)
(a) SO2 and NaHSO3 (b) S and Na2SO3 (a) AsH3 (b) BiH3
(c) SO2 and Na2SO3 (d) SO3 and NaHSO3 (c) PH3 (d) SbH3
39. Number of Cl = O bonds in chlorous acid, chloric acid and
31. The reaction of NO with N 2 O 4 at 250K gives: perchloric acid respectively are: (2021)
(2020) (a) 3, 1 and 1 (b) 4, 1 and 0
(a) N 2 O (b) NO 2 (c) 4, 1 and 0 (d) 1, 2 and 3
(c) N 2 O5 (d) N 2 O3 40. The incorrect statement is: (2021)
(a) Cl2 is more reactive than ClF
32. Given below are two statements:
(b) F2 is more reactive than ClF
Statement I:  and  forms of sulphur can change (c) On hydrolysis CIF froms HOCl and HF.
reversibly between themselves with slow heating or slow (d) F2, is a stronger oxidizing agent than Cl2 in aqueous
cooling. solution
Statement II: At room temperature the stable crystalline 41. The number of non-ionisable hydrogen atoms present in
form of sulphur is monoclinic sulphur. the final product obtained from the hydrolysis of PCl5 is
In the light of the above statements, choose the correct (2021)
answer from the options given below (2020) (a) 0 (b) 2
(a) Statement I is true but statement II is false (c) 1 (d) 3
(b) Both Statement I and Statement II are true 42. Chalcogen group elements are: (2021)
(c) Both Statement I and Statement II are false (a) Se, Tb and Pu (b) Se, Te and Po
(d) Statement I is false but Statement II is true (c) S, Te and Pm (d) O, Ti and Po
33. The correct order of bond dissociation enthalpy of 43. In polythionic acid, H2SxO6 (x = 3 to 5) the oxidation state(s)
halogens is (2020) of sulphur is/are: (2021)
(a) Cl2 > Br2 > F2 > I2 (b) Cl2 > F2 > Br2 > I2 (a) + 5 only (b) + 6 only
(c) F2 > Cl2 > Br2 > I2 (d) I2 > Br2 > Cl2 > F2 (c) + 3 and + 5 only (d) 0 and + 5 only
34. A group 15 element, which is a metal and forms a hydride 44. Which one of the following is used to remove most of
with strongest reducing power among group 15 hydrides. plutonium from spent nuclear fuel? (2021)
The element is: (2020)
(a) ClF3 (b) O2F2
(a) As (b) Sb
(c) I2O5 (d) BrO3
(c) Bi (d) P
p -BLOCK ELEMENTS (GROUP 15-18) 59
45. Which one of the following is formed (mainly) when red (A)  -sulphur
phosphorus is heated in a sealed tube at 803 K? (B)  -sulphur
(2021)
(C) S2-form
(a) White phosphorus (b) Yellow phosphorus
55. Among the following, the number of halide(s) which is/
(c)  -Black phosphorus (d)  -Black phosphorus are inert to hydrolysis is_____. (2021)
46. Which one of the following correctly represents the order (a) BF3 (b) SiCl4
of stability of oxides, X2O; (X = halogen)? (2021) (c) PCl5 (d) SF6
(a) Br > Cl > I (b) Br > I > Cl 56. A xenon compound ‘A’ upon partial hydrolysis give
(c) Cl > I > Br (d) I > Cl > Br XeO 2 F2 . The number of lone pair of electrons present in
47. The number of S=O bonds present in sulphurous acid,
compound A is .................... . (Round off to the Nearest
peroxodisulphuric acid and pyrosulphuric acid,
Integer) (2021)
respectively are: (2021)
57. These are physical properties of an element (2021)
(a) 2, 3 and 4 (b) 1, 4 and 3
(a) Sublimation enthalpy (b) Ionisation enthalpy
(c) 2, 4 and 3 (d) 1, 4 and 4
(c) Hydration enthalpy (d) Electron gain enthalpy
48. The oxide without nitrogen-nitrogen bond is : (2021)
The total number of above properties that affect the
(a) N2O (b) N2O4
reduction potential is...... .
(c) N2O3 (d) N2O5
58. The number of halogen(s) forming halic (V) acid is
49. The set that represents the pair of neutral oxides of __________. (2021)
nitrogen is : (2021)
(a) N 2 O and NO2 (b) NO and N 2 O Match the Following
(c) N 2 O and N 2 O3 (d) NO and N 2 O3 Each question has two columns. Four options
50. The number of ionisable hydrogens present in the product are given representing matching of elements
obtained from a reaction of phosphorus trichloride and from Column-I and Column-II. Only one of
phosphonic acid is : (2021) these four options corresponds to a correct
(a) 2 (b) 3 matching. For each question, choose the
(c) 1 (d) 0
option corresponding to the correct matching
Numeric Value Type Questions 59. Match List –I with List – II
List I List II
51. Calculate the oxoacid of Sulphur that does not contain
Industrial process Application
bond between Sulphur atoms in the given compounds. A Haber’s process (i) HNO synthesis
H2S4O6 ; H2S2O3 ; H2S2O7 ; H2S2O4 (2019) B Ostwald’s process (ii) Aluminium extraction
C Contact process (iii) NH3 synthesis
52. Chlorine reacts with hot and concentrated NaOH and D Hall-Heroult (iv) H2SO4 synthesis
produces compounds (X) and (Y). Compound (X) gives process
white precipitate with silver nitrate solution. The
AChoose the correct answer from the options given below
average bond order between Cl and O atoms in (Y) is
(2021)
(2020)
(a) A – (iii), B – (iv), C – (i), D – (ii)
53. The number of Cl = O bonds in perchloric acid is,
(b) A – (ii), B – (iii), C – (iv), D – (i)
“……..” (2020)
(c) A – (iii), B – (i), C – (iv), D – (ii)
54. Among the following allotropic forms of sulphur, the (d) A – (iv), B – (i), C – (ii), D – (iii)
number of allotropic forms, which will show
paramagnetism is (2021)
p -BLOCK ELEMENTS (GROUP 15-18) 60
60. Match List-I with List-II

List I List II
Name of oxo acid Oxidation
state of ‘P’
A Hypophosphorous acid (i) +5
B Orthophosphoric acid (ii) +4
C Hypophosphoric acid (iii) +3
D Orthophosphorous acid (iv) +2
(v) +1
Choose the correct answer from the options given below:
(2021)
(a) A – (iv), b – (i), C – (ii), D – (iii)
(b) A – (iv), b – (v), C – (ii), D – (iii)
(c) A – (v), b – (iv), C – (ii), D – (iii)
(d) A – (v), b – (i), C – (ii), D – (iii)
p -BLOCK ELEMENTS (GROUP 15-18) 61

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only one correct option] (d) decomposition of nitrogenous compounds to yield
free nitrogen.
1. Which one of the following elements is most metallic ?
10. Which one of the following is the strongest base ?
(a) P (b) As
(c) Sb (d) Bi (a) AsH3 (b) NH3
2. A white precipitate is obtained on hydrolysis of (c) PH3 (d) SbH3
(a) PCl5 (b) NCl3 11. Which of the following phosphorus is most reactive ?
(c) BiCl3 (d) AsCl3 (a) Red phosphorus (b) White phosphorus
3. In the cationic parts of solid N2O5 and solid N2O4, the (c) Scarlet phosphorus (d) Violet phosphorus
bond order of N–O are, respectively, 12. The reaction of white phosphorus with aqueous NaOH
(a) 3.0 and 2 (b) 2 and 3 gives phosphine and another phosphorus containing
(c) 2.5 and 3.0 (d) 3 in both compound. The reaction type, the oxidation states of
phosphorus in phosphine and other product are
4. Which of the following oxides of nitrogen is a coloured
respectively:
gas ?
(a) redox reaction, -3 and -5
(a) N2O (b) NO (b) redox reaction, +3 and +5
(c) N2O4 (d) NO2 (c) disproportionation reaction, -3 and +1
5. Which of the following compounds consists of a P–P (d) disproportionation reaction, -3 and +3
linkage? 13. There is no S—S bond in
(a) hypophosphoric acid
(b) pyrophosphorous acid (a) S2 O 24 (b) S2 O52
(c) dipolyphosphoric acid (c) S2 O32 (d) S2 O 72
(d) metaphosphoric acid
6. Sulphuric acid reacts with PCl5 to give 14. Which of the following has the highest boiling point?
(a) thionyl chloride H 2 O, H 2S, H 2Se and H 2 Te
(b) sulphur monochloride
(a) H 2 O because of hydrogen bonding
(c) sulphuryl chloride
(d) sulphur tetrachloride (b) H 2 Te because of higher molecular weight
7. Liquid ammonia bottles are opened after cooling them (c) H 2S because of hydrogen bonding
in ice for sometime. It is because liquid NH3
(a) Brings tears to the eyes (d) H2Se because of lower molecular weight
(b) Has a high vapour pressure 15. The products of the chemical reaction between Na2S2O3,
Cl2 and H2O are:
(c) Is a corrosive liquid
(d) Is a mild explosive (a) S, HCl, Na2SO4 (b) S, HCl, Na2S
8. What causes nitrogen to be chemically inert ? (c) S, HCl, Na2SO3 (d) S, NaClO3
(a) Multiple bond formation in the molecule 16. Sodium thiosulphate is prepared by
(b) Absence of bond polarity (a) reducing Na2SO4 solution with H2S
(c) Short internuclear distance (b) boiling Na2SO3 solution with S in alkaline medium
(d) High bond energy (c) neutralising H2S2O3 solution with NaOH
9. Fixation of nitrogen means :
(d) boiling Na2SO3 solution with S in acidic medium
(a) reaction of nitrogen with oxygen.
17. The formation of which of the substance is known as
(b) conversion of free atmospheric nitrogen into tailing of mercury?
nitrogen compounds.
(a) Hg2O (b) HgO
(c) the action of denitrifying bacteria on nitrogen
compounds. (c) Hg(NO3)2 (d) HgS
p -BLOCK ELEMENTS (GROUP 15-18) 62
18. Tailing of mercury test can be used for which of the 28. N 2 H 4 reacts with conc. H 2 SO 4 to produce a salt
following gas?
[NH3 – NH3]2+ SO24  in which
(a) Dioxygen (b) Dihydrogen
(c) Dinitrogen (d) Ozone (a) dN–N (salt) > dN–N (N2H4)
19. O3 cannot oxidise: (b) dN–N (salt) < dN–N (N2H4)
(a) KI (b) FeSO4 (c) dN–N (salt) = dN–N (N2H4)
(c) KMnO4 (d) K2MnO4 (d) Cannot be predicted
20. Which of the following does not have S—S linkage?
29. Sulphur on reaction with concentrated HNO3 gives (A)
(a) S2O 82  (b) S2O 26  which reacts with NaOH gives (B). (A) and (B) are:
(a) H2SO3, Na2S2O3 (b) NO2, Na2S
(c) S2O 52  (d) S2O 32 
(c) H2SO4, Na2SO4 (d) H2S2O3, Na2S2O3
21. Which has maximum pH in aqueous solution?
30. White phosphorus on reaction with limewater gives
(a) NaClO (b) NaClO2 calcium salt of an acid (A) along with a gas (X). Which of
(c) NaClO3 (d) NaClO4 the following is correct?
22. What products are expected from disproportionation (a) (A) on heating gives (X) and O2
reaction of hypochlorus acid? (b) The bond angle in (X) is less than that in case of
(a) HClO3 and Cl2O (b) HClO2 and HClO4 ammonia
(c) HCl and Cl2O (d) HCl and HClO3 (c) (A) is a dibasic acid
(d) (X) is more basic than ammonia
23. HClO4 + P2O5 (A) + (B)
31. Among the oxides given below which are acidic?
(A) and (B) are:
CrO3, Mn2O7, CuO, CO, SO2
(a) HClO3, H3PO4 (b) Cl2O6, HPO3
(a) Only SO2 (b) CrO3, Mn2O7 and SO2
(c) ClO2, H3PO4 (d) Cl2O7 , HPO3
(c) Mn2O7 and SO2 (d) CO and SO2
24. Which of the following is the life saving mixture for an
asthma patient ? 32. In which of the following reactions O2 is not formed as
(a) Mixture of helium and oxygen one of the product?
(b) Mixture of neon and oxygen MnO2
(a) KClO3  
(c) Mixture of xenon and nitrogen Heat
(d) Mixture of argon and oxygen (b) SnCl2 + HCl + O3 


25. The oxidation state of xenon atom in XeF4, HXeO and4 (c) FeSO4 + H2SO4 + O3 

Na4XeO6 are respectively:
(d) PbS + O3 

(a) + 4, + 6, + 6 (b) + 4, + 6, + 7
33. In the following statements which combination of true
(c) + 4, + 6, + 8 (d) + 4, + 5, + 8
(T) and false (F)options is correct?
26. Which of the following compounds is explosive?
(I) Ionic mobility is the highest for I– in water as
(a) XeF2 (b) XeF4
compared to other halides.
(c) XeO3 (d) XeF3
(II) Stability order is : Cl3 > Br3 > I3
27. In the reaction
(III) Reactivity order is F < Cl < Br < I
3Br2  6CO32   3H 2 O  5Br  BrO3  6HCO3
(IV) Oxidizing power order is : F2 < Cl2 < Br2 < I2
(a) bromine is oxidised and carbonate is reduced
(a) TFTF (b) TFFF
(b) bromine is both oxidised and reduced
(c) TFFT (d) FTFT
(c) bromine is reduced and water is oxidised
34. The number of S—S bonds in sulphur trioxide trimer S3O9
(d) bromine is neither oxidised nor reduced
is:
(a) three (b) two
(c) one (d) zero
p -BLOCK ELEMENTS (GROUP 15-18) 63
35. When an inorganic compound reacts with SO2 in aqueous 41. Match the Oxides with solutions in which they are
medium produces (A). (A) on reaction with Na2CO3 gives absorbed
the compound (B) which with sulphur gives a substance Column I Column II
(C) used in photography. The compound (C) is: (A) CO (p) Absorbed by ethanol amine.
(a) Na2S2O3 (b) Na2SO4 (B) CO2 (q) Absorbed by FeSO4 solution
(c) Na2S (d) Na2S2O7 (C) NO (r) Absorbed by aqueous
36. When sulphur is boiled with Na2SO3, a compound (A) is suspension of Cu2Cl2.
produced. (A) with excess of AgNO3 solution gives a (s) Absorbed by KOH solution
compound (B) which is water soluble and produces a 42. Match the compounds with their properties
black coloured sulphide (C). Compounds (A), (B) and (C) Column I Column II
will be respectively:
(A) N2O (p) Neutral towards water
(a) Na2S2O3, Ag2S2O3, Ag2S
(B) NO (q) Acidic towards water
(b) Na2SO4, Ag2SO4, Ag2S
(C) N2O3(unsymmetrical) (r) N–N linkage is present
(c) Na2S2O7, Ag2SO4, Ag2S
(D) N2O4 (s) Molecule having the highest
(d) Na2SO5,Ag2SO5,Ag2SO4 bond order of N–O bond
37. Which of the following is/are correct? (E) N2O5
(a) O3 + moist iodine  HIO3 43. Match the xenon compounds with their properties.
(b) FeCl3 + H2S  colloidal sulphur Column I Column II
(c) O3 + Ag  black silver (A) XeO64– (p) Central atom is sp3d2
(d) All hybridized
38. The following acids have been arranged in the order of (B) XeF4 (q) On treatment with conc.
decreasing acid strength. Identify the correct order. H2SO4 produces XeO4
ClOH (I), BrOH (II), IOH (III) (C) XeO3 (r) Only one lone pair is present
(a) I > II > III (b) II > I > III on the central atom
(c) III > II > I (d) I > III > II (D) XeO2F2 (s) Central atom of the molecule
39. Which of the following reactions of xenon compounds is has four surrounding atoms.
not feasible?
(a) XeO3 + 6HF  XeF6 + 3H2O
Fill in the Blanks
(b) 3XeF4 + 6H2O  2Xe + XeO3+12HF + 1.5 O2
44. ................ phosphorus is reactive because of its highly
(c) 2XeF3 + 2H2O  2Xe + 4HF + O2 strained tetrahedral structure.
(d) XeF6 + RbF  Rb [XeF7] 45. The oxidation state of S atom in H2S2O7 is ....... .
40. White phosphorus (P4) does not have
(a) six P—P single bonds
(b) four P–—P single bonds
(c) four lone pairs of electrons
(d) PPP angle of 60º

Match the Following

Each question has two columns. Four options are
given representing matching of elements from
Column-I and Column-II. Only one of these four
options corresponds to a correct matching, for
each question.
p -BLOCK ELEMENTS (GROUP 15-18) 64

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS

Objective Questions [Only one correct option] 11. Which of the following is not oxidised by O3 ? (2005)
1. The number of P—O—P bonds in cyclic metaphosphoric (a) KI (b) FeSO4
acid is (2000) (c) KMnO4 (d) K2MnO4
(a) zero (b) two 12. The percentage of p-character in the orbitals forming
(c) three (d) four P—P bonds in P4 is (2007)
2. The correct order of acidic strength is (2000) (a) 25 (b) 33
(a) Cl2O7 > SO2 > P4O10 (b) CO2 > N2O5 > SO3 (c) 50 (d) 75
(c) Na2O > MgO > Al2O3 (d) K2O > CaO > MgO 13. Aqueous solution of Na2S2O3 on reaction with Cl2 gives
3. Amongst H2O, H2S, H2Se and H2Te, the one with the (2008)
highest boiling point is (2000) (a) Na2S4O6 (b) NaHSO4
(a) H2O because of hydrogen bonding (c) NaCl (d) NaOH
(b) H2Te because of higher molecular weight 14. The reaction of P4 with X leads selectively to P4O6. The X,
(c) H2S because of hydrogen bonding is (2009)
(d) H2Se because of lower molecular weight (a) dry O2
4. The number of S—S bonds in sulphur trioxide trimer, (S3O9) (b) a mixture of O2 and N2
is (2001) (c) moist O2
(a) three (b) two (d) O2 in the presence of aqueous NaOH
(c) one (d) zero 15. Extra pure N2 can be obtained by heating (2010)
5. Polyphosphates are used as water softening agents (a) NH3 with CuO (b) NH4NO3
because they (2002) (c) (NH4)2Cr2O7 (d) Ba (N3)2
(a) form soluble complexes with anionic species 16. The product formed in the reaction of SOCl 2 with
(b) precipitate anionic species phosphorous is (2014)
(c) form soluble complexes with cationic species (a) PCl3 (b) SO2Cl2
(d) precipitate cationic species (c) SCl2 (d) POCl3
6. For H3PO3 and H3PO4 the correct choice is (2003) 17. The order of the oxidation state of the phosphorus atom
(a) H3PO3 is dibasic and reducing in H3PO2, H3PO4, H3PO3 and H4P2O6 is (2018)
(b) H3PO3 is dibasic and non-reducing (a) H3PO4 > H3PO2 > H3PO3 > H4P2O6
(c) H3PO4 is tribasic and reducing
(b) H3PO4 > H4P2O6 > H3PO3 > H3PO2
(d) H3PO3 is tribasic and non-reducing
7. Which of the following has —O—O— linkage ? (2004) (c) H3PO2 > H3PO3 > H4P2O6 > H3PO4
(a) H2S2O6 (b) H2S2O8 (d) H3PO3 > H3PO2 > H3PO4 > H4P2O6
(c) H2S2O3 (d) H2S4O6
8. Which of the following isomers of phosphorus is Objective Questions II
thermodynamically most stable ? (2005)
[One or more than one correct option]
(a) Red (b) White
(c) Black (d) Yellow
9. A pale blue liquid which obtained by equimolar mixture of 18. The nitrogen oxide (s) that contain (s) N—N bonds (s) is
two gases at – 30ºC is (2005) (are) (2009)
(a) N2O (b) N2O3 (a) N2O (b) N2O3
(c) N2O4 (d) N2O5 (c) N2O4 (d) N2O5
10. Which gas is evolved when PbO2 is treated with conc.
HNO3 ? (2005)
(a) NO2 (b) O2
(c) N2 (d) N2O
p -BLOCK ELEMENTS (GROUP 15-18) 65
19. The correct statement(s) regarding. (i) HClO, (ii) HClO2,
(iii) HClO3 and (iv) HClO4, is (are) (2015)
Numerical Value Type Questions
(a) The number of Cl = O bonds in (ii) and (iii) together is
two
26. Reaction of Br2 with Na2CO3 in aqueous solution gives
(b) The number of lone pairs of electrons on Cl in (ii) and
sodium bromide and sodium bromate with evolution of
(iii) together is three
CO2 gas. The number of sodium bromide molecules
(c) The hybridization of Cl in (iv) is sp3 involved in the balanced chemical equation is (2008)
(d) Amongst (i) to (iv), the strongest acid is (i) 27. Among the following, the number of compounds that
20. The nitrogen containing compound produced in the can react with PCl5 to give POCl3 is O2, CO2, SO2, H2O,
reaction of HNO3 with P4O10 (2016) H2SO4, P4O10. (2009)
(a) can also be prepared by reaction of P4 and HNO3 28. The total number of compounds having at least one
(b) is diamagnetic bridging oxo group among the molecules given below is
(c) contains one N–N bond ......... . (2018)
(d) reacts with Na metal producing as brown gas N2O3, N2O5, P4O6, P4O7, H4P2O5, H5P3O10, H2S2O3, H2S2O5
21. The correct statement(s) about the oxoacids, HClO4 and 29. Ozonolysis of ClO produces an oxide of chlorine. The
HClO, is (are) (2017) average oxidation state of chlorine in this oxide is ____.
(a) The central atom in both HClO 4 and HClO is (2021)
sp3-hybridised Paragraph Type Questions
(b) HClO4 is formed in the reaction between Cl2 and H2O Use the following passage, to solve Q. 30 to Q. 32
(c) The conjugate base of HClO4 is weaker base than H2O Passage
(d) HClO4 is more acidic than HClO because of the The noble gases have closed-shell electronic configuration and
resonance stabilisation of its anion are monoatomic gases under normal conditions. The low boiling
22. The colour of the X2 molecules of group 17 elements points of the lighter noble gases are due to weak dispersion forces
changes gradually from yellow to violet down the group. between the atoms and the absence of other interatomic
This is due to (2017) interactions.
(a) decrease in * – * gap down the group The direct reaction of xenon with fluorine leads to a series of
(b) decrease in ionisation energy down the group compounds with oxidation numbers +2, +4 and +6. XeF4 reacts
(c) the physical state of X2 at room temperature changes violently with water to give XeO3. The compounds of xenon exhibit
from gas to solid down the group rich stereochemistry and their geometries can be deduced
(d) decreases in HOMO-LUMO gap down the group considering the total number of electron pairs in the valence shell.
(2007)
23. The compound(s) which generates N2 gas upon thermal
decomposition below 300ºC is (are) (2018) 30. Argon is used in arc welding because of its
(a) NH4NO3 (b) (NH4)2Cr2O7 (a) low reactivity with metal
(c) Ba(N3)2 (d) Mg3N2 (b) ability to lower the melting point of metal
24. Based on the compounds of group 15 elements, the correct (c) flammability
statement(s) is (are) (2018) (d) high calorific value
(a) Bi2O5 is more basic than N2O5 31. The structure of XeO3 is
(b) NF3 is more covalent than BiF3 (a) linear (b) planar
(c) PH3 boils at lower temperature than NH3 (c) pyramidal (d) T-shaped
(d) The N-N single bond is stronger than the P-P single 32. XeF4 and XeF6 are expected to be
bond (a) oxidising (b) reducing
25. The correct statement(s) related to oxoacids of (c) unreactive (d) strongly basic
phosphorous is(are) (2021)
(a) Upon heating, H3PO3 undergoes disproportionation
reaction to produce H3PO4 and PH3.
(b) While H3PO3 can act as reducing agent, H3PO4 cannot.
(c) H3PO3 is a monobasic acid.
(d) The H atom of P-H bond in H3PO3 is not ionizable in
water.
p -BLOCK ELEMENTS (GROUP 15-18) 66
Use the following passage, to solve Q. 32 to Q. 35
Passage
There are some deposits of nitrates and phosphates in earth’s
crust. Nitrates are more soluble in water. Nitrates are difficult to
reduce under the laboratory conditions but microbes do it easily.
Ammonia forms large number of complexes with transition metal
ions. Hybridisation easily explains the ease of sigma donation
capability of NH3 and PH3. Phosphine is a flammable gas and is
prepared from white phosphorus. (2008)

33. Among the following, the correct statement is

(a) Phosphates have no biological significance in humans
(b) Between nitrates and phosphates, phosphates are
less abundant in earth’s crust
(c) Between nitrates and phosphates, nitrates are less
abundant in earth’s crust
(d) Oxidation of nitrates is possible in soil
34. Among the following, the correct statement is
(a) Between NH3 and PH3, NH3 is a better electron donor
because the lone pair of electrons occupies spherical
‘s’ orbital and is less directional
(b) Between NH3 and PH3, PH3 is a better electron donor
because the lone pair of electrons occupies sp3 orbital
and is more directional
(c) Between NH3 and PH3, NH3 is a better electron donor
because the lone pair of electrons occupies sp3 orbital
and is more directional
(d) Between NH3 and PH3, PH3 is a better electron donor
because the lone pair of electrons occupies spherical
‘s’ orbital and is less directional
35. White phosphorus on reaction with NaOH gives PH3 as
one of the products. This is a
(a) dimerisation reaction
(b) disproportionation reaction
(c) condensation reaction
(d) precipitation reaction
p -BLOCK ELEMENTS (GROUP 15-18) 67

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METALLURGY
 Chapter 12 69

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.

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

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2. METALLURGY
The scientific and technological process used for extraction/
isolation of the metal from its ore is called as metallurgy.
The isolation and extraction of metals from their ores involve the
following major steps :
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 available for concentration of ores. The
selection of the method depends upon the physical properties of
metal and the gangue.
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.
Hydraulic washing
70
2.2.2 Electromagnetic Separation
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.
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.
Froth floatation method
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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 2.3 Extraction of Crude Metal from Concentrated Ore
dried for recovery of the ore particles.
Before reduction, the concentrated ore must be converted into a
When a mineral contains other minerals as impurities. The addition form which is more suitable for reduction. Usually the sulphide
of these agents activates or depresses the flotation property of ore is converted to the metal oxide before reduction, because
other minerals present as impurities and thus helps in separating metal oxides are easier to reduce. Thus isolation of metals from
the impurities. For example galena (PbS) usually contains the concentrated ore involves two major steps as given below:
minerals namely zinc blende (ZnS) and pyrites (FeS2) as impurities.
(i) Conversion to metal oxide
Flotation is carried out by using potassium ethyl xanthate (used
(ii) Reduction of the metal oxide to metal.
as a collector) along with NaCN and Na2CO3 (used as depressing
2.3.1 Conversion to Metal Oxide
agent). It selectively prevents ZnS from coming to the froth but
allows PbS to come with the froth. Conversion of ore into metal oxide is carried out in two ways
depending upon the nature of ore.
2.2.4 Leaching
2.3.1.1 Calcination
Leaching is used if the ore is soluble in some suitable solvent.
It is a process of heating the concentrated ore strongly in a limited
(i) Alumina from Bauxite :
supply of air or in the absence of air. The process of calcination
The principal ore of aluminium, bauxite, usually contains SiO2, brings about the following changes :
iron oxides and titanium oxide (TiO2) as impurities. Concentration
(a) The carbonate ore gets decomposed to form the oxide of the
is carried out by digesting the powdered ore with a concentrated metal, e.g.,
solution of NaOH at 473-523 K and 35 - 36 bar pressure. This way,
FeCO3 (siderite) FeO + CO2;
Al2O3 is leached out as sodium aluminate (and also SiO2 as sodium
silicate) leaving behind the impurities, iron oxide and titanium PbCO3 (cerrusite)) PbO + CO2
oxide.
CaCO3 (calcite ore/lime stone) CaO + CO2
Al2O3(s) + 2NaOH (aq) + 3H2O (l) 2Na [Al(OH)4] (aq)
The aluminate in solution is neutralised by passing CO2 gas and ZnCO3 (calamine) ZnO + CO2
hydrated Al2O3 is precipitated. At this stage, the solution is seeded (b) Water of crystallisation present in the hydrated oxide ore
with freshly prepared samples of hydrated Al2O3 which induces gets lost as moisture, e.g.,
the precipitation of Al(OH)3. 2Fe2O3.3H2O (limonite) 2Fe2O3 (s) + 3H2O(g)-
2Na[Al(OH)4] (aq) + CO2(g) Al2O3.xH2O(s) + 2NaHCO3 (aq)
Al2O3.2H2O (bauxite) Al2O3 (s) + 2H2O(g)-
The sodium silicate remains in the solution and hydrated alumina
(c) Organic matter, if present in the ore, gets expelled and the ore
is filtered, dried and heated to give back pure Al2O3 :
becomes porous. Volatile impurities are removed.
1470 K/calcination
Al2O3.xH2O(s)   Al2O3 (s) + xH2O(g)
or1200o C

These steps comprises the Bayer’s process.

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2.3.1.2 Roasting
It is a process of heating the concentrated ore (generally sulphide
ore) strongly in the excess of air or O2 below its melting point.
Roasting is an exothermic process, once started it does not require
additional heating.
Some of the reactions involving sulphide ores during roasting :

2PbS + 3O2   2PbO + 2SO2 ;
 Acidic flux : Borax, SiO2 (remove basic impurity)
2ZnS + 3O2  2ZnO + 2SO2

2Cu2S + 3O2  2Cu2O + 2SO2
Some times roasting may not bring about complete oxidation.
2 CuFeS2 (copper pyrite) + 4O2 Cu2S + 2FeO + 3SO2
The reduction of the sulphide ore directly into metal by heating it
in air or O2 is called by various names like self-reduction, auto-
reduction, air-reduction etc. The SO2 produced is utilised for
manufacturing of H2SO4.
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
72
2.3.3 Pyrometallurgy
The oxides of less electropositive metals like Pb, Zn, Fe, Sn, Cu
etc. are reduced by strongly heating them with coal or coke, in the
blast furnace.
“The process of extracting the metal by heating the metal oxide
with a suitable reducing agent is called pyrometallurgy.”
Flux : The substance used for remove impurities from the ore to
from fusible material (slag) is called flux.
Basic impurity + Flux  slag
(a) MgCO3 + SiO2  MgSiO3 + CO3 ¯
(b) FeO + SiO2  FeSiO3
Basic flux : MgO, MgCO2, CaCO3 (remove acidic impurity)
Slag : Fusible material formed during reduction process.
(gangue) Acidic impurity + flux  slag
(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)
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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METALLURGY 73
Condition for Spontaneous Process
As in the equation
ΔG TΔS Favourable conditions Gº = Hº – TSº
– ve + ve Any temperature TSº is subtracted, therefore, Gº becomes less negative, i.e., Gº
– ve – ve H  T S is likely to increase with rise in temperature and this trend is
confirmed from the curves.
(Temp. should be low)
(i) The slope of the curves of the formation of metal oxides is
+ ve + ve TS  H
+ve because Gº becomes less negative or increases with
(Temp. should be high) the rise in temperature.
(ii) Each curve is a straight line except when some change takes
(ii) If two reactions are put together in a system and the net G place in phase (s  l or l  g). The temperature at which
of both the reactions is –ve, the overall reaction will occur, such a change occurs is indicated by an increase in the slope
i.e., a reaction with G positive can be made to occur if it is on the +ve side. For example, in the Zn–ZnO curve, the melting
of zinc is indicated by an abrupt increase in the +ve slope at
coupled with another reaction having a large negative G
temperature 692 K.
so that the net G of both the reactions is negative.
(iii) In the case of less reactive metals like silver and mercury, Gº
Such coupling reactions can be easily understood through becomes positive at high temperatures. It indicates that both
Ellingham diagram. silver oxide (Ag2O) and mercury oxide (HgO) are unstable
3.1 Ellingham Diagram and decompose at high temperature.
Ellingham diagram consists of graphs which represent the
variation of standard free energy with temperature of the formation 2Ag 2 O Heat
 4Ag  O 2

of oxides of various elements, i.e., of f G vs T. Similar plots can 2HgO Heat

 2Hg  O 2
also be plotted for sulphides and halides. (iv) In the curve of CO, Gº decreases as Sº increases. This is
These were first plotted by H.J.T. Ellingham. These diagrams help indicated by the downward trend.
us in predicting the feasibility of thermal reduction of an ore. (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
smelting.
Ellingham diagram for formation of some oxides When carbon is to act as a reducing agent, the following three
reactions are possible :
Consider the formation of a metal oxide (MxO). C(s) + O2(g)  CO2(g) ...... (i)
2xM (s) + O2(g)  2 MxO(s) 2C(s) + O2(g)  2CO(g) ...... (ii)
In this reaction, there is decrease in the value of Sº as MxO is 2CO(g) + O2(g)  2CO2(g) ...... (iii)
solid and O2 is a gas, i.e., S is negative. Thus, if temperature is In the first reaction (formation of CO2) there is hardly any change
increased, TSº becomes more negative. in entropy, i.e., Sº  0 and therefore, Gº remains nearly the same

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METALLURGY
with rise in temperature, i.e., Gº is independent of temperature.
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
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.
74
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
the  r G o vs T plots.
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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.

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)
Blast furnace
is considerable negative and thus, reduction of ZnO with coke
At 500 – 800 K temperature range in the blast furnace: occurs easily.

3Fe2 CO3  CO 
 2Fe3O3  CO2
4. ELECTROCHEMICAL PRINCIPLES OF
Fe3CO4  4CO 
 2FeO  4CO2 METALLURGY
Just like principles of thermodynamics are applied to
Fe 2CO3  CO 
 2FeO  CO2 pyrometallurgy, the electrochemical principles are applied in the
At 900 – 1500 K temperature range in the blast furnace: electrolytic reduction of a molten metal salt. This could be
understood through the equation,
C  CO2 
 2CO
G o   nFE o
FeO  CO 
 Fe  CO2
here n is the number of electrons and EO is the electrode potential
Limestone removes silicate impurity of the ore as slag. The slag is of the redox couple formed in the system.
in molten state and separates out from iron. More reactive metals have large negative values of the electrode
The iron obtained from Blast furnace contains about 4% carbon potential. So their reduction is difficult.
and many impurities in smaller amount (e.g., S, P, Si, Mn). This is In simple electrolysis, the Mn+ ions are discharged at negative
known as pig iron and cast into variety of shapes. Cast iron is electrodes (cathodes) and deposited there. Sometimes a flux is
different from pig iron and is made by melting pig iron with scrap added for making the molten mass more conducting.
iron and coke using hot air blast. It has slightly lower carbon
content (about 3%) and is extremely hard and brittle.

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4.1 Application of Electrolysis
Electrolytic reduction is mainly used for the extraction of highly
electropositive metals.
Electrolysis is carried out in a large cells and a small amount of
another suitable electrolyte is added which :
(a) Lowers the melting point of the main electrolyte
(b) Enhances its conductivity
(c) Reduces corrosion troubles
4.1.1 Manufacture of Metallic Sodium (Down’s Process)
Molten NaCl containing a little CaCl2 is electrolyzed between
graphite anode and iron cathode. The various reactions that take
place are :

On Fusion : NaCl  Na   Cl
(Ions become mobile)
On Electrolysis : At Cathode : Na   e  
 Na
At Anode : 2Cl– 
 Cl2 (g) + 2e–
4.1.2 Electrolytic Reduction of Alumina
(Hall-Heroult process)
The purified Al2O3 is mixed with Na3AlF6 (cryolite) or CaF2
(fluorspar) which lowers the melting point of the mixture and
increases conductivity. The fused matrix is electrolysed. Steel
cathode and graphite anode are used. The graphite anode is useful
for reduction to the metal. The overall reaction may be taken as :
2Al2O3 + 3C 4Al + 3CO2
Electrolytic cell for extraction of aluminium
The electrolysis of the molten mass is carried out in an electrolytic
cell using carbon electrodes. The oxygen liberated at anode reacts
with the carbon of anode producing CO and CO2. This way for
76
each kg of aluminium produced, about 0.5 kg of carbon anode is
burnt away. The electrolytic reactions are :
Cathode : Al3+ (melt) + 3e– Al (l)
Anode : C(s) + O (melt)
2–
CO (g) + 2e–
C(s) + 2O2– (melt) CO2(g) + 4e–
5. PURIFICATION OR REFINING OF METALS
Metals obtained by reducing processes still contains some
objectionable impurities and have to be refined. Refining
techniques vary widely from metal to metal and also depend on
the use to which a metal has to be put.
5.1 Liquation Process
This process is used for the purification of the metal, which itself
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
point of the metal to be purified should be lower than than of each
of the impurities associated with the metal. This process is used
for the purification of Sn and Zn, and for removing Pb from Zn-Ag
alloy, which is obtained at the end of Parke’s process and contains
Pb as impurity.
5.2 Distillation Process
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.
Zone refining method
For example pure Si and Ge are used in semiconductors and hence
are purified by this method. Zone refining method is based on the
principle that an impure molten metal on gradual cooling will
deposit crystals of the pure metal, while the impurities will be left
in the remaining part of the molten metal.
5.4 Chromatographic Methods
This method is based on the principle that different components
of a mixture are differently adsorbed on an adsorbent. The mixture
is put in a liquid or gaseous medium which is moved through the
adsorbent. Different components are adsorbed at different levels
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on the column. Later the adsorbed components are removed
(eluted) by using suitable solvent (eluant).
Chromatography method
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
ion (Al3+), and at the cathode (top layer), these ions are reduced
to the pure metal. In operation, molten metal is added to the bottom
of the cell and pure aluminum is drawn off the top. Aluminium
obtained is 99.98% pure.
At anode : Al Al3+ + 3e–
At cathode : Al3+ + 3e– Al
5.6 Vapour Phase Refining
In this method, the metal is converted into its volatile compound
and then collected. It is then heated so that it gets decomposed to
give pure metal. So, following two requirements are essential for
vapour phase refining.
77
(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.
ZrI 4  Zr  2I2
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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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 :

Extraction of Iron

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6.2.1 Various Forms of Iron
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.
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.
80
Varieties of Steel :
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 iron 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.
(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).

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.

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.

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

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SUMMARY

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SOLVED EXAMPLES

Example-1 Sol. 20 karat gold means it consists of 20 parts gold out of 24

parts and four parts of copper.
In blast furnace, iron oxide is reduced by-
(a) Silica (b) CO 20
% of gold = 100  83.33%
(c) C (d) lime stone 24
Ans. (b)
Sol. CO is the main reducing agent in the furnace. Iron oxide is Example-4
reduced to iron by CO. In a blast furnace, a substance
called coke (mainly C) reacts with oxygen, O2, to form High purity copper is obtained by-
carbon monoxide, CO. The carbon monoxide (a strong (a) Zone refining (b) Poling
reducing agent) then reacts with iron oxide (in the form of
hematite or magnetite) to form pig iron (mainly Fe) and (c) Electrolytic refining (d) Cupelling
carbon dioxide. Ans. (c)
Sol. After electrolytic refining. Purity of copper is 99.99% which
Example-2 is enough for electrical applications.
Purple of cassius is –
(a) Pure gold (b) Solid solution of gold Example-5
(c) Gold (I) hydroxide (d) Gold (III) chloride A metal is extracted from its sulphide ore and
the process of extraction involves the following steps.
Ans. (b)
Sol. It is obtained by treating gold (III) chloride solution with Metal sulphide 
(A) Concentrated ore 
(B) Matte
SnCl2 
(C) Impure metal  (D) Pure metal. Identity the
steps (A), (B), (C) and (D).
2AuCl3 + 3SnCl2  2Au + 3 SnCl4
Sol.
Sol. (A) Froth floatation process. Sulphide ores are
SnCl4 so formed hydrolyses as follows

SnCl4 + 4H2O  Sn(OH)4 + 4HCl concentrated by froth-floatation process.

stannic acid
(B) Roasting Metal sulphides are roasted to convert into
The colloidal precipitate of stannic acid absorbs colloidal metal oxide and to remove impurities.
particles of gold. This has beautiful purple colour and is In roasting; 2CuFeS2 + O2  Cu2S + 2FeS + SO2.
known as purple of cassius. It is used for colouring glass
2FeS + 3O2  2FeO + 2SO2.
(ruby red) and pottery.
2Cu2S + 3O2  2Cu2O + 2SO2.
Example-3
Percentage of gold in 20 Carat gold- FeO + SiO2  FeSiO3

(a) 80% (b) 83.33% (C) Bessemerisation/self reduction. Reduction of metal

(c) 86.66% (d) 96% oxide by its sulphide takes place in Bessemer
Ans. (b) converter.
(D) Electro-refining. Pure metal is obtained at cathode.
Mn+ + n e–  M
METALLURGY 86

Example-6 (b) Because sulphide ores are preferentially wetted by

oil and impurities by water.
Write chemical equations for metallurgical processes to
Example-9
represent :
Write a non-exothermic reaction taking place in the blast
(i) roasting of galena (PbS) in limited supply of air at furnace during extraction of iron.
moderate temperature.
heat
(ii) reduction of Cu2O using coke as a reducing agent. Sol.
Sol. CaCO 3  CaO  CO 2
Calcium Calcium
Carbonate oxide
(iii) deposition of pure silver from an aqueous solution
of Ag+.

Sol.
Sol. (i) 2PbS + 3O2  2PbO + 2SO2 ; Example-10

PbS + 2O2  PbSO4 What is a flux ? What is the role of flux in the metallurgy
of Iron and Copper ?
(ii) Cu2O + C  2Cu + CO
Sol.
Sol. Flux : Flux is a substance that combines with gangue to
(iii) Ag+ + e– (   Ag  (at cathode)
Electrolys is )
form slag. The gangue may be present in roasted or the
calcined ore.

Example-7 In metallurgy of Cu

Write the overall reaction taking place in the process

FeO  SiO 2  Fe SiO 3
used for the electrolysis of Alumina by Hall-Heroult (Slag )
process.
In the blast furnace, CaO (flux) removes silica present in
Sol.
Sol. The reaction taking place in process used for the
the ore
electrolysis of Alumina by Hall-Heroult process is
In metallurgy of iron
2Al 2O 3  3C 
 4Al  3CO 2
( Carbon )
( Alumina ) ( Aluminium ) CaO  SiO 2  Ca SiO 3
(Slag )

Example-8 Example-11

(a) Extraction of Au by leaching with NaCN involves Why can’t aluminium be reduced by carbon ?
both oxidation and reduction. Justify by giving
equations for the reactions involved. Sol. Aluminium is a strong reducing agent than carbon. Hence
Sol.
(b) Why is the froth flotation method selected for the aluminium (Al) cannot be reduced by carbon.
concentration of sulphide ores ?
Sol.
Sol. (a) Oxidation of Au to Au+ Example-12
4Au(s) + 8 CN– (aq) + 2H2(aq)O + O2(g)  4[Au(CN)2(aq)]– (a) What is the role of depressant in froth floatation
process ?
4OH aq 
(b) Out of C and CO which is a better reducing agent
Reduction of Au to Au + for FeO
(i) In the lower part of blast furnace
 2 (Higher temperature)
2  Au  CN  2   Zn s    Zn  CN 4   2 Au s 
 aq   aq  (ii) In the upper part of blast furnace
(Lower temperature)
METALLURGY 87

Sol.
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-13
What are chief ores of Zinc ? Write chemical reactions
taking place in the extraction of zinc from zinc blende.
Sol. The chief ores of zinc are :
Sol.
(i) Zinc blende, ZnS This method is very useful for producing semiconductor
(ii) Calamine, ZnCO3 and other metals of very high purity like germanium,
silicon, boron etc.
(iii) Zincite, ZnO
(ii) Electrolytic refining : In this method, the impure metal is
Extraction of zinc : The zinc from zinc blende is extracted made to act as anode. A strip of the same metal in pure
by roasting followed by reduction with coke. form is used as Cathode. They are put in a suitable
(a) Roasting : The concentrated ore is heated with oxygen at electrolyte both containing soluble salt of the same metal.
900°C in reverberatory furnace to convert zinc sulphide to The more basic metal remains in the solution and the less
zinc oxide. basic ones go to the anode mud. The reactions are
Anode : M  Mn+ + ne–
2 ZnS  3O 2  2 ZnO  2SO 2
( Zinc blende ) ( Zinc oxide )
Cathode : Mn+ + ne–  M
(b) Reduction : The reduction of zinc oxide is done using Copper and zinc are refined by this method.
coke.
(iii) Distillation : In this method, the impure metal is evaporated
ZnO  C  Zn  CO673 K to obtain the pure metal as distillate. This method is very
useful for low boiling metals like zinc and mercury.
The metal is distilled off and collected by rapid chilling.

Example-15
Example-14
Explain the vapour phase refining method for extraction
Outline the principles of refining of metals by the of metal. Give example.
following methods :
Sol.
Sol. Vapour phase refining : In this method, the metal is
(i) Zone refining converted into its volatile compound and collected
(ii) Electrolytic refining elsewhere. It is then decomposed to give pure metal. There
are two requirements :
(iii) Distillation
(i) the metal should form a volatile compound with an
Sol.
Sol. (i) Zone refining : This method is based on the principle available reagent.
that the impurities are more soluble in the melt than in the
solid state of the metal. (ii) the volatile compound should be easily decomposable,
so that recovery is easy.
A circular mobile heater is fixed at one end of the rod of the
impure metal. The molten zone moves along with the heater
which is moved forward. As the heater moves forward, the
pure metal crystalises out of melt and the impurities pass
on into the adjacent molten zone. This process is repeated
several times and the heater is moved in the same direction.
At one end, impurities get concentrated.
METALLURGY 88
is produced at Cathode and oxygen gas is evolved at the
anode reacts with carbon of anode producing CO and
Example-16
CO2. The molten aluminium is drawn from the bottom of
Name the principal ore of aluminium and describe how the tank.
aluminium metal is extracted from this ore.
The overall reactions may be written as
Sol. Extraction of Aluminium :
Sol.
Cathode : 2Al3+ (melt) + 6e–  2Al ()
Principal (main) ore of aluminium = Bauxite (Al2 O3× H2O)
Anode : C(s) + O2– (melt)  CO (g) + 2e–
Other ores :
C(s) + 2O2–  CO2 (g) + 4e–
(i) cryolite - Na3 Al F6
The anodes burn away. Therefore, they must be replaced
(ii) Orthoclase - K Al Si3O8 from time to time.
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-1 : (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.
Al2O3 + 2NaOH + 3H2O  2Na[Al(OH)4]
Or Electrolytic reduction of alumina

Al2O3 (s) + 2NaOH (aq) + 3H2O ()  2Na[Al(OH)4] (aq)

The filtrate sodium aluminate and sodium silicate is diluted Example-17
with aluminium hydroxide which precipitates the aluminium Explain the Froth Floatation Method.
hydroxide leaving behind sodium silicate in solution.

Na[Al(OH) 4 ] H
2O
 Al(OH)3  NaOH Sol.
Sol. Froth Floatation Method :
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
METALLURGY 89

The method has been in use for removing gangue from from the bottom of the furnace and coke is burnt to give
sulphide ores. In this process, a suspension of the temperature upto 2200 K in the lower portion itself. The
burning of coke supplies most of the heat required in this
powdered ore is made with water. To it, collectors and
process. The CO (Carbon monoxide) and heat moves to
froth stabilisers are added. Collectors (e.g., pine oils, fatty upper part of the furnace. The temperature is lower in upper
acids, xanthates, etc.) enhance non-wettability of the part.
mineral particles and froth stabilisers (e.g., Cresols, aniline)
The reduction of Fe2O3 takes place at about 500-800 K
stabilise the froth.
The mineral particles become wet by oils while the gangue 3Fe 2 O 3  CO  2Fe 3O 4  CO 2
( Iron ore )
particles by water. A rotating paddle agitates the mixture
and draws air in it. As a result, froth is formed which carries Fe3O4 + CO  3FeO + CO2
the mineral particles. The froth is light and is skimmed off. At 900-1500 K, the carbon-dioxide reacts with coke to give
It is then dried for recovery of the ore particles. CO which combine FeO to give Iron.
C + CO2  2 CO
Example-18 FeO + CO  Fe + CO2
Explain the magnetic separation process.
Limestone is decomposed to CaO which removes silicate
Sol. Magnetic separation process : This process is based on
Sol. impurity of the ore as slag
differences in magnetic properties of the ore components.
If either the ore or the gangue (one of these two) is capable CaCO 3  CaO  CO 2
of being attracted by a magnetic field, then such ( Limestone )

separations are carried out (e.g., in case of iron ores). The

ground ore is carried on a conveyer belt which passes CaO  SiO 2  CaSiO 3
over a magnetic roller. Slag

The slag is in molten state and separated out from iron.

Example-21
(a) Write the names of two ores of copper.
(b) Which method is commonly used to extract copper.
Sol.
Sol. (a) Main ores of copper are :
(i) Copper pyrites - CuFeS2
(ii) Copper glance - Cu2S
Example-19
(iii) Malachite - CuCO3Cu (OH)2
Give the names of two chief ores of aluminium.
(b) Commonly used method to extract the copper metal from
Sol.
Sol. (i) Bauxite : Al2O3 × H2O its ore is roasting of sulphide partially and reduction.
(ii) Cryolite : Na3AlF6
Example-22
Example-20 (a) Write the names of any two principal ore of zinc.
Write down the reactions taking place in different zones (b) What are its uses.
in the blast furnace during the extraction of iron. Sol. (a) The principal ore of zinc
Sol.
Sol. Extraction of iron : In the Blast furnace, reduction of iron
Sol. (i) Zinc blende - ZnS
oxides takes place in different temperature. Hot air is blown
(ii) Calamine - ZnCO3
METALLURGY
(iii) Zincite - ZnO
(b) Uses : (i) Zinc is used for galvanising iron.
(ii) Zinc dust is used as a reducing agent in the manufacture
of dye-stuffs, paints, etc.
Example-23
(a) What are main ores of iron.
(b) What is Pig Iron and Cast Iron.
(c) Give the uses of cast iron.
Sol.
Sol. (a) Main ores of Iron :
(i) Haematite - Fe2O3
(ii) Magnetite - Fe3O4
(b) The iron obtained from Blast furnace contains about 4%
carbon and many impurities in smaller amount is known as
Pig Iron.
Cast Iron is made by melting pig iron with scrap iron and
coke using hot air blast. It is extremely hard and brittle.
(c) Uses : (i) Cast Iron is used for casting stoves, railway
sleepers, gutter pipes and toys etc.
(ii) It is used in the manufacture of wrought iron and steel.
Example-24
Why is the froth flotation method selected for the
concentration of Sulphide ores ?
Sol.
Sol. Froth flotation method is used for concentration of sulphide
ores because pine oil selectively wets the sulphide ore
and hence brings it to froth. The sulphide orer are
preferably wetted by the oil & the gangue with water.
Example-25
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.
Sol. (i) Cryolite lowers the melting point of the mixture and
improves the electrical conductivity of the cell.
90
(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-26
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.
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.
Example-27
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.
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.
METALLURGY 91
(ii) Role of NaCN in the extraction of silver is to do the 2FeS + 3O2  2FeO + 2SO22
Leaching of silver ore in the presence of air from which
the silver is obtained Later by replacement FeO + SiO2  FeSiO3
4Ag(s) + 8 CN– (aq) + 2H2O (aq) + O2 (g)  2Cu2S + 3O2  2Cu2O + 2SO2
4[Ag(CN)2]– (aq) + 4 OH– (aq) 2Cu2O + Cu2S  6Cu + SO2
2[Ag(CN)2]– (aq) + Zn (s)  2Ag(s) + [Zn(CN4)]2– (aq) The solidified copper obtained has blistered appearance
due to the evolution of SO2 and so it is called blister copper.

Example-28
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.
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.
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.
Example-29
Differentiate between a mineral and an ore.
Sol.
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-30
What type of ores can be concentrated by magnetic
separation method ?
Sol.
Sol. The ores in which either the ore or gangne [one of these 2]
is capable of being attracted by a magnetic field then such
separations are carried by magnetic separation.
Example-31
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.
Sol.
(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.

FeO  SiO 2 
 Fe SiO 3 2Al2O3 + 3C  4Al + 3CO2
(Slag )
Al 2 O3 electrolys
 is
 2Al3  3O 2
Copper matte is then charged into silica lined convertor.
Some silica is also added and hot air blast is blow to At cathode : Al3+ (melt) + 3e–  Al ()
convert the remaining FeS2, FeO and Cu2S/Cu2O to metallic At anode : O2– – 2e–  O
copper. Following reactions take place :
METALLURGY 92

O + O  O2
C + O2  CO2 Example-34
Graphite rods get burnt forming CO and CO2. The How is “cast iron” different from “pig iron” ?
aluminium thus obtained is refined electrolytically using Sol. Pig iron contains 4% carbon and impurities such as P, S,
Sol.
impure Al as anode, pure Al as cathode and mother cryolite
as electrolyte. Si, Mn in small amounts, while cast iron is obtained by
melting pig iron. It has lesser carbon content (3%) and is
At anode : Al  Al3+ + 3e– more hard and brittle than pig iron.
(impure)
At cathode : Al3+ + 3e–  Al (pure) Example-35
Why copper matte is put in silica-lined converter ?
Example-32 Sol.
Sol. Copper matte is put in silica-lined converter to remove the
Why is the extraction of copper from pyrites more remaining FeO and FeS present in the matte as slag
difficult than that from its oxide ore through reduction ? (FeSiO3).
Sol. The standard Gibbs energy of formation of Cu2S is more
Sol.
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-33
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
Sol.
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.
METALLURGY 93

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Occurrence of Elements in Nature Concentration of Ore
1. Among the following, the most abundant metal in the earth’s
crust is 12. Identify the incorrect statement.
(a) Fe (b) Al (a) The scientific and technological process used for
(c) Cu (d) Na isolation of the metal from its ore is known as
2. Which of the following statements is correct? metallurgy.
(a) All ores are minerals. (b) Minerals are naturally occurring chemical substances
in the earth’s crust.
(b) All minerals are ores.
(c) Ores are minerals that may contain a metal.
(c) A mineral cannot be an ore.
(d) Gangue is an ore contaminated with undesired
(d) An ore is always obtained in a pure form.
materials.
3. Cryotite is the ore of :
13. The impurities present in a mineral are called
(a) Al (b) Cu
(a) gangue (b) flux
(c) Ag (d) Fe
(c) froth (d) nuggets
4. Cassiterite is an ore of
14. Concentration of ores is not done by the
(a) manganese (b) tin
(a) gravity separation process
(c) silicon (d) zinc
(b) electromagnetic separation process
5. Which of the following is a fluoride ore?
(c) froth-floatation process
(a) Cryolite (b) Carnallite
(d) roasting process
(c) Feldspar (d) Ilmenite
15. In the froth-floatation process, the sulphide ores are
6. The mineral carnallite contains
concentrated by mixing the ore with
(a) Ca and Na (b) Ca and Mg
(a) water, pine oil and sodium ethyl xanthate
(c) Mg and K (d) Al and K
(b) water, wax and benzene
7. Which of the following minerals contains calcium as well
(c) water, benzene and sodium ethyl xanthate
as magnesium?
(d) water, matrix and air
(a) Tridymite (b) Aragonite
16. For which ore of the metal, froth floatation method is used
(c) Dolomite (d) Carnallite
for concentration?
8. Among the following statements, the incorrect one is :
(a) Horn silver (b) Bauxite
(a) Calamine and siderite are carbonates
(c) Cinnabar (d) Haematite
(b) Argentite and pyrites are oxides
17. Which one of the following ores is not concentrated by
(c) Zinc blende and pyrites are sulphides froth floatation process?
(d) Malachite and azurite are ores of copper (a) Copper pyrites (b) Pyrargyrite
9. The ore of calcium which contains phosphorus is (c) Pyrolusite (d) Zinc blende
(a) gypsum (b) talc 18. Sulphide ores of metals are usually concentrated by froth
(c) fluorapatite (d) asbestos floatation process. Which one of the following sulphide
10. Which of the following is a sulphide ore? ores offer an exception and is concentrated by chemical
(a) Argentite (b) Cuprite leaching?
(c) Azurite (d) Cerussite (a) Galena (b) Copper pyrite
11. Malachite is an ore of (c) Sphalerite (d) Argentite
(a) iron (b) copper 19. Wolframite (FeWO4), present as an impurity in cassiterite
(c) mercury (d) zinc (SnO2), can be removed by the process of
(a) froth floatation (b) gravity separation
(c) electromagnetic separation (d) zone refining
METALLURGY 94
20. Sulphide ores are generally concentrated by the 29. Which of the following reactions represents the self-
(a) gravity separation process reduction process?
(b) electro magnetic separation process
 2HgS  3O2  2HgO  2SO 2
(c) froth-floatation process (a)  2HgO  HgS  3Hg  SO
(d) chemical leaching process  2

21. In the froth-floatation process, the ore particles float

because  2Cu 2S  3O 2  2Cu 2 O  2SO 2
(b) Cu S  2Cu O  6Cu  SO
(a) they are light  2 2 2

(b) their surface is not easily wetted by water

(c) they bear electrostatic charge  2PbS  3O2  2PbO  2SO 2
(c)  2PbO  PbS  3Pb  SO
(d) they are insoluble  2

22. Which one of the following ores is best concentrated by (d) All of these
froth-flotation method ? 30. Copper and lead are mainly extracted by
(a) Magnetite (b) Malachite (a) electrolysis
(c) Galena (d) Cassiterite (b) the carbon reduction process
(c) the self-reduction process
Extraction of Crude Metal from Concentrated Ore (d) the thermite process
31. Which one of the following reactions represents a
23. Calcination of ores involves heating the ore below its fusion calcination reaction?
temperature (a) HgS + O2  Hg + SO2
(a) in presence of air (b) Ag2S + 2NaCl  2AgCl + Na2S
(b) in an atmosphere of nitrogen (c) CuCO3.Cu(OH)2  2CuO + CO2 + H2O
(c) in absence of air (d) Al2O3 + 2NaOH  2NaAlO2 + H2O
(d) in presence of superheated steam 32. Which of the following metals cannot be extracted by the
24. Roasting of ores is done carbon reduction process?
(a) in absence of air (a) Zn (b) Fe
(b) in presence of a limited supply of air (c) Al (d) Sn
(c) in presence of superheated steam 33. Which of the following factors is of no significance for
(d) in presence of an excess of oxygen roasting sulphide ores to the oxides and not subjecting the
sulphide ores to carbon reduction directly.
25. A flux is often added to remove impurites from an ore in a
blast furnace. In the reaction (a) Metal sulphides are thermodynamically more stable
than CS2
CaO + SiO2  CaSiO3
(b) CO2 is thermodynamically more stable than CS2
the slag and the flux are
(c) Metal sulphides are less stable than the corresponding
(a) SiO2 and CaO (b) CaSiO3 and CaO
oxides.
(c) CaO and SiO2 (d) SiO2 and CaSiO3
(d) CO2 is more volatile than CS2
26. Calcination is used in metallurgy for removal of ?
34. The metal which is extracted by electrolytic reduction is
(a) Water and sulphide (b) Water and CO2
(a) Sn (b) Pb
(c) CO2 and H2S (d) H2O and H2S
(c) Zn (d) Ca
27. By which of the following processes is an oxide ore reduced
35. Which of the following changes takes place during
to the free metal?
roasting?
(a) Leaching (b) Smelting
(a) Oxidation-reduction
(c) Roasting (d) Calcination
(b) only oxidation
28. Which one of the following is not a basic flux?
(c) Neither oxidation nor reduction
(a) CaCO3 (b) SiO2
(d) Expulsion of metals
(c) CaO (d) MgO
METALLURGY 95
36. The main function of roasting is 44. Refining of impure copper with zinc impurity is to be done
(a) to remove the volatile impurities by electrolysis using electrodes as
(b) to oxidize the metal Cathode Anode
(c) to reduce the metal oxide (a) pure copper pure zinc
(d) to make a slag (b) pure zinc pure copper
(c) pure copper impure copper
(d) pure zinc impure zinc
Thermodynamic Principles of Metallurgy 45. The zone-refining process for purification of metals is based
on
37. Considering Ellingham diagram, which of the following (a) the difference in volatilities of the metal and the impurities
metals can be used to reduce alumina? (b) the difference in fusibilities of the metal and the impurities
(a) Fe (b) Zn (c) the difference in solubilities of the impurities in the molten
(c) Mg (d) Cu and solid states of the metal
38. The metal oxide which cannot be reduced to metal by (d) the difference in the oxidizabilities of the metal and the
carbon is impurities
(a) Al2O3 (b) PbO 46. Certain metals can be obtained in the ultrapure state by
(c) ZnO (d) Fe2O3 heating with iodine and then decomposing the metal iodide
39. The most electropositive metals are isolated from their at a much higher temperature. This method is known as
ores by (a) the van Arkel process (b) the Mond process
(a) high temperature reduction with carbon (c) the liquation process (d) the zone-refining process
(b) self reduction 47. Which of the following metals is refined by the van Arkel
process?
(c) thermal decomposition
(a) Au (b) Cu
(d) electrolysis of fused ionic salts
(c) Ni (d) Ti
Refining 48. The van Arkel method for purification of metals involves
the conversion of the metal into a
40. The liquation process is used for the purification of (a) volatile stable compund
(a) Sn (b) Al (b) volatile unstable compound
(c) Zn (d) Hg (c) nonvolatile stable compound
41. The distillation process (under reduced pressure) is used (d) metal carbonyl
for the purification of 49. Which method of purification is represented by the
(a) Pb (b) Hg following equation?
(c) Sn (d) Cs 773K 1675K
Ti  2I 2  TiI 4 
 Ti  2I 2
42. In electrorefining of metals, the anode is made of
(a) the impure metal concerned (a) Cupellation (b) Poling
(b) the pure metal concerned (c) van Arkel method (d) Zone-refining process
(c) graphite
(d) silica Extraction of Iron, Copper, Gold and Silver
43. During the process of electrolytic refining of copper, some
metals present as impurity settle as ‘anode mud’. These are 50. Which one is the ore of iron :
(a) Fe and Ni
(a) Cuprite (b) Magnatite
(b) Ag and Au
(c) Bauxite (d) None of these
(c) Pb and Zn
51. Which of the following mixtures is called matte?
(d) Sn and Ag
(a) CuO + Cu2S (b) PbS + PbSO4
(c) Cu2S + FeO (d) Cu2S + FeS
METALLURGY 96
52. Blister copper is obtained in 62. The electrometallurgical process (electrolysis of fused salts)
(a) Bessemer converter (b) blast furnace is employed to extract
(c) muffle furnace (d) reverberatory furance (a) lead (b) silver
53. Which of the following elements is present as the impurity (c) sodium (d) copper
to the maximum extent in the pig iron? 63. Calcium is obtained by :
(a) Manganese (b) Carbon (a) Roasting of lime stone
(c) Silicon (d) Phosphorus (b) Electrolysis of calcium chloride in H2O
54. Among the following, the maximum amount of carbon is (c) Electrolysis of molten anhydrous calcium chloride
present in (d) Reduction of calcium chloride with carbon
(a) pig iron (b) steel
(c) wrought iron (d) Invar Extraction of Titanium, Nickel , Zinc, Chromium and
55. In the extraction of iron, slag is produced. Slag is Manganese
(a) CO (b) FeSiO3
(c) MgSiO3 (d) CaSiO3
64. Impure nickel is purified by
56. In the extraction of iron, Fe2O3 is reduced by
(a) the distillation process (b) the Mond process
(a) carbon dioxide
(c) liquation (d) the zone-refining process
(b) aluminium
65. In extractive metallurgy of zinc, partial fusion of ZnO with
(c) carbon and carbon monoxide coke is called
(d) electrolytic reduction (a) smelting (b) calcination
57. Identify the correct statement from the following : (c) roasting (d) sintering
(a) Wrought iron is impure iron with 4% carbon.
(b) Blister copper has blistered appearance due to
Extraction of Aluminium
evolution of CO2
(c) Vapour phase refining is carried out for Nickel by van
66. Aluminium is not present in which of the following
Arkel method.
mineral ?
(d) Pig iron can be moulded into a variety of shapes.
(a) Cryolite (b) Feldspar
58. The cyanide process is used for the extraction of
(c) Fluorspar (d) Mica
(a) Cu (b) Ag
67. Fused cryolite is used in the elctrolytic extraction of
(c) Zn (d) Al
aluminium :
59. Which of the following ligands is used to form the complex
(a) To decomposes alumina (b) To oxidise alumina
from which silver is extracted?
(c) To protect anode (d) To protect cathode
(a) NaCNS (b) NH3
68. Aluminium is extracted by the electrolysis of
(c) NaCN (d) NaCNO
(a) alumina
(b) bauxite
Extraction of Sodium, Calcium and Magnesium (c) molten cryolite
(d) alumina mixed with molten cryolite
60. Of the following metals the one which cannot be obtained 69. During the electrolytic reduction of aluminium, the carbon
by electrolysis of the aqueous solution of its self : anodes are replaced from time to time because
(a) Ag (b) Mg (a) the carbon anodes get decayed
(c) Cu (d) Al (b) the carbon prevents atmospheric oxygen from coming
61. How can we extract sodium from its salt/ore in contact with aluminium
(a) by electrolysis of aqueous NaCl (c) oxygen liberated at the carbon anodes reacts with
(b) by electrolysis of fused NaCl anodes to form CO2
(c) by reduction of NaCl using carbon (d) carbon converts Al2O3 to Al
(d) by reduction of NaCl using aluminium
METALLURGY 97
70. Electrolytic reduction of alumina to aluminium by the Hall- (d) Conduct heat and electricity very easily
Heroult process is carried out 73. Several blocks of magnesium are fixed to the bottom of a
(a) in the presence of NaCl ship to
(b) in the presence of fluorite (a) prevent puncturing by under-sea rocks
(c) in the presence of cryolite which forms a melt at lower (b) keep away the sharks
temperature and increases the electrical conductivity (c) make the ship lighter
(d) in the presence of cryolite which forms a melt at higher (d) prevent action of water and salt
temperature and increases the electrical conductivity 74. In the aluminothermic process, aluminium acts as
71. Which of the following metals is obtained by elctrolytic (a) an oxidizing agent (b) a reducing agent
reduction process : (c) a flux (d) a solder
(a) Fe (b) Cu 75. Which of the following represents the thermite reaction?
(c) Ag (d) Al (a) Mn3O4 + Al  Mn + Al2O3
(b) MgCO3 + SiO2  MgSiO3 + CO2
Uses of Metals (c) Cu2S + Cu2O  Cu + SO2
(d) Fe2O3 + CO  Fe + CO2
72. Which of the following properties of pure metal makes them
more useful than alloys :
(a) They are more harder than alloys
(b) They have high density
(c) Can be extracted very easily
METALLURGY 98

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS

1. In the context of the Hall - Heroult process for the extraction 7. The correct statement regarding the given Ellingham
of Al, which of the following statements is false ?
diagram is:
(2015)
(a) Al is reduced at the cathode to form Al
3+

(b)Na3AlF6 serves as the electrolyte

(c) CO and CO2 are produced in this process
(d)Al2O3 is mixed with CaF2 which lowers the melting point
of the mixture and brings conductivity
2. Which one of the following ores is best concentrated by
froth floatation method ? (2016)
(a) Siderite (b) Galena
(c) Malachite (d) Magnetite
3. Give the correct order of initials T or F for following
statements. Use T if statement is true and F if it is false.
(i) Every mineral is an ore but every ore is not a mineral.
(ii) Slag is product formed during extraction of metal by
combination of flux and impurities.
(iii) Highly pure metals can be obtained by zone refining.
(iv) Carnallite is an ore of magnesium and sodium.
(2019)
(2016)
(a) At l400°C, Al can be used for the extraction of Zn
(a) TTTF (b) FTTF
(c) FTTT (d) TFTF from ZnO

4. Extraction of copper by smelting uses silica as an additive (b) At 500°C, coke can be used for the extraction of Zn
to remove : (2016 ) from ZnO
(a) Cu2S (b) FeO (c) Coke cannot be used for the extraction of Cu from
(c) FeS (d) Cu2O Cu2O
5. In the leaching method, bauxite ore is digested with a (d) At 800°C, Cu can be used for the extraction of Zn
concentrated solution of NaOH that produces ‘X’. When from ZnO
CO2 gas is passed through the aqueous solution of ‘X’, a
8. Hall-Heroult’s process is given by: (2019)
hydrated compound ‘Y’ is precipitated. ‘X’ and ‘Y’
respectively are : (2018) (a) Cu 2
 aq   H2  g   Cu  s   2H  aq 


(a) NaAlO2 and Al2(CO3)3.x H2O (b) Cr2 O3  2AI  Al 2 O3  2Cr

(b) Al(OH)3 and Al2O3.x H2O
(c) 2Al2 O3  3C  4Al  3CO 2
(c) Na[Al(OH)4] and Al2O3.x H2O
(d) ZnO  C 
Coke,1673K
 Zn  CO
(d) Na[Al(OH)4] and Al2(CO3)3.x H2O
9. The reaction that does NOT define calcination is:
6. In the extraction of copper from its sulphide ore, metal is
finally obtained by the oxidation of cuprous sulphide with (2019)
: (2018) (a) Fe 2 O3 +XH 2 O 
Δ
 Fe 2 O3 + XH 2 O
(a) Fe2O3 (b) Cu2O
(b) 2Cu 2S+3O 2 
Δ
 2Cu 2 O + 2SO 2
(c) SO2 (d) CO
(c) ZnCO3 
Δ
 ZnO + CO 2

(d) CaCO3 + MgCO3 

Δ
 CaO + MgO + 2CO 2
METALLURGY 99
10. With respect to an ore, Ellingham diagram helps to predict 17. The correct statement is: (2019)
the feasibility of its (2019) (a) leaching of bauxite using concentrated NaOH solution
(a) Electrolysis (b) Zone refining gives sodium aluminate and sodium silicate.
(c) Vapour phase refining (d) Thermal reduction (b) the Hall-Heroult process is used for the production of
11. The Mond process is used for the: (2019) aluminum and iron.
(a) purification of Ni (b) extraction of Mo (c) pig iron is obtained from cast iron.
(c) purification of Zr and Ti (d) extraction of Zn (d) the blistered appearance of copper during the
12. The one that is not a carbonate ore is: metallurgical process is due to the evolution of CO2.
(2019) 18. Cast iron is used for the manufacture of : (2020)
(a) malachite (b) calamine (a) Wrought iron and steel
(c) siderite (d) bauxite (b) Wrought iron and pig iron
13. The correct statement is (2019) (c) Wrought iron, pig iron and steel
(a) aniline is a froth stabilizer (d) Pig iron, scrap iron and steel
(b) zincite is a carbonate ore. 19. Among the statements (i)-(iv), the correct ones are:
(c) sodium cyanide cannot be used in the metallurgy of (2020)
silver. (i) Lime stone is decomposed to CaO during the extraction
(d) zone refining process is used for the refining of titanium. of iron from its oxides.
14. The electrolytes usually used in the electroplating of gold (ii) In the extraction of silver, silver is extracted as an
and silver, respectively, are: (2019) anionic complex.
  (iii) Nickel is purified by Mond’s process.
(a)  Au  CN  2  and  Ag  CN  2 
(iv)Zr and Ti are purified by Van Arkel method.

(b)  Au  CN  2  and  Ag Cl 2 

(a) (iii) and (iv) only (b) (ii), (iii) and (iv) only

 
(c) (i), (ii), (iii) and (iv) (d) (i), (iii) and (iv) only
(c)  Au  OH  4  and  Ag  OH 2 
20. The processes of calcination and roasting in metallurgical
  industries, respectively, can lead to: (2020)
(d)  Au  NH 3 2  and  Ag  CN 2 
(a) Photochemical smog and ozone layer depletion
15. The idea of froth floatation method came from a person
(b) Photochemical smog and global warming
X and this method is related to the process Y of ores, X
(c) Global warming and photochemical smog
and Y, respectively, are: (2019)1)
(12-04-2019/Shift
(d) Global warming and acid rain
(a) fisher woman and concentration
21. Boron and silicon of very high purity can be obtained
(b) washer woman and concentration
through : (2020)
(c) fisher man and reduction
(a) Liquation (b) Electrolytic refining
(d) washer man and reduction
(c) Zone refining (d) Vapour phase refining
16. In the Hall-Heroult process, aluminium is formed at the
cathode. The cathode is made out of (2019)
(a) Pure Aluminium (b) Carbon
(c) Copper (d) Platinum
METALLURGY 100
22. An Ellingham diagram provides information about : 27. Among the reactions (a) – (d), the reaction(s) that doe s/
(2020) do not occur in the blast furnace during theextraction of
(a) The pressure dependence of the standard electrode iron is/are: (2020)
potentials of reduction reactions involved in the A. CaO + SiO2  CaSiO3
extraction of metals. B. 3Fe2O3 + CO  2Fe3O4 + CO2
(b) The conditions of pH and potential under which a C. FeO +SiO2  FeSiO3
species is thermodynamically stable. 1
D. FeO  Fe + O
(c) The kinetics of the reduction process. 2 2
(d) The temperature dependence of the standard Gibbs (a) A (b) D
energies of formation of some metal oxides. (c) C and D (d) A and D
23. The INCORRECT statement is: (2020) 28. According to the following diagram, A reducesBO2 when
(a) Cast iron is used to manufacture wrought iron the temperature is: (2020)
(b) Brass is an alloy of copper and nickel
(c) German silver is an alloy of zinc, copper and nickel
(d) Bronze is an alloy of copper and tin
24. For a reaction,
4M  s   nO 2  g   2M 2 On  s 
the free energy change is plotted as a function of
temperature. The temperature below which the oxide is
stable could be inferred from the plot as the point at which:
(2020) (a) >1400 °C (b) < 1400 °C
(a) the free energy change shows a change from negative (c) > 1200 °C but < 1400 °C (d) < 1200 °C
to positive value. 29. The element that can be refined by distillation is :
(b) the slope changes from positive to zero (2020)
(a) tin (b) gallium
(c) the slope changes from positive to negative
(c) zinc (d) nickel
(d) the slope changes from negative to positive. 30. Which of the following ore is concentrated using group 1
25. The purest form of commercial iron is: (2020) cyanide salt? (2021)
(a) cast iron (b) wrought iron (a) Calamine (b) Sphalerite
(c) scrap iron and pig iron (d) pig iron
26. The refining method used when the metal and the (c) Siderite (d) Malachite
impurities have low and high melting temperatures, 31. Al2O3 was leached with alkali to get X. The solution of X
respectively, is: (2020) on passing of gas Y, forms Z, X and Z respectively are
(2021)
(a) vapour phase refining (b) distillation
(c) liquation (d) zone refining (a) X  Na  Al  OH 4  , Y  SO 2 , Z  Al 2 O 3

(b) X  Al  OH 3 , Y  SO 2 , Z  Al2 O3 .xH 2 O

(c) X  Al  OH 3 , Y  CO 2 , Z  Al2 O3

(d) X  Na  Al  OH  4  , Y  CO 2 , Z  Al 2 O 3 .xH 2 O
METALLURGY 101
32. Ellingham diagram is a graphical representation of 37. The chemical that is added to reduce the melting point of
(2021) the reaction mixture during the extraction of aluminium is :
(2021)
(a) H vs T (b) G vs T
(a) Kaolite (b) Bauxite
(c) G vs P (d)  G  TS vs T (c) Cryolite (d) Calamine
33. The method used for the purification of Indium is 38. The metal that can be purified economically by fractional
(2021) distillation method is: (2021)
(a) Van Arkel method (b) Liquation (a) Fe (b) Zn
(c) Vapour phase refining (d) Zone refining (c) Cu (d) Ni
34. The process that involves the removal of sulphur from the 39. Consider two chemical reactions (A) and (B) that take place
ores is (2021) during metallurgical process:
(a) Roasting (b) Refining (A) ZnCO 3 s    ZnO s   CO 2  g 
(c) Smelting (d) Leaching
35. Which of the following reduction reaction CANNOT be (B) 2ZnS s   3O 2  g    2ZnO s   2SO 2  g 
carried out with coke? (2021)
The correct option of names given to them respectively is:
(a) Cu 2 O  Cu (b) Fe 2 O 3  Fe (2021)
(a) (A) is calcination and (B) is roasting
(c) Al 2 O3  Al (d) ZnO  Zn (b) Both (A) and (B) are producing same product so both
are roasting
36. The point of intersection and sudden increase in the slope,
(c) Both (A) and (B) are producing same product so both
in the diagram given below, respectively, indicates:
are calcination
(2021)
(d) (A) is roasting and (B) is calcination
40. Sulphide ion is soft base, and its ores are common for
metals.
(a) Pb, (b) Al, (c) Ag, (d) Mg
Choose the correct answer from the options given below:
(2021)
(a) (a) and (c) only (b) (a) and (d) only
(c) (a) and (b) only (d) (c) and (d) only
41. In the leaching of alumina from bauxite, the ore expected to
leach out in the process by reacting with NaOH is:
(2021)

(a) TiO 2 (b) Fe 2 O3

(c) ZnO (d) SiO2

42.
(a) G  0 and reduction of the metal oxide
(b) G  0 and decomposition of the metal oxide
(c) G  0 and decomposition of the metal oxide
(d) G  0 and melting or boiling point of the metal oxide
The addition of silica during the extraction of copper from
its sulphide ore (2021)
(a) converts copper sulphide into copper silicate
(b) converts iron oxide into iron silicate
(c) reduces copper sulphide into metallic copper
(d) reduces the melting point of the reaction mixture
METALLURGY 102
43. The statement that is INCORRECT about Ellingham diagram 49. Given below are two statements.
is (2021) Statement I: The choice of reducing agents for metals
(a) provides idea about the reaction rate. extraction can be made by using Ellingham diagram, a plot
(b) provides idea about free energy change of G vs temperature.
(c) provides idea about changes in the phases during the Statement II: The value of S increases from left to right
reaction in Ellingham diagram.
(d) provides idea about reduction of metal oxide In the light of the above statements, choose statements,
44. Which refining process is generally used in the purification choose the most appropriate answer from the options given
of low melting metals? (2021) below.
(a) Chromatographic method (2021)
(b) Liquation (a) Both Statement I and Statement II are true
(c) Electrolysis (b) Statement I is false, but Statement II is true
(d) Zone refining (c) Both Statement I and Statement II are false
45. Calamine and Malachite, respectively, are the ores of: (d) Statement I is true, but Statement II is false
(2021) 50. Given below are two statements:
(a) Nickel and Aluminium (b) Zinc and Copper Statement I: Sphalerite is a sulphide ore of zinc and copper
(c) Copper and Iron (d) Aluminium and Zinc glance is a sulphide ore of copper.
46. The major components of German Silver are (2021) Statement II: It is possible to separate two sulphide ores
by adjusting proportion of oil to water or by using
(a) Ge, Cu and Ag (b) Cu, Zn and Ni
'depressants' in a froth flotation method.
(c) Zn, Ni and Ag (d) Cu, Zn and Ag
Choose the most appropriate answer from the options given
Numerical Value Type Questions below:
47. In the electrolytic refining of blister copper, the total number (2021)
of main impurities, from the following, removed as anode (a) Statement I is true but Statement II is false.
mud is ________
(b) Both Statement I and Statement II are true.
Pb, Sb, Se, Te, Ru, Ag, Au and Pt (2021)
(c) Statement I is false but Statement II is true.
Assertion Reason
(d) Both Statement I and Statement II are false.
48. Assertion: For the extraction of iron, haematite ore is used.
51. Given below are two statements: one is labelled as Assertion
Reason: Haematite is a carbonate ore of iron. (A) and the other is labelled as Reason (R).
(2019) Assertion (A): Aluminium is extracted from bauxite by the
(a) Only the reason is correct. electrolysis of molten mixture of Al2O3 with cryolite.
(b) Both the assertion and reason are correct, but the Reason (R): The oxidation state of Al in cryolite is +3.
reason is not the correct explanation for the assertion. In the light of the above statements, choose the most
(c) Both the assertion and reason are correct and the appropriate answer from the options given below:
(2021)
reason is the correct explanation for the assertion
(a) (A) is true but (R) is false
(d) Only the assertion is correct
(b) (A) is false but (R) is true
(c) Both (A) and (R) are correct and (R) is the correct
explanation of (A)
(d) Both (A) and (R) are correct but (R) is not the correct
explanation of (A)
METALLURGY 103
Match the Following (a) (a) – (ii); (b) - (iv); (c) - (i); (d) – (iii)

Each question has two columns. Four options are (b) (a) – (iii); (b) - (i); (c) - (iv); (d) – (ii)

given representing matching of elements from (c) (a) – (i); (b) - (iii); (c) - (iv); (d) – (ii)
Column-I and Column-II. Only one of these four (d) (a) – (iv); (b) - (iv); (c) - (ii); (d) – (i)
options corresponds to a correct matching. For 55. Match List-1 with List-2.
each question, choose the option corresponding
List-1 (ore) List-2 (Element Present)
to the correct matching (a) Kernite (i) Tin
52. Match the ores (column A) with the metals (column B): (b) Cassiterite (ii) Boron
(Column A) (Column B) (c) Calamine (iii) Fluorine
Ores Metals (d) Cryolite (iv) Zinc
(I) Siderite (a) Zinc
(II) Kaolinite (b) Copper Choose the most appropriate answer from the options given
(III) Malachite (c) Iron below : (2021)
(IV) Calamine (d) Aluminium
(a)  a    ii  ,  b    iv  ,  c    i  ,  d    iii 
(2019)
(a) (I) - (a); (II) - (b); (III) - (c); (IV) - (d) (b)  a    ii  ,  b    i  ,  c    iv  ,  d    iii 
(b) (I) - (c); (II) - (d); (III) - (b); (IV) - (a)
(c)  a    iii  ,  b    i  ,  c    ii  ,  d    iv 
(c) (I) - (c); (II)- (d); (III) - (a); (IV) - (b)
(d) (I) - (b); (II) - (c); (III)- (d); (IV) - (a) (d)  a    i  ,  b    iii  ,  c    iv  ,  d    ii 
53. Match the refining methods (Column I) with metal (Col-
umn II). (2019) 56. Match List-I with List-II

List – I List-II List-I List-II

(Refining Methods) (Metals) (A) Siderite (i) Cu
(I) Liquation (a) Zr (B) Calamine (ii) Ca
(II) Zone Refining (b) Ni (C) Malachite (iii) Fe
(III) Mond Process (c) Sn (D) Cryolite (iv) Al
(IV) van Arkel Method (d) Ga (v) Zn
Choose the correct answer from the options given below
(a) (I)-(c); (II)-(a); (III) -(b); (IV)-(d) (2021)
(a) A – (i), B – (ii), C – (iii), D – (iv)
(b) (I)-(b); (II) -(c); (III) -(d); (IV)-(a)
(b) A – (iii), B – (v), C – (i), D – (iv)
(c) (I)-(c); (II) -(d); (III)-(b); (IV)-(a) (c) A – (iii), B – (i), C – (v), D – (ii)
(d) (I)-(b); (II)-(d); (III)- (a); (IV)-(c) (d) A – (i), B – (ii), C – (v), D – (iii)
54. Match List -I with List -II.
57. Match List-I with List-II :
List – I (Metal) List-II (Ores)
List-I List-II
(a) Aluminium (i) Siderite (A) Haematite (i) Al2 O 3 .xH 2 O
(b) Iron (ii) Calamine
(B) Bauxite (ii) Fe 2 O3
(c) Copper (iii) Kaolinite
(d) Zinc (iv) Malachite
(C) Magnetite (iii) CuCO 3 .Cu  OH 2
(D) Malachite (iv) Fe3 O 4
Choose the correct answer from the options given below:
(2021)
METALLURGY 104
Choose the correct answer from the options given below: 60. Match List – I with List – II:
(2021)
(a) (A) – (ii), (B) – (iii), (C) – (i), (D) – (iv) List-I List-II
(Name of ore/mineral) (Chemical formula)
(b) (A) – (iv), (B) – (i), (C) – (ii), (D) – (iii)
(A) Calamine (i) ZnS
(c) (A) – (i), (B) – (iii), (C) – (ii), (D) – (iv) (B) Malachite (ii) FeCO3
(d) (A) – (ii), (B) – (i), (C) – (iv), (D) – (iii) (C) Siderite (iii) ZnCO3
58. Match List-I with List-II : (D) Sphalerite (iv) CuCO3.Cu(OH)2

List-I List-II Choose the most appropriate answer from the options given
(A) Mercury (i) Vapour phase refining below : (2021)
(B) Copper (ii) Distillation Refining (a) (a)-(iii), (b)-(iv), (c)-(ii), (d)-(i)
(C) Silicon (iii) Electrolytic Refining
(b) (a)-(iii), (b)-(iv), (c)-(i), (d)-(ii)
(D) Nickel (iv) Zone Refining
(c) (a)-(iv), (b)-(iii), (c)-(i), (d)-(ii)
Choose the most appropriate answer from the option given (d) (a)-(iii), (b)-(ii), (c)-(iv), (d)-(i)
below : (2021)
(a) (A) – (i), (B) – (iv), (C) – (ii), (D) – (iii)
(b) (A) – (ii), (B) – (iii), (C) – (i), (D) – (iv)
(c) (A) – (ii), (B) – (iv), (C) – (iii), (D) – (i)
(d) (A) – (ii), (B) – (iii), (C) – (iv), (D) – (i)
59. Which one of the following metal complexes is most stable?

List-I List-II
(A) Concentration of Ag ore (i) Reverberatory furnace
(B) Blast furnace (ii) Pig Iron
(C) Blister copper (iii) Leaching with dilute
NaCN
(D) Froth floatation method (iv) Sulfide ores
Choose the correct answer from the options given below:
(2021)
(a) (a)–(iii), (b)–(ii), (c)–(i), (d)–(iv)
(b) (a)–(iii), (b)–(iv), (c)–(i), (d)–(ii)
(c) (a)–(iv), (b)–(i), (c)–(iii), (d)–(ii)
(d) (a)–(iv), (b)–(iii), (c)–(ii), (d)–(i)
METALLURGY 105

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

10. Blister copper is refined by stirring molten impure metal
Objective Questions I [Only one correct option]
with green logs of wood because such a wood liberates
1. The two most abundant metals in the earth crust are: hydrocarbon gases (like CH4). This process is called X and
(a) Al, Zn (b) Ag, Au the metal contains impurities of Y. X and Y are
(c) Fe, Cu (d) Fe, Al (a) X = cupellation, Y = CuO2
2. Which of the following is not an ore of iron? (b) X = polling, Y = Cu2O
(a) Haematite (b) Limonite (c) X = polling, Y = CuO
(c) Cassiterite (d) Magnetite
(d) X = cupellation, Y = CuO
3. Select correct matching
(a) Pyrometallurgy  Extraction of Fe 11. The anode mud in the electrolytic refining of silver contains:
(b) Electrometallurgy  Extraction of Al (a) Zn, Cu, Ag, Au (b) Zn, Ag, Au
(c) Hydrometallurg  Extraction of Au (c) Cu, Ag, Au (d) Au only
(d) All above are correct 12. Formation of metallic copper from the sulphide ore in the
4. Copper is extracted from sulphide ore using the method: commercial metallurgical process involves.
(a) carbon reduction 3
(a) Cu 2S  O2  Cu 2 O  SO 2 ; Cu 2 O  C  2Cu  CO
(b) carbon monoxide reduction 2
(c) auto reduction 3
(b) Cu 2S  O2  Cu 2 O  SO2 ; 2Cu 2 O  Cu 2S  6Cu  SO2
(d) none of these 2
5. Which of the following reactions show the process of smelt- (c) Cu 2S  2O 2  CuSO 4 ; CuSO 4  Cu 2S  3Cu  2SO 2
ing?
(a) 2PbO + PbS  3Pb + SO2 3
(d) Cu 2S  O2  Cu 2 O  SO2 ; Cu 2 O  CO  2Cu  CO2
2
(b) 2Na[Au(CN) 2 ]  Zn  Na 2 [Zn(CN) 4 ]  2Au 13. From which of the folowing reaction blister copper is
(c) PbO  C  Pb  CO obtained?
(a) Cu2S + FeO  2Cu + FeO
(d) 2HgS  3O 2  2HgO  2SO 2
(b) Cu2S + FeS  2Cu + FeS2
6. Which of the following reaction forms the basis of (c) Cu2S + 2Cu2O  6Cu + SO2
Goldschmidt alumino-thermite process? (d) Cu2+ + Fe  Fe2+ + Cu
(a) 2Al + N2  2AlN
14. Which of the following pair is incorrectly matched?
(b) 2Al + 3Cl2  2AlCl3
(a) van Arkel method — Zirconium
(c) 2Al + 6HCl 2AlCl3 + 3H2
(b) Kroll’s process — Titanium
(d) 2Al + Fe2O3  Al2O3 + 2Fe
(c) Froth Floatation — Cerussite
7. Chemical leaching is useful in the concentration of :
(d) Distillation — Zinc
(a) Copper pyrite (b) Bauxite 15. Which of the following steps is correctly related to differ-
(c) Cassiterite (d) Cinnabar ent steps inovled in the extraction of Zn from Zinc blende?
8. Which of the following is an ore of magnesium? (a) Gravity method  Froth Floatation  Roasting at
900 - 1000oC  Reduced with coke  Electrolytic
(a) Magnetite (b) Magnesite
refining
(c) Haematite (d) Limonite (b) Roasting at 100o C  Leached with H2SO4 
9. The metal which mainly occurs as oxide ore in nature is: Treatement with milk of lime  Acidified & Electrolysed
(a) Silver (b) Lead (c) Both (a) and (b)
(c) Aluminium (d) Copper (d) None of these.
METALLURGY 106
16. Which of the following process is used in the extractive
hot conc. bubble gas  III 
metallurgy of magnesium?  Product  II  
Al 2 O3 .2H 2 O 
(Impure bauxite)
 I (aqueous soln .)
to change pH
(a) Fused-salt electrolysis
mixed with  IV 
(b) aq. solution electrolysis Al 2 O 3 .2H 2 O  Al at  V 
electrolysed with carbon electrodes
( Pure)
(c) self-reduction
(d) Thermite reduction Which of the following entries correctly summarises
reagents, electrodes & products of the process?
17. Boron can be obtained by various methods but not by:
I II III IV V
(a) thermal decomposition of B2H6 (a) NaOH Al3+ HF Na3AlF6 Cathode
(b) pyrolysis of BI3 (van Arkel) (b) NaOH NaAlO2 CO2 NaF Anode
(c) reducing BCl3 with H2 (c) H2SO4 Al2(SO4 )3 NH3 Na3AlF6 Cathode
(d) NaOH NaAlO2 CO2 Na3AlF6 Cathode
(d) electrolysis of fused BCl3
18. Silver can be separated from lead by:
(a) fractional crystallisation
Objective Questions II
[One or more than one correct option]
(b) amalgamation
23. Which of the following is (are) correct statement(s)?
(c) cupellation
(a) Calamine is the ore of zinc
(d) addition of zinc (Parke’s method)
(b) Pyrolusite is the ore of manganese
19. Which of the following pair of ores cannot be converted
into corresponding metals by pyrometallurgy? (c) Cassiterite is the ore of tin
(a) Ag2S, ZnS (b) Cu2S, HgS (d) Calcite is the ore of calcium
(c) MnO2, SnO2 (d) None of these 24. Which of the following pair consists of ore of the same
metal?
20. Consider the following metallurgical processes:
(a) Bauxite, Limonite (b) Haematite, Siderite
(I) Heating impure metal with CO and distilling the resulting
volatile metal carbonyl (b.p. 430C) and finally (c) Cinnabar, Cassiterite (d) Galena, Cerrusite
decomposition at 1500-2000C to get the pure metal. 25. Pick up the correct statement (s)
(II) Heating the sulphide ore in air until a part is converted (a) All minerals are ores
to oxide and then further heating in the absence of air (b) All minerals cannot be an ore
to let the oxide react with unchanged metal sulphide.
(c) All ores are minerals
(III)Electrolysis of the molten electrolyte containing
approximately equal amounts of the metal chloride and (d) The minerals from which metals can be extracted
NaCl to obtain the metal. profitably are called ores

The processes used for obtaining magnesium nickel and 26. The process (es) by which lighter earthy particles are freed
copper are respectively: from the heavier particles using water is/are:

(a) I, II and III (b) II, III and I (a) Gravity separation (b) Levigation

(c) III, I and II (d) II, I and III (c) Hydraulic washing (d) Leaching
27. The chemical treatment of the ore for concentration is done
21. Select correct statement:
in the case of:
(a) In the decomposition of an oxide into oxygen and metal
(a) aluminium (b) silver
vapour, entropy increases.
(c) copper (d) gold
(b) Decomposition of an oxide is an endothermic change.
28. Which of the following metal (s) is/are commercially
(c)To make G0 negative, temperature should be high extracted by self reduction method from their corresponding
enough so that T S0 > H0. ore?
(d) All are correct statement. (a) Cu (b) Fe
22. In the extraction of aluminium metal, one of the process is (c) Pb (d) Hg
summarised as follows:
METALLURGY 107
29. Froth floatation: (c) carbon combines with oxygen to form poisonous CO
(a) is a physical method of separating mineral from the (d) carbon cannot be used with highly electropositive
gangue metals
(b) is a method to concentrate the ore depending on the 37. Highly electropositive metals can not be extracted by carbon
difference in wettability of gangue and the ore reduction process because these:
(c) is used for the sulphide ores (a) Metals combine with carbon to form carbides
(d) is a method in which impurities sink to the bottom (b) Metals do not react with carbon
(c) Metal oxides are not reduced by carbon
30. The function of adding cryolite in the electrolytic
reduction of alumina by Hall-Heroult process is to : (d) Loss of metal is more by vaporisation
(a) dissolve alumina 38. The extraction of metals from oxide ores involve:
(b) lower the melting point of alumina (a) Reduction with carbon
(c) lower the fuel bill (b) Reduction with aluminium
(d) increase the electrical conductivity of alumina (c) Electrolyte reduction
31. Which of the following ores is/are oxide ore (s)? (d) Reduction with CO

(a) Tinstone (b) Bauxite 39. Which of the following process makes the ore porous?

(c) Cryolite (d) Carnallite (a) Roasting (b) Calcination

32. The smelting of iron in a blast furnace involves the following (c) Reduction (d) Distillation
processes: 40. The difference (s) between roasting and calcination is are:
(a) combustion (b) reduction (a) roasting is highly endothermic while calcination is not
(c) slag formation (d) sublimation (b) partial fusion occurs in calcination but not in
33. The chief reaction(s) occurring in blast furnace during roasting
extraction of iron from haematite is/are: (c) calcination is performed in limited amount of air but
(a) Fe2O3 + 3CO  2Fe + 3CO2 roasting employs excess air
(b) FeO + SiO2  FeSiO3 (d) combustion reaction occur in roasting but not in
(c) Fe2O3+C  2Fe + 3CO calcination
(d) CaO + SiO2  CaSiO3 41. Roasting of copper pyrites is done:
34. Which of the following reaction in the blast furnace (a) to remove moisture
is/are endothermic? (b) to oxidise free sulphur
(a) C(s)  O 2 (g)  CO2 (g) (c) to decompose pyrite into Cu2S and FeS

(b) CO2 (g)  C(s)  2CO(g) (d) to remove volatile organic impurities
42. Metals which can be extracted by smelting process are:
(c) CaCO3 (s)  CaO(s)  CO 2 (g)
(a) Pb (b) Fe
(d) Fe 2 O3 (s)  3CO(g)  2Fe(l ) + 3CO 2 (g) (c) Zn (d) Al
35. The advantage (s) of using carbon to reduce a number of 43. Which one of the following metals can be extracted by
oxides and other compounds are: aluminothermite process?
(a) easy availability of coke (a) Manganese (b) Iron
(b) low cost of carbon (c) Chromium (d) Magnesium
(c) tendency of carbon to show catenation 44. Roasting is carried out to:
(d) presence of carbon lowers the melting point of the oxides (a) Convert sulphide to oxide and sulphate
36. The disadvantage of carbon reduction method are: (b) remove water of hydration
(a) high temperature needed which is expensive and (c) melt the ore
requires the use of a blast furnace
(d) remove arsenic and sulphur impurities
(b) many metals combine with carbon forming carbides
METALLURGY 108
45. Which of the following reaction (s) occur during 53. For how many of the following ores calcination is done
calcination? during extraction of metals?
(a) CaCO3  CaO + CO2 (a) Haematite (b) Calamine (c) dolomite
(d) limestone (e) zinc blende
(b) 4FeS2 + 11O2  2Fe2O3 + 8SO2
54. How many of the following metals and method of their
(c) 2Al (OH)3  Al2O3 + 3H2O
reduction are correctly matched?
(d) CuS + CuSO4  2Cu + 2SO2
1. Al; Electrolytic reduction
46. Which of the following is true for calcination of a metal 2. Pb; Self reduction
ore? 3. Sn; Carbon reduction
(a) It makes the ore more porous 4. Mg; Electrolytic reduction
(b) The ore is heated to a temperature when fusion just 5. Hg; Self reduction
begins 6. Cu; Self reduction
7. Ag; Hydrometallurgy
(c) Hydrated salts lose their water of crystallisation 8. Fe; Carbon reduction
(d) Impurities of S, As and Sb are removed in the form of 9. Zn; Carbon reduction
their volatile oxides
47. Which of the following metals are extracted from its ore by
Assertion Reason
using self-reduction method?
(a) Copper (b) Mercury (A) If both Assertion and Reason are correct and
(c) Lead (d) Silver Reason is the correct explanation of assertion.
48. Amphoteric nature of aluminium is employed in which of (B) If both Assertion and Reason are true but
the following process for extraction of aluminium? reason is not the correct explanation of
(a) Baeyer’s process (b) Hall’s process assertion.
(c) Serpek’s process (d) Dow’s process
(C) If Assertion is true but Reason is false.
49. Which of the following are true for electrolytic extraction of
aluminium? (D) If Assertion is false but Reason is true.
(a) Cathode material contains graphite 55. Assertion (A): Cryolite is used in electrolytic extraction of Al
(b) Anode material contains graphite from alumina.
(c) Cathode reacts away forming CO2 Reason (R): It helps in melting and electrolysis of alumina.
(d) Anode reacts away forming CO2
(a) A (b) B
50. For which of the following metal, the carbon reduction
cannot be used? (c) C (d) D
56. Assertion (A): Reduction of ZnO with carbon is done at 1100oC
(a) Lead (b) Manganese
Reason (R): Go is negative at this temperature thus, process is
(c) Tungsten (d) Iron
spontaneous.
51. Which of the following reduction reactions are actually
employed in commercial extraction of metals? (a) A (b) B
(a) Fe2O3 + 2Al  Al2O3 + 2Fe (c) C (d) D
(b) Cr2O3 + 2Al  Al2O3 + 2Cr 57. Assertion (A): All the ores are mineral.
(c) 2Na [Au (CN)2]+ Zn  Na2 [Zn (CN)4] + 2Au Reason (R): Ores contains metals in combined state.
(d) Cu2S + Pb  Cu + PbS (a) A (b) B
(c) C (d) D
Numerical Value Type Questions

52. Number of oxide ores among the following is –

(i) Cassiterite (ii) Pyrolusite
(iii) Kieserite (iv) Azurite
(v) Chromite (vi) Siderite
METALLURGY 109
58. Assertion (A): Lead, tin and bismuth are purified by liquation (a) A (b) B
method.
(c) C (d) D
Reason (R): Lead, tin and bismuth have low m.p. as compared
to impurities. 66. Assertion (A): Wrought iron is more malleable and ductile
(a) A (b) B than steel.

(c) C (d) D Reason (R): Steel contains slightly less percentage of carbon.
(a) A (b) B
59. Assertion (A): CuFeS2 is concentrated by froth floatation
method. (c) C (d) D
Reason (R): CuFeS2 is main ore of copper.
Match the Following
(a) A (b) B
(c) C (d) D
Each question has two columns. Four options are
given representing matching of elements from
60. Assertion (A): Ores are generally converted into oxides, prior
to reduction. Column-I and Column-II. Only one of these four
Reason (R): Metal oxides can be easily reduced. options corresponds to a correct matching,
(a) A (b) B For each question.
(c) C (d) D
61. Assertion (A): In the extraction of Ag, complex Na [Ag (CN)2]
is reacted with Zn. 67. Column-I Column-II
Reason (R): Zn is d-block transition metal. (A) Ca (p) Found as its native state

(a) A (b) B (B) Zn (q) Found as its sulphide

(C) Cr (r) Found as its carbonate
(c) C (d) D
(D) Ag (s) Found as its oxide
62. Assertion (A): In froth floatation process sodium ethyl
xanthate is used as collector. 68. Column-I Column-II
Reason (R): Sulphide ores are water soluble. (A) Poling (p) Titanium
(B) Cupellation (q) Copper
(a) A (b) B
(C) Electro-refining (r) Silver
(c) C (d) D
(D) van Arkel method (s) Tin
63. Assertion (A): In the electrolytic reduction of Al2O3, cryolite is
used. 69. Column-I Column-II
(A) Metal which occur in the native (p) Hg
Reason (R): Cryolite is an ore of aluminium.
state in nature is
(a) A (b) B
(B) The oxides of metal that can be (q) Ti
(c) C (d) D commercially reduced by
64. Assertion (A): Al2O3 is converted into Al by reduction with Alumino-thermite reduction
carbon at high temp. process is
Reason (R): Carbon has greater affinity for oxygen than (C) Van Arkel method is used for (r) Cr
aluminium. preparing ultrapure metal of
(a) A (b) B (D) Auto reduction process is (s) Ag
(c) C (d) D employed for the sulphide ore of
65. Assertion (A): Thermite mixture Fe2O3+ Al (powder) is used in
the welding.
Reason (R): Al is a good reductant.
METALLURGY 110
70. Column-I Columan-II
Column-II
(A) Mond’s process (p) Cr2 O3  2Al 

 2Cr  Al2 O3

(B) van Arkel process (q) TiCl4  2Mg 


 Ti  2MgCl2

(C) Thermite process (r) Ni(CO) 4   Ni  4CO

(D) Kroll’s process (s) ZrI4   Zr  2I2
METALLURGY 111

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS

Objective Questions I [Only one correct option] 7. The methods chiefly used for the extraction of lead and tin
1. Electrolytic reduction of alumina to aluminium by Hall- from their ores are respectively (2004)
Heroult process is carried out (2000) (a) self reduction and carbon reduction
(a) in the presence of NaCl (b) self reduction and electrolytic reduction
(b) in the presence of fluorite (c) carbon reduction and self reduction
(c) in the presence of cryolite which forms a melt with lower (d) cyanide process and carbon reduction
melting temperature
8. Which ore contains both iron and copper ? (2005)
(d) in the presence of cryolite which forms a melt with higher
(a) Cuprite (b) Chalcocite
melting temperature
(c) Chalcopyrite (d) Malachite
2. The chemical process in the production of steel from
haematite ore involve (2000) 9. Extraction of zinc from zinc blende is achieved by
(2007)
(a) reduction
(a) electrolytic reduction
(b) oxidation
(b) roasting followed by reduction with carbon
(c) reduction followed by oxidation
(c) roasting followed by reduction with another metal
(d) oxidation followed by reduction
(d) roasting followed by self-reduction
3. The chemical composition of ‘slag’ formed during the
smelting process in the extraction of copper is (2001) 10. Native silver metal forms a water soluble complex with a
dilute aqueous solution of NaCN in the presence of
(a) Cu2O + FeS (b) FeSiO3
(c) CuFeS2 (d) Cu2S + FeO (2008)

4. Anhydrous ferric chloride is prepared by (2002) (a) nitrogen (b) oxygen

(a) Heating hydrated ferric chloride at a high temperature (c) carbon dioxide (d) argon
in a stream of air 11. Calamine, malachite, magnetite and cryolite, respectively,
(b) Heating metallic iron in a stream of dry chlorine gas are (2019)
(c) Reaction of ferric oxide with hydrochloric acid (a) ZnSO4, Cu(OH)2, Fe3O4, Na3AlF6
(d) Reaction of metallic iron with hydrochloric acid (b) ZnCO3, CuCO3, Fe2O3, Na3AlF6
5. Which of the following processes is used in extractive (c) ZnSO4, CuCO3, Fe2O3, AlF3
metallurgy of magnesium ? (2002)
(d)ZnCO3, CuCO3.Cu(OH)2, Fe3O4, Na3AlF6
(a) Fused salt electrolysis
(b) Self reduction
(c) Aqueous solution electrolysis Objective Questions II
(d) Thermite reduction [One or more than one correct option]
6. In the process of extraction of gold, (2003)
–
Roasted gold ore + CN + H2O  O
2 [X] + HO 12. Upon heating with Cu2S, the reagent(s) that give copper
metal is/are (2014)
[X] + Zn  [Y] + Au (a) CuFeS2 (b) CuO
Identify the complexes [X] and [Y] (c) Cu2O (d) CuSO4
– 2–
(a) X = [Au(CN)2] , Y = Zn(CN)4]
3– 2–
(b) X = [Au(CN)4] , Y = [Zn(CN)4]
– 4–
(c) X = [Au(CN)2] , Y = [Zn(CN)6]
– 2–
(d) X = [Au(CN)4] , Y = [Zn(CN)4]
METALLURGY 112
13. Copper is purified by electrolytic refining of blister copper.
So  SnO 2  s    56.0JK 1 mol 1 ,
The correct statement(s) about this process is (are)
(2015) So  Sn  s    52.0JK 1mol 1
(a) Impure Cu strip is used as cathode
So  C  s    6.0JK 1 mol 1 ,
(b) Acidified aqueous CuSO4 is used as electrolyte
So  CO 2  g    210.0 JK 1 mol1
(c) Pure Cu deposits at cathode
(d) Impurities settle as anode-mud Assume that the enthalpies and the entropies are
14. Extraction of copper from copper pyrite (CuFeS2) involves temperature independent.
(2016)
(a) crushing followed by concentration of the ore by Match the Following
froth-flotation Each question has two columns. Four options are
(b) removal of iron as slag
given representing matching of elements from
(c) self-reduction step to produce ‘blister copper’ following
evolution of SO2
Column-I and Column-II. Only one of these four
(d) refining of ‘blister copper’ by carbon reduction.
options corresponds to a correct matching,
15. The cyanide process of gold extraction involves leaching
for each question.
out gold from its ore with CN– in the presence of Q in water
to form R. Subsequently, R is treated with T to obtain Au
and Z. Choose the correct option(s) (2019) 18. Match the extraction processes listed in column I with metals

(a) R is [Au(CN)4]– (b) T is Zn listed in column II. (2006)

(c) Q is O2 (d) Z is [Zn(CN)4]2– Column I Column II

16. The correct statement(s) related to the metal extraction (A) Self reduction (p) Lead
processes is(are) (2021) (B) Carbon reduction (q) Silver
(a) A mixture of PbS and PbO undergoes self-reduction
(C) Complex formation and (r) Copper
to produce Pb and SO2
displacement by metal
(b) In the extraction process of copper from copper
pyrites, silica is added to produce copper silicate (D) Decomposition of iodide (s) Boron
(c) Partial oxidation of sulphide ore of copper by roasting, 19. Match the conversions in column I with the type(s) of
followed by self-reduction produces blister copper reaction(s) given in column II. (2008)
(d) In cyanide process, zinc powder is utilized to Column I Column II
precipitate gold from Na[Au(CN)2] (A) PbS  PbO (p) Roasting
(B) CaCO3  CaO (q) Calcination
Numerical Value Type Questions (C) ZnS  Zn (r) Carbon reduction
(D) Cu2S  Cu (s) Self reduction
17. Tin is obtained from cassiterite by reduction with coke.
Use the data given below to determine the minimum
temperature (in K) at which the reduction of cassiterite by
coke would take place. (2020)
1
At 298K :  f H (SnO 2 (s))  581.0 kJ mol ,
0

 f H 0  CO 2  g    394.0 kJ mol1
METALLURGY 113
20. Match each of the reactions given in column I with the 23. Write the balanced chemical reactions involved in the
corresponding product(s) given in column II. (2009) extraction of lead from galena. Mention oxidation state of
Column I Column II lead in litharge. (2003)

(A) Cu + dil. HNO3 (p) NO 24. A1 and A2 are two ores of metal M. A1 on calcination gives
black precipitate, CO2 and water.
(B) Cu + conc. HNO3 (q) NO2
(C) Zn + dil. HNO3 (r) N2O black solid + CO2 + H2O
ion
(D) Zn + conc. HNO3 (s) Cu(NO3)2 l ci nat
c a
A1 dil. H ; A2 roasting metal + gas
(t) Zn(NO3)2 Cl.
KI
I2 + ppt. K2Cr2O7
+ H2SO4
Subjective Type Questions
21. Write the balanced chemical equation for developing green colour
photographic films. (2000)
Identify A1 and A2. (2004)
22. Write the chemical reactions involved in the extraction of 25. Give the number of water molecule (s) directly bonded to
silver from argentite. (2000) the metal centre in CuSO4. 5H2O. (2009)
METALLURGY 114

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d & f BLOCK ELEMENTS
 Chapter 13 116

d & f BLOCK ELEMENTS

1. d BLOCK ELEMENTS - INTRODUCTION

1.1 Definition
“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.
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, 104
Rf to 112
Cn, 10 elements)  4th Transition
series.

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d & f Block Elements
d & f BLOCK ELEMENTS 117
1.3 Electronic Configuration Thus, the electronic configuration of chromium (Z = 24) and copper
In d-block elements with increase in atomic number, the d-orbitals (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2 2s2 2p6 3s6 3p6 3d10 4s1
of penultimate shell i.e. (n-1) d are gradually filled by electrons. respectively.
The general electronic configuration of d-block element is, (n-1) 1.4 General Properties of Transition Elements
d1-10, ns0-2.
1.4.1 Physical Properties
Depending upon the d-orbitals of which penultimate shell (i.e. n =
All the transition elements show typical metallic properties like
4, 5, 6, 7) are filled, four rows (called series) of ten elements each
high tensile strength, ductility, malleability, high thermal and
obtained. They correspond to 3d, 4d, 5d and 6d subshells.
electrical conductivity and metallic lustre. With the exceptions of
Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’ subshell, Zn, Cd, Hg and Mn, they have one or more typical metallic
hence ns orbital is filled first then (n – 1) d orbitals. structures at normal temperatures.
The electronic configuration of d-block elements of four series is Lattice Structures of d-Block Elements
shown as follows : Sc Ti V Cr Mn Fe Co Ni Cu Zn
First (3d) Transition Series (Sc–Zn) hcp hcp bcc bcc X bcc ccp ccp ccp X
(bcc) (bcc) (bcc, (hcp) (hcp) (hcp)
At. No. 21 22 23 24 25 26 27 28 29 30 ccp)
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
4s 2 2 2 1 2 2 2 2 1 2 hcp hcp bcc bcc hcp hcp ccp ccp ccp X
3d 1 2 3 5 5 6 7 8 10 10 (bcc) (bcc) (hcp)
La Hf Ta W Re Os Ir Pt Au Hg
Second (4d) Transition Series (Y-Cd) hcp hcp bcc bcc hcp hcp ccp ccp ccp X
At. No. 39 40 41 42 43 44 45 46 47 48 (ccp, (bcc)
bcc)
Element Y Zr Nb Mo Tc Ru Rh Pd Au Cd
5s 2 2 1 1 1 1 1 0 1 2 The melting and boiling points of transition metals are very high.
4d 1 2 4 5 6 7 8 10 10 10 The high melting points of these metals are attributed to the
Third (5d) Transition Series (La–Hg) involvement of greater number of electrons from (n-1)d in addition
At. No. 57 72 73 74 75 76 77 78 79 80 to the ns electrons.
Element La Hf Ta W Re Os Ir Pt Au Hg
6s 2 2 2 2 2 2 2 1 1 2
5d 1 2 3 4 5 6 7 9 10 10
Fourth (6d) Transition Series
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 additional
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 exactly half-filled with
configuration 3d5 4s1 and that in case of copper, it gets completely Melting points of transition elements
filled with configuration 3d10 4s1. This can be explained on the In any series of transition elements the melting points rise to a
basis of exchange energy. 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

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d & f Block Elements
d & f BLOCK ELEMENTS
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.
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.
(iii) At the end of the period, there is a slight increase in the
atomic radii.
118
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.)
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.
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d & f Block Elements
d & f BLOCK ELEMENTS 119
Ionisation Enthalpies of 3d Series of Transition Elements
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Ionisation enthalpy/ i Ho /kJ mol-1

lHo I 631 656 650 653 717 762 758 736 745 906
lH o
II 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734
lH o
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 M 3+/M 2+  -0.37 -0.26 -0.41 +1.57 +0.77 +1.97   

Explanation
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.
(vi) The first ionisation enthalpies of 5d elements are higher as
compared to those of 3d and 4d elements. This is because
the weak shielding of nucleus by 4f electrons in 5d elements
results in greater effective nuclear charge acting on the outer
valence electrons.
1.4.5 Oxidation State
(1) With the exception of few elements, most of the d-block
elements show more than one oxidation state i.e. they show
variable oxidation states. The elements show variable
oxidation state because of following reasons:
(i) ‘(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.
(ii) After removing ‘s’ electrons, the remainder is called Kernel
of the metal cations. In d-block elements, the Kernel is
unstable and therefore it loses one or more electrons from (n
– 1)d electrons. This results in formation of cations with
different oxidation states.
(2) All transition elements show variable oxidation state except
last element in each series.
(3) Minimum oxidation state = Total number of 4s electrons lost.
Maximum oxidation state = (Total number of 4s electrons
lost + 3d electrons lost).
In ‘3d’ series all elements contain 2 electrons in ‘4s’ and hence
they all give a common minimum oxidation state of +2. (Except
‘Cr’ and ‘Cu’ where minimum oxidation state is +1.] The
maximum oxidation state is given by Mn i.e. Mn+7 in which
two electrons are removed from 4s and five unpaired electrons
are removed from 3d orbitals.
(4) The highest oxidation state is shown by Ruthenium (Ru) and
Osmium (Os) i.e. +8.
(5) Across the period oxidation state increases and it is maximum
at the centre and than decreases even if atomic number
increases. The element which shows highest oxidation state
occur in the middle or near the middle of the series and than
decreases.
(6) Transition metals also show zero oxidation states in metal
carbonyl complex.
Example : Ni in [Ni(CO)4] (Nickel tetracarbonyl) has zero
oxidation state.
(7) The bonding in the compounds of lower oxidation state (+2,
+3) is mostly ionic and the bonding in the compounds of
higher oxidation state is mostly covalent.

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(8) The relative stabilities of some oxidation states can be
explained on the basis of rule extra stability, according to
which d0, d5 and d10 are stable configurations.
For example, the stability order of some ions is as follows:
Ti4+ (3d0, 4s0) > Ti3 (3d1, 4s0)
Mn2+ (3d5, 4s0) > Mn3+ (3d4, 4s0)
Fe3+, (3d5, 4s0) > Fe2+ (3d6, 4s0)
120
(9) Cu+2 is more stable than Cu+ even when Cu+ is 3d10 while
Cu+2 is 3d due to high heat of hydration.
Variable oxidation states shown by 3d-series of d-block
elements.

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

1.4.6 Standard Electrode Potentials (Eo)

In solution, the stability of the compounds of transition metals
depends upon electrode potentials. Electrode potential values
depend upon factors such as enthalpy of sublimation (or
atomisation) of the metal, the ionisation enthalpy and the hydration
enthalpy, i.e.,

M  s  
 sub H
 M  g  , (  sub H is enthalpy of sublimation)
Trends in the M2+/M Standard Electrode Potentials:
M  g  
 iH
 M   g   e , (  i H is ionisation enthalpy) (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.
M   g   aq   M   aq  , (  hyd H is enthalpy of hydration)
hyd  H

(ii) The general trend towards less negative Eo values along the
The total energy, T H , for the process involving sublimation, series is due to the general increase in the sum of first and
ionisation and hydration simultaneously, i.e., for the process, second ionization enthalpies.
(iii) Copper shows a unique behaviour in the series as it is the
M  s  
 M   aq   e  , will be the sum of the three types of
only metal having positive value for Eo. This explains why is
enthalpies, i.e., does not liberate H2 gas from acids. It reacts only with the
 T H   sub H   i H   hyd H. oxidizing acids (HNO3 and H2SO4) which are reduced. The
reason for positive Eo value for copper is that the sum of
Thus, T H , is the total enthalpy change when solid metal, M is enthalpies of sublimation and ionization is not balanced by
brought in the aqueous medium in the form of monovalent ion, hydration enthalpy.
M+ (aq).

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Eo ( M 2+  M o ) Values for Ti to Zn Chemical Reactivity and Eo Values:

The transition metals vary widely in their chemical reactivity. Some
M a Ho 1H1o 1H o2  Hyd H o  M 2   Eo/V
of them are highly electropositive and dissolve in mineral acids
Ti 469 656 1309 –1866 –1.63 whereas a few of them are ‘noble’, i.e., they do not react with simple
V 515 650 1414 –1895 –1.18 acids. Some results of chemical reactivity of transition metals as
Cr 398 653 1592 –1925 –0.90 related to their Eo values are given below :
Mn 279 717 1509 –1862 –1.18 (i) The metals of the first transition series (except copper) are
Fe 418 762 1561 –1998 –0.44 relatively more reactive than the other series. Thus, they are
Co 427 758 1644 –2079 –0.28 oxidized by H+ ions though the actual rate is slow, e.g., Ti and
Cu 339 745 1958 –2121 0.34 V are passive to dilute non-oxidizing acids at room
Zn 130 906 1734 –2059 –0.76 temperature.
(ii) As already explained, less negative Eo values for M2+/M along
(iv) The values of Eo for Mn, Ni and Zn are more negative than
the series indicate a decreasing tendency to form divalent
expected from the general trend. This is due to greater stability
cations.
of half-filled d-subshell (d5) in Mn2+, and completely filled d-
subshell (d10) in Zn2+. The exceptional behaviour of Ni towards (iii) More negative Eo values than expected for Mn, Ni and Zn
Eo value from the regular trend is due to its high negative show greater stability for Mn2+, Ni2+ and Zn2+.
enthalpy of hydration. (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)
1.4.7 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.
Some Common Catalysts
Catalysts Uses
TiCl4 + Al (C2H5)3 Ziegler-Natta catalyst, used in
Eo ( M 2  Mo ) values for Ti to Zn polymerisation of ethylene
Trends in the M3+/M2+ Standard Electrode Potentials: V2O5 Contact process SO2  SO3
Fe Haber Bosch process
(i) A very low value for Eo (Sc3+/Sc2+) reflects the stability of
PdCl2 Wacker’s process for CH3CHO
Sc3+ ion which has a noble gas configuration.
manufacturing
(ii) The highest value for Zn is on account of very high stability
Pd Hydrogenation of alkene,
of Zn2+ ion with d10 configuration. It is difficult to remove an
alkyne
electron from it to change it into +3 state.
Pt/PtO Adam’s catalyst for selective
(iii) The comparatively high value of Eo (Mn3+/Mn2+) shows that
reduction
Mn 2+ is very stable which is on account of stable d 5
Pt Catalytic convertor, for
configuration of Mn2+.
cleaning car exhaust fumes
(iv) The comparatively low value of Eo (Fe3+/Fe2+) is on account
Pt/Rh Ostwald’s process :
of extra stability of Fe3+ (d5), i.e., low third ionization enthalpy
NH3  NO
of Fe.
Cu Oxidation of alcohols

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1.4.8 Magnetic Behaviour [Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+, [Zn(NH3)4]2+, [Ni(CN)4]2–
When a magnetic field is applied to substances, mainly two types and [PtCl4]2–
of magnetic behaviour are observed: diamagnetism and Such complex compounds are not formed by s - and p - block
paramagnetism. elements.
Diamagnetic substances are repelled by the applied field while Explanation. The transition elements form complexes because of
the paramagnetic substances are attracted. Most of the transition the following reasons :
metal ions are paramagnetic due to the presence of unpaired (i) Comparatively smaller size of their metal ions.
electrons. Each such electron having a magnetic moment
(ii) Their high ionic charges and high charge/size ratio.
associated with its spin angular momentum and orbital angular
momentum. (iii) Availability of vacant d-orbitals so that these orbitals can
accept lone pairs of electrons donated by the ligands.
In first transition elements series the orbital angular magnetic
moment is insignificant the orbital contribution is quenched by 1.4.10 Formation of Coloured Compounds
the electric fields of the surrounding atoms so magnetic moment Transition elements form coloured ions due to presence of
is equal to the spin magnetic moment only. incompletely filled d-orbitals and unpaired electrons. They can
It can be calculated by using the formula: undergo d-d transition by absorbing colour from visible region
and radiating complementary colour, e.g. Cu2+ (blue), V2+(violet),
 eff  n (n  2) BM Cr3+(green). Cu+(3d10), Zn2+(3d10), Cd2+(4d10), Sc3+(3d0 ) are white
due to presence of no unpaired electrons and cannot undergo d-
n  no. of unpaired electron.
d transition.
The magnetic moment increases with the increasing number of
Colour of Ions of 3d Series
unpaired electrons. Thus, the observed magnetic moment is
directly related to the number of unpaired electrons present in the Configuration Example Colour
atom, molecule or ion. 3d0 Sc3+ colourless
Magnetic Moments of 3d Series Ions 3d0 Ti4+ colourless
1 3+
3d Ti purple
Ion Unpaired Magnetic moment 3d 1
V 4+
blue
electron(s) Calculated Observed 2 3+
3d V green
Sc3+ 3d0 0 0 0 3d3 V2+ violet
Ti3+ 3d1 1 1.73 1.75 3d3 Cr3+ violet
2+ 2
Tl 3d 2 2.84 2.76 3d 4
Mn 3+
violet
V2+ 3d3 3 3.87 3.86 3d 4
Cr 2+
blue
Cr2+ 3d4 4 4.90 4.80
3d5 Mn2+ pink
Mn2+ 3d5 5 5.92 5.96
3d5 Fe3+ yellow
Fe2+ 3d6 4 4.90 5.3 – 5.5 6 2+
3d Fe green
Co2+ 3d7 3 3.87 4.4 – 5.2 6 7 3+ 2+
3d 3d Co Co bluepink
Ni2+ 3d8 2 2.84 2.9 – 3, 4
3d8 Ni2+ green
Cu2+ 3d9 1 1.73 1.8 – 2.2 9 2+
3d Cu blue
Zn2+ 3d10 0 0
10 2+
3d Zn colourless
1.4.9 Complex Formation
1.4.11 Interstitial 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 lattices
lone pairs of electrons. These ions or molecules are called ligands.
(Fig.).
They donate lone pairs of electrons to the central transition metal
ion forming coordinate bonds. They are represented by formulae like TiC, TiH2, Mn4N, Fe3H,
Fe3C etc. However, actually they are non-stoichiometric materials,
A few examples are given below :

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e.g., TiH1.7, VH0.56 etc. and the bonds present in them are neither
typically ionic nor covalent. Some of their important characteristics
are as follows:
(i) They are very hard and rigid, e.g., steel which is an interstitial
compound of Fe and C is quite hard. Similarly, some borides
are as hard as diamond.
(ii) They have high melting points which are higher than those
of the pure metals.
(iii) They show conductivity like that of the pure metal.
(iv) They acquire chemical inertness.
123
metal is equal to its group number, e.g., 7 in Mn2O7. Beyond
group 7, no higher oxides of iron above Fe2O are known.
Some metals in higher oxidation state stabilize by forming
oxocations, e.g., VV as VO2 , VIV as VO2+ and TiIV as TiO2+.
(iv) All the metals except scandium form the oxides with the
formula MO which are ionic in nature. As the oxidation number
of the metal increases, ionic character decreases, e.g., Mn2O7
is a covalent green oil. Even CrO3 and V2O5 have low melting
points.
2 8 / 3 3 4 7

1.4.12 Alloy Formation MnO Mn 3O 4 Mn 2O 3 MnO 2 Mn 2O 7

Alloys are homogeneous solid solutions of two or more metals (v) In general, the oxides in the lower oxidation states of the
obtained by melting the components and then cooling the melt. metals are basic and in their higher oxidation states, they are
These are formed by metals whose atomic radii differ by not more acidic whereas in the intermediate oxidation state, the oxides
than 15% so that the atoms of one metal can easily take up the are amphoteric.
positions in the crystal lattice of the other. For example, the behaviour of the oxides of manganese may
As transition metals have similar atomic radii and other be represented as follows :
characteristics, hence they form alloys very readily.
2 8/ 3 3 4 7
Alloys are generally harder, have higher melting points and more MnO Mn 3O 4 Mn 2 O3 MnO 2 Mn 2 O 7
Basic Amphoteric Amphoteric Amphoteric Acidic
resistant to corrosion than the individual metals.
The most commonly used are the ferrous alloys the metals Thus, Mn2O7 dissolves in water to give the acid HMnO4.
chromium, vanadium, molybdenum, tungsten and manganese are 2.2 Potassium Dichromate, K2Cr2O7
used in the formation of alloy steels and stainless steels. Some 2.2.1 Preparation Process
alloys of transition metals with non-transition metals are also very
It is prepared from the ore called chromite or ferrochrome or chrome
common. e.g., brass (Cu + Zn) and bronze (Cu + Sn)
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.

4FeCr2O4 + 8Na2CO3+ 7O2 

 8Na2CrO4 + 2Fe2O3 + 8CO2

Alloy Formation Chromite ore Sod. chromate Ferric oxide

After the reaction, the roasted mass is extracted with water
when sodium chromate is completely dissolved while ferric
2. IMPORTANT COMPOUNDS OF TRANSITION oxide is left behind. Ferric oxide is separated out by filtration.
ELEMENTS (ii) Conversion of Sodium Chromate into Sodium Dichromate:

2.1 Oxides and Oxocations The filtrate containing sodium chromate solution is treated
with concentrated sulphuric acid when sodium chromate is
(i) The metals of the first transition series form oxides with
converted into sodium dichromate.
oxygen at high temperature.
2Na 2 CrO 4  H 2SO 4   Na 2 Cr2 O 7  Na 2SO 4  H 2 O
(ii) The oxides are formed in the oxidation, states +1 to +7. Sod.chromate  Conc. Sod. dichromate

(iii) The highest oxidation state in the oxides of any transition Sodium sulphate being less soluble crystallizes out as

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decahydrate, Na2SO4. 10H2O and is removed. The clear equilibrium with CrO24  ions at pH = 4, i.e.,
solution is then evaporated in iron pans to a specific gravity
of 1.7 when a further crop of sodium sulphate is formed. It is 
pH  4
Cr2 O72   H 2 O  2
 2CrO 4  2H


Yellow
removed and the solution is cooled when orange crystals of Orange red
 dichromate   chromate 
sodium dichromate, Na2Cr2O7. 2H2O separate on standing.
(e) Action of Concentrated Sulphuric Acid :
(iii) Conversion of Na2Cr2O7 into K2Cr2O7 : (i) In cold, red crystals of chromic anhydride (chromium trioxide)
Hot concentrated solution of sodium dichromate is treated are formed.
with calculated amount of potassium chloride when potassium K 2 Cr2 O7  2H 2SO 4 
 2CrO3  2KHSO4  H 2 O
dichromate, being much less soluble than sodium salt,
(ii) On heating the mixture, oxygen is evolved.
crystallizes out on cooling as orange crystals.
 2K 2SO 4  2Cr2 SO 4 3 + 8H2O + 3O2
2K 2 Cr2 O7  8H 2SO 4 
Na 2 Cr2 O7  2KCl 
 K 2 Cr2 O7  2NaCl
Sodium dichromate Potassium dichromate (f) Oxidising Properties: It is a powerful oxidising agent. In the
2.2.2 Structures of Chromate and Dichromate Ions presence of dilute sulphuric acid, one molecule of potassium
dichromate furnishes 3 atoms of available oxygen as indicated
The chromate ion, CrO42– is tetrahedral and the dichromate ion, by the equation :
Cr2O72– is made up of two tetrahedra sharing one corner with Cr–
 K 2SO 4  Cr2  SO 4 3 + 4H2O + 3O
K 2 Cr2 O7  4H 2SO 4 
O–Cr bond angle of 126°.
or Cr2 O72   14H   6e 
 2Cr 3  7H 2 O

Mol. wt. 294

 Eq. wt. of K 2 Cr2 O 7    49
6 6
(i) It liberates I2 from KI
 4K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  7H 2SO 4  6KI 

Structure of chromate and dichromate ions 3I2  7H 2 O

2.2.3 Properties of Potassium Dichromate (ii) It oxidises ferrous salts to ferric salts
(a) Colour and Melting Point: It forms orange crystals which  K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  7H 2 SO 4  6FeSO 4 
melt at 669 K.
(b) Solubility: It is moderately soluble in cold water but freely 3Fe2  SO4 3  2H 2 O
soluble in hot water. (iii) It oxidises H2S to sulphur
(c) Action of Heat: When heated to a white heat, it decomposes
with the evolution of oxygen.  K 2 SO 4  Cr2 SO 4 3
K 2 Cr2 O7  4H 2SO 4  3H 2S 

4K 2 Cr2 O7 
 4K 2 CrO4  2Cr2 O3  3O2 + 7H2O + 3S
(iv) It oxidises sulphites to sulphates and thiosulphates to
(d) Action of Alkalies: When an alkali is added to an orange red sulphates and sulphur
solution of dichromate, a yellow solution results due to the
formation of chromate.  K 2SO4  Cr2  SO 4 3
K 2 Cr2 O7  4H 2SO 4  3Na 2SO3 
K Cr O  KOH 
2 2 7  2K 2 CrO 4  H 2 O + 4H2O + 3Na2SO4
Pot. dichromate Pot.chromate (v) It oxidises nitrites to nitrates
or Cr2 O72   2 OH  
 2 CrO42   H 2 O  K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  4 H 2SO 4  3NaNO 2 
On acidifying, the colour again changes to orange red due to + 3 NaNO3 + 4 H2O
the reformation of dichromate.
(vi) It oxidises halogen acids to halogen
2 K 2 CrO 4  H 2SO4 
 K 2 Cr2 O7  K 2SO4  H 2 O
K 2 Cr2 O7  14 HCl 
 2KCl  2CrCl3  7H 2 O  3Cl2
2  2
or 2 CrO 4  2 H 
 Cr2 O  H 2 O
7 (vii) It oxidises SO2 to sulphuric acid
This interconversion is explained by the fact that in  K 2 SO 4  Cr2  SO 4 3  3H 2 O
K 2 Cr2 O 7  H 2 SO 4  3SO 2 
2
dichromate solution, the Cr2 O 7
ions are invariably in

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(viii) It oxidises stannous salts to stannic salts NOTE
C r2 O 72   14 H   3Sn 2   
 2 C r 3   3 Sn 4   7 H 2 O
Unlike K2Cr2O7, Na2Cr2O7 is not used in volumetric analysis
(ix) It oxidises ethyl alcohol to acetaldehyde and acetic acid.
because it is deliquescent.
 K 2SO 4  Cr2  SO 4 3  4H 2 O  3O
K 2 Cr2 O7  4H 2SO 4  2.3 Potassium Permanganate (KMnO4)
CH 2 CH 2 OH  O 
 CH3CHO  H 2 O 2.3.1 Preparation Methods
Ethyl alcohol
On a large scale, it is prepared from the mineral, pyrolusite, MnO2.
CH 3 CHO O 
 CH 3 COOH The preparation involves the following two steps:
Acetaldehyde Acetic acid
(i) Conversion of MnO2 into Potassium Manganate:
Test for a drunken driver : The above reaction helps to test The finely powdered pyrolusite mineral is fused with
whether a driver has consumed alcohol or not. He is asked to potassium hydroxide or potassium carbonate in the presence
breathe into the acidified K2Cr2O7 solution taken in a test tube. If of air or oxidising agent such as potassium nitrate or
the orange colour of the solution changes into green colour (due potassium chlorate when green coloured potassium
to Cr2(SO4)3 formed in the reaction), the driver is drunk, otherwise manganate is formed.
not.
(g) Chromyl Chloride test : (Reaction with a chloride and conc. 2MnO2 + 4KOH + O2 
 2K2MnO4 + 2H2 O
sulphuric acid). When heated with concentrated hydrochloric acid Potassium manganate
or with a chloride and strong sulphuric acid, reddish brown
vapours of chromyl chloride are obtained. 2MnO2 + 2K2CO3 + O2 
 2K2MnO4 + 2 CO2

K 2 Cr2 O 7  4KCl  6H 2SO 4 

 2CrO 2 Cl2  6KHSO 4  3H 2 O MnO2 + 2KOH + KNO3 
 K2MnO4 + KNO2 + H2O
Chromyl chloride
 Re d vapour 

(h) Reaction with Hydrogen Peroxide : Acidified K2Cr2O7 solution 3MnO2 +6KOH+KClO3 
 3K2MnO4 +KCl+2H2O
reacts with H2O2 to give a deep blue solution due to the formation (ii) Oxidation of Potassium Manganate to Potassium
of peroxo compound, CrO (O2)2. Permanganate:
Potassium manganate thus formed undergoes
Cr2 O72   2 H   4 H 2 O2 
 2 CrO5  5 H 2 O
disproportionation in the neutral or acidic solution as follows,
The blue colour fades away gradually due to the decomposition if allowed to stand for some time :
VI VII IV
of CrO5 into Cr3+ ions and oxygen. 3 MnO 24   4 H  
2 MnO 4  MnO 2  2 H 2 O
Manganate ion Permanganate ion

The structure of CrO5 is in which Cr is in +6 oxidation The fused mass is extracted with water and the solution after
filtration is converted into potassium permanganate by
state. bubbling carbon dioxide, chlorine or ozonised oxygen through
2.2.4 Uses of Potassium Dichromate the green solution.
(i) In volumetric analysis, it is used as a primary standard for the 3K 2 MnO4  2CO2 
 2KMnO 4  MnO 2  2K 2 CO3
estimation of Fe2+ (ferrous ions) and I– (iodides) in redox
2K 2 MnO4  Cl2 
 2KMnO4  2KCl
titrations.
(ii) In industry, it is used 2K 2 MnO4  H 2 O  O3 
 2KMnO4  2KOH  O2
(a) In chrome tanning in leather industry. The carbon dioxide process is uneconomical as one third of the
original manganate is reconverted to manganese dioxide. However,
(b) In the preparation of chrome alum K2SO4.Cr2(SO4)3. 24H2O
this process has the advantage that the potassium carbonate
and other industrially important compounds such as Cr2O3,
formed as a by-product can be used for the oxidative fusion of
CrO3, CrO2Cl2, K2CrO4, CrCl3 etc.
manganese dioxide. In the chlorine process, potassium chloride
(c) In calico printing and dyeing. obtained as a by-product is lost.
(d) In photography and in hardening gelatine film.
(iii) In organic chemistry, it is used as an oxidising agent.

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2.3.2 Structure of Manganate and Permanganate ions or MnO4  8H   5 e  
 Mn 2   4H 2 O.
Both manganate  MnO 4  and permanganate  MnO 4  ions are
2 
Since in the above reaction, MnO4 ion gains 5 electrons of
tetrahedral. Here the  -bonding takes place by overlap of p five atoms of oxygen are available from two molecules of
KMnO4. Hence.
orbitals of oxygen with d orbitals of manganese. The green
manganate ion is paramagnetic because of one unpaired electron Mol. wt. 158
Eq. wt. of KMnO 4    31.6
but the permanganate ion is diamagnetic due to the absence of 5 5
any unpaired electron. Some oxidizing properties of KMnO4 in the acidic medium:
Its intense colour and diamagnetism along with temperature- These are given below :
dependent weak paramagnetism can be explained by molecular (i) It oxidises H2S to S.
orbital theory. 2KMnO4  3H 2SO4  5H 2S 
 K 2SO 4  2MnSO 4  2H 2 O  5O
(ii) It oxidises sulphur dioxide to sulphuric acid.
2KMnO 4  5 SO 2  2H 2 O 
 K 2SO4  2MnSO4  2H 2SO 4

(iii) It oxidises nitrites  NO 


2 to nitrates  NO  , arsenites

3

 AsO 
3
3
3
to arsentates AsO 4   and sulphites and
thiosulphates to sulphates.
2KMnO 4  3H 2SO4  5KNO 2 
 K 2SO4  2MnSO4 
Structure of manganate and permanganate ions 3H 2 O  5KNO3
2.3.3 Properties of Potassium Permanganate (iv) It oxidises oxalates or oxalic acid to CO2
(a) Colour : Potassium permanganate exists as deep purple black 2KMnO4  3H 2SO4  5C2 H 2 O4 
 K 2SO4  2MnSO4 
prisms with a greenish lustre which become dull in air due to
8H 2 O  10 CO2
superficial reduction.
(v) It oxidises ferrous sulphate to ferric sulphate (i.e., ferrous
(b) Solubility : It is moderately soluble in water at room salt to ferric salt).
temperature and it is more soluble in hot water.
2KMnO4  8H 2SO4  10FeSO4 
 K 2SO 4  2MnSO 4 
(c) Action of Heat : When heated to 513 K, it readily decomposes
giving oxygen. 5Fe2  SO4 3  8H 2 O
2KMnO 4 
 K 2 MnO 4  MnO 2  O 2 (vi) It oxidises H2O2 to H2O and O2. This is because acidified
Pot. manganate KMnO4 is a stronger oxidising agent than H2O2.
At red heat, potassium manganate formed decomposes into 2KMnO4  3H 2SO4  5H 2 O 2 
 K 2SO4  2MnSO 4 
potassium manganite (K2MnO3) and oxygen.
8H 2 O  5O 2
2K 2 MnO4 
 2K 2 MnO3  O 2
(vii) It oxidises potassium iodide to iodine
(d) Action of heat in current of hydrogen : When heated in a
current of H2, solid KMnO4 gives KOH, MnO and water 2KMnO 4  3H 2SO 4  10KI 
 K 2SO 4  2MnSO 4 
vapours. 8H 2 O  5I 2

2KMnO4  5H 2 
 2KOH  2MnO  4H 2 O (viii) It oxidises HX (where X = Cl, Br, I) to X2
(e) Oxidising Property. Potassium permanganate is powerful 2KMnO4  3H 2SO 4  10 HX 
 K 2SO 4  2MnSO 4 
oxidising agent. The actual course of reaction depends on
the use of the permanganate in (a) acidic medium (b) neutral 8H 2 O  5X 2
medium or (c) alkaline medium. (ix) It oxidises ethyl alcohol to acetaldehyde
(i) In acidic medium : Potassium permanganate in the presence 2KMnO 4  3H 2SO4  5CH3 CH 2 OH 
 K 2SO 4  2MnSO 4 
of dil. sulphuric acid, i.e., in acidic medium, acts as a strong 5CH 3 CHO  8H 2 O.
oxidising agent because of the reaction
(ii) In neutral solution :
2KMnO4  3H 2SO 4 
 K 2SO 4  2MnSO 4  3H 2 O  5O Potassium permanganate acts as a moderate oxidising agent
in neutral aqueous solution because of the reaction :

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2KMnO4  H 2 O   2KOH  2MnO2  3O Some oxidizing properties of KMnO4 in the alkaline medium:
These are given below :
or
MnO 4  2H 2 O  3 e  
 MnO2  4OH  (i) It oxidises potassium iodide to potassium iodate.
2KMnO 4  H 2 O  KI 
 2MnO 2  2KOH  KIO3
Thus, MnO4 ion gains 3 electrons. Also, according to the Pot. iodate
above equation, in neutral medium, from two moles of or
permanganate, three oxygen atoms are available. In fact,
during the course of reaction, the alkali generated renders I   6OH  
 IO3  3H 2 O  6 e
the medium alkaline even when we start with neutral solutions.
In this case, iodine is not liberated unlike the case of acidic
Hence, Eq. wt. of KMnO4 in neutral or weakly alkaline medium medium.
Mol. wt. 158 Similar reaction takes place with KBr.
   52.67
3 3 (ii) It oxidises olefinic compounds to glycols, i.e., when an olefinic
Some oxidizing properties of KMnO4 in the neutral medium.
These are given below : compound is shaken with alkaline KMnO4, pink colour of
(i) It oxidises hot manganous sulphate to manganese dioxide. KMnO4 is discharged.

2KMnO4  3MnSO4  2H 2 O 
 K 2SO 4  2H 2SO 4  5MnO2
Presence of ZnSO4 or ZnO catalyses the oxidation.
(ii) It oxidises sodium thiosulphate to sodium sulphate.
8KMnO 4  3Na 2S2 O3  H 2 O 
 3K 2SO4  8MnO 2  Alkaline KMnO4 used for this test is known as Baeyer’s
reagent. It is used for oxidation of a number of organic
3Na 2SO 4  2KOH compounds.
(iii) It oxidises hydrogen sulphide to sulphur. 2.3.4 Uses of Potassium Permanganate
2KMnO4  4H 2S 
 2MnS  S  K 2SO4  4H 2 O (i) It is often used in volumetric analysis for the estimation of
ferrous salts, oxalates, iodides and hydrogen peroxide.
(iii) In alkaline solution : In strongly alkaline solution, MnO 24  However, it is not a primary standard because it is difficult to
(manganate) ion is produced.
obtain it in the pure state and free from traces of MnO2. It is,
2KMnO4  2KOH 
 2K 2 MnO4  H 2 O  O or therefore, always first standardised with a standard solution
  2 of oxalic acid.
MnO  e 
4  MnO 4
(ii) Volumetric titrations inolving KMnO4 are carried out only in
Mol. wt. 158
 Eq. wt. of KMnO 4    158 presence of dilute H2SO4 but not in the presence of HCl or
1 1
HNO3. This is because oxygen produced from KMnO4 + dil.
Potassium manganate is also further reduced to MnO2 when
H2SO4 is used only for oxidizing the reducing agent. Moreover,
a reducing agent is present. H2SO4 does not give any oxygen of its own to oxidize the
K 2 MnO4  H 2 O 
 MnO2  2KOH  O reducing agent. In case HCl is used, the oxygen produced
from KMnO4 + HCl is partly used up to oxidize HCl to chlorine
or MnO24   2H 2 O  2 e   MnO2  4OH  and in case HNO3 is used, it itself acts as oxidizing agent and
So the complete reaction is : partly oxidizes the reducing agent.

2KMnO4  H 2 O   2MnO2  2 KOH  3O (iii) It is used as a strong oxidising agent in the laboratory as well
as in industry. Alkaline potassium permanganate is used for
or
testing unsaturation in organic chemistry and is known as
MnO 4  2H 2 O  3 e  
 MnO2  4OH 
Baeyer’s reagent.
which is the same as that for neutral medium. Hence,
(iv) Potassium permanganate is also widely used as a disinfectant
equivalent weight of KMnO4 in weakly alkaline medium is
and germicide. A very dilute solution of permanganate is used
same as that in the neutral medium, viz., 52.67
for washing wounds and gargling for mouth sore. It is also
used for purifying water of stinking wells.
(v) Because of its strong oxidizing power, it is also used for
bleaching of wool, cotton, silk and other textile fibres and
also for decolourisation of oils.

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1. f BLOCK ELEMENTS - INTRODUCTION 2.2 Oxidation State

The innter transition elements are also known as f-block elements.
There are two f-block series, lanthanoids (the fourteen elements
following lanthanum) and actinoids (the fourteen elements
following actinium). The lanthanoids resemble each other closely.
They have only one stable oxidation state and their chemistry
resembles largely with each other. On the other hand, the chemistry
of the actinoids is much more complicated due to the occurrence
of a wide range of oxidation states and radioactive nature.
2. THE LANTHANIDE SERIES
The 14 elements after La-57 are collectively called lanthanoides or
lanthanide series or 4f series. Some times, lanthanoides are
collectively represented by symbol Ln.
2.1 Electronic Confignration
These elements have electronic configration [Xe]4f1-14 5d0-1 6s2.
They have 6s2 common but with variable occupancy of 4f and 5d
level. The electronic configurations of all tripositive ions are of
the form 4f1-14.
The sum of the first three ionization energies for each element are
low. Thus the oxidation state (+III) is ionic and Ln3+ dominates
the chemistry of these elements. The Ln2+ and Ln4+ ions that do
occur are always less stable than Ln3+.
Oxidation numbers (+II) and (+IV) do occur, particularly when
they lead to :
1. a noble gas configuration e.g. Ce4+ (f 0)
2. a half filled f shell, e.g. Eu2+ and Tb4+ (f7)
3. a completely filled f level, e.g. Yb2+ (f14).
NOTE
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
take part in bonding. Whether the f orbitals are filled or empty
has little effect on the normal chemical properties. However, it
does affect their spectra and their magnetic properties.

Electronic Configuration and Oxidation States of Lanthanoides

Element Electronic Electronic Oxidation States
Configuration Configuration of M 3+

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
6s 2
[Xe] 4f 2
+3 (+ 4)
Neodymium Nd [Xe] 4f 4
6s 2
[Xe] 4f 3
(+2) +3
Promethium Pm [Xe] 4f 5 6s2 [Xe] 4f 4 (+2) +3
Samarium Sm [Xe] 4f 6
6s 2
[Xe] 4f 5
(+2) +3
Europium Eu [Xe] 4f 7
6s 2
[Xe] 4f 6
(+ 2) +3
Gadolinium Gd [Xe] 4f 5d7 1
6s 2
[Xe] 4f 7
+3
Terbium Tb [Xe] 4f 9 6s2 [Xe] 4f 8 +3 (+ 4)
Dysprosium Dy [Xe] 4f 10
6s 2
[Xe] 4f 9
+3 (+ 4)
Holmium Ho [Xe] 4f 11
6s 2
[Xe] 4f 10
+3
Erbium Er [Xe] 4f 12
6s 2
[Xe] 4f 11
+3
Thulium Tm [Xe] 4f 13 6s2 [Xe] 4f 12 (+ 2) +3
Ytterbium Yb [Xe] 4f 14
6s 2
[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 (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
Trends in ionic radii of lanthanoids
of the third transition series to be very similar to those of the
corresponding members of the second series. The almost identical

Atomic and Ionic Radii of Lanthanoides

Atomic Electronic configurations Radii/pm

Number Name Symbol Ln Ln2+ Ln3+ Ln 4+
Ln Ln3+
1 2 1
57 Lanthanum La 5d 6s 5d 4f0 187 106
58 Cerium Ce 4f 15d16s2 4f2 4f1 4f0 183 103
3 2 3
59 Praseodymium Pr 4f 6s 4f 4f2 4f1 182 101
60 Neodymium Nd 4f46s2 4f4 4f3 4f2 181 99
5 2 5
61 Promethium Pm 4f 6s 4f 4f4 181 98
62 Samarium Sm 4f66s2 4f6 4f5 180 96
7 2 7
63 Europium Eu 4f 6s 4f 4f6 199 95
7 1 2 7 1
64 Gadolinium Gd 4f 5d 6s 4f 5d 4f7 180 94
65 Terbium Tb 4f96s2 4f9 4f8 4f7 178 92
10 2 10
66 Dysprosium Dy 4f 6s 4f 4f9 4f8 177 91
67 Holmium Ho 4f 116s2 4f11 4f10 176 89
12 2 12
68 Erbium Er 4f 6s 4f 4f11 175 88
69 Thulium Tm 4f 136s2 4f13 4f12 174 87
14 2 14
70 Ytterbium Yb 4f 6s 4f 4f13 173 86
71 Lutetium Lu 4f145d16s2 4f145d1 4f14 – –

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2.4 Magnetic Behaviour
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.
NOTE
Separation of the Lanthanide Elements
Since the change in ionic radius is very small, the chemical
properties are similar. This makes the separation of the element
in pure state difficult. Separation is done by Ion Exchange
methods which is based on the ionic size.
2.5 Colour
The lanthanides are silvery white metals. However, most of the
trivalent metal ions are coloured, both in the solid state and in
aqueous solution. This is due to the partly filled-f-orbitals which
permit f-f transition.
NOTE
Lanthanides ions with x f electrons have a similar colour to those
with (14–x) f electrons e.g., La3+ and Lu3+ are colourless, Sm3+
and Dy3+ are yellow and Eu3+ and Tb3+ are pink.
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).
130
They form oxides M2O3 and hydroxides M(OH)3. The oxides and
hydroxides are basic like alkaline earth metal oxides and
hydroxides.
Chemical reactions of the lanthanoids
The hydroxides Ln(OH) 3 are precipitated as gelationous
precipitates by the addition of NH4OH to aqueous solutions. These
hydroxides are ionic and basic. They are less basic than Ca(OH)2
but more basic than Al(OH)3 which is amphoteric. The metals,
oxides and hydroxides all dissolve in dilute acids, forming salts.
Ln(OH)3 are sufficiently basic to absorb CO2 from the air and form
carbonates. The basicity decreases as the ionic radius decreases
from Ce to Lu. Thus Ce(OH)3 is the most basic, and Lu(OH3),
which is the least basic, is intermediate between Scandium and
Yttrium in basic strength. The decrease in basic properties is
illustrated by the hydroxides of the later elements dissolving in
hot concentrated NaOH, forming complexes.
Yb(OH)3 + 3NaOH  3Na+ + [Yb(OH)6]3–
Lu(OH)3 + 3NaOH  3Na+ + [Lu(OH)6]3–
2.7 Uses of Lanthanides
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 Oxidation State

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

Atomic and Ionic Radii of Actinoids

Atomic Electronic configurations* Radii/pm
Number Name Symbol M M3+ M4+ M 3+
M4+
1 2 0
89 Actinium Ac 6d 7s 5f 111
90 Thorium Th 6d27s2 5f1 5f0 99
2 1 2 2
91 Protactinium Pa 5f 6d 7s 5f 5f1 96
3 1 2 3
92 Uranium U 5f 6d 7s 5f 5f2 103 93
93 Neptunium Np 5f46d17s2 5f4 5f3 101 92
6 2 5
94 Plutonium Pu 5f 7s 5f 5f4 100 90
95 Americium Am 5f77s2 5f6 5f5 99 89
7 1 2 7
96 Curium Cm 5f 6d 7s 5f 5f6 99 88
97 Berkelium Bk 5f97s2 5f8 5f7 98 87
10 2 9
98 Callifornium Cf 5f 7s 5f 5f8 98 86
11 2 10
99 Einstenium Es 5f 7s 5f 5f9 – –
100 Fermium Fm 5f127s2 5f11 5f10 – –
13 2 12
101 Mendelevium Md 5f 7s 5f 5f11 – –
102 Nobelium No 5f147s2 5f13 5f12 – –
14 1 2 14
103 Lawrencium Lr 5f 6d 7s 5f 5f13 – –

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3.4 Magnetic Behaviour 4. COMPARISON OF LANTHANIDES AND
Like lanthanides, the actinides are strongly paramagnetic. The ACTINIDES
variation in magnetic susceptibility of actinides with the
increasing number of unpaired electrons is similar to that of Similarities :
lanthanides but the values are higher for the actinides than the As both lanthanides and actinides involve filling of f-orbitals,
lanthanides. 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
having seven 5f-electrons (i.e., exactly half-filled f-subshell) are (iv) Actinides exhibit actinide contraction like lanthanide
colourless. The cations containing 2 to 6 electrons in the 5f- contraction shown by lanthanides.
subshell are coloured both in the crystalline state as well as in Differences :
aqueous solution. The colour arises due to f–f transition e.g. The show differences in some of their characteristics as follows :
Ac3+ (5f 0) = colourless, U3+ (5f 3) = Red, Np3+ (5f 4) = Blue, Pu3+
Difference between Lanthanides and Actinides
(5f 5) = Violet, Am3+ (5f 6) = Pink, Cm3+ (5f 7) = Colourless,
Lanthanides Actinides
Th3+ (5f 0) = Colourless as so on.
(i) Besides + 3 oxidation (i) Besides +3 oxidation
3.6 Chemical Reactivity
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  , PuO22  and UO  .
(vi) Except promethium, (vi) They are radioactive.
they are non-radioactive.
Chemical reactions of the actinides (vii) Their magnetic (vii) Their magnetic
properties can be explained properties cannot be
easily. explained easily.

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d & f Block Elements
d & 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.
133
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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d & f Block Elements
d & f BLOCK ELEMENTS 134

SCAN CODE
d & f Block Elements
d AND f BLOCK ELEMENTS
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 ns 2 np 1–6 . 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.
135
(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 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] 5s 4d2 10
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
d AND f BLOCK ELEMENTS 136
(iv) They exhibit variable oxidation states and have large
surface area, hence acts as good catalysts
2
3CrO 43  8H   2CrO 4  Cr 3  4H 2 O
Example - 5  Cr in  5 o.s.  Cr in  o.s.

How would you account for the following :

3MnO 43  4H   2MnO 4   MnO 2  2H 2O
(a) Of the d4 species Cr2+ is strongly reducing while Mn in  6 o.s. Mn in Mn in
7 o.s 4 o.s.
manganese(III) is strongly oxidising.

(b) Cobalt(II) is stable in aqueous solution but in the
presence of complexing reagents it is easily
oxidized.
(c) The d1 configuration is very unstable in ions?
Sol.
(a) Of d4 species, Cr2+ has 3d4 configuration and tends to
loose one electron to acquire d3 configuration as it is
highly stable and best metallic specie available for
complex formation. Cr3+ can accommodate six lone pair of
electrons from ligands due to sp3d2 hybridisation e.g.
[Cr(NH3)6]3+ Mn3+ although have d4 configuration but
tends to become Mn2+ stable specie by acquiring one
electron to attain d5 configuration. It becomes exactly
half filled on one hand and more energy is released in
gain of electron due to higher nuclear charge.
(b) Co 2+ is stable in aqueous solution because it get
surrounded and weakly bonded to water molecules. In
presence of strong ligands and air it gets oxidised tc
Co(III) as strong ligands get co-ordinated more strongly
with Co(III). The electronic configuration of Co(II) and
Co(III) are :
Co(II) = [Ar]18 4s 3d and Co(III) = [Ar]18 4s 3d
0 7 0 6
In Co(III) specie, 6 lone pairs of electrons from ligands
are accommodated by sp3d2 hybridisation which is not
possible in Co(II).
Here, we can say that Cr in +5 oxidation state undergo
disproportionation into its +6 and +3 states. Similarly,
Mn in +6 oxidation state undergo disproportionation into
+7 and +7 oxidation states.
Example - 7
Give reasons for the following :
(a) Transition metals have high enthalpies of
atomisation.
(b) Among the lanthenoids Ce(III) is easily oxidised
to Ce(IV).
(c) Fe3+/Fe2+ redox couple has less positive electrode
potential than Mn3+/Mn2+ couple.
(d) Copper (I) has d10 configuration while copper(II)
has d9 configuration, still copper(II) is more stable
in aqueous solution than copper(I).
(e) The second and third transition series elements
have almost similar atomic radii.
Sol.
(a) 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.

(c) Some species with d1 configuration are reducing and tends (b) Ceo3 o 
Ceo4 o eo 
 4f 5d 6s   4f 5d 6s 
to loose one electron to acquire d4 stable configuration.
Some other species with d1 configuration like Cr(V) and
Spontaneous oxidation due to more stability of Ce4+ ion
Mn(VI) undergo disproportionation.
as compared to Ce3+ ion due to more stable configuration
Example - 6 of Ce4+ ion.
What is meant by disproportionation ? Give two examples
of disproportionation reaction in aqueous solution. (c) Mn3  3e 
Mn2
Sol. Some time transition metal species in same oxidation state
(more spontaneous due to higher stability of Fe3+)
undergo a chemical change in such a way that some species
get both oxidised and reduced. For example, Cr(V) and
Mn(VI) species undergo disproportionation reaction in Fe3  e  
 Fe2
acidic medium as follows: (less spontaneous due to higher stability of Fe3+)
d AND f BLOCK ELEMENTS 137
Due to stability of half filled d-orbitals, Mn2+ is more used for chemical bond formation. Therefore all elements
stable than Mn 3+ and thus its reduction is more except Sc and Zn, of the first transition series show a
spontaneous. Similarly Fe3+ is more stable than Fe2+ and number of oxidation states as shown in table.
thus its reduction is less spontaneous. Sc Ti V Cr Mn Fe Co Ni Cu Zn
2 2 2 2 2 2 2 1
(d) Copper (II) has lower reduction electrode potential than 3 3 3 3 3 3 3 3 2 2
copper (I), hence. Copper(I) is oxidised to copper (II) in 4 4 4 4 4 4 4
the presence of strong ligands and air. 5 5 5
6 6 6
(e) It is due to lanthanoid contraction. It arises due to poor 7
shielding effect of d and f electrons.
(ii) Atomic radii of the first transition series decreases from
Example - 8
Sc to Cr, then reamins almost constant till Ni and then
Explain the following facts increases from Cu to Zn.

(a) transition metals act as catalysts.
(b) chromium group elements have the highest melting
points in their respective series.
(c) transition metals form coloured complexes.
Sol.
(a) The catalytic activity of transition metals is attributed
to the following reasons :
(i) Because of their variable oxidation states transition
metals form unstable intermediate compounds and
provide a new path with lower activation energy for the
reaction.
(ii) In some cases, the transition metal provides a suitable
large surface area with free valencies on which reactants
are adsorbed.
(b) Because they have strong metallic bonds due to greater
number of unpaired d electrons.
(c) this is due to d-d transition.
The reason of this variation in atomic radii has been
attributed to the increase in nuclear charge in the
beginning of the series. But as the electrons continue to
be filled in d-orbitals, they screen the outer 4s electrons
from the influence of nuclear charge. When the increased
nuclear charge. When the increased nuclear charge and
the increased screening effect balance each other in the
middle of transition series, the atomic radii becomes
almost constant (Mn to Fe). Towards the end of the series,
the repulsive interaction between electrons in d orbitals
become very dominant. As a result there is an expansion
of the electron cloud; consequently, the atomic size
increases.
(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.
The magnetic moment () of the elements of the first
transition series can be calculated with the unpaired
electrons (n) by the spin-only formula
 n  n  2  B.M.

Ion Configuration Unpaired Magnetic moment ()

electrons calculated
Example - 9
Mn2+ 3d54s0 5 5 5  2   5.92 B.M.
Describe the trends in the following properties of the
first series of the transition elements: Cu2+ 3d94s0 1 11  2   1.73B.M.

(i) Oxidation states Zn2+ 3d10 4s0 0 0 0  3  0

(ii) Atomic sizes

Example - 10
(iii) Magnetic behaviour of dipositive gaseous ions
(M2+). How would you account for the following :

Sol. (i) Many of the transition elements and their

compounds can act as good catalysts.
(i) As there is very little energy difference between 4s and
3d orbitals, electrons from both energy levels can be
d AND f BLOCK ELEMENTS
(ii) The metallic radii of the third (5d) series of
transition elements are virtually the same as those
of the corresponding members of the second
series.
(iii) There is a greater range of oxidation states among
the actinoids than among the lanthanoids.
Sol.
(i) The catalytic activity of transition metals is attributed to
the following reasons:
(a) Because of their variable oxidation states transition
metals form unstable intermediate compounds and
provide a new path with lower activation energy
for the reaction.
(b) In some cases, the transition metal provides a
suitable large surface area with free vacancies on
which reactants are adsorbed.
(ii) This due to filling of 4f orbitals which have poor shielding
effect or due to lanthanoid contraction.
(iii) This is due to comparable energies of 5f, 6d and 7s orbital
in actinoids.
Example - 11
Decide giving reasons which one of the following pairs
exhibits the property indicated:
(i) Sc3+ or Cr3+ exhibits paramagnetism.
(ii) V or Mn exhibits more number of oxidation states.
(Atomic Numbers: Sc = 21; Cr = 24; V = 23; Mn = 25)
Sol.
(i) The electronic configurations of Sc3+ and Cr3+ are given
below.
Sc3 :  Ar  3d 0 4s0 Cr 3 :  Ar  3d3 4s0
Because of the presence of three unpaired electrons in
the 3d subshell Cr3+ is paramagnetic. Sc3+ is diamagnetic
as it does not have any unpaired electrons.
(ii) The electronic configurations of V and Mn are given
below:
23 V :  Ar  3d3 4s 2
25 Mn :  Ar  3d 5 4s 2
138
Mn exhibits more number of oxidation states than V
because of the greater number of electrons in its valence
shell.
Example - 12
How would you account for the following :
(i) Cr2+ is reducing in nature while with the same d-
orbital configuration (d4) Mn3+ is an oxidising agent.
(ii) In a transition series of metals, the metal which
exhibits the greatest number of oxidation states
occurs in the middle of the series.
Sol.
(i) Eo value of Cr3+/Cr2+ is negative (–0.04V) while that of
Mn3+/Mn2+ is positive (1.5 V). This means Cr2+ can lose
electrons to form Cr3+ and thus is reducing in nature while
Mn3+ can gain electrons to form Mn2+ and is thus oxidising
in nature.
(ii) In a transition series maximum number of oxidation states
are shown by that element which has maximum number of
unpaired electrons. That is why the metal in the middle of
the series exhibits maximum number of oxidation states.
For example, manganese, present in the middle of the first
transition series exhibits maximum oxidation states i.e., +2,
+3, +4, +5, +6, +7.
Example - 13
Assign reasons for each of the following :
(i) Transition metals generally form coloured
compounds.
(ii) Manganese exhibits the highest oxidation state of
+7 among the 3d series of transition elements.
Sol.
(i) Transition metals generally form coloured compounds.
The colour of compounds of transition metals may be
attributed to the presence of incomplete (n – 1) d subshell.
In the compounds of transition metals the d–orbitals split

into two sets-t2g d x 2  y2 , d z2  of lower energy and eg
 d xy , d yz , d xz  of high energy. The electron can jump
from lower energy t2g orbitals to higher energy eg orbitals
(d–d transition) by absorption of light of some particular
wavelength from visible light. The remainder light is
emitted as coloured light and the compound appears
coloured.
(ii) In a transition series the element with maximum oxidation
state occurs in or near the middle of the transition series
d AND f BLOCK ELEMENTS
and maximum oxidation state exhibited is equal to sum of
(n – 1) d and ns electrons. In Mn (3d5 4s2) the sum of
(n – 1) d and (ns) electron is 7 and therefore it exhibits
maximum o.s. of + 7. The lesser no. of oxidation states on
extreme ends are either due to too few electrons to lose
or share or too many d-electrons so that fewer orbitals
are available to share electrons with others.
Example - 14
Explain:
(i) CrO42– is a strong oxidizing agent while MnO42– is
not.
(ii) Zr and Hf have identical sizes.
(iii) The lowest oxidation state of manganese is basic
while the highest is acidic.
(iv) Mn (II) shows maximum paramagnetic character
amongst the divalent ions of the first transition
series.
Sol.
(i) CuF2 and CCl2 compounds will be coloured because they
incompletely filled d-orbitals and unpaired electrons, they
can undergo d-d transition by absorbing colour from
visible region and radiating complementary colour.
(ii) Zr and Hf have identical sizes because paring of electrons
takes place in d-orbitals causing repulsion and effective
nuclear charge does not increase apprecialby. or becaule
of canthanoide contraction.
(iii) Manganese (Z = 25) exhibits the largest number of
oxidation states because its atoms has the maximum
number of unpaired electrons. The lowest oxidation state
of manganese is basic while the highest is acidic.
(iv) Mn(II) shows maximm paramagnetic character amongst
the divalent ions of the first transition series because it
has the largest number of unpaired electrons.
Example - 15
Explain the following facts :
(a) Transition metals acts as catalyst.
(b) Chromium group elements have highest melting
points in their respectively series.
(c) Transition metals form coloured complexes.
Sol.
(a) Transition metals acts as catalyst due to the following
reasons :
139
(i) Their partially empty d-orbitals provide surface area for
reactant molecules.
(ii) They combine with reactant molecules to form transition
states and lowers their activation energy.
(iii) They show multiple oxidation states and by giving
electrons to reactants they form complexes and lower
their energies.
(b) The melting point of chromium groups elements have
the highest melting points in their respective serves due
to presence of strong intermetallic bonds (formed by
valence electrons and covalent bonds formed due to d–
d overlapping of impaired d-elelctrons.)
(c) Their colour due to the presence of incomplete d-
subshell. The electrons can be excited from one energy
lavel to another with in the d-subshell. The energy
required to cause such d–d promotions or transition falls
within the visible range for all transition elements. When
white light falls on an ion or compound, some of its wave
lengths are absorbed due to d–d transition and others
are reflected. Therefore, colour of the transition metal
ion is that of the reflected light.
Example - 16
Give reasons :
(i) Among transition metals, the highest oxidation
state is exhibited in oxoanins of a metal.
(ii) Ce4+ is used as an oxidising agent in volumetric
analysis.
(iii) Transition metals form a number of interstitial
compounds.
(iv) Zn2+ salts are white while Cu2+ salts are blue.
Sol.
(i) Highest oxidation state is shown in flourides and oxides
because F2 and O2 are strong oxidising agents.
(ii) Ce4+ = [Xe], 4f0, 5d0, 6s0
Ce4+ has the tendency to accept one electron to get the
+3 oxidtion state, hence Ce4+ is a good oxidising agent.
(iii) In these compounds small size atoms like hydrogen,
carbon, nitrogen, boron, etc. occupy the empty space of
metal lattice (interstices). The small entrapped atom in
the interstices form the bonds with metals due to which
d AND f BLOCK ELEMENTS 140
mobility and ductility of the metals decrease, when as (a) The stability of Fe3+ in acid solution as compared
tensile strength increases. Example : steel is the interstitial to that of Cr3+ or Mn3+ and
compound of iron and carbon.
(b) In case with which iron can be oxidised as
(iv) In Cu2+ salts (3d9) d–d transition is possible. Therefore
compared to the similar process for either
Cu2+ salts are coloured.
chromium or manganese metal.
In Zn2+ salts (3d10) no. d–d transition is possible due to
completely filled d-orbitals. Hence Zn2+ salts are white. Sol.

Example - 17 (a) We know that higher the reduction potential of a species,

there is larger tendency for its reduction to take place.
In transition series, with an increase in atomic number, Let us represent the reduction potential i.e., Eo values of
the atomic radius does not change very much. Why is three M3+/M2+ systems on number line.
it so ? Cr3+ / Cr2+ F3+/Fe2+ Mn3+/Mn2+
Sol. With the increase in atomic number along a transition
series the nuclear charge increases which tends to – 0.4 V 0.8 V 1.5 V
increasing reduction potential
decrease the size of the atom. But the addition of electrons
in the d subshell increases the screening effect which From values of reduction potentials, it is clear that the
counterbalances the increased nuclear charge. Hence, stability of Fe3+ in acid solution is more than that Cr3+ but
along a transition series the atomic radius does not less than that of Mn3+.
change very much. (b) Mn2+/Mn Cr2+/Cr Fe2+/Fe

Example - 18 – 1.2 V 0.9 V –0.4 V 0V

The Eo (M2+/M) value for copper is positive (+0.34 V). The lower the reduction potential of a species, its
What is the possibility reason for this ? oxidation will take place more readily.

Sol. Copper has high aHo and low hyd Ho.  Mn is oxidised most readily to Mn2+ and Fe is oxidised
least readily among given metals Mn, Cr and Fe.
Example - 19
Example - 21
Explain why Cu ion is not stable in aqueous solutions ?
+
Which is a stronger reducing agent Cr2+ or Fe2+ and why?
Sol. Cu+ in aqueous solution undergoes disproportionation
i.e., Sol. Cr2+ is strong reducing agent than Fe2+.

2Cu   aq  
 Cu 2   aq   Cu  s  Reason : d4  d3 occurs in case of Cr2+ to Cr3+.

The Eo, value for this is favourable. But d6 d5 occurs in case of Fe2+ to Fe3+. In a medium
(like water) d3 is more stable as compared to d5.
Example - 20
Example - 22
For M2+/M and M3+/M2+ systems the Eo values for some
metals are as follows : What may be the stable oxidation state of the transition
element with the following d electronic configurations in
Cr2+/Cr – 0.9 V Cr3+/Cr2+ – 0.4 V
the ground state of their atoms : 3d3, 3d5, 3d8 and 3d4?
Mn2+/Mn – 1.2 V Mn3+/Mn2+ + 1.5
Sol. The stable oxidation state of transition element with the
V
d electron configuration in ground state of atoms are as
Fe2+/Fe – 0.4 V Fe3+/Fe2+ + 0.8 V follows :

Use this data to comment upon

d AND f BLOCK ELEMENTS 141

Sol. Silver (Z = 47) can exhibit +2 oxidation state wherein it

S. No. d-electron Symbol of Stable oxidation will have incompletely filled d-orbitals (4d), hence a
configuration element states transition metal.
3 2 3
1. 3d V(4s 3d ) +2, +3, +5
2. 3d4 Cr(4s 3d4)
2
+2, +3, +6 Example - 25
5 2 5
3. 3d Mn(4s 3d ) +2, +7
On what ground can you say that scandium (Z = 21) is a
4. 3d8 Ni(4s23d8) +2, +4
transition element but zinc (Z = 30) is not ?

It should be noted that lower stable oxidation state
generally leads to ionic bond and higher oxidation state
corresponds to covalent bond.
Example - 23
Among the ionic species Sc3+, Ce4+ and Eu2+ which one
is a good oxidising agent? Give a suitable reason for
your answer. (Atomic numbers ; Sc = 21; Ce = 58;
Eu = 63).
Sol. The electronic configurations of given species are:
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 - 26
In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of
atomisation of zinc is the lowest i.e., 26, kJ mol. Why ?

Sol. In the formation of metallic bonds no electrons from 3d-

21 18 Sc3
Sc  orbitals are involved in case of zinc, while in all other
metals of the 3d series, electrons from the d-orbitals are
 Ar  3d1 4s 2  Ar  3d 0 4s0 always involved in the formation of metallic bonds.

58 54 Ce 4 
Ce  Example - 27

[Xe] 4f1 3d1 6s2 [Xe] Calculate the ‘spin only’ magnetic moment of M(aq)2+ ion
(Z = 27).

63 61 Eu 2 
Eu  Sol. Atomic number (27) = [Ar]3d7 4s2
 M aq2    Ar  3d 7
 Xe 4f 7
6s 2
 Xe 4f 7

n=1
Ce4+ is a good oxidising agent because it can readily
change to the most stable +3 oxidation state by gaining   n  n  2   1 3  1.73 BM.
one electron.
Example - 28
Ce4  e 
 Ce3
What are alloys ? Mention an important alloy which
Because of their stable configuration Sc3+ and Eu2+ cannot contains some of the lanthanoid metals. Mention its
gain electrons. uses.

Sol. An alloy is a mixture of a metal with other metals or non-

Example - 24 metals.

Silver atom has a completely filled d orbitals (4d10) in its An important alloy which contains some of the lanthanoid
ground state. How can you say that it is a transition is mischmetall. Mischmetall consists of a lanthanoid metal
element ? (~95%) and iron (~5%) and traces of S, C, Ca and Al.

Uses : (i) Mischmetall is used in Mg based alloy to produce

bullets, shell and lighter flint.
d AND f BLOCK ELEMENTS
Some individual Ln oxides are used as phosphorus in
television screens and similar fluorescing surfaces.
Example - 29
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 - 30
How would you account for the irregular variation of
ionisation enthalpies (first and second) in the first series
of the transition elements ?
Sol. Irregular variation of ionisation enthalpies in mainly
attributed to varying degree of stability of different 3d-
configurations (e.g., d0, d5, d10 are exceptionally stable).
Example - 31
Assign a reason for each of the following :
(i) The third ionization energy of Mn(Z = 25) is higher
than that of either Cr (Z = 24) or Fe (Z = 26).
(ii) Simple copper (I) salts are not stable in aqueous
solutions.
142
Sol.
(i) This is because Mn2+ is more stable as it has exactly half
filled configuration 3d5 4s0.
(ii) Cu2+ (aq) is much more stable than Cu+ (aq). This is
because, although second ionization enthalpy of copper
is large but for Cu2+ (aq) is much more negative than that
of Cu + (aq) and therefore, it more compensate for the
second ionisation enthalpy of copper. Therefore, Cu+ ion
aqueous solution undergoes disproportionation.
2Cu 2   aq  
 Cu 2   aq   Cu  s 
Example - 32
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.
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 - 33
Which of the 3d series of the transition metals exhibits
the largest number of oxidation states and why ?
Sol. Manganese (Z = 25), as its atoms has the maximum
number of unpaired electrons.
Example - 34
Explain briefly how +2 state becomes more and more
stable in the first half of the first row transition elements
with increasing atomic number ?
d AND f BLOCK ELEMENTS
Sol. In transition elements, there are greater horizontal
similarities in the properties in constrast to the main
group elements because of similar ns 2 common
configuration of the outermost shell.
An examination of common oxidation states reveals that
excepts scandium, the most common oxidation state of
first row transition elements is +2 which arises from the
loss of two 4s electrons. This means that after scandium,
d-orbitals become more stable than the s-orbital.
Further, +2 state becomes more and more stable in the
first half of first row transition elements with increasing
atomic number because 3d orbitals acquire only one
electron in each of five 3d orbitals (i.e. remains half filled)
and electronic repulsion is the least and nuclear charge
increases. In 2nd half of first row transition elements,
electrons starts pairing up in 3d orbitals.
(Ti2+ to Mn2+ electronic configuration changes from 3d2 to
3d5 but in 2nd half i.e. Fe2– to Zn2+ it changes from d6 to d10).
Example - 35
To what extent do the electronic configurations decide
the stability of oxidation states in the first series of the
transition elements ? Illustrate your answer with example.
Sol. One of the main characteristic of a transition element is
that it can show large variety of oxidation states in its
compounds. It is due to its characteristic electronic
configuration i.e., (n – 1) d and ns electrons take part in
bond formation either by loosing or by sharing of
electrons with other combining atoms.
The stability of oxidation state depends mainly on
electronic configuration and also on the nature of other
combining atom.
The elements which show largest number of oxidation
states occur in or near the middle of series (i.e., 4s23d3 to
4s23d 7 configuration). For example, Mn exhibits all
oxidation states from +2 to +7 as it has 4s 23d 5
configuration. The lesser number of oxidation states at
extreme ends arise from either too few electrons to loose
or share (e.g. Sc and Ti) or too many d electrons (hence
fewer orbitals available in which to share electrons with
others) for higher elements at upper end of first transition
series (i.e., Cu and Zn). Thus electronic configuration,
to large extent, the existence and stability of oxidation
states.
The other factors which determine stability of oxidation
state are:
143
(i) Enthalpy of atomisation (ii) Ionisation energy
(iii) Enthalpy of solvation (iv) E.N. of other element.
Example - 36
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 - 37
Discuss the relative stability in aqueous solutions of
+2 oxidation state among the elements: Cr, Mn, Fe and
Co. How would you justify this situation ?
(At. Nos. Cr = 24, Mn = 25, Fe = 26, Co = 27)
Sol. On the basis of electrochemical series the standard
electrode potential shows the following order
E o Mn 2 / Mn  E o Cr2 / Cr  E o Fe2 / Fe  E o Co2 / Co
Therefore Co2+ gets easily reduced to metallic cobalt
while it is difficult to reduce Mn2+. Hence Mn2+ will be
most stable and the increasing stability order will be
Co2+ < Fe2+ < Cr2+ < Mn 2+
Example - 38
Which metal in the first series of transition metals
exhibits +1 oxidation state most frequently and why ?
Sol. Copper metal (Cu, at, no. 29) shows + 1 oxidation state
i.e., it exists as Cu+ in large number of copper compounds
d AND f BLOCK ELEMENTS 144
e.g., cuprous oxide (Cu2O), cuprous sulphide (Cu2S); The mass is then extracted with water, when sodium
cuprous chloride (Cu 2 Cl 2 ) etc. The electronic chromate is completely dissolved while Fe2O3 is left
configuration of Cu+ is [Ar] 3d10 4s0. behind.

This configuration is very stable as all five 3d orbitals (ii) Conversion of sodium chromate into sodium dichromate
are fully filled. (NaCr2O7) : The sodium chromate extracted with water
in previous step is acidified.
Example - 39
3Na2CrO4 + H2SO4  Na2Cr2O7 + Na2SO4 + H2O
Why is the highest oxidation state of a metal exhibited in
On cooling Na2SO4 separates out as Na2SO4. 10H2O and
its oxide or fluoride only ?
Na2Cr2O7 is remains in solution.
Sol. Because of small size and high electronegativity oxygen
(iii) Conversion of Na2Cr2O7 into K2Cr2O7 : The solution
or fluorine can make the metal to exhibit its highest
containing Na2Cr2O is treated with KCl
oxidation state.
Na2Cr2O7 + KCl  K2Cr2O7 + 2NaCl
Example - 40
Sodium chloride (NaCl) being less soluble separates out
Name the oxometal anions of the first series of the
on cooling. On crystallising the remaining solution,
transition metals in which the metal exhibits the oxidation
orange coloured crystals of K2Cr2O7 separate out.
state equal to its group number.
Effect of Change of pH : When pH of solution of K2Cr2O7
Sol.
is increased slowly the medium changes from acidic to
basic. The chromates and dichromates are
Name of oxometal Name of metal with Group no. to which
anion oxidation state metal belong
interconvertible in aqueous solution depending upon pH
1. CrO 4
2–
Cr in +6 state of 6th group of of solution.
(chromate ion) oxidation periodic table
–
2. MnO 4 Mn in +7 state 7th group
(permanganate ion)

Example - 41
At low pH (acidic medium), K2Cr2O7 solution is oranged
Why are Zn, Cd and Hg softer and volatile metals ? coloured while at higher pH (alkaline medium) it changes
to yellow due to formation of chromate ions.
Sol. Due to their completely filled d-orbitals, they have weak
Example - 43
metallic bonding and least compact packing therefore
they all are volatile in nature. Describe the preparation of potassium permanganate.
How does the acidified permanganate solution reacts
Example - 42
with (a) iron(II) ions (b) SO2 and (c) oxalic acid ? Write
Describe the preparation of potassium dichromate from the ionic equations for the reactions.
iron chromite one. What is the effect of increasing pH
Sol. Preparation of KMnO4 from pyrolusite ore (MnO2)
on a solution of potassium dichromate ?
involves the following steps :
Sol. The following steps are involved in preparation of
(i) Fusion of ore with alkali in presence of air : Pyrolusite
K2Cr2O7 from iron chromite (FeCr2O4) ore :
ore is fused with alkali in the presence of air when
(i) Preparation of sodium chromate : The chromite ore potassium manganate is obtained as green mass.
(FeO.Cr2O3) is finely powdered and mixed with sodium 2MnO2 + 4KOH + O2  2K2MnO4 + 2H2O
carbonate and quick lime and then heated to redness in (green mass)
a reverberatory furnace with free supply of air.
4FeO.Cr2O3 + O2  2Fe2O3 + 4Cr2O3 The green mass is dissolved in water to obtain aqueous
[4Na2CO3 + 2Cr2O3 + 3O2  4Na2CrO4 + 4CO2] × 2 solution of potassium manganate. The insoluble
impurities of sand and other metal oxides are removed by
4FeO.Cr2O3 + 8Na2CO3 + 7O2  8Na2CrO4 + 2Fe2O3 + 8CO2
filtration.
d AND f BLOCK ELEMENTS 145
(ii) Oxidation of manganate into permanganate : The (iii) A calculated quantity of potassium chloride is added to
aqueous solution of K2MnO4 is oxidised electrolytically a hot concentrated solution of sodium dichromate.
or by using ozone or Cl 2 to obtain potassium Potassium dichromate is less soluble therefore it
permanganate. The process is carried out till green colour crystallizes out first.
disappear and solution acquires distinct pink colour.
Na 2 Cr2 O7  2KCl  K 2 Cr2 O 7  2NaCl

MnO 4 2  
 MnO 4  e  Sodium Potassium

 at anode  (oxidation at anode) dichromate dichromate

green coloure pink

(b) (i) Pyrolusite ore is fused with alkali in the presence of
H2O + e  1/2H2 + (OH)– (reduction at cathodes)
–
air when potassium manganate is formed.
(at cathode)
2MnO 2  4KOH  O 2  2K 2 MnO 4  2H 2 O
Potassium manganate
or 2K 2 MnO4  CI 2  2KMnO4  2KCI
 green colour   pink colour 
(ii) Potassium manganate is oxidised by using either
CO2, ozone or chlorine to potassium permanganate.
Potassium permanganate is crystallised out from the
solution. 2K 2 MnO 4  Cl2  2KMnO 4  2KCl
Potassium
permanganate
Oxidising Properties : It acts as a powerful oxidising (iii) Potassium permanganae is crystallized from the
agent in different media differentily. In acidic medium, it solution.
oxidises iron(II) salts to iron(III) salts, SO2 to H2SO4 and
oxalic acid to CO2 and H2O. Example - 45

(a) It oxidises iron(II) salt to iron(III) salts. Write complete chemical equations for :

2MnO42- + 16+ + 10Fe2+  2Mn2+ + 8H2O + 10Fe3+ (i) Oxidation of Fe2+ by Cr2O72– in acid medium.

(b) It oxidise sulphur dioxide to sulphuric acid. (ii) Oxidation of S2O32– by MnO4 in neutral aqueous
2MnO4– + 5SO2 + 2H2O  5SO42– + 2Mn2+ 4H+ solution.
(c) It oxidises oxalic acid to CO2 and H2O
Sol. (i) 6Fe2+ + Cr2O72– + 14 H+ 
 6Fe3+ + 2Cr3+ + 7H2O
2MnO + 16H + 5C2O4  2Mn + 8H2O + 10CO2
4
– + 2– 2+

Example - 44 (ii) 2MnO4– + 3S2O32– + H2O 

 2MnO2 + 3SO42– +
3S + 2OH–.
Indicate the steps in the preparation of :
Example - 46
(a) K2Cr2O7 from chromite ore
Complete the following chemical equations :
(b) KMnO4 from pyrolusite ore.
(i) MnO 4  aq   S2 O32   aq   H 2 O    
Sol.

(a) The preparation of potassium dichromate from chromite (ii) Cr2 O72   aq   Fe2   aq   H   aq  
involves the following main steps :
Or
(i) The chromate ore is finely ground and heated strongly
with molten alkali in the presence of air. State reasons for the following :
2FeCr2 O4  8NaOH  7 / 2O2  4Na 2 Cr2 O 4  Fe 2 O3  4H 2 O (i) Cu (I) ion is not stable in an aqueous solution.
Chromite Sodium chromate

(ii) The solution of sodium chromate is filtered and acidified (ii) Unlike Cr3+, Mn2+, Fe3+ and the subsequent other
with dilute sulphuric acid so that sodium dichromate is M2+ ions of the 3d series of elements, the 4d and
obtained. the 5d series metals generally do not form stable
cationic species.
2Fe 2Cr2 O 4  H3SO 4  Na 2Cr2 O7  Na 2SO 4  H 2 O
Sodium Chromate Sodium dichromate
d AND f BLOCK ELEMENTS 146
Sol. H2S is passed in (E), a white turbidity (F) and apple
green solution (G) are obtained. The solution (E) on
(i) 8MnO4  aq   3S2 O32   aq   H 2 O    
 6 SO24  treatment with thiocyanate ions gives a blood red
coloured compound (H). Identify the compounds from
(aq) + 8MnO2 + 2OH– (aq) (A) to (H).

(ii) Cr2 O72   aq   6Fe2   aq   14H   aq  

 2 Cr 3 Sol. The compound (A) on strong heating gives two oxides of
sulphur, it may be a sulphate. The solution (E) on treatment
(aq) + 6 Fe3+ (aq) + 7H2O (l) with thiocyanate ions gives blood red coloured compound
Or (H) indicates that the solution (E) consists Fe3+ ions. Thus,
the compound (A) is ferrous sulphate, FeSO4.7H2O.
(i) Cu2+ (aq) is much more stable than Cu+ (aq. This is due Reactions :
to more negative hydH more than compensates for iH2.
As a result Cu(I) is unstable in aqueous solution and FeSO 4 .7H 2 O 
Heat
7H 2 O
 FeSO 4
(A )
undergoes disproportionation as below :

Heat
 Fe 2 O3  SO 2  SO 3
 2
2Cu 
 Cu  Cu (B)
Blackish
(C) (D)

brown powder

(ii) The valence shell electronic configuration of Cr3+, Mn2+,

Fe3+ is d3, d5 respectively. Due to symmetrical distribution Fe 2O3  6HCl 
 2FeCl3  3H 2 O
(B) (E)
3 3 2
of electrons (Either t 2g or t 2g e ) they form stable
g
Yellow solution

cationic complexes. The atomic radii of 4d and 5d 2FeCl3  H 2S 

 2FeCl 2  2HCl  S
transition metal at elements are more than those of 3d (G ) (F)
White
Apple
series. Hence. they generally do not form stable cationic green solution turbidity

complexes.
FeCl3  3CNS 
 Fe(CNS)3  3Cl 
Example - 47 (E) Blood red
coloured solution

Complete the following chemical reaction equations:

Example - 49
(i) MnO  aq   C2 O
 2
 aq   H  aq  

 (i) A black mineral (A) on treatment with dilute sodium
4 4
cyanide solution in presence of air gives a clear
solution of (B) and (C).
(ii) Cr2 O72   aq   Fe2   aq   H   aq  

(ii) The solution (B) on reaction with zinc gives
precipitate of a metal (D).
Sol. (i) MnO 4  8H   5e  
 Mn 2   4H 2 O]  2
(iii) (D) is dissolved in dilute HNO3 and the resulting
C 2 O42   2CO 2  2 ]  5
 solution gives a white precipitate (E) with dilute
HCl.
2MnO 4  5C 2 O 24   16H  
 2Mn 2   10CO 2  8H 2 O
(iv) (E) on fusion with sodium carbonate gives (D).
(v) (E) dissolves in ammonia solution giving a colourless
(ii) Cr2 O72   14H   6e  
 2Cr 3  7H 2 O solution of (F). Identify (A) to (F) and give chemical
Fe 2   Fe3  e  ]  6
 equations for reactions at steps (i) to (v).

Cr2 O72   6Fe2   14H  

 2Cr 3  6Fe3  7H 2 O Sol. On the basis of the given data, the black mineral (A) is
silver glance, Ag2S. It is confirmed by the following :
Example - 48 (i) It dissolves in sodium cyanide solution in presence
A certain inorganic compound (A) on heating loses its of air.
water of crystallisation. On further heating, a blackish
Ag2S + 4NaCN + 2O2  2[NaAg(CN) 2 ]  Na 2SO 4
brown powder (B) and two oxides of sulphur (C and D) Sodium Sodium
argento cyanide sulphate
are obtained. The powder (B) on boiling with (B) (C)

hydrochloric acid gives a yellow solution (E). When

d AND f BLOCK ELEMENTS 147
(ii) Iron reacts with cold dilute nitric acid.
(ii) 2[NaAg(CN) 2 ]  Zn  Na 2 Zn(CN) 4  2Ag
(D)
(B)
(iii) Potassium ferricyanide is added to ferrous sulphate.

(iii) 3Ag  4HNO 3  3AgNO3  NO  2H 2 O (iv) Excess of potassium iodide is added to mercuric
(D)
chloride.
AgNO 3  HCl  AgCl  HNO 3
(E)
(v) Green vitriol is strongly heated.
1 (vi) Silver chloride is treated with aqueous sodium
(iv) 2AgCl Na 2 CO 3  2Ag  2NaCl  CO 2  O 2
(E) (D) 2 cyanide and the product thus formed is allowed to
react with zinc in alkaline medium.
AgCl  2NH 4 OH  Ag(NH 3 ) 2 Cl  2H 2 O
(v) (E ) (F)
Colourless solution (vii) Zinc oxide is treated with excess of sodium
(A) = Silver glance, Ag2S hydroxide solution.
(B) = Sodium argentocyanide, NaAg(CN)2
(viii) Ammonium thiocyanate is added to ferric chloride
(C) = Sodium sulphate, Na2SO4
solution.
(D) = Silver metal, Ag
(E) = Silver chloride, AgCl Sol. (i) Prussian blue is formed.
(F) = Diamminsilver (I) chloride, Ag (NH3)2Cl
4FeCl3  3K 4 Fe(CN ) 6  Fe 4 [ Fe(CN ) 6 ]3  12KCl
Example - 50 Prussian blue
(Ferri ferrocyanide)
Write the main differences in lanthanides and actinides.

Sol. (ii) Ammonium nitrate is formed.

Lanthanides
1. Lanthanides shows +3
oxidation state only
except in few cases
where it is +2 or +4.
Oxidation states exhi-
bited by lanthanides is
never more than +4.
2. Paramagnetic properties
of lanthanides can be
easily explained.
3. Lanthanides do not form 3.
form complexes.
5.
4. 4.
Lanthanides do not form 5.
axo ions.
6.
5. Except promethium,
these are ion-radioactive
Example - 51
What happens when ?
(i) Ferric chloride is added to potassium ferrocyanide.
Actinides
1. Actinides show higher
oxidation states such as
+4, +5, +6, +7 also in
addition to +3.
2. Paramagnetic proper-
ties are difficult to
interpret.
They have a greater
tendency to complex
formation. Even p -
complexes are formed
by actinides.
These in higher oxidation
states form axo ions.
5.
6. Such as Uo22+, NbO+,
PuO22+ etc.
[Fe + 2HNO3  Fe(NO3)2 + 2H] × 4
HNO3 + 8H  NH3 + 3H2O
NH3 + HNO3  NH4NO3
4Fe + 10HNO3  4Fe(NO3)2 + NH4NO3 + 3H2O
(iii) Ferrous ion is first oxidised to ferric ion while
ferricyanide ion is reduced to ferrocyanide ion. Then,
ferric ions react with ferrocyanide ions to form
potassium ferric ferrocyanide (Turnbull’s blue).
Fe2+ + K3 [Fe (CN)6]3–  KFe [Fe(CN)6 ]
(Turnbull 's Blue)
(iv) First scarlet precipitate is formed which then dissolves
in excess of potassium iodide forming a complex.
HgCl2 + 2KI  HgI2 + 2KCl
HgI2 + 2KI  K2HgI4
Potassiumtetraiodomercurate(II)
(colourless)

(v) When heated strongly, a mixture of gases consisting

d AND f BLOCK ELEMENTS
of SO2 and SO3 is evolved and a red residue, Fe2O3
is formed.
[FeSO4.7H2O  FeSO4 + 7H2O] × 2
2FeSO4  Fe2O3 + SO2 + SO3
SO3 + H2O  H2SO4
2FeSO4.7H2O  Fe2O3 + SO2 + H2SO4 + 13H2O
Green vitriol Red
(vi) AgCl dissolves in KCN forming a complex, potassium
argentocyanide. The addition of zinc precipitates
silver.
AgCl + 2KCN  KAg(CN)2 + KCl
2KAg(CN)2 + Zn  K2Zn(CN)4 + 2Ag
Potassium zincocyanide
(vii) ZnO dissolves in NaOH forming sodium zincate.
ZnO + 2NaOH  Na2ZnO2 + H2O
(viii) Deep red colouration due to the formation of a
complex is developed.
FeCl3 + NH4CNS  Fe(CNS)Cl2 + NH4Cl
or FeCl3 + 3NH4CNS  Fe(CNS)3 + 3NH4Cl
Example - 52
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 NH4OH solution
but FeSO4 does not.
(viii) Copper hydroxide is soluble in ammonium
hydroxide but not in sodium hydroxide.
148
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
Green
+ 3Na2SO4 + 4H2O
(ii) When zinc is exposed to moist air, the surface is
affected with the formation of a film of basic zinc
carbonate on it. Due to this zinc becomes dull.
[2Zn + 2H2O + O2  2Zn (OH)2] × 2
Zn(OH)2 + CO2  ZnCO3 + H2O
ZnCO3 + 3Zn(OH)2  ZnCO3.3Zn (OH)2
4Zn + 3H2O + CO2 + 2O2  ZnCO3.3Zn(OH)2
Basic zinccarbonate
(iii) Ferrous sulphate is a salt of a weak base and a strong
acid. Thus, its hydrolysis occurs when it is dissolved
in water and solution becomes turbid due to
formation of ferrous hydroxide.
FeSO4 + 2H2O Fe(OH)2 + H2SO4
Addition of a small amount of acid shifts the
equilibrium towards left and thus prevents hydrolysis.
(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 NH 4 OH to form
insoluble Fe(OH)2. It does not form any complex with
NH4OH.
d AND f BLOCK ELEMENTS
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 - 53
A metal chloride (x) shows the following reactions :
(a) When H2S is passed in an acidified solution of (x)
a black precipitate is obtained.
(b) The black precipitate is not soluble in ammonium
sulphide.
(c) The solution of stannous chloride is added to an
aqueous solution of (x), a white precipitate is
obtained which turns grey on addition of more
stannous chloride.
(d) When aqueous solution of KI is added to an
aqueous solution of (x), a red precipitate is obtained
which dissolves on addition of excess of KI.
Identify (x) and write down the equations for the
reactions.
Sol. The acidified solution of (x) gives a black sulphide with
H2S indicates that the chloride is of a basic cation of
second group. The sulphide is insoluble in ammonium
sulphide, hence, the cation belongs to IIA group of
mixture analysis.
It gives white precipitate with SnCl2 which turns to
grey in excess of SnCl2 suggests that (x) is HgCl2. It is
further confirmed by the reaction with KI.
Reactions :
HgCl2 + H2S  HgS + 2HCl
Black
2HgCl2 + SnCl2  Hg2Cl2 + SnCl4
white
Hg2Cl2 + SnCl2  2Hg + SnCl4
Grey
HgCl2 + 2KI  HgI2 + 2KCl
Red ppt.
HgI2 + 2KI  K2HgI4
Soluble
149
Example - 54
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)
(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 - 55
Write the electronic configurations of the elements with
the atomic numbers 61, 91, 101 and 109.
Sol. Atomic number (61) = [Xe] 4f5 6s2.
Atomic number (91) = [Rn] 5f2 6d1 7s2
Atomic number (101) = [Rn] 5f14 7s1
Atomic number (109) = [Rn] 5f14 6d7 7s2.
Example - 56
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.
d AND f BLOCK ELEMENTS 150
 Magnetic moment of Ce3+ (iii) Decrease in basicity : With the decrease in ionic radii,
covalent character of their hydroxides goes on increasing
  11  2  B.M. from Ce(OH)3 to Lu(OH)3 and so base strength goes on
decreasing.

Example - 58
 3 B.M.  1.732 B.M.
What is meant by ‘lanthanoid contraction’ ?
Example - 57
Sol. The regular decrease (contraction) in the atomic and ionic
What is lanthanoid contraction ? What are the radii with increasing atomic number from lanthanum to
consequences of lanthanoid contraction ? lutetium along the lanthanoid series is called lanthanoid
contraction.
Sol. A group of fourteen elements following lanthanum i.e.
from 58Ce to71 Lu placed in 6th period of long form of Example - 59
periodic talbe are known as lanthanoids (or lanthanide
series). These fourteen elements are represented by Name the members of the lanthanoid series which exhibit
common general symbol ‘Ln’. In these elements, the last +4 oxidation states and those which exhibit +2 oxidation
electron enters the 4f-subshells (pre penultimate shell). It state. Try to correlate this type of behaviour with the
may be noted that atoms of these elements have electronic electronic configurations of these elements.
configuration with 6s2 common but with variable occupancy Sol. Cerium (Ce) and Terbium (Tb) show +4 oxidation state.
of 4f level. However, the electronic configuration of all the Their electronic configurations are given below :
tripositive ions (the most stable oxidation state of all
lanthanoids) are of the form 4f n(n = 1 to 14) with increasing Ce = [Xn] 4f1 5d1 6s2
atomic number). These elements constitute one of the two
Tb = [Xn] 4f0 6s2
series of inner transition elements or f-block.
It is clear from the configuration of Ce that Ce+4 is favoured
Lanthanoid contraction : In the lanthanoide series with
by its noble gas configuration i.e., [Xn] 4f0 5d0 5s0, but can
the increase in atomic number, atomic radii and ionic radii
be easily converted into Ce3+ ([Xn]) 4f1 5d0 6s0). Due to
decrease from one elements to the other, but this decrease
this reason Ce+4 is an oxidising agent. Tb4+ ion is stabilized
is very small. the regular small decrease in atomic radii
due to half filled f-subshell i.e., [Xn] 4f7. It also acts as an
and ionic radii of lanthanides with increasing atomic
oxidant.
number along the series is called lanthanoid contraction.
Europium (63) and ytterbium (70) show +2 oxidation state,
Cause of lanthanoid contraction: When one moves from
this acts as reducing agents because they can be
58
Ce to 71Lu along the lanthanide series nuclear charge
converted into common oxidation state +3. The electronic
goes on increasing by one unit every time. Simultaneously
configuration of Eu and Y are as follows :
an electron is also added which enters to the inner f
subshell. The shielding effect of f-orbitals in very poor Eu = [Xn] 4f7 6s2
due to their diffused shape. It results in the stronger
force of nuclear attraction of the 4f electrons and the Y = [Xn] 4f14 6s2
outer electrons causing decrease in size.
Formation of Eu2+ ion leaves 4f7 configuration and Y2+ ion
Consequences of lanthanoid contraction: leaves 4f14 configuration. These configurations can stable
due to half filled and full filled f-subshell. Samarium, Sm
(i) Similarly in the properties of elements of second and third (62) 4f6 6s2 also shows both +2 and +3 oxidation states like
transition series e.g. Zr and Hf; Nb and Ta; Mo and W. europium.
This resemblance is due to the similarity in size due to
the presence of lanthanoids in between.

(ii) Similarity among lanthanoids : Due to the very small

change in sizes, all the lanthanoids resemble one another
in chemical properties.
d AND f BLOCK ELEMENTS 151

Example - 60

Account for the following:

(i) Cerium (atomic number = 58) forms tetra positive ion,

Ce4+ in aqueous solution.

(ii) The second and third members in each group of

transition element have similar atomic radii.

Sol.

(i) The electronic configuration of Ce (Z = 58) is 58Ce = [Xe]

4f1 5d1 6s 2

Cerium can lose four electrons (4f1 5d1 6s2) in aqueous

solution to acquire stable configuration of rare gas xenon.
Moreover due to small size and high charge, Ce4+ ion has
high hydration energy.

(ii) The second and third members in each group of transition

elements have very similar atomic radii due to lanthanoid
contraction. It arises due to poor shielding effect of
electrons.
d AND f BLOCK ELEMENTS 152

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

General Introduction of d Block Elements
1. Transition elements have 11. The electronic configuration of chromium is actually
(a) completely filled ‘d’ levels [Ar]3d54s1 instead of normally expected [Ar]3d44s2. This
is because
(b) completely filled ‘s’ levels and d levels
(a) an exactly half-filled d level gives additional stability,
(c) incompletely filled ‘s’ levels and completely filled ‘d’
according to the Hund rule of maximum multiplicity
levels
(b) the 4s orbital has higher energy than the 3d orbitals
(d) incompletely filled ‘d’ levels
(c) the 4s orbitals has lower energy than the 3d orbitals
2. The general electronic configuration of the transition
elements is (d) the 3d and 4s orbitals have equal energies and hence
electron migration occurs readily
(a) (n – 1)d10 (n + 1)s2 (b) (n – 1)d1–10 (n + 1)s1–2
(c) (n – 1)d np ns
1–10 6 2
(d) (n – 1)d1–10 ns0–2 12. Which of the following ions has the maximum number of
unpaired d electrons ?
3. Which of the following transition elements has completely
filled d orbitals (the d10 configuration) (a) Fe3+ (b) V3+
(a) Co (b) Cr (c) Ti3+
(d) Mg2+
(c) Hg (d) Ni
13. Which of the following ions possesses the maximum
4. The last electron of a d-block element occupies the orbital
number of unpaired electrons ?
(a) (n – 1)d (b) nd
(a) Ni2+ (b) Fe2+
(c) np (d) (n – 1)s
(c) Cu +
(d) Zn2+
5. The general electronic configuration of group 12 elements
is 14. Which of the following does not possess unpaired
electrons ?
(a) ns2 (b) ns2np6
(a) Co3+ (b) Cu2+
(c)  n  1 d10 ns 2 (d)  n  1 d110 ns 2
(c) Ti2+ (d) Hg2+
6. The transition elements are 15. Which of the following electronic configurations
(a) more reactive than group 1 elements represents Fe3+ ?
(b) more reactive than group 2 elements (a) [Ar]3d64s2 (b) [Ar]3d54s1
(c) less reactive than group 1 elements but more reactive (c) [Ar]3d 4s
5 2
(d) [Ar]3d54s0
than group 2 elements 16. Which of the following is not true about the transition
(d) less reactive than group 1 and 2 elements elements ?
7. Transition elements (a) They show variable oxidation states
(a) exhibit inert-pair effect (b) Their ions have a strong tendency to form complexes
(b) show nonmetallic character (c) Their compounds usually do not absorb ultraviolet
(c) do not form complex compounds and visible lights
(d) exhibit variable oxidation states (d) Their ions and complex ions usually possess magnetic
moments.
8. The electronic configuration of silver is
17. Which of the following transition metals does not show
(a) [Ar]3d10 4s1 (b) [Ar]4d10 4s1
variable oxidation states ?
(c) [Kr]4d10 5s1 (d) [Kr]4d8 5s2
(a) Mercury (b) Zinc
9. The electronic configuration of palladium is
(c) Gold (d) Silver
(a) [Ar]3d84s2 (b) [Kr]4d85s2
(c) [Kr]5d86s2 (d) [Ar]4d105s0
10. The electronic configuration of platinum is
(a) [Xe] 4f145d96s1 (b) [Ar] 4f145d106s2
(c) [Ar] 4f 6d 7s
14 10 2
(d) [Ar] 4f146d97s1
d AND f BLOCK ELEMENTS 153
18. Which of the following statements is incorrect ? 23. For a given ion, the magnetic moment is 2.83 BM. The
(a) The compounds formed by the 3d transition metals in total spin (s) of all the unpaired electrons is
lower valence states are ionic but those in higher (a) 2 (b) 1
valence states are covalent. (c) 3/2 (d) 1/2
(b) The 4d and 5d transition metals form less ionic 24. The oxidation states shown by transition elements is
compounds than do the 3d transition metals. related to their
(c) The compounds formed by the 3d transition metals (a) electropositive characters
are less ionic than the corresponding compounds
formed by the 4d and 5d transition metals. (b) electronic configurations
(d) The ionization energies of 3d, 4d and 5d transition (c) atomic weights
metals are greater than those of group 1 and 2 metals. (d) atomic sizes
19. The noble character of platinum and gold is favoured by 25. Identify the species having an atom in +6 oxidation state.
(a) high enthalpies of sublimation, high ionization (a) MnO4 (b) Cr(CN)36
energies and low enthalpies of solvation
(b) high enthalpies of sublimation, low ionization energies (c) NiF63 (d) CrO2Cl2
and low enthalpies of solvation
26. Which one of the following exhibits the largest number of
(c) low enthalpies of sublimation, high ionization energies oxidation states?
and low enthalpies of solvation
(a) Mn (25) (b) Ti (22)
(d) high enthalpies of sublimation, high ionization
energies and high enthalpies of solvation (c) Cr (24) (d) V (23)
27. Formation of interstitial compound makes the transition
metal
Physical Properties of d Block Elements (a) more soft (b) more metallic
(c) more ductile (d) more hard
20. Which of the following arrangements does not represent 28. Which of the following ions is colourless in solution ?
the correct order of the property stated against it ? (a) V3+ (b) Cr3+
(c) Co2+ (d) Sc3+
(a) V 2  Cr 2  Mn 2  Fe2 : paramagnetic behaviour
29. Which one of the following ionic species will impart colour
(b) Ni 2  Co 2  Fe2  Mn 2 : ionic size to an aqueous solution ?
(a) Ti4+ (b) Cu+
(c) Co3  Fe3  Cr 3  Sc3 : stability in aqueous solution
(c) Zn2+ (d) Cr3+
(d) Sc  Ti  Cr  Mn : number of oxidation states 30. Which of the following ions is expected to be coloured in
21. The covalent radii of transition metals decrease from left solution ?
to right in a period because (a) Cu+ (b) Cu2+
(a) the densities of the metals decrease with increasing (c) Ti 4+
(d) Sc3+
atomic number due to poor shielding of electrons 31. Which of the following compounds is expected to be
(b) the screening of nuclear charge by d electrons is poor coloured ?
and hence the nuclear charge attracts all the electrons (a) Ag2SO4 (b) CuF2
strongly, causing a decrease in size (c) MgF2 (d) CuCl
(c) the ionization energies also decrease correspondingly
(d) the metallic character decreases as the atomic number
increases Chemical Properties of d Block Elements
22. Among the transition metals, the melting points of Zn,
Cd and Hg are relatively low because 32. Which of the following statements is incorrect for CrO3 ?
(a) their d shells are not completely filled (a) It is a bright orange solid.
(b) their d electrons do not participate in metallic bonding (b) It is commonly called chromic acid.
(c) It is prepared by adding concentrated H2SO4 to a
(c) their densities are higher
saturated solution of sodium dichromate.
(d) of all the above
(d) The colour arises due to d–d transition.
d AND f BLOCK ELEMENTS 154
33. Which of the following oxides of chromium is amphoteric 41. Which one of the following oxides of chromium is
in nature ? amphoteric in nature ?
(a) CrO (b) CrO3 (a) CrO (b) Cr2O3
(c) Cr2O3 (d) CrO5 (c) CrO3 (d) CrO5
34. Transition metals 42. Which of the following oxides of manganese is
(a) form only ionic compounds amphoteric ?
(a) MnO2 (b) Mn2O3
(b) form exclusively covalent compounds
(c) Mn2O7 (d) MnO
(c) may form either ionic or covalent compounds 43. Four successive members of the first series of the
depending on the condition transition metals are listed below. For which one of
(d) exclusively form coordination compounds but no
simple compounds 
o
them the standard potential E M 2 / M  value has a
35. Which of the following is an incorrect statement? positive sign?
(a) The lowest oxidation state oxide of a transition metal (a) Co (Z = 27)
is acidic whereas the highest one is usually basic. (b) Ni (Z = 28)
(b) A transition metal usually exhibits higher oxidation (c) Cu (Z = 29)
states in its fluorides than in its iodides. (d) Fe (Z = 26)
(c) Transition metal halides become more covalent with 44. Deep red-yellow vapour of CrO2Cl2 is passed into an
the increasing oxidation state of the transition metal aqueous solution of NaOH. The solution turns
and are more susceptible to hydrolysis. (a) yellow due to the formation of Na2Cr2O7
(d) The highest oxide of a transition metal is acidic whereas (b) yellow due to the formation of Na2CrO4
the lowest one is usually basic. (c) green due to the formation of CrCl3
36. The highest possible oxidation state shown by osmium (d) red due to the formation of Na2CrO4
in its compounds is 45. Which of the following oxides of manganese is acidic ?
(a) +4 (b) +8 (a) MnO (b) Mn2O3
(c) +6 (d) +10 (c) Mn2O7 (d) MnO2
37. Iron exhibits +2 and +3 oxidation states. Which of the 46. Which of the following oxides of manganese is stable as
following statements about iron is incorrect ? well as basic ?
(a) Ferrous oxide is more basic in nature than the ferric (a) MnO2 (b) Mn2O7
oxide. (c) MnO (d) Mn2O3
(b) Ferrous compounds are relatively more ionic than the 47. Which of the following compounds is colourless?
corresponding ferric compounds. (a) K2MnO4 (b) HgI2
(c) Ferrous compounds are less volatile than the (c) ZnSO4 (d) FeSO4
corresponding ferric compounds. 48. Ammonia forms the complex ion [Cu(NH3)4]2+ with copper
ions in alkaline solutions but not in acidic solutions. What
(d) Ferrous compounds are more easily hydrolysed than
is the reason for it ?
the corresponding ferric compounds.
(a) In acidic solutions protons coordinate with ammonia
38. The transition metals sometimes form nonstoichiometric molecules forming NH4+ ions and NH3 molecules are
compounds. These compounds have not available
(a) definite structures and definite proportions (b) In alkaline solutions insoluble Cu(OH)2 is precipitated
(b) indefinite structures and definite proportions which is soluble in excess of any alkali
(c) definite structures and indefinite proportions (c) Copper hydroxide is an amphoteric substance
(d) indefinite structures and indefinite proportions (d) In acidic solutions hydration protects copper ions
39. Which of the following ions is paramagnetic ?
(a) Zn2+ (b) N3– Potassium Permanganate
(c) Mn 4+
(d) Cu+
40. Which of the following ions is diamagnetic ? 49. Which of the following compounds has colour but no
(a) Ni2+ (b) Ti4+ unpaired electrons?
(a) KMnO4 (b) MnSO4
(c) Cr3+
(d) Co3+
(c) K2MnO4 (d) MnC12
d AND f BLOCK ELEMENTS 155

50. MnO 4 is prepared by treating a solution containing Mn2+ Potassium Dichromate

ions with a very strong oxidizing agent such as 57. When hydrogen peroxide is added to an acidic solution
of a dichromate, the most probable product is
(a) PbO2 (b) C2 O42 (a) K2CrO4 (b) CrO3
(c) I2 (d) Fe3+ (c) Cr2O3 (d) CrO(O2)2
51. Which of the following compounds is green in colour ? 58. Number of moles of K2Cr2O7 reduced by one mole of
(a) KMnO4 (b) (NH4)2Cr2O7 Sn2+ ions is
(c) MnO2 (d) K2MnO4 1
(a) (b) 3
52. KMnO4 is manufactured on a large scale by 3
(a) fusing MnO2 with KOH and then oxidizing the fused 1
mixture with KNO3 (c) (d) 6
6
(b) fusing MnO2 with Na2CO3 in the presence of O2
59. CrO3 dissolves in aqueous NaOH to give
(c) fusing MnO2 with KOH and KNO3 to form K2MnO4
which is then electrolytically oxidized in an alkaline (a) CrO 24  (b) Cr(OH)2
solution
(c) Cr2 O 72  (d) Cr(OH)3
(d) fusing MnO2 with KNO3 and then acidifying the fused
mixture 60. Cr2 O 72  reacts with OH– as
53. When KMnO4 acts as an oxidising agent and ultimately
forms [MnO4]2–, MnO2 Mn2O3, Mn+2 then the number of Cr2 O 27   2(OH  )  2CrO 42   H 2 O
electrons transferred in each case repectively is The change in oxidation number of Cr is
(a) 4, 3, 1, 5 (b) 1, 5, 3, 7 (a) 6 (b) 3
(c) 1, 3, 4, 5 (d) 3, 5, 7, 1 (c) zero (d) 4
54. Amount of oxalic acid present in a solution can be 61. CrO 24  reacts with H+ as
determined by its titration with KMnO4 solution in the
presence of H2SO4. The titration gives unsatisfactory 2CrO 24   2H   Cr2 O 72   H 2 O
result when carried out in the presence of HCl, because
The change in oxidation number of Cr is
HCl
(a) +5 (b) +7
(a) reduces permanganate to manganate
(c) +6 (d) zero
(b) furnishes H+ ions in addition to those from oxalic acd 62. Acidified K2Cr2O7 on treatment with KI produces
(c) reduces permanganate to Mn2+ (a) KIO3 (b) I2
(d) oxidises oxalic acid to carbon dioxide and water (c) KIO4 (d) I3
55. KMnO4 in an acidic medium will not oxidize 63. What would happen when a solution of potassium
(a) NO 2 (b) SO24 chromate is treated with an excess of dilute nitric acid ?
(a) Cr2O72– and H2O are formed
(c) HN3 (d) H2O2
(b) CrO42– is reduced to +3 state of Cr
56. Which of the following is an incorrect statement ?
(a) In a redox reaction in acidic medium, KMnO4 produces (c) CrO42– is oxidized to +7 state of Cr
Mn2+ ions. (d) Cr3+ and Cr2O72– are formed
(b) In a redox reaction in strongly alkaline medium, KMnO4 64. Which of the following is not formed when H2S reacts
produces MnO24 ions. with acidic K2Cr2O7 solution?
(a) CrSO4 (b) Cr2(SO4)3
(c) In a redox reaction in neutral medium, KMnO4 produces (c) K2SO4 (d) S
MnO2.
65. K 2 Cr2 O7 on heating with aqueous NaOH gives
(d) In a redox reaction in alkaline medium, KMnO4
produces Mn2O7. (a) Cr2 O 72  (b) Cr  OH  2

(c) CrO 24  (d) Cr  OH 3

d AND f BLOCK ELEMENTS 156
Other Compounds of d-Block Elements 74. Permanent magnets are generally made from the alloy of
(a) Co (b) Zn
66. The value of magnetic moment (m spin only) for Cu2+ in
CuSO4.5H2O is (c) Al (d) Pb
(a) 5.92 BM (b) 4.92 BM 75. Match the catalyst with the process :
Catalyst Process
(c) 2.83 BM (d) 1.73 BM
(i) V2 O 5 (p) The oxidation of ethyne to
67. Calomel (Hg2Cl2) on reaction with ammonium hydroxide
ethanal
gives
(ii) TiC14 (q) Polymerisation of alkynes
(a) HgO (b) Hg2O (iii) PdC12 (r) Oxidation of SO2 in the
manufacture of H2SO4
(c) NH2 – Hg – Hg – Cl (d) Hg NH2 Cl (iv) Nickel Complexes (s) Polymerisation of ethylene
68. A red solid is insoluble in water. However it becomes Which of the following is the correct option?
soluble if some KI is added to water. Heating the red solid (a) (i)-(r), (ii)-(s), (iii)-(p), (iv)-(q)
in a test tube results in liberation of some violet coloured (b) (i)-(p), (ii)-(q), (iii)-(r), (iv)-(s)
fumes and droplets of a metal appear on the cooler parts (c) (i)-(p), (ii)-(r), (iii)-(q), (iv)-(s)
of the test tube. The red solid is (d) (i)-(r), (ii)-(p), (iii)-(s), (iv)-(q)
(a) HgI2 (b) HgO
(c) Pb3O4 (d) (NH4)2Cr2O7
General Characteristics of f-block Elements
69. Na2CrO4 on treatment with lead acetate gives a precipitate.
This precipitate is dried and the solid is used as a pigment
for road signs and markings. The solid is known as 76. Lanthanides are characterized by the filling of the
(a) white lead (b) chrome green (a) penultimate 4f energy level
(c) chrome yellow (d) red lead (b) antepenultimate 4f energy level
70. The compound ZnSO4 is white because (c) penultimate 3f energy level
(a) charge is transferred from the metal to the oxygen (d) antepenultimate 3f energy level
atoms 77. The general electronic configuration f-block elements is
(b) electron transfer to d level does not occur as the level represented by
is already filled to capacity in zinc (a) (n – 2)f1–14 (n – 1)d0–1ns2
(c) Zn2+ has d10 configuration and d–d transition occurs (b) (n – 2)f1–14 (n – 1)d0–5ns0–2
easily (c) (n – 2)f1–14 (n – 1)d0–10ns1–2
(d) Zn2+ ions absorb light of the visible range (d) (n – 2)f1–14 (n – 1)d0–2 (n – 1)s2
71. Consider the following equilibrium 78. The electronic configurations of the first four members of
 the actinide series cannot be written accurately in a regular
AgCl + 2NH3  [Ag (NH3)2]+ + Cl– manner because of
White precipitate of AgCl appears on adding which of the (a) small difference in energy between 5f and 6d orbitals
following? (b) large difference in energy between 5f and 6d orbitals
(a) aqueous HNO3 (b) aqueous NaCl (c) small difference in energy between 5f and 6s orbitals
(c) aqueous NH4Cl (d) NH3 (d) violation of the Pauli exclusion principle
72. Which of the following compounds gives red precipitate 79. The electronic configuration of cerium is
with AgNO 3 ? (a) [Xe]4f15d16s2 (b) [Xe]4f25d06s1
(a) KI (b) NaBr (c) [Xe]4f15d26s2 (d) [Xe]4f25d06s2
(c) K2CrO4 (d) NaNO3 80. The outer electronic configuration of Gd (At. No. 64) is
(a) 4f3 5d5 6s2 (b) 4f8 d0 6s2
Uses of d Block Elements
(c) 4f4 5d4 6s2 (d) 4f7 5d1 6s2
73. Corrosion of iron can be prevented by coating the
surface with
(a) Zn (b) Sn
(c) Ni (d) Any of these
d AND f BLOCK ELEMENTS
81. Which of the following statements concerning
lanthanide elements is false?
(a) All lanthanides are highly dense metals.
(b) More characteristic oxidation state of lanthanide
elements is +3.
(c) Lanthanides are separated from one another by ion
exchange method.
(d) Ionic radii of trivalent lanthanides steadily increases
with increase in the atomic number.
82. Which of the following statements is correct for the
lanthanoids ?
(a) The 4f electrons do not take part in bonding.
(b) The 4f electrons can neither be removed to produce
ions nor be made to take part in crystal field
stabilization of complexes.
(c) The 4f electrons in the antepenultimate shell are very
effectively shielded by the 5s and 5p electrons.
(d) All of these
83. Identify the incorrect statement among the following :
(a) 4f and 5f orbitals are equally shielded.
(b) d–Block elements show irregular and erratic chemical
properties among themselves.
(c) La and Lu have partially filled d–orbitals and no other
partially filled orbitals.
(d) The chemistry of various lanthanoids is very similar.
84. In context of the lanthanoids, which of the following
statements is not correct ?
(a) There is a gradual decrease in the radii of the members
with increasing atomic number in the series.
(b) All the member exhibit +3 oxidation state.
(c) Because of similar properties the separation of
lanthanoids is not easy.
(d) Availability of 4f electrons results in the formation of
compounds in +4 state for all the members of the
series.
85. Arrange Ce+3, La+3, Pm+3 and Yb+3 in increasing order of
their ionic radii.
(a) Yb+3 < Pm+3 < Ce+3 < La+3
(b) Ce+3 < Yb+3 < Pm+3 < La+3
(c) Yb+3 < Pm+3 < La+3 < Ce+3
(d) Pm+3 < La+3 < Ce+3 < Yb+3
86. The radius of La3+ (Atomic number of La = 57) is 1.06 Å.
Which one of the following given values will be closest
to the radius of Lu3+ (Atomic number of Lu = 71) ?
157
(a) 1.40 Å (b) 1.06 Å
(c) 0.85 Å (d) 1.60 Å
87. The atomic and ionic radii (M3+ ions) of lanthanide
elements decrease with increasing atomic number. This
effect is called
(a) lanthanide contraction (b) lanthanide expansion
(c) actinide contraction (d) none of these
88. Lanthanide contraction occurs because
(a) the 4f electrons, which are gradually added, create a
strong shielding effect
(b) the 4f orbitals are greater in size than the 3d and 3f
orbitals
(c) the 5f orbitals strongly penetrate into the 4f orbitals
(d) the poor shielding effect of 4f electrons is coupled
with increased attraction between the nucleus and the
added electrons
89. Which of the following statements is correct ?
(a) The second-row elements have smaller radii than the
corresponding third-row ones.
(b) Because of lanthanide contraction, the radii of the third-
row elements are almost the same as those of the first-
row elements.
(c) Because of lanthanide contraction, the radii of the third-
row elements are almost the same as those of the
second-row elements.
(d) Because of lanthanide contraction, the separation of
second-row elements from one another is easier.
90. The lanthanide contraction is responsible for the fact that
(a) Zr and Zn have the same oxidation state
(b) Zr and Hf have about the same radius
(c) Zr and Nb have similar oxidation state
(d) Zr and Y have about the same radius
91. Which of the following factors may be regarded as the
main cause of lanthanide contraction ?
(a) Greater shielding of 5d electrons by 4f electrons
(b) Poorer shielding of 5d electrons by 4f electrons
(c) Effective shielding of one of 4f electrons by another in
the subshell
(d) Poor shielding of one of 4f electron by another in the
subshell
92. Which of the following elements shows the maximum
number of different oxidation states in its compounds ?
(a) Eu (b) La
(c) Gd (d) Am
d AND f BLOCK ELEMENTS 158
93. The most common and stable oxidation state of 97. Lanthanide elements have
lanthanides is (a) similar lattice energies but widely different solvation
(a) +II (b) +IV and ionization energies
(c) +VII (d) +III (b) similar lattice and solvation energies but widely
94. Knowing that the chemistry of lanthanoids (Ln) is different ionization energies
dominated by its +3 oxidation state, which of the (c) similar lattice and ionization energies but widely
following statements is incorrect ? different hydration energies
(a) The ionic size of Ln (III) decrease in general with (d) similar lattice energies, solvation energies and
increasing atomic number ionization energies
98. The hardness, melting point and boiling point of elements
(b) Ln (III) compounds are generally colourless.
increase from Ce to Lu because
(c) Ln (III) hydroxide are mainly basic in character. (a) the attraction between the atoms increases as the size
(d) Because of the large size of the Ln (III) ions the bonding increases
in its compounds is predominantly ionic in character. (b) the attraction between the atoms decreases as the size
95. The actinoids exhibit more number of oxidation states in increases
general than the lanthanoids. This is because (c) the attraction between the atoms increases as the size
decreases
(a) The 5f orbitals extend further from the nucleus than
the 4f orbitals (d) the attraction between the atoms remains the same as
the size increases
(b) The 5f orbitals are more buried than the 4f orbitals
99. Select the correct statement(s) for comparison of
(c) There is a similarity between 4f and 5f orbitals in their lanthanoids with actinoids.
angular part of the wave function (a) Actinide contraction is greater from element to
(d) The actinoids are more reactive than the lanthanoids. element due to poor shielding by 5f electrons
96. Larger number of oxidation states are exhibited by the (b) Magnetic properties of actinoids are more complex,
actinoids than those by the lanthanoids, the main reason with corresponding lanthanides having higher values
being (c) Lanthanoids have higher I.E.
(a) 4f orbitals more diffused than the 5f orbitals (d) All of the above
100. Colour of lanthanide ions are observed mainly due to :
(b) lesser energy difference between 5f and 6d than
between 4f and 5d orbitals (a) f-f transitions
(c) more energy difference between 5f and 6d than between (b) crystal field splitting
4f and 5d orbitals (c) full f-orbital
(d) more reactive nature of the actinoids than the (d) partially filled d-subshell
lanthanoids
d AND f BLOCK ELEMENTS 159

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS

Objective Questions I [Only one correct option] 8. Which of the following ions does not liberate hydrogen
1. The colour of KMnO4 is due to : (2015) gas on reaction with dilute acids ? (2017)
(a) Ti2+ (b) V2+
(a) L  M charge transfer transition
(c) Cr2+ (d) Mn2+
(b)    * transition 9. In Wilkinson’s catalyst, the hybridization of central metal
(c) M  L charge transfer transition ion and its shape are respectively : (2018)
(d) d – d transition (a) sp3d, trigonal bipyramidal
(b) sp3, tetrahedral
2. Which of the following statements is false ? (2015)
(c) dsp2, square planar
(a) Na2Cr2O7 is less soluble than K2Cr2O7
(d) d2sp3, octahedral
(b) Na2Cr2O7 is primary standard in volumetry
10. When XO2 is fused with an alkali metal hydroxide in
(c) CrO 24  is tetrahedral in shape
presence of an oxidizing agent such as KNO3; a dark green
(d) CrO 72  has a Cr-O-Cr bond
product is formed which disproportionates in acidic
3. A pink coloured salt turns blue on heating. The presence solution to afford a dark purple solution. X is :
of which cation is most likely? (2015) (2018)
(a) Co2+ (b) Cu2+ (a) Ti (b) V
(c) Zn2+ (d) Fe2+
(c) Cr (d) Mn
4. Which of the following compounds is metallic and
11. Calculate the highest value of the spin only magnetic
ferromagnetic ? (2016)
moment (in BM) among all the transition metal complexes.
(a) CrO2 (b) VO2
(2019)
(c) MnO2 (d) TiO2
(a) 5.92 (b) 3.87
5. Which one of the following species is stable in aqueous (c) 6.93 (d) 4.90
solution (2016)
12. The transition element that has lowest enthalpy of
(a) Cr2+ (b) Cu+ atomisation is: (2019)
3
(c) MnO 4
(d) MnO 24  (a) Fe (b) Cu
6. Sodium extract is heated with concentrated HNO3 before (c) V (d) Zn
testing for halogens because : (2016) 13. The correct order of atomic radii is:
(a) Silver halides are totally insoluble in nitric acid. (2019)
(b) Ag2S and AgCN are soluble in acidic medium. (a) Nd > Ce > Eu > Ho (b) Ho > Nd > Eu > Ce
(c) S2 and CN  , if present, are decomposed by conc. (c) Ce > Eu > Ho > Nd (d) Eu > Ce > Nd > Ho
HNO3 and hence do not interfere in the test. 14. The statement that is INCORRECT about the interstitial
(d) Ag reacts faster with halides in acidic medium compounds is: (2019)
(a) they are chemically reactive
7. In the following reactions, ZnO is respectively acting as
(b) they are very hard
a/an (2017)
(c) they have metallic conductivity
(i) ZnO + Na2O 
 Na2ZnO2 (d) they have high melting points
15. The number of water molecules (s) not coordinated to
(ii) ZnO + CO2 
 ZnCO2
copper ion directly in CuSO4.5H2O, is: (2019)
(a) base and acid (b) base and base (a) 4 (b) 3
(c) acid and acid (d) acid and base (c) 1 (d) 2
d AND f BLOCK ELEMENTS 160
16. The maximum number of possible oxidation states of (a) [Xe]5f7 and 7.9 (b) [Xe] 4f7 and 7.9
actinoides are shown by: (2019) (c) [Xe]and 8.9 (d) [Xe] and 8.9
(a) Nobelium (No) and lawrencium (Lr) 24. The lanthanoid that does NOT shows +4 oxidation state
(b) Actinium (Ac) and thorium (Th) is: (2020)
(c) Berkelium (Bk) and californium (Cf) (a) Dy (b) Ce
(d) Neptunium (Np) and plutonium (Pu) (c) Tb (d) Eu
17. Consider the hydrated ions of Ti2+, V2+, Ti3+, and Sc3+. 25. The atomic radius of Ag is closest to : (2020)
The correct order of their spin-onlymagnetic moments is: (a) Ni (b) Cu
(2019) (c) Au (d) Hg
(a) V2+ < Ti2+ < Ti3+ < Sc3+ (b) Sc3+ < Ti3+ < Ti2+ < V2+ 26. The electronic configuration of bivalent europium and
trivalent cerium, are: (Atomic Number : Xe = 54, Ce = 58,
(c) Ti3+ < Ti2+ < Sc3+ < V2+ (d) Sc3+ < Ti3+ < V2+ < Ti2+
Eu = 63) (2020)
18. The highest possible oxidation states of uranium and
(a) [Xe]4f 7,[Xe]4f 1 (b) [Xe]4f 76s2,[Xe]4f 26s2
plutonium, respectively, are: (2019)
(c) [Xe]4f 2,[Xe]4f 7 (d) [Xe]4f 4,[Xe]4f 9
(a) 6 and 7 (b) 6 and 4
27. Mischmetal is an alloy consisting mainly of :
(c) 7 and 6 (d) 4 and 6
(2020)
19. The metal that gives hydrogen gas upon treatment
(a) lanthanoid and actinoid metals
with both acid as well as base is (2019)
(b) lanthanoid metals
(a) magnesium (b) mercury
(c) actinoid metals
(c) zinc (d) iron
(d) actinoid and transition metals
20. Thermal decomposition of a Mn compound (X) at 513 K 2+
28. The electrode potential of M /M of 3d-series elements
results in compound Y, MnO2 and a gaseous product.
shows positive value for (2021)
MnO2 reacts with NaCl and concentrated H2SO4 to give a
pungent gas Z. X, Y, and Z, respectively, are: (a) Fe (b) Co
(2019) (c) Zn (d) Cu
(a) K3MnO4, K2MnO4 and Cl2 29. Which is the correct order of the following elements with
(b) K2MnO4, KMnO4 and SO2 respect to their density? (2021)
(c) KMnO4, K2MnO4 and Cl2 (a) Cr < Zn < Co < Cu < Fe (b) Zn < Cu < Co < Fe < Cr
(d) K2MnO4, KMnO4 and Cl2 (c) Zn < Cr < Fe < Co < Cu (d) Cr < Fe < Co < Cu < Zn
21. The incorrect statement is : (2020) 30. In which of the following pairs, the outer most electronic
(a) Manganate and permanganate ions are tetrahedral configuration will be the same? (2021)
2+ + 2+ +
(b) In manganate and permanganate ions, the- bonding (a) Ni and Cu (b) Fe and Co
+ 2+ 2+ +
takes place by overlap of p-orbitals of oxygen and d- (c) Cr and Mn (d) V and Cr
orbitals of manganese 31. Which one of the following lanthanoids does not form
MO2? [M is lanthanoid metal] (2021)
(c) Manganate and permanganate ions are paramagnetic
(a) Dy (b) Nd
(d) Manganate ion is green in colour and permanganate
(c) Yb (d) Pr
ion is purple in colour
32. On treating a compound with warm dil. H2SO4, gas X is
22. The incorrect statement(s) among (a) – (c) is (are) : evolved which turns K2Cr2O7 solution acidified with dil.
(2020) H2SO4 to a green compound Y. X and Y respectively are :
(A) W(VI) is more stable than Cr(VI).
(2021)
(B) in the presence of HCl, permanganate titrations
provide satisfactory results. (a) X = SO2, Y = Cr2(SO4)3 (b) X = SO2, Y = Cr2O3
(C) some lanthanoid oxides can be used as phosphors. (c) X = SO3, Y = Cr2(SO4)3 (d) X = SO3, Y = Cr2O3
(a) (A) only (b) (B) and (C) only 33. The oxide that shows magnetic property is : (2021)
(c) (A) and (B) only (d) (B) only
(a) SiO2 (b) Na 2 O
23. The correct electronic configuration and spin-only
magnetic moment (BM) of Gd3+ (Z = 64),respectively, are: (c) Mn 3 O 4 (d) MgO
(2020)
d AND f BLOCK ELEMENTS 161
34. The set having ions which are coloured and paramagnetic 41. What is the spin-only magnetic moment value (BM) of a
both, is - (2021) divalent metal ion with atomic number 25, in it’s aqueous
solution? (2021)
(a) Cu 2  , Cr 3 ,Sc  (b) Cu 2  , Zn 2  , Mn 4 
(a) 5.26 (b) 5.92
(c) Sc 2  , Zn 2  , Mn 4  (d) Ni 2  , Mn  , Hg 2  (c) zero (d) 5.0
3+ 2+
35. The spin only magnetic moments (in BM) for free Ti , V 42. The common positive oxidation states for an element with
3+
and Sc ions respectively are (At. No. - Sc: 21, Ti: 22, V: 23) atomic number 24, are:
(2021) (2021)
(a) 3.87, 1.73, 0 (b) 1.73, 3.87, 0 (a) + 2 to + 6 (b) + 1 and + 3
(c) 1.73, 0, 3.87 (d) 0, 3.87, 1.73 (c) + 1 to + 6 (d) + 1 and + 3 and + 6
36. The nature of oxides V2O3 and CrO is indexed as 'X' and 'Y' 43. The major components of German Silver are (2021)
type respectively. The correct set of X and Y is (a) Ge, Cu and Ag (b) Cu, Zn and Ni
(2021) (c) Zn, Ni and Ag (d) Cu, Zn and Ag
(a) X = basic, Y = amphoteric
(b) X = amphoteric, Y = basic
Numerical Value Type Question
(c) X = acidic, Y = acidic
(d) X = basic, Y = basic 44. Consider the following reactions :
37. Potassium permanganate on heating at 573 K gives a
NaCl + K 2 Cr2 O7 + H 2SO4   A   side products
product which is (2021)
(a) paramagnetic and colourless  A   NaOH   B  side products
(b) diamagnetic and green
 B  H2SO4  dil.  H 2 O2   C   side products
(c) diamagnetic and colourless
The sum of the total number of atoms in one molecule of
(d) paramagnetic and green
38. In the structure of the dichromate ion, there is a: (A),(B) & (C) is _______ . (2020)
45. The sum of total number of bonds between chromium and
(2021)
oxygen atoms in chromate and dichromate ions is
(a) linear symmetrical Cr–O–Cr bond.
(2020)
(b) non-linear symmetrical Cr–O–Cr bond. 46. In a mildly alkaline medium, thiosulphate ion is oxidized by
(c) linear unsymmetrical Cr–O–Cr bond.
MnO 4 to “A”. The oxidation state of sulphur in “A” is
(d) non-linear unsymmetrical Cr–O–Cr bond
_________.
39. Which one of the following lanthanides exhibits +2
(2021)
oxidation state with diamagnetic nature?
47. In the ground state of atomic Fe (Z = 26), the spin-only
(Given Z for Nd = 60, Yb = 70, La = 57, Ce =58)
(2021) magnetic moment is _______ 10 1 BM . (Round off to
(a) Nd (b) Yb the Nearest Integer).
(c) La (d) Ce [Given: 3  1.73, 2  1.41 ]
2+
40. The Eu ion is a strong reducing agent in spite of its (2021)
ground state electronic configuration (outermost): [Atomic 3+
48. Number of electrons present in 4f orbital of Ho ion is
number of Eu = 63] (2021)
7 2 6
_________.(Given Atomic No. of Ho = 67) (2021)
(a) 4f 6s (b) 4f
7 6 2
49. The number of 4f electrons in the ground state electronic
(c) 4f (d) 4f 6s 2+
configuration of Gd is ______.
[Atomic number of Gd = 64] (2021)
50. The number of f electrons in the ground state electronic
configuration of Np (Z = 93) is ________. (Nearest integer)
(2021)
d AND f BLOCK ELEMENTS 162
Assertion Reason 54. Given below are two statements:
Statement I: Potassium permanganate on heating at 573 K
51. For the following Assertion and Reason, the correct forms potassium manganate.
option is: Statement II: Both potassium permanganate and potassium
Assertion: For hydrogenation reactions, the catalytic manganate are tetrahedral and paramagnetic in nature.
activity increases from group-5 to group-11 metals with In the light of the above statements, choose the most
maximum activity shown by group 7-9 elements appropriate answer from the options given below:
Reason: The reactants are most strongly adsorbed on
(2021)
group 7-9 elements (2020)
(a) Both statement I and statement II are false
(a) If both assertion and reason are correct and reason
is the correct explanation of assertion. (b) Statement I is true but statement II is false
(b) If both assertion and reason are true but reason is (c) Statement I is false but statement II is true
not the correct explanation of assertion. (d) Both statement I and statement II are true
(c) If assertion is true but reason is false.
(d) If assertion is false but reason is true.
Match the Following
52. Given below are two statements:
o 4+ 3+ Each question has two columns. Four options are
Statement I: The E value for Ce /Ce is + 1.74 V.
4+ 3+ given representing matching of elements from
Statement II: Ce is more stable in Ce state than Ce state.
Column-I and Column-II. Only one of these four
In the light of the above statements, choose the most
options corresponds to a correct matching. For
appropriate answer from the options given below.
each question, choose the option corresponding
(2021)
(a) Statement I is incorrect but statement II is correct to the correct matching
(b) Statement I is correct but statement II is incorrect 55. Match the catalysts (Column I) with products
(c) Both statement I and statement II are correct (Column II). (2019)
Column I Column II
(d) Both statement I and statement II are incorrect
Catalyst Product
53. Given below are two statement: one is labelled as Assertion
(A) V2O5 (i) Polyethylene
A and the other is labelled as Reason R:
3+ 3+
(B) TiCl4/Al(Me)3 (ii) ethanal
Assertion A: Size of Bk ion is less than Np ion. (C) PdCl2 (iii) H2SO4
Reason R: The above is a consequence of the lanthanoid (D) Iron oxide (iv) NH3
contraction.
(a) (A) – (iii); (B) – (iv); (C) – (i); (D) – (ii)
In the light of the above statements, choose the correct
answer from the options given below: (b) (A) – (ii); (B) – (iii); (C) – (i); (D) – (iv)
(2021) (c) (A) – (iii); (B) – (i); (C) – (ii); (D) – (iv)
(a) Both A and R are true but R is not the correct explanation (d) (A) – (iv); (B) – (iii); (C) – (ii); (D) – (i)
of A.
(b) A is true but R is false.
(c) A is false but R is true.
(d) Both A and R are true and R is the correct explanation of
A.
d AND f BLOCK ELEMENTS 163

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only one correct option] 11. Hybridization of Cr in K2Cr2O7 is
(a) sp3 (b) sp2
1. The compound in which nickel has the lowest oxidation
state is : (c) dsp2 (d) dsp3
(a) Ni(CO)4 (b) (CH3COO)2Ni 12. Which of the following statements regarding copper salts
(c) NiO (d) NiCl2(PPh3)2 is not true ?
2. Spiegeleisen is an alloy of : (a) Copper (I) ion disproportionates to copper metal and
copper (II) ion in aqueous solution.
(a) Cu + Zn + Ni (b) Ni + Cr
(b) Copper (I) ion can be stablised by the formation of
(c) Mn + Fe + C (d) Fe + Cr + Ni
insoluble complex compounds such as CuC l 2 and
3. Wilkinson’s catalyst consists of
(a) (C2H5)3 Al and TiCl4 Cu(CN) 2 .
(b) RhCl3 and Ph3P (c) Copper (II) oxide is red powder.
(c) HCo(CO)4 (d) The water of crystallization of copper sulphate is five
(d) trans-[(Rh(CO)(H)(PPh3)3] 13. Mercury is transported in the containers made of :
4. Which of the following is known as Adams’ catalyst ? (a) Ag (b) Pb
(a) Pt/PtO (b) V2O5/TiCl4 (c) Al (d) Fe
(c) Cu/V (d) Pt/Rh 14. When steam is passed over red hot iron, the substances
5. Malachite and azurite are used respectively are : formed are :
(a) Blue and green pigment (a) Fe2O3 + H2 (b) Fe3O4 + H2
(b) Red and green pigment (c) FeO + H2 (d) FeO + H2 + O2
(c) Green and blue pigment 15. Fe is made passive by :
(d) Green and red pigment (a) dil. H2SO4 (b) dil. HCl
6. Chloroplatinic acid is : (c) conc. HNO3 (d) conc. H2SO4
(a) monobasic (b) dibasic 16. Mark the correct statements :
(c) tribasic (d) tetrabasic (a) Hg forms an amalgam with iron
(b) Hg vapour is non-poisonous
7. The solubility of silver bromide in hypo solution is due to
the formation of : (c) Hg is monovalent in mercurous compound
(a) Ag2SO3 (b) Ag2S2O3 (d) Oxysalts of mercury are thermally unstable
(c) [Ag(S2O3)] –
(d) [Ag(S2O3)2]3– 17. Chemically philosopher’s wool is :
8. Sodium thiosulphate is used to remove the unexposed AgBr (a) ZnO (b) BaO
from photographic films by forming a complex. In this (c) HgCl (d) Hg2Cl2
complex of silver, the coordination number of silver is : 18. Philosopher’s wool when heated with BaO at 1100ºC gives
(a) 2 (b) 4 the compound :
(c) 6 (d) 8 (a) BaCdO2 (b) Ba + ZnO2
9. Na2CO3 + Fe2O3  A + CO2 what is A in the reaction ? (c) BaO2 + Zn (d) BaZnO2
(a) NaFeO2 (b) Na3FeO3 19. Which of the following is the correct formula for a
(c) Fe3O4 (d) Na2FeO2 compound of scandium and oxygen ?
10. The formula of azurite is : (a) Sc2O (b) ScO
(a) CuCO3 . Cu(OH)2 (b) 2CuCO3 . Cu(OH)2 (c) Sc3O2 (d) Sc2O3
(c) CuCO3 .2Cu(OH)2 (d) CuSO4 .Cu(OH)2 20. Dilute and slightly alkaline KMnO4 is called
(a) Fenton’s reagent (b) Lucas reagent
(c) Baeyer’s reagent (d) Tollens reagent
d AND f BLOCK ELEMENTS 164
21. When acidified K2Cr2O7 solution is added to Sn+2 salt then 30. Ferrous sulphate on heating gives :
Sn+2 changes to (a) SO2 and SO3 (b) SO2 only
(a) Sn (b) Sn+3 (c) SO3 only (d) H2S only
(c) Sn+4 (d) Sn+ 31. Fe(OH)2 is precipitated from Fe(II) solutions as a white
22. Silver nitrate solution is kept in brown bottles in laboratory solid but turns dark green and then brown due to the
because : formation of :
(a) it reacts with ordinary white bottles (a) Fe(OH)2 and Fe(OH)3 (b) only Fe(OH)3
(b) brown bottles cut the passage of light through (c) Fe2O3 . (H2O)n (d) Fe2O3 . 2H2O
(c) brown bottles do not react with it 32. Which of the following mixture is known as Fenton’s
reagent ?
(d) ordinary bottles catalyse its decomposition
23. Sodium thiosulphate, Na2S2O3.5H2O is used in photography (a) FeSO4 + K4[Fe(CN)6] (b) FeSO4 + PdCl2
to : (c) FeSO4 + H2O2 (d) TiCl4 + (C6H5)3P
(a) Reduce the silver bromide to metallic silver 33. Oxide of metal cation which is not amphoteric?
(b) Convert the metallic silver to silver salt (a) Al3+ (b) Cr3+
(c) remove undercomposed AgBr as soluble silver (c) Cr2+ (d) Zn2+
thiosulphate complex 34. The false statement about iron (III) hydroxide is that :
(d) remove reduced silver
(a) it is a weaker base than Fe(OH)2
24. When AgNO3 comes in contact with skin, it leaves a black
(b) with concentrated KOH, it forms a complex K3[Fe(OH)6]
stain. This is because of :
(c) it gradually loses water and transforms into Fe2O3
(a) HNO3 prorduced by hydrolysis of AgNO3
(b) AgOH produced by hydrolysis of AgNO3 (d) it exhibits amphoteric properties with acid ones
predominating
(c) Its reduction of silver
35. A blood red colour is obtained when ferric chloride solution
(d) Its oxidation to silver oxide reacts with :
25. A white precipitate of AgCl dissolves in excess of : (a) KCN (b) KSCN
(I) NH3 (aq) (II) Na2S2O3 (c) K4[Fe(CN)6] (d) K3[Fe(CN)6]
(III) NaCN 36. Calomel is the name of :
(a) III only (b) I, II, III (a) HgCl2 (b) Hg2Cl2
(c) I, II (d) I only (c) HgCl2 + Hg (d) Hg2Cl2 + Hg
26. Boiling CuCl2 with Cu in conc. HCl gives : 37. HgCl2 is a covalent compound, sparingly soluble in water,
(a) CuCl (b) CuCl2 the solubility increases by the addition of chloride ions
(c) H[CuCl2] (d) Cu2Cl due to :
27. Verdigris is : (a) common ion effect
(a) Basic copper acetate (b) Basic lead acetate (b) formation of complex [HgCl4]2–
(c) Basic lead (d) None (c) weakening of Hg – Cl bonds
28. The oxidation state of copper changes when aqueous (d) strong ion – dipole forces
copper (II) ions react with : 38. Identify P in given reaction
(I) NaOH (aq) (II) Fe(s) 
KI  MnO 4 
OH
 IO3  P
(III) KI (aq)
(a) MnO2 (b) Mn+2
(a) I, II, III (b) II only
(c) II, III (d) I only (c) Mn+3 (d) None of these.
29. Copper is very slowly oxidised on the surface in moist air, 39. ZnO shows yellow colour on heating due to :
giving a green coating. The formula of this green coating (a) d-d transition
is : (b) C-T spectra
(a) Cu2O (b) CuCO3
(c) Higher polarisation caused by Zn2+ ion
(c) Cu(CH3COO)2.Cu(OH)2 (d) CuSO4
(d) F-centres
d AND f BLOCK ELEMENTS 165
40. Zinc (II) ion on reaction with NaOH first give a white (d) W =Ag2O X = N2 Y=AgNO3 Z= Na[Ag(S2O3)2]
precipitate which dissolves in excess of NaOH due to the
47. Which of the following ores is known as pyrolusite ?
formation of :
(a) ZnO (b) Zn(OH)2 (a) Fe2O3
(c) [Zn(OH)4]2– (d) [Zn(H2O)4]2+ (b) SnO2
41. Mercury on heating with aqua-regia gives : (c) MnO2
(a) Hg(NO3)2 (b) HgCl2 (d) PbS
(c) Hg(NO2)2 (d) Hg2Cl2
42. Gold dissolves in a aqua-regia forming : Objective Questions II
(a) Auric chloride (b) Aurous chloride [One or more than one correct option]
(c) Chloroauric acid (d) Aurous nitrate 48. Choose correct statement(s) regarding the following
reaction.
43. KMnO4 oxidizes thiosulphate to SO 24  as per reaction
Cr2 O 72  (aq)  3SO 32  (aq)  8H  

xMnO 4  3S2 O32   H 2 O  xMnO 2  6SO 42   2OH  2Cr 3  (aq)  3SO 24  (aq)  4H 2 O
Find the value of x in above reaction (a) Cr2 O 72  is oxidising agent
(a) 8 (b) 4
(b) SO 32  is reducing agent
(c) 2 (d) 1
44. Mercury is the only metal which is liquid at 0ºC. This is (c) The oxidation number per ‘S’ atom in 3SO 32  is
due to its : increase by two
(a) Very high ionisation energy and weak metallic bond
(d) The oxidation number per ‘Cr’ atom in Cr2 O 72  is
(b) Low ionisation potential decreased by three
(c) High atomic weight 49. An element of 3d-transition series shown two oxidation
(d) High vapour pressure states x and y, differ by two units then:
45. Give the correct order of initials T or F for following (a) compounds in oxidation state x are ionic if x > y
statements. Use T if statement is true and F if it is false.
(b) compounds in oxidation state x are ionic if x < y
(I) Sulphide ions reacts with Na2 [Fe(CN)5(NO)] to form a
(c) compounds in oxidation state y are covalent if x < y
purple coloured compound Na4 [Fe(CN)5 (NOS)]. In the
reaction, the oxidation state of iron changes . (d) compounds in oxidation state y are covalent if y < x
(II) Pt(IV) compounds are relatively more stable than 50. Which statements about mercury are correct?
Ni(IV) compounds (a) Hg is a liquid metal
(III)The welding of magnesium can be done in the (b) Hg forms two series of salts
atmosphere of Helium (c) Hg forms no amalgam with iron and platinum
(IV) LiAlH4 on hydrolysis will give H2 (d) Anhydrous Hg does not show variable valency
(a) FFTT (b) FTTT 51. Identify the correct statements :
(c) TFTF (d) TFTT (a) Iron belongs to first transition series of the periodic
46. 
AgNO 3   (W )  (X)  O 2 table
(b) The purest form of commerical iron is wrought iron
(X)  H 2 O 
 HNO2  HNO3 (c) Anhydrous ferrous sulphate is called as yellow vitriol
(d) Iron is the most abundant transition metal
(W)  HNO 3 
 Y  NO  H 2 O
52. The metal oxide which decomposes on heating is/are :
(Y)  Na 2 S 2 O 3 (excess) 
 (Z)  NaNO 3 (a) ZnO
Identify (W) to (Z). (b) Al2O3
(a) W = Ag X = N2O Y = AgNO3 Z = Na2[Ag(S2O3)2] (c) Ag2O
(d) HgO
(b) W = Ag2O X= NO Y=AgNO3 Z = Na3[Ag(S2O3)2]
(c) W = Ag X = NO2 Y=AgNO3 Z = Na3[Ag(S2O3)2]
d AND f BLOCK ELEMENTS 166
53. Pick out the correct statement(s) : 58. Assertion (A): KMnO4 has different equivalent weights in
(a) MnO2 dissolves in conc. HCl, but does not form Mn4+ acid, neutral or alkaline medium.
ions Reason (R): In different medium, change in oxidation number
(b) Decomposition of acidic KMnO4 is not catalysed by shown by manganese is altogether different.
sunlight (a) A (b) B
(c) MnO 24  is strongly oxidising and stable only in very (c) C (d) D
strong alkali. In dilute alkali, water or acidic solutions 59. Assertion (A): KMnO4 is purple in colour due to charge
it disproportionates transfer.
(d) KMnO4 does not act as oxidising agent in alkaline Reason (R): There is no electron present in d-orbitals of
medium manganese in MnO 4 .
54. To an acidified dichromate solution, a pinch of Na2O2 is
added and shaken. What is observed? (a) A (b) B
(a) Blue colour (c) C (d) D
(b) Orange colour changing to green 60. Assertion (A): AgNO3 reacts with KCN to form white ppt. of
AgCN. This white ppt. disappears when excess KCN is
(c) Evolution of oxygen
added.
(d) Bluish-green precipitate
Reason (R): AgCN decomposes to form silver-carbide and
evolve N2 gas.
Assertion Reason (a) A (b) B
(A) If both Assertion and Reason are correct and (c) C (d) D
Reason is the correct explanation of assertion. 61. Assertion (A): CrO3 reacts with HCl to form chromyl chloride
gas.
(B) If both Assertion and Reason are true but Reason (R): Chromyl chloride (CrO2Cl2) has tetrahedral shape.
Reason is not the correct explanation of (a) A (b) B
assertion. (c) C (d) D
(C) If Assertion is true but Reason is false. 62. Assertion (A): Zn gives H2 gas with dil. HCl and also with dil.
H2SO4.
(D) If Assertion is false but Reason is true.
Reason (R): NO3 ion is reduced in preference to hydronium
55. Assertion (A): Melting point of Mn is more than that of Fe.
ion.
Reason (R): Mn has higher number of unpaired e– than Fe in
atomic state. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D 63. Assertion (A): Zn(OH)2 is dissolved in both NH4OH and
NaOH solution.
56. Assertion (A): CuSO4.5H2O and FeSO4.7H2O are blue and
green colour compounds respectively. Reason (R): Both NaOH and NH4OH being basic can dissolve
amphoteric Zn(OH)2.
Reason (R): Both compounds have their specific colour due
to phenomenon of polarisation of anion. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D 64. Assertion (A): Cu is more stable than Cu+.
2+

57. Assertion (A): Cu+ is less stable than Cu2+ but Fe3+ is more Reason (R): Electrode potential is more important in
stable than Fe2+. determining stable oxidation state than electronic
configuration.
Reason (R): Half filled and completely filled subshells are
more stable. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D
d AND f BLOCK ELEMENTS 167
Paragraph Type Questions Use the following passage, to solve Q. 68 to Q. 70
Use the following passage, to solve Q. 65 to Q. 67 Passage
Passage A white substance ‘X’ when heated in a test tube, it pro-
A certain metal (X) is boiled in dilute HNO3 to give a salt duces a colourless, odourless gas, leaving a residue,
(Y) and an oxide of nitrogen (Z). An aqueous solution of yellow when hot and white when cold. The residue was
(Y) with brine solution gives a white precipitate (P). When dissolved in dil. HCl, made alkaline with NH4Cl and NH4OH
(Y) was treated with Na2S2O3 solution a white precipitate and H2S gas was passed through it. A white. ppt ‘Y’ was
(Q) was obtained which on standing turns to a black com- formed. It was dissolved in dil. HCl to give ‘Z’ which on
pound (R). treatment with K4[Fe(CN)6] gave bluish white precipitate.
65. Salt (Y) and the oxide of nitrogen (Z) is 68. ‘X’ is
(a) AgNO3 + NO2 (b) AgNO3 + NO (a) ZnO (b) ZnSO4 . 7H2O
(c) AgNO3 + N2 (d) AgNO3 + NH3 (c) Cu2Cl2 (d) ZnCO3
66. The precipitate (Q) formed is 69. ‘Y’ and ‘Z’ are respectively
(a) Ag2S (b) Ag2S2O3 (a) ZnO, ZnSO4 (b) ZnS, ZnCl2
(c) Ag2O (d) Ag2SO3 (c) ZnCl2 Zn(OH)2 (d) ZnO, ZnS
67. The compound (R) formed is 70. Bluish white precipitate formed is
(a) Ag2O (b) Ag (a) Zn2[Fe(CN)6] (b) K2[Zn(CN)4]
(c) Ag2S (d) Ag2SO3 (c) Zn3[Fe(CN)6]2 (d) None of these
d AND f BLOCK ELEMENTS 168

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS

Objective Questions I [Only one correct option]
8. Which of the following will not be oxidised by O3 ?
1. Amongst the following, identify the species with an atom
in +6 oxidation state (2000) (2005)
(a) KI (b) FeSO4
(a) MnO4 (b) Cr(CN)36
(c) KMnO4 (d) K2MnO4

(c) NiF62- (d) CrO2Cl2 9. Native silver metal forms a water soluble complex with a
dilute aqueous solution of NaCN in the presence of
2. In the process of extraction of gold.
(2008)
O2 (a) nitrogen (b) oxygen
Roasted gold ore + CN– + H2O  [X] + OH–
(c) carbon dioxide (d) argon
[X] + Zn 
 [Y] + Au
10. Among the following, the coloured compound is
Identify the complexes [X] and [Y] (2003) (2008)
(a) X = [Au(CN)2]–, Y = [Zn(CN)4]2– (a) CuCl (b) K3[Cu(CN)4]
(b) X = [Au(CN)4]3–, Y = [Zn(CN)6]4– (c) CuF2 (d) [Cu(CH3CN)4]BF4
(c) X = [Au(CN)2]–, Y = [Zn(CN)6]4– 11. The colour of light abosrbed by an aqueous solution of
(d) X = [Au(CN)4]–, Y = [Zn(CN)4]2– CuSO4 is (2011)
3. When MnO2 is fused with KOH, a coloured compound is (a) orange-red (b) blue-green
formed, the product and its colour is (2003)
(c) yellow (d) violet
(a) K2MnO4, purple green (b) KMnO4, purple
12. Which of the following combination will produce H2 gas?
(c) Mn2O3, brown (d) Mn3O4, black (2018)
4. (NH4)2Cr2O7 on heating gives a gas which is also given by (a) Fe metal and conc. HNO3
(2004)
(b) Cu metal and conc. HNO3
(a) heating NH4NO2 (b) heating NH4NO3
(c) Au metal and NaCN (aq) in the presence of air
(c) Mg3N2 + H2O (d) Na(comp.) + H2O2
(d) Zn metal and NaOH (aq)
5. The pair of compounds having metals in their highest
oxidation state is (2004)
Objective Questions II
(a) MnO2, FeCl3 (b) [MnO4]–, CrO2Cl2
[One or more than one correct option]
(c) [Fe(CN)6]3–, [Co(CN)3] (d) [NiCl4]2–, [CoCl4]–
13. The correct statement(s) about Cr2+ and Mn3+ is (are)
6. When I– is oxidised by MnO4– in alkaline medium, I– [Atomic numbers of Cr = 24 and Mn = 25] (2015)
converts into (2004) (a) Cr2+ is a reducing agent

(a) IO3– (b) I2 (b) Mn3+ is an oxidizing agent

(c) Both Cr2+ and Mn3+ exhibit d4 electronic configuration
(c) IO –
4
(d) IO– (d) When Cr2+ is used as a reducing agent, the chromium
7. Which of the following pair is expected to exhibit same ion attains d5 electronic configuration
colour in solution ? (2005)
(a) VOCl2 ; FeCl2 (b) CuCl2 ; VOCl2
(c) MnCl2 ; FeCl2 (d) FeCl2 ; CuCl2
d AND f BLOCK ELEMENTS
14. Fe3+ is reduced to Fe2+ by using
(a) H2O2 in presence of NaOH
(b) Na2O2 in water
(c) H2O2 in presence of H2SO4
(d) Na2O2 in presence of H2SO4
15. Fusion of MnO2, with KOH in presence of O2 produces a
salt W. Alkaline solution of W upon electrolytic
oxidation yields another salt X. The manganese
containing ions present in W and X, respectively are Y
and Z. Correct statement(s) is (are)
(2019)
(a) In both Y and Z,  -bonding occurs between p
orbitals of oxygen and d-orbitals of manganese
(b) Both Y and Z are coloured and have tetrahedral
shape
(c) In aqueous acidic solution, Y undergoes
disproportionation reaction to give Z and MnO2
(d) Y is diamagnetic in nature while Z is paramagnetic
16. Consider the following reaction (unbalanced)
Zn + hot conc. H2SO4 G + R + X
Zn + conc. NaOH  T + Q
G + H2S + NH4OH  Z (a precipitate) + X + Y
Choose the correct option(s)
(a) Bond order of Q is 1 in its ground state
(b) The oxidation state of Zn in T is +1.
(c) R is a V-shaped molecule
(d) Z is dirty white in colour
17. A mixture of two salts is used to prepare a solution S, which
gives the following results: (2021)
S Dilute HCl
 White ppt only
 aq solution
of thesalt  Room temperature
169
(2015) Numerical Value Type Questions
18. Consider the following list of reagents:
Acidified K2Cr2O7, alkaline KMnO4, CuSO4, H2O2, Cl2, O3,
FeCl3, HNO3 and Na2S2O3. The total number of reagents
that can oxidise aqueous iodide to iodine is
(2014)
19. In neutral or faintly alkaline solution, 8 moles of
permanganate anion quantitatively oxidize thiosulphate
anions to produce X moles of a sulphur containing product.
The magnitude of X is (2016)
20. Among the species given below, the total number of
diamagnetic species is ___.
H atom, NO2 monomer, O2 (superoxide), dimeric sulphur
in vapour phase, Mn3O4, (NH4)2[FeCl4], (NH4)2[NiCl4],
K2MnO4, K2CrO4 (2018)
21. To measure the quantity of MnCl2 dissolved in an aqueous
solution, it was completely converted to KMnO4 using the
reaction.
MnCl2 + K2S2O8 + H2O  KMnO4 + H2SO4 + HCl
(equation not balanced).
Few drops of concentrated HCl were added to this solution
and gently warmed. Further, oxalic acid (225 mg) was added
(2019) in portions till the colour of the permanganate ion
disappeared. The quantity of MnCl2 (in mg) present in the
initial solution is ____.
(Atomic weights in g mol–1: Mn = 55, Cl = 35.5)
(2018)
22. An acidified solution of potassium chromate was layered
with an equal volume of amyl alcohol. When it was shaken
after the addition of 1 mL of 3% H2O2, a blue alcohol layer
was obtained. The blue color is due to the formation of
a chromium (VI) compound ‘X’. What is the number of
oxygen atoms bonded to chromium through only single

S Dilute NaOH
 White ppt only bonds in a molecule of X? (2020)
 aq solution
of thesalt  Room temperature

Subjective Type Questions

(a) Pb(NO3)2 and Zn(NO3)2 23.
(b) Pb(NO3)2 and Bi(NO3)3
(B) Moist air
 MCl 4
Zn
 A
(c) AgNO3 and Bi(NO3)3 white fumes  M=Transition   purple colour 
with pungent smell  element colourless 
 
(d) Pb(NO3)2 and Hg(NO3)2
Identify the metal M and hence MCl4. Explain the difference
in colours of MCl4 and A. (2005)
d AND f BLOCK ELEMENTS 170
Use the following passage, to solve Q. 24 to Q. 25 25. Among the following, the brown ring is due to the forma-
tion of (2021)
Passage 2 3
The reaction of K3[Fe(CN)6] with freshly prepared FeSO4 (a)  Fe  NO 2  SO 4  2  (b)  Fe  NO 2  H 2 O 4 
solution produces a dark blue precipitate called Turnbull's 2
blue. Reaction of K4 [Fe(CN)6] with the FeSO4 solution in (c)  Fe  NO 4  SO 4  2  (d)  Fe  NO  H 2 O 5 
complete absence of air produces a white precipitate X,
which turns blue in air. Mixing the FeSO4 solution with
NaNO3, followed by a slow addition of concentrated H2SO4
through the side of the test tube produces a brown ring.

24. Precipitate X is (2021)

(a) Fe 4  Fe  CN 6  3 (b) Fe  Fe  CN 6 

(c) K 2 Fe  Fe  CN 6  (d) KFe  Fe  CN 6 

d AND f BLOCK ELEMENTS 171

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CHEMISTRY IN EVERYDAY LIFE
 Chapter 14 173

CHEMISTRY IN EVERYDAY LIFE

1. INTRODUCTION 2.2 Drug-enzyme interaction

When the substrate comes closer to the enzyme then it binds to
Chemical substances helping to a human body or an animal either
the enzyme and then with the help of reagent, chemical reaction
for treatment of diseases or to reduce suffering from pain are
happen and then the product is formed.Now, drugs inhibit this
called medicine or drug.
activity of the enzyme. Drugs itself bind to the active site of the
The treatment of disease by chemical compound which destroy enzyme and lock the space for the substrate to bind and thus the
the micro organism without attacking the tissue of the human chemical reaction does not proceed. This inhibition by drugs is
body is known as chemotherapy, and the compounds used are done in two different ways:
called chemotherapeutic agent.
(a) When the drug binds to the enzyme at the active site and
1.1 Classification of Drugs thus no space available for the substrate and thus no chemical
(a) On the basis of pharmalogical effect : This classification is reaction proceeds.
useful for doctors because it provides them the whole range (b) When the drug binds to the enzyme at some different site
of drugs available for the treatment of a particular type of also known as allosteric site, but due to this binding, the
problem.e.g., Aangesics have pain killing effect, antiseptics shape of the enzyme changes and thus substrate is not able
kill or arrest the growth of microorganisms. to bind with the enzyme and thus no chemical reaction
(b) On the basis of drug action : It is based on the action of a proceeds.
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.

Competitive Inhibition
(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.
2.1 Enzymes as Drug Targets
Enzymes hold the substrate molecule in a suitable position, so Non-competitive Inhibition
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.

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Chemistry in Everyday Life
CHEMISTRY IN EVERYDAY LIFE 174
3. THERAPEACTION OF DIFFERENT CLASSES (a) Sedative : Reduce nervous tension and promote relaxation.
OF DRUG e.g. Reserpine, barbituric acid and its derivatives as luminal &
seconal.
3.1 Antacids (b) Mood elevators or Antidepressants : A drug used for treatment
of highly depressed patient, who has lost his confidence.e.g.,
Antacid is a base which neutralizes excess of acid secreted in the
Benzedrine (amphetamine).
stomach during digestion of food.Histamine stimulate the
secretion of pepsin and HCl in stomach.e.g. Histamine and Some tranquilizers namely, chlordiazepoxide and meprobamate,
ranitidine. 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). Chlordiazepoxide
They interfere with the natural action of histamine by competing
with histamine for binding sites of receptor where histamine exerts
its effect.

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
Terfenadine (Seldane) (b) Non-narcotics (non-addictive)

3.3 Neurologically Active Drugs (a) Narcotics : These are alkaloids and mostly opium products,
causes sleep and unconciousness when taken in higher
3.3.1 Tranquilizers doses. These analgesics are chiefly used for the relief of
postoperative pain, cardiac pain and pains of terminal cancer,
The chemical substances which act on the central nervous system
and in child birth.e.g., Morphine, codeine, heroine.
and has a calming effect. Since these are used for mental diseases
so are known as psycotherapeutic drugs.
They are of two types :
(a) Sedative or hypnotics (b) Mood elevators

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Chemistry in Everyday Life
CHEMISTRY IN EVERYDAY LIFE
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 :
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
175
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.
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.
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Chlorine in the concentration of 0.2 to 0.4 ppm in aqueous solution
and sulphur dioxide in very low concentrations, are disinfectants.
3.5 Antipyretics
To bring down the body temp. in high fever are called antipyretics.
Aspirin Paracetamol
3.6 Anaesthetics
These are chemical substances helping for producing general or
local insensibility to pain and other sensation. These are of two
types: (a) General (b) Local
(a) General anaesthetics: Produce unconciousness and are given
at the time of major surgical operations.e.g. Gaseous form –
Nitrous oxide, ethylene, cyclopropane etc.
Liquid form – Chloroform, divinyl ether and sodium pentothal etc.
(b) Local anaesthetics: Produce loss of sensation on a small
portion of the body. It is used for minor operations.e.g. Jelly
form – Oxylocain
Spray form – Ethyl chloride
Injection form – Procain
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.
Norethindrone
176
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
food additives are as follows:
4.1 Artificial Sweetening Agents
Sucrose and fructose are the most widely used natural sweetners.
Since they add to our calorie-intake and promote tooth decay,
therefore, many people use artificial sweeteners. For example,
saccharin, aspartame, alitame, sucralose, cyclamate and L-glucose.
(i) Saccharin : It is used in form of its sodium or calcium salt
which is highly soluble in water. It is not biodegradable and
hence does not have calorific value of food. It is primarily
used as a sweetening agent by diabetic patients and by those
who need to control intake of calories.
(ii) Aspartame : It is the methyl ester of the dipeptide derived
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.
(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
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Artificial Sweetning Agent
Artificial Sweetener Structural formula
Aspartame
Saccharin
Sucralose
Altrame
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
177
Sweetness value comparison
to cane sugar
100
550
600
2000
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).
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.
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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.
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.
178
(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.
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. H 2 SO 4 followed by
neutralization with NaOH. For example,
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These sodium alkyl sulphates are 100% biodegradable.
(ii) Alkylbenzene sulphonates (ABS) : These are obtained by
F.C. alkylation of benzene with long chain alkyl halide or an
alkene or an alcohol followed by sulphonation and
neutralization with NaOH. The most widely used domestic
detergent is the sodium dodecylbenzenesulphonate (SDS).
Another important example is sodium
2-dodecylbenzenesulphonate :
These detergents are also effective in slightly acidic solutions since
they form the corresponding alkyl hydrogen sulphates which are
soluble materials whereas soaps react with acidic solutions to
form insoluble fatty acids.
(b) Cationic detergents : These are quaternary ammonium salts
(chlorides, bromides, acetates etc.) containing one or more long
chain alkyl groups. Being more expensive than the anionic
detergents, they find limited use. Such detergents, however,
possess germicidal properties and hence are used quite
extensively as germicides, e.g., cetyltrimethylammonium
chloride .
(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.
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5.3 Detergent Pollution
Detergents having branched hydrocarbon chains cause pollution
in rivers and other waterways. The reason being that side chains
stop bacteria from attacking and breaking the chains. This results
in slow degradation of detergent molecule leading to their
accummulation.
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.
(iii) The combustion should proceed at a fast rate.
6.1 Classification of Propellant
Depending upon physical state of fuel and oxidiser, the propellants
are of three types :
(a) Solid propellants
(b) Liquid propellants
(c) Hybrid propellants
6.1.1 Solid Propellants
In which fuel and oxidiser both are solid. These are of two types:
(i) Composite propellant : It contains polymeric binder as fuel
and ammonium perchlorate as oxidiser.
Fuel - Polyurethane or polybutadiene,
Oxidiser - Ammonium perchlorate
(ii) Double base propellant : It consists of nitro cellulose and
nitroglycerine
Disadvantage of solid propellant :
Once they ignite, they burn with a predetermined rate.
These do not have the start and stop capability.
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6.1.2 Liquid Propellants
These are of two types :
(i) Monoliquid propellant : When a single liquid acts as fuel and
oxidiser. eg. Nitromethane, Methyl nitrate, H2O2 etc.
(ii) Biliquid propellant : It comprises a liquid fuel and a liquid
oxidiser e.g. Fuel – Kerosene, alcohol, hydrazine, monomethyl
hydrazine (MMH) or liquid hydrogen.
Oxidiser : Liquid oxygen, dinitrogen tetraoxide (N2O4) or
nitrous acid.
Advantages :
(i) These provide higher thrust than solid propellants.
(ii) The thrust can be controlled by switching on and off the flow
of liquid propellant.
6.1.3 Hybrid Propellants
These consist of a solid fuel and a liquid oxidizer. e.g.
Fuel – Acrylic rubber
Oxidiser – Liquid N2O4
6.2 Specific Impulse (Is)
The superiority and performance of a propellant is expressed in
terms of specific impulse (Is).
T congo red, methyl orange and methyl red. These dyes do
Is 
M not have any affinity for cotton but are used to dye wool,
Where T = Flame temperature, M = average molecular mass.
Thus the performance of rocket propellant will be better if flame
temperature is higher and the average mass of the product gas is
lower.
7. DYES
Dyes are coloured substances which can be applied in solution
or dispersion to a substrate such as textile fibres (cotton, wool,
silk, polyester, nylon), paper, leather, hair, fur, plastic material etc.
giving it a coloured appearance.
If a compound absorbs light in the visible region, its colour will be
that of the reflected light, i.e. complementary to that absorbed.
For example, if a dye absorbs blue colour, it will appear yellow
which is the complementary colour of blue.
Auxochromes are groups which themselves do not absorb light
(i.e. are not chromophores) but deepen the colour when introduced
into the coloured compounds, i.e., OH, NH2, Cl, CO2H etc.
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7.1 Classification of Dyes
A large number of dyes are used for various purposes. These are
classified on the basis of their
(i) Sources, (ii) constitution, (iii) and Application
7.1.1 Source
(i) Natural dyes are obtained from plants. For example, alizarin,
indigo etc.
(ii) Synthetic dyes are prepared in the laboratory. For example,
martius yellow, malachite green, orange-I, orange-II, congo
red, aniline yellow etc.
7.1.2 Constitution
(i) Nitro dyes : martius yellow
(ii) Azo dyes : aniline yellow, methyl orange, orange-I, congo red
etc.
(iii) Triphenylmethane dyes : malachite green, magneta
(iv) Indigoid dyes : Indigo, indigosol
(v) Anthraquinone dyes : alizarin
(vi) Phthalein dyes : phenolphthalein
7.1.3 Application
(i) Acid Dyes are sodium salts of azo dyes containing sulphonic
acid or carboxylic acid groups, e.g. orange-I, orange-II,
silk, polyurethane fibres. The affinity of acid dyes for nylon
is higher than that for other types because polycaprolactam
fibres contain a higher proportion of free amino groups.
(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.
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(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
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
(viii) Mordant Dyes are applied to the fabric after treating them
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
181
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.
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.
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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
183
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.
Example - 10
Important function of the drug with the following structure
(a) Reducing fever (b) Relieving pain
(c) Anti blood clotting action (d) All of these
CHEMISTRY IN EVERYDAY LIFE 184
Ans. (d) Ans. (d)
Sol.
Sol. The correct structure of Bithional is

This is Aspirin Example - 15

• Reduce fever Which is mismatched regarding the structure?
• Reduce pain
• Anti blood cloting agent (a)
Example - 11
Non-narcotics includes all, except
(a) Ibuprofen (b) Paracetamol
(c) Opiate (d) Diclofenac sodium (b)
Ans. (c)
Sol. Opiate is Narcotic drug.
Example - 12
Antibiotics which do not have bactericidal action among
the following is (c)
(a) Penicillin (b) Tetracycline
(c) Ofloxacin (d) Streptomycin (d) Both (b) & (c)
Ans. (b) Ans. (b)
Sol. Antibiotics which do not have bactericidal action among Sol. Choice (2) is incorrect because the correct structure of
the following is Tetracycline. Aspirin is
Example - 13
Antiseptic which is a mixture of chloroxylenol and -
terpineol is.
(a) Savlon (b) Dettol
(c) Bithinal (d) Salol
Example - 16
Ans. (b)
How do antiseptics differ from disinfectants? Give one
Sol. Dettol  Chloroxylenol + Terpineol
example of each.
Example - 14
Sol. Antiseptics and disinfectants are effective against
The correct structure of Bithional is
microorganisms. They differ in the function that antiseptics
are applied to the living tissues such as wounds, cuts,
ulcers, and diseased skin surfaces, while disinfectants are
(a) (b) useful upon inanimate objects such as cleaning floors,
drainage system, instruments, etc. Disinfectants are harmful
to the living tissues.
Iodine is an example of a strong antiseptic. Tincture of
iodine (2 - 3 percent of solution of iodine in alcohol - water
mixture) is applied to wounds. one percent solution of
(c) (d)
phenol is used as a disinfectant.
CHEMISTRY IN EVERYDAY LIFE 185
Example - 17 Ans. (c)
Name a substance which can be used as an antiseptic as Sol. Birth control pills essentially contains
(1) Synthetic estrogen
well as disinfectant.
(2) Synthetic progesterone
Sol. Phenol can be used as an antiseptic as well as a disinfectant.
Example - 22
0.2 percent solution of phenol is used as an antiseptic,
Which is mismatched, regarding the examples?
while one percent of its solution is used as a disinfectant.
(a) Broad spectrum Antibiotic – Chloramphenicol
Example-18
(b) Narrow spectrum antibiotic – Ampicillin
0.2% of solution of phenol and 0.2-0.4 ppm chlorine in
(c) Antiseptic – Furacine
aqueous solution respectively behave as
(d) Antifertility – Novestrol
(a) Antiseptic, Disinfectant
(b) Disinfectant, Antiseptic Ans. (b)
(c) Disinfectant, Disinfectant Sol. Ampicillin is categorised in Broad-spectrum antibiotics.
(d) Antiseptic, Antiseptic Example - 23
Chemicals are added to food for
Ans. (a)
(a) Preservation
Sol. 0.2% solution of phenol  Antiseptic
(b) Enhancing the appeal
0.2-0.4 ppm chlorine in aq. solution  Disinfectant
(c) Adding nutritive value
Example - 19
(d) All of these
Salvarsan is an antimicrobial agent which is used for curing
Ans. (d)
(a) Malaria (b) Allergy
Sol. Chemicals are added to food for
(c) Syphilis (d) Depression
(1) Preservation (2) Enhancing the appeal (3) Adding
Ans. (c) nutritive value
Sol. Salvarsan is an antimicrobial agent used to cure syphilis. Example - 24
The first popular artificial sweetening agent is
(a) Saccharin (b) Aspartame
(c) Alitame (d) Both (b) & (c)
Ans. (a)
Example - 20 Sol. The first popular artificial agent is Saccharin
Drugs which contain mixture of norethindrone and
ethynylestradiol are
(a) Antibiotics (b) Antifertility
(c) Antiseptic (d) Antacid
Ans. (b)
Sol. Example - 25
What are food preservatives?
Sol. Food preservatives are chemicals that are used to prevent
food from spoilage due to microbial growth. Table salt,
Example - 21
sugar, vegetable oil, sodium benzoate(C6H5COONa) and
Birth control pills essentially contains
salts of propanoic acid are some examples of food
(a) Synthetic estrogen preservatives.
(b) Synthetic progesterone
(c) Both (a) & (b)
(d) Neither (a) nor (b)
CHEMISTRY IN EVERYDAY LIFE 186

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Therapeutic Action of Different Classes of Drugs
1. How do enzyme catalyse the reaction? 7. Which of the following can possibly be used as analgesic
(a) By holding the substrate molecule for chemical reaction without causing addiction and modification?
(b) By providing functional groups which will attack the (a) morphine
substrate to carry out chemical reaction (b) N-acetyl-para-aminophenol
(c) Both (a) & (b) (c) diazepam
(d) Neither (a) nor (b) (d) tetrahydrocational
2. Find the incorrect statement. 8. Antiseptic chloroxylenol is
(a) Drugs which produce sleep and unconsciousness are (a) 4-chloro-3, 5-dimethylphenol
called narcotics
(b) 3-chloro-4, 5-dimethylphenol
(b) 4-Acetamidophenol is antipyretic
(c) 4-chloro-2, 5-dimethylphenol
(c) All tranquilizers work by same mechanism
(d) 5-chloro-3, 4-dimethylphenol
(d) The substance which kills micro-organisms called
antimicrobial 9. Which of the following drugs is an analgesic?
3. Further growth of cancerous cells in the body is arrested (a) Sulphaguanidine (b) Paludrin
by (c) Analgin (d) Iodex
(a) Physiotherapy (b) Chemotherapy 10. Compounds used to produce unconsciousness and
(c) Electrotherapy (d) Psychotherapy muscular relaxation, sufficient to carry out surgical
4. Which of the following is not used as an antidepressant? operations are called

(a) Iproniazid (b) Phenelzine (a) Sedatives (b) Tranquilizers

(c) Salvarsan (d) Nardil (c) Anesthetics (d) Antibiotics
5. Assertion: Equanil is a tranquilizer. 11. When a mixture of salicylic acid, acetic anhydride and acetic
Reason: Equanil is used to cure depression and acid is refluxed, the product obtained is
hypertension. (a) Aspirin (b) Acetophenone
(a) If both assertion and reason are true and the reason is (c) p-Acetamidophenol (d) Chloroxylenol
the correct explanation of the assertion. 12. Which of the following is not a Narcotics?
(b) If both assertion and reason are true but reason is not (a) Opium (b) Heroin
the correct explanation of the assertion.
(c) Pethidine (d) Bithional
(c) If assertion is true but reason is false.
13. Ampicillin is also called
(d) If the assertion and reason both are false.
(a) Penicillin G (b) Penicillin V
6. Assertion: Sedatives are given to patients who are mentally
agitated and violent. (c) Penicillin K (d) None of these
Reason: Sedatives are used to suppress the activities of 14. Phenylbutazone is another name for
central nervous system. (a) Brufen (b) Phenacetin
(a) If both assertion and reason are true and the reason is (c) Butazolidine (d) None of these
the correct explanation of the assertion.
15. Which of the following is used as a ‘morning after pill’?
(b) If both assertion and reason are true but reason is not
(a) Norethindrone (b) Ethynylestradiol
the correct explanation of the assertion.
(c) Promethazine (d) Bithional
(c) If assertion is true but reason is false.
(d) If the assertion and reason both are false.
CHEMISTRY IN EVERYDAY LIFE 187

16. One of the most widely used drug in medicine iodex is 25. The first antibiotic was ______ and was discovered by __.
(a) Methyl salicylate (b) Ethyl salicylate (a) Ofloxacin – Ehrlich
(c) Acetylsalicylic acid (d) o-Hydroxybenzoic acid (b) Streptomycin – Alexander Fleming
17. Which of the following is a sedative? (c) Streptomycin – Ehrlich
(a) Barbiturates (b) Bithional (d) Penicillin – Alexander Fleming
(c) Penicillin (d) Benzyl penicillin. 26. Which of the following drugs combination is not correct?
18. Which of the following is a hypnotic drug? (a) Bithional – Tranquilizer
(a) Catechol (b) Luminal (b) Chloramphenicol – Broad spectrum antibiotics
(d) Chemisol (d) Salol (c) Equanil – Sedative
19. Streptomycin is an example of (d) Phenacetin – Antipyretic
(a) Antibiotic (b) Analgesic 27. The following compound is used as:
(c) Antipyretic (d) Anaesthetic
20. Which of the following drugs is a tranquilizer and sedative?
(a) Sulphadiazine (b) Papaverine
(c) Equanil (d) Mescaline
21. Which one of the following is employed as a Tranquilizer (a) An anti-inflammatory compound
drug?
(b) Analgesic
(a) Promethazine (b) Valium
(c) Hypnotic
(c) Naproxen (d) Mifepristone
(d) Antiseptic
28. Match List I with List II and select the correct answer using
the codes given below the list.
List I List II
22.
I. Iodoform A. Anaesthetic
II. Methyl salicylate B. Antiseptic
The compound is used as III. Diethyl ether C. Insecticide
(a) An anti-inflammatory compound IV. Hexachlorocyclohexane D. Detergent
(b) Analgesic E. Pain balm
(c) Hypnotic Codes :
(d) Antiseptic (a) I-B, II-E, III-C, IV-D (b) I-D, II-B, III-A, IV-C
23. Which one of the following statements is not true? (c) I-B, II-E, III-A, IV-C (d) I-C, II-A, III-D, IV-B
(a) Ampicillin is a natural antibiotic 29. Which of the following is used as anesthesia?
(b) Aspirin is both analgesic and antipyretic (a) CH4 (b) CO2
(c) Sulphadiazine is a synthetic antibacterial drug (c) N2O (d) N2
(d) Some disinfectants can be used as antiseptics 30. A drug that is antipyretic as well as analgesic is
24. Chloramine-T is a (a) Chloropromazine hydrochloride
(a) Disinfectant (b) Antiseptic (b) para-Acetamidophenol
(c) Analgesic (d) Antipyretic (c) Chloroquinol
(d) Penicillin
CHEMISTRY IN EVERYDAY LIFE 188
31. Bacteriostatic drugs work by 42. A medicine which promotes the secretion of urine is called
(a) Arresting the growth of organisms (a) Uretic (b) Monouretic
(b) By increasing immunity and resistance of body to (c) Diuretic (d) Triuretic
infection
43. An example of a psychedelic agent is
(c) By killing the organism in the body
(a) DNA (b) LSD
(d) Both (a) & (c)
(c) DDT (d) TNT
32. Which of the following is not an antiseptic drug?
44. 2, 4-dichlorophenoxyacetic acid is used as a
(a) Iodoform (b) Dettol
(a) Fungicide (b) Insecticide
(c) Gammaxene (d) Gentian violet
(c) Herbicide (d) Moth repellent
33. Aspirin is obtained by the reaction of CH3COCl with
45. Various phenol derivatives, tincture of iodine (2– 3% I2 in
(a) Phenol (b) Benzoic acid water / alcohol) and some dyes like methylene blue are
(c) Salicylic acid (d) Benzaldehyde (a) Antiseptics (b) Disinfectants
34. The drug which is effective in curing malaria is (c) Analgesics (d) Antipyretics
(a) Quinine (b) Aspirin 46. The correct structure of the drug paracetamol is
(c) Analgin (d) Equanil
35. Which of the following is a hallucinogenic drug ?
(a) Methedrine (b) Calmpose (a) (b)
(c) LSD (d) Seconal
36. The formulation of dettol contains
(a) Chloroxylenol (b) Terpineol
(c) Alcohol (d) All of these (c) (d)
37. Which of the following is not antibiotic ?
(a) Tetracyclin (b) Neomycin 47. An ester used as medicine is
(c) Carbomycin (d) Cyclohexane (a) Ethyl acetate (b) Methyl acetate
38. Morphine is (c) Methyl salicylate (d) Ethyl benzoate
(a) An alkaloid (b) An enzyme 48.
(c) A carbohydrate (d) A protein
39. A large number of antibiotics have been isolated from
(a) Bacteria actinomycetes (b) Acids
(c) Alkanals (d) Bacteria rhizobium
40. An antibiotic contains nitro group attached to aromatic The compound is
nucleus. It is (a) Antipyretic (b) Antihistamine
(a) Penicillin (b) Streptomycin (c) Tranquilizers (d) Antiseptic
(c) Tetracycline (d) Chloramphenicol 49. Which of the following is used as an antibiotic ?
41. An antibiotic with a broad spectrum (a) Ciprofloxacin (b) Paracetamol

(a) Kills the antibodies (c) Ibuprofen (d) Tocopherol

(b) Acts on a specific antigen

(c) Acts on different antigens
(d) Acts on both the antigens and antibodies
CHEMISTRY IN EVERYDAY LIFE 189

50. The structure given below is known as 55. Assertion: Antiseptics are applied to living tissues.
Reason: Iodine is a powerful antiseptic.
(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.
(a) Penicilline F (b) Penicillin G
(c) If assertion is true but reason is false.
(c) Penicillin K (d) Ampicillin
(d) If the assertion and reason both are false.
51. Which of the following can possibly be used as analgesic
56. Which of the following is not a constituent of talcum
without causing addiction and any modification?
powder?
(a) Morphine
(a) Talc (b) Zinc sulphide
(b)N-acetylparaaminophenol
(c) Zinc stearate (d) Perfume
(c) Diazepam
57. A drug effective in the treatment of pneumonia, bronchitis,
(d) Tetrahydrocational etc., is:
52. Assertion: The drugs which act on the central nervous (a) Streptomycin (b) Chloramphenicol
system and help in reducing anxiety are called antibiotics.
(c) Penicillin (d) Sulphaguanidine
Reason: Penicillin is an antibiotic.
58. Major point of difference between antiseptic and
(a) If both assertion and reason are true and the reason is disinfectant is
the correct explanation of the assertion.
(a) Antiseptic prevents growth of micro-organism
(b) If both assertion and reason are true but reason is not
(b) Disinfectant kills micro-organism
the correct explanation of the assertion.
(c) Disinfectant are not safe to be applied to living tissues
(c) If assertion is true but reason is false.
(d) Both (a) & (b)
(d) If assertion is false but reason is true.
59. Which of the following is not correctly match?
53. Antiseptics and disinfectants either kill or prevent growth
of microorganisms. Identify which of the following Column-I Column-II
statements is not true ? (a) Iodoform – Antiseptic powder
(a) Chlorine and Iodine are used as strong disinfectants (b) Barbiturates – Hypnotic drug
(b) Dilute solutions of Boric acid and Hydrogen, Peroxide
(c) Hydrogen peroxide – Strong antiseptic
are strong antiseptics
(d) Boric acid – Antimicrobial
(c) Disinfectants harm the living tissues
(d) A 0.2% solution of phenol is an antiseptic while 1% Cleansing Agents
solution acts as a disinfectant
60. Glycerylester of
54. Assertion: Tetracyclin is a broad spectrum antibiotic.  Sodium  'A '
 NaOH 
Stearic acid stearate
Reason: Tetracyclin is effective against a number of types
of bacteria, large viruses and typhus fever. Product ‘A’ in the above reaction is
(a) If both assertion and reason are true and the reason is (a) Acetone (b) Glycol
the correct explanation of the assertion. (c) Methanol (d) Glycerol
(b) If both assertion and reason are true but reason is not 61. Soaps which are made by dissolving the soap in ethanol
the correct explanation of the assertion. and then evaporating the excess solvent
(c) If assertion is true but reason is false. (a) Transparent soap (b) Shaving soap
(d) If the assertion and reason both are false.
(c) Medicated soap (d) Toilet soap
CHEMISTRY IN EVERYDAY LIFE 190

62. The fillers that can be present in laundry soap is/are 70. Which is correctly matched regarding the use?
(a) Sodium rosinate (b) Borax (a) Anionic detergent – Hair conditioners
(c) Sodium silicate (d) All of these (b) Cationic detergent –Household work and in toothpaste
63. Which of the following represents a synthetic detergent ? (c) Non-ionic detergent–Liquid dishwashing

(a) C15 H 31COOH (d) All of these

71. Which of the following soap/detergents is least
(b) CH 3  CH 2 16 COONa biodegradable?
(a) C17H35-Coonan

(c) (b) CH3 – (CH2)11 – OSO2Na

(d) None of these

64. Which of the following represents soap ? (c)

(a) C17 H 35 COOK (b) C17 H 35 COOH

(c) C15 H 31COOH (d)  C17 H35 COO  2 Ca

(d)
65. Which of the following is an anionic detergent?
(a) CH3(CH2)15(CH3)3N+Br–
(b) CH3(CH2)16CH2OSO3–Na+
(c) CH3(CH2)16COO(CH2CH2O) nCH2CH2OH
(d) CH3(CH2)16COO–Na+
Chemicals in Food
66. Detergents are prepared by the action of H2SO4 followed
72. Which is correct about saccharin ?
by neutralization by starting with
(a) It is
(a) cholesterol (b) lauryl alcohol
(b) cyclohexanol (d) p- nitrophenol
67. 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 (b) It is 600 times sweeter than sugar
alkyl benzene sulphonic acid with alkali (c) It is used as sweetening agent
(c) Branched chain detergents are more easily (d) All of these
biodegradable
73. Among the following, the maximum high potency sugar is
(d) All of these
(a) Saccharin (b) Alitame
68. Glyceryl oleate can be represented by the formula
(c) Sucralose (d) Aspartame
(a) (C15H31COO)3C3H (b) (C17H33COO)3C3H5
74. Which of the following will not enhance nutritional value
(c) (C17H35COO)3C3H5 (d) Both (b) & (c) of food?
69. Which of the following enhances lathering property of (a) Minerals (b) Artificial sweeteners
soap?
(c) Vitamins (d) Amino acids
(a) Sodium carbonate (b) Sodium rosinate
(c) Sodium stearate (d) Trisodium phosphate
CHEMISTRY IN EVERYDAY LIFE 191
75. The compound with structure 78. Which is incorrect regarding antioxidants?
(a) They retard the action of oxygen on food
is used as (b) Helps in food preservation for long time
(c) Butylated hydroxy toluene and Butylated hydroxy
anisole are important antioxidant
(a) Food preservative (b) Artificial sweetener (d) They are flavoring agent
(c) Medicine (d) Edible colour 79. Which is correct about vanillin ?
76. Artificial sweetener used in soft drinks is (a) A flavoring agent having vanillaflavor
(a) lactose (b) aspartame (b) o-hydroxy-m-methoxy benzaldehyde
(c) glycerol (d) fructose. (c) A food additive
77. Nitrogen dioxide and sulphur dioxide have some properties (d) All of these
in common. Which property is shown by one of these 80. Substance used for the preservation of colored fruit juices
compounds, but not by the other? is
(a) Is used as a food-preservative (a) Benzene (b) Benzoic acid
(b) Forms ‘acid-rain’ (c) Phenol (d) Sodium metabisulphite
(c) Is a reducing agent
(d) Is soluble in water
CHEMISTRY IN EVERYDAY LIFE 192

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS

Objective Questions I [Only one correct option] (a) Tetrachloroethylene (b) Carbon dioxide
1. Under ambient conditions, which among the following
(c) Sulphur dioxide (d) Nitrogen dioxide
surfactants will form micelles in aqueous solution at lowest 7. Which of the following is an anionic detergent?
molar concentration ? (2015) (2016)
(a) Sodium stearate
(a) CH3(CH2)8COO Na

(b) Sodium lauryl sulphate
(b) CH3  CH2 11 N  CH3 3 Br  (c) Cetyltrimethyl ammonium bromide
(d) Glyceryl oleate
(c) CH3(CH2)13OSO3 Na

8. Which of the following is a bactericidal antibiotic?
(d) CH3  CH2 15 N  CH3 3 Br  (2016)
2. Which of the following compounds is not an antacid? (a) Erythromycin
(2015) (b) Tetracycline
(a) Aluminium hydroxide (c) Chloramphenicol
(b) Cimetidine (d) Ofloxacin
(c) Phenelzine 9. Which of the following is an anionic detergent?
(d) Ranitidine (2016)
(a) Glyceryl oleate
(b) Sodium stearate
3. (c) Sodium lauryl sulphate
(d) Cetyltrimethyl ammonium bromide

is used as: (2015) 10. An antibiotic contains nitro group attached to aromatic
(a) Insecticide nucleus in its structure. It is (2017)
(b) Antihistamine
(c) Analgesic (a) pencillin (b) streptomycin
(d) Antacid (c) tetracyclin (d) chloramphenicol
4. Which of the following compounds is not an antacid? 11. The reason for “drug induced poisoning” is:
(2015) (2017)
(a) Aluminium hydroxide (b) Cimetidine (a) Binding reversibly at the active site of the enzyme
(c) Phenelzine (d) Ranitidine (b) Bringing conformational change in the binding site of
enzyme
5. The artificial sweetener that has the highest sweetness
(c) Binding irreversibly to the active site of the enzyme
value in comparison to cane sugar is : (2016) (d) Binding at the allosteric sites of the Enzyme
(a) Aspartane (b) Saccharin 12. Which of the following is a bactericidal antibiotic ?
(c) Sucralose (d) Alitame (2018)
6. Which one of the following substances used in dry (a) Erythromycin (b) Tetracycline
cleaning is a better strategy to control environmental
(c) Chloramphenicol (d) Ofloxacin
pollution. (2016)
CHEMISTRY IN EVERYDAY LIFE 193

13. Noradrenaline is a/an ? (2019) 20. If a person is suffering from the deficiency of nor

(a) Neurotransmitter (b) Antidepresessant adrenaline, what kind of drug can be suggested ?

(c) Anstihistamine (d) Antacid (2020)

14. In which of the following processes, the bond order has (a) Anthistamine (b) Antidepressant

increased and paramagnetic character has changed to (c) Anti-inflammatory (d) Analgesic
diamagnetic? (2019) 21. The following molecule acts as an : (2020)
(a) NO to NO +
(b) N2 to N 2

(c) O2 to O2 (d) O2 to O22

15. The compound used in the treatment of lead poisoning

is: (2019)

(a) D-penicillamine (b) desferrioxime B

(c) Cis-platin (d) EDTA

(a) Anti-histamine (b) Antiseptic
16. If you spill a chemical toilet cleaning liquid on your hand,
(c) Anti-depressant (d) Anti-bacterial
your first aid would be : (2020)
22. The functions of antihistamine are
(a) Aqueous NH3 (b) Aqueous NaHCO3 (2021-03-16/Shift-1)
(a) Antiallergic and Analgesic
(c) Aqueous NaOH (d) Vinegar
(b) Antiallergic and antidepressant
17. Glycerol is separated in soap industries by : (2020) (c) Antacid and antiallergic
(a) Fractional distillation (d) Analgesic and antacid
23.
(b) Distillation under reduced pressure

(c) Differential extraction

(d) Steam distillation

18. The antifertility drug “Novestrol” can react with :

(2020)
(a) Br2/water; ZnCl2/HCl; FeCl3
(b) Br2/Water; ZnCl2\HCl; NaOCl Chlordiazepoxide

(c) Alcoholic HCN; NaOCl; ZnCl2/HCl The class of drug to which chlordiazepoxide with above
structure belongs is: (2021-08-26/Shift-2)
(d) ZnCl2/HCl;FeCl3; Alcoholic HCN (a) Antacid
19. The mechanism of action of “Terfenadine” (Seldane) is : (b) Analgesic
(2020) (c) Tranquilizer
(d) Antibiotic
(a) Helps in the secretion of histamine
(b) Activates the histamine receptor
(c) Inhibits the secretion of histamine
(d) Inhibits the action of histamine receptor
CHEMISTRY IN EVERYDAY LIFE 194
24. 26. Which one of the following chemical agents is not being
used for dry-cleaning of clothes?
(2021-07-25/Shift-1)
(a) H2O2 (b) CCl4
(c) Liquid CO2 (d) Cl2C = CCl2
Numerical Value Type Questions
27. The number of chiral carbons in chloramphenicol is:

(2020)

28. The number of chiral centres in Penicillin is (2020)

29. The mass percentage of nitrogen in histamine is ———

(2020)
30. The number of sp hybridised carbons present in
2

“Aspartame” is_____. (2020)

The correct statement about (A), (B), (C) and (D) is
(2021-08-27/Shift-1)
(a) (A), (B) and (C) are narcotic analgesics
(b) (B), (C) and (D) are tranquillizers
(c) (A) and (D) are tranquillizers
(d) (B) and (C) are tranquillizers
25. Which one of the following chemicals is responsible for
the production of HCl in the stomach leading to irritation
and pain? (2021-08-27/Shift-2)
(a)
Match the following
Each questions has two columns. Four options are
given representing matching elements from
Column-I and Column-II. Only one of these four
options corresponds to a correct matching for each
questions.
31. The correct match between items of List-I and List-II is:
(2018)

(b)
(a) (A)-(R), (B)-(S), (C)-(P), (D)-(Q)
(b) (A)-(S), (B)-(R), (C)-(P), (D)-(Q)
(c) (A)-(S), (B)-(R), (C)-(Q), (D)-(P)
(d) (A)-(R), (B)-(S), (C)-(Q), (D)-(P)
(c) 32. The correct match between Item I and Item II is: (2019)
Item -I Item -II
(A) Allosteric effect (P) Molecule binding to the
active site of enzyme
(B) Competitive inhibitor (Q) Molecule crucial for
(d) communication in body
(C) Receptor (R) Molecule binding to a
siteother than the active site
of enzyme
(D) Poison (S) Molecule binding to the
enzyme covalently
CHEMISTRY IN EVERYDAY LIFE 195

(a) (A)  (R); (B) (P); (C)  (Q); (D)  (S) (E) Analgesic

(b) (A)  (P); (B)  (R); (C)  (Q); (D) (S) (a) (i) – (D); (ii) – (A); (iii) – (B); (iv) – (C)

(c) (A)  (R); (B)  (P); (C)  (S); (D) (Q) (b) (i) – (D); (ii) – (C); (iii) – (A); (iv) – (E)

(d) (A)  (P); (B)  (R); (C)  (S); (D) (Q) (c) (i) – (A); (ii) – (C); (iii) – (B); (iv) – (E)

33. The correct match between Item-I and Item-II is: (2019) (d) (i) – (E); (ii) – (A); (iii) – (C); (iv) – (D)

Item - I Item-II 36. Match List-I and List-II. (2021-02-24/Shift-2)

(drug) (test)

A. Chloroxylenol P. Carbylamine test

B. Norethindrone Q. Sodium hydrogen

carbonate test

C. Sulphapyridine R. Ferric chloride test

D. Penicillin S. Bayer’s test (a) (a)-(i); (b)-(iii); (c)-(iv); (d)-(ii)

(a) A - R ; B - P ; C - S ; D - Q
(b) A - Q ; B - S ; C - P ; D - R
(c) A - R ; B - S ; C - P ; D - Q
(d) A - Q ; B - P ; C - S ; D - R
34. The correct match between item(I) and item (II) is: (2019)
(b) (a)-(iv); (b)-(iii); (c)-(ii); (d)-(i)
(c) (a)-(iv); (b)-(iii); (c)-(i); (d)-(ii)
(d) (a)-(ii); (b)-(iv); (c)-(iii); (d)-(i)
37. Match List-I with List-II.
(2021-03-17/Shift-2)

(a) (A)-(Q); (B)-(R); (C)-(S)

(b) (A)-(Q); (B)-(P); (C)-(R)

Choose the correct match:
(c) (A)-(R); (B)-(P); (C)-(S)
(a) (A)-(iii); (B)-(ii); (C)-(iv); (D)-(i)
(d) (A)-(R); (B)-(P); (C)-(R)
(b) (A)-(i); (B)-(ii); (C)-(iv); (D)-(iii)
35. Match the following drugs with their therapeutic actions:
(c) (A)-(ii); (B)-(i); (C)-(iv); (D)-(iii)
(2020)
(d) (A)-(iv); (B)-(iii); (C)-(ii); (D)-(i)
(i) Ranitidine (A) Antidepressant

(ii) Nardil (Phenelzine) (B) Antibiotic

(iii) Chloramphenicol (C) Antihistamine

(iv) Dimetane (Brompheniramine) (D) Antacie

CHEMISTRY IN EVERYDAY LIFE 196

38. Match List-I with List-II: (a) (A)-(ii); (B)-(iv); (C)-(i); (D)-(iii)
(b) (A)-(iii); (B)-(iv); (C)-(i); (D)-(ii)
(c) (A)-(ii); (B)-(iii); (C)-(iv); (D)-(i)
(d) (A)-(iv); (B)-(iii); (C)-(ii); (D)-(i)
40. Match List-I with List-II.

Choose the most appropriate match:

(2021-03-18/Shift-1) Choose the most appropriate answer from the options

(a) (A)-(iv); (B)-(iii); (C)-(i); (D)-(ii)
(b) (A)-(ii); (B)-(iv); (C)-(i); (D)-(iii)
(c) (A)-(ii); (B)-(iv); (C)-(iii); (D)-(i)
given below: (2021-07-27/Shift-1)
(a) (a)-(i); (b)-(iii); (c)-(iv); (d)-(ii)
(b) (a)-(iii); (b)-(iv); (c)-(ii); (d)-(i)
(c) (a)-(ii); (b)-(i); (c)-(iii); (d)-(iv)

(d) (A)-(iv); (B)-(i); (C)-(ii); (D)-(iii) (d) (a)-(iii); (b)-(i); (c)-(iv); (d)-(ii)

39. Match List-I with List-II

Choose the most appropriate match:

(2021-03-18/Shift-2)
CHEMISTRY IN EVERYDAY LIFE 197

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PRACTICAL ORGANIC CHEMISTRY
 Chapter 15 199

PRACTICAL ORGANIC CHEMISTRY

1. FUNCTIONAL GROUP DETECTION (iii) The chemical properties of compound containing same
functional group are similar.
(i) All organic compound are grouped into smaller number, each
For example methyl alcohol (CH3OH) & ethyl alcohol
group exhibits similar chemical properties.
(C2H5OH) have similar chemical properties. Therefore,
(ii) This means that all the compounds of the group must have
(iv) Chemical identification of a class of compounds involues
something common, this common feature is known as
the same type of tests.
functional group or reactive functional group.
1.3 Identification Tests
(iii) It is defined as the group which largely determine the
properties of a compound e.g., CH3OH, C2H5OH, C3H7OH are 1.3.1 Test for Unsaturation
all collectively called alcohol as the common reactive group (i) Unsaturation in an organic is indicated by or
in all is – OH.
–C  C – bonds in its structure.
1.1 Some common Functional groups
(ii) Because of the presence of this -bonds these compounds
Name of the Functional group Example
are bound to undergo addition reaction & therefore,
family or group
unsaturation in the organic compound (aliphatic) can be
Alkene CH2 = CH2 detect by exporting their this addition reaction.
(iii) Two methods used for detecting unsaturation in organic
Alkyne –CC– HC  CH
compounds are-
Alcohol –OH, (Alcoholic) CH3OH
(a) Bromine test :
Phenol Ar–OH (Phenolic) C6H5OH
(i) Discharge bromine solution to colourless without evolving
(–OH group attached HBr.
to aromatic ring)
Aldehyde –CHO, Aldehydic CH3CHO

Ketone CH3COCH3

Carboxylic –COOH, Carboxylic CH3COOH (b) Baeyer’s test or Permanganate test:

acid (i) When alkaline solution of potassium permanganate (2%) is
added, decolourization of pink colour of kMnO4 indicates
Amine – NH2, amino CH3NH2
unsaturation. A brown ppt. of MnO2 is also observed.
Nitro alkane – NO2 – Nitro CH 3 – NO2
CH 3 – CH  CH 2  2KMnO 4  4H 2 O 
Cyanide – CN – Cyano CH3 – CN
2KOH + MnO 2  3CH 3  CH  CH 2
1.2 Characteristic of Functional Group | |
Brown
(i) The physical and chemical properties of compound ppt OH OH
containing different functional groups are different.  
Colourless

(ii) There exists a homologous series of compound containing CH  CH  KMnO 4  H 2O 

each type of functional group.
 COOH 2  MnO2  KOH
For example, homologous series of alcohol like CH3OH, Oxalicacid Brown
CH3CH2OH, CH3CH2OH etc. ppt

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NOTE NOTE
• Apply both tests, since some compounds react slowly Test tube & alcohol should not contain even trace of moisture
with bromine. as water also reacts with sodium metal to evolve hydrogen
gas.
• Enols (–OH group containing compounds) are also found
to decolourise bromine as well as permanganate solution. (b) Cerric ammonium nitrate test: To about 1 ml. of the
but the type of reaction which takes place with bromine is substance in test tube add a few drops of cerric ammonium
somewhat different in this case than with unsaturated nitrate solution. Appearance of red colour indicate the
compounds. Enols are substituted by bromine and an presence of alcohols.
equivalent of HBr is evolved. So during the reaction white CH 3 OH   NH 4  2 Ce  NO3 6 
fumes will come, when a glass rod moistened with  Colourless  Cerric ammonium nitrate
 Yellow 
concentrated ammonia solution is held near the mouth of
the test tube.
 CH 3 OH 2 Ce  NO3 4  2NH 4 NO3
 Re d   Colourless 

HBr  NH 3 
 NH 4 Br (c) Ester test:
(i) When alcohol is treated with acetic acid in the presence of
1.3.2 Test for Terminal Alkyne conc. H2SO4, a characteristic fruity smell due to the formation
Acetylene and other terminal alkyne (1 – alkyne) are weakly acidic of ester indicates the presence of alcohol.
in character. They react with ammonical solution of cuprous
C2 H 5 OH  CH 3 COOH 
Conc. H 2SO 4
 CH3 COOC2 H 5  H 2 O
chloride and silver nitrate to form the corresponding copper and
silver alkynide. (ii) When a compound is treated with acetyl chloride and a rod
dipped in NH4OH is brought in contact with gas. If the white
H  C  C  H  2[Cu(NH 3 ) 2 ] OH – 
 fume are produced, indicate the presence of alcohol.
Cu C  C Cu  2H 2 O  4NH3
Dicopper ethynide ROH  CH 3 COCl  CH 3 COOR  HCl
 Red ppt  Alcohol Acetylchloride Ester

H  C  C  H  2[Ag(NH3 ) 2 ]+ OH – 
 HCl  NH 4 OH  NH 4 Cl  H 2 O
Tollens' reagent  white fumes 

Ag C  C Ag  2H 2 O  4NH 3 1.3.4 Test for Phenolic Group

Disilver acetylide
 white ppt  Compound containing one or more hydroxyl group attached to a
 Non terminal Alkynes will not give this test 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.
Phenol Cresol Catechol
(ii) For example, – OH group of sodium hydroxide and methanol
have entirely different properties. Sodium hydroxide is a base Phenolic group in organic compound can be detected by following
and turns red litmus blue but methanol does not give this test:
test. (a) Ferric chloride test:
(a) Sodium metal test or Xanthate test :- (i) Take about 5 ml of ferric chloride solution (neutral) in test
(i) Take compound in an absolutely, dry test tube. Add a small tube.
quantity of anhydrous calcium chloride to absorb moisture, (ii) Add into it 2-3 drops or pitch of compound.
decant it into another test tube.
(iii) Appearance of dark green, red or violet colour indicate the
(ii) Add a small piece of dry sodium metal to it. Effervescence presence of phenolic group in the compound.
with the evolution of hydrogen gas indicate the presence of
alcoholic group in the compounds.
1
R – OH  l   Na  s   R – ONa  H 2  g 
Sodium Alkoxide 2

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(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.
(d) Cerric Ammonium nitrate test : To Cerric Ammonium nitrate
add a pinch of given compound. Appearance of green or
201
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
• Nitrophenols and p-substituted phenol do not give this
test.
• This test is also shown by o-cresol.
1.3.. 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.
CH 3 COOH  C 2 H 5 OH 
Conc. H 2 SO 4
 CH 3 COOC 2 H 5  H 2 O
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
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.
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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
(b) Fehling’s test: In a test tube mix 1 ml each of Fehling A compound is heated with excess hydroiodic acid, forming
(CuSO4 in water with few drops of acetic acid) and Fehling B an alcohol and iodomethane.
(Rochelle salt and NaOH solution) solutions when a deep R–O–CH3 + HI  ROH + CH3I
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 The iodomethane is distilled off and led into an alcoholic
solution slowly fades away and a reddish-brown precipitate solution of silver nitrate, where it precipitates silver iodide.
of Cu2O is obtained indicating the presence of aldehydic The weight of this AgI precipitate which gives us the number
group. of methoxy groups present. In other words, the number of
moles of AgI will be equal to the number of
(–OCH3) groups.
(b) Feigl’s test: Take 2 ml of substance in a boiling tube and
cover the mouth of the tube with a filter paper moistened
with a mixture of cupric acetate and benzidine hydrochloride.
Heat the tube or 3-5 minutes when a deep blue colour appears
on filter paper due to formation of benzidine blue, confirming
the presence of ether group.

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(c) Iodine test: Ethers may be distinguished from hydrocarbons
by iodine test.
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
(a) 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
(b) To 3-4 drops or 0.2 gm of substance add 0.2 gm solid
hydroxylamine hydrochloride and 5m 10% NaOH solution.
Boil the solution gently for 2 minutes, cool and acidify the
solution with dilute HCl. Then add 2-3 drops of FeCl3 solution
when a violet or deep red brown colour due to formation of
ferric complex of hydroxamic acid, indicates the presence of
ester group.

RCOOR  NH 2 OH   RCONHOH  R OH
Ester Hydroxylamine Hydroxamine acid

3RCONHOH  FeCl3  Ferric complex of

hydroxamic acid
 Violet 
 or 
 Deep Re d Brown 
(c) Reaction with carbon di-sulphide: Primary amines react with
 
carbon disulfide to form dithioalkyl carbamic acids which
1.3.10 Test for Primary Amines decompose on heating with mercuric chloride to give alkyl
Whether aliphatic or aromatic, all primary amines respond to isothiocyanates.
carbylamine test. These have a characteristic smell like mustard oil. This
(a) Carbylamine test: To a small amount of substance add 2ml reaction is called the Hoffmann mustard oil reaction and is
alcoholic KOH solution, 3-4 drops of chloroform and heat used as a test for primary amines.
the mixture. Highly offensive odour of carbylamine or S
isocyanide is produced. ||
RNH 2  S  C  S  RNH – C – SH  
HgCl 2

RNH 2  CHCl3  3KOH 

 RNC  3KCl  3H 2 O RN  C  S  HgS  2HCl
alkyl isocyanide Alkyl isothiocynate
unpleasant smell
1.3.11 Test for Secondary Amines
Some derivatives of amines such as acetyl derivatives which
get hydrolysed under the conditions of the reaction, may Dissolve a small amount of substance in 2 ml HCl, dilute it with 3-
also respond to this test. 4 ml water and add 2 ml of 2% NaNO2 solution. If white or yellow
oily emulsion is obtained or a low melting solid separates the
(b) Dye test: In addition, aromatic primary amines respond to
compound is a secondary amine.
dye test. Dissolve a small amount of substance in 2 ml dil.
HCl. If the substance is insoluble add 3-4 ml water and cool Ar–NHR  HNO 2 
 Ar– NR  H 2 O
|
the mixture to 0°. To this then add precooled 2 ml 2% NaNO2 NO
solution in such small amounts that no brown fumes escape
from the solution. If light turbidity is obtained, ignore it.
Add 1 ml of this solution to a solution of -naphthol in alkali
when an orange-red coloured dye is obtained.

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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.
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.
RNO 2  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
204
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).
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
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methanol, alkyl group is CH3 whereas in ethanol it is C2H5. This 2.3 Distinction between Ethanol and Phenol
difference in alkyl group makes some of the properties of the two Ethanol, C2H5OH and phenol, C6H5OH, both contain – OH group.
different. But in ethanol this – OH group is attached an alkyl group whereas
(i) Boiling point of ethanol is 78C whereas that of methanol is in phenol, it is attached to a aromatic benzene ring. This different
60C. This is because of the high molecular weight of ethanol in the two makes the following properties different.
as compared to methanol. (i) Phenol is acidic in nature while ethanol is not.
(ii) Both get oxidised by mild oxidising agent, but the products (ii) Phenol gives characteristic colour with ferric chloride
formed in the two are different solution while ethanol does not give any.
CH 3 OH 
Oxidation
 HCHO (iii) Ethanol undergoes iodoform reaction i.e. it gives yellow
Methanol Formaldehyde
precipitates with I2/NaOH. Phenol does not exhibit this
CH3 CH 2 OH 
Oxidation
 CH 3CHO reaction.
Ethanol Acetaldehyde
(iv) Being aromatic, Phenol burns with a sooty flame. Ethanol
As acetaldehyde forms iodoform with I2 and alkali, therefore,
burns with a blue flame.
iodoform test can be employed to distinguish ethanol from
methanol. (v) Viscosity and boiling points of the two are also different.
Phenol is more viscous and has high boiling point as
CH 3 CH 2 OH 
I 2 / NaOH
 CHI3 compared to ethanol.
Iodoform
2.4 Distinction between Phenol and Benzoic Acid
CH3 OH 
 No Iodoform
I2 / NaOH

Phenol, C6H5OH and benzoic acid, C6H5COOH, both are aromatic

2.2 Distinction between Benzaldehyde and Acetone in nature and turn blue litmus red. Thus, both exhibit acidic
Benzaldehyde, C 6H 5CHO, both contain carbonyl group, character also. But with sodium bicarbonate only benzoic acid
> C = O. Both are liquids and colourless. The two can be gives effervescence. Phenol, being a very weak acid, does not
distinguished by exploting the reducing nature of aldehyde. That evolve carbon dioxide with sodium bicarbonate.
is, aldehydes are reducing in nature, whereas ketones are not. So C6 H5 COOH  NaHCO3 
 C6 H 5 COONa  H 2 O  CO 2
aldehydes respond to Schiff’s reagent, Fehling’s solution and Benzoic acid Sod. bicarbonate Carbon dioxide

Tollen’s reagent, whereas ketones do not. C6 H 5 OH  NaHCO 3 

 No reaction

C6 H 5 CHO   Ag  NH 3 2   3OH – 
 Phenol gives violet colour with neutral ferric chloride solution
Benzaldehyde Tollen ' s reagent whereas benzoic acid does not give any.
C6 H 5 OCOO –  2Ag 2.5 Distinction between Aniline and Phenol
Benzoate ion Metallic silver
Aniline C6H5NH2 and phenol, C6H5OH, both are aromatic. Both
CH 3 COCH 3  Tollen 's reagent 
 No Silver Mirror
have almost same boiling point. Except these two similarities, the
On the other hand, acetone undergoes iodoform test whereas two compounds differ widely.
benzaldehyde does not, because iodoform test given by aldehydes
  (i) Aniline is basic in nature whereas phenol is acidic.
  (ii) Aniline contains amino, –NH 2, group whereas phenol
CH3 – C – 
or ketones containing acetyl group  || . contains –OH group. Therefore, aniline respond to
 O 
 carbylamine test whereas phenol does not.
CH 3 COCH 3  3I 2  4NaOH 
 (iii) Phenol gives violet colour with ferric chloride solution
Acetone

CHI3  CH 3 COONa  3NaI  3H 2 O whereas aniline does not.

Iodoform
(iv) Aniline also gives dye test whereas phenol does not.
C 6 H 5 CHO  I 2  NaOH 
 No reaction. 2.6 Distinction between 1° , 2° and 3° Amine
Some physical properties, like odour and boiling point, of the (a) Hinsberg test: Benzenesulphonyl chloride (C6H5SO2Cl),
two are also different. Benzaldehyde possesses smell of bitter which is also known as Hinsberg’s reagent, reacts with
almonds whereas acetone has a pleasant smell. primary and secondary amines to form sulphonamides.

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water milky. The hydrogen present in the organic compound is

oxidised to water which turns anhydrous copper sulphate in the
bulb to blue.

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)

C  2CuO 
Heat
 CO 2  2Cu
from organic
compound

Tertiary amines do not react with benzenesulphonyl chloride.
3. QUALITATIVE ESTIMATION OF ELEMENTS
The qualitative analysis of an organic compound involves the
detection of all the elements present in it.
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
CO 2  Ca(OH) 2 
 CaCO3  H 2 O
lime water milky
(white)
2H  CuO 
Heat
 H 2 O  Cu
from organic
compound
This method is known as copper oxide test.
3.2 Detection of Other Element
Nitrogen, sulphur and halogens in an organic compound are
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.

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C  N  Na 
 NaCN (CH3 COO) 2 Pb  Na 2S  2 CH 3 COONa  PbS 
(Black)
S  2Na 
 Na 2S
(iii) Silver coin test: On adding a silver coin to the sodium ex-
X  Na 
 NaX (Where X  Cl, Br or I)
tract, the coin turns black.
When nitrogen and sulphur both are present in the organic com-
(iv) Oxidation test of sulphur : The unknown compound is
pound, then sodium thiocynate is formed.
heated with fusion mixture (Na2CO3+KNO3) in an ignition
Na  C  N  S 
 NaSCN tube when sulphur is oxidized to sulphate.
All the sodium salts being soluble in water, can be easily
Na 2 CO 3  S  3[O]  Na 2 SO 4   CO 2 
detected.
The fused mass is extracted with hot water, filtered and a few
3.2.1 Detection of Nitrogen drops of barium chloride solution are added. The appear-
If the organic compound contains nitrogen, the sodium fusion ance of a white precipitate which is insoluble in conc. HCl or
extract will contain sodium cyanide (NaCN). A small portion of HNO3, confirms the presence of sulphur.
the extract is boiled with ferrous sulphate solution and acidified
with dilute sulphuric acid. A blue precipitate of prussian blue Na 2 SO4  BaCl2  BaSO4   2NaCl
(ferric ferrocyanide) confirms the presence of nitrogen. (white)
2NaCN  FeSO 4  Fe(CN) 2  Na 2SO 4
BaSO 4  HNO3  Insoluble
Fe(CN) 2  4 NaCN  Na 4 [Fe(CN) 6 ]
excess (Conc.)
FeSO 4  Fe2 (SO 4 )3
Oxidised by
H 2SO4 3.2.3 Detection of Halogens
3Na 4 [Fe(CN)6 ]  2Fe2 (SO 4 )3 
 Fe 4 [Fe(CN)6 ]3  6Na 2SO 4 (i) Lassaigne test : The extract is boiled with conc. HNO3 to
Prussian blue expel nitrogen and sulphur, because NaCN and Na2S react
If the organic compound contains sulphur along with nitrogen with AgNO3 to give white and black precipitates, respec-
and the sodium, present is in insufficient amount then sodium tively
thiocyanate is formed, which gives blood NaCN  AgNO3  AgCN   NaNO3
red colouration by reaction with ferric ions.
NaS  2AgNO3  Ag 2S   2NaNO3
3 NaSCN  Fe 3 
[Fe(SCN)3 ]  3Na 
Boiling with conc. HNO3 evolves HCN and H2S as volatile
Blood red colour gases.
However, the absence of blood red colouration does not neces- 
NaCN  HNO3   NaNO3  HCN 
sarily mean that sulphur is absent in the organic compound be-

cause NaCNS combines with Na to give NaCN and Na2S. Na 2S  2HNO 3   2NaNO 3  H 2 S 

2Na  NaSCN   Na 2S  NaCN Now add AgNO3 solution
(a) Formation of a curdy precipitate which is soluble in
3.2.2 Detection of Sulphur
NH4OH solution shows the presence of chlorine.
The test of sulphur from sodium extract many be done in three
NaCl  AgNO3  AgCl   NaNO3
ways
(white)
(i) Sodium nitroprusside test : Only a little reagent is added to
sodium extract, (b) Formation of a light yellow ppt, which is sparingly
soluble in NH4OH shows the presence of iodine.
Na 2 [Fe(NO)(CN)5 ]  Na 2S  Na 4 [Fe(NOS)(CN)5 ]
NaI  AgNO3  AgI   NaNO3
Sodium nitroprusside Voilet complex
(Light
(ii) Lead acetate test : Add a few drops of lead acetate solution yellow)
to sodium extract, appearance of a black ppt. shows the
presence of sulphur. (c) Formation of a lemon yellow ppt. insoluble in NH4OH
shows the presence of bromine.

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NaBr  AgNO3  AgBr   NaNO3 4. QUANTITATIVE ESTIMATION OF ELEMENTS

(Lemon
yellow)
(ii) Layer test for bromine and iodine : The presence of nitro-
gen and sulphur does not interfere in this test. In this test
acidify a little sodium extract with dil. HNO3 or dil. H2SO4 and
add CHCl3 or CCl4 and excess of chlorine water. If organic
layer becomes yellow or brown, bromine is present and if
violet, iodine is present.
4.1 Estimation of Carbon and Hydrogen
4.1.1 Liebig Combustion Method
Principle: A known weight of the given dry organic
compound is heated strongly with dry cupric oxide in an atmo-
sphere of air or oxygen free from CO2. The carbon and hydrogen
of the organic compound are oxidised to The CO2 and water
vapour as :

2NaBr + Cl2  2NaCl + Br2. C  2CuO 

 CO 2  2Cu
CHCl3 + Br2  Yellow brown layer (from compound)
2NaI + Cl2  2NaCl + I2 2H  CuO 
 H 2 O  Cu
CHCl3 + I2  Violet layer (from compound)

(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 Estimation of Carbon and Hydrogen
contain halide ion. If the aqueous solution of any compound
Procedure : Let the mass of organic compound taken = w g
gives a white or yellow ppt. on addition of AgNO3, halide
ions are present. Mass of water formed = x g (increase in CaCl2 U-tube)
Mass of carbon dioxide formed = y g (increase in potash tubes)
C 6 H 5 N 2  Cl   AgNO 3  C 6 H 5 N 2  NO 3   AgCl 
(a) Percentage of Carbon: We know that 1 mole of carbondioxide
Benzene diazonium (44 g) contains
chloride 1 gram atom of carbon (12g)
C6 H 5 N 2 Br  AgNO3  C 6 H 5 N 2 NO 3  AgBr  CO 2  C
44 g of CO2 contain C = 12 g
C 6 H 5 NH 3 Cl  AgNO 3  C 6 H 5 NH 3  NO 3  AgCl 
12
3.2.4 Detection of Phosphorus Y g of CO2 contains C   yg
44
The organic compound containing phosphorus is fused with
sodium peroxide and extracted with water. The aqueous solution 12y
is boiled with concentrated nitric acid and ammonium molybdate Hence, Percentage of carbon   100
44  w
is added. A canary yellow precipitate indicates the presence of
phosphorus. (b) Percentage of Hydrogen: We know that one mole of water
(18 g) contains 2 gram atom of hydrogen (2g)
Na 3 PO 4  3HNO 3 
 H 3 PO 4  3NaNO3
H2O  2H
H 3 PO 4  12  NH 4 2 MoO4  21HNO3 18 g of H2O contain H = 2 g
Ammonium
molybdate
2
  x g of H2O contains H  xg
18
 NH 4 3 PO4 12MoO3  21NH 4 NO3  12H 2 O
2x
Ammonium
Phosphomolybdate Percentage of hydrogen  100
(yellow ppt) 18  w

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Percentage of C Experimental conditions S.T.P. conditions

P1 = (P - a) mm Hg P2 = 760 mm
12 Mass of CO 2 formed
   100 T1 = (273 + t) K T2 = 273
44 Mass of compound taken
V1 = V cm 3
V2 = ?
Percentage of H
P1V1 P2 V2
2 Mass of H 2 O formed Applying gas equation T  T
   100 1 2
18 Mass of compound taken

4.2 Estimation of Nitrogen P1V1T1 (P  a)  V  273

 V2    x cm3 (say)
P2 T2 760(273  t)
There are two methods for the estimation of nitrogen
(i) Duma’s Method Now 22400 cm3 of N2 at S.T.P. weight = 28 g
(ii) Kjeldahl’s Method x cm3 of N2 at S.T.P. will weigh
4.2.1 Duma’s Method 28
 xg
Principle of the method: A known mass of an organic compound 22400
is heated with dry cupric oxide in an atmosphere of carbon diox- Mass of Nitrogen
ide. The carbon and hydrogen are oxidised to carbon dioxide and Percentage of Nitrogen = 100
Mass of organic compound
water respectively while nitrogen is set free. If any oxide of nitro-
28x 100
gen is produced during this process, it is reduced to nitrogen by 
22400  w
passing over a heated copper gauze. The gaseous mixture is
collected over an aqueous solution of KOH when all the gases 4.2.2 Kjeldahl’s Method
except nitrogen are absorbed. The volume of nitrogen produced This method cannot be used for
is measured at room temperature and atmospheric pressure. From (i) Organic compounds containing nitrogen in the ring such as
the volume of N2 produced, percentage of nitrogen in the sample pyridine, quinoline, etc.
can be calculated.
(ii) Organic compounds containing nitrogen (-NO2) and diazo
C  2CuO 
 CO 2  2Cu (-N = N-) groups.
Principle: A known weight of the organic compound is heated
2H  CuO 
 H 2 O  Cu with conc. H2SO4 so that nitrogen is quantitatively converted
into ammonium sulphate. The solution is then heated with excess
2N  CuO 
 N 2  oxide of nirogen
of sodium hydroxide. The ammonia gas evolved is passed into a
Oxides of nitrogen + Cu  CuO + N2 known but excess volume of standard acid (HCl or H2SO4). The
Calculation: acid left unused is estimated by titrating the solution with
standard alkali. From the amount of acid left unused the amount
 Y of acid used for neutralisation of ammonia can be calculated.
C x H Y N Z   2x   CuO 
 2 From this percentage of nitrogen can be calculated.
Y Z  Y C, H, S 
Conc. H 2 SO 4
 CO 2  H 2 O  SO 2
x CO 2    H 2 O    N 2   2x   Cu
2
  2
   2 (from organic
Let the mass of organic compound = w g compound)
The volume of nitrogen collected = Vcm3
N 
Conc. H 2 SO 4
 (NH 4 )2 SO 4
Atmospheric pressure (from barometer) = P mm of Hg
(from organic ammonium sulphate
Room temperature = t0C compound)
Aqueous tension at t0C = a mm of Hg
(NH 4 ) 2 SO 4  2NaOH 
Heat
 Na 2SO 4  2NH 3  2H 2 O
Pressure of dry nitrogen = (P - a) mm of Hg
Let us first convert the volume of nitrogen to volume at 2NH3 + H2SO4  (NH4)2SO4
S.T.P. NH3 + HCl  NH4Cl

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Calculations 108 + X parts by weight of silver halide contains X parts by

Let the mass of organic compound = w g weight of halogen

Volume of standard acid taken = V cm3 (X is its atomic mass)

Normality of acid = N1 (108 + X) g of silver halide give halogen = X

Let vol. of standard alkali used for neutralisation of unused X

a g of silver halide will give halogen  (108  X)  a g
acid = V2 cm3
Normality of standard alkali = N2  Percentage of halogen
Mass of halogen Xa 100
N1V1  N 2 V2  100  
  Mass of organic compound (108  X) w
alkali acis

Let this volume of v cm3 Here X is the atomic mass of halogen, e.g.
Cl = 35.5, Br = 80 (79.9 exact), I = 127
 Vol. of acid used for neutralisation of ammonia
= (V - v) cm3 of N1 normality (126.9 exact)

 Ammonia liberated = (V - v) cm3 of N1 solution Percentage of halogen=

Now, 1000 cm3 of 1N NH3 solution contains nitrogen = 14 g Atomic mass of halogen  Mass of silver halide
 100
(V - v) cm3 of N1 NH3 solution contains nitrogen (108  At.mass of halogen)  Mass of org. substance
14(V  v)  N1 4.4 Estimation of Sulphur
 g
1000 Sulphur is estimated by Carius method.
Mass of Nitrogen Principle: A known mass of the organic compound is heated
Percentage of Nitrogen  100
Mass of organic compound with fuming HNO3 in a sealed tube when sulphur is quantitatively
converted into sulphuric acid. It is then precipitated with barium
1.4(V  v)  N1 100 1.4(V  v)  N1
N%    chloride as barium sulphate. The precipitate is filtered, washed,
1000 w w
dried and weighed. From the The weight of BaSO4 formed, the
4.3 Estimation of Halogens percentage of sulphur can be calculated. The main reactions are:
4.3.1 Carius Method
S  H 2 O  3O 
HNO3
 H 2SO 4
Principle: A known mass of the organic substance is heated
with fuming HNO3 in a Carius tube. The silver halide so obtained H 2SO 4  BaCl 2 
 BaSO 4 ppt.
is separated, washed, dried and weighed. From the weight of
silver halide formed, the percentage of halogen can be calculated. Calculations
Let the mass of organic compound = w g
X  AgNO3 
 AgX
Mass of BaSO4 formed = a g
Halogen, Carbon, hydrogen or sulphur present in the compound
BaSO4  S
will be oxidised to CO2, H2O and H2SO4 respectively.
137 + 32 + 64 = 32 = 233
C  2O 
HNO3
 CO2 233 g of BaSO4 contain sulphur = 32 g

2H  O 
HNO3
 H2O 32  a
a g of BaSO4 will contain sulphur  g
233
S  H 2 O  3O 
HNO3
 H 2SO 4
Percentage of sulphur
Calculations
Mass of sulphur
Let the mass of organic compound be w g  100  32a  100
Mass of organic compound 233 w
Mass of silver halide formed = a g
Now, AgX = X

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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
31 m1  100
Percentage of P = %
1877  m
If phosphorus is estimated as Mg2P 2O7,
62  m1 100
Percentage of P = %
222  m
4.6 Estimation of Oxygen
Percentage of oxygen in an organic compound
= 100 – percentage of other elements
A definite mass of an organic compound is decomposed by
heating in a stream of nitrogen gas. The mixture of gaseous
products containing oxygen is passed over red-hot coke when
all the oxygen is converted to carbon monoxide. This mixture
is passed through warm iodine pentoxide (I2O5) when carbon
monoxide is oxidised to carbon dioxide producing iodine.
heat
Compound   O 2  other gaseous products
1373K
2C  O 2  2CO
I 2 O5  5CO  I 2  5CO 2
5. GENERAL SEPARATION TECHNIQUES
5.1 Sublimation
• Some solid substances change from solid to vapour state
without passing through liquid state.
• The purification technique is used to separate sublimable
compounds from nonsublimable impurities.
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.
211
• 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.
• 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.
Simple Distillation
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5.3.2 Fractional Distillation Example:

Fractional distillation is required if the difference in boiling points Crude oil in petroleum industry.
of two liquids is not much or less than 25ºC. The vapours of such Types of Fractionating Columns
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.

Fractionating columns
5.3.3 Distillation under Reduced Pressure
• 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
Fractional Distillation pressure is reduced with the help of a water pump or
Fractionating columns vacuum pump.
• A fractionating column provides many surfaces for heat Example:
exchange between the ascending vapours and the Glycerol can be separated from spent-lye in soap industry.
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.
• 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. Distillation under Reduced Pressure

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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.
Differential Extraction Apparatus
• Thus, if one of the substances in the mixture is water and
the other, a water insoluble substance, then the mixture 5.5 Chromatography
will boil close to but below, 373K. Chromatography is used to separate mixtures into their
• A mixture of water and the substance is obtained which components, purify compounds and also to test the purity of
can be separated by using a separating funnel. compounds. It is based on adsorption.
Example: Aniline–Water Mixture 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.
• 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
Steam Distillation adsorbed, complete separation takes place. The most readily
5.4 Differential Extraction adsorbed substances are retained near the top and others
come down to various distances in the column.
• 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. Column Chromatography

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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.
Distance travelled by substance from the baseline (x)
Rf =
Distance travelled by solvent from the baseline (y)
TLC Apparatus
214
Detection of Movement:
The spots of coloured compounds are visible on TLC plate
due to their original colour.
Other Detection Techniques:
• Colourless compounds can be detected by putting the
plate under ultraviolet light.
• 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.
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Summary

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SOLVED EXAMPLES
Example - 1 Example-4
In Lassaigne’s test for nitrogen, the blue colour is due to An organic compound contains about 52% carbon. It could
the formation of– be–
(a) Ferric ferrocyanide (a) Only ethanol (b) Only dimethyl ether
(b) Potassium ferrocyanide (c) Both (d) None
(c) Sodium ferrocyanide Ans. (c)
(d) Sodium cyanide Sol. Ethanol (C2H5OH) and dimethyl ether (CH3OCH3) have
Ans. (a) same molecular formula (C2H6O), hence % of each element
Sol. In Lassaigne’s test substance is heated strongly with (C, H and O) in the two must be same.
sodium metal then water extract is boiled with alkaline FeSO4 Example - 5
solution and after cooling FeCl3 solution and excess of
Liebig method is used for the estimation of–
HCl is added in it. If prussian blue or green ppt. is obtained
(a) Nitrogen
then Nitrogen is confirmed –
(b) Sulphur
Na  C  N 
 NaCN
(c) Carbons and Hydrogen
FeSO 4  2NaOH 
 Fe(OH) 2  Na 2SO 4
(d) Halogens
6NaCN  Fe(OH) 2 
 Na 4 [Fe(CN)6 ]  2NaOH Ans. (c)
Fe 4 [Fe(CN) 6 ]3  12NaCl Sol. Liebig method is used for the estimation of carbon and
prussian blue or green hydrogen.
(ferric ferrocyanide)- Example - 6
Example - 2 An organic compound has the % composition as follows
C = 40%, H = 6.67%. Its vapour density is 45. The molecular
In sodium fusion test of organic compounds, the nitrogen
formula of the compound is–
of an organic compound is converted to–
(a) CH2O (b) C2H4O2
(a) Sodamide (b) Sodium cyanide
(c) C3H6O3 (d) C2H6O
(c) Sodium nitrite (d) Sodium nitrate
Ans. (c)
Ans. (b)
Sol.
Sol. Na  C  N 
fusion
 NaCN Element % Atomic Relative Simple Ratio
Example - 3 amout weight Number
A compound which give a positive test in the Lassaigne’s of atom
test for ‘N’ is– 3.33
40
(a) Phenyl hydrazine (b) Urea C 40 12  3.33
12 3.33
(c) Azobenzene (d) All of these
Ans. (d) 6.67 6.67
H 6.67 1  6.67 2
Sol. Lassaigne’s test is given by the compound which contain 1 3.33
C atom bonded N atom.
53.33 3.33
Hence all the given compound gives Lassaigne’s test for O 53.33 16  3.33 1
16 3.33
‘N’.
Therefore the empirical formula of molecule is CH2 and the
empirical formula weight is 30
Molecular weight = 45 × 2 = 90
PRACTICAL ORGANIC CHEMISTRY 217

Example - 9
Molecula weight 90
n   3
empirical formula weight 30 0.1877 g of an organic substance when analysed by the
Dumas method yield 31.7 ml of moist nitrogen measured at
and molecular formula is C3H6O3 14C and 758 mm mercury pressure. Determine the
Example - 7 percentage of nitrogen in the substance. (Aqueous tension
at 14C = 12 mm).
An organic compound has C and H percentage in the ratio
6:1 and C and O percentage in the ratio 3:4. The compound v(P  a) 273
Sol. Volume of N2 at NTP  
is– t  273 760
(a) HCHO (b) CH3OH = V ml
(c) CH3CH2OH (d) (COOH)2 substituting the various values in the above equation,
Ans. (a) 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
22400 0.1877
% H   100  6.66,  6.6
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
 g
18 alkali. The ammonia gas evoled was absorbed in 50 ml of
Hence, percentage of C N/10 hydrochloric acid which required 23.2 ml of
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
18 0.2475 26.8 ml of N/10 HCl = 26.8 ml of N/10 NH3
= 26.8 ml of N/10 N (combined)
PRACTICAL ORGANIC CHEMISTRY 218

26.8 ml of N/10 N solution contains Now,

14 26.8 0.18725
 g of nitrogen % of N in 0.4g   100  46.8%
10 1000 0.4
This weight of Nitrogen was originally present in 0.257 g N 31
of the organic substance.  Vml H 2SO 4  150 ml of  N  H 2SO 4
2 400
14  26.8 100 31
 Percentage of Nitrogen    14.6 V  150   2  23  25 m1  46.8%
10  1000 0.257 400
Example - 12 Example - 13
0.4 g of an organic compound was kjeldahlised and 0.197 g of an organic substance when heated with excess
ammonia evolved was absorbed into 50 ml of semi-normal of strong nitric acid and silver nitrate gave 0.3525 g of
solution of sulphuric acid. The residual acid solution was silver iodide. Find the percentage of iodine in the
diluted with distilled water and the volume was made up to compound.
150 ml. 20 ml of this diluted solution required 31ml of N/20
Sol. 1 mol AgI  1 mol I
NaOH solution for complete neutralisation. Calculate the
percentage of nitrogen in the compound. 234.77g AgI  127 g I
Sol. Given, mass of organic compound = 0.4 g 127
1g AgI  g of I
M N 234.77
50ml H 2SO 4  50ml H 2SO 4 127
4 2 0.3525 g AgI  0.3525  g
N 234.77
Let us assume that V ml of H 2SO 4 is unused.  0.19068 g of I
2
N Now,
V ml of H 2SO 4 is diluted to 150 ml & 20 ml of this solution
2 mass of I
%I   100
M mass of substance
is titrated against 30 ml NaOH solution.
20 0.19068
Now,   100  96.7%
0.197
M N Example - 14
For NaOH solution =
20 20
0.395 g of an organic compound by Carius method of the
Now, V1S1  V2S2 estimation of sulphur gas afforded 0.582 g of BaSO4. Find
N 1 1 31 the percentage of sulphur in the compound.
20ml  s1  31  S1  31   N
20 20 20 400 Sol. Mass of BasSO4 = 0.582g
N 233g of BaSO4 Contains sulphur = 32g
23.25ml   H 2SO 4 is unused used amount of
2 32
0.582g of BaSO4 Contains sulphur   0.582 g
H 2SO4   20  23.25  233
Now,
N N
26.75 ml H 2SO 4  26.75 ml NH 3 wt. of sulphur
2 2
% of Sulphur  wt. of compound 100
N
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 
PRACTICAL ORGANIC CHEMISTRY 219

Example - 15 Ans. (a,b,c,d)

Sol. Iodoform test is given by Carbonyl compounds having
Dil. H2SO 4  O 
O P1 + P2  || 
 R  C   group.
P1 and P2 product are identify by  
 
(a) Tollen’s reagent
(b) Iodoform test Alcohol having  R  CH 2  OH  group and secondary
(c) Br2 + H2O test alk– 2 – ol and 1, 3-dicarbonyl.
(d) 1 per cent alkaline KMnO4 Hence, all gives iodoform.
Ans. (a, b) Example - 18
Sol.
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.
P2 gives Tollen's test while P1 gives iodoform test Ans. (a, b, c)
Example - 16 Sol. (a) and (b) and (c) are true because sodium has weak
Which of the following compound can liberate CO2 when metallic bond due to larger size, as well as ionisation enery.
treated with NaHCO3? Sodium salts are soluble in water because hydration energy
dominates over lattic energy. It follows that (d) is incorrect.
Example - 19

(a) (b) CH3CO2H Ethanol and Ethanal are distinguished by

(a) Fehling’s solution test
(b) Tollen’s reagent test
(c) Iodoform test
(d) Cerric ammonium nitrate
(c) HCO2H (d)
Ans. (a, b, d)
Sol. a. Fehling solution
Ans. (a,b,c)
Ethanal + Fehling solution  Brick Red ppt
Sol. Those acids which are stronger then H2CO3 liberates CO2
Ethanal + Fehling solution No reaction
gas. Here Option a b & c are correct.
b. Ethanal gives silver mirror test with Tollen's reagent
Example - 17 where as Ethanol does not react
Among the following, which will respond to iodoform test? c. Iodoform can't be used because both respond to
iodotorm test
(a) (b) d. Ethanol gives wine red colouration with CAN while
Ethanal does not react.

(c) (d)
PRACTICAL ORGANIC CHEMISTRY 220

Example - 20 Example - 23

Which of the following statements are correct? HCOOH and CH3COOH can be distinguished by
(a) An organic compound is pure if mixed melting point is (a) Tollen’s reagent (b) Fehling’s solution
same. (c) KMnO4 (d) NaHCO3
(b) Ethanol and water can be separated by azeotropic Ans. (a, b, c)
distillation because it forms azeotrope. Sol. a. Tollen's test is used to distinguish
(c) Impure aniline is purified by steam distillation as it is HCOOH & CH3COOH
steam volatile. HCOOH gives silver mirror test where as acetic acid do
(d) Glycerol is purified by vacuum distillation because it not give
decomposes at its normal boiling point. b. Formic acid reduces fehling solution while acetic acid
Ans. (a, b, c, d) does not react with Fehling Solution.
Sol. All statments are self explanatory. c. KMnO4 reacts with formic acid to give red-brown
Example - 21 coloured compound.
Example - 24
Which of the following will respond to iodoform test?
O OH The desiccants used for absorbing water during Liebig’s
|| | method for estiamtion of carbon and hydrogen are
(a) CH 3  C  COOH (b) CH 3  CH  COOH
(a) anhydrous CaCl2 (b) anhydrous Na2SO4
OH
| (c) Mg(ClO4)2 (d) MgSO4.7H2O
(c) CH 3  CH  CH 3 (d) CH3CH2OH Ans. (a, c)
Ans. (a, b,c, d) Sol. Anhydrous CaCl2 and Mg(CIO4)2 are used as desiccants
Sol. Iodoform test is given by Carbonyl compounds having because they are different absorbent of water.
 O 
 ||  Example - 25
 R  C   group. Column - I Column - II
 
  (Reagents) (Compound)
(a) Tollen’s reagent (p) Me - CH = CH - Me
Alcohol having  R  CH 2  OH  group and secondary
give white ppt. with
alk– 2 – ol
(b) Br2 + H2O test (q) Me - C  C - H
Hence, all gives iodoform.
given by
Example - 22
 
Which of the following will not show iodoform test? (c) Product of reaction (r) Cl NH 3  NH 2
O O of acetylene with
|| ||
(a) CH 3  C  CH 3 (b) CH3  C  Cl 1 percent HgSO4 and
O Dil. H2SO4
|| O
(c) CH 3  C  NH 2 (d) CH3 - COOH ||
Ans. (b, c, d) (d) Pd/H2 reacts with (s) Me  C  H
Sol. Iodoform test is given by aldehyde & Ketone having O
||
O (t) Me  C  Me
||
R  C  group.
So, b, c, d can’t show iodoform test.
PRACTICAL ORGANIC CHEMISTRY 221
Ans. (a-q,r) (b-p,q) (c-s) (d-p,q,s,t)
O
Sol. ||
(c) HC 1% HgSO4
 CH 
dilH2SO4  CH3  C H
(a) Tollen's reagent gives white ppt with terminal alkynes

  (d) Pd/H2 is a strong reducing agent & reduces carbonyl

& Cl NH  NH
3 2 compounds and - bond containing species (Alkenes
& alkynes).
T.R
R – C  CH   R – C  CAg 
 white ppt 

(b) Br2  H 2 O test : – Bromine water test is used for

alkenes & alkynes.
Me – CH = CH – Me + Br2 + H2O 
CH3 CH CH  CH 3  HBr
| |
OH Br
PRACTICAL ORGANIC CHEMISTRY 222

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Functional Group Detection 10. Drying agent for amine is
1. Which of the following test is not used for protein/amino (a) KOH (b) H2SO4
acids– (c) HCl (d) HNO3
(a) Biuret test (b) Ninhydrin test 11. Test which is given by all  -amino acids?
(c) Xanthoproteic test: (d) Iodine test (a) Iodine test (b) Molish test
2. Which of the following is the test of primary amine? (c) Ninhydrin test (d) Barfoed test
(a) Carbylamine test 12. Dye test given by the
(b) Reaction with carbon di-sulphide (a) Benzene
(c) Heinsberg test (b) Toluene
(d) All of these (c) Aniline
3. Which of the following is the test of carbohydrates? (d)Methane amine
(a) Molish test (b) Biuret test Distinguish and Separate Organic Compounds
(c) Ninhydrin test (d) None of these 13. Barfoed test is used for the distinguish:
4. Zeisel’s method is use for the determination of (a) Phenol from carboxylic acid
(a) Ether (b) Alcohol (b) Amino acids
(c) Phenol (d) Carboxylic acid (c) Monosaccharides from reducing disaccharides
5. Schiff test is used for the identification: (d) Peptide linkage
(a) Ketones (b) Aldehydes 14. Seliwanoff’s test is used for the distinguish:
(c) Phenol (d) Alcohols (a) Aldoses from ketoses
6. Which of the following will give Tollen’s test? (b) Primary and secondary structure of proteins
(a) Acetone (b) But-2-one (c) Polysaccharides
(c) Benzaldehyde (d) Cyclohexanone (d) Amino acids.
7. Which of the following compound Discharge bromine 15. Which of the following test can use for separation of
solution to colourless without evolving HBr? alcohol and phenol?
(a) Alkene (b) Alkane (a) Tollen’s test
(c) Cyclo alkane (d) Benzene (b) Sodium bicarbonate test
8. Which of the following is the test of alcohol? (c) Reaction with neutral FeCl3 solution
(a) Sodium metal test (d) Fehling’s test
(b) Cerric ammonium nitrate test 16. Aromatic aldehydes and aliphatic aldehydes can be
(c) Ester test separated by
(d) All of these (a) Fehling solution (b) Tollens reagent
9. Test of unsaturatution is used to determine (c) Both (a) and (b) (d) None of this.
(a) Alkenes (b) Alkanes 17. formic acid and acetaldehydes separated by
(c) Benzne (d) None of these (a) Tollens test (b) NaHCO3 test
(c) Fehling solution (d) None of these.
PRACTICAL ORGANIC CHEMISTRY 223
Qualitative Estimation of Elements (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 29. What conclusion would you draw if during Lassaigne‘s
20. The oxygen is estimated in the organic compound by 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 (c) Both P and S is present
red colour obtained is due to the formation of–
(d) Only S is present
(a) Ferric ferrocyanide (b) Ferric sulpocyanide
30. What type of organic compounds cannot be Kjeldahlised?
(c) Ferric cyanide (d) None
(a) Nitro compound (b) Azo compound
22. Kjeldahl’s method is used in the estimation of–
(c) Both (a) and (b) (d) None of these
(a) Nitrogen (b) Halogens
31. How is phosphorus estimated in an organic compound?
(c) Sulphur (d) Oxygen
(a) Ammonium Phosphomolybdate
23. Dumas method involves the determination of nitrogen
(b) Magnesium Pyrophosphate
content in the organic compound in form of–
(c) Both (a) and (b)
(a) NH3 (b) N2
(d) Ammonium Pyrophosphate
(c) NaCN (d) (NH4)2SO4
32. Will you get any precipitate if you add silver nitrate
24. Which of the following statements is wrong?
solution to chloromethane? If not, why?
(a) Using Lassaigne’s test nitrogen and sulphur present
(a) Chloromethane is a covalent compound
in an organic compound can be tested
(b) Chloromethane is a ionic compound
(b) Using Beilstein’s test the presence of halogen in a
compound can be tested (c) Both (a) and (b)

(c) In Lassaigne’s filtrate, the nitrogen present in the (d) None of these
organic compound is converted into NaCN 33. Beilstein test is used for
(d) In the estimation of carbon, an organic compound (a) Halogens (b) Hydrogens
is heated with CaO in a combustion tube (c) Nitrogen (d) Carbon
25. Sulphur is estimated by Carius method in the form of 34. The prussian blue colouration obtained in the test for
(a) Ba(OH)2 (b) BaSO4 nitrogen in the organic compound is
(c) BaCO3 (d) None of these (a) K4[Fe(CN)]6 (b) Fe4[Fe(CN)6]3
26. Compounds which do not contain halogen but give (c) Fe[Fe(CN)6] (d) Fe3[Fe(CN)6]2
positive Beilstein test? 35. Which element can not separated by carius method.
(a) Urea (b) Thiourea (a) Halogens (b) Carbon
(c) CH3COOH (d) Both (a & b) (c) Phosphorus (d) Sulphur
27. Which Metal cyanide give a positive Lassaigne’s test for
nitrogen?
PRACTICAL ORGANIC CHEMISTRY 224
36. Which of the following is used for the detection of sulphur 44. Which of the following test is used for quantitative
(a) Sodium nitroprusside test estimation of N
(b) Lead acetate (a) Duma’s Method (b) Kjeldahl’s Method
(c) Both (a) and (b) (c) Carius Method (d) Both (a) and (b)
(d) None of these 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
compound gave 50 cm3 of nitrogen collected at 300 K and
(c) NH2 - NH2 (d) 715 mm pressure. The percentage of nitrogen in the
compound (vapour pressure of water at 300K is 15 mm) is
SO3H
(a) 15.46 (b) 17.46
Quantitative Estimation of Elements
(c) 50 (d) 70
38. The molecular mass of a organic compound which
contains only one nitrogen atom can be General Separation Techniques
(a) 73 (b) 76 47. A mixture of benzene and chloroform is separated by–
(c) 146 (d) 152 (a) Sublimation (b) Separating funnel
39. When 0.32g of a compound is heated with conc. HNO3 (c) Crystallization (d) Distillation
and BaCl2, 0.932g BaSO4 is obtained. The percentage of
48. How will you purify a liquid having non-volatile impurities?
sulphur in the compound is
(a) Sublimation (b) Crystallization
(a) 20 (b) 40
(c) Simple Distillation (d) Chromatography
(c) 60 (d) 80
49. Which of the following compound is/are purified by
40. 0.2475g of an organic compound gave on combustion
0.4950g of carbon dioxide and 0.2025g of water. The sublimation?
percentage of carbon and hydrogen are: (a) Naphthalene (b) Benzoic acid
(a) 54.54, 9.09 (b) 52.54,8.09 (c) Camphor (d) All of these
(c) 120, 5.8 (d) None 50. How will you separate iodine from sodium chloride?
41. 0.15 g of an organic compound gave 0.12 g of AgBr by (a) Sublimation (b) Distillation
Carius method. The percentage of bromine in the (c) Both (a) and (b) (d) Crystalisation
compound is
51. An organic liquid decomposes below its boiling point.
(a) 43 (b) 54
How will you purify it?
(c) 34 (d) 66
(a) Chromatography
42. 0.395 g of an organic compound by Carius method for the
(b) Crystallization
estimiation of sulphur gave 0.582 g of BaSO 4. The
(c) Sublimation
percentage of sulphur in the compound is–
(d) Distillation under reduced pressure
(a) 20.24 (b) 35
52. The best method for the sepration of naphthalene and
(c) 40 (d) 45
benzoic acid from their mixture is
43. Find out the percentage of carbon in acetic acid.
(a) sublimation (b) chromatography
(a) 40 (b) 45
(c) crystallisation (d) distillation
(c) 70 (d) 50
PRACTICAL ORGANIC CHEMISTRY 225
53. The separation of the constituents of a mixture by column 54. A mixture of water and ethanol can be separated by
chromatography depends upon their (a) Fractional distillation
(a) different solubilities (b) Azeotropic distillation
(b) different boiling points (c) Steam distillation
(c) different refractive indices (d) vacuum distillation
(d) differential adsorption 55. Sublimation is used for the purification of
(a) Alcohols (b) Anthracene
(c) Carboxylic acids (d) None of these
PRACTICAL ORGANIC CHEMISTRY 226

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS

Objective Questions I [Only one correct option] 8. Observation of “Rhumann’s purple” is a confirmatory test
for the presence of : (Online 2016 Set-2)
1. The compound formed in the positive test for nitrogen with
the Lassaigne’s solution of an organic compound is (2004) (a) Reducing sugar (b) Cupric ion
(a) Fe4[CN)6]3 (b) [Na3[Fe(CN)6] (c) Protein (d) Starch
(c) Fe(CN)3 (d) Na4[Fe(CN)5NOS] 9. Which of the following compounds will be suitable for
Kjeldahl's method for nitrogen estimation? (2018)
2. An organic compound having molecular mass 60 is found
to contain C = 20%, H = 6.67% and N = 46.67% while rest is
oxygen. On heating it gives NH3 alongwith a solid residue. (a) (b)
The solid residue give violet colour with alkaline copper
sulphate solution. The compound is (2005)
(a) CH3CH2CONH2 (b) (NH2)2CO (c) (d)

(c) CH3CONH2 (d) CH3NCO 10. An organic compound 'A' is oxidized with Na2O2 followed by
3. 29.5mg of an organic compound containing nitrogen was boiling with HNO3. The resultant solution is then treated
digested according to Kjeldahl's method and the evolved with ammonium molybdate to yield a yellow precipitate. Based
ammonia was absorbed in 20 mL of 0.1 M HCl solution. The on above observation, the element present in the given
excess of the acid required 15 mL of 0.1M NaOH solution for compound is: (2019)
complete neutralization. The percentage of nitrogen in the (a) Nitrogen (b) Phosphorus
compound is (2010)
(c) Fluorine (d) Sulphur
(a) 59.0 (b) 47.4
11. Which one of the following is likely to give a precipitate with
(c) 23.7 (d) 29.5 AgNO3 solution? (2019)
4. Copper wire test for halogens is known as (2012) (a) CH=CH – Cl (b) CCl4
(a) Duma's Test (b) Beilstein's Test (c) CHCl3 (d) (CH3)3CCl
(c) Liebig's Test (d) Lassigne's Test 12. The principle of column chromatography is: (2019)
5. Beilstein’s test is used for the estimation of which one of (a) Gravitational force.
the following elements? (2012)
(b) Capillary action
(a) S (b) Cl
(c) Differential absorption of the substances on the solid
(c) C and H (d) N phase.
6. Which of the following statement is incorrect? (2013) (d) Differential adsorption of the substances on the solid
(a) Fe ion also gives blood red colour with SCN ion.
2+ – phase.
(b) Fe3+ ion also gives blood red colour with SCN– ion. 13. In chromatography, which of the following statement is
(c) On passing H2S into Na2ZnO2 solution a white ppt of INCORRECT for Rf ? (2019)
ZnS is formed. (a) Rf value depends on the type of chromatography.
(d) Cupric ion reacts with excess of ammonia solution to (b) The value of Rf can not be more than one.
2
give deep blue colour of Cu  NH 3 4  ion. (c) Higher Rf value means higher adsorption.
7. An aqueous solution of a salt X turns blood red on treatment (d) Rf value is dependent on the mobile phase.
with CNS– and blue on treatment with K4[Fe(CN)6].X also 14. The organic compound that gives following qualitative
gives a positive chromyl chloride test. The salt X is: (2015) analysis is: (2019)
(a) CuCl2 (b) FeCl3 Test Inference
(c) Cu(NO3)2 (d) Fe(NO3)3 (a) Dil. HCl Insoluble
(b) NaOH solution soluble
(c) Br2/water Decolourization
PRACTICAL ORGANIC CHEMISTRY 227
19. Which of the following tests cannot be used for identifying
(a) (b) amino acids? (2019)
(a) Biuret test (b) Barfoed test
(c) (d) (c) Ninhydrin test (d) Xanthoproteic test
20. The tests performed on compound X and their inferences
15. An organic compound 'X' showing the following solubility are:
profile is:
Test Inference
(a) 2,4 - DNP test Coloured precipitate
(b) Iodoform test Yellow precipitate
(c) Azo-dye test No dye formation
Compound 'X' is: (2019)

(a)

(2019)
(a) o -Toluidine (b) Oleic acid
(c) m - Cresol (d) Benzamide (b)
16. An organic compound is estimated through Dumas method
and was found to evolve 6 moles of CO2, 4 moles of H2O and
1 molc of nitrogen gas. The formula of the compound is:
(2019)
(a) C12H8N (b) C12H8N2 (c)

(c) C6H8N2 (d) C6H8N

17. Which of the following compounds will produce a precipitate
with AgNO3 ? (2019)

(d)
(a) (b)
21. Consider the following reactions:

'A'  
ozonolysis
 'B'  'C'
 C7 H14 
(c) (d)

18. If dichloromethane (DCM) and water (H2O) are used for

differential extraction, which one of the following statements
is correct? (2019)
(a) DCM and H2Owould stay as lower and upper layer
respectively in the S.F.
(b) DCM and H2O will make tur bid/colloidal mixture
(c) DCM and H2O would stay as upper and lower layer
‘A’ is : (2020)
respectively in the separating funnel (S.F.)
(d) DCM and H2O will be miscible clearly
PRACTICAL ORGANIC CHEMISTRY 228
25. Kjeldahl's method cannot be used to estimate nitrogen for
(a) (b) which of the following compounds? (2020)
(a) C6H5NH2 (b) CH3CH2C º N
(c) (d) O
||

22. The Kjeldahl method of Nitrogen estimation fails for which (c) C6H5NO2 (d) NH 2  C  NH 2
of the following reaction products? (2020) 26. A solution of m-chloroaniline, m- chlorophenol and m-
chlorobenzoic acid in ethyl acetate was extracted initially
with a saturated solution of NaHCO3 to to give fraction A.
The left over organic phase was extracted with dilute NaOH
(1) (2) solution to give fraction B. The final organic layer was
labelled as fraction C. Fractions A, B and C, contain
respectively: (2020)
(a) m-chlorobenzoic acid, m-chloroaniline and m-
chlorophenol
(3)
(b) m-chlorobenzoic acid, m-chlorophenol and m-
chloroaniline
(c) m-chlorophenol, m- chlorobenzoic acid and m-
chloroaniline
(4) (d) m- chloroaniline, m- chlorobenzoic acid and m-
chlorophenol
(a) (3) and (4) (b) (1) and (4) 27. In Carius method of estimation of halogen, 0.172g of an
(c) (1),(3) and (4) (d) (2) and (3) organic compound showed presence of 0.08g of bromine.
23. A, B and C are three biomolecules. The results of the tests Which of these is the correct structure of the compound?
performed on them are given below: (2020)
Molisch's Test Barfoed Test Biuret Test
A Positive Negative Negative
B Positive Positive Negative
C Negative Negative Positive
(a) H3C– CH2 – Br (b)
A, B and C are respectively: (2020)
(a) A = Glucose, B = Fructose, C = Albumin
(b) A = Lactose, B = Glucose, C = Albumin
(c) A = Lactose, B = Glucose, C = Alanine
(d) A = Lactose, B = Fructose, C = Alanine
24. The strength of an aqueous NaOH solution is most accurately (c) (d) H3C– Br
determined by titrating:
(Note: consider that an appropriate indicator is used)
(2020)
(a) Aq. NaOH in a pipette and aqueous oxalic acid in a burette
(b) Aq. NaOH in a burette and aqueous oxalic acid in a
conical flask
(c) Aq. NaOH in a burette and concentrated H2SO4 in a
conical flask
(d) Aq. NaOH in a volumetric flask and concentrated H2SO4
in a conical flask
PRACTICAL ORGANIC CHEMISTRY 229
28. Two compounds A and B with same molecular formula 30. A chromatography column, packed with silica gel as
(C3H6O) undergo Grignard's reaction with methylmagnesium stationary phase, was used to separate a mixture of
bromide to give products C and D. Products C and D show compounds consisting of (A) benzanilide (B) aniline and (C)
following chemical tests. acetophenone.
Test C D When the column is eluted with a mixture of solvents, hexane:
Ceric ammonium Positive Positive ethyl acetate (20 : 80), the sequence of obtained compound is:

nitrate Test (2020)

Turbidity Turbidity (a) (B), (C) and (A)

Lucas Test obtained after obtained (b) (B), (A) and (C)

five minutes immediately (c) (C), (A) and (B)

Iodoform Test Positive Negative (d) (A), (B) and (C)

C and D respectively are: (2020) 31. Which of the following compound is added to the sodium
OH extract before addition of silver nitrate for testing of
|
(a) C  H C – CH – CH – CH ; halogens? (2021-02-25/Shift-2)
3 2 3

CH3 (a) Ammonia

|
D  H 3 C – C – OH; (b) Hydrochloric acid
|
CH3 (c) Nitric acid

(b) C  H 3 C  CH 2  CH 2  CH 2  OH; (d) Sodium hydroxide

D  H 3 C  CH 2  CH  CH 3 32. Which of the following is 'a' FALSE statement?
|
OH
(2021-03-16/Shift-1)
(c) C  H3C  CH2  CH2  CH 2  OH ;
(a) Kjeldahl's method is used for the estimation of nitrogen
CH3
| in an organic compound
D  H 3 C  C  OH
|
CH3 (b) Carius tube is used in the estimation of sulphur in an
organic compound
CH3
| (c) Carius method is used for the estimation of nitrogen in
(d) C  H 3 C – C – OH;
| an organic compound
CH3
(d) Phosphoric acid produced on oxidation of phosphorus
D  H 3 C – CH 2 – CH – CH 3
| present in an organic compound is precipitated as
OH
Mg2P2O7 by adding magnesia mixture
29. Consider the following reaction: (2020)
33. In chromatography technique, the purification of compound
is independent of (2021-03-16/Shift-1)

(a) Length of the column or TLC plate

The product 'X' is used:
(a) in protein estimation as an alternative to ninhydrin (b) Solubility of the compound
(b) in acid base titration as an indicator (c) Mobility or flow of solvent system
(c) as food grade colourant
(d) Physical state of the pure compound
(d) in laboratory test for phenols
PRACTICAL ORGANIC CHEMISTRY 230
34. Given below are two statements: 38. Which one of the following set of elements can be detected

Statement I: Retardation factor (Rf) can be measured in using sodium fusion extract? (2021-07-27/Shift-2)

meter/centimetre. (a) Sulfur, Nitrogen, Phosphorous, Halogens

Statement II: Rf value of a compound remains constant in (b) Phosphorous, Oxygen, Nitrogen, Halogens
all solvents. (c) Nitrogen, Phosphorous, Carbon, Sulfur
Choose the most appropriate answer from the options given (d) Halogens, Nitrogen, Oxygen, Sulfur
below : (2021-03-17/Shift-1)
Numerical Value Type Question
(a) Statement I is true but statement II is false
39. Using the provided information in the following paper
(b) Statement I is false but statement II is true chromatogram: (2021-02-25/Shift-1)
(c) Both statement I and statement II are true

(d) Both statement I and statement II are false

35. Nitrogen can be estimated by Kjeldahl’s method for which

of the following compound ? (2021-03-17/Shift-2)

(a) (b)
The calculated R value of A is _______ × 10 .
40. An organic compound is subjected to chlorination to get
compound A using 5.0 g of chlorine. When 0.5 g of
compound A is reacted with AgNO3 [Carius method], the
(c) (d)
percentage of compound A is _______ when it forms 0.3849
g of AgCl. (Round off to the nearest integer) (Atomic masses
of Ag and Cl are 107.87 and 35.5 respectively)
36. In Carius method, halogen containing organic compound is
(2021-07-27/Shift-1)
heated with fuming nitric acid in the presence of:
41. In the sulphur estimation, 0.471 g of an organic compound
(2021-07-20/Shift-2)
gave 1.44 g of barium sulphate. The percentage of sulphur
(a) HNO3 (b) AgNO3 in the compound is _____%. (Nearest integer) (Atomic Mass
(c) CuSO4 (d) BaSO4 of Ba = 137 u (2021-08-26/Shift-2)
37. Which purification technique is used for the organic 42. In Carius method for estimation of halogens, 0.2 g of an
compound that decomposes near its boiling point? organic compound gave 0.188g of AgBr . The percentage of
(2021-07-22/Shift-2) bromine in the compound is _____. (Nearest integer)

(a) Simple distillation (b) Steam distillation [Atomic mass : Ag = 108, Br = 80] (2021-08-27/Shift-1)
(c) Fractional distillation (d) Reduced pressure
distillation
PRACTICAL ORGANIC CHEMISTRY 231
43. The number of moles of CuO, that will be utilized in Dumas (a) A-(ii); B-(iii); C-(i) (b) A-(iii); B-(i); C-(ii)
method for estimation nitrogen in a sample of 57.5 g of N, (c) A-(iii); B-(ii); C-(i) (d) A-(ii); B-(i); C-(iii)
N-dimethylaminopentane is ___ × 10–2. (Nearest integer): 48. The correct match between items of List-I and List-II is :
(2018)
(2021-08-27/Shift-1)
List-I List-II
44. The transformation occurring in Duma’s method is given
A. Coloured impurity (p) Steam distillation
below:
B. Mixture of o-nitrophenol (q) Fractional
 y
C2 H 7 N   2x   CuO  and p -nitrophenol distillation
 2 
C. Crude naphthalene (r) Charcoal treatment
y z  y
xCO 2  H 2 O  N 2   2x   Cu
2 2  2 D. Mixture of glycerol (s) Distillation under
The value of y is ________. (Integer answer and sugars reduced pressure
(2021-08-31/Shift-2) (a) A-(r), B-(s), C-(p), D-(q) (b) A-(r), B-(p), C-(q), D-(s)
45. When 0.15 g of an organic compound was analyzed using (c) A-(r), B-(p), C-(q), D-(s) (d) A-(r), B-(p), C-(s), D-(q)
Carius method for estimation of bromine, 0.2397 g of AgBr 49. The correct match between items I and II is: (2019)
was obtained. The percentage of bromine in the organic Item-I Item-II
compound is ___. (Nearest integer) (Mixture) (Separation method)
[Atomic mass: Silver = 108, Bromine = 80] (A) H2O : Sugar (P) Sublimation

(2021-07-20/Shift-2) (B) H2O : Aniline (Q) Recrystallization

(C) H2O : Toluene (R) Steam distillation
46. 0.8 g of an organic compound was analysed by Kjeldahl's
(S) Differential extraction
method for the estimation of nitrogen. If the percentage of
(a) (A) (S); (B) (R); (C) (P)
nitrogen in the compound was found to be 42%, then___
(b) (A) (Q); (B) (R); (C) (S)
mL of 1 M H2SO4 would have been neutralized by the
(c) (A) (R); (B) (P); (C) (S)
ammonia evolved during the analysis.
(d) (A) (Q); (B) (R); (C) (P)
(2021-07-25/Shift-2)
50. The correct match between Item I and Item II is: (2019)
Match the Following
Item I Item II
Each question has two columns. Four options are
given representing matching of elements from (A) Ester test (P) Tyr
Column-I and Column-II. Only one of these four (B) Carbylamine test (Q) Asp
options corresponds to a correct matching. For (C) Phthalein dye test (R) Ser
each question, choose the option corresponding
(S) Lys
to the correct matching
(a) (A) (Q, R); (B) (S); (C) (P)
47. Match the organic compounds in column-I with the
Lassaigne's test results in column-II appropriately: (2015) (b) (A) (R); (B) (Q); (C) (P)

Column - I Column - II (c) (A) (R); (B) (S); (C) (Q)

(A) Aniline (i) Red colour with FeCl3 (d) (A) (Q); (B) (S); (C) (R)

(B) Benzene sulfonic (ii) Violet colour with

acid sodium nitroprusside
(C) Thiourea (iii) Blue colour with hot
and acidic solution of
FeSO4
PRACTICAL ORGANIC CHEMISTRY 232
51. The correct match between item 'I' and item 'II' is: (2019) 54. Match the following: (2020)
Item ‘I’ Item ‘II’ Column-I Column-I
(Compound) (reagent) Test / Method Reagent
(A) Lysine (P) 1-Naphthol (i) Lucas Test (A) C6H5SO2Cl/aq.KOH
(B) Furfural (Q) Ninhydrin (ii) Dumas method (B) HNO3/AgNO3
(C) Benzyl alcohol (R) KMnO4 (iii) Kjeldahl's method (C) CuO/CO2
(D) Styrene (S) Ceric ammonium nitrate (iv) Hinsberg Test (D) Conc. HCl and ZnCl2
(a) (A) (Q); (B) (P); (C) (S); (D) (R) (E) H2SO4
(b) (A) (Q); (B) (P); (C) (R); (D) (S) (a) (i)-(D), (ii)-(C),(iii)-(B),(iv)-(A)
(c) (A) (R); (B) (P); (C) (Q); (D) (S) (b) (i)-(B), (ii)-(D),(iii)-(E),(iv)-(A)
(d) (A) (Q); (B) (R); (C) (S); (D) (P) (c) (i)-(D), (ii)-(C),(iii)-(E),(iv)-(A)
52. The correct match between Item-I and Item-II is: (2019) (d) (i)-(B), (ii)-(A),(iii)-(C),(iv)-(D)
Item - I Item - II 55. Match List-I with List-II: (2021-03-16/Shift-2)
(drug) (test) List-I List-II
(A) Chloroxylenol (P) Carbylamine test Test/Reagents /Observation(s) Species detected
(B) Norethindrone (Q) Sodium
(a) Lassaigne’s Test (i) Carbon
hydrogen carbonate test
(b) Cu(II) oxide (ii) Sulphur
(C) Sulphapyridine (R) Ferric chloride test (c) Silver nitrate (iii) N, S, P and halogen
(D) Penicillin (S) Bayer's test (d) The sodium fusion (iv) Halogen Specifically
extract gives black
(a) (A) (R); (B) (P); (C) (S); (D) (Q)
precipitate with acetic
(b) (A) (Q); (B) (S); (C) (P); (D) (R) acid
(c) (A) (R); (B) (S); (C) (P); (D) (Q) The correct match is:
(d) (A) (Q); (B) (P); (C) (S); (D) (R) (a) (a)-(iii), (b)-(i), (c)-(ii), (d)-(iv)
53. The correct match between Item I and Item II is: (2019)
(b) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii)
Item - I Item - II
(c) (a)-(i), (b)-(iv), (c)-(iii), (d)-(ii)
(A) Benzaldehyde (P) Mobile phase
(B) Alumina (Q) Adsorbent (d) (a)-(i), (b)-(ii), (c)-(iv), (d)- (iii)
(C) Acetonitrile (R) Adsorbate
(a) (A) (Q); (B) (P); (C) (R)
(b) (A) (R); (B) (Q); (C) (P)
(c) (A) (Q); (B) (R); (C) (P)
(d) (A) (P); (B) (R); (C) (Q)
PRACTICAL ORGANIC CHEMISTRY 233

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only one correct option]
1. Sodium nitrorusside Na2[Fe(CN)5NO] is used as reagent for 9.. Among the following which compound gives precipitate
detection of ______ and the compound formed is ____. with AgNO3 solution?
(a) Sulphur, Na4[Fe(CN)5NOS]
(b) Nitrogen, Na4[Fe(CN)6]
(a) (b)
(c) Sulphur, Na2[Fe(CN)4NOS]
(d) Sulphur, Na2[Fe(CN)5NOS]
2. The prussian blue colouration obtained in the test for nitrogen
in the organic compound is (c) (d) None of these.
(a) K4[Fe(CN)]6 (b) Fe4[Fe(CN)6]3
(c) Fe[Fe(CN)6] (d) Fe3[Fe(CN)6]2 10. Disodium pentacyanonistrosyl ferrate reagent gives
purple colour when which of the following element is
3. If N and S both are present in an organic compound during
present?
Lassaigne’s test, both will change into
(a) N (b) Cl
(a) Na2S and NaCN (b) NaSCN
(c) F (d) S
(c) Na2SO3 and NaCN (d) Na2S and NaCNO
4. Phenol and benzoic acid can be separated by 11. Phenol + Phthalic anhydride 
Conc.H 2 SO4
fusion
 B. B gives
(a) NaHCO3 (b) NaOH solution which of the following colour in alkaline medium?
(c) FeCl3 solution (d) All of these. (a) Yellow (b) Colourless
5. Anthracene can be purified by (c) Pink (d) Violet
(a) Distillation (b) Sublimation 12. To separate a mixture of amines from each other, one
(c) Filtration (d) Fractional distillation should follow
6. KOH can be used as a drying agent for (a) Beckmann’s method
(a) Amines (b) Phenols (b) Hinsberg’s method
(c) Acids (d) Esters (c) Zeisel’s method
7. Silver salt method is used to determine molecular (d) Victor Merye’s Method
weight of 13. Phenol can be distinguished from ethanol by
(a) Organic acids (b) Organic bases (a) Tollen’s reagent (b) Benedict’s reagent
(c) Both acids and bases (d) None of these. (c) FeCl3 (d) Schiff’s base
8. Rectified spirit contains 14. Which of the following will not give test for ‘N’ in sodium
(a) 95.6 percent ethanol and 4.4 per cent methanol extract?
(b) 100 percent ethanol (a)C6H5NHNH2 (b) NH2CONH2

(c) 95.6 percent ethanol and 4.4 per cent water

(d) 95.6 percent ethanol and 4.4 per cent benzene
(c) NH2- NH2 (d)
PRACTICAL ORGANIC CHEMISTRY 234
15. A mixture of acetone and CCl4 can be separated by (c) 3Na4[Fe(CN)6] + 2Fe(SO4)3 
 Fe4[Fe(CN)6]3
(a) Azeotropic distillation (b) Fractional distillation
+ 6Na2SO4
(c) Steam distillation (d) vacuum distillation
(d) Na + S 
 Na2S
16. Which of the following observations is correct and is used
in the identification of carboxylic acids? 21. Compound A reacts with CHCl3 and KOH and gives an
offesnive smelling compound. A can be
(a) Carboxylic acids liberate CO2 gas from NaHCO3 solution.
(a) Primary aliphatic amine
(b) They produce fruity smell of esters when heated with
alcohol in presence of Conc. H2SO4 (b) Primary aromatic amine
(c) Both (a) and (b) (c) Secondary amine
(d) Iodoform test (d) Tertiary amine
17. An organic compound is heated with HNO2 at 0 C and then
o 22. HCOOH and HCHO may be distinguished by
the resulting solution is added to a solution -napthol (a) Tollen’s test (b) Sodium bicarbonate test
whereby a brilliant red dye is produced. The observations
(c) 2, 4-DNP test (d) Benedict’s test
indicate that the compound possesses.
CHO
(a) -NO2 group (b) -CONH2 group
23. and CH3CHO can be distinguished by
(c) aromatic NH2 group (d) aliphatic NH2 group
18. An organic compound contains C, H, N, S and Cl. For the (a) Tollen’s test (b) Benedict’s test
detection of chlorine, the sodium extract of the compound
(c) Iodoform test (d) 2, 4-DNP test
is first heated with a few drops of concentrated HNO3 and
then AgNO3 is added to get a white ppt. of AgCl. The 24. Acetic acid and CH3COCl can be distinguished by
digestion with HNO3 before the addition of AgNO3 is (a) NaHCO3 test (b) Na metal test
(a) to prevent the formation of NO2 (b) Ester formation test (d) Br2(aq.) test
(b) to create a common ion effect 25. An organic compound has the structure
(c) to convert CN and S to volatile HCN and H2S, or else
- 2-

they will interfere with the test forming AgCN or Ag2S

(d) to prevent the hydrolysis of NaCN and Na2S
19. Among the following, which statement is not correct?
O It will give
||
(a) H 3 C  C  OH will not respond to haloform test (a) Cerric ammonium nitrate test
(b) Brick effervescene with sodium bicarbonate
(b) Schiff ’s regent and Schiff ’s base are different
compounds (c) A characteristic colouration with neutral ferric chloride
after decarboxylation and reduction by Clemenson’s
(c) Fehling’s solution is a good ragent to detect aromatic
method
aldehydes
(d) Fehling’s test
(d) Both aldehyde and ketone can react with 2,
4- dinitrophenylhydrazine reagent 26. Which of the following organic compounds will give white
precipitate with AgNO3?
Objective Questions II
(a) C6H5NH3+Cl-
[One or more than one correct option]
(b) NaCl
20. Which of the following reactions occur during the
detection of nitrogen in organic substances by (c) 2,4,6-trinitro chlorobenzene
Lassaigne’s test? (d) Benzyl chloride
(a) Na + C + N 
 NaCN
(b) FeSO4 + 6NaCN 
 Na4[Fe(CN)6] + Na2SO4
PRACTICAL ORGANIC CHEMISTRY 235
Match the Following
Each question has two columns. Four options are (C) Additioin of HBr (r)

given representing matching of elements from can be with

Column-I and Column-II. Only one of these four (D) Tollen’s reagent (s) Me - CH = CH2
options corresponds to a correct matching, for
give white ppt. with
each question.
27. Column - I Column - II O
||
(pair of compounds) (test to distinguish) (t) Me  C  Me
OH OH 30. Column - I Column - II
(A) and (p) Liebermann’s nitroso (compound) (tests)
test
(A) (p) 2,4-DNP test

(B) (q)
(B) (q) Yellow ppt. with NaOH + I2
NH 2 Me
(C) and NH (r) Iodoform test O
Me ||
(D) CH3– CH2 – CHO (s) Lucas test (C) CH 3  C  H (r) Red ppt. with Fehling’s
and CH3– CHO solution
(t) NaHSO3
28. Column - I Column - II (D) (s) Silver mirror with Tollen’s
(pair of compounds) (identification test)
reagent
(A) and (p) Tollen’s reagent test Paragraph Type Questions
OH OH
Use the following passage, to solve Q. 31 to Q. 35
Passage
(B) and (q) Br2 + H2O test
Steam distillation is used to purify a compound which is steam
volatile and insoluble in water. The impurities should not be steam
O
|| volatile. It is based on the principle that liquid will boil when
(C) H  C  OH and (r) Lucas test partial vapour pressure of liquid and partial vapour pressure of
O steam both become equal to atmospheric pressure, P = p1 + p2. It
|| reduces the boiling point of a liquid.
CH 3  C  OH
Wt. of water distilled M.Wt. of water × VP of steam
(D) and (s) Iodoform test 
Wt. of substance distilled M.Wt. of substance × VP of aniline
(t) Ammonical Cu2Cl2 test
29. Column - I (reagents) Column - II
31. Isolation of essential oils from flowers, etc. is done by
(A) Product of reaction (p) Me - CH = CH - Me
(a) Steam distillation
of propyne with 1 per
(b) Distillation
cent HgSO4 and
(c) Fractional distillation
Dil. H2SO4
(d) Distillation under reduced pressure
(B) Br2 water test (q) Me - C  C - H
given by
PRACTICAL ORGANIC CHEMISTRY 236
32. Which of the following is steam volatile? 38. Compound Y contain
(a) o-nitrophenol (a) N (b) S
(b) p-nitrophenol (c) X (d) P
(c) p-hydroxy benzaldehyde 39. The chemical reaction taking place in Y, when it is fused
(d) Ethanol with fusion mixture is

33. Steam distillation is based on (a) 3Na + P + 4O 

 Na3PO4
(a) Dalton’s law of partial pressures
(b) 3Na2CO3 + 2P + [O] 
 2Na3PO4 + 3CO2
(b) Graham’s law of diffusion
(c) 3KNO3 + P + 30 
 K3PO4 + 3NO2 + O2
(c) Raoult’s law of non-volatile solute
(d) None of these (d) None of these
34. Which of the following cannot be separated by steam 40. The formula of yellow precipitate is
distillation? (a) (NH4)3PO4
(a) Nitrobenzene (b) Essential oil (b) Mo(PO4)
(c) Aniline (d) Glycerol (c) (NH4)3PO4. 12MoO3
35. Calculate weight of aniline distilled if weight of water (d) Mo(PO4)2
distilled is 100g when Porganic compound =100 mm and Use the following passage, to solve Q. 41 to Q. 45
Passage
PH 2O = 200 mm.
The 0.2 g of anhydrous organic acid gave on combustion
(a) 250 g (b) 258 g 0.04 g of water and 0.195 g of CO2. The acid is a dibasic
(c) 100 g (d) 25.8 g acid and 0.5 g of its silver salt leaves on ignition 0.355 g of
silver.
Use the following passage, to solve Q. 36 to Q. 40
41. The percentage of carbon in the compound is
Passage
(a) 50 (b) 52
Test (Q). A compound X was fused with Na metal and the
(c) 26.6 (d) 90
extract gave a white precipitate with AgNO 3. The
42. The percentage of hydrogen in the compound is
Lassaigne’s extract gave a red colouration with neutral
(a) 5.6 (b) 2.22
FeCl3.
(c) 4.44 (d) 10
Test (R). While compound Y when fused with Na metal
43. The molecular weight of the compound is
and subsequent analysis on its Lassaigne’s extract did
not give any characteristic test. (a) 90 (b) 100
Test (S). While compound Y on fusion with fusion mixture (c) 10 (d) 45
(sodium carbonate + potassium nitrate) or Na2O2, followed 44. The molecular formula of the compound is
by extraction, followed by addition of Conc. HNO3 and
(a) CHO (b) CHO2
ammonium molybdate gave a yellow precipitate.
(c) C2H2O4 (d) C3H6O2
36. Compound X contains
45. The empirical weight of the compound is
(a) N (b) S
(a) 90 (b) 100
(c) N + S (d) P
(c) 10 (d) 45
37. Compound X
(a) will contain halogens
(b) may contain halogens
(c) may contain only sulphur
(d) will contain only nitrogen
PRACTICAL ORGANIC CHEMISTRY 237

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QUALITATIVE ANALYSIS
 Chapter 16 239

QUALITATIVE ANALYSIS

1. INTRODUCTION
You know that the qualitative analysis involves the detection of 2.3 Anions of Class III
the anions and the cations present in an inorganic mixture. It is The anions of this class do not evolve any gas on treatment with
desirable to first detect the presence of anions and after that the acids. These are identified by formation of precipitate on treatment
cations. In this unit, we will discuss the scheme of detection of with certain reagents. Sulphate, borate and phosphate ions are
anions which will be followed by the scheme of analysis of the anions of Class III.
cations.
3. PRELIMINARY TESTS FOR THE ANIONS
2. CLASSIFICATION OF THE ANIONS
We shall first discuss the preliminary tests for detecting the
For the systematic identification of the anions present in any presence of anions of Class I and Class II, which will be followed
mixture, the anions are divided into following three classes: by their confirmatory tests. As there are no preliminary tests for
2.1 Anions of Class I the anions of Class III only their confirmatory tests will be
discussed.
The anions of Class I evolve gases or vapours on treatment with
dil. HCl or dil. H2SO4. These anions are carbonate, sulphite, 3.1 Preliminary Tests for the Anions of Class I
sulphide, thiosulphate, nitrite and oxalate. Take about 0.2g of dry mixture in a test tube. Add 2 cm3 of dilute
hydrochloric or sulphuric acid. If a gas is evolved, note its colour
2.2 Anions of Class II
and odour and draw inference with the help of Table. Heat the
The anions of Class II evolve gases or vapours on treatment test tube if necessary. If no gas is evolved, anions of this class
with conc. HCl or conc. H2SO4. These anions are fluoride, chloride, are absent in the mixture.
bromide, iodide, nitrate and oxalate.
Preliminary Tests for the Anions of Class I
Sl. Observation Inference Explanation / Reaction
No.
Colourless, suffocating SO 32  SO 32–(aq) + 2H +(aq)  H 2 O (l) + SO 2(g)
1 gas with smell of burning 2
may be present Cr2 O 7(aq) + 2H +(aq) + 3SO 2(g)
sulphur; the gas turns
acidified K 2Cr2O 7 paper 3
 2Cr(aq) 
 3SO 24(aq)  H 2 O (l)
green. green

2 Colourless gas with odour S 2–

S 2–
(aq) + 2H +(aq)  H 2 S(g)
of rotten egg which turns may be present Pb 2+(aq) + H 2S(g)  PbS(s) + 2H +(aq)
paper moist with Black
Pb(OAc)2 black.
Light brown gas which NO 2 2NO 2(aq) + 2H +(aq)  H 2O (l) + NO (g) +
3. turns KI starch paper blue.
may be present NO 2(g)
Colourless vapours with CH 3COO – CH 3COO –(aq) + H +(aq)  CH 3 COOH (g)
4. smell of vinegar on may be present
warming the test tube
Brisk effervescence in CO 32  (Carbonate) Pass the gas in a test tube containing small
5. cold with evolution of quantity of lime water. It turns milky.
colourless and odo-urless May be present
gas

SCAN CODE
Qualitative Analysis
QUALITATIVE ANALYSIS 240
When salts of the anions of Class I are treated with strong, non-
oxidising acids, corresponding acids are generated in the solution. H 2SO3(aq) 
 SO 2(g) +H 2 O(l)

2 
SO3(aq)  2H (aq) 
 H 2SO3(aq) 2HNO 2(aq) 
 NO(g)  NO2(g)  H 2 O(l)

NO 2(aq)  H (aq)


 HNO 2(aq) H 2 CO3(aq)  CO2(g)  H 2 O(l)

3.2 Preliminary Tests for the Anions of Class II

2 
S(aq)  2H (aq) 
 H 2S(aq) Take 0.2 to 0.3g of the mixture in a dry test tube and add 2-3
cm3 of conc. sulphuric acid drop-wise. Observe the reaction at
 
CH3COO(aq)  H (aq)  CH3COOH(g) room temperature and then warm the test tube gently. If no gas or
vapours are evolved, the anions of this class are absent. Draw
Out of these H2CO3, H2SO3 and HNO2 are thermally unstable and inference with the help of Table.
decompose into gaseous products, whereas H2S and CH3COOH
are evolved as vapours on warming:

Preliminary Tests for the Anions of Class II

Sl. N o. O bservation Inference Explanation / Reaction
–
1 Colourless, pungent Cl may be Cl (aq) + H + (aq)  HCl (g)
–

smelling gas is evolved, present HCl(g) + NH 3(g)  NH 4 Cl (g)

which gives white dense
fum es of NH 4 Cl when a
glass rod dipped in
aqueous amm onia is
placed in the evolved
gas.
2 Reddish brown gas is B r – may be Br – (aq) + 6H + (aq) + 3SO 4 2– (aq) 
evolved and the solution present 2H SO 4 – (aq) + B r 2(g) + 2H 2 O (l)
in the test tube acquires
a yellow-red colour.
3. Violet vapours of I 2 are I – may be 2I – (aq) + 6H + (aq) + 3SO 4 2– (aq) 
evolved, which turn the present
2HSO 4 2– (aq) + SO 2(g) + I 2(g) + 2H 2 O (l)
moist starch paper blue.
4. Pungent sm elling, NO 3 – may be NO 3 aq   H   aq   HNO 3  aq 
brown fumes of N O 2 are present
4H NO 3(aq)  4N O 2(g) + O 2(g) + 2H 2 O (l)
evolved. The evolution
Cu (s) + 4HNO 3(aq) 
of NO 2 increases on
Cu(NO 3 ) 2(aq) + 2NO 2(g) + 2H 2 O (l)
heating the reaction
mixture with copper
turnings.

SCAN CODE
Qualitative Analysis
QUALITATIVE ANALYSIS 241
3.3 Preparation of Solution for Identification of the Anions 2 2
S(aq )  Pb 
 PbS(s)
The preliminary tests described in the preceding section do  Black 
not always offer very conclusive evidence for the presence of
3.4.2 Tests for Sulphite Ions
anions in a mixture. Therefore, further tests have to be
performed for confirmation of those anions which are indicated Take 2 – 3 ml of S.E. and add 2 – 3 cm3 of BaCl2 solution to it.
by the preliminary tests and for the detection and confirmation A white precipitate may appear due to the presence of
of the anions of Class III which have no preliminary tests. SO 32  , SO 42- or excess of CO32  ions present in the solution.
These tests are called confirmatory tests and are performed on Filter the precipitate and divide into three parts.
the solution of anions which is prepared as described below.
1. To the first part, add dil. HCl. Evolution of SO2 gas which
3.3.1 Preparation of Water Extract (W.E.) turns acidified dichromate paper green confirms the
All common acetates, nitrites, nitrates and thiosulphates are presence of SO 32  ions
soluble in water. Confirmatory tests for these anions can be

performed with the water extract of the mixture. Water extract can BaSO3(s)  2H (aq)  5e   2
 Ba (aa )  SO 2(g)  H 2 O (l)

be prepared by boiling 1-2g of the mixture with 10-15 cm3 distilled

SO 2  Cr2 O 7 2   H  
 SO 4 2   Cr 3  H 2 O
water in a boiling tube for a minute or two. Residue, if any, is
2. To the second part, add a few drops of KMnO4 solution
filtered. The filtrate is called water extract (W.E.). and acidify with dil. H2SO4. If the pink colour of KMnO4 is
3.3.2 Preparation of Sodium Carbonate Extract (S.E.) discharged, the presence of SO 32  ions is confirmed.
If the mixture is found to be partially or wholly insoluble in water, 
BaSO3(s)  H 2 O(l) 
 BaSO4(s)  2H (aq)  2e]  5
it is boiled with saturated sodium carbonate solution. This
treatment converts the anions present in mixture into soluble MnO4(aq)  8H(aq)

 5e  2
 Mn (aq)  4H2 O(l) ]  2
sodium salts as a result of double decomposition e.g., –––––––––––––––––––––––––––––––––––––––––––
BaSO 4(s)  Na 2 CO3(aq) 
 BaCO 3(s)  Na 2SO 4(aq)
H2 O
5BaSO3(s)  2MnO 4(aq)  6H (aq)



2
PbCl 2(s)  Na 2 CO3(aq) 
H2O
 PbCO 3(s)  2NaCl(aq) 5BaSO 4(s)  2Mn (aq)  3H 2 O(l)
For preparing sodium carbonate extract, take 0.5-1.0g of powdered 3. To the third part, add I2 solution. If colour of iodine is
mixture, 1.0-2.0g of sodium carbonate and 5-10 cm3 of distilled discharged, SO 32  is confirmed.
water in a boiling tube or a 50 ml beaker. Heat with stirring for 5-
BaSO3(s)  I2(aq )  H 2 O(l) 
 BaSO4(s)  2HI(aq)
10 minutes. Cool the contents and filter. The filtrate is called
sodium carbonate extract (S.E.). This extract is used for confirming 3.4.3 Tests for the Nitrite Ions
the presence of most anions except for carbonate since sodium 1. Take 5 drops of W.E. in a test tube. Dilute with 5 drops of
carbonate has been added during its preparation. distilled water. Add 5M acetic acid until the solution is just
3.4 Confirmatory Tests for the Anions acidic. Cool the test tube in a cold water bath. Add 2-3 drops
After preparation of the water extract or the sodium carbonate of freshly prepared 0.2M FeSO4 solution to the cooled
extract, the following tests are performed to confirm the solution. Appearance of a brown colour throughout the
presence of various anions in the mixture. solution confirms the presence of nitrite ions.

3.4.1 Tests for the Sulphide Ions NO2(aq)  CH3 COOH (aq)  
 HNO 2(aq)  CH3 COO (aq)
1. Take 1 ml of sodium carbonate extract in a test tube and add 3HNO 2(aq) 
 HNO3(aq)  H 2 O(l)  2NO(g)
1 – 2 ml of sodium nitroprusside solution. A purple or violet 2 2
colour confirms sulphide ions: [Fe(H 2 O)6 ](aq)  NO(g) 
[Fe(H 2 O)5 NO](aq)  H 2 O(l)

2 2 4
2. To 1 cm3 of W.E. add 5 drops of KI solution, 1 cm3 of starch
S(aq)  [Fe(CN)5 NO](aq) 
 [Fe(CN)5 NOS]aq
purple or violet colour
solution and 1 cm3 of dil. H2SO4. Appearance of a deep blue
colour confirms the presence of nitrite ions.
2. Take 1 – 2 ml of S.E. in a test tube, acidify it with acetic acid
and boil to remove CO2. Then add 1 – 2 ml of lead acetate 2NO2(aq)  4H (aq)  2I(aq

) 
 2NO(g)  I2(aq)  2H 2 O(l)
solution. Formation of black precipitate confirms sulphide
ions: I2(aq) + Starch 
 Blue coloured complex

SCAN CODE
Qualitative Analysis
QUALITATIVE ANALYSIS 242
You should note that the nitrite ion is a moderately strong 4NaCl(s)  K2Cr2O7(s)  3H2SO4(l) 

oxidizing agent in acidic medium. It oxidizes
K2SO4(s)  2Na2SO4(s)  CrO2Cl2(g)  3H2O(l)
S2  , SO 32  , S2 O 32  and I– ions to S, SO 2-4 , S + SO42- and I2 Chromyl chloride gas

respectively. Therefore, these anions cannot be present if CrO2Cl2(g)  4NaOH(aq) 


NO2– ions are present in the mixture.
2
Na2CrO4(aq) 2NaCl(aq) 2H2O(l)
S(aq)  NO2(aq)  2H (aq)


 S(s)  NO(g)  H 2 O(l)
2 Na 2 CrO 4(aq )  Pb(CH 3 COO) 2(aq ) 

SO3(aq)  2NO2(aq)  2H(aq)

 2
 SO4(aq)  2NO(g)  H 2 O(l)
2   PbCrO 4(s)  2CH 3 COONa (aq )
S2 O3(aq )  2NO2(aq)  2H (aq ) 
 SO24(aq)  S(s)  2NO(g)  H 2 O(l)
yellow
2I(aq)  2NO2(aq)  4H (aq)


 I 2(s)  2NO(g)  2H 2 O(l)
Due to the formation of chromyl chloride gas, this test is
3.4.4 Test for the Nitrate Ions
called chromyl chloride test. The test fails if the mixture
Take 2 cm3 W.E. in a test tube. Add 4 cm3 concentrated sulphuric contains chlorides of Hg2+, Sn2+, Pb2+ or Ag+.
acid, mix two liquids thoroughly and cool the mixture under a
3.4.6 Test for the Bromide Ions
stream of cold water from the tap. Pour few cc of saturated
1. Acidify 2-3 ml of S.E. with dil. HNO3 and boil off CO2. Add
solution of FeSO4 slowly down the side of the test tube so that it AgNO3 solution. Formation of a light yellow precipitate which
forms a separate layer on top of the solution in the test tube. A is partially soluble in aqueous ammonia solution, confirms
brown ring will be formed at the zone of contact of the two liquids. the presence of bromide ions.
 

NO3(aq) 
 4H (aq) 
 3Fe2(aq)  
 3Fe3(aq)  NO(g)  2H 2 O(l) Br(aq)  Ag (aq) 
 AgBr(s)
Light yellow ppt.
2 2
[Fe(H 2 O)6 ](aq)  NO(g) 
[Fe(H 2 O)5 NO](aq)  H 2 O(l) 2. Take 2 cm of S.E. acidify it with dil. HCl and boil off CO2.
3

This test for nitrate ion is based on its ability to oxidize Fe2+ to Add 2 cm3 of carbon disulphide, dichloromethane or carbon
tetrachloride. Then add chlorine water drop-wise and shake.
Fe3+ in acidic solution with the product of NO gas. Since NO is
Bromide ions are oxidized to bromine, which imparts an
more soluble in water at low temperature, in well cooled solution orange colour to the organic layer. This confirms the
it reacts with excess Fe2+ present in solution to form brown presence of bromide ions in the mixture.
nitrosyliron (II) complex ion, [Fe(H2O)5NO]2+. Nitrite, bromide and  
2Br(aq)  Cl 2(aq) 
 2Cl(aq)  Br2(l)
iodide ions interfere in this test.
Br2(l)  CS2(l) 
 Orange colour
3.4.5 Test for the Chloride Ions
3.4.7 Tests for the Iodide Ions
1. Acidify 2–3 cm3 of S.E. with dil. HNO3. Boil off CO2. Then
1. Acidify 2 – 3 cm3 of S.E., with dil. HNO3 and boil off CO2. Add
add AgNO3 solution. Formation of a curdy white precipitate,
AgNO3 solution. Formation of a pale yellow precipitate
which is soluble in aqueous ammonia, confirms the presence insoluble in aqueous ammonia confirms the presence of
of chloride ions in the mixture. iodide ions in the mixture.
 
Cl(aq)  Ag (aq) I(aq )  Ag (aq) 
 AgI (s)


 AgCl(s)
Pale yellow ppt.

AgCl(s)  2NH3(aq) 
[Ag(NH ) ] 
 Cl  2. Take 2 cm of S.E. in a test tube. Acidify it with dil. HCl and
3
3 2 (aq) (aq)
boil off CO2. Add 2 cm3 carbon disulphide or dichloromethane
2. Heat 0.5g of dry mixture with 0.5g of K2Cr2O7 and 2 ml of or carbon tetrachloride. Then add chlorine water drop-wise
conc. H2SO4 in a dry test tube, red vapours of chromyl and shake. Iodide ions are oxidized to iodine, which imparts
chloride will be evolved. Pass the vapours in dil. NaOH a violet colour to the organic layer.
 
solution, a yellow solution will be obtained. Acidify the 2I(aq)  Cl 2(aq) 
 I 2(s)  2Cl(aq)
solution with acetic acid and then add lead acetate solution.
CS2(l)  I 2(s) 
 Violet colour
Formation of a yellow precipitate of lead chromate, which is
soluble in NaOH, confirms the presence of chloride ions.

SCAN CODE
Qualitative Analysis
QUALITATIVE ANALYSIS 243
The violet colour disappears on addition of excess of chlorine Colour of flame Inference
water. This confirms the presence of iodide ions in the
1. Golden yellow Sodium
mixture.
2. Violet Potassium
I 2(s)  Cl 2(aq) 
 2ICl(aq )
Iodine monochloride (colourless) 3. Brick red Calcium

3.4.8 Test for the Sulphate Ions Crimson red Strontium

Take 1 – 2 cm3 of S.E. in a test tube. Acidifiy it with dil. HCl and 5. Apple green Barium
boil off CO2. Add BaCl2 solution. Appearance of a white precipitate, 6. Green with a blue centre Copper
which is insoluble in conc. HCl and conc. HNO3, confirms the
presence of sulphate ions. NOTE
 2 Flame test should not be performed in the presence of As, Sb,
SO 24(aq)  Ba (aq) 
 BaSO4(s)
Bi, Sn and Pb as these radicals form alloy with platinum and
hence, the wire is spoiled.
4. TEST OF CATIONS
4.1.2 Charcoal Cavity Test
4.1 Flame Test on Dry Samples
This test is carried out on a charcoal block in which a small cavity
4.1.1 Bunsen Flame has been made by a knife. About 0.1 g of the substance is mixed
Some volatile salts impart characteristic colour to the non- with 0.2 g of anhydrons Na2CO3 or fusion mixture and the mixture
luminous flame. The chlorides of the metals are more volatile in is place din the cavity. The mass is moistened with a drop of
comparison to other salts. The metal chloride volatilises and its water and heated in a reducing flame with the blow pipe. The
thermal ionisation takes place. head or incrustation formed is observed. When metallic salt is
heated with Na 2CO 3, the metal carbonate is formed which
NaCl  Na   Cl  decomposes into oxide. The carbon of the block reduces the
CaCl2  Ca 2   2Cl  oxide into metal. For example.

The cations impart a characteristic colour to the flame as these CuCl 2  Na 2 CO3  CuCO3  2NaCl
absorb energy from the flame and transmit the smae as light of CuCO3  CuO  CO 2
characteristic colour. CuO  C  Cu  CO

Colour of Bead and Inference

Colour of Bead Colour of Residue or Incrustation Inference

White bright bead which does Incrustation does not form Ag 
not impart mark on paper on
rubbing
White brittle bead White Incrustation Sb3
Red bead Reddish brown incrustation Cu 2 
Brittle bead Violet Red when hot and yellow incrustation Bi3
when cold
White soft ball which mark on Brown incrustation when hot and yellow when Pb 2 
paper cold
Bead does not from Yellow incrustation when hot while white when Zn 2
cold
–– Garlic smell like fumes As3
–– Yellow incrustation on hot while on cold dirty Sn 2 
white incrustation
–– Reddish brown incrustation Cd 2 
–– Incrustation does not form but black residue is Fe, CO, Ni, Mn
left in the cavity

SCAN CODE
Qualitative Analysis
QUALITATIVE ANALYSIS 244
4.1.3 Cobalt Nitrate Bead Test obtained in the oxidizing and the reducing flames, borates
This is also like charcoal cavity test. This test is performed in corresponding to varying stages of oxidation of the metal are
oxidizing flame rather than in reducing flame. produced. Thus, with the copper salts in the oxidizing flame.

The oxides of Al, Ca, Sr, Ba and Mg are not reduced by charcoal; Na 2 B 4 O 7 
 2NaBO 2  B2 O 3
they are infusible and glow brightly when strongly heated. If the
white residue or white incrustation left on a charcoal block is CuO  B2 O3 
 Cu(BO) 2
Copper(II)metaborate
treated with a drop of cobalt nitrate solution and again heated, a
bright blue colour, which probably consists of either a compound
or a solid solution of cobalt II and aluminium oxide indicates the The reaction CuO  NaBO 2 
 NaCuBO 3
Orthoborate

presence of aluminium. Other colours are listed in Table.

probably also occurs. In the reducing flame (i.e. in the presence
ZnSO 4  Na 2 CO3 
 ZnCO3  Na 2SO 4 of carbon), two reactions may take place.
1. The coloured copper (II) is reducing to colourless copper (I)
ZnCO3 
 ZnO  CO 2
metaborate.
2Co(NO3 )2  2CoO  4NO2  O 2
2Cu(BO 2 )2  2NaBO 2  C 

CoO  ZnO  CoZnO 2
Cobalt zincate
2CuBO 2  Na 2 B4 O7  CO 
(green residue)
2. The copper (II) borate is reduced to metallic copper, that the
Colour of Residue and Inference bead appears red and opaque.
Colour of Residue Inference
2Cu(BO 2 ) 2  4NaBO2  2C 

Green Zn2+
Blue Al3+ 2Cu  2Na 2 B4 O7  2CO 
Light Pink Mg2+ With iron salts Fe(BO2)2 and Fe(BO2)3 are formed in
Bluish Pink PO34 , AsO34 , silicates borates reducing and oxidizing flames respectively.
Luminous and Non-luminous flame
4.1.4 Borax Bead Test 1. Inner blue cone ADB consisting largely of unburnt gas.
A point wire is used for borax bead test. The free end of the point 2. A luminous tip at D (this is only visible when the air holes are
wire is coiled into small loop through which ordinary match will slightly closed).
barely pass. The loop is heated in Bunsen flame until it is red hot 3. An outer mantle ACBD in which complete combustion of gas
and then quickly dipped into powdered borax Na2B4O7×10H2O. occurs.
The adhering solid is held in the hottest part of the flame, the salt C
swells up as it loses its water of crystallization and shrinks upon Upper oxidizing zone
the loop forming a colourless, transparent, glass like bead D
consisting of a mixture of sodium metaborate and boric anhydride. Hottest portion of the flame

Lower temperature zone

Na 2 B 4 O 7 
 2NaBO 2  B2 O 3
the head is moistened and dipped into the finely powdered AA B

substance so that a minute amount of it adheres to the bead. It is

important to employ a minute amount of substance as otherwise
the bead will become dark and opaque in the subsequent heating.
The head and adhering substance are first heated in the lower
reducing flame, allowed to cool and the colour is observed again.
The coloured borax beads are due to the formation of colour (Luminous flame is obtained when air holes are completely closed)
borates; in those cases when different coloured beads are
(Non luminous flame is obtained when air holes are completely
opened)

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QUALITATIVE ANALYSIS 245

Colours of Borax Beads

Oxidizing Flame Reducing Flame
Metal
Hot Cold Hot Cold
Green Blue Colourless Opaque Red brown Copper
Yellowish green Yellow Green Green Iron
Yellow Green Green Green Chromium
Violet Amethyst Colourless Colourless Manganese
Blue Blue Blue Blue Cobalt
Violet Reddish Brown Green Grey Nickel
Yellow Colourless Brown Brown Molybdenum
Rose Violet Rose Violet Red Violet Gold
Yellow Colourless Yellow Yellowish brown Tungeston
Yellow Pale Yellow Green Bottle green Uranium
Yellow Greenish Yellow Brownish Green Vanadium
Yellow Colourless Grey Pale violet Titanium
Orange Red Colourless Colourless Colourless Cerium

4.2 First Group Radicals 2. H2S (gas or saturated aqueous solution) in neutral or dilute
2
Radicals: Pb2+, Hg , Ag+ acid medium, black ppt. of lead sulphide is obtained
2

Pb 2   H 2 S 
 PbS  2H 
Group Reagent – dil. HCl
Precipitates as – Chlorides When H2S gas is introduced into a mixture which contains a
ppt. of white lead chloride, the latter is converted into lead
Since PbCl2 is not completely precipitated in group I as chloride
because of its solubility in hot water is 33.4g/litre of solvent. So sulphide (black) in a precipitate exchange reaction.
Pb2+ has been placed in both the groups.  PbS  2H   2Cl 
PbCl2   H 2 S 
4.2.1 Reactions of Pb2+ ion 3. NH3 solution: White ppt of Pb(OH)2 is obtained
1. Dilute HCl: A white ppt. in cold solution of the acid is not
Pb 2   2NH 3  2H 2 O 
 Pb(OH) 2  2H 
too soluble.
Pb(OH)2 is insoluble in NH3 solution excess.
 PbCl 2 
Pb 2   2Cl 
White 4. NaOH: White ppt. of Pb(OH)2
Soluble in hot water (33.4g/L at 100°C, 9.9 g/L at 20°C)
Pb 2   2OH  
 Pb(OH) 2 
It is also soluble in conc. HCl or conc. KCl when the
tetrachloroplumbate (II) ion is formed. The ppt. is dissolved in excess of NaOH, when
tetrahydroxoplumbate (II) ions are formed.
PbCl 2  2Cl  
[PbCl 4 ]2 
Pb(OH) 2   2OH  
[Pb(OH) 4 ]2 
If the ppt is washed and dil. NH3 is added, no visible change
thus, lead hydroxide has an amphoteric character.
occurs (difference from Hg22+ or Ag+ ions), through a ppt.
exchange reaction takes place and lead hydroxide is formed. 5. H2SO4 (or soluble sulphate) white ppt. of PbSO4 is obtained
Pb 2   SO42  
 PbSO 4 
(white)

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6. K2CrO4: Potassium chromate in neutral, acetic acid or 3. Ammonia Solution: Brown ppt. of Ag2O is obtained.
ammonium solution yellow ppt of lead chromate is obtained.
2Ag   2NH 3  H 2 O 
 Ag 2 O  2NH 4
2 2 Brown
Pb  CrO 4 
 PbCrO 4  (yellow)
The reaction reaches an equilibrium and therefore
7. KI: yellow ppt of lead iodide is formed.
precipitation is incomplete at any stage (if the NH4NO3 is
Pb 2   2I  
 PbI2  present in the original solution or the solution is strongly
yellow ppt.
acidic, no precipitation occurs). The ppt dissolves in excess
The ppt. is moderately soluble in boiling water to yield a of NH3 solution, and diammine silver (I) complex is formed.
colourless solution, from which it separates as golden yellow
 2[Ag(NH 3 ) 2 ]  2OH 
Ag 2 O  4NH 3  H 2 O 
plates on cooling.
4. Sodium Hydroxide: Brown ppt. of Ag2O is obtained.
An excess of a more conc.(6M) solution of the reagent
dissolves the ppt. and tetraiodoplumbate (II) ions are formed 2Ag   2OH  
 Ag 2 O  H 2 O
Brown

[PbI 4 ]2
PbI 2  2I   A well washed suspension of the ppt. shows a slight alkaline
The reaction is reversible, on cooling ppt. reappears. reaction owing to the hydrolysis reaction.

4.2.2 Reactions of Silver (I) Ions  2Ag(OH) 2  

Ag 2 O  H 2 O   2Ag   2OH 
1. Dilute Hydrochloric Acid (or Soluble Chlorides): White ppt. The ppt. is insoluble in excess of NaOH. The ppt. dissolves
of AgCl is obtained. in NH3 solution and in HNO3.

Ag   Cl  
 AgCl   2[Ag(NH 3 ) 2 ]  2OH 
Ag 2 O  4NH 3  H 2 O 
White
Ag 2 O  2H  
 2Ag   H 2 O
With conc. HCl precipitation does not occur. After decanting
the ppt., it can be dissolved in conc. HCl, when 5. Potassium Iodide: Yellow ppt.. of AgI is obtained.
dichloroargentate complex is formed.
Ag   I  
 AgI 
[AgCl2 ]
AgCl  Cl   
The ppt. is insoluble in dil. or conc. NH3 solution, but
On dilution with H2O, the equilibrium shifts back to the left dissolves readily in KCN and in Na2S2O3.
and the ppt. reappears.
AgI  2CN  
[Ag(CN) 2 ]  I
Dilute NH3 solution dissolves the ppt., to form the diamine
silver ion. AgI  2S2 O 32  
[Ag(S2 O 3 ) 2 ]3  I 

[Ag(NH3 ) 2 ]  Cl 6. Potassium Chromate: Red ppt. of Ag2CrO4 is obtained.

AgCl  2NH3 
Dilute HNO3 or HCl neutralizes the excess of NH3, and the 2Ag   CrO 24  
 Ag 2 CrO 4 
Re d
ppt. reappears because the equilibrium is shifted back
The ppt. is soluble in diluted HNO3 acid and NH3 solution.
towards the left.
 2Ag   Cr2 O 72   H 2 O
Ag 2 CrO 4  2H  
2. H2S (Gas or Saturated aqueous Solution): Black ppt. of Ag2S Orange
is formed.
 2[Ag(NH 3 ) 2 ]  CrO 42 
Ag 2 CrO 4  4NH 3 
2Ag   H 2 S 
 Ag 2 S  2H 
Black 7. Potassium Cyanide: When added drop wise to a neutral
Hot conc.HNO3 decomposes the Ag2S, and sulphur solution of AgNO3; white ppt. of AgCN is obtained.
remains in the form of a white ppt. Ag   CN  
 AgCN 
White
3Ag 2S  8HNO3 
 When KCN is added in excess, ppt. dissolves owing to
3S  2NO  6Ag   6NO3  4H 2 O formation of dicyanoargentate (I) ion.
white
If the mixture is heated with conc. HNO3 for a considerable AgCN   CN  
[Ag(CN) 2 ]
time, sulphur is oxidized to SO 24  and the precipitate
disappears.

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QUALITATIVE ANALYSIS 247

4.3 Second Group Radicals As3+, Sb3+ and Sn2+ ions can be oxidized to As5+, Sb5+ and Sn4+
ions respectively. On the other hand, the latter three can be
Group Reagent H2S in presence of dil. HCl
reduced by proper reducing agents.
IIA Cu2+, Pb2+, Bi3+, Cd2+, Hg2+
4.3.3 Reactions of Mercury (II) Ions: [Hg(NO3)2]
IIB As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+
1. Hydrogen Sulphide (Gas or Saturated Aqueous Solutions):
Precipitates as Sulphides In the presence of dilute (1M) HCl, initially a white ppt of
Black PbS, CuS, HgS mercury (II) chlorosulphide forms, which reacts with further
Yellow CdS, As2S3, As2S5, SnS2 amounts of H2S and finally a black ppt. of HgS is formed.

Orange Sb2S3, Sb2S5 3Hg 2   2Cl  

 Hg 3 S2 Cl 2  4H 
White
Brown Bi2S3, SnS
4.3.1 Copper Sub-Groups  HgS  2H   2Cl 
Hg 3 S2 Cl 2   H 2 S 
Black
The copper sub-group consists of Hg(II), Pb(II), Bi(III), Cu(II)
and Cd(II). Although the bulk of the lead ions are precipitated HgS is one of the least soluble precipitates known (Ksp = 4 ×
with dil. HCl together with other ions of the group –I. In the 10–54).
course of systematic analysis therefore, lead ions will still be HgS is insoluble in water, hot dilute HNO3, alkali hydroxides
present when the precipitation of the second group of the or colourless ammonium sulphide.
cations is the task. Sodium sulphides (2M) dissolves the precipitate when the
The chlorides, nitrates and sulphates of the cations of the copper disulphomercurate (II) complex ion is formed:
sub-group are quite soluble in water. The sulphides, hydroxides
HgS  S2 
[HgS2 ]2 
and carbonates are insoluble. Black

4.3.2 Arsenic Sub-Group Adding NH4Cl to the solution, HgS precipitates again
The arsenic sub-group consists of As , As , Sb , Sb and Sn
3+ 5+ 3+ 5+ 4+
aqua-regia dissolves the precipitate.
ions. These ions both acids and bases. Thus As(III) oxide can be
3HgS  6HCl  2HNO3 

dissolved in HCl (6M) and As(III) cations are formed.
3HgCl2  3S  2NO  4H 2 O
 2As3  6Cl  3H 2 O
As 2 O3  6HCl 
(Basic) HgCl 2 is practically undissociated under these
The same time As2O3 dissolves in NaOH (2M) forming arsenite circumstances. Sulphur remains as a white ppt., which
anions. however dissolves readily if the solution is heated, to form
H2SO4.
As 2 O3  6OH  
 2AsO33   3H 2 O
The dissolution of sulphides in ammonium polysulphide can be  SO 42   2H   2NO 
2HNO 3  S  
White
regarded as the formation of thiosalts from anhydrous thioacids.
2. Ammonia Solution: White precipitate with a mixed
Thus the dissolution of As2S3 (anhydrous thioacid) in ammonium
composition is obtained, essentially it consists of HgO
sulphide (anhydrous thiobase) yield the formation of ammonium
and mercuryamidonitrate.
and thioarsenite ions (a thiosalt)
As 2 S3  3S2  
 2AsS33 2Hg 2   NO3  4NH 3  H 2 O 


All the sulphides of the arsenic sub-group dissolve in ammonium HgO  Hg(NH 2 )NO3  3NH 4
White
sulphide except tin (II) sulphide (SnS); to dissolve latter,
3. Sodium Hydroxide: When added in small amounts,
ammonium polysulphide is needed, which acts partly as an
brownish-red precipitate with varying composition is
oxidizing agent, thiostannate ions being formed:
obtained; if added in stoichiometric amounts, the
SnS  S22  
 SnS32  precipitate turns to yellow when HgO is formed.
Note that while tin is bivalent in the tin (II) sulphide ppt., it is
tetravalent in the thiostannate ion. Hg 2  2OH  
 HgO  H 2 O
Yellow

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QUALITATIVE ANALYSIS 248
4. Potassium Iodide: When added slowly to the solution, red 2Cu 2   SO 24   2NH 3  2H 2 O 

precipitate of HgI2 is obtained. Cu(OH) 2 CuSO 4  2NH 4
Blue
Hg 2   2I  
 HgI 2 (Red)
The precipitate dissolves in excess reagent, when Which is soluble in excess reagent, when a deep blue
colourless tetraiodomercurate (II) ions are formed colouration is obtained owing to the formation of tetrammine
copper (II) complex ion.
HgI 2  2I  
[HgI 4 ]2 
Re d
Cu(OH) 2  CuSO 4  8NH 3 

An alkaline solution of K2[HgI4] serves as a selective and
2[Cu(NH 3 ) 4 ]2   SO 42  2OH 

sensitive reagent for NH ion (Nessler’s Reagent).
4
Blue

7. Cobalt (II) Thiocyanate Test: To the test solution add an If the solution contains NH 4 salt (or it was highly acidic
equal volume of Co(SCN)2 (about 10% freshly prepared), larger amounts of NH3 were used up for its neutralization)
and stirr the wall of the vessel with a glass rod. A deep precipitation does not occur at all, but the blue colour
blue crystalline precipitate of cobalt appears right away.
tetrathiocyanatomercurate (II) is formed.
Hg 2   Co 2   4SCN  
 Co[Hg(SCN) 4 ]  3. NaOH: In cold solution blue precipitate of Cu(OH)2 is
Deep blue crystalline
formed.
4.3.4 Reactions of Copper (II) Ions
Cu 2   2OH  
 Cu(OH) 2 
1. Hydrogen Sulphide (Gas or Saturated aqueous solution): Blue

Black precipitate of CuS is formed. The precipitate is insoluble in excess reagent. When
heated, the precipitate is converted to black CuO by
Cu 2   H 2 S 
 CuS  2H 
dehydration.
Ksp (CuS) = 10–44
Cu(OH) 2  
 CuO  H 2 O
Black
The solution must be acidic (1M in HCl) in order to obtain a Blue

crystalline, easily filterable precipitate. In the absence of

acid, or in very slightly acid solutions a colloidal, brownish 4. KCN: When added sparingly forms first a yellow
black precipitate or colouration is obtained. By adding some precipitate of copper (II) cyanide.
acid and boiling, coagulation can be achieved.
Cu 2   2CN  
 Cu(CN)2 
The precipitate is insoluble in boiling dilute (1M) H2SO4 Yellow

(distinction from Cd), in sodium hyodrixide, Na2S and (NH4)2S. The precipitate quickly decomposes into copper (II) cyanide
It is only very slightly soluble in polysulphides. and cyanogens (highly poisonous gas) is liberated.
Hot conc. HNO3 dissolves the CuS, leaving behind sulphur 2Cu(CN) 2  
 2CuCN   (CN) 2 
as a white precipitate.
Excess of KCN dissolves the precipitate and the
3CuS  8HNO3 
 colourless tetracyanocuprate (I) complex is formed.
3Cu 2  6NO3  3S  2NO  4H 2 O CuCN + 3CN-  [Cu(CN) ]3-
White 4
Colourless
When boiled for longer, sulphur is oxidized to H2SO4 and a
clear solution is obtained. The complex is so stable that H2S cannot precipitate
copper I sulphide from this solution (distinction from Cd).
 SO 24   2NO  2H 
S  2HNO 3  4.3.5 Reactions of Bi3+ Ions
2. Ammonia Solution: When added slowly blue precipitate of 1. With H2S (Gas or saturated aqueous solution): Blackish
basic copper sulphate is formed. brown precipitate of Bi2S3 is obtained.
2Bi 3  3H 2 S 
 Bi 2 S3  6H 
Black

Insoluble in cold. Dilute acid in (NH4)2S

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QUALITATIVE ANALYSIS 249
Boiling conc. HCl dissolves the precipitate when H2S gas 4.4.1 Reactions of Fe3+ ions
is evolved. 1. NH3 Solution: Reddish brown, gelatinous precipitate of
Fe(OH)3 insoluble in excess of the reagent, but soluble in
 2Bi 3  6Cl  3H 2 S 
Bi 2 S3  6HCl 
acids.
Hot dil. HNO3 dissolves Bi2S3, leaving behind sulphur in
the form of a white precipitate. Fe3  2NH 3  3H 2 O 
 Fe(OH)3  3NH 4
(K sp  3.81038 )

Bi2S3  8H  2NO3 
 Iron (III) hydroxide is converted during strong heating into
3 Fe2O3 the ignited oxide is soluble with difficulty in dilute
2Bi  3S  2NO  4H 2 O
acids, but dissolves in vigorous boiling with conc. HCl.
2. With NH3 Solution: White basic salt of variable
composition. The approximate chemical reaction is 2Fe(OH)3  
 Fe 2 O3  3H 2 O
Bi 2S3   NO3  2NH 3  2H 2 O 
 Fe 2 O 3  6H  
 2Fe 3  3H 2 O
Bi(OH) 2 NO3   2NH 4 2. NaOH Solution: Reddish brown precipitate of Fe(OH)3 in
white
solute in excess of NaOH.
Bi(OH)2NO3 does not dissolve in excess NH3
Fe3  3OH  
 Fe(OH) 3 
(distinction from Cu and Cd) Reddish brown

3. With NaOH: White precipitate of Bi(OH)3 is obtained. 3. Hydrogen Sulphide: In acidic solution reduces Fe3+ to Fe2+
and sulphur is formed as a milky white precipitate.
Bi 3  3OH  
 Bi(OH)3 
White
2Fe3  H 2 S 
 2Fe 2   2H   S 
Slightly soluble in excess NaOH Soluble in acid White

If a neutral solution of FeCl3 is to a freshly prepared, saturated

Bi(OH)3  3H  
 Bi 3  3H 2 O
solution of H2S, a bluish colouration appear first, followed
When boiled precipitate loses water and turns yellowish by the precipitation of sulphur. The blue colour is due to a
white colloidal solution of sulphur of extremely small particle size.
Bi(OH) 3  
 BiO  OH  H 2 O
Yellowish white 4. Ammonium Sulphide: A black precipitate, consisting of Fe
Both the hydrated and the dehydrated precipitate can be and sulphur is formed.
oxidised by 4-6 drops of conc. H2O2 when yellowish brown 2Fe3  2S2  2FeS  S 
bismuthate ions are formed.
In HCl black FeS precipitate dissolves and white colour of
 BiO 3  H   H 2 O
BiO  OH   H 2 O 2  sulphur becomes visible.
4. Potassium Iodide: When added drop-wise black FeS  2H  
 H 2 S   Fe 2 
precipitate of BiI3 is obtained.
From alkaline solution black iron (II) sulphide is obtained.
Bi3  3I  
 BiI3 
Black 2Fe 3  3S 
 Fe 2 S3 
The precipitate dissolves readily in excess reagent when On acidification with HCl, Fe3+ ions are reduced to Fe2+ and
orange coloured tetraiodobismuthate ions are formed. sulphur is formed.

[BiI 4 ]
BiI3  I   Fe 2 S3  4H  
 2Fe 2   2H 2 S  S 
The damp iron (II) sulphide precipitate, when exposed to air,
When diluted with H2O, the above reaction is reversed and
is slowly oxidized to brown Fe(OH)3.
black precipitates of BiI3 reappear.
4FeS  6H 2 O  3O 2 
 4Fe(OH)3  4S
4.4 Third Group Radicals Reddish brown

Radicals Fe2+, Fe3+, Al3+, Cr3+, Cr6+ 5. KCN: When added slowly, produces a reddish brown
Group Reagent NH4OH in presence of NH4Cl precipitate of Fe(CN)3.
Fe(OH)3 Red Brown Fe3  3CN  
 Fe(CN)3 
Al(OH)3 Gelatinous white Re ddish brown

Cr(OH)3 Green (cotton like)

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QUALITATIVE ANALYSIS 250
In excess, reagent dissolves giving a yellow solution,  Al(OH)3   H 2 O
[Al(OH) 4 ]  H  
when hexacyanoferrate (III) ions are formed.
 Al3  3H 2 O
Al(OH)3  3H  
Fe(CN) 3  3CN  
[Fe(CN) 6 ]3
The precipitation of Al(OH)3 by solutions of NaOH and NH3
6. K4[Fe(CN)6]: Solution intense blue precipitate of Fe(III) does not take place in the presence of tartaric acid, citric
hexacyanoferrate (Prussian blue)
acid because of the formation of soluble complex salt.
4Fe3  3[Fe(CN)6 ]4  
 Fe 4 [Fe(CN)6 ]3  3. Ammonium Sulphide Solution: A white precipitate
Iron(III)hexacyanoferrate(II)
(Prussian blue) Al(OH)3 is obtained.
The precipitate is insoluble in dilute acids, but decomposes
2Al3  3S2   6H 2 O 
 2Al(OH) 3  3H 2 S 
in conc. HCl. A large excess of the reagent dissolves it partly
or entirely, when an intense blue solution is obtained. NaOH 4. Sodium Acetate Solution: No precipitate is obtained in
turns the precipitate red as Fe2O3 and [Fe(CN)6]4– ions are cold, neutral solution, but on boiling with excess reagent,
formed. a voluminous precipitate of basic aluminium acetate
Al(OH)2(CH3COO) is formed
Fe 4 [Fe(CN)6 ]3  12OH  

Al3  3CH 3COO  2H 2 O 

4Fe(OH)3  3[Fe(CN)6 ]4
Al(OH) 2 (CH3 COO)  2CH 3COOH
4.4.2 Reactions of Al3+ Ions White

1. Ammonia Solution: White gelatinous precipitate of Al(OH)3,
slightly soluble in excess of reagent. The solubility is
decreased in presence of NH4+ ions. A small proportion of
the precipitate passes into the solution as colloidal Al(OH)3
[Al(OH)3 solution], the solution is coagulated on boiling the
solution or upon the addition of soluble salts (e.g. NH4Cl)
yielding a precipitate of Al(OH)3, known as Al(OH)3 gel. To
ensure complete precipitation NH-3 solution is added in slight
excess and the mixture is boiled until the liquid has a slight
odour of NH3. When freshly precipitated, it dissolves readily
in strong acids and bases, but after boiling it becomes
sparingly soluble.
3
Al  3NH 3  3H 2 O 
 Al(OH)3  3NH  precipitates of Cr(OH)3 is obtained.
4
4.4.3 Reactions of Cr3+ Ions
1. Ammonia Solution: Green-grey or grey-blue gelatinous
precipitate of Cr(OH)3, slightly soluble in excess of reagent
in cold forming a violet or pink solution containing complex
hexamine chromium (III) ion; upon boiling the solution,
Cr(OH)3 is precipitated. Hence for complete precipitation of
chromium as the hydroxide, it is essential that the solution
be boiling and excess aqueous ammonia solution be avoided.
Cr 3  3NH 3  3H 2 O 
 Cr(OH)3  3NH 4
[Cr(NH 3 )6 ]3  3OH 
Cr(OH)3  6NH 3 
2. Sodium Hydroxide Solution: The green-grey or grey blue

2. Sodium Hydroxide: White precipitate of Al(OH)3 is obtained. Cr 3  3OH  

 Cr(OH)3 

Al3  3OH  
 Al(OH)3  The reaction is reversible; the addition of the acids, the
White
precipitates readily, tetrahydroxochromate (III) ions are
The precipitate dissolves in excess NaOH forming formed
tetrahydroxoaluminate (III) iron.
 [Cr(OH) 4 ]
Cr(OH)3  OH  
[Al(OH)4 ]
Al(OH)3  OH    Green

The solution is green. The reaction is reversible on (slight)

The reaction is a reversible one, and any reagent which will
reduce the OH– concentration sufficiently should cause the
reaction to proceed from sight to left with the consequently
precipitation of Al(OH)3. This may be effected by AlCl3 or by
adding the acid; in the latter case, a large excess of acid
causes the precipitated hydroxide to redissolve.
acidification and also on boiling Cr(OH)3 precipitates
again.
On adding H2O2 to alkaline solution of [Cr(OH)4]–, a yellow
solution is obtained, owing to the oxidation of Cr3+ to
CrO42-.

[Al(OH) 4 ]  NH 4 
 Al(OH)3   NH 3   H 2 O
2[Cr(OH) 4 ]  2H 2 O 2  2OH  
 2CrO 24   8H 2 O
Yellow

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Qualitative Analysis
QUALITATIVE ANALYSIS 251
3. Sodium Carbonate Solution: Precipitate of Cr(OH)3 is Zn  OH  2  2NaOH  Na 2  Zn  OH  4  (soluble)
obtained.
When H2S is passed through aqueous solution of
2Cr 3  3CO 32   3H 2 O 
 2Cr(OH)3  3CO 2  Na 2  Zn  OH  4  , a white precipitate of ZnS is obtained
4. Ammonium Sulphide Solution: Precipitate of Cr(OH)3 is Na 2  Zn  OH  4   H 2 S  ZnS   NaOH
obtained.
3. With aq. NH3
2Cr 3  3S2   6H 2 O 
 2Cr(OH)3  3H 2 S 
When a solution of Zn 2  ions is treated with NH4OH
2Cr 3  3S2   6H 2 O 
 2Cr(OH)3  3H 2 S 
solution, a white precipitate is formed which dissolves in
5. Chromate Test: Cr3+ ions can be oxidized to CrO42– in several excess of NH4OH
ways
Zn 2   NH 4 OH  Zn  OH  2   NH 4
a) Adding an excess of NaOH to a Cr salt followed by a few
3+
2
ml of 10% H2O2. The excess of H2O2 can be removed by Zn  OH 2  NH 4 OH   Zn  NH 3 4   OH 
boiling the solution for few minutes. soluble

2[Cr(OH) 4 ]  3H 2 O 2  2OH  
 2CrO 42   8H 2 O 4.5.2 Reactions of Mn2+ ions
Yellow
1. With H2S
b) Oxidation can be carried out by Br2/H2O in alkaline
A pink or buff coloured precipitate of MnS is obtained.
solution (i.e. by OBr–).
Mn 2   H 2 S  MnS  2H 
2Cr 3  3OBr   10OH  
 2CrO 24   3Br   5H 2 O Pink or Buff
c) In acid solution Cr3+ ions can be oxidized by potassium (or MnS dissolves in HCl as well as AcOH (difference from
ammonium) peroxodisulphate. Zn2+, Ni2+, Co2+ ions).
2Cr 3  3S2 O82   8H 2 O 
 2CrO 42   16H   6SO 42  MnS  HCl  Mn 2   H 2 S  Cl

4.5 Fourth Group Radicals MnS  AcOH  Mn 2   AcO   H 2 S

Radicals Co2+, Ni2+, Zn2+, Mn2+ 2. With Br2 water

Group Reagent H2S in presence of NH4OH and NH4Cl When a solution of Mn2+ ion is treated with Br2 water and
NaOH, MnO2 precipitates.
Black CoS, NiS
3. With powerful oxidizing agents:
Pink MnS
When a solution of Mn2+ ion is treated with powerful oxidants
White ZnS such as PbO2 in presence of HNO3, it is oxidized to purple
coloured permanganic acid.
4.5.1 Reaction for Zn2+ ions Mn 2   PbO 2  HNO3  HMnO 4  Pb  NO 3 2  H 2 O
1. With H2S Permangnic acid
(purple)
Zn 2   H 2 S  ZnS  2H  4. With Na2HPO4 :

ZnS dissolves in dil. HCl Na 2 HPO 4  Mn 2   Mn 2 (PO 4 )3     Na 

Pink

ZnS  2HCl  ZnCl 2  H 2 S 4.6 Fifth Group Radicals

2. With NaOH Radicals Ba2+, Sr2+, Ca2+
When a solution of Zn 2  ion is treated with NaOH, it first Group Reagent (NH4)2CO3 in presence of NH-4OH
forms a white precipitate which dissolves in excess of Precipitates as Carbonates
NaOH White BaCO3, SrCO3, CaCO3
Zn 2   2NaOH  Zn  OH 2  2Na 

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Qualitative Analysis
QUALITATIVE ANALYSIS 252
4.6.1 Reactions of Ba2+ ions The precipitate is insoluble in dilute CH3COOH (distinction
1. Reactions with NH3 Solution: No precipitate of Ba(OH)2 is from Ca2+ and Sr2+ ions), but readily soluble in mineral acids.
obtained because of its relatively high solubility. If the The addition of acid to K2CrO4 solution causes the yellow
alkaline solution is exposed to the atmosphere some CO2 colour of the solution to change to reddish orange, owing to
gas is absorbed and a turbidity due to BaCO3 is produced. the formation of dichromate.
2. (NH4)2CO3 Solution: White precipitate of BaCO3, soluble in
 Cr2 O72   H 2 O
2CrO24   2H  
acetic acid and dilute mineral acids
The solubility products for SrCrO4 and CaCrO4 are much
Ba 2   CO 32  
 BaCO 3 
White larger than for BaCrO4 and hence they require a larger CrO42–
The precipitate is slightly soluble in ammonium salts of ion concentration to precipitate them. The addition of acetic
strong acids. acid to the K 2 CrO 4 solution lowers the CrO 4 2– ion
concentration sufficiently to prevent the precipitation of
3. (NH4)2C2O4 Solution: A white precipitate of Ba(C2O4) is
SrCrO4 and CaCrO4 but it is maintained high enough to
obtained slightly soluble in water (0.09 g L–1) but readily
precipitate BaCrO4.
dissolved by hot dilute acetic acid (distinction from Ca2+)
and by mineral acid. 4.6.2 Reaction for Sr2+ ion

 Ba(COO) 2  (CH3COO)2Sr + (NH4)2SO4 

 SrSO4 (white ppt.) +
Ba 2   C2 O42  
2CH3COONH4
4. Dilute Sulphuric Acid: Heavy, white, finely divided (CH3COO)2Sr + (NH4)2 C2O4 
 SrC2O4 (white ppt.) +
precipitate of BaSO4, practically insoluble in water (2.5 × 10– 2CH3COONH4
3
g/L), almost insoluble in dilute acids and in (NH4)2SO4 4.6.3 Reactions of Ca2+ Ions
solution, but appreciably soluble in boiling conc. H2SO4. By
1. (NH4)2CO3 Solution: White amorphours precipitate of CaCO3
precipitation in boiling solution, or preferably in the presence
is obtained.
of NH4OOCCH3, a more readily filterable form is obtained.
Ca 2   CO 32  
 CaCO 3 
Ba 2   SO 24  
 BaSO 4 
On boiling the precipitate becomes crystalline. The
 Ba 2   2HSO 4
BaSO 4  H 2 SO 4 
precipitate is soluble in water which contains excess carbonic
If BaSO4 is boiled with a conc. solution of Na2CO3 partial acid (freshly prepared soda water) because of the formation
transformation into the less soluble BaCO 3 occurs in of soluble Ca(HCO3)2.
accordance with the equation.
 Ca 2   2HCO32 
CaCO3   H 2 O  CO 2 
 BaCO3  SO
BaSO4  CO  2 2
3 4 On boiling, precipitate appears again, because CO2 is
5. Saturated CaSO4 Solution: Immediate white precipitate of removed during the process and the reaction proceeds
BaSO4. A similar phenomenon occurs if saturated SrSO4 is towards the left. Ba2+ and Sr2+ ions reacts in a similar way.
used. The precipitate is soluble in acids, even in CH3COOH.
This is because among the three alkaline earth metal 2. Dilute Sulphuric Acid: White precipitate of CaSO 4 is
sulphates, BaSO4 is the least soluble. In the solutions of obtained.
saturated CaSO4 or SrSO4 the concentration of SO42– ion is
high enough to cause precipitation with larger amounts of Ca 2   SO 24  
 CaSO 4 
Ba2+, because the product of ionic concentrations exceeds The precipitate is appreciably soluble in water, i.e., more
the value of the solubility product. soluble than BaSO4 and SrSO4. In the presence of C2H5OH
solubility is much less.
 BaSO4 
SO24   Ba 2  
 2H   [Ca(SO4 ) 2 ]2 
CaSO4  H 2 SO4 
6. K2CrO4 Solution: A yellow precipitate of BaCrO4, practically
The same complex is formed if a precipitate is heated with a
insoluble in water
10% of (NH4)2SO4, leading to partial dissolution.
Ba 2   CrO 42  
 BaCrO 4 
Yellow

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Qualitative Analysis
QUALITATIVE ANALYSIS
3. (NH 4) 2C 2O 4 Solution: White precipitate of CaC 2 O 4 ,
immediately from concentrated and slowly from dilute
solution.
Ca 2   C 2 O 24  
 Ca(C 2 O 4 ) 
Precipitation is facilitated by making the solution alkaline by
NH3. The precipitate is practically insoluble in H2O and
CH3COOH but readily soluble in mineral acids.
4. K2CrO4 Solution: No precipitate from dilute solution nor
from conc. solution in the presence of CH3COOH.
5. K4[Fe(CN)6] Solution: White precipitate of a mixed salt is
obtained.
253
3. (NH4)2CO3 Solution: In the absence of NH4+ salts, a white
precipitate of basic magnesium carbonate is obtained.
5Mg 2   6CO32   7H 2 O 

4MgCO3  Mg(OH) 2  5H 2 O  2HCO3
In the presence of NH4+ salts, no precipitation occurs,
because the equilibrium is shifted to left
 NH3  HCO3
NH 4  CO32  
4. Na2CO3 Solution: White voluminous precipitate of basic
carbonate as above is formed, insoluble in bases but readily
soluble in acids and in solutions of NH4+ ions.

Ca 2   2K   [Fe(CN) 6 ]4  
 K 2 Ca[Fe(CN) 6 ]  5. Na 2HPO 4 Solution: White crystalline precipitate of
Mg(OH)4PO4 6H2O in the presence of NH4Cl (to prevent
In the presence of NH4Cl the test is more sensitive. In this precipitation of Mg(OH)2) and NH3 solution.
case potassium is replaced by ammonium ions in the
precipitate. The tests can be used to distinguish calcium Mg 2   NH 3  HPO 42  
 MgNH 4 PO 4 
from strontium, barium and Mg2+ ions however interfere.
The precipitate is sparingly soluble in water, soluble in
4.7 Sixth Group Radicals CH3COOH and in mineral acids. The precipitate separates
slowly from dilute solutions because of its tendency, to form
Radicals Mg2+, Na+, K+ supersaturated solutions, this may usually be overcome by
Group Reagent No common group reagent cooling and by rubbing the test tube or beaker beneath the
surface of the liquid with a glass rod.
4.7.1 Reaction of Mg2+ ions
A white flocculants precipitate of MgHPO4 is produced in
1. Ammonium Solution: Partial precipitation of white
neutral solutions.
gelatinous Mg(OH)2.
Mg 2   HPO 42  
 MgHPO 4 
Mg 2   2NH 3  2H 2 O 
 Mg(OH) 2  2NH 4
The precipitate is very sparingly soluble in water (1.2 × 10–
2
g/L) but readily soluble in ammonium salts.
2. NaOH Solution: White precipitate of Mg(OH)2, insoluble in
excess NaOH, but readily soluble in NH4+ salts.

Mg 2   2OH  
 Mg(OH) 2 

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Qualitative Analysis
QUALITATIVE ANALYSIS 254

SUMMARY
IDENTIFICATION OF BASIC RADICALS

Zero Group ( NH4 ) First Group (Ag+, Pb2+, Hg22  ions)

aq solution + dil HCl  white ppt.

1. Salt + dil Smell of NH4 may be White ppt. + water – boil

NaOH heated NH3

2. Salt + dil White NH4 Ppt. dissolves which appears Ppt. insoluble – Ag+ or Hg22  may be
NaOH heated fumes on cooling – Pb2+ may be
confirmed
and then
glass rod
dipped in
HCl is
brought near
the mouth of
test tube

3. aq. solution Brown NH4 ppt. is dissolved in water ppt. dissolved – ppt. becomes black Hg22 
of salt + ppt. and divided into three parts Ag+ may be
confirmed may be
NaOH + solution is
K2[HgI4] i. 1 part + KI  yellow
st
divided into three
ppt. parts ppt is dissolved in aqua
regia and then divided into
Pb2+ confirmed i. 1st part + dil two parts
HNO3
ii. 2nd part + K2CrO4  i. 1st part + SnCl2  white
yellow ppt. – white ppt. ppt. which becomes
shiny black
Pb2+ confirmed – Ag+
confirmed – Hg22  confirmed
iii. 3rd part + dil H2SO4 
white ppt. which ii. 2nd part +
ii. 2nd part + copper turning
dissolves in NH4OAc KI 
 white deposits on
yellow ppt.
Pb2+ confirmed – Ag+ copper turning – Hg22 
confirmed confirmed

iii. 3rd part +

AcOH +
K2CrO4 
Red ppt. –
Ag+
confirmed

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Qualitative Analysis
QUALITATIVE ANALYSIS 255

Second group Hg2+, Pb2+, Bi3+, Cu2+, Cd2+, As3+, Sb3+, Sn2+, Sn4+

Filtrate of 1st group + H2S gas  Black, brown, white, orange ppt. ammonium sulphide, then heating

ppt. insoluble  II A group – Hg2+, Pb2+, Bi3+, Cu2+, Cd2+ ppt. dissolves – II B group As3+, Sb3+, Sn2+, Sn4+

ppt. + dil HNO3  Boil ppt. + dil HCl  Boil

Black ppt. ppt. dissolves – Pb2+, Bi3+, Cu2+, Cd2+ solution is divided into two Yellow ppt. Orange ppt – Sb3+ may be
parts
– Hg2+ may be As3+ may be
st 2+ nd
1 part + dil If Pb is absent, then 2 part + NH4OH Brown ppt. – Sn2+ may be
– ppt. is dissolved
H2SO4 +
in aqua regia and
C2H5OH  White ppt.  Blue Colourless i. Ppt. + Hot Light yellow ppt. – Sn4+ may be
divided into 3 parts
white ppt solution solution And Conc.
– Bi3+ may be HNO3 Then Divide the Divide the
i. 1st part + SnCl2 2+
– Pb may be – Cu2+ may  Cd2+ Cool Then orange ppt. brown ppt. into
 white ppt. – ppt. is be may be Add into 2 parts two parts
(which turns Solution of dissolved in dil
grey –Hg+ white ppt. in HCl and then Blue solution Solution + (NH4)2MoO4
i. 1st part + i. 1st part +
confirmed NH4OAc + divided into + AcOH + H2S  heat
 NH4OH + HgCl2 
K2CrO4  three parts K4[Fe(CN)6] yellow ppt. Yellow Ppt. H2S  Hg2Cl2
ii. 2nd part + KI 
yellow ppt  chocolate As3+ orange
yellowish orange i. 1st part (1 – Cd2+
brown ppt. Confirmed ppt. white ppt.
ppt. 2+
– Pb confirmed drop in confirmed  Sn2+
excess of – Cu2+ – Sb3+ confirmed
– ii. Solution Of
H2O)  confirmed confirmed
Hg2+ confirmed Ppt. In Hot
white ppt. ii. 2nd part +
(NH4)2CO3
rd
iii. 3 part + Cu – Bi3+ ii. 2nd part + NaOH 
+ Dil HCl +
turning  white excess of white ppt.
ii. 2nd part + H2S 
deposits on Cu Yellow Ppt. H2O  which
HNO3 + white ppt. dissolves
turnings thio urea
As3+ in excess
– Hg2+  yellow – Sb3+ of NaOH
confirmed
confirmed ppt. confirmed  Sn2+
confirmed
– Bi3+
confirmed
Light yellow
iii. 3rd part + ppt. + Fe
Na2SnO2 turning + dil
 Black H2SO4  Boil
ppt. + HgCl2 
white ppt.
– Bi3+ which turns
confirmed black – Sn4+
confirmed

SCAN CODE
Qualitative Analysis
QUALITATIVE ANALYSIS 256

SOLVED EXAMPLES

Example - 1 Sol. The given reactions (i) to (iii) of the compound (X) points
out that (X) is sulphur dioxide, SO2. The given reactions of
An unknown inorganic compound (X) loses its water of (SO2) can be represented as below.
crystallization on heating and its aqueous solution gives
(i) K 2 Cr2 O 7  4H 2 SO 4 
 K 2 SO 4  Cr2 (SO 4 ) 3  4H 2 O  3O
the following reactions.
(i) It gives a white turbidity with dilute hydrochloric acid H 2 O  SO 2  O 
 H 2 SO 4
solution.
(ii) H 2 O 2 
 H2 O  O
(ii) It decolourises a solution of iodine in sodium iodide.
(iii) It gives a white precipitate with silver nitrate solution H 2 O  SO 2  O 
 H 2 SO 4
which turns black on standing.
Identify the compound (X) and give chemical equations BaCl 2  H 2 SO 4 
 BaSO 4  2HCl
for the reactions at steps (i), (ii) and (iii). (iii) 2H 2 S  SO 2 
 3S  2H 2 O
Sol. Since the compound X decolourises a solution of iodine
in potassium iodide, it should contain ion, S2 O 32  which Example - 3
also confides with the two other given facts, i.e., (i) and A coloulress solid A on heating gives a white solid B and
(iii). Hence the compound is sodium thiosulphate, a coloulress gas, C; B gives off reddish brown fumes on
Na2S2O3.5H2O which explains the given reactions as below. treatment with dilute acids. On heating with NH4Cl, B gives
heat a colourless gas D and a residue E.
Na 2S2 O3  5H 2 O   Na 2S2 O3  5H 2 O 
The compound A also gives a coloulress gas F on heating
(i) with ammonium sulphate and white residue G. Both E and
G impart bright yellow colour to Bunsen fumes. The gas C
Na 2S2 O3  2HCl 
 2NaCl  H 2 O  SO 2  S forms white powder with strongly heated magnesium
(white turbidity)
metal. The white powder forms magnesium hydroxide with
2Na 2S 2 O3  I2 
 Na 2S4 O6  2NaI water. The gas D, on the other hand, is absorbed by heated
(ii) Sodium thiosulphate Sodium tetrathionate calcium which gives off ammonia on hydrolysis.
Identify the substance A to G and gives reactions for the
Na 2S2 O 3  2AgNO3 
 Ag 2S2 O3   2NaNO3 changes involved.
(iii) Silver thiosulphate
Sol. It is advisable to summarise the given facts in the form of
(white ppt.)
a chart.
Ag 2S2 O3  H 2 O 
 As 2S   H 2SO 4 G  F 
(NH4 )2 SO4
 A 
heat
 B  C
heat
(black ppt.) colourless residue colourless gas colourless solid colourless solid colourless gas

Example - 2 D  E   B  acid
NH 4Cl
heat

dil
 R eddish brow n fum es
colourless gas residue

An aqueous solution of gas (X) gives the following C  Mg 

 White powder 
H2 O
 Mg(OH) 2
reactions. colourless residue

(i) It decolourizes on acidified K2Cr2O7 solution D  C a ( heated )  H

colourless gas
(ii) On boiling it with H2O2, cooling it and then adding an
aqueous solution of BaCl2 a precipitate insoluble in dilute
hydrochloric acid is obtained.
(iii) On passing H2S in the solution, a white turbidity is
obtained.
Identify (X) and give equations for the reactions at steps
(i), (ii) and (iii)
2O
 NH 3
The above reactions lead to the following conclusions.
(A) and (D) reacts with calcium forming a compound which
on hydrolysis gives ammonia indicating that D must be
nitrogen.
Residues E and G give yellow flame on burning indicating
that these are sodium salts. Hence compounds B (which
give E) and A (which give G) must be sodium salts.
The colourless solid B gives reddish brown fumes with
dilute acids, the reddish brown fumes are probably of NO2.
QUALITATIVE ANALYSIS 257
Hence compound B must be nitrite (recall that NO3– ions Example - 6
are not attacked by dil. Acids). Consequently, A must be A mixture of two salts was treated as follows.
NO3– which can give NO2– (B) on heating. (i) The mixture was heated with MnO2 and concentrated
Thus compound A is NaNO3 which explains all the given H2SO4 when yellowish – green gas liberated.
reactions as below. (ii) The mixture on heating with NaOH solution gave a
(i) 2 N aNO 3  
 2 N aNO 2  O 2  gas which turned red litmus blue.
(A ) (B) C  (iii) Its solution in water gave blue precipitate with
potassium ferricyanide and red colouration with ammonium
(ii) 2NaNO 2  H 2SO 4 (dil.) 
 NaSO 4  2HNO 2
thiocyanate.
(B)
(iv) The mixture was boiled with potassium hydroxide and
3HNO 2 
 HNO 3  H 2 O  2NO the liberated gas was bubbled through an alkaline solution
of K2HgI4 to give brown precipitate. Identify the two salts.
2NO  O 2 
 2NO  2
Reddish brown fumes Give ionic equations for the reactions involved.
Sol. The reaction Mixture + MnO2(conc.) + H2SO4 
(iii) NaNO 2  NH 4 Cl   NaCl N 2  2H 2 O
heat
(E)
yellowish-green gas indicates that the mixture contains
(B) (D)
Cl- ion as the gas Cl2, i.e.
3  (NH 4 ) 2 SO 4  Na 2SO 4  2NH3  2HNO3
2Cl- + MnO2 + H2SO4 + 2H+  MnSO4 + 2H2O + Cl2
(iv) 2NaNO
(A) (G) (F)
The reactions
(v) 2Mg  O2 
 2MgO Mixture + NaOH 
heat
 Gas turns red litmus blue
(C) white powder

Mixture + KOH 

heat
 Gas
MgO  H 2 O 
 Mg(OH) 2
HgI 24  + Gas   Brown precipitate
(vi) 3Ca  N 2 
 Ca 3 N 2
indicate that the gas is NH3. It is a basic gas so it turns
(D)
red litmus to blue. With HgI 24  , the reaction is
Ca 3 N 2  6H 2 O 
 3Ca(OH) 2  2NH 3 
Thus substance (A) to (G) can be represented as
(A) NaNO3 (B) NaNO2 (C) O2
(D) N2 (E) NaCl (F) NH3 From these facts, we conclude that the mixture contains
(G) Na2SO4 NH +4 ions. The reaction Mixture + K3[Fe(CN)6]  blue
precipitate indicates that the mixture contains Fe2+ ions .
Example - 4 i.e.
3
What is Nessler’s reagent? 3Fe2   2  Fe  CN 6   Fe3 [Fe(CN)6 ]2
Sol. An alkaline solution of K2HgI4 is called Nessler's reagent blue ppt.

The red coloration with NH4CNS must be due to Fe3+ ions

Example - 5
which is probabily formed by aerial oxidation of Fe2+ ions,
A substance on treatment with dil. H2SO4 liberates a i.e.
colourless gas which produces (i) turbidity with baryta Fe3  3CNS  Fe(CNS)3
water and (ii) turns acidified dichromate solution green. red
The reaction indicates the presence of:
Thus, the mixture contains NH +4 , Fe2+ and Cl- ions or
(a) CO 32  (b) S2 
NH4Cl and FeCl2 salts.
(c) SO 32  (d) NO 2
Example - 7
Ans. (c)
Sol. Explain the following:
(i) Lead (Pb2+) is placed in the first as well as second
BaSO3  2HCl  dil.  2NaCl  H 2 O  SO 2 group of qualitative analysis.
K 2 Cr2 O 7  H 2SO 4  SO 2  K 2SO 4  H 2 O (ii) The colour of mercurous chloride, Hg2Cl2, changes
from white to black when treated with ammonia.
QUALITATIVE ANALYSIS 258
(iii) During the qualitative analysis of a mixture containing Identify the cation of (X) and give chemical equations for
Cu2+ and Zn2+ ions, H2S gas is passed through an acidified
reactions at steps (i), (iii) and (iv)
solution containing these ions in order to test Cu2+ alone.
Explain briefly. Sol. Acidified solution of (X) gives brown precipitate with H2S,
Sol. (i) PbCl2 is partly soluble in water and hence Pb2+ ions soluble in yellow ammonium sulphide, indicates that (X)
place to the first group filtrate, i.e. to the II group. should be a salt of Sn2+. The given reactions of the cation
(ii) Due to the formation of finely divided mercury. of X, i.e., Sn2+ can be written as below.
(iii) a) Ksp (CuS) is less than Ksp (ZnS) b) Ionization of (i) Sn 2   H 2 S 
 SnS  2H 
H2S is further suppressed in presence of acid (common
ion effect) (ii) Sn 2   2NaOH 
 Sn(OH) 2  2Na 
 2H   S2 
H 2 S  (iii) Sn(OH)2  2NaOH 
 Na 2 SnO 2  2H 2 O
So, when H2S gas is passed through acidified solution (iv) Sn 2   2FeCl3 
 Sn 4   2FeCl 2
containing Cu2+ and Zn2+, only Cu2+ ions will be precipitated
due to low concentration of S2– ions. Example - 11

Example - 8 A hydrated metallic salt. A, light green in colour, gives a

white anhydrous residue B after being heated gradually. B
Conc. H2SO4 on addition to dry KNO3 gives brown fumes is soluble in water and it’s aqueous solution reacts with
of: NO to give a dark brown compound C. B on strong heating
(a) SO2 (b) SO3 gives a brown residue and a mixutre of two gases E and F.
(c) NO (d) NO2 The gaseous mixture, when passed through acidified
permanganate, discharges the pink colour and when
Ans. (d)
passed through acidified BaCl2 soltuion, gives a white
Sol. KNO 3  H 2 SO 4  KHSO 4  HNO3 ; precipitate. Identify A, B, C, D , E and F.
Sol. The given observations are as follows.
4HNO3  2H 2 O  4NO2  O2
Brown (i)
Example - 9 Hydrated metallic salt   white anhydrous residue
heat
3
A  B
A salt having BO on burning with conc. H2SO4 gives
3
(ii)
____ edge flame.
NO
(a) Green (b) Yellow Aqueous solution of B   Dark brown compound
(c) Red (d) White  C
Ans. (a) Strong
Salt B   Brown residue + Two gases
Sol. 2Na 3 BO3  3H 2SO 4  3Na 2SO 4  2H 3 BO3 ; (iii) Heating D  E  F

H 3 BO3  3C2 H 5 OH   C 2 H 5 3 BO3  3H 2 O (iv)

Burns with green edge flame
acidified KMnO4
Pink colour is discharged
Example - 10 Gaseous mixture
BaCl2 Solution
(E) + (F) White precipitate
A certain inorganic compound (X) shows the following The observation (ii) shows that B must be ferrous
reactions: sulphate since with NO, it gives dark brown compound
(i) On passing H2S through an acidified solution of (X) a according to the reaction
brown precipitate is obtained. [Fe(H2O)6]2+ + NO  [Fe(H2O)5(NO)]2+ + H2O
(ii) The precipitate obtained at step (i) dissolves in excess dark brown
of yellow ammonium sulphide. Hence, the salt A must be FeSO4.7H2O
The observation
(iii) On adding an aqueous solution of NaOH to a solution
of (X), first a white precipitate is obtained which dissolves 2FeSO 4  F2 O 3  SO 2  SO3
(iii) is (D)  
in excess of NaOH. brown (E)  (F)

(iv) The aqueous solution of (X) reduces ferric chloride.

QUALITATIVE ANALYSIS 259

The gaseous mixture of SO 2 and SO 3 explains the

observation (iv), namely, Na 2 Cr2 O7  2KCl 
 K 2 Cr2 O7  2NaCl
(iv) (E) (F)

K2Cr2O7 (F) is well known oxidizing agent

2MnO -4 + 5SO2 + 2H2O  2Mn2+ + 5 SO 24  + 4H+
(v)
Pink colour no colour
K 2 Cr2 O7  7H 2 C2 O 4 



2H2O + SO2 + SO3  2 2
 4H + SO 3 + SO 4
+
oxalic acid

Ba2+ + SO 2 K 2 C2 O4  Cr2 (C2 O 4 )3  6CO 2  7H 2 O

3  BaSO3 (whtie ppt.)
Ba2+ + SO 24   BaSO4 (white ppt.) Cr2 (C 2 O 4 )3  3K 2 C 2 O 4 
 2K 3 [Cr(C 2 O 4 )3 ]
Potassium oxalate Potassium trioxalatochromium
Hence, the various compounds are Blue crystals (G)
A = FeSO4. 7H2O ; B = FeSO4 ;
C = [Fe(H2O)5NO]SO4 D = Fe2O3 Example - 13
E and F = SO2 and SO3
(i) A black mineral (A) on heating in presence of air gives
Example - 12 a gas (B).
(ii) The mineral (A) on reaction with dilute H2SO4 gives a
(i) An ore (A) on roasting with sodium carbonate and lime
gas (C) and solution of a compound (D).
in the presence of air gives two compounds, (B) and
(iii) On passing gas (C) into an aqueous solution of (B) a
(C).
white turbidity is obtained.
(ii) The solution of (B) in conc. HCl on treatment with
(iv) The aqueous solution of compound (D) on reaction
potassium ferrocyanide gives a blue colour or
with potassium ferricyanide gives a blue compound
precipitate of compound (D).
(E).
(iii) The aqueous solution of (C) on treatment with conc.
Identify (A) to (E) and give chemical equations for reactions
H-2SO4 gives a yellow coloured compound (E).
at steps (i) to (iv).
(iv) Compound (E) when treated with KCl gives an orange-
red compound (F) which is used as an oxidizing Sol. Formation of blue coloured compound E by treating
reagent. solution of compound D with potassium ferricyanide
(v) The solution of (F) on treatment with oxalic acid and indicates that compound D contains Fe2+ ion which is also
then with an excess of potassium oxalate gives blue the constituent ion of the compound A. Further A, is a
crystals of compound (G). black mineral of Fe2+ion, it should be ferrous sulphide (FeS)
which is confirmed by the various given reactions.
Identify (A) to (G) and give balanced chemical equations
for reactions at steps (i) to (v) (i) 4FeS  7O 2 
 2Fe2 O3  4SO2
(A) (B)
Sol. Reaction (i) suggests that the ore contains Fe.
Reaction (ii) and (iv) suggest that the ore also contains (ii) FeS  H 2 SO 4 
 FeSO 4  H 2 S S
chromium. (A) (D) (C)

In fact, if we review our memory, we will remember that the (iii) (a) SO 2  H 2 O 
 H 2 SO 3
reaction sequence (i), (iii) and (iv) are involved in the
preparation of K2Cr2O7 from chromite ore, FeO×Cr2O3. (b) 2H 2 S H 2 SO3 
 3S  3H 2 O
(C) Turbidity
Hence the given reactions can be written as below
(i) (iv) FeSO 4  K 3 [Fe(CN) 6 ] 
 KFe[Fe(CN) 6 ] K 2 SO 4
( D) (E)
lim e
4 FeO  C r2 O 3  8 N a 2 C O 3  7 O 2  (  
Roasting )
Chromite ore (A) Example - 14
2Fe 2 O 3   8 N a 2 C rO 4  8C O 2 
(B) (C ) Some pale-green crystals are strongly heated. The gases
given off are passed into a container surrounded by ice
(ii) Fe 2 O3  6HCl 
 2FeCl3  3H 2 O
and thenthrough a solution of acidified KMnO 4. The
4FeCl3  3K 4 [Fe(CN)6 ] 
 Fe 4 [Fe(CN)6 ]3  12KCl KMnO4 is decolorised, a waxy white solid is formed in the
Blue (D) ice container; this is dissolved in water. The solution will
(iii) (a) Give a precipitate with silver nitrate solution
2Na 2 CrO 4  H 2SO 4 
 Na 2 Cr2 O7  Na 2SO 4  H 2 O (b) Give a precipitate with barium chloride solution
Soluble (C) Yellow colour (E) (c) Turn red litmus blue
QUALITATIVE ANALYSIS 260
(d) Give blue colour with starch solution
Ans. (b) Al 2Cl6  6NaOH 
 2AlOH  6NaCl
Sol. Asumme gree crystal of FeSO4 Excess of NaOH

FeSO 4 
 Fe 2 O 3  SO 2  SO 3

2NaAlO 2  2H 2O
SO 2  MnO 4  Mn 2   SO 42 
Example - 17
SO3 forms waxy white solide (H2SO4) in ice container which An inorganic Lewis acid (X) shows the following reactions:
is dissolved in water and gives SO 24  ion. When BaCl2 (i) It fumes in moist air.
reacts with SO 24  ion, it forms white ppt. of BaSO4. (ii) The intensity of fumes increases when a rod dipped in
NH4OH is brought near to it.
Example - 15 (iii) An acidic solution of (X) on addition of NH4Cl and
NH4OH gives a precipitate which dissolves in NaOH
The compound formed in the borax bead test of Cu2+ ion in solution.
oxidising flame is (iv) An acidic solution of (X) does not give a precipitate
(a) Cu (b) CuBO2 with H2S. Identify (X) and give chemical equations for
(c) Cu(BO2)2 (c) none of these reactions at steps (i) to (iii).
Ans. (c) Sol. The inorganic Lewis acid (X) which fumes in moist air is
Sol. Na 2 B4 O 7  2B2 O 3  Na 2 O probably anhydrous aluminium chloride, AlCl3 which is in
accordance with the fact that its acidic solution does not
CuO  B2 O3  Cu  BO2 2 give a precipitate with H2S. Thus the given reactions of
compound (X) can be written as below.
Example - 16 (i) AlCl3  3H 2 O 
 Al(OH) 3  3HCl 
An inorganic compound (A) shows the following (ii) HCl  NH 4 OH 
 NH 4 Cl   H 2 O
reactions.
(i) It is white solid and exists as dimmer; gives fumes of (iii) AlCl3  3NH 4 OH 
 Al(OH)3  3NH 4 Cl
(B) with wet air.
(ii) It sublimes on 180°C and forms monomer if heated to Al(OH)3  NaOH 
 NaAlO 2  2H 2 O
400°C. Example - 18
(iii) Its aqueous solution turns blue litmus to red.
A white substance A reacts with dilute H2SO4 to produce a
(iv) Addition of NH4OH and NaOH separately to a solution
colourless gas B and a colourless solution C. The reaction
of (A) gives white precipitate which is however soluble
in excess of NaOH. between B and acidified K2Cr2O7 solution produces a green
solution and a slightly coloured precipitate D. The sub-
Sol. (i) (A) is a characteristic dimerized compound which
sublimes on 180°C and forms monomer if heated to 400°C stance D burns in air to produce a gas E which reacts with
and thus, (A) is (AlCl3)2 or Al2Cl6. B to yield D and a colourless liquid. Anhydrous copper
It fumes with wet air sulphate is turned blue on addition of this colourless liq-
uid. Addition of aqueous NH3 or NaOH to C produces first
Al2 Cl6  6H 2 O 
 2Al(OH)3  6HCl 
Fumes (B) a precipitate which dissolves in the excess of the respec-
180 C 400 C
tive reagent to produce a clear solution in each case. Iden-
(ii) Al2 Cl6(s)   Al2 Cl6(v)   2AlCl3 tify A, B, C, D and E. Write the equation of the reactions
(iii) Its solution in water is acidic due to hydrolysis involved.
2AlCl3  6H 2 O 
 2Al(OH)3  6HCl(aq)
dil. H SO
(iv) (A) gives white ppt. with NH4OH and NaOH, soluble Sol. A 
2 4
 B  C
(white) (colourless) (colourless solution)
in excess of NaOH.
E   B  
D
Al2 Cl6  6NH 4 OH 
 2Al(OH)3  6NH 4 Cl anhy. CuSO
colourless liquid 
4
 Blue
aq. NH excess of
C  3
or NaOH
 Precipitate 
reagent
 Clear solution
QUALITATIVE ANALYSIS 261
The above set leads to following conclusions. Example - 19
(i) Since the gas (B) is colourless and turns acidified A certain compound (X) shows the following reactions.
K2Cr2O7 solution green, it should be H2S.
(i) When KI is added to an aqueous suspension of (X)
(ii) Since H2S gas is obtained by the reaction of dil. H-2SO4
containing acetic acid, iodine, is liberated.
on A, the latter must be sulphide.
(ii) When CO2 is passed through an aqueous suspension
(iii) The white colour of the sulphide (A) points out
of (X) the turbidity transforms to a precipitate.
towards ZnS.
(iii) When a paste of (X) in water is heated with ethyl
Thus the various reactions can be written as below. alcohol a product of anesthetic use is obtained.
ZnS H 2 SO 4 (dil) 
 ZnSO 4  H 2 S  Identify (X) and write down chemical equation for
(A) (C) (B) reactions at steps (i), (ii) and (iii).
Sol. The given reactions indicate that the compound (X) is
CaOCl2 (bleaching powder). Its various reactions may be
3H 2 S K 2 Cr2 O 7  4H 2 SO 4 
 written as below.
(B) (i)
K 2 SO 4  Cr2 (SO 4 ) 3  7H 2 O  3S CaOCl2  CH 3 COOH 
(CH3 COO) 2 Ca  Cl 2  H 2 O
(green ) (D)

2KI  Cl 2 
 2KCl  I2
S  O 2 
 SO 2  
2H 2S(B)
 2H 2 O  3S 
(D) (E ) (colourless liq) (D) (ii) CaOCl2  CO2 
 CaCO3  Cl 2

CuSO 4 (white) (iii) CaOCl2  H 2 O 

 Ca(OH) 2  Cl 2

CuSO 4  5H 2 O C 2 H 5 OH  Cl2 
 CH 3 CHO  2HCl
(blue)
CH 3 CHO  3Cl 2 
 CCl3 CHO  3HCl
2NaOH
ZnSO 4  2NaOH 
 Zn(OH) 2    CCl3 CHO  2Ca(OH) 2 
 CHCl3  (HCOO) 2 Ca
(C)

Na 2 ZnO 2  2H 2 O Example - 20
(so lub le)
Carbonates of Ba, Sr and Ca are
(a) White (b) blue
(c) Green (d) Yellow
Ans. (a)
Sol. All are white in colour.
QUALITATIVE ANALYSIS 262

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Tests for Acid Radicals 9. A mixture upon adding conc. H2SO4 gives deep red fumes.
It may contain the anions pair :
1. A mixture when rubbed with dilute acid smells like vinegar.
It contains : (a) Cr2O72- and Cl– (b) Br – and Cr2O72-

(a) sulphite (b) nitrate (c) NO3– and Cl– (d) CrO42– and NO32–

(c) nitrite (d) acetate 10. A solution of a salt in concentrated sulphuric acid H2SO4
acid produced a deep blue colour with starch iodide
2. SO2 and CO2 both turn lime water (X) milky, SO2 also turns solution. The salt may be
K2Cr2O7/H+ (Y) green while O2 is soluble in pyrogallol (Z)
turning it black. These gases are to be detected in order (a) chloride (b) carbonate
by using these reagents. The order is: (c) acetate (d) bromide
(a) (X), (Y), (Z) 11. A colourless solution of a compound gives a precipitate
(b) (Y), (X), (Z) with AgNO3 solution but no precipitate with a solution of
Na 2CO 3. The action of concentrated H 2SO 4 on the
(c) (X), (Z), (Y) compound liberates a suffocating reddish brown gas. The
(d) The correct order cannot be predicted. compound is :

3. Colourless salt (A) + dil. H2SO4 or CH3COOH + Kl 

 (a) Ba(CH3COO)2 (b) CaCl2
blue colour with starch. (A) can be (c) Nal (d) NaBr
(a) K2SO3 (b) Na2CO3 12. When chlorine (Cl2) water in excess is added to a salt
(c) NH4NO2 (d) NH4Cl solution containing chloroform, chloroform layer turns
pale yellow. Salt contains :
4. A substance on treatment with dilute H2SO4 liberates a
colourless gas which produces (i) turbidity with baryta (a) Br

(b) I–
water and (ii) turns acidified dichromate solution green.
(c) NO3- (d) S2–
The reaction indicates the presence of:
13. An aqueous solution of salt containing an acidic radical
(a) CO32- (b) S2-
X– reacts with sodium hypochlorite in neutral medium.
(c) SO32- (d) NO2- The gas evolved produces blue black colour spot on the
5. Which of the following combines with Fe(II) ions to form starch paper. The anion X- is :
a brown complex? (a) CH3COO- (b) Br-
(a) N2O (b) NO (c) I– (d) NO2-
(c) N2O3 (d) N2 O4 14. When chlorine water is added to an aqueous solution of
6. Which of the following reagents turns white precipitate potassium halide in the presence of chloroform, a colour
of AgCl to yellow ? is developed but on adding more of chlorine water the
(a) NaNO (b) Na AsO colour disappears, and a colourless solution is obtained.
This test confirms the presence of the following in
(c) Na3AsO3 (d) NaCN aqueous solution.
7. When a mixture of solid NaCl and solid K2Cr2O7 is heated (a) Iodide (b) Bromide
with concentrated H2SO4, deep red vapours are obtained.
This is due to the formation of : (c) Chloride (d) Iodide and bromide
(a) chromous chloride (b) chromyl chloride 15. Nitrate is confirmed by ring test. The brown colour of the
ring is due to formation of :
(c) chromic chloride (d) chromic sulphate
(a) ferrous nitrite (b) nitroso ferrous sulphate
8. AgCl dissolves in ammonia solution giving :
(c) ferrous nitrate (d) FeSO4.NO2.
(a)Ag+,NH4+and Cl–
(b) [Ag(NH3)2]+ and Cl– 16. Nitrates of all the metals except mercury and bismuth are:
(c) [Ag2(NH3)]2+ and Cl– (a) coloured (b) unstable
(d) [Ag(NH3)]+ and Cl– (c) soluble in water (d) insoluble in water
QUALITATIVE ANALYSIS 263
17. [X] + H2SO4  green solution [X] and [Y] are 26. Cu2+ and Ag+ are both present in the same solution.
To precipitate one of the ions and leaves the other in
(a) SO32- & SO2 (b) Cl–, HCl
solution, add
(c) S2–, H2S (d) CO32-, CO2
(a) H2S(aq) (b) HCl (aq)
Tests for Basic Radicals (c) HNO3(aq) (d) NH4 NO3 (aq)
18. Nessler’s reagent is : 27. Consider the following observation :
(a) K2HgI4 (b) K2HgI4 + KOH 
Mn+ + HCl (dilute) 
 white precipitate   water
(c) K2HgI2 + KOH (d) K2HgI4 + KI
2

19. When bismuth chloride is poured into a large volume of soluble 
CrO 4
 yellow precipitate.
water the white precipitate produced is of : The metal ion Mn+ will be :
(a) BiO.OH (b) Bi2O3 (a) Hg2+ (b) Ag+
(c) BiOCl (d) Bi(OH)3 (c) Pb2+ (d) Sn2+
20. Turnbull’s blue is a..................... . 28. A white crystalline substance dissolves in water. On
(a) ferricyanide (b) ferrous ferricyanide passing H2S in this solution, a black precipitate is obtained.
The black precipitate dissolves completely in hot HNO3
(c) ferrous cyanide (d) ferri ferrocyanide
On adding a few drops of concentrated H2SO4, a white
21. Precipitate of PbSO4 is soluble in : precipitate is obtained. This precipitate is that of
(a) ammonium acetate (b) dilute HCl (a) BaSO4 (b) SrSO4
(c) dilute H2SO4 (d) none (c) PbSO4 (d) CdSO4
22. There are four test tubes containing dilute HCl, BaCl2, 29. H2S in the presence of HCl precipitates II group but not
CdCl2 and KNO3 solutions. Which of the following IV group because :
reagents will help in the identification of BaCl2?
(a) HCl activates H2S
(a) NaOH (b) K2CrO4
(b) HCl increases concentration of Cl-
(c) AgNO3 (d) both (b) and (c)
(c) HCl decreases concentration of S2–
23. Ammonia/ammonium ion gives yellow precipitate with :
(d) HCl lowers the solubility of H2S in solution
(a) H2PtCl6 (b) HgCl2
30. Yellow ammonium sulphide solution is a suitable reagent
(c) Na3[Co(NO2)6] (d) (a) and (c) both for the separation of :
24. Ammonium salts on heating with slaked lime liberates a (a) HgS and PbS (b) PbS and Bi2S3
colourless gas (X). Identify the correct statement for gas
(c) Bi2S3 and CuS (d) CdS and As2S3
(X).
31. In which of the following pairs the precipitates are red
(a) (X) turns red litmus blue and produces dense white
and black coloured respectively and both precipitates are
fumes in contact with dilute HCl.
soluble in excess KI solution ?
(b) (X) turns filter paper moistened with mercurous nitrate
(a) HgI2, Hg2I2 (b) HgI2 , BiI3
black and gives intense blue coloured solution with
CuSO4 (aq). (c) Cu2I2, AgI (d) CdI2, PbI2
(c) (X) when passed through Nessler’s reagent produces 32. Which one of the following salts will produce clear and
a brown colour precipitate. transparent original solution in 2M HCl?
(d) All of these. (a) Ag2CO3 (b) Pb(CO3)2
25. Three separate samples of a solution of a single salt gave (c) Hg2CO3 (d) CuCO3
these results. One formed a white precipitate with excess 33. A metal chloride original solution (i.e. O.S) on mixing with
ammonia solution, one formed a white precipitate with K2CrO4 solution gives a yellow precipitate soluble in
dilute NaCl solution and one formed a black precipitate aqueous sodium hydroxide. The metal may be :
with H2S. The salt could be : (a) mercury (b) iron
(a) AgNO3 (b) Pb(NO3)2 (c) silver (d) Lead
(c) Hg(NO3)2 (d) Mn(NO3 )2
QUALITATIVE ANALYSIS 264
34. Which of the following is insoluble in dil. HNO3 but 43. Ferric alum gives deep red colour with NH4SCN due to
dissolves in aquaregia ? the formation of :
(a) HgS (b) PbS (a) Al(SCN)3 (b) [Fe(SCN)3]-
(c) Bi2S3 (d) CuS. (c) Fe(SCN)3 (d) None of these.
35. When small amount of SnCl2 is added to a solution of 44. NH4SCN can be used to test one or more out of Fe3+, Co2+,
Hg2+ ions, a silky white precipitate is obtained. The silky Cu2+ :
white precipitate is due to the formation of : (a) Fe3+ only (b) Co2+, Cu2+ only
(a) Hg2Cl2 (b) SnCl4 (c) Fe3+ Cu2+ only (d) All
(c) Sn (d) Hg 45. K4[Fe(CN) ] can be used to detect one or more out of
36. Which of the following reagents gives white precipitate Fe2+ , Fe3+, Zn2+, Cu2+, Ag+ , Ca2+ :
with Hg(NO)2 solution ? (a) only Fe2+, Fe3+ (b) only Fe3+, Zn2+, Cu2+
(a) Cobalt (II) thiocyanate (c) all but not Ca2+ (d) all of these.
(b) Tin (II) chloride (excess) 46. To increase significantly the concentration of free Zn2+
(c) Ammonia solution ion in a solution of the complex ion [Zn(NH3)4]2+
(d) Potassium cyanide solution  [Zn(NH ) ]2+ (aq)
Zn2+ (aq) + 4NH3(aq)  3 4
37. When excess of dilute NH4OH is added to an aqueous
add to the solution some _________
solution of copper sulphate an intense blue colour is
developed. This is due to the formation of : (a) H2O (b) HCl (aq)
(a) [Cu(NH3)6]2+ (b) Cu(OH)2 (c) NH3(aq) (d) NH4Cl (aq)
(c) [Cu(NH3)4] 2+
(d) (NH4)2SO4 47. CoS (black) obtained in group IV of salt analysis is
dissolved in aqua regia and is treated with an excess of
38. A black sulphide is formed by the action of H2S on :
NaHCO3 and then Br2 water. An apple green coloured
(a) cupric chloride (b) cadmium chloride stable complex is formed. It is :
(c) zinc chloride (d) ferric chloride. (a) sodium cobaltocarbonate
39. When NH4Cl is added to a solution of NH4OH : (b) sodium cobaltibromide
(a) the dissociation of NH4OH increases. (c) sodium cobalticarbonate
(b) the concentration of OH- increases. (d) sodium cobaltobromide
(c) the concentrations of both OH– and NH+ increase. 48. A metal salt solution when treated with dimethyl glyoxime
(d) the concentration of OH ion decreases.
-
and NH4OH gives a rose red complex. The metal is -
40. An original solution of an inorganic salt in dilute HCl (a) Ni (b) Zn
gives a brown colouration with potassium (c) Co (d) Mn.
hexacyanidoferrate (III) and reddish brown colouration
49. An aqueous solution of colourless metal sulphate M, gives
with sodium acetate solution. The cation of the salt is :
a white precipitate with NH4OH. This was soluble in excess
(a) Ni2+ (b) Fe3+ of NH4OH. On passing H2S through this solution a white
(c) Cu2+ (d) none precipitate is formed. The metal M in the salt is:
41. Intense blue precipitate of Fe4[Fe(CN)6]3 and potassium (a) Ca (b) Ba
hydroxide solution when mixed gives : (c) Al (d) Zn
(a) K2Fe[Fe(CN)6] - white precipitate 50. Which one of the following ions does not give borax
(b) Fe(OH)3 - reddish-brown precipitate bead test?
(c) Fe(CN)3 - reddish-brown precipitate (a) Cr3+ (b) Cu2+
(d) KFe[Fe(CN)6]- Turnbull’s blue (c) Mn2+ (d) Zn2+
42. Fe(OH)3 and Cr(OH)3 precipitates can be completely 51. Which of the following compound is formed in borax bead
separated by : test?
(a) Aq.NH3 (b) HCl (a) Orthoborate (b) Metaborate
(c) NaOH/H2O2 (d) H2SO4 (c) Double oxide (d) Tetraborate
QUALITATIVE ANALYSIS 265
52. Aqueous Solution of BaBr2 gives yellow precipitate with: 58. Mg is not precipitated in V group because :
(a) K2CrO4 (b) AgNO3 (a) MgCO3 is soluble in water.
(c) (CH3COO)2Pb (d) (a) and (b) both (b) Ksp of MgCO3 is high.
53. The addition of K2CO3(aq) to the following solution is (c) MgCO3 is soluble in NH4OH.
expected to produce a precipitate in every case but that (d) None.
one which does not produce precipitate is :
59. An aqueous solution of a substance gives a white
(a) BaCl2(aq) (b) CaBr2(aq) precipitate on treatment with dilute hydrochloric acid,
(c) Na2SO4(aq) (d) Pb(NO3)2(aq) which dissolves on heating. When hydrogen sulphide is
54. An aqueous solution of salt gives white precipitate with passed through the hot acidic solution, a black precipitate
AgNO3 solution as well as with dilute H2SO4. It may be is obtained. The substance is a
(a) Pb(NO3)2 (b) Ba(NO3)2 (a) Hg22+ salt (b) Cr2+ salt
(c) BaCl2 (d) CuCl2 (c) Ag+ salt (d) Pb2+ salt
55. If crimson flame is given when an inorganic mixture is 60. A metal nitrate reacts with KI solution to give yellow
tested by flame test, it may be due to the presence of precipitate which on addition of excess of more
concentrated solution (6 M) of KI dissolves forming a
(a) potassium (b) strontium solution. The cation of metal nitrate is :
(c) barium (d) calcium (a) Hg22+ (b) Ag+
56. A brick red colour is imparted to Bunsen flame by a : (c) Pb2+ (d) Cu2+
(a) Ca salt (b) Sr salt
(c) Na salt (d) Co salt
57. The presence of magnesium is confirmed in the qualitative
analysis by :
(a) titan yellow solution + 2M NaOH solution
(b) disodium hydrogen phosphate + NH4Cl + NH3(aq.)
(c) magneson (I) reagent
(d) all of these
QUALITATIVE ANALYSIS 266

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS/ADVANCED QUESTIONS

JEE MAINS QUESTIONS
Objective Questions I [Only one correct option]

1. [X] + H2SO4 
 [Y] a colourless gas with irritating smell; 7. A solution of a metal ion when treated with KI gives a red
[Y] + K2Cr2O7 + H2SO4 
 green solution. [X] and [Y] precipitate which dissolves in excess KI to give a colourless
solution. Moreover, the solution of metal ion on treatment
are respectively : (2003)
with a solution of cobalt(II) thiocyanate gives rise to a
(a) SO32- , SO2 (b) Cl–, HCl deep blue crystalline precipitate. The metal ion is :
(c) S2–, H2 S (d) CO32-, CO2 (2007)
2. A sodium salt on treatment with MgCl 2 gives white (a) Pb2+ (b) Hg2+
precipitate only on heating. The anion of the sodium salt (c) Cu2+ (d) Co2+
is: (2004)
8. Passing H2S gas into a mixture of Mn2+, Ni2+, Cu2+ and Hg2+
(a) HCO3- (b) CO32– ions in an acidified aqueous solution precipitates:
(c) NO3- (d) SO42– (2011)
3. A metal nitrate reacts with KI to give a black precipitate (a) CuS and HgS
which on addition of excess of KI is converted into orange
(b) MnS and CuS
colour solution. The cation of the metal nitrate is :
(c) MnS and NiS
(2005)
(d) NiS and HgS
(a) Hg2 (b) Bi3+
9. an aqueous solution of salt X turns blood red on treatment
(c) Pb2+ (d) Cu+
with SCN– and blue on treatment with K4[Fe(CN)6]. X also
4. A white precipitate is obtained when a solution is diluted gives a positive chromyl chloride test. The salt X is:
with H2O and boiled. On addition of excess NH 4Cl/ (2015)
NH4OH, the volume of precipitate decreases leaving behind
a white gelatinous precipitate. Identify the precipitate which (a) CuCl2 (b) FeCl3
dissolves in ammonia solution or NH4Cl. (2006) (c) Cu(NO3)2 (d) Fe(NO3)3
(a) Al(OH)3 (b) Zn(OH)2 10. The cation that will not be precipitated by H2S in the
(c) Mg(OH)2 (d) Ca(OH)2 presence of dil. HCl is. (2015)
5. In blue solution of copper sulphate excess of KCN is added (a) Cu2+ (b) Pb2+
then solution becomes colourless due to the formation of:
(c) As3+ (d) Co2+
(2006)
11. A pink coloured salt turned blue on heating. The presence
(a) [Cu(CN)4]2-
of which cation is most likely? (2015)
(b) Cu2+ get reduced to form [Cu(CN)4]3–
(a) Cu2+ (b) Fe2+
(c) Cu(CN)2
(c) Zn2+ (d) Co2+
(d) CuCN

6. MgSO4 + NH4OH + Na2 HPO4   white crystalline

precipitate. The formula of crystalline precipitate is :
(2006)
(a) MgCl2. MgSO4 (b) MgSO4
(c) Mg(NH4)PO4 (d) Mg(PO4)2
QUALITATIVE ANALYSIS 267
12. The hottest region of Bunsen flame shown in figure below (c) Ferric ion give blood red colour with potassium
is (2016) thiocyanate.
(d) Cu2+ ion give chocolate coloured precipitate with
potassium ferrocyanide solution.
18. Given below two statements:
Statement I: Colourless cupric metaborate is reduce to
cuprous meta borate in a luminous flame.
Statement II: Cuprous metaborate is obtained by heating
boric anhydride and copper sulphate in a non-luminous
flame.
(a) Region 1 (b) Region 2
In the light of above statements choose the most
(c) Region 3 (d) Region 4 appropriate answer from the options given below.
13. Sodium extract is heated with concentrated HNO3 before (2021-02-24/Shift -1)
testing for halogens because (2016)
(a) Both Statement I and Statement II are false.
(a) Silver halides are totally insoluble in nitric acid
(b) Statement I is false but Statement II is true.
(b) Ag2S and AgCN are soluble in acidic medium.
(c) Statement I true but Statement II is false.
(c) S2- and CN- , if present are decomposed by
(d) Both statement I and Statement II are true.
conc. HNO3 and hence do not interfere in the test.
19. Given below two statements:
(d) Ag reacts faster with halides in acidic medium.
Statements I: The identification of Ni2+ is carried out by
14. Sodium salt of an organic acid ‘X’ produce effervescence
dimethyl glyoxime in presence of NH4OH.
with conc. H2SO4 . X reacts with acidified aqueous CaCl2
solution to give a white precipitate which decolourises Statement II: The dimethyl glyoxime is a bidentate neutral
acidic solution of KMnO4. ‘X’ is : (2017) ligand.

(a) CH3COONa (b) Na2C2O4 In the light of above statements choose the most
appropriate answer from the options given below.
(c) C6H5COONa (d) HCOONa
(2021-02-25/Shift -2)
15. A solution containing a group-IV cation gives a precipitate
(a) Both Statement I and Statement II are false.
on passing H2S. A solution of this precipitate in dil. HCl
produce a white precipitate with NaOH solution and bluish- (b) Statement I true but Statement II is false.
white precipitate with basic potassium ferrocyanide. The (c) Both statement I and Statement II are true.
cation is: (2017) (d) Statement I is false but Statement II is true.
(a) Co2+ (b) Ni2+ 20. An inorganic compound ‘X’ on treatment with
(c) Mn 2+
(d) Zn 2+ concentrated H2SO4 produce brown fumes and dark brown
16. A white sodium salt dissolve readily in water to give a ring with FeSO4 in presence of concentrated H2SO4. Also
solution which is neutral to litmus when silver nitrate compound ‘X’ give precipitate ‘Y’ , when its solution in
solution is added to the aforementioned solution, a white dilute HCl is treated with H2S gas. The precipitate ‘Y’ on
precipitate is obtained which does not dissolve in dil. nitric treatment with concentrated HNO3 followed by excess of
acid. The anion is (2018) NH 4 OH further give deep blue coloured solution,
compound ‘X’ is: (2021-07-20/Shift -1)
(a) CO32- (b) SO42-
(a) Co(NO3) 2 (b) Pb(NO2) 2
(c) Cl- (d) S2-
(c) Cu(NO3) 2 (d) Pb(NO3) 2
17. The incorrect statement is (2018)
21. Cu salt react with potassium iodide to give
2+
(a) Cu2+ salt give red coloured borax bead test in reducing
(2021-07-20/Shift -2)
flame.
(a) Cu2I2 (b) Cu2I3
(b) Cu2+ and Ni2+ ions give black precipitate with H2S in
presence of HCl solution. (c) CuI (d) Cu(I3 ) 2
QUALITATIVE ANALYSIS 268
22. To an aqueous solution containing ions such as Al3+, Zn2+, 29. The equilibrium
Ca2+,Fe3+,Ni2+,Ba2+ and Cu2+ added /are
 Cu 0  Cu II
2Cu I 
(2021-07-27/Shift -2)
(a) 1 (b) 3 in aqueous medium at 25° C shifts towards the left in the
presence of : (2011)
(c) 4 (d) 2
(a) NO3- (b) Cl-
23. Which one of the following when dissolve in water gives
coloured solution in nitrogen atmosphere? (c) SCN– (d) CN–
(2021-08-26/Shift -1) 30. For the given aqueous reaction which of the statements)
(a) CuCl2 (b) AgCl is (are) true ? (2012)
dilute
(c) ZnCl2 (d) Cu2Cl2 H2SO4
excess KI + K3 [Fe(CN)6] brownish-yellow solution
24. Acidic ferric chloride solution on treatment with excess of ZnSO4
potassium ferrocyanide gives a Prussian blue coloured ppt. (white precipitate + brownish - yellow filtrate)
It is (2021-08-27/Shift -1)
(a) Fe4[Fe(CN)6]3 (b) K3Fe[Fe(CN)6]2 Na2S2O3

(c) HFe[Fe(CN)6] (d) KFe[Fe(CN)6] colourless solution

25. The addition of dilute NaOH to Cr salt solution will give

3+ (a) The first reaction is a redox reaction
(2021-08-27/Shift -2) (b) White precipitate is Zn3 [Fe(CN)6]2
(a) A solution of [Cr(OH) 4]- (c) Addition of filtrate to starch solution gives blue colour.
(b) Precipitate of Cr2O3(H2O) n (d) White precipitate is soluble in NaOH solution
(c) Precipitate of [Cr(OH)6]3-
Numerical Value Type Questions
(d) Precipitate of Cr(OH) 3
26. In the given chemical reaction, colour of Fe2+ and Fe3+ ions 31. On complete reaction of FeCl3 with oxalic acid in aqueous
are respectively: (2021-09-01/Shift -2) solution containing KOH, resultant in the formation of
product A. The secondary valency of Fe in product A is
5Fe 2   MnO 4  8H   Mn 2   4H 2 O  5Fe3 ……..(Round off to the nearest integer).
(2021-03-17/Shift -2)
(a) Yellow, orange (b) Yellow, green
32. Consider the sulphides-HgS, PbS, CuS, Sb2S3 ,As2S3, and
(c) Green, orange (d) Green, yellow
CdS. Number of these sulphide soluble in 50% HNO3 is……..
27. The potassium ferrocyanide solution gives a Prussian blue (2021-08-31/Shift -1)
colour, when added to : (2021-09-01/Shift -2) JEE ADVANCED QUESTIONS
(a) CoCl3 (b) FeCl2 Objective Questions I [Only one correct option]
(c) CoCl2 (d) FeCl3 33. Concentrated nitric acid, upon long standing, turns yellow-
brown due to the formation of : (2013)
Objective Questions II (a) NO (b) NO2
[One or more than one correct option] (c) N2O (d) N2O4
28. A solution of colourless salt H on boiling with excess NaOH 34. Upon treatment with ammoniacal H2S, the metal ion that
produces a non & flammable gas. The gas evolution ceases precipitates as a sulfide is : (2013)
after some time. Upon addition of Zn dust to the same (a) Fe(III) (b) Al (III)
solution, the gas evolution restarts. The colourless salt(s) (c) Mg(II) (d) Zn(II)
H is (are) : (2008) 35. The green colour produced in the borax bead test of the
(a) NH4 NO3 (b) NH4NO2 chromium(III) salt is due to (2019)
(c) NH4Cl (d) (NH4 )2SO4 (a) CrB (b) Cr2O3
(c) Cr(BO2)3 (d) Cr2(B4O7)3
QUALITATIVE ANALYSIS 269
36. A colourless aqueous solution contains nitrates of two Paragraph Type Questions
metals, X and Y when it was added to an aqueous solution Use the following passage, to solve Q. 41 to Q. 43
of NaCl, a white precipitate was formed. This precipitate Passage
was found to be partly soluble in hot water to give a residue
p-Amino-N, N-dimethylaniline is added to a strongly acidic
P and a solution Q. The residue P was soluble in aq. NH3 solution of X. The resulting solution is treated with a few
and also in excess sodium thiosulphate. The hot solution drops of aqueous solution of Y to yield blue coloration
of Q give a precipitate with KI. The metals X nad Y due to the formation of methylene blue. Treatment of the
respectively are (2020) aqueous solution of Y with the reagent potassium
hexacyanoferrate(II) leads to the formation of an intense
(a) Ag and Pb (b) Ag and Cd blue precipitate. The precipitate dissolves on excess
(c) Cd and Pb (d) Cd and Zn addition of the reagent. Similarly, treatment of the solution
of Y with the solution of potassium hexacyanoferrate(III)
Objective Questions II
leads to a brown coloration due to the formation of Z.
[One or more than one correct option] (2009)
37. The pair(s) of ions where BOTH the ions are precipitated 41. The compound X is :
upon passing H2S gas in presence of dilute HCl, is(are) (a) NaNO3 (b) H2S
(2014) (c) Na2 SO4 (d) Na2 S
(a) Ba2+,Zn2+ (b) Bi3+,Fe3+ 42. The compound Y is :
(c) Cu2+,Pb2+ (d) Hg2+,Bi3+ (a) MgCl2 (b) FeCl2
38. The correct option(s) to distinguish nitrate salt of Mn 2+ (c) FeCl3 (d) ZnCl2
and Cu 2+
taken separately is (are) (2018) 43. The compound Z is :
(a) Mn2+ shows the characteristic green colour in flame (a) Mg2 [Fe(CN)6] (b) Fe[Fe(CN)6]
test. (c) Fe4 [Fe(CN)6 ]3 (d) K2Zn3 [Fe(CN)6]2
(b) Only Cu2+ shows the formation of precipitate by Use the following passage, to solve Q. 44 to Q. 46
passing H2S in acidic medium Passage
(c) Only Mn2+ shows the formation of precipitate by When a metal rod M is dipped into an aqueous colourless
passing H2S in faintly acidic medium concentrated solution of compound N the solution turns
light blue. Addition of aqueous NaCl to the blue solution
(d) Cu2+/ Cu has higher reduction potential than Mn2+/
gives a white precipitate O. Addition of aqueous NH3
Mn (measured under similar conditions) dissolves O and gives an intense blue solution. (2011)

Numerical Value Type Questions 44. The metal rod M is :

(a) Fe (b) Cu
39. Among PbS, CuS, HgS, Ag2S, NiS, CoS, Bi2S3 and SnS2 ,
(c) Ni (d) Co
the total number of yellow coloured sulphides is (2014)
45. The compound N is :
40. An acidified solution of potassium chromate was layered
(a) AgNO3 (b) Zn(NO3)2
with an equal volume of amyl alcohol. When it was shaken
(c) Al(NO3)3 (d) Pb(NO3)2
after the addition of 1ml of 3% H2O2, a blue alcohol layer
46. The final solution contains
was obtained. The blue colour is due to the formation of a
(a) [Pb(NH3)4]2+ and [CoCl4]2–
chromium (IV) compound ‘X’. What is the number of
(b) [Al(NH3)2]+ and [Cu(NH3 )4]2+
oxygen atom bonded to chromium through only single
bond in a molecule of ‘X’? (2020) (c) [Ag(NH3)2]+ and [Cu(NH3)4]2+
(d) [Ag(NH3)2]+ and [Ni(NH3)6]2+
QUALITATIVE ANALYSIS 270
Use the following passage, to solve Q. 47 to Q. 48 Use the following passage, to solve Q. 49 to Q. 50
Passage Passage
An aqueous solution of a mixture of two inorganic salts, The reaction of K4[Fe(CN)6] with freshly prepared FeSO4
when treated with dilute HCl, gave a precipitate (P) and a Solution produce a dark blue precipitate called Turnbull’s
filtrate (Q). The precipitate P was found to dissolve in hot
blue. Reaction of K4[Fe(CN)6] with FeSO4 Solution in
water. The filtrate (Q) remains unchanged, when treated
with H2S in a dilute mineral acid medium. However, it gave complete absence of air produce a white precipitate X,
a precipitate (R) with H2S in an ammoniacal medium. The which turn blue in air, Mixing the FeSO4 solution with
precipitate R gave a coloured solution (S), when treated NaNO3 followed by a slow addition of concentrated H2SO4
with H2O2 in an aqueous NaOH medium. (2013) through the side of test tube produce a brown ring.
47. The precipitate P contains (2021)
(a) Pb2+ (b) Hg 2+
49. Precipitate X is
(c) Ag+ (d) Hg2+
(a) K4[Fe(CN)6]3 (b) Fe[Fe(CN)6]
48. The coloured solution S contains
(c) K2[Fe(CN)6] (d) KFe[Fe(CN)6]
(a) Fe2(SO4)3 (b) CuSO4
(c) ZnSO4 (d) Na2CrO4 50. Among the following the brown ring is due to formation
of
(a) [Fe(NO2)2(SO4)2]2- (b) [Fe(NO2)2(H2O)4]3+
(c) [Fe(NO2)4(SO4)2] (d) [Fe(NO)(H2O)5]2+
QUALITATIVE ANALYSIS 271

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ANSWER KEY 272

Answer Key
CHAPTER -11 p -BLOCK ELEMENTS (GROUP 15-18)

EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

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

1. (c) 2. (a) 3. (c) 4. (c) 5. (b) 1. (c) 2. (c) 3. (b) 4. (d) 5. (c)
6. (a) 7. (a) 8. (a) 9. (b) 10. (d) 6. (d) 7. (d) 8. (d) 9. (b) 10. (d)
11. (a) 12. (a) 13. (c) 14. (c) 15. (b) 11. (c) 12. (a) 13. (d) 14. (b) 15. (c)
16. (c) 17. (a) 18. (c) 19. (c) 20. (d) 16. (a) 17. (d) 18. (a) 19. (d) 20. (b)
21. (a) 22. (d) 23. (c) 24. (d) 25. (c) 21. (a) 22. (b) 23. (b) 24. (c) 25. (d)
26. (a) 27. (b) 28. (a) 29. (c) 30. (d) 26. (c) 27. (d) 28. (b) 29. (d) 30. (a)
31. (c) 32. (b) 33. (c) 34. (a) 35. (d) 31. (d) 32. (a) 33. (a) 34. (c) 35. (b)
36. (a) 37. (a) 38. (d) 39. (a) 40. (c) 36. (a) 37. (d) 38. (b) 39. (d) 40. (a)
41. (b) 42. (c) 43. (c) 44. (a) 45. (d) 41. (a) 42. (b) 43. (d) 44. (b) 45. (d)
46. (c) 47. (a) 48. (a) 49. (a) 50. (c)
46. (d) 47. (d) 48. (d) 49. (b) 50. (a)
51. (d) 52. (d) 53. (a) 54. (a) 55. (d) 51. (1.00) 52. (1.67) 53. (3.00) 54. (1.00) 55. (1.00)
56. (a) 57. (b) 58. (b) 59. (a) 60. (b)
56. (19.00) 57. (3.00) 58. (3.00) 59. (c) 60. (d)
61. (a) 62. (d) 63. (a) 64. (d) 65. (b)
66. (a) 67. (b) 68. (c) 69. (d) 70. (c)
71. (d) 72. (a) 73. (a) 74. (c) 75. (c)
76. (c) 77. (d) 78. (b) 79. (c) 80. (c)
81. (b) 82. (d) 83. (d) 84. (d) 85. (c)
86. (c) 87. (c) 88. (b) 89. (d) 90. (a)
91. (c) 92. (b) 93. (a) 94. (b) 95. (a)
96. (b) 97. (a) 98. (b) 99. (d) 100. (b)
101. (a) 102. (d) 103. (a) 104. (a) 105. (d)
106. (b) 107. (a) 108. (a) 109. (c) 110. (c)
111. (b) 112. (d) 113. (c) 114. (c) 115. (a)
ANSWER KEY 273

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

EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS

DIRECTION TO USE -
DIRECTION TO USE -
Scan the QR code and check detailed solutions.
Scan the QR code and check detailed solutions.

1. (d) 2. (c) 3. (b) 4. (d) 5. (a) 1. (c) 2. (a) 3. (a) 4. (d) 5. (c)
6. (c) 7. (b) 8. (d) 9. (b) 10. (b) 6. (a) 7. (b) 8. (c) 9. (b) 10. (b)
11. (b) 12. (c) 13. (d) 14. (a) 15. (a) 11. (c) 12. (d) 13. (b) 14. (b) 15. (d)
16. (b) 17. (a) 18. (d) 19. (c) 20. (a) 16. (a) 17. (b) 18. (a,b,c)19. (b,c) 20. (b,d)
21. (a) 22. (d) 23. (d) 24. (a) 25. (c) 21. (a,c,d) 22. (a,d) 23.(b,c) 24.(a,b,c) 25. (a,b,d)
26. (c) 27. (b) 28. (b) 29. (c) 30. (b)
26. (5.00) 27. (4.00) 28. (6.00) 29. (6.00) 30. (a)
31. (b) 32. (b) 33. (b) 34. (d) 35. (a)
36. (a) 37. (d) 38. (a) 39. (a) 40. (b) 31. (c) 32. (a) 33. (c) 34. (c) 35. (b)
41. (A - r, B - p,s, C - q)
42. (A - p,r, B - p,s, C - q,r, D - q,r, E - q)
43. (A - p,q, B - p,s, C - r, D - r,s)
44. (white) 45. (6.00)
ANSWER KEY 274

CHAPTER -12 METALLURGY

EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

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

1. (b) 2. (a) 3. (a) 4. (b) 5. (a) 1. (b) 2. (b) 3. (b) 4. (b) 5. (c)
6. (c) 7. (c) 8. (b) 9. (c) 10. (a) 6. (b) 7. (a) 8. (c) 9. (b) 10. (d)
11. (b) 12. (d) 13. (a) 14. (d) 15. (a) 11. (a) 12. (d) 13. (a) 14. (a) 15. (b)
16. (c) 17. (c) 18. (d) 19. (c) 20. (c) 16. (b) 17. (a) 18. (a) 19. (c) 20. (d)
21. (b) 22. (c) 23. (c) 24. (d) 25. (b) 21. (c) 22. (d) 23. (b) 24. (a) 25. (b)
26. (b) 27. (b) 28. (b) 29. (d) 30. (c) 26. (c) 27. (c) 28. (a) 29. (c) 30. (b)
31. (c) 32. (c) 33. (c) 34. (d) 35. (a) 31. (d) 32. (b) 33. (d) 34. (a) 35. (c)
36. (a) 37. (c) 38. (a) 39. (d) 40. (a) 36. (d) 37. (d) 38. (b) 39. (a) 40. (a)
41. (b) 42. (a) 43. (b) 44. (c) 45. (c) 41. (d) 42. (b) 43. (a) 44. (b) 45. (b)
46. (a) 47. (d) 48. (a) 49. (c) 50. (b) 46. (b) 47. (6.00) 48. (d) 49. (d)
51. (d) 52. (a) 53. (b) 54. (a) 55. (d) 50. (b) 51. (d) 52. (b) 53. (c) 54. (b)
56. (c) 57. (d) 58. (b) 59. (c) 60. (b) 55. (b) 56. (b) 57. (d) 58. (d) 59. (a)
61. (b) 62. (c) 63. (c) 64. (b) 65. (d) 60. (a)
66. (c) 67. (a) 68. (d) 69. (c) 70. (c)
71. (d) 72. (d) 73. (d) 74. (b) 75. (a)
ANSWER KEY 275

CHAPTER -12 METALLURGY

EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

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

1. (d) 2. (c) 3. (d) 4. (c) 5. (c) 1. (c) 2. (d) 3. (b) 4. (b) 5. (a)
6. (d) 7. (b) 8. (b) 9. (c) 10. (b) 6. (a) 7. (a) 8. (c) 9. (b) 10. (b)
11. (d) 12. (b) 13. (c) 14. (c) 15. (a) 11. (d) 12. (b.c.d)
16. (a) 17. (d) 18. (d) 19. (a) 20. (c) 13. (b,c,d) 14. (a,b,c,d)
21. (d) 22. (d) 23. (a,b,c,d) 15. (b,c,d) 16. (a,c,d)
24. (b,d) 25. (b,c,d) 26. (a,b,c) 17. (935K)
27. (a.b.d) 28. (a.c,d) 18. (A–p,r; B–p; C–q; D–s)
29. (a.b.c.d) 30. (a,b,c,d) 19. (A – p; B – q; C – r,s; D – p,s)
31. (a.b) 32. (a,b,c) 20. (A – p,s; B – q, s; C – r,t; D – q,t)
33. (a,d) 34. (b,c) 35. (a,b) 36. (a.b)
37. (a.d) 38. (a,b,c,d) 39. (a,b) 40. (c,d)
41. (a,b,c,d) 42. (a,b,c) 43. (a,b,c)
44. (a,b,d) 45. (a,c) 46. (a,c)
47. (a,b,c) 48. (a,b) 49. (a,b,d) 50. (b,c)
51. (b,c) 52. (3.00) 53. (3.00) 54. (9.00)
55. (a) 56. (a) 57. (c) 58. (a)
59. (b) 60. (a) 61. (b) 62. (c)
63. (b) 64. (c) 65. (b) 66. (a)
67. (A – r; B – q,r,s ; C – s; D – p,q)
68. (A – q,s; B – r; C – q,r,s; D – p)
69. (A – s; B – r; C – q; D – p)
70. (A – r; B – s; C – p; D – q)
ANSWER KEY 276

CHAPTER -13 d AND f BLOCK ELEMENTS

EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

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

1. (d) 2. (d) 3. (c) 4. (a) 5. (c) 1. (a) 2. (a,b) 3. (a) 4. (a) 5. (d)
6. (d) 7. (d) 8. (c) 9. (d) 10. (a) 6. (c) 7. (d) 8. (d) 9. (c) 10. (d)
11. (a) 12. (a) 13. (a) 14. (d) 15. (d) 11. (a) 12. (d) 13. (d) 14. (a) 15. (c)
16. (c) 17. (b) 18. (c) 19. (a) 20. (a) 16. (d) 17. (b) 18. (a) 19. (c) 20. (c)
21. (b) 22. (b) 23. (b) 24. (b) 25. (d) 21. (c) 22. (d) 23. (b) 24. (d) 25. (c)
26. (a) 27. (d) 28. (d) 29. (d) 30. (b) 26. (a) 27. (b) 28. (d) 29. (c) 30. (c)
31. (b) 32. (d) 33. (c) 34. (c) 35. (a) 31. (c) 32. (a) 33. (c) 34. (a) 35. (b)
36. (b) 37. (d) 38. (d) 39. (c) 40. (b) 36. (d) 37. (d) 38. (b) 39. (b) 40. (c)
41. (b) 42. (a) 43. (c) 44. (b) 45. (c) 41. (b) 42. (a) 43. (b) 44. (18.00) 45. (18.00)
46. (c) 47. (c) 48. (a) 49. (a) 50. (a) 46. (6.00) 47. (49.00) 48. (10.00)
51. (d) 52. (c) 53. (c) 54. (c) 55. (b) 49. (7.00) 50. (18.00) 51. (c)
56. (d) 57. (d) 58. (a) 59. (a) 60. (c) 52. (b) 53. (d) 54. (b)
61. (d) 62. (b) 63. (a) 64. (a) 65. (c) 55. (c)
66. (d) 67. (d) 68. (a) 69. (c) 70. (b)
71. (a) 72. (c) 73. (d) 74. (a) 75. (a)
76. (b) 77. (a) 78. (a) 79. (a) 80. (d)
81. (d) 82. (d) 83. (a) 84. (d) 85. (a)
86. (c) 87. (a) 88. (d) 89. (c) 90. (b)
91. (d) 92. (d) 93. (d) 94. (b) 95. (a)
96. (b) 97. (d) 98. (c) 99. (d) 100. (a)
ANSWER KEY 277

CHAPTER -13 d AND f BLOCK ELEMENTS

EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

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

1. (a) 2. (c) 3. (b) 4. (a) 5. (c) 1. (d) 2. (a) 3. (a) 4. (a) 5. (b)
6. (b) 7. (d) 8. (b) 9. (a) 10. (b) 6. (a) 7. (b) 8. (c) 9. (b) 10. (c)
11. (a) 12. (c) 13. (d) 14. (b) 15. (c) 11. (a) 12. (d) 13. (a,b,c)14. (c,d) 15. (a,b,c)
16. (d) 17. (a) 18. (d) 19. (d) 20. (c) 16. (a,c,d)17. (a,b) 18. (7.00) 19. (6.00) 20. (1.00)
21. (c) 22. (b) 23. (c) 24. (c) 25. (b) 21. (126.00) 22. (4.00) 24.(c) 25. (d)
26. (a) 27. (a) 28. (c) 29. (c) 30. (a)
31. (c) 32. (c) 33. (c) 34. (d) 35. (b)
36. (b) 37. (b) 38. (a) 39. (d) 40. (c)
41. (b) 42. (c) 43. (a) 44. (a) 45. (b)
46. (c) 47. (c) 48. (a,b,c,d) 49. (b,c)
50. (a,b,c,d) 51. (a,b,d) 52. (c,d)
53. (a,c) 54. (a,b,c)55. (d) 56. (c) 57. (b)
58. (a) 59. (b) 60. (b) 61. (b) 62. (b)
63. (a) 64. (a) 65. (b) 66. (b) 67. (c)
68. (d) 69. (b) 70. (a)
ANSWER KEY 278

CHAPTER -14 CHEMISTRY IN EVERYDAY LIFE

EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

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

1. (c) 2. (c) 3. (b) 4. (d) 5. (a) 1. (d) 2. (c) 3. (c) 4. (c) 5. (d)
6. (a) 7. (b) 8. (a) 9. (c) 10. (c) 6. (a) 7. (b) 8. (d) 9. (c) 10. (d)
11. (a) 12. (d) 13. (d) 14. (c) 15. (c) 11. (d) 12. (d) 13. (a) 14. (a) 15. (d)
16. (a) 17. (a) 18. (b) 19. (c) 20. (c) 16. (b) 17. (b) 18. (a) 19. (d) 20. (b)
21. (b) 22. (b) 23. (a) 24. (b) 25. (d) 21. (a) 22. (c) 23. (c) 24. (d) 25. (b)
26. (a) 27. (b) 28. (c) 29. (c) 30. (b) 26. (b) 27. (2.00) 28. (3.00) 29. (37.84) 30. (9.00)
31. (a) 32. (c) 33. (c) 34. (a) 35. (c) 31. (a) 32. (a) 33. (c) 34. (b) 35. (a)
36. (d) 37. (d) 38. (a) 39. (a) 40. (d) 36. (c) 37. (c) 38. (b) 39. (b) 40. (d)
41. (c) 42. (c) 43. (b) 44. (c) 45. (a)
46. (b) 47. (c) 48. (d) 49. (a) 50. (b)
51. (b) 52. (d) 53. (b) 54. (a) 55. (b)
56. (b) 57. (c) 58. (c) 59. (d) 60. (d)
61. (a) 62. (d) 63. (c) 64. (a) 65. (b)
66. (b) 67. (c) 68. (b) 69. (b) 70. (c)
71. (d) 72. (d) 73. (b) 74. (b) 75. (b)
76. (b) 77. (a) 78. (d) 79. (d) 80. (b)
ANSWER KEY 279

CHAPTER -15 PRACTICAL ORGANIC CHEMISTRY

EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS

DIRECTION TO USE - DIRECTION TO 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) 5. (b) 1. (a) 2. (b) 3. (c) 4. (b) 5. (b)
6. (c) 7. (a) 8. (d) 9. (a) 10. (a) 6. (a) 7. (b) 8. (c) 9. (b) 10. (b)
11. (c) 12. (c) 13. (c) 14. (a) 15. (c) 11. (d) 12. (d) 13. (c) 14. (a) 15. (c)
16. (a) 17. (b) 18. (c) 19. (d) 20. (d) 16. (c) 17. (b) 18. (a) 19. (b) 20. (b)
21. (b) 22. (a) 23. (b) 24. (d) 25. (b) 21. (d) 22. (a) 23. (b) 24. (b) 25. (c)
26. (d) 27. (a) 28. (a) 29. (b) 30. (c) 26. (b) 27. (b) 28. (a) 29. (b) 30. (c)
31. (c) 32. (a) 33. (a) 34. (b) 35. (b) 31. (c) 32. (c) 33. (d) 34. (d) 35. (c)
36. (c) 37. (c) 38. (a) 39. (b) 40. (a) 36. (b) 37. (d) 38. (a) 39. (4.00) 40. (19.00)
41. (c) 42. (a) 43. (a) 44. (b) 45. (d) 41. (42.00) 42. (40.00)
46. (b) 47. (d) 48. (c) 49. (d) 50. (a) 43. (1125.00) 44. (7.00) 45. (68.00) 46. (12.00)
51. (d) 52. (c) 53. (d) 54. (b) 55. (b) 47. (b) 48. (c) 49. (b) 50. (a) 51. (a)
52. (c) 53. (b) 54. (c) 55. (b)
ANSWER KEY 280

CHAPTER -15 PRACTICAL ORGANIC CHEMISTRY

EXERCISE - 3 :
ADVANCED OBJECTIVE QUESTIONS

DIRECTION TO USE -
Scan the QR code and check detailed solutions.

1. (a) 2. (b) 3. (b) 4. (a) 5. (b)

6. (a) 7. (a) 8. (c) 9. (b) 10. (d)
11. (c) 12. (b) 13. (c) 14. (c) 15. (b)
16. (c) 17. (c) 18. (c) 19. (c) 20. (a,b,c)
21. (a,b) 22. (b,c) 23. (b,c) 24. (a,b) 25. (a,b,c)
26. (a,b,c,d)
27. (A-r,s;B-p,q; C-p; D-r)
28. (A-q, B-r,s, C-p, D-p,t)
29. (A-t, B-p,q,r,s, C-p,q,r,s, D-q)
30. (A-p,s, B-p,q, C-p,q,r,s, D-p,q)
31. (a) 32. (a) 33. (a) 34. (d) 35. (b)
36. (c) 37. (b) 38. (d) 39. (b) 40. (c)
41. (c) 42. (b) 43. (a) 44. (c) 45. (d)
ANSWER KEY 281

CHAPTER -16 QUALITATIVE ANALYSIS

EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS/ADVANCED
QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

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

1. (d) 2. (b) 3. (c) 4. (c) 5. (b) 1. (a) 2. (a) 3. (b) 4. (b) 5. (c)
6. (c) 7. (b) 8. (b) 9. (a) 10. (d) 6. (c) 7. (b) 8. (a) 9. (b) 10. (d)
11. (d) 12. (a) 13. (c) 14. (a) 15. (b) 11. (d) 12. (b) 13. (c) 14. (b) 15. (d)
16. (c) 17. (a) 18. (a) 19. (c) 20. (b) 16. (c) 17. (b) 18. (a) 19. (b) 20. (c)
21. (a) 22. (d) 23. (d) 24. (d) 25. (b) 21. (a) 22. (a) 23. (a) 24. (a) 25. (b)
26. (b) 27. (c) 28. (c) 29. (c) 30. (c) 26. (d) 27. (d) 28. (a,b) 29. (b,c,d) 30. (a,c,d)
31. (6.00) 32. (4.00) 33. (b) 34. (d) 35. (c)
31. (b) 32. (d) 33. (d) 34. (a) 35. (a)
36. (a) 37. (c,d) 38. (b,d) 39. (1.00) 40. (4.00)
36. (c) 37. (c) 38. (a) 39. (d) 40. (b)
41. (b) 42. (c) 43. (b) 44. (b) 45. (a)
41. (b) 42. (c) 43. (c) 44. (d) 45. (d)
46. (c) 47. (a) 48. (d) 49. (c) 50. (d)
46. (b) 47. (a) 48. (a) 49. (d) 50. (d)
51. (b) 52. (d) 53. (c) 54. (c) 55. (b)
56. (a) 57. (d) 58. (b) 59. (d) 60. (c)
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 Acid 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
Qualitative Analysis

VOLUME 4:
Coordination Compounds
Chemical Kinetics
Electrochemistry
Surface Chemistry
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