Aakash Modules 04

Chapter 9
Electrochemistry
Chapter Contents
z Metallic / Electrolytic METALLIC / ELECTROLYTIC CONDUCTORS
Conductors
z Equivalent Conductivity
Conductors
Substances which allow electric current to flow through them are called
z Molar Conductivity conductors while those which do not permit the flow of electric current
z Variation of Molar are called insulators. There are two types of conductors namely
Conductivity with (i) metallic conductors and (ii) electrolytic conductors.
Concentration Differences between Metallic and Electrolytic Conduction
z Kohlrausch Law of Metallic conduction Electrolytic conduction
Independent Migration of Ions
1. Metallic conduction is Electrolytic conduction is
z Electrolysis carried by the movement of carried by the movement of
electrons. ions.
z Quantitative Aspects of
Electrolysis and Faraday's 2. It involves no change in the It involves the decomposition of
Laws chemical properties of the the electrolyte as a result of the
conductor. chemical reaction.
z Electrode Potential and EMF
of a Cell 3. It does not involve the It involves the transfer of matter
transfer of any matter. as ions.
z Nernst Equation
4. Metallic conduction Electrolytic conduction
z Commercial Cells decreases with increase in increases with increase in
temperature. temperature.
z Corrosion
Factors affecting electrolytic conduction
a. Nature of the electrolyte : Conductivity  extent of ionization
b. Size of the ions produced and their solvation : Greater the size of
the ions or greater the solvation of the ions, lesser is the
conductance.
c. Nature of the solvent and its viscosity : Greater the polarity of the
solvent, greater is the ionization and hence greater is the
conductance. Similarly, greater is the viscosity of a solvent, lesser
is the conductance.
d. Concentration of the solution : Higher the conc. of the solution lesser
is the conduction.
e. Temperature Conductance  Temperature.
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68 Electrochemistry NEET
Conductance (G) : The reciprocal of resistance is called as conductance i.e.
1
G
R
It measures the ease with which current flows through a conductor.
1
Units. G  ohm1 or mho or siemen (S) (1S = 1–1) (S.I. unit : siemen (S))
ohm
Resistivity (Specific Resistance)

The resistance of a conductor is
(i) Directly proportional to its length
Rl
(ii) Inversely proportional to its area of cross section.
1
R
a
Combining equations (i) and (ii)
l l
R or R  
a a
where  = Constant of proportionality known as resistivity or specific resistance.

If l = 1 cm; a = 1 cm2 then R = 
Thus resistivity may be defined as,
"The resistance offered by a conductor of unit length with unit area of cross-section."
In other words, specific resistance is the resistance offered by all the ions present in 1 cm3 of an electrolytic
solution.
l Ra ohm cm2
Units : R  or l = Ra or    = ohm - cm
a l cm
Specific Conductance (Conductivity)

The reciprocal of the specific resistance is called as specific conductance. It is denoted by  (Kappa)
1 Ra
 We know,  
 l
1 l 1 1
 l   Now G
Ra a R R
l
  G
a
If l = 1 cm, a = 1 cm2, then  = G
Hence conductivity or specific conductance of a solution may be defined as the conductance of a conductor
of unit length with unity area of cross section.
It may be defined as conducting power of all the ions present in 1 cm3 of an electrolytic solution.
1 1
Units :    ohm1cm1
 ohm  cm
S.I. units : Conductivity : Sm–1.
NEET Electrochemistry 69
Cell Constant
For a particular cell, l/a is constant and this constant is called Cell constant,
l = distance between two electrodes
a = area of cross section of the electrodes
 Specific conductivity () = Conductance × Cell constant
EQUIVALENT CONDUCTIVITY
Equivalent conductivity (eq) of an electrolyte in solution is defined as the conductance of a solution containing
one gram equivalent of an electrolyte. If V ml is the volume of a solution containing 1 gm equivalent of an
electrolyte and  is its conductivity in S cm–1, then equivalent conductance (eq) of the electrolyte is given by
  1000
eq =  × V or  eq  Scm2 equiv.1
Normality
The SI unit of equivalent conductivity is S m2 equiv–1.
MOLAR CONDUCTIVITY
It is defined as, "the conducting power of all the ions produced by dissolving one gram mole of an electrolyte
in solution". It is expressed as m and is defined as
 1000
m 
M
where M is the concentration in moles per litre.
Units : Molar conductance has unit ohm–1 cm2 mol–1 or S cm2 mol–1.
z Affecting parameters of molar conductivity
1. Nature of electrolyte
2. Concentration of the solution
3. Temperature
z Relation of m and eq
m = eq × n-factor
Example 1 : The conductivity of 0.25 M solution of KCl at 300 K is 0.0275 S cm–1. Calculate molar
conductivity.
Conductivity  1000
Solution : Molar conductivity 
Molarity
0.0275  1000
m   110 S cm2 mol1
0.25
Example 2 : The resistance of conductivity cell containing 0.001 M KCl solution at 298 K is 1500 ohm. What
is the cell constant if the conductivity of 0.001 M KCl solution at 298 K is
0.146 × 10–3 S cm–1?
Solution : Cell constant = Conductivity × Resistance
= 0.146 × 10–3 × 1500
= 0.219 cm–1
VARIATION OF MOLAR CONDUCTIVITY WITH CONCENTRATION

The values of both conductivity and molar conductivity of an electrolyte in solution change with the concentration
of the electrolyte. Conductivity of all electrolytes always decreases with decrease in concentration because
it is the conductance of all the ions present in unit volume and the number of ions per unit volume decreases
with the decrease in concentration.
Molar conductivity of an electrolyte not only depends on the nature of electrolyte but also on its concentration.
Depending upon the values of molar conductivity, the electrolytes can be divided into two groups, namely
(i) strong electrolytes and (ii) weak electrolytes. For the same concentration, the molar conductivity of a strong
electrolyte is higher than that of weak electrolyte because a strong electrolyte is completely ionised at all
concentrations and a weak electrolyte is partially ionised in the high concentration region. As concentration
of an electrolyte decreases the molar conductivity of a strong electrolyte marginally increases whereas it
increases appreciably in case of a weak electrolyte. The former is due to increase in interionic distance on
dilution which reduces the influence of cation on anion and vice versa whereas the latter is due to increase
in the extent of ionisation of weak electrolytes on dilution. The plot of a graph between molar conductivity
(m) vs conc. for a strong electrolyte and a weak electrolyte is shown in the figure.
Strong electrolyte
m m
Weak electrolyte
conc. conc.
Molar conductivity of a strong electrolyte varies linearly with concentration . It can be extrapolated when
concentration approaches zero. The molar conductivity at infinite dilution is known as limiting molar conductivity
o 
and is represented by m or m . It can be experimentally determined for strong electrolytes only because
m slowly increases linearly with dilution and can be represented as
o
m  m A C
o
The intercept of the plot along Y-axis is m and slope equal to (–A). The magnitude of slope for a given solvent
and temperature depends on the charges on cations and anions produced on dissociation of the electrolyte
in the solution. Thus, all electrolytes having same type of charges have same value for A.
Explanation for the Variation of Molar Conductivity with Concentration
Conductance Behaviour of Weak Electrolytes
z The variation of  with dilution can be explained on the basis of number of ions in solution.
z The number of ions furnished by the electrolyte in solution depends upon the degree of dissociation with
dilution.
z With the increase in dilution, the degree of dissociation increases and as a result molar conductance
increases.
z The limiting value of molar conductance (m ) corresponds to degree of dissociation equal to 1 i.e., the
whole of the electrolyte dissociates.
z Thus, the degree of dissociation can be calculated at any concentration as :
C
m
 
m
C
where  is the degree of dissociation, Λm , is the molar conductance at concentration C and m is the
molar conductance at infinite dilution.
Conductance Behaviour of Strong Electrolytes
z For strong electrolytes, there is no increase in the number of ions with dilution because strong electrolytes
are completely ionised in solution at all concentrations (by definition).
z If in concentrated solutions of strong electrolytes there are strong forces of attraction between the ions
of opposite charges called inter-ionic forces. Due to these interionic forces the conducting ability of the
ions is less in concentrated solutions.
z With dilution, the ions become far apart from one another and interionic forces decreases.
KOHLRAUSCH LAW OF INDEPENDENT MIGRATION OF IONS

z This law states that at infinite dilution when the dissociation is complete, each ion makes a definite
contribution towards molar conductance of the electrolyte irrespective of the nature of the other ion with
which it is associated.
z If molar conductivity of the cation is denoted by + and that of anion by – , then the law of independent
migration of ions is :

m  v     v –  –
where v+ and v– are the number of cations and anions per formula units of electrolyte (e.g., v+ = v– =1 for
HCl, v+ = 1 and v– = 2 for MgCl2).  and  are also called molar ionic conductances at infinite dilution.
z For example,
For NaCl m (NaCl) =  (Na+) + (Cl–)
For KNO3 m (KNO3) =  (K+) + (NO3–)
For MgCl2 m (MgCl2) =  (Mg2+) + (Cl–)
For Al2(SO4)3 m (Al2(SO4)3) =  (Al3+) + (SO42–)
o o
Example 3 : Calculate m for NH4OH given that values of m for Ba(OH)2, BaCl2 and NH4Cl as 523.28,
280.0 and 129.8 S cm2 mol–1 respectively.
Solution : o
m o
(NH4OH)  m (NH4 )  m
o
(OH )
Now,
1 o 1 o
o
m o
(NH4 OH)   m (NH4 )   m
o
(OH )   m (Ba2 )   m (Ba2 )   m
o
(Cl )   m
o
(Cl )
2 2
o 1 o 1 o
 m (NH4Cl)  m (Ba(OH)2 )  m (BaCl2 )
2 2
1
 129.8  (523.28  280.0)  251.44 Scm2 mol1
2
Example 4 : The resistance of 0.01 M CH3COOH solution is found to be 2220 ohm when measured in a
o
cell of cell constant 0.366 cm –1 . Given that m (H ) and m
o
(CH3COO ) as 349.1 and
2 –1
40.9 S cm mol . Calculate
(a) Conductivity (b) Molar conductivity
(c) Degree of dissociation (d) Dissociation constant
Solution : o
m o
(CH 3COOH)  m (H )  m
o
(CH3COO )
= 349.1 + 40.9 = 390.0 S cm2 mol–1
Cell constant 0.366

(a) Conductivity    1.648  10 4 S cm1
Resistance 2220
Conductivity  1000 1.648  10 4  1000
(b) m    16.48 S cm2 mol1
Molarity 0.01
m 16.48
(c)  o
  0.0422
m 390
C 2
(d) Ka  C 2  0.01(0.0422)2  1.78  10 5
1 
Electrolytic Cells & Galvanic Cells

The chemical changes which involve the flow of the electric current are called electrochemical changes. These
are broadly of two types
(1) The changes in which electrical energy causes chemical reaction to occur. This phenomenon is called
electrolysis and the devices or cells used to carry out electrolysis is called electrolytic cell. These
reactions are non-spontaneous and are forced to occur by the passage of electricity.
(2) The change in which electrical energy is produced as a result of chemical change. The devices used to
produce electrical energy (or electric current) from chemical reactions are called galvanic cells (e.g. cells
or batteries). These reactions are spontaneous and the system can do work (e.g. it can run a motor).
Electrolytic Cells
(D.C.)
–
e
–
e
Anode Cathode
(1) The instrument used to bring about electrolysis is called electrolytic cell.
(2) In such a cell electrolyte is in the form of an aqueous solution or in the molten state is taken.
(3) Two metal rods are dipped into it and are connected to a source of electricity. These rods are called
electrodes; the anode is the electrode at which oxidation takes place, in electrolytic cell it is
positively charged. While the electrode at which reduction takes place is known as cathode and
in electrolytic cell it is negatively charged.
ELECTROLYSIS
It is a process in which an electrolyte is broken down into simple substance by passing electric current through
it in molten state or in aqueous solution.
Product of Electrolysis
Ions having lower discharge potentials are discharged in preference to those having high discharge potentials.
(i) Electrolysis of molten lead bromide
PbBr2 +2
Pb + 2Br
At cathode
Pb+2(l) + 2e–  Pb(l)
At anode
Br–  Br + e–
Br + Br  Br2(g)
(ii) Electrolysis of an aqueous solution of sodium chloride
NaCl and H2O ionize as under
NaCl(aq)  Na+(aq) + Cl–(aq)

 
H (aq)  OH (aq)
H2O(l)
At cathode
Discharge potential of H ions is lower than that of Na ions. Therefore, H ions are discharged in
preference to Na ions.
H+ + e–  H (Primary change)
H + H  H2(g) (Secondary change)
H2 gas is evolved at the cathode while Na ions remain in the solution.
At anode
Discharge potential of Cl– ion is lower than that of OH ions, therefore, Cl ions are discharged in
preference to OH ions.
Cl–  Cl + e– (Primary change)
Cl + Cl  Cl2(g) (Secondary change)
Cl2 gas is evolved at the anode while OH ions remain in the solution.
QUANTITATIVE ASPECTS OF ELECTROLYSIS AND FARADAY'S LAWS

Faraday's First Law of Electrolysis
Amount of a substance deposited or liberated at any electrode is directly proportional to the charge passed.
W(g)  Q where, Q is amount of charge flowing in the circuit
W = Z  Q or W = Z  i  t, i = current, t = time
Z = electrochemical equivalent of the substance deposited
Eq. wt. of the substance

96500
Faraday's Second Law of Electrolysis

When the same quantity of electricity is passed through solutions of different electrolytes connected in se-
ries, the weights of the substances produced at the electrodes are directly proportional to their equivalent
weights.
Example : For AgNO3 solution and CuSO4 solution connected in series if the same quantity of electricity is
passed.
WAg Eq. wt. of Ag


WCu Eq. wt. of Cu
Note : (i) 1F = 1eq

= 96500 coulombs
= 6.02 × 1023 electrons
volume of gas given at STP

(ii) Eq. of gas =
volume of 1eq. of gas at STP
(iii) q = nF
n is number of electrons transferred
Example 5 : How much copper is deposited on the cathode if a current of 3A is passed through aqueous CuSO4
solution for 15 minutes ?
Solution : Quantity of electricity passed = Current in amperes × time in seconds
Q = 3 × 15 × 60 = 2700 C
Cu2+ + 2e–  Cu
Two mole electrons or 2F charge can deposit 1 mole copper i.e., 63.5 g and so 2700 C will deposit
2700  63.5
 0.889 g
2  96500
Example 6 : How much time would be needed to deposit 0.25g of metallic nickel (Atomic mass = 58.5) on a
metal object using a current of 1A during electroplating?
Solution : Ni2+ + 2e–  Ni
2F or 2 × 96500 C of electricity is required to deposit 58.5 g of Ni.
58.5g of Ni requires 2 × 96500 C
2  96500  0.25
0.25g of Ni requires = = 824.8 C
58.5
Amount of electricity = Current in amperes × time in seconds
Amount of electricity
Time in seconds =
Current in amperes
824.8
= = 824.8 sec = 13.74 minutes
1
Example 7 : Exactly 0.2 mole electrons passed through two electrolytic cells in series containing CuSO4 and
ZnSO4 respectively. How many grams of each metal will be deposited on the respective cathodes
in the two cells?
63.5
Solution : Gram equivalent mass of copper =  31.75g
2
65.0
Gram equivalent mass of zinc=  32.50g
2
Now 1.0 mole of electrons deposit copper = 31.75 g
31.75  0.2
0.2 mole of electrons deposit copper = = 6.35 g
1.0
Similarly, 1.0 mole of electrons deposit zinc = 32.50 g
32.5  0.2
0.2 mole of electrons deposit zinc = = 6.50 g
1.0
EXERCISE
1. Electrolysis of dil. H2SO4 liberates gases at anode and cathode respectively

(1) O2, SO2 (2) SO2, O2
(3) O2, H2 (4) H2, SO2
2. When aqueous solution of KCl is electrolysed, resultant solution has
(1) pH > 7 (2) pH < 7
(3) pH = 7 (4) Initially less than 7 then increases
3. Ionic conductance of H+ and SO42 – are x and yS cm2 mol–1. Hence, equivalent conductivity of H2SO4 is
y y
(1) 2x + (2) x +
2 2
x x y
(3) +y (4) 
2 2 2
4. Specific conductivity of 0.01 N H2SO4 solution is 6 × 10–3 S cm–1. Its molar conductivity is
(1) 1200 S cm2 mol–1 (2) 600 S cm2 mol–1
(3) 60 S cm2 mol–1 (4) 2400 S cm2 mol–1
5. Which relation is correct?
(1) Molar conductance = conductivity × concentration
Conductivity
(2) Equivalent conductance =
Volume
Conductivity
(3) Cell constant =
Conductance
(4) Conductance = specific conductivity × cell constant
6. From the following molar conductivities at infinite dilution,
o
m for Al2(SO4)3 = 858 S cm2 mol–1
o
m for NH4OH = 238.3 S cm2 mol–1
o
m for (NH4)2SO4 = 238.4 S cm2 mol–1
o
Calculate m for Al(OH)3
(1) 715.2 S cm2 mol–1 (2) 1575.6 S cm2 mol–1
(3) 786.3 S cm2 mol–1 (4) 157.56 S cm2 mol–1
7. Four faradays of electricity were passed through AgNO3 () , CdSO4 ( ) , AlCl3 () and PbCl4 ( ) kept in four
vessels using inert electrodes. The ratio of moles of Ag, Cd, Al and Pb deposited will be
(1) 12 : 4 : 6 : 3 (2) 1 : 2 : 3 : 4
(3) 12 : 6 : 4 : 3 (4) 4 : 3 : 2 : 1
Galvanic cells : “A device employed to convert the chemical energy of a redox reaction into electrical energy” is
called an electrochemical cell or simple chemical cell. The most common example is that of Daniel cell. It consist
of two beakers one containing solution of ZnSO4 (say 0.1 M) and Zinc plate is dipped in it. The other beaker
contains CuSO4 solution (say 0.1 M) and a copper plate is dipped in it. The two solutions are connected by a salt
bridge containing concentrated solution of an inert electrolyte like KCl, KNO3 etc.On connecting the two electrodes
by a wire, the redox reaction takes place and the electron flow from Zn to the Cu. This flow of electrons constitute
electric current. The electrode (Zn) at which oxidation takes place i.e., electrons are lost, is called anode and the
electrode (Cu) at which reduction takes place i.e., electrons are gained, is known as cathode.
V
–
e flow
current
Zinc Salt bridge
electrode Copper
electrode
ZnSO4 CuSO4
solution solution
Half-cell Half-cell
DANIEL CELL
The net reaction is the sum of two half-cell reactions.
At anode : Zn(s)  Zn2 (aq)  2e

At cathode : Cu2 (aq)  2e  Cu(s)
Net reaction : Zn(s)  Cu2  Zn2 (aq)  Cu(s)
Schematic Representation : Zn | Zn+2 || Cu+2 | Cu
ELECTRODE POTENTIAL AND EMF OF A CELL

z When an electrode is kept in contact with a solution of its ions, the metal tends to lose electrons and
thus passes into the solution in the form of metal ions or the metal ions tend to gain electron from metal
electrode and deposit on electrode.
M  Mn+(aq) + ne– or Mn+(aq) + ne–  M
z Thus, an electrical potential difference is set up between metal and its solution. This is known as half
cell electrode potential.
z If the electrons are released during the process, this is called oxidation potential and if the electrons
are accepted, this is called reduction potential.
z Separately, these are known as single electrode potentials.
z The electrode potential is a measure of tendency of an electrode in a half cell to lose or gain electrons.
z According to the present convention the half reactions are always written as reduction half reactions
and their potentials are represented as reduction potentials.
Electromotive Force or Cell Potential :
z The difference between the electrode potentials of two electrodes constituting an electrochemical cell is
called electromotive force (EMF) or cell potential of a cell.
z It is expressed as:
Standard reduction  Standard reduction 

E°cell =   —  
potential of cathode  potential of anode 
or E°cell = E° (cathode) – E° (anode)
Standard Electrode Potential
z The absolute value of the electrode potential cannot be determined experimentally because neither the
oxidation nor the reduction reaction can occur by itself.
z The electrode potentials are always determined with respect to a standard hydrogen electrode.
Standard Hydrogen Electrode :
z It consists of platinum wire sealed in a glass tube and has a platinum foil attached to it. The foil is coated
with finely divided platinum and acts as platinum electrode. It is dipped into an acid solution containing
H+ ions in 1 M concentration (1 M HCl). Pure hydrogen gas at 1 bar pressure is constantly bubbled into
the solution at constant temperature of 298 K. The following reaction occurs in this half cell depending
upon whether it acts as an anode or as a cathode.
If S.H.E. acts as anode
H2 (g) 2H+ + 2e–
If S.H.E. acts as cathode
2H+ + 2e– H2 (g)
z The standard hydrogen electrode is also regarded as reversible electrode.
H2 (g) 2H+ + 2e—
z The electrode potential of an electrode can be determined by connecting that with a standard hydrogen
electrode. The electrode potential of the standard hydrogen electrode is taken as zero. The electrode
potential of a metal electrode as determined with respect to a standard or normal hydrogen electrode is
called standard electrode potential (E°).
Voltmeter
– –
e e
0.34 V
Copper + Salt bridge

+ – –
(cathode) Na NO3
H2(g) (1 atm)
+
– H
NO 3 Standard hydrogen
2+
(1 M)
Cu – electrode (anode)
NO 3
(1 M)
–
NO 3
2+ – + –
Cu (aq) + 2e  Cu(s) H 2(g)  2H (aq) + 2e
Electrochemical Series
Table in which the reduction potentials of various electrodes have been arranged in the increasing order is called
electrochemical series or activity series or electromotive series.
Electrode Electrode reaction E°(volts)
Li+/Li Li+ + e– = Li –3.045 (Lowest)
Zn2+/Zn Zn2+ + 2e– = Zn –0.763
H+/H2, Pt 2H+ + 2e– = H2 0.0 Standard
Cu2+/Cu Cu2+ + 2e– = Cu +0.334

– –
F2/F , Pt F2 + 2e– = 2F +2.887 (Highest)
Applications of Electrochemical Series

The important applications of electrochemical series are:
z Relative strength of oxidising and reducing agents. In the series, the metals are arranged in the
increasing order of reduction potentials or decreasing order of oxidation potentials. Therefore, the elements
at the top are good reducing agents while those at the bottom are good oxidising agents.
z Calculating e.m.f. of the cell : The e.m.f. of the cell can be determined by knowing the standard electrode
potentials from the series as:
E°cell = E° (right) – E° (left) (If standard reduction potential are given)
z Predicting feasibility of a redox reaction. In general, a redox reaction is feasible only if the species
which has higher reduction potential is reduced i.e., accepts the electrons and the species which has lower
reduction potential is oxidised i.e., loses the electrons. Otherwise, a redox reaction is not feasible. In other
words, the species to release electrons must have lesser reduction potential as compared to the species
which is to accept electrons.
z To predict whether a metal can liberate hydrogen from acid or not. The metals which have negative reduction
potentials can only liberate hydrogen from the acids.
z Metals which have low S.R.P. value have greater rate of corrosion.
z Cations having higher S.R.P. value will discharge first at cathode and anions having low S.R.P. value
discharge first at onode
(i) K+ < Ca2+ < Na+ < Mg2+ < Al3+ < Zn2+ < Fe2+ < H+ < Cu2+ < Ag+ < Au3+ (order of discharging at cathode)
(ii) SO24  OH  Cl  Br   I (order of discharging at anode).
Example 8 : Write each half cell reaction as well as redox reaction for the following electrochemical cell
 2
A( s ) | A(31M ) || B( 1M ) | B( s )
Solution : Oxidation half cell reaction: A(s)   A3+ + 3e–] × 2
Reduction half cell reaction: B2+ + 2e–   B(s) ] × 3
___________________________________________________
Net redox reaction: 2A(s) + 3B2+   2A3+ + 3B(s)
Example 9 : Write the cell reaction that occurs when the following half cells are combined
I2 + 2e–   2I– ; E° = + 0.54 V
Br2 + 2e – 
 2Br– ; E° = + 1.08 V
Solution : The half cell reaction with lesser value of E° takes place at the anode while the other takes place
at cathode. Thus,
At anode: 2I–   I2 + 2e–
At cathode: Br2 + 2e–   2Br–
___________________________________
Cell reaction: 2I– + Br2   I2 + 2Br
–
EMFCell = E°c – E°a

= 1.08 – 0.54 = 0.54 V
NERNST EQUATION
It is used when concentration of ions in which electrode is dipped is not equal to 1M.
Mn+ + ne–  M.
2.303 RT 1
EMn /M  EMn /M  log n
nF [M ]
R = 8.314 JK–1 mol–1, F = 96500C, T = 298 K. 'n' is no. of electrons involved in balanced half cell reactions.
After substituting these values we get :
0.05916 1
EMn /M = EMn /M – log
n [Mn ]
For Example :
Cl2 + 2e–  2Cl–
0.0591 [Cl– ]2
ECl – = ECl2 /Cl– – log [p ] where p Cl 2 is partial pressure of Cl2 (g), [Cl–] is molar conc. of
2 /Cl
2 Cl2
Cl–.
In general
2.303RT
Ecell = E°cell – log Q (Q is the reaction quotient)
nF
Example 10 : Calculate the emf of the cell in which the following reaction takes place
Ni(s) + 2Ag+(0.002M)  2+
 Ni (0.160M) + 2Ag(s)
Given: E°cell = 1.05 V
Solution : At anode: Ni(s)   Ni2+ + 2e–
At cathode: 2Ag+ + 2e–   2Ag
____________________________________________
The net reactions: Ni(s) + 2Ag+  2+
 Ni + 2Ag(s)
 0.0591 [Anode]
Ecell  Ecell  log
n [Cathode]
0.0591 [Ni2  ]
Ecell  1.05  log
2 [Ag ]2
0.0591 0.16
 1.05  log
2 (0.002)2 = 0.914 V
Example 11 : Calcualte the electrode potential of given electrode
Pt, Cl2(1.5 bar) | 2Cl–(0.01M) ; EClº / 2Cl 

 1.36 V
2
Solution : The reaction of electrode is
Cl2 (g) 2e   2Cl 

1.5 bar 0.01M
0.0591 [Cl ]2 0.0591 (0.01)2

E = E  log  1.36  log = 1.483 V
n PCl 2 1.5
2
Equilibrium Constant and emf

At equilibrium E(Cell) = 0, so
2.303 RT
E°(Cell) = log KC
nF
At 298 K it may be written as
0.0591
E°(Cell) = log KC
n
Example 12 : Calculate the equilibrium constant for the cell reaction
4Br – + O2 + 4H+ 
 2Br2 + 2H2O ; E°cell = 0.16 V
n Ecell
Solution : log K c 
0.0591
E°cell = 0.16 V, n=4
4  0.16
log K c   10.8
0.0591
Kc = antilog 10.8 = 6.31 × 1010
Concentration Cell
When same metal electrodes are dipped in same electrolyte having different conc. in two half cells, such a
cell is called concentration cell. For concentration cell, Eocell = 0 but Ecell  0.
2.303RT C
Ecell = – log 1 , C1 is concentrations of electrolyte in which anode is dipped, C2 is concentrations
nF C2
of electrolyte in which cathode is dipped. Reaction is spontaneous, when Ecell > 0 i.e., C2 > C1.
Electrochemical Cell and Free Energy

–G = WElec
= nFEcell
G = –nFEcell
G° = 0 only when equilibrium constant (K) = 1
∵ G° = –2.303 RT log K
Example 13 : Find out work done for the given cell
Cr Cr+3 Fe+2 Fe
o o
ECr/Cr = 0.74 V ; EFe
3+ 2+
/Fe
= –0.44 V
Solution :  
E cell 
E Cathode  
E Anode
(Reduction potential) (Reduction potential)
= –0.44V + 0.74V = 0.30 V Since cell reaction 

 2 3 
W = nFE° 2Cr  3Fe  2Cr  3Fe 
n  6 mol electron 
= 6 × 96500 × 0.30  
 W = 173700 J
 W = 173.7 kJ
Example 14 : Calculate G° for the given reaction occuring in fuel cell
(i) O2 + 4H+ + 4e–  2H2O ; E° = 1.229 volt
(ii) 2H2  4H+ + 4e– ; E° = 0 volt
Solution : E°Cell = E°cathode – E°Anode
= 1.229 – 0.0
= 1.229 V
G° = –nFE°
= – 4 × 96500 × 1.229
= 474.4 kJ
EXERCISE
8. Half cell reactions for some electrodes are given below :
I. A + e–  A– ; E° = 0.96 V
II. B– + e–  B2– ; E° = – 0.12 V
III. C+ + e–  C ; E° = + 0.18 V
IV. D2+ + 2e–  D ; E° = – 1.12 V

Largest potential will be generated in which cell?
(1) A– | A || B– | B2– (2) D | D2+ || A | A–
(3) B2– | B– || C+ | C (4) D | D2+ || C+ | C
9. Select correct statement.
(1) If salt bridge is removed, potential falls to zero
(2) KCl cannot be used as electrolyte in salt bridge in case of silver electrode
(3) Cell reaction is spontaneous if emf is positive
(4) All of these

10. The measured potential for Mg2+ + 2e–
Mg (s) does not depend upon
(1) Raising the temperature
(2) Increasing the concentration of Mg2+ ion
(3) Making the magnesium plate bigger
(4) Decreasing the concentration of Mg2+ ion
11. Which of the following metal do not evolve H2 gas from dil. acid?

(1) A EoA  / A  0.25 V  
o
(2) B EB/B    0.22 V 

(3) C EoC /C   0.30 V  
o
(4) D ED/D    0.44 V 
12. The standard electrode potentials EIo /I , EBr

o

/Br
o
and EFe/Fe 2  are respectively + 0.54 V, – 1.09 V and 0.44 V. On
2 2
the basis of above data which of the following process is nonspontaneous?
(1) Br2 + 2I–  2Br– + I2 (2) Fe + Br2  Fe2+ + 2Br–
(3) Fe + I2  Fe2+ + 2I– (4) I2 + 2Br–  2I– + Br2
13. Pb+2 + 2e–  Pb(s), E° = – 0.13 V

Sn+2 + 2e–  Sn(s), E° = – 0.16 V
Ni+2 + 2e–  Ni(s), E° = – 0.25 V
Cr+3 + 3e–  Cr(s), E° = – 0.74 V
Based on the above data, the reducing power of Pb, Sn, Ni and Cr is in the order
(1) Pb > Sn > Ni > Cr (2) Cr > Ni > Sn > Pb
(3) Cr > Sn > Ni > Pb (4) Sn > Ni > Cr > Pb
14. Consider the following equations for a cell reaction:
A + B  C + D ; E° = x volt, G = G1
2A + 2B  2C + 2D ; E° = y volt, G = G2
Then,
(1) x = y, G1 = G2 (2) x > y, G1 > G2
(3) x = y, G2 = 2G1 (4) x < y, 2G2 = G1
2 2
15. Zn | Zn(C1)
|| Zn(C 2)
| Zn (s) . The G is –ve if
(1) C1 = C2 (2) C1 > C2

(3) C2 > C1 (4) C1 > 2C2
16. Calculate the half cell potential at 298 K for the reaction, Zn +2 + 2e –  Zn if [Zn +2 ] = 2 M,
EoZn2 /Zn = – 0.76 V
(1) – 0.90 V (2) – 0.75 V
(3) – 0.85 V (4) – 0.65 V
17. Calculate G° for the galvanic cell:
2Cr (s) + 3Cd+2 (aq)  2Cr+3 (aq) + 3Cd (s)
EoCr 3 /Cr = – 0.74 V, EoCd2 /Cd = – 0.40 V

(1) – 196.86 kJ/mol (2) – 98.43 kJ/mol
(3) – 65.62 kJ/mol (4) – 164.05 kJ/mol
18. If the standard electrode potential of Cu2+/Cu electrode is 0.34 V, what is the electrode potential of 0.1 M
concentration of Cu2+?
(1) 3.99 V (2) 0.3105 V
(3) 0.222 V (4) 0.176 V
19. For a spontaneous reaction, G, equilibrium constant K and Eºcell will be respectively
(1) –ve, > 1, +ve (2) +ve, > 1, –ve
(3) –ve, < 1, –ve (4) –ve, > 1, –ve
COMMERCIAL CELLS
(i) Primary Cells are those in which the redox reaction occurs only once and the cell becomes dead after
sometime e.g., dry cell, mercury cell.
(ii) Secondary Cells are those which can be recharged by passing an electric current through them and
hence can be used over and again e.g., lead storage.
(iii) Fuel Cells are those in which the energy produced from the combustion of fuels like H2, CO, CH4 etc.
is converted into electric current.
z Dry Cell : Anode : Zinc, cathode: a graphite rod, electrolyte in contact of Zn is a paste of NH4Cl and
ZnCl2. While electrolyte in contact with graphite rod is powdered MnO2 and carbon. Anode reaction Zn
 Zn++ + 2e–
Insulator
Graphite rod
(cathode)
MnO2 and carbon
black paste
NH4Cl and ZnCl2
paste (electrolyte)
Zinc metal can
(anode)
A commercial dry cell

Cathode reaction :
2MnO2 + 2NH4+ + 2e–  Mn2O3 + 2NH3 + H2O
Zn2+ + 2Cl– + 4NH3  [Zn(NH3)4]Cl2 complex.
It does not give a constant voltage. Voltage is continuously dropped as concentration of electrolyte is
decreased
z Mercury Cells: Zn as anode while carbon rod as cathode, Moist HgO mixed with KOH as electrolyte is
filled between two electrodes.
Anode reaction: Zn + 2OH–  ZnO + H2O + 2e–
Cathode reaction: HgO + H2O + 2e–  Hg + 2OH–. It gives constant potential of 1.35 V used in hearing
aids, watches etc.
z Lead Storage Battery: Anode: Lead plates, cathode: grid of lead packed with PbO2. Electrolyte: dil
H2SO4 (30% by mass, sp. gravity 1.30).
The reaction occuring during discharging.
Cathode reaction :
PbO2 + 4H+ + 2e–  Pb2+ + 2H2O (Reduction)
Pb 2+
+ SO4 2-
 PbSO4 (Precipitation)
+
Net cathode reaction = PbO2 + 4H + 2e + SO4 – 2–
 PbSO4 + 2H2O
Anodic reaction :
Pb  Pb2+ + 2e– (Oxidation)
Pb 2+
+ SO4 2–
 PbSO4 (Precipitation)
Net anodic reaction = Pb + SO4 2–
 PbSO4 + 2e –
Total cell reaction = PbO2 + Pb + 4H+ + 2SO42–  2PbSO4 + 2H2O
Sulphuric acid is consumed during discharging and when the conc. of H2SO4 falls to 1.20 g ml–1, it requires
recharging. In recharging current is passed from outside source to reverse the reactions of anode and
cathode till the conc. of H2SO4 again rises to 1.30 g cm–3.
H2SO4
(electrolyte)
Lead grid packed with Lead grid packed

spongy lead (anode) with PbO2 (cathode)
The lead storage battery
z Fuel Cells : Hydrogen oxygen fuel cell is one of the important fuel cells. It consists of porous carbon
electrodes containing suitable catalysts. Conc. KOH or NaOH is placed between the electrodes to act
as electrolyte. H2 and O2 gases are bubbled through the porous electrodes into KOH solution, operational
temp. 70º – 140ºC.
At anode : H2  2H, 2H + 2OH–  2H2O + 2e–
At cathode : 2H2O + 4e– + O2  4 OH–
Net cell reaction : 2H2 + O2 2H2O + energy
Its cell potential is 0.9 V. Do not cause any pollution, used in space crafts.
Anode Cathode
– +
H2 O2
Porous carbon
electrodes containing
metallic catalysts
H 2O H2O
Hot aqueous KOH
Fuel Cell
CORROSION
Process of slowly eating away of the metal due to attack of atmospheric gases, on the surface of the metal
resulting into the formation of oxides, sulphides, carbonates. Corrosion of iron is called rusting. Rust is
hydrated ferric oxide Fe2O3 . x H2O.
z Mechanism of Rusting: Electrochemical theory
(i) Iron in contact with the dissolved CO2 and oxygen undergoes oxidation
Fe  Fe++ + 2e– (Anode reaction);
(ii) Electrons lost by iron are taken up by the H+ ions produced on the surface of metal.
H+ + e–  H, 4H + O2  2H2O
O2 + 4H+ + 4e–  2H2O.
The dissolved oxygen may take up electron directly to form OH– ions.
O2 + 2H2O + 4e–  4OH–

(cathode)
overall reaction:
2Fe + O2 + 4H+  2Fe2+ + 2H2O, Eº = +1.67 V.
(iii) 4Fe2+ + O2 + 4H2O  2Fe2O3 + 8H+
Fe2O3 + x H2O  Fe2O3  x H2O
Air Water droplet

O2
Rust (Fe2O3  xH2O)
O2 Fe3+
O2
2+
Fe
Anode region Cathode region
Fe  Fe + 2e
2+ –
e
–
O2 + 4H+ + 4e–  2H2O
Iron metal
Corrosion of iron in atmosphere
z Factors which Promote Corrosion : Reactivity of metal, presence of impurity, presence of air and
moisture; strains in metals; presence of electrolyte.
z Prevention of Corrosion:
(i) Barrier protection: by using paints, thin film of oil, grease etc.
(ii) Sacrificial Protection covering the surface of iron with a layer of metal which is more active than
iron thus prevents the iron from losing electrons.
Galvanisation: Covering iron with more active metal like zinc. The layer of Zn on the iron surface
when comes in contact with moisture, oxygen and CO2 in air, protective invisible thin layer of basic
zinc carbonate ZnCO3. Zn(OH)2 is formed due to which the galvanised iron sheets lose their lusture
and tends to protect it from further corrosion. Iron can be coated with Cu or by Sn. Now if the coating
is broken, iron is exposed and being more reactive than Cu and Sn corrodes more rapidly.
(iii) Electrical Protection (Cathodic protection): More electropositive metals like Zn, Mg or Al may be
connected with the iron pipes burried in the moist soil, canals, storage tanks etc.
(iv) Using Anti Rust Solutions: These are alkaline phosphate and alkaline chromate solutions. The
alkaline nature of solutions prevents availability of H+ ions. On the surface of iron, a protective, insoluble
thin film of iron phosphate is formed. These are used in car radiators to prevent rusting.
EXERCISE
20. In the electrorefining of metals, impure metal is
(1) Cathode and oxidation takes place (2) Anode and oxidation takes place
(3) Anode and reduction takes place (4) Cathode and reduction takes place
21. Rusting on the surface of iron involves
(1) Fe (s)  Fe2+ (aq) + 2e– (at anodic site)
(2) O2 (g) + 4H+ (aq) + 4e–  2H2O (l) (at cathodic site)
(3) 4Fe2+ (aq) + O2 (g) + 4H2O (l)  2Fe2O3 (s) + 8H+
(4) All of these
22. When a lead storage battery is recharged
(1) Pb is formed (2) H2SO4 is formed
(3) H2SO4 is consumed (4) Both (1) & (2)
23. Which of the following reactions occurs at the cathode?
(1) 2OH–  H2O + O + 2e– (2) Zn  Zn2+ + 2e–
(3) Sn2+  Sn4+ + 2e– (4) Cu2+ + 2e–  Cu
24. Select the correct statement
(1) Cathode is negative terminal, both in galvanic and electrolytic cells
(2) Anode is negative terminal, both in galvanic and electrolytic cells
(3) Cathode is negative terminal in electrolytic cell and anode is negative terminal in galvanic cell
(4) Cathode and anode respectively are negative and positive terminal in galvanic and electrolytic cell
respectively

nt
me nment
sigAnssig
Assignment
As
Assignment
7. Two different electrolytic cells are connected in
SECTION - A
series, containing aq.AgNO 3 and aq.CuSO 4
NCERT Based MCQs respectively. The mole ratio of copper to silver
1. In lead storage battery, cathode is made up of deposited at cathodes in the two cells will be
[NCERT Pg. 89] [NCERT Pg. 85]
(1) Pb grid packed with PbO2  2  1

(1)   (2)  
(2) Pd plates 1 2
(3) Platinum
 3  2
(4) Zinc plates (3)   (4)  
2 3
2. After operating the electrolytic cell for sometime, if
anode is removed then, what will happen? 8. When aqueous solution of KBr is electrolysed
[NCERT Pg. 85] using Pt electrodes, the resultant solution will have
(1) The cell will work as a capacitor [NCERT Pg. 87]
(2) Ions will start moving randomly (1) pH > 7 (2) pH < 7
(3) Current will continue to flow for sometime (3) pH = 7 (4) Any value of pH
(4) Cathode rod will start working as both anode 9. Function of salt bridge is/are
and cathode a. It completes the cell circuit
3. In a mercury cell, product at anode is b. It allows the movement of ions from one
[NCERT Pg. 88] solution to other without mixing of the two
(1) HgO(s) (2) Hg(l) solutions
(3) ZnO(s) (4) Zn(Hg) c. It maintains the electrical neutrality of the
4. How many Faraday’s of charge are required to solution in two half cells [NCERT Pg. 66]
reduce 1 mol of Cr2O72– to Cr+3? [NCERT Pg. 88] (1) a & b (2) a, b & c
(1) 6 F (2) 3 F (3) Only a (4) b & c
(3) 2 F (4) 1 F 10. The conductance of 0.01 N CH3COOH solution is
5. A solution of concentration CuSO4 is electrolysed 4.5  10–4 ohm–1 which is present in a tube having
for 965 s with a current of 20 A and 50% efficiency. length 6 cm and cross sectional area 36 cm2. The
The amount of Cu deposited at cathode will be molar conductivity of the solution is
(1) 4.175 g (2) 3.175 g (1) 7.5 S cm2 mol–1 (2) 8.5 S cm2 mol–1
(3) 5.35 g (4) 6.35 g (3) 2.5 S cm2 mol–1 (4) 1.5 S cm2 mol–1
6. The decreasing order of standard electrode 11. If Zn2+/Zn electrode is diluted 1000 times, then the
potential is [NCERT Pg. 71] change in electrode potential is [NCERT Pg. 72]
(1) Li, Al, Zn, Ba (1) Increase of 29.5 mV
(2) Ba, Al, Zn, Li (2) Increase of 59 mV
(3) Zn, Al, Ba, Li (3) Decrease of 88.5 mV
(4) Zn, Ba, Al, Li (4) Increase of 88.5 mV
12. What will be the emf of the cell in which the 2. Equivalent conductance of a substance increases
following reaction takes place at 298 K? on dilution because of
Mn(s)  Cu 2+  aq   aq  Cu  s (1) Increase in number of ions per unit volume
 Mn2+
0.01 M 0.0001 M
(2) Increase in molecular attraction
(Given: Eocell  1.52 V ) [NCERT Pg. 73] (3) Increase in degree of association
(1) 1.58 V (4) Increase in degree of ionisation of the
substance
(2) 1.52 V
3. The specific conductivity of 0.5N solution is
(3) 0.059 V
0.01287 ohm–1 cm–1. What would be its equivalent
(4) 1.21 V conductance (in ohm–1 cm2 eq–1)?
13. The electrode potential of hydrogen electrode is (1) 257.4 (2) 2.574
when H 3 O + ion concentration is 10 –5 M
(3) 25.74 (4) 0.2574
(pH2 = 1 atm) [NCERT Pg. 68]
4. Deduced from the following E° values of half cells,
(1) – 0.059 V what combination of two half cells would result in
(2) – 0.295 V a cell with the largest potential?
(3) – 0.118 V (i) A3–  A2– + e–, E° = 1. 5 V
(4) – 0.59 V (ii) B2+ + e–  B+, E° = 2.1 V
14. Cell constant is maximum in case of (iii) C2+ + e–  C+, E° = +0.5 V
[NCERT Pg. 75] (iv) D D2+ + 2e–, E° = –1.5 V
(1) Wire of length 100 m and cross sectional area (1) (i) and (iii) (2) (i) and (ii)
100 m2
(3) (ii) and (iv) (4) (iii) and (iv)
(2) Wire of length 10 m and cross sectional area
5. The number of Faradays required to deposit 1g
10 m2
equivalent of aluminium (At.wt 27) from a solution
(3) One meter cube of a material of AlCl3 is
(4) Equal in all cases (1) 1 (2) 2
15. The molar conductivity of an infinitely diluted (3) 3 (4) 4
solution of NH4Cl is 150 S cm2 mol–1 and the ionic
6. The standard reduction potential of Pb and Zn
conductances of OH– and Cl– ions are 198 S cm2
electrodes are –0.126 and –0.763 volts
mol–1 and 76 S cm2 mol–1 respectively. The molar
respectively. The e.m.f. of the cell
conductivity (S cm2 mol–1) of the solution of NH4OH
at infinite dilution is [NCERT Pg. 83] Zn | Zn2+ (0.1 M) || Pb2+ (1 M) | Pb is
(1) 272 (2) 424 (1) 0.637 V (2) 0.607 V
(3) 124 (4) 226 (3) 0.667 V (4) 0.889 V

7. When dil HNO3 is electrolysed
SECTION - B (1) H2(g) is formed at anode

(2) O2 gas is formed at anode
Objective Type Questions
(3) NO2 is formed at cathode
1. Which of the following is not correct?
(4) N2 is formed at anode
(1) Molar conductance of a solution increases with
8. Three faraday of electricity is passed through three
dilution
electrolytic cells connected in series containing
(2) Equivalent conductance increases with dilution Ag+, Ca2+ and Al+3 ions respectively. The molar
(3) Specific conductance increases with dilution ratio in which the three metal ions are liberated at
the electrodes is
(4) At infinite dilution each ion (cation or anion)
(1) 1 : 2 : 3 (2) 3 : 2 : 1
plays a definite role towards electrical
conductance (3) 6 : 3 : 2 (4) 3 : 4 : 2
9. The quantity of electricity required to reduce 12.3 15. Electrochemical equivalent of Cu in the reaction
g of nitro benzene to aniline assuming 50% Cu2+(aq) + 2e– Cu is
current effeciency is
(1) 115800 C (2) 57900 C 63.5 63.5
(1) (2)
(3) 231600 C (4) 28950 C 96.5 96500  2
10. The EMF of a chemical cell is positive when free 63.5  2 96500
energy change of reaction (3) (4)
96500 63.5  2
(1) > 0
16. For given cell; Zn |Zn+2 (C1) || Zn+2 (C2)| Zn; G is
(2) < 0 negative if
(3) = 0 (1) C1 = C2
(4) No relationship of free energy change and (2) C1 > C2
e.m.f.
(3) C2 > C1
11. A 0.1M solution of monobasic acid has specific
resistance of ‘r’ ohm-cm, its molar conductivity is (4) None of these
(1) 10/r (2) 10r 17. For given half cell; Al 3+ + 3e – Al ; on

increasing [Al+3], the reduction electrode potential
(3) 104/r (4) 104r
(1) Increases
12. Find out the Eºcell from the given data
(2) Decreases
(a) Zn | Zn+2 || Cu+2 | Cu ; Eºcell = 1.10 V
(3) No change
(b) Cu | Cu+2 || Ag+ | Ag ; Eºcell = 0.46 V
(4) First increases then decreases
(c) Zn | Zn+2 || Ag+ | Ag ; Eºcell = ?

(Given ECu2 /Cu  0.34V ) 18. If EºFe2 |Fe is x 1, EºFe3 |Fe is x 2; then Eº 3 2
Fe |Fe
will be
(1) – 0.04 V (2) + 0.04 V
(1) 3x2 – 2x1 (2) x2 – x1
(3) + 0.30 V (4) 1.56 V
(3) x2 + x1 (4) 2x1 + 3x2
13. Consider the following equations for a cell
19. What will be the molar conductance ‘’, (in S cm2
A+B C+D; E° = x volt , Keq = K1
mol–1)if resistivity is ‘x’ for 0.1 N H2SO4 solution?
2A + 2B 2C + 2D ; E° = y volt , Keq = K2
(1)   x  1000 (2)   2  1000
Then 0.1 x  0.1
(1) x = y, K1 = K2 (2) x =2y, K12 = K2 0.5
(3)   x  1000 (4) 
(3) x = y, K12 = K2 (4) x2 = y, K12 = K2 0.5 1000 x
14. For strong electrolytes the values of molar 20. E° values of Mg+2|Mg, Zn+2|Zn and Fe+2|Fe are
conductivities at infinite dilution are given below –2.37 V, –0.76 V and –0.44 V respectively. Which
of the following is correct ?
Electrolyte 0
m (Sm2 mol1 )
(1) Mg oxidises Fe (2) Zn oxidises Fe
BaCl2 280 × 10–4
(3) Zn reduces Mg+2 (4) Zn reduces Fe+2
NaCl 126.5 × 10–4
21. The standard reduction potential value of three
NaOH 248 × 10–4 metallic cations X, Y and Z are 0.52, –3.303 and
The molar conductance at infinite dilution for –1.18 V respectively. The order of reducing power
Ba(OH)2 is of the corresponding metals is
(1) 523 × 10–4 Sm2 mol–1 (1) Y > Z > X
(2) 52.3 × 10–4 Sm2 mol–1 (2) X > Y > Z
(3) 5.23 × 10–4 Sm2 mol–1 (3) Z > Y > X
(4) 523 × 10–2 Sm2 mol–1 (4) Z > X > Y
22. The conductivities at infinite dilution of NH4Cl, NaOH 30. What volume of gases at STP will evolve if 1 L of
and NaCl are 130, 218, 120 ohm –1 cm 2 eq –1 . 0.01 M solution of H2SO4 is electrolysed?
N (1) 33.6 L (2) 336 ml
If equivalent conductance of solution of NH4OH
100 (3) 3.36 ml (4) 3.36 L
is 10, then degree of dissociation of NH4OH at this
31. Which of the following does not affect the value of
dilution is
Ecell?
(1) 0.005 (2) 0.044
(1) Volume of container
(3) 0.01 (4) 0.02
(2) Concentration
23. During electrolysis of aqueous solution of a salt pH
(3) Temperature
in the space near one of the electrodes is increased.
Which of the following salt solution was electrolysed? (4) All of these
(1) KCl (2) CuCl2 32. Which of the following is secondary cell?
(3) Cu(NO3)2 (4) CuSO4 (1) Dry cell
24. The oxidation potential of hydrogen electrode at (2) Mercury cell
pH = 10 and pH2  1atm (3) Lead storage battery
(4) All of these
(1) 0.51 V (2) 0.00 V
33. Find the value of ‘Z’ in the following reaction
(3) 0.59 V (4) 0.059 V
25. Faradays charge required for conversion of 1 mol 1 x volt y volt
Cl2 ClO– ClO3–
MnO4 to Mn2 , is 2
z volt
(1) 5 (2) 2.5
(3) 3 (4) 7 4x + y
(1) x + y (2)
5
26. Eº for F2 + 2e–  2F– is
1 5x + 4y x + 4y
2.8V, Eº for F2 + e–  F– is (3) (4)
2 1 5

(1) 2.8 V (2) 1.4 V 34. The value of  eq (cm2–1eq–1) of Al3+ is x and Cl–
(3) –2.8 V (4) –1.4 V 
is y then, the value of m (cm2–1mole–1) of AlCl3
27. On electrolysis, 1 mole of calcium will be
will be
deposited from its molten salt by
(1) 1 mole of electrons (2) 2 mole of electrons x
(1) y (2) 3x + 3y
(3) 3 mole of electrons (4) 4 mole of electrons 3
28. A solution of sodium sulphate in water is x y y

electrolysed using inert electrodes. The products at (3)  (4) 3x 
3 3 3
the anode and cathode respectively are
35. Which of the following can change the conductivity
(1) O2, H2 (2) H2, O2
of a electrolytic solution?
(3) O2, Na (4) Na, O2
(1) Temperature (2) Viscosity
29. In electrochemical corrosion of metals, the metal
(3) Interionic attraction (4) All of these
undergoing corrosion
36. For an electrochemical cell Ag/Ag+(0.1 M) || Ag+/Ag
(1) Acts as anode
(1M), which of the following electrolyte cannot be
(2) Acts as cathode used in salt bridge?
(3) Is reduced (1) NaNO3 (2) KCl
(4) Either of these (3) KNO3 (4) Both (2) & (3)
37. For an electrochemical cell Al |Al3+ (1 M) || Cu2+(1M)|Cu, –
2. The standard electrode potential E values of
it is given that EAl Al3  1.66V and ECu/Cu2   0.34V .
Al3+/Al, Ag+/Ag, K+/K and Cr3+/Cr are –1.66 V, 0.80
The value of Ecell is V, –2.93 V and –0.74 V, respectively. The correct
(1) 2.00 V (2) 3.02 V decreasing order of reducing power of the metal is
(3) 1.75 V (4) 2.25 V [NEET-2019 (Odisha)]

(1) Al > K > Ag > Cr (2) Ag > Cr > Al > K
38. CuSO4 (aq) electrolysed using platinum electrodes
A current is passed until 1.6 g of O2 liberated at (3) K > Al > Cr > Ag (4) K > Al > Ag > Cr
anode. The amount of Cu deposited at the cathode 3. For the cell reaction
during same time period
(1) 6.35 g (2) 63.5 g 2Fe3 (aq)  2I (aq)  2Fe2 (aq)  I2 (aq)
(3) 12.7 g (4) 3.2 g EΘ
cell  0.24 V at 298 K. The standard Gibbs
1 energy ( r GΘ ) of the cell reaction is :
39. For a half cell having reaction Cl2  e  Cl , if
2 [Given that Faraday constant F = 96500 C mol–1]
1MCl – solution is diluted to 100 times
[NEET-2019]
(ECl 2Cl–
 1.36V) , then ECl 2Cl
will be (Given
2 2
PCl2  1atm ) (1) – 46.32 kJ mol–1 (2) – 23.16 kJ mol–1
(3) 46.32 kJ mol–1 (4) 23.16 kJ mol–1
(1) 1.18 V (2) 1.48 V
4. For a cell involving one electron E°cell = 0.59 V at 298
(3) 1.68 V (4) 3.48 V
K, the equilibrium constant for the cell reaction is :
40. For the given reactions
 2.303 RT 
Given that  0.059 V at T  298 K 
Sn 4 
 2e  Sn 2 E  x V F 
[NEET-2019]
Sn  Sn2  2e E  y V
(1) 1.0 × 102 (2) 1.0 × 105
The value of E° for the reaction
(3) 1.0 × 1010 (4) 1.0 × 1030
Sn4   4e  Sn will be 5. Consider the change in oxidation state of Bromine
corresponding to different emf values as shown in
x  y x  y the diagram below :
(1) (2)
2 2 – 1.82 V – 1.5 V
BrO4 BrO3 HBrO
y
(3) 2x + 2y (4) 2x  –
2 Br Br2
1.0652 V 1.595 V
Then the species undergoing disproportionation is
SECTION - C [NEET-2018]
Previous Years Questions (1) BrO3 (2) BrO4
1. Following limiting molar conductivities are given as (3) HBrO (4) Br2
º 2 –1 6. In the electrochemical cell :
m (H2SO4 )  x S cm mol
Zn|ZnSO4(0.01M)||CuSO4(1.0 M)|Cu, the emf of this
º
m (K 2SO4 )  y S cm2 mol–1 Daniel cell is E 1 . When the concentration of
º ZnSO4 is changed to 1.0 M and that of CuSO4
m (CH3COOK)  z S cm2 mol–1
changed to 0.01 M, the emf changes to E2. From
º the following, which one is the relationship between
m (in S cm2 mol–1) for CH3COOH will be
E1 and E2?
[NEET-2019 (Odisha)] RT
(Given, = 0.059) [NEET-2017]
(x – y) F
(1) z (2) x – y + 2z
2 (1) E1 = E2 (2) E1 < E2
(3) x + y + z (4) x – y + z (3) E1 > E2 (4) E2 = 0 ≠ E1
7. If the Eºcell for a given reaction has a negative 14. A device that converts energy of combustion of
value, which of the following gives the correct fuels like hydrogen and methane, directly into
relationships for the values of G° and Keq? electrical energy is known as [AIPMT-2015]
[NEET (Phase-2) 2016] (1) Ni-Cd cell
(1) G° > 0; Keq < 1 (2) G° > 0; Keq > 1 (2) Fuel cell
(3) G° < 0; Keq > 1 (4) G° < 0; Keq < 1 (3) Electrolytic cell
8. The molar conductivity of a 0.5 mol/dm3
solution of (4) Dynamo
AgNO 3 with electrolytic conductivity of
15. When 0.1 mol MnO24 is oxidised the quantity of
5.76 × 10–3 S cm–1 at 298 K
[NEET-Phase-2-2016] electricity required to completely oxidise MnO24 to
(1) 2.88 S cm2/mol (2) 11.52 S cm2/mol MnO4 is [AIPMT-2014]
(3) 0.086 S cm2/mol (4) 28.8 S cm2/mol (1) 96500 C
9. During the electrolysis of molten sodium chloride, (2) 2 × 96500 C
the time required to produce 0.10 mol of chlorine (3) 9650 C
gas using a current of 3 amperes is
(4) 96.50 C
[NEET-Phase-2-2016]
16. The weight of silver (At. Wt. = 108) displaced by a
(1) 55 minutes (2) 110 minutes quantity of electricity which displaces 5600 mL of
(3) 220 minutes (4) 330 minutes O2 at STP will be [AIPMT-2014]
10. The number of electrons delivered at the cathode (1) 5.4 g (2) 10.8 g
during electrolysis by a current of 1 ampere in
(3) 54.0 g (4) 108.0 g
60 sec. is (charge on electron = 1.60 × 10–19 C)
17. A button cell used in watches functions as following
[NEET-Phase-2-2016]

Zn(s)  Ag2O(s)  H2O(l )

(1) 6 × 1023 (2) 6 × 1020
2Ag(s) + Zn2+ (aq) + 2OH– (aq)
(3) 3.75 × 1020 (4) 7.48 × 1023
If half cell potentials are
11. Zinc can be coated on iron to produce galvanized
iron but the reverse is not possible. It is because Zn2+ (aq) + 2e–  Zn(s) ; E° = –0.76 V
[NEET-Phase-2-2016] Ag2O(s) + H2O(l) + 2e–  2Ag(s) + 2OH– (aq),
(1) Zinc is lighter than iron E° = 0.34 V
(2) Zinc has lower melting point than iron The cell potential will be [NEET-2013]
(3) Zinc has lower negative electrode potential than (1) 0.42 V (2) 0.84 V
iron (3) 1.34 V (4) 1.10 V
(4) Zinc has higher negative electrode potential 18. At 25°C molar conductance of 0.1 molar aqueous
than iron solution of ammonium hydroxide is 9.54 ohm–1 cm2
12. The pressure of H2 required to make the potential mol–1 and at infinite dilution its molar conductance is
of H2 electrode zero in pure water at 298 K is 238 ohm–1 cm2 mol–1. The degree of ionisation of
ammonium hydroxide at the same concentration and
[NEET-2016]
temperature is [NEET-2013]
(1) 10–4 atm (2) 10–14 atm
(1) 20.800% (2) 4.008%
(3) 10–12 atm (4) 10–10 atm (3) 40.800% (4) 2.080%
13. Aqueous solution of which of the following 19. A hydrogen gas electrode is made by dipping
compounds is the best conductor of electric platinum wire in a solution of HCl of pH = 10 and by
current? [Re-AIPMT-2015] passing hydrogen gas around the platinum wire at
(1) Ammonia, NH3 one atm pressure. The oxidation potential of electrode
(2) Fructose, C6H12O6 would be? [NEET-2013]
(3) Acetic acid, C2H4O2 (1) 0.59 V (2) 0.118 V
(4) Hydrochloric acid, HCl (3) 1.18 V (4) 0.059 V
20. Limiting molar conductivity of NH 4 OH 25. Standard electrode potential for Sn4 / Sn2 couple
   is +0.15 V and that for the Cr 3 / Cr couple is
 i .e.  m (NH4 OH)  is equal to
  –0.74 V. These two couples in their standard state
[AIPMT (Prelims)-2012]
are connected to make a cell. The cell potential will
o
(1) m o
(NH4OH)  m o
(NH4Cl) – m (HCl) be [AIPMT (Prelims)-2011]
(1) + 1.83 V
(2) mo (NH4Cl)  mo (NaOH) – mo (NaCl)
(2) + 1.19 V
(3) mo (NH4Cl)  mo (NaCl) – mo (NaOH) (3) + 0.89 V
(4) + 0.18 V
(4) mo (NaOH)  mo (NaCl) – mo (NH4Cl)
21. Standard reduction potentials of the half reactions 26. If the Eocell for a given reaction has a negative
are given below value, then which of the following gives the correct
F2(g) +2e–  2F–(aq); E = +2.85 V relationships for the values of G° and Keq?
Cl2(g) + 2e–  2Cl–(aq) ; E = +1.36 V [AIPMT (Prelims)-2011]
Br2(l) + 2e–  2Br–(aq) ; E = +1.06 V (1) G  0; K eq  1

2(s) + 2e– 2–(aq) ; E = +0.53 V (2) G  0; K eq  1
The strongest oxidising and reducing agents
respectively are [AIPMT (Mains)-2012] (3) G  0; K eq  1
(1) F2 and – (2) Br2 and Cl– (4) G  0; K eq  1
(3) Cl2 and Br– (4) Cl2 and 2 27. An increase in equivalent conductance of a strong
22. Molar conductivities  
o
m
at infinite dilution of NaCl,
electrolyte with dilution is mainly due to
HCl and CH3COONa are 126.4, 425.9 and 91.0 S [AIPMT (Prelims)-2010]
o
cm2 mol–1 respectively m for CH3COOH will be (1) Increase in ionic mobility of ions
[AIPMT (Mains)-2012] (2) 100% ionisation of electrolyte at normal dilution
(1) 425.5 S cm2 mol–1 (2) 180.5 S cm2 mol–1 (3) Increase in both i.e. number of ions and ionic
(3) 290.8 S cm2 mol–1 (4) 390.5 S cm2 mol–1 mobility of ions
23. The Gibb’s energy for the decomposition of Al2O3 at (4) Increase in number of ions
500C is as follows 28. For the reduction of silver ions with copper metal,
the standard cell potential was found to be +0.46V
2 4
Al O Al+O2 ; rG = +960 kJ mol–1 at 25C. The value of standard Gibbs energy, G
3 2 3 3
will be (F = 96500 C mol–1) [AIPMT (Prelims)-2010]
The potential difference needed for the electrolytic
(1) –89.0 kJ
reduction of aluminium oxide (Al2O3) at 500C is at
least [AIPMT (Mains)-2012] (2) –89.0 J
(1) 4.5 V (2) 3.0 V (3) –44.5 kJ
(3) 2.5 V (4) 5.0 V (4) –98.0 kJ
24. The electrode potentials for Cu2  e  Cu 29. Which of the following expressions correctly
(aq) (aq) represents the equivalent conductance at infinite
o
and Cu  e  Cu are +0.15 V and +0.50 V dilution of Al2(SO4)3. Given that  oAl3 and SO24 are
(aq) (s)
the equivalent conductances at infinite dilution of the
respectively. The value of Eo will be respective ions? [AIPMT (Mains)-2010]
Cu2  /Cu
o o o o
[AIPMT (Prelims)-2011] (1) 2 Al3  3 SO24 (2)  Al3  SO24
(1) 0.150 V (2) 0.500 V 1 o 1 o
o o
(3) (  Al3   SO24 )  6 (4)  Al3   SO 2
(3) 0.325 V (4) 0.650 V 3 2 4
30. Consider the following relations for emf of a (3) Infinite dilution each ion makes definite
electrochemical cell contribution to equivalent conductance of an
(a) emf of cell = (Oxidation potential of anode) electrolyte depending on the nature of the other
– (Reduction potential of cathode) ion of the electrolyte
(b) emf of cell = (Oxidation potential of anode) (4) Infinite dilution, each ion makes definite
+ (Reduction potential of cathode) contribution to conductance of an electrolyte
whatever be the nature of the other ion of the
(c) emf of cell = (Reductional potential of anode) + electrolyte
(Reduction potential of cathode)
35. Standard free energies of formation (in kJ/mol) at
(d) emf of cell = (Oxidation potential of anode) 298 K are –237.2, –394.4 and –8.2 for H2O (l), CO2
– (Oxidation potential of cathode)
(g) and pentane (g) respectively. The value of Ecell
Which of the above relations are correct?
for the pentane-oxygen fuel cell is
Options: [AIPMT (Mains)-2010] [AIPMT (Prelims)-2008]
(1) (c) and (a) (2) (a) and (b) (1) 0.0968 V (2) 1.968 V
(3) (c) and (d) (4) (b) and (d) (3) 2.0968 V (4) 1.0968 V
31. Given 36. On the basis of the following E° values, the
(i) Cu2+ + 2e–  Cu, Eo = 0.337 V strongest oxidizing agent is
(ii) Cu2+ + e–  Cu+, Eo = 0.153 V [Fe(CN)6]4–  [Fe(CN)6]3– + e–1; E° = – 0.35 V
Electrode potential, Eo for the reaction, Fe2+  Fe3+ + e–1; E° = – 0.77 V
Cu+ + e–  Cu, will be [AIPMT (Prelims)-2009] [AIPMT (Prelims)-2008]
(1) 0.90 V (2) 0.30 V (1) [Fe(CN)6]3– (2) [Fe(CN)6]4–

(3) Fe2+ (4) Fe3+
(3) 0.38 V (4) 0.52 V
37. The equilibrium constant of the reaction
32. Al2O3 is reduced by electrolysis at low potentials
and high currents. If 4.0 × 104 amperes of current Cu(s) + 2Ag+ (aq)  Cu2+(aq) + 2Ag(s) ; E=0.46V
is passed through molten Al2O3 for 6 hours, what at 298 K is [AIPMT (Prelims)-2007]
mass of aluminium is produced? (Assume 100% (1) 4.0 × 1015 (2) 2.4 × 1010
current efficiency, At. mass of Al = 27 g mol–1)
(3) 2.0 × 1010 (4) 4.0 × 1010
38. The efficiency of a fuel cell is given by
(1) 8.1 × 104 g (2) 2.4 × 105 g
(3) 1.3 × 104 g (4) 9.0 × 103 g
S H
M (1) (2)
33. The equivalent conductance of solution of a G G
32
weak monobasic acid is 8.0 mhos cm2 and at G G
(3) (4)
infinite dilution is 400 mhos cm2. The dissociation S H
constant of this acid is [AIPMT (Prelims)-2009]
39. If E° = –0.441 V and E° = 0.771 V,
Fe2+ / Fe Fe3+ /Fe2+
(1) 1.25 × 10–6 (2) 6.25 × 10–4
the standard EMF of the reaction Fe + 2Fe3+ 
(3) 1.25 × 10–4 (4) 1.25 × 10–5
3Fe2+ will be [AIPMT (Prelims)-2006]
34. Kohlrausch's law states that at
(1) 0.330 V (2) 1.653 V
(3) 1.212 V (4) 0.111 V
(1) Infinite dilution, each ion makes definite
40. A hypothetical electrochemical cell is shown below
contribution to equivalent conductance of an
A|A+(xM)||B +(yM)|B, the emf measured is +0.20 V.
electrolyte, whatever be the nature of the other
The cell reaction is [AIPMT (Prelims)-2006]
ion of the electrolyte
(1) A+ + B  A + B+
(2) Finite dilution, each ion makes definite
contribution to equivalent conductance of an (2) A+ + e–  A ; B+ + e–  B
electrolyte, whatever be the naure of the other (3) The cell reaction cannot be predicted
ion of the electrolyte (4) A + B+  A+ + B
41. 4.5 g of aluminium (at. mass 27 amu) is deposited 47. How many grams of cobalt metal will be deposited
at cathode from Al3+ solution by a certain quantity when a solution of cobalt(II) chloride is electrolyzed
of electric charge. The volume of hydrogen with a current of 10 amperes for 109 minutes?
produced at STP from H+ ions in solution by the (1 Faraday = 96,500 C; Atomic mass of Co = 59 u)
same quantity of electric charge will be (1) 0.66 (2) 4.0
[AIPMT (Prelims)-2005] (3) 20.0 (4) 40.0
(1) 22.4 L (2) 44.8 L 48. A 5 ampere current is passed through a solution of
(3) 5.6 L (4) 11.2 L zinc sulphate for 40 minutes. The amount of zinc
Questions asked Prior to Medical Ent. Exams. 2005 deposited at the cathode is
42. A solution contains Fe2+, Fe3+ and I– ions. This (1) 0.4065 g (2) 65.04 g
solution was treated with iodine at 35°C. E° for (3) 40.65 g (4) 4.065 g
Fe3+/Fe2+ is +0.77 V and E° for I2/2I– = 0.536 V. 49. The molar conductances of NaCl, HCl and
The favourable redox reaction is CH3COONa at infinite dilution are 126.45, 426.16 and
(1) I– will be oxidised to I2 91 ohm –1 cm 2 mol –1 respectively. The molar
(2) Fe2+ will be oxidised to Fe3+ conductance of CH3COOH at infinite dilution is
(3) I2 will be reduced to I– (1) 698.28 ohm–1 cm2 mol–1
(4) There will be no redox reaction (2) 540.48 ohm–1 cm2 mol–1
43. Standard reduction potentials at 25°C of Li+ / Li, (3) 201.28 ohm–1 cm2 mol–1
Ba2+ / Ba, Na+ / Na and Mg2+ / Mg are –3.05, –2.90, (4) 390.71 ohm–1 cm2 mol–1
–2.71 and –2.37 volt respectively. Which one of the
50. E° for the cell, Zn|Zn2+(aq)||Cu2+(aq)|Cu is 1.10 V at
following is the strongest oxidizing agent?
25ºC, the equilibrium constant for the reaction
(1) Ba2+ (2) Mg2+ Zn + Cu2+ (aq) Cu + Zn2+ (aq) is the order of
(3) Na+ (4) Li+ (1) 10+18 (2) 10+37
44. To protect iron against corrosion, the most suitable (3) 10–28 (4) 10–37
metal plating on it, is
51. For the cell reaction,
(1) Copper plating
Cu2+ (C1 · aq) + Zn(s) = Zn2+ (C2 · aq) + Cu(s) of an
(2) Zinc plating electrochemical cell, the change in Free Energy (G)
(3) Nickel plating at a given temperature is a function of
(4) Tin plating (1) ln (C2) (2) ln (C2/C1)
45. An electrochemical cell is set up as : (3) ln (C1) (4) ln (C1 + C2)
Pt; H2 (1 atm) |HCl (0.1 M) || CH3COOH (0.1M) | 52. The specific conductance of a 0.1 N KCl solution at
H2 (1 atm) ; Pt. The e.m.f. of this cell will not be zero, 23°C is 0.012 ohm–1 cm–1. The resistance of cell
because containing the solution at the same temperature was
found to be 55 ohm. The cell constant will be
(1) Acids used in two compartments are different
(1) 0.918 cm–1 (2) 0.66 cm–1
(2) e.m.f. depends on molarities of acids used
(3) 1.142 cm–1 (4) 1.12 cm–1
(3) The temperature is constant
53. For the disproportionation of copper 2Cu+  Cu2+ +
(4) pH of 0.1 M HCl & 0.1 M CH3COOH is not same Cu, E° is (Given E° for Cu2+/Cu is 0.34 V and E° for
46. Electrode potential for the following half-cell reactions Cu2+/Cu+ is 0.15 V)
are (1) 0.49 V (2) –0.19 V
Zn  Zn2+ + 2e–; E° = + 0.76 V; (3) 0.38 V (4) –0.38 V
Fe  Fe2+ + 2e–; E° = + 0.44 V 54. Cell reaction is spontaneous when
The EMF for the cell reaction Fe2+ + Zn  Zn2+ + Fe (1) G° is negative
will be (2) G° is positive
(1) – 0.32 V (2) + 1.20 V (3) E°Red is positive
(3) – 1.20 V (4) + 0.32 V (4) E°Red is negative
55. Equivalent conductances of Ba2+ and Cl– ions are 127 61. The e.m.f. of a Daniel cell at 298 K is E1
and 76 ohm–1 cm2 eq–1 respectively. Equivalent
Zn ZnSO4 CuSO4 Cu
conductance of BaCl2 at infinite dilution is (in the unit (0.01M) (1.0M)
ohm–1 cm2 eq–1)
When the concentration of ZnSO4 is 1.0 M and that
(1) 139.5 (2) 101.5 of CuSO4 is 0.01 M, the e.m.f. changed to E2. What
(3) 203 (4) 279 is the relationship between E1 and E2?
56. Standard electrode potentials are (1) E1 > E2
Fe2+/Fe ; E° = –0.44 volts (2) E1 < E2
Fe3+/Fe2+ ; E° = 0.77 volts (3) E1 = E2
Fe2+, Fe3+ and Fe blocks are kept together, then (4) E2 = 0  E1
(1) Fe3+ increases 62. The standard e.m.f. of a galvanic cell involving cell
(2) Fe3+ decreases reaction with n = 2 is found to be 0.295 V at 25°C.
The equilibrium constant of the reaction would be
(3) Fe2+/Fe3+ remains unchanged
(Given F = 96500 C mol–1, R = 8.314 J K–1 mol–1)
(4) Fe2+ decreases
(1) 2.0 × 1011 (2) 4.0 × 1012
57. PbO2  PbO ; G298 < 0
(3) 1.0 × 102 (4) 1.0 × 1010
SnO2  SnO ; G298 > 0
63. The mass of carbon anode consumed (giving only
Most probable oxidation state of Pb and Sn will be carbon dioxide) in the production of 270 kg of
(1) Pb4+, Sn4+ aluminium metal from bauxite by the Hall process is
(2) Pb4+, Sn2+ (Atomic Mass of Al = 27)
(3) Pb2+, Sn2+ (1) 270 kg (2) 540 kg
(4) Pb2+, Sn4+ (3) 90 kg (4) 180 kg
58. The most convenient method to protect the bottom 64. Consider the half-cell reduction reaction :
of ship made of iron is Mn2+ + 2e–  Mn, Eo = –1.18 V
(1) Coating it with red lead oxide Mn2+  Mn3+ + e–, Eo = –1.51 V
(2) White tin plating The Eo for the reaction 3 Mn2+  Mn0 + 2 Mn3+, and
(3) Connecting it with Mg block possibility of the forward reaction are, respectively
(4) Connecting it with Pb block (1) –2.69 V and no (2) –4.18 V and yes
59. In electrolysis of NaCl when Pt electrode is taken then (3) +0.33 V and yes (4) +2.69 V and no
H2 is liberated at cathode while with Hg cathode it
forms sodium amalgam SECTION - D
(1) Hg is more inert than Pt NEET Booster Questions
(2) More voltage is required to reduce H+ at Hg than 1. Given :
at Pt Mn2+  MnO4–; E° = – 1.51 V
(3) Na is dissolved in Hg while it does not dissolve MnO2  Mn2+; E° = 1.23 V
in Pt
What is the E° value for the reaction?
(4) Conc. of H+ ions is larger when Pt electrode is
MnO4–  MnO2
taken
(1) 1.7 V (2) 2.74 V
60. On the basis of the information available from the
reaction of O2, (3) 5.09 V (4) 1.1 V
4 2 2. For the following cell reaction :
Al  O2  Al2O3 , G  827 kJ mol1 ,
3 3 Cu(s) + 2Ag+(aq)  2Ag(s) + Cu2+(aq)
the minimum e.m.f. required to carry out electrolysis E°cell is 0.46 V at 300 K and 0.50 V at 340 K, then
of Al2O3 is (F = 96500 C mol–1) what will be entropy change?
(1) 2.14 V (2) 4.28 V (1) 386 JK–1 (2) 276 JK–1
(3) 6.42 V (4) 8.56 V (3) 96.5 JK–1 (4) 193 JK–1
3. The chemical species undergoing reduction in dry 11. Reactivity of metals increases as electropositivity
cell is increases, what will happen if a copper spoon is
used to stir a solution of aluminium nitrate?
(1) Zn (2) NH4
(1) The spoon will get coated with aluminium
(3) MnO2 (4) NH3 (2) An alloy of aluminium and coper is formed
4. The amount of Cu deposited when 10 A of current (3) The solution becomes blue
is passed for 10 minute through CuSO4(aq) is
(4) There is no reaction.
(1) 1.97 g (2) 2.89 g
12. Resistance of decimolar solution is 50 ohm. If
(3) 4 g (4) 3.5 g electrodes of surface area 0.0004 m2 each are
5. The volume of O2(g) released by 1 C electricity at placed at a distance of 0.02 m then conductivity of
NTP would be solution is
5.6 (1) 1 S cm–1 (2) 0.01 S cm–1
(1) 5.6 L (2) L
96500 (3) 0.001 S cm–1 (4) 10 S cm–1
13. The conductivity of a saturated solution of BaSO4
11.2 22.4 is 3.06 × 10 –6 ohm –1 cm –1 and its equivalent
(3) L (4) L
96500 96500 conductance is 1.53 ohm–1cm2eq–1. The Ksp for
6. The value of specific conductivity is maximum for BaSO4 will be
(1) 0.1 M NaCl (1) 4 × 10–12 (2) 2.5 × 10–13

(2) 0.01 M NaCl (3) 25 × 10–9 (4) 10–6
(3) 10–4 M NaCl 14. The EMF of a concentration cell consisting of two
(4) All will have equal specific conductivity M
zinc electrodes, one dipping into solution of
7. The net reaction in Ni–Cd cell is 4
(1) Cd + 2Ni(OH)3  CdO + 2Ni(OH)2 + H2O M
zinc sulphate & other into solution of the
(2) Ni(s) + 2Cd(OH)3  NiO + 2Cd(OH)2 + 16
H2O same salt at 25ºC is :-
(3) Cd + Ni2+  Cd2+ + Ni (1) 0.0125 V (2) 0.0250 V
(4) Ni + Cd2+  Ni2+ + Cd (3) 0.0178 V (4) 0.0356 V
8. The product released at anode in the electrolysis 15. The charge required for the reaction of 1 mole
of 50% concentrated H2SO4 is
Cr2O72 to Cr3+ in acidic medium is
(1) H2(g) (2) O2(g)
(3) S2O82– (4) All of these (1) 3 F (2) 6 F
9. L–1
If the electrical resistance of a column of 0.1 mol (3) 12 F (4) 2 F
NaOH solution of diameter 1 cm and length 10 cm 16. Given standard electrode potentials :-
is 5 × 10 3 ohm, what would be the molar
Fe3+ + 3e– Fe; Eº = –0.036 volt
conductivity of the solution?
Fe2+ + 2e– Fe; Eº = –0.440 volt
(1) 254.8 S cm2 mol–1
The standard electrode potential Eº for
(2) 50.96 S cm2 mol–1
Fe3+ + e– Fe2+
(3) 102.3 S cm2 mol–1
(1) –0.476 volt (2) –0.440 volt
(4) 25.48 S cm2 mol–1
(3) 0.440 volt (4) 0.772 volt
10. The emf of the cell,
17. The EMF of the cell;
Ni|Ni2+(1.0 M)||Ag+(1.0 M)|Ag (Eº of Ni2+|Ni = –0.25
volt, Eº for Ag+| Ag = 0.80 volt) Cr|Cr3+(0.1 M)|| Fe2+ (0.01 M)| Fe
(1) 0.55 volt
(2) – 1.05 volt
Given E 0
Cr 3  |Cr
 0.75 V, E0
Fe2 |Fe
 0.45 V 
(3) + 1.05 volt (1) 0.30 V (2) 0.36 V
(4) – 0.55 volt (3) 0.26 V (4) 0.22 V
18. Same quantity of current is passed through molten 24. The coulombic charge on one mole electron is
NaCl and molten Al 2 O 3 . If 2.3 g of Na was (1) 1.6 × 10–19 C
deposited in one cell, the mass of al deposited in
(2) 96500 C
other cells
(3) 6.02 × 10–23 C
(1) 1.8 gm (2) 0.9 gm
(4) 1.6 × 10–23 C
(3) 2.7 gm (4) 3.6 gm
25. Zn rod is placed in 100 mL of 1M CuSO4 solution
19. Standard electrode potential of some half cell
so that molarity of Cu2+ changes to 0.7 M. The
reactions are given below
molarity of SO42– at this stage will be
(i) Sn4+ + 2e–  Sn2+, Eº = + 0.15 V
(1) 0.8 M
(ii) 2Hg2+ + 2e–  Hg22 , Eº = + 0.92 V (2) 1 M
(iii) PbO2 + 4H+ + 2e–  Pb2++2H2O, Eº = + 1.45 V (3) 0.7 M
Which of the following statement is correct (4) 1.8 M
according to electrode ? 26. The time taken by the galvanic cell which operates
(1) Pb2+ is more powerful reducing agent than almost ideally under reversible conditions at a
Sn2+. current of 10–16A to deliver 1 mole of electron is
(2) Sn4+ is more powerful oxidising agent than (1) 19.30 × 1020 s (2) 4.825 × 1020 s
Pb4+. (3) 9.65 × 1020 s (4) 3.4 × 1011 s
(3) Sn2+ is more powerful reducing agent than 27. A direct current deposits 54 g of silver
Hg22+ (atomic mass = 108) during the electrolysis. The
(4) Hg2+ is more powerful oxidising agent than same quantity of electricity would deposit
Pb4+. aluminium (atomic mass = 27) from aluminium
chloride in molten state equal to
20. In a cell that utilizes the reaction
(1) 4.5 g (2) 5.4 g
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
(3) 54 g (4) 27 g
Addition of H2SO4 to cathode compartment will
28. During the electrolysis of water, 4 mol of electrons
(1) Lower the E and shift equilibrium to left. were transferred from anode to cathode. The total
(2) Lower the E and shift equilibrium to the right. volume of gases produced at STP will be
(3) Increase the E and shift equilibrium to the right. approximately
(4) Increase the E and the equilibrium to left. (1) 67.2 L (2) 22.4 L
(3) 44.8 L (4) 89.4 L
o
21. The EM3  |M2  values for Cr, Mn, Fe and Co are 29. The quantity of electricity required to reduce
–0.41, + 1.57, + 0.77 and + 1.97 respectively. For 12.3 g of nitro benzene to aniline assuming 50%
which one of these metals, the change in oxidation current effeciency is
state from +2 to +3 is easiest (1) 115800 C (2) 57900 C
(1) Cr (2) Mn (3) 231600 C (4) 28950 C
(3) Fe (4) Co 30. A 100 watt, 110 volt lamp is connected in series
22. The resistance of 0.0025 M solution of K2SO4 is with an electrolytic cell containing CdSO4 solution,
326 ohm. The specific conductance of the solution, the weight of Cd deposited by the current for
if cell constant is 4 (in ohm). 10 hrs is (At. wt. of Cd = 112.4)
(1) 4.997 × 10–4 (2) 5.997 × 10–7 (1) 19.06 g (2) 38.12 g
(3) 6.997 × 10–4 (4) 1.20 × 10–2 (3) 1.906 g (4) 3.812 g
23. The conductivity of four electrolytes P, Q, R, S in ohm– 31. The two platinum electrodes fitted in a conductance
1 cm–1 are as follows P(5 × 10–5), Q(1× 10–10), R(7 × cell are 1.5 cm apart while the cross sectional area
10–8); S(9.2 ×10–3). The one which offers highest of each electrode is 0.75 cm2. What is the cell
resistance to the passage of electric current is constant?
(1) P (2) S (1) 1.25 cm–1 (2) 0.5 cm–1
(3) R (4) Q (3) 2.0 cm–1 (4) 0.2 cm–1
32. A current of 2.0 A is passed for 5 hours through a 41. The hydrogen electrode is dipped in a solution of
molten metal salt deposits 22.2 g of metal pH = 3 at 25°C. The reduction potential of the
(At. mass: 177). The oxidation state of the metal in electrode would be
metal salt is (1) 0.177 V (2) 0.087 V
(1) +1 (2) +2 (3) –0.177 V (4) 0.059 V
(3) +3 (4) +4 2 2
42. Zn | Zn(aq) || Cu(aq) | Cu E° for the cell is 1.10 V at
33. A current of 0.965 ampere is passed through
500 ml of 0.2 M solution of ZnSO4 for 10 minutes. 25°C. The equilibrium constant for the cell reaction
The molarity of Zn2+ after deposition of zinc is is of the order of
(Atomic mass of Zn is 65 u) (1) 10–37 (2) 1037
(1) 0.1 M (2) 0.5 M (3) 10–17 (4) 1017
(3) 0.8 M (4) 0.194 M 43. What will be the emf of the given cell?
34. Electrolysis of H2SO4 (conc.) gives the following at 
Pt | H2(P1 ) | H(aq) | H2(P2 ) | Pt
anode
(1) H2 (2) O2 RT P1 RT P
(1) ln (2) ln 1
(3) H2S2O3 (4) H2S2O8 F P2 2F P2
35. In SHE, the pH of the acid solution should be RT P2 RT P
(3) ln (4) ln 2
(1) 7 (2) 14 F P1 2F P1
(3) 0 (4) 4 44. Which of the following can oxidise fluoride ions?
36. E.M.F. of Ni(s)|Ni2+ (aq) || Cu2+ (aq)|Cu(s) cell can (1) O3
be increased by (2) Cl2
(1) Adding NH3 in the right half-cell (3) Br2
(2) Increasing the conc. of Ni2+ ions (4) No chemical substance
(3) Adding dimethyl glyoxime into the left half-cell 45. If the standard reduction potential E° for four divalent
(4) Changing the electrolyte present in salt bridge elements X, Y, Z, W are –1.46 V, –0.36V, 0.15 V and
37. For given cell; Zn |Zn2+ (C1) || Zn2+ (C2)| Zn; G is –1.24 V respectively then
negative if (1) X will replace Z2+ from aqueous solution
(1) C1 = C2 (2) C1 > C2 (2) Y will replace Z2+ from aqueous solution
(3) C2 > C1 (4) Can't predicted (3) W will replace Z2+ from aqueous solution
38. The emf of the cell, Zn|Zn2+||Cu2+|Cu is independent (4) All statements are correct
of 46. The following facts are available
(1) The volume of Zn2+ and Cu2+ solution 2A– + B2  2B– + A2
(2) The molarity of Zn2+ ions in solution 2C– + B2  No reaction
(3) The molarity of Cu2+ ions in solution 2D– + A2  2A– + D2
(4) Temperature Which of the following statement is correct?
39. Standard cell voltage for the cell Pb/Pb2+||Sn2+/Sn
(1) Eo   Eo   Eo   Eo 
is –0.01V. If the cell is to exhibit Ecell = 0 then the C /C2 B /B2 A /A 2 D /D2
value of log [Sn2+] /[Pb2+] should be
(2) Eo   Eo   Eo   Eo 
(1) 0.33 (2) 0.5 C /C2 B /B2 A /A 2 D /D2
(3) 1.5 (4) –0.5 (3) Eo   Eo   Eo   Eo 

C /C2 B /B2 A /A 2 D /D2
40. The voltage of a cell whose half cell reactions are (4) Can’t predict
given below is
47. The specific conductance of a 0.1 N KCl solution at
Mg2  2e   Mg(s); E  –2.37 V 23°C is 0.012 ohm–1cm–1. The resistance of cell
containing the solution at the same temperature was
Cu2  2e   Cu(s); E  0.34 V found to be 55 ohm. The cell constant will be
(1) 1.02 V (2) 1.36 V (1) 0.142 cm–1 (2) 0.66 cm–1
(3) 2.71 V (4) 2.03 V (3) 0.918 cm–1 (4) 1.12 cm–1
48. Saturated solution of KNO3 is used to make salt 55. If equivalent conductance of 1M benzoic acid is 12.8
bridge because ohm–1 cm2 eq–1 and if the equivalent conductances
(1) Velocity of K+ is greater than that of NO3 of benzoate ion and H+ ion at infinite dilution are 42
and 288.42 ohm–1 cm2 eq–1 respectively, then its
(2) Velocity of NO3– is greater than that of K+
degree of dissociation is
(3) Velocity of both K+ and NO3– are nearly the same
(1) 39%
(4) KNO3 is highly soluble in H2O
(2) 3.9%
49. Cu 2+ + 2e –  Cu. On increasing [Cu 2+ ]
concentration, electrode potential (3) 0.35%
(1) Increases (4) 0.039%
(2) Decreases 56. Four alkali metals A, B, C & D have standard electrode
potentials –3.05, –1.66, –0.40 and 0.80 V
(3) Will remain unchanged
respectively. Which metal will be the most reactive
(4) First increases, then decreases
(1) A
50. In the electrochemical cell
(2) B
Pt | H2(g) 1atm | H+(1M) || Cu2+ (1M) | Cu(s)
(3) C
Which of the following statements is true?
(4) D
(1) H2 is cathode, Cu is anode
57. Consider the cell given below :
(2) Oxidation occurs at Cu electrode
Ag(s) / Ag+ || Cu2+/Cu(s)
(3) Reduction occurs at H2 electrode
Ag+ + e–  Ag ; E° = x
(4) H2 is anode, Cu is cathode
51. If hydrogen electrode is dipped in two solutions of Cu2+ + 2e–  Cu ; E° = y
pH = 3 and pH = 6 and salt bridge is connected, the E°Cell is
emf of resulting cell is (1) x + 2y (2) 2x + y
(1) 0.177 V (2) 0.3 V (3) y – x (4) y – 2x
(3) 0.052 V (4) 0.104 V 58. If the specific conductance of 1M H2SO4 solution is
52. The emf of the cell reaction 26 × 10–2 S cm–1, then the equivalent conductivity
Ag | Ag+(0.1M) || Ag+(1M) | Ag at 298 K is would be
(1) 0.0059 V (2) 0.059 V (1) 1.3 × 102 S cm2 eq–1
(3) 5.9 V (4) 0.59 V (2) 1.6 × 102 S cm2 eq–1
53. An electrolytic cell contains aqueous solution of (3) 13 S cm2 mol–1

Ag2SO4 and has Platinum electrodes. A current is (4) 1.3 × 103 S cm2 mol–1
passed until 1.6 g of O2 is liberated at anode. The 59. How many atoms of calcium will be deposited from
amount of silver deposited at cathode would be molten CaCl2 by a current of 25 milliamperes flowing
(1) 107.88 g (2) 1.6 g for 60 seconds?
(3) 0.8 g (4) 21.6 g (1) 4.68 × 1018 (2) 4.68 × 1015
54. E° values of Mg2+/Mg, Zn2+/Zn and Fe2+/Fe are (3) 4.68 × 1012 (4) 4.68 × 1019
–2.37 V, –0.76 V and –0.44 V respectively. Which of 60. Limiting molar conductivity of which among the
the following statements is correct following ion is maximum in water at 298 K
(1) Zn will reduce Fe2+ (2) Zn will reduce Mg2+ (1) H+ (2) Na+
(3) Mg oxidises Fe (4) Zn oxidises Fe (3) K+ (4) Ca2+

Chapter 12
Chemical Kinetics
Chapter Contents
z Rate of Chemical Reaction z Chemical kinetics deals with the rate of the reactions and factors
influencing the rate of a reaction.
z Rate Law or Rate Equation of
a Reaction z Gibb's free energy concerns with the spontaniety of the reaction
whereas the kinetics will deal with the speed of the reaction.
z Integrated Rate Equations z The rate of reaction are affected by light and also by electric and
z Methods to Determine the magnetic fields.
Order of Reaction
RATE OF CHEMICAL REACTION
z Factors Affecting Rate of a
Chemical Reaction [R]0
z Effect of Temperature
– [ R ] – (C2 – C1)
C1 rav = = rinst = d[ P] slope
Collision Theory of Reaction
Concentration
Concentration
z t (t2 – t1) C1 dt
Rates C2 – d[ R ] [P]
rinst = = – slope
dt C2
t rav =  [ P] = C2 – C1
t (t2 – t1)
t1 t2 t t1 t2 t
time time
[Reactant] [Product]
(a) (b)
Rate of reaction is defined as the speed with which the reactants are
converted into products at a given time. It may be expressed as the
change in concentration of any one reactant or product per unit time.
A  B
Decrease in conc. of A Increase in conc. of B
Rate = =
time taken time taken
–Δ  A  Δ B 
Rate = =+
Δt Δt
Negative sign with the reactant concentration is to nullify the minus sign
of change of concentration of the reactants and to make the rate a
positive term.
H2 + I2  2HI
Δ H2  Δ I2  1 Δ HI

Rate =  =  =+
Δt Δt 2 Δt
158 Chemical Kinetics NEET
For a general chemical transformation,

nA + mB  pC + qD
The rates of disappearance of reactants and rates of appearance of products are equalized by dividing them
with the coefficients in the balanced chemical equation. Thus,
1 [A] 1 [B] 1 [C] 1 [D]

 
  
n t m t p t q t
Average and Instantaneous rate of reaction : By dividing the total change in concentration of reactant
or product by a time interval, we actually get the average rate of the reaction. The instantaneous rate is
obtained when a very small change in concentration (dC) is divided by very small time interval (dt). It is
assumed that in dt time, the rate of the reaction remains constant. Thus, instantaneous rate,
dC

dt
Let us consider the change,
2SO2(g) + O2(g)  2SO3(g)
the rate of the reaction can be represented by
1 d[SO2 ] d[O2 ] 1 d[SO3 ]

  
2 dt dt 2 dt
The theoretical rate of a reaction is given by law of mass action. Thus, for the general chemical change
mA + nB  Products
dx
Theoretical Rate   k[A]m  [B]n
dt
The observed rate of reaction is given by the kinetic study of the reaction.
Rate can be measured by plotting a curve between concentration of reactant and time and drawing a tangent
at a specified time. Rate at time t
dx
=– = slope of the tangent
dt
conc
dx
dt
time
Example 1 : For a reaction, 2A + B 3C , the rate of appearance of C at time t is 1.2 × 10–4 mol L–1 s–1.
Find the rate of reaction.
d[C]
Solution : = 1.2 × 10−4
dt
1 d[C] 1 −4
Rate of reaction = = × 1.2 × 10
3 dt 3
–5 –1 –1
= 4 × 10 mol L s .
NEET Chemical Kinetics 159
Example 2 : The decomposition of NH3 on platinum surface is a zero order reaction. What would be the rate
–4 –1 –1
of production of N2 and H2 if k = 2.5 × 10 mol L s ?
Solution : For zero order reaction
Rate of reaction = Rate constant (k)
2NH 3 N2 + 3H2
d[N2 ]
Rate of reaction =
dt
–4 –1 –1
Hence, rate of production of N2 = 2.5 × 10 mol L s
1 d[H2 ]
Again, Rate of reaction =
3 dt
d[H2 ]
= 3 × Rate of reaction
dt
–4
= 3 × 2.5 × 10
–4 –1 –1
= 7.5 × 10 mol L s
Law of Mass Action :

z (Guldberg and Waage Law): The rate at which a substance reacts is proportional to its active mass
(molar concentration) and the rate of a reaction is directly proportional to the product of molar concentrations
raised to the powers equal to the number of participating molecules A  B.
z For the reaction, 2A + 3B  products, theoritically.
Rate  [A]2 [B]3 or Rate = k[A]2[B]3, where k is called specific reaction rate or velocity constant. It is
defined as the rate of the reaction at a given temperature when the molar concentration of each reactant
at a given temperature is unity.
RATE LAW OR RATE EQUATION OF A REACTION

The mathematical expression which gives a relation between rate of the reaction and concentrations of reactants
is known as rate law or rate equation. The rate law is established by the kinetic study of a reaction
experimentally.
Let us consider a general reaction
mA + nB  pC + qD
dx
 [A]a  [B]b
dt
dx
or  k [A]a  [B]b
dt
The reaction is said to be of 'a' order with respect to reactant 'A' and of 'b' order with respect to
reactant 'B'.
The overall order of the reaction is (a+b).
Thus rate law is given by experimental observation. Sometimes for elementary or simple reactions rate law
can be written according to law of mass action.
Molecularity of a Reaction
It is defined as the number of reactant species which collide simultaneously to form the products. It is always
a positive integer like 1, 2, 3, ..... Higher molecularity (> 3) are rare because chances of colliding more than
three molecules at a time are very less. Molecularity is defined only for elementary (one step) reactions. There
is no meaning of molecularity for complex (reactions occurring in more than one steps) reactions.
Order of Reaction :
z The order of a reaction with respect to a reactant is the power of the concentration term of that reactant
to which the rate of the reaction is directly proportional.
z The overall order of a reaction is the sum of the powers or exponents to which the concentration terms
are raised in the rate law expression.
Let us consider a general reaction
aA + bB  pC + qD
If the rate law for this reaction comes out to be
dx
 k [A]m  [B]n ,
dt
m is the order of reaction with respect to A and n is order of the reaction with respect to B.
then, the overall order of the reaction is m + n.
z Order of a reaction is always experimentally determined quantity.
z Order of a reaction cannot be written from the balanced chemical equation.
z Order of a reaction may be zero, whole number, fractional or even negative.
Molecularity and order of a reaction may be the same for bimolecular or termolecular reactions..
z Order is defined for elementry as well as complex reactions.
2
Example 3 : The form of the rate law for a reaction is expressed as : Rate = k[Cl2] [NO] . Find out the order
of reaction with respect to Cl2 and with respect to NO and also the overall order of reaction.
Solution : Order with respect to Cl2 = 1
Order with respect to NO = 2
Overall order = 3
EXERCISE
1. For the reaction,
2N2O5  4NO2 + O2
Select the correct statement

(1) Rate of formation of O2 is same as rate of formation of NO2
(2) Rate of disappearance of N2O5 is two times the rate of formation of NO2
(3) Rate of formation of O2 is 0.5 times rate of disappearance of N2O5
(4) Rate of formation of NO2 is equal to rate of disappearance of N2O5
dx
2. = K [A]0.5 [B]0.5 [c]0.5. What will be the order of the reaction?
dt
(1) 1
(2) 1.5
(3) Zero
(4) 2
3. H2 + I2  2HI (An elementary reaction)
If the volume of the container containing the gaseous mixture is increased to two times, then final rate of the
reaction
1
(1) Become four times (2) Become th of the original rate
4
1
(3) Become 2 times (4) Become of the original rate
2
4. In a certain reaction shown below,
4A + 2B  3C
If rate of formation of C is 9.6 × 10–2 mol/L s. What will be rate of reaction?
(1) 9.6 × 10–2 mol/L s
(2) 3.2 × 10–2 mol/L s
(3) 2.4 × 10–2 mol/L s
(4) 4.8 × 10–2 mol/L s
H2O2 + 2H+ + 3I–  I3– + 2H2O
Select the correct statement
(1) Rate of disappearance of H2O2 will be three times the rate of disappearance of I–
1
(2) Rate of disappearance of H2O2 is of rate of formation of I3–
3
(3) Rate of disappearance of I– ions will be three times the rate of formation I3– ions
1
(4) Rate of formation of H2O is of rate of formation of I3–
2
6. The value of rate constant depends upon
(1) Temperature (2) Concentration
(3) Catalyst (4) Both (1) & (3)
INTEGRATED RATE EQUATIONS

1. Zero Order Reaction
The reaction whose rate does not depend upon the concentration of reactants is called a zero order reaction.
If the hypothetical chemical change.
A  B is a zero order reaction, then,
dx
 k [A]0  k , a constant
dt
Unit of Zero Order Rate Constant

dx
 k [A]0
dt
dx Change in concentration
or k 
dt Time interval
Mole / litre
=
Sec
Example of Zero Order Reaction
z Decomposition of hydrogen iodide(g) and ammonia(g) on metal surfaces.
z Combination of hydrogen and chlorine gases in the presence of sun light.
Sun light
H2 (g)  Cl2 (g)  2HCl(g)
dx
 k[H2 ]0 [Cl2 ]0
dt
2. First order reaction
If a general reaction A  B,
dx
Follows first order kinetics, then its rate law is,  k[A]
dt
where k is the rate or velocity constant.
Units of k : (rate constant) Rate = k [A]
Rate mol L1 L

k    s 1
[A] mol s
Integral rate equation for first order reactions: A  Products, dx/dt is rate of reaction; a is initial conc.
while (a – x) is the concentration after time t i.e. x is the reacted amount in time t.
dx dx
 (a  x),  k (a  x)
dt dt
on integrating –ln (a – x) = kt + I
When t = 0, x = 0
I = –ln a
–ln (a – x) = kt – ln a
a
kt = ln a – ln (a – x) = ln
ax
2.303 a
k log
t ax
z Example of first order reactions
(i) Decomposition of H2O2 in aqueous solution
1
H2O2  H2O + O2
2
(ii) Hydrolysis of Methyl acetate in presence of mineral acids.
Acid
CH3COOCH3  H2O   CH3COOH  CH3OH
(iii) Inversion of cane sugar in presence of mineral acids
Acid
C12H22O11  H2O   C6H12O6  C6H12O6
(iv) Radioactive decay
226 222 4
88 R  86 Rn  2 He
Radium Radon   particle
(v) Decomposition of nitrogen pentaoxide in CCl4 solution, N2O5  2NO2 + ½ O2

Half Life Period (t1/2) : The time in which half of the initial amount of reactants is converted to products or
the time taken for 50% completion of reaction is known as half life period.
z For zero order reaction A  Products
d(a  x) dx
  k(a  x)0
dt dt
dx
 k
dt
 x = kt
a
 t1/2  2 a
k 2k
z For first order reaction
2.303 a
k log
t ax
0.693
t1/2 
k
Pseudo-Unimolecular Reactions
Those first order reactions whose molecularity is not one are called Pseudo-unimolecular reactions.
Examples :
z Hydrolysis of an ester :

H
CH3COOC2H5 + H2O  
 CH3COOH + C2H5OH
dx
 k[CH3COOC2H5 ]
dt
So, order of the reaction is one.
Example 4 : The t1/2 of first order reaction is 60 minutes. What percentage will be left after 240 minutes?
0.693 0.693
Solution : k= =
t1/2 60
2.303 [A ]
t= log 0
k [A t ]
2.303 [A ]
240  log 0
 0.693  [A t ]
 
 60 
4  0.693 [A ]
 log 0
2.303 [A t ]
A0
At = = 0.0625 [A 0 ]
16
[At] = 6.25% of [A0]
–3 –1
Example 5 : A first order reaction has a specific reaction rate of 10 s . How much time will it takes for
10 g of the reactant to reduce to 2.5 g?
2.303 [A ]
Solution : k= log 0
t [A t ]
2.303 10
t= −3
log
10 2.5
t = 2303 × 0.301 × 2 = 1386 s.
Example 6 : Half life time for a first order reaction is 25 minutes. What time will be required for 99% completion
of reaction?
Solution : t1/2 = 25 min
0.693 0.693
k= =
t1/2 25
2.303 [A ] 2.303  100 

t = log 0 = log   = 166.16 min
k [A t ]  0.693   1 
 
 25 
EXERCISE
7. 2A + B  C + D
In this reaction, if we double the concentration of A, reaction rate become two times. And in other experiment,
we double the concentration of A and B, reaction rate again become two times. What is the order of this
reaction?
(1) 1
(2) 3
(3) 2
(4) 1.5
8. If the half-life of the first order reaction is 50 s, what will be the value of its rate constant?
(1) 1.38 × 10–2 s–1
(2) 25 s–1
(3) 34.66 s–1
(4) 1.38 × 10–4 s–1
9. In a first order reaction, on plotting a graph between t1/2 and concentration of reactant
(1) A curve is obtained
(2) A straight line is obtained having slope 45°
(3) A straight line is obtained having slope 60°
(4) A straight line parallel to the concentration axis
10. In data given below,
[A] [B] rate
mol/L mol/L mol L–1 s–1
a. 0.02 1.2 3.0 × 10–3
b. 0.04 2.4 6.0 × 10–3
The reaction may be
(1) First order (2) Second order
(3) Pseudo second order (4) Second order w.r.t. A
11. For certain first order reaction, 75% of the reaction complete in 30 min. How much time it require to complete
99.9% of the reaction?
(1) 150 min (2) 100 min
(3) 90 min (4) 300 min
12. In pseudo-order reactions
(1) The actual order of reaction is different from that expected using rate law expression
(2) The concentration of at least one reactant is taken in large excess
(3) The concentration of reactant taken in excess may be taken as constant
(4) All of these
13. The depletion of ozone involves the following steps:
K1

Step 1: O3 O2 + O (fast)
K 2
Step 2: O3 + O 
K
 2O2 (slow)
The predicted order of the reaction will be
(1) 1 (2) 1.5
(3) – 1.5 (4) Zero
METHODS TO DETERMINE THE ORDER OF REACTION
The different experimental methods used for the determination of the rate law, rate constant and order of
reaction are briefly described below :
1. Graphical Method. This method can be used when there is only one reactant. For example consider
the raction
n A  Products
If this reaction is of the first order,
Rate  [A]
or Rate = k[A] ...(i)
So that the plot of rate vs. molar concentration of the reactant would be linear and equation (i) will be
the 'rate law'
If the above reaction is of the second order,
Rate  [A]2
or Rate = k[A]2 ...(ii)
So that the plot of rate vs. [A]2 would be linear and equation (ii) would be the 'rate law' and so on.
Some Typical Linear Plots for the Reactions of Different Orders :

z Plots of rate vs concentrations [Rate = k (conc.)n]
th
Zero order Ist order 2nd order n (n  1) order
Rate
Rate
Rate
Rate
2 n
Concentration Concentration (Concentration) (Concentration)
z Plots from integrated rate equations
th
1
Conc [A]
1
Log [A]
n–1
[A] [A]
Time (t) Time (t) Time (t) Time (t)

z Plots of half-lives vs concentration (t1/2  a1 – n)
th
t1/2 t1/2 t1/2 t1/2
n–1
Concentration Concentration 1/a 1/a
2. Initial Rate Method (Ostwald's isolation method). This method can be used irrespective of the number
of reactants involved e.g., consider the reaction,
n1 A + n2B + n3C —— Products
The method consists in finding the initial rate of the reaction known concentration of the different reactants
(A, B, C,). Now the concentration of one of the reactants is changed (say that of A) taking the
concentrations of other reactants (B and C) same as before. The initial rate of the reaction is determined
again. This gives the rate expression with respect to A and hence the order w.r.t. A. The experiment is
repeated by changing the concentration of B and taking the same concentration of A and C and finally
changing the concentration of C and taking the same concentrations of A and B. These will give rate
expression w.r.t. B and C and hence the orders w.r.t. B and C respectively. Combining the different rate
expressions, the overall rate expression and hence the overall order can be obtained.
Suppose it is observed as follows :
z Keeping the concentrations of B and C constant, if concentration of A is doubled, the rate of reaction
becomes four times. This means that
Rate  [A]2 i.e., order w.r.t. A is 2
z Keeping the concentrations of A and C constant, if concentration of B is doubled, the rate of reaction
is also doubled. This means that
Rate  [B] i.e., order w.r.t B is 1
z Keeping the concentrations of A and B constant, if concentration of C is doubled, the rate of reaction
remains unaffected. This means that rate is independent of the concentration of C i.e, order w.r.t. C
is zero.
Hence the overall rate law expression will be
Rate = k[A]2[B][C]0
 Overall order of reaction = 2 + 1+ 0 = 3
3. Half-life Method : This method is based on the fact that half-change time is inversely proportional to
the initial concentration of reactant raised to the power one less than the order of reaction.
1
i.e., t1/2 
(a)n1
4. Differential Method : When the order of a reaction with respect to a particular component is 'n' and r1
and r2 are the rates of the reaction at different concentrations c1 and c2 of that reactant, then
n
r1  c1 
 
r2  c 2 
Thus, order of reaction with respect to individual reactants is determined.
5. Some reactions which seem to involve very large number of reacting particles, are in fact complex reaction
which take place through a sequence of 2 or more consective steps. The detailed study of various steps
by which reactants change into products is called mechanism of the reaction. The step which contributes
to the over all rate is the slowest step in the sequence. It is called rate controlling step.
2NO2 + F2  2NO2F
slow  fast
NO2 + F2  NO2F + F; NO2 + F  NO2F
It is confirmed by the experimental rate which is given by Rate = k [NO2][F2].

Rate Constant, Velocity Constant or Specific Reaction Rate (k) :
z The rate constant of a reaction is a measure of its rate of reaction. Fast reactions have higher value of
'k' while for slow reactions 'k' is low.
z At a given temperature, the rate constant is equal to the rate of reaction when the concentration of all
the reactants is unity.
z Rate constant, k is not affected by the concentration change of reactions, nor does it depend upon the
initial concentration of a reactant.
z 'k' remains constant throughout the progress of the reaction.
z Positive catalyst increases the value of 'k', the rate constant.
z Rate constant, 'k' is always increased when temperature rises.
z Unit of 'k' depends upon the order of the reaction.
z Unit of k for nth order reaction is (mole L–1)1–n sec–1.
z Expressions for rate constant for reaction of different orders
Reaction Order Rate law equation Rate constant
[A 0 ]  [A]
A  product 0 Rate = k k
t
2.303 [A ]
A  product 1 Rate = k[A] k log 0
t [A]
FACTORS AFFECTING RATE OF A CHEMICAL REACTION
The reaction rate is influenced by the following factors :

z Effect of Concentration : The rate of a reaction depends on the concentration of the reactants according
to rate law expression. Hence, the rate of a reaction decreases as the reaction proceeds towards the
products because the concentration of reactant (s) decreases.
z Nature of Reactants and Products : Chemical reaction which involves complex molecules as reactants
and in which complex molecules are formed as products, proceed at a slower rate. The reason is that,
greater number of bond rearrangements are involved in complex reactants and products which make the
reaction slow. Reactions involving lesser number of bond rearrangements are fast reactions. For example,
oxidation of Fe++ by MnO4– ion in acidic medium takes place faster than the oxidation of oxalate ion
(C2O42–) under the same condition.
5Fe2+ + MnO4– + 8H+  Mn2+ + 5Fe3+ + 4H2O (fast)
2MnO4– + 16H+ + 5C2O42 –  2Mn2+ + 8H2O + 10CO2 (slow)
z Presence of a Catalyst : Generally, a positive catalyst enhances the rate of a reaction by decreasing
the activation energy. But negative catalyst retards a chemical reaction.
Potential energy
Energy of
activation
without
Energy of catalyst
activation
with catalyst
Reaction coordinate
z Surface Area of Solid Reactant : This factor is important for heterogeneous reactions involving a solid
as one of the reactants. The rate of such a reaction increases with increasing surface area of solid reactant,
i.e.,
Rate of reaction  Surface area of solid reactant
For example : Wood shavings burn more rapidly than a log of wood of same mass.
Coal dust burns at a faster rate than large piece of coal.
z Exposure to Radiations : Rates of certain reactions increase by absorption of photons of a particular
radiation. Such reactions are called photochemical reactions. For example, Hydrogen and chlorine
gases do not combine with each other in dark.
EFFECT OF TEMPERATURE
Generally, the rate of a reaction increases with rise of a temperature. It has been found that in most of the
cases, a rise of 10 K in temperature doubles and in some cases triples the rate of a reaction.
Effect of Temperature on Rate Constant (Arrhenius Equation)
k = A. e–Ea/RT
Where A is a constant known as frequency factor, Ea is the energy of activation of the reaction and R is
gas constant. Both A and Ea are the characteristics of the reaction.
log k = log A – Ea/2.303 RT
Ea 1
or log k = –  + log A
2.303R T
Ea
If a plot of log k against 1/T is a straight line, the slope of this line is . Knowing the slope, Ea can
2.303R
easily be evaluated.
–Ea
slope =
2.303 R
log k
1
T
If k1 and k2 are the values of rate constants at temperature T1 and T2, then
k 2 Ea  1 1 
or ln    
k1 R  T1 T2 
k2 Ea 1 1
log    
k1 2.303 R  T1 T2 
Example 7 : The rate constant k for the first order gas phase decomposition of ethyl iodide, C2H5IC2H4 +
HI is 1.60 × 10–5 s–1 at 600 K and 6.36 × 10–3 s–1 at 700 K. Calculate the energy of activation
for this reaction.
Solution : We are given
k1 = 1.60  10–5 s–1 ; T1 = 600 K
k2 = 6.36  10–3 s–1 ; T2 = 700 K
k2 Ea 1 1
We know that log    
k1 2.303 R  T1 T2 
Substituting the values of k1, k2 and R ( = 8.314 JK–1 mol–1), we get,
6.36  10 3 Ea  1 1 

2.303  8.314  600 700 
log 5 =
1.60  10
Ea
log (3.98  102) =
(19.15)  ( 4200 )
 Ea = 2.6  19.15  4200 J mol–1 = 2.09  105 J mol–1 = 209 kJ mol–1
Example 8 : Rate constant k of a reaction varies with temperature according to the equation
Ea ⎛ 1 ⎞
log k = constant − ⎜ ⎟
2.303 R ⎝ T ⎠
where Ea is the energy of activation for the reaction. When a graph is plotted for log k versus
1
, a straight line with a slope –6670 K is obtained. Calculate the energy of activation for this
T
reaction.
−Ea
Solution : Slope of the line = = –6670 K
2.303R
Ea = 2.303 × 8.314 × 6670
= 127.7114 kJ/mol
COLLISION THEORY OF REACTION RATES
According to collision theory the reactants (atoms, ions or molecules) collide with one another to bring about
the chemical change. The number of collisions that take place per second per unit volume in the reaction
mixture is called collision frequency, z. The collisions which bring about the chemical reactions are known
as effective collisions.
The effective collisions are those which fulfill the following two conditions.
(1) Energy condition : The minimum amount of energy possessed by the colliding molecules to bring
about the chemical change is called threshold energy, ET.
(2) Proper orientation : The reacting molecules must collide in a proper orientation so that the old bonds
break and new bonds are formed. The proper orientation and improper orientation are shown below :
X Y
X Y X Y
+
X Y X Y
X Y
Proper orientation
Hence from collision theory of reaction rates it is concluded that
Rate of reaction  collision frequency (z)
or Rate of reaction = f × z
where, f represents the fraction of the total collisions which are effective.
z Activation Energy
Exothermic Endothermic
(Ea)f ETH (Ea)b (Ea)f ETH (Ea)b
Energy Energy
H H
HR
HR HP
HP
Progress of reaction Progress of reaction
ETH = Threshold Energy
HR = Enthalpy or Energy of reactants.
HP = Enthalpy or Energy of product.
(Ea)f = Activation energy for forward reaction.
(Ea)b = Activation energy for backward reaction.
Note : H = HP – HR, H = (Ea)f – (Ea)b, ETH = HR + (Ea)f or ETH = HP + (Ea)b.
The minimum amount of energy which the colliding molecules must possess as to make the chemical reaction
to occur, is known Threshold Energy.
The minimum amount of energy required by reactant molecules to participate in a reaction is called Activation
energy. (Ea)
Ea = ETH –average K.E. of reacting molecules.
EXERCISE
14. A catalyst cannot change

(1) Rate constant of the reaction
(2) Equilibrium constant of the reaction
(3) Activation energy of reaction
(4) All of these
15. Select the incorrect statement
(1) The minimum amount of energy required by reactant molecules to give product is threshold energy
(2) Activation energy is the sum of threshold energy and average kinetic energy
(3) Threshold energy is the sum of initial potential energy of reactants and activation energy
(4) Lower is the activation energy faster is the reaction
16. If the rate of reaction increases to two times with every 10° rise in temperature, then if we raise the temperature
by 40°, the new rate of the reaction will be
(1) 4 times
(2) 8 times
(3) 16 times
(4) 32 times
17. A + B  C; H = + 60 kJ/mol
Eaf is 150 kJ. What is the activation energy for the backward reaction?
(1) 210 kJ
(2) 105 kJ
(3) 90 kJ
(4) 145 kJ
18.
A
1 C
Energy 2
Reaction progress
(1) It is a 2 steps reaction, step 1 is slower than step 2
(2) It is a 2 steps reaction, step 2 is slower than step 1
(3) Single step reaction where B is a activated complex
(4) Single step reaction in which B is a reaction intermediate
19. The correct expression for Arrhenius equation is (where K is rate constant)
(1) k  eH/RT  A
E a
(2) ln k = + ln A
RT
Ea
(3) ln k = ln A +
RT
A E
(4) ln    a
 k  RT
20. The temperature coefficient of a certain reaction is found to be 3. If temperature changes from 25° to 55°, the
new rate of reaction will be
(1) 8 times (2) 9 times
(3) 16 times (4) 27 times

nt
me nment
sigAnssig
Assignment
As
Assignment
(1) Decrease to 8 times of the initial value
SECTION - A
NCERT Based MCQs (2) Increase to 8 times of the initial value
1. For a zero order reaction, the relationship between (3) Increase to 4 times of the initial value
st nd
t11 t 21 (4) Decrease to 4 times of the initial value
and is [NCERT Pg. 110]
2 2
5. Which of the following given graph represents first
st nd order reaction? [NCERT Pg. 106]
t11  t 21
(1)
2 2
(1)
st nd
t11  2 t 21
(2) t1/2
2 2
nd st
t 21  2t11 [A0]
(3)
2 2
st nd
t11  2 t 21 (2)
(4)
2 2
[At]
2. The rate constant of a reaction is 1.2  10–2 mol–2
L2 s–1. The order of the reaction is
t
[NCERT Pg. 103]
(1) 0
(3)
(2) 1 log [At ]
(3) 2
(4) 3
3. A chemical reaction can never have fractional log t
[NCERT Pg. 103]

(4)
(1) Order
(2) Half-life
[At ]
(3) Molecularity
(4) Rate constant t
4. For the reaction, 2NO(g) + O2(g) 2NO(g), the
volume is suddenly reduced to half of its value by 6. For first order reaction, t93.75% = x  t75%, the value
increasing pressure on it. If reaction is of first order of x will be [NCERT Pg. 107]
w.r.t. O2 and second order w.r.t. NO, the rate of the (1) 10 (2) 6
reaction will [NCERT Pg. 106]
(3) 3 (4) 2
7. The rate of the reaction, 2A + B products is 12. For effective collisions, the condition(s) to be fulfilled
given by the rate expression, rate = k[A]1.5 [B]0.5. is/are [NCERT Pg. 117]
If [A] is 2 molar and [B] is 100 molar, then the
(1) Energy of the colliding molecules should be
order of reaction will be [NCERT Pg. 102] less than threshold energy
(1) 2 (2) 0.5
(2) Colliding molecules must collide in a proper
(3) 1.5 (4) 1.0 orientation
8. Which of the following statement is incorrect? (3) Colliding molecules must possess energy
[NCERT Pg. 97] equal or greater than threshold energy
(1) Average rate of reaction and instantaneous (4) Both (2) & (3)
rate of reaction are always different 13. Select the incorrect statement among the following
(2) Stoichiometry of a reaction tells about the order [NCERT Pg. 117]
of the elementary reaction
(1) Acidic hydrolysis of an ester is a pseudo first
(3) Rate of chemical reactions is independent of order reaction
molecularity of reactions
1
(4) In multistep reactions, the rate determining (2) A plot of log k against has slope equal to
step is the slowest step of the reaction T
9. For the first order reaction, 2.303 R

Ea
A(g)   3B(g)  2C(g). If initial pressure of A is
p0 and after time ‘t’ from the start of reaction, the (3) Catalyst alters the rate of reaction without itself
total pressure is p, then the rate constant of undergoing any permanent chemical change
reaction is given by [NCERT Pg. 106]
(4) Fraction of molecules capable of bringing
effective collisions increases on increasing
1  p0  1  p0 
(1) ln   (2) ln  0  temperature
t  p  t  5 p  4 p 

14. If the activation energy of forward and backward
reactions in a chemical reaction, A B is 15.5
1  4p0  1  4p0  and 22.7 kJ mol–1 respectively, then select the
(3) ln (4) ln
t  p0  5p  t  5p0  p  correct option for the reaction. [NCERT Pg. 113]
(1) H of reaction is 38.2 kJ/mol.
10. A catalyst increases the rate of reaction by
(2) Reaction is always spontaneous
[NCERT Pg. 113]
(3) Reaction is exothermic
(1) Decreasing the value of Arrhenius constant
(4) Reaction is endothermic
(2) Increasing the enthalpy of the reaction
15. For the two first order reactions, rate constants in
(3) Decreasing the activation energy
terms of temperature are given below
(4) Decreasing the rate constant  1500 
 
11. If the rate constant of a reaction is 0.5  106 sec–1  P , k1  1015 e
A  T 
at 50 K and 1.5  106 sec–1 at 100 K. Then the  1000 

 T 
activation energy (Ea) for the reaction is  Q , k 2  1014 e
B  
[NCERT Pg. 115] If initially (t = 0), both reaction started with same
initial concentration of A and B, then at what
(1) 9.135 J mol–1
temperature both the reaction will have same initial
(2) 913.5 J mol–1 rate? [NCERT Pg. 112]
(3) 91.35 kJ mol–1 (1) 217 °C (2) 217 K
(4) 9.135 kJ mol–1 (3) 500 ºC (4) 500 K
6. The rate constant is numerically the same for three
SECTION - B
reaction of first, second and third order respectively.
Objective Type Questions Which one is true for rate of three reaction, if
1. For the reaction A + B  products, it is found that concentration of reactant is greater than 1M?
order of A is 2 and the order of B is 3 in the rate (1) r1 = r2 = r3
expression. When the concentrations of both A and
B are doubled the rate will increase by a factor (2) r1 > r2 > r3
(1) 10 (3) r1 < r2 < r3

(2) 16 (4) All of these
(3) 32 7. The inversion of cane sugar represented by
(4) 28 C 12 H 22 O 11 + H 2O  C 6H 12 O 6 + C 2H 12 O 6 is a
reaction
2. For the hypothetical reaction 2A  3C, the
reaction rate ‘r’ in terms of the rate of change of the (1) Zero order (2) Second order
concentration is given by (3) Bimolecular (4) Pseudo first order
d[A] 8. Consider the data below for a reaction A  B
(1) r  –
dt Time
0 10 20 30
1 d[A] (sec)
(2) r  – Rate 1.60×10
–2
1.60×10
–2
1.60×10
–2
1.59×10
–2
2 dt
1 d[A] From the above data the order of reaction is
(3) r 
3 dt (1) Zero (2) 1
d[A] (3) 2 (4) 3
(4) r 
dt 9. For the reaction N2 + 3H2  2NH3, the rate of
3. If the volume of closed vessel in which the following change of concentration for hydrogen is
simple reaction is carried out is reduced to one –0.3 × 10 –4 Ms –1 . The rate of change of
third of original volume, the rate of reaction concentration of ammonia is
becomes
(1) –0.2 × 104 Ms–1
2NO (g) + O2 (g)  2NO2 (g)
(2) 0.2 × 10–4 Ms–1
(1) One third (2) Three times
(3) 0.1 × 10–4 Ms–1
(3) Nine times (4) Twenty seven times
4. Which order reaction obeys the expression (4) 0.3 × 10–4 Ms–1
t1/2  1/[A]? 10. For the reaction H2O2 + 3I– + 2H+ – 2H2O + I3–, the
(1) First (2) Second effect on the rate of this reaction brought about by
doubling the concentration of I– without changing
(3) Third (4) Zero
the order
(1) The rate would increase by a factor of 3
1
N2O5  2NO2 + O2 . Given, (2) The rate would increase by a factor of 8
2
(3) The rate would decrease by a factor of 1/3
d[N2O5 ]
– = K1 [N2O5] (4) The rate would increase by a factor of 9
dt
d[NO2 ] 1
= K2 [N2O5] 11. The graph between the log k versus is a
dt T
straight line. The slope of the line is
d[O2 ]
and = K3 [N2O5]
dt 2.303R Ea
(1)  Ea (2) 
The relation between K1, K2 and K3 is 2.303R
(1) 2K1 = K2 = 4K3 (2) K1 = K2 = K3 2.303R Ea
(3) Ea (4)
(3) 2K1 = 4K2 = K3 (4) K1 = 2K2 = 4K3 2.303R
12. The rate law of a reaction between the substance (1) It gives rate of disappearance of reactant
A and B is given by, rate = k[A] n [B] m . On
d[C2  C1]
doubling the concentration of A and making the (2) Rate  
volume of B half the ratio of new rate to the earlier t 2  t1
rate of reaction will be (3) Both (1) & (2)
1 (4) It predicts the order of reaction
(1) nm (2) m + n
2 17. The unit of rate constant and rate of reaction are
(3) 2n + m (4) 2n – m same for
13. For a chemical process energies are plotted in graph. (1) First order (2) Zero order
(3) Second order (4) Third order
c 18. The rate of a reaction becomes 2 times for every

Energy
d 10°C rise in temperature. How many times rate of

e
reaction will be increased when temperature is
a increased from 30°C to 80°C?
b
Progress of reaction (1) 16 (2) 32
Which of the following is correct ? (3) 64 (4) 128
(1) It is the exothermic reaction, H = b – a 19. The rate constant, the activation energy and
(2) Threshold energy, e = a + c Arrhenius parameter of a chemical reaction at 25°C
are x s–1, 10x kJ/mol and 2x s–1. Value of rate
(3) (Ea)f < (Ea)b
constant as T   is
(4) All of these
(1) x s–1 (2) 2x s–1
14. Which of the following is correct?
(3)  (4) 10x s–1
k2 Ea  T  20. For a gaseous phase reaction 2A + B2  2AB, the
(1) log   
k1 2.303  T1T2  following rate data was obtained at 300K
(2) For zero order reaction, t 12 is inversely Rate of disappearance Concentration
proportional to initial concentration of B2 (mol/litre min) [A] [B2]

(3) Catalyst decreases the activation energy (i) 1.8 × 10–3 0.015 0.15
(4) All of these (ii) 1.08 × 10–2 0.09 0.15
(iii) 5.4 × 10–3 0.015 0.45
15. The given graph of t 12 vs initial concentration ‘a’ is
The rate constant for the reaction is
for
(1) 0.5 mol–1 min–1 litre (2) 0.8 mol–1 min–1 litre
t1/2 (3) 1.5 mol–1 min–1 litre (4) 2 mol–1 min–1 litre
21. For a homogeneous first order gaseous reaction
a A  B + C + D, the initial pressure was P0 while
(1) First order reaction pressure after time ‘t’ was P if (P > P 0). The
(2) Second order reaction expression for the rate constant K is
(3) Zero order reaction
2.303  2P0 
(4) Can’t predict (1) K  log  
t  3P0  P 
16. Consider the given graph plotted between
concentration Vs time 2.303  3P0 
(2) K  log  
t  2P0  P 
C1 2.303  P 
(3) K  log  0 
Conc.
C2
t  P0  P 
2.303  2P0 
Time (4) K  log  
t1 t2 t  4P0  P 
22. For a first order reaction, the time taken to reduce 29. Temperature coefficient is represented by
1 kT
the initial concentration by a factor of is 10 min.
4 (1) k (2) kT
T+10
If the reduction in concentration is carried out by a
1 k T+10
factor of , then time required (in minutes) will be (3) (4) 10 kT
16 kT
(1) 10 (2) 20 30. Which of the following can change rate constant of
(3) 40 (4) 60 the reaction?
23. With increase in temperature, rate constant (1) Temperature (2) Pressure
increase (3) Catalyst (4) Both (1) & (3)
(1) Only for endothermic reactions 31. Unit of rate constant for first order reaction is
(2) Only for exothermic reactions (1) sec–1 (2) sec
(3) Neither for exothermic nor endothermic (3) mol L–1 s–1 (4) mol–1 L s–1
reactions
32. For a first order reaction, a straight line is obtained
(4) Both for exothermic and endothermic reactions if you plot
24. For the first order reaction,
1
A(g)  2B(g) + C(g) the initial pressure (1) conc. Vs. time (2) conc. Vs.
time
PA = 90 mm Hg, the pressure after 10 minute is
(3) conc. Vs. (time)2 (4) log conc. Vs. time
found to be 180 mm Hg. The rate constant of the
reaction is 33. For an exothermic reaction (H = –60 kJ). If
activation energy for forward reaction is 130 kJ,
(1) 1.15 × 10–3 sec–1 (2) 2.3 × 10–3 sec–1
then activation energy for backward reaction will be
(3) 3.45 × 10–3 sec–1 (4) 4.6 × 10–3 sec–1
(1) 130 kJ (2) 190 kJ
25. The rate constant for the first order decomposition
(3) 70 kJ (4) 10 kJ
of a certain reaction is described by the equation
7.2  103 K 34. The half life for radioactive sample is 1386 s then
log k  9.27  . its decay constant () is
T
The activation energy of reaction is (1) 5 × 10–2 sec–1 (2) 5 × 10–3 sec–1
(1) 2 × 10–3 cal (2) 7.2 × 10–3 cal (3) 5 × 10–4 sec–1 (4) 5 × 10–5 sec–1
(3) 3.32 × 10–2 cal (4) 1.44 × 10–4 cal 35. Correct graph for first order reaction is/are
26. Hydrolysis of ester in basic medium is of

[R]
(1) Zero order (2) First order (1)
(3) Second order (4) Third order
time
27. 5 mg radioactive sample 90% disintegrate in
3 years then 99% disintegration will be in
t1
2
(1) 3 years (2) 3.1 years (2)
(3) 6 years (4) 9 years
[R0]
28. Adsorption of hydrogen gas on metal surface at
high pressure follows t1
2
(1) Zero order
(3)
(2) 1st order
(3) 2nd order [ R0]
(4) 3rd order (4) All of these
6. The correct difference between first and second

SECTION - C
order reactions is that [NEET-2018]
Previous Years Questions (1) The rate of a first-order reaction does not
1. A first order reaction has a rate constant of depend on reactant concentrations; the rate of
2.303 × 10–3 s–1. The time required for 40 g of this a second-order reaction does depend on
reactant to reduce to 10 g will be reactant concentrations
[Given that log102 = 0.3010] (2) The half-life of a first-order reaction does not
depend on [A]0; the half-life of a second-order
[NEET-2019 (Odisha)]
reaction does depend on [A]0
(1) 602 s (2) 230.3 s
(3) The rate of a first-order reaction does depend
(3) 301 s (4) 2000 s on reactant concentrations; the rate of a
2. For a reaction, activation energy Ea = 0 and the second-order reaction does not depend on
rate constant at 200 K is 1.6 × 106 s–1. The rate reactant concentrations
constant at 400 K will be (4) A first-order reaction can catalyzed; a second-
[Given that gas constant, R = 8.314 J K–1 mol–1] order reaction cannot be catalyzed
[NEET-2019 (Odisha)] 7. A first order reaction has a specific reaction rate of
(1) 3.2 × 106 s–1 10–2 s–1. How much time will it take for 20 g of the
reactant to reduce to 5 g? [NEET-2017]
(2) 3.2 × 104 s–1
(1) 238.6 second (2) 138.6 second
(3) 1.6 × 106 s–1
(3) 346.5 second (4) 693.0 second
(4) 1.6 × 103 s–1
8.* Mechanism of a hypothetical reaction
3. If the rate constant for a first order reaction
X2 + Y2  2XY is given below :
is k, the time (t) required for the completion of
99% of the reaction is given by: [NEET-2019] (i) X2 X + X
(1) t = 0.693/k (ii) X + Y2  XY + Y (slow)
(2) t = 6.909/k (iii) X + Y  XY (fast)
(3) t = 4.606/k The overall order of the reaction will be [NEET-2017]
(4) t = 2.303/k (1) 1 (2) 2
4. For the chemical reaction (3) 0 (4) 1.5
(* Modified)

N2 (g)  3H2 (g)
2NH3 (g)
9. The decomposition of phosphine (PH3) on tungsten
The correct option is: [NEET-2019] at low pressure is a first-order reaction. It is
because the [NEET-Phase-2-2016]
1 d[H 2 ] 1 d[NH 3 ]
(1)   (1) Rate is proportional to the surface coverage
3 dt 2 dt
(2) Rate is inversely proportional to the surface
d[N 2 ] d[NH 3 ] coverage
(2)  2
dt dt (3) Rate is independent of the surface coverage
d[N 2 ] 1 d[NH 3 ] (4) Rate of decomposition is very slow
(3)  
dt 2 dt 10. The addition of a catalyst during a chemical
reaction alters which of the following quantities?
d[H 2 ] d[NH 3 ]
(4) 3 2 [NEET-2016]
dt dt
(1) Activation energy (2) Entropy
5. When initial concentration of the reactant is
doubled, the half-life period of a zero order reaction (3) Internal energy (4) Enthalpy
[NEET-2018] 11. The rate of a first-order reaction is 0.04 mol l–1 s–1
at 10 seconds and 0.03 mol l–1 s–1 at 20 seconds
(1) Is halved
after initiation of the reaction. The half-life period of
(2) Is doubled the reaction is [NEET-2016]
(3) Remains unchanged (1) 54.1 s (2) 24.1 s
(4) Is tripled (3) 34.1 s (4) 44.1 s
12. The rate constant of the reaction A  B is (1) Rate = k[A] [B]
0.6 × 10 –3 mole per litre per second. If the
(2) Rate = k[A]2[B]
concentration of A is 5 M, then concentration of B
after 20 minutes is [Re-AIPMT-2015] (3) Rate = k[A] [B]2
(1) 0.36 M (2) 0.72 M (4) Rate = k[A]2[B]2
(3) 1.08 M (4) 3.60 M 19. Which one of the following statements for the order
13. The activation energy of a reaction can be of a reaction is incorrect? [AIPMT (Prelims)-2011]
determined from the slope of which of the following (1) Order of reaction is always whole number
graphs? [AIPMT-2015]
(2) Order can be determined only experimentally
T 1 (3) Order is not influenced by stoichiometric
(1) ln K vs T (2) ln K vs T
coefficient of the reactants
(4) Order of reaction is sum of power to the
ln K 1
(3) vs T (4) ln K vs concentration terms of reactants to express
T T the rate of reaction
14. When initial concentration of a reactant is doubled 20. The unit of rate constant for a zero order reaction
in a reaction, its half-life period is not affected. The is [AIPMT (Mains)-2011]
order of the reaction is [AIPMT-2015]
(1) L2 mol–2 s–1 (2) s–1
(1) More than zero but less than first
(3) mol L –1 s –1 (4) L mol–1 s–1
(2) Zero
21. The half life of a substance in a certain enzyme-
(3) First catalysed reaction is 138 s. The time required for
(4) Second the concentration of the substance to fall from
1.28 mg L–1 to 0.04 mg L–1 is
15. A reaction having equal energies of activation for
forward and reverse reactions has [NEET-2013] [AIPMT (Mains)-2011]
(1) G = 0 (1) 690 s (2) 276 s
(2) H = 0 (3) 414 s (4) 552 s
(3) H =G =S = 0 22. For the reaction, N2O5(g)  2NO2(g) + 1/2 O2(g),
(4) S = 0 the value of rate of disappearance of N2O5 is given
as 6.25×10–3 mol L–1s–1. The rate of formation of
16. What is the activation energy for a reaction if its NO2 and O2 is given respectively as
rate doubles when the temperature is raised from
20C to 35C? (R = 8.314 J mol–1K–1) [NEET-2013] [AIPMT (Prelims)-2010]
(1) 269 kJ mol–1 (2) 34.7 kJ mol–1 (1) 6.25 × 10–3 mol L–1s–1 & 6.25 × 10–3 mol L–1s–1
(3) 15.1 kJ mol–1 (4) 342 kJ mol–1 (2) 1.25 × 10–2 mol L–1s–1 & 3.125 × 10–3 mol L–1s–1
17. In a zero order reaction for every 10° rise of (3) 6.25 × 10–3 mol L–1s–1 & 3.125 × 10–3 mol L–1s–1
temperature, the rate is doubled. If the temperature
(4) 1.25 × 10–2 mol L–1s–1 & 6.25 × 10–3 mol L–1s–1
is increased from 10°C to 100°C, the rate of the
reaction will become [AIPMT (Prelims)-2012] 23. For an endothermic reaction, energy of activation is
Ea and enthalpy of reaction is H (both of these in
(1) 64 times (2) 128 times
kJ/mol). Minimum value of Ea will be
(3) 256 times (4) 512 times
18. In a reaction, A + B  Product, rate is doubled
when the concentration of B is doubled, and rate (1) Less than H
increases by a factor of 8 when the concentrations (2) Equal to H
of both the reactants (A and B) are doubled, rate
law for the reaction can be written as (3) More than H
[AIPMT (Prelims)-2012] (4) Equal to zero
24. During the kinetic study of the reaction,

d(Br2 ) 5 d(Br  )
2A+BC+D, following results were obtained (1) 
dt 3 dt
Run [A]/mol L–1 [B]/mol L–1 Initial rate of
formation of d(Br2 ) 5 d(Br  )
D/mol L–1 min–1 (2) 
dt 3 dt
I 0.1 0.1 6.0×10–3
II 0.3 0.2 7.2×10–2 d(Br2 ) 3 d(Br  )
(3) 
dt 5 dt
III 0.3 0.4 2.88×10–1
IV 0.4 0.1 2.40×10–2 d(Br2 ) 3 d(Br  )
(4) 
Based on the above data which one of the following dt 5 dt
is correct ? [AIPMT (Prelims)-2010]
28. Half life period of a first-order reaction is 1386
(1) Rate = K[A]2 [B] seconds. The specific rate constant of the reaction
is [AIPMT (Prelims)-2009]
(2) Rate = K[A][B]
(1) 0.5 × 10–2 s–1
(3) Rate = K[A]2 [B]2
(2) 0.5 × 10–3 s–1
2
(4) Rate = K[A][B]
(3) 5.0 × 10–2 s–1
25. The rate of the reaction, 2NO + Cl2  2NOCl
(4) 5.0 × 10–3 s–1
is given by the rate equation rate = k[NO]2[Cl2]
29. For the reaction A + B  Products, it is observed
The value of the rate constant can be increased by that
[AIPMT (Mains)-2010] (a) On doubling the initial concentration of A only,
(1) Increasing the temperature the rate of reaction is also doubled and
(2) Increasing the concentration of NO (b) On doubling the initial concentrations of both A
and B, there is a change by a factor of 8 in
(3) Increasing the concentration of the Cl2 the rate of the reaction.
(4) Doing all of these The rate of this reaction is given by
26. For the reaction, N2 + 3H2  2NH3, [AIPMT (Prelims)-2009]

(1) Rate = k [A] [B]2
d[NH3 ]
if  2  104 mol L –1 s –1 , the value of (2) Rate = k [A]2[B]2
dt
(3) Rate = k [A] [B]
d[H2 ]
would be [AIPMT (Prelims)-2009] (4) Rate = k[A]2[B]
dt
30. The rate constants k1 and k2 for two different
(1) 4×10–4 mol L–1 s–1 reactions are 10 16 e –2000/T and 10 15 e –1000/T
(2) 6×10–4 mol L–1 s–1 respectively. The temperature at which k1 = k2 is
(3) 1×10–4 mol L–1 s–1 [AIPMT (Prelims)-2008]
(4) 3×10–4 mol L–1 s–1 1000

(1) K
27. In the reaction, 2.303
(2) 1000 K
BrO3 (aq)  5Br  (aq)  6H  3Br2 (l)  3H2O(l)
2000
The rate of appearance of bromine (Br2) is related (3) K
2.303
to rate of disappearance of bromide ions as
following [AIPMT (Prelims)-2009] (4) 2000 K
31. The bromination of acetone that occurs in acid Mechanism B:
solution is represented by this equation
H2(g) + ICI(g)  HCl(g) + HI(g); slow
CH3 COCH3 (aq)  Br2 (aq)  CH3 COCH2Br(aq) HI(g) + ICI(g)  HCl(g) + I2(g); fast
 H (aq)  Br  (aq) Which of the above mechanism(s) can be

consistent with the given information about the
These kinetic data were obtained for given reaction reaction? [AIPMT (Prelims)-2007]
concentrations
(1) A only
Initial concentrations, M
(2) B only
[CH3COCH3] [Br2] [H+]
(3) Both (1) and (2)
0.30 0.05 0.05
(4) Neither (1) nor (2)
0.30 0.10 0.05
34. If 60% of a first order reaction was completed in
0.30 0.10 0.10
60 minutes, 50% of the same reaction would be
0.40 0.05 0.20 completed in approximately (log 4 = 0.60,
log 5 = 0.69) [AIPMT (Prelims)-2007]
Initial rate, disappearance of Br2, M s–1
(1) 40 minutes
5.7 × 10–5
(2) 50 minutes
5.7 × 10–5
1.2 × 10– 4 (3) 45 minutes
3.1 × 10–4 (4) 60 minutes
Based on these data, the rate equation is 35. For the reaction, 2A + B  3C + D. Which of the
following does not express the reaction rate?
(1) Rate = k [CH3COCH3][Br2][H+]
(2) Rate = k [CH3COCH3][H+] d  C d B
(1) – (2) –
3 dt dt
O
(3) Rate = k [ CH 3 C CH 3 ][Br2]
dD d A 
(3) (4) –
(4) Rate = k [CH3COCH3][Br2][H+]2 dt 2dt
32. In a first-order reaction A  B, if K is rate 36. Consider the reaction, N2(g) + 3H2(g)  2NH3(g).
constant and initial concentration of the reactant A
is 0.5M then the half-life is d NH3 
The equality relationship between and
[AIPMT (Prelims)-2007] dt
d H2 
ln2 0.693 – is [AIPMT (Prelims)-2006]
(1) (2) dt
K 0.5K
d NH3  1 d H2 
log 2 (1) 
log2 dt 3 dt
(3) (4)
K K 0.5
d NH3  2 d H2 
33. The reaction of hydrogen and iodine monochloride (2)  
is given as dt 3 dt
H2(g) + 2ICI(g)  2HCl(g) + I2(g)
d NH3  3 d H2 
This reaction is of first order with respect to H2(g) (3)  
dt 2 dt
and ICI(g), following mechanisms were proposed
Mechanism A: d NH3  d H2 
(4) 
H2(g) + 2ICI(g)  2HCl(g) + I2(g) dt dt
37. For a first order reaction A  B, the reaction rate 43. The rate of the reaction, 2N2O5  4NO2 + O2
at reactant concentration of 0.01 M is found to be
can be written in three ways :
2.0 × 10–5 mol L–1 s–1. The half life period of the
reaction is [AIPMT (Prelims)-2005] d[N2 O5 ]
 k[N2O5 ]
(1) 220 s (2) 30 s dt
(3) 300 s (4) 347 s
d[NO2 ]
38. A nuclide of an alkaline earth metal undergoes  k[N2 O5 ]
dt
radioactive decay by emission of three -particles
in succession. The group of the periodic table to
d[O2 ]
which the resulting daughter element would belong  k [N2 O5 ]
is [AIPMT (Prelims)-2005] dt
(1) Group 14 (2) Group 16 The relationship between k and k and between k
and k are
(3) Group 4 (4) Group 6
(1) k = 2k; k = 2k (2) k = k; k = k
39. The rate of reaction between two reactants A and
B decreases by a factor of 4, if the concentration k
of reactant B is doubled. The order of this reaction (3) k = 2k; k = k (4) k = 2k; k =
2
with respect to reactant B is
44. For the following reaction
(1) –1 (2) –2 C6H12O6(aq) + H2(g) C6H14O6(aq)
(3) 1 (4) 2 Which one of the following is not affected by the

addition of catalyst?
Questions asked Prior to Medical Ent. Exams. 2005
(1) Rate of forward reaction
40. A reaction is 50% complete in 2 hours and 75%
complete in 4 hours. The order of reaction is (2) Rate of backward reaction
(1) 0 (2) 1 (3) Time required to reach the equilibrium
(3) 2 (4) 3 (4) Spontaneity
41. Activation energy (Ea) and rate constants (k1 and 45. A chemical reaction proceeds into the following
k 2 ) of a chemical reaction at two different steps
temperatures (T1 and T2) are related by Step I, 2A X fast
k2 Ea  1 1 Step II, X + B  Y slow

(1) ln k   R   
T T
1  1 2  Step III, Y + B Product fast
The rate law for the overall reaction is
k E  1 1
(2) ln 2   a    (1) Rate = k[A]2 (2) Rate = k[B]2
k1 R  T2 T1 
(3) Rate = k[A][B] (4) Rate = k[A]2[B]
k2 E  1 1 46. The data for the reaction A + B  C, is

(3) ln  a   
k1 R T
 2 T1 Exp. [A]0 [B]0 Initial rate
(i) 0.012 0.035 0.10
k 2 Ea  1 1
(4) ln     (ii) 0.024 0.070 0.80
k1 R  T1 T2 
(iii) 0.024 0.035 0.10
42. The half life time of 2g sample of radioactive nuclide (iv) 0.012 0.070 0.80
‘X’ is 15 min. The half life time of 1g sample of X
is The rate law corresponds to the above data is
(1) 7.5 min (2) 15 min (1) Rate = k[A][B]3 (2) Rate = k[A]2[B]2
(3) 22.5 min (4) 30 min (3) Rate = k[B]3 (4) Rate = k[B]4
47. Half-life for radioactive 14C is 5760 years. In how many 53. Activation energy of a chemical reaction can be
years 200 mg of 14C will be reduced to 25 mg? determined by
(1) 17280 years (2) 23040 years (1) Evaluating rate constants at two different
temperatures
(3) 5760 years (4) 11520 years
(2) Evaluating velocities of reaction at two different
48. A chemical reaction is catalyzed by a catalyst X.
Hence X temperatures
(1) Reduces enthalpy of the reaction (3) Evaluating rate constant at standard
temperature
(2) Does not affect equilibrium constant of reaction
(4) Changing concentration of reactants
(3) Decreases rate constant of the reaction
54. For a first-order reaction, the half-life period is
(4) Increases activation energy of the reaction independent of
49. The given reaction 2 FeCl3 + SnCl2  2 FeCl2 + (1) First power of final concentration
SnCl4 is an example of
(2) Cube root of initial concentration
(1) Third order reaction (2) First order reaction
(3) Initial concentration
(3) Second order reaction (4) None of these
(4) Square root of final concentration
50. Carbon-14 dating method is based on the fact that
55. The half-life of 6C14, if its  is 2.31 × 10–4 year –1, is
(1) Ratio of carbon-14 and carbon-12 is constant
(1) 3.5 × 104 years (2) 3 × 103 years
(2) Carbon-14 is the same in all objects
(3) 2 × 102 years (4) 4 × 103 years
(3) Carbon-14 is highly insoluble
56. A 300 gram radioactive sample has a half life
(4) All of these
3 hours. After 18 hours remaining quantity
51. For the reaction H2(g) + I2(g) 2HI(g), the rate
(1) 4.68 gram (2) 2.34 gram
of reaction is expressed as
(3) 3.34 gram (4) 9.37 gram
[H2 ] 1 [I2 ] [HI]
(1)   57. How enzymes increases the rate of reactions?
t 2 t t
(1) By lowering activation energy
[I2 ] [H2 ] 1 [HI]
(2)    (2) By increasing activation energy
t t 2 t
(3) By changing equilibrium constant
[I2 ] [H2 ] [HI] (4) By forming enzyme substrate complex
(3)   
t t 2t
58. For the reaction; 2N2O5  4NO2 + O2 rate and rate
(4) None of these constant are 1.02 × 10–4 Ms–1 and 3.4 × 10–5 s–1
respectively, then concentration of N2O5 at that time
52. The experimental data for the reaction will be (in molarity)
2A + B2  2AB is (1) 1.732 (2) 3
Experiment [A] [B2] Rate(mole s–1)
(3) 1.02 × 10–4 (4) 3.4 × 105
1 0.50 0.50 1.6 × 10–4
59. A human body required 0.01 m activity of
2 0.50 1.00 3.2 × 10–4 radioactive substance after 24 hours. Half life of
radioactive substance is 6 hours. Then injection of
3 1.00 1.00 3.2 × 10–4
maximum activity of radioactive substance that can
The rate equation for the above data is be injected
(1) rate = k [A]2 [B]2 (1) 0.08
(2) rate = k [A]2 [B] (2) 0.04
(3) rate = k [B2] (3) 0.16
(4) rate = k [B2]2 (4) 0.32
60. When a biochemical reaction is carried out in 66. The temperature dependence of rate constant (k) of
laboratory, outside the human body in absence of a chemical reaction is written in terms of Arrhenius
enzyme, then rate of reaction obtained is 10–6 times, *
equation, k  A . e E /RT . Activation energy (E*) of
the activation energy of reaction in the presence of
enzyme is the reaction can be calculated by plotting
6 1
(1) (1) k Vs T (2) k Vs logT
RT
(2) P is required 1
(3) log k Vs (4) log k Vs T
(3) Different from Ea obtained in laboratory T
(4) Can’t say anything
67. The radioisotope, tritium (13 H) has a half-life of
d(B) 12.3 years. If the initial amount of tritium is 32 mg,
61. 3A  2B, rate of reaction is equal to how many milligrams of it would remain after
dt
49.2 years?
3 d(A) 2 d(A) (1) 1 mg (2) 2 mg
(1)  (2) 
2 dt 3 dt
(3) 4 mg (4) 8 mg
1 d(A) d(A) 68. The rate of a first order reaction is 1.5 × 10–2 mol
(3)  (4)  2 L–1 min–1 at 0.5 M concentration of the reactant.
3 dt dt
The half-life of the reaction is
62. 2A  B + C
(1) 0.383 min (2) 23.1 min
It would be a zero order reaction when
(3) 8.73 min (4) 7.53 min
(1) The rate of reaction is proportional to square of
conc. of A
(2) The rate of reaction remains same at any conc. SECTION - D
of A
NEET Booster Questions
(3) The rate remains unchanged at any conc. of B
and C 1. Consider the following graph for Arrhenius equation
(4) The rate of reaction doubles if conc. of B is
Ea
increased to double log k = logA –
2.303 RT
63. The activation energy for a simple chemical
reaction A  B is Ea in forward direction. The
activation energy for reverse reaction
(1) Is negative of Ea log k 
(2) Is always less than Ea
(3) Can be less than or more than Ea
1/T
(4) Is always double of Ea
If tan  = –1 and T = 300 K, then the activation
64. The reaction A  B follows first order kinetics. The
energy is
time taken for 0.8 mole of A to produce 0.6 mole
of B is 1 hour. What is the time taken for (1) 5.74 kJ (2) 19.14 J
conversion of 0.9 mole of A to produce 0.675 mole
of B? (3) 9.57 J (4) 19.14 kJ
(1) 1 hour (2) 0.5 hour 2. Which of the following statement is incorrect for
zero order reaction?
(3) 0.25 hour (4) 2 hours
[R]0 – [R] [R]0
65. If the rate of the reaction is equal to the rate (1) k = (2) t 1 =
constant, the order of the reaction is t 2 2k
(1) 0 (2) 1
(3) t 3 = 2  t 1 (4) All are incorrect
(3) 2 (4) 3 4 2
3. The number of collisions per second per unit
volume of the reaction mixture is known as
(1) Collision number (2) [P]
(2) Collision frequency

Time
(3) Collision path
(4) Collision density
4. Consider the following equation based on collision [P]
theory Rate = PZABe–Ea/RT (3)
The term ‘P’ is known as Time
(1) Probability factor
(2) Steric factor
(3) Frequency factor (4) [R]
(4) Both (1) & (2)

Time
5. Choose the correct statement(s) among the
8. Choose the correct statement
following
(1) A catalyst changes the H of reaction
(1) Molecularity is defined only for an elementary
reaction (2) A catalyst changes the path of the reaction
(2) Molecularity of a reaction cannot be zero or (3) A catalyst initiates the chemical reaction
fraction (4) A catalyst does not change the thereshold
(3) Order of reaction can be 0, 1, 2, 3 or even a energy
fraction 9. A first order reaction is completed 50% in 50
(4) All are correct minutes, then the time required for initial
concentration to be reduced to 12.5% is
6. Consider the decomposition of hydrogen peroxide
(1) 150 minute
I(–) (2) 12.5 minute
2H2O2   2H2O + O2
OH(–)
(3) 100 minute
The rate law is given by
(4) 200 minute
d[H2O2 ] 10. The rate constant for a reaction depends on
R= – = k[H2O2] [I–]
dt (1) Temperature
The conclusion which can be drawn is (2) Concentration
(1) The order of reaction is 2 (3) Volume of container
(2) The reaction is a complex reaction (4) All of these
(3) Order of reaction with respect to H2O2 is 1

B(g), H is –40 kJ/
11. For the equilibrium, A(g)
(4) All are correct mol. If the ratio of the activation energies of the
7. Choose the correct graph for the first order 2
reaction : R  P forward (Ef) and reverse (Eb) reactions is then
3
(1) Ef = 80 kJ/mol, Eb = 120 kJ/mol
(1) [R] (3) Ef = 30 kJ/mol, Eb = 45 kJ/mol
Time
12. A2 + B2  2AB: ROR = k[A2]a[B2]b 17. A reaction rate constant is given by :
Initial ROR 2500

Initial [A 2 ] Initial [B2 ]
(Ms1) 14
k = 1.2  10 e RT sec 1 . It means
0.2 0.2 0.04 (1) log k versus log T will give a straight line with
0.1 0.4 0.04 a slope as 25000
0.2 0.4 0.08
(2) log k versus log T will give a straight line with
Order of reaction with respect to A2 and B2 are a slop as – 25000
respectively (3) log k versus T will give a straight line with a
(1) a = 1, b = 1 (2) a = 2, b = 0 slop as – 25000
(3) a = 2, b = 1 (4) a = 0, b = 2 1
(4) log k versus will give a straight line
T
13. Decomposition of N2O5 is first order reaction. t1/2 of
1 1
the reaction N2O5  2NO2 + O is 2.4 hr at 18. The reaction N2O5  2NO2 + O is of first
2 2 2 2
STP. Starting with 10.8 gm of N2O5, how much order in N2O5 with rate constant 6.2 × 10–1 s–1.
oxygen will be obtained after a period of 9.6 hr ? What is the value of rate of reaction when
mol
(1) 1.5 litre (2) 3.36 litre [N2O5]  1.25
litre
(3) 1.05 litre (4) 0.07 litre (1) 6.35 × 10–3 mol L–1S–1
14. The following mechanism has been proposed for (2) 7.75 × 10–1 mol L–1S–1
the reaction of NO with Br2 to form NOBr
(3) 5.15 × 10–5 mol L–1S–1

NO(g) + Br2(g)
NOBr2(g) ....Fast
(4) 3.38 × 10–1 mol L–1S–1
NOBr2(g) + NO(g)  2NOBr(g) ....Slow 19. In the following reaction :
Order of reaction with respect to NO(g) is A  B + C, rate constant = 0.001 Ms–1. If we
start with 1 M of A then conc. of A and B after 10
(1) 1 (2) 0
minutes respectively are
(3) 3 (4) 2
(1) 0.5 M, 0.5 M (2) 0.6 M, 0.4 M
15. Rate of formation of SO3 in the following reaction
(3) 0.4 M, 0.6 M (4) 0.1 M, 0.9 M
2SO2 + O2  2SO3 is 100 gm min–1.
20. At 300 K the half life of sample of gaseous
Hence rate of disappearance of O2 is
compound initially at 1 atm is 100 sec. When the
(1) 50 g min–1 pressure is 0.5 atm the half life is 50 sec, the order
of reaction is
(2) 40 gm min–1
(1) 1
(3) 200 g min–1
(2) 0
(4) 20 g min–1
(3) 2
16. For the reaction system : 2NO(g)+O2(g)  2NO2(g)
volume is suddenly reduced to half its value by (4) 3
increasing the pressure on it. If the reaction is of 21. Which of the following represents expression for
first order with respect to O2 and second order with
3
respect to NO, the rate of reaction will th life of first order reaction?
4
(1) Diminish to one-fourth of its initial value
k 4 2.303 3
(2) Diminish to one-eight of its initial value (1) log (2) log
2.303 3 k 4
(3) Increase to eight times of its initial value 2.303 2.303
(3) log4 (4) log3
(4) Increase to four times of its initial value k k
22. The rate of reaction is expressed in different ways (1) Unchange
as follows
(2) Increase four times
1 d[C] 1 d[D] 1 d[A] d[B] (3) Increase eight times
   
2 dt 3 dt 4 dt dt
(4) Decrease eight times
The reaction is 28. In the following reaction A  2B + C, rate constant
(1) 4A + B  2C + 3D is 0.002 Ms–1. If we start with 2 M of A then conc.
of B after completion of reaction is
(2) B + 3D  4A + 2C
(1) 0.5 M (2) 4 M
(3) A + B  C + D (3) 0.4 M (4) 0.06 M
(4) B + D  A + C 29. The decomposition of N2O5 in chloroform was
23. The unit of rate constant of elementary reaction followed by measuring the volume of O 2 gas
depends upon the evolved : 2N2O5(CCl4)  2N2O4 (CCl4) + O2(g).
The maximum volume of O2 gas obtained was
(1) Temperature of the reaction 100 cm 3. In 500 minutes, 90 cm 3 of O 2 were
evolved. The first order rate constant (in min–1) for
(2) Concentration of reactant
the disappearance of N2O5 is
(3) Activation energy of the reaction
2.303
(4) Molecularity of the reaction (1)
500
24. If 'a' is the initial concentration of the reactant, the 2.303 100
half-life period of the reaction of n th order is (2) log
500 90
proportional to
2.303 90
(1) an – 1 (3) log
500 100
(2) an
100
(3) a1 – n (4)
10  500
(4) an + 1 30. Hydrolysis of ester in acidic medium is an
example of
25. 99% of a first order reaction was completed in 32
minutes when 99.9% of the reaction will complete (1) Psuedo first order reaction
(1) 50 min (2) Zero order reaction
(2) 46 min (3) Second order reaction
(3) 48 min (4) Third order reaction

k
(4) 49 min 31. For a complex reaction A   products
26. In the reaction, A + 2B  6C + 2D, if the initial Ea  180 kJ/mol; Ea  80 kJ/mol;
1 2
d[A]
rate – at t = 0 is 2.6 × 10–2 M sec–1, what Ea  50 kJ/mol overall rate constant k is related
dt 3
d[B] to individual rate constant by the equation
will be the value of – at t = 0?
dt 2/3
k k 
(1) 8.5 × 10–2 M sec–1 k   1 2  .
 k3 
(2) 2.5 × 10–2 M sec–1
Activation energy (kJ/mol) for the overall reaction is:
(3) 5.2 × 10–2 M sec–1
(1) 100
(4) 7.5 × 10–2 M sec–1
(2) 43.44
27. For an elementary gaseous reaction 2A + B 
A2B if the volume of vessel is quickly reduced to (3) 150
half of it's original volume then rate or reaction will (4) 140
1
k 0.1 M min
32. Consider a reaction A(g)   2B(g). 1
35. The half-life for the reaction N2O5  2NO2  O
2 2
If initial concentration of A is 0.5 M then select
correct graph is 2.4 h at STP. Starting with 10.8 g of N2O5,
how much oxygen will be obtained after a period
of 9.6 h?
(1) 1.5 L (2) 3.36 L
(1) 0.5 M (3) 1.05 L (4) 0.07 L
[B] 36. For a chemical reaction at 27ºC, the activation

energy is 600R. The ratio of the rate constants at
5 10 327ºC to that of at 27ºC will be
time (in min)
(1) 2 (2) 40
(3) e (4) e2
1.0 M
[B] 37. For a reaction 2A + B  Product, if
(2) concentration of B double then half life is
0.5 M
unchanged but if only A double then rate of reaction
is also double, unit of k is
5 10 (1) mol–1 L1 s–1 (2) s–1
time (in min)
(3) mol L–1 s–1 (4) mol–2 L2 s–1
38. What will be the order of reaction for a chemical
change having log t1/2 vs log a? (where a = initial
concentration of reactant ; t1/2 = half-life)
1.0 M
(3) [B]
log t1/2 45°
5 10
time (in min)
log a
2.0 M
(1) Zero order (2) First order
(4) 1.0 M (3) Second order (4) None of these

39. Reaction A  B follows second order kinetics.
[B]
Doubling the concentration of A will increase the
5 10 rate of formation of B by a factor of
time (in min)
(1) 1/4 (2) 1/2
33. After how many seconds will the concentration of (3) 2 (4) 4
the reactants in a first-order reaction be halved, if
the decay constant is 1.155 × 10–3 sec–1 40. Two reactions proceed at 25ºC at the same rate.
The temperature coefficient of the first reaction is
(1) 100 sec (2) 200 sec 2 and that of the second is 2.5, find the ratio of
(3) 400 sec (4) 600 sec the rates of second reaction to first reaction at
95ºC
34. A first-order reaction was started with a decimolar
solution of the reactant, 8 minutes and 20 seconds (1) 0.83
later its concentration was found to be M/100. So
the rate constant is (2) 1.13
(1) 2.303 × 10–5 sec–1 (2) 2.303 × 10–4 sec–1 (3) 1.87
(3) 4.606 × 10–3 sec–1 (4) 2.603 × 10–4 sec–1 (4) 4.76
k
41. For the reaction 3A(g)  46. For the reaction A + B  products, it is found that
 B(g) + C(g), k is
–4 order of A is 2 and the order of B is 3 in the rate
10 L/mol-min.
expression. When the concentrations of both A and
d[A] B are doubled the rate will increase by a factor
if [A] = 0.5M then the value of  (in Ms –1 )
dt (1) 10 (2) 16
is
(3) 32 (4) 28
(1) 7.5 × 10–5 (2) 3 × 10–4
47. Nitric oxide (NO) reacts with oxygen to produce
(3) 2.5 × 10–5 (4) 1.25 × 10–6 nitrogen dioxide
42. Half-life (t 1/2 ) and completion time (T) of the 2NO(g) + O2(g)  2NO2(g),
–1
reaction A k = 0.001 Mmin 2B are : if initial If the mechanism of reaction is

concentration of A is 1M
K
NO + O2 NO3 (fast)
(1) 500 min, 1000 min (2) 500 sec, 750 sec
K1
(3) 500 sec, 1000 sec (4) 250 min, 500 min NO3+ NO NO2 + NO2 (slow)
43. For a first order reaction nA  B half life is then rate law is
18 minute. Then with the help of graph find value (1) Rate = K [NO][O2] (2) Rate = K [NO][O2]2
of n :
(3) Rate = K [NO]2[O2] (4) Rate = K [NO]3[O2]
B
48. If the volume of closed vessel in which the following
Concentration
A simple reaction is carried out is reduced to one

third of original volume, the rate of reaction
becomes
2NO (g) + O2 (g)  2NO2 (g)
36 t(min)
(1) One third
(1) 2 (2) 3
(2) Three times
(3) 4 (4) 1
(3) Nine times
1
44. For the reaction, N2O5  2NO2 + O2 . (4) Twenty seven times
2
d[N 2 O 5 ] 49. For a gaseous phase reaction 2A + B2  2AB, the
Given : – = K1 [N2O5] following rate data was obtained at 300K
dt
Rate of disappearance Concentration
d[NO 2 ]
= K2 [N2O5] of B2 (mole/litre min) [A] [B2]
dt
d[O 2 ] (i) 1.8 × 10–3 0.015 0.15
and = K3 [N2O5]
dt (ii) 1.08 × 10–2 0.09 0.15
The relation between K1, K2 and K3 is (iii) 5.4 × 10–3 0.015 0.45
(1) 2K1 = K2 = 4K3 (2) K1 = K2 = K3 The rate constant for the reaction is
(3) 2K1 = 4K2 = K3 (4) K1 = 2K2 = 3K3 (1) 0.5 mol–1 min–1 litre (2) 0.8 mol–1 min–1 litre
K1 (3) 1.5 mole–1 min–1 litre (4) 2 mol–1 min–1 litre

45. For the reaction, N2O4 (g) 2NO2(g), the 50. For a first order reaction, the time taken to reduce
K2
1
rate of disappearance of NO2 will be the initial concentration to a factor of is 10 minute
4
(1) K1[N2O4] – K2[NO2]2 If the reduction in concentration is carried out to a
1
(2) 2K1[N2O4] – 2K2[NO2]2 factor of , then time required will be
16
(3) K2[NO2]2 – K1[N2O4] (1) 10 minutes (2) 20 minutes
(4) 2K2[NO2]2 – 2K1[N2O4] (3) 40 minutes (4) 60 minutes
51. Consider the data below for a reaction A  B 55. Two substances A and B are present such that
[A]0 = 4[B]0 and half life of A is 5 minute and that
Time of B is 15 minute. If they start decaying at the
(sec) 0 10 20 30
same time following first order kinetics how much
-2 -2 -2 -2 time will the concentration of both of them would be
Rate 1.60×10 1.60×10 1.60×10 1.59×10
the same?
From the above data the order of reaction is (1) 15 minute (2) 10 minute
(1) Zero (2) 1 (3) 5 minute (4) 12 minute
(3) 2 (4) 3 56. The reaction A  B follows first order kinetics.
52. For a homogeneous gaseous reaction The time taken for 0.80 mole of A to produce
A  B + C + D, the initial pressure was P0 while 0.60 mole of B is 1 hour. What is the time taken
pressure after time ‘t’ was P if (P > P 0). The for conversion of 0.90 mole of A to produce
expression for the rate constant k is 0.675 mole of B?
(1) 1 hour (2) 30 minute
2.303  2P0 
(1) k  log   (3) 15 minute (4) 5 minute
t  3P0  P 
3 –1
k1 = 2 × 10 s
2.303  3P0  B
(2) k  log  
t  2P0  P  57. If, A
3 –1
k2 = 6 × 10 s
2.303  P  C
(3) k  log  0 
t  P0  P  %B in the product is
2.303  2P0  (1) 25% (2) 50%
(4) k  log  
t  4P0  P  (3) 75% (4) 80%
53. Inversion of a sugar follows first order rate equation 1
58. The graph between the log K versus is a
which can be followed by noting the change in T
rotation of the plane of polarization of light in the straight line. The slope of the line is
polarimeter. If r, rt and r0 are the rotations at
t = , t = t and t = 0 then, first order reaction can 2.303R Ea
(1)  (2) 
be written as Ea 2.303R
1 rt –r 1 r0 – r
(1) k = log10 r – r (2) k = ln r – r 2.303R Ea
t 0  t t  (3) (4)
Ea 2.303R
1 r – r0 1 r – rt
(3) k = ln r – r (4) k = ln r – r 59. The temperature coefficient for most of the reaction
t t  t  0 lies between
54. The rate constant of the production of 2B(g) by the (1) 1 & 3 (2) 2 & 3
reaction,
(3) 1 & 4 (4) 2 & 4

A(g)  2B(g) is 2.48 × 10–4 s–1 60. Which of the following is correct?
A 1 : 1 molar ratio of A to B in the reaction mixture
K2 E a  T 
is attained after (1) log   
K 1 2.303  T1T2 
(1) 26.25 minute
(2) For zero order t1/2 is inversely proportional to
(2) 27.25 minute initial concentration
(3) 28.25 minute (3) Catalyst decreases the activation energy
(4) 0 minute (4) All of these

Chapter 13
Surface Chemistry
Chapter Contents
z Adsorption ADSORPTION
z Type of Adsorption
The phenomenon of increase in concentration of the molecular species
z Adsorption of Gases on Solids on the surface of the solid than in the bulk is called adsorption.
z Langmuir Isotherm
The solid substance on the surface of which adsorption occurs is called
z Colloids adsorbent.
¾ Classification of Colloids The molecular species that get adsorbed on the solid surface due to
¾ Preparation of Colloidal intermolecular attractions are called adsorbate.
Solutions
Sorption
¾ Purification of Colloidal
Solutions The process in which both adsorption and absorption take place
¾ Properties of Colloidal simultaneously.

Solutions Example of Sorption :
z Emulsion z When hydrogen gas is taken up by charcoal, it first condenses on
z Catalysis the surface. This is a case of adsorption. After some time,
¾ Homogeneous and hydrogen diffuse slowly into the interior of the charcoal forming a
Heterogeneous Catalysis true solid solution. This is a case of absorption. Thus hydrogen is
¾ Enzyme Catalysis adsorbed as well as absorbed by charcoal.
TYPE OF ADSORPTION
Physisorption
A process in which the particles of the adsorbate are held to the

surface of the adsorbent by physical forces such as van der Waal
forces.
Chemisorption
A process in which the molecules of the adsorbate are held to the

surface of the adsorbent by chemical bonds.
192 Surface Chemistry NEET
Physical Adsorption Chemical Adsoption

1. The force responsible for the physical 1. The force responsible for the chemical
adsorption are very weak and they are adsorption are quite strong and they are
known as van der Waal's forces. known as chemical bonds.
2. It occurs at low temperature. 2. It occurs at high temperature.
3. Heat of adsorption is low and is in the 3. Heat of adsorption is high and is in the
–1 –1
range of 20-40kJ mol . range of 40-400 kJ mol .
4. It is not specific in nature and depends 4. It is highly specific and also depends on
on the nature of gas. Easily liquefiable nature of gas gases which can interact
gases are adsorbed readily. chemically with the adsorbent show
chemisorption.
5. It is reversible process. 5. It is an irreversible process.
6. In this, multilayer adsorption occurs 6. In this, single layer adsorption occurs.
and thus adsorbed layer is several Thus adsorbed layer is only unimolecular
molecules thick. in thickness.
7. No appreciable activation energy is 7. Activation energy may be involved in this
involved in this process. adsorption process.
8. It increases with increase of surface area 8. It too increases with an increase
of the adsorbent. of surface area of the adsorbent.
9. Low temperature is favourable for 9. High temperature is favourable for
adsorption. It decreases with increase adsorption. It increases with the increase
of temperature. of temperature.
ADSORPTION OF GASES ON SOLIDS
As the adsorption occurs through the forces of attraction of the molecular species with the surface therefore
it is in general an exothermic process. The enthalpy change when one mole of an adsorbate (gas or liquid)
is adsorbed on the surface of an adsorbent is called enthalpy of adsorption.
Adsorption depends upon a number of factors, i.e.
z Nature of adsorbent
z Nature of adsorbate
z Pressure
z Temperature
Gases are generally adsorbed on the surface of finely-divided metals such as Ni, Pt, Pd, etc. This phenomenon
is also called occlusion.
z Nature of the Gas(adsorbate) : Since physical adsorption is non-specific in nature, every gas will get
adsorbed on the surface of any solid to some extent. However, it has been observed that the easily
liquifiable gases, such as NH3, HCl and CO2 etc., are adsorbed more than gases like H2, N2 and O2etc.
which are liquified with difficulty.
However, chemisorption is specific in nature. Hence, in case of chemisorption, a gas gets adsorbed on
the solid only if it forms chemical bonds with it.
NEET Surface Chemistry 193
z Nature of Solid (adsorbent) : Activated charcoal is the most common adsorbent of the easily liquifiable
gases. Most of the poisonous gases belong to this type. It is generally used in gas masks for adsorbing
poisonous gases. Gases like H2, N2 and O2 are generally adsorbed over finely divided metals.
The amount of adsorption also depends on the surface area of the adsorbent. The greater the surface
area per unit mass of the adsorbent (called specific surface area), the greater the extent of adsorption.
Effect of Temperature
Adsorption is accompanied by evolution of heat. In adsorption, a true equilibrium is established between the
gas in contact with the solid and the gas on the surface.
adsorption
Gas + Solid Gas adsorbed on solid surface ; H = –ve
(Adsorbate) (Adsorbent)desorption
Adsorption isobar : A graph between the amount of adsorbate per gram of adsorbent
(x/m) and the temperature (t) at a constant pressure is called adsorption isobar. The adsorption isobars for
physisorption and chemisorption are shown in figure.
Constant Constant
pressure pressure
x/m
x/m
t t
Physical adsorption Chemisorption
Effect of Pressure
Adsorption is a reversible process. Hence adsorption and desorption occur simultaneously. If the adsorbate
and the adsorbent are placed in a closed vessel, after some time, a stage is reached when the rates of
adsorption and desorption become equal. This is called the state of adsorption equilibrium. At this stage,
the surface of the adsorbent gets saturated with the adsorbed gas and no more adsorption occurs.
Adsorption Isotherm
x
A plot of versus of the pressure (p) at constant temperature is called adsorption isotherm. A simple
m
adsorption isotherm is shown in figure below.
The pressure at adsorption equilibrium, when no more adsorption occurs, is called saturation pressure (ps).
x
On the basis of experimental studies, Freundlich gave the following relationship between and p.
m
Constant
temperature
x
= kp°
x 1 m
= kp n
m
x/m
x Saturation pressure,s P
m = kp
p
Adsorption isotherm with variation of x/m
against pressure at constant temperature
x
z At an intermediate pressure, will obviously depend on a power of pressure (p) which lies
m
between 0 and 1. This may be expressed mathematically as :
1 1
x x
 pn or  k.p n where n > 1 ...(i)
m m
where n is a constant which depends on the nature of adsorbate as well as adsorbent. The value of
1
lies between 0 and 1. Freundlich isotherm is accurately valid for moderate pressures.
n
The above relationship is called a Freundlich's adsorption isotherm.
The value of k and n can be determined experimentally as follows :
Taking log on both sides of equation (ii), we get
x 1
log    log p  log k ...(ii)
m n
1
pe= n
Slo
m
x
log
Intercept = log k
log p
Linear graph between log x/m and log p.
x
Hence, if we plot a graph between log   and log p, a linear plot will be obtained. The slope of
m
1 x
the straight line will be while the intercept on the log   axis will correspond to log k.
n m
LANGMUIR ISOTHERM
Freundlich isotherm fails at high pressures. Langmuir adsorption isotherm is based on following assumptions:
(i) Every adsorption site on the surface of adsorbent is equivalent.
(ii) Ability of adsorption of a particle on every adsorption site is independent of the vacancy of nearly sites.
(iii) Adsorption is a reversible process.
(iv) Adsorption is unimolecular layer (hence more accurately valid for chemical adsorption)
Langmuir isotherm is represented as :
x ap
 (a and b are constants)
m 1  bp 1
slope = a
At very high pressure (bp >> 1)
m
x a x
 b
m b a
At very low pressure (bp << 1)
1
x p
 ap
m
Thus the relation is correct at every pressure. To get the values of constants a and b we draw a curve
m 1
between and .
x p
m 1 b
 
x ap a
Application of Adsorption
The phenomenon of adsorption finds a large number of applications. A few important applications are given
below :
z Removal of unwanted gases or vapours : Many times, poisonous vapours are present in air. These
can be adsorbed by a suitable adsorbent. In fermentation industry the odour of carbon dioxide can make
the product unpalatable. Excess carbon dioxide is removed by charcoal.
z Removal of colouring matter : In the production of sugar, vinegar etc., there are a number of colouring
impurities. These are removed by adsorbents like charcoal, fuller's earth etc.
z Creation of high vacuum : Charcoal adsorbs all gases at low temperature. Thus if a vessel is first
evacuated by conventional techniques and then connected to charcoal at low temperature, the residual
gases will be adsorbed by it and ultra high vacuum in the vessel will be obtained.
z Catalysis : In heterogeneous catalysis, adsorption of the reactants and desorption of the products are
very important processes.
z Chromatographic analysis : All types of chromatographic techniques are based upon selective adsorption
of different types of substances on a given adsorbent.
Example 1 : Which adsorption has high energy of activation?

Solution : Chemisorption
Example 2 : Which adsorption is specific and which is not specific in nature?

Solution : Physisorption is not specific in nature but chemisorption is specific in nature.
Example 3 : What is the effect of surface area on adsorption?

Solution : Both physisorption and chemisorption increase with increase in surface area.
EXERCISE
1. Which is not a characteristic of physical adsorption?
(1) Enthalpy of adsorption is low
(2) It is due to weak intermolecular van der Waal forces
(3) It forms unimolecular layer on adsorbent
(4) It require very small activation energy for the adsorption
2. Adsorption depends upon
(1) Activation of the adsorbent (2) Surface area
(3) Pressure on the gas (4) All of these
3. According to Langmuir adsorption isotherm amount of gas adsorbed at very low pressure
(1) Directly proportional to the pressure (2) Proportional to P1/n (where n > 1)
(3) Inversely proportional to the pressure (4) Independent to the pressure of the gas
4. 50 mL of 1 M oxalic acid (molar mass = 126) is shaken with 0.5 g of wood charcoal. The final concentration
of the solution after adsorption is 0.5 M. Calculate the amount of oxalic acid adsorbed per gram of charcoal.
(1) 6.1 (2) 6.2
(3) 6.4 (4) 6.3
5. In case of chemical adsorption,
(1) It continuously increases with increase in temperature
(2) It continuously decreases with decrease in temperature
(3) It increases with increase in temperature in low temperature zone than decreases
(4) Adsorption is not effected by the temperature
6. For the adsorption, generally
(1) H = +ve, S = +ve, G = –ve (2) H = +ve, S = –ve, G = –ve
(3) H = –ve, S = –ve, G = –ve (4) H = –ve, S = –ve, G = +ve
COLLOIDS
On the basis of size of particles of solute, solutions have been classified into three types
True solutions Colloidal solutions Suspensions
Less than 10 –9 m or Between 10 –9 and 10 –6 m or 1 nm to More than 10 –6 m or 1000

1 nm i.e., < 10 Å 1000 nm i.e., 10 Å – 10000 Å nm i.e., > 10000 Å
Colloidal particles can pass through filter paper but not through animal or vegetable membrane. A colloid is a
heterogeneous system in which one substance is dispersed (dispersed phase) as very fine particles in another
substance called dispersion medium.
Classification of Colloids :
(1) Classification based on physical states of dispersed phase and dispersion medium : Colloids have
been classified into eight types.
S. No. Dispersed phase Dispersion medium Type of Examples

colloids
1. Solid Solid Solid sol Some coloured glasses

and gem stones
2. Solid Liquid Sol Paints, cell fluids
3. Solid Gas Aerosol Smoke, dust
4. Liquid Solid Gel Cheese, butter, jellies
5. Liquid Liquid Emulsion Milk, hair cream
6. Liquid Gas Aerosol Fog, mist, cloud,

insecticide sprays
7. Gas Solid Solid foam Pumice stone, foam

rubber
8. Gas Liquid Foam Froth, whipped cream,

soap lather
If dispersed phase and dispersion medium both are gases then homogeneous mixture so colloids is not
formed.
(2) Classification based on the nature of interaction between dispersed phase and dispersion medium:
On this basis colloidal sols are divided into two types, namely lyophilic (solvent attracting) and lyophobic
(solvent repelling). If dispersion medium is water then called hydrophilic and hydrophobic.
S. No. Property Lyophilic sols Lyophobic sols
1. Ease of preparation By directly mixing with Prepared by special method

the liquid dispersion only
medium
2. Stability Quite stable and are Easily precipitated by addition

not easily precipitated of a small amount of suitable
or coagulated electrolyte
3. Reversible and Reversible in nature Irreversible in nature

irreversible nature
4. Hydration Highly hydrated Not much hydrated
5. Nature of substances Organic substances Usually inorganic substances

like starch, gum,
proteins etc.
6. Viscosity Much higher than Almost same as that of

medium medium
7. Surface tension Usually lower than Nearly same as that of

that of medium medium
(3) Classification based on type of particles of dispersed phase :

Divided into three types
(i) Multimolecular colloids : On dissolution, a large number of atoms or smaller molecules of a substance
aggregate together to form species having size in colloidal range (diameter < 1 nm)
Example : Gold sol, sulphur sol
(ii) Macromolecular colloids : They are formed when macromolecules added in suitable solvent for solution
in which the size of macromolecules in the colloidal range. Such colloids are quite stable and resembles
true solution in many respects.
Example : Starch, cellulose, proteins and enzymes are natural macromolecular colloids but polythene,
nylon, polystyrene, synthetic rubber etc. are man-made colloids.
(iii) Associated colloids (Micelles)
The substances which when dissolved in a medium at low concentration behave as normal strong
electrolyte but at higher concentration exhibit colloidal behaviour due to formation of aggregates. The
aggregates particle is called micelles. The concentration above which micelles can be formed called
critical micelles concentration (CMC) and temperature above which micelles can be formed called Kraft
temperature.
Example : Synthetic detergent and soaps. CMC for soaps is 10–4 to 10–3 mol L–1.
Condition for Micelles Formation : Substances which contain polar head and non-polar tail form micelles
Mechanism of micelles formation : When soap dissolve in water it dissociates into RCOO– & Na+. RCOO–
ions consist of two parts i.e., non-polar part R (called tail) which is water repelling and polar part COO– (called
head) which is water loving. The RCOO– ion present on the surface with their COO– groups in water and R group
staying away from water. But at the CMC, anions are pulled into the bulk of the solution and aggregate to form a
spherical shape with their hydrocarbons chain pointing towards centre of the sphere with COO– part remaining
outward on the surface of the sphere. An aggregate thus formed called ionic micelles. These micelles may
contain as many as 100 such ions.
COO
Ionic
O
O micelle
CO
O
C O
Stearate CO
ion
OOC COO
Water C CO
OO O
COO
C
OO
(a) (b)
Fig : (a) Arrangement of stearate ions on the surface of water at low concentrations of soap
(b) Arrangement of stearate ions inside the bulk of water (ionic micelle) at critical micelle concentrations of
soap
Cleansing action of soaps
The cleansing action of soap is due to the fact that soap molecules form micelle around the oil droplet in such a
way that hydrophobic part of the stearate ions is in the oil droplet and hydrophilic part projects out of the grease
droplet like the bristles. Since the polar groups can interact with water, the oil droplet surrounded by stearate
ions is now pulled in water and removed from the dirty surface. Thus soap helps in emulsification and washing
away of oils and fats. The negatively charged sheath around the globules prevents them from coming together
and forming aggregates.
(a) (b)
(c)
Fig: (a) Grease on cloth (b) Stearate ions
arranging around the grease droplet and
(c) Grease droplet surrounded by stearate
ions (micelle formed)
Anionic detergent : [CH3(CH2)11OSO3–Na]
Sodium Lauryl sulphate
Cationic detergent: [CH3(CH2)15(CH3)3NBr–]

Cetyltrimethyl bromide
Preparation of Colloid solutions

Following methods are used.
(i) Chemical method :
As2O3 + 3H2S   As2 S3 + 3H2O
Double decomoposition
(sol)
SO2 + 2H2S  3S  2H2 O

Oxidation
(sol)
2AuCl3 + 3HCHO + 3H2O  2Au  3HCOOH  6HCl

Re duction
(sol)
FeCl3 + 3H2O  Fe(OH)3  3HCl

Hydrolysis
(sol)
(ii) Peptisation : The process of conversion of a fresh precipitate into colloids by shaking it with the dispersion
medium in the presence of a small amount of suitable electrolyte is called peptisation and the electrolyte is
called peptising agent.
Example : Colloids of Fe(OH)3 is obtained by adding small quantity of FeCl3 solution.
(iii) Electrical disintegration or Bredig’s Arc method : By this method colloidal solution of metals like Au, Ag,
Pt etc., is prepared. Electric arc is struck between electrodes of metal immersed in the dispersion medium. The
intense heat produced vapourises the metal which then condensed to form particles of colloidal size.
+ Electrodes –
Dispersion
medium
Ice-bath
Bredig's Arc method

Purification of Colloidal Solutions
The following methods are commonly used for the purification of a sol. :
z Dialysis : The process of removing a dissolved substance from the colloidal solution (system) by means
of diffusion through a suitable membrane is called dialysis and the apparatus used for this purpose is
known as dialyser.
z Electrodialysis : The process of dialysis can be accelerated by applying an electric field. This process
is called electrodialysis. In this process, dialysing bag is surrounded by two electrodes. When a high
potential is applied, the cation and anion of the electrolyte are attracted by the oppositely charged
electrodes and the impurities are easily and quickly removed from the colloidal solution (sol.).
z Ultrafiltration : This process of separating the colloidal particles from the solvent and solute present by
specially prepared filters in a colloidion solution (4% solution of nitro cellulose in a) (mixture of alcohol
and ether) hardening by formaldehyde and the finally drying. which are permeable to all substances present
except the colloidal particles is called Ultrafiltration. Speed of filtration can be increased by applying
pressure.
Properties of Colloidal Solutions
(a) Colligative Properties : The values of colligative properties of colloidal particles are small because of
their bigger in size and so lesser in number.
(b) Colour : The colour of the colloidal solution is not always the same as the colour of the substances in
the bulk. The colour of the colloidal solution depends upon the following factors:
I. Size and shape of colloidal particles
II. Wavelength of the source of light
III. Method of preparation of the colloidal solution
IV. Nature of the colloidal solution
V. The way an observer receives the light, i.e., whether by reflection or by transmission.
Example : A mixture of milk and water appears blue when viewed by the reflected light and red when viewed
by the transmitted light. Finest gold sol is red in colour, as the size of particle increases, it appears purple
and finally golden.
(c) Mechanical Properties :
z Brownian movement : Colloid particles exhibit a ceaseless random and swarming motion. This
kinetic activity of particles suspended in the liquid is called Brownian movement. With increase
is size of DP particles brownian movement decrease and with increase in temperature this movement
increase.
(d) Optical Properties (Tyndall effect) :
When a strong and converging beam of light is passed through a colloidal solution, its path becomes
visible (bluish light) when viewed at right angles to the beam of light.
Tyndall effect is observed only when the following two conditions are satisfied.
(a) The diameter of the dispersed particles is not much smaller than the wavelength of the light used
(b) The refractive indices of the dispersed phase and the dispersion medium differ greatly in magnitude
(e) Electrical Properties
z Electrophoresis or Cataphoresis : In a colloidal solution particles are electrically charged and the
dispersion medium has equal but opposite charge. The phenomenon involving the migration of colloidal
particles under the influence of electric field towards the oppositely charged electrode is called
electrophoresis or cataphoresis.
Origin of Charge : Various reasons have been given regarding the origin of charge on the colloidal
particles. These are given below :
I. Dissociation of the Surface Molecules : It leads to electric charge on colloidal particles. For
example, an aqueous solution of soap (sodium palmitate) dissociates into ions.

 
C15H31COO  Na
C15H31COONa
Sod. palmitate
The Na+ ions pass into the solution while C15H31COO¯ ions have a tendency to form aggregates
due to weak attractive forces present in the hydrocarbon chains. Thus, the anions which are
of colloidal size bear negative charge.
II. Preferential Adsorption of Ions from Solution : The charge on the colloidal particles is
generally acquired by preferentially adsorbing positive or negative ions from the electrolyte. Thus
AgCl particles can adsorb Cl¯ ions from chloride solutions and Ag+ ions from solution having
Ag+ ions; the sol. will be negatively charged in the first case and positively charged in the second
case.
Electrical charged sols
Positively charged sols Negatively charged sols

Hydrated metallic oxides Metals such as Cu, Au, Ag sols. Metal
e.g., Al2O3  xH2O, CrO3  xH2O and sulphides, e.g., As2S3, Sb2S3,CdS sols.
Fe2O3  xH2O etc.
Basic dyes such as methylene blue Sols of starch, gum, gelatin, clay, charcoal etc.
Haemoglobin. Oxides, e.g. : TiO2 sol. Acid dyes, such as eosin, congo red sols.
z Electro-osmosis : The phenomenon involving the migration of the dispersion medium and not
the colloidal particles under influence of an electric field is electro-osmosis.
(f) Coagulation or Flocculation :
The colloidal sols are stable due to the presence of electric charges on the colloidal particles. Because
of the electrical repulsion, the particles do not come close to one another to form precipitates. The removal
of charge by any means will lead to the aggregation of particles and hence precipitation will occur
immediately. This process by means of which the particles of the dispersed phase in a sol. are pecipitated
is known as coagulation.
The minimum amount of an electrolyte (in milimoles) required to cause precipitation of one litre of a colloidal
solution is called coagulation value or flocculation value of the electrolyte for the sol.
The reciprocal of coagulation value is regarded as the coagulating power.
z Hardy-Schulze Rules :
"Higher is the valency of the active ion, the greater will be its power to precipitate the sol."
Thus, coagulation power of cations is in the order Al3+ > Ba2+ or Mg2+ > Na+ or K+.
Similarly, to coagulating the positively charged sol the coagulation power of anion is in the order
[Fe(CN)6 ]4   PO34  SO24  Cl¯
(g) Gold Number :

The number of milligrams of the protective colloid required to just prevent the coagulation of 10 ml a
standard gold sol when 1 ml of 10% solution of sodium chloride is added to it.
EMULSIONS
The colloidal solution of two immiscible liquids in which the liquid acts as the dispersed phase as well as
the dispersion medium. There are two types of emulsions i.e., (i) oil in water (ii) water in oil emulsions.
Emulsion of oil in water are unstable and sometimes they separate into two layers on standing. For
stabilisation of an emulsion, a third component called emulsifying agent is used. The principal emulsifying
agents for O/W emulsions are proteins, gums, natural and synthetic soaps etc and for W/O, heavy metal
salts of fatty acids, long chain alcohol, lampblack etc.
The droplets in emulsions are often negatively charged and can be precipitated by electrolytes. They also
show Brownian movement & Tyndall effect. Emulsions can be broken into constituent liquids by heating,
freezing, centrifuging etc.
CATALYSIS
The process of changing the rate of a chemical reaction by addition of a foreign substance (catalyst) is called
catalysis. The catalyst is specific in nature and change the rate of a particular reaction by providing an alternate
path of different activation energy.
Positive and negative catalysis : When a catalyst increases the rate of a reaction, it is called positive
catalyst and the phenomenon is called positive catalysis.
Example of positive catalysis :
MnO2 (s)
2KClO3 (s)  2KCl(s)  3O2 (g)
Fe(s)
N2 (g)  3H2 (g)  2NH3 (g)

H or OH¯
CH3COOC2H5 (aq)  H2O(l)   CH3COOH(aq)  C2H5OH(aq)
When a catalyst decreases the rate of a reaction, it is called a negative catalyst and the phenomenon is
called negative catalysis.
Example of negative catalysis :
acetanilide(s)
2H2O2 (l )   2H2O(l )  O2 (g)
C H OH( l )
2CHCl3 (l )  O2 (g) 
2 3
 2COCl2 (g)  2HCl(l )
Chloroform Phosgene
Promoters and Inhibitors : In certain cases, there is a substance which is itself not necessarily a catalyst
but it can increase the efficiency of a catalyst. Such substances which can act as catalyst for a catalyst
are called promoters.
Sometimes, the presence of impurities in the reactants renders the catalyst inactive. Such substances are
called inhibitors or catalytic poisons. For example, arsenious oxide inhibits the catalytic activity of platinized
asbestos used as catalyst in the manufacture of H2SO4 by contact process.
Homogeneous and Heterogeneous Catalysis
z A reaction in which the catalyst and the reacting substances are present in the same phase, is called
homogeneous catalysis.
NO(g)
2SO2 (g)  O2 (g)   2SO3 (g)

H (aq)
CH3COOCH3 (aq)  H2O(l )   CH3COOH(aq)  CH3OH(aq)
z A reaction in which the catalyst is present in a phase different from that of the reacting substances is
called heterogeneous catalysis. All the reaction in this case occur at the surface of the catalyst.
finely
N2 (g)  3H2 (g)  2NH3 (g)
divided Fe(s)
P(s)
2SO2 (g)  O2 (g)   2SO3 (g)
or V2O5 (s)
z Shape selective catalysis by Zeolites : Zeolites are the most important metal oxide catalysts. These
catalysts are widely used in the petrochemical industries for (i) cracking of hydrocarbons and (ii) for
aromatisation. Zeolites are microporous silicates having the general formula
Mx/n [(AlO2 )x (SiO2 )y ] . mH2O
Shape-selectivity is the most remarkable feature of zeolite catalysts. The reactions depend on the size
of the cavities (Cages) and pores (apertures) present on the surface of zeolite. The pore size varies
between 260pm and 760pm.
Hence depending upon the size of the reactant and product molecules, as compared to the size and the
shape of the cavities and the pores of the zeolite, the reactions can move in a specified manner.
A special catalyst, called ZSM-5 (Zeolite of Sieve Molecular Porosity 5), is used to convert alcohols such
as methanol, ethanol directly to gasoline or petrol.
ZSM 5
xCH3OH   (CH2 )x  xH2O
Methanol Catalyst Gasoline
Zeolites are also used in water softening.
Enzyme Catalysis
Enzyme is biochemical catalyst and the biological reactions are catalysed by enzyme catalyst. Enzymes
are complex nitrogenous compounds which are produced by living plants and animals having high molecular
mass ranging from 15000 to 1,000,000 g mol–1. Enzyme forms colloidal solution in water.
Example of few enzyme catalysed reactions are given below
S. No. Reaction Enzyme Source
(i) Inversion of cane sugar Invertase Yeast

Invertase
C12H22O11(aq) + H2O(l) C6H12O6(aq) + C6H12O6(aq)
Glucose Fructose
(ii) Conversion of glucose into ethyl alcohol Zymase Yeast

Zymase
C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g)
(iii) Conversion of starch into maltose Diastase Malt

Diastase
2(C6H10O5)n(aq) + nH2O(l) nC12H22O11(aq)
Maltose
(iv) Conversion of maltose into glucose Maltase Yeast

Maltase
C12H22O11 (aq) + H2O(l) 2C6H12O6(aq)
Glucose
(v) Manufacture of acetic acid from ethyl alcohol Mycoderma aceti Old vinegar
CH3CH2OH(l) + O2(g) CH3COOH(l) + H2O(l)
(vi) Decomposition of urea into NH3 and CO2 Urease Soyabean

Urease
NH2CONH2(aq) + H2O(l) 2NH3(g) + CO2(g)
(vii) Conversion of proteins into peptides in the stomach Pepsin Stomach
(viii) Conversion of proteins into amino acids by Trypsin Intestine

hydrolysis in intestine
(ix) Conversion of milk into curd Lacto bacilli Curd
Characteristics of enzyme catalysis

(i) Specificity : Each enzyme catalyses only one reaction, so highly specific in nature.
(ii) Efficiency : Enzymes are highly efficient catalysts, one molecule of an enzyme may transform one million
molecules of the reactant per minute.
(iii) Optimum temperature and pH : The optimum temperature range for enzymatic activity is 298–310 K
whereas optimum pH range is 5–7.
(iv) Increasing activity in the presence of activators and co-enzymes : The enzymatic activity is increased
in the presence of certain substances, known as co-enzyme. Activators are generally metal ions like Na+,
Mn2+, Co+2, Cu2+, etc. These metal ions are weakly bonded to the enzyme molecules and increase their
catalytic activity.
Example : Enzyme, amylase in the presence of NaCl, which provides Na+ ion shows a very high catalytic
activity.
(v) Influence of inhibitors and poisons : The activity of enzyme is slowed down in the presence of certain
substances are called inhibitor or poison. Inhibitors interact with the active functional groups thereby
reducing or completely destroying the catalytic activity of enzymes. The use of many drugs is on account
of their action as enzyme inhibitors in our body.
Catalysts in Industry
Some Industrial Catalytic Processes
S. No. Process Reactions with catalyst and other conditions
(i) Haber's process for the N2(g) + 3H2(g)

Finely divided iron (catalyst)
2NH3(g)
manufacture of ammonia Molybdenum (Promoter)
200 bar pressure
723–773 K temp.
(ii) Ostwald's process for the 4NH3(g) + 5O2(g)

Platinised
4NO(g) + 6H2O(g)
manufacture of nitric acid asbestos (catalyst)
573 K
2NO(g) + O2(g) 2NO2(g)
4NO2(g) + 2H2O(l) + O2(g) 4HNO3(l)
Platinised asbestos
(iii) Contact process for the 2SO2(g) + O2(g) 2SO3(g)
manufacture of sulphuric acid or V2O5 (catalyst)
673–723 K
SO3(g) + H2SO4(l) H2S2O7(l) + H2O(l) 2H2SO4(aq)
Oleum
(iv) Bosch's process for the Fe2O3(Catalyst)

CO + H2O(g) CO2(g) + H2(g)
manufacture of hydrogen +Cr2O3 (promoter)
673–873 K
(v) Deacon's process for the CuCl2

4HCl(g) + O2(g) 2H2O(l) + 2 Cl2(g)
manufacture of chlorine 773 K
ZnO + Cr2O3
(vi) Synthesis of methanol CO(g) + 2H2(g) CH3OH(l)
200 bar
423 K
Finely divided Ni
(vii) Hydrogenation of vegetable Oil(l) + H2(g) Vanaspati ghee(s)
423–473 K
oils High pressure
EXERCISE
7. Tyndall effect in colloidal solution is due to
(1) Reflection of light (2) Refraction of light
(3) Scattering of light by dispersed phase (4) Scattering of light by dispersion medium
8. Select the positive sol in the following
(1) Al(OH)3 sol (2) Gold sol
(3) CdS sol (4) Gum
9. 0.25 g lyophilic colloid is added to 100 ml gold solution to prevent the coagulation on adding 1 ml 10% NaCl
solution. What will be gold number of lyophilic colloid?
(1) 250 (2) 125
(3) 25 (4) 0.25
10. The gold number of Gelatin, Gum and Starch are 0.005, 0.15 and 25 respectively. Which colloid has highest
protection power?
(1) Gelatin (2) Starch
(3) Gum (4) All have equal protection power
11. What will be nature of charge on colloidal particle when FeCl3 is added to excess of hot water?
(1) Positive (2) Negative
(3) Neutral (4) Some times positive and some times negative
12. Tyndall effect is more effectively shown by
(1) True solution (2) Lyophilic colloid
(3) Lyophobic colloid (4) Suspensions
13. Which one of the following statements is not correct?
(1) Tyndall effect in colloidal solution is due to scattering of light
(2) Hardy–Schulze rule is applicable only to the coagulation of lyophilic sols
(3) Blue colour of the sky is due to scattering of light by dust particles
(4) Greater flocculation value of an electrolyte means its poor coagulating power

t
en
nm nment
ssigAssig
Assignment
Assignment
A
6. Which of the following match containing example

SECTION - A
of colloids and its dispersion medium is incorrect?
NCERT Based MCQs
[NCERT Pg. 136]
1. For spontaneous physical adsorption
(1) Fog – Gas
[NCERT Pg. 125]
(2) Paints – Liquid
(1) G < 0, S < 0 (2) G < 0, S > 0
(3) Jellies – Solid
(3) H > 0, S > 0 (4) H > 0, S < 0
(4) Froth – Gas
2. The correct order of temperature in the given
Freundlich adsorption isotherm is 7. The formation of micelles which occurs only above
a particular concentration is called
[NCERT Pg. 127]
[NCERT Pg. 138]
T1 (1) Kraft concentration
x T2 (2) Micelle concentration
m
T3 (3) Absolute concentration
(4) Critical micelle concentration
P 8. Incorrect statement for enzyme catalysis is

(1) T1 > T2 > T3 (2) T3 > T2 > T1 [NCERT Pg. 134]
(3) T1 > T3 > T2 (4) T2 > T1 > T3 (1) Highly specific in nature
3. Which of the following statements is wrong for (2) The enzymic activity is decreased in the
chemisorption? [NCERT Pg. 126] presence of co-enzymes
(1) It forms unimolecular layer (3) The optimum temperature range for enzymatic
(2) No appreciable activation energy is needed activity is 298-310 K
(3) Initially it increases with the increase of (4) The optimum pH for enzymatic activity is 5-7
temperature 9. 4.8 g of oxygen is adsorbed on 1.2 g of metal
(4) It is irreversible powder. The volume of oxygen adsorbed per gram
of the adsorbent at NTP is [NCERT Pg. 124]
4. Which of the following is an example of
homogeneous catalysis? [NCERT Pg. 130] (1) 2.8 L
(2) 3.6 L
(1) 2SO2 (g) + O2 (g) 
Pt( s)
 2SO3 (g)
(3) 4.6 L
(2) N2 (g) + 3H2 (g) 
Fe( s )
 2NH3 (g)
(4) 3.2 L
(3) 4NH3 (g)+5O2 (g)   4NO(g) + 6H2O(l)
Pt(s)
10. Colloidal solution of gold can be prepared by
(4) 2SO2 (g) + O2 (g) 
 2SO3 (g)
NO( g)
[NCERT Pg. 139]
5. Example of macromolecular colloids is (1) Bredig’s arc method
[NCERT Pg. 138] (2) Double decomposition
(1) Starch (2) Sulphur sol (3) Hydrolysis
(3) Detergents (4) Gold sol (4) Peptization
11. Which of the following is not a colloid? 2. Lyophobic colloids are
[NCERT Pg. 136] (1) Reversible colloids
(1) Milk (2) Irreversible colloids
(2) Blood (3) Protective colloids
(3) Gem stones (4) Gum, proteins
(4) Urea solution 3. At CMC, the surfactant molecule undergoes
12. Substances whose solutions can pass through filter (1) Association (2) Aggregation
paper as well as animal membrane are called (3) Micelle formation (4) All of these
[NCERT Pg. 136]
4. When dilute aqueous solution of AgNO3 (excess)
(1) Crystalloids (2) Colloids is added to KI solution, positively charged sol
particles of AgI are formed due to adsorption of ion
(3) Suspensions (4) Both (1) & (3)
13. Which of the following is the correct adsorption (1) K+ (2) Ag+
isobar for physical adsorption? [NCERT Pg. 127] (3) I– (4) NO3–
5. The process of froth floatation and chromatography
are based on
x x
(1) Emulsification (2) Adsorption
(1) m (2) m
(3) Absorption (4) Evaporation
T T 6. The best coagulant for a negative sol is
(1) NaCl (2) MgCl2
(3) AlCl3 (4) K4[Fe(CN)6]
x x 7. Movement of colloidal particles under the influence
(3) m (4) m of electric field is called
(1) Electrophoresis
T T
(2) Dialysis
14. Brownian movement belongs to which of the (3) Ionisation
following given property? [NCERT Pg. 142]
(4) Electrodialysis
(1) Mechanical (2) Electrical
8. Emulsifier is an agent which
(3) Colligative (4) Optical
(1) Accelerates the dispersion
15. The sol which cannot coagulate blood
(2) Stabilises the emulsion
(haemoglobin) is [NCERT Pg. 142]
(3) Homogenizes the emulsion
(1) Gold sol
(4) None of these
(2) Clay
9. Which of the following method is not employed for
(3) As2S3
the purification of colloids?
(4) TiO2 sol
(1) Electrodialysis (2) Dialysis
(3) Ultracentrifugation (4) Peptisation
SECTION - B
10. Which of the following has minimum protecting
Objective Type Questions power?
1. Freundlich adsorption isotherm gives a straight line (1) Gelatin (Gold no. = 0.01)
on plotting (2) Dextrin (Gold no. = 15)
(1) x/m vs P (2) Log x/m vs P (3) Potato starch (Gold no. = 25)
(3) Log x/m vs log P (4) x/m vs 1/P (4) Albumin (Gold no. = 0.25)
11. Positive sol in the following is 16. Which of the following is positively charged
(1) CdS sol (2) TiO2 sol colloidal particle ?
(3) Congo red sol (4) Clay (1) As2S3 (2) Al(OH)3
12. Which of the following is with highest and lowest (3) Au (4) Cu
coagulating value among Al3+, Na+, Mg2+, Ba2+? 17. Most effective coagulant for a colloidal solution of
(1) Al3+, Na+ arsenic sulphide in water
(2) Na+, Al3+ (1) 0.1 M Sodium phosphate
(3) Ba2+, Al3+ (2) 0.1 M Zinc sulphate
(4) They have same coagulating value (3) 0.1 M Zinc nitrate
13. The graph plotted against adsorption Vs pressure (4) 0.1 M Aluminium chloride
P at constant temperature, the Freundlich equation 18. Activated charcoal will adsorb which gas most
at A, B, C respectively are (if n  1) effectively ?
C (1) He (2) O2
B
x (3) CO2 (4) N2
m A
19. Which of the following is not a characteristic of
chemisorption?
p (1) Adsorption is irreversible
x x 1 x (2) H is of the order of 400 J

(1)  kp,  kp n ,  kp0
m m m (3) Adsorption is specific
(4) Adsorption increases with increase of surface
x x x 1
(2)  kp,  kpn ,  kp n area
m m m
20. Colloids can be purified by
x 1 x x 1
(3)  kp n ,  kpn ,  kp n (1) Electrophoresis
m m m
(2) Coagulation
x x x
 kp ,  kp n ,  kpn
1
(4) (3) Peptization
m m m
(4) Ultrafiltration
14. Which of the following is correct about the
adsorption of N2 over Iron? 21. Which is not a colloidal solution?
(1) It is always physically adsorbed (1) Smoke (2) Ink
(2) It’s adsorbed molecules over iron decreases (3) Air (4) Blood
with the increase in temperature first and then 22. Gelatin is often used as an ingredient in the
increases manufacture of ice-cream. The reason for this is
(3) It is always chemically adsorbed (1) To prevent the formation of a colloid
(4) N2 is never adsorbed over iron (2) To stabilize the colloid and prevent crystal
15. During purification of colloidal sol by growth
ultracentrifugation which of the following is (3) To cause the mixture to solidify
observed?
(4) To improve the flavour
(1) Colloidal particles are settled at the bottom of
ultracentrifuge tube 23. Which can adsorb larger volume of hydrogen gas?
(2) Impurities are settled at the bottom of the (1) Colloidal solution of palladium
ultracentrifuge tube (2) Finely divided nickel
(3) Impurities are removed through ultrafilters (3) Finely divided platinum
(4) Its rate can be increased by applying pressure (4) Colloidal Fe(OH)3
24. Colloidal solution commonly used in treatment of
eye disease is
SECTION - C
(1) Colloidal sulphur Previous Years Questions
(2) Colloidal silver 1. The correct option representing a Freundlich
(3) Colloidal gold adsorption isotherm is [NEET-2019 (Odisha)]
(4) Colloidal antimony x x

(1)  k p –1 (2)  k p0.3
25. The stability of lyophilic colloid is due to m m
(1) Charge on their particles
x x
(2) A layer of dispersion medium on their particles (3)  k p2.5 (4)  k p –0.5
m m
(3) The smaller size of their particles
2. Match the catalyst with the process
(4) The large size of their particles
26. Which of the following forms a colloidal solution in
water? Catalyst Process
(1) NaCl (i) V2O5 (a) The oxidation of
(2) Glucose ethyne to ethanal
(3) Ba(NO3)2 (ii) TiCl4 + Al(CH3)3 (b) Polymerisation of

alkynes
(4) Starch
27. Whipped cream is an example of (iii) PdCl2 (c) Oxidation of SO2
in the manufacture
Dispersed phase Dispersed medium
of H2SO4
(1) Liquid – Gas
(iv) Nickelcomplexes (d) Polymerisation of
(2) Gas – Liquid ethylene
(3) Liquid – Liquid Which of the following is the correct option?
(4) Solid – Liquid
(1) (i)-(c), (ii)-(a), (iii)-(d), (iv)-(b)
28. Crystalloids differ from colloids mainly in respect of
(2) (i)-(c), (ii)-(d), (iii)-(a), (iv)-(b)
(1) Electrical behaviour
(3) (i)-(a), (ii)-(b), (iii)-(c), (iv)-(d)
(2) Particle size
(3) Particle nature (4) (i)-(a), (ii)-(c), (iii)-(b), (iv)-(d)
(4) Solubility 3. Which mixture of the solutions will lead to

the formation of negatively charged colloidal
29. Which of the following is an example of associated
[Agl]l– sol? [NEET-2019]
colloid?
(1) Protein + water (1) 50 mL of 1 M AgNO3 + 50 mL of 1.5 M KI
(2) Soap + water (2) 50 mL of 1 M AgNO3 + 50 mL of 2 M KI

(3) Rubber + benzene (3) 50 mL of 2 M AgNO3 + 50 mL of 1.5 M KI
(4) As2O3 + Fe(OH)3 (4) 50 mL of 0.1 M AgNO3 + 50 mL of 0.1 M KI
30. Point out the false statement 4. On which of the following properties does the
(1) Brownian movement and Tyndall effect are coagulating power of an ion depend? [NEET-2018]
shown by colloidal system
(1) The magnitude of the charge on the ion alone
(2) Gold number is a measure of the protective
power of a lyophilic colloid (2) Size of the ion alone
(3) The colloidal system of a liquid in liquid is (3) The sign of charge on the ion alone
called gel (4) Both magnitude and sign of the charge on the
(4) Hardy-Schulze rule is related with coagulation ion
5. Which one of the following statements is not 11. Which of the following statements is correct for the
correct? [NEET-2017] spontaneous adsorption of a gas? [AIPMT-2014]
(1) Catalyst does not initiate any reaction (1) S is negative and, therefore, H should be highly
(2) The value of equilibrium constant is changed in positive
the presence of a catalyst in the reaction at (2) S is negative and therefore, H should be highly
equilibrium
negative
(3) Enzymes catalyse mainly bio-chemical
(3) S is positive and, therefore, H should be
reactions
negative
(4) Coenzymes increase the catalytic activity of
enzyme (4) S is positive and, therefore, H should also be
highly positive
6. The coagulation values in millimoles per litre of the
electrolytes used for the coagulation of As2S3 are 12. Which one of the following statement is incorrect
given below : [NEET-Phase-2-2016] about enzyme catalysis? [AIPMT (Prelims)-2012]
I. (NaCl) = 52 (1) Enzymes are denaturated by ultraviolet rays and
II. (BaCl2) = 0.69 at high temperature
III. (MgSO4) = 0.22 (2) Enzymes are least reactive at optimum

temperature
The correct order of their coagulating power is
(1) I > II > III (2) II > I > III (3) Enzymes are mostly proteinous in nature
(3) III > II > I (4) III > I > II (4) Enzyme action is specific
7. Which one of the following characteristics is 13. In Freundlich Adsorption isotherm, the value of 1/n is
associated with adsorption? [NEET-2016]
(1) G and S are negative but H is positive
(1) 1 in case of physical adsorption
(2) G is negative but H and S are positive
(2) 1 in case of chemisorption
(3) G, H and S all are negative
(3) Between 0 and 1 in all cases
(4) G and H are negative but S is positive
(4) Between 2 and 4 in all cases
8. Fog is a colloidal solution of [NEET-2016]
(1) Gas in gas 14. The protecting power of lyophilic colloidal sol is
expressed in terms of [AIPMT (Prelims)-2012]
(2) Liquid in gas
(1) Critical miscelle concentration
(3) Gas in liquid
(4) Solid in gas (2) Oxidation number
9. Which property of colloidal solution is independent (3) Coagulation value

of charge on the colloidal particles? [AIPMT-2015] (4) Gold number
(1) Tyndall effect
15. If x is amount of adsorbate and m is amount of
(2) Coagulation adsorbent, which of the following relations is not
(3) Electrophoresis related to adsorption process?
(4) Electro-osmosis [AIPMT (Prelims)-2011]

10. Which property of colloids is not dependent on the
x
charge on colloidal particles? [AIPMT-2014] (1)  pT
m
(1) Coagulation
(2) x/m = f(p) at constant T
(2) Electrophoresis
(3) Electro-osmosis (3) x/m = f(T) at constant P
(4) Tyndall effect (4) p = f(T) at constant (x/m)
16. The Langmuir adsorption isotherm is deduced using 22. At the critical micelle concentration (CMC) the
the assumption [AIPMT (Prelims)-2007] surfactant molecules
(1) The adsorbed molecules interact with each other (1) Associate
(2) The adsorption takes place in multilayers (2) Dissociate
(3) The adsorption sites are equivalent in their ability (3) Decompose
to adsorb the particles (4) Become completely soluble
(4) The heat of adsorption varies with coverage 23. Which one of the following method is commonly
17. A plot of log x/m versus log p for the adsorption of a used method for destruction of colloid?
gas on a solid gives a straight line with slope equal (1) Dialysis
to [AIPMT (Prelims)-2006]
(2) Condensation
(1) – log k
(3) Filteration by animal membrane
(2) n
(4) By adding electrolyte
1 24. Pure water can be obtained from sea water by
(3)
n (1) Centrifugation
(4) log k (2) Plasmolysis
18. Which one of the following forms micelles in aqueous (3) Reverse osmosis
solution above certain concentration?
(4) Sedimentation
25. Which is not correct regarding the adsorption of a
(1) Urea gas on surface of a solid?
(2) Dodecyl trimethyl ammonium chloride (1) On increasing temperature adsorption
(3) Pyridinium chloride increases continuously
(4) Glucose (2) Enthalpy and entropy change is negative

(3) Adsorption is more for some specific
Questions asked Prior to Medical Ent. Exams. 2005 substance
19. When a few typical solutes are separated by a (4) It is a reversible reaction
particular selective membrane such as protein
particles, blood corpuscles, this process is called 26. Position of non polar and polar part in micelle
(1) Transpiration (2) Endosmosis (1) Polar at outer surface but non polar at inner
surface
(3) Dialysis (4) Diffusion
(2) Polar at inner surface non polar at outer surface
20. A colloidal system has particles of which of the
following size? (3) Distributed over all the surface
(1) 10–9 m to 10–12 m (4) Are present in the surface only

27. According to the adsorption theory of catalysis, the
(2) 10–6 m to 10–9 m
speed of the reaction increases because
(3) 10–4 m to 10–10 m
(1) The concentration of reactant molecules at the
(4) 10–5 m to 10–7 m active centres of the catalyst becomes high
21. The ability of anion, to bring about coagulation of due to adsorption
a given colloid, depends upon (2) In the process of adsorption, the activation
(1) Magnitude of the charge energy of the molecules becomes large
(2) Both magnitude and sign of charge (3) Adsorption produces heat which increases the
speed of the reaction
(3) Its charge only
(4) Adsorption lowers the activation energy of the
(4) Sign of the charge alone reaction
28. Which of the following forms cationic micelles (1) CH3 – (CH2)8 – COO– Na+
above certain concentration?
(2) CH3 – (CH2)11 N (CH3)3 Br–
(1) Sodium dodecyl sulphate
(3) CH3 – (CH2)13 – SO3\ Na
(2) Sodium acetate
(4) CH3 – (CH2)15 N(CH3)3 Br–
(3) Urea
6. Peptisation is
(4) Cetyltrimethylammonium bromide
(1) Conversion of a colloidal into precipitate form
(2) Conversion of precipitate into colloidal sol
SECTION - D
(3) Conversion of metal into colloidal sol by
NEET Booster Questions passage of electric current
1. Consider the following statements: (4) Conversion of colloidal sol into macromolecules.
I. More easily liquefiable gases adsorb easily 7. Gold number of a lyophilic sol is such property that
II. Silica gels are used to remove moisture (1) The larger its value, the greater is the peptising
III. x/m = K.p1/n ; (n > 1) power.
Choose the correct statement (s) (2) The lower its value, the greater is the peptising
power.
(1) I & II
(3) The lower its value, the greater is the protecting
(2) II & III
power.
(3) I & III
(4) The larger its value, the greater is the
(4) I, II & III protecting power.
2. The catalyst used for the following reaction 8. Adsorption is accompanied by
KClO3  KCl + O2 is (1) Decrease in entropy
(1) MgO (2) Increase in enthalpy
(2) Na (3) Increase in Gibb's energy
(3) Li2O2 (4) All of these
(4) MnO2 9. Enzyme are
3. Which of the following is not an action of enzyme ? (1) Proteins (2) Minerals
(1) Conversion of milk into curd (3) Oils (4) Fatty acids
(2) Inversion of cane sugar 10. Which of the following is mismatched ?
Diastase
(3) Starch  maltose Dispersed Dispersion Specific
ZSM-5
(4) CH3OH  gasoline phase medium name
4. Which of the following is the hydrolytic method for (1) Liquid Liquid Emulsion
the preparation of colloidal solution? (2) Liquid Solid Solid foam
(1) As2O3 + 3H2S  As2S3 + 3H2O (3) Liquid Gas Liquid aerosol
(2) SO2 + 2H2S  3S + 2H2O (4) Solid Liquid Sol
(3) 2AuCl 3 + 3HCHO + 3H 2 O  2Au + 11. Example of anionic detergent is
3HCOOH + 6HCl
(1) Sodium lauryl sulphate
(4) FeCl3 + 3H2O  Fe(OH)3 + 3HCl
(2) Cetyltrimethyl ammonium bromide
5. Under ambient conditions, which among the
following will form micelles in aqueous solution at (3) Sodium dodecylbenzenesulphonate
lowest molar concentration ? (4) Both (1) and (3)
12. Coagulation of the lyophobic sols can be carried 19. Which of the colloidal property is not dependent on
out by charge of colloidal particles?
(1) By boiling (1) Electro-osmosis
(2) By persistent dialysis (2) Tyndall effect
(3) By addition of electrolytes (3) Coagulation
(4) All (4) Electrophoresis
13. Principal emulsifying agents for oil-water emulsions 20. Absorption and adsorptions are respectively
is (1) Surface phenomena, bulk phenomena
(1) Long chain alcohols (2) Bulk phenomena, surface phenomena
(2) Lampblack (3) Both are bulk phenomena
(3) Heavy metal salts of fatty acids (4) Both are surface phenomena
(4) Natural and synthetic soaps 21. Adsorption is multilayer in case of
14. Negative sol is (1) Physical adsorption
(1) Methylene blue sol (2) Fe2O3·xH2O (2) Chemisorption
(3) TiO2sol (4) As2S3 (3) Both (1) and (2)
15. Potential different between fixed layer and diffused (4) None of these
layer in colloidal sol is known as
22. Fog is an example of colloidal system of
(1) Standard hydrogen electrode potential
(1) Liquid in a gas
(2) Zeta potential
(2) Gas in a liquid
(3) Electrokinetic potential
(3) Gas in a solid
(4) Both (2) and (3)
(4) Solid in a liquid
16. Which of the following is an incorrect statement
23. Which of the following is multimolecular colloid
(1) Physical adsorption is a multilayered (1) Lyophilic sol.
adsorption
(2) Starch
(2) Chemical adsorption is irreversible
(3) Gold sol
(3) On increasing the temperature physical
adsorption first increases then decreases (4) Soap solution
(4) Explanation of chemical adsorption is done by 24. Colloidal solution cannot be prepared by
langmuir adsorption isotherm. (1) Hydrolysis
17. ZSM-5 converts (2) Reduction of AuCl3
(1) Alcohol to gasoline (petrol) (3) Peptization
(2) Benzene to toluene (4) Electrophoresis
(3) Toluene to benzene 25. During electro-osmosis of Fe(OH)3 sol
(4) Heptane to toluene (1) Sol particles move towards anode
18. Which of the following is true with respect to (2) Sol particles move towards cathode
chemical adsorption ? (3) Dispersion medium moves towards anode
(1) H < 0, S > 0, G > 0 (4) Dispersed phase moves towards cathode
(2) H < 0, S < 0, G < 0 26. The charge on As2S3 sol is due to the adsorbed
(3) H > 0, S > 0, G < 0 (1) H+ (2) OH–
(4) H > 0, S < 0, G > 0 (3) O–2 (4) S–2
27. Role of catalyst in a reversible reaction is to 29. The statement not applicable to chemisorption is
(1) Increase the rate of forward reaction only (1) Highly specific
(2) Increase the rate of backward reaction only (2) Dependent of temperature
(3) Alter the equilibrium constant (3) Irreversible

(4) Multilayered
(4) Achieve equilibrium quickly
30. Freundlich adsorption isotherm gives a straight line
28. Which one has the highest coagulation power ? on plotting
(1) K+ (1) x/m vs log P
(2) Al3+ (2) log x/m vs P
(3) Ca2+ (3) log x/m vs log P
(4) Sn4+ (4) x/m vs 1/P

Chapter 25
General Principles and Processes

of Isolation of Elements
Chapter Contents
z Introduction Introduction
z Occurrence of Metals Out of 117 elements known so far, noble metals, noble gases, N2, O2,
and a few others are available in native state while others are available
z Some Terms as their compounds. All of these are useful to us in one or the other
z Extraction of Metals and form. Fe is present in haemoglobin. Zn is present in insulin, Co is
Non-Metals (General) present in vitamin B-12, Mg is present in chlorophyll, etc. Al is used
in making transmission cables, utensils, etc, Cu is used in making
z Thermodynamical Principles
electrical appliances and in increasing hardness of gold, in making
of Metallurgy
many alloys etc. Zn is used in galvanometer, extraction of gold and
z Ellingham Diagrams silver, etc. Fe is extensively used as wrought iron, cast iron, steel,
alloy steel for making many articles of day-to-day needs.
z Applications of Ellingham
Diagrams This unit mainly deals with the extraction of Fe, Zn, Cu, Al and many
other metals and their purification.
z Electrochemical Principles of
Metallurgy
OCCURRENCE OF METALS
z Extraction of Aluminium
(Electrometallurgy) Metals generally occur in the form of their oxides, sulphides, carbonates,
sulphates, halides, etc. Principal minerals of some metals are listed below.
z Hydrometallurgy
Metal Mineral Average composition
z Refining
Iron Haematite * Fe2O3
z Uses of Some Metals
Magnetite Fe3O4
z Glossary Iron pyrites FeS2
Siderite FeCO3
Chromite FeOCr2O3
Copper Chalcopyrites or copper CuFeS2 [Actual form :
pyrites (Fool’s gold)* Cu2SFe2S3]
Copper glance Cu2S
Cuprite Cu2O
Malachite CuCO3Cu(OH)2
Azurite 2CuCO3Cu(OH)2
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2 General Principles and Processes of Isolation of Elements NEET
Metal Mineral Average composition

Aluminium Bauxite * AlOx (OH)3– 2x [0 < x < 1]
Major form is
Cryolite Al2 O3 2H2 O
Kaolinite (a clay) Na 3AlF6
China clay [Al2(OH) 4 Si2O 5]
Al2 O3 SiO2 2H2 O
Zinc Sphalerite or Zinc Blende * Zn S
Zincite ZnO
Smithsonite or Calamine ZnCO 3
Silver Argentite or Silver glance * Ag2S
Horn silver AgCl
* Main minerals called as ores, from which metals are mainly extracted.
Note :
The most abundant element in the earth’s crust is oxygen (46.6%) followed by Si (27.7%), Al (8.3%),
Fe (5.1%). The most abundant metal in the earth’s crust is Al. Atmosphere contains about 78% by
volume of N2 gas and 21% of O2 gas.
Example 1 : Name the compound that contains Mg and helps green plants during photosynthesis.
Solution : The compound that contains Mg and helps green plants during photosynthesis is chlorophyll.
Example 2 : Write the names and formulae of main ores of Fe, Cu, Al and Zn.
Solution : Fe – Haematite – Fe2O3
Cu – Copper pyrites – CuFeS2
Al – Bauxite – Al2O32H2O
Zn – Zinc blende – ZnS
SOME TERMS
(i) Minerals : Naturally occurring solid substances having metals in combined state or native state are called
minerals. Minerals do not contain NO3– ion because all nitrate salts are water soluble.
(ii) Ore : A mineral is an ore from which one or more metals can be extracted easily and profitably.
(iii) Matrix or Gangue : Minerals are always associated with earthy impurities known as matrix or gangue.
(iv) Flux : It is a substance used to decrease the melting point of an ore or a substance used to react with
impurities to form slag.
(a) Acidic flux : It converts basic impurities to slag. For example, SiO2 is used in the metallurgy of
copper to remove FeO as FeSiO3 (slag). Other acidic fluxs are  B2O3, P4O10 etc.
FeO + SiO2  FeSiO3
(b) Basic flux : It converts acidic impurities to slag. For example, CaO is used in the metallurgy of iron
to remove SiO2 as CaSiO3 (slag). Other basic fluxs are  CaCO3, MgCO3. MgO etc.
SiO2 + CaO  CaSiO3
(v) Slag : The low fusible substance produced by the reaction of flux with impurities during extraction of
metals, is called slag. The process is called slagging operation.
NEET General Principles and Processes of Isolation of Elements 3
(vi) Alloy : It is a homogeneous mixture of a metal with one or more elements that may be metals or non-
metals.
(vii) Metallurgy : The complete scientific and technological process employed for the extraction of a metal
from its ore is called metallurgy.
It also includes purification of metal and formation of its alloys.
Example 3 : Define ‘Slagging operation’.

Solution : It is the process of formation of slag (low fusible substance ) by the reaction of flux with impurities
of the ore, during metallurgy. For example, in the metallurgy of iron, CaO (a basic flux) is used
to convert the acidic impurity SiO2 to CaSiO3 (slag).
CaO + SiO2  CaSiO3
EXTRACTION OF METALS AND NON-METALS (GENERAL)

Different non-metals are extracted by de-electronation using different processes. Metals are extracted by
electronation using certain definite methods as mentioned below.
(i) Pulverisation : The lumps of ore are converted to small pieces by using jaw crushers and to powder
by employing stamp mill or ball mill.
(ii) Concentration of ores :
(1) Magnetic separation : This method is employed to separate the magnetic and non-magnetic
components present in the ore. For example, magnetic impurity of wolframite (FeWO4) is separated
from tin stone (the ore of tin). Other cases are chromite ore FeOCr2O3, magnetite Fe3O4, pyrolusite
MnO2, etc. are magnetic.
Finely ground ore
Magnetic roller
Magnetic
particles
Non-magnetic
particles
Magnetic Separation (Schematic)
(2) Hydraulic washing (gravity separation method)
This method is employed to purify heavier ore such as oxides (e.g., haematite, tin stone etc.),
carbonates (e.g., calamine, malachite, etc.), native gold, etc.
The ore is washed with running water using big tubs or wilfley table that has sluices (grooves). The
lighter impurities are washed away and the heavier particles of the ore settle down.
(3) Froth floatation process : This method is employed to purify/concentrate sulphide ores. This method uses:
(a) Water
(b) Pine oil or eucalyptus oil to produce foam and work as collector / transforming agent
(c) Cresols or aniline to stabilise foam called stabilizer
S
(d) Xanthate (commonly employed xanthate is potassium ethyl xanthate, C2H5 – O – C – S K+ )
is used collector to increase wetting of sulphide ore.
(e) Depressants and activators to collect the required sulphide part from the ore. For example,
Galena contains a good quantity of ZnS with PbS. NaCN is used to convert most of ZnS into
water soluble complex Na2[Zn(CN)4].
The powdered ore is put in a tank containing a stirrer, a device of passing compressed air and all
the above material. Foam is produced by wetting and lifting of sulphide ore to the surface. It is
washed with acidulated water to collect the ore.
Rotating paddle
Air
Mineral froth
Pulp of ore + oil
Paddle draws in air

and stirs the pulp
Enlarged view of an air bubble showing
mineral particles attached to it
Froth floatation process (Schematic)
(4) Leaching : It is the method of collecting the required metal from an ore, in the form of aqueous
solution of its selected compound, by treating the ore with acid or base or some other reagent. In
Bayer’s process, for red bauxite, the ore is continuously stirred with 45% NaOH at 200 – 250°C
and 35 – 36 bar pressure. This process is called digestion. This way, Al2O3 is extracted out as
sodium aluminate. The impurity, SiO2 too dissolves forming sodium silicate. Other impurities are
left behind.
Al2O3(s) + 2NaOH(aq) + 3H2O(I)  2Na[Al(OH)4](aq)
The sodium aluminate present in solution is neutralised by passing CO2 gas and hydrated Al2O3
is precipitated. At this stage, small amount of freshly prepared sample of hydrated Al2O3 is added
to the solution. This is called seeding. It induces the precipitation.
2Na[Al(OH)4](aq) + CO2(g)  Al2O3.xH2O(s) + 2NaHCO3(aq)
Sodium silicate remains in the solution and hydrated alumina is filtered dried and heated to give
back pure Al2O3.
Al2 O3  xH2 O  s  

1470 K
 Al2 O3  s   xH2 O  g
In Serpeck’s method white bauxite is generally heated with coke in the presence of N2 gas. AlN produced
is reacted with water to produce Al(OH)3 which on ignition gives Al2O3.

Al2O3 + N2 + 3C   3CO + 2 AlN
AlN + 3H2O  NH3 + Al (OH)3
Example 4 : Tin stone (cassiterite) is purified by magnetic separation method. Name and formulate the magnetic
chemical present with it.
Solution : Wolframite (ferrous tungstate) FeWO4 is the magnetic impurity present with tin stone which is
separated by magnetic separation method.
(iii) Extraction of crude metal from concentrated ore :
(1) Conversion of Ore to Oxide Form : Sulphide ores are thermodynamically more stable than CS2
and hence cannot be converted by using coke (general and common reducing agent) as reducing
agent. Moreover CO2 is more volatile and thermodynamically more stable than CS2. This all means that
fG° of a metal sulphide is not compensated by the energy of reaction of metal sulphide with coke.
Hence, it is better to convert the sulphide ore to oxide form and then apply smelting, i.e., carbon
reduction method.
(a) Calcination : Conversion of hydrated oxides, carbonates, basic carbonates and hydroxide ores
to their oxides by heating in the abscence of O2 below their melting point is known as
calcination. Calcination makes the oxide porous thus increasing the surface area for further
reaction.
Fe2O3 . x H2O(s) 

 Fe2O3 (s) + x H2O 

ZnCO3 (s)   ZnO(s) + CO2 
(b) Roasting : Sulphide ores are generally roasted in reverberatory furnace in free supply of air
below melting point. Ore changes to oxide with larger surface area and volatile impurities are
removed.
Δ
2 ZnS + 3O2   2 ZnO + 2 SO2
Δ
2 PbS + 3O2   2 PbO + 2 SO2
Note :
 Though tin stone (cassiterite) SnO2 is an oxide ore, it is roasted because of good amount of
sulphur present in it as impurity.
 In case the ore contains impurity of iron, a small amount of silica SiO2 is added during roasting
to slag it out as FeSiO3.
FeO + SiO2  FeSiO3
 SO2 gas produced during roasting is generally used by industries to produce sulphuric acid.
VO H SO HO
SO2  O2  2 5
2atm / 400–500C
 SO3 
2 4
 H2 S2O7 
2
 2H2 SO4
 In some cases, metal is produced during roasting which may leave the chamber (furnace) if
heating is done above m.p. of metal during roasting.
O 1
HgS 
2
 HgO  Hg  O
2 2
HgS
2HgO   3Hg  SO2
Example 5 : Write two points of similarities between calcination and roasting.

Solution : (i) The end product of both the processes is oxide of metal.
(ii) Volatile impurities are removed from the ore and surface area for the further reaction increases.
Example 6 : Though tin stone is oxide of tin, yet roasting is carried out for this ore. Why?
Solution : Tin stone contains a good amount of sulphur with it, which is removed by roasting.
S(s) + O2(g)  SO2
(2) Reduction of oxide to metal :

(a) Smelting : Carbon reduction method
This method can be applied for the reduction of ZnO, PbO, etc.
1400°C
ZnO + C   CO + Zn
ZnO can be reduced by CO (g) above 1800°C.
Fe2O3 can be reduced by coke above 1079 K (approx) and by CO gas at a temperature below
than that.
(b) Reduction by H2
Though, the use of H2 is expensive and not very safe, yet H2 is used as reducing agent when
carbon becomes ineffective for reduction.
WO3 + 3H2  W + 3H2O
NiO + H2  Ni + H2O
H2 cannot reduce Al2O3 and B2O3.
(c) Metals as reducing agents
(a) Kroll’s process for titanium
TiCl4 + 2Mg  2MgCl2 + Ti
(b) Gold Schmidt alumino thermite process
Oxides of manganese, chromium, iron, etc. can be reduced by using aluminium powder as reducing
agent. A mixture of BaO2 and Mg is used as ignition mixture to supply heat.
3Mn3O4 + 8Al  4Al2O3 + 9Mn
(d) Auto reduction or self reduction or air reduction method
Less reactive metals form unstable sulphides. Roasting produces their oxides which may react
with sulphide to produce metal or the oxide formed may decompose to give metal.
O2 /Δ Cu2 S/Δ
Cu2 S 
–SO
 Cu2 O   Cu + SO2
2
O2 /Δ PbS/Δ
PbS  PbO 
–SO2
Pb + SO2
O2/ HgS/
HgS HgO Hg + SO2
Hg + 12 O2

Example 7 : What is the process of smelting? Give one suitable example also.
Solution : The method of reduction of a metal oxide by using coke as reducing agent is called smelting.
1400°C
ZnO + C   Zn + CO
THERMODYNAMICAL PRINCIPLES OF METALLURGY
Gibbs free energy for a reaction is given by the equations G = H – TS and G° = – RT lnK. Negative value
of G and positive value of K favour the formation of products.
The reaction Cr2O3(s) + 2Al(s)  Al2O3 + 2Cr(s);G = – 421 kJ is thermodynamically feasible but does
not take place at room temperature, because unless the temperature is so high to melt Cr(s) to liquid form,
TS will not overcome H.
If any product of a reaction having positive value of G1 can be used up by another reactant to carry out a
reaction having negative value of G2, the two reactions can occur together (coupling of reactions) only if the
numerical value of G2 is greater than G1.
–1
2 FeO 2Fe + O2 ; G1250 k = 320 kJ mole
–1
2C + O2 2CO ; G1250 k = –430 kJ mole
(Coke)
Net reaction, 2 FeO + 2C 2Fe + 2CO ; GNet = – 110 kJ (approx)
ELLINGHAM DIAGRAMS
Ellingham plotted graphs of formation of oxides, sulphides and halides versus temperature. The plots of
fG (metal oxide) per mole of oxygen versus temperature are useful in deciding the reducing agent and
temperature for reducing a specific metal oxide. All these graphs have positive slopes showing decrease
of entropy except for the formation of CO(g) from coke that shows increase in entropy with increase in
temperature.
A sudden increase in slope, as in case of Zn or Mg, indicates melting.
The temperature at which two graphs intersect give G = 0 for the reaction of one oxide with other element.
The element of the lower graph works as reducing agent for the oxide of the other, e.g.,
Below temperature 1623 K (approx) Mg metal will reduce Al2O3 (but not economical) and above this temperature
it is Al that reduces MgO (but not economical).
0
-100
 2C u 2O
4Cu + O 2
G fº (metal oxide) per mol of O 2 in kJ
-200
eO
-300  2F
+ O2
2 Fe C + O2  CO2
-400
2CO
2
+ O2  2C +
O2 
-500 2CO
2CO ZnO
O2 2
+
-600 2Zn
-700
A
-800
O3
/3Al 2
-900 2
/3Al + O2
4
gO
-1000  2M
+ O2
2Mg
-1100
-1200
0°C 400°C 800°C 1200°C 1600°C 2000°C

273 K 673 K 1073 K 1473 K 1873 K 2273 K
Temperature
* The limitations of this method are that it does not discuss the rate of reaction and takes every reaction
as an equilibrium process.
Example 8 : In Ellingham diagrams plots of fG (oxide formation) show positive slopes except for the formation
of CO(g) from coke. Why?
Solution : In the following reaction,
2C(s) + O2 (g) 
 2CO(g)
Coke 1 mol 2 mol
H is negative (exothermic reaction) and S is positive (moles of gaseous substances increasing).

The value of G (which is, H – TS) becomes more and more negative by increasing
temperature, The slope of graph becomes negative.
In all other cases, O2 gas is consumed to produce solid metal oxides. Here, entropy decreases
(becomes negative). TS dominates H and the value of G increases constantly, thereby increasing
the slope of the graph.
APPLICATIONS OF ELLINGHAM DIAGRAMS

Extraction of iron : In Ellingham diagram, the
graph of CO  CO 2 conversion remains
Ore, limestone, and coke
below Fe  Fe2O3 upto 1123K (for Fe  FeO).
It is 1073 K approximately. So, CO(g) acts as
reducing agent upto this temperature.
3Fe2O3 + CO  2Fe3O4 Exhaust gases (CO, CO2)
(i.e., FeOFe2O3) + CO2 3Fe2O3 + CO  2Fe3O4 + CO2
(Iron ore)
Fe3O4 + CO  3FeO + CO2
1070 K Fe3O4 + CO  3FeO + CO2
FeO + CO  Fe + CO2 FeO + CO  Fe + CO2
Also, graph of C  CO is below the graph of Fe CaCO3  CaO + CO2
 Fe 2 O 3 after 1123 K. So, carbon acts as 1270 K (Limestone)
reducing agent above this temperature. CaO + SiO2  CaSiO3
(Slag)
Fe2O3 + C  3CO + 2Fe 1570 K C + CO2  2CO
Coke
Zones in Blast furnace : Near the bottom coke C + O2  CO2
2170 K
is filled and in the upper part 8 : 4 : 1 proportion Molten slag FeO + C  Fe + CO
of Fe2O3, coke and lime stone. Height of blast
furnace is about 150 feet. Molten iron Blast of air and oxygen
(a) Zone of combustion : Near the bottom, hot

air is blown that burns coke to produce a
temperature of 2100–2200 K. Solid
Solid waste Pig iron
Pig iron
Waste
C + O2  CO2 + 393.5 kJ
(b) Zone of heat absorption : Upgoing CO2 reacts with coke to reduce to temperature to about 1500–1600 K.
C + CO2  2CO – 163 kJ
(c) Zone of reduction : Upto 1123 K, reduction of Fe2O3 by CO gas gives Fe (in the upper part).
Left of Fe2O3 is reduced by coke above 1123 K.
(d) Zone of slag formation : Slagging operation takes place at about 1273 K.
CaCO3 CaO + CO2
CaO + SiO2 (Impurity)  CaSiO3
At the base molten iron is collected under the slag. This iron is called pig iron and contains about 4%
carbon with many other impurities like, S, P, Si, Mn, etc.
The metal iron is collected from slag by pressing under rollers.
* The height of the blast furnace used for the extraction of Fe from Fe2O3 or Fe3O4, is about 150 feet
to 200 feet.
Other Forms of Iron
Cast Iron : It is hard but brittle form of raw iron produced by melting and cooling of pig iron, its colour is gray.
Fast cooling keeps the impurity of carbon as graphite. Slow cooling converts most of the carbon into cementite
Fe3C and the colour becomes white. The carbon content in cast iron comes down to about 3%.
Wrought iron or malleable iron : It is prepared by heating cast iron in reverberatory furnace lined with
haematite which oxidises carbon to CO. Lime stone is added to remove Si, S and P as slag. The wrought
iron is separated from slag by passing through rollers. It is the purest form of iron and contains carbon only
upto 0.5%.
Steel : It contains 0.1 to 1.7% carbon and remaining iron only. It is commonly prepared in Bessemer converter
or open hearth furnace or electric furnace.
Example 9 : Fe2O3 can be reduced by CO gas below 1123 K. How do you relate this statement with Ellingham
diagram?
Solution : Because CO gas is reducing Fe2O3 below 1123 K, the graph of CO  CO2 is lower than the graph
of Fe  Fe2O3, below this temperature.
Example 10 : What is the percentage of carbon in pig iron and cast iron?
Solution : Percentage of carbon in pig iron about 4% while in cast iron it is about 3%.
Example 11 : Name the zone of blast furnace and its importance that has temperature close to 1273K, in the
metallurgy of Fe.
Solution : The zone of blast furnace, close to 1273 K, in the metallurgy of iron, is called zone of slag formation.
Here, the flux CaO reacts with impurity of SiO2 to produce slag CaSiO3.
CaO + SiO 2  CaSiO3

Flux Impurity Slag
EXERCISE
1. Concentration of copper glance is done by
(1) Leaching
(2) Magnetic separation
(3) Hydraulic washing
(4) Froth floatation method
2. Leaching is used for the concentration of ores of
(1) Ag (2) Au
(3) Al (4) All of these
3. Concentrated ore, calamine is heated to get metal oxide and the volatile impurities escapes away. This process
is called
(1) Roasting (2) Calcination
(3) Reduction (4) Oxidation
4. The most commonly used reducing agent for reduction of metal oxides into metals is
(1) B (2) C
(3) Al (4) Fe
5. In the froth floatation process the collectors such as pine oils and xanthates etc. enhance
(1) Non-wettability of the mineral particles in froth
(2) Non-wettability of the mineral particles in water
(3) Non-wettability of the gangue particles in froth
(4) Non-wettability of the gangue particles in water
6. 2PbS + 3O2  2PbO + 2SO2

The above process is called
(1) Roasting (2) Calcination
(3) Smelting (4) Leaching
7. In the metallurgy of iron, limestone is also added with coke. It acts as
(1) Reducing agent (2) Oxidising agent
(3) Slag (4) Flux
8. The plot of Gº versus temperature for the formation of oxides of elements is called
(1) Ellingham diagram (2) Free energy curve
(3) Entropy curve (4) Isobar
9. Decreasing order of carbon content in different forms of iron is
(1) Wrought iron > Pig iron > Cast iron
(2) Pig iron > Cast iron > Wrought iron
(3) Cast iron > Pig iron > Wrought iron
(4) Cast iron > Wrought iron > Pig iron
10. The pair having oxide and carbonate ore respectively
(1) Chromite, Pyrolusite (2) Cassiterite, Calamine
(3) Haematite, Galena (4) Malachite, Bauxite
Extraction of Copper from Cuprite and Copper Pyrites (Fool’s Gold)

In the Ellingham diagram of G° versus T, the graph of C  CO and C  CO2 both are much below the graph
of Cu  Cu2O. Hence, coke can be used to reduce Cu2O to Cu.
After crushing, grinding, hydraulic washing and calcination, the ore is heated with coke to collect Cu.
Cu2O + C  CO + 2Cu
However, the actual method uses copper pyrites (chalcopyrites-CuFeS2). After crushing, grinding and froth
floatation, the ore is roasted in reverberatory furnace. Next, it is heated with coke and silica in a blast furnace
of about 30 feet height. The material collected from the blast furnace is called copper matte that contains high
percentage of copper as Cu2S.
In reverberatory furnace,
2CuFeS2 + O2 Cu2S + 2FeS + SO2
3
FeS + O2  FeO + SO2
2
FeO + SiO2  FeSiO3
Impurity Slag
In Bessemer converter
3
FeS + O2  FeO + SO2
2
3
Cu2S + O2  Cu2O + SO2
2
Cu2O + FeS  Cu2S + FeO
FeO + SiO2  FeSiO3
Finally, the copper matte is subjected to bessemerisation in silica lined Bessemer converter. Cu2S oxidized
to Cu2O is changed to Cu by reaction of Cu2O with Cu2S. Metallurgy called Autoreduction or self reduction
or air reduction method. The reaction are same as shown for blast furnace except the production of Cu.
Cu2S + 2Cu2O  6Cu + SO2
The copper collected is 98-99% pure and has blisters on the surface because of evolution of entrapped SO2.
Example 12 : What is the main ore of copper from which it is extracted?
Solution : Copper is mainly extracted from copper pyrites also known as chalcopyrites CuFeS2.
Example 13 : What is the material collected from reverberatory furnace in the metallurgy of copper?
Solution : The material collected from reverberatory furnace, in case of metalluray of copper, is called matte.
It contains high percentage of copper as Cu2S.
Extraction of Zn : The main ore of Zn is zinc blende or sphalerite (ZnS). It is crushed, powdered then purified
by hydraulic washing. Now it is roasted in reverberatory furnace to obtain ZnO.
2ZnS + 3O2 2ZnO + 2SO2
2O2 1
ZnS   ZnSO 4  ZnO + SO2 + O2
2
ZnO, after converting to bricklettes with coke and clay is now subjected to smelting in horizontal earthen clay
retort or vertical retort, to get Zn.
1673K
ZnO + C  Zn + CO
The metal is distilled off and collected by rapid chilling. This impure zinc is called spelter and contains Cd,
Pb and Fe as major impurities.
Example 14 : In which form is ZnO subjected to smelting in retorts made of clay?
Solution : Before subjecting to reduction, ZnO is converted into bricklettes by mixing with coke and clay.
Example 15 : Which elements are present with zinc when it is extracted from zinc oxide?
Solution : The main impurities are Cd, Pb and Fe.
ELECTROCHEMICAL PRINCIPLES OF METALLURGY
(i) For simple electrolysis when a salt in molten form is electrolysed using suitable electrodes, metal ion
Mn+ is deposited at cathode. Sometimes a suitable electrolyte is also used to decrease the melting point
and to increase the conductivity of the melt.
(ii) Electrolysis of molten NaCl gives Na metal and Cl2 gas. Electrolysis of aqueous NaCl using Hg cathode
and graphite anode gives Na at cathode and Cl2 at anode.
EXTRACTION OF ALUMINIUM (ELECTROMETALLURGY)

Bauxite Al2O32H2O is converted to alumina (purified Al2O3) by leaching [already discussed].
Carbon
anode Copper
clamp
Iron
Carbon lining
Molten Al2O3 + Na3AlF6 + CaF2
(cathode)
Outlet for
aluminium
Molten aluminium
Electrolytic cell for the extraction of aluminium
A mixture of 3-5% Al2O3, 3-8% CaF2 (Flux), 80-85% cryolite, Na3AlF6 (main electrolyte) and 3-8% AlF3 is
electrolysed using steel cathode lined with carbon and graphite anode. Molten Al (99.5% pure) is tapped from
the bottom. The method is commonly known as Hall Heroult method. The reaction can be written as
Cathode : Al3+ (melt) + 3e–  Al(l)
Anode : C(s) + O2– (melt)  CO(g) + 2e–
C(s) + 2O2– (melt)  CO2(g) + 4e–
The overall reaction is
2Al2O3 + 3C  4Al + 3CO2
Anodes are periodically changed as they are consumed by oxygen liberated at anode.
* For the production of about 1 kg of Al, about 0.5 kg of carbon of anode is used up.
HYDROMETALLURGY
When metal is collected from the material obtained by the application of leaching by using some reducing agent
through displacement reaction, the process is called hydrometallurgy.
(i) Extraction of Au or Ag from native ore : Leaching is carried out with 0.2 to 0.5% NaCN and zinc dust
is used as reducing agent 4Au(s) + 8CN–(aq) + 2H2O (aq) + O2(g)  4[Au(CN)2]–(aq) + 4OH– (aq)
Zn(s) + 2[Au(CN)2]–(aq)  2Au(s) + [Zn(CN)4)]2–(aq)
(ii) Extraction of Ag from argentite or silver glance (Ag2S) : The same method as mentioned above, is
used. In the absence of O2, the reaction is reversible.
Ag2S + 4NaCN + 2O2  Na2SO4 + 2Na[Ag(CN)2]
2Na[Ag(CN)2] + Zn  Na2 [Zn(CN)4] + 2Ag
The process is commonly known as Mac Arthur Forrest cyanide method.
Note :
Copper from low grade ores and scraps.
Copper is extracted by hydrometallurgy from low grade ores. It is leached out using acid or bacteria.
The solution containing Cu2+ is treated with scrap iron or H2.
Cu2+(aq) + H2(g)  Cu(s) + 2H+(aq)
REFINING
Refining of a metal depends upon the nature of the metal and nature of impurities. Commonly used methods
are given below.
(a) Liquation : Impure metal that has low m.p., e.g., Pb, Sn etc., are heated in a furnace having sloping
base. The low melting metal flows down leaving high melting impurities in the furnace.
(b) Distillation : Impure metal that has low b.p., e.g., Zn, Cd, Hg, etc., are purified by distillation. Impure
metal is evaporated to obtain the pure metal as distillate.
(c) Oxidative refining : If the impurities can be easily oxidised, oxidative refining is used for the purification
of metal. For example, pig iron and cast iron are converted to wrought iron by oxidative refining using
Bessemer converter.
(d) Poling : This method is used to purify a metal that has its oxide as impurity, e.g., Cu and Sn.
The molten metal is stirred with green logs of wood (best is bamboo) The hydrocarbon (mainly CH4)
produced by logs of wood reduce the metal oxide to metal.
3Cu2O + CH4  CO + 2H2O + 6Cu
(e) Electrorefining : In this method, blocks of impure metal are taken as anode and strips of pure metal
at cathode. Electrolyte is aqueous solution of some suitable salt of the same metal. On passing current,
impure metal from anode gives metal ions into the solution and from the solution the metal ions produce
metal at cathode. Sometimes the waste under the anode (anode mud) may contain precious metals, as
in case of copper, the anode mud may contain gold and silver. Other impurities in anode mud contains
Sb, Se, Te and Pt.
+ –
+ –
Impure Cu Pure Cu
(anode) (cathode)
Acidified
CuSO4 Anode mud
At anode Cu  Cu++ + 2e–

(Impure)
At cathode Cu++ + 2e –  Cu

(Pure)
(f) Vapour phase refining : In this method, metal is converted to a stable volatile compound which on strong
heating produces pure metal.
(i) Van Arkel method : This method is used to collect ultra pure titanium and zirconium by using I2
as specific reagent.
870 K
523 K
Ti + 2I2   TiI4 Zr(s)  2I2 (g)   ZrI4 (g)
(Impure) (Volatile)
; (Impure) ( Volatile)
1700 K 2070 K
TiI4   Ti + 2I2 ; ZrI4 (g) 
at filament
 Zr(s) 2I2 (g)
(Pure) (Pure)
(ii) Mond’s process : This method is used to purify nickel. The reagent used is carbon monoxide.
330–350K
Ni + 4CO   Ni(CO)4
(Impure) (Volatile)
450–470K
Ni(CO)4   Ni + 4CO
(Pure)
(g) Zone refining : This method is very useful for producing semiconductors and other metals of very high
purity, e.g., germanium, silicon, boron, gallium and indium are purified by this method.
The underlying principle is that, impurities are highly soluble in molten metal than in solid metal. This
method is basically fractional crystallisation.
A circular heater surrounds a rod of impure metal. The heater is moved forward. The pure metal crystallises
out and impurities pass into the adjacent molten metal. The method is repeated to shift the impurities
to one end which is cut off.
(h) Chromatographic method : The underlying principle is the differential adsorption of different components
on an adsorbent. Different types are column chromatography, paper chromatography, thin layer
chromatography, etc.
In column chromatography a glass tube is packed with a suitable adsorbent such as Al2O3, silica, etc.
The mixture to be separated is either liquid or is taken as solution in suitable solvent.
It is put at the top of the column. More adsorbable component moves down slowly. After some time,
when the separation of components is visible in the column, the eluent (solvent) is poured from the top.
The component which is least adsorbed is collected at the bottom, the first, followed by the other
components.
Example 16 : When is ‘poling’ used as the method of purification of metals?

Solution : Poling is used as a method of purification of metals when they have their oxides as impurity. For
example, Cu has Cu2O as impurity, Sn has SnO2 as impurity, etc.
Example 17 : Which chemical works as reducing agent in the process of poling?
Solution : Hydrocarbons, mainly CH4.
Example 18 : What is the nature of elements which are purified by zone-refining method?
Solution : Semiconductors, e.g., Si, Ge, Ga, etc.
Example 19 : Write the equations for the Van Arkel method used for the refining of Zirconium, the two
temperatures being 870 K and 2070 K.
870 K
Solution : Zr + 2I2   Zr I4
Impure
2070 K
ZrI4   Zr + 2I2
USES OF SOME METALS

(a) Aluminium : It is used for
(i) Making electric wires
(ii) Making silver paint
(iii) Kitchen utensils
(iv) Extraction of Mn, Cr, etc.
(b) Copper : It is used for
(i) Making steam pipes
(ii) Making electrical wires
(iii) Making calorimeters
(iv) Making alloys, like brass (with Zn), bronze (with tin), coinage alloy (with Ni), german silver
(with Zn and Ni) etc.
(c) Zinc : It is used for
(i) Making alloys, like brass (with Cu), german silver (with Cu 25-30%, Zn 25-30%, Ni 40-50%) etc.
(ii) For galvanisation of iron
(iii) For making dry cell
(iv) For extraction of Ag and gold as reducing agent
(d) Iron : It is used for
(i) Making wrought iron and different varieties of steel.
(ii) Wrought iron is used for making agricultural implements, anchors, bolts etc.
(iii) Steel is used for making parts of automobiles and aeroplanes, cutting tools, utensils, etc.
(iv) Cast iron is used for making gutter pipes, railway sleepers, etc.
Example 20 : Which metal is used for reducing Cr2O3 and Mo2O3 to metal?
Solution : Al powder is used for reducing Cr2O3 and Mo2O3.
BaO /Mg
Cr2O3 + 2Al 
2
Δ
 2Cr + Al2O3
Example 21 : Name some materials made from cast iron.

Solution : Gutter pipes, railway sleepers, drainage pipes, etc.
Example 22 : Write some uses of aluminium.

Solution : (i) In making silver paint
(ii) In making utensils
(iii) In making alloys for parts of aeroplane
(iv) As reducing agent in the extraction of Cr from Cr2O3, Mn from Mn2O3, Mo from Mo2O3, etc
Note :
 Topaz (pukhraj), Ruby (lal) and sapphire (neelam) are impure forms of Al2O3.
 Bells of temples are made from alloy Bell-metal that contains Cu and Sn.
 Cu is mixed with Au and Ag to harden them for making ornaments.
 ZnO is called philospher's wool and chinese white and is amphoteric.
 FeS2 and CuFeS2 have gold-like yellow shining. Both are called fool’s gold.
 Common thermite is 3 : 1 mixture of Fe2O3 and Al.
 German silver does not contain silver, rolled gold does not contain gold and lead pencil does not
contain lead.
 Ti and Zr are used in making parts of jet engine.
EXERCISE
11. In the electrolytic refining of Cu
(1) Impure metal is made as anode and pure metal forms cathode
(2) Impure metal forms cathode and pure metal forms anode
(3) Pure metal forms both anode and cathode
(4) Cu metal is not used as electrodes
12. Si is refined by
(1) Vapour phase refining (2) Zone refining
(3) Liquation (4) van Arkel method
13. Vapour phase refining is used for refining of
(1) In (2) Ni
(3) Zn (4) Hg
14. Chromatography is based on the principle of
(1) Adsorption (2) Absorption
(3) Concentration (4) Vaporisation
15. Refining of Zn is done using the processes called
(1) Electrolytic refining (2) Distillation
(3) Liquation (4) Both (1) & (2)
16. In column chromatography
(1) Component more soluble in stationary phase takes longer time to travel through it
(2) Component less soluble in stationary phase takes longer time to travel through it
(3) Both components travel with same speed initially and then their speed changes
(4) Solubility has no effect for the process of chromatography
17. Solidified Cu obtained from the reverberatory furnace has blistered appearance. This is due to
(1) Evolution of CO2 gas (2) Evolution of SO2 gas
(3) Due to evaporation of volatile materials (4) Evolution of NO2
18. Poling is used to
(1) Oxidise impurities present in blister copper (2) Reduce impurities present in blister copper
(3) Reduce impurities using carbon (4) Remove impurities in the form of slag
19. Sodium, Magnesium and Aluminium can be obtained from their ore by
(1) Electrometallurgy (2) Pyrometallurgy
(3) Hydrometallurgy (4) Smelting
20. Which of the following pair can be refined using same basic principle?
(1) Cu, Ag (2) Si, Ge
(3) Ti, Ni (4) All of these
Note :
 Pyrometallurgy : Method of thermal reduction (using reducing agent and heat) of ore to metal.
 Hydrometallurgy : Method of extraction of metals using leaching and displacement employing
cheaper and reactive metal.
 Leaching : Method of reacting an ore with some reagent to collect the required metal as water
soluble salt.
 Smelting : Heating purified oxide form of ore with coke. It may give metal or matte. It is generally
known as carbon reduction method.
 Aluminothermy: Method of reducing oxide of a metal by heating with powdered aluminium
 Metals which are very reactive like Al, Na, K, Ca are extracted from the ores or oxides by electrolytic
reduction. For e.g., NaCl, MgCl2 (Downs cell), Al2O3 (Hall’s process)
 Spontaneity of reduction of oxides is estimated by Ellingham diagram thermodynamically.

 Purification of the metal is done depending on its nature.
For e.g.,
Zn, Cd, Hg  Distillation
Pb, Sn, Bi  Iiquation
Cu, Ag, Au  Electrolytic refining
Si, Ge, Ga  Zone refining
Ni, Ti, Zr  Vapour phase refining
 Lapis-Lazuli is a blue coloured precious stone which is a mineral of class sodium-aluminosilicate.
 Desilverisation of lead is done by using Parke’s process, which is based on distribution law / partition
coefficient law.
 Separation of silver from gold can be carried out porting with conc. H2SO4.
Extraction of Al from Bauxite :
(i) Baeyer’s Method :
(Used for red bauxite containing Fe2O3 as major impurities)

Al2 O3 2H2 O  2NaOH   2NaAlO2  3H2 O
Fe2O3 insoluble separated as red mud by filteration.


H
NaOH  Al  OH3 
NaAlO2  2H2O

2Al  OH3  
1200C
Al2O3  3H2O
(ii) Hall’s Method :

(Used for red bauxite containing Fe2O3 as major impurities)
Fuse
Al2 O3 2H2O  Na2 CO3   2NaAlO2  CO2  2H2 O
60C
2NaAlO2  3H2 O  CO2   2Al  OH3   Na2CO3

2Al  OH3  
1200C
Al2O3  3H2O
(iii) Serpeck’s Method :

(Used for white bauxite containing silica as major impurities)
1800
Al2 O3 2H3 O  3C  N2   2AlN  3CO  2H2 O
1800C
SiO2  2C   2CO   Si 
2AlN  3H2 O  Al  OH 3   NH3 

2Al  OH3  
1200C
Al2O3  3H2O
GLOSSARY 3. Barium xenate — Ba2XeO6

4. Baryta—BaO
A 5. Bauxite — Al2O3 . 2H2O
1. Adam’s catalyst — Mixture of Pt and PtO 6. Barytes — BaSO4
2. Agate—SiO2 7. Bell Metal — An alloy of Cu and Sn
3. Albite — NaAlSi3O8 8. Beacon lights — Ne lamps
4. Aluminium Bronze — An alloy of Al and Cu 9. Benitoite — BaTiSi3O9
5. Alum stone — Al2(SO4)3 . K2SO4 . 4Al(OH)3 10. Beryl — 3BeO Al2O3 6SiO2
6. Alunite — Al2(SO4)3 . K2SO4 . 4Al(OH)3 11. Bismuthine — BiH3
7. Alumshale — Al2O3 . xSiO2 and FeS2
12. Bleaching powder — CaOCl2
8. Alane—(AlH3)n
13. Blue vitriol — CuSO4.5H2O
9. Amatol —NH4NO3 + TNT
14. Bituminous — Coal containing 88%C
10. Amblygonite — LiFAlPO4
15. Borax — Na2B4O7 10H2O
11. Ammonal — A mixture of Al and Al(NO3)3
16. Bomargyrite — AgBr
12. Analcite — A zeolite Na[AlSi2O6]H2O
17. Borazine — B3N3H6
13. Anglesite — PbSO4
18. Boracite — 2Mg3B8O15 MgCl2
14. Anhydrite — CaSO4
19. Bordeaux mixture — CuSO4 and lime
15. Anhydrone — Mg(ClO4)2
20. Boric acid — H3BO3
16. Anthracite — Hard and black coal containing 92-
21. Bornite — Cu3FeS2
98% carbon
17. Apatite — 3Ca3(PO4)2 . CaF2 22. Boronatrocalcite — CaB4O7 NaBO2 8H2O
18. Aqua dag — Suspension of graphite in water 23. Brass—An alloy of Cu (60-80) and Zn (20-40%)
19. Argentite — Ag2S 24. Bremston—S3
20. Argentiferrous galena — PbS + Ag2S 25. Britannia Metal — An alloy having 86% Sn, 12%
Sb and 2% Cu
21. Artificial carborundum — BN
26. Braunite — Mn2O3
or Inorganic Graphite
27. Bronze–An alloy of Cu (75-90) and Sn (10-25%)
22. Asbestos — Ca Mg3(SiO3)4
28. Bromocarnallite — KBr MgBr2 . 6H2O
23. Azidocarbondisulphide — (SCSN3)2
29. Butter of tin — SnCl4 . 5H2O
24. Azurite — Cu(OH)2 .2CuCO3
25. Aragonite — CaCO3
C
B 1. Cadmipone — A mixture of CdS and BaSO4
2. Calamine — ZnCO3
1. Babbit Metal — Iron alloy containing 10% Sb and
1-2% of Cu 3. Calcite — CaCO3
2. Baking powder – 4. Calgon — Na2[Na4(PO3)6] or (NaPO3)n
5. Caliche — NaNO3 containing about 0.2% NaIO3
CH (OH) COOH
NaHCO3 + 6. Calomel — Hg2Cl2
CH (OH) COOK
7. Candy fluid — KMnO4 solution
8. Carbogen — A mixture of oxygen and 5-10% 40. Copper pyrites — CuFeS2
CO2 for artificial respiration
41. Corundum — Al2O3
9. Carborundum — SiC
42. Cream of tartar — Potassium hydrogen tartarate
10. Carnallite — KCl MgCl2.6H2O
43. Cryolite — Na3AlF6
11. Carnotite — Mineral of uranium containing a very
44. Crystal carbonate — Na2CO3·H2O
small amount of radium
12. Caro’s acid — H2SO5 45. Cuprite — Cu2O
13. Cassiterite — SnO2 46. Cyanogen (CN)2
14. Catapleite — Na2ZrSi3O9.2H2O

D
15. Caustic lotion — AgNO3
1. Diaspore — Al2O3·H2O
16. Celestine — SrSO4
2. Dithionic acid — H2S2O6
17. Cementite — Fe3C
3. Dolomite — CaCO3·MgCO3
18. Ceria — CeO2
4. Drikold — Solid CO2
19. Cerite — Mineral containing Silicates of Ce, La,
5. Duralumin — An alloy having 95% Al, 0.5% Mg,
Pr, Nd and Sm
0.5% Mn and 4% Cu
20. Cerrusite — PbCO3
21. Chalcopyrite — CuFeS2 E
22. Chile Salt Peter — NaNO3 1. Electron Metal — An alloy containing 95% Mg,
23. China Clay — Al2O3·SiO2·2H2O 4.5% Zn and 0.5% Cu
24. Chinese white—ZnO 2. Emarld — Al2O3
25. Chlorapatite — 3Ca3(PO4)2·CaCl2 3. Epsomite or Epsomsalt — MgSO4 . 7H2O
26. Chlorargyrite — AgCl 4. Euchlorine — A mixture of Cl2 and ClO2
27. Chlorine azide — ClN3

F
28. Chrome ochre—Cr2O5
1. Felspar — K AlSi3O8
29. Chrome red — PbCrO4·PbO
2. Fenton’s reagent — A mixture of FeSO4 and
30. Chrome yellow — PbCrO4 H2O2 in alkaline medium
31. Chromite — FeCr2O4 3. Ferrocene — [Fe(n5-C5 H5)2]
32. Cinnabar — HgS 4. Ferrosilicon — An alloy of Fe and Si
33. Cisplatin — Cis-[PtCl2(NH3)2] 5. Fluorapatite — 3Ca3(PO4)2CaF2
34. Clevite — Mineral having He 6. Fluorspar or fluorite — CaF2
35. Coal gas — A mixture of 5% H 2, 22.8% CH4, 7. Fool’s gold — CuFeS2

10.9% CO, 5% N2 and 2.5% ethyne 8. Fermy's salt—KHF2
36. Colemanite — Ca2B6O11·5H2O 9. Fowler's solution—NaAsO2 solution
37. Constantan — An alloy containing 60% Cu and 10. Franklinite — (Zn, Mn)O . Fe2O3
40% Ni. 11. Fulminating gold—Au N2H3
38. Copper coins — Coins containing alloy of Cu, Zn 12. Fusion mixture — A mixture of Na 2CO 3 and
and Sn K2CO3
39. Copper glance — Cu2S 13. Fischer's salt—K3[Co(NO2)6]
G I
1. Icelandspar — CaCO3
1. Galena — PbS
2. Iron pyrites—FeS2
2. Garnietrite — NiMg SiO 3 . H 2O An ore of Ni
containing hydrated silicates of Ni and Mg 3. Indian salt peter — KNO3
4. Inorganic benzene — B3N3H6
3. Germanite—GeO2
5. Inorganic graphite — BN
4. German silver — An alloy containing 56% Cu,
24% Zn and 20% Ni 6. Invar — An alloy containing 64% Fe and 36% Ni
7. Ilmenite—FeOTiO2
5. Gibsite — Al2O3 . 3H2O
8. Iron bugg—Hydrated Fe2O3 used as a dye.
6. Glauber’s salt — Na2SO4 10H2O
7. Golden spangles — PbI2
J
8. Grahm’s salt — (NaPO3)n
1. Jadeite — Na Al(SiO3)2
9. Green vitriol—FeSO4·7H2O
2. Jasper—A hard silicious clay used as precious
10. Guigret's green—Cr2O3·2H2O stone
11. Gun cotton — Nitro cellulose

12. Gun metal — An alloy of Cu, Zn, Sn
K
1. Kainite — KCl . MgSO4·MgCl2 3H2O
13. Gun powder — A mixture of KNO 3 having
charcoal and sulphur 2. Kaolin or Kaolinite — Al 2O3 . 2SiO 2 . 2H 2O or
Al2(OH)4 Si2O5
14. Gypsum — CaSO4·2H2O
3. Kali—German word for potash
4. Kings yellow—As2S3 + As2O3 used as a pigment
H 5. Kernite — Na2 B4O7 . 4H2O
1. Haematite (red) — Fe2O3 6. Kiesserite — MgSO4 . H2O
7. Kupfer nickel — An alloy of Ni and As
2. Haematite (brown) — Fe2O3·3H2O
8. Kieselguhr—Porous clay used as adsorbent and
3. Hausmanite — Mn3O4 filler for dynamite
4. Heavy spar — BaSO4
L
5. Hemimorphite — Zn3(Sb2O7)Zn(OH)2 . H2O
1. Lanakite — PbO. PbSO4
6. Holme’s signal — Signal produced by calcium
2. Lapis Lazuli — sodium aluminosilicate
phosphide and carbide
3. Laughing gas—N2O
7. Horn silver — AgCl 4. Lead shot — Alloy of Pb and As
8. Hydrolith — CaH2 5. Lepidolite—Si3O9 Al2(Li;K)2 (F,OH)2
6. Lignite — coal containing about 67%C
9. Hydroxyapatite — Ca5(PO4)3(OH)
7. Limestone — CaCO3
10. Hypo — Na2S2O3 8. Limonite — Fe2O3. 3H2O
11. Hyponitrous acid — H2N2O2 9. Litharge — PbO; Lithia—Li2O
10. Lithopone — ZnS + BaSO4
12. Hypophosphoric acid — H4P2O6
11. Lunar caustic — Ag NO3
13. Hypophosphorous acid—H3PO2
12. Lienar salt petre—NH4NO3 + (NH4)2 SO4
M O
1. Maddrell's salt—(NaPO3)n 1. Oil gas — A mixture of hydrocarbons obtained by
cracking of kerosene oil
2. Magnalium — An alloy having 90% Al and 10% Mg
2. Oil of vitriol — H2SO4 ; Oxone–Na2O2
3. Magnesia — MgO
3. Oleum — H2S2O7
4. Magnesia alba — [Mg CO3]X[Mg(OH)2]Y·z H2O
4. Olivine — Mg2SiO4
5. Magnesia cement — MgCl2 5MgO·xH2O
5. Oxymuriate of tin — SnCl4 . 5H2O
6. Magnesite — MgCO3
6. Oxycyanogen — (OCN)2
7. Magnetite — Fe3O4
8. Malachite — CuCO3. Cu(OH)2 P
9. Marshall’s acid — H2S2O8
1. Paris green–Cu(CH3COO)2
10. Massicot — PbO
2. Pearl ash — K2CO3
11. Metaphosphoric acid — (HPO3)n
3. Pearl white—BiOCl
12. Mica — KH2Al2(SiO4)3
4. Peat — Coal containing about 60% carbon
13. Microcosmic salt — Na (NH4) HPO4
5. Peerwhite — SbOCl
14. Millerite—NiS
6. Pentalandite — Sulphides of Cu, Fe and Ni
15. Minium — Pb3O4 containing about 22% Ni
16. Mohr’s salt — FeSO4 (NH4)2SO4 6H2O
7. Perhydrol — H2O2
17. Molybdenite — MoS2
8. Perm alloy — An alloy containing 21% Fe, 78%
18. Monazite sands — contain phosphates of Th, Ce, Ni
Nd, Pr, La
9. Permutit–Na2 Al2Si2O8.xH2O
19. Monel Metal — An alloy having 67% Ni, 30% Cu
and 3% Fe 10. Pernitric acid — HNO4
20. Mosaic gold — SnS2 11. Pewter alloy — An alloy containing 80% Sn and
21. Muniz metal—A brass having 60% Cu, 40% Zn 20% Pb
22. Muriate of potash — KCl 12. Pharoh's serpents—Hg(CNS)3

23. Muriatic acid — HCl 13. Phenacite — Be2SiO4
24. Mischmetal—Alloys of lanthanides with other 14. Philosopher’s wool — ZnO
metals
15. Phosphatic rock — Ca3(PO4)2
N 16. Phosphorite — Ca3(PO4)2
1. Natron — Na2CO3 . H2O 17. Pink salt — (NH4)2 SnCl6
2. Natural gas — A gas mixture having 85% CH4, 18. Pitch blende — A mineral of U containing a little
9% C2H6 and 3% C3H8 of Ra
3. Nessler’s reagent — K2HgI4 19. Polyhalite — K2SO4 . MgSO4 . CaSO4 . 6H2O
4. Nichrome — An alloy having 60% Ni, 25% Fe and 20. Potassium feldspar — K2O Al2O3 . 6SiO2
15% Cr
21. Producer gas — A gaseous mixture of CO and N2
5. Nickeloy — An alloy having 95% Al, 4% Cu, 1% Ni
22. Prussian blue — Fe4[Fe(CN)6]3
6. Nitre cake — NaHSO4
23. Pseudo alum — FeSO4 Al2(SO4)3 24H2O
7. Nitrolim — CaCN2 + C
8. Norwegian saltpeter—Ca(NO3)2 . CaO 24. Purple of cassius — Colloidal solution of gold
25. Pyrargyrsite — Ag2S. Sb2S3 13. Soda ash — Na2CO3

26. Pyrolusite — MnO2 14. Soda bleach — A mixture of Na2O2 and dil. HCl
27. Pyrophosphoric acid— H4P2O7, also called 15. Soda Feldspar — NaAlSi3O8
diphosphoric acid
16. Sodium Xenate — Na4XeO6
Q 17. Solder — An alloy of 67% Sn and 33% Pb
1. Quartz—SiO2 18. Sorrel’s cement — MgCl2 5MgO. x H2O
2. Quick lime — CaO 19. Spathic iron ore — FeCO3
3. Quick silver–Hg 20. Spelter — Impure Zn
21. Spodumene — Li Al(SiO3)2

R 22. Stalactite—CaCO3
1. Realgar — As4S4
23. Stalagmite—CaCO3
2. Red lead — Pb3O4
24. Steam coal — Coal containing 93% C
3. Rock salt — NaCl
25. Sterling silver—solution of Cu in Ag
4. Roled gold — An alloy having 95% Cu and
26. Stibine — SbH3
5% Al
27. Stibinite—Sb2S3
5. Roschelle salt—sod. pot tartarate
28. Strontia — SrO
6. Rose metal — An alloy of 50% Bi, 28% Sn
and 22% Pb 29. Sugar of lead — Pb(CH3COO)2
7. Rubies — Al2O3 30. Super halogen — F2
8. Ruby copper — Cu2O 31. Sylvanite — AgAuTe2
9. Ruby silver — Ag2S 32. Sylvine — KCl
10. Rutile — TiO2 33. Spiegeleisen—An alloy of Fe, Mn, C used in the
manufacture of steel.
S
T
1. Sal ammoniac — NH4Cl
1. Talc — Mg2(Si2O5)2 Mg(OH)2
2. Sal volatile—(NH4)2 CO3
2. Tellurocyanogen — (TeCN)2
3. Salt cake — Na2SO4
3. Termolite — Ca2 Mg5 Si4O11 (OH)2
4. Salt peter—KNO3
4. Thermite — Fe2O3 and Al mixture
5. Sapphire — Al2O3
5. Thiocyanogen — (SCN)2
6. Schonite — K2SO4·MgSO4·6H2O
6. Thomas slag — Ca3(PO4)2 and CaSiO3, a by
7. Schweitzer reagent — [Cu(NH3)4]SO4 reagent
product of steel industry.
used for dissolving cellulose
7. Thoria — ThO2
8. Seildlitz powder — NaHCO3
9. Selenocyanogen — (SeCN)2 8. Thortevitite — Sc2(Si2O7)
10. Siderite — FeCO3 9. Tincal — Borax, Na2B4O7
11. Silver glance — Ag2S 10. Triphylite — (Li, Na) PO4(Fe Mn)3(PO4)2
12. Smaltite — An ore of Ni 11. Trona — Na2 CO3 2NaHCO3 . 3H2O
12. Tungsten steel — An alloy of 94%Fe and 6% W 4. Water glass — Na2SiO3, Sod. Silicate
13. Turnbull’s blue — Fe3[Fe(CN)6]2 5. White lead — 2PbCO3·Pb(OH)2
14. Turquoise — AlPO4 Al(OH)3 H2O
6. White Vitriol — Zn SO47H2O
15. Type metal — An alloy of 82% Pb, 15% Sb and
3% Sn 7. Wilkinson’s catalyst — [(C6H5)3P]3Rh Cl
16. Tridymite : A form of quartz. 8. Willemite — Zn2SiO4
9. Witherite — BaCO3
U
10. Wolframite — FeWO4
1. Ultramarine—Na5 Al3 Si2S3O12
2. Urainite—UO2 11. Wood’s metal — A fusible alloy containing
cadmium
V
1. Verdigris — Green layer containing CuCO3 Cu(OH)2
Y
and CuSO4. Cu(OH)2 H2O and some CuCl2 Cu(OH)2 1. Y-alloy — An alloy of Cu and Al
2. Veridian—Cr2O3
Z
3. Vermallic, Vermillion red —HgS
1. Zeigler -Natta Catalyst- R3Al + TiCl4
W 2. Zeise’s salt — K[Pt Cl3 (n2 – C2H4)]
1. Wackenroder’s liquid — Solution of H2S in the 3. Zeolite — Hydrated sodium aluminium silicate
aqueous solution of SO2 4. Zinc blende — ZnS
2. Wallastonite — Ca3Si3O9 5. Zincite — ZnO
3. Washing Soda — Na2CO3 · 10H2O 6. Zircon — ZrSiO4

t
en
nm nment
s s igAs s ig
A ssignment
Assignment
A
7. Which of the following is not a method of

SECTION - A concentration of ores? [NCERT Pg. 153]
NCERT Based MCQs (1) Magnetic separation
1. The incorrect statement about refining of copper by (2) Hydraulic washing
electrolysis is [NCERT Pg. 164] (3) Froth floatation method
(1) CuSO4 15% solution and H2SO4 5% is used (4) Distillation
as electrolyte 8. The boiling point of zinc is 907ºC and cadmium is
767ºC. Separation of Zn and Cd is done by
(2) Pure copper act as anode and blister copper
[NCERT Pg. 164]
used as cathode
(1) Distillation (2) Liquation
(3) More electropositive impurities like Fe, Zn, Ni
(3) Vacuum heating (4) All of these
dissolves in solution
9. Roasting is the process of heating the ore in
(4) Less electropositive impurities like, Ag, Au, Pt
[NCERT Pg. 155]
collected below anode and called as anode mud
(1) Presence of inert gas
2. The ore which does not contain iron is
(2) Regular supply of air
[NCERT Pg. 152]
(3) Absence of oxygen
(1) Siderite (2) Haematite
(4) Presence of a suitable reducing agent
(3) Malachite (4) Magnetite
10. In the electrometallurgy of aluminium, the anode
3. The process of leaching cannot be done for the
used is [NCERT Pg. 163]
extraction of [NCERT Pg. 154]
(1) Graphite (2) Steel
(1) Al (2) Ag
(3) Nickel (4) Platinum
(3) Au (4) Na
11. Which of the following match is not correct for the
4. The Slag obtained during the smelting process in refining of given metals? [NCERT Pg. 165]
the extraction of copper from copper pyrites is
(1) Ni : Mond’s process
[NCERT Pg. 156]
(2) Ga : Zone refining
(1) Cu2S (2) FeSiO3
(3) Ti : Van Arkel method
(3) CuSiO3 (4) SiO2
(4) Si : Electrolysis
5. In Hall-Heroult process, CaF2 is used
12. In the extraction of copper, the solidified copper
[NCERT Pg. 163] has blistered appearance due to [NCERT Pg. 162]
(1) As filler in process (1) Vigorous heating of copper ore
(2) To reduce boiling point of Al2O3 (2) Impurities present in copper
(3) To reduce melting point of Al2O3 (3) Evolution of SO2 gas
(4) To decrease electrical conductance (4) Evolution of NO2 gas
6. The incorrect statement about metallurgy of iron is 13. The metal which can be refined by liquation is
(1) In blast furnance C is oxidised to CO2 and (1) Tin (2) Zinc
CO2 is reduced to CO by C (3) Sodium (4) Silicon
(2) Haematite is reduced by CO 14. The metal which is not present in german silver is
(3) The slag formed is FeSiO3 [NCERT Pg. 167]
(4) The final product obtained in blast furnance is (1) Ag (2) Cu
pig iron (3) Zn (4) Ni
15. The most common method employed for the 5. For which of the following reaction G° versus
extraction of zinc is [NCERT Pg. 162] temperature have negative slope?
(1) Roasting followed by reduction with coke
(2) Electrolysis (1) C(s)  O2 (g)  CO2 (g)
(3) Calcination followed by oxidation
1
(4) Reduction of the oxide with CO and coke in (2) CO(g)  O2 (g)  CO2 (g)
blast furnace 2
SECTION - B 1
(3) C(s)  O2 (g)  CO(g)
2
1. Which of the following does not contain (4) Mg(s)  O2 (g)  MgO(s)
magnesium? 6. Thomas slag is
(1) Carnallite (1) Calcium silicate
(2) Dolomite (2) Calcium phosphate
(3) Magnesite (3) Tricalcium phosphate and calcium silicate
(4) Malachite (4) Calcium ammonium phosphate
2. Correct match among the following are 7. Which of the following reaction occur in reverberatory
furnace?
Column I Column II

a. Frothers (i) KCN (1) CuCO3 . Cu(OH)2  2CuO  H2 O  CO2
b. Depressant (ii) K-ethyl xanthate 
(2) 2PbS  3O2   2PbO  2SO2
c. Collectors (iii) CaCO3

d. Basic flux (iv) Pine oil (3) ZnS  2O2   ZnSO4
(1) a(i), b(iii), c(iv), d(ii) (4) All of these

(2) a(iv), b(i), c(ii), d(iii) 8. Correct for the following graph is/are
(3) a(iv), b(ii), c(iii), d(i)
(4) a(i), b(iii), c(ii), d(iv)
2 Al2O3
3. Purification of bauxite ore containing chief 4 Al + O2  3
impurities of Fe2O3 can be done by 3
G° gO
O  2M
+
2Mg
2
(1) Bayer’s process (2) Serpeck’s process
(3) Hall’s process (4) All of these
4. For the following reaction 1673
T (K)
4Ag  8NaCN  2H2 O  O2  A
(complex)
(1) Mg will be good reducing agent below 1673 K

Zn

 B  Ag  (2) Al will be good reducing agent below 1673 K
(complex )
(3) Al2O3 will be good reducing agent after 1673 K
Correct for the above reaction is/are
(4) Both (1) & (3)
(1) Co-ordination number is 4 in complex B
9. Which of the following metals is not extracted by
(2) Process is oxidation-reduction electrolysis?
(3) Complex ‘A’ is soluble (1) Na (2) Al
(4) All are correct (3) Cu (4) Fe
10. Copper matte is 17. For the removal of basic impurities; flux will be
(1) Cu2S + FeSiO3 (2) Cu2S + FeO (1) Lime
(3) Cu2S + FeS (4) FeSiO3 + Cu (2) Silica
11. Maximum percentage of iron is present in (3) Limestone
(1) Cast iron (2) Pig iron (4) Magnesite
(3) Wrought iron (4) Steel 18. (a) Cryolite lowers the melting point of alumina.
12. Reactions occurs in the blast furnace during the (b) Cinnabar may reduced to mercury during
extraction of Fe are roasting.
 1073 K (c) Chromite ore can be separated from silica by
(1) Fe2O3  3CO  2Fe  3CO2
magnetic separation method.
 1073 K Correct statement is/are
(2) Fe2O3  3C  2Fe  3CO
(1) a & c (2) a, b & c
(3) CaO  SiO2  CaSiO3 (3) b only (4) c only
(4) All of these
19. Ag  NaCN  H2O  O2  Soluble complex
 0.5%  'A'
13. Incorrect match among the following are
Zn
a. Purification of Ni – Van Arkel method 
 B  Ag
complex
b. Zn, Cd, Hg – Distillation method
Correct for above reaction.
c. Si, Ge, Ga – Zone refining
(1) A = Na [Ag(CN)2]
d. Lanthanoid separation – Chromatography
(2) B = Na2[Zn(CN)4]
(1) b, c only (2) a only
(3) Oxidation-reduction process
(3) c only (4) a, d only
(4) All of these
14. NH3 + Cl2 A + HCl 20. Metal not extracted by self-reduction process:
(excess) H2O (1) Hg
(B) + 3HOCl (2) Pb
H2O + CrCl3 (3) Cu
C (4) Fe
(green ppt.)
21. Correct statement for the following graph is
A, B and C are
(1) A = NH4Cl, B = NCl3, C = H2CrO4 CO 2

1 O 2
(2) A = NCl3, B = N2, C = Cr(OH)3
O + —2
(3) A = N2, B = N2H4, C = H2CrO3 C
Fe + O2  Fe2O3
(4) A = NCl3, B = NH3, C = Cr(OH)3 G° C+
—1
15. Which of the following ore contain both K and Mg? 2 O2 
CO
(g)
(1) Dolomite (2) Carnallite
(3) Malachite (4) Chile saltpeter
1073 K
16. Which of the following is correct for froth-floatation T
method?
(1) Process is applicable for sulphide ore (1) CO will reduce Fe2O3 below 1073 K
(2) Ethyl xanthate act as frother (2) CO2 will oxidise Fe2O3 after 1073 K
(3) NaCN act as depressants (3) Fe2O3 can be reduced by C or CO
(4) Both (1) and (3) (4) Both (1) and (3)
22. Alumino-thermite process is used for reduction 29. In Ellingham diagrams of fG (oxide formation)
of versus temperature (T), which of the following
(1) Pb3O4 (2) Ag2S graphs has negative slope?
(3) Cr2O3 (4) AuCl3 4 2

(1) Al  O2  Al2O3
23. Which of the following pairs of metal is purified by 3 3
vapour-phase refining? (2) 2Mg  O2  2MgO
(1) Ni and Zr
(3) 2CO  O2  2CO2
(2) Ge and Ti
(3) Zr and Ti (4) 2C  O2  2CO
(4) Both (1) and (3) 30. Which of the following is not a concentration
24. On heating a mixture of Cu2O and Cu2S, product technique?
obtained is (1) Leaching
(1) Cu + SO2 (2) Hydraulic washing
(2) Cu + SO3 (3) Froth floatation process
(3) CuO + CuS (4) Chromatographic method
(4) CuO 31. Which of the following statement(s) is/are correct?
25. Which of the following is not correctly matched? (1) Elements used as semiconductor are purified
(1) Pyrolusite — MnO2 by zone refining.
(2) Mohr’s salt — FeSO4.(NH4)2 SO46H2O (2) Wrought iron is purest form of iron with
respect to other forms.
(3) Cinnabar — HgS
(3) In the manufacturing of iron from haematite,
(4) Azurite — CaCO3·CuCO3 silicon dioxide is added as flux.
26. Which process of purification is represented by (4) Both (1) & (2)
following scheme?
32. Which of the following has lowest percentage of
870K
Zr   2I2 (g) 
2070K
 ZrI4 (g)  Zr(s) 2I2 (g)
carbon?
(impure) W filament
(volatile) (pure) (1) Wrought iron (2) Steel
(1) Poling (3) Cast iron (4) Pig iron
(2) Zone refining 33. The common metal in bronze and german silver is
(3) Van Arkel process (1) Cu (2) Mg
(4) Mond’s method (3) Sn (4) Cr
O / Cu S 34. Which of the following processes involves
27. Cu2S 2
 SO

 Cu2O 

2
Cu  SO2 smelting?
2
heat
The above process is called (1) 2PbS + 3O2   2PbO + 2SO2
(1) Roasting as well as auto reduction heat
(2) Al2O3.2H2O   Al2O3 + 2H2O
(2) Only roasting
(3) PbO + C 
 Pb + CO
(3) Only auto reduction
heat
(4) Neither roasting nor auto reduction (4) CaCO3.MgCO3   CaO + MgO + CO2
28. Which of the following acts as depressant in froth 35. Which of the following is the example of auto
floatation process? reduction process?
(1) Cresol (1) 2PbS + PbO  3Pb + SO2
(2) NaCN (2) Cu2S + 2Cu2O  6Cu + SO2
(3) Xanthate (3) 2HgO + HgS  3Hg + SO2
(4) ZnS (4) All of these
36. Which of the following can form slag? 2. Which one is malachite from the following?
(1) MgCO3 & SiO2 [NEET-2019]
(1) CuFeS2 (2) Cu(OH)2
(2) SiO2 & CaO
(3) Fe3O4 (4) CuCO3.Cu(OH)2
(3) FeO & SiO2
3. Considering Ellingham diagram, which of the
(4) All of these
following metals can be used to reduce alumina?
37. Select the incorrect statement. [NEET-2018]
(1) Roasting is a process in which the ore is (1) Fe (2) Zn
heated in presence of air
(3) Cu (4) Mg
(2) Carnallite is a mineral of magnesium
4. Extraction of gold and silver involves leaching with
(3) All minerals are ores CN– ion. Silver is later recovered by [NEET-2017]
(4) Metals of high purity are obtained by zone (1) Liquation (2) Distillation
refining (3) Zone refining (4) Displacement with Zn
38. Which of the following metal is purified by 5. Match items of Column I with the items of
distillation process? Column II and assign the correct option:
(1) Zn (2) Fe
Column I Column II
(3) Al (4) Cu
(a) Cyanide process (i) Ultrapure Ge
39. Molecular formula of sphalerite is
(b) Froth floatation (ii) Dressing of ZnS
(1) Cu2S (2) FeS process
(3) SiO2 (4) ZnS (c) Electrolytic (iii) Extraction of Al
reduction
40. Ellingham diagram is a plot of fG° versus ‘T’ for
the formation of (d) Zone refining (iv) Extraction of Au
(v) Purification of Ni
(1) Oxides (2) Carbonates
(3) Sulphates (4) All of these [NEET-2016]
41. Which of the following is/are correct statement(s)? (1) a(iii)b(iv)c(v)d(i) (2) a(iv)b(ii)c(iii)d(i)
(1) Sulphide ores are concentrated by froth (3) a(ii)b(iii)c(i)d(v) (4) a(i)b(ii)c(iii)d(iv)
floatation process 6. Aluminium is extracted from alumina (Al2O3) by
(2) Nickel is purified by Mond’s process electrolysis of a molten mixture of
(3) Wolframite and cassiterite are concentrated by [AIPMT (Prelims)-2012]

magnetic separation method (1) Al2O3 + Na3AIF6 + CaF2
(4) All of these (2) Al2O3 + KF + Na3AIF6
(3) Al2O3 + HF + NaAIF4
SECTION - C
(4) Al2O3 + CaF2 + NaAIF4
Previous Years Questions 7. In the extraction of copper from its sulphide ore, the
metal is finally obtained by the reduction of cuprous
1. Identify the incorrect statement. oxide with [AIPMT (Prelims)-2012]
(1) Gangue is an ore contaminated with undesired (1) Iron sulphide (FeS)
materials
(2) Carbon monoxide (CO)
(2) The scientific and technological process used
for isolation of the metal from its ore is known (3) Copper () sulphide (Cu2S)
as metallurgy (4) Sulphur dioxide (SO2)
(3) Minerals are naturally occurring chemical 8. Identify the alloy containing a non-metal as a
substances in the earth's crust constituent in it [AIPMT (Prelims)-2012]
(4) Ores are minerals that may contain a metal
(1) Bell metal (2) Bronze
(3) Invar (4) Steel
9. Which one of the following is a mineral of iron ? 15. Sulphides ores of metals are usually concentrated
[AIPMT (Prelims)-2012] by Froth Floatation process. Which one of the
following sulphides ores offers an exception and is
(1) Pyrolusite (2) Magnetite concentrated by chemical leaching ?
(3) Malachite (4) Cassiterite [AIPMT (Prelims)-2007]
10. Which of the following pairs of metals is purified by (1) Sphalerite (2) Argentite
Van Arkel method? [AIPMT (Prelims)-2011]
(3) Galena (4) Copper pyrite
(1) Ni and Fe (2) Ga and In
16. The mass of carbon anode consumed (giving only
(3) Zr and Ti (4) Ag and Au carbondioxide) in the production of 270 kg of
11. Which of the following elements is present as the aluminium metal from bauxite by the Hall process
impurity to the maximum extent in the pig iron? is (Atomic mass Al= 27)
[AIPMT (Prelims)-2011] [AIPMT (Prelims)-2005]
(1) Phosphorus (2) Manganese (1) 180 kg (2) 270 kg

(3) 540 kg (4) 90 kg
(3) Carbon (4) Silicon
Questions asked Prior to Medical Ent. Exams. 2005
12. The following reactions take place in the blast
furnace in the preparation of impure iron. Identify 17. In which of the following process fused sodium
the reaction pertaining to the formation of the slag chloride is electrolysed for extraction of sodium?
[AIPMT (Mains)-2011] (1) Castner process
(1) CaO(s) + SiO2(s)  CaSiO3(s) (2) Cyanide process
(2) 2C(s) + O2(g)  2CO(g) (3) Down's process
(3) Fe2O3(s) + 3CO(g)  2Fe(l) + 3CO2(g) (4) Both (2) & (3)
18. Which of the following does not contain
(4) CaCO3(s)  CaO(s) + CO2(g)
aluminium?
13. Match List-I (substances) with List-II (process)
(1) Cryolite (2) Fluorspar
employed in the manufacture of the substances and
select the correct option (3) Feldspar (4) Mica
List - I List - II 19. Which of the following does not contain Mg?
(Substances) (Processes) (1) Magnetite (2) Asbestos
a. Sulphuric acid (i) Haber's process (3) Magnesite (4) Carnalite
b. Steel (ii) Bessemer's 20. Carborundum is
process (1) CaC2 (2) CaCO3
c. Sodium hydroxide (iii) Leblanc process
(3) Fe3C (4) SiC
d. Ammonia (iv) Contact process
21. Bessemer converter is used for manufacture of
[AIPMT (Mains)-2010]
(1) Steel (2) Wrought iron
(1) a(i), b(iv), c(ii), d(iii) (2) a(i), b(ii), c(iii), d(iv)
(3) Pig iron (4) Cast iron
(3) a(iv), b(iii), c(ii), d(i) (4) a(iv), b(ii), c(iii), d(i)
22. Mond's process is used for
14. Which of the following statements, about the
(1) Ni (2) Al
advantage of roasting sulphide ore before reduction
is not true? [AIPMT (Prelims)-2007] (3) Fe (4) Cu
(1) Roasting of the sulphide to the oxide is 23. Which process of purification is represented by
thermodynamically feasible following scheme?
250ºC 1400ºC
(2) Carbon and hydrogen are suitable reducing Ti  2I2   TiI4   Ti  2I2
(Impure) (Pure)
agents for metal sulphides
(1) Poling
(3) The fG of the sulphide is greater than those
for CS2 and H2S (2) Electro refining
(4) The fG is negative for roasting of sulphide ore (3) Zone refining
to oxide (4) van Arkel process
24. Which of the following sulphides when heated 36. Roasting of sulphides gives the gas X as a by-
strongly in air gives the corresponding metal? product. This is a colorless gas with choking smell
(1) CuS (2) Fe2S3 of burnt sulphur and causes great damage to
respiratory organs as a result of acid rain. Its
(3) FeS (4) HgS aqueous solution is acidic acts as a reducing
25. Most important ore of tin is agent and its acid is known only in solution. The
(1) Cassiterite (2) Cryolite gas X is
(3) Malachite (4) All of these (1) SO2 (2) CO2
26. Heating of ore in presence of air to remove sulphur (3) SO3 (4) H2S
impurities is called 37. Which of the following mineral contains calcium as
(1) Calcination (2) Roasting well as magnesium?
(3) Smelting (4) None of these (1) Tridymite (2) Aragonite
27. Sodium is extracted from (3) Dolomite (4) Carnalite
(1) NaCl(aq) (2) NaCl(l)

SECTION - D
(3) NaOH(aq) (4) NaNO3(aq)
28. Among the metals, the one that cannot be NEET Booster Questions
obtained by reduction of its metal oxide
(1) Cr (2) Fe 1. Calamine is an ore of
(3) Mn (4) Mg (1) Zn (2) Mg
29. Which of the following is used as depressant in the (3) Ca (4) Pb
separation of mixture of PbS and ZnS? 2. NaCN is added in the froth floatation process as a
(1) NaCN (2) NaCl depressant during metallurgy of galena, whereas
unwanted ZnS is present as impurity, because
(3) AgCl (4) All of these
30. Which contains both iron and copper? (1) Pb(CN)2 is precipitated while no effect on ZnS
(1) Cuprite (2) Chalcocite (2) ZnS forms soluble complex Na2[Zn(CN)4] while
PbS forms froth
(3) Chalcopyrite (4) Malachite
(3) PbS forms soluble complex Na2[Pb(CN)4] while
31. To dissolve argentite ore which of the following is
ZnS forms froth
used?
(4) NaCN is never added in froth flotation process
(1) Na[Ag(CN)2] (2) NaCN
3. Selection of temperature to carry out a reduction
(3) NaCl (4) HCl
process depends so as to make :
32. Iron obtained from blast furnace is
(1) G negative (2) G positive
(1) Wrought iron (2) Cast iron
(3) H negative (4) H positive
(3) Pig iron (4) Steel
4. Which of the following metal is obtained by self
33. Elements used as semiconductor are purified by reduction process?
(1) Van Arkel method (1) Copper (2) Iron
(2) Mond process
(3) Aluminium (4) Magnesium
(3) Distillation
5. In the leaching of Ag2S with NaCN, a stream of air
(4) Zone refining is also passed. It is because of
34. Which of the following oxide is least stable? (1) Reversible nature of reaction between Ag2S
(1) CO2 (2) CO and NaCN
(3) MgO (4) HgO (2) To oxidise Na 2 S formed into Na 2SO 4 and
35. The inner layer of a blast furnace is made of sulphur
(1) Graphite bricks (2) Silica bricks (3) To make Ag2S insoluble
(3) Basic bricks (4) Fireclay bricks (4) Both (1) & (2)
6. In electrolysis of Al2O3 by Hall Heroult process 13. Which method of purification is represented by the
(1) Cryolite Na3[AlF6] lowers the melting point of equation?
Al2O3 and increases its electrical conductivity 500 K
Ti + 2I2  TiI4 1675

K
 Ti + 2I2
(2) Al is obtained at cathode and O2 at anode
(Impure) (Pure)
(3) Graphite anode is converted into CO2
(1) Cupellation (2) Poling
(4) All of these
(3) van Arkel method (4) Zone refining
7. Poling process
14. In the alumino-thermite process, Al acts as
(1) Reduces SnO2 to Sn
(1) An oxidising agent (2) A flux
(2) Involves purification of metals containing their
own oxides (3) Solder (4) A reducing agent
(3) Uses green poles 15. Which of the following elements constitutes a
major impurity in pig iron?
(4) All of these
(1) Carbon (2) Oxygen
8. High purity copper metal is obtained by
(3) Sulphur (4) Silicon
(1) Carbon reduction
(2) Hydrogen reduction 16. Cinnabar is the ore of
(3) Electrolytic reduction (1) Zn (2) Cd
(4) Thermite reduction (3) Hg (4) Ag

9. The zone refining of metal is based on the 17. Froth floatation process for the concentration of
principle of sulphide ore is an illustration of the practical
application of
(1) Greater mobility of pure metal than that of
impurity (1) Adsorption (2) Absorption
(2) Higher melting point of the impurity than that (3) Sedimentation (4) Coagulation
of the pure metal 18. In which of the following metallurgy, no reducing
(3) Greater noble character of the solid metal than agent is required?
that of the impurity (1) Mercury from cinnabar
(4) Greater solubility of the impurity in the molten (2) Zn from zinc blende
state than in the solid
(3) Iron from haematite
10. During the process of electro-refining of copper
some metals present as impurity settle as anode (4) Aluminium from bauxite
mud, may contain 19. The technique used to separate relatively
(1) Sn and Ag chemically unreactive metals such as Ag, Au, Pt
and Pd from impurities by blast of hot air at higher
(2) Pb and Zn
temperature is called
(3) Ag and Au
(1) Liquation (2) Distillation
(4) Fe and Ni
(3) Zone refining (4) Cupellation
11. The slag consists of molten impurities, generally in
the form of 20. In zone refining method, the molten zone
(1) Metal carbonate (1) Consists of impurities only
(2) Metal silicate (2) Contains more impurity than the original metal
(3) Metal oxide (3) Contains the purified metal only
(4) Metal nitrate (4) Moves to either side
12. During extraction of iron from haematite, which of 21. In the electrolytic refining of copper, Ag and Au can
the following acts as flux? be found
(1) Silica (2) Calcium silicate (1) On anode (2) In electrolyte solution
(3) Limestone (4) Coke (3) In anode mud (4) In cathode mud
22. The function of fluorspar (CaF2) in the electrolytic 29. Match the column:
reduction of alumina is (A) Cinnabar (i) Zn
(1) As a catalyst
(B) Calamine (ii) Cu
(2) To lower the temperature of the melt and to
(C) Malachite (iii) Hg
make the fused mixture more conducting
(D) Feldspar (iv) K-Al
(3) To decrease the rate of oxidation of carbon at
the anode (A) (B) (C) (D)
(4) All of these (1) (iii) (i) (ii) (iv)
23. Identify the alloy containing a non-metal as a (2) (iii) (ii) (i) (iv)
constituent in it (3) (ii) (iii) (iv) (i)
(1) Invar (2) Steel (4) (iv) (i) (iii) (ii)
(3) Bell metal (4) Bronze 30. In serpeck process by-product obtained in
24. The element which is not present in the alloy, purification of bauxite is
german silver, is
(1) Al2O3 (alumina) (2) N2
(1) Cu (2) Ag
(3) NH3 (4) CaSiO3
(3) Zn (4) Ni
31. In which metallurgical process metal is obtained in
25. Which is correct as per the Ellingham diagram? fused state?
(1) More negative the G° of oxide formation of a (1) Smelting (2) Roasting
metal, more is the stability of the oxide
(3) Calcination (4) Froth floatation
(2) More negative the G° of oxide formation of a
metal, better is the reducing property of the 32. List-I List-II
metal (P) [M(CN)2]– (A) Ni (during refining
(3) Gº vs T plot representing the change C  Metal)
CO goes downward (Q) [M(CO)4] (B) Ti (during refining
(4) All of these Metal)
26. Consider the following reaction at 1100°C (R) Ml4 (C) Pb (during roasting
(i) 2C + O2  2CO; G = –460 kJ/mol of ore)
(ii) 2Zn + O2  2ZnO; G = –360 kJ/mol (S) MO (D) Ag (during leaching
Based on these, select the correct alternative of ore)
(1) Zinc can be oxidised by CO (P) (Q) (R) (S)
(2) Zinc oxide can be reduced by carbon (1) (D) (A) (B) (C)
(3) Both (1) and (2) are correct (2) (D) (B) (A) (C)
(4) Both (1) and (2) are incorrect (3) (C) (A) (B) (D)
27. Heating mixture of Cu2O and Cu2S will give (4) (A) (B) (D) (C)
(1) Cu + SO2 33. Consider the following reactions:
(2) Cu + SO3 
2XS + 3O2   2XO + 2SO2
(3) CuO + CuS

2XO + XS 
(4) Cu2SO3  3'X' + SO2
28. Thomas slag is Then 'X' can not be:
(1) Ca3(PO4)2·2H2O (1) Hg
(2) Ca3(PO4)2·CaSiO3 (2) Pb
(3) MgSiO3 (3) Zn
(4) CaSiO3 (4) No such metal exists
34. Which of the following statement is not correct? 43. Zincite and calamine respectively are
(1) In froth floatation process, pine oil decreases (1) Oxide and carbonate ore of Zn
the surface tension of the solution (2) Carbonate and oxide ore of Zn
(2) In poling refining, non volatile oxides are (3) Oxide and sulphate ore of Zn
removed as scum
(4) Sulphate and sulphite ore of Zn
(3) Dolomite ore can be considered as ore of both
44. Which of the following is chalcopyrite?
Ca and Mg
(1) CuFeS2 (2) FeS2
(4) Aqueous Al2(SO4)3 is used for electrorefining of
Al (3) KMgCl2.6H2O (4) Al2O3.2H2O
35. Correct complex formed in the given methods are 45. The alloy used in dental filling contains
(1) Cyanide process: [Ag(CN)2]– (1) Ag and Sn (2) Ag and Sb
(2) Mond's process: Ni(CO)4 (3) Hg, Ag and Sn (4) Hg, Ag and Sb
(3) Photographic fixed process: [Ag(S2O3)2]3– 46. What is the slag formed from P 2O5 impurity in
metallurgy of iron?
(4) All of these
(1) Ca3(PO4)2 (2) CaSiO3
36. A substance which reacts with gangue to form
fusible material is called (3) Fe3(PO4)2 (4) FeSiO3
(1) Flux (2) Catalyst 47. Which of the following oxides is thermally least
stable?
(3) Ore (4) Slag
(1) CaO (2) Al2O3
37. Cyanide process is used for the extraction of
(3) Fe2O3 (4) Ag2O
(1) Au (2) Cu
48. Thomas slag is
(3) Zn (4) Fe
(1) Calcium carbonate
38. Calcination is the process of
(2) Anode mud
(1) Heating the ore in presence of air
(3) FeSiO3
(2) Heating the ore in absence of air
(4) Calcium phosphate
(3) Heating of reduced metal in vacuum
49. Which of the following metals can be extracted
(4) Heating of ore in presence of N2 without using reducing agent?
39. Which of the following is not a concentration (1) Sn (2) Pb
technique?
(3) Fe (4) Both (1) & (2)
(1) Levigation (2) Froth- flotation
50. Which of the following metals is extracted by using
(3) Leaching (4) Calcination coke and carbon monoxide as reducing agent?
40. The ores that are generally concentrated by Froth (1) Na (2) Cu
flotation method are
(3) Fe (4) Al
(1) Carbonate (2) Sulphides
51. Which of the following metals is extracted by the
(3) Oxides (4) Phosphates use of cyanide solution?
41. In blast furnace, iron oxide is reduced by (1) Pb (2) Zn
(1) Silica (2) CO (3) Mn (4) Ag
(3) H2S (4) Limestone 52. Electrolytic reduction method is used for extraction
42. The silver complex formed during cyanide process is of
(1) Na2[Ag(CN)] (1) Highly electronegative elements
(2) Na[AgCN] (2) Transition metals
(3) Na2[Ag(CN)2] (3) Highly electropositive elements
(4) Na[Ag(CN)2] (4) Metalloids
53. Which of the following metals is not, usually, 57. Which of the following statement is incorrect?
extracted by carbon reduction process? (1) Usually, Al2O3 cannot be reduced into Al by
(1) Pb Cr2O3
(2) Al (2) Ca is stronger reducing agent than Mg
(3) Fe (3) At 673 K, CO is poor reducing agent than
(4) Zn carbon
54. What will happen, if anode is made of nickel (4) CO is used for reducing Fe2O3
instead of graphite in the extraction of aluminium 58. By which process zinc is extracted from zinc
from AlCl3? blende?
(1) Nickel will be affected by high temperature (1) Electrolytic reduction
(2) Nickel will combine with Cl2 (2) Roasting followed by reduction with carbon
(3) Nickel is insulator (3) Calcination followed by reduction with
(4) All of these carbon
55. When molten NaCl is electrolysed by using inert (4) Roasting followed by self reduction
electrode, the product obtained at cathode is
59. Which of the following is not a refining process?
(1) Na
(1) Mond’s process
(2) Cl2
(2) van-Arkel process
(3) H2
(3) Poling
(4) Na-Hg amalgam
(4) Leaching
56. Which of the following will give respective metal by
self reduction? 60. From gold amalgam, gold may be recovered by
(1) PbS (1) Distillation
(2) HgS (2) Oxidation
(3) ZnS (3) Electrolytic refining
(4) Both (1) & (2) (4) Dissolving in HNO3

Chapter 23
The p-Block Elements

Chapter Contents
z Introduction Introduction
The elements in which last electron enters into p-subshell are called as
z Boron Family p-block elements. The number of p-orbitals are three and, therefore, the
maximum number of electrons that can be accommodated in a set of
z Group 14 Elements: p-orbitals is six, hence p-block contains six groups. The general
The Carbon Family electronic configuration of these elements is ns2np1 – 6 (except for He).
p-block elements can be either metals, metalloids or non-metals.
z Group 15 Elements: Maximum oxidation state shown by p-block elements is equal to the
Nitrogen Family sum of valence electrons (i.e., sum of s-and p-electrons) or the group
number minus 10 known as group oxidation state.
z Group 16 Elements: Absence of d-orbitals in the elements of second period and presence
Oxygen Family of d- and f-orbitals in rest of elements have significant effects on
the properties as a result lower oxidation state will be more stable.
z Group 17 Elements : This effect is known as inert pair effect.
Halogen Family Boron (of group 13) forms three covalent bonds in its compounds
hence need two more electrons to complete its octet, hence its
z Group 18 Elements : compounds are electron deficient or Lewis acid.
Noble Gases Carbon (of group 14) occurs both in free state and combined state
in nature. All living systems contain carbon. Carbohydrates, fats,
proteins, vitamins, hormones, nucleic acids etc. all contain carbon.
The first member of each of these groups also displays the ability of
forming p-p bonds to itself (C=C, CC, NN) and also to other
elements of second period (C=O), CN, N=O and so on).
Nitrogen (of group 15) occurs as adiatomic gas N2 it makes about
78% by volume of the atmosphere N2 mainly occurs as nitrates
NaNO3 (Chile-saltpetre) and KNO3 (Indian saltpetre). Nitrogen is the
essential constituents of proteins, amino acids and nucleus acid.
Group 16 are also called chalcogens (ore forming) O, S are typical
non-metals, Se, Te are metalloids and Po is metallic and radioactive.
Group 17 are known as halogens (sea salt forming) F2, Cl2, Br2, I2
and astatine are all non-metallic elements.
Group 18 consists of six monoatomic gases i.e., helium (He), Neon
(Ne), Argon (Ar), Krypton (Kr), Xenon (Xe) and Radon (Rn). Except Rn
other gases are known as Rare gases. These gases do not show
reactivity at ordinary temperature and are known as Inert gases.
108 The p-Block Elements NEET
Table : General Electronic Configuration and Oxidation States of p-Block Elements

Group 13 14 15 16 17 18
2 6
ns np
General electronic configuration 2
ns np
1
ns2np2
2
ns np
3
ns np
2 4
ns2np5 (1s2 for He)
First member of the group B C N O F He
Group oxidation state +3 +4 +5 +6 +7 +8
Other oxidation state +1 +2, –4 +3, –3 +4, +2, –2 +5, +3, +1, –1 +6, +4, +2
BORON FAMILY
Group III A contains six elements : boron, aluminium, gallium, indium, thallium and ununtrium. The penultimate
shell (next to the outermost) conains 1s 2 in boron, 2s 2 2p 6 (8 electrons) in aluminium and
(n – 1)s2 (n – 1)p6 (n – 1)d10 (18 electrons) in other elements. This shows why boron differs from aluminium
and both boron and aluminium having noble gas kernel differ from other four elements.
Boron is a non-metal and always form covalent bonds. Boron family is known as most heterogeneous family
as there is no regular trend in all properties, as it comes after d-block, lanthanoid contraction, poor shielding
of d-orbital, they have large deviation in properties.
The heavier members of this group show inert pair effect. Boron compounds, especially the hydrides are
electron deficient compounds which can accept a lone pair of electrons hence behave as Lewis acids.
Physical Properties
General electronic configuration is ns2np1.
Atomic Number Atomic Radii Element Configuration Metallic Character

2 1
5 85 pm B [He] 2s 2p Non-metal
2 1
13 143 pm Al [Ne] 3s 3p Metal
10 2 1
31 135 pm Ga [Ar] 3d 4s 4p Metal
10 2 1
49 167 pm In [Kr] 4d 5s 5p Metal
14 10 2 1
81 170 pm Tl [Xe] 4f 5d 6s 6p Metal
Decrease in metallic character in gallium is because of shielding effect. In Gallium 10 electrons are filled in
d orbitals hence have less shielding so size decreases and metallic character decreases.
Aluminium is most metallic among boron family due to its least electronegativity.
Atoms B Al Ga In Tl
Electronegativity 2 1.5 1.6 1.7 1.8
Due to poor shielding of 3d and 4d and

lanthanoid contraction.
Atomic Size
Atomic size of boron family is smaller than alkaline and larger than carbon family. Down the group atomic
size increases irregularly. Gallium is smaller than aluminium due to poor shielding of 3d orbital.
Ionization Energy : Ionization enthalpy, the general trend do not decrease smoothly down the group.
Ionization energy decreases from B to Al, but increases from Al to Ga.
NEET The p-Block Elements 109
Element First Ionization energy in kJ/mole

Boron 801
Aluminium 577
Gallium 579
Indium 558
Thallium 589
Decreasing order of 1st ionization energy is as follows

B > Tl > Ga > Al > In
Oxidation States
Oxidation states are possible from +3 to –5. Stability of +3 oxidation state decreases down
the group due to inert pair effect, as well as stability of +1 oxidation state increases.
Note : Indium in +1 oxidation state is reducing agent.
Chemical Properties
1. Reactivity towards air
Amorphous boron and aluminium metal on heating in air forms trioxide and forms nitride at very high
temperature. Gallium and indium are not affected with air while thallium does.
B2O3  Acidic oxide
Al2O3  Amphoteric oxide
Ga2O3  Amphoteric oxide
In2O3  Basic oxide
Tl2O3  Basic oxide

4E(s)  3O2 (g)  2E2O3 (s)

2E(s)  N2 (g)  2EN(s) (Where E = B, Al, Ga, In, Tl)
B2O3 is called boric anhydride as it is anhydride of boric acid.

2. Reactivity towards acids
Boron is not affected by acids agents like HCl and dil. H2SO4 while all other elements react with conc.
H2SO4 and HNO3. Ga and Al develop protective layer of oxide with conc. HNO3.
2 Al(s)  6HCl(aq)  2 Al3  (aq)  6 Cl (aq)  3H2 (g)
2B(s)  3H2SO4 (aq)  2H3BO3  3SO2 (g)
B(s)  3HNO3 (aq)  3H (aq)  BO33 (aq)  3NO2 (g)
3. Reactivity towards alkalies

Except indium and thallium all other elements react with alkali solutions
2M(s)  2NaOH(aq)  2H2O 
 2NaMO2 (s)  3H2 (g) (M = Al or Ga)
Example, Al also reacts with aq. Alkali and liberates dihydrogen.
2 Al(s)  2NaOH(aq)  6H2O(l)  2Na [Al(OH)4 ] (aq)  3H2 (g)

Sodium tetrahydroxoaluminate (III)
4. Reactivity towards halogens

Trihalides are formed when these elements react with halogens. All these halides exist as discrete
molecular species which are sp2 hybridised and covalently bonded. TlI3 is unstable.
AlCl3 achieves stability by forming a dimer.
Cl 20 Cl 22 Cl
6p 1
m pm
101º
Al 79º Al 118º
Cl Cl Cl
Acidic strength is inversely proportional to back-bonding, as back-bonding decreases from BF3 to BI3 as given
below
BF3 > BCl3 > BBr3 > BI3
Hence, Lewis acidic strength will increase as under
BF3 < BCl3 < BBr3 < BI3
p-p back-bonding is strongest in BF3 because both B and F involve 2p orbital in back-bonding.
IMPORTANT TRENDS AND ANOMALOUS PROPERTIES OF BORON

Trihalides of these elements are covalent in nature and are hydrolysed in water and produces species like
tetrahedral [M(OH)4]– and octahedral [M(H2O)6]3+ except in boron.
 
NH3  BF 3 H3N BF3  NH3 BF3
In this reaction, hybridisation of BF3 changes to sp3 as one more bond is formed with nitrogen. Here shape
changes to tetrahedral (irregular).
BF3  HF  H [BF4 ]
In above reaction, [BF4]– is having sp3 hybridisation with tetrahedral geometry.

Due to absence of d-orbital maximum covalency of B is 4 while other elements of that group have d-orbitals
hence, maximum covalency can be expected beyond 4.
Borax is a white crystalline solid and can be prepared by boric acid.
4H3BO3  Na2 CO3  Na2B 4 O7  6H2O  CO2 
Example 1 : Give electronic configuration of Ga.

Solution : Group configuration is ns2np1
Ga is in 4th period
Hence, electronic configuration is 4s24p1
Example 2 : Why boron compounds behave as lewis acid?
Solution : Boron compounds have three covalent bonds hence, require two electrons to complete octet hence,
electron deficient compounds.
Example 3 : Write oxidation state of boron family.
Solution : Group oxidation state of boron family is +3.
SOME IMPORTANT COMPOUNDS OF BORON

The important minerals of boron are
(i) Borax : Na2B4O7·10H2O
(ii) Colemanite : Ca2B6O11 : 5H2O OH
(iii) Boric acid : H3BO3 B

1
1. Borax O O
Na2B4O710 H2O / Na2 [B4O5 (OH)4]8 H2O 2Na HO B 2 4 B OH  8H O

2
O
Number of B in sp2 hybridisation = 2 (1, 3) O O
3 3
Number of B in sp hybridisation = 2 (2, 4) B
Oxidation state of all boron present = +3 state
OH
n-factor = 2
Number of B—O—B bonds = 5
Number of B—O bonds = 14
Number of bridging oxygen between two boron = 5
It furnishes two OH– from 2nd and 4th, then octet of B cannot be completed. After cleavage it will be
highly unstable structure.
On heating borax first looses water molecules and swells up and gives sodium metaborate which on
further heating turns into a transparent liquid which solidifies into glassy bead.
Pt
Na2B4 O7 10H2O 
loop
 Na2B4 O7  10H2 O NaBO2  B2O3
Anhydrous borax Glassy bead

This glassy bead reacts with CuO or CoO to give blue bead and reacts with TiO to give yellow bead.
Glassy bead  CuO 
 Cu(BO2 )2
Blue bead
Glassy bead  CoO 

 Co(BO2 )2
Blue bead
Glassy bead  TiO 

 Ti(BO2 )2
Yellow bead
2. Orthoboric acid (H3BO3)

It is prepared by treating concentrated sulphuric acid with borax.
Na2B4O7  H2SO4  5H2O 

 Na2SO4  4H3BO3
It is white, soft, needle-like crystals having a soapy touch.

It does not loose 3H+ but accepts one lone pair from H2O, so n-factor = 1. This is a monobasic Lewis
acid as oxygen gives one electron to boron, so it acquires positive charge and becomes unstable, so
it furnishes 1H+ and gets stable.
O H
 + –
H O B + H2O
 H [B(OH)4]
O H
In H [B(OH)4] hybridisation of boron is sp3.
+ –
100C 160 Re d hot

H3BO3   HBO2   H2B4 O7   B 2 O3
Orthoboric Metaboric Tetraboric Boric Oxide
acid acid acid
H
O
H B
O O
H H
O O
H B H H
O O
B O
H H H B
O O O O
H H
Fig. Structure of boric acid; the dotted lines represent hydrogen bonds.
It is used as an antiseptic, in manufacturing of enamels, as food preservative and in glass industry. Boric
acid is layered structure. B(OH)3 units are joined by hydrogen bonds and form two dimensional sheet.
3. Hydrides of boron
B2H6 (Diborane)
Preparations of diborane are :
(i) 3LiAlH4  4BF3 
 2B2H6  3 AlF3  3LiF
(ii) 2NaBH4  I2 
 B2H6  2NaI + H2
450K
(iii) 6NaH  2BF3  B2H6  6NaF
Bonding in diborane:
H H H
H H
H
B B 
120º B 97º B
H
H H H H
H
H 119 H 13 H
pm m 4p m
4p m 9p
13 11
120º B 97º 97º B 120º

m 13 119
4 m
9p pm 4p pm
H 11 H 13 H
It is 3 centre 2 electron bonding called banana bonding or bridge bonding.
Number of atoms present in same plane = 6
Number of terminal hydrogen = 4
Number of bridging hydrogen = 2
Since boranes have vacant p or vacant d-orbitals in central boron atom hence, it reacts with water and
thus shows hydrolysis.
B2H6 (g)  6H2O(l) 

 2B(OH)3 (aq)  6H2 (g)
NH3(Excess)
B 2H 6 + –
B2 H6 ·2NH3 [(H 3N  BH 2  NH 3 ) and BH 4 ]
NH3(Excess)
at high temperature Boron nitride (Inorganic graphite)
B2H6 : NH3 = 1 : 2
at high temperature
B3N3H6 [(Inogranic benzene)
Note :
Diborane is colourless gas and bursts into flame in air and is stable at low temperatures in the absence
of moisture and grease. Boranes either belong to Bn Hn + 4 or Bn Hn + 6 series.
Example 4 : How many B atoms are sp2 hybridised in borax structure?
Solution : 2 (Two)
Example 5 : Give colour of bead when glassy bead reacts with TiO.
Solution : Yellow bead
Example 6 : Why is basicity of orthoboric acid one?
Solution : It does not lose 3H+ while it accepts one lone pair of electrons from H2O.
USES OF BORON AND ALUMINIUM AND THEIR COMPOUNDS
Boron Compounds
Boron is a hard solid having high melting point low density and very low electrical conductivity. Some important
boron compounds are :
(a) Boron fibers : It is mixed with plastic to form a material which is lighter than aluminium but tougher
and stiffer than steel hence it is used in body armour, missiles and aircrafts.
(b) Boron-10 (10B) isotope : Boron carbide rods or boron steel are used to control nuclear reactions as
neutron absorbers.
5B
10
 0n
1  5B
11
(c) Borax : It is used in manufacture of enamels and glazes for pottery and tiles. It is also used in making
optical glasses and also borosilicate glasses which is very resistant to heat and shock. It is used as
an antispectic.
(d) Boric acid : It is used in glass industry, in food industry as preservative. It is also used as an antiseptic
and eye wash under the name ‘boric lotion’. It is also used in manufacture of enamels and glazes for pottery.
Aluminium Compounds
Aluminium and its alloy are used in packing industry, utensil industry, aeroplane and transportation industry etc.
1. Alumina (Al2O3)
(a) Used in chromatography.
(b) Used in making bauxite bricks which are used for lining furnaces.
2. Aluminium chloride (AlCl3)
Used in manufacture of dyes, drugs and perfumes and also in manufacture of gasoline. It is also used
as catalyst in Friedel Craft reaction.
3. Potash Aluminium [K2SO4Al2(SO4)324 H2O] or [KAl(SO4)2.12H2O]
Used in purification of water, leather tanning, as antiseptic and as a mordant.
Note :
z Use of aluminium and its compounds for domestic purposes is now reduced considerably because
of their toxic nature.
z Ultrmarine is a compound of aluminium which is an artificial Lapis-Lazuli (rare mineral having fine
blue colour). It is a complex silicate of sodium and aluminium having 12% of sulphur which is
used in calico printing and in making blue paints.
Example 7 : Why boron fibre is used in body armour?

Solution : On mixing with plastic it forms a material which is lighter than aluminium but tougher and stiffer
than steel hence, used in body armour.
Example 8 : How boron isotope controls nuclear reactions?
Solution : 5B
10
 0n
1  5B
11
Example 9 : Name an aluminium compound that can be used in chromatography.

Solution : Alumina
EXERCISE
1. Number of B–O–B bond in borax is
(1) Four (2) Five
(3) Three (4) Zero
2. Among the group 13 the only element which is non-metallic
(1) B (2) Al
(3) Ga (4) In
3. Products formed are
Polyether
2NaBH4 + I2   
(1) HI, NaI and H2 (2) B2H6, NaI and HI
(3) B2H6, NaI and H2 (4) H3BO3 + H2
4. What is the hybridisation state of B and N in inorganic benzene respectively?
(1) sp2 and sp3 (2) sp3 and sp2
(3) Both have sp2 (4) Both have sp3
5. Which type of hydride is BH3?
(1) Electron deficient (2) Electron precise
(3) Electron excess (4) Lewis base
6. Which one of the following is the correct statement ?
(1) The hydroxide of boron is basic in nature
(2) The hydroxide of boron is neutral in nature
(3) The hydroxide of boron is acidic in nature
(4) Boron shows maximum oxidation state of +1 due to inert pair effect
7. Which of the following statement is correct regarding B2H6?
(1) Each boron atom is sp 3 hybridised
(2) B2H6 is electron deficient
(3) B2H6 has banana bond
(4) All of these
8. Boric acid is polymeric due to
(1) Its acidic nature
(2) The presence of hydrogen bonds
(3) Its monobasic nature
(4) Its geometry
9. Which of the following element has exceptionally high melting point?
(1) Al (2) Ga
(3) B (4) In
10. In which of the following compounds banana bond is present?
(1) BCl3 (2) B2H6
(3) B(OH)3 (4) All of these
GROUP 14 ELEMENTS: THE CARBON FAMILY

Group IV A contains six elements : carbon, silicon, germanium, tin, lead and ununquadium . The penultimate
shell (prior to outermost) contains 1s2-grouping in carbon, 2s22p6 (8 electrons) in silicon and (n – 1)s2 (n –
1)p6 (n – 1)d10 (18 electrons) in other elements. This shows why carbon differs from silicon in some respects
and these two differ from rest of the members of this group.
General electronic configuration is ns2np2.
Silicon is second most abundant element in earth crust (27.7%). Carbon is the seventeenth most abundant
element in earth crust. Carbon is important element of all living organisms. Till yet more than 5 million organic
compounds have been discovered, 40,000 new organic compounds are discovering every year.
Silicon is used in cement, glass, transistors, semiconductors.

Tin is used in alloys.
Tin mainly occurs as cassiterite, SnO2 and lead occurs as galena, PbS.
Germanium is used in transistors.
Lead is used in glass, paints and varnish
Element Electronegativity
C 2.5
Si 1.8
Ge 1.8 three members have
same electronegativity.
Sn 1.8
Pb 1.9
Still properties of silicon differs from germanium due to poor shielding effect of 3d subshell and properties of
germanium differs from tin due to poor shielding effect of 4f subshell (Lanthanoid contraction).
Properties of tin are different from lead due to poor sheilding effect of 5f subshell (Actinoid contraction).
Order of electronegativities is C > Pb > Si = Ge = Sn
All elements of this family except carbon have tendency to show maximum covalency of six due to absence
of vacant d-orbitals.
Note :
Most abundant element in earth crust is oxygen (46.6%) by mass. Second most abundant element is silicon
(27.7%). Third most abundant element is aluminium (8%) and fourth abundant element is iron.
Physical Properties
Atomic Number Element Atomic radii (pm) Electronic configuration Metallic character
2 2
6 C 77 [He] 2s 2p Non-metal
2 2
14 Si 117 [Ne] 3s 3p Non-metal
10 2 2
32 Ge 122 [Ar] 3d 4s 4p Metalloid
10 2 2
50 Sn 140 [Kr] 4d 5s 5p Metals
10 14 2 2
82 Pb 146 [Xe] 5d 4f 6s 6p Metals
The elements of this group form covalent bonds with each other and therefore there are strong binding forces
between their atoms in both solid and liquid states.
Consequently the melting and boiling points of group 14 elements are much higher in comparison to group
13 elements. The atomic radius, ionic radius and density increase when one moves from top to bottom in a
group in periodic table while melting point decreases from B to Ga and then increases from (Ga to In)
Atomic Size
Size of this family is smaller than boron family but larger than nitrogen family, down the group atomic size
increases regularly. There is a considerable increase in covalent radius from C to Si, thereafter from Si to
Pb, a small increase in radius is observed. This is due to the presence of completely filled d & f orbitals in
heavier members.
Ionization Energy
Ionization energy of this group is higher than boron family and lower than nitrogen family. Down the group
ionization energy decreases irregularly.
Element First Ionization energy in kJ/mole

C 1086
Si 786
Ge 760
Sn 707
Pb 715
Decreasing order of first ionization energy is as follows:

C > Si > Ge > Pb > Sn
Large decrease in ionization potential from C to Si is due to increase in size of atom. Ionization energy
decreases from silicon is due to less screening effect of d10 electrons in Ge and Sn, and due to d10f14
electrons in Pb.
Ionization energy increases from Sn to Pb, it increases slightly due to Lanthanide contraction and increase
of 32 units of nuclear charge in Pb over Sn.
Catenation
Catenation power of carbon family is higher than boron family and nitrogen family. Down the group, catenation
tendency decreases.
Catenation tendency is highest in carbon among all elements of family while silicon has second highest
tendency of catenation among all elements of family and the decreasing tendency of catenation is as follows:
C >> Si > Ge  Sn, Pb do not show catenation.
All the elements of the carbon family with the exception of lead exhibit allotropy and this tendency decreases
from C to Pb. It is due to decreasing bond energy.
Bond C—C Si—Si Ge—Ge Sn—Sn

Bond energy (kJ/mol) 348 297 260 240
Chemical Properties
1. Reactivity towards air
All members of this group form monoxide of the general formula MO such as CO, SiO, SnO and PbO.
All members of this group form dioxides of molecular formula MO2 such as CO2, SiO2, GeO2, SnO2 and
PbO2.
CO2 is monomeric, SiO2 is 3-D network solid.
Dioxides (CO2, SiO2 and GeO2) are acidic whereas dioxides (SnO2 and PbO2) and mono-oxides
(SnO and PbO) are amphoteric. Mono-oxide CO is neutral while GeO is distinctly acidic.
2. Reactivity towards water
In this family carbon, silicon and germanium are unaffected by water while lead becomes inert towards
water due to formation of protective oxide film. Tin is converted into tin dioxide and hydrogen gas is
libreated on reaction with steam.

Sn  2H2O(g)   SnO2  2H2
3. Reactivity towards halogen

Element in pure state Type of bonding Melting Point
C Covalent 4100ºC
Si Covalent 1420ºC
Ge Covalent 945ºC
Sn Metallic 232ºC
Pb Metallic 327ºC
On moving down the group from carbon to lead stability of +4 oxidation state decreases while stability
of +2 oxidation state increases and hence decreases oxidising power decreases down the group due
to inert pair effect.
These elements form two types of hallides - MX2 and MX4. Most of the MX4 are covalent. SnF4 and PbF4
are ionic in nature.
Thermal stability decreases with increasing atomic size or molecular mass of tetrahalide or due to
decreasing polarity.
CX4 > SiX4 > GeX4 > SnX4 > PbX4 and
CF4 > CCl4 > CBr4 > CI4
In these componds:
Hybridisation  sp3
Geometry  Regular tetrahedral
Polarity  non-polar
Bond angle  109º 28
PbI4 is not stable as I is strong reducing agent which reduces Pb+4 to Pb+2 and also stability of +4
–
oxidation state of Pb is lesser than +2 state.
Hydrolysis of halides
The chlorides except CCl4 are hydrolysed readily by water
SiCl4  4H2O  Si(OH)4  4HCl

Silicic acid
Hydrolysis of silicon tetrafluoride gives silicic acid and fluorosilicic acid

3 SiF4  4H2O  Si(OH)4  2H2 SiF6
(Silicic acid) (Fluorosilicic acid)
Due to unavailability of vacant d-orbitals, carbon tetrahalides cannot increase its co-ordination number
hence does not form complexes while those having vacant d-orbitals form.
Example 10 : On moving down the group in carbon family stability of group oxidation state +4 decreases why?
Solution : Due to inert pair effect.
Example 11 : SiO2 is solid while CO2 is gas. Why?
Solution : CO2 is monomeric linear structure while SiO2 is 3-D network solid.
Example 12 : Why [SiCl6] – cannot exist?
Solution : Because six large Cl– cannot be accommodated around silicon ion.
Example 13 : Give correct order of increasing first ionization energy in carbon family.
Solution : C > Si > Ge > Pb > Sn
ANOMALOUS BEHAVIOUR OF CARBON

Carbon shows anomalous behaviour due to its smaller size, higher electronegativity, higher ionization enthalpy
and unavailability of d orbitals.
Carbon atom forms double or triple bonds involving p-p bonding. Carbon has also the property to form closed
chain compounds with O, S and N atoms as well as forming p-p multiple bonds with other elements
particularly N, S and O.
When we move down the group size increases and electronegativity decreases hence catenation tendency
decreases. Order is
C >> Si > Ge  Sn
Note :
Carbon has smallest atomic radius, lowest atomic volume and highest melting and boiling points amongst
the elements of group 14. CO2 is a gas while the dioxides of other elements are solids. It has the highest
ionization energy and most electronegative element of group 14. Carbon is the element among the group
which can form maximum number of hydrides and is the only element of group which does not dissolve in
aqueous NaOH to evolve hydrogen gas.
ALLOTROPES OF CARBON
Carbon shows allotropism due to catenation and p-pbond formation. Carbon exists in two allotropic forms
– crystalline and amorphous. The crystalline forms are diamond and graphite while the amorphous forms are
coal, charcoal and lamp-black. The third form is fullerenes discovered by Kroto, Smalley and Curl.
Tin has maximum number of allotropes.
Diamond
In diamond each carbon is joined to other four carbon tetrahedrally and carbon-carbon bond length is 1.54Å
and bond angle is 109º28 having sp3 hybridisation on each carbon. All four electrons in carbon are involved
in bonding hence, it is good conductor of heat but bad conductor of electricity.
It is hardest natural substance known. It is transparent and has a specific gravity 3.52 and its refractive index
is high (2.45).
C C C C 154 pm
C C C C
C C C C
C C C C
Fig. The structure of diamond

Difficult to break due to extented covalent bonding.
Diamond is used for making cutters. Blades of diamond are used in eye surgery and as an abrasive for
sharpening hard tools. Impure diamonds (black) are used in knives for cutting glass.
Graphite
141.5 pm
2
Each carbon is sp hybridised. It has layered structure. These layers
are attracted by van der Waals force. Each carbon has one free
340 pm
electron in p-orbital, so it is a good conductor of electricity. All
electrons get delocalized in one layer and form -bond. Electron
jumps from one orbital to another hence it is a good conductor of
heat and electricity. In graphite carbon-carbon bond length is 141.5
pm and distance between adjacent graphite layer is 340 pm.
Graphite is used as a lubricant at high temperature. Oil gets burn

or denatured at high temperature but graphite does not get denatured
even at high temperature so, preferred over oil and grease.
Fig. The structure of graphite
Note :
z Graphite is of two forms :  and .
z In -graphite, layers are arranged in sequence ABAB... with the third layer exactly above first layer.
z In -graphite, the layers are arranged as ABCABC... the two forms are interconvertible.
z Graphite is thermodynamically more stable than diamond and its free energy of formation is 1.9 kJ less,
than diamond. However entropy of graphite is more than diamond.
Fullerene
It was made as a result of action of a laser beam or strong heating of a sample of graphite in presence of
inert atmosphere. The sooty material mainly contains C60 with C70 (small amount).
Most common fullerene is C60 called Buckminsterfullerene which has football-like structure. It contains 20
hexagonal six-membered ring and 12 pentagonal five-membered ring. Every ring in this structure is aromatic.
It is used to make ball bearings. All the carbon atoms are equal and they undergo sp2 hybridisation. Fullerenes
are the only pure form of the carbon because they have smooth structure without having dangling bonds.
Fig.The structure of C60, Buckminsterfullerene :

Note that molecule has the shape of a soccer ball (football).
Coal
It is the crude form of carbon. It has been formed in nature as a result of slow decomposition of vegetable
matter under the influence of heat, pessure and limited supply of air.
The successive stages of transformation are : peat, lignite, bituminous, steam coal and anthracite.
Bituminous is hard stone, burns with smoky flame. The superior quality is anthracite which burns with
non-smoky flame.
Lamp black or carbon black : It is obtained by burning substances rich in carbon content such as kerosene,
petroleum, turpentine oil, acetylene etc. in a limited supply of air.
Example 14 : Name two elements of carbon family which have nearly same catenation tendency.
Solution : Ge and Sn.
Example 15 : Which element of the carbon family does not dissolve in aqueous NaOH to evolve hydrogen gas?
Solution : Carbon.
Example 16 : Given three reasons for anomalous behaviour of carbon.

Solution : Small size, high electronegativity, unavailability of vacant d-orbitals.
Example 17 : Which is thermodynamically more stable - diamond or graphite?

Solution : Graphite.
Uses of carbon
Graphite : In making lead pencils, electrodes of electric furnances, as a moderator in nuclear reactor, as a
lubricant in machinery.
Charcol : In removing offensive odour from air, in removing fused oil from crude spirit, in decolourising sugar
syrup, in gas masks etc.
Carbon black : For making printing inks, black paints, Indian inks, boot polishes and ribbons of typewriters.
Coal : For the manufacture of coal gas, coal tar, coke and synthetic petrol.
SOME IMPORTANT COMPOUNDS OF CARBON AND SILICON
Carbon Monoxide
Preparation :
(a) Formed due to incomplete combustion of carbon.

2C(s)  O2 (g)  2CO(g)
(b) Dehydration of formic acid.
373 K
HCOOH 
conc. H SO
 H2 O  CO
2 4
(c) Passing steam over coke.

437–1273 K
C(s)  H2O(g)  CO(g) + H2 (g) (Synthesis gas)

Water gas
(d) Passing air over coke.

1273 K
2C(s)  O2 (g)  4N2 (g) 
 2CO(g)  4N2 (g)

Producer gas
It is colourless, odourless and water insoluble and is a strong reducing agent.

CO molecule acts as a donor and reacts with certain metals when heated to form metal carbonyls. It is also
called silent killer because reacts 300 times with haemoglobin than O2.
Carbon Dioxide
It is prepared by
(a) Thermal decomposition of calcium carbonate.

CaCO3  CaO  CO2
(b) Action of calcium carbonate with dil. HCl.
CaCO3 (s)  2HCl(aq) 
 CaCl2 (aq)  CO2 (g)  H2 O(l)
(c) Combustion of carbon containing fuels.


C  O2  CO2

CH4  2O2  CO2  2H2O
It is colourless, odourless and acidic gas as it combines with water to form carbonic acid which helps to
maintain pH of blood. Plants make food from it.
h
6CO2  6H2O 
Chlorophyll
 C6H12O6  6 O2
Green plants convert atmospheric CO2 into glucose (carbohydrates) by photosynthesis. By this process, CO2
is reduced from atmosphere.
If CO2 underpressure is allowed to escape through a nozzle, a white solid is obtained that is called dry ice
or cardice.
It can be used as refrigerant for frozen food or ice cream under the commercial name drikold.
Gaseous CO2 is used in soft drinks it is also used as fire extinguisher as it is non-supporter of combustion
and heavy. With water it gives weak dibasic acid called carbonic acid which dissociates in two steps as below.
HCO3 (aq)  H3 O (aq)

H2CO3 (aq)  H2O(l)
HCO3 (aq)  H2O(l)
CO32 (aq)  H3O (aq)

H2CO3 / HCO3 buffer system helps to maintain pH of blood between 7.26 to 7.42. It combines with alkalies
to form metal carbonates.
Silicon Dioxide
It is commonly known as silica and is nearly non-reactive because of its very high silicon-oxygen bond
enthalpy. It is resistant to acids, halogens, metals and dihydrogen.
It is attacked by HF and NaOH.
SiO2  2NaOH 
 Na2SiO3  H2O
SiO2  4HF  SiF4  2H2O
The entire solid crystal may be considered as giant molecule in which eight-membered rings are formed with
alternate silicon and oxygen atoms.
Uses : SiO2 (silica gel) is used as a drying agent and as a support for chromatographic materials and catalysts.
Kieselghur, an amorphous form of silica is used in filtration plants.
Si O Si O Si O Si
O O O O
Si O Si O Si O Si
Silicones
Alkyl chloride reacts with silicon at 537 K in presence of copper catalyst to give dialkyl dichlorosilane with
other substituted chlorosilane.
Cu powder
2RCl  Si 
570 K
 R2SiCl2
Which on hydrolysis gives dialkyl dihydroxy silane.

 2H O
R2SiCl2  2  R Si(OH)
 2HCl 2 2 (Here R is methyl group)
Which on polymerisation gives silicones.

R R R R R R
Polymerisation
HO Si O H + HO Si O H + HO Si OH Si O Si O Si O
–H2O
R R R R R R
Silicone
Silicones are water repellants, good electrical insulators, stable towards heat, non-toxic resistant to chemicals.
Silicone oils remain viscous at different temperature.
These can be used in surgical and cosmetic plants. It is a polymer having ( Si O )n monomer. It can
be used as lubricant.
Silicates
Oxide anion of silicon is known as silicates.
1. Orthosilicates (SiO4–4 )
O
Si or
O O
O
Here is silicon and is oxygen. Here Si is sp3 hybridised.
Sodium orthosilicate is Na4SiO4 Zirconium silicate is ZrSiO4
Calcium orthosilicate is Ca2SiO4
2. Pyrosilicates ( Si2O76 )
O O
Si Si
O O O
O O
No charge
(Neutral)
Sodium Pyrosilicate is Na6Si2O7 Calcium Pyrosilicate is Ca3Si2O7
Other examples of silicates are cyclic silicate (SiO32 )n , chain silicates (Si2O3 )n2n (Si4 O11 )n6n etc.
Some examples of natural silicates are feldspar, zeolites, mica and asbestos. Synthetic silicates are
glass and cement.
Note :
CLASSIFICATION OF SILICATES
(i) Orthosilicates : These do not share any corner. The anions are discrete SiO44– units.
Examples - Zircon (ZrSiO4) and Forestrite (Mg2SiO4).
(ii) Pyrosilicate : Here, two tetrahedral share one corner to form Si2O76– anion. The structure
posessed by them is called island structure. Example - Thortveitite (Sc2Si2O7).
(iii) Cyclic or ring silicates : Here two corners of each tetrahedron are shared to form closed rings.
The anionic unit are (SiO32–)n. Examples - Wollastonite- Ca3Si3O9, Beryl - Be3Al2Si6O18.
(iv) Chain silicates : Here two corners of each tetrahedron are shared to form a linear chain. The
anionic unit is again (SiO32–)n. Linear silicate chain is present in pyroxenes. Example -
6
Spodumene - LiAl(SiO3)2. If two chains are cross linked, the double stranded silicates (Si 4 O11 )n
are called amphiboles. Example - asbestos.
(v) Sheet silicates : These silicates are formed by the sharing of three corners of each
tetrahedron. The anion has a two dimensional sheet structure with general formula (Si2O52–)n.
Example - Clay
(vi) Three dimensional silicates : These are formed by the sharing of all the four corners.
Example - All the crystalline forms of silica. Example : Zeolites, Feldspar
Tetrahedral unit (ii)

(i)
Cyclic silicate
(iii)
(iv)
Sheet silicate
(vi)
Chain silicate (Pyroxene)
(v)
Zeolites
If Al atoms replace few silicon atoms in 3D-network of SiO2, overall structure known as aluminosilicates
acquires a negative charge.
Cations such as Na+, K+, Ca2+ etc balance the negative charge. e.g., feldspar and Zeolites.
Uses
(i) Softening hard water by ion-exchanging.
(ii) Converting alcohols directly into gasoline (ZSM-5).
(iii) As catalyst in petrochemical industries.
Glass
It is a transparent or translucent amorphous supercooled solid soution of silicates and borates. Its composition
is variable as it is not a true compound it is also referred as pseudo solid.
Example 18 : What is hybridisation of carbon in CO2?

Solution : sp hybridisation.
Example 19 : Write use of silicones.

Solution : Used in surgical and cosmetics.
Example 20 : Why silicon dioxide is non-reactive?

Solution : Due to very high silicon-oxygen bond enthalpy.
EXERCISE
11. Most stable allotrope of carbon thermodynamically is
(1) Fullerene (2) Diamond
(3) Graphite (4) Coke
12. What is the correct order of I.E.?
(1) C < Si < Ge < Pb < Sn
(2) C > Si > Pb > Ge > Sn
(3) C > Si > Ge > Sn < Pb
(4) C > Si > Ge > Sn > Pb
13. In group 14, which element show inert pair effect?
(1) Si (2) Pb
(3) C (4) Ge
14. Which of the following is neutral oxide?
(1) CO
(2) CO2
(3) SiO2
(4) Na2O
15. Which of the following halide cannot hydrolysed?

(1) CCl4 (2) SiCl4
(3) GeCl4 (4) SiF4
16. Which polymorph of carbon act as hardest allotrope?
(1) Diamond
(2) Fullerene
(3) Graphite
(4) All of these
17. SiC is popular with name
(1) Acetylide (2) Methanide
(3) Carborundum (4) Plumbago
18. On heating oxalic acid with H2SO4, we get
(1) H2CO3
(2) CO2 and O2
(3) CO2 and CO
(4) H2CO3 + CO2 + O2
19. Which allotrope of carbon leads to the formation of bucky ball?
(1) Graphite
(2) Diamond
(3) Fullerene
(4) Nano tube
20. Which of the following is correct structure of anion of pyrosilicates?
–
–
(1)
– –
– –
– –
(2)
– –
(3) – –
– –
– –
– –
– –
(4)
– –
– –
GROUP 15 ELEMENTS : NITROGEN FAMILY
General electronic configuration  [inert gas] ns2np3
As exactly half-filled p-orbital, hence electronic configuration is extra stable.
Nitrogen (7N)
Non-metals
Phosphorous (15P)
Arsenic (33As)
Metalloids
Antimony (51Sb)
Bismuth (83Bi) Typical metal
Commonly called Pnictogens means chocking elements.
Occurrence
Nitrogen :
 Atmosphere comprises 78% by volume of N2.
 In form of proteins in plants and animals.
 Earth crust : Chile saltpeter (NaNO3)
Indian saltpeter (KNO3)
Phosphorus :
 Minerals of apatite family [Ca9(PO4)6CaX2]
(X = F, Cl or OH)
E.g., Fluorapatite [Ca9(PO4)6CaF2].
These are main components of phosphate rocks.
 Also phosphorus is present in bones, living cell, plant matter.
Arsenic, Antimony, Bismuth :
 Present mainly as sulphide minerals.
Table : Atomic and Physical Properties of Group 15 Elements
Property N P As Sb Bi
Atomic number 7 15 33 51 83
–1
Atomic mass / g mol 14.01 30.97 74.92 121.75 208.98
2 3 2 3 10 2 3 10 2 3 14 10 2 3
Electronic configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p
Ionization enthalpy I 1402 1012 947 834 703
 i H /(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
a
Covalent radius / pm 70 110 121 141 148
b b b c
Ionic radius / pm 171 212 222 76 103c
Melting point / K 63* 317d 1089 e 904 544
d f
Boiling point / K 77.2* 554 888 1860 1837
–3 g h
Density / [g cm (298 K)] 0.879 1.823 5.778 6.697 9.808
a E III single bond (E = element); b E 3– ; c E 3+; d White phosphorus; e Grey  -form at 38.6 atm; f Sublimation temperature;
g At 63 K; hGrey -form; * Molecular N2.
Atomic Properties of Group 15
Nitrogen is a diatomic gas, while other elements are polyatomic solid.
 Boiling point : Increases down the group, but that of Sb is greater than Bi.
 Melting point : Increases upto arsenic and then decreases upto bismuth.
 Allotropy : All elements of group 15 show allotropy except nitrogen.
Anomalous properties of nitrogen

Nitrogen differs from rest of the members of Group 15 due to its small size, high electronegativity, high ionization
enthalpy and absence of vacant d orbitals.
(1) Nitrogen exists as diatomic molecule with triple bond, thus its bond enthalpy (941.4 kJ/mol) is very high.
But P, As, Sb form single bond, while bismuth forms metallic bond in elemental state.
(2) Catenation tendency is weaker in nitrogen as single N–N bond is weaker than single P–P bond, as high
interelectronic repulsion of non-bonding electrons, owing to small bond length in nitrogen.
(3) Nitrogen has unique ability to form p–p multiple bond with itself and other elements having small size
and high electronegativity (e.g., C, O). But heavier elements do not form p–p bond as their atomic orbitals
are so large and diffuse that they can not have effective overlapping.
(4) Nitrogen shows maximum covalency of four, because of absence of vacant d orbitals. Thus, nitrogen
cannot form d–p bond, but heavier elements can like P, As can from d–p [e.g., R 3P = O,
R3P = CH2], [R = alkyl group] and d–d bond with transition metals, when compounds like P(C2H5)3
and As(C6H5)3 act as ligands.
Chemical Properties and Trends in Chemical Reactivity

Oxidation State
Common oxidation state of Group 15 elements are –3, +3 and +5.
Tendency to show –3 oxidation state decreases down the group due to increase in size and metallic character.
Bi hardly forms any compound in –3 oxidation state.
The stability of +5 oxidation state decreases and that of +3 oxidation state increases down the group due to
inert pair effect. The only well characterised Bi (V) compound is BiF5.
Nitrogen shows +1, +2, +4 oxidation state also when it reacts with oxygen. All oxidation state from +1 to +4
disproportionate in acid solution in case of nitrogen, e.g.,
3HNO2  HNO3  H2O  2NO
Phophorous also shows +1 and +4 oxidation states in some oxoacids. All intermediate oxidation state
disproportionate in both acid and alkali into –3 and + 5.
However +3 oxidation state for As, Sb, Bi become increasingly stable with respect to disproportionation.
Covalency
Nitrogen shows maximum covalency of four, as only four orbitals (one s and three p) orbitals are available for
bonding. The heavier element with vacant d orbital can show covalency more than four. e.g., in PF6 , P has
covalency of six.
Reactivity towards Hydrogen :
All Group 15 elements form hydrides of the type EH3. (E = N, P, As, Sb or Bi.)
NH3, PH3, AsH3, SbH3, BiH3
Thermal Stability decreases


decreases
Bond dissociation enthalpy  
Basicity decreases

Reducing character increases

 
Bond angle decreases


Boiling Point : PH3 < AsH3 < NH3 < SbH3 < BiH3.
Table : Properties of Hydrides of Group 15 elements
Property NH3 PH3 AsH3 SbH3 BiH3

Melting point / K 195.2 139.5 156.7 185 –
Boiling point / K 238.5 185.5 210.6 254.6 290
(E–H) Distance / pm 101.7 141.9 151.9 170.7 –
HEH angle (º) 107.8 93.6 91.8 91.3 –
T –1
f H /kJ mol –46.1 13.4 66.4 145.1 278
T –1
diss H (E–H) / kJ mol 389 322 297 255 –
Reactivity towards Oxygen :

All Group 15 elements form oxides of type E2O3 and E2O5. The oxide in higher oxidation state is more acidic
than in lower oxidation state. In a particular state the acidic character decreases down the group.
Oxides of E2O3 type of N and P – Purely acidic
As and Sb – Amphoteric
Bi – Basic
Tendency to form pentoxide decreases down the group due to inert pair effect.
Oxides :
Acidic Character Increases
Ac idic Char ac te r D ec rea se s
N 2O NO N 2O 3 NO 2 N 2O5
P2O 3 P2O5
As2O3 As 2O 5
Sb2O3 Sb 2O 5
Bi2O 3 Bi2O5
*NO2 is mixed anhydride
Reactivity towards Halogens :

Elements of group 15 reacts to form halide of type EX3 and EX5.
All trihalides except that of nitrogen are stable.
In case of nitrogen only NF3 is known to be stable.
Except BiF3, other trihalides are predominantly covalent.
Nitrogen does not form pentahalide due to absence of vacant d subshell. Pentahalide are more covalent than
trihalides.
Hydrolysis of ECl3 :
NCl3 + 3H2O  NH3 + 3HOCl
PCl3 + 3H2O  H3PO3 + 3HCl
2AsCl3 + 3H2O  As2O3 + 6HCl
SbCl3 + H2O  SbOCl + 2HCl
BiCl3 + H2O  BiOCl + 2HCl
Reactivity towards Metals :
Group 15 elements react with metals to form binary compounds showing –3 oxidation state e.g.,
Ca3N2, Ca3P2, Na3As, Zn3Sb2, Mg3Bi2
DINITROGEN
Preparation
1. Commercially by liquefaction and fractional distillation of air, liquid N2 (b.p. 77.2 K) distills out first leaving
O2 (b.p. 90 K)
2. In laboratory it is prepared by :
NH4 Cl(aq)  NaNO2 (aq)  N2 (g)  2H2O(l)  NaCl(aq)
Small amount of NO and HNO3 are also formed in this reaction as impurities can be removed by passing
the gas through aqueous H2SO4 containing K2Cr2O7.
3. By thermal decomposition of (NH4)2Cr2O7
Heat
(NH4 )2 Cr2O7  N2  4H2O  Cr2O3
4. Very pure N2 can be obtained by the thermal decomposition of sodium or barium azide.

Ba(N3 )2  Ba  3N2

2NaN3  2Na  3N2
Properties
1. It is colourless, odourless, tasteless and nontoxic gas. It has two stable isotopes N14 and N15.
2. It has very low solubility in water (23.2 cm3 per litre of water at 273 K and 1 bar P) and low freezing
and boiling point.
3. Dinitrogen is inert at room temperature because of high bond enthalpy of N  N bond. With increase in
temperature reactivity increases.
It directly combines with some metals to form predominantly ionic nitrides.

6Li  N2  2Li3N

3Mg  N2  Mg3N2
4. It combines with H2 at about 773 K in presence of catalyst (Haber’s process) to form ammonia
773K

N2 (g)  3H2 (g)
2NH3 (g) ; Hf  46.1 kJ/mol
5. At high temperature (2000 K)


N2 (g)  O2 (g)
2NO(g)
Uses :
(i) In manufacture of NH3 and other industrial chemical containing N2 (e.g., calcium cyanamide).
(ii) Used to create inert atmosphere (e.g., in iron and steel industry)
(iii) Liquid N2 is used as refrigerant to preserve biological materials, food items and in cryosurgery.
AMMONIA
Ammonia is present in small quantities in air and soil, formed by decay of nitrogenous organic compounds
e.g., urea.
NH2CONH2  2H2O  (NH4 )2 CO3

2NH3
 H2 O  CO2
On small scale, it is obtained from ammonium salts which decompose when treated with caustic soda or
lime,
2NH4 Cl  Ca(OH)2  2NH3  2H2O  CaCl2
(NH4 )2 SO4  2NaOH  2NH3  2H2O  Na2SO4
On large scale, ammonia is manufactured by Haber’s process.

2NH3 (g) ;  H Θ = – 46.1 kJ/mol–1
N2 (g)  3H2 (g) f
In accordance with Le Chatelier’s principle, the optimum conditions for the formation of NH3 are :
High pressure : 200 × 105 Pa (about 200 atm).
Temperature : 700 K.
Catalyst : Iron oxide with small amount of K2O and Al2O3. Earlier, Iron with molybdenum used as catalyst.
Properties
Physical :
Ammonia is colourless gas with pungent odour. Freezing point = 198.4 K. Boiling point = 239.7 K.
As it is associated through hydrogen bonding in solid and liquid states it has higher melting and boiling point,
than expected on the basis of its molecular mass.
Structure :
The NH3 molecule is trigonal pyramidal having sp3 hybridized N with a lone pair of electrons.
pm N
1.7
10
H 107° H
H
Chemical :
Ammonia is highly soluble in water. Its aqueous solution is weakly basic due to formation of OH– ions.
NH4 (aq)  OH (aq)

NH3 (g)  H2O (l)
It forms ammonium salt with acids e.g., NH4Cl, (NH4)2SO4 etc.

As a weak Lewis base, it precipitates hydroxide of many metals from their salt solutions e.g.,
FeCl3 (aq)  3NH4OH (aq)  Fe2O3  xH2O  3NH4Cl (aq)
(brown ppt.)
ZnSO4 (aq)  2NH4OH (aq)  Zn(OH)2  (NH4 )2 SO4 (aq)

(white ppt.)
As NH3 is a Lewis base (due to lone pair of electron on N), it donates electron pair and forms linkage with
metal ions and this helps in detection of metal ions such as Cu2+, Ag+.
Cu2 (aq)  4NH3 (aq)

[Cu(NH3 )4 ]2 (aq)
(blue) (deep blue)
Ag (aq)  Cl (aq)  AgCl (s)

( colourless ) ( white ppt.)
AgCl (s)  2NH3 (aq)  [Ag(NH3 )2 ]Cl (aq)

(White ppt.) (colourless)
Note :
Some more reactions of NH3
(Test for NH3) Sodamide (Bronze Colour)

NaNH2
(Iodide of Millon's base)
NH2.HgO.HgI
(Brown) (BN)x Boron Nitride
Na (Inorganic graphite)
Ne
at
ss
He
le
K2
d N2 + H2O
Re 2 H6
r 's
Hg
te
d
B
re mi
I4
ag Li
N2 en O2
NaOCl t Ex
+ NaCl + H2O ce
NH3 ss
NO + H2O
Cl2
B 2H
6
0K Limited
45 PbO CuO N2 + NH4Cl
Exce
(Hot) (Hot)
B3N3H6
(Borazine)
ss
(Inorganic benzene)
NCl3 + HCl
N2
N2
+ Cu + H2O
+ Pb + H2O
Uses of NH3
(i) To produce nitrogenous fertilizers [NH4NO3, NH2CONH2, (NH4)3PO4, (NH4)2SO4].
(ii) To manufacture some inorganic nitrogen compounds like nitric acid (HNO3).
(iii) Liquid ammonia is used as refrigerant.
OXIDES OF NITROGEN
Nitrogen froms a number of oxides in different oxidation states. The detail is given below :
Table : Oxides of Nitrogen
Oxidation Physical
Common methods of
Name Formula state of appearance and
preparation
nitrogen chemical nature
Heat
Dinitrogen oxide N 2O +1 NH4NO3 N2O + 2H2O Colourless gas,
[Nitrogen(I) oxide] Neutral
Nitrogen monoxide NO +2 2NaNO2 + 2FeSO4 + 3H2SO4 Colourless gas,
[Nitrogen(II) oxide] Fe2(SO4)3 + 2NaHSO4 + 2H2O + 2NO Neutral
250K
Dinitrogen trioxide N 2O3 +3 2NO  N2O4 2N2O3 Blue solid, Acidic
[Nitrogen(III) oxide)
673K
Nitrogen dioxide NO2 +4 2Pb(NO3 )2 4NO2  2PbO + O2 Brown gas, Acidic
[Nitrogen(IV) oxide]
Cool
Dinitrogen tetroxide N 2O 4 +4 2NO2 N 2 O4 Colourless solid /
Heat
[Nitrogen(IV) oxide] liquid, Acidic
Dinitrogen pentoxide N 2O 5 +5 4HNO3  P4O10 4HPO3 + 2N2O5 Colourless solid,
[Nitrogen(V) oxide] Acidic
Table : Lewis dot main resonance structures and bond parameters of oxides of nitrogen.
Formula Resonance Structures Bond Parameters

N2O N N O N N O N N O
113 pm 119 pm
Linear
NO N O N O N O
115 pm
O O O O 105º O
O 11
N2O3 4
pm
N N N N N N 130º
186 pm
O O 117º O
121 pm
Planar
N N N
NO2 120 pm
O O O
O O 134º O
Angular
O O O O O O
175 pm 1 pm
N2O4 N N N N 12
N N 135º
O O O O O Planar O
O m
O O O O 1 pm 9p O
O O 15 O 11
N2O5 N N N N N N 134º
112º
O O O O O O
Planar
Example 21 : Though nitrogen exhibits +5 oxidation state, it does not form pentahalide. Give reason.
Solution : Nitrogen has s and p orbitals only. As it does not have d orbital to expand its covalency beyond four.
Example 22 : PH3 has lower boiling point than NH3. Why?

Solution : Unlike NH3, PH3 is not associated through hydrogen bonding in liquid state.
Example 23 : Write reaction of thermal decomposition of sodium azide.

Solution : 2NaN3  2Na + 3N2
Example 24 : Why does NH3 act as lewis base?

Solution : Nitrogen atom in NH3 has one lone pair of electron which is available for donation, hence Lewis base.
Example 25 : Why does NO2 dimerise?

Solution : NO2 contains odd number of valence electron. On dimerisation it gets converted to stable N2O4
with even number of electrons.
NITRIC ACID
Nitrogen forms oxoacids such as :
H2N2O2 (Hyponitrous acid), HNO2 (Nitrous acid) and HNO3 (Nitric acid).
HNO3 is the most important.
Preparation
 In laboratory HNO3 prepared by heating KNO3 or NaNO3 and conc. H2SO4 in glass retort.
NaNO3  H2SO4  NaHSO4  HNO3
 Large scale (by Ostwald’s process)

(i) Based on catalytic oxidation of NH3 by atmospheric oxygen.
Pt / Rh gauge catalyst
4NH3 (g)  5O2  4NO(g)  6H2O(g)
500K,9 bar
(from air)
(ii) Nitric oxide combines with O2 giving NO2.

2NO(g)  O2 (g)
2NO2 (g)
(iii) Nitrogen dioxide so formed dissolves in water to give HNO3.
3NO2 (g)  H2O(l)  2HNO3 (aq.)  NO(g)
Aqueous HNO3 can be concentrated by distillation upto ~68% by mass. Further concentration upto 98%
achieved by dehydration with conc. H2SO4.
Properties
It is colourless liquid. (Freezing point : 231.4 K and boiling point : 355.6 K)
Lab. HNO3 contains ~68% of HNO3 by mass and has specific gravity 1.504.
Structure :
In the gaseous state HNO3 has planar structure.
H O
m
1p
102º
96
12
pm
O N 130º
140.6 pm
O
In aqueous solution, HNO3 behaves as strong acid giving hydronium and nitrate ions.
HNO3 (aq)  H2O(l)  H3 O (aq)  NO3 (aq)
Concentrated nitric acid is strong oxidising agent and attacks most metals except noble metals such as gold
and platinum.
The products of oxidation depend upon the concentration of the acid, temperature and the nature of material
undergoing oxidation.
 3Cu  8HNO3 (dilute)  3Cu(NO3 )2  2NO  4H2O
Cu  4HNO3 (conc.)  Cu(NO3 )2  2NO2  2H2O
 4Zn  10HNO3 (dilute)  4Zn(NO3 )2  5H2O  N2O
Zn  4HNO3 (conc.)  Zn(NO3 )2  2H2O  2NO2
Due to formation of passive film of oxide on the surface of some metals like Cr, Al do not dissolve in
concentrated nitric acid.
 Conc. HNO3 also oxidises non-metals and their compounds.
I2  10HNO3  2HIO3  10NO2  4H2O
C  4HNO3  CO2  2H2O  4NO2
S8  48HNO3  8H2SO 4  48NO2  16H2O

(conc.)
P4  20HNO3  4H3PO 4  20NO2  4H2O

(conc.)
Brown Ring Test for Nitrates :

This depends on the ability of Fe2+ to reduce nitrates to nitric oxide, which reacts with Fe2+ to form brown-
coloured complex.
This test is done by adding dil. FeSO4 to an aqueous solution containing NO3 , and then adding conc. H2SO4
along the sides of test tube. Brown ring at interface between solution and H2SO4 layer indicates the presence
of NO3 in solution.
NO3  3Fe2   4H  NO  3Fe3   2H2O
[Fe(H2O)6 ]2   NO  [Fe(H2O)5 (NO)]2   H2O

brown
Uses of HNO3 :
1. In the manufacture of ammonium nitrate for fertilisers and other nitrates for use in explosives and
pyrotechnics.
2. Also used for the preperation of nitroglycerin, trinitrotoluene (TNT) and other organic nitro compounds.
3. Other uses are in pickling of stainless steel, etching of metals and as an oxidiser in rocket fuels.
ALLOTROPIC FORMS OF PHOSPHORUS
The important allotropic forms of phosphorus are white, red and black.
1. White phosphorus :
(a) It consists of discrete tetrahedral P4 molecule.
(b) It is less stable and more reactive than other solid phases because of P
angular strain in P4 molecules, having angle of 60º.
60°
(c) It is translucent white waxy solid.
P P
(d) It is poisonous, insoluble in water but soluble in CS2 and glows in dark
(chemiluminescence). P
(e) It dissolves in boiling NaOH solution in inert atmosphere giving PH3.
P4  3NaOH  3H2O  PH3  3NaH2PO2

(Sodium hypophosphite)
(f) It readily catches fire in air to give dense white fumes of P4O10.
P4  5O2  P4 O10
2. Red phosphorus
P P P
(a) It is polymeric consisting of chains of P4
tetrahedra linked together.
(b) It is obtained by heating white phosphorus P P P P P P

at 573 K in inert atmosphere for several
days. P P P
(c) When red P is heated under high pressure, a series of phases of black P is formed.
(d) Red P has iron grey lustre.
(e) It is odourless, non-poisonous and insoluble in water and CS2.
(f) Chemically it is much less reactive than white P.
(g) It does not glow in dark.
3. Black phosphorus
(a) It has two forms : -black and -black phosphorus.
(b) -black phosphorus is formed when red phosphorus is heated in a sealed tube at 803 K. It can
sublime in air and has opaque monoclinic or rhombohedral crystals.
(c) -black phosphorus is prepared by heating white phosphorus at 473 K under high pressure. It does
not burn in air upto 673 K.
PHOSPHINE, PH3
Preparation
 By reaction of calcium phosphide with water or dil. HCl.
Ca3P2  6H2O  3Ca(OH)2  2PH3
Ca3P2  6HCl  3CaCl2  2PH3
 Lab preparation : By heating white P with conc. NaOH in an inert atmosphere of CO2.
P4  3NaOH  3H2O  PH3  3NaH2PO2

(Sodium hypophosphite)
When pure it is non-inflammable but becomes inflammable due to presence of P2H4 or P4 vapours.
To purify it from impurities, it is absorbed in HI to form phosphonium iodide (PH4I), which on treating with
KOH gives phosphine.
PH4I  KOH  KI  H2O  PH3
Properties
 PH3 is colourless gas with rotten fish smell and is highly poisonous.
 It explodes in contact with traces of oxidising agent like HNO3, Cl2 and Br2 vapours.
 It is slightly soluble in water, solution of PH3 in water decomposes in presence of light giving red P and
H2.
 When absorbed in CuSO4 or HgCl2, phosphides are obtained.
3CuSO4  2PH3  Cu3P2  3H2SO4
3HgCl2  2PH3  Hg3P2  6HCl
 PH3 is weakly basic and like NH3, give phosphonium compounds with acids.
PH3  HBr  PH4Br
Uses of PH3
1. Used in Holme’s signals, due to spontaneous combustion of phosphine. Containers containing CaC2 and
Ca3P2 are pierced and thrown in sea when gases evolve burn and serve as signal.
2. Also used in smoke screens.
PHOSPHORUS HALIDE
Phosphorus forms halides of type PX3 (X = F, Cl, Br, I) and PX5 (X = F, Cl, Br)
Phosphorus Trichloride, PCl3 :

Preparation :

P4  6Cl2  4PCl3
(white P) (dry)
P4  8SOCl2  4PCl3  4SO2  2S2Cl2

(white P) Thionyl chloride
Properties :
 Colourless oily liquid and hydrolyse in the presence of moisture.
PCl3  3H2O  H3PO3  3HCl
 It reacts with organic compounds containing –OH group.
3CH3 COOH  PCl3  3CH3 COCl  H3PO3
3C2H5 OH  PCl3  3C2H5 Cl  H3PO3
Structure :
It has sp3 hybridised P and has pyramidal structure.
Cl Cl Cl
Phosphorus pentachloride, PCl5 :

Preparation :
P4  10Cl2  4PCl5

(white) (excess)
P4  10SO2Cl2  4PCl5  10SO2

Sulphuryl chloride
Properties :
It is yellowish white powder and in moist air, it hydrolyses to POCl3 and finally forms phosphoric acid.
PCl5  H2O  POCl3  2HCl
POCl3  3H2O  H3PO4  3HCl
 When heated, it sublimes but decomposes on stronger heating.


PCl5  PCl3  Cl2
 It reacts with organic compound containing –OH group.
C2H5 OH  PCl5  C2H5 Cl  POCl3  HCl

(Phosphorous oxychloride
or phosphoryl chloride)
CH3 COOH  PCl5  CH3 COCl  POCl3  HCl
 Finely divided metals on heating with PCl5 give corresponding chloride.
2Ag  PCl5  2AgCl  PCl3
Sn  2PCl5  SnCl4  2PCl3
 It is used in the synthesis of some organic compounds e.g., C2H5Cl, CH3COCl.
Structure :
Cl
 In gaseous and liquid phases, it is sp3d hybridised and Cl
240 pm
has trigonal bipyramidal structure. The two axial bonds
are longer than three equatorial bonds. This is due to
fact that axial bond pair suffer more repulsion as 202
P pm
compared to equatorial bond pairs.
Cl Cl
 In solid state, it exists as an ionic solid [PCl 4 ] +
[ P C l 6 ] – . [P C l 4 ] + is tetrahedral and [PCl 6 ] – is
octahedral. Cl
Oxides of Phosphorus :
It forms two oxides P4O6 and P4O10.
P4O6 : P4  3O 2  P4 O 6
(Limited )
..
P
O O
O
Structure : :P P:
O
O O
P
..
It is white solid with garlic odour. It dissolves in cold and hot water to form phosphorus acid and phosphoric
acid respectively.
P4O6 + 6H2O  4H3PO3

(cold)
P4O6 + 6H2O  3H3PO4 + PH3

(hot)
P4O10 : P4 + 5O 2  P4O10
(excess)
O
||
P
O O
O
O P P O
||
||
Structure :
O
O O
P
||
O
It is a white solid with snow like appearance and sublimes on heating. It readily dissolves in both cold
and hot water.
P4O10 + 2H2O  4HPO3 (Meta phosphoric acid)

(cold)
P4O10 + 6H2O  4H3PO4 (Phosphoric acid)

(hot)
It is a powerful dehydrating agent.
OXOACIDS OF PHOSPHORUS
Phosphorus forms number of oxoacids. The formulae, method of preparation and structures of important
oxoacids of phosphorus are given below :
Table : Oxoacids of Phosphorus
Oxidation state Characteristic bonds

Name Formula Preparation
of phosphorus and their number
Hypophosphorous acid H3PO2 +1 One P – OH white P4 + alkali
(Phosphinic) Two P – H
One P = O
Orthophosphorous H3PO3 +3 Two P – OH P2 O 3 + H 2 O
acid (Phosphonic) One P – H
One P = O
Pyrophosphorous acid H4P2O5 +3 Two P – OH PCl3 + H3PO3
Two P – H
Two P = O
Hypophosphoric acid H4P2O6 +4 Four P – OH Red P4 + alkali
Two P = O
One P – P
Orthophosphoric acid H3PO4 +5 Three P – OH P4O10 + H2O
One P = O
Pyrophosphoric acid H4P2O7 +5 Four P – OH On heating
Two P = O phosphoric acid
One P – O – P
Metaphosphoric* acid (HPO3)3 +5 Three P – OH Phosphorus acid
Three P = O + Br2, heat in a
Three P – O – P sealed tube
* Exists in polymeric forms only. Characteristic bonds of (HPO3)3 have been given in the Table.
The compositions of the oxoacids are interrelated in terms of loss or gain of H2O molecule or O-atom.
The structures of some important oxoacids are given below :
O
O O O O
P P
P P P
HO OH H OH
HO O H OH
OH OH OH
OH OH H
H3PO4 H4P2O7 H3PO3 H3PO2
Orthophosphoric acid Pyrophosphoric acid Orthophosphorous acid Hypophosphorous acid
O O O
O OH O
P P
HO OH P P P
O O O O O O
P OH O OH
O OH
Polymetaphosphoric acid, (HPO3)n
Cyclotrimetaphosphoric acid, (HPO3)3
Fig : Structures of some important oxoacids of phosphorus
In oxoacids, phosphorus is tetrahedrally surrounded by other atoms. They contain at least one P = O and one
P–OH bond. The one with lower oxidation state (less than +5) also has either P–P (e.g., in H4P2O6) or P–H
(e.g., H3PO2). In + 3 oxidation state, P shows disproportionation e.g., orthophosphorus acid

4H3PO3  3H3PO 4  PH3
The acids containing P–H bond have strong reducing properties. Thus hypophosphorus acid having two
P–H bonds is a good reducing agent and reduces AgNO3 to metallic silver.
4AgNO3  2H2O  H3PO2  4Ag  4HNO3  H3PO4
These P–H bonds are not ionisable to give H+ and do not involve in basicity of the acids.
Only those H atoms attached with oxygen in P–OH form are ionisable and cause basicity. Thus H3PO3
containing two P–OH bonds is dibasic and H3PO4 with three P–OH bonds is tribasic.
Example 26 : How can it be proved that PH3 is basic in nature?

Solution : PH3 can react with acid like HI,
PH3  HI  PH4I
As PH3 has lone pair of electron, hence it acts as Lewis base.
Example 27 : Why does PCl3 fume in moisture?
Solution : PCl3  3H2O  H3PO3  3HCl
PCl3 on hydrolysis gives fumes of HCl.
Example 28 : Are all the five bonds in PCl5 equivalent? Justify your answer.
Solution : PCl5 has trigonal bipyramidal structure, the two axial bonds are longer, as they experience more
repulsion than three equatorial bonds.
Example 29 : How do you account for reducing behaviour of H3PO2 on the basis of its structure?
O
P
Solution :
H OH
H
The two H atoms bonded directly to phosphorus atom impart reducing characters.
Example 30 : Draw structure of pyrophosphoric acid.

O O
P P
Solution : H4P2O7 : HO O OH
HO OH
EXERCISE
21. Catenation property of group 15 elements follow the order

(1) N >> P > As > Sb > Bi
(2) P >> N > As > Sb > Bi
(3) N < P < As < Sb < Bi
(4) P < N < As < Sb < Bi
22. Melting point of hydrides of nitrogen family follows the order
(1) NH3 < PH3 < AsH3 < SbH3
(2) PH3 < NH3 < AsH3 < SbH3
(3) PH3 < AsH3 < NH3 < SbH3
(4) PH3 < AsH3 < SbH3 < NH3
23. Which of the following halides of group 15 is not hydrolysed?
(1) NF3 (2) NI3
(3) PF3 (4) Both (1) & (3)
24. Brown ring test is used for the identification of
(1) PO43 (2) NO3
(3) SO24 (4) HCO3
25. White phosphorus occurs as discrete P4 units, where P atoms lie at the corners of a regular tetrahedron.
The PPP bond angle is
(1) 90°` (2) 109°28
(3) 60° (4) 120°
26. Orthophosphorus acid on heating gives
(1) Hypophosphorus acid (2) Orthophosphoric acid
(3) Phosphene gas (4) Both (2) & (3)
(1) H3PO3 is dibasic and reducing
(2) H3PO3 is dibasic and non-reducing
(3) H3PO4 is tribasic and reducing
(4) H3PO3 is tribasic and non-reducing
28. The correct order of decreasing acidic strength of oxyacids of group 15 element is
(1) HNO3 > H3SbO4 > H3AsO4 > H3PO4
(2) H3PO4 > H3AsO4 > H3SbO4 > HNO3
(3) HNO3 > H3PO4 > H3AsO4 > H3SbO4
(4) HNO3 > H3AsO4 > H3PO4 > H3SbO4
29. The bond angle is maximum in
(1) NH3 (2) PH3
(3) AsH3 (4) SbH3
2
30. When excess of NH3(aq) is added to a blue solution containing Cu(aq) ions
(1) Solution turns red due to formation of Cu+ ions
2
(2) Solution becomes red due to formation of Cu(NH3 )4  aq
2
(3) Solution become deep blue due to formation of Cu(NH3 )4  aq
(4) Solution becomes colourless due to excess colourless NH3
GROUP 16 ELEMENTS : OXYGEN FAMILY
General electronic configuration : [inert gas] ns2np4
Oxygen (8O)
Non-metals
Sulphur (16S)
Selenium (34Se)
Metalloids
Tellurium (52Te)
Polonium (84Po) Radioactive metal (half-life 13.8 days)
Group 16 is known as chalcogens, means ore forming elements such as oxides and sulphides.
Occurrence
Oxygen :
Most abundant of all the elements on earth. It forms about 46.6% by mass of earth’s crust. Dry air contains
20.946% oxygen by volume.
Sulphur :
In earth curst only 0.03–0.1%
 Combined sulphur exists primarily as sulphates as : gypsum (CaSO42H2O), epsom salt (MgSO47H2O),
baryte (BaSO4).
 Sulphides such as : galena (PbS), zinc blende (ZnS), copper pyrites (CuFeS2).
 Traces of sulphur occur as H2S in volcanoes.
 Organic materials such as eggs, proteins, garlic, onion, mustard, hair and wool contain sulphur.
Selenium and Tellurium :
Found as metal selenides and tellurides in sulphide ores.
Polonium :
Occurs as decay product of thorium and uranium minerals.
Table : Some Physical Properties of Group 16 elements
Property O S Se Te Po
–1
Atomic mass/g mol 16.00 32.06 78.96 127.60 210.00
Electronic configuration [He]2s 2 2p4 [Ne]3s 2 3p4 [Ar]3d 104s2 4p 4 [Kr]4d10 5s 25p4 [Xe]4f14 5d 106s2 6p 4
a
Covalent radius /(pm) 66 104 117 137 146
2– b
Ionic radius, E /pm 140 184 198 221 230
Electron gain enthalpy, –141 –200 –195 –190 –174
/egH kJ mol–1
Ionisation enthalpy 1314 1000 941 869 813
–1
(iH1 )/kJ mol
Electronegativity 3.50 2.44 2.48 2.01 1.76
–3 c d e
Density /g cm (298 K) 1.32 2.06 4.19 6.25 –
f
Melting point / K 55 393 490 725 520
Boiling point / K 90 718 958 1260 1235
Oxidation states* –2, –1, 1, 2 –2, 2, 4, 6 –2, 2, 4, 6 –2, 2, 4, 6 2, 4
a Single bond; b Approximate value; c At the melting point; d Rhombic sulphur; e Hexagonal grey; f Monoclinic form, 673 K.
* Oxygen shows oxidation state of +2 and +1 in oxygen fluorides OF2 and O2F2 respectively.
Physical Properties of Group 16
 All these elements exhibit allotropy.
 The melting and boiling point increase with increase in atomic number down the group. The large difference
in melting and boiling points of oxygen and sulphur is due to their atomicity.
 Oxygen exists as diatomic molecule (O2) and sulphur as polyatomic molecule (S8).
Anomalous behaviour of oxygen in Group 16

This is due to its small size and high electronegativity.
 Presence of strong hydrogen bonding in H2O, which is absent in H2S.
 Due to absence of d orbital in oxygen, limits its covalency to four and in practice, rarely exceeds to two.
Other elements can show covalency more than four.
Chemical Properties and Trends in Chemical Reactivity
 Oxidation State :
Since electronegativity of oxygen is very high, it shows only negative oxidation state as –2 (except in
OF2, where it is + 2). Stability of –2 state decreases down the group. Polonium hardly shows –2 state.
Other elements of the group show +2, +4, +6, where +4 and +6 are more common. S, Se, Te show +4
state with oxygen and +6 with fluorine. Bonding in +4 and +6 are primarily covalent.
Down the group stability of +6 decreases and that of +4 increases due to inert pair effect.
 Reactivity with Hydrogen :
Table : Properties of Hydrides of Group 16 Elements
Property H2O H2S H2Se 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 (º) 104 92 91 90
–1
f H /kJ mol –286 –20 73 100
–1
diss H (H–E) / kJ mol 463 347 276 238
a –6 –7 –4 –3
Dissociation constant 1.8 × 10 1.3 × 10 1.3 × 10 2.3 × 10
a Aqueous solution, 298 K
All elements of Group 16 form hydride of type H2E (E = S, Se, Te, O)

H2O H2S H2Se H2 Te
increases
Acidic character  
(As bond dissociation energy decreases)
decreases
Thermal stability 
increases
Reducing character  
Note : Water does not show reducing property
Boiling point : H2S < H2Se < H2Te < H2O
Melting point : H2S < H2Se < H2Te < H2O
 Reactivity with oxygen :
All elements form oxides of type EO2 and EO3 (E = S, Se, Te, or Po). O3 and SO2 are gases, but SeO2
is solid. From SO2 to TeO2 reducing property decreases. TeO2 is an oxidising agent. Sulphur, selenium
and tellurium also form EO3 type oxide. Both type of oxides are acidic in nature.
Tendency to form EO3 decreases down the group due to inert pair effect.
 Reactivity towards Halogens :

(i) Group 16 elements form halides of type EX6, EX4 and EX2, (E = Group 16 element) (X = Halogen).
Stability of halides decreases from F– > Cl– > Br– > I–.
(ii) Among hexahalides, hexafluorides are only stable halide. SF6 is exceptionally stable for steric reason.
Hexafluorides are gaseous in nature, sp3d2 hybridised central atom and has octahedral structure.
F
F F
F F
F
(iii) Among tetrafluorides, SF4 is gas, SeF4 is liquid and TeF4 is solid. They have sp3d hybridised central
atom and have trigonal bipyramidal geometry. One of equitorial positions is occupied by lone pair
of electron, so its shape becomes see-saw.
F
F
F
F
(iv) All elements except selenium form dichlorides and dibromides. They are sp3 hybridised and have
tetrahedral structure. Monohalides like S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2 are dimeric in nature
and undergo disproportionation.
2Se2Cl2  SeCl4  3Se
Example 31 : Name the radioactive element of Group 16.

Solution : Polonium.
Example 32 : Elements of Group 16 show lower value of 1st ionization enthalpy compared to Group 15, why?
Solution : Due to extra stable half-filled p orbitals of Group 15, larger amount of energy is required to remove
electron as compared to group 16.
Example 33 : H2S is less acidic than H2Te, why?

Solution : Down the group, E–H bond dissociation enthalpy decreases and hence acidic character increases.
Example 34 : Give hybridisation and structure of SF4.

Solution : sp3d, trigonal bipyramidal geometry and see-saw structure.
DIOXYGEN
Preparation
In lab O2 can be obtained by
1. By heating oxygen containing salt as chlorates, nitrates and permanganates.

2KClO3 
 2KCl  3O2
MnO2
2. By thermal decomposition of oxides of metals.
2Ag2O(s)  4Ag(s)  O2 (g)
2HgO(s)  2Hg(l)  O2 (g)
2Pb3 O4 (s)  6PbO(s)  O2 (g)
2PbO2  2PbO(s)  O2 (g)
3. By decomposition of H2O2.
finely divided metals
2H2O2 (aq) 
 2H2O (l)  O2 (g)
and MnO2
On large Scale, O2 is prepared from electrolysis of H2O releasing O2 at anode.

Industrially, O2 is obtained from air by removing CO2 and H2O vapours and gases are liquefied and fractionally
distilled to give N2 and O2.
Properties
 O2 is colourless and odourless gas.
 Solubility in water is approx. 3.08 cm3 in 100 cm3 water at 293 K, sufficient for marine and aquatic life.
 It liquefies at 90 K and freezes at 55 K.
 It has three stable isotopes : O16, O17 and O18.
 O2 is paramagnetic and this can be explained on basis of MO theory.
Dioxygen directly reacts with nearly all metals and non-metals (except Au, Pt and some noble gases). These
reactions are exothermic, however to initiate reaction, some external heating is required as bond dissociation
enthalpy of O=O is high (493.4 kJ/mol).
Some reactions are :
2Ca  O2  2CaO
4Al  3O2  2Al2O3
P4  5O2  P4 O10
C  O2  CO2
2ZnS  3O2  2ZnO  2SO2
CH4  2O2  CO2  2H2O
V O
2 5
2SO2  O2   2SO3
CuCl
4HCl  O2 
2  2Cl
2  2 H2 O
Uses of O2 :
1. It is an important gas for normal respiration and combustion.
2. O2 is used in oxyacetylene welding.
3. For manufacturing of many metals and steel.
4. O2 cylinders are used in hospitals, high altitude flying and in mountaineering.
5. Combustion of fuels, e.g., hydrazines in liquid oxygen provides thrust in rockets.
SIMPLE OXIDES
Binary compound of oxygen with other elements. Oxides vary widely in nature and properties.
Simple oxides can be classified as :
(i) Acidic Oxide :
Non metal oxides are acidic but oxides of some metals in higher oxidation state also show acidic
character. They combine with water to give acid e.g.,
SO2, Cl2O7, CO2, N2O5, Mn2O7 , CrO3 , V2O5

metal oxide
For example, SO2 combines with water to give sulphurous acid.

SO2  H2O  H2SO3
Sulphurous acid
(ii) Basic Oxide :

In general metallic oxides are basic. These oxides give base with water e.g.,
Na2O, CaO, BaO etc.
For example, CaO combines with water to given Ca(OH)2, a base.
CaO  H2O  Ca(OH)2
(iii) Amphoteric Oxide :

Some metallic oxides show dual behaviour of both acid as well as alkali e.g., Al2O3
Al2O3 (s)  6HCl (aq)  9H2O (l)  2[Al(H2O)6 ]3  (aq)  6Cl (aq)
Al2O3 (s)  6NaOH (aq)  3H2O (l)  2Na3 [Al(OH)6 ] (aq)
(iv) Neutral oxides :

They are neither acidic nor basic e.g., CO, NO, H2O and N2O
(v) Mixed oxides :
Oxides containing more than one cations with different oxidation states are called mixed oxides.
e.g., Pb3O4, MgAl2O4, Fe3O4 etc.
OZONE
It is allotropic form of oxygen. Being too reactive it cannot remain in atmosphere at sea level. At height of
20 km, it is formed from atmospheric oxygen in the presence of sunlight. Ozone layer prevents earth’s surface
from excessive exposure of UV radiations.
Preparation
On passing dry stream of O2 through silent electrical discharge, so as to prevent decomposition of O3.
3O 2  2O 3 ;  H298K  142 kJ / mol 

(10% formed)
The product is known as ozonized oxygen.

If concentration of O3 required is greater than 10%, a battery of ozonisers can be used and pure ozone can
be condensed.
Properties
 O3 is pale blue gas, dark blue liquid and violet black solid.
 It has characteristic smell and in small concentration it is harmless. But in concentration above 100 ppm
breathing becomes uncomfortable resulting in headache and nausea.
 O3 is thermodynamically unstable with respect to oxygen, as its decomposition liberates heat. Its
conversion to O2 is favourable as G is negative. [H = –ve and S = + ve]
 Due to ease to release nascent oxygen O3 acts as strong oxidising agent, [O3  O2 + O].
e.g., PbS(s)  4O3 (g)  PbSO4 (s)  4O2 (g)
2I (aq)  H2O  O3 (g)  2OH (aq)  I2 (s)  O2 (g)
 Quantitative estimation of O3 :
On reaction of O3 with excess of KI buffered with borate buffer (pH 9.2), I2 is liberated which can be titrated
against standard sodium thiosulphate.
2KI(aq)  H2O(l)  O3 (g)  2KOH(aq)  I2 (s)  O2 (g)
 Nitrogen oxides (especially NO) emitted from exhaust systems of supersonic jet aeroplanes might slowly
deplete the concentration of O3 in upper atmosphere.
NO(g)  O3 (g)  NO2 (g)  O2 (g)
Use of freons (in aerosol sprays and as refrigerants) can also damage ozone layer.
Some more reactions of O3 :
O2
2RCHO O2
( i)
H2O2
R
(ii
)Z
–
C
n/
H
H
=
O
CH
Ag2O
–
Ag
R
3+
Fe Fe 2+
O3
Hg
O
I 2/H
2
P/H
S/H
Hg2O (Tailing)
HIO3
2
(Test of O3)
2
O
O
H2SO4
H3PO4
Structure
It has angular structure and two oxygen-oxygen bond length in ozone are identical (128 pm) and bond angle
117º.
O O or O
O O O O O O
Uses :
1. Used as germicide, disinfectant and for sterilising water.
2. Used for bleaching oils, ivory, flour, starch, etc.
3. As oxidising agent in manufacturing of KMnO4.
ALLOTROPES OF SULPHUR
The various allotropes of sulphur are :
1. -sulphur) :
Rhombic sulphur (
It is yellow in colour, melting point 385.8 K and specific gravity 2.06. It is stable form of sulphur at room
temperature.
It is formed on evaporating the solution of roll sulphur in CS2. It is insoluble in water, readily soluble in
CS2 and dissolves to some extent in benzene, alcohol and ether.
2. -sulphur) :
Monoclinic sulphur (
Its melting point is 393 K and specific gravity 1.98.
 It is prepared by melting rhombic sulphur in a dish and cooling, till crust is formed. Two holes are
made in crust and remaining liquid is poured out. On removing crust, colourless needle-shaped
crystals of -sulphur is formed.
 Monoclinic suphur is stable above 369 K and below 369 K -sulphur is stable. At 369 K both forms
are stable and this temperature is called transition temperature.
Both rhombic and monoclinic suphurs have S8 molecules, these are packed to give different crystal
structure. S8 form is puckered and has crown shape.
S 20
4p
S S
m
107º
S S
S
S S
 Several other modifications containing 6–20 sulphur atoms per ring are synthesised. In cyclo-S6, the
ring adopts chair form.
205.7 pm
S S
102.2º
S S
 At elevated temperatures (1000 K), S2 is dominant species and is paramagnetic like O2.
SULPHUR DIOXIDE
Preparation
It is formed when sulphur is burnt.
S(s)  O2 (g)  SO2 (g)
In laboratory : SO32 (aq)  2H (aq)  H2O (l)  SO2 (g)
Industrially : As by-product of roasting of sulphide ores.
4FeS2 (s)  11O2 (g)  2Fe2O3 (s)  8SO2 (g)
The gas after drying is liquefied under pressure and stored in steel cylinders.
Properties
 SO2 is colourless gas with pungent smell and is highly soluble in water. It liquefies at room temperature
under pressure of two atmosphere and boils at 263 K.
 SO2 when passed through water, forms sulphurous acid.
H2SO3 (aq)
SO2 (g)  H2O(l)
 It readily reacts with sodium hydroxide.

2NaOH  SO2  Na2SO3  H2O
Na2SO3  H2O  SO2  2NaHSO3
 It reacts with Cl2 in the presence of charcoal which acts as catalyst.
SO2 (g)  Cl2 (g)  SO2Cl2 (l)

(sulphuryl chloride)
 It is converted into SO3 by the action of O2 in the presence of V2O5.
V O
2SO2 (g)  O2 (g) 
2 5  2SO (g)
3
 Moist SO2 acts as reducing agent e.g.,
2Fe3  SO2  2H2O  2Fe2  SO24  4H
5SO2  2MnO4  2H2O  5SO24  4H  2Mn2

(pink colour) (colourless)
The above reaction is used as test for SO2.
Note :
Some more reactions of SO2 :
2+
Fe
SO2 acting as reducing agent
SO2Cl2
Fe3+
Cl2 SO3
O2
H2S SO2 Ca(

OH
)2
S + H2O
Mg Fe CaSO3 + H2O
(Milky)
MgS
FeS + FeO
+MgO
SO2 acting as oxidizing agent
Structure of SO2
It is angular and is resonance hybrid of the following two canonical forms :
S S
O O O O
Uses of SO2 :
1. In refining petroleum and sugar.
2. In bleaching wool and silk.
3. As an anti-chlor, disinfectant and preservative.
4. In preperation of H2SO4, NaHSO3, CaHSO3.
5. Liquid SO2 used as solvent to dissolve organic and inorganic compounds.
OXOACIDS OF SULPHUR
Sulphur forms a number of oxoacids such as H2SO3, H2S2O3, H2S2O4, H2S2O5, H2SxO6 (x = 2 to 5),
H2SO4, H2S2O7, H2SO5, H2S2O8 . Some of these acids are unstable and cannot be isolated. They are known
in aqueous solution or in the form of their salts. Structures of some important oxoacids are shown.
O O O O
O
S S S S S
S
HO O O O O O
HO O O O O
HO OH OH HO
HO HO
Sulphurous acid Sulphuric acid Peroxodisulphuric acid Pyrosulphuric acid (Oleum)
(H2SO3) (H2SO4) (H2S2O8) (H2S2O7)
Fig. : Structure of some important oxoacids of sulphur
SULPHURIC ACID
One of the most important industrial chemicals.
Manufacturing : By Contact Process which involves three steps :
(i) Burning of sulphur or sulphide ores in air to generate SO2.
The SO2 is purified by removing impurities such as arsenic compound.
(ii) Conversion of SO2 to SO3 by reaction with oxygen in the presence of V2O5 (catalyst).
V O
2SO2 (g)  O2 (g) 2 5
  2SO3 (g) ; H = – 196.6 kJ/mol
Reaction is exothermic, reversible and forward reaction leads to decrease in volume. Therefore, low
temperature and high pressure are favourable conditions. In practice 720 K and 2 bar pressure is used.
(iii) Absorption of SO3 in H2SO4 to give oleum (H2S2O7)
SO3  H2SO4  H2S2O7

(oleum )
Finally dilution of oleum with water gives H2SO4 of desired concentration. H2SO4 obtained is 96–98% pure.
Properties of Sulphuric Acid
Physical Properties:
(i) Concentrated sulphuric acid is a dense, oily liquid also known as oil of vitriol.
(ii) Concentrated sulphuric acid has a specific gravity of 1.84 and a boiling point of 611 K. The high
boiling point and high viscosity indicate that sulphuric acid has associated structure due to hydrogen
bonding as shown below:
HO O HO O
Hydrogen
S bond S
HO O HO O
(iii) The concentrated acid is soluble in water and the dissolution process is highly exothermic. So acid is
always diluted by adding acid to the water slowly and not by adding water to acid. This is done because
in the later case, lot of heat is produced which causes the acid to spurt out of the container.
Chemical Properties
1. Decomposition. Sulphuric acid is quite stable but on strong heating it dissociates as
H2SO4  SO3 + H2O
2. Acidic nature.
(i) It is a typical acid and it turns blue litmus red.
(ii) It ionises in water as
Water
H2SO4 H+ + HSO4–
HSO4– H+ + SO42–
(iii) It reacts with metals, oxides and carbonates etc. as:
Zn + H2SO4  ZnSO4 + H2
CaO + H2SO4 CaSO4 + H2O
2NaOH +H2SO4  Na2SO4 + H2O
Na2CO3 + H2SO4  Na2SO4 + H2O + CO2 
3. Dehydrating agent. Concentrated sulphuric acid is a good dehydrating agent as it has a great affinity
for water. Some of its properties which illustrate its strong affinity for water are:
(i) Charring of sugar
Conc.H2SO4
C12H22O11   12C  11H2O
(ii) Action with formic acid and oxalic acid
Conc. H SO
HCOOH   
2

4
 CO  H2O
Formic acid
COOH
Conc.H2SO4
CO + CO2 + H2O
COOH
Oxalic acid
(iii) Dehydration of ethyl alcohol

CH2
Conc.H2SO4
C2H5OH + H 2O
443 K
CH2
4. Oxidising agent. Hot concentrated sulphuric acid is moderately strong oxidising agent. Its oxidizing
behaviour is intermediate between phosphoric and nitric acid. Both metals and non-metals are oxidised
by concentration sulphuric acid which is reduce to SO2.
H2SO 4  H2O  SO 2  [O]

Nascent oxygen
It oxidises a number of substances as :
(a) C + 2[O]  CO2
(b) 1/8 S8 + 2[O]  SO2
(c) 2HBr + [O]  H2O + Br2
(d) H2S + [O]  H2O + S
(e) Cu + [O] + H2SO4  CuSO4 + H2O
5. Action with metal salts. Sulphuric acid decomposes the salts like nitrates and chlorides to liberate
their acids on heating.
NaNO3 + H2SO4  NaHSO4 + HNO3
NaCl +H2SO4  NaHSO4 + HCl
6. Miscellaneous reactions
(i) The salts of barium, calcium, strontium and lead form precipitates with sulphuric acid.
BaCl2 + H2SO4  BaSO4  + 2HCl
White ppt
Pb(NO3)2 +H2SO4  PbSO4  + 2HNO3
White ppt
(ii) Aromatic compounds react with conc. H2SO4 to form sulphonic acids.
C6H6 + H2SO4  C6H5SO3H + H2O

Benzene Benzene
sulphonic acid
Uses of sulphuric acid

It is an important industrial chemical and is used in many industries. Its major uses are:
(i) For preparation of fertilizers like ammonium sulphate, super–phosphate of lime etc.
(ii) For the manufacture of rayon
(iii) In storage batteries and lead accumulators
(iv) As a dehydrating agent
(v) For pickling (cleaning of metal surfaces before electroplating)
Example 35 : Which form of sulphur shows paramagnetic behaviour?
Solution : In vapour state, sulphur exists as S2, which has two unparied electron in * orbitals like O2, hence
paramagnetic.
Example 36 : What happens when
(i) Conc. H2SO4 is added to calcium fluoride.
(ii) SO3 is passed through water.
Solution : (i) CaF2  H2SO4  CaSO4  2HF
(ii) SO3  H2O  H2SO4
Example 37 : Give one example each of Acidic, Basic, Amphoteric and Neutral Oxides.
Solution : Acidic oxide  SO2
Basic oxide  MgO
Amphoteric oxide  Al2O3
Neutral oxide  CO
Example 38 : Draw structure of peroxodisulphuric acid.
O O
S S
Solution : H2S2O8 : O O
O O
OH OH
EXERCISE
31. The correct order of acidity of hydrides of oxygen family
(1) H2O > H2S > H2Se > H2Te
(2) H2O < H2S < H2Se < H2Te
(3) H2S > H2O > H2Se > H2Te
(4) H2S < H2O < H2Se < H2Te
32. S and O both are non-metals in the oxygen family, but their melting points are largely different,
O = 90 K and S = 718 K. This is because
(1) S is larger in size than O
(2) S exhibits more oxidation state + 2, + 4 and + 6 whereas O exhibits only – 2 and + 2 oxidation states
(3) O exists as diatomic molecule whereas S exists as polyatomic molecule (S8)
(4) S has more allotropes than O
33. Which of the following is not a reducing oxide?

(1) SO2 (2) SeO2
(3) TeO (4) SO3
34. Which of the following compounds does not exist?
(1) SF6 (2) S2Cl2
(3) SCl2 (4) SeBr2
35. O3 molecule is a resonance hybrid of the two structures I and II.
O O
O O O O
I II
The two oxygen-oxygen bond lengths in ozone molecule are

(1) Identical
(2) Slightly different
(3) Largely different
(4) Cannot be measured due to resonance
36. S8 ring of both rhombic sulphur and monoclinic sulphur has crown shaped structure. The S – S – S bond angle
in S8 ring is
(1) 109°28 (2) 107°
(3) 104° (4) 120°
37. In the contact process of manufacturing of H2SO4, the catalyst used is
(1) P2O5 (2) V2O5
(3) Rh (4) NO
38. Number of S = O bonds in pyrosulphuric acid are
(1) Two (2) Four
(3) Five (4) Six
39. H2SO4 in aqueous medium ionises in two steps.
H2SO4 (aq) + H2O (l)  H3O+ (aq) + HSO4– (aq), K a1  x
HSO4– (aq) + H2O (l)  H3O+ (aq) + SO42–, K a2  y
What is relation between x and y?

(1) x < y (2) x  y
(3) x > y (4) x >> y
40. What is the product when Mg react with SO2?
(1) MgO (2) MgSO4
(3) MgS (4) Both (1) & (3)
GROUP 17 ELEMENTS : HALOGEN FAMILY
General electronic configuration : [inert gas] ns2np5.
Fluorine (9F); Chlorine (17Cl); Bromine (35Br); Iodine (53I)
Astatine (85At)  Radioactive element.
Collectively known as halogens (Greek halo means salt and genes means born i.e., salt producers). They
are highly reactive non-metallic elements. Great similarity among Group 17 elements observed.
Occurrence
Fluorine : Mainly as insoluble fluorides.
Fluorspar – CaF2, Cryolite – Na3AlF6, Fluoroapatite – 3Ca3(PO4)2CaF2.
Small quantities are also present in soil, river water plants, bones and teeth of animals.
 Sea water contains chlorides, bromides and iodides of Na, K, Mg, Ca, but mainly NaCl (2.5% by mass).
Deposits of dried up seas contain NaCl and carnallite ( KClMgCl26H2O).
 Certain forms of marine life contain iodine in their system, various seaweeds contain 0.5% iodine, chile
saltpetre contains up to : 0.2% sodium iodate.
Table : Atomic and Physical Properties of Halogens
a
Property F Cl Br I At
–1
Atomic mass / g mol 19.00 35.45 79.90 126.90 210
Electronic
configuration
Covalent radius / pm
–
Ionic radius X / pm
Ionisation enthalpy
–1
/ kJ mol
Electron gain
–1
enthalpy / kJ mol
b
Electronegativity
– –1
HydH(X ) / kJ mol
Melting point / K
Boiling point / K
–3
Density / g cm
Distance X – X / pm
Bond dissociation
–1
enthalpy / (kJ mol )
e
E /V
aRadioactive; b Pauling scale; c For the liquid at temperatures (K) given in the parentheses; d solid; e The
half-cell reaction is x2(g) + 2e–  2X–(aq).
Physical Properties
All halogens are coloured.
Fluorine (F2)  Yellow gas
Chlorine (Cl2)  Greenish yellow gas
Bromine (Br2)  Reddish liquid
Iodine (I2)  Violet colour solid
The colour is due to absorption of different quanta of radiation in visible region which results in excitation of
outer electrons to higher energy level, thus different colours are observed.
 With increase in atomic number boiling and melting point steadily increase.
 Bromine and iondine are sparingly souble in water but soluble in solvents like CHCl3, CCl4, CS2,
hydrocarbons to give coloured solutions.
 Anomaly is observed among bond dissociation enthalpy. From Cl2 to I2 it decreases as expected. But
bond dissociation enthalpy of F2 is less than that of Cl2, as large electron-electron repulsion among lone
pairs in F2 where they are close to each other in comparison to Cl2.
Bond dissociation enthalpy : Cl2 > Br2 > F2 > I2.
Chemical Properties
Anomalous behaviour of fluorine :
Due to its small size, high electronegativity, low F–F bond dissociation enthalpy, non-availability of vacant
d orbital and higher value of electrode potential. Fluorine shows some difference in properties from the rest of
the members of the group. Also ionic and covalent radii, melting and boiling point and electron gain enthalpy
are lower than expected.
 Most reactions of fluorine are exothermic due to small and strong bonds formed by it.
 It forms only one oxoacid, while other halogens form number of oxoacids.
 HF is a liquid below 293 K due to strong hydrogen bonding, other hydrogen halides are gases at room
temperature.
Oxidation State :
All the halogens exhibit –1 oxidation state. However, chlorine, bromine and iodine exhibit +1, +3, +5 and +7
oxidation states also, as explained below :
Halogen atom in ns np nd
ground state 1 unpaired electron accounts
(other than fluorine)
for –1 or +1 oxidation states
3 unpaired electron account
First excited state for +3 oxidation states
Second excited state for +5 oxidation states
Third excited state
for +7 oxidation states
Fluorine :
Being the most electronegative element, it shows oxidation state of –1 only. As fluorine does not have any
d orbitals in valence shell, hence cannot expand its octet.
Higher oxidation state of chlorine, bromine and iodine are realised when these halogens form compounds
with small and high electronegative elements like fluorine and oxygen atoms, e.g., interhalogens, oxides and
oxoacids. Oxidation state of +4 and +6 occur in oxides and oxoacids of chlorine and bromine.
Chemical Reactivity :
All halogens are highly reactive. They react with metals and non-metals to form halides. Reactivity of halogen
decreases down the group.
Halogens show strong oxidising nature. F2 is the strongest oxidising halogen and it oxidises other halide ions
in solution and even in solid phase.
F2  2X  2F  X2 ; (X  Cl, Br or I)
Cl2  2X  2Cl  X2 ; (X  Br or I)
Br2  2I  2Br   I2
Decreasing oxidising ability of halogens in aqueous solution down the group is evident from standard electrode
potentials, which is dependent on the parameters indicated below:
o
1 1 Ho  egHo Hhyd
X2 (g) 
2 diss  X(g)   X (g)   X (aq)
2
 The relative oxidising power of halogens illustrated by reactions with water.

F2 oxidises water to oxygen whereas Cl2 and Br2 react with water to form hydrohalic acid and hypohalous
acids.
2F2 (g)  2H2O (l)  4H (aq)  4F (aq)  O2 (g)
X2 (g)  H2O (l)  HX (aq)  HOX (aq); (X = Cl or Br)
The reaction of iodine with water is nonspontaneous. I– can be oxidised by oxygen in acidic medium.
Which is just reverse of the case of fluorine.
4I (aq)  4H (aq)  O2 (g)  2I2 (s)  2H2O (l)
Reactivity towards Hydrogen :

They react with hydrogen to give hydrogen halide. Affinity for hydrogen decreases from fluorine to iodine. They
dissolve in water to form hydrohalic acids.
HF HCl HBr HI
increases
Acidic strength  
increases
Reducing power  
decreases
Bond dissociation enthalpy 
decreases
Stability 
Table : Properties of Hydrogen Halides
Property HF HCl HBr HI

Melting point / K 190 159 185 222
Boiling point / K 293 189 206 238
Bond length (H – X) / pm 91.7 127.4 141.4 160.9
–1
diss HΘ / kJ mol 574 432 363 295
pKa 3.2 –7.0 –9.5 –10.0
Reactivity towards Oxygen :
 Fluorine forms two oxides OF2 and O2F2. Only OF2 is thermally stable at 298 K. They are actually oxygen
fluorides, as fluorine is more electronegative than oxygen. Both OF2 and O2F2 are strong fluorinating
agents. O2F2 oxidises plutonium to PuF6 and used in removing plutonium from spent nuclear fuel.
 Chlorine, bromine and iodine form oxides in which halogen shows oxidation state from +1 to +7,
combination of kinetic and thermodynamic factors lead to decrease stability of oxides by halogens,
I > Cl > Br. Higher oxides are more stable than lower ones.
 Chlorine oxides Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive oxidising agents and tend to explode.
ClO2 is used as bleaching agent for paper pulp, textiles and in water treatment.
 Bromine oxides (Br2O, BrO2, BrO3) are least stable halogen oxides and exist only at low temperature.
They are powerful oxidising agents.
 Iodine oxides (I2O4, I2O5, I2O7) are insoluble solids and decompse on heating. I2O5 is strong oxidising
agent and used in estimation of CO.
Reactivity towards Metals :
Halogens form metal halides on reaction with metals e.g.,
Mg(s)  Br2 (l)  MgBr2 (s)
The ionic character of halides decrease in order
MF > MCl > MBr > MI (M = Monovalent metal)

 The metal in higher oxidation state will be more covalent than the one in lower oxidation state e.g., SnCl4,
PbCl4, SbCl5 and UF6 are more covalent then SnCl2, PbCl2, SbCl3 and UF4 respectively.
Example 39 : Why do halogens have maximum negative electron gain enthalpy in the respective periods of the
periodic table?
Solution : Halogens have the smallest size and high effective nuclear charge in their respective periods. Thus
they readily accept one electron to have noble gas configuration.
Example 40 : Although egH of fluorine is less negative than that of chlorine, but fluorine is a stronger oxidising
agent than chlorine, why?
Solution : This is due to
(i) Low bond dissociation enthalpy of F–F bond.
(ii) High hydration enthalpy of F–.
Example 41 : Fluorine exhibits only –1 oxidation state whereas other halogens show +1, +3, +5 and +7 oxidation
states also. Explain.
Solution : Fluorine being the most electronegative element cannot have positive oxidation state. Other halogens
have d orbitals, therefore can expand their octet.
Example 42 : Give correct order of boiling point of hydride of group 17.

Solution : HCl < HBr < HI < HF
CHLORINE
Preparation
(i) By heating manganese dioxide with conc. HCl.
MnO2  4HCl  MnCl2  Cl2  2H2O
Also, 4NaCl  MnO2  4H2SO4  MnCl2  4NaHSO4  2H2O  Cl2
(ii) By the action of HCl on KMnO4.
2KMnO4  16HCl  2KCl  2MnCl2  8H2O  5Cl2
Manufacturing of chlorine
(i) Deacon’s process :
By oxidation of HCl (g) by atomspheric oxygen in presence of CuCl2 (catalyst) at 723 K.
CuCl
4HCl  O2 
2  2Cl
2  2H2 O
723 K
(ii) Electrolytic process :

Chlorine is obtained by electrolysis of brine (conc. NaCl solution) where Cl2 is liberated at anode. Also
as by-product in chemical industries.
Properties
 It is greenish yellow gas with pungent and suffocating odour. It is 2–5 times heavier than air. It can be
liquefied easily into greenish yellow liquid which boils at 239 K. It is soluble in water.
 It reacts with number of metals and non-metals to form chlorides.
2Al  3Cl2  2AlCl3 ; P4  6Cl2  4PCl3
2Na  Cl2  2NaCl ; S8  4Cl2  4S2Cl2
2Fe  3Cl2  2FeCl3 ;
 It has great affinity for hydrogen.

H2  Cl2  2HCl
H2S  Cl2  2HCl  S
C10H16  8Cl2  16HCl  10C
 On reaction with NH3.
8NH3  3Cl2  6NH4 Cl  N2

(excess)
NH3  3Cl2  NCl3  3HCl

(excess) (explosive)
 On reaction with alkali they form mixture of chloride and hypochlorite or chlorate.
2NaOH + Cl2  NaCl  NaOCl + H2O

(cold & dilute) (Sodium hypochlorite)
6NaOH + 3Cl2  5NaCl  NaClO3 + 3H2O

(hot & conc.) (Sodium chlorate)
 With dry slaked lime it gives bleaching powder.

2Ca(OH)2  2Cl2  Ca(OCl)2  CaCl2  2H2O
Composition of bleaching powder is Ca(OCl)2CaCl2Ca(OH)22H2O

 Chlorine gives substitution products with saturated hydrocarbons and addition products with unsaturated
hydrocarbons e.g.,
UV
CH4  Cl2 
 CH3 Cl  HCl
Room temp.
C2H4  Cl2 
 C2H4 Cl2
 Chlorine water on standing loses its yellow colour due to formation of HCl and HOCl. HOCl so formed,
gives nascent oxygen, responsible for oxidising and bleaching properties of chlorine.
(i) Oxidising action :
2FeSO4  H2SO4  Cl2  Fe2 (SO4 )3  2HCl
Na2SO3  Cl2  H2O  Na2SO4  2HCl
SO2  2H2O  Cl2  H2SO4  2HCl
I2  6H2O  5Cl2  2HIO3  10HCl
(ii) Bleaching action :

Cl2  H2O  2HCl  [O]
Coloured substance + [O]  Colourless substance.

Its bleaching action is permanent and is due to oxidation. It bleaches vegetable or organic matter
in presence of moisture.
Uses :
1. For bleaching woodpulp used in manufacturing paper and rayon.
2. In the extraction of gold and platinum.
3. Manufacturing dyes, drugs and organic compounds such as CCl4, CHCl3, DDT, refrigerants, etc.
4. In sterilising drinking water.
5. Preparation of poisonous gases such as phosgene (COCl2), tear gas (CCl 3NO 2), mustard gas
(ClCH2CH2SCH2CH2Cl).
HYDROGEN CHLORIDE
Preparation
In laboratory : By heating NaCl with conc. H2SO4.
420 K
NaCl  H2SO 4 
 NaHSO4  HCl
823 K
NaHSO 4  NaCl 
 Na2SO 4  HCl
HCl gas dried by passing through conc. H2SO4.
Properties
Colourless and pungent smelling gas. It is easily liquefied to colourless liquid (b.p. 189 K) and freezes to white
crystalline solid (f.p. 159 K)
 It is extremely soluble in water and ionises as :
HCl (g)  H2O (l)  H3 O (aq)  Cl (aq); K a  107
Its aqueous solution called as hydrochloric acid. High value of Ka shows it is strong acid in water.
NH3  HCl  NH4 Cl

white fumes
 When three parts of conc. HCl and one part of conc. HNO3 are mixed, aqua regia is formed, which is
used for dissolving noble metals e.g., gold, platinum.
Au  4H  NO3  4Cl  AuCl4  NO  2H2O
3Pt  16H  4NO3  18Cl  3PtCl62  4NO  8H2O
 HCl decomposes salts of weaker acids, e.g., carbonates, bicarbonates, sulphites, etc.
Na2CO3  2HCl  2NaCl  H2O  CO2
NaHCO3  HCl  NaCl  H2O  CO2
Na2SO3  2HCl  2NaCl  H2O  SO2
Uses :
1. In manufacturing chlorine, NH4Cl and glucose from corn starch.
2. For extracting glue from bones and purifying bone black.
3. In medicines and as a laboratory reagent.
OXOACIDS OF HALOGENS
Due to high electronegativity and small size, fluorine forms only one oxoacid, HOF known as Fluoric (I) acid
or hypofluorous acid. Other halogens form number of oxoacids, most of them cannot be isolated in pure state.
They are stable only in aqueous solution or in form of their salts.
Oxoacids of Halogens
Decreasing acidic strength
Halic (I) acid HOF HOCl HOBr HOI
Increasing acidic strength

(Hypohalous acid) (Hypofluorous acid) (Hypochlorous acid) (Hypobromous acid) (Hypoiodous acid)
Halic (III) acid – HOCIO – –

(Halous acid) (chlorous acid) – –
Halic (V) acid – HOCIO2 HOBrO2 HOIO2

(Halic acid) – (chloric acid) (bromic acid) (iodic acid)
Halic (VII) acid – HOCIO3 HOBrO3 HOIO3

(Perhalic acid) – (perchloric acid) (perbromic acid) (periodic acid)
O
H H
H Cl
Hypochlorous acid O O
Cl Cl
O O O
O O
H Cl O O
Chlorous acid Chloric acid Perchloric acid
Fig. : The structures of oxoacids of chlorine
INTERHALOGEN COMPOUNDS
When two different halogens react with each other, interhalogen compounds are formed. They can have general
composition as XX , XX  , XX  and XX
3 5 7
where X = larger size halogen and less electronegative.
X = Small size halogen and more electronegative.
As the ratio between radii of X and X increases, the number of atoms per molecule also increases. Iodine(VII)
fluoride should have maximum number of atoms as ratio of radii between I and F should be maximum, so its
formula is IF7.
Preparation
The interhalogen compounds can be prepared by the direct combination or by the action of halogen on lower
interhalogen compounds. The product formed depends upon some specific conditions, e.g.,
437 K
Cl2 + F2 
 2ClF; l2 + 3Cl2  2ICl3 ;
(equal volume) (excess)
573 K
Cl2 + 3F2 
 2ClF3 ; Br2  3F2  2BrF3
(excess) (diluted with water)
l2 + Cl2  2ICl; Br2  5F2  2BrF5

(equimolar) (excess)
Properties
Some properties of interhalogen compounds are given in
Some Properties of Interhalogen Compounds
Type Formula Physical state and colour Structure
XX1 ClF Colourless gas –
BrF Pale brown gas –

a Detected spectroscopically gas –
IF
b Gas –
BrCl
Ruby red solids (-form) –
ICl
Brown red solid (-form) –
IBr Black solid –
XX3 ClF3 Colourless gas Bent T-shaped
BrF3 Yellow green liquid Bent T-shaped
IF3 Yellow powder Bent T-shaped

c
ICl3 Orange solid Bent T-shaped
XX5 IF5 Colourless gas but solid below 77 K Square pyramidal
BrF5 Colourless liquid Square pyramidal
ClF5 Colourless liquid Square pyramidal

Pentagonal
XX7 IF7 Colourless gas
bipyramidal
a Very unstable; b The pure solid is known at room temperature; c Dimerises as
Cl-bridged dimer (I2Cl6)
 These are all covalent molecules and are diamagnetic in nature. Their physical properties are in between
that of constituent halogens, except that their melting and boiling point are little higher than expected.
 In general interhalogen compound are more reactive than halogens, except fluorine. As X – X bond in
interhalogen is weaker than X–X bond in halogens except F–F bond.
 All these undergo hydrolysis giving halide ion derived from smaller halogen and hypohalite (when XX),
halite (when XX3 ), halate ( XX5 ) and perhalate ( XX7 ).
XX  H2O  HX  HOX
Uses :
These compounds can be used as
(i) Non-aqueous solvents.
(ii) Fluorinating agents.
(iii) ClF3 and BrF3 are used for the production of UF6 in enrichment of U235.
U (s)  3ClF3 (l)  UF6 (g)  3ClF (g)
Note :
Pseudohalide ions and Pseudohalogens.

Ions which consist of two or more atoms of which at least one is nitrogen and have properties similar to
those of halide ions are called pseudohalide ions. Some of these pseudohalide ions can be oxidized to
form covalent dimers comparable to halogens (X2).
Such covalent dimers of pseudohalide ions are called pseudohalogens. Some important pseudohalide ions
and pseudohalogens are given below :
Pseudohalide ions Pseudohalogen
CN –, cyanide ion (CN)2, cyanogen
OCN –, cyanate ion (SCN)2, thiocyanogen
SCN –, thiocyanate ion (SeCN)2, selenocyanogen
SeCN – selenocyanate ion ----
NCN2-, cyanamide ion ----
N3–, azide ion ----
OCN–, fulminate ion ----
Example 43 : Write balanced equation for reaction of Cl 2 with hot and conc. NaOH. Is this reaction a
disproportionation one? Justify.
Solution : 3Cl2  6NaOH  5NaCl  NaClO3  3H2O
As ‘Cl’ changes from zero to –1 and +5. Hence it is disproportionation.
Example 44 : Give two uses of Cl2.

Solution : (i) In manufacturing CCl4, DDT, CHCl3 etc.
(ii) Sterilising drinking water.
Example 45 : When HCl reacts with finely powdered iron, it forms ferrous chloride and not ferric chloride, why?
Solution : Fe  2HCl  FeCl2  H2
Liberation of H2 prevents the formation of FeCl3.
Example 46 : Deduce the molecular shape of BrF3 on the basis of VSEPR theory.
Solution : The two lone pairs occupy corners of a trigonal
bipyramid (equatorial positions).
F
So its shape would be slightly bent (T).
Br F
EXERCISE
41. Electron affinity of halogens follows the order

(1) F < Cl < Br < I
(2) F > Cl > Br > I
(3) Cl > F > Br > I
(4) Cl > Br > I > F
42. The oxidation states shown by halogen are – 1, + 1, + 3, + 5 and + 7. The oxidation state(s) shown by all
the halogens is
(1) – 1 and + 3 (2) – 1, + 1 and + 3
(3) Only – 1 (4) Only + 3
43. When F2 gas reacts with H2O, it forms
(1) O2 gas (2) O2F2 gas
(3) HOF (4) Both (2) & (3)
44. F2 combines with O2 to form OF2 and O2F2 which are
(1) Oxygen fluorides (2) Oxides of fluorine
(3) Anhydride of HOF (4) Both (2) & (3)
45. The order of acidity of oxides of chlorine
Cl2O Cl2O3 Cl2O5 Cl2O7
I II III IV
is
(1) I < II < III < IV (2) I > II > III > IV
(3) I > III > II > IV (4) IV > I > II > III
46. Deacon’s process is used for the manufacture of
(1) HNO3 (2) I2
(3) Cl2 (4) Br2
47. Aqua regia, which is used for dissolving noble metals like gold and platinum etc. is
(1) 1 : 3 mixture of conc. HCl and conc. HNO3
(4) 3 : 1 mixture of dil. HCl and conc. HNO3
48. Halogens react with oxygen to form many oxoacids, commonly named as hypohalous acid, halous acid, halic
acid and perhalic acid. The halogen(s) which form(s) halous acid is/are
(1) F2
(2) Cl2
(3) Cl2, Br2 and I2
(4) F2, Cl2 and Br2
49. The number of peroxide linkages in perchloric acid is
(1) Zero
(2) One
(3) Two
(4) Four
50. Which is the correct order of bond length?
(1) F2 < Cl2 < Br2 < I2
(2) Cl2 < F2 < Br2 < I2
(3) I2 < Br2 < F2 < Cl2
(4) Br2 < I2 < F2 < Cl2
GROUP 18 ELEMENTS : NOBLE GASES

General electronic configuration : [inert gas] ns2np6
(Except He : 1s2)
Helium (2He) ; Neon (10Ne); Argon (18Ar); Krypton (36Kr); Xenon (54Xe); Radon (86Rn)
All these are gases and chemically unreactive.
As they form very few compounds hence termed as noble gas.
Occurrence
 All noble gas except radon occur in atmosphere. This abundance in dry air is  1% by volume of which
argon is main constituent.
 He and Ne are sometimes found in minerals of radioactive origin e.g., pitchblende, monazite, cleveite.
 Main commerical source of He is natural gas.
 Xenon and radon are rarest elements of the group.
 Radon obtained as radioactive decay product of Ra226.
226  Rn222 4
Ra88 86
 2
He
Table : Atomic and Physical Properties of Group 18 Elements
Property He Ne Ar Kr Xe Rn*
Atomic number 2 10 18 36 54 86
Atomic mass/ g 4.00 20.18 39.95 83.80 131.30 222.00
–1
mol
2 2 6 2 6 10 2 6 10 2 14 10
Electronic 1s [He]2s 2p [Ne] 3s 3p [Ar]3d 4s 4p [Kr]4d 5s [Xe]4f 5d
6 2 6
configuration 5p 6s 6p
Atomic radius / pm 120 160 190 200 220 –
Ionisation enthalpy 2372 2080 1520 1351 1170 1037
–1
/ kJ mol
Electron gain 48 116 96 96 77 68
–1
enthalpy / kJ mol
–4 –4 –3 –3 –3 –3
Density (at STP) / 1.8 × 10 9.0 × 10 1.8 × 10 3.7 × 10 5.9 × 10 9.7 × 10
–3
gcm
Melting point / K – 24.6 83.8 115.9 161.3 202
Boiling point / K 4.2 27.1 87.2 119.7 165.0 211
–4 –3 –4 –6
Atmospheric 5.24 × 10 1.5 × 10 0.934 1.14 × 10 8.7 × 10 –
content (% by
volume)
* Radioactive
Physical Properties
 They are monoatomic, colourless, odourless and tasteless.
 Sparingly soluble in water
 Very low melting and boiling points as weak dispersion forces present.
 Helium has lowest boiling point (4.2 K) of any known substance. It has unusual property of diffusing
through commonly used laboratory materials like rubber, glass or plastics.
Chemical Properties
Noble gases are least reactive. Their chemical inertness is due to
(i) Completely filled valence shell.
(ii) High ionization enthalpy and more positive electron gain enthalpy.
In 1962, Neil Bartlett prepared a red compound O2 PtF6 and realised that the ionization enthalpy of molecular
oxygen (1175 kJ/mol) is identical with xenon (1170 kJ/mol) and he became successful in preparing similar red
colour compound of xenon by mixing Xe with PtF6 i.e., XePtF6 .
Thus number of compounds of Xe, especially with electronegative elements like F and O have been synthesised.
Compounds of krypton are fewer. Only KrF2 has been studied. Compounds of radon have not been isolated
but only identified (e.g., RnF2) by radiotracer technique. No true compound of Ar, He and Ne are yet known.
(a) Xenon-fluorine compounds :
Three binary fluorides of Xe is XeF2, XeF4, XeF6 prepared.
673 K, 1 bar
Xe(g)  F2 (g) 
 XeF2 (s)
(Excess)
873 K, 7 bar
Xe(g)  2F2 (g) 
 XeF4 (s)
(1 : 5 ratio)
573 K, 60-70 bar

Xe(g)  3F2 (g) 
 XeF6 (s)
(1 : 20 ratio)
XeF6 is also prepared by :
143 K
XeF4  O2F2 
 XeF6  O2
 XeF2, XeF4 and XeF6 are colourless crystalline solids and sublime readily at 298 K. They are powerful
fluorinating agents. Readily hydrolysed by traces of water.
2XeF2 (s)  2H2O(l)  2Xe(g)  4HF(aq)  O2 (g)
 Xenon fluorides react with fluoride ion acceptors to form cationic species and fluoride ion donors to
forms fluoroanions
XeF2  PF5  [XeF] [PF6 ]
XeF4  SbF5  [XeF3 ] [SbF6 ]
XeF6  MF  M [XeF7 ] ; (M = Na, K, Rb or Cs)
(b) Xenon-Oxygen Compounds :

Hydrolysis of XeF4 and XeF6 with water gives XeO3.
6XeF4  12H2O  4Xe  2XeO3  24HF  3O2
XeF6  3H2O  XeO3  6HF
Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2.
XeF6  H2O  XeOF4  2HF
XeF6  2H2O  XeO2F2  4HF
XeO3 is a colourless explosive solid and has a pyramidal molecular structure. XeOF4 is a colourless
volatile liquid and has a square pyramidal molecular structure.
F F
F
F
Xe F F
Xe Xe
F F F
F
F F
(a) Linear (b) Square planar (c) Distorted octahedral
O
F
F
Xe
Xe
O O
F F
O
(d) Square pyramidal (e) Pyramidal

Fig. : The structures of (a) XeF2 (b) XeF4 (c) XeF6 (d) XeOF4 and (e) XeO3
Uses of Noble Gases

Helium :
It is non-inflammable and light gas. Hence used in
(i) Filling balloons for meterological observations.
(ii) Also used in gas-cooled nuclear reactors.
(iii) Liquid helium (b.p. 4.2 K) used as cryogenic agent for carrying experiments at low temperatures.
(iv) It is used to produce and sustain powerful superconducting magnets which form part of NMR
spectrometers and MRI (Magnetic Resonance Imaging) systems for clinical diagnosis.
(v) Used as diluent for oxygen in modern diving apparatus as it has low solubility in blood.
Neon :
Used in discharge tube and fluorescent bulbs for advertising display purpose. Neon bulbs are used in botanical
gardens and in greenhouses.
Argon :
(i) Used to provide inert atmosphere in high temperature metallurgical processes (arc welding of metals or
alloys) and for filling electric bulbs.
(ii) Used in laboratory for handling air-sensitive substances.
No significant uses of Xenon and Krypton. They are used in light bulbs designed for special purposes.
Example 47 : Why elements of Group 18 known as noble gases?

Solution : Elements of Group 18 have valence shell orbitals completely filled and therefore react with few
elements only under certain conditions.
Example 48 : Noble gases have low boiling points, why?

Solution : Noble gases being monoatomic have weak dispersion forces and therefore liquefied at very low
temperature.
Example 49 : Does the hydrolysis of XeF6 lead to redox reaction?

Solution : No, the products of hydrolysis are XeOF4 and XeO2F2, where the oxidation state of all the elements
remains same as it was in the reacting state.
Example 50 : Give equation for preparation of Radon from Radium.
226  -decay 222 4

Solution : 88
Ra 
 86
Rn  2
He
Note :
1. Inert pair effect : Reluctance of s-subshell to participate in bond formation. Thus down the group
stability of lower oxidation state increases and that of higher oxidation state decreases.
2. Catenation : Tendency of self linkage of element. It depends on element-element bond strength.
3. Acetylide : Ionic carbide which yield actylene on hydrolysis.
4. Methanide : Ionic carbide which yield methane on hydrolysis.
5. Allylide : These carbide evolve allylene on hydrolysis .
6. CO2 is gas whereas, SiO2 (Silica) has three dimensional structure which makes it solid.
7. The P4 units of white phosphorus are held together by weak van der Waal forces of attraction. As a result,
its ignition temperature (303 K) is very low and easily catches fire in air. It is, therefore, kept under water.
8. P4S3 is used in safety matches or strike anywhere matches. The head of a safety match stick
contains KClO3, KNO3 or Pb3O4 alongwith Sb2S3 and ground glass pieces while the sides of a match
box contain red P and sand powder.
9. Sulphur exists in three allotropic forms i.e., rhombic, monoclinic and plastic sulphur. Rhombic sulphur
is the most stable form of sulphur.
10. Both rhombic and monoclinic sulphur are soluble in CS2 but plastic sulphur is insoluble.
11. Sulphuric acid or oil of vitriol is manufactured either by lead chamber or contact process. Lead
chamber process gives H2SO4 of 80% strength while contact process gives H2SO4 of 100% purity.
12. Like SO2, Cl2 also bleaches vegetable colouring matter in the presence of moisture. The bleaching action
of Cl2 is due to oxidation and hence is permanent while that of SO2 is due to reduction and
hence is temporary.
13. The noble gases occupy about 1% by volume of the atmosphere. However, argon is the most abundant
of all the noble gases in the atmosphere.
14. Water containing dissolved air dissolve lead, forming water soluble lead hydroxide. This solvent effect
of water is known as plumbo solvency. Litharge or massicot is PbO, red lead is Pb3O4 or PbO2.
2PbO (double oxide). Lead is soluble in acetic acid. Pb (CH3COO)2 is called sugar of lead. Basic
lead carbonate is known as white lead.
15. Phosphorus is the tenth element in order of abundance in the earth’s crust and occurs to the
extent of 1120 ppm. All the known minerals of phosphorus are orthophosphate.
16. The metaphosphoric acid (HPO3) can be obtained by heating ammonium phosphate. It can also be obtained
by heating microcosmic salt, NaNH4. HPO4. It is known as glacial phosphoric acid. It is a monobasic
acid.
17. PCl5 is molecular in the gas phase and ionic in the solid phase, [PCl4]+ [PCl6]–. PBr5 is also ionic in
solid state but exists as [PBr4]+ [Br]–.
18. In general, in the oxidation of SO2, SeO2, TeO2 etc to their higher oxides, all the three O atoms of O3
are used up. Ozone is known as dry bleach as it bleaches in the absence of moisture.
19. Gun powder is a mixture of sulphur, charcoal and KNO3.
20. The colour of halogens is because of absorption of visible light, as a result, valence electrons are excited
from the higher energy occupied * molecular orbital to the lowest energy un-occupied * molecular orbital.
21. Both ClO– and HOCl are good oxidising agents. Sodium hypochlorite solutions are used as laundry bleach.
Clorox is a 5.25% solution of NaOCl in water.
22. Tincture of iodine contains I2 + KI + rectified spirit.

23. Oxides of chlorine are Cl2O, ClO2, ClO3 (Cl2O6) and Cl2O7. Among halogens, maximum number of oxides
are formed by chlorine. Cl2O7 is the most stable and Cl2O is the least stable oxide of chlorine. The only
exothermic oxide is Cl2O7. ClO2 and ClO3 are paramagnetic oxides, while ClO3 is paramagnetic but Cl2O6
is diamagnetic. The order of stability follows the order Cl2O < ClO2 < Cl2O6 < Cl2O7. The oxidising power
of oxides follows the order Cl2O > ClO2 > Cl2O6 > Cl2O7.
24. Reasons for the difference in the bond angles of H2O, H2Se, H2S and H2Te. Though oxygen, sulphur,
tellurium etc. belong to the same group viz group 16, yet their bond angles decrease as follows:
H2O H2S H2Se H2Te
104.5º 92.1º 91º 90º
This can be explained as follows :
The outer shell electronic configuration of O, S, Se and Te is ns2 np4 or ns2 npx2 np1y np1z .
They undergo sp3 hybridisation forming four hybrid orbitals, two of which are occupied by lone pairs of
electrons. The expected bond angle is, therefore, 109.5º. But the lone pairs repel bond pairs thereby
decreasing the angle.
Due to smaller size and high electronegativity of O-atom, the bond pairs are closer and hence the
repulsions between them are larger. As a result, the repulsions by the lone pairs on the bond pairs
decrease the angle to only 104.5º. (from 109.5º). As we move from oxygen to tellurium, the size of the
atom increases and electronegativity decreases. As a result, the bond pairs move away from the central
atom. Hence the repulsions between the bond pairs decrease and the repulsion by the lone pairs on the
bond pairs increase so that the bond angle decreases much more (i.e. to nearly 90º from 104.5º)
25. Photosensitive elements : Selenium exists in two crystalline allotropic forms viz grey (metallic) and
red (non-metallic). Tellurium exists only in one stable form which is grey. Grey form of selenium and
tellurium consist of parallel chains held by weak metallic bonds. In the presence of light, the weak metallic
bonds are excited and as a result, the number of free electrons increases and so does the conductivity.
That is why Se and Te are called photosensitive metals.
26. Brief Review of discovery of noble gases.
(i) Discovery of argon (by Henry Cavendish in 1785). This was the first noble gas to be discovered.
Electric spark was passed through air mixed with excess of oxygen. Nitrogen was completely
converted into NO2 which was absorbed in NaOH solution and the excess oxygen present was
absorbed by passing through potassium pentasulphide solution (K2S5). The residual gas left was
named as argon (the lazy one).
(ii) Discovery of helium (by Janssen and Lockyer in 1868 in sun’s atmosphere spectroscopically and
by Ramsay in 1885 on the earth by heating the uranium mineral Cleveite). The name helium comes
from the Greek word helius which means sun.
(iii) Discovery of neon, krypton and xenon (by Ramsay and Travers by fractional distillation of liquid air).
(iv) Discovery of radon (by Dorn in 1900) by disintegration of radium.

t
en
nm nment
sig ssig
As A Assignment
Assignment
8. Select the correct statement(s) regarding borax
SECTION - A [NCERT Pg. 320]
NCERT Based MCQs (1) Boron is both sp2 and sp3 hybridised
1. The abnormally smaller size of Ga among its group (2) Its aqueous solution is basic in nature
can be explained by [NCERT Pg. 317]
(3) Oxidation state of boron is +3
(1) Poor shielding of p orbitals
(4) All of these
(2) Poor shielding of d orbitals
9. A compound ‘A’ when reacts with LiAlH4 it gives
(3) Poor shielding of d and f orbitals two compounds B and C along with LiF.
(4) Poor shielding of f orbitals Compounds A, B and C respectively are
[NCERT Pg. 321]
2. The oxide which is amphoteric in nature is
[NCERT Pg. 324] (1) HF, H2 and AlF3
(1) CO2 (2) SnO2 (2) BF3, H2 and AlF3
(3) SiO2 (4) GeO2 (3) BF3, B2H6 and AlF3
3. Which among the following is not a silicate? (4) B2H6, BF3 and AlF3
[NCERT Pg. 330]
10. Orthoboric acid is a monobasic acid because
(1) Mica (2) Zeolite [NCERT Pg. 321]
(3) Feldspar (4) Carborundum
(1) It forms H3O+ and H3BO2 ions in water
4. Which of the following compounds on hydrolysis
will form cross linked silicones? [NCERT Pg. 329] (2) It forms H3O+ and BO32  ions in water
(1) CH3SiCl3 (2) (CH3)2SiCl2
(3) It forms H3O+ and [B(OH)2]– ions in water
(3) (CH3)3SiCl (4) SiCl4
(4) It forms H3O+ and [B(OH)4]– ions in water
5. In Al2Cl6, the bond angle of Al – Cl – Al bond is
[NCERT Pg. 319] 11. The stability order of +2 oxidation state among Si,
Ge, Sn and Pb is [NCERT Pg. 324]
(1) 79° (2) 90°
(1) Pb < Sn < Ge < Si
(3) 101° (4) 118°
(2) Sn < Pb < Ge < Si
6. Which of the following is passive towards conc.
HNO3? [NCERT Pg. 319] (3) Si < Ge < Sn < Pb
(1) Al (2) Mg (4) Ge < Si < Sn < Pb
(3) Na (4) K 12. With respect to graphite and diamond, the

incorrect statement is [NCERT Pg. 326]
7. When boric acid reacts with sodium carbonate a
white crystalline solid X is formed which on heating (1) Graphite has higher electrical conductivity than
above 750°C gives [NCERT Pg. 320] diamond
(1) Na2B2O5 + B2O3 (2) Diamond is thermodynamically more stable
(2) Na2B4O7 than graphite
(3) NaBO2 + Na2BO3 (3) Graphite has higher bond order than diamond
(4) NaBO2 + B2O3 (4) Graphite is softer than diamond
13. Which of the following is not isostructural with (1) It is non-poisonous in nature
SiCl4? [NCERT Pg. 325] (2) It does not glow in dark
(1) NH4+ (2) AlCl4– (3) It is less reactive than white phosphorous
(3) BCl3 (4) SiO44– (4) It readily catches fire in air to give dense white
fumes of P4O10
14. Lewis acid among the following is
[NCERT Pg. 321] 20. The chemical formula of the compound that
contains one P — OH, two P — H and One P = O
(1) B2H6 (2) [B(OH)]4
bond in its one molecule is [NCERT Pg. 185]
(3) CH4 (4) CCl4
(1) H3PO3
15. Which of the following forms a more stable (2) H4P2O5
complex with haemoglobin? [NCERT Pg. 328]
(3) H3PO4
(1) CO (2) CO2
(4) H3PO2
(3) O2 (4) H2
21. The hybridisation state of phosphorus atom in PCl5
16. The correct order of acidic character of given is [NCERT Pg. 183]
oxides is [NCERT Pg. 177, 178]
(1) sp 3
(1) NO > N2O3 > NO2 > N2O5
(2) sp 3d
(2) NO > NO2 > N2O3 > N2O5
(3) sp 3d 2
(3) NO > N2O3 > N2O5 > NO2
(4) dsp3
(4) N2O5 > NO2 > N2O3 > NO
22. All of the given statements are correct except
17. Compound X is prepared by Haber’s process and
is used to produce nitrogenous fertilisers like urea. [NCERT Pg. 187]
The shape of compound and the hybridisation state
(1) Negative electron gain enthalpy of S is greater
of central atom in (X) are [NCERT Pg. 176]
than that of Se
(1) sp 3, trigonal pyramidal
(2) Fluorine has higher electronegativity than
(2) dsp 3, square planar oxygen
(3) sp 3d 2, octahedral (3) Elements of group 16 have higher ionisation
enthalpy than elements of group 15
(4) sp 2, linear
18. All of the given statements are true for nitric acid (4) On moving down the group, the atomic size
except [NCERT Pg. 179, 180] generally increases
(1) It is a colourless liquid X

23. Consider the given reaction, PbS   PbSO 4
(2) In aqueous solution, HNO3 behaves as strong
and if X is a thermodynamically unstable compound
acid giving hydronium ion and nitrate ion
then X is [NCERT Pg. 191]
(3) Conc. HNO3 is a strong oxidising agent and
attacks most metals except noble metals (1) O2
(4) The product of oxidation does not depend on (2) O3

concentration of acid, temperature or nature of (3) I2
material undergoing oxidation
(4) SO2
19. Consider the given figure [NCERT Pg. 181]
24. The shape of XeOF4 is [NCERT Pg. 210]
P P P (1) Pyramidal
P P P P P P (“X phosphorous”) .
P P P (2) Square pyramidal

(3) Tetrahedral
All the given properties are possessed by type ‘X’
phosphorus except (4) Octahedral
25. The compound in which nitrogen exhibits lowest 2. NaOH can absorb
oxidation state is [NCERT Pg. 172]
(1) N2O5 (2) N2O
(1) N3H (2) NH3
(3) NO (4) All of these
(3) N2H4 (4) NH2OH
26. The correct order of the reducing strength of the 3. H2N–CONH2 + HNO2  gas
given compounds is [NCERT Pg. 173] Gas can be
(1) PH3 < NH3 < AsH3 < SbH3 < BiH3 (1) N2 (2) N2O
(2) NH3 < AsH3 < PH3 < SbH3 < BiH3 (3) NO (4) NO2
(3) NH3 < PH3 < AsH3 < SbH3 < BiH3
Cu + HNO3 Cu(NO3)2 + gas A
(4) BiH3 < SbH3 < AsH3 < PH3 < NH3 4. dil
< 250
Product C
Cu + HNO3 Cu(NO3)2 + gas B
27. Which of the given acids is most acidic in nature?
Conc
[NCERT Pg. 205]
Correct for the above reaction is
(1) HClO4 (2) HClO3
(1) A = NO (2) C = N2O3
(3) HClO2 (4) HClO
(3) B = NO2 (4) All of these
28. Interhalogen which is very unstable among the
Cold
following is [NCERT Pg. 206] 5. P2O5  H2O   Pr oduct A
(1) ICl (2) BrCl Product A is
(3) IF (4) IBr (1) Orthophosphoric acid (2) Metaphosphoric acid
29. Which of the given noble gases has highest (3) Pyrophosphoric acid (4) Hypophosphoric acid
positive electron gain enthalpy? [NCERT Pg. 208]
6. Number of P–O–P bonds present in P4O6 are
(1) Kr (2) Xe
(1) 4 (2) 5
(3) Rn (4) Ne
(3) 6 (4) 8
30. When sulphur is oxidised using conc H2SO4 the
obtained major product is [NCERT Pg. 196] 7. The hybridisation of S in SF4 is:
(1) SO2 (2) H2S2O8 (1) dsp2 (2) sp3

(3) sp3d (4) sp3d2
(3) H2SO4 (4) H2S
8. Oxidation state of NO in brown ring complex is
SECTION - B
(1) 0 (2) +1
(3) +2 (4) –1
1. NH3 + Cl 2 A + HCl 9. Which of the following does not contain S–S
(excess) H2O
linkage?
(B) + HOCl (1) H2S2O3 (2) H2S2O6
H2O + CrCl3
(3) H2S2O8 (4) All of these
C
(green ppt.) 10. O3 can oxidise
Correct for the above reaction is (1) K4[Fe(CN)6] (2) BaO2
(1) A = NH4Cl, B = NCl3, C = Cr(OH)3 (3) HgO (4) KMnO4
(2) A = NCl3, B = N2, C = Cr2O3 11. The anhydride of HClO4 is
(3) A = N2, B = NH3, C = Cr2O3 (1) Cl2O (2) ClO2

(4) A = NCl3, B = NH3, C = Cr(OH)3 (3) Cl2O6 (4) Cl2O7
12. Consider the following statements
18. NCl3  3H2O  ' A '
(a) OF2 is an acid anhydride
Correct for above reaction is
(b) Bleaching action of SO2 is due to reduction
(1) Hydrolysis occurs due to d-orbital of Cl
(c) Ozone reacts with moist iodine to form HIO3
(2) Product A is NH3
Incorrect among the following is/are
(3) Product A is N2
(1) (a), (b) (2) (b), (c)
(4) Both (1) and (2)
(3) (a), (c) (4) (a) only 19. Incorrect reaction among the following is/are
13. Acidified KIO3 converts into I2 by

(1) NH4NO3   N2O  H2O
(1) O3

(2) KMnO4 (2) (NH4 )2Cr2O7   Cr2O7  O2
(3) SO2
 250K
(3) NO + NO2   N2O3
(4) H2SO4
14. Which of the following pair are mixed anhydride? (4) NO2 + H2O  HNO2 + HNO3
(1) Cl2O, ClO2 20. Ammonia can be identified by
(2) ClO2, Cl2O6 (1) K2HgI4 (2) CuSO4(aq)
(3) NO2, Cl2O6 (3) Red litmus paper (4) All of these
(4) Both (2) & (3)
21. Fe  dil HNO3  Fe(NO3 )2  ' A ' H2O
15. Correct match among the following are
(a) ClO4– > ClO3– > ClO2– > ClO– Stability order Cu  dil HNO3  Cu(NO3 )2  'B' H2O
(b) Cl2 > Br2 > F2 > I2 Bond strength

Ag  conc. HNO3  AgNO3  'C'
(c) OF2 < OCl2 < ClO2 Bond angle
Product A, B, C will be
(d) l– > Br– > Cl– Reducing power
(1) A = NO2, B = NO, C = N2O
(1) (a), (b), (d) (2) (b), (d)
(2) A = N2O, B = NO, C = NO2
(3) (a), (c), (d) (4) All of these
16. Hydrolysis of which of the following is not the (3) A = NO, B = N2O, C = NO2
example of redox reaction? (4) A = NO2, B = NO2, C = N2O
(1) XeF2 (2) XeF4 22. Product formed during hydrolysis of P4O10 is/are
(3) XeF6 (4) All of these (1) HPO3 (2) H4P2O7
17. a. NH3 > PH3 > AsH3 Thermal stability (3) H3PO4 (4) All of these
b. NH3 < PH3 < AsH3 Reducing power 23. Number of P–O–P bonds present in
c. NI3 > NBr3 > NCl3 Lewis basic character cyclotrimetaphosphoric acid (HPO3)3 are
d. N2O5 > P2O5 > As2O5 Acidic character (1) 1 (2) 2
Correct order is (3) 3 (4) 6
(1) a, b & c 24. Which of the following gas is used for artificial
(2) a, b, c and d respiration?
(3) c & d (1) CO2 + O2 (2) CO + O2
(4) a & d (3) H2 + O2 (4) All of these
25. Consider the following statement 32. Total number of lone pair of electron on Xe atom in
XeOF4 is
a. KI  O3  KOH  O2  I2
neutral (1) 0 (2) 1
b. CO can be estimated by I2O5 (3) 2 (4) 3

33. Which of the following is most acidic ?
c. Pb3O4, Fe3O4 are mixed oxide
(1) HClO4 (2) HClO3
d. Bleaching action of SO2 is due to reducing
nature (3) HClO2 (4) HClO
Correct statement is/are 34. Which of the following is not a disproportionation

reaction?
(1) a, c & d
(1) MnO2 + 4HCl  MnCl2 + 2H2O + Cl2
(2) b, c & d
(2) Cl2 + 2NaOH  NaCl + NaClO + H2O
(3) a & b only (3) 4H3PO3  3H3PO4 + PH3
(4) All of these (4) 3HNO2  HNO3 + 2NO + H2O
26. On heating oxalic acid with concentrated H2SO4, 35. Which of the following is not correct?
the gas evolved is
(1) White phosphorus is soluble in CS2
(1) SO2 (2) CO 2 only (2) Holme’s signal uses Ca3P2 and CaC2
(3) CO only (4) CO + CO2
(3) Nitrogen exhibits +5 oxidation state but it does
27. Fluorine reacts with water to give not form pentahalide
(1) HF only (2) HF, O2 or O3 (4) NH3 has lower boiling point than PH3
(3) O2 only (4) O3 only 36. The element in group-15 having maximum melting
point is
28. Incorrect statement from the following is
(1) Sb (2) Bi
(1) Cl2 disproportionate in NaOH aq. solution
(3) As (4) P
(2) Cl2 have permanent bleaching action
37. The shape and hybridisation of some xenon-
–
(3) ClO < ClO 2 < ClO 3 < ClO4 basic nature oxyfluorides are given below. Which of these is
incorrect?
(4) ClO 4 < BrO 4 > IO4 oxidising power (1) XeOF2 – Bent T-shaped and sp3d
29. Deacon’s process is (2) XeOF4 – Square pyramidal and sp3d2
CuCl2 /723 K (3) XeO2F2 – See-saw and sp3d

(1) 4HCl  O2   2H2 O  2Cl2
(4) XeO3F2 – Square planar and sp3
(2) MnO2 + 4HCl  MnCl2 + H2O + Cl2
38. The catalyst used in Contact process is
(3) Ca(OH)2 + Cl2  Ca(OCl)2 (1) SO2Cl2 (2) MnO2
(4) Na2S2O3 + H2O + Cl2  Na2SO4 + 2HCl + S (3) V2O5 (4) H2O2
30. Bleaching action of Bleaching powder is due to the 39. Which of the following is not correct?
formation of
(1) Cane sugar, on heating with concentrated
(1) OCl– (2) O2 H2SO4 produces carbon
(3) Cl2 (4) Cl– (2) In brown ring compound [Fe(H2O)5 NO]SO4,
the oxidation number of Fe is +1
31. XeF6 on complete hydrolysis gives
(3) Brown ring test is used for the identification of
(1) XeO3 (2) XeO NO–3 ion.
(3) XeO2F2 (4) Xe (4) N2O5 is the anhydride of HNO2
40. Clatherates are not formed by 48. Which of the following has maximum bond angle?
(1) He (2) Ne (1) H2S (2) H2O
(3) Ar (4) Both (1) & (2) (3) H2Te (4) H2Se
41. Which of the following compound does not have S – 49. Which of the following statements is incorrect?
S bond ?
(1) Oxygen is more electronegative than sulphur
(1) Solid S3O9 (2) Na2S4O6
(2) Bond energy of F2 is less than Cl2
(3) Na2S2O3 (4) H2S2O6
(3) HOCl is stronger acid than HOBr
42. How many lone pairs are present in P 4 O 6
(4) Ka >>> Ka for H2SO4 in water
molecule? 2 1
50. Which one of the following does not exist?

(1) 4 (2) 8
(1) XeOF4 (2) NeF2
(3) 16 (4) 12
(3) XeF2 (4) XeF4
43. On heating K4[Fe(CN)6] with concentrated H2SO4
gives the gas 51. Predict the product of the following reaction:
(1) CO (2) (CN)2 2Au + 3HNO3 + 11HCl 
(3) C3O2 (4) SO2 (1) HAuCl4 (2) AuCl3
44. Which one of the following compounds on heating (3) NO2 (4) All of these
evolves ammonia gas?
52. Graphite is a good conductor of electricity. Its electrical
(1) (NH4)2Cr2O7 (2) NH4NO2 conductivity is due to the fact that
(3) NH4NO3 (4) (NH4)2SO4 (1) It is an allotrope of carbon
45. Which of the following complex is known as (2) It has C-atoms arranged in large plates of rings
Nessler’s reagent? of strongly bound C-atoms
(1) K4[Fe(CN)6] (2) H2[PtCl6] (3) In it C-atoms are sp2 hybridised
(3) K2[HgI4] (4) [Fe(H2O)5NO]SO4 (4) It is a non-crystalline substance
46. Which of the following is/are correct about the 53. Borax is used as a cleansing agent because on
reaction? dissolving in water, it gives
Hot (1) Alkaline solution
Cl2 + NaOH 
Conc.
 NaCl + NaClO3 + H2O
(2) Acidic solution
(1) It is a disproportionation reaction
(3) Bleaching solution
(2) Oxidation number of chlorine decreases as well
as increases in this reaction (4) Amphoteric solution
(3) n-factor of chlorine is equal to 5/3 54. TII3 (ionic solid) dissociate as
(4) All of these (1) Tl+ + I3– (2) Tl3+ + 3I–
47. Which of the following statements is wrong? (3) Tl+ + 3I– (4) Tl3+ + I3–
(1) The maximum covalency of sulphur is 6 55. The lead of the lead pencils melts at
(2) O3 molecule is angular in shape (1) 2000°C (2) 350°C

(3) 3170°C (4) 75°C
(3) The most stable allotropic form of sulphur is
rhombic sulphur 56. Darkling of surface painted with white lead is due to
(4) When PCl5 reacts with H2SO4, thionyl chloride (1) H2S (2) CO2
is formed (3) Cu (4) O2
57. The main reason that SiCl4 is easily hydrolysed as 66. Which of the following is not correct?
compared to CCl4 is that
(1) Al reacts with NaOH and liberate H2
(1) Si — Si bond is weaker
(2) AlCl3 is a Lewis acid
(2) SiCl4 can form hydrogen bonds
(3) SiCl4 is covalent (3) Al is used in the manufacture of electrical cables
(4) Si can extend its coordination number beyond four (4) NaOH is used during Hall's process of
58. SiCl4 on hydrolysis forms 'X' and HCl. Compound 'X' purification of bauxite
loses water at 1000°C and gives 'Y'. Compounds 'X' 67. X reacts with aqueous NaOH solution to form Y and
and 'Y' respectively are H2. Aqueous solution of Y is heated to 323-333 K
(1) H2SiCl6, SiO2 (2) H4SiO4,Si and on passing CO2 into it, Na2CO3 and Z were
formed. When Z is heated to 1200°C, Al2O3 is
(3) SiO2,Si (4) H4SiO4, SiO2
formed. X, Y and Z respectively are
59. Inorganic graphite is
(1) Al, AlCl3, NaAlO2
(1) B3N3H6 (2) BN
(2) Zn, Na2ZnO2, Al(OH)3
(3) SiC (4) Fe(CO)5
(3) Al, Al(OH)3, AlCl3
60. A fibrous mineral which can withstand red hot flames
without any damage is (4) Al, NaAlO2, Al(OH)3
(1) Talc (2) Glass wool 68. Sindoor is represented by
(3) Soap stone (4) Asbestos (1) Pb(NO3)2 (2) PbCO3Pb(OH)2
61. Product of the following reaction is (3) Pb(OH)24PbCO3 (4) Pb3O4

Al4C3 + D2O  69. Which one of the following statements about the
(1) Al(OD)3 + CD4 (2) Al(OD)2 + CD4 zeolites is false?
(3) Al(OD)4 + CD4 (4) Al(OD)3 + CD (1) They are used as cation exchangers
62. A when added to silicon will give B. A and B are (2) They have open structure which enables them
to take up small molecules
(1) HF, H2SiF4 (2) HF, H2SiF6
(3) Zeolites are aluminosilicates have three
(3) HCl, H2SiCl6 (4) Hl, H2Sil6
dimensional network
63. Monosilane on coming in contact with air burns with
a luminous flame producing vortex rings. These rings (4) Some of the SiO 44– units are replaced by
are of AlO45– and AlO69– ions in zeolites.
(1) SiO2 (2) SiO 70. Gas A is bubbled through slaked lime when a white
precipitate is formed. On prolonged bubbling, the
(3) Si (4) H2SiO3 precipitate is dissolved. On heating the resultant
64. For prevention of rusting to iron, which paint is used? solution, the white precipitate reappears with the
evolution of gas B. The gases A and B respectively
(1) PbO (2) PbO2
are
(3) Pb3O4 (4) PbSO4
(1) CO2 and CO
65. The number of isomers possible for disubstituted
borazine, B3N3H4X2 is (2) CO and CO2
(1) 3 (2) 4 (3) CO and CO
(3) 6 (4) 2 (4) CO2 and CO2
Which of the following is the correct option?
SECTION - C
(a) (b) (c) (d)
Previous Years Questions
(1) (i) (ii) (iii) (iv)
1. Aluminium chloride in acidified aqueous solution
forms a complex 'A', in which hybridisation state of (2) (ii) (iv) (i) (iii)
Al is 'B'. What are 'A' and 'B', respectively? (3) (iii) (iv) (ii) (i)
[NEET-2019 (Odisha)] (4) (iv) (iii) (ii) (i)
(1) [Al(H2O)6]3+ , d2sp3 7. Identify the incorrect statement related to PCl5
from the following: [NEET-2019]
(2) [Al(H2O)6]3+, sp3d2
(1) Three equatorial P–Cl bonds make an angle of
(3) [Al(H2O)4]3+, sp3
120° with each other
(4) [Al(H2O)4]3+, dsp2
(2) Two axial P–Cl bonds make an angle of 180°
2. Which of the following compounds is used in with each other
cosmetic surgery? [NEET-2019 (Odisha)]
(3) Axial P–Cl bonds are longer than equatorial P–
(1) Zeolites (2) Silica Cl bonds
(3) Silicates (4) Silicones (4) PCl5 molecule is non-reactive
3. Which of the following is incorrect statement? 8. The correct order of atomic radii in group 13
elements is [NEET-2018]
[NEET-2019]
(1) B < Al < In < Ga < Tl
(1) PbF4 is covalent in nature
(2) B < Al < Ga < In < Tl
(2) SiCl4 is easily hydrolysed
(3) B < Ga < Al < In < Tl
(3) GeX4 (X = F, Cl, Br, I) is more stable than
GeX2 (4) B < Ga < Al < Tl < In
(4) SnF4 is ionic in nature 9. Which one of the following elements is unable to
form MF63– ion? [NEET-2018]
4. Which of the following species is not stable?
(1) Ga (2) Al
[NEET-2019]
(3) In (4) B
(1) [SiF6]2– (2) [GeCl6]2–
10. Name the gas that can readily decolourises
(3) [Sn(OH)6]2– (4) [SiCl6]2– acidified KMnO4 solution [NEET-2017]
5. Which is the correct thermal stability order for (1) CO2 (2) SO2
H2E (E = O, S, Se, Te and Po)? [NEET-2019]
(3) NO2 (4) P2O5
(1) H2S < H2O < H2Se < H2Te < H2Po
11. In which pair of ions both the species contain
(2) H2O < H2S < H2Se < H2Te < H2Po S–S bond? [NEET-2017]
(3) H2Po < H2Te < H2Se < H2S < H2O (1) S2O72–, S2O32– (2) S4O62–, S2O32–
(4) H2Se < H2Te < H2Po < H2O < H2S (3) S2O72–, S2O82– (4) S4O62–, S2O72–
6. Match the following : [NEET-2019] 12. It is because of inability of ns2 electrons of the
valence shell to participate in bonding that
(a) Pure nitrogen (i) Chlorine
[NEET-2017]
(b) Haber process (ii) Sulphuric acid
(1) Sn2+ is reducing while Pb4+ is oxidising
(c) Contact process (iii) Ammonia
(2) Sn2+ is oxidising while Pb4+ is reducing
(d) Deacon’s process (iv) Sodium azide or
(3) Sn2+ and Pb2+ are both oxidising and reducing
Barium azide
(4) Sn4+ is reducing while Pb4+ is oxidising
13. Match the interhalogen compounds of column I 19. Which one of the following orders is correct for the
with the geometry in column II and assign the bond dissociation enthalpy of halogen molecules?
correct code [NEET-2017]
[NEET-2016]
Column I Column II
(1) F2 > Cl2 > Br2 > I2
(a) XX (i) T-shape
(2) I2 > Br2 > Cl2 > F2
(b) XX3 (ii) Pentagonal bipyramidal (3) Cl2 > Br2 > F2 > I2
(c) XX5 (iii) Linear (4) Br2 > I2 > F2 > Cl2
20. Match the compounds given in Column-I with the
(d) XX7 (iv) Square-pyramidal hybridisation and shape given in Column-II and
mark the corect option. [NEET-2016]
(v) Tetrahedral
Column-I Column-II
(1) a(iii), b(iv), c(i), d(ii) (2) a(iii), b(i), c(iv), d(ii)
(a) X3F6 (i) Distorted octahedral
(3) a(v), b(iv), c(iii), d(ii) (4) a(iv), b(iii), c(ii), d(i)
14. AIF3 is soluble in HF only in presence of KF. It is (b) XeO3 (ii) Square planar
due to the formation of [NEET-(Phase-2)-2016] (c) XeOF4 (iii) Pyramidal
(1) K3[AIF3H3] (2) K3[AIF6] (d) XeF4 (iv) Square pyramidal
(3) AIH3 (4) K[AIF3H]
(a) (b) (c) (d)
15. When copper is heated with conc. HNO 3 , it
(1) (iv) (i) (ii) (iii)
produces [NEET-2016]
(1) Cu(NO3)2 and N2O (2) (i) (iii) (iv) (ii)
(2) Cu(NO3)2 and NO2 (3) (i) (ii) (iv) (iii)
(3) Cu(NO3)2 and NO (4) (iv) (iii) (i) (ii)

(4) Cu(NO3)2, NO and NO2 21. The stability of +1 oxidation state among Al, Ga,
16. Which is the correct statement for the given In and Tl increases in the sequence
acids? [NEET-2016] [Re-AIPMT-2015]
(1) Phosphinic acid is a diprotic acid while (1) TI < In < Ga < Al
phosphonic acid is a monoprotic acid
(2) In < Tl < Ga < Al
(2) Phosphinic acid is a monoprotic acid while
phosphonic acid is a diprotic acid (3) Ga < In < Al < Tl
(3) Both are diprotic acids (4) Al < Ga < In < Tl

(4) Both are triprotic acids 22. The variation of the boiling points of the hydrogen
17. Among the following, the correct order of acidity is halides is in the order HF > HI > HBr > HCl.
[NEET-2016] What explains the higher boiling point of hydrogen

fluoride? [Re-AIPMT-2015]
(1) HCIO4 < HCIO2 < HCIO < HCIO3
(1) The bond energy of HF molecules is greater
(2) HCIO3 < HCIO4 < HCIO2 < HCIO
than in other hydrogen halides
(3) HCIO < HCIO2 < HCIO3 < HCIO4
(2) The effect of nuclear shielding is much reduced
(4) HCIO2 < HCIO < HCIO3 < HCIO4 in fluorine which polarises the HF molecule
18. The product obtained as a result of a reaction of (3) The electronegativity of fluorine is much higher
nitrogen with CaC2 is [NEET-2016] than for other elements in the group
(1) Ca2CN (2) Ca(CN)2 (4) There is strong hydrogen bonding between HF
(3) CaCN (4) CaCN3 molecules
23. Which of the statements given below is incorrect? 30. Which of the following is electron-deficient?
[Re-AIPMT-2015] [NEET-2013]
(1) ONF is isoelectronic with O2N– (1) (SiH3)2 (2) (BH3)2
(2) OF2 is an oxide of fluorine (3) PH3 (4) (CH3)2
(3) Cl2O7 is an anhydride of perchloric acid 31. Which is the strongest acid in the following?
(4) O3 molecule is bent [NEET-2013]
24. Strong reducing behaviour of H3PO2 is due to (1) HClO3
[Re-AIPMT-2015] (2) HClO4
(1) High oxidation state of phosphorus (3) H2SO3
(2) Presence of two –OH groups and one P – H (4) H2SO4
bond
32. Roasting of sulphides give the gas X as by product.
(3) Presence of one –OH group and two P – H This is a colourless gas with choking smell of burnt
bonds sulphur and causes great damage to respiratory
(4) High electron gain enthalpy of phosphorus organs as a result of acid rain. Its aqueous solution
is acidic, acts as a reducing agent and its acid has
25. Acidity of diprotic acids in aqueous solutions never been isolated. The gas X is [NEET-2013]
increases in the order [AIPMT-2014]
(1) SO2 (2) CO2
(1) H2S < H2Se < H2Te
(3) SO3 (4) H2S
(2) H2Se < H2S < H2Te
33. XeF2 is isostructural with [NEET-2013]
(3) H2Te < H2S < H2Se
(1) ICI2– (2) SbCl3
(4) H2Se < H2Te < H2S
(3) BaCl2 (4) TeF2
26. Which of the following structure is similar to
34. Which of the following does not give oxygen on
graphite? [NEET-2013]
heating? [NEET-2013]
(1) B (2) B4C
(1) Zn(ClO3)2
(3) B2H6 (4) BN
(2) K2Cr2O7
27. Which of these is not a monomer for a high molecular
(3) (NH4)2Cr2O7
mass silicone polymer? [NEET-2013]
(4) KClO3
(1) Me2SiCl2
35. Which of the following species contains three bond
(2) Me3SiCl pairs and one lone pair around the central atom ?
(3) PhSiCl3 [AIPMT (Prelims)-2012]
(4) MeSiCl3 (1) NH2– (2) PCl3
28. Which of these is least likely to act as a Lewis (3) H2O (4) BF3
base ? [NEET-2013]
36. When Cl2 gas reacts with hot and concentrated
(1) F– (2) BF3 sodium hydroxide solution, the oxidation number of
(3) PF3 (4) CO chlorine changes from [AIPMT (Prelims)-2012]
(1) Zero to –1 and zero to +3
29. The basic structural unit of silicates is [NEET-2013]
(2) Zero to +1 and zero to –3
(1) SiO44  (2) SiO32 
(3) Zero to +1 and zero to –5
(3) SiO24 (4) SiO– (4) Zero to –1 and zero to +5
37. A mixture of potassium chlorate, oxalic acid and (1) Three dimensional (2) Linear chain silicate
sulphuric acid is heated. During the reaction which
(3) Sheet silicate (4) Pyrosilicate
element undergoes maximum change in the
oxidation number? [AIPMT (Prelims)-2012] 43. Which of the following oxide is amphoteric ?
(1) Cl (2) C [AIPMT (Mains)-2011]
(3) S (4) H (1) SiO2 (2) CO2
38. Sulphur trioxide can be obtained by which of the (3) SnO2 (4) CaO
following reaction [AIPMT (Prelims)-2012]
44. Which one of the following molecular hydrides acts
 as a Lewis acid ? [AIPMT (Prelims)-2010]
(1) S + H2SO4 
(1) NH3 (2) H2O

(2) H2SO4 + PCl5 
(3) B2H6 (4) CH4BF3

(3) CaSO4 + C  45. The tendency of BF3, BCl3 and BBr3 to behave as
Lewis acid decreases in the sequence

(4) Fe2(SO4)3 
39. Which of the following statements is not valid for
(1) BCl3 > BF3 > BBr3 (2) BBr3 > BCl3 > BF3
oxoacids of phosphorus? [AIPMT (Prelims)-2012]
(3) BBr3 > BF3 > BCl3 (4) BF3 > BCl3 > BBr3
(1) All oxoacids contain tetrahedral four
coordinated phosphorus 46. The correct order of increasing bond angles in the
following species are [AIPMT (Prelims)-2010]
(2) All oxoacids contain atleast one P = O unit and
one P–OH group (1) Cl2O < ClO2 < ClO2–
(3) Orthophosphoric acid is used in the (2) ClO2 < Cl2O < ClO2–
manufacture of triple superphosphate (3) Cl2O < ClO2– < ClO2
(4) Hypophosphorous acid is a diprotic acid (4) ClO2– < Cl2O < ClO2
40. In which of the following arrangements the given 47. How many bridging oxygen atoms are present in
sequence is not strictly according to the property P4O10? [AIPMT (Mains)-2010]
indicated against it? [AIPMT (Mains)-2012]
(1) 6 (2) 4
(1) HF < HCl < HBr < HI : increasing acidic
(3) 2 (4) 5
strength
48. Which of the following molecules acts as a Lewis
(2) H2O < H2S < H2Se < H2Te : increasing pKa acid? [AIPMT (Prelims)-2009]
values
(1) (CH3)2O (2) (CH3)3P
(3) NH3 < PH3 < AsH3 < SbH3 : increasing acidic
character (3) (CH3)3N (4) (CH3)3B
(4) CO 2 < SiO 2 < SnO 2 < PbO 2 : increasing 49. Among the following which is the strongest oxidising
agent? [AIPMT (Prelims)-2009]
oxidising power
(1) Br2 (2) I2
41. Which of the following is least likely to behave as
Lewis base? [AIPMT (Prelims)-2011] (3) Cl2 (4) F2
(1) OH– (2) H2O 50. Which one of the following anions is present in the
chain structure of silicates? [AIPMT (Prelims)-2007]
(3) NH3 (4) BF3
42. Name the type of the structure of silicate in which (1) SiO44  (2) Si2O76 
one oxygen atom of [SiO4]4– is shared?
[AIPMT (Prelims)-2011] (3)  SiO 
2
3
n
(4)  Si O 
2
2
5
n
51. Which of the following oxidation states are the most 58. Which of the following is the electron deficient
characteristic for lead and tin respectively ? molecule? [AIPMT (Prelims)-2005]
[AIPMT (Prelims)-2007] (1) B2H6 (2) C2H6
(1) +2, +2 (2) +4, +2 (3) PH3 (4) SiH4
(3) +2, +4 (4) +4, +4 Questions asked Prior to Medical Ent. Exams. 2005
52. Which one of the following orders correctly represents 59. Which statement is wrong?
the increasing acid strengths of the given acids ?
(1) Feldspars are not aluminosilicates
(2) Beryl is an example of cyclic silicate
(1) HOClO3 < HOClO2 < HOClO < HOCl
(3) Mg2SiO4 is orthosilicate
(2) HOCl < HOClO < HOClO2 < HOClO3
(3) HOClO3 < HOCl < HOClO3 < HOClO2 (4) Basic structural unit in silicates SiO44  is the
(4) HOClO2 < HOClO3 < HOClO < HOCl tetrahedron
53. Al2O3 can be converted to anhydrous AlCl3 by heating 60. Carbon and silicon belong to (IV) group. The
maximum coordination number of carbon in
commonly occurring compounds is 4, whereas that
(1) Al2O3 with HCl gas of silicon is 6. This is due to
(2) Al2O3 with NaCl in solid state (1) Availability of low lying d-orbitals in silicon
(3) A mixture of Al2O3 and carbon in dry Cl2 gas (2) Large size of silicon
(4) Al2O3 with Cl2 gas (3) More electropositive nature of silicon
54. Which of the following is the most basic oxide ? (4) Both (2) & (3)
[AIPMT (Prelims)-2006] 61. Which of the following statements about H3BO3 is

not correct?
(1) Al2O3 (2) Sb2O3
(1) It has a layer structure in which planar BO3
(3) Bi2O3 (4) SeO2 units are joined by hydrogen bonds
55. Which of the following is not isostructural with (2) It does not act as proton donor but acts as a
SiCl4 ? [AIPMT (Prelims)-2006] Lewis acid by accepting hydroxyl ion
(3) It is a strong tribasic acid
(1) SCl4 (2) SO24
(4) It is prepared by acidifying an aqueous solution
of borax
(3) PO34 (4) NH4
62. Aluminium (III) chloride forms a dimer because
56. In which of the following molecules are all the bonds aluminium
not equal? [AIPMT (Prelims)-2006]
(1) Belongs to 3rd group
(1) ClF3 (2) BF3 (2) Can have higher coordination number
(3) AlF3 (4) NF3 (3) Cannot form a trimer
57. Which one of the following orders is not in accordance (4) Has high ionization energy
with the property stated against it?
63. Boron compounds behave as Lewis acids, because
of their
(1) F2 > Cl2 > Br2 > I2 : Oxidising power (1) Ionisation property
(2) HI > HBr > HCl > HF : Acidic property in water (2) Electron deficient nature
(3) F2 > Cl2 > Br2 > I2 : Electronegativity (3) Acidic nature
(4) F2 > Cl2 > Br2 > I2 : Bond dissociation energy (4) Covalent nature
64. In graphite, electrons are 72. Which of the following displaces Br 2 from an
aqueous solution containing bromide ions?
(1) Localised on each C-atom
(1) I2 (2) I3–
(2) Localised on every third C-atom
(3) Cl2 (4) Cl–
(3) Delocalised within the layer
73. Repeated use of which one of the following
(4) Present in anti-bonding orbital fertilizers would increase the acidity of the soil?
65. In borax bead test which compound is formed? (1) Ammonium sulphate
(1) Orthoborate (2) Metaborate (2) Superphosphate of lime
(3) Double oxide (4) Tetraborate (3) Urea
66. Which one of the following statements about the (4) Potassium nitrate
zeolite is false?
74. Which of the following oxides is most acidic?
(1) They are used as cation exchangers (1) As2O5 (2) P2O5
(2) They have open structure which enables them (3) N2O5 (4) Sb2O5
to take up small molecules
75. Which of the following phosphorus is the most
(3) Zeolites are aluminosilicates having three reactive?
dimensional network
(1) Scarlet phosphorus (2) White phosphorus
(4) Some of the SiO 44– units are replaced by
(3) Red phosphorus (4) Violet phosphorus
AlO45– and AlO69– ions in zeolites
76. The decomposition of organic compounds, in the
67. The straight chain polymer is formed by
presence of oxygen and without the development of
(1) Hydrolysis of (CH 3 ) 2 SiCl 2 followed by odoriferous substances, is called
condensation polymerisation
(1) Nitrification (2) N2-fixation
(2) Hydrolysis of (CH 3 ) 3 SiCl followed by (3) Decay (4) Denitrification
77. Nitrogen forms N2, but phosphorus does not form
(3) Hydrolysis of CH 3 SiCl 3 followed by P2, however, it forms P4, reason is
(1) Triple bond present between phosphorus atom
(4) Hydrolysis of (CH3)4 Si by addition polymerisation
(2) p – p bonding is weak
68. The metal oxide which cannot be reduced to metal
(3) p – p bonding is strong
by carbon is
(4) Multiple bonds form easily
(1) Fe2O3 (2) Al2O3
78. Which reaction is not feasible?
(3) PbO (4) ZnO
(1) 2KI + Br2  2KBr + I2
69. Oxalic acid on heating with conc. H2SO4 gives
(2) 2KBr + I2  2KI + Br2
(1) CO only (2) CO2 only
(3) 2KBr + Cl2  2KCl + Br2
(3) CO2 + H2O (4) CO + CO2 + H2O
(4) 2H2O + 2F2  4HF + O2
70. Chemical formula of phosgene is
79. Which one of the following statements is not true?
(1) COCl2 (2) CaOCl2
(1) Among halide ions, iodide is the most powerful
(3) CaCO3 (4) COCl reducing agent
71. In which of the following compounds, nitrogen (2) Fluorine is the only halogen that does not show
exhibits highest oxidation state? a variable oxidation state
(1) N3H (2) NH2OH (3) HOCl is a stronger acid than HOBr
(3) N2H4 (4) NH3 (4) HF is a stronger acid than HCl
80. Oxidation states of P in H4P2O5, H4P2O6, H4P2O7,
SECTION - D
are respectively
NEET Booster Questions
(1) + 3, + 4, + 5
1. Tendency to form puckered ring structure of eight
(2) + 3, + 5, + 4
atoms follows the order
(3) + 5, + 3, + 4
(1) S > Se > Te (2) Se > S > Te
(4) + 5, + 4, + 3
(3) Te > Se > S (4) Te > S > Se
81. In which one of the following species the central
2. Aluminium chloride exists as dimer Al2Cl6, when
atom has the type of hybridisation which is not the
dissolved in water forms
same as that present in the other three?
(1) [Al(H2O)6]3+ + 3Cl– (2) [Al(OH)6]3– + 3HCl
(1) PCl5 (2) SF4
(3) I3– (4) SbCl52– (3) Al+3 + 3Cl– (4) Al2O3 + 6HCl
82. Least volatile hydrogen halide is 3. Inorganic graphite is
(1) HF (2) HCl (1) B3N3H6 (2) C
(3) HBr (4) HI (3) (BN)x (4) SiC
83. Pb + conc. HNO3 gives 4. Orthoboric acid

(1) Pb(NO3)2 + NO2 (1) Is a Lewis acid
(2) PbNO3 + N2O (2) Forms a layer structure due to hydrogen bonds
(3) Pb(NO3)2 + N2O3 among BO33  units
(4) Pb(NO3)2 + N2O (3) Burns with ethyl alcohol to give green edged
84. Which has ability to release bromine from KBr? flame due to formation of volatile B(OC2H5)3
(1) I2 (2) Br2 (4) All of these
(3) F2 (4) SO2 5. Repeating unit of organosilicon polymers is
85. Which of the following has P-P linkage? (1) ( R2Si )n (2) ( R2Si – O2 )n
(1) H4P2O6 (2) H4P2O7 (3) ( R2SiO )n (4) All of these
(3) HPO3 (4) H3PO4 6. What is not correct about P4O10?
86. Bonds present in N2O5 are (1) It is anhydride of H3PO4
(1) Only covalent (2) It contains 16 sigma bonds
(2) Only ionic (3) It is anhydride of H4P2O7
(3) Covalent and coordinate
(4) It contains 4  bonds
(4) Covalent and ionic
7. Which is not formed?
87. Which of the following dissolves in water but does
(1) PCl5 (2) AsF5
not gives any oxyacid solution?
(3) SbF5 (4) BiCl5
(1) SO2 (2) OF2
8. CaC2, Be2C and Mg2C3 are known as respectively
(3) SCl4 (4) SO3
(1) Acetylide, methanide and acetylide
88. Which of the following is used during the
preparation of fluorine by Whytlaw Gray method? (2) Acetylide, methanide and allylide
(1) KF(aq) (2) HF(aq) (3) Allylic, methanide and acetylide
(3) Molten KHF2 (4) NH4F (4) Acetylide, methanide and methanide
9. Oxide of phosphorus reacts with water to produce 16. Consider the following statements
an acid. Acid is dibasic and can form two types of
I. PCl3 hydrolyses in the presence of moisture
salts with NaOH. Salts will be
giving fumes of HCl.
(1) NaH2PO3 and Na2HPO3
II. PCl5 exists as [PCl4]– [PCl6]+ in solid state.
(2) NaH2PO4 and Na2HPO4
III. All the five bonds in PCl 5 molecule are
(3) NaH2PO2 and Na2HPO2 equivalent.
(4) NaHPO3 and NaHPO4 Choose the correct statement(s) :
10. Two gases ‘X’ and ‘Y’ act as bleaching agents, ‘X’ (1) Only I (2) I & II
is due to its reducing character and ‘Y’ is due to
(3) II & III (4) I, II & III
its oxidising character. Identify ‘X’ and ‘Y’.
(1) X = SO2, Y = Cl2 (2) X = Cl2, Y = SO2 17. Correct order of acidic strength is
(3) X = NH3, Y = SO2 (4) X = Cl2, Y = NH3 (1) HClO4 > HClO3 > HClO2 > HClO
11. How many B atoms are sp2 hybridised in borax (2) H3PO2 > H3PO3 > H3PO4
structure? (3) HI > HBr > HCl > HF
(1) 1 (2) 2 (4) All of these
(3) 3 (4) 4 18. Give the correct order of stability of trivalent cations
12. Which of the following is responsible factor for of group 13.
weak acidic nature of BF3? (1) In+3 > Tl3+ > Ga3+ (2) Ga+3 > In3+ > Tl3+
(1) p – p back bonding (3) Ga3+ > Tl3+ > In3+ (4) In3+ > Ga3+ > Tl3+
(2) p – d back bonding 19. Borax on strong heating produces
(3) High electronegativity of fluorine (1) Na2B4O7 (2) NaBO2
(4) sp2 hybridisation of boron (3) B2O3 (4) Both (2) & (3)
13. The valency and oxidation number of sulphur in S8
573 K, 60  70 bar
are 20. Xe + F2   A . What is A?
(1 : 20)
(1) 2 and 2 respectively
(2) 0 and 0 respectively (1) XeF2 (2) XeF4
(3) 2 and 0 respectively (3) XeF6 (4) XeF5
(4) 0 and 2 respectively 21. Boron compounds behave as Lewis acids because
of their
14. Which of the following is sesquioxide?
(1) Acidic nature
(1) NO2
(2) Covalent nature
(2) N2O3
(3) Ionisation energy
(3) N2O5
(4) Electron deficient nature
(4) N2O
22. The compound that can act as Lewis base is
15. What is not correct regarding N(CH 3 ) 3 and
N(SiH3)3? (1) BF3 (2) AlCl3
(1) N(CH3)3 is more basic than N(SiH3)3 (3) PCl3 (4) SnCl4
(2) N(CH3)3 is pyramidal in shape 23. In which of the following reaction boron does not
act as reducing agent?
(3) N(SiH3)3 is planar
(4) Central atom is sp 3 hybrid in both the (1) B + CO2  (2) B + Mg 
compounds (3) B + SiO2  (4) B + HNO3 
24. Which of the following statement is correct? 30. Diborane can't be obtained from
(1) Boron and aluminium halides behave as Lewis (1) Na2B4O7 + HCl (2) NaBH4 + I2
acids
(3) BF3 + LiAlH4 (4) BF3 + NaH
(2) Al forms [AlF 6] 3– ion but B does not form
31. Number of hydroxyl group attached to Boron in
[BF6]3– ion
Borax are
(3) The p – p back bonding occurs in the halides
(1) Four (2) Five
of boron and not in those of aluminium
(3) Six (4) Ten
(4) All of these
32. In Diborane, the incorrect statement is
25. White fumes appear around the bottle of anhydrous
AlCl3 due to (1) All 6 B–H bond are on same plane
(1) Decomposition of AlCl3 (2) 4 B–H bonds are on the plane and two B–H
(2) Hydrolysis of AlCl3 liberating H2 gas bonds above and below the plane
(3) Hydrolysis of AlCl3 liberating Cl2 gas (3) It is the 12 valance e– species
(4) Hydrolysis of AlCl3 liberating HCl gas (4) Two BH3 are attached with three centre electron
pair bond
26. Borax is
33. On strong heating, boric acid yields
(1) Na2[B4O5(OH)4].8H2O
(1) B (2) B2H6
(2) Na2[B4O5(OH)6].7H2O
(3) Na2[B4O3(OH)8].6H2O (3) B2O3 (4) BO2
(4) Na2[B4O2(OH)10].5H2O 34. The correct match is
27. Aluminium chloride in acidified aqueous solution (1) C60 – Buckminster fullerene
forms (2) Na2B4O7.4H2O – Kernite
(1) Tetrahedral [Al(H2O)4]+3 ion (3) Borazole – B3N3H6
(2) Octahedral [Al(H2O)4]+3 ion (4) All of these
(3) Tetrahedral [Al(H2O)6]+3 ion 35. The correct match is
(4) Octahedral [Al(H2O)6]+3 ion
(1) B(OH)3 – basic
740°C
28. Na2B4O7 2NaBO2 + B2O3 (2) SnO, PbO – amphoteric
 X + Y
(3) GeO2 – basic
Transparent
(4) PbO2 – only acidic
Z + CuO(s)  Cu(BO2)2
36. C – O bond length is maximum in
Blue Bead
The 'Z' will be (1) CH3CHO (2) CO2
(1) X
(3) CO (4) CO32
(2) Y
37. Dry ice is composed of
(3) Mixture of X & Y in 2 : 1 ratio
(1) Solid He (2) Solid CO2
(4) Mixture of X & Y in 1 : 2 ratio
(3) Solid SO2 (4) Solid C6H6
29. Reaction of ammonia with diborane gives initially
B2H6.2NH3 which can also be written as 38. The metallic character of group 14
(1) [BH2(NH3)2]+[BH4]– (1) Decreases from top to bottom
(2) [BH4]+[BH2(NH3)2]– (2) Increases from top to bottom
(3) [BH3NH3]+[BH4]– (3) Does not change gradually
(4) [B2N2H6]+[H3]– (4) Metallic character is not seen
39. In carbon family the tendency to show +2 45. Catalyst used in Deacon's process is
oxidation state increases in order of
(1) CuCl2 (2) MnO2
(1) Ge < Sn < Pb (3) Fe (4) NO
(2) Pb < Sn < Ge 46. The geometry of SiCl4 is
(3) Sn < Ge < Pb (1) Tetrahedral (2) Square planar
(4) Sn < Pb < Ge (3) Octahedral (4) Planar triangular

47. The correct statement is
40. Which one of the following is correct statement of
fullerenes –C60? (1) Diamond is covalent yet it has high melting
point
(1) Fullerenes are made by heating of graphite in
an electric arc in the presence of Hydrogen (2) [SiF6]2– is known whereas [SiCl6]2– is not
(3) SiO only exist at high temp.
(2) Fullerenes are the only impure form of carbon
due to presence of dangling bonds (4) All of these
(3) Both (1) & (2) 48. The silicates which contain discrete tetrahedral
units are
(4) It contains twenty six-membered rings and
(1) Sheet silicates
twelve five membered rings
(2) Orthosilicates
41. The mixture of CO & H2 is known as
(3) Three dimensional silicates
(1) Water gas or producer gas
(4) Pyrosilicate
(2) Water gas or synthesis gas
Cu Powder 2H2O
49. CH3Cl  Si   x  y
(3) Synthesis gas or producer gas 570 K
(4) Producer gas y & x respectively are

42. When SiCl4 is allowed to undergo hydrolysis it gives
(1) (CH3)2SiCl2, (CH3)2Si(OH)2
(1) SiO2 – Silicic acid (2) (CH3)2Si(OH)2, (CH3)2SiCl2
(2) Si(OH)4 – Silicic acid (3) SiCl4, Si(OH)4
(3) Si(OH)Cl3 – Silicic acid (4) Si(OH)4, SiCl4
(4) SiCl4 do not undergo hydrolysis 50. Hydrolysis of dimethyldichloro silane; (CH3)2SiCl2
followed by condensation polymerisation yields
43. Which statement is correct for carbon family? straight chain polymer of
(1) Tin mainly occurs as Cassiterite, SnO2
O O
(2) Silicon is the third most abundant element on
earth's crust (1) O Si Si O
(3) Only two isotopes of carbon are present C12 O O

and C13
(2) Si O O Si
(4) Germanium is most abundant than other
members of carbon family CH3 CH3
44. p–p multiple bond is seen in (3) O Si O Si O
(1) Mostly carbon CH3 CH3
(2) All carbon family member CH3 CH3

(3) Sn but not in carbon (4) O Si Si O
(4) Boron family and not in carbon family CH3 CH3
51. Silicons are 59. In P4O10 the number co-ordinate bonds is
(1) Water repelling in nature (1) 1 (2) 8
(2) With high thermal stability (3) 3 (4) 4
(3) With high dielectric strength 60. Calomel (Hg2Cl2) on reaction with NH4OH gives
(4) All of these (1) Hg2O (2) HgO
52. Which one is correct statement for zeolite? (3) HgNH2Cl (4) NH2Hg2Cl
(1) They are alumino silicates 61. Nitrogen is obtained when NaNO2 reacts with
(2) Hydrated zeolites are used as ion exchangers (1) NH4Cl (2) NH4NO3
in hardening of soft water
(3) (NH4)2CO3 (4) NH4OH
(3) ZSM-5 is used to convert gasoline to alcohol
62. Oxide which has ‘N – O – N’ bond is
(4) All of these
(1) N2O4 (2) N2O5
53. (i) SiO2 + NaOH ?
(3) N2O (4) N2O3
(ii) SiO2 + HF ?
63. HNO3 + HCl A + NOCl + H2O
The products of (ii) & (i) respectively are
Pt/HCl
(1) H2SiF6, SiO44– (2) SiF4, Na2SiO3
‘P’
(3) Na2SiO3, SiF4 (4) Na2SiO4, H2SiF6
The product ‘P’ will be
54. Calcium carbide on hydrolysis gives
(1) H2PtCl4 (2) H2PtCl6
(1) Ethylene (2) Acetylene
(3) H2PtCl2 (4) H3PtCl3
(3) Methane (4) Propyne
64. What is the product formed when NH3 reacts with
55. Carbon suboxide has the formula
excess of Cl2?
(1) H2CO3 (2) C2O3
(1) NH4Cl & HCl (2) NH4Cl & N2
(3) C3O2 (4) CO
(3) NCl3 & HCl (4) NH4Cl & NCl3
56. NH3  O2  A  H2O
Pt
 65. Hybridisation of central ‘N’-atom in N2O is
A + O2  B (1) sp (2) sp2
B + H2O  C + D (3) sp3 (4) sp & sp2
A, B, C and D respectively are 66. In solid state PBr5 exist as
(1) NO, NO2, HNO3 and HNO2 (1) [PBr4]+ [PBr6]– (2) [PBr5]+ [PBr5]–
(2) NO2, HNO2, NO and HNO3 (3) [PBr4]+ [Br–] (4) PBr5
(3) HNO2, NO2, HNO3 and N2O 67. Which of the following metal gives NH4NO3 with very
dilute HNO3?
(4) HNO2, N2O, NO and HNO3
(1) Fe (2) Ti
57. Which of the following can be hydrolysed?
(3) Cu (4) Hg
(1) TeF6 (2) NF3
68. In iodide of Millon’s base formed by the reaction of
(3) SF6 (4) All of these
Nessler’s reagent with NH3, the coordination number
58. Phosphine on reaction with hydrobromic acid gives of Hg will be
(1) PBr3 (2) P2H4Br2 (1) 2 (2) 3
(3) PBr5 (4) PH4Br (3) 4 (4) 6
69. The compound insoluble in aqueous NH3 is 77. Which of the following is most basic?
(1) AgI (2) AgCl (1) Cl– (2) F–
(3) ZnSO4 (4) HgCl2 (3) I– (4) Br–
70. Which of the following is called mixed anhydride? 78. The final product formed, when alkaline KI solution
reacts with ozone, is
(1) NO2 (2) N2O3
(1) I2
(3) N2O5 (4) All of these
(2) KIO3
71. Which of the following do not exist?
(3) HI
(1) NCl5 (2) PH5
(4) Reaction will not occur
(3) [BCl6]3– (4) All of these
79. The shape of ClF2–, is
72. PCl3 + H2O  A + B. What are A and B
(1) Linear (2) Trigonal bipyramidal
(1) H3PO2 + HCl (2) H3PO4 + HCl
(3) Square pyramidal (4) T-shape
(3) H3PO3 + HCl (4) HPO3 + HClO3
80. Reaction of Cl2 with hot and conc. NaOH produces
(1) NaClO (2) NaClO3
(1) In PF 5 , axial and equatorial bonds are
interchanged, known as pseudo rotation (3) NaClO4 (4) NaClO2
(2) In solid state PF5 remains covalent 81. Hydrolysis of ICI3 forms
(3) PH5 cannot be obtained, because H is not (1) HOI (2) HIO2
sufficiently electronegative to make the
(3) HIO3 (4) HIO4
d-orbitals contact sufficiently
82. Which one of the following does not form during
(4) All of these
the hydrolysis of XeF6?
74. When Cu is reacted with hot concentrated solution
(1) XeO3
of H2SO4 then the gas obtained is
(2) XeOF4
(1) O2 (2) H2
(3) XeO2F2
(3) SO2 (4) SO3
(4) XeOF3
75. A metal X when burnt in air, X-forms oxide and nitride
both, X can be 83. In xenon fluorides most reactive in XeF6, XeF4 and
XeF2 is
(1) Rb (2) Mg
(1) XeF6
(3) Na (4) K
(2) XeF2
76. The most acidic oxide among the following is
(1) SO3 (2) P2O5 (3) XeF4
(3) Cl2O7 (4) SiO2 (4) All are equally reactive


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Chapter 9

Conductance (G) : The reciprocal of resistance is called as conductance i.e.

It measures the ease with which current flows through a conductor.

Resistivity (Specific Resistance)

where  = Constant of proportionality known as resistivity or specific resistance.

Specific Conductance (Conductivity)

Solution : Cell constant = Conductivity × Resistance

= 0.146 × 10–3 × 1500

VARIATION OF MOLAR CONDUCTIVITY WITH CONCENTRATION

KOHLRAUSCH LAW OF INDEPENDENT MIGRATION OF IONS

Cell constant 0.366

Electrolytic Cells & Galvanic Cells

QUANTITATIVE ASPECTS OF ELECTROLYSIS AND FARADAY'S LAWS

Faraday's Second Law of Electrolysis

WAg Eq. wt. of Ag

Note : (i) 1F = 1eq

volume of gas given at STP

1. Electrolysis of dil. H2SO4 liberates gases at anode and cathode respectively

The net reaction is the sum of two half-cell reactions.

At anode : Zn(s)  Zn2 (aq)  2e

Schematic Representation : Zn | Zn+2 || Cu+2 | Cu

ELECTRODE POTENTIAL AND EMF OF A CELL

Standard reduction  Standard reduction 

Copper + Salt bridge

Li+/Li Li+ + e– = Li –3.045 (Lowest)

Zn2+/Zn Zn2+ + 2e– = Zn –0.763

H+/H2, Pt 2H+ + 2e– = H2 0.0 Standard

Cu2+/Cu Cu2+ + 2e– = Cu +0.334

Applications of Electrochemical Series

(ii) SO24  OH  Cl  Br   I (order of discharging at anode).

EMFCell = E°c – E°a

Example 11 : Calcualte the electrode potential of given electrode

Pt, Cl2(1.5 bar) | 2Cl–(0.01M) ; EClº / 2Cl 

Solution : The reaction of electrode is

Cl2 (g) 2e   2Cl 

0.0591 [Cl ]2 0.0591 (0.01)2

Equilibrium Constant and emf

Example 12 : Calculate the equilibrium constant for the cell reaction

E°cell = 0.16 V, n=4

Kc = antilog 10.8 = 6.31 × 1010

Electrochemical Cell and Free Energy

G° = 0 only when equilibrium constant (K) = 1

∵ G° = –2.303 RT log K

Example 13 : Find out work done for the given cell

= –0.44V + 0.74V = 0.30 V Since cell reaction 

(i) O2 + 4H+ + 4e–  2H2O ; E° = 1.229 volt

(ii) 2H2  4H+ + 4e– ; E° = 0 volt

Solution : E°Cell = E°cathode – E°Anode

II. B– + e–  B2– ; E° = – 0.12 V

III. C+ + e–  C ; E° = + 0.18 V

IV. D2+ + 2e–  D ; E° = – 1.12 V

12. The standard electrode potentials EIo /I , EBr

(3) Fe + I2  Fe2+ + 2I– (4) I2 + 2Br–  2I– + Br2

13. Pb+2 + 2e–  Pb(s), E° = – 0.13 V

(1) C1 = C2 (2) C1 > C2

EoCr 3 /Cr = – 0.74 V, EoCd2 /Cd = – 0.40 V

A commercial dry cell

Total cell reaction = PbO2 + Pb + 4H+ + 2SO42–  2PbSO4 + 2H2O

Lead grid packed with Lead grid packed

Hot aqueous KOH