XII-M-4 JEE Chemistry Final

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1
2. Hexagonal Packing
Hexagonal packing is more
efficient. Its coordination
number is 6 and voids in the
packing are smaller than square
packing. If we place another Scan the QR Code in each
layer on square packing then chapter’s theory section to
there are the following
view micro concept videos
related to the chapter, on
SCAN CODE the Vedantu app.
Solid State

Exercise - 2:

2
Solve all types of
1. CsBr crystallizes in a body
centered cubic lattice. The edge
length of unit cell is 436.6 pm.
Given that the atomic mass of
Cs = 133u and Br = 80u, the
exercise questions density of CsBr is:
based on the latest JEE (JEE 2019)
pattern.
(a) 42.5 g/cm3 (b) 0.425 g/cm3
(c) 4.25 g/cm3 (d) 8.5 g/cm3

Answer Key

3
CHAPTER-1: SOLID STATE
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TABLE OF CONTENTS

COORDINATION COMPOUNDS

Theory ................................................................................................................................................ 8
Solved Examples ............................................................................................................................... 28

Exercise - 1 : Basic Objective Questions........................................................................................... 37

Exercise - 2 : Previous Year JEE MAINS Questions .......................................................................... 45


Exercise - 3 : Advanced Objective Questions ................................................................................. 54
Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 58
Answer Key ........................................................................................................................................ 225

CHEMICAL KINETICS

Theory ................................................................................................................................................ 63

Solved Examples ............................................................................................................................... 76

Exercise - 1 : Basic Objective Questions........................................................................................... 88

Exercise - 2 : Previous Year JEE MAINS Questions .......................................................................... 96

Exercise - 3 : Advanced Objective Questions ................................................................................. 103

Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 113

Answer Key ........................................................................................................................................ 227


ELECTROCHEMISTRY

Theory ..................................................................................................................................................... 119

Solved Examples ..................................................................................................................................... 132

Exercise - 1 : Basic Objective Questions.................................................................................................. 144

Exercise - 2 : Previous Year JEE MAINS Questions ................................................................................. 152

Exercise - 3 : Advanced Objective Questions ....................................................................................... 159


Exercise - 4 : Previous Year JEE Advanced Questions ....................................................................... ... 169

Answer Key .............................................................................................................................................. 229

SURFACE CHEMISTRY

Theory ...................................................................................................................................................... 175


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

Exercise - 1 : Basic Objective Questions.................................................................................................. 204

Exercise - 2 : Previous Year JEE MAINS Questions.................................................................................. 209


Exercise - 3 : Advanced Objective Questions ....................................................................................... 216

Exercise - 4 : Previous Year JEE Advanced Questions .......................................................................... 222

Answer Key .............................................................................................................................................. 232


COORDINATION COMPOUNDS
44
Chapter 17 9

COORDINATION COMPOUNDS

Coordination Compounds : A coordination compound is a


1. INTRODUCTION molecular compound that results from the combination of two or
more simple molecular compounds and retains its identity in the
Coordination compounds play a vital role. The importance can
solid as well as in dissolved state
be realised that life would not have been possible without the
existence of chlorophyll (Mg - complex) in plants and haemoglobin Example :
(Fe- complex) in the blood of human beings. The study of these
[Cu (NH3)4]SO4 [Cu (NH3)4]2+ + SO 24
compounds will enlarge our understanding of chemical bonding,
physical properties such as magnetic properties of co-ordination
K4 [Fe(CN)6] 4K+ + [Fe (CN)6]4–
compounds
1.1 Molecular or Addition Compounds 2. COORDINATION COMPOUNDS AND
When solution containing two or more simple stable compounds TERMINOLOGY
in molecular proportions are allowed to evaporate, crystals of
new substances called molecular or addition compounds are A coordination compound consists of a ligand, central atom,
obtained. complex ion, a cation or an anion. The complex ion is generally
written in a square box and the ion (cation or anion) is written
Example :
outside complex ion.
KCl + MgCl2 + 6H2O KCl.MgCl 2 .6H 2 O eg : [Co (NH3)6] Cl3
( Carnallite )
[Complex ion] anion
CuSO4 + 4 NH3 [Cu(NH 3 ) 4 ]SO 4
(Tetrammin e copper (II) eg : K4 [Fe (CN)6]
sulphate)
cation [Complex ion]
Fe(CN)2 + 4KCN K 4 [Fe(CN ) 6 ]
( Potassium ferrocyanide ) General formula : Ax [MLn]/[MLn]By
1.2 Types of Molecular Compounds where : M is the central metal atom/ion
L is the ligand
MOLECULAR COMPOUNDS
A is the cation
B is the anion
DOUBLE SALTS COORDINATION Coordination compounds are the compounds in which the central
COMPOUNDS
metal atom is linked to a number of ligands (ions or neutral
Double Salt : A double salt is a substance obtained by the molecules) by co-ordinate bonds i.e. by donation of lone pairs of
combination of two different salts which crystallize together as a electrons by these ligands to the central metal atom ion.
single substance but ionise as two distinct salts when dissolved If a such a compound carries positive or negative charge, it is
in water. These salts lose their identity in solution i.e. when 4– 2+
called a complex ion, e.g. [Fe(CN)6] , [Cu(NH3)4] . Hence
dissolved in water they give test of all the ions present in the
Coordination compounds may also be defined as those
salt. eg. Potash alum, Mohr’s salt
compounds which contain complex ions, e.g., K4[Fe(CN)6],
FeSO4. (NH4)2 SO4.6H2O  Fe2+ (aq) + 6H2O + 2NH4+ (aq) [Cu(NH3)4]SO4, etc. In general, a complex ion is represented as
(Mohr’s salt) + 2 SO42– (aq) [MLn]  X. Where M is the metal ion, L represents ligands, n is the
K2SO4. Al2 (SO4)3 . 24 H2O  2K+ (aq) + 2Al3+ (aq) + coordination number of metal ion and x is the net charge on the
(Potash alum) 4SO43– (aq) + 24H2O complex.

SCAN CODE
Coordination Compounds
COORDINATION COMPOUNDS 10
There are four types of complexes : Coordination Numbers (C.N.) of Some Common Metal Ions
(i) Cation as complex ion, (carrying a net positive charge) e.g., Univalent C.N. Divalent C.N.
3+
[Cr (NH3)6] in [Cr(NH3)6]Cl3. + 2+
Ag 2 V 6
(ii) Anion as complex ion, (carrying a net negative charge) e.g., + 2+
3– Au 2, 4 Fe 6
[Fe(CN)6] in K3 [Fe(CN)6]. + 2+
Ti 2 Co 4, 6
(iii) Cation and anion both as complex ion. Carrying both + ive + 2+
and –ive change. For e.g., [Pt(Py)4] [PtCl4]. Cu 2, 4 Ni 4,6
2+
(iv) Neutral complex (A complex carrying no net charge) e.g., Cu 4, 6
2+
[Ni(CO)4] etc. Zn 4
2+
Some Important Terms Pertaining to Coordination Compounds: Pd 4
2+
2.1 Coordination Entity Pt 4
It is the central metal atom or ion which is bonded to a definite Coordination Numbers (C.N.) of Some Common Metal Ions
number of ions or molecules which is fixed. For example, in
Trivalent C.N. Tetravalent C.N.
[Co(NH3)6]Cl3, a coordination entity, six ammonia molecules are 3+ 4+
surrounded by three chloride ions. Sc 6 Pt 6
3+ 4+
2.2 Central Atom/Ion Cr 6 Pd 6
3+
The cation or neutral atom to which one or more ligands (neutral Fe 6
molecules or anions) are attached or coordinated is the centre of 3+
Co 6
coordination.
2.5 Coordination Sphere
The central atom/ion must have empty orbitals as it acts as an
The central metal atom or ion and the ligands that are directly
acceptor and thus has to accommodate electron pairs donated by
the donor atom of the ligand. This explains why the transition metal attached to it are enclosed in a square bracket. This had been
called coordination sphere or first sphere of attraction. It behaves
having empty d-orbitals, form coordination compounds very readily.
2+ –3 2+ as a single unit because the ligands present in the coordination
For example in the complexes [Ni(NH3)6] and [Fe(CN)6] , Ni sphere are held tightly by the metal ion.
3+
and Fe respectively are the central ions.
2.3 Ligands
The ions or molecules bound to the central atom/ion in the
coordination entity are called ligands. These may be simple ions
such as Cl–, small molecules such as H2O or NH3, larger molecules
such as H2NCH2CH2NH2.
2.4 Coordination Number (C.N)
The number of atoms of the ligands that directly bound to the
central metal atom or ion by coordinate bonds is known as the 2.6 Coordination Polyhedron
coordination number of the metal atom or ion. It is also equal to A coordination polyhedron is the spatial arrangement of the ligand
the secondary valency. atoms that are directly attached to the central atom/ion. For
Coordination Number of Various Complex example, [Co(NH3)6]3+ is octahedral, [Ni(CO)4] is tetrahedral and
[PtCl4]2– is square planar.
Complex Coordination numbers
2.7 Oxidation Number of Central Metal Atom
K4 [Fe (CN)6] 6
It is defined as the charge that the central metal ion would carry
[Ag (CN)2]– 2
if all the ligands are removed along with electron pairs. It is
[Pt (NH3)2 Cl2] 4
calculate as follows :
[Ca (EDTA)]2– 6
Example:
K4 [Fe (CN)6]
+ 4–
K4 [Fe (CN)6]  4 K + [Fe (CN)6]

SCAN CODE
Coordination Compounds
COORDINATION COMPOUNDS 11
Charge on complex ion = – 4
Let charge on Fe = x, 3. 4.

Now charge on cyanide ion (CN ) = –1
 x + 6 × (–1) = – 4
(Can behave as a
 x=+ 2 monodentate ligand)
Hence oxidation no of Fe = + 2 (or II)
2.8 Homoleptic and Hetroleptic Complexes
Complexes in which central atom is coordinated with only one kind 5. 6.
3+
of ligands are called homoleptic complexes, eg. [Co(NH3)6] .
Complexes in which central atom is coordinated with more than one
+
kind of ligands are called hetroleptic complexes, eg. [Co (NH3)4 Cl2] .

3. CLASSIFICATION OF LIGAND
An atom, ion or molecule which can donate alteast a pair of
electrons to the central atom to form a coordinate bond (or dative
linkage) is called as a ligand or a coordinating group. Further in a 7. 8.
ligand, the particular atom which actually donates the electron
pair is called the donor atom.
The ligands act as Lewis bases as they donate one or more
electron pair to the central metal atoms or ions witch act as Lewis
acids by accepting electrons.
Example: H2O, NH3, CN–, Cl–, OH– 9.

3.1 Types of Ligands on Basis of Denticity


Ligands can be classified on the number of lone pair electrons
they donate to the central metal atom or ion.
(i) Monodentate or unidentate ligands : They have one donor (iii) Tridentate Ligand: The ligands having three donor atoms
atom that donates only one electron pair to central metal are called tridentate ligands.
atom. eg : Example:
– –
F , Cl , Br– , H2O, NH3, CN , NO 2 , OH , NH 2 , CO, R–OH,
– –

pyridine.
(ii) Bidentate ligands : Ligands which have two donor atoms
and have the ability to link with central metal at two positions 1. 2.
are called bidentate ligands
Example:
(iv) Tetradentate Ligand:These ligand possess four donor atoms
Example:

1. 2.

SCAN CODE
Coordination Compounds
COORDINATION COMPOUNDS 12
(v) Pentadentate Ligands:They have five donor atoms 3.2 Types of Ligands on Basis of Charge
Example: (i) Positive Charge Ligands : NO+, N2H5+
(ii) Negative Charge Ligands : CN– , F–, Br–
(iii) Neutral Ligands : CO, NH3

4. NOMENCLATURE OF COORDINATION
COMPOUNDS
4.1 Nomenclature
(vi) Hexadentate Ligands: They have six donor atoms. Following rules are adopted for naming a complex ion :
Example: (i) Cations are named before anions
(ii) Oxidation state (O.S.) of the central metal ion is denoted
by Roman numeral.
Oxidation State in Various Compounds
Compound Cation O.S. Anion
CuCl Copper (I) chloride
CuCl2 Copper (II) chloride

(vii) Chelating Ligands : A bidentate or a polydentate ligand is FeCl2 Iron (II) chloride
known as a chelating ligand if on co-ordination it results in FeCl3 Iron (III) chloride
the formation of a cyclic ring structure. The complex thus (iii) The names of ligands are given first followed by the name of
formed are called chelates. the central metal ion.
(iv) The names of ligands that are anions and ending with
‘ide’ are changed to ‘o’
‘ite’ are changed to ‘ito’
‘ate’ are changed to ‘ato’
The chelates containing 5 or 6 membered rings are more
(v) Many ligands that are molecules carry the unmodified name
stable. Ligands with larger groups form more unstable rings than
with smaller groups due to steric hinderance. (vi) Positive groups end in – ium
(viii) Ambidentate Ligands : The ligands which have two donor NH 2  NH3 hydrazinium.
atoms but in forming complexes only one donor atom is
(vii) When there are several ligands of the same kind, we normally
attached to the metal atom at a given time. Such ligands are
use the prefixes di, tri, tetra, penta and hexa to show the
called ambidentate ligands.
number of ligands of that type. An exception occurs when
Example: the name of the ligands includes a number, for example as in
ethylenediamine (en). To avoid confusion in such cases,
bis, tris and tetrakis are used instead of di, tri and tetra, and
the name of the ligand is placed in brackets.
e.g. bis (ethylenediamine)
(viii) If anion is a complex, then metal ends with ‘ate’

[ Ni(CN) 4 ]2 : tetracyanonickelate (II) ion

SCAN CODE
Coordination Compounds
COORDINATION COMPOUNDS 13
Name of Various Metals in Anionic Complex Sol.
Metal Name (a) Hexaammineiron (III) Chloride
Lead Plumbate (b) Pentaamminechloridocobalt (III) ion
Gold Aurate (c) Tetraamminesulphatocobalt (III) nitrate
Zinc Zincate (d) Tetrapyridineplatinum (II) tetrachloridoplatinate (II)
Tin Stannate (e) Tris (ethylenediamine) chromium (III) chloride
Silver Argentate (f) Tetrakis (ethylenediamine)–-hydroxo--imidodicobalt (III) ion.
Cobalt Cobaltate 5. WERNER’S THEORY
Iron Ferrate
Werner explained the nature of bonding in complexes Alfred
Aluminium Aluminate Werner (considered as the father of coordination chemistry)
Manganese Manganate studied the structure of coordination complexes such as
Copper Cuprate CoCl3.6NH3 and CuSO4.4NH3 in 1893.

Chromium Chromate 5.1 Postulate of Werner’s Coordination Theory

Platinum Platinate (a) Each metal in coordination compound possesses two type
of valencies:
(ix) If the complex contains two or more metal atoms, it is termed
polynuclear. The bridging ligands which link the two metal (i) Primary valency or principal valencies or ionisable
atoms together are indicated by the prefix  – valencies.

(x) Ambidentate ligands may be attached through different (ii) Secondary valency or nonionisable valencies
atoms (b) Primary valencies are satisfied by anions only. The number
M  NO2 (NO2 joined to metal M through of primary valencies depends upon the oxidation state of
N; it is nitrito-N) the central metal. It may change from one compound to other.
M  ONO (NO2 joined to metal M through These are represented by dotted lines between central metal
O; it is nitrito-O) atom and anion.

Similarly, the SCN group may bond M – SCN (thiocyanato) (i) Electrical conductance of complexes – More the number
or M – NCS (isothiocyanato). of ions provided greater is the electrical conductance
of the complex in aqueous medium.
(xi) When writing (not naming) the formula of the complex :
e.g., The electrical conductance of aqueous [Fe(NH3)6]Cl3 is
* Complex ion should be enclosed by square brackets and
greater than that of aqueous solution of [Fe(NH3)5Cl].
Example: [Fe(NH3)5Cl]Cl2  [Fe(NH3)5Cl]2  2Cl Total 3 ions
Write the name of the following compounds? Representation of complexes – Werner’s representation for
(a) [Fe(NH3)6]Cl3 Fe(NH3)6Cl3
2+
(b) [CoCl(NH3)5]
(c) [CoSO4 (NH3)4] NO3
(d) [Pt (Py)4] [PtCl4]
(e) [Cr (en)3] Cl3
4+
NH
Representation of primary and secondary valency
(f) (en)2 Co Co (en)2
OH (Dotted lines indicate primary Valency and continuous lines
indicate secondary valency of metal ion.)

SCAN CODE
Coordination Compounds
COORDINATION COMPOUNDS 14
(ii) Fe(NH3)5Cl3 in this complex ‘Cl’ groups act as primary K4 [Fe (CN)6] : six ligands are coordinated to Fe. Hence secondary
valencies and one of the ‘Cl’ act as secondary valency valency is 6.
also. Thus werner’s representation for this complex will
The primary valency is satisfied by ions attached to the complex
be
ions. It is shown by dotted lines. Primary valency is also known
as ionisable valency.
The secondary valency is satisfied by the ligands, they are non
ionisable and are shown by a solid line [Co (NH3)6] Cl3 can be
represented as
Cl Cl
Representation of primary and secondary valency H3N NH3
(iii) Fe(NH3)4Cl3 In this complex ‘Cl’ groups act as primary H3N NH3
Co
valencies and two of the ‘Cl’ act as secondary valency
also. Thus this complex is represented as H3N NH3
Cl
Representation of primary and secondary valency
An anion present in co-ordination and ionization sphere is shown
by
Every element tends to satisfy both its primary and secondary
valencies. A negative ion when present in the coordination sphere
Representation of primary and secondary valency
shows a dual behaviour. It may satisfy both primary and
Example: secondary valencies.
What are the secondary valency of [Co(NH3)6]Cl3 & K4[Fe (CN)6]?
Sol. In [Co (NH3)6] Cl3 the secondary valency is 6.

Examples of Primary and Secondary Valency in Various Complex


Coordination Modern Charge on Coordination no. Primary Total no. of
Compounds formula the complex (secondary val.) valency ions
PtCl4.6NH3 [Pt(NH3)6]Cl4 +4 6 4 5
PtCl4.5NH3 [Pt(NH3)5Cl]Cl3 +3 6 4 4
PtCl4.4NH3 [Pt(NH3)4Cl2]Cl2 +2 6 4 3
PtCl4.3NH3 [Pt(NH3)3Cl3]Cl +1 6 4 2
PtCl4.2NH3 [Pt(NH3)2Cl4] 0 6 4 Non-electrolyte

SCAN CODE
Coordination Compounds
COORDINATION COMPOUNDS 15
The ligand which satisfy the secondary valencies are directed since penultimate d-orbitals are near in energy to s and p-orbitals
toward fixed positions in space. The geometry of the complex ion of the outer most shell, various kinds of hybridization is possible.
depends on the coordination number. If the metal has coodination 7.1 Postulates of VBT
number 6, the complex is octahedral, i.e. six positions around the
VBT makes the following assumption :
metal are occupied by six donor atoms of the ligands octahedrally.
On the other hand, if the coordination number is 4, the geometry (i) A number of empty orbitals are available on the central metal
of the complex may be tetrahedral or square planar. This postulate ion which can accomodate electrons donated by the ligands.
predicted the existence of different types of isomerism in The number of empty d-orbitals is equal to the coordination
coordination compounds. number of the metal ion for the particular complex.
(ii) The metal orbitals and ligand orbitals overlap to form strong
6. EFFECTIVE ATOMIC NUMBER (EAN) bonds. Greater the extent of overlapping, more is the stability
Sidgwick proposed effective atomic number abbreviated as EAN, of the complex. Different orbitals (s, p or d) hydridize to give
which is defined as the resultant number of electrons with the a set of equivalent hybridized orbital which take part in
metal atom or ion after gaining electrons from the donor atoms of bonding with the ligands.
the ligands. The effective atomic number (EAN) generally (iii) Each ligand donates a pair of electrons to the central metal
coincides with the atomic number of next inert gas in some cases. ion/atom.
EAN is calculated by the following relation : (iv) The non-bonding metal electrons present in the inner orbitals
EAN = Atomic number of the metal – number of electrons lost in do not take part in chemical bonding.
ion formation + number of electrons gained from the donor atoms (v) If the complex contains unpaired electrons, the complex is
of the ligands. (2 × CN) paramagnetic. If it does not contain unpaired electron, the
If EAN number is less than next inert gas configuration complex complex is diamagnetic in nature.
behave as a oxidising agent, If EAN number is more than next (vi) Under the influence of strong ligand (CN, CO) the electrons
inert gas configuration complex behave as a reducing agent. can be forced to pair up against the Hund’s rule of multiplicity.
The EAN values of various metals in their respective complexes Structure of Complexes
are tabulated below: Coordination Hybridi- Shape Geometry
Effective Atomic Number Number zation
Complex Metal Atomic Coordination Effective 2 sp Linear X —A— X
(O.S) No. Number Atomic Number
K4[Fe(CN)6] +2 26 4 (26 –2)+(6×2) 4 sp3 Tetrahedron
=36[Kr]
[Cu(NH3)4]SO4 +2 29 4 (29–2)+(4×2) 4 dsp2 Square
=35 d orbital planar
[Co(NH3)6]Cl3 +3 27 6 (27–3)+(6×2) involve is
=36[Kr] d x 2 – y2
Ni(CO)4 0 28 4 (28–0)+(4×2)
5 dsp3 Trigonal
=36[Kr]
bipyramid
K2[Ni(CN)4] +2 28 4 (28–2)+(4×2)
=34
6 d2sp3 or Octahedral
7. BONDING IN COORDINATION COMPOUND sp 3d 2
(VALENCE BOND THEORY) d orbital
involve is
The bonding in coordination compounds can be explained by
Valence Bond Theory (VBT) since majority of the complexes d x 2 – y2 ,
formed by the transition metals have their d-orbitals incomplete. d z2
Valence bond takes into account the hybridisation of orbitals

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Coordination Compounds
COORDINATION COMPOUNDS 16

NOTE The lobes of the eg orbitals (d x 2  y2 and d z 2 ) point along the x, y


In d sp hybridisation, the inner d-orbitals (3d orbital) has been
2 3

used for bonding, such complexes are called inner orbital and z axes. the lobes of the t2g orbitals (d xy , d xz and d yz ) point in
complexes or low spin complexes. between the axes. The approach of six ligands along the x, y, z, -x,
In sp d hybridisation the outer d-orbitals (4d orbital) has been
3 2
– y and – z directions will increase the energy of the d x 2  y2 and
used for bonding, such complex are called outer orbital complexes
or high spin complexes. d z 2 orbitals (which point along the axes) much more than it
increases the energy of the dxy, dxz and dyz orbitals (which point
The magnetic moment is given by n ( n  2) BM where n is between the axes). Thus under the influence of an octahedral
the number of unpaired electrons.
ligand field the d orbitals split into two groups of different energies.
7.2 Limitations of VBT
(i) The change in the properties of the ligands and the metal
ions could not be explained.
(ii) The valence bond theory does not explain why certain
complexes are more labile than other.
(iii) The VBT does not provide satisfactory explanation for the
existence of inner orbital and outer orbital complexes.
(iv) The VBT could not explain the colour of complexes

8. CRYSTAL FIELD THEORY


The Crystal Field Theory is more widely accepted than the valence
bond theory. It assumes that the attraction between the central Splitting in Octahedral Complex
metal and the ligands in a complex is purely electrostatic. In the Ligands which cause only a small degree of crystal field splitting are
crystal field the following assumptions are made : termed weak field ligands. Ligands which cause a large splitting are
(i) Ligands are treated as point charges. called strong field ligands. The common ligands can be arranged in
ascending order of crystal field splitting .
(ii) There is no interaction between metal orbitals and ligand
orbitals. 8.2 Spectrochemical Series

(iii) The d orbitals on the metal all have the same energy (that is I– < Br– < S2– < Cl– < NO3 < F– < OH– < EtOH < oxalate < H2O
degenerate) in the free atom. However, when a complex is
formed the ligands destroy the degeneracy of these orbitals, (Weak field ligands)
i.e. the orbitals now have different energies. < EDTA < (NH3 = pyridine) < ethylenediamine < dipyridyl < o-
8.1 Octahedral complexes phenanthroline < NO 2 < CN– < CO
In an octahedral complex, the metal is at the centre of the
(Strong field ligands)
octahedron, and the ligands are at the six corners. The directions
x, y and z point to three adjacent corners of the octahedron as A pattern of increasing s donation is followed :
shown. Halide donors < O donors < N donors < C donors
z
8.3 CFSE and its Calculation
The total crystal field stabilization energy is given by
y CFSE (octahedral)   –n t 2 g   O  n eg   O   n * p

Here n* is number of extra pair formed due to ligand.

x
Approach of Ligands in Octahedral Complex

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COORDINATION COMPOUNDS 17
where n ( t 2 g ) and n ( eg ) are the number of electrons occupying
the t2g and eg orbitals respectively. The CFSE is zero for ions with d0
and d10 configurations in both strong and weak ligand field. The
CFSE is also zero for d5 configurations in a weak field.
8.4 Tetrahedral Complexes
A regular tetrahedron is related to a cube. One atom is at the
centre of the cube, and four of the eight corners of the cube are
occupied by ligands as shown. Approach of Ligands in Tetrahedral Complex

Effects of Crystal Field Splitting


Number Arrangement in weak ligand field Arrangement in strong ligand field
of d electrons
t2g eg CFSE Spin only t2g eg CFSE Spin only
o magnetic moment o magnetic moment
s (D) s (D)

d1 1.73 1.73

d2 2.83 2.83

d3 3.87 3.87

d4 4.90 2.83

– 0.6
d5 5.92 1.73

– 0.0
d6 4.90 0.00
– 0.4
7
d 3.87 1.73

– 0.8 – 1.8
d8 2.83 2.83
– 1.2 – 1.2
d9 1.73 1.73
– 0.6 – 0.6
10
d 0.00 0.00
0.0 0.0

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Coordination Compounds
COORDINATION COMPOUNDS 18
The directions x, y and z point to the centres of the faces of the (ii) The direction of the orbitals does not coincide with the
cube. The eg orbitals point along x, y and z axes (that is to the direction of the ligands. This reduces the crystal field splitting
centres of the faces). The t2g orbitals point between x, y and z axes by roughly a further two third.
(that is towards the centres of the edges of the cube). The direction Thus the tetrahedral crystal field splitting  t is roughly
of approach of the ligands does not coincide exactly with either 2/3 × 2/3 = 4/9 of the octahedral crystal field splitting o.
the eg or the t2g orbitals.
Thus the t2g orbitals are nearer to the direction of the ligands than
the eg orbitals. The approach of the ligands raises the energy of
both sets of orbitals. The energy of the t2g orbitals is raised most
because they are closest to the ligands. The crystal field splitting
is the opposite way round to that in octahedral complexes
The t2g orbitals are 0.4t above weighted average energy of the
two groups (the Bari centre) and the eg orbitals are 0.6t below
the average.
The magnitude of the crystal field splitting t in tetrahedral
Splitting in Tetrahedral Complex
complexes is considerably less than in octahedral fields. There
8.5 Colour in Coordination Compounds
are two reasons for this :
The colour of the complex is complementary to that which is
(i) There are only four ligands instead of six, so the ligand field
absobed. The complemantary colour is the colour generated from
is only two third the size ; hence the ligand field splitting is the wavelength left over; if green light is absorbed by the complex,
also two third the size. it appears red.

Relationship between the Wavelength of Light absorbed and the Colour observed in some Coordination Entities
Coordination Wavelength of Light Colour of Light Colour of Coordination Entity
Entity Absorbed (nm) Absorbed
2+
[CoCl(NH3)5] 535 Yellow Violet
3+
[Co(NH3)5(H2O)] 500 Blue Green Red
3+
[Co(NH3)6] 475 Blue Yellow Orange
3–
[Co(CN)6] 310 Ultraviolet Pale Yellow
2+
[Cu(H2O)4] 600 Red Blue
3+
[Ti(H2O)6] 498 Blue Green Violet

9. ORGANOMETALLIC COMPOUNDS (i) Sigma () bonded complexes.


(ii) Pi () bonded complexes,
Compounds that contain at least one carbon–metal bond are called
organometallic compounds. (iii) Complexes containing both – and –bonding characteristics.
Grignard reagent, RMgX is a familiar example of organometallic 9.1 Sigma Bonded Complexes
compounds where R is an alkyl group. Diethyl zinc [Zn(C2H5)2], In these complexes, the metal atom and carbon atom of the ligand are
lead tetraethyl [Pb(C2H5)4], ferrocene [Fe(C5H5)2], dibenzene joined together with a sigma bond, i.e., the ligand contributes one
chromium [Cr(C6H6)2], metal carbonyls are other examples of electron and is, therefore, called one electron donor. Examples are:
organometallic compounds.
(i) Grignard reagent, R–Mg–X where R is an alkyl or aryl group
Organometallic compounds may be classified in three classes: and X is halogen.

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COORDINATION COMPOUNDS 19
(ii) Zinc compounds of the formula R2Zn such as (C2H5)2Zn.
This was first isolated by Frankland in 1849. Other similar
compounds are (CH3)4Sn, (C2H5)4Pb, Al2(CH3)6, Al2(C2H5)6 Metal Carbonyl Bonding
and Pb(CH3)4, etc.
Formation of –bond is caused when a filled orbital of the metal
9.2 –bonded Organometallic Compounds atom overlaps with a vacant antibonding * orbital of C atom of
These are the compounds of metals with alkenes, alkynes, benzene carbon monoxide. This overlap is also called back donation of
and other ring compounds. In these complexes, the metal and electrons by metal atom to carbon. It has been shown below :
ligand form a bond that involves the  electrons of the ligand.
Three common examples are Zeise’s salt, ferrocene and dibenzene
chromium. These are shown here :

Synergic Bonding in Metal Carbonyls


The –overlap is perpendicular to the nodal plane of –bond.
In olefinic complexes, the bonding –orbital electrons are donated
to the empty orbital of the metal atom and at the same time back
bonding occurs from filled orbital of the metal atom to the
antibonding –orbital of the olefin.

10. ISOMERISM
–bonded Organometallic Compounds
The number of carbon atoms bound to the metal in these The compounds having same molecular formula but different
compounds is indicated by the Greek letter ‘’ (eta) with a number. structural formula are called isomers.
2 5 6
The prefixes  ,  and  indicate that 2, 5 and 6 carbon atoms
are bound to the metal in the compound.
9.3 – and –bonded Organometallic Compounds
Metal carbonyls, compounds formed between metal and carbon
monoxide belong to this class. These compounds posses both
– and – bonding. The oxidation state of metal atoms in these
compounds is zero. Carbonyls may be monomeric, bridged or
polynuclear.

10.1 Structural Isomerism


10.1.1 Ionisation Isomerism
This type of isomerism arises when the coordination compounds
– and –bonded Organometallic Compounds give different ions in solution. For example, there are two isomers
of the formula Co (NH3)5 BrSO4.
In a metal carbonyl, the metal–carbon bond possesses both the
– and –character. A –bond between metal and carbon atom is [Co(NH 3 ) 5 Br]2   SO 24 
[Co( NH 3 )5 Br ] SO 4
formed when a vacant hybrid orbitals of the metal atom overlaps ( Violet ) Pentaammin ebromido
 cobalt (III) ion
with an orbital on C atom of carbon monoxide containing a lone
pair of electrons.

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COORDINATION COMPOUNDS 20
This isomer gives a white percipitate of BaSO4 with BaCl2 solution. 10.1.6 Coordination Position Isomerism

[Co( NH 3 )5 SO 4 ]Br [Co(NH 3 ) 5 SO 4 ]  Br  This type of isomerism is exhibited by polynuclear complexes by


(Red) Pentaammin esulphato changing the position of ligands with respect to different metal
 cobalt (III) ion
atoms present in the complex. For example,
Above isomer gives light yellow precipitate with AgNO3 solution.
10.1.2 Hydrate Isomerism
This type of isomerism arises when different number of water
molecules are present inside and outside the coordination sphere.
This isomerism is best illustrated by the three isomers that have
the formula CrCl3.6H2O.
[Cr(H2O)6]Cl3 , [Cr(H2O)5Cl]Cl2.H2O, and [Cr(H2O)4Cl2] Cl.2H2O are
its Hydrate Isomers.
10.1.3 Cordination Isomerism
This type of isomerism is observed in the coordination compounds 10.2 Stereo Isomerism
having both cationic and anionic complex ions. The ligands are
Stereo isomerism is exhibited by those compounds which have
interchanged in both the cationic and anionic ions to form isomers.
the same position of atoms or groups but these atoms or groups
An examples is :
have different arrangement around the central atom.
[Pt ( NH3 ) 4 ] [CuCl 4 ] and [Cu ( NH3 ) 4 ] [PtCl 4 ]
Tetraammineplatinum (II) Tetraamminecopper (II) (In space around the metal ion).
tetrachloridocuprate (II) tetrachloridoplatinate (II)
10.2.1 Geometrical Isomerism
10.1.4 Linkage Isomerism
The complex compounds which have the same ligands in the
This type of isomerism occurs in complex compounds which
coordination sphere but the relative position of the ligands around
contain ambidentate ligands like NO 2 , SCN  . the central metal atom is different are called geometrical isomers
For example, [Co(NH3)5NO2] Cl2 and [Co(NH3)5ONO] Cl2 are and the phenomenon is called geometrical isomerism.
linkage isomers as NO 2 is linked through N or through O. (a) Geometrical isomerism in square planar complexes: A square
planar complexe having similar ligands at adjacent positions
10.1.5 Ligand Isomerism
(90º a part) is called cis - isomer while a square planar complex
Some ligands themselves are capable of existing as isomers, e.g.,
having two similar ligands at opposite positions (180º a part)
diamino propane can exist both as 1, 2-diamino propane (pn) and
1, 3-diamino propane, also called trimethylene diamine (tn). is called trans-isomer.
1 2 3 1. [Ma4]: Does not show Geometrical Isomerism.
CH3 CH2 CH3
propane 2. [Ma3b] : Does not show Geometrical Isomerism.
3. [Ma2b2]

When these ligands (i.e., pn and tn) are associated into complexes
the complexes are isomers of each other. One example of isomeric
complexes having this ligand is : [Co(pn)2 Cl2]+ and [Co(tn)2 Cl2]+
ions.

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COORDINATION COMPOUNDS 21
Example: Example:
Draw the geometrical isomers of [PtCl2(NH3)2] Draw the geometrical isomers of [PtClBr(Py) (NH3)]
Sol. Sol.

Cis and trans forms of the complex [PtCl2(NH3)2] 6. [M (AB)2]


4. [Ma2bc] Example:
Draw the geometrical isomers of [Pt(gly)2]
Sol.

Cis and trans forms of the complex of the type [Ma2bc]


Example:
Draw the geometrical isomers of [PtCl2(NH3)py]
Sol.

Cis and trans forms of the complex [Pt(gly)2]


5. [Mabcd] (b) Geomertical isomerism in tetrahedral complexes
Does not show Geometrical Isomerism.
(c) Geomertical isomerism in octahedral complexes
1. [Ma6] : Does not show Geometrical Isomerism.
2. [Ma5b] : Does not show Geometrical Isomerism.
3. [Ma4b2]

Three isomeric structures of the complex Mabcd

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Coordination Compounds
COORDINATION COMPOUNDS 22
Example: Sol.
Draw the geometrical isomers of [CrCl2(NH3)4]+
Sol.

7. [M(AA)2b2]

Cis and trans forms of [CrCl2(NH3)4]+ complex


4. [Ma3b3]

Example:
Draw the geometrical isomers of [CoCl2(en)2]+
Sol.

Example:
Draw the geometrical isomers of [RhCl3(py)3]
Sol.

Cis and trans-isomers of [CoIII (en)2 Cl2]+ ion.


(a) Cis-isomer (b) trans-isomer
8. [M (AA)2bc]
Cis and trans forms of complex [Rh Cl3(py)3] Example:
5. [Mabcdef] : They form 15 isomers Draw the geometrical isomers of [CoIII (en2) (NH3) (Cl)]2+
6. [M (AB)3] Sol.

Example:
Cis and trans-isomers [CoIII (en2) (NH3) (Cl)]2+ ion
Draw the geometrical isomers of [Cr(gly)3]

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Coordination Compounds
COORDINATION COMPOUNDS 23
10.2.2 Optical Isomerism Sol.
(a) Optical isomerism in square planar complex: Does not show
Optical Isomerism
(b) Optical isomerism in tetrahedral complex: Does not show
Optical Isomerism (only Mabcd show optical isomerism).
(c) Optical isomerism in octahedral complex:
1. [Ma6] : Optical inactive.
2. [Ma5b] : Optical inactive. 8. cis [M (AA)2b2]
3. [Ma4b2] : Optical inactive. Example:
4. [Ma4bc] : Optical inactive.
Draw the optical isomers of RhCl2(en)2]+
5. cis [Ma2b2c2] : Out of 5 Geometrical Isomers only cis is
Sol.
optically active.

Optical active isomers of cis [RhCl2(en)2]+


6. [Mabcdef] : 15 Geometrical Isomers are possible, all are optical
9. cis [M(AA)2bc]
active.
Example:
Example:
Draw the optical isomers of [CoCl (en)2 Br]2+
Draw the optical isomers of [Pt(Cl)(Br)(I)(py)(NO2)(NH3)]
Sol.

10. [M (AA)3]
Example:
Draw the optical isomers of [Co(en)3]3+
Sol.

Optical d and 1-forms [PtIV (py) (NH3) (NO2) (Cl) (Br) (I)]0
7. cis [M(AA)b2c2]
Example:
Two optical isomeric forms of the complex [Co(en)3]3+
Draw the optical isomers of [CoCl2 (en) (NH3)2]+

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COORDINATION COMPOUNDS 24
11. [M (AB)3] 11.1 Stability of Coordination Compounds in Solutions
(i) In general, higher the charge density on the central ion, the
greater is the stability of its complexes, i.e., the higher value
charg e
of radius of the ion , the greater is the stability of its
complexes.
Electronegativity of the central ion influences the stability.
The higher the electronegativity of the central ion, the greater
is the stability of its complexes.
(Both optically active)
(ii) The higher the oxidation state of the metal, the more stable is
11. Stability of Coordination Compounds 3+
the complex. The charge density of Co ion is more than
2+ 3+
The stability of a complex in solution refers to the degree of Co ion and thus, [Co (NH3)6] is more stable than [Co
2+ 3– 4–
association between the two species involved in the state of (NH3)6] . Similarly, [Fe (CN)6] is more stable than [Fe (CN)6] .
equilibrium.
(iii) The cyano and ammine complexes are far more stable than
If we have a reaction of the type : those formed by halide ions. This is due to the fact that NH3

 ML and CN are strong Lewis bases.
M + 4L  4
(iv) The complexes of bivalent cations (M2+) of 3d-series shown
then the larger the stability constant, the higher the proportion of
the following order of stability :
ML4 that exists in solution. Free metal ions rarely exist in the 2+ 2+ 2+ 2+ 2+
solution so that M will usually be surrounded by solvent Mn < Fe < Co < Ni < Cu
molecules which will compete with the ligand molecules, L, and 0.91 0.83 0.82 0.78 0.69
be successively replaced by them. For simplicity, we generally Irving William order
ignore these solvent molecules and write four stability constants (v) Chelating ligands form more stable complexes as compared
as follows : to monodentate ligands. Greater is the chelation, more is the
stability of complex.
M + L 
 ML K1 = [ML]/[M][L]
3 3 3
Cr  NH3 6    Cr  en  NH3 4    Cr  en 2  NH3 2 
ML + L 
 ML2 K2 = [ML2]/[ML][L] 3
 Cr  en 3 
ML2 + L 
 ML3 K3 = [ML3]/[ML2][L] Increasing order of stability
ML3 + L 
 ML4 K4 = [ML4]/[ML3][L] 12. IMPORTANCE AND APPLICATIONS OF
where K1, K2, etc., are referred to as stepwise stability constants. COORDINATION COMPOUNDS
Alternatively, we can write the overall stability constant thus :
a. Analytical chemistry : The analytical applications of
M + 4L 
 ML4 4 = [ML4]/[M][L]4 coordination chemistry are in
The stepwise and overall stability constant are therefore related (i) Qualitative and quantitative analysis : Metals ions form
as follows : colored coordination compounds on reaction with a number
of ligands. These reactions are used for detection of the metal
 4 = K1 × K2 × K3 × K4 or more generally,
ions. The colored complexes formed can be used for the
 n = K1 × K2 × K3 × K4 ................. Kn estimation of metals by classical or instrumental methods
The instability constant or the dissociation constant of such as gravimetry or colorimetry. Some examples are given
coordination compounds is defined as the reciprocal of the as follows :
formation constant. The presence of iron ions (Fe3+) can be detected by the
addition potassium ferrocyanide solution, which results in
formation of Prussian blue complex.
Fe2+ + K3Fe(CN)6  KFe[Fe(CN)6] + 2K+

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COORDINATION COMPOUNDS 25
(ii) Volumetric analysis : Hardness of water can be estimated example, in silver plating, K[Ag(CN) 2] is used as an
by titration with EDTA. The metal ions causing hardness, electrolyte; in gold plating, K[Au(CN)2] is used as an
that is Ca and Mg , form stable complexes with EDTA.
2+ 2+
electrolyte; and in copper plating, K3[Cu(CN)4] is used as an
b. Metal extraction and purification : Extraction of metals, such electrolyte.
as silver and gold, is carried out by forming their water soluble e. Biological importance : Some important biological
cyanide complexes with the ore. Pure gold can then be compounds are coordination complexes. For example,
obtained from the solution by addition of zinc. Similarly, metals chlorophyll is a complex of Mg2+. This green pigment plays a
can be purified by formation and then decomposition of their vital role in photosynthesis in plants. Similarly, haemoglobin,
coordination compounds. For example, impure nickel the red pigment present in blood, is a coordination complex
obtained after extraction may be converted into pure nickel of Fe2+ and vitamin B12, an essential nutrient, is a complex
by first converting it to nickel carbonyl and then compound of Co3+.
decomposing. f. Medicinal uses : Complexing or chelating agents are used in
c. Catalysis : Coordination compounds are used as catalysts treating metal poisoning, wherein, the coordination complex
in important commercial processes. For example, is formed between toxic metal in excess metal and the
(i) The Zeigler-Natta catalyst (TiCl4 and trialkyl aluminium) is complexing agent. For example, EDTA is used in lead
used as a catalyst in the formation of polyethene. poisoning. EDTA, when injected intravenously into the
bloodstream, traps lead forming a compound that is flushed
(ii) The Wilkinson catalyst - RhCl(PPh 3) 3 is used in the
out of the body with the urine. Other heavy metal poisonings
hydrogenation of alkenes.
that can be treated similarly with chelation therapy are
(iii) In the Monsanto acetic acid process, various rhodium mercury, arsenic, aluminium, chromium, cobalt, manganese,
complexes, such as [Rh(CO)2I2], [Rh(Cl)(CO)(PPh3)2] or nickel, selenium, zinc, tin and thallium. Similarly, chelating
[Rh(Cl)(CO)2]2, are used as catalyst in the presence of CH3I, ligands D-penicillamine and desferrioxime B are used for
I2 or HI as activator. removal of excess copper and iron, respectively. New potent
d. Electroplating : Coordination compounds of gold, silver and drugs are being created using various derivatives of
copper are used as components in the baths used for metallocene. A platinum complex [PtCl2(NH3)2] called cis-platin
electroplating articles of other metals with these metals. For is used in treatment of cancer.

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COORDINATION COMPOUNDS 26

SUMMARY

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Coordination Compounds
COORDINATION COMPOUNDS 27

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Coordination Compounds
COORDINATION COMPOUNDS 28

SOLVED EXAMPLES
Example - 1 Sol. Chlorobis(ethylene diammine)nitritocobalt(III) chloride.
Write the IUPAC name for any of the isomers with the Example - 7
molecular formula [Pt(NH3)2Cl2]Cl2
Write the IUPAC name of the linkage isomer of
Sol. Diammine dichloro platinum (IV) chloride. [Co(NH3)5NO2]Cl2.
Example- 2 Sol. Pentamminenitritocobalt (III) chloride.
Write the formulas of the following coordination Example - 8
compounds :
Write the IUPAC names of the following coordination
(i) Tetraammine aquachloridocobalt (III) Chloride.
compounds.
(ii) Potassium tetrahydroxozincate (II).
(a) [CoCl2(en)2]Cl
(iii) Tetracarbonylnickel.
(b) [Co(NH3)5(CO3)]Cl
Sol. (i) [Co(NH3)4(H2O)Cl]Cl2
Sol. (a) Dichloridobis(ethane –1, 2-diamine)cobalt(III) Chloride.
(ii) K2[Zn(OH)4]
(b) Pentaammine carbonatocobalt(III) Chloride.
(iii) [Ni(CO)4]
Example - 9
Example - 3
Write the IUPAC names of the following coordination
Write the formula of (i) hexaaquairon (II) sulphate compounds :
(ii) potassium hexacyanoferrate (III) (iii) hexaammine (a) [Co(H2NCH2CH2NH2)3]2(SO4)3
platinum (IV) chloride (iv) potassium trioxalatoaluminate
(III). (b) [Cr(NH3)3(H2O)3]Cl3

Sol. (i) [Fe(H2O)6]SO4 (c) [Ag(NH3)2] [Ag(CN)2]

(ii) K3[Fe(CN)6] Sol. (a) Tris (ethane –1, 2-diamine) cobalt (III) sulphate
(b) Triamminetriaquachromium (III) Chloride
(iii) [Pt(NH3)6]Cl4
(c) Diamminesilver (I) dicyanoargentate (I).
(iv) K3[Al(C2O4)3]
Example - 10
Example - 4
Write the IUPAC name of [Pt(NH3)3(NO)Cl2]Br2.
Write the IUPAC name for any one of the isomers of
[Cr(NH3)4Cl2]+. Sol. Triamminedichloridonitrosoniumplatinum(II) bromide.

Sol. Tetraamminedichlorochromium (III) ion. Example - 11

Example - 5 Write the IUPAC name of [Pt(NH3)4Cl2]Cl2.

Write IUPAC name of the complex [Cr(H2O)5Cl]Cl2. Sol. Tetraamminedichloridoplatinum (IV) chloride.

Sol. Pentaaquachlorochromium (III) chloride. Example - 12

Example - 6 Write the name and draw the structures of each of the
following complex compounds :
Name the following complex using IUPAC norms :
(i) [Co(NH3)4(H2O)2]Cl3
[Co(en)2(ONO)Cl]Cl (ii) [Pt(NH3)4] [NiCl4]
COORDINATION COMPOUNDS 29
Sol. (i) Tetraaminediaquacobalt(III) chloride
(ii)Tetraammineplatinum(II) tetrachloronickelate (II).
Structures :

(i) Example - 17

What is a bidentate ligand ?


Sol. A ligand which contains two donor atoms so that it can
form two coordinate bonds with the central metal atom.
(ii) For example, Ethylene diammine : NH2 – CH2 – CH2 – NH2

Example - 18
Example - 13
(a) Write the IUPAC name and indicate the shape of the
Using the IUPAC norms, write the systematic name of the complex ion [Co(en)2Cl(ONO)]+. [At. No. Co = 27]
following : (b) What is meant by chelate effect ?
[Co(NH3)6] [Cr(CN)6] Sol. (a) IUPAC name : Chlorobis (ethylenediamine) nitrito-O-
Sol. Hexaammine-cobalt (III) hexacyanochromate (III). cobalt (III) ion.

Example - 14 (b) Chelate effect : It may be noted that chelate ligands


form more stable complexes than similar ordinary
Write the IUPAC name of [Cr(NH3)6] [Co(CN)6]. complexes in which the ligand acts as monodenate.
This is called Chelate effect.
Sol. Hexaamminecobalt (III), hexacyanochromate (III)
Example - 19
Example - 15
Why are low spin tetrahedral complexes not formed?
Define ligand.
Sol. Low spin tetrahedral complexes are rarely observed because
Sol. A ligand is an ion or molecule (functional group) that binds
orbital splitting energies for tetrahedral complexes are
to a central metal atom to form a coordination complex
sufficiently large for forcing pairing.
Example - 16
Example - 20
(a) What are ambidentate ligands ? Give an example.
What is the coordination number of central metal ion in
(b) Write IUPAC names of the following :
[Fe(C2O4)3]2– ?
(i) K3[Fe(C2O4)3]
Sol. Six
(ii) [Pt(NH3)6]Cl4
Example - 21
(c) Draw the structure of cis isomer of [Co(NH3)4Cl2]+.
What type of hybrid orbitals are associated with Ni atom
Sol. (a) The ligands which can bond to the central metal atom/ in [Ni(CN)4]2–
ion through two different atoms present in it are called
ambidentate ligands. For example NO2–, which can Sol. dsp 2
attach itself through N atom or O atom. Example - 22
(b) (i) Potassium trioxalatoferrate (III)
Write a neutral molecule in which the central atom is sp3d2
(ii) Hexaammine platinum (IV) chloride
hybridized.
(c) cis – [Co(NH3)4Cl2]+
Sol. K3[CoF6]
COORDINATION COMPOUNDS 30

Example - 23 Co (Z = 27) atom in ground state

(a) Draw the structure of cis - [Co(NH3)4Cl2]+.


(b) Using the IUPAC norms name the following complex :
[Co(NH3)4Cl(ONO)]Cl
Sol. (a) Structure of cis - [Co(NH3)4Cl2]+

(b) Tetraamminechloridonitrito-N-cobalt (III) Chloride.

Example - 24

Draw the structures of the following :


Due to d2sp3 hybridisation, the complex ion has octahedral
(i) Cis-dichlorotetracyanochromate (III) shape. Due to the absence of unpaired electrons, the complex
(ii) Pentaamminenitrito-N-cobalt (III) ion is diamagnetic.
(iii) Hexamethyldialuminium Example - 26

Using the valence bond approach, predict the shape and


magnetic character of [Ni(CO)4]. (At. No. of Ni = 28).
Sol. (i)
Sol. In the complex [Ni(CO)4], the oxidation state of Ni is ‘0’. Its
electronic configurations is [Ar] 3d84s2.

(ii)

The resulting complex has tetrahedral shape and is


(iii) diamagnetic due to absence of unpaired electrons.

Example - 27

Explain each of the following observations :


Tetrahedral Ni (II) Complexes are paramagnetic but square
Example - 25 planar Ni(II) complexes are diamagnetic
Using the valence bond approach predict the shape and Sol. In the complex [NiCl4]2–, nickel undergoes sp3
magnetic character of [Co(NH3)6]3+. (Atomic number of hybridisation and the complex has tetrahedral geometry.
Co is 27) In the presence of weak ligand field Cl–, the unpaired
Sol. In [Co(NH3)6]3+, the oxidation state of Co is +3. electrons of nickel do not paired up. So the complex is
paramagnetic.
COORDINATION COMPOUNDS 31
In complex like, [Ni(CN)4]2–, the unpaired electrons
Sol.
of 3d orbitals are forced to pair in the presence of strong
ligand field of CN–, Ni2+ ion undergoes dsp2 hybridisation
resulting in square planar geometry. As there are no
unpaired electrons, the complex is diamagnetic.

Example - 28

Using valence bond approach, predict the shape and


magnetism (i.e., paramagnetic or diamagnetic) of
[Co(CO)4]+. (Atomic number of Co = 27)
Sol. [Co(CO)4]+
In it oxidation state of Co is +1.
Atomic number of Co = 27

Fe3+ ion has configuration of 3d5. Two unpaired electrons


paired up in 3d subshell. Two 3d-orbital’s one 4s-orbital
and three 4p-orbitals hybridise to give six equivalent d2sp3
hybrid orbitals. The complex ion has octahedral geometry
and is paramagnetic due to the presence of one unpaired
electron.

Example - 30

(a) Give the IUPAC name of [PtCl(NH2CH3) (NH3)2]Cl.


(b) Difine linkage isomerism.
Sol. (a)Diamminechloro (methyl amine) platinum (II) chloride.
(b) Linkage isomerism: When more than one atom in an
ambidentate ligand is linked with central metal ion to form
two types of complexes, then the formed isomers are called
linkage isomers and the phenomenon is called linkage
(x = lone pair of electron of CO)
isomerism.
So, apparently the shape is tetrahedral and since the
complex has two unpaired electrons, therefore, it is Example - 31
paramagnetic.
Using valence bond theory of complexes, explain the
Example - 29
geometry and magnetic nature of [Ni(CN) 4 ] 2– ,
Using the valence bond approach, predict the shape and (At. No. Ni = 28)
magnetic character of [Fe(CN)6]3– ion. [At. no. of Fe = 26]
COORDINATION COMPOUNDS 32
Sol. Ni atom (Z = 28) Ground state Example - 33

(a) Using valence bond theory, predict the shape and


magnetic character of [Ni(CO)4]. [Ni = 28]
(b) Give one example of application of coordination
compounds in medicine.
Sol. (a) Oxidation number of Ni in [Ni (CO)4] is zero.

The Ni2+ ion is dsp2 hybridised. Four pairs of electrons


from four CN– ions occupy the four vacant hybrid orbitals.
So the complex ion has a square planar geometry. As it has
no unpaired electron, so it is diamagnetic.

Example - 32
The complex molecule has tetrahedral shape because
(a) Draw the structure of ferrocene. of sp3 hybridisation. As it has no unpaired electron,
(b) Using valence bond theory explain the geometry and so it is diamagnetic.
magnetic behaviour of pentacarbonyliron (0). (b) The platinum complex cis-[Pt(NH3)Cl2] is known as
Sol. (a) Structure of ferrocene Cisplatin and is used in the treatment of cancer.

Example - 34

Describe type of hybridization, shape and magnetic


property of the following:
(i) [Fe(H2O)6]2+
(ii) [Co(NH3)6]3+
(iii) [NiCl4]2–
(At. Nos. Fe = 26, Co = 27, Ni = 28)
(b) Fe atom (Z = 26) Ground state Sol. (i) [Fe(H2O)6]2+
Fe (26) = 1s2 2s2 2p6 3s2 3p6 4s2 3d6

Fe atom is dsp3 hybridised. Five pairs of electrons from five


CO molecules occupy five hybrid orbital. The [Fe(CO)5]
molecule has trigonal bipyramidal shape. As it has no
unpaired electron, so it is diamagnetic.
COORDINATION COMPOUNDS 33

Hybridization - d2sp3 Example - 35


Shape - octahedral Low spin octahedral complexes of nickel are not known.
Magnetic property - diamagnetic Explain

(ii)[Co(NH3)6]3+ Sol. The electronic configuration of Ni is [Ar]3d8 4s2 which


shows that it can only form two types of complexes i.e.
Co (27) = 1s2 2s2 2p6 3s2 3p6 4s2 3d7 square planar (dsp 2) in presence of strong ligand and
tetrahedral (sp3) in presence of weak ligand. There are four
empty orbitals in Ni while octahedral complexes require six
empty orbitals.

Example - 36

Explain denticity of a ligand with example.


Sol. The number of donor atoms in a ligand which forms
coordinate bond with the central metal atom are called
denticity of a ligand. For example, If donor atom is one then
it is called Monodentate ligand, if it is two, then it is called
Bidendentate and so on.

Example - 37

How is a double salt different from a complex?

Hybridization - d2sp3 Sol. Double salt dissociates completely into its constituent ions
in their aqueous solution. For example, KCl.MgCl2.6H2O
Shape - octahedral dissociates into K+, Cl–, Mg2+ and H2O
Magnetic property - diamagnetic
Example - 38
(iii) [NiCl4]2–
Write the structure and hybridisation in
Ni (28) = 1s2 2s2 2p6 3s2 3p6 4s2 3d8
(i) [Fe(CO)5] (ii) trans-[Co(NH3)4Cl2]+
(iii) Ni(CO)4 (iv) cis-[Co(NH3)4Cl2]+
(v) [NiCl4]2–
Sol. (i) dsp3 (trigonal bipyramidal)
(ii) d2sp3 (octahedral)
(iii) sp3 (tetrahedral)
(iv) d2sp3 (octahedral)
(v) sp3 (tetrahedral)

Example - 39

(a) What is the basis of formation of the spectro-chemical


series ?
Hybridization - sp3 (b) Draw the structures of geometrical isomers of the
following coordination complexes :
Shape - Tetrahedral
Magnetic property - paramagnetic [Co(NH3)3Cl3] and [CoCl2(en)2]+
(en = ethylenediamine and atomic number of Co is 27)
COORDINATION COMPOUNDS 34
Sol. (a) Spectro-chemical series : The arrangement of ligands Example - 43
in order of their increasing field strength i.e. increasing
crystal field splitting energy value is called spectro- Give an example of coordination isomerism.
chemical series. Sol. [Cr(NH3)6] [CoF6] and [Co(NH3)6] [CrF6]
Crystal field splitting energy is the basis of formation
Example - 44
of the spectro-chemical series
(b) (i) The cis and trans isomers of Draw the structures of stereoisomers of the following
compound : [Co(en)3]Cl3
[Co(NH3)3Cl3] may be represented as
Sol. [Co(en)3]Cl3

(ii) [CoCl2(en)2]+ ion exists in two geometrical isomers as


shown below Example - 45

Give an example of ionization isomerism.


Sol. [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl

Example - 46

(a) Give the IUPAC name of [PtCl(NH2CH3)2(NH3)2]Cl


(b) Write the name of linkage isomer of
[Co(ONO) (NH3)5]2+
Example - 40 (c) Though CO is a weak lewis base yet it forms a number
of stable metal carbonyls. Explain.
Give an example of linkage isomerism.
Sol. (a) Diamminechlorobis(methylamine)platinum(II)
Sol. [Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)]Cl2 chloride.
Example - 41 (b) Pentaammine nitrito – O – cobalt (III).

Predict the number of unpaired electrons in (c) CO is a weak electron donar and still metal carbonyls
hexaaquamanganese(II) ion. are stable. This is because of back bonding resulting
from delocalisation of electrons from filled d-orbitals
Sol. It has 5 unpaired electrons.
of metal into the empty antibonding molecular orbitals
Example - 42 of CO ligands.

Draw structures of geometrical isomers of [Fe(NH3)2(CN)4] –. Example - 47

(a) Give the electronic configuration of the d-orbitals of


Ti in [Ti(H2O)6]3+ ion and explain why this complex is
coloured ? [At. No. of Ti = 22]
(b) Write IUPAC name of [Cr(NH3)3(H2O)3]Cl3
Sol
COORDINATION COMPOUNDS 35
Sol. (a) Ti3+ = 3d1 4s0 (ii) CO can form  as well as  bond, therefore, it is stronger
ligand than NH3which can form only a bond.
 Due to d-d-transition, the complex [Ti(H2O6)]3+ is
coloured. Example - 51
(b) IUPAC name is Triamminetriaquachromium (III) Among Octahedral and Tetrahedral crystal fields, in which
Chloride. case the magnitude of crystal field splitting is larger ?
Example - 48 Sol. Octahedral crystal field.

Giving a suitable example for each, explain the following Example - 52


(i) Crystal field splitting Draw a figure to show splitting of degenerate d orbitals in
(ii) Ambidentate ligand an octahedral crystal field. How does the magnitude of
Sol. (i) Crystal field splitting : In a free transition metal ion, o, decide the actual configuration of d orbitals in a
all the five d-orbitals are degenerate, but when it is complex entity ?
involved in a complex formation, the degeneracy is Sol. Greater the value of o, the greater are the electron pairing.
split. This is called crystal field splitting. Figure shows the splitting of degenerate d orbitals in an
(ii) Ambidentate ligand : Unidentate ligands containing octahedral crystal field.
more than one coordinating atoms are called
ambidentate ligands. For example,
NO2–, CN–, SCN– are all ambidentate ligands.

Example - 49

Describe the followings :


(i) Optical isomerism
(ii) Preparation of tetraethyl lead
Sol. (i) Optical isomerism is shown by compounds having
chiral molecules, i.e., molecules which do not have
The actual configuration adopted is decided by the relative
plane of symmetry. These isomers are non-
superimpossable mirror images of each other. They values of o and P. Here P represents energy required for
are optically active and rotate the plane of polarisation electron pairing in a single crystal.
equally but in opposite directions. The isomer which (i) If o < P, we have the so called weak field, high spin
rotated the plane of polarised light towards left is called situation. The fourth electron enters one of the eg
laevorotatory (–) while the isomer which rotates plane
orbitals giving the configuration t32ge1g. If now a fifth
towards right is called dextro-rotatory (+).
electron is added to a weak field coordination entity,
(ii) Tetraethyl lead is prepared by reaction of PbCl4 with the configuration becomes t32ge2g.
ethyl magnesium bromide.
(ii) If o > P, we have the strong field, low spin situation
PbCl4  4C2 H5 .MgBr   C2 H5 4 Pb 4Mg  Br  Cl  and pairing will occur in the t2g level with the eg level
Tetraethyl lead
remaining unoccupied in entities of d1 of d6 ions.
Example - 50 Example - 53
State a reason for each of the following situations: Give names of two complexes which are used in medicines.
(i) Co2+ is easily oxidised to Co3+ in presence of a strong Sol. (i) EDTA, used in the treatment of lead poisoning.
ligand.
(ii)cis-platin, [Pt(NH3)2Cl2], used in the treatment of cancer.
(ii) CO is a stronger complexing reagent than NH3.
Sol. (i) Strong ligands provide energy which overcomes 3rd
ionisation enthalpy and Co2+ gets oxidised to Co3+.
COORDINATION COMPOUNDS 36

Example - 54 Example - 55

Define Coordination entity of coordination compounds. What are homoleptic complexes? Give an example.
Sol. A coordinate entity constitutes a central metal atom or ion Sol. Homoleptic complexes are the complexes in which central
bonded to a fixed number of ions or molecules (ligands). metal ion or atom is bound to only one type of donor groups.

For example, K4[Fe(CN)6]


COORDINATION COMPOUNDS 37

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS


Introduction and Components of Coordination (a) + 2 (b) 0
Compounds (c) – 1 (d) + 1
1. Which of the following is a coordination compound? 10. The oxidation state of Cr in [Cr(NH3)4 Cl2]+ is
(a) KCl.MgCl2.6H2O (b) FeSO4.(NH4)2SO4.6H2O (a) +1 (b) 0
(c) NaNH4HPO4.4H2O (d) K3Fe(CN)6.2H2O (c) +3 (d) +2
2. Which of the following is a double salt? 11. The oxidation states of Cr in[Cr(H2O)6]Cl3, [Cr(C6H6)2] and
(a) Alum (b) Chrome alum K2[Cr(CN)2(O)2(O2)(NH3)] respectively are:
(c) Microcosmic salt (d) All of these
(a) + 3, 0 and + 4 (b) + 3, + 4 and + 6
3. When potash alum is dissolved in water, the total number of
ions produced is (c) + 3, + 2 and + 4 (d) + 3, 0 and + 6
(a) four (b) eight 12. The oxidation number of Fe in K3[Fe(CN)5NO] is
(c) ten (d) thirty-two (a) +4 (b) +2
4. The coordination number of Ag in [Ag(NH3)2]Cl is (c) +3 (d) + 6
(a) one (b) two 13. The oxidation number of Co in [Co(en)3]2(SO4)3 is
(c) three (d) zero (a) +2 (b) +4
5. The coordination number of Pt in [Pt(NH3)4Cl2] is (c) +3 (d) +6
(a) 12 (b) 2 14. The oxidation number of Cr in [Cr(C6H6)2] is
(c) 6 (d) 4 (a) +2 (b) +6
6. The coordination number of Fe in K4[Fe(CN)6] is (c) +3 (d) zero
(a) four (b) three 15. In the complex ion [Fe(H2O)5NO]
2+

(c) six (d) ten (a) Fe is in the +1 oxidation state, and NO coordinates as
+
7. The coordination number of central metal atom in a complex NO (nitrosonium ion)
is determined by (b) Fe is in the +2 oxidation state, and NO coordinates as
(a) the number of ligands around a metal ion bonded by neutral NO (nitrosyl) radical
sigma bonds (c) Fe is in the +3 oxidation state and NO coordinates as

(b) the number of ligands around a metal ion bonded by pi NO
bonds (d) Fe is in the +2 oxidation state and NO coordinates as
+
(c) the number of ligands around a metal ion bonded by NO
sigma and pi bonds both 16. Ammonia forms complex ion [Cu(NH3)4]2+ with copper ions
(d) the number of only anionic ligands bonded to the metal in alkaline solution but not in acidic solution. What is the
reason for it?
ion.
(a) Copper hydroxide is an amphoteric substance
8. The coordination number and the oxidation state of the
element ‘E’ in the complex [E(en)2(C2O4)]NO2 (where (en) is (b) In acidic solution hydration protects copper ions
ethylene diamine) are, respectively. (c) In acidic solution protons coordinate with ammonia
(a) 6 and 2 (b) 4 and 2 molecules forming NH 4 ions and NH3 molecules are
(c) 4 and 3 (d) 6 and 3 not available
9. In the coordination compound, K4 [Ni(CN)4], the oxidation (d) In alkaline solution insoluble Cu (OH)2 is precipitated
state of nickel is which is soluble in excess of any alkali
COORDINATION COMPOUNDS 38
Ligands formula of this complex would be
17. The neutral molecules or ions which coordinate with the (a) [Co(NH3)4NO2Cl][NH3Cl]
central atom or ion in a complex ion are called (b) [Co(NH3)Cl][ClNO2]
(a) combinants (b) cryptands (c) [Co(NH3)5NO2]Cl2
(c) spherands (d) ligands (d) [Co(NH3)5][(NO2)2Cl2]
18. Which of the following statements is correct with regard to 23. The IUPAC name of the coordination compound K3 [Fe(CN)6]
a complex ion? is
(a) A complex ion consists of a central ion bonded to two or (a) potassium hexacyanoiron (II)
more donor ions or molecules, usually does not dissociate
(b) tripotassium hexacyanoiron (II)
into simple ions or molecules even in a solution and
exhibits properties different from its constituent ions or (c) potassium hexacyanoferrate (II)
molecules. (d) potassium hexacyanoferrate (III)
(b) The donor ions and molecules which coordinate with 24. The IUPAC name for the complex
the central atom or ion in a complex are called ligands. [Co (NO2) (NH3)5] Cl2 is
(c) The sum of the number of electrons present in the central (a) nitrito-N-pentaamminecobalt (II) chloride
metal ion or atom and those donated by the ligands is
(b) pentaamminenitrito-N-cobalt (II) chloride
called the effective atomic number of the central metal
atom and this number is usually the same as the atomic (c) pentaamminenitrito-N-cobalt (III) chloride
number of the next higher noble gas. (d) nitrito-N-pentaamminecobalt (III) chloride.
(d) All of these 25. Which among the following will be named as dibromidobis-
19. Which of the following is a bidentate ligand? (ethylenediamine) chromium (III) bromide ?
(a) Oxalato (b) Carbonate (a) [Cr(en)3]Br2 (b) [Cr(en)2Br2] Br
(c) Glycinato (d) All of these (c) [Cr(en)Br4]– (d) [Cr(en) Br2] Br
20. Which of the following is a hexadentate ligand? 26. The IUPAC name for the complex compound Li[AlH4] is
(a) Acetylacetonato (a) lithium aluminium hydride
(b) 8–Hydroxy quinolinato (b) hydrido-aluminiumlithium (III)
(c) Ethylenediamine tetraacetato (c) lithium tetrahydridoaluminate(III)
(d) Ethylenediamine (d) lithium tetrahydridoaluminate(I)
21. Among the properties, (A) reducing, (B) oxidizing, 27. The IUPAC name for the coordination compound
(C) complexing, the set of properties shown by CN– ion Na3[Ag(S2O3)2] is
towards metal species is (a) sodium silverthiosulphate (I)
(a) A, B (b) B, C (b) sodium silverhyposulphate
(c) C, A (d) A, B, C (c) sodium bis[argentothiosulphate(I)]
Nomenclature of Coordination Compounds (d) sodium bis (thiosulphato) argentate (I)

22. A coordination compound of cobalt has the molecular 28. The IUPAC name for the coordination compound Fe(C5H5)2
formula containing five ammonia molecules, one nitro group is
and two chlorine atoms for one cobalt atom. One mole of (a) ferrocene
this compound produces three moles of ions in an aqueous (b) bis(cyclopentadienyl)iron (II)
solution. The aqueous solution on treatment with an excess
(c) dicyclopentadienyliron (0)
of AgNO3 gives two moles of AgCl as a precipitate. The
(d) bis(cyclopentyl)iron (II)
COORDINATION COMPOUNDS 39
Werner's Theory and Sidgwick's EAN Rule 37. A square planar complex is formed by hybridisation of the
following atomic orbitals
29. The number of ions formed from a molecule of potassium
ferrocyanide in aqueous solution is (a) s, px, py, pz (b) s, px, py, pz, d

(a) 2 (b) 3 (c) d, s, px, py (d) s, px, py, pz, d, d


38. Which of the following ions has the maximum magnetic
(c) 5 (d) 1
moment ?
30. One mole of the complex Compound Co (NH3)5 Cl3, gives 3
moles of ions on dissolution in water. One mole of the same (a) Mn2+ (b) Fe2+
complex reacts with two moles of AgNO3 solution to yield (c) Ti2+ (d) Cr2+
two moles of AgCl (s). The structure of the complex is 39. Which one of the following complexes is an outer orbital
(a) [Co (NH3)4 Cl] Cl2.NH3 complex ?
(b) [Co(NH3)5 Cl] Cl2
(Atomic numbers : Mn = 25, Fe = 26, Co = 27, Ni = 28)
(c) [Co (NH3)3 Cl3]. 2NH3
(a) [Fe (CN)6]4– (b) [Mn (CN)6]4–
(d) [Co(NH3)4 Cl] Cl.NH3
(c) [Co (NH3)6]3+ (d) [Ni (NH3)6]2+
31. Which of the following complex ions obeys Sidgwick’s
effective atomic number (EAN) rule? 40. The hybridization states of the central atom in the complexes
3– 4–
(a) [Fe(CN)6] (b) [Fe(CN)6] Fe(CN)36 , Fe(CN)46  and Co(NO2 )36 are
3+ 2+`
(c) [Cr(NH3)6] (d) [Ni(en)3] 2 3 3 2
(a) d sp , sp d and dsp respectively
2

32. Which of the following complex ions violates the EAN rule? 2 3 3
(b) d sp , sp d and sp d respectively
3 2

4+ 2 3 3 4 2
(a) [Pt(NH3)6] (b) [Fe(CO)5] (c) d sp , sp and d s respectively
4– 2+ 2 3
(c) [Fe(CN)6] (d) [Mn(H2O)6] (d) all d sp
2–
33. The effective atomic number for the complex ion [Ni(CN)4] 41. The hydrization states of the central atom in the complex
3– 3+ 2+
is ions [FeF6] , [Fe(H2O)6] and [Ni(NH3)6] are
3 2 2 4 2
(a) 34 (b) 38 (a) sp d , dsp and d s respectively
2 3
(c) 36 (d) 54 (b) all 3 d sp
3 2
34. The effective atomic number for the complex ion (c) all 3 sp d
3 2 3 4 2
4 (d) sp d , dsp and p d respectively
 Pd(NH 3 )6  is?
3+
42. The formation of the complex ion [Co(NH3)6] involves
3 2 3+
(a) 50 (b) 86 sp d hybridization of Co . Hence, the complex ion should
(c) 54 (d) 36 possess

VBT Theory in Coordination Compounds (a) octahedral geometry


(b) tetrahedral geometry
35. Which of the following facts about the complex
[Cr(NH3)6]Cl3 is wrong ? (c) square planar geometry
(d) tetragonal geometry
(a) The complex involves d2sp3 hybridization and is
43. Which of the following statements is correct ?
octahedral in shape. 2–
(a) The [Ni(CN)4] ion has a tetrahedral geometry and is
(b) The complex is paramagnetic.
diamagnetic.
(c) The complex is an outer orbital complex. 2–
(b) The [Ni(CN)4] ion has a square planar geometry and is
(d) The complex gives white precipitate with silver nitrate paramagnetic.
solution. 2–
(c) The [Ni(CN)4] ion has a square planar geometry and is
36. Most stable ion is diamagnetic.
(a) [Fe(OH)6 ]3– (b) [Fe(Cl)6]3– 2+
(d) The [Cu(NH3)4] ion has a tetrahedral geometry and is
3– 3+
(c) [Fe (CN)6] (d) [Fe (H2O)6] diamagnetic.
COORDINATION COMPOUNDS 40
44. The correct order of magnetic moments (spin only values in 52. The compound which does not show paramagnetism is
B.M.) is (a) [Cu(NH3)4]Cl2 (b) [Ag(NH3)2]Cl
(a) [MnCl4]2– > [CoCl4]2– > [Fe (CN)6]4– (c) NO (d) NO2
(b) [MnCl4]2– > [Fe (CN)6]4– > [CoCl4]2– 53. Among TiF62  , CoF63 , Cu 2 Cl 2 and NiCl 24  (atomic numbers
(c) [Fe(CN)6]4– > [MnCl4]2– > [CoCl4]2– of Ti = 22, Co = 27, Cu = 29, Ni = 28), the colourless
(d) [Fe (CN)6]4– > [CoCl4]2– > [MnCl4]2– species are
45. The value of the ‘spin only’ magnetic moment for one of the (a) CoF63  and NiCl 42  (b) TiF62  and NiCl 24 
following configurations is 2.84 BM. The correct one is
(a) d5 (in strong ligand field) (c) Cu 2 Cl2 and NiCl42 (d) TiF62  and Cu 2 Cl 2
(b) d3 (in weak as well as in strong fields) 2– 2–
54. Among [Ni(CO)4], [Ni(CN)4] and [NiCl4]
4
(c) d (in weak ligand field) 2–
(a) [Ni(CO)4] and [Ni(Cl)4] are diamagnetic and [Ni(CN)4]
2–

(d) d4 (in strong ligand field) is paramagnetic


2– 2–
46. The magnetic moment (spin only) of [NiCl 4 ] 2– (b) [NiCl4] and [Ni(CN)4] are diamagnetic and [Ni(CO)4]
is is paramagnetic
2– 2–
(a) 1.82 BM (b) 5.46 BM (c) [Ni(CO)4] and [Ni(CN)4] are diamagnetic and [NiCl4]
is paramagnetic
(c) 2.82 BM (d) 1.41 BM 2– 2–
(d) [Ni(CO)4] is diamagnetic and [NiCl4] and [Ni(CN)4]
47. Which of the following complex ions is diamagnetic?
are paramagnetic.
3– 2+
(a) [FeF6] (b) [Cu(NH3)6] 55. Which one of the following has a square planar geometry ?
2+ 2+
(c) [Cr(H2O)6] (d) [Zn(NH3)6] (At. no. Co = 27, Ni = 28, Fe = 26, Pt = 78)
48. Which of the following octahedral complex ions is (a) [CoCl4]2– (b) [FeCl4]2–
diamagnetic ?
4– (c) [NiCl4]2– (d) [PtCl4]2–
(a) [Cr(CO)6] (b) [Mn(CN)6]
2+ 3– 56. Nickel (Z = 28) combines with a uninegative monodentate
(c) [Ni(NH3)6] (d) [CoF6]
ligand X– to form a paramagnetic complex [NiX4]2–. The
49. Which of the following is diamagnetic? number of unpaired electron (s) in the nickel and geometry
2+ 2–
(a) [Ni(NH3)4] (b) [NiCl4] of this complex ion are respectively
2+
(c) [Ni(H2O)4] (d) [Ni(CO)4] (a) two, tetrahedral (b) one, square planar
50. Which of the following complex ions/molecules of nickel is (c) two, square planar (d) one, tetrahedral
paramagnetic? 57. The structures of Ni(CO)4 and Ni(PPh3)2Cl2 are
2+
(a) [Ni(NH3)4] (b) Ni(dimethylglyoxime)2 (a) square planar
(c) [Ni(CO)4] (d) None of these (b) tetrahedral and square planar respectively
51. Which of the following statements is incorrect? (c) tetrahedral
2+
(a) Most of the four-coordinated complexes of Ni ion are (d) square planer and tetrahedral respectively
square planar rather than tetrahedral.
3+
58. Which of the following complex ions is paramagnetic ?
(b) The [Fe(H2O)6] ion is more paramagnetic than the 4– 3–
3– (a) [Fe(CN)6] (b) [Fe(CN)6]
[Fe(CN)6] ion.
2– 3–
(c) [Fe(CN)5NO] (d) [Co(NO2)6]
(c) Square planar complexes are more stable than octahedral
complexes.
4– 3–
(d) The [Fe(CN)6] ion is paramagnetic but [Fe(CN)6] is
diamagnetic.
COORDINATION COMPOUNDS 41
59. Which one of the following cyano complexes would exhibit 67. Zeise salt, an organometallic compound, has the formula
the lowest value of paramagnetic behaviour? +
(a) (C6H6)2Cr AlCl4 (b) (CH3)2AlF
(At. no. Cr = 24, Mn = 25, Fe = 26, Co = 27)
+ –
(c) Ni(CO)4 (d) K [PtC2H4Cl3] H2O
(a) [Co(CN)6]3– (b) [Fe(CN)6]3–
68. Which of the following mixtures is known as Ziegler–Natta
3– 3– catalyst ?
(c) [Mn(CN)6] (d) [Cr(CN)6]
Crystal Field Theory (a) Al(OCH3)3 + TiCl4
(b) (C2H5)3Al +TiCl4
60. By how much percentage does the energy of eg orbitals
increase by from the average field splitting energy in (c) {(CH3)2CHO}3Al + TiCl4
octahedral complexes? (d) LiCH3 + TiCl4
(a) 40% (b) 45% 69. Which of the following is an organometallic compound?
(c) 50% (d) 60% (a) Cyclobutadiene
61. In which of the following octahedral complexes of Co (b) Thiotetraamminecopper (II) sulphate
(at no 27), will the magnitude of o be the highest? (c) Potassium tetrafluorooxochromate (V)
(d) Bis (cyclopentadienyl) iron (II)
(a) [Co (CN)6]3– (b) [Co (C2O4)3]3–
70. Which of the following is not an organometallic compound?
(c) [Co (H2O)6]3+ (d) [Co (NH3)6]3+
(a) Ferrocene
62. Among the ligands NH3, en, CN– and CO, the correct order (b) Ruthenocene
of their increasing field strength, is (c) Beryllium acetylacetonate
– – (d) bis(benzene) chromium
(a) CO < NH3 < en < CN (b) NH3 < en < CN < CO
(c) CN– < NH3 < CO < en (d) en < CN– < NH3 < CO 71. Which is not a -bonded complex?
(a) Zeise salt (b) Ferrocene
63. The octahedral complex of a metal ion M3+ with four
(c) bis(benzene) chromium(d) Tetraethyl lead
monodentate ligands L1, L2, L3 and L4 absorb wavelengths
72. Which of the following is an organometallic compound?
in the region of red, green, yellow and blue, respectively.
(a) Lithium methoxide (b) Lithium acetate
The increasing order of ligand strength of the four ligands
(c) Lithium dimethylamide (d) Methyllithium
is:
73. Which of the following statements is correct for ferrocene?
(a) L1  L 3  L 2  L 4 (b) L 3  L 2  L 4  L1
(a) It has a sandwich structure.
(c) L1  L 2  L 4  L 3 (d) L 4  L 3  L 2  L1 (b) The iron atom is placed between the two cyclopentadiene
rings.
64. The crystal field theory considers the metal-ligand bond to
be a _______ bond. (c) It has a pentagonal antiprismatical arrangement.
(a) covalent (b) ionic (d) All of these
(c) polar (d) hydrogen 74. Which of the following ligands can form an organometallic
compound?
Organometallic Compounds
(a) NO (b) C2H4
65. The organometallic compound formed during the – –
(c) SCN (d) Cl
purification of Ni by the Mond process is
(a) K4[Ni(CN)4]
2+
(b) [Ni(en)3] Isomerism in Coordination Compounds
(c) Ni(CO)4 (d) NiBr3(PMe3)3 75. Type of isomerism shown by [Cr(NH3)5NO2]Cl2 is
66. In Fe(CO)5, the Fe – C bond possesses (a) optical (b) hydration
(a)-character only (b) both  and -characters (c) geometrical (d) linkage
(c) ionic character (d) -character only
COORDINATION COMPOUNDS 42
76. The pair [Co(NH3)5NO3]SO4 and [Co(NH3)5SO4]NO3 will (a) [Zn(en) (NH3)2]2+ (b) [Co(en)3]3+
exhibit
(c) [Co(H2O)4 (en)]3+ (d) [Zn(en)2]2+
(a) hydrate isomerism (b) linkage isomerism
86. Which of the following complex species is not expected to
(c) ionization isomerism (d) coordinate isomerism
exhibit optical isomerism ?
77. Which one of the following has largest number of isomers ?
(a) [Co(en)3]3+ (b) [Co(en)2 Cl2]+
(R = alkyl group, en = ethylenediamine)
(c) [Co(NH3)3Cl3] (d) [Co(en) (NH3)Cl2]+
(a) [Ru(NH3)4 Cl2]+ (b) [Co (NH3)5 Cl]2+
87. Which of the following will have three stereoisomeric forms?
(c) [Ir (PR3)2 H (CO)]2+ (d) [Co (en)2 Cl2]+
(i) [Cr(NO3)3(NH3)3] (ii) K3[Co(C2O4)3]
78. Which one of the following coordination compounds
(iii) K3[Co(C2O4)2Cl2] (iv)[Co(en)2ClBr]
exhibits ionization isomerism?
(where en = ethylene diamine)
(a) [Cr(NH3)6]Cl3 (b) [Cr(en)3Cl3]
(a) (iv) and (iii) (b) (iv) and (i)
(c) [Cr(en)3]Cl3 (d) [Co(NH3)5Br]SO4
(c) (iii) and (ii) (d) (i) and (ii)
79. Which of the following pairs represents linkage isomers?
88. Which of the following types of square planar complexes
(a) [Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4]
can show geometrical isomerism (where M = metal, a, b =
(b) [Pd(PPh3)2(NCS)2] and [Pd(PPh3)2(SCN)2] achiral ligands)?
(c) [Co(NH3)5NO3]SO4 and [Co(NH3)5SO4]NO3 (a) Ma4 (b) Ma3b
(d) [PtCl2(NH3)4]Br2 and [PtBr2(NH3)4]Cl2
(c) Ma2b2 (d) Mab3
80. Which one among the following pairs of complex
89. Consider the following spatial arrangements of the
compounds indicates linkage isomerism? +
octahedral complex ion [Co(NH3)4Cl2] .
(a) [PtCl2(NH3)4]Br2 and [PtBr2(NH3)4]Cl2
(b) [Cu(NH3)4][PtCl4] and [CuCl4][Pt(NH3)4]
(c) [Co(NO2)(NH3)5]Cl2 and [Co(ONO)(NH3)5]Cl2
(d) All of these
81. How many hydrate isomers are possible with the formula
CrCl3.6H2O?
(a) Six (b) Four
(c) Three (d) Two
82. The compounds [Cr(H2O)6Cl3], [Cr(H2O)5Cl]Cl2. H2O and
[Cr(H2O)4Cl2]Cl.2H2O exhibit
(a) linkage isomerism (b) geometrical isomerism
(c) ionization isomerism (d) hydrate isomerism
83. Which of the following compounds shows optical isomerism ?
(a) [Co(CN)6]3– (b) [Cr(C2O4)3]3–
Which of the following statements is incorrect regarding
(c) [ZnCl4]2– (d) [Cu(NH3)4]2+ these structures?
84. Which of the following has an optical isomer ? (a) I and II are enantiomers.
+ 2+
(a) [Co(NH3)3Cl] (b) [Co(en)(NH3)2] (b) II and III are cis and trans isomers respectively.
(c) [Co(H2O)4(en)]3+ (d) [Co(en)2(NH3)2]3+ (c) III and IV are trans and cis isomers respectively.

85. Which one of the following has an optical isomer ? (d) II and IV have identical structures.

(en = ethylenediamine)
COORDINATION COMPOUNDS 43
3+
90. Which of the following pairs of structures represent facial 92. The tris (ethylenediamine) cobalt (III) cation, [Co(en)3] ,
and meridional isomers (geometrical isomers) respectively? can have
(a) three stereoisomers, all chiral and optically active
(b) two chiral stereoisomers (enantiomers)
(a)
(c) three stereoisomers, all achiral
(d) two stereoisomers, both achiral
93. Which of the following complex compounds exhibits
geometrical isomerism?
(b) (a) [PtCl2(NH3)2] (b) [PdCl2BrI]
(c) [Pt(NH3)(py)(Cl)(Br)] (d) All of these
94. Which of the following complex compounds exhibits
geometrical isomerism?
(a) [Co(NH3)4(H2O)Cl] (b) [Co(NH3)3Cl3]
(c) (b) [Co(NH3)4Cl2] (d) All of these
95. What type of isomerism could you assign to the following
pair of complex compounds?
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
(a) coordination isomerism

(d) (b) Polymerization isomerism


(c) Coordination position isomerism
(d) Ligand isomerism
91. Which of the following statements is correct regarding the 96. Which one of the following complex ions has geometrical
chirality (optical isomerism) of the cis and trans isomers of isomers ?
the type M(aa)2b2 (M stands for a metal, a and b are achiral
ligands and aa is a bidentate ligand)? (a) [Co(en)3]3+ (b) [Ni (NH3)5 Br]+

(c) [Co(NH3)2(en)2]3+ (d) [Cr(NH3)4(en)]3+


97. Tetrahedral complexes of the types of [Ma4] and [Ma3b]
(where M = metal, a, b = achiral ligands) are not able to show
optical isomerism because
(a) these molecules/ions possess Cn axis of symmetry

(a) The trans form is achiral and optically inactive while the (b) These molecules/ions possess a plane of symmetry and
cis form is chiral and exists in two enantiomeric forms. hence are achiral.
(b) Both the cis and trans forms are achiral and optically (c) these molecules possess a centre of symmetry
inactive.
(d) these molecules/ions have nonsuperimposable mirror
(c) The trans form is chiral and exists in two enantiomeric
images
forms while the cis form is achiral and optically inactive.
(d) Both the cis and trans forms are chiral, and each exists in
two enantiomeric forms.
COORDINATION COMPOUNDS 44
98. How many geometrical isomers are possible for the square 100. Coordination compounds have great importance in biological
planar complex [Pt(NO2)(py)(NH3)(NH2OH)]NO2? systems. In this context which of the following statements
is incorrect ?
(a) Four (b) Five
(a) Chlorophylls are green pigments in plants and contain
(c) Eight (d) Three
calcium
99. Which of the following types of octahedral complexes will
not exhibit geometrical isomerism (where M = metal, a, b = (b) Haemoglobin is the red pigment of blood and contains
achiral ligands)? iron
(a) [Ma2b2] (b) [Ma5b] (c) Cyanocobalamin is B12 and contains cobalt
(c) [M(aa)3] (d) [Ma4b2] (d) Carboxypeptidase-A is an enzyme and contains zinc
COORDINATION COMPOUNDS 45

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS


Objective Questions I [Only one correct option] 6. The complex that has highest crystal field splitting
1. The number of geometric isomers that can exist for energy () is: (2019)
square planar [Pt (Cl) (py) (NH3) (NH2OH)]+ is
(a) [Co(NH3)5 (H2O)] Cl3
(py = pyridine): (2015)
(b) K2[CoCl4]
(a) 4 (b) 6
(c) [Co(NH3)5Cl]Cl2
(c) 2 (d) 3 (d) K3[Co(CN)6]
2. The pair having the same magnetic moment is: (2016)
7. Homoleptic octahedral complexes of a metal ion ‘M3+’, with
[At, No. : Cr = 24, Mn = 25, Fe = 26, Co = 27]
three monodentate ligands L1, L2 and L3 absorb wavelengths
(a) [Cr(H2O)6]2+ and [Fe(H2O)6]2+
in the region of green, blue and red respectively. The
(b) [Mn(H2O)6]2+ and [Cr(H2O)6]2+
increasing order of the ligand strength is: (2019)
(c) [CoCl4]2– and [Fe(H2O)6]2+
(a) L3 < Ll < L2 (b) L3 < L2 < L1
(d) [Cr(H2O)6]2+ and [CoCl4]2–
3. On treatment of 100 mL of 0.1 M solution of CoCl3.6H2O (c) L1 < L2 < L3 (d) L2 < L1 < L3
with excess of AgNO3; 1.2 × 1022 ions are precipitated. The 8. Wilkinson catalyst is: (2019)
complex is (2017)
(a) [(Ph3P)3IrCl] (b) [(Et3P)3RhCl]
(a) [Co(H2O)4 Cl2] Cl.2H2O (b) [Co(H2O)3 Cl3].3H2O
(c) [Co(H2O)6] Cl3 (d) [Co(H2O)5Cl] Cl2.H2O (c) [(Ph3P)3RhCl] (d) [(Et3P)3IrCl]

4. The following ligand is: (2019) 9. The coordination number of Th in


K4[Th(C2O4)4(H2O)2] is : (2019)
(a) 14 (b) 6
(c) 8 (d) 10
10. Mn2(CO)10 is an organometallic compound due

to the presence of : (2019)

(a) Mn – C bond (b) Mn – Mn bond


(a) hexadentate (b) tetradentate
(c) Mn – O bond (d) C – O bond
(c) bidentate (d) tridentate
11. The pair of metal ions that can give a spin only magnetic
5. Two complexes [Cr(H2O)6]Cl3 (A) and [Cr(NH3)6]Cl3 (B) are moment of 3.9 BM for the complex
violet and yellow coloured, respectively. The incorrect
[M(H2O)6]Cl2, is (2019)
statement regarding them is : (2019)
(a) V2+ and Co2+ (b) V2+ and Fe2+
(a)  value of (A) and (B) are calculated from energies of
(c) Co2+ and Fe2+ (d) Cr2+ and Mn2+
violet and yellow light, respectively
12. The metal d-orbitals that are directly facing the ligands in
(b) Both are paramagnetic with three unpaired electrons.
K3[Co(CN)6] are: (2019)
(c) Both absorb energies corresponding to their
(a) dxy and d x 2  y2 (b) d x 2  y2 and d z 2
complementary colors.
(c) dxz, dyz and d z 2 (d) dxy, dxz and dyz
(d)  value for (A) is less than that of (B).
COORDINATION COMPOUNDS 46
13. The magnetic moment of an octahedral homoleptic Mn(II) 3
16. The degenerate orbitals of Cr  H 2 O 6  are: (2019)
complex is 5.9 BM. The suitable ligand for this complex is:
(2019) (a) d xy and d yz (b) d yz and d z 2

(a) Ethylene diamine (b) CN–


(c) d z2 and d xz (d) d x 2  y2 and d xy
(c) NCS– (d) CO
17. The correct statements among I to III are: (2019)
14. The compound that inhibits the growth of tumours is:
(I) Valence bond theory cannot explain the color exhibited
(2019)
by transition metal complexes.
(a) trans -[Pt(Cl)2(NH3)2] (b) cis- [Pd(Cl)2(NH3)2]
(II) Valence bond theory can predict quantitatively the
(c) cis- [Pt(Cl)2(NH3)2] (d) trans- [Pd(Cl)2(NH3)2]
magnetic properties of transition metal complexes.
15. The one that will show optical activity is:
(III) Valence bond theory cannot distinguish ligands as
(en = ethane 1, 2-diamine) (2019) weak and strong field ones.

(a) (II) and (III) only

(b) (I), (II) and (III)


(a)
(c) (I) and (III) only

(d) (I) and (II) only

18. The maximum possible denticities of a ligand given below


towards a common transition and inner-

transition metal ion, respectively, are: (2019)


(b)

(a) 8 and 6 (b) 6 and 8

(c) 6 and 6 (d) 8 and 8

(c) 19. The species that can have a trans-isomer is:


(en = ethane - 1, 2-diamine, Ox= oxalate) (2019)
(a) [Zn(en)Cl2] (b) [Pt(en)Cl2]

(c) [Cr(en)2(ox)]+ (d) [Pt(en)2C12]2+

20. Three complexes, [CoCl(NH3)5]2+(I), [Co(NH3)5H2O]3+(II) and


[Co(NH3)6)]3+ (III) absorb light in the visible region. The
correct order of the wavelength of light absorbed by them
(d)
is: (2019)

(a) (III) > (I) > (II) (b) (III) > (II) > (I)

(c) (II) > (I) > (III) (d) (I) > (II) > (III)
COORDINATION COMPOUNDS 47
21. The INCORRECT statement is: (2019) optically inactive. What type of isomers does A and B
(a) the gemstone, ruby, has Cr 3+
ions occupying the represent? (2019)
octahedral sites of beryl. (a) Geometrical isomers (b) Coordination isomers
(b) the spin-only magnetic moment of (c) Linkage isomers (d) Ionisation isomers
2 25. The coordination numbers of Co and Al in
 Ni  NH 3  4  H 2 O  2  is 2.83 BM.
[Co(Cl)(en)2]Cl and K3[Al(C2O4)3], respectively are :
2
(c) the color of CoCl  NH3 5  is violet as it absorbs the (2019)

yellow light. (a) 5 and 3 (b) 3 and 3


(d) the spin-only magnetic moments of (c) 6 and 6 (d) 5 and 6
2 2 26. For octahedral Mn(II) and tetrahedral Ni(II)
 Fe  H 2 O 6  and Cr  H 2 O 6  are nearly similar..
complexes, consider the following statements: (2020)
22. The complex ion that will lose its crystal field stabilization
(I) Both the complexes can be high spin.
energy upon oxidation of its metal to + 3 state is : (2019)
(II) Ni(II) complex can very rarely be low spin.

(III) With strong field ligands, Mn(II) complexes can be


low spin.

(IV) Aqueous solution of Mn(II) ions is yellow in colour.

The correct statements are :

(a) (I), (III) and (IV) only (b) (I), (II) and (III) only
2+ 2+
(a) [Co(phen)3] (b) [Ni(phen)3]
(c) (II), (III) and (IV) only (d)(I) and (II) only
2+ 2+
(c) [Zn(phen)3] (d) [Fe(phen)3]
27. Consider that a d6 metal ion (M2+) forms a complex with
23. Complete removal of both the axial ligands (along the z- aqua ligands, and the spin only magnetic moment of the
axis) from an octahedral complex leads to which of the complex is 4.90 BM. The geometry and the crystal field
following splitting patterns ? (relative orbital energies not stabilization energy of the complex is : (2020)
on scale) (2019)
(a) tetrahedral and 0.6 t
(b) tetrahedral and 1.6 t  1P

(a) (b) (c) octahedral and 1.6 0


(d) octahedral and 2.4 0  2P
28. The one that is not expected to show isomerism is :
(2020)
(c) (d)
2 2
(a)  Ni  NH 3 4  H 2 O  2  (b)  Ni  en 3 

24. A reaction of cobalt(III) chloride and ethylenediamine in a (c)  Pt  NH 3  2 Cl2  (d)  Ni  NH 3 2 Cl2 
1 : 2 mole ratio generates two isomeric products A (violet
coloured) and B (green coloured). A can show optical
activity, but, B is
COORDINATION COMPOUNDS 48
29. The complex that can show optical activity is : (2020) 35. The Crystal Field Stabilizion Energy (CFSE) of

[CoF3(H2O)3]   0  P  is:
3
(a) cis   CrCl 2  ox 2   ox = oxalate  (2020)

(b) trans   Fe  NH 3 2  CN 4  (a) 0.8 0 (b) 0.8 0  2P

3 (c) 0.4 0  P (d) 0.4 0


(c) trans  Cr  Cl 2  ox 2 
36. The values of the crystal field stabilization energies for a

(d) cis   Fe  NH 3 2  CN 4  high spin d6 metal ion in octahedral and tetrahedral fields,
3 respectively, are: (2020)
30. The electronic spectrum of Ti  H 2 O 6  shows
(a)  2.4  0 and  0.6  t
a single broad peak with a maximum at 20,300 cm–1. The
crystal field stabilization energy (CFSE) of the complex ion, (b)  1.6  0 and  0.4  t
in kJ mol–1, is : (1 kJ mol–1 = 83.7 cm–1) (2020)
(c) 0.4 0 and  0.27 t
(a) 83.7 (b) 242.5

(c) 145.5 (d) 97 (d) 0.4 0 and  0.6 t

31. The d-electron configuration of [Ru (en)3] Cl2 and [Fe (H2O)6] 37. Consider the complex ions, trans-[Co(en)2Cl2]+
Cl2, respectively are : (2020) (A) and cis-[Co(en)2Cl2]+ (B)

(a) t 42g eg2 and t 62g eg0 (b) t 62g eg0 and t 62g eg0 The correct statement regarding them is : (2020)

(a) Both (A) and (B) can be optically active.


(c) t 42g eg2 and t 2g
4 2
eg (d) t 62g eg0 and t 2g
4 2
eg
(b) (A) can be optically active, but (B) cannot be optically
32. The pair in which both species have the same magnetic
active.
moment (spin only) is: (2020)
(c) Both (A) and (B) cannot be optically active.
(a) [Co(OH)4]2- and [Fe(NH3)6]2+
(d) (A) cannot be optically active, but (B) can be optically
(b) [Mn(H2O)6]2+ and [Cr(H2O)]2+
active.
2+ 2-
(c) [Cr(H2O)6] and [CoCl4]
38. The species that has a spin-only magnetic moment
2+ 2+
(d) [Cr(H2O)6] and [Fe(H2O)6]
of 5.9 BM, is : (Td = tetrahedral) (2020)
33. The number of isomers possible for [Pt(en)(NO2)2] is: 2
(a)  Ni  CN 4   square planar 
(2020)
(a) 2 (b) 3 (b) Ni  CN 4  Td 
2
(c) 4 (d) 1 (c)  MnBr4   Td 
2
34. The one that can exhibit highest paramagnetic behaviour (d)  NiCl4   Td 
among the following is : gly = glycinato; bpy = 2, 2’–
39. The IUPAC name of the complex
bipyridine (2020)
[Pt(NH3)2Cl(NH2CH3)]Cl is : (2020)
(a) [Ti(NH3)6]3+ (b) [Co(ox)2 (OH)2]–
(a) Diamminechlorido(methanamine)platinum(II)chloride
(c) [Pd(gly)2] (d) [Fe(en)(bpy)(NH3)2]2+
(b) Bisammine(methanamine)chloridoplatinum(II) chloride
(c) Diammine(methanamine)chloridoplatinum(II)chloride

(d) Diamminechlorido (aminomethane) platinum(II) chloride


COORDINATION COMPOUNDS 49
40. The complex that can show fac- and mer-isomers is: 45. The correct order of the calculated spin-only magnetic
(2020) moments of complexes A to D is: (2020)

(a) [Co(NO2)3(NH3)3] (b) [PtCl2(NH3)2] A. [Ni(CO)4] B. [Ni(H2O)6]2+

(c) [Co(NH3)4Cl2]+ (d) [CoCl2(en)2] C. Na2[Ni(CN)4] D. [PdCl2(PPh3)2]

41. Among (a) – (d), the complexes that can display geometrical (a)  A    B   C    D 
isomerism are: (2020) (b)  C    D    B    A 
A. [Pt(NH3)3Cl]+ B. [Pt(NH3)Cl5]-
(c)  C    D    B   A 
C. [Pt(NH3)2Cl(NO2)] D. [Pt(NH3)4ClBr]2+
(d)  A    C    D    B
(a) B and D (b) D and A
46. Complex X of compositionCr(H2O)6Cln, has a spin only
(c) C and D (d) B and C magnetic moment of 3.83 BM. It reacts with AgNO3 and
42. For a d4 metal ion in an octahedral field, the correct shows geometrical isomerism.

electronic configuration is : (2020) The IUPAC nomenclature of X is : (2020)


(a) Hexaaqua chromium(III) chloride
(a) eg2 t 2g
2
when  o  P (b) t 42g e0g when  o  P
(b) Tetraaquadichlorido chromium(III) chloride dihydrate
3 1 3 1
(c) t e when  o  P
2g g (d) t e when  o  P
2g g (c) Hexaaquachromium(IV) chloride
43. The number of possible optical isomers for the complexes (d) Tetraaquadichlorido chromium(IV) chloride dihydrate
3 2
[MA 2 B 2 ] with sp or dsp hybridized metal atom, 47. [Pd(F)(Cl)(Br)(I)]2+,has n number of geometrical Isomers.
respectively, is: Then, the spin-onlymagnetic moment and crystal field
Note: A and B are unidentate neutral and unidentate stabilisation energy [CFSE] of [Fe(CN)6]n–6, respectively,
monoanionic ligands, respectively. (2020) [Note: Ignore pairing energy]. (2020)

(a) 0 and 1 (b) 2 and 2 (a) 1.73 BM and –2 0 (b) 2.84 BM and –1.6 0

(c) 0 and 0 (d) 0 and 2 (c) 0 BM and –2.4 0 (d) 5.92 BM and 0

44. Among the following statements A-D, the incorrect ones 48. The correct order of spin-only magnetic moments of the
are: (2020) following complexes is : (2020)

A. Octahedral Co(III) complexes with strong field ligands I. [Cr(H2O)6]Br2 II. Na4[FeCN6]
have high magnetic moments III. Na3[Fe(C2O4)3] (o> P) IV. (Et4N)2[CoCl4]
B. When Δo< P, the d- electron configuration of Co(III) in
(a) (III) > (I) > (II) > (IV) (b) (III) > (I) > (IV) > (II)
4 2
an octahedral complex is t ,e .
2g g (c) (I) > (IV) > (III) > (II) (d) (II) > (I) > (IV) > (III)
3+
C. Wavelength of light absorbed by [Co(en)3] is lower 49. The isomer(s) of [Co(NH3)4Cl2] that has/have a
than that of [CoF6]3–.
Cl–Co–Cl angle of 90o, is/are: (2020)
D. If the Δo for an octahedral complex of Co(III) is 18000
(a) cis only (b) trans only
cm–1, the Δt for its tetrahedral complex
with the same ligand will be16000 cm–1 . (c) meridional and trans (d) cis and trans

(a) B and C only (b) A and D only


(c) A and B only (d) C and D only
COORDINATION COMPOUNDS 50
50. The incorrect statement among the following is: 55. The correct strucutres of trans-[NiBr2(PPh3)2] and meridonial-
(2021-02-24/Shift - 2) [Co(NH3)3(NO2)3], respectively, are:

(a) Red colour of ruby is due to the presence of Co3+ (2021-03-18/Shift - 1)

(b) VOSO4 is a reducing agent


(c) RuO4 is an oxidising agent
(d) Cr2O3 is an amphoteric oxide (a)

51. The calculated magnetic moments (spin only value) for


species [FeCl4]2–, [Co(C2O4)3]3– and MnO42– respectively:
(2021-02-24/Shift - 2)
(a) 4.90, 0 and 1.73 BM (b) 5.82, 0 and 0 BM
(c) 5.92, 4.90 and 0 BM (d) 4.90, 0 and 2.83 BM (b)
52. The hybridization and magnetic nature of [Mn(CN)6]4– and
[Fe(CN)6]3–, respectively are (2021-02-25/Shift - 1)
(a) sp3d2 and diamagnetic
(b) d2sp3 and paramagnetic
(c) d2sp3 and diamagnetic (c)
(d) sp3d2 and paramagnetic
53. In which of the following order the given complex ions are
arranged correctly with respect to their decreasing spin only
magnetic moment? (2021-02-25/Shift - 2)

(d)

56. According to the valence bond theory the hybridization of


(a) (i) > (iii) > (iv) > (ii) (b) (ii) > (i) > (iii) > (iv) central metal atom is dsp2 for which one of the following
compounds? (2021-07-20/Shift - 1)
(c) (iii) > (iv) > (ii) > (i) (d) (ii) > (iii) > (i) > (iv)
(a) NiCl2.6H2O (b) K2[Ni(CN)4]
54. Arrange the following metal complex/compounds in the
increase order of spin only magnetic moment. Presume all (c) [Ni(CO)4] (d) Na2[NiCl4]
the three, high spin system. 57. The correct order of intensity of colors of the compounds
(Atomic numbers Ce = 58, Gd = 64 and Eu = 63). is: (20-07-2021/Shift - 1)
(2021-03-16/Shift - 2) (a) [Ni(CN)4]2+ > [NiCl4]2– > [Ni(H2O)6]2+
(A) (NH4)2[Ce(NO3)6] (b) [Ni(H2O)6]2+ > [NiCl4]2– > [Ni(CN)4]2–
(B) Gd(NO3)3 and (c) [NiCl4]2– > [Ni(H2O)6]2+ > [Ni(CN)4]2–
(C) Eu(NO3)3 (d) [NiCl4]2– > [Ni(CN)4]2– > [Ni(H2O)6]2+
(a) (B) < (A) < (C) (b) (A) < (C) < (B) 58. Spin only magnetic moment of an octahedral complex of
Fe2+ in the presence of a strong field ligand in BM is:
(c) (C) < (A) < (B) (d) (A) < (B) < (C)
(2021-07-20/Shift - 2)
(a) 4.89 (b) 2.82
(c) 0 (d) 3.46
COORDINATION COMPOUNDS 51
59. Which one of the following species responds to an external Choose the correct option: (2021-08-26/Shift - 2)
magnetic field? (a) A < B < C < D (b) B < A < C < D
(2021-07-25/Shift - 1) (c) B < C < D < A (d) C < D < B < A
(a) [Fe(H2O)6]3+ (b) [Ni(CN)4]2– 66. The denticity of an organic ligand, biuret is
(c) [Co(CN)6]3– (d) [Ni(CO)4] (2021-08-31/Shift - 1)
60. Which one of the following metal complexes is most stable? (a) 2 (b) 4
(2021-07-25/Shift - 2)
(c) 3 (d) 6
(a) [Co(en)(NH3)4]Cl2 (b) [Co(en)3]Cl2
67. Spin only magnetic moment in BM of [Fe(CO)4(C2O4)]+ is:
(c) [Co(en)2(NH3)2]Cl2 (d) [Co(NH3)6]Cl2 (2021-08-31/Shift - 2)
61. Given below are two statements: (a) 5.92 (b) 0
Statement I : [Mn(CN)6]3–, [Fe(CN)6]3– and [Co(C2O4)3]3– are (c) 1 (d) 1.73
d2sp3 hybridized.
68. The Crystal Field Stabilization Energy (CFSE) and magnetic
Statement II : [MnCl6]3– and [FeF6]3– are paramagnetic and moment (spin-only) of an octahedral aqua complex of a metal
have 4 and 5 unpaired electrons, respectively. ion (Mz+) are –0.8 0 and 3.87 BM, respectively. Identify
In the light of the above statements, choose the correct (MZ+): (2021-09-01/Shift - 2)
answer from the options given below: (a) V3+ (b) Cr3+
(2021-07-27/Shift - 2) (c) Mn4+ (d) Co2+
(a) Statement I is correct, but statement II is false.
Match the Following
(b) Both statement I and statement II are false
Each question has two columns. Four options are
(c) Statement I is incorrect, but statement II is true.
given representing matching of elements from
(d) Both statement I and statment II are true.
Column-I and Column-II. Only one of these four
62. The type of hybridization and magnetic property of the options corresponds to a correct matching . For
complex [MnCl6]3–, respectively, are:
the question, choose the option corresponding to
(2021-07-27/Shift - 1)
the correct matching.
3 2
(a) sp d and diamagnetic
69. Match the metals (column I) with the coordination
(b) d2sp3 and diamagnetic
compound(s)/enzyme(s) (column II) : (2019)
(c) d2sp3 and paramagnetic
Coloumn–I Coloumn–II
(d) sp3d2 and paramagnetic
(Metals) (coordination
63. The number of geometrical isomers found in the metal compound (s)/enzyme(s))
complexes [PtCl2(NH3)2], and [Ni(CO)4], [Ru(H2O)3Cl3] and
(A) Co (p) Wilkinson catalyst
[CoCl2(NH3)4]+ respectively, are (2021-07-27/Shift - 1)
(B) Zn (q) Chlorophyll
(a) 1,1,1,1 (b) 2,1,2,2
(c) 2,0,2,2 (d) 2,1,2,1 (C) Rh (r) Vitamin B12

64. Indicate the complex/complex ion which did not show any (D) Mg (s) Carbonic anhydrase
geometrical isomerism: (2021-08-26/Shift - 2)
(a) (A)-(r); (B)-(s); (C)-(p); (D)-(q)
(a) [CoCl2(en)2] (b) [Co(CN)5(NC)]3–
(b) (A)-(p); (B)-(q); (C)-(r); (D)-(s)
(c) [Co(NH3)3(NO2)3] (c) [Co(NH3)4Cl2]+
65. Arrange the following cobalt complexes in the order of (c) (A)-(q); (B)-(p); (C)-(s); (D)-(r)
increasing Crystal Field Stabilization Energy (CFSE) value. (d) (A)-(s); (B)-(r); (C)-(p); (D)-(q)
Complexes [CoF6]3–(A), [Co(H2O6)]2+(B), [Co(NH3)6]3+(C) and
[Co(en)3]3+(D)
COORDINATION COMPOUNDS 52
70. Match List - I with List - II The value of stability constants K1, K2, K3 and K4 are 104,
List - I List - II 1.58 × 103, 5 × 102 and 102 respectively. The overall equilibrium
(A) Chlorophyll (p) Ruthenium
constants for dissociation of [Cu(NH3)4]2+ is
(B) Vitamin-B12 (q) Platinum
(C) Anticancer drug (r) Cobalt x × 10–12. The value of x is _______. (rounded off the nearest
(D) Grubbs catalyst (s) Magnesium integer). (2021-02-24/Shift - 1)
Choose the most appropriate answer from the options given 76. Number of bridging CO ligands in [Mn2(CO)10] is
below (2021-03-18/Shift - 1)
(2021-02-26/Shift - 1)
(a) (A) - (r), (B) - (q), (C) - (s), (D) - (p)
77. The numbe rof stereoisomers possible for
(b) (A) - (s), (B) - (r), (C) - (q), (D) - (p)
[Co(ox)2(Br)(NH3)]2– is ________ [ox = oxalate]
(c) (A) - (s), (B) - (q), (C) - (r), (D) - (p)
(2021-02-26/Shift - 1)
(d) (A) - (s), (B) - (r), (C) - (p), (D) - (q)
71. Match List-I with List-II: 78. The equivalents of ethylene diamine required to replace the
List - I List - II neutral ligands from the coordination sphere of the trans-
(A) [Co(NH3)6][Cr(CN)6] (p) Linkage isomerism complex of CoCl3.4NH3 is ______. (Round off to the nearest
(B) [Co(NH3)3(NO2)3] (q) Solvate isomerism
integer). (2021-03-16/Shift - 1)
(C) [Cr(H2O)6]Cl3 (r) Coordination isomerism
(D) cis-[CrCl2(ox)2]3– (s) Optical isomerism 79. [Ti(H2O)6]3+ absorbs light of wavelength 498 nm during a d-
Choose the correct answer from the options given below: d transition. The octahedral splitting energy for the above
(2021-03-17/Shift - 2) complex is ______ × 10–19J. (Round off to the nearest
(a) (A) - (r), (B) - (p), (C) - (q), (D) - (s) integer). h = 6.626 × 10–34Js; c = 3 × 108 ms–1

(b) (A) - (q), (B) - (p), (C) - (r), (D) - (s) (2021-03-16/Shift - 2)
(c) (A) - (p), (B) - (q), (C) - (r), (D) - (s) 80. The total number of unpaired electrons present in the
(d) (A) - (s), (B) - (q), (C) - (r), (D) - (p) complex K3[Cr(oxalate)3] is (2021-03-18/Shift - 2)

Numerical Value Type Questions 81. The spin-only magnetic moment value for the complex
[Co(CN)6]4– is ______ BM. Round off your answer to the
72. The total number of coordination sites in
nearest integer. [At. no. of Co = 27].
ethylenediaminetetraacetate (EDTA4–) is ……………. .
(2021-07-20/Shift - 1)
(2020)
82. An aqueous solution of NiCl2 was heated with excess sodium
73. Considering that  0  P, the magnetic moment (in BM) cyanide in presence of strong oxidizing agent to form
of [Ru (H2O)6]2+ would be …………. (2020) [Ni(CN)6]2–. The total change in number of unpaired electrons
on metal centre is _______.
74. Complexes [ML5] of metals Ni and Fe have ideal square
(2021-07-20/Shift - 2)
pyramidal and trigonal bipyramidal and geometries,
respectively. The sum of the 900, 1200 and 1800 L-M-L angles 83. The total number of unpaired present in [Co(NH3)6]Cl2 and
in the two complexes is ______. (2020) [Co(NH3)6]Cl3 is
(2021-07-22/Shift - 2)
75. The step wise formation of [Cu(NH3)4]2+ is given below:
2 84. Three moles of AgCl get precipitated when one mole of an

K1
Cu   NH 3  
 Cu  NH 3   octahedral co-ordination compound with formula
2 2
Cu  NH 3   
K2
 NH 3  
 Cu  NH 3  2  CrCl3.3NH3.3H2O reacts with excess of silver nitrate. The
2
K3 2 number of chloride ions satisfying th secondary valency of
Cu  NH 3 2   NH 3  Cu  NH 3 3 
the metal ion is _______. (2021-07-25/Shift - 1)
2 2
Cu  NH 3 3  
 NH 3 
4

K
  Cu  NH 3  4 
COORDINATION COMPOUNDS 53
85. 3 moles of metal complex with formula Co(en)2Cl3 gives 3 87. The overall stability constant of the complex ion [Cu(NH3)4]2+
moles of silver chloride on treatment with excess of silver is 2.1 × 1013. The overall dissociations constant is y × 10–4.
nitrate. The secondary valency of Co in the complex is _____ Then y is _____ (Nearest Integer)
. (2021-07-27/Shift - 2) (2021-08-26/Shift - 2)
86. The number of geometrical isomers possible ing 88. 1 mol of an octahedral metal complex with formula MCl3.2L
triamminetrinitrocobalt (III) is X and in trioxalatochromate on reaction with excess of AgNO3 gives 1 mol of AgCl. The
(III) is Y. Then the value of X + Y is _____. denticity of Ligand L is _______. (Integer
(2021-07-27/Shift - 1) answer). (2021-08-27/Shift - 1)
89. The number of optical isomers possible for [Cr(C2O4)3]3– is
_______. (2021-08-27/Shift - 2)
90. The sum of oxidation states of two silver ions in
[Ag(NH3)2][Ag(CN)2] complex is (2021-09-01/Shift - 2)
COORDINATION COMPOUNDS 54

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS


Objective Questions I [Only one correct option] 9. The IUPAC name for [Be4O(CH3COO)6] is
1. Tollens reagent contains (a) basic beryllium acetate (II)
(a) AgNO3 (b) AgOH (b) hexa--acetato (O, O)-4-oxo-tetraberyllium (II)
(c) [Ag(NH3)2]+ (d) [Ag(NO3)2]+ (c) hexa--hexakis (acetato) beryllium (II)
2. The IUPAC name for [Co(ONO) (NH3)5]SO4 is (d) hexaacetato--oxo-beryllate (II)
(a) pentaammine (nitrito-O) cabalt (III) sulphate 10. The IUPAC name for [(CO)5Mn-Mn(CO)5] is
(b) pentaammine (nitroso-N) cobalt (III) sulphate (a) bis (pentacarbonyldimanganese)
(c) pentaammine (nitro-O) cobalt (III) sulphate (b) bis [pentacarbonylmanganate (VIII)]
(d) pentaammine (nitroyl-O) cobalt (III) sulphate (c) decacarbonyldimanganate (VIII)
3. The IUPAC name for [Co(NCS)(NH3)5]Cl2 is (d) bis [pentacarbonylmanganese (0)]
(a) pentaammine (isothiocyanato-n2 N, S) cobalt (III) 11. The IUPAC name for [Pt(py)4] [PtCl4] is
chloride (a) tetrakis(pyridine) platinum(II) tetrachloroplatinate (II)
(b) pentaammine (mercapto-N) cobalt (III) chloride (b) tetrapyridine tetrachlorodiplatinum (IV)
(c) pentammine (thiocyanato-N) cobalt (III) chloride (c) tetrachloro tetrapyridinediplatinum (II)
(d) pentaamine (thiocyanato-S) cobalt (III) chloride (d) tetrakis (pyridine) platinum (IV) tetrachloroplatinum (IV)
4. Which of the following complexes is most easily oxidized? 12. The IUPAC name for [Co(NH3)6] [Cr(CN)6] is
(a) Ni(CO)4 (b) [Mn(CN)6 ]6– (a) hexaamminecobalt (III) hexacyanochromium (VI)
(c) Cr(CO)4 (d) Fe(CO)5 (b) hexaamminecobalt (III) hexacyanochromate (III)
5. Which of the following complexes is the most stable ? (c) hexacyanochromium (III) hexaamminecobalt (III)
(a) [Ni(CN)4]4– (b) [Pd(CN)4]4– (d) hexacyanochromium cobalt hexaamminecobalt (VI)
(c) [Ni(CN)4]3– (d) Fe(CO)5 13. Which of the following is a high-spin (spin-free) complex?
6. Which of the following is a low-spin (spin-paired) complex? (a) [Co(NH3)6]3+ (b) [Fe(CN)6]4–
(a) [Co(NH3)6]2+ (b) [Fe(C2O4)3]3– (c) [CoF6]3– (d) [Zn(NH3)6]2+
(c) [Ni(NH3)6]2+ (d) [Co(NH3)6]3+ 14. The formula of the complex potassium trichloro (ethylene)
7. The IUPAC name for [(NH3)5 Cr – (OH) – Cr(NH3)5]5+ is platinate (II) is
(a) -hydroxo-bis (pentaammine dichromium) (5+) ion (a) K[PtCl3 (C2H4)] (b) K2[PtCl3 (C2H4)3]
(b) -hydroxo-bis (decaamminedichromium) (5+) ion (c) K4[PtCl3 (C2H4)] (d) K3[Pt2Cl3 (C2H4)3]
(c) -hydroxo-bis (octaamminechromium) (5+) ion 15. The formula of the complex triammine trinitrocobalt (III) is
(d) -hydroxo-bis [(pentaamminechromium (III)] (a) [Co(ONO2) (NH3)3] (b) [Co(ONO2)3 (NH3)3]
8. The IUPAC name for [(CO)3 Fe(CO)3 Fe(CO)3] is (c) [Co(ONO)3 (NH3)3] (d) [Co(NO2)3 (NH3)3]
(a) tri--hexacarbonyl iron (II) 16. Which of the following is correct arrangement of ligands in
terms of the Dq values of their complexes with any particular
(b) tri--carbonyl-bis[tricarbonyliron (0)]
‘hard’ metal ion :
(c) tri--carbonyl-bis[tricarbonyldiiron (0)]
(a) Cl– < F– < NCS– < NH3 < CN–
(d) tri--nanocarbonyl iron (III)
(b) NH3 < F– < Cl– < NCS– < CN–
(c) Cl– < F– < NCS– < CN– < NH3
(d) NH3 < CN– < NCS– < Cl– < F–
COORDINATION COMPOUNDS 55
(At. No. Cr-24, Mn-25, Fe-26, Ni = 28)
17. The geometry of the compound  Pt  NH 3  2 Cl2  is
26. Which of the following complex ions is octahedral ?
(a) square planar (b) tetrahedral
(a) [Fe(C2O4)3]3– (b) [Fe(NO3)4]–
(c) pyramidal (d) octahedral
(c) [Fe(CO)2(NO)2] (d) [Fe(NSiMe3)2]3
18. The shape of cuprammonium ion is
27. Which of the following is organo-metallic compound?
(a) octahedral (b) trigonal
(a) Ti  C2 H 4 4 (b) Ti  OC2 H5 4
(c) tetrahedral (d) square planar
(c) Ti  OCOCH3 4 (d) Ti  OC6 H5 4
19. Which of the following is paramagnetic ?
Objective Questions II
(a)  Fe  CN 6 
4
(b)  Ni  CO  4  [One or more than one correct option]
28. Complex ions [NiCl6]4–, [Ni(CN)6]4– similar in their given
2
(c)  Ni  CN 4  (d)  CoF6 
3 properties :
(a) oxidation state, geometry
20. The magnetic moment of a complex is 2.83 BM. The complex
(b) co-ordination number, EAN
ion is
(c) magnetic moment, geometry
(a) [Cr(H2O)6]3+ (b) [Cu(CN)4]2–
(d) Stability, Colour
(c) [V(H2O)6]3+ (d) [MnCl4]2–
29. Select the correct statement :
4
21. Which is correct in the case of  Fe  CN 6  complex ? (a) Chelation effect is maximum for five and six membered
rings.
(a) Diamagnetic (b) d2sp3 - hybridisation
(b) Greater the charge on the central metal cation, greater
(c) Octahedral (d) All are correct
the value of  (CFSE)
22. Which has highest paramagnetism ?
(c) In complex ion [CoF6]3–, F– is a weak field ligand, so that
3 2 oct < P (Pairing energy) and it is high spin complex.
(a) Cr  H 2 O 6  (b)  Fe  H 2 O 6 
(d) [CoCl2(NH3)2(en)]+ complex ion will have four different
2 2 isomers.
(c) Cu  H 2 O 6  (d)  Zn  H 2 O 6 
30. Which of the following statement(s) is/are correct ?
23. Which of the following is paramagnetic ? (a) The oxidation state of iron in sodium nitro prusside
3 Na2[Fe(CN)5(NO)] is + 2
(a) Co  NH3 6  (b)  Ni  CO  4 
(b) [Ag(NH3)2]+ is linear in shape
2 2 (c) In [Fe(H2O)6]3+, Fe is d2sp3 hybridized
(c)  Ni  Cl 4  (d)  Ni  CN 4 
(d) In [Co(H2O)6]3+ complex ion, Co is d2sp3 hybridized
24. Which is paramagnetic ? 31. For which of the following dn configuration of octahedral
2 4 complex(es), cannot exist in both high spin and low spin
(a)  Ni  H 2 O 6  (b)  Fe  CN 6 
forms?
2 (a) d3 (b) d5
(c)  Ni  CO  4  (d)  Ni  CN 4 
(c) d6 (d) d8
2+ 2+ 2+
25. The d electronic configurations of Cr , Mn , Fe and 32. Complex compound [Co(SCN)2 (NH3)4]Cl exhibits :
Ni2+ are 3d4, 3d5, 3d6 and 3d8 respectively. Which one of
(a) ionization isomerism
the following aqua complexes will exhibit the minimum
paramagnetic behaviour? (b) geometrical isomerism
(c) optical isomerism
(a) [Fe(H 2 O)6 ]2  (b) [Ni(H 2 O)6 ]2 
(d) linkage isomerism
(c) [Cr(H 2 O) 6 ]2  (d) [Mn(H 2 O) 6 ]2 
COORDINATION COMPOUNDS 56
Numerical Value Type Questions Match the Following
33. The coordination number of Co in [Co(NH3)5Cl]Cl2 is
Each question has two columns. Four options are
34. The number of isomers of [Cu(NH3)4] [PtCl4] are
given representing matching of elements from
35. EAN of iron in K4[Fe(CN)6] is Column-I and Column-II. Only one of these four
36. Give the ratio of trans-isomers in [M(AA)b2c2] (A) and options corresponds to a correct matching for each
[Ma4b2], (B) respectively.
question.
Assertion Reason
42. Match the Column–I with Column–II
(A) If both Assertion and Reason are correct and Column–I Column–II
Reason is the correct explanation of Assertion.
(Complex ions) (Number of unpaired electrons)
(B) If both Assertion and Reason are true but (A) [CrF6]4– (p) One
Reason is not the correct explanation of (B) [MnF6]4– (q) Two
Assertion. (C) [Cr(CN)6]4– (r) Three
(C) If Assertion is true but Reason is false. (D) [Mn(CN)6]4– (s) Four
(D) If Assertion is false but Reason is true. (t) Five
37. Assertion (A) : Hydrazine is a neutral ligand. 43. Match the Column–I with Column–II
Reason (R) : It has two N as donor atoms and behaves as a Column–I Column–II
chelating ligand. (Complexes) (Hybridization of central atom)
(a) A (b) B
(A) Ni  CO  4 (p) sp3
(c) C (d) D
2
38. Assertion (A) : Zeise’s salt is a -bonded organometallic (B)  Ni  CN 4   (q) dsp 2
compound. 4
(C)  Fe  CN 6  (r) sp3 d 2
Reason (R) : Zeise’s salt contain C2H4 molecules as one of
4
the ligand. (D) Mn  CN6  (s) d 2 sp3
(a) A (b) B
44. Match the Column–I with Column–II
(c) C (d) D
Column–I Column–II
39. Assertion (A) : Oxidation state of Fe in Fe(CO)5 is zero.
(A) [Cr(CN)3 (NO2)3]4– (p) Outer orbital complex
Reason (R) : Synergic bonding takes place in this metal
(B) [Co(C2O4)3]3– (q) Inner orbital complex
carbonyl complex.
(C) [Fe(EDTA)]– (r)  = 2.83 BM
(a) A (b) B
(D) [Ni(en)3] (NO3)2 (s) Shows optical activity
(c) C (d) D
(t)  = 0
40. Assertion (A) : [Ti(H2O)6]4+ is coloured while [Sc(H2O)6]3+
is colourless. 45. Match the Column–I with Column–II

Reason (R) : d-d transition is not possible in [Sc(H2O)6]3+. Column–I Column–II

(a) A (b) B (A) [Fe(CN)6]4– (p) Paramagnetic

(c) C (d) D (B) [Fe(H2O)6]2+ (q) Diamagnetic

41. Assertion (A) : [CoCl 3(NH 3) 3] does not give white (C) [Cu(NH3)6]2+ (r) Inner orbital complex
precipitate with AgNO3 solution. (D) [Ni(CN)6]4– (s) Outer orbital complex.
Reason (R) : [CoCl3(NH3)3] complex is optically inactive.
(a) A (b) B
(c) C (d) D
COORDINATION COMPOUNDS 57
Paragraph Type Questions (a) I only (b) II and IV only
Use the following passage, to solve Q. 46 to Q. 50 (c) II, III and IV (d) II and IV
Passage 48. Which is low spin complex?

Valence bond theory successfully explains the magnetic (a) [Fe(CN)6]3– (b) [Co(NO2)6]3–
behaviour of complexes. The substances which contains (c) [Mn(CN)6]3– (d) All of these
unpaired electrons are paramagnetic and its character 49. Aqueous solution of Ni2+contains [Ni(H2O)6]2+ and its
increases as the number of unpaired electrons increases. magnetic moment is 2.83 B.M. when ammonia is added in
Magnetic moment of a complex can be determined it, the predicted change in the magnetic moment of
experimentally and by using formula n  n  2  and we solution is:
(a) It will remain same
can determine the number of unpaired electrons in it. This
information is important in writing the electronic structure (b) It increases from 2.83 B.M.
of complex which in turn also useful in deciding the (c) It decreases from 2.83 B.M.
geometry of complex (d) It cannot be predicted theoretically
46. The magnetic moments (spin only) of [NiCl4]2– and 50. Which of the following complexes is a paramagnetic
[Ni(CN)4]2– are: complex?
(a) 0, 0 (b) 2.82 B.M., 2.82 B.M (a) K2[Ni(CN)4] (b) [Ni(H2O)6](NO3)2
(c) 0, 2.82 B.M (d) 2.82 B.M., 0 (c) [Co(NH3)6]Cl3 (d) [Pt(NH3)4Cl2
47. There are four complexes of Ni. Select the complex/es
which will be attracted by magnetic field:
(I) [Ni(CN)4]2– (II) [NiCl4]2–
(III) Ni(CO)4 (IV) [Ni(H2O)6]2+
COORDINATION COMPOUNDS 58

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS


Objective Questions I [Only one correct option] (a) sp3, sp3 (b) sp3, dsp2
1. The complex ion which has no d electrons in the central (c) dsp2, sp3 (d) dsp2, dsp2
metal atom is (2001)
9. The IUPAC name of [Ni(NH3)4] [NiCl4] is (2008)
(a) [MnO4]– (b) [Co(NH3)6]3+
(a) Tetrachloronickel (II)-tetraamminenickel (II)
(c) [Fe (CN)6]3– (d) [Cr (H2O)6]3+
(b) Tetraamminenickel (II)-tetrachloronickel (II)
2. Mixture X = 0.02 mole of [Co (NH3)5 SO4] Br and 0.02 mole of
(c) Tetraamminenickel (II)-tetrachloronickelate (II)
[Co(NH3)5 Br] SO4 was prepared in 2L of solution.
(d) Tetrachloronickel (II)- tetraamminenickelate (0)
1 L of mixture X + excess AgNO3  Y
10. The spin only magnetic moment value (in Bohr magneton
1 L of mixture X + excess BaCl2  Z
units) of Cr (CO)6 is (2009)
Number of moles of Y and Z are (2003)
(a) 0 (b) 2.84
(a) 0.01, 0.01 (b) 0.02, 0.01
(c) 4.90 (d) 5.92
(c) 0.01, 0.02 (d) 0.02, 0.02
11. As per IUPAC nomenclature, the name of the complex
3. The species having tetrahedral shape is (2004) [Co(H2O)4 (NH3)2] Cl3 is (2012)
(a) [PdCl4]2– (b) [Ni(CN)4]2– (a) tetraaquadiaminecobalt (III) chloride
(c) [Pd (CN4)]2– (d) [NiCl4]2– (b) tetraaquadiamminecobalt (III) chloride
4. Spin only magnetic moment of the compound Hg[Co(SCN)4] (c) diaminetetraaquacobalt (III) chloride
is (2004)
(d) diamminetetraaquacobalt (III) chloride
(a) 3 (b) 15 12. NiCl2 [P(C2H5)2 (C6H5)]2 exhibits temperature dependent
magnetic behaviour (paramagnetic/diamagnetic) the
(c) 24 (d) 8 coordination geometries of Ni2+ in the paramagnetic and
5. Which kind of isomerism is exhibited by octahedral diamagnetic states are respectively (2012)
[Co (NH3)4 Br2] Cl ? (2005) (a) tetrahedral and tetrahedral
(a) Geometrical and Ionization (b) square planar and square planar
(b) Geometrical and Optical (c) tetrahedral and square planar
(c) Optical and Ionization (d) square planar and tetrahedral
(d) Geometrical only 13. Among [NiCO)4], [NiCl4]2–, [Co(NH3)4Cl2] Cl, Na3 [CoF6],
6. If the bond length of CO bond in carbon monoxide is Na 2 O 2 and CsO 2, the total number of paramagnetic
1.128 Å, then what is the value of CO bond length in compounds is (2016)
Fe (CO)5 ? (a) 2 (b) 3
(a) 1.15 Å (b) 1.128 Å (c) 4 (d) 5
(c) 1.72 Å (d) 1.118 Å 3

7. Among the following, the coloured compound is (2008) 14. The calculated spin magnetic of Cr  NH3 6  and

(a) CuCl (b) K3 [Cu (CN)4] 3


CuF6  in BM, respectively, are (Atomic numbers of Cr
(c) CuF2 (d) [Cu (CH3CN)4] BF4
and Cu are 24 and 29, respectively) (2021)
8. Both [Ni (CO)4] and [Ni (CN)4]2– are diamagnetic. The
hybridisations of nickel in these complexes, respectively, (a) 3.87 and 2.84 (b) 4.90 and 1.73
are (2008)
(c) 3.87 and 1.73 (d) 4.90 and 2.84
COORDINATION COMPOUNDS 59
Objective Questions II (a) If X is H 2 O  l  , deflection of the pan is upwards.
[One or more than one correct option]
(b) If X is K 4  Fe  CN 6   s  , deflection of the pan is
15. The compound(s) that exhibit(s) geometrical isomerism is
(are) (2009) upwards.
(a) [Pt(en) Cl2] (b) [Pt (en)2] Cl2 (c) If X is O2(g), deflection of the pan is downwards.
(c) [Pt (en)2 Cl2] Cl2 (d) [Pt (NH3)2 Cl2] (d) If X is C6H6(l), deflection of the pan is downwards.
16. The pair (s) of coordination complexes/ions exhibiting the 19. The pair(s) of complexes wherein both exhibit tetrahedal
same kind of isomerism is (are) (2013)
geometry is(are) (Note: py = pyridine
(a) [Cr(NH3)5Cl] Cl2 and [Cr(NH3)4Cl2]Cl
Given: Aomic numbers of Fe, Co Ni and Cu are 26, 27,
(b) [Co(NH3)4Cl2]+ and [Pt(NH3)2(H2O)Cl]+
28 and 29, respectively) (2021)
(c) [CoBr2Cl2]2– and [PtBr2Cl2]2–
 2
(d) [Pt(NH3)3(NO3)] Cl and [Pt(NH3)3Cl]Br (a)  FeCl4  and  Fe  CO 4 
17. The correct statement(s) regarding the binary transition  2
(b) Co  CO 4  and  CoCl 4 
metal carbonyl compounds is (are)
2
(Atomic numbers : Fe = 26, Ni = 28) (2018) (c)  Ni  CO  4  and  Ni  CN 4 
(a) Total number of valence shell electrons at metal centre  3
in Fe(CO)5 or Ni(CO)4 is 16 (d) Cu  py 4  and Cu  CN  4 
(b) These are predominantly low spin in nature. Numerical Value Type Questions
(c) Metal-carbon bond strengthens when the oxidation
20. EDTA 4  is ethylene diaminetetraacetate ion. The total
state of the metal is lowered 
numberof N-Co-O bond angle in Co  EDTA   complex
(d) The carbonyl C-O bond weakens when the oxidation
state of the metal is increased ion is (2013)
21. Among the species given below, the total number of
18. In an experiment, m grams of a compound X (gas/liquid/
diamagnetic species is ............ .
solid) taken in a container is loaded in a balance as
shown in figure I below. In the presence of a magnetic H atom, NO2 monomer, O 2 (superoxide), dimeric sulphur in
field, the pan with X is either deflected upwards (figure vapour phase,
II), or deflected downwards (figure III), depending on Mn3O4, [FeCl4], (NH4)2 [NiCl4], K2MnO4, K2CrO4 (2018)
the compound X. Identify the correct statement(s) 22. Total number of cis N–Mn–Cl bond angles (that is, Mn–N

(2020) and Mn–Cl bonds in cis position) present in a molecule of


cis [Mn(en)2Cl2] complex is________
(en = NH2CH2CH2NH2) (2019)

23. The total number of possible isomers for


 Pt  NH 3  4 Cl 2  Br2 is (2021)
COORDINATION COMPOUNDS 60
Assertion Reason LIST-I LIST-II
(A) If both Assertion and Reason are correct and (P) dsp2 (1) [FeF6]4–
Reason is the correct explanation of Assertion. (Q) sp3 (2) [Ti(H2O)3Cl3]
3 2
(B) If both Assertion and Reason are true but (R) sp d (3) [Cr(NH3)6]3+
Reason is not the correct explanation of (S) d2sp3 (4) [FeCl4]2–
Assertion. (5) Ni(CO)4
(C) If Assertion is true but Reason is false. (6) [Ni(CN)4]2–
(D) If Assertion is false but Reason is true. The correct option is
24. Assertion(A) : [Fe(H2O)5NO]SO4 is paramagnetic (a) P - 5; Q - 4,6; R - 2,3; S - 1

Reason(R) : The Fe in [Fe (H2O)5 NO] SO4 has three unpaired (b) P - 5,6; Q - 4; R - 3; S - 1,2
electrons. (2008) (c) P - 6; Q - 4, 5; R - 1; S - 2,3
(d) P - 4,6; Q - 5,6; R - 1,2; S - 3
(a) A (b) B
(c) C (d) D
Paragraph Type Questions
25. Assertion(A) : The geometrical isomers of the complex Use the following passage, to solve Q. 28 to Q. 30
[M(NH3)4 Cl2] are optically inactive. Passage
The coordination number of Ni2+ is 4.
Reason(R) : Both geometrical isomers of the complex [M
NiCl2 + KCN (excess)  A (cyano complex)
(NH3)4 Cl2] possess axis of symmetry. (2008)
A + conc. HCl (excess)  B (chloro complex) (2006)
(a) A (b) B
28. The IUPAC name of A and B are
(c) C (d) D
(a) potassium tetracyanonickelate (II),
Match the Following potassium tetrachloridonickelate (II)
Each question has two columns. Four options are (b) potassium tetracyanonickelate (II)
given representing matching of elements from tetrachloridopotassium nickelate (II)
Column-I and Column-II. Only one of these four (c) tetracyanonickel (II), tetrachloridonickel (II)
options corresponds to a correct matching for each (d) potassium tetracyanonickel (II),
question. potassium tetrachloridonickel (II).
26. Match the complexes in column I with their properties listed 29. Predict the magnetic nature of A and B.
in column II. (2007)
(a) Both are diamagnetic
Column I Column II
(b) A is diamagnetic and B is paramagnetic with one
(A) [Co(NH3)4 (H2O)2] Cl2 (p) geometrical isomers unpaired electron
(B) [Pt (NH3)2 Cl2] (q) paramagnetic (c) A is diamagnetic and B is paramagnetic with two
(C) [Co (H2O)5 Cl] Cl (r) diamagnetic unpaired electrons
(D) [Ni (H2O)6] Cl2 (s) metal ion with +2 (d) Both are paramagnetic.
oxidation state 30. The hybridisation of A and B are
27. Match each set of hybrid orbitals from LIST-I with (a) dsp2, sp3 (b) sp3, sp3
complex(es) given is LIST-II. (2018) (c) dsp2, dsp2 (d) sp3d2, d2sp3
COORDINATION COMPOUNDS 61
Subjective Type Qustions 33. Deduce the structures of [NiCl4]2– and [Ni(CN)4]2– considering
the hybridisation of the metal ion. Calculate the magnetic
31. Draw the structures of [Co(NH3) 6] 3+, [Ni(CN)4]2– and
moment (spin only) of the species. (2002)
[Ni(CO)4]. Write the hybridisation of atomic orbitals of the
transition metal in each case. (2000) 34. Write the IUPAC name of the compound K2[Cr(NO) (CN)4
(NH3)]. Spin magnetic moment of the complex  = 1.73 BM.
32. A metal complex having composition Cr(NH3)4 Cl2Br has
Give the structure of anion. (2003)
been isolated in two forms A and B. The form A reacts with
AgNO3 to give a white precipitate readily soluble in dilute 35. NiCl2 in the presence of dimethyl glyoxime (DMG) gives a
aqueous ammonia, whereas B gives a pale yellow precipitate complex which precipitates in the presence of NH4OH, giving
soluble in concentrated ammonia. Write the formula of A a bright red colour. (2004)
and B and state the hybridisation of chromium in each. (a) Draw its structure and show H-bonding
Calculate their magnetic moments (spin-only value). (b) Give oxidation state of Ni and its hybridisation
(2001)
(c) Predict whether it is paramagnetic or diamagnetic.
COORDINATION COMPOUNDS 62

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CHEMICAL KINETICS
Chapter 18 64

CHEMICAL KINETICS
THEORY

1. INTRODUCTION 2.2 Instantaneous rate


The branch of chemistry which deals with the study of the rates
Rate of change of concentration of any one of the reactants or
of chemical reactions, the factors affecting the rates of the
reactions and the mechanism by which the reactions proceed is products at that particular instant of time is called instantaneous
called Chemical Kinetics. rate.
Classification of reactions d [R] d [P]
As t  0 or rinst  
On the basis of rates : dt dt

 Very fast reactions NOTE


e.g. precipitation of AgCl Rate of a reaction is always positive.

 Very slow reactions Since,  [R] is a negative quantity (as concentration of


reactants is decreasing), it is multiplied with –1 to make the
e.g. rusting of iron
rate of the reaction a positive quantity.
 Reactions taking place at moderate speeds
2.3 Units of rate of a reaction
e.g. hydrolysis of starch
Units of rate of reaction are concentration time–1
or mol L–1s–1; atm s–1 (for gaseous reactions)
2. RATE OF A CHEMICAL REACTION
2.4 Overall rate of a reaction
The rate of a reaction can be defined as the change in
concentration of a reactant or a product in unit time.
When there are several reactants and products the individual
2.1 Average rate rates of the various components may differ as they would depend
on the stoichiometric coefficients.
The rate of reaction measured over a definite time interval is
called average rate of a reaction. For a reaction,
Consider a hypothetical reaction, A + 2B 3C + 4D
R P Rate of disappearance of B = 2 × Rate of disappearance of A (2:1)
Decrease in concentration of R Rate of formation of C = 3 × Rate of disappearance of A (3:1)
Average rate of reaction 
Time taken Rate of formation of D = 4 × Rate of disappearance of A (4:1)
  R  To define a unique value for the overall rate of the reaction we

t
divide the individual rates by the respective coefficients and
Increasein concentration of P
or  equate their signs.
Time taken
A / t   1/ 2  B / t
 P  Overall Rate 
 1 / 3 C / t   1/ 4  D / t
=
t

SCAN CODE
Chemical Kinetics
CHEMICAL KINETICS 65
NOTE 3.2 Order of a Reaction

aA + bB cC + dD aA + bB cC + dD

Rate = k [A]x [B]y


 1/ a  A / t   1/ b  B / t
Overall Rate =  1 / c C / t  1/ d D / t
    Sum of these exponents, i.e., x + y gives the overall order of a
reaction where x and y represent the order with respect to the
reactants A and B respectively.
 1/ a  dA / dt   1 / b  dB / dt
Instantaneous Rate  1 / c dC / dt  1 / d dD / dt
    Hence, the sum of powers of the concentration terms of the
reactants in the rate law expression is called the order of that
chemical reaction.
3. DEPENDENCE OF RATE ON CONCENTRATION
Order of a reaction can be 0, 1, 2, 3 and even a fraction.
Factors influencing rate of a reaction: 3.3 Units of rate constant
 concentration of reactants (pressure in case of gases),
Rate = k [A]x [B]y
 temperature and
 catalyst. Rate concentration 1
k  
[A]x [B]y time (concentration) n
3.1 Rate law

Consider a general reaction Reaction Order Units of rate constant


aA + bB cC + dD
The rate expression for this reaction is mol L1 1
Zero order reaction 0 
Rate  [A]x [B]y s (mol L1 ) 0
where exponents x and y may or may not be equal to the
= mol L–1 s–1
stoichiometric coefficients (a and b) of the reactants.
Rate = k [A]x [B]y mol L1 1
First order reaction 1   s 1
d  R  s (mol L1 )1
 k  A  B 
x y

dt
Above equation is known as differential rate equation, k is a mol L1 1
Second order reaction 2 
s (mol L1 ) 2
proportionality constant called rate constant.
Rate law is the expression in which reaction rate is given in terms
= mol–1 L s–1
of molar concentration of reactants with each term raised to some
power, which may or may not be same as the stoichiometric
coefficient of the reacting species in a balanced chemical 4. INTEGRATED RATE EQUATIONS
equation. 4.1 Zero order reaction
The rate of the reaction is proportional to zeroth power of the
NOTE
concentration of reactants.
Rate law for any reaction cannot be predicted by merely
R P
looking at the balanced chemical equation, i.e., theoretically
but must be determined experimentally.
d  R 
e.g. 2NO(g) + O2(g)  2NO2 (g) ; Rate = k [NO]2[O2] Rate   k[R]0
dt
CHCl3 + Cl2  CCl4 + HCl ; Rate = k [CHCl3] [Cl2]1/2

SCAN CODE
Chemical Kinetics
CHEMICAL KINETICS 66

For example,
 The decomposition of gaseous ammonia on a hot platinum
surface at high pressure.
dA

K
dt

1130K
2NH3 (g)   N 2 (g)  3H 2 (g)
Rate

Pt catalyst

Rate = k [NH3]0 = k
 Thermal decomposition of HI on gold surface
0
time 4.2 First order reaction

The rate of the reaction is proportional to the first power of the


Consider the reaction, concentration of the reactant R.
RP
d  R 
d [R] Rate   k R 
Rate =   k [R]0 dt
dt

d [R]
Rate =   k 1
dt
d [R] = – k dt
Integrating both sides
[R] = – k t + I ..........(1)
where, I is the constant of integration.
At t = 0, the concentration of the reactant R = [R]0, where [R]0 is
initial concentration of the reactant.
Substituting in equation (1)
[R]0 = – k × 0 + I R P
[R]0 = I
d [R]
Substituting the value of I in the equation Rate    k [R]
dt
[R] = –kt + [R]0
d [R]
or   kdt
[R]

Integrating this equation, we get


In [R] = –kt + I ........ (1)
Again, I is the constant of integration and its value can be
determined easily.

When t = 0, R = [R]0, where [R]0 is the initial concentration of the


reactant.

Therefore, equation can be written as


k
 R    R 
0

t In [R]0 = – k × 0 + I

In [R]0 = I

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Substituting the value of I in equation (1) The first order rate equation (3) can also be written in the form

In [R] = –kt + ln [R]0 ......... (2) 2.303 [R]0


k log
t [R]
Rearranging this equation
[R]0 kt
[R] log 
ln  kt [R] 2.303
[R]0

1 [R]0
or k  ln ......... (3)
t [R]

At time t1 from equation (2)

In [R]1 = – kt1 + ln [R]0 ..........(4)

At time t2

ln [R]2 = – kt2 + ln [R]0 ..........(5)

where, [R]1 and [R]2 are the concentrations of the reactants at For example,
time t1 and t2 respectively.
 Hydrogenation of ethene,
Subtracting equation (5) from (4)
C2 H 4 (g)  H 2 (g)  C2 H 6 (g)
ln [R]1 – ln [R]2 = – kt1 – (–kt2) Rate = k [C2H4]

[R]1  Decomposition of N2O5 and N2O


ln [R]  k (t 2  t1 )
2
4.3 Half-Life of a Reaction

1 [R]1 The half-life of a reaction is the time in which the concentration


k= ln
(t 2 - t1 ) [R]2 of a reactant is reduced to one half of its initial concentration.

Comparing equation (2) with y = mx + c, if we plot ln [R] against Represented as : t1/2.


t, we get a straight line with slope = –k and intercept equal to ln  For a zero order reaction, rate constant is given by equation.
[R]0 .
[R]0  [R]
k
t

ln[R0] 1
At t = t1/2, [R] = [R]0
k = – slope 2
The rate constant at t1/2 becomes
ln[R]

[R]0  1/ 2 [R]0
k
t1/ 2

[R]0
0 t t1/ 2 
2k

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 For the first order reaction, 4.5 Practical Analysis of First Order Reactions

2.303 [R]0 Case - 1: In gaseous phase reactions we prefer to measure the


k log
t [R] pressure of the gases. For example

[R]0  For a first order gas phase reaction of the type :


at t1/2, [R] 
2
A(g) B(g) + C(g)
So, the above equation becomes
Let pi be the initial pressure of A and pt the total pressure at time
2.303 [R]0 ‘t’.
k log
t1/ 2 [R]/ 2
Integrated rate equation for such a reaction can be derived as :
2.303
or t1/ 2  log 2 Total pressure pt = pA + pB + pC (pressure units) pA, pB and pC are
k
the partial pressures of A, B and C, respectively.
2.303
t1/ 2   0.301 If x atm be the decrease in pressure of A at time t and one mole
k
each of B and C is being formed, the increase in pressure of B and
C will also be x atm each.
0.693
t1/ 2 
k
A(g)  B(g)  C(g)
4.4 Pseudo First Order Reactions At t  0 pi atm 0 atm 0 atm
At time t (pi  x) atm x atm x atm
Reactions which are not truly of the first order but under certain
conditions become reactions of the first order. where, pi is the initial pressure at time t = 0.

For example, pt = (pi – x) + x + x = pi + x

 x = (pt – pi)
CH 3COOC2 H 5  H 2 O 
H
CH 3 COOH  C 2 H 5OH
pA = pi – x = pi – (pt – pi)
Rate = k [CH3COOC2H5] [H2O]
= 2pi – pt
The concentration of water does not get altered much during the
course of the reaction. So, in the rate equation the term [H2O] can
be taken as constant.  p 
 2.303 
k = t   log i 
Rate = k  [CH3COOC2H5]    p 
 A
where k  = k [H2O]
2.303 pi
Inversion of Cane sugar is another pseudo first order reaction  log
t (2pi  p t )

H
C12 H 22 O11  H 2O  
 C6 H12 O6  C6 H12 O6  For a first order gas phase reaction of the type :
Cane Sugar Glu cose Fructose

A(s)  B(s)  C(g)


Rate = k [C12H22O11]

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The data given to us is: Case 2 : If one of reactants is titrated with a redox reagent:

Time Pressure of gas C/Total Pressure Suppose we have a reaction of the type:
0 0 AB+C
t Pt
And suppose we detect the amount of A left by titrating it with
 P some reagent and volume of that reagent reacting with the left
over A is given at different time intervals:
If we have to find the expression for k or verify that its a first
order reaction then we will use the expression for k: Time Volume of the reagent

a 0 V0
ln  kt
ax t Vt
But we don’t know the values for a or a – x but we can find the Now the volume of the reagent will be proportional to the moles
above ratio by relating the given data with concentration values. of A present. Therefore:
For gases, P  number of moles V0  a
A(s)  B(s) + C(g) Vt  a – x
t=0 a 0 0
We can evaluate k:
t=t a–x x x
V0
kt  ln
t=  0 a a Vt
Now we can write:
If the same reagent reacts with all the reactants and products:
Pt  x
V0  a
P  a
Vt  a + x
P – Pt  a – x 2V0 – Vt  a – x

a/(a –x) = P /( P – Pt) V0


kt  ln
2V0  Vt
Now we can substitute this into the expression for k.
4.6 Practical Methods of determining order of a reaction
1 P
k  ln i. Initial Rate Data Method:
t P  Pt
We take different set of initial concentration and measure the
The above expression can be used to evaluate the value of k initial rate. Then by keeping the concentration of one of the
from the pressure data and also verify that the reaction is of first reactants constant and varying the other one we can study
order by checking 2-3 data points. In the above analysis the the effect on the rate of reaction and hence find out the order.
expression would have been same for the following reactions as ii. Logarithmic data method:
well as the constants will cancel out.
For any order, fractional or integral, if we plot log (rate) vs log
A(s)  B(s) + 2C(g) (concentration) graph it will always be a straight line for the
reactions of the type:
A(s)  2B(g) + C(g) (if total pressure is given)
A  products
And the results will be same if the similar data is given in terms of
volume. Rate, r = k[A]n
log r = log k + n log [A]

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Expression of Rate Constant for Some Important Reactions
Reaction Expression for rate constant

1 2.303 V
N 2 O 5  2NO 2  O2 k log
2 t V  Vt
Here V t = volume of O 2 after time t and V 
volume of O2 after infinite time.
NH4 NO2 (aq)  2H2O + N2 Same as above, here Vt and V are volumes
of N2 at time t and at infinite time respectively.
1 .303 V
H 2O2  H 2O  O2 k log 0
2 t Vt
Here V o and V t are the volumes of KMnO 4
solution used for titration of same volume
of reaction mixture at zero time (initially)
and after time t.
2.303 V  V0
H
CH 3COOC 2 H 5  H 2 O  

 CH 3COOH k log 
t V  Vt
 C2 H5 OH Here V 0 ,V t and V  are the volumes of NaOH
solution used for titration of same volume
of reaction mixture after time, 0, t and
infinite time respectively.

H 2.303 r r
C12 H 22 O11  H 2 O  
 C 6 H12O 6  C6 H12 O6 k log 0 
d sucrose d Glucose   Fructose t rt  r
(After the reaction is complete the Here, r 0 ,r t and r  are the polarimetric
equimolar mixture of glucose and fructose readings after time 0, t and infinity
obtained is laevorotatory) respectively.

We can take various data points and convert them to log iii. Half Life Method:
values and plot them. We will obtain a straight line after If we take various concentrations of reactant and measure
curve-fitting with slope n and intercept log k. And hence we half life for all of them then we can find out the order of the
can find out the order and rate constant from the graph. reaction by mere observation or with the help of some
calculations.
t1/2  [A]01-n
If simple observation is not possible then we can calculate
the order of the reaction by taking two data points and using
log for calculating n.
iv. By integrated rate Equations:
If we have simple data of concentration and time we can use
the integrated rate equations to find out the order. For this
we will have to try and fit the data into the equation at various
intervals and calculate the value of rate constants. If the
values come out to be the same in all intervals then the data
fits into the equation taken and we will know the order. For
example, we have the following data:
Time: 0 t1 t2 t3 ....... t
Conc: A0 A1 A2 A3.......At

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And if we assume that it can be of first order then we will When a sequence of elementary reactions (called mechanism)
calculate the values of k at minimum three data points by gives us the products, the reactions are called complex reactions.
using the equation for first order:
The different steps in which the complex reaction takes place is
1 A0 called the mechanism of the reaction.
In K
t At
Rate determining step :
Let these values be k1, k2 and k3. If k1 = k2 = k3 then it means
The overall rate of the reaction is controlled by the slowest step
that this data fits into the above equation hence the order is
1. If it doesn’t we will have to try other equations as well. in a reaction called the rate determining step.

v . Isolation method: A complex reaction can be represented as a series of elementary


In this method we try and eliminate one of the two reactants steps.
from the rate equation by taking it in excess. What happens For example
is when the amount of a reactant is in excess its effect on the
rate becomes marginal or negligible and then we can vary the 2NO2(g) + F2(g)  2NO2F(g)
concentration of the other reactant and observe its effect on
Experimentally, Rate of reaction = k[NO2][F2]
rate and find out the order.
Probable mechanism :
5. MOLECULARITY AND REACTION MECHANISM
Step-1:
5.1 Molecularity
The number of reacting species (atoms, ions or molecules) taking NO 2  F2 
Slow
 NO 2 F  F
part in an elementary reaction, which must collide simultaneously
Step-2 :
in order to bring about a chemical reaction is called molecularity
of a reaction. NO 2  F  
Fast
 NO 2 F
5.1.1 Classification of reactions on the basis of Molecularity
Slow step : bimolecular
Unimolecular reactions : when one reacting species is involved,
Hence, a bimolecular reaction.
for example, decomposition of ammonium nitrite.
Reaction intermediates :
NH4NO2  N2 + 2H2O
There are some species which are formed during the course of
Bimolecular reactions : involve simultaneous collision between the reaction but do not appear in the overall reaction. They are
two species called reaction intermediates.
for example, dissociation of hydrogen iodide. 5.3 Distinction between Order and Molecularity of a reaction
2HI  H2 + I2
Order:
Trimolecular or termolecular reactions : Involve simultaneous
1. Order is the sum of the powers of the concentration of the
collision between three reacting species
reactants in the rate law expression.
For example,
2. It can be zero and even a fraction.
2NO + O2   2NO2 3. It is applicable to elementary as well as complex reactions.
Reactions with molecularity greater than three are very rare. 4. It can be determined experimentally only and cannot be
5.2 Reaction Mechanism calculated.
5. For complex reaction, order is given by the slowest step.
The reactions taking place in one step are called elementary
reactions.

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Molecularity:
1. Molecularity is the number of reacting species taking part
in an elementary reaction, which must collide
simultaneously in order to bring about a chemical reaction.
2. It cannot be zero or a non integer.
3. It is applicable only for elementary reactions. For complex
reaction molecularity has no meaning.
4. It can be calculated by simply adding the molecules of the
slowest step.
5. Generally, molecularity of the slowest step is same as the
order of the overall reaction.
Reaction profile of an endothermic reaction
6. TEMPERATURE DEPENDENCE

6.1 Activation Energy

According to collision theory, a reaction takes place because the


reactant molecules collide with each other.

The minimum energy required for an effective collision is called


threshold energy.

The minimum extra amount of energy absorbed by the reactant


molecules so that their energy becomes equal to threshold value
is called activation energy.

Threshold energy = Activation energy + Energy possessed by 6.2 Temperature Dependence of the Rate of a Reaction
the reactants For a chemical reaction with rise in temperature by 10°, the rate
Less is the activation energy, faster is the reaction. constant is nearly doubled.

In order that the reactants may change into products, they have Rate constant at T  10
Temperature coefficient 
to cross an energy barrier (corresponding to threshold energy). Rate constant at T 

Reactant molecules absorb energy and form an intermediate called Explanation:


activated complex which immediately dissociates to form the At a particular temperature, if fractions of molecules are plotted
products. versus corresponding kinetic energies, a graph of the type shown
is obtained. The peak of the curve represents the kinetic energy
For example,
possessed by the maximum fraction of molecules and is called
most probable kinetic energy.

Reaction profile of an exothermic reaction

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The factor e Ea / RT corresponds to the fraction of molecules that
have kinetic energy greater than Ea.

Thus, it has been found from Arrhenius equation that increasing


the temperature or decreasing the activation energy will result in
an increase in the rate of the reaction and an exponential increase
in the rate constant.

Taking natural logarithm of both sides of equation

Ea
ln k    ln A
Distribution curve showing energies among gaseous RT
molecules
Ea
The plot of ln k vs 1/T gives a straight line with slope  
R
and intercept = ln A.
At temperature T1, equation

Ea
ln k1   ln A
RT1
At temperature T2, equation is

Ea
ln k 2   ln A
RT2
(since A is constant for a given reaction)
Distribution curve showing temperature dependence of rate of
k1 and k2 are the values of rate constants at temperatures T1 and
a reaction
T2 respectively.
With increase in temperature : Substracting equation form, we obtain
(i) maximum of the curve moves to the higher energy value
Ea E
i.e., most probable kinetic energy increases ln k 2  ln k1   a
RT1 RT2
(ii) the curve spreads to the right i.e., there is a greater
proportion of molecules with much higher energies.
k2 Ea  1 1 
ln k  R  T  T 
The area under the curve remains constant since total probability 1  1 2 

must be one at all times. At (t + 10), the area showing the fraction
of molecules having energy equal to or greater than activation
k2 Ea  1 1 
energy gets doubled leading to doubling the rate of a reaction. log    
k1 2.303R  T1 T2 
6.3 Arrhenius equation

Quantatively, the temperature dependence of the rate of a chemical k2 E a  T2  T1 


log   
reaction can be explained by Arrhenius equation k1 2.303R  T1T2 

k  Ae Ea / RT

where A is the Arrhenius factor or the frequency factor or pre-


exponential factor. R is gas constant and Ea is activation energy
measured in joules/mole.

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7. EFFECT OF CATALYST 7.1 Important characteristics of catalyst

 A small amount of the catalyst can catalyse a large amount


A catalyst is a substance which alters the rate of a reaction without
of reactants.
itself undergoing any permanent chemical change.
 A catalyst does not alter Gibbs energy, G of a reaction.
For example,
 It catalyses the spontaneous reactions but does not
MnO2
2KClO3  2 KCl  3O2 catalyse non-spontaneous reactions.

Action of the catalyst:  A catalyst does not change the equilibrium constant of a
reaction rather, it helps in attaining the equilibrium faster.
According to intermediate complex theory, reactants first combine
with catalyst to form intermediate complex which then 8. COLLISION THEORY OF CHEMICAL REACTIONS
decomposes to form the products and regenerating the catalyst.
According to this theory, the reactant molecules are assumed to
be hard spheres and reaction is postulated to occur when
molecules collide with each other.
Rate of reaction depends on the number of effective collisions
which in turn depends on :
(i) Energy factor : colliding molecules must have energy more
than threshold energy.
Effect of catalyst on activation energy: (ii) Steric or probability factor (P) : colliding molecules must
have proper orientations at the time of collision.
Thus, the Arrhenius equation is modified to

k  PZAB e – Ea / RT

Catalyst provides an alternate pathway by reducing the activation


energy between reactants and products and hence lowering the
potential energy barrier.

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SUMMARY
 The rate of a reaction is concerned with decrease in  Molecularity and order of an elementary reaction are the
concentration of reactants or increase in the concentration same.
of products per unit time.  Temperature dependence of rate constants is described by
 A number of factors such as temperature, concentration of Arrhenius equation,k=Ae -Ea/RT , E a corresponds to the
reactants and catalyst affect the rate of a reaction. activation energy and is given by the energy difference
 Order of a reaction with respect to a reactant is the power of between activated complex and the reactant molecules, and
its concentration which appears in the rate law equation.
A (Arrhenius factor or pre-exponential factor) corresponds
The order of a reaction is the sum of all such powers of
to the collision frequency.
concentration of terms for different reactants.
 According to collision theory, another factor P called steric
 Molecularity is defined only for an elementary reaction. Its
factor which refers to the orientation of molecules which
values are limited from 1 to 3 whereas order can be 0, 1, 2, 3,
collide, is important and contributes to effective collisions,
an integer or even a fraction.
thus, modifying the Arrhenius equation to k = PZABe-Ea/RT

Points Related to Different Order of Reaction

Zero-Order First Order Second Order nth-Order

d[ A] d[ A] d[ A] d[ A]
Rate Law  k   k[A ]   k[ A ]2   k[ A ]n
dt dt dt dt

1 1 1 1
Integrated [A] = [A]0 – kt [A] = [A]0e–kt   kt n 1
  ( n  1) kt
[ A ] [ A ]0 [A ] [ A ]0n 1

Rate Law (Except first Order)

M 1 1 1
Units of Rate M.s n 1
s s M .s

Constant (k)

1 1
Linear Plot to [A] vs. t ln([A]) vs. t vs. t vs. t
[ A] [A]n1

determine k (Except first Order)

[ A ]0 ln(2) 1 2 n 1  1
Half-life t1/ 2  t1 / 2  t1/ 2  t1 / 2 
2k k [ A ]0 k (n  1)k [A ]0n 1

(Except first Order)

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SOLVED EXAMPLES

Example-1 Example-4
For the assumed reaction X2 + 3Y2  2XY3, write the
What do you understand by ‘Rate of reaction’ ?
rate of equation in terms of rate of disappearance of Y2.
Sol. The change in the concentration of any one of the reactants
or products per unit time is termed as the rate of reaction. d [X 2 ] 1 d [Y2 ] 1 d [XY3 ]
Sol. Rate = –  
Example-2 dt 3 dt 2 dt
In a reaction R  P the concentration of R was observed. Rate of disappearance of Y2
Find the rate of the reaction d [Y2 ] d [X 2 ] 3 d [XY3 ]
=  3 
dt dt 2 dt
Conc., Mol/L 50 25 15 10
Example-5
Time (s) 0 10 20 30
For an elementary reaction 2A + B  3C the rate of
d R 
Sol: The rate of reaction   mol L-1s-1 appearance of C at time ‘t’ is 1.3 × 10–4 mol L–1 s–1.
dt Calculate at this time
 25  50  (i) rate of the reaction.
In 1st time interval rate   (ii) rate of disappearance of A.
10
= 2.5 mol L-1s-1.
1 d [C] 1
Sol. (i) Rate    1.3  104
15  25 3 dt 3
In 2nd time interval rate  
10
= 1 mol L-1s-1. = 0.43 × 10–4 mol L–1 s–1

10  15 d [A] 2 d [C]


In 3rd time interval rate  
10 (ii) Rate   
dt 3 dt
= 0.5mol L-1s-1.
Example-3  0.86  10 4 mol L1 s 1
In a reaction H2 + I2  2HI the rate of disappearance of
I2 is found to be 10–6 mole per litre per second. What Example-6
would be the corresponding rate of appearane of HI ?
Sol. In the given reaction Differentiate between rate of reaction and reaction rate
rate = rate of disappearance of H2 per mole constant.
= rate of disappearance of I2 per mole
= rate of appearance of HI per mole Sol. Rate of Reaction
d[ H 2 ] d[ I ] 1 d[ HI] 1. Rate of reaction is the change in concentration of a reactant
    2    10 6
dt dt 2 dt or product in a unit interval of time.
d[ HI] 2. The rate of reaction at any instant of time depends upon
  2 × 10–6 mole L–1s–1.
dt the molar concentrations of the reactants at that time.

3. Its units are always mol litre–1 time–1.


CHEMICAL KINETICS 77
Reaction Rate Constant Example-10

1. It is the rate of reaction when the molar concentration of


Following reaction takes place in one step :
each of the reactants is unity.
 2NO
2NO(g) + O2(g) 
2. The rate constant does not depend upon the 2(g)

concentrations of the reactants. How will the rate of the above reaction change if the
3. Its units depend upon the order of reaction. volume of the reaction vessel is diminished to one-third
of its original volume ? Will there be any change in the
Example-7 order of the reaction with reduced volume ?

What is meant by an elementary reaction ? Sol. Rate = k [NO]2 [O2]

Sol. A reaction that takes place in one step is called an Let initially, moles of NO = a, moles of O2 = b, volume of the
elementary reaction. Say, for example, reaction between H2 vessel = V. Then
and I2 to form 2HI is an elementary reaction. Each step of a
complex reaction is an elementary reaction. a b
[NO]  M, [O2 ]  M
V V
Example-8
2
a b a 2b
Define the following :  Rate (r1 )  k      k 3 ....... (i)
V V V
(i) Elementary step in a reaction
V
(ii) Rate of a reaction Now, new volume = .
3
Sol. (i) Elementary step : Each step of a complex reaction is
called an elementary step. a 3a
 New concentrations : [NO]  
V/3 V
(ii) Rate of reaction : It is the change in the concentration
of any of the reactants or products per unit time. b 3b
[O 2 ]  
V/3 V
Example-9
2 2
The specific reaction rate of a reaction is  3a   3b  27ka b
 New rate (r2) = k      ....... (ii)
6.2 × 10–3 mol lit–1 s–1. What is the order of reaction ? V V V3

Sol. Comparing with (mol L–1)1–n s–1, we get r2


1–n 1  r  27 or r2 = 27 r1 = rate becomes 27 times.
mol = mol 1

1–n=1 Thus, there is no effect on the order of reaction.

n=0

i.e., zero order reaction.


CHEMICAL KINETICS 78
Example-11 Example-13

Distinguish between order and molecularity of reaction. The rate of reaction, 2NO + Cl2  2NOCl is doubled
when concentration of Cl2 is doubled and it becomes
Sol. Order: eight times when concentration of both NO and Cl2 are
1. Order is the sum of the powers of the concentration of the doubled. Deduce the order of the reaction.
reactants in the rate law expression. Sol. Let r = k [NO]x [Cl2]y
2. It can be zero and even a fraction. 2r = k [NO]x [2Cl2]y ...... (i)
3. It is applicable to elementary as well as complex reactions. 8r = k [2NO]x [2Cl2]y ........ (ii)
4. It can be determined experimentally only and cannot be
Dividing (ii) by (i), we get
calculated.
5. For complex reaction, order is given by the slowest step. 8r k[2NO]x [2Cl2 ]y

Molecularity: 2r k [NO]x [2Cl2 ]y
1. Molecularity is the number of reacting species taking part 22 = [2]x
in an elementary reaction, which must collide
x=2
simultaneously in order to bring about a chemical reaction.
Putting the value of x in (i), we get
2. It cannot be zero or a non integer.
3. It is applicable only for elementary reactions. For complex 2r = k [NO]2 [2Cl2]y
reaction molecularity has no meaning. Also r = k [NO]2 [Cl2]y
4. It can be calculated by simply adding the molecules of the
2r [2Cl2 ]y
slowest step. 
r [Cl 2 ]y
5. Generally, molecularity of the slowest step is same as the
order of the overall reaction. 2 = [2]y

Example-12 y=1

Rate = k [NO]2 [Cl2]1


Calculate the overall order of a reaction which has the
rate expression Overall order of reaction = x + y = 2 + 1 = 3.

(a) Rate = k [A]1/2 [B]3/2 Example-14


(b) Rate = k [A]3/2 [B]–1
When could order and molecularity of a reaction
x y
Sol. (a)Rate = k [A] [B] (i) be the same and (ii) be different ?
order = x + y
Sol. (i) If the rate determining step involves all the reactants
taking part in the reaction, i.e., it is a one-step reaction,
1 3
So, order    2, i.e., second order then order and molecularity of the reaction is same.
2 2
(ii) If reaction involves more than one step, then order
3 1 and molecularity are different.
(b) Order   (1)  , i.e., half order.
2 2
CHEMICAL KINETICS 79
Example-15 8r = k [2A]n ....... (ii)
Dividing (ii) by (i), we get
Define the following terms giving an example for each :
(i) The order of a reaction 8r k [2A]n

r k [A]n
(ii) The molecularity of a reaction.

Sol. (i) Order of reaction may be defined as the sum of powers 8 = [2]n
of the concentration of the reactants in the rate law n=3
expression.
The order of reaction is 3.
For example consider the reaction
Example-18
NH4NO2 
 N2 + 2H2O
Experimentally, it is observed that the rate law for this A + 2B  3C + 2D. The rate of disappearance of B is
reaction is 1 × 10–2 mol L–1 s–1. What will be

Rate = k [NH4NO2] (i) Rate of the reaction

Hence, the order of reaction is 1. (ii) Rate of change in concentration of A and C ?

(ii) Molecularity of a reaction may be defined as the 1 d [B] 1


Sol. (i) Rate =    1 102
number of reacting species (atoms, ions or molecules) 2 dt 2
taking part in an elementary reaction which must collide
simultaneously in order to bring about a chemical = 0.5 × 10–2 mol L–1 s–1
reaction.
d [A] 1 d [B] 1 d [C]
For example molecularity of the reaction (ii) Rate =   
dt 2 dt 3 dt
2HI   H2 + I2 is 2 as it involves simultaneous Rate of change in concentration of A
collision between two HI molecules.
d [A] 1 d [B]
Example-16  
dt 2 dt

For the reaction N2(g) + 3H2(g)  2NH3(g), how are the = 0.5 × 10–2 mol L–1 s–1

d[H 2 ] d [NH 3 ] Rate of change in concentration of C


reaction expressions  and
dt dt
interrelated ? d [C] 3 d [B] 3
   102
dt 2 dt 2
1 d [H 2 ] 1 d [NH3 ]
Sol.   = 1.5 × 10–2 mol L–1 s–1
3 dt 2 dt
Example-19
Example-17
Define specific reaction rate or rate constant.
The rate of decomposition of a substance A becomes
eight times when its concentration is doubled. What is Sol. Specific reaction rate is the rate of reaction when the molar
the order of this reaction ? concentration of each of the reactants is unity.

Sol. Rate law is,

Rate = k [A]n

r = k [A]n ........ (i)


CHEMICAL KINETICS 80
Example-20
1 1
  kt
Rate of a reaction is given by the equation : [ A ] [A 0 ]

Rate = k [A]2 [B]


1 1
What are the units for the rate and the rate constant for  = (0.0606) (300) = 18.18
[A] 3.5  10 3
this reaction ?

Sol. Units of rate = mol L–1 s–1 1


 18.18 + 285.7 = 303.9
[A]
Rate mol L1s 1
Units of k = 
[A]2 [B] (mol L1 ) (mol L1 ) 2 [A] = 3.29 × 10–3 M = [B]

= L2 mol–2 s–1. Example-23

Example-21
Why is it that instantaneous rate of reaction does not
change when a part of the reacting solution is taken
What is meant by the ‘rate constant, k’ of a reaction ? If out ?
the concentration is expressed in mol L–1 units and time
in seconds, what would be the units of k (i) for a zero order Sol. Instantaneous rate is measured over a very small interval
reaction and (ii) for a first order reaction ? of time, hence, it does not change when a part of solution
is taken out.
Sol. Rate constant is the rate of the reaction when the
concentration of each reactant is taken as unity. Example-24

 rate = k [A]n
The reaction 2NO(g) + Cl2(g)  2NOCl was studied at – 10
1 n
ºC, and the following data were obtained :
 General unit of k = 
mol. 
 s 1 Initial concentration, mol/L
 lit. 
RXN NO Cl2 Initial rate of
(i) For a zero order reaction n = 0 formation of NOCl,
mol/L. min
 Unit of k = mol lit–1s–1
1 0.10 0.10 0.18
(ii) For a first order reaction n = 1 2 0.10 0.20 0.35
3 0.20 0.20 1.45
 Unit of k = s–1
What is the order of reaction with respect to NO and
Example-22 with respect to Cl2 ?
Sol. When the Cl2 concentration is doubled, holding the NO
At 25ºC, the second order rate constant for the reaction I– +
concentration constant (compare reactions 1 and 2), the
ClO– IO– + Cl– is 0.0606 M–1  s–1. If solution is initially initial rate doubles. Hence the reaction is first order with
respect to Cl2. When the NO concentration is doubled
3.50 × 10–3M with respect to each reactant, what will be
(compare reactions 2 and 3), the initial rate quadruples.
the concentration of each species present after 300 s? Hence the reaction is second order with respect to NO.

Sol. Since the concentrations of the two reactants are equal


at the start and remain so throughout the entire reaction,
the reaction can be treated as a simple second order
reaction.
k = 0.0606 M–1  s–1 [B0] = [A0] = 3.50 × 10–3 M
CHEMICAL KINETICS 81
Example-27
Example-25
What are zero order reactions ? Derive integrated rate
A reaction : Reactant  Product is represented by
equation for zero order reaction.

Sol. Zero order reaction means that the rate of the reaction is
proportional to zero power of the concentration of
reactants. Consider the reaction,
[R0]
Conc. of R P
reactant
(R)
d [R]
Rate =   k [R]0
dt

Time (t) As any quantity raised to power zero is unity

(i) the order of the reaction in this case. d [R]


Rate    k 1
(ii) What does the slope of the graph represent ? dt

d [R] = – k dt ...(i)
Sol. (i) The reaction is of the zero order.
Integrating both sides (i)
d [R]
(ii) Slope of the straight line graph =  k  . [R] = – k t + I ...(ii)
dt
where, I is the constant of integration.
Example-26
At t = 0, the concentration of the reactant R = [R]0 ...(iii)

where [R]0 is initial concentration of the reactant.

Substituting in equation (ii)

[R]0 = –k × 0 + I

[R]0 = I

Substituting the value of I in the equation (ii)

[R] = –kt + [R]0


Answer the following questions on the basis of the above
Example-28
curve for a first order reaction A  P :
(a) What is the relation between slope of this line and State any one condition under which a bimolecular
rate constant ? reaction may be kinetically of first order.
(b) Calculate the rate constant of the above reaction if Sol. A bimolecular reaction may become kinetically of first order
the slope is 2 × 10–4 s–1. if one of the reactants is present in excess.

Sol. (a) slope = k/2.303


(b) k = 2.303 × slope

= 2.303 × 2 × 10–4

= 4.606 × 10–4 s–1


CHEMICAL KINETICS 82
Example-29 Time (min) 0 1435 11360 

What is meant by a pseudo first order reaction ? Give an Change in 34.50 – 31.10– 13.98 – –10.77 –
example of a pseudo first order reaction and write the
rotation (º) (–10.77) (–10.77) (–10.77) (–10.77)
rate equation for the same.
= 45.27 = 41.87 = 24.75 =0
Sol. A reaction which is of higher order but follows the kinetics
of first order under special conditions is called a pseudo (a) (a – x) (a – x)
first order reaction.
Substituting the data in Equation (5),
Example, Acid hydrolysis of ethyl acetate.
2.303 45.27
H
CH3 – COOC2H5 + H2O   CH3 – COOH + C2H5 – OH for t = 1435 min k 1  log  5.442  10 5
1435 41.87
Here, the rate law is given by expression
and, for t = 11360 min
Rate = k [CH3 – COOC2H5]
2.303 45.27
The concentration of H 2 O is so large that it hardly k1  log  5.311 10 5
11360 24.75
undergoes any change during the reaction, therefore, it
does not appear in the rate law. The values of k1 are fairly constant and so the reaction is
of first order.
Example-30
Example-31
The optical rotation of cane sugar in 0.5 N lactic acid at
25ºC at various time intervals are given below :
What is half life period ? Show that the time required for
the completion of half of the reaction is independent of
Time (min) 0 1435 11360 
intial concentration.
Rotation (º) 34.50º 31.10º 13.98º –10.77º
Sol. The half-life of a reaction is the time in which the
Show that the reaction is of first order. concentration of a reactant is reduced to one half of its
initial concentration. It is represented ast t1/2.
Sol. C12 H 22 O11  H 2 O Lactic
 acid C 6 H12 O 6  C 6 H12 O 6 For the first order reaction,

Sucrose (excess) Glucose Fructose 2.303 [R]0


k log
Dextrorotatory Dextro Laevo t [R]

[R]0
at t1/2 [R] =
Laevorotatory 2
So, the above equation becomes
Since in this reaction dextro form changes to laevo form,
the optical rotation decreases with the progress of the 2.303 [R]0
k log
reaction. Thus change in rotation is proportional to the t1/2 [R]0 / 2
amount of sugar remained after different time intervals.
We now have, 2.303
or t1/ 2  log 2
k

2.303
t1/ 2   0.301
k

0.693
t1/ 2 
k
CHEMICAL KINETICS 83

It can be seen that for a first order reaction, half-life period [R] = 0.04 M
is constant, i.e., it is independent of initial concentration
of the reacting species. Example-34

Example-32 A first order reaction is 20% complete in 10 minutes.


Calculate the time for 75% completion of reaction.
What is Arrhenius equation to describe the effect of
temperature on rate of a reaction ? 2.303 a
Sol. t 20%  log
Sol. The temperature dependence of the rate of a chemical k a  0.2a
reaction can be accurately explained by Arrhenius
2.303 10 2.303
equation. t 20%  log   .0969
k 8 k
k = A e Ea / RT
2.303 a
t 75%  log
where A is the Arrhenius factor or the frequency factor. It k a  0.75a
is also called pre-exponential factor. It is a constant specific
to a particular reaction. R is gas constant and Ea is activation 2.303 a 2.303 2.303
 log  log 4   0.6021
energy measured in joules/mole (J mol–1). k 0.25a k k

Example-33 t 75% 2.303 k 0.6021


  
t 20% k 2.303 0.0969
A first order reaction has a rate constant of 0.0051 min–1. If
we begin with 0.10 M concentration of the reactant, t 75% 0.6021

what concentration of reactant will remain in solution 10 0.0969
after 3 hours ?
10  0.6021
Sol. For a first order reaction t 75%  = 62.13 min
0.0969

2.303 [R]0 Example-35


t log
k [R]
The reaction SO2Cl2  SO2 + Cl2 is a first order reaction
t = 3, h = 3 × 60 min = 180 min
with k = 2.2 × 10–5 at 320ºC. Calculate the percentage of
k = 0.0051 min–1, [R]0 = 0.10 M, [R] = ? SO2Cl2 that is decomposed on heating this gas for 30
minutes.
2.303 0.10
180 min = 0.0051 min 1 log [R] 2.303 a
Sol. k log
t ax
2.303 a
0.1 180 min  0.0051 min 1 918 2.2 105  log
log   30  60 ax
[R] 2.303 2303
a 2.2  105  1800
log   0.1719
0.1 (a  x) 2.303
log  0.3986
[R] a
= antilog 0.1719 = 1.486
(a  x)
0.1 a = 1.486a – 1.486x
= Anti log (0.3986) = 2.503
[R] 0.486a = 1.486x
x 0.486
0.1   0.327 = 32.7%
[R] =  0.03995M a 1.486
2.503
CHEMICAL KINETICS 84
Example-36 Example-39

Show that time required for the completion of three- The half-life for decay of radioactive 14C is 5730 years.
fourths of a first order reaction is twice the time required An archaeological artefact containing wood has only
for the completion of half reaction.
80% of the 14C activity as found in living trees. Calculate
the age of the artefact.
2.303 a
Sol. t log
k ax Sol. t1/2 = 5730 year
2.303 a
log 0.693 0.693
t 3/ 4
 k a  3a / 4  log 4  k t   1.209  104 year 1
t1/ 2 2.303 log a log 2 1/ 2 5730
k a a/2
2.303 [R]0 2.303 100
t log  log
t 3/ 4 2log 2 k [R] 1.2 104 80

t1/ 2 log 2
2.303  104 2.303  10 4
t 3/ 4 t (log 10  log 8)  (1  3 log 2)
2 1.2 1.2
t1/ 2
2.303
t 3/ 4  2t1/ 2 t 104 (1  3  0.3010)
1.2
Example-37 2.303  0.097  10 4

1.209
Show that in case of a first order reaction, the time required
for 99.9% of the reaction to take place is about ten times t = 1847.7 years
than that required for half the reaction.
Example-40
2.303 100 Decomposition of phosphine (PH3) at 120ºC proceeds
log
t 99.9%
 k 0.1 log 103 3 log 10 30.0 according to the equation :
Sol. t 50% 2.303 100  log 2  
log 0.3010 3.01 4PH3(g)  P4(g) + 6H2(g)
k 50
It is found that this reaction follows the following rate
t 99.9%  10t 50% equation :
Rate = k [PH3]
Example-38
The half life of PH3 in 37.9 s at 120ºC.

The decomposition of N2O5(g) is a first order reaction (i) How much time will be required for 3/4 of PH3 to
decompose ?
with a rate constant of 5 × 10–4 s–1 at 45ºC. i.e., 2N2O5(g)
 4NO2(g) + O2(g). If initial concentration of N2O5 is (ii) What fraction of the original amount of PH3 will
0.25M, calculate its concentration after remain undecomposed after 1 minute ?
2 min. Also calculate half life for decomposition of Sol. (i) Given t1/2 = 37.95
N2O5(g).
0.693
2.303 [R]0 t1/ 2 
k log k
Sol. t [R]t
2.303 0.25 0.693
5  104  log k  1.83  10 2 s 1
2  60 [R]t t1/ 2
[R]t = 0.23 M
0.693 1 2.303 [A]0
0.693 k s ,t log
t1/ 2  s = 1386s 37.9 k [A]
5 104
CHEMICAL KINETICS 85

2.303 [A]0 2.303 [A]0 100


t 3/ 4  2 1
log   100 log 22 s Given : k  1.06 103 min 1 , 
1.83  10 s [A]0 1.83 [A] 85
4
2.303 100 2303
t log 
2.303  100  2  0.30105 138.64 1.06  103 min 1 85 1.06
t 3/ 4   s
1.83 1.83
[2 log 10 – log 85] min
t3/4 = 75.76 s
2303 2303  0.0706
t [2 1  1.9294] =  153.39 min
0.693 0.693 1 1.06 1.06
(ii) k  t  s  1.83  102 s 1
1/ 2 37.9
t = 153.4 min.
t = 1 minute = 60s
3 1 [A]0 100
(ii) Given : k  1.06 10 min , 
2.303 [A]0 [A] 15
t log
k [A]
2.303 100 2303
t log 
1.06  10 3 min 1 15 1.06
2.303 [A]0
60s  2 1
log
1.83  10 s [A] [2 log 10 – log 15] min

[A]0 60 1.83 102 2303 2303  0.8239


log   0.4768  [2  1  1.1761] = min
[A] 2.303 1.06 1.06

t = 1790 min.
[A]
log 0   0.4768  1.5232 Example-42
[A]

For a reaction, the energy of activation is zero. What is the


[A]
value of rate constant at 300 K, if k = 1.6 × 106 s–1 at 280 K
[A]0 = Anti log 1.5232  0.3336 ? [R = 8.31 JK–1 mol–1]

[A] Sol. Given T1 = 280 K, k1 = 1.6 × 106 s–1, k2 = ?,


= 0.334
[A]0 Ea = 0, T2 = 300 K
By Arrhenius equation,
Example-41
k2 Ea  T2  T1 
Hydrogen peroxide, H2O2 (aq) decomposes to H2O(l) and log   
k1 2.303 R  T1T2 
O2(g) in a reaction that is of first order in H2O2 and has a
rate constant, k = 1.06 × 10–3 min–1. As, Ea = 0
(i) How long will it take 15% of a sample of H2O2 to
k2
decompose ?  log k  0
1
(ii) How long will it take 85% of a sample of H2O2 to
decompose ? k2
 1 (log 1 = 1og 10º = 0)
k1
2.303 [A]0
Sol. (i) t log k2 = k1
k [A]
Thus, the rate constant at 300 K is 1.6 × 106 s–1.
CHEMICAL KINETICS 86
Example-43 Example-45

Rate constant k of a reaction varies with temperature (a) A reaction is of first order in A and of second order
according to the equation in B. Write the differential rate equation for this
reaction.
Ea (b) The rate constant k of a reaction increases four fold
log k = Constant 
2.303RT when the temperature changes from 300 K to 320 K.
Calculate the activation energy for the reaction.
where Ea is the activation energy. When a graph is plotted (R = 8.314 J mol–1 k–1)
for log k vs 1/T, a straight line with a slope
– 6670 K is obtained. Calculate the energy of activation
dx
for the reaction in proper units. (R = 8.314 JK–1 mol–1) Sol. (a) Rate =  k [A] [B]2
dt
Ea
Sol. Slope     6670 k k2
2.303 R (b) k2 = 4k1 i.e. k = 4
1

Ea = 6670 × 2.303 × 8.314 = 127711.43 J mol–1 T1 = 300k T2 = 320 k


–1
= 127.711 kJ mol
k2 E a  T2  T1 
log   
Example-44 k1 2.303 R  T1T2 

The decomposition of phosphine


Ea  320  300 
log 4   
4PH3(g)  P4(g) + 6H2(g) 2.303  8.314  300  320 

has the rate law, Rate = k [PH3] Ea  20 


2log 2   
19.147  300  320 
The rate constant is 6.0 × 10–4 s–1 at 300 K and activation
energy is 3.05 × 105 J mol–1. What is the value of rate  0.3010  19.147  300  320
constant at 310 K. [R = 8.314 JK–1 mol–1] Ea   55327J
20
Sol. k1 = 6.0 × 10–4 s–1 T1 = 300 K Ea = 55.327 kJ

k2 = ? T2 = 310 K Example-46
Ea = 3.05 × 105 J mol–1
In the course of the reaction
CH3COOCH3(g)  C2H4(g) + H2(g) + CO(g)
k2 3.05  105  310  300 
log 
k1 2.303  8.314  310  300  the initial pressure was found to be 0.42 atm while after
6.5 minutes, it was 0.54 atm. If the reaction follows first
order kinetics, find the rate constant.
3.05  105  10

2.303  8.314  310  300 Sol. Let the initial number of moles of CH3COOCH3 be a.
Initial moles : a 0 0 0
k2 CH3COOCH3  C2H4 + H2 + CO
log  1.718
k1 Moles after t : (a – x) x x x

According to the given data,


k2
 antilog 1.718 = 51.62 a = 0.42 (initial moles corresponds to 0.42 atm)
k1
and {a – x) + x + x + x} = 0.54
–4 –1
k2 = 51.62 × k1 = 51.62 × 6.0 × 10 s = 3.1 × 10 s –2 –1 (Mole after 6.5 min corresponds to 0.54 atm)
CHEMICAL KINETICS 87
or a + 2x = 0.54 value of activation energy for this reaction ?
(R = 8.314 JK–1 mol–1)
0.54  0.42
or x =  0.06. Sol. T1 = 295 K k1 = k (say), T2 = 305K k2 = 2k
2

Applying first-order rate equation, k2 Ea  T2  T1 


log   
k1 2.303 R  T1T2 
2.303 0.42
k log  0.0237 min 1
6 .5 0.42  0.06 2k E a [305  295]
log 
k 2.303 R 305  295
Example-47
log 2  2.303  8.314  305  295
Ea 
Define threshold energy of a reaction. 10

Sol. Threshold energy is the minimum energy which must be 0.3010  2.303  8.314  305  295

possessed by reacting molecules in order to undergo 10
effective collision which leads to formation of product
molecule. = 51855.2 J mol–1 = 51.855 kJ mol–1

Example-48 Example-50

For a decomposition reaction, the values of rate constant The rate of a particular reaction triples when temperatures
k at two different temperatures are given below : changes from 50ºC to 100ºC. Calculate the activation
k1 = 2.15 × 10–8 L mol–1 s–1 at 650 K energy of the reaction.

k2 = 2.39 × 10–7 L mol–1 s–1 at 700 K [log 3 = 0.4771; R = 8.314 JK–1 mol–1]

Calculate the value of activation energy for this reaction. k2


–1 –1 Sol. k 2  3k1  3
(R = 8.314 JK mol ) k1

T1 = 50 + 273 = 323 K, T2 = 100 + 273 = 373 K


k Ea  T2  T1 
Sol. log 2   
k1 2.303R  T1 T2  k2 Ea  T2  T1 
log   
k1 2.303 R  T1T2 
2.303  R  T1  T2 k
Ea  log 2
T2  T1 k1
Ea  373  323 
log 3   
2.303  8.314J mol1K 1  650K  700K 2.39  107 2.303 8.31  373 323 
Ea  log
700K  650K 2.15  108
E a  50 
0.4771   
19.147  650  700 19.147  120479 
Ea   log 23.9  log 2.15  J mol1
50
0.477119.127 120479
Ea = 174237.7 (1.3783 – 0.3324)J mol–1  Ea 
50
Ea = 174237.7 × 1.0459 J mol–1 = 182235.2 J mol–1
 50  0.477119.127 120479
Ea = 182.24 kJ mol–1.  E a   120479  
  50
Example-49
 E a  22011.59J  E a  22.0122 kJ mol 1
In general it is observed that the rate of a chemical reaction
doubles with every 10º rise in temperature, If this
generalization holds good for a reaction in the
temperature range 295 K and 305 K, what would be the
CHEMICAL KINETICS 88

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS


Rate of a Chemical Reaction 5. In the reaction of formation of sulphur trioxide by contact
process 2SO2+O2  2SO3 the rate of reaction was measured
1 d  HI
1. For the reaction. 2 HI  H2 + I2, the expression 
2 dt d  O2 
as = –2.5 × 10–4 mol L–1 s–1. The rate of reaction in
represents dt
(a) The rate of formation of HI terms of [SO2] in mol L–1 s–1 will be:
(b) The rate of disappearance of HI (a) –3.75 ×10–4 (b) –5.00 × 10–4
(c) The instantaneous rate of the reaction (c) –1.25 × 10–4 (d) –2.50 ×10–4
(d) The average rate of reaction. Rate Law
1 6. For the reaction, 2N 2 O5  4NO 2  O 2 , the rate equation
2. For a reaction A  2B, rate of disappearance of ‘A’ is
2
d[N 2 O5 ]
related to the rate of appearance of ‘B’ by the expression can be expressed in two ways – = k [N2O5] and
dt
d[ A] 1 d[B] d[ A] 1 d[B]
(a)  (b)   d[NO 2 ]
dt 2 dt dt 4 dt + = k [N2 O5] k and k are related as:
dt
d[ A] d[ B] d[ A ] d[ B] (a) 2k = k (b) k = k
(c)   (d)  4
dt dt dt dt
(c) k = 2k (d) k = 4k
3. The rate of a reaction is expressed in different ways as 7. A reaction was found to be second order with respect to the
follows : concentration of carbon monoxide. If the concentration of
1 d[C] 1 d[D] 1 d[A] d[B] carbon monoxide is doubled, with everything else kept the
    . same, the rate of reaction will
2 dt 3 dt 4 dt dt
(a) Double (b) Remain unchanged
The reaction is
(c) Triple (d) Increase by a factor of 4
(a) 4 A + B  2 C + 3 D (b) B + 3 D  4 A + 2 C
8. A reaction is of first order when
(c) A + B  C + D (d) B + D  A + C
(a) The amount of product formed increases linearly with
4. The rate of formation of ammonia by the reaction :
time
N2 + 3 H2  2 NH3 (b) The rate decreases linearly with time
d[NH 3 ] –4 –1 –1
(c) The rate is linearly related to the concentration of the
expressed as = 2.5 × 10 mol L s . The rate of reactant
dt
(d) The concentration of the reactant decreases linearly with
d[H 2 ]
consumption expressed in terms of H2 as will be time.
dt
9. For the reaction 2 A + B  D + E the following mechanism
(a) double has been proposed :
(b) Three times A + B  C + D (slow)
(c) same A + C  E (fast)
(d) one and a half time of that expressed in terms of NH3. The rate law expression for the reaction is
(a) Rate = k [A]2 [B] (b) Rate = k [A] [B]
(c) Rate = k [A] [C] (d) Rate = k [A]2 [B] [C]
CHEMICAL KINETICS 89

10. For the gaseous reaction 2A + B  C + D, the rate is given 16. The units of rate of reaction are
by k [A] [B]. The volume of the container containing the –1 –1 –1 –1
(a) mol L s (b) mol L s
reaction mixture is suddenly reduced to one fourth of its
–1 –1
original volume. with respect to the original rate, now the (c) mol s (d) mol s
rate would be
17. Consider the reaction,
1 1
(a) (b) Cl2 (aq) + H2S (aq)  S (s) + 2H+ (aq) + 2Cl– (aq)
16 8
The rate equation for this reaction is, rate = k [Cl2] [H2S]
(c) 16 times (d) 8 times
11. In the reaction 2 A + B  Products, the order w.r.t. A is found to Which of these mechanisms is/are consistent with this rate
be one and w.r.t. B equal to 2. Concentration of A is doubled equation ?
and that of B is halved, the rate of reaction will be (A) Cl2 + H2S  H+ + Cl– + Cl+ + HS– (slow)
(a) doubled (b) halved
Cl+ + HS–  H+ + Cl– + S (fast)
(c) remain unaffected (d) four times.
12. For the reaction A + B  C + D, doubling the concentration (B) H2S  H+ + HS– (fast equilibrium)
of both the reactants increases the reaction rate by 8 time
Cl2 + HS–  2Cl– + H+ + S (slow)
and doubling the initial concentration of only B simply
doubles the reaction rate. The rate law for the reaction is (a) (B) only (b) Both (A) and (B)
2
(a) r = k [A] [B] (b) r = k [A] [B] (c) Neither (A) nor (B) (d) (A) only
1/2 2
(c) r = k [A] [B] (d) r = k [A] [B]. 18. For the reaction 2A + B  D + E the following mechanism
has been proposed :
13. The chemical reaction, 2O3  3O 2 proceeds as
A + B  C + D (slow)
O3  O 2  [O] (fast)
A + C  E (fast)
[O]  O3  2O 2 (slow) The rate law expression for the reaction is
The rate law expression will be 2
(a) Rate = k [A] [B] (b) Rate = k [A] [B]
2 –1
(a) Rate = k [O] [O3] (b) Rate = k [O3] [O2] (c) Rate = k [A] [C]
2
(d) Rate = k [A] [B] [C]
2
(c) Rate = k [O3] (d) Rate = k [O2] [O]
19. The half-life period of a first order reaction is
14. The rate law for a reaction between the substance A and B
n m (a) directly proportional to the initial concentration ‘a’
is given by rate = k [A] [B] . On doubling the
concentration of A and halving the conc. of B, the ratio of (b) inversely proportional to ‘a’
the new rate to the earlier rate of reaction will be (c) independent of ‘a’

1 (d) independent of the rate constant of the reaction


(a) m n (b) m + n
2 20. For a reaction pA + qB  products, the rate law expression
m n
(c) n – m (d) 2 ( n  m ) is r = k [A] [B] then
(a) (p + q)  (m + n)
Order and Molecularity of Reaction
(b) (p + q) = (m + n}
15. The rate constant for the first and zero reaction in terms of
molarity, M units respectively (c) (p + q) may or not be equal to (m + n)
–1 –1 –1
(a) sec , M sec (b) sec , M (d) (p + q) > (m + n)
–1 –1 –1
(c) M sec , sec (d) M, sec
CHEMICAL KINETICS 90

21. Which one of the following statements is incorrect about 28. For the reaction,
the molecularity of a reaction ? 3A + 2B  C + D
(a) It is the number of molecules of the reactants taking part in The differential rate law can be written as :
single step chemical reaction.
(b) It depends on the rate of determining step in the reaction. 1 d  A d  C n m
(a)    k  A   B
(c) Molecularity is always a whole number 3 dt dt
(d) There is no difference between order and molecularity of
a reaction. 1 d  A  d  C n m
(b)    k  A   B
3 dt dt
22. For a single step reaction ;
A + 2 B  Products, the molecularity is
d  A d  C n m
(a) zero (b) 1 (c)    k  A   B
dt dt
(c) 2 (d) 3
23. For a reaction X + Y  Z, rate  [X]. What is (i) molecularity 1 d  A  d  C n m
(d)   k  A   B
and (ii) order of reaction ? 3 dt dt
(a) (i) 2, (ii) 1 (b) (i) 2, (ii) 2
29. The time for half-life period of a certain reaction,
(c) (i) 1, (ii) 1 (d) (i) 1, (ii) 2 A  products is 1 h. When the initial concentration of the
24. The rate equation for the reaction, 2A + B  C is found to reactant ‘A’, is 2.0 mol L–1, how much time does it take for its
be : rate = k [A] [B]. The correct statement in relation to this concentration to come from 0.50 to 0.25 mol L–1, if it is a zero
reaction is that the order reaction ?
–1
(a) unit of k must be s (a) 4 h (b) 0.5 h
(b) value of k is independent of the initial concentrations of (c) 0.25 h (d) 1 h
A and B 30. In a first order reaction, the conc. of reactant decreases from
(c) rate of formation of C is twice the rate of disappearance 0.8 M to 0.4 M in 15 minutes. The time taken for the
of A concentration to change from 0.1 M to 0.025 M is
(d) t1/2 is a constant. (a) 30 min (b) 60 min
25. A reaction involving the different reactants can never be (c) 7.5 min (d) 15 min
(a) bi molecular reaction (b) second order reaction 31. The half life period of a first order chemical reaction is 6.93
(c) first order reaction (d) Unimolecular reaction minutes. The time required for the completion of 99% of the
26. Which of the following statements is false ? chemical reaction will be (log 2 = 0.301)
(a) For a first order reaction, the rate of reaction doubles as (a) 230.3 minutes (b) 23.03 minutes
the concentration of reactant (s) doubles (c) 46.06 minutes (d) 460.6 minutes
(b) Active mass of 64g of HI present in a two-litre flask is 32. For the first order reaction A  Products, which one of the
0.25 following is the correct plot of log [A] versus t time ?
(c) For zero order reaction, the rate changes with temperature
(d) Both order and molecularity of a reaction are always the
same. (a) (b)
Differential and Integral forms of Rate Law
27. If ‘a’ is the initial concentration of the reactant, the time
taken for completion of the reaction, if it is of zero order, will
be
(a) a/k (b) a/2k (c) (d)

(c) 2a/k (d) k/a


CHEMICAL KINETICS 91

33. Which of the following represents the expression for 38. The half life period of a first order reaction is 15 minutes.
3/4th life of a first order reaction The amount of substance left after one hour will be:

k 2.303 1
(a) log 4 / 3 (b) log 3/ 4 (a) of the original amount
2.303 k 4

2.303 2.303 1
(c) log 4 (d) log 3 (b) of the original amount
k k 8
34. The correct expression for the rate constant for reactions of
1
zero order is (c) of the original amount
16
1
(a) k = [A0]/2t (b) k  {[A 0 ]  [A]} 1
t
(d) of the original amount
32
1 2.303
(c) k  {[A]  [A]0} (d) k  log {[A 0 ]  [A]} 39. The rate of reaction A + B + C  Products is given by
t t
1/2 1/3
Rate = k [A] [B] [C]
35. Which one of the following formula represents the first order
reaction ? The order of the reaction is :
(a) 1 (b) 3
2.303 [A] 2.303 ax
(a) k  t log [A] (b) k  log
5 11
0 t a
(c) (d)
6 6
2.303 a
(c) [A] = [A0] e–kt (d) k  log
H
t ax 40. For the reaction CH3COCH3 + I2   Products, the rate
36. The differential rate law for the reaction is governed by the expression
H2 + I 2 2HI is dx
 k [Acetone] [H+]
dt
d[ H 2 ] d[I 2 ] d[ HI]
(a)  
dt dt dt The order w.r.t. iodine is
(a) 0 (b) 1
dH 2 d[I 2 ] d[ H ]
(b)   (c) 2 (d) 3
dt dt dt
41. The rate of a reaction 2X + Y  Products is given by
1 d[H 2 ] 1 d[ I 2 ] d[ HI]
(c)   d[Y] 2
2 dt 2 dt dt = k [X] [Y]
dt

d[ H 2 ] d[I ] d[ HI] if X is present in large excess, then order of the reaction


(d)  2  2 2 
dt dt dt is :
(a) zero (b) two
Determination of Order of Reaction
(c) one (d) three
37. For a reaction, A + 2B  C rate is given by
2 42. In the presence of acid, the initial concentration of
R = K [A] [B] . The order of reaction is
cane-sugar was reduced from 0.2 M to 0.1 M in 5 hrs and to
(a) 3 (b) 6 0.05 M in 10 hrs. The reaction must be of
(c) 5 (d) 7 (a) zero order (b) first order
(c) second order (d) fractional order
CHEMICAL KINETICS 92

43. For a reaction, 2NO  2H 2  N 2  2H 2O, the possible 47. Half life of a chemical reaction at a particular concentration
is 50 min. When the concentration of the reactant is doubled,
mechanism is
the half life becomes 100 min, then the order of the reaction
2NO  N 2O 2 is :
(a) zero (b) first
slow
N 2O 2  H 2   N 2O  H 2O
(c) second (d) third
fast
N 2 O  H 2 O  N 2  H 2O 48. For a first order reaction, (A)   product the
concentration of A changes from 0.1 M to 0.025 M in 40 min.
What is the rate law and order of the reaction ?
The rate of reaction when the concentration of A is 0.01 M is
(a) Rate = k [N2O2], order = 1
(a) 1.73 × 10–5 M/min (b) 3.47 × 10–4 M/min
(b) Rate = k [N2O2] [H2], order = 2
(c) 3.47 × 10–5 M/min (d) 1.73 × 10–4 M/min
2
(c) Rate = k [N2O2] , order = 2 49. The following data were obtained during the first order
2
(d) Rate= k [N2O2] [H2], order = 3 thermal decomposition of SO2Cl2 at a constant volume.

44. For a general reaction X   Y, the plot of conc. of X vs SO 2Cl 2(g)  SO 2(g )  Cl 2(g)
time is given in the figure. What is the order of the reaction Experiment Time/s
–1
Total pressure/atm
and what are the units of rate constant ?
1 0 0.5
2 100 0.6
What is the rate of reaction when total pressure is 0.65 atm ?
–1 –3 –1
(a) 0.35 atm s (b) 2.235 × 10 atm s
–4 –1 –4 –1
(c) 7.8 × 10 atm s (d) 1.55 × 10 atm s
Arrhenius Equation
–1 –1 –1 –1
(a) Zero, mol L s (b) First, mol L s 50. The rate of a chemical reaction doubles for every 10ºC rise
–1 –1 –1 of temperature. If the temperature is raised by 50ºC, the rate
(c) First, s (d) Zero, L mol s
of the reaction increases by about
45. The following mechanism has been proposed for the (a) 10 times (b) 24 times
reaction of NO with Br2 to form NOBr,
(c) 32 times (d) 64 times
NO(g) + Br2(g) NOBr2(g) 51. Mark the correct statement.
NOBr2(g) + NO(g)  2NOBr(g) (a) The catalyst catalyses the forward reaction
(b) the catalyst catalyses the backward reaction
If the second step is the rate determining step, the order of
the reaction with respect to NO(g) is (c) The catalyst influences the direct and the reverse reaction
to the same extent
(a) 2 (b) 1
(d) The catalyst increases the rate of forward reaction and
(c) 0 (d) 3 decreases the rate of backward reaction
–2 –1 52. The rate of reaction increases with increase of temperature
46. The rate constant of a reaction is 2.5 × 10 minutes . The
order of the reaction is because

(a) one (b) zero (a) the fraction of molecules having energy  ET (threshold
energy) increases
(c) two (d) three
(b) the average energy of the products increases
(c) threshold energy changes
(d) activation energy is lowered.
CHEMICAL KINETICS 93

53. Which of the following statement is/are correct ? 58. The rates of reactions increase with increase of temperature
because
(a) A catalyst is used in the rate determining step of a
mechanism, but then is formed again in some subsequent (a) activating energy of the reacting molecules increases
step so that there is no change in the concentration of (b) kinetic energy of the product molecules increases
the catalyst during the course of the reaction.
(c) the fraction of the reacting molecules possessing an
(b) Catalyst does not appear in the overall stoichiometric energy equal to the activation energy or more increases
equation for the reaction. (d) the collisions between molecules decrease.
(c) The role of the catalyst is to provide an alternate activated 59. The activation energy for a reaction is 9.0 Kcal/mol. The
complex, one with a lower activation energy. increase in the rate constant when temperature is increased
(d) All are correct. from 298 to 308 K

54. Rate of a reaction can be expressed by Arrhenius equation (a) 10% (b) 100%
–E/RT
as k = A e In this equation, E represents (c) 50% (d) 63%

(a) the energy above which all the colliding molecules will 60. The rate constant of a reaction is given by
–1 4
react InK (sec ) = 14.34 – (1.25 × 10 )/T
(b) the energy below which colliding molecules will not react What will be the energy of activation ?
(c) the total energy of the reacting molecules at a (a) 24.83 Kcal mole (b) 12.42 Kcal/mole
temperature, T (c) 49.96 Kcal/mole (d) None
(d) the fraction of molecules with energy greater than the 61. The temperature dependence of the rate constant k is
activation energy of the reation. expressed as k = Ae  Ea / RT . When a plot between logk and
55. Which one is correct for k = Ae  E a / RT ? 1/T is plotted we get the graph as shown. What is the value
of slope in the graph ?
(a) Ea is energy of activation
(b) R is Rydberg constant
(c) k is equilibrium constant
(d) A is adsorption factor
56. The rate of reaction is doubled for every 10ºC rise in
temperature. The increase in rate as result of increase in
temperature from 10ºC to 100ºC is Ea Ea
(a) (b) 
RT 2.303R
(a) 112 (b) 512
(c) 400 (d) 256 Ea Ea R
(c)  2.303 RT log A (d) 
57. For the two gaseous reactions, following data are given 2.303 T

 B; k1  1010 e 20,000 / T
A  Activated Complex Theory and Collision Theory
62. The rate coefficient (k) for a particular reactions is
 D; k 2  1012 e 24,606 / T
C  1.3 × 10–4 M–1 s–1 at 1000C, and 1.3 ×10–3 M–1 s–1 at 1500C.
the temperature at which k1 becomes equal to k2 is What is the energy of activation (Ea) (in kJ) for this reaction?
(R = molar gas constant = 8.314 JK–1 mol–1)
(a) 400 K (b) 1000 K
(a) 132 (b) 99
(c) 800 K (d) 1500 K
(c) 16 (d) 60
CHEMICAL KINETICS 94

63. The energies of activation for forward and reverse reaction 68. The reactions of higher order are rare because
–1 –1
for A2 + B2 2AB are 180 kJ mol and 200 kJ mol (a) many body collisions involve very high activation energy.
respectively. The presence of catalyst lowers the activation (b) many body collisions have a low probability energy
energy of both (forward and reverse) reactions by
–1 (c) many body collisions are not energetically favoured
100 kJ mol . The enthalpy change of the reaction
(d) many body collisions can take place only in the gaseous
(A2 + B 2  2AB) in the presence of catalyst will be
phase.
(in kJ mol–1).
69. According to collision theory of reaction rates, the rate of
(a) 300 (b) –120
reaction depends
(c) 280 (d) –20
(a) only upon the total number of collisions per second
64. In a 1st order reaction the fraction of molecules at 450ºC
(b) upon the colliding molecules with energy greater than
having sufficient energy (or fraction of effective collisions)
–16 threshold energy
is 1.92 × 10 . What is activation energy value of this
(c) upon the orientation of molecules at the time of collision
reaction ?
2 –1 3 –1 (d) both on (b) and (c)
(a) 21.757 × 10 J mole (b) 21.757 × 10 J mole
4 –1 Numerical Value Type Questions
(c) 21.75 × 10 J mole (d) None
65. In a reaction A  B threshold energy of the reactant is 120 70. Consider the reaction, 2N 2O 5 
 4NO 2  O 2 . In the
–1 –1 –1
kJ mole and the normal energy of the reactant is reaction NO2 is being formed at the rate of 0.0125mol L s .
–1
20 kJ mole what is the activation energy barrier of the What is the rate of reaction at this time ?
reaction A  B. 71. For a reaction R P, the concentration of a reactant changes
(a) 6 kJ mole
–1
(b) 100 kJ mole
–1 from 0.05 M to 0.04 M in 30 minutes. What will be the average
–1 –1
rate of reaction in minutes ?
(c) 140 kJ mole (d) 2400 kJ mole
72. In a reaction 2HI  H2 + I2, the concentration of HI decreases
66. A reactant (A) forms two products –1 –1
from 0.5 mol L to 0.4 mol L in 10 minutes. What is the rate
k1 of reaction during this interval ?
A   B, Activation energy E a1

k2 73. For the reaction 4NH 3  5O 2 


 4NO  6H 2O, if the rate
A  C, Activation energy E a 2
–3 –1 –1
of disappearance of NH3 is 3.6 × 10 mol L s , what is the
If E a2  2E a1 , then k1 and k2 are rate of formation of H2O ?

Ea 2 / RT Ea1 / RT
74. Nitrogen dioxide (NO2) dissociates into nitric oxide (NO)
(a) k1  2k 2 e (b) k1  k 2 e
and oxygen (O2) as follows :
Ea 2 / RT Ea1 / RT
(c) k 2  k1e (d) k1  A k 2 e 2NO 2  2NO  O 2

67. The rate of a reaction doubles when its temperature changes If the rate of decrease of concentration of NO 2 is
–12 –1 –1
from 300 K to 310 K. Activation energy of such a reaction 6.0 × 10 mol L s . What will be the rate of increase of
will be (R = 8.314 JK–1 mol–1 and log 2 = 0.301) concentration of O2 ?
(a) 53.6 kJ mol–1 (b) 48.6 kJ mol–1 75. The rate of formation of a dimer in a second order dimerisation
–1 –1 –1
reaction is 9.1 × 10 mol L s at 0.01 mol L monomer
(c) 58.5 kJ mol–1 (d) 60.5 kJ mol–1
concentration. What will be the rate constant for the
reaction?
76. The rate constant of a first order reaction is 15 × 10–3 s–1.
How long will 5.0 g of this reactant take to reduce to 3.0 g ?
CHEMICAL KINETICS 95

77. What will be the half-life of the first order reaction for which 79. Half-life period of a first order reaction is 10 min. What
–1
the value of rate constant is 200 s ? percentage of the reaction will be completed in 100 min ?
78. 1.386 hours are required for the disappearance of 75% of a 80. The half-life of a radioactive isotope is three hours. If the
reactant of first order reaction. What is the rate constant of initial mass of the isotope was 300 gm, the mass which
the reaction ? remained undecayed in 18 hours would be
 4.68 gram is left undecayed.
CHEMICAL KINETICS 96

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS


Objective Questions I [Only one correct option] (a) k (b) k/3

1. Higher order (>3) reactions are rare due to : (2015) (c) 3k (d) 9k
5. The rate of a reaction A doubles on increasing the
(a) shifting of equilibrium towards reactants due to elastic temperature from 300 to 310 K. By how much, the
collisions temperature of reaction B should be increased from 300 K
so that rate doubles if activation energy of the reaction B is
(b) loss of active species on collision twice to that of reaction A. (Online 2017 Set -1)
(c) low probability of simultaneous collision of all the (a) 9.84 K (b) 4.92 K
reacting species (c) 2.45 K (d) 19.67 K

(d) increase in entropy and activation energy as more 6. The rate of a reaction quadruples when the temperature
molecules are involved changes from 300 to 310 K. The activation energy of this
reaction is :
2. Decomposition of H2O2 follows a first order reaction. In
fifty minutes the concentration of H2O2 decreases from 0.5 (Assume activation energy and pre-exponential factor are
to 0.125 M in one such decomposition. When the independent of temperature; ln 2 = 0.693;
concentration of H2O2 reaches 0.05 M, the rate of formation R = 8.314 J mol–1 K–1) (Online 2017 Set - 2)
of O2 will be: (2016) (a) 107.2 kJ mol–1
(b) 53.6 kJ mol–1
(a) 6.93 × 10–4 mol L–1 min–1 (c) 26.8 kJ mol–1 (d) 214.4 kJ mol–1
(b) 2.66 L min–1 at STP 7. Two reactions R1 and R2 have identical pre-exponential
(c) 1.34 × 10–2 mol L–1 min–1 factors. Activation energy of R1 exceeds that of R2 by
(d) 6.93 × 10–2 mol min–1 10 kJ mol–1. If k1 and k2 are rate constants for reactions R1
3. The reaction of ozone with oxygen atoms in the presence
of chlorine atoms can occur by a two step process shown k 
and R2, respectively at 300 K, then ln  2  is equal to
below (Online 2016 Set -1)  k1 
–1 –1
(R = 8.314 J mol K ) (2017)
O3  g   Cl  g   O 2  g   ClO  g    i  (a) 8 (b) 12
9 1 1
k i  5.2  10 L mol s (c) 6 (d) 4
ClO  g   O  g   O 2  g   Cl  g    ii  8. Which of the following lines correctly show the temperature
10
K ii  2.6 10 L mol s 1 1 dependence of equilibrium constant, K, for an exothermic
reaction ? (2018)
The closet rate constant for the overall reaction
O3  g   O  g   2O2  g  is

(a) 5.2 × 109 L mol–1 s–1 (b) 2.6 × 1010 L mol–1 s–1
(c) 3.1 × 1010 L mol–1 s–1 (d) 1.35 × 1020 L mol–1 s–1
4. The rate law for the reaction below is given by the
expression K [A] [B]
A  B  Product (a) C and D (b) A an1d D
If the concentration of B is increased from 0.1 to 0.3 mole, (c) A and B (d) B and C
keeping the value of A at 0.1 mole, the rate constant will be:
(Online 2016 Set -2)
CHEMICAL KINETICS 97

9. At 518ºC, the rate of decomposition of a sample of gaseous 2 2 2


(a) Rate  k  A   B (b) Rate  k  A  B
acetaldehyde, initially at a pressure of 363 Torr, was
1.00 Torr s-1 when 5% had reacted and 0.5 Torr s-1 when 33%
2
had reacted. The order of the reaction is (2018) (c) Rate  k  A  B (d) Rate  k  A   B
(a) 1 (b) 0 15. The given plots represent the variation of the concentration
(c) 2 (d) 3 of a reactant R with time for two different reactions (i) and
10. N2O5 decomposes to NO2 and O2 and follows first order (ii). The respective orders of the reactions are:
kinetics. After 50 minutes, the pressure inside the vessel
increases from 50 mmHg to 87.5 mmHg. The pressure of the
gaseous mixture after 100 minutes at constant temperature
will be: (Online 2018 Set-1)
(a) 175.0 mmHg (b) 116.25 mmHg (2019)
(c) 136.25 mmHg (d) 106.25 mmHg (a) 1, 1 (b) 0, 2
11. For a first order reaction, A  P, t1/ 2 (half- life) is 10 days. (c) 0, 1 (d) 1, 0
16. A bacterial infection in an internal wound grows as
1th
The time required for conversion of A (in days) is : N '(t)  N 0 exp(t) , where the time t is in hours. A dose of
4
antibiotic, taken orally, needs 1 hour to reach the wound.
(In 2 = 0.693, In 3 = 1.1) (Online 2018 Set-2)
Once it reaches there, the bacterial population goes down
(a) 5 (b) 3.2
dN N
(c) 4.1 (d) 2.5 as  5N 2 . What will be the plot of 0 vs, t after 1
dt N
12. If 50 percent of a reaction occurs in 100 second and
hour? (2019)
75 percent of the reaction occurs in 200 second, the order
of this reaction is : (Online 2018 Set-3)
(a) Zero (b) 1
(c) 2 (d) 3 (a) (b)
k1 k2
13. For a reaction scheme. A   B   C if the rate of
formation of B is set to be zero then the concentration of B
is given by (2019)
(c) (d)
 k1 
(a)  k   A  (b)  k1  k 2   A 
 2
17. For the reaction of H 2 with I 2 , the rate constant is
(c) k1k 2  A (d)  k1  k 2   A 
2.5 104 dm3 mol1 s1 at 327°C and 1.0 dm3 mol1 s1 at
14. For the reaction 2A  B  C the values of initial rate at
different reactant concentrations are given in the table 527°C. The activation energy for the reaction, in kJ mol1
below: The rate law for the reaction is:
is: (R = 8.314 J K 1 mol1 ) (2019)
 A   mol L 
1
 B  mol L  Initial Rate  mol L
1 1
s 1
 (a) 72 (b) 166
0.05 0.05 0.045
0.10 0.05 0.090 (c) 150 (d) 59
0.20 0.10 0.72

(2019)
CHEMICAL KINETICS 98

18. In the following reaction; xA  yB 21. For the reaction, 2A  B  products , when the
concentrations of A and B both were doubled, the rate of
 d A   d  B  the reaction increased from 0.3 mol L1s 1 to 2.4 mol L1s 1 .
log10     log10    0.3010
 dt   dt  When the concentration of A alone is doubled, the rate
1 1 1 1
‘A’ and ‘B’ respectively can be : (2019) increased from 0.3 mol L s to 0.6 mol L s
Which one of the following statements is correct?
(a) C2 H 2 and C6 H 6 (b) n-Butane and Iso-butane
(2019)
(c) N 2 O 4 and NO2 (d) C2 H 4 and C4 H8 (a) Total order of the reaction is 4
(b) Order of the reaction with respect to B is 2
19. NO 2 required for a reaction is produced by the
(c) Order of the reaction with respect to B is 1
decomposition of N 2 O5 in CCl 4 as per the equation
(d) Order of the reaction with respect to A is 2
2N 2 O5 (g)  4NO 2 (g)  O 2 (g) The initial concentration 22. Consider the given plots for a reaction obeying Arrhenius
equation (0  C < T < 300  C) : (k and E a are rate constant
of N 2 O5 is 3.00 mol L1 and it is 2.75 mol L1 after 30
and activation energy respectively)
minutes. The rate of formation of NO 2 is : (2019)
Choose the correct option: (2019)
(a) 1.667  102 mol L1 min 1

(b) 4.167  103 mol L1 min 1

(c) 8.333 103 mol L1 min 1

(d) 2.083  103 mol L1 min 1


(a) I is right but II is wrong (b) Both I and II are correct
20. The following results were obtained during kinetic studies (c) I is wrong but II is right (d) Both I and II are wrong
of the reaction

1
23. For an elementary chemical reaction, A 2  2A .the
k
k 1
2A  B  products
d A
Experiment [A] [B] Initial rate of reaction expression for is (2019)
(in mol L-1) (in mol L-1) (in mol L-1 min-1) dt
I 0.10 0.20 6.93 × 10-3
II 0.10 0.25 6.93 × 10-3 (a) k1  A 2   k 1  A 
2
(b) 2k1  A 2   k 1  A 
2
III 0.20 0.30 1.386 × 10-2

2 2
The time(in minutes) required to consume half of A is (c) k1  A 2   k 1  A  (d) 2k1  A 2   2k 1  A 

(2019) 24. If a reaction follows the Arrhenius equation, the plot Ink v
(a) 5 (b) 10 1/(RT) gives straight line with a gradient (–y) unit. The energy
required to activate the reactant is: (2019)
(c) 1 (d) 100
(a) y/R unit (b) y unit
(c) yR unit (d) –y unit
CHEMICAL KINETICS 99

25. The reaction 2X  B is a zeroth order reaction. If the initial 29. It is true that : (2020)
concentration of X is 0.2M, the half life is 6 h. When the (a) A second order reaction is always a multistep reaction
initial concentration of X is 0.5 M, the time required to reach
(b) A first order reaction is always a single step reaction
its final concentration of 0.2 M will be: (2019)
(c) A zero order reaction is a multistep reaction
(a) 9.0 h (b) 12.0 h
(d) A zero order reaction is a single step reaction
(c) 18.0 h (d) 7.2 h
26. Decomposition of X exhibits a rate constant for 0.05  g/ 3
30. For the reaction 2A  3B  C  3P, which statement
year. How many years are required for the decomposition of 2
5  g of X into 2.5  g? (2019) is correct ? (2020)
(a) 50 (b) 25 dn A dn B dn C
(a)  
(c) 20 (d) 40 dt dt dt
27. For a certain reaction consider the plot of nk versus 1/T
dn A 3 dn B 3 dn C
given in the figure. If the rate constant of this reaction at 400 (b)  
5 1
dt 2 dt 4 dt
K is 10 s , then the rate constant at 500 K is: (2019)
dn A 2 dn B 4 dn C
(c)  
dt 3 dt 3 dt

dn A 2 dn B 3 dn C
(d)  
dt 3 dt 4 dt
31. The rate of a certain biochemical reaction at physiological
temperature (T) occurs 106 times faster with enzyme than
(a) 106 s 1 (b) 2  10 4 s 1 without. The change in activation energy upon adding
enzyme is: (2020)
(c) 104 s 1 (d) 4  10 4 s 1 (a) - 6RT (b) -6  2.303 RT
T
28. The results given in the below table were obtained during (c) + 6RT (d) +6  2.303 RT
T
kinetic studies of the following reaction :
1
2A  B  C  D 32. Consider the following plots of rate constant versus for
T
Experiment [A] [B] Initial rate/mol four different reactions. Which of the following orders is
/mol L-1 /mol L-1 L-1 min-1 correct for the activation energies of these reactions?
I 0.1 0.1 6.00 × 10-2
II 0.1 0.2 2.40 × 10-2
III 0.2 0.1 1.20 × 10-2
IV X 0.2 7.20 × 10-2
V 0.3 Y 2.88 × 10-1
X and Y in the given table are respectively : (2020)
(a) 0.4, 0.4 (b) 0.3, 0.4
(c) 0.4, 0.3 (d) 0.3, 0.3

(2020)
(a) Ea>Ec> Ed> Eb (b) Ec>Ea> Ed> Eb
(c) Eb> Ed>Ec>Ea (d) E >Ea> Ed>Ec
CHEMICAL KINETICS 100

33. For following reactions


700 K
A   Product
Catalyst,700 K
A   Product;
It was found that the Eais decreased by 30 kJ/mol in the
presence of catalyst. If the rate remains unchanged , the
activation energy for catalysed reaction is (Assume pre
exponential factor is same) (2020) Among the following the correct sequence for the order of
(a) 75 kJ/mol (b) 135 kJ/mol the reactions is: (2020)
(c) 105 kJ/mol (d) 198 kJ/mol (a) c > a > b > d (b) d > a > b > c
On Solving, Ea = 105 kJmol”1 (c) d > b > a > c (d) a > b > c > d
34. A flask contains a mixture of compound A and B. Both 37. Which one of the following given graphs represents the
compounds decompose by first order kinetics. The half- variation of rate constant (k) with temperature (T) for an
lives for A and B are 300 s and 180 s, respectively. If the endothermic reaction? (2021-09-01/Shift-2)
concentrations of A and B are equal initially, the time
required for the concentration of A to be four times that of
B (in s) is : (Use ln 2 = 0.693) (2020)
(a) 180 (b) 300 (a) (b)
(c) 120 (d) 900
35. The rate constant (k) of a reaction is measured at different
temperatures (T), and the data are plotted in the given figure.
The activation energy of the reaction in kJ mol–1 is : (R is
gas constant) (2020) (c) (d)

Numeric Value Type Questions


38. The rate of a reaction decreased by 3.555 times when the
temperature was changed from 40ºC to 30ºC. The activation
energy (in KJ mol-1) of the reaction is (2020)
.......[Take; R = 8.314 J mol-1 K-1 In 3.555 = 1.268]
(a) R (b) 2/R 39. During the nuclear explosion, one of the products is 90Sr
with half of 6.93 years. If 1 µg of 90Sr was absorbed in the
(c) 1/R (d) 2R bones of a newly born baby in placeof Ca, how much time,
36. Consider the following reactions in years, is required to reduce it by 90% if it is not lost
metabolically (2020)
A  P1; B  P2; C  P3; D  P4,
40. A sample of milk splits after 60 min. at 300K and after
The order of the above reactions are a,b,c and d, 40 min at 400K when the population of lactobacillus
respectively. The following graph is obtained when log acidophilus in it doubles . The activation energy (in
[rate] vs. log [conc.] are plotted: kJ/mol) for this process is closest to —— . (Given, R

2
= 8.3 J mol-1K-1), ln    0.4 , e-3 = 4.0) (2020)
3
CHEMICAL KINETICS 101

41. Gaseous cyclobutene isomerizes to butadiene in a first order 47. The decomposition of formic acid on gold surface follows
process which has a ‘k’ value of 33 × 10-4 s-1 at 153OC . The first order kinetics. If the rate constant at 300 K is
time in minutes it takes for the isomerization to proceed 1.0 × 10-3s-1 and the activation energy Ea = 11.488 kJ mol-1,
40% to completion at this temperature is _______. the rate constant at 200 K is ______ × 10-5s-1. (Round off to
(Rounded off to the nearest integer) the Nearest Integer). (2021-03-16/Shift-1)
(2021-02-24/Shift-1) (Given: R = 8.314 J mol-1 K-1)
42. Sucrose hydrolyses in acid solution into glucose and 48. A and B decompose via first order kinetics with half-lives
fructose following first order rate law with a half-life of 3.33 54.0 min and 18.0 min respectively. Starting from an equimolar
h at 25 °C. After 9 h, the fraction of sucrose remaining is f. non reactive mixture of A and B, the time taken for the
concentration of A to become 16 times that of B is ____min
1 (Round off to the Nearest Integer).
The value of log10   is __ × 10-2. (Rounded off to nearest
f 
(2021-03-16/Shift-2)
integer)
49. For a certain first-order reaction 32% of the reactant is left
[Assume: ln 10 = 2.303, ln 2 = 0.693] after 570 s. The rate constant of this reaction is … × 10–3 s–1.
(2021-02-24/Shift-2) [Given: log102 = 0.301, ln 10 = 2.303]

43. For the reaction, A  b  cC  dD, the plot of log k (2021-03-17/Shift-1)

50. The reaction 2A  B2  2AB is an elementary reaction.


1
vs is given below :
T For a certain quantity of reactants, if the volume of the
reaction vessel is reduced by a factor of 3, the rate of the
reaction increases by a factor of ...... (Round off to the Nearest
Integer). (2021-03-17/Shift-2)

51. 2NO(g)  Cl 2 (g)  2NOCl(s)


This reaction was studied at – 10ºC and the following data
was obtained
The tempeature at which the rate constant of the reaction Run [NO]o [Cl2]o ro
is 10-4s-1 is ______ K. (Rounded-off to the nearest integer) 1 0.10 0.10 0.18
2 0.10 0.20 0.35
[Given: The rate constant of the reaction is 10-5s-1 at 500K.] 3 0.20 0.20 1.40
(2021-02-25/Shift-1)
[NO]0 and [Cl2]0 are the initial concentrations and r0 is the
initial reaction rate. The overall of the reaction is ........................
44. The rate constant of a reaction increases by five times on
(Round off to the Nearest Integer).
increase in temperature from 27 oC to 52oC. The value of
(2021-03-18/Shift-1)
activation energy in kJ mol-1 is _______. (Rounded-off to
the nearest integer) 52. A reaction has a half life of 1 min. the time required for 99.9%
completion of the reaction is .................... min. (Round off to
[R = 8.314 J K-1 mol-1] (2021-02-25/Shift-2)
the Nearest Integer).
45. An exothermic reaction X  Y has an activation energy 30
[Use: ln 2 = 0.69; ln 10 = 2.3] (2021-03-18/Shift-2)
kJ mol–1. If energy change E during the reaction is
–20 kJ, then the activation energy for the reverse reaction in 53. The inactivation rate of a viral preparation is proportional to
kJ is _____. (2021-02-26/Shift-1) the amount of virus. In the first minute after preparation,
10% of the virus is inactivated. The rate constant for viral
46. If the activation energy of a reaction is 80.9 kJ mol-1, the
inactivation is ________× 10-3 min-1. (Nearest integer)
fraction of molecules at 700 K, having enough energy to
react to form products is e-x. The value of x is ______. [Use : ln 10 = 2.303 ; log10 3 = 0.477 ; property of logarithm :
log xy = y log x] (2021-07-20/Shift-1)
[Use R = 8.31 J K-1 mol-1] (2021-02-26/Shift-2)
CHEMICAL KINETICS 102

54. PCl5 (g)  PCl3 (g)  Cl 2 (g) 61. The reaction that occurs in a breath analyzer, a device used
to determine the alcohol level in a person's blood stream is:
In the above first order reaction the concentration of PCl5
2K2Cr2O7 + 8H2SO4 + 3C2H6O  2Cr2 (SO4)3 + 3C2H4O2 +
reduces from initial concentration 50 mol L-1 to 10 mol L-1 in
2K2SO4 + 11H2O.
120 minutes at 300 K. The rate constant for the reaction at
300 K is x × 10-2 min-1. The value of x is ____ If the rate of appearance of Cr2(SO4)3 is 2.67 mol min–1 at a
particular time, the rate of disappearance of C2H6O at the
[Given log 5 = 0.6989] (2021-07-20/Shift-2)
same time is ________ mol min–1. (Nearest integer)
55. If 75% of a first order reaction was completed in 90
(2021-08-27/Shift-1)
minutes, 60% of the same reaction would be completed in
approximately (in minutes) _____. 62. The first order rate constant for the decomposition of CaCO3
at 700K is 6.36×10–3s–1 and activation energy is 209kJ mol–1.
(take : log 2 = 0.30; log 2.5 = 0.40) (2020-09-04/Shift-1)
Its rate constant (in s–1 ) at 600 K is x × 10–6 . The value of x is
56. The number of molecules with energy greater than the _______.? (Nearest integer)
threshold energy for a reaction increases five fold by a rise
[Given R = 8.31 J K–1 mol–1 ; log 6.36 × 10–3 = –2.19, 10–4.79
of temperature from 27ºC to 42ºC. Its energy of activation
= 1.62 × 10–5] (2021-08-27/Shift-2)
in J/mol is _____. (Take ln 5 = 1.6094; R = 8.314 J mol–1K–1)
(2020-09-04/Shift-2) 63. For a first order reaction, the ratio of the time for 75%
completion of a reaction to the time for 50% completion is
1 _______. (Integer answer) (2021-08-31/Shift-1)
57. N 2 O5(g)  2NO 2(g)  O 2(g)
2 64. According to the following figure, the magnitude of the
In the above first order reaction the initial concentration of enthalpy change of the reaction A + B  M + N in
kJ mol–1 is equal to _________. (Integer answer)
N2O5 is 2.40 102 mol L1 at 318 K. The concentration of
N2O5 after 1 hour was 1.60 × 10-2 mol L-1. The rate constant
of the reaction at 318 K is ______× 10-3 min-1. (Nearest
integer) [Given: log 3 = 0.477, log 2 = 0.3010]
(2021-07-22/Shift-2)
58. For a chemical reaction A  B, it was found that
concentration of B is increased by 0.2 mol L–1 in 30 min. The
average rate of the reaction is ______ × 10–1 mol L–1 h–1.
(2021-07-25/Shift-2) (2021-08-31/Shift-1)
59. For the first order reaction A  2B, 1 mole of reactant A 65. For the reaction A  B, the rate constant k(in s–1) is given
gives 0.2 moles of B after 100 minutes. The half-life of the
reaction is ...... min. (Round off to the nearest integer). (2.47  103 )
by log k  20.35 
[Use: ln 2 = 0.69, ln 10 = 2.3, ln 3 = 1.1] T

(2021-07-27/Shift-2) The energy of activation in kJ mol –1 is _______.


(Nearest integer) [Given : R = 8.314 J K–1 mol–1 ]
60. The following data was obtained for chemical reaction given
below at 975 K. (2021-08-31/Shift-2)

2NO (g )  2H 2(g )  N 2(g )  2H 2 O (g )

[NO] [H2] Rate


-1 -1
Mol L Mol L Mol L-1S-1
(a) 8 × 10-5 8 × 10-5 7 × 10-9
(b) 24 × 10-5 8 × 10-5 2.1 × 10-8
(c) 24 × 10-5 32 × 10-5 8.4 × 10-8
The order of the reaction with respect to NO is _____
(2021-08-26/Shift-1)
CHEMICAL KINETICS 103

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS


Objective Questions I [Only one correct option] 6. What is the order of a reaction which has a rate expression
1. The rate of reaction is defined as rate = k [A]3/2 [B]–1 ?

(a) decrease in the concentration of a reactant (a) 3/2 (b) 1/2

(b) increase in the concentration of a product (c) zero (d) none of these.

(c) change in the concentration of any one of the reactants 7. Order of a reaction can be
or products per unit time. (a) fractional (b) zero
(d) all the above three are correct. (c) integer (d) all the above.
2. For the reaction A + 2B  C, the rate of reaction at a given 8. The rate constant of a reaction is 2.1 × 10–2 mol–2 litre2 min–1. The
instant can be represented by order of reaction is
(a) zero (b) 1
d[A] 1 d[B] d[C]
(a)    (c) 2 (d) 3.
dt 2 dt dt
9. When concentration of reactant in reaction A  B is
d[A] 1 d[B] d[C] increased by 8 times, the rate increases only 2 times. The
(b)  
dt 2 dt dt order of the reaction would be
(a) 2 (b) 1/3
d[A] 1 d[B] d[C]
(c)    (c) 4 (d) 1/2
dt 2 dt dt
10. For a given reaction half life period was found to be directly
d[A] 1 d[B] d[C] proportional to the initial concentration of the reactant. The
(d)   
dt 2 dt dt order is
3. For a gaseous reaction, the units of rate of reaction are (a) Zero (b) 1
–1 –1
(a) L atm s (b) atm s (c) 2 (d) 3
–1 –1 –1
(c) atm mol s (d) mol s 11. In the presence of acid, the initial concentration of cane-
4. Which one of the following statements is incorrect ? sugar was reduced from 0.2 M to 0.1 M in 5 hrs and to 0.05
M in 10 hrs. The reaction must be of
(a) Rate law expression cannot be written from the
stoichiometric equation. (a) zero order (b) first order

(b) Law of mass action expression can be written from the (c) second order (d) fractional order
balanced equation. 12. When concentration of reactant in reaction A  B is
(c) Specific reaction rate of a reaction is constant at constant increased by 9 times, the rate increases only 3 times. The
temperature. order of the reaction would be

(d) Rate of reaction and rate constant have same units. (a) 3 (b) 1/3

5. Rate of a reaction (c) 6 (d) 1/2

(a) increases with increase in temperature 13. The rate of reaction between A and B increases by a factor
of 100, when the concentration of A is changed from
(b) decreases with increase in temperature 0.1 mol L–1 to 1 mol L–1. The order of reaction with respect to
(c) does not depend upon temperature A is :
(d) does not depend upon concentration. (a) 10 (b) 1
(c) 3 (d) 2
CHEMICAL KINETICS 104

14. For the reaction, A  B, the rate of reaction is quadrupled 20. The rate law of gaseous reaction : A(g) + B(g)  Products
when the concentration of A is doubled, the rate expression 2
is given by k[A] [B]. If the volume of the reaction vessel is
of the reaction is r = k [A]n, when the value of n is suddenly doubled, which of the following will happen ?
(a) 1 (b) zero (a) The rate w.r.t. A will decrease two times
(c) 3 (d) 2 (b) The rate w.r.t. A will decrease four times
15. A reaction involves two reactants. The rate of reaction is (c) The rate w.r.t. B will decrease two times
directly proportional to the concentration of one of them (d) The overall rate will decrease 8 times of the original value
and inversely proportional to the concentration of the other.
21. The unit of rate constant for a zero order reaction is
The overall order of reaction will be
(a) litre sec–1 (b) litre mol–1 sec–1
(a) one (b) two
(c) mol litre–1 sec–1 (d) mol sec–1.
(c) zero (d) none of these.
22. The equilibrium constant of reaction is 20.0 At equilibrium,
16. If order of reaction is zero. It means that the rate constant of forward reaction is 10.0. The rate constant
(a) rate of reaction is independent of temperature for backward reaction is

(b) rate of reaction is independent of the concentration of (a) 0.5 (b) 2.0
the reacting species (c) 10.0 (d) 200.0
(c) the rate of formation of activated complex is zero 23. The rate constant for the reaction

(d) rate of decomposition of activated complex is zero 2N2O5  4NO2 + O2 is 3.0 × 10–5 sec–1
If the rate is 2.4×10–5 mol L–1 sec–1 the concentration of N2O5
17. The rate constant of a reaction has same units as the rate of
(in mol litre–1) is
reaction. The reaction is of
(a) 1.4 (b) 1.2
(a) zero order (b) first order
(c) 0.04 (d) 0.8
(c) second order (d) none of these.
18. Two gases A and B are filled in a container. The experimental 24. For a first order reaction P(g) 
 Q(g) + R(g). After 10 minutes the
rate law for the reaction between them, has been found to volume of R gas is 10 L and after complete reaction 50L. Hence
be Rate = k [A]2 [B] rate constant will be (in min–1).

Predict the effect on the rate of the reaction when pressure 1 1 1


is doubled : (a) ln 5 (b) ln
10 10 5
(a) the rate is doubled
1 1 5
(b) the rate becomes four times (c) ln 4 (d) ln
10 10 3
(c) the rate becomes six times
25. The activation energy of a reaction is zero. The rate constant
(d) the rate becomes eight times of the reaction
19. The rate law expression for the hypothetical reaction (a) increases with increase of temperature
dx (b) decreases with increase of temperature
2 A + 3 B  2 C is = k [A] [B]2
dt (c) decreases with decrease of temperature
The order of reaction is (d) is nearly independent of temperature.
(a) 1 (b) 2
(c) 3 (d) 5
CHEMICAL KINETICS 105

26. The ratio of the rate constant of a reaction at any temperature 32. For the reaction A + B  C + D, the variation of the
T to the rate constant T   is equal to concentration of the product with time is given by the curve.
(a) Energy of activation of the reaction
(b) Fraction of molecules in the activated state II
(c) Average life of the reaction IV

(d) Pre-exponential factor in the Arrhenius equation

Conc
27. The half-life period of a radio active element is 30 min. One
sixteenth the original quantity of the element will remain
III
unchanged after
I
(a) one hour (b) sixteen hour Time
(c) four hour (d) two hour (a) I (b) II
28. Half life period of 2nd order reaction is : (c) III (d) IV
(a) proportional to initial conc. of reactants 33. Under a given set of experimental conditions, with increase
(b) independent of initial concentration of reactants of concentration of the reactants, the rate of a chemical
reaction
(c) inversely proportional to initial concentration of reactants
(a) Decreases
(d) inversely proportional to square of initial concentration
(b) increases
of reactants.
(c) Remains unaffected
29. The half-life period of a zero order reaction is
(d) First decreases, then increases.
(a) directly proportional to initial concentration
34. For a single step reaction;
(b) inversely proportional to initial concentration
A + 2B  Products, the molecularity is
(c) independent of initial concentration
(a) Zero (b) 1
(d) proportional to the square of initial concentration.
(c) 2 (d) 3
30. As the reaction progresses, the rate of reaction
35. In the accompanied diagram, ER, EP and EX represent the
(a) increases
energy of the reactants, products and activated complex
(b) decreases respectively. Which of the following is the activation energy
(c) remains constant for the backward reaction ?
(d) first increases, then decreases. EX
31. For the reaction 4 A + B  2 C + 2D, which of the following
A
statement is not correct ? D
B
ENERGY

(a) the rate of disappearance of B is one fourth of the rate of


disappearance of A EP
C
(b) the rate of formation of C is one-half of the rate of ER
consumption of A
(c) the rate of appearance of D is half of the rate of (a) A (b) B
disappearance of B
(c) C (d) D
(d) the rates of formation of C and D are equal.
CHEMICAL KINETICS 106

36. In the sequence of reaction 43. For the decomposition of N2O5 at a particular Temperature
according to the equations
k1 k2 k3
A   B   
 C  D
2N2O5   4NO2 + O2
k3 > k2 > k1, then the rate determining step of the reaction is:
1
(a) A  B (b) B  C N2O5  2NO2 + O
2 2
(c) C  D (d) A  D
the activation energies are E1 and E2 respectively, then
37. If Ef and Er are the activation energies of the forward and
reverse reactions and the reaction is known to be exothermic, (a) E1 > E2 (b) E1 < E2
then (c) E1 = 2E2 (d) E1 = E2
(a) Ef < Er
 dx 
(b) Ef > Er 44. The rate of a reaction at different times    is found as
 dt 
(c) Ef = Er follows :
(d) No relation can be given between Ef and Er as data are Time (in minute) Rate in (mol L–1 s–1)
not sufficient. 0 2.80 × 10–2
38. An endothermic reaction A  B has an activation energy as 10 2.78 × 10–2
x kJ mol–1 of A. If energy change of the reaction is y kJ, the
20 2.81 × 10–2
activation energy of the reverse reactions is :
30 2.79 × 10–2
(a) – x (b) x – y
The order of reaction is
(c) x + y (d) y – x.
(a) zero (b) one
39. Energy of activation of an exothermic reaction is (c) two (d) three.
(a) zero (b) negative 45. Ea and H values of reactions R1, R2, R3 and R4 carried out at
(c) positive (d) can’t be predicted the same temperature are as given below :
40. If a reaction A + B  C is exothermic to the extent of R1 Ea = 40 kJ mol–1, H = – 80 kJ mol–1
30 kJ/mol and the forward reaction has an activation energy R2 Ea = 20 kJ mol–1, H = – 30 kJ mol–1
70 kJ/mol, the activation energy for the reverse reaction is R3 Ea = 60 kJ mol–1, H = + 40 kJ mol–1
(a) 30 kJ/mol (b) 40 kJ/mol R4 Ea = 30 kJ mol–1, H = + 20 kJ mol–1
(c) 70 kJ/mol (d) 100 kJ/mol At a given temperature and assuming that the backward
41. Radioactive decay is a reactions of all these reactions have the same frequency
factor, the rates of R1, R2, R3 and R4 in their respective
(a) zero-order reaction (b) first-order reaction backward reactions are in the increasing order of
(c) second order reaction (d) third order reaction (a) R2 < R3 < R4 < R1 (b) R4 < R3 < R2 < R1
42. For an endothermic reaction, where H represents the (c) R1 < R4 < R3 < R2 (d) R1 < R2 < R3 < R4
enthalpy of reaction in kJ mol, the minimum value for the 46. The half-life period for a reaction at initial concentrations of
energy of activation will be 0.5 and 1.0 mol lit–1 are 200 sec and 100 sec respectively. The
(a) Less than H (b) zero order of the reaction is
(c) More than H (d) Equal to H (a) zero (b) 1
(c) 2 (d) 3
CHEMICAL KINETICS 107

47. In the decomposition of Ammonia it was found that at 53. For a first order reaction : A  B, Whose concentration vs.
50 torr pressure T1/2 was 3.64 hour while at 100 torr T1/2 was time curve is as shown in the figure. The rate constant is
1.82 hours. Then order of reaction would be equal to
(a) 0 (b) 1
(c) 2 (d) 3
48. A hypothetical reaction A2 + B 2  2 AB follows the
mechanism as given below :

 A + A (fast)
A2 

A + B2  AB + B (slow)
A + B  AB (fast)
The order of the over all reaction is :
(a) 41.58 h–1 (b) 4.158 s–1
(a) 2 (b) 1 (c) 1.155 × 10–3 s–1 (d) 6.93 min–1

1 54. Milk turns sour at 40ºC three times faster at 0ºC. Hence Ea in
(c) 1 (d) 0 calories of turning of milk sour is
2
49. The rate constant for a zero order reaction is 2.303  2  313  273
(a) log 3
2 × 10–2 mol L–1 sec–1. If the concentration of the reactant after 40
25 sec is 0.5 M, the initial concentration must have been
(a) 0.5 M (b) 1.25 M 2.303  2  313  273
(b) log(1 / 3)
40
(c) 12.5 M (d) 1.0 M
50. SO2Cl2  SO2 + Cl2 is the first order as gas reaction with k 2.303  2  40
(c) log 3
= 2.2 × 10–5 sec–1 at 320ºC. The percentage of SO2Cl2 273  313
decomposed on heating for 90 minutes is
(d) none
(a) 1.118 (b) 0.1118
55. The rate constant of a reaction A  B + C at 27ºC is
(c) 18.11 (d) 11.30
3.0 × 10–5 s–1 and at this temperature 1.5 × 10–4 percent of the
51. Four vessels 1, 2, 3 and 4 contain respectively, 10 mol atom reactant molecules are able to cross-over the P.E. barrier.
(t1/2 = 10 hours), 1mol atom (t1/2 = 5 hours), 5 mol atom (t1/2 = The maximum rate constant of the reaction is
2 hour) and 2 mol atom (t1/2 = 1 hour) of different radioactive
(a) 4.5 × 10–9s–1 (b) 4.5 × 10–11 s–1
nuclides. In the beginning, the maximum radioactivity would
be exhibited by the vessel (c) 0.2 s–1 (d) 20 s–1
(a) 4 (b) 3 56. The half-life a first order reaction is 24 hours. If we start with
10M initial concentration of the reactant then conc. after 96
(c) 2 (d) 1
hours will be
52. The chemical reaction, 2O3 
 3O2 proceeds as follows (a) 6.25 M (b) 1.25 M
O3  O2 + O (Fast) (c) 0.125 M (d) 0.625 M
57. The half-life period of a radioactive element is 120 days.
O + O3 
 2O2 (slow) Starting with 1 gm, the amount of element decayed in 600
The rate law expression should be days will be
(a) Rate = K [O3]2 (b) Rate = K[O3]2 [O2]–1 1 15
(a) g (b) g
(c) Rate = K [O3] [O2] (d) None 16 16

1 31
(c) g (d) g
32 32
CHEMICAL KINETICS 108

58. Which one of the following statements is incorrect ? 62. The rate constant of a reaction at 27ºC is 2.3 × 10–3 min–1 and
at this temperature 0.002% of the reactant molecules are
(a) The temperature coefficient of a reaction is the ratio of
able to cross over the energy barrier existing between the
the rate constant at any two temperatures
reactants and products. By increasing the temperature, the
(b) The temperature coefficient of a reaction is the ratio of rate constant of reaction will increase to a maximum of
the rate constants at 298 K and 308 K
(a) 2.3 × 10–2 min–1 (b) 4.6 × 10–2 min–1
(c) The temperature coefficient of most of the reactions lies
(c) 2.30 min–1 (d) 115 min–1
between 2 and 3
63. For the reaction
(d) In an endothermic reaction, activation energy of
reactants is more than that of the products CH3Cl(aq) + OH– (aq)  CH3OH(aq) + Cl–(aq)

59. The thermal decomposition of A  B + C has rate constant The kinetic data are as given below :
[CH3Cl] [OH–] + d [CH3OH]/dt (M min–1)
dA
x mole–1/2 lit1/2 min–1 at a given temperature. How would  0.2 0.1 2 × 10–3
dt
will change if concentration of A is doubled keeping 0.4 0.1 4 × 10–3
temperature constant 0.4 0.2 8 × 10–3
(a) will increase by 2.828 times If Kc for the above reaction is 1 × 1014, then the specific
reaction rate (M–1 min–1) for the replacement of –OH group
(b) will increase by 4 times
of methanol by Cl atom is :
(c) will increase by 11.313 times
(a) 10–18 (b) 10–15
(d) will not change (c) 1015 (d) 10
60. The thermal decomposition of acetaldehyde : 64. A sample of rock from the moon contains equal number of
CH3CHO  CH4 + CO atoms of U and Pb (t½ for uranium = 4.5×109 years). The age
of rock would be
has rate constant of 1.8 × 10–3 mole–1/2 L1/2 min–1 at a given
(a) 4.5 × 109 years (b) 90 × 109 years
d[CH 3CHO]
temperature. How would  will change if (c) 13.5 × 109 years (d) 2.25 × 109 years
dt
65. According to the collision model of kinetics, certain
concentration of acetaldehyde is doubled keeping the
activation energy must be overcome before a reaction can
temperature constant ?
proceed. Based on the data given below, what is a reasonable
(a) will increase by 2.828 times estimate of the activation energy for the decomposition of
(b) will increase by 11.313 times NOCl ?
2 NOCl(g)  2 NO(g) + Cl2(g)
(c) will not change
Temperature (K) Rate constant, k (L/mol s)
(d) will increase by 4 times
400 6.6 × 10–4
61. The decomposition of ozone is believed to occur by the
mechanism : 500 2.9 × 10–1
600 1.63 × 101
O3  O2 + O (fast)
(a) 1.00 × 102 J/K mol (b) 1.23 × 103 J/K mol
O + O3  O2 (slow)
(c) 1.05 × 105 J/K mol (d) 1.34 × 106 J/K mol
When the concentration of O2 is increased, then the rate
(a) increases (b) decreases
(c) remains same (d) cannot be predicted
CHEMICAL KINETICS 109

Objective Questions II (c) HX is a weaker acid than HY, their relative strength being
[One or more than one correct option] 0.6
(d) none is correct
66. When the temperature of a reaction is changed from T1 to T2
+
half-life is found to decrease. Thus : 70. Hydrolysis of a sugar is catalysed by H ion. Half-life of the
reaction is independent of initial concentration of sugar at a
(a) T2 > T1
particular pH. At a constant concentration of sugar rate
(b) The reaction is exothermic increases 10 times when pH is decreased by one unit. Pick
(c) The reaction is endothermic out the correct statements of the following :

(d) The reaction can be exothermic or endothermic (a) Rate  [sugar]


+
67. For the hypothetical reaction (b) Rate  [H ]

A2 + B2 2AB, the mechanism is given as below (c) Rate law : rate = k (sugar)
+
A2 A + A(fast reaction) (d) Rate law : rate = k [sugar] [H ]

A + B2 AB + B (slow reaction) 71. Estrification of acetic anhydride by ethanol takes place as

A+ B AB (fast reaction) (CH3CO)2 O + C2H5OH  CH3COOC2H5 + CH3COOH

then Select the correct statements of the following :

(a) the rate determining step is A + B2 AB + B (a) When reaction is carried out in dilute hexane solution,
the rate law is given by k [Anhydride] [Alcohol]
(b) the order of the reaction is 3/2
(b) When ethanol is the solvent, the rate law is given by k
(c) the overall molecularity is 4 [Anhydride]
(d) the rate expression is Rate = k [A] [B2] (c) The values of k in the two cases are the same
68. Which of the following statements about the Arrhenius (d) Using ethanol as the solvent, its concentration changes
equation is/are correct ? significantly during the course of the reaction
(a) The pre-exponential factor becomes equal to the rate 72. Which of the following statements are correct ?
constant of the reaction at extremely high temperature
(a) Time required for 75% completion is 1.5 times of half-life
(b) When the activation energy of the reaction is zero, the for zero order reaction
rate becomes independent of temperature
–Ea/RT
(b) Time needed for a definite fraction of first order reaction
(c) The term e represents the fraction of the molecules does not vary with the initial concentration
having energy in excess of threshold value
(c) Time for 25% reaction is one-third of half-life in second
(d) On raising temperature, rate constant of the reaction of order process
greater activation energy increases less rapidly than that
of the reaction of smaller activation energy. (d) Rate of zero order reaction gets doubled if the
+
concentration of the reactant is increased to a two fold
69. Hydrolysis of an ester is catalysed by H ion. value
Using equimolar concentrations of two acids HX and HY,
both being strong acids, the rate constants of the reaction
–3 –1 –3 –1
are found to be 3 × 10 min and 5 × 10 min respectively at
a fixed temperature. It can be concluded that
(a) Rate constant may be taken as the measure of degree of
ionization of the acid used as catalyst
(b) HX is a stronger acid than HY, their relative strength
being 1.7
CHEMICAL KINETICS 110

73. Which of the following graphs plotted are true ? 74. Which of the following graphs are properly represented
(a) For a zero order reaction

(a) (b)

For normal reaction For exposive reaction

(b) For a zero order reaction

(c) (d)

For all normal reaction For exposive reaction

75. An increase in the rate of reaction with rise in temperature is


due to
(c) For a 3rd order reaction
(a) an increase in the number of collisions
(b) an increase in the number of activated molecules
(c) lowering of activation energy
(d) shortening of mean free path.
Numerical Value Type Questions
76. For the reaction : A + B  P, if concentration of B is doubled,
(d) For a 1st order reaction
maintaining concentration of A constant, rate of reaction is
also doubled. If concentration of A is tripled. maintaining
concentration of B constant, rate of reaction increases by a
factor of nine. If concentrations both A and B are doubled
simultaneously, the rate of reaction will increase by a factor
of____.
77. For the reaction : A  P
when initial concentration of reactant is halved, the half-life
increases by a factor of eight. Order of reaction is____.
78. Temperature coefficient is defined as the factor by which
the rate of reaction increases on increasing the temperature
by 10ºC at a given temperature. If activation energy of a
reaction is 85 kJ, determine the temperature coefficient at
300 K (Rounded off to the nearest whole number).
CHEMICAL KINETICS 111

Assertion Reason Match the Following


(A) If both Assertion and Reason are correct and Each question has two columns. Four options are
given representing matching of elements from
Reason is the correct explanation of Assertion. Column-I and Column-II. Only one of these four
(B) If both Assertion and Reason are true but options corresponds to a correct matching, for
Reason is not the correct explanation of each question.
Assertion. 84. C0 = Initial concentration of reactant; C = Concentration of
reactant at any time t; k = rate constant
(C) If Assertion is true but Reason is false.
Match the following :
(D) If Assertion is false but Reason is true. Colume-I Colume-I
79. Asseration (A) : The rate of the reaction is the rate of change
Plots Slopes
of concentration of a reactant or a product.
(A) C vs (abscissa) for zero order (p) Unity
Reason (R) : Rate of reaction remains constant during the
(B) log C vs t (abscissa) for first order (q) Zero
complete reaction.
80. Asseration (A): If in a zero order reaction, the concentration  dc 
of the reactant is doubled, the half-life period is also doubled. (C)    vs C for zero order (r) – k
 dt 
Reason (R): For a zero order reaction, the rate of reaction is
(D) ln (–dc/dt) vs ln C for first order (s) -k/2.303
independent of initial concentration.
81. Assertion (A) : According to steady state hypothesis, in a
Paragraph Type Questions
multistep reaction, the change in concentration with time
for reactive intermediates is zero. Use the following passage, to solve Q. 85 to Q. 87
Reason (R) : The intermediates are so reactive that after a Passage
brief initial period their concentrations rise from zero to a Concentrations measured as a function of time when gaseous
small value and remains constant for most of the duration of N2O5 at initial concentration of 0.0200 M decomposes to gaseous
the reaction. NO2 and O2 at 55ºC. The change in concentration with time is
82. Asseration (A) : If the activation energy of a reaction is given by the following graph.
zero, temperature will have no effect on the rate constant.
Reason (R) : Lower the activation energy, faster is the
reaction.
83. Assertion (A) : For the 2N2O5  4NO2 + O2 ; Rate = K[N2O5].
Reason (R): Rate of decomposition of N2O5 is determined
by slow step.

85. The instantaneous rate of reaction at the beginning of the


reaction is
–5 –5
(a) 2.2 × 10 M/s (b) 1 × 10 M/s
–5
(c) 6.3 × 10 M/s (d) zero
CHEMICAL KINETICS 112
86. The rate of formation of NO2 during the period 600 – 700 s is
–5 –5
(a) 3.7 × 10 M/s (b) 2.2 × 10 M/s
–5 –5
(c) 4.8 × 10 M/s (d) 1.6 × 10 M/s
87. The rate of decomposition of N2O5 during the period 300 –
400 s is
–4 –5
(a) 3.7 × 10 M/s (b) 2.6 × 10 M/s
–5 –8
(c) 1.9 × 10 M/s (d) 3.6 × 10 M/s
Use the following passage, to solve Q. 88 to Q. 90
Passage The rate constants of most reactions increase as the temperature
is increased. The rate constant increases by about 100-200% for
The dependence of rate on concentrations of reactants is
expressed in terms of rate law, which is established experimentally. a temperature rise of 10K . It is found experimentally for many
a reactions that a plot of n k against 1 T gives a straight line.
Rate = k  A   Bb (Rate law) ..........(i)
This behaviour is expressed in the form of equation.
The exponents a, b, etc. (determined experimentally) may or may
not be equal to the respective stoichiometric coefficients. k is the Ea
n k  n A  .............. (iii)
velocity constant of the reaction. The determination of rate law is RT
simplified by the isolation method in which the concentration of 88. The rate of change of molar concentration of C in Reaction – 1, is
all the reactants except one are in large excess. If B is in large –3 –1 –1
found to be 3.0 × 10 mol L s . The rate of reaction and rate
excess. we can approximate [B]by  B0 of disappearance of the reactant B are respectively.
–3 –1 –1
(a) 3.0 × 10 mol L s each
a b a b a
Hence, Rate = k  A   B = k  A  B0 = k' A  –3
(b) 1.0 × 10 mol L s each
–1 –1

–3 –1 –1 –3 –1 –1
(k   k[B]0b ) (c) 1.0 × 10 mol L s and 2.0 × 10 mol L s
(d) None of these.
or log  initial rate  = log  0  log k   a log [A ] ...... (ii) 89. According to the fig-1 (a) and 1 (b), the rate law for the
reaction
A plot of log (rate) against log  A  values will be a straight line
2I(g) + Ar(g)  I2(g) + Ar(g) is given by
which enables to calculate both k and a. Similarly orders with 2
respect to other reactants. taken in much smaller concentrations (a) Rate = k [I] [Ar] (b) Rate = k[I]
2 2 2
turn by turn, can be determined. Consider the reaction : (c) Rate = k[I] [Ar] (d) Rate = k[I] [Ar]
2I (g )  Ar(g ) 
 I 2(g )  Ar(g) 90. The greater slope of the plot of n k against 1/T for a reaction
shows the rate constant to be
The following figures show the variation of log 0 against (a) (a) Independent of temperature
log I0 for a given  Ar 0 and (b) log  Ar 0 for a given  I 0 (b) Strongly dependent on temperature
(c) Poorly dependent on temperature
(d) Insufficient information to predict
CHEMICAL KINETICS 113

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS


Objective Questions I [Only one correct option] 7. Consider an endothermic reaction X  Y with the activation
1. The rate constant for the reaction 2N2O5  4NO2 + O2, is energies Eb and Ef for the backward and forward reactions
–5 –1 –5 –1 –1 respectively. In general (2005)
3.0 × 10 sec . If the rate is 2.40 × 10 mol litre sec ,
–1
then the concentration of N2O5 (in mol litre ) is (2000) (a) there is no definite relation between Eb and Ef
(a) 1.4 (b) 1.2 (b) Eb = Ef
(c) 0.04 (d) 0.8 (c) Eb > Ef
2. If ‘I’ is the intensity of absorbed light and ‘C’ is the (d) Eb < Ef
concentration of AB for the photochemical process,
8. Which one of the following statement for order of reaction
AB + hv AB*, the rate of formation of AB* is directly
is not correct ? (2005)
proportional to (2001)
(a) Order can be determind experimentally
(a) C (b) I
2
(b) Order of reaction is equal to sum of the powers of
(c) I (d) C.I concentration terms in differential rate law.
3. The rate constant of a reaction depends on : (2003) (c) It is not affected with the stoichiometric coefficient of
(a) the temperature of a reaction the reactants
(b) the time of a reaction (d) Order cannot be fractional
(c) the extent of reaction 9. For the reaction A + B  C, it found that doubling the
(d) the initial conc. of the reactant concentration of A increases the rate by 4 times, and
4. The reaction, X  Product, follows first order kinetics. In 40 doubling the concentration of B doubles reaction rate. What
minutes the concentration of X changes from 0.1 to 0.025 is the overall order of the reaction ? (2006)
M. The rate of reaction, when concentration of X is 0.01 M (a) 4 (b) 3/2
is (2004)
–4 –1 –4 –1 (c) 3 (d) 1
(a) 1.73 × 10 M min (b) 3.47 × 10 M min + + –3
–4 –1 –5 –1
10. Ag NH3  [Ag(NH3) ] ; k1 = 6.8 × 10
(c) 3.47 × 10 M min (d) 1.73 × 10 M min
+ + –3
[Ag(NH3)] + NH3  [Ag(NH3)2] ; k2 = 1.6 × 10
5. The rate constant of a reaction depends upon : (2004)
+
(a) extent of reaction then the formation constant of [Ag(NH3)2] is (2006)
–6 –5
(b) time of reaction (a) 6.8 × 10 (b) 1.08 × 10
(c) temperature of the system –6 –5
(c) 1.08 × 10 (d) 6.8 × 10
(d) concentration of the system 11. The following mechanism has been proposed for the
6. t1/4 can be taken as the time taken for the concentration of a reaction of NO with Br2 to form NOBr
reactant to drop to 3/4 of its initial value. If the rate constant
NO(g) + Br2(g)  NOBr2(g)
for a first order reaction is k, the t1/4 can be written as
(2005) NOBr2(g) + NO(g) 2NOBr(g)
(a) 0.75/k (b) 0.69/k If the second step is the rate determining step, the order of
(c) 0.29/k (d) 0.10/k the reaction with respect to NO (g) is (2006)
(a) 1 (b) 0
(c) 3 (d) 2
CHEMICAL KINETICS 114

12. Consider the reaction, 2A + B  products 17. Under the same reaction conditions, initial concentration of
When concentration of B alone was doubled, the half-life 1.386 mol dm–3 of a substance becomes half in 40 s and 20 s
did not change. When the concentration of A alone was through first order and zero order kinetics respectively. Ratio
doubled, the rate increased by two times. The unit of rate
constant for this reaction is (2007)  k0 
  of the rate constants for first order (k1) and zero order
–1 –1
(a) L mol s (b) no unit  k1 
–1 –1 –1 (k0) of the reaction is (2008)
(c) mol L s (d) s
–1 3 –3
13. Consider a reaction aG + bH  Products. When (a) 0.5 mol dm (b) 1.0 mol dm
concentration of both the reactants G and H is doubled, the 3
(c) 1.5 mol dm–3 (d) 2.0 mol–1 dm
rate increases by eight times. However, when concentration
of G is doubled keeping the concentration of H fixed, the 18. For a first order reaction A  P, the temperature (T)
rate is doubled. The overall order of the reaction is dependent rate constant (k) was found to follow the
(2007) equation:
(a) 0 (b) 1 2000
log k    6.0
(c) 2 (d) 3 T
14. The temperature dependence of rate constant (k) of a The pre-exponential factor A and the activation energy Ea,
chemical reaction is written in terms of Arrhenius equation
respectively, are (2009)
k  Ae  E a / RT . Activation energy (Ea) of the reaction can (a) 1.0 × 106 s–1 and 9.2 kJ mol–1
be calculated by ploting (2007)
(b) 6.0 s–1 and 16.6 kJ mol–1
1 (c) 1.0 × 106 s–1 and 16.6 kJ mol–1
(a) log k vs T (b) log k vs
T 6
(d) 1.0 × 10 s–1 and 38.3 kJ mol–1
1 19. Plots showing the variation of the rate constant (k) with
(c) k vs T (d) k vs log T temperature (T) are given below. The plot that follows
Arrhenius equation is (2010)
15. A radioactive element gets spilled over the floor of a room.
Its half-life period is 30 days. If the initial activity is ten
times the permissible value, after how many days will it be
safe to enter the room ? (2007)
(a) 1000 days (b) 300 days
(c) 10 days (d) 100 days (a) (b)

16. T 50 of first-order reaction is 10 min. Starting with


–1
10 mol L , rate after 20 min is (2008)
–1 –1
(a) 0.0693 mol L min
–1 –1
(b) 0.0693 × 2.5 mol L min
–2 –1
(c) 0.0693 × 5 mol L min
(c) (d)
–1 –1
(d) 0.0693 × 10 mol L min
CHEMICAL KINETICS 115

20. In the reaction, Objective Questions II


P + Q 
 R+S
[One or more than one correct option]
23. According to the Arrhenius equation, (2016)
the time taken for 75% reaction of P is twice the time taken
for 50% reaction of P. The concentration of Q varies with (a) a high activation energy usually implies a fast reaction.
reaction time as shown in the figure. The overall order of the (b) rate constant increases with increase in temperature.
reaction is (2013) This is due to a greater number of collisions whose energy
exceeds the activation energy.
(c) higher the magnitude of activation energy, stronger is
the temperature dependence of the rate constant.
(d) the pre-exponential factor is a measure of the rate at
which collisions occur, irrespective of their energy.
24. In a bimolecular reaction, the steric factor P was experimentaly
(a) 2 (b) 3 determined to be 4.5. the correct option(s) among the
following is (are) (2017)
(c) 0 (d) 1
21. For the elementary reaction M  N, the rate of (a) The activation energy of the reaction is unaffected by
disappearance of M increases by a factor of 8 upon doubling the value of the steric factor
the concentration of M. The order of the reaction with
respect to M is (2015) (b) Experimentally determined value of frequency factor is
(a) 4 (b) 3 higher than that predicted by Arrhenius equation
(c) 2 (d) 1 (c) The value of frequency factor predicted by Arrhenius
22. Which of the following plots is(are) correct for the given equation is higher than that determined experimentally

reaction? ([P]0 is the initial concentration of P) (d) Since P = 4.5, the reaction will not proceed unless an
effective catalyst is used

25. For a first order reaction A(g)  2B(g)  C(g) at constant


volume and 300 K, the total pressure at the beginning (t - 0)
and at time t are P0 and Pt , respectively. Initially, only A is
present with concentration [A]0 , and t1/3 is the time
required for the partial pressure of A to reach 1/3rd of its
(2020) initial value. The correct option(s) is (are) (Assume that all
these gases behave as ideal gases) (2018)

(a) (b)
(a) (b)

(c) (d)
(c) (d)
CHEMICAL KINETICS 116
26. In the decay sequence, 31. Consider the following reversible reaction,
238
92 U
 x1
  234  x2
90Th   234  x3
91 Pa   A(g)  B(g)  AB(g).

234 x
4  230 Th
The activation energy of the backward reaction exceeds
Z  90 that of the forward reaction by 2RT (in J mol –1). If the pre-
x1, x2, x3 and x4 are particles/radiation emitted by the exponential factor of the forward reaction is 4 times that of
respective isotopes. The correct option(s) is(are): –1
the reverse reaction, the absolute value of G  (in J mol )
(2019) for the reaction at 300 K is ........... .
(a) x1 will deflect towards negatively charged plate. (Given; ln(2) = 0.7, RT = 2500 J mol–1 at 300 K and G is the
(b) x2 is   Gibbs energy) (2018)

(c) x3 is  -ray 32. Consider the kinetic data given in the following table for
the reaction A + B + C  product.
(d) 234Z is an isotope of Uranium
27. For the following reaction Experiment [A] [B] [C] Rate of
k
number (mol dm–3) (mol dm–3) (mol dm–3) reaction
2X  Y  P (mol dm–3s–1)
1 0.2 0.1 0.1 6.0 × 10–5
d[P]
the rate of reaction is  k[X]. Two moles of 2 0.2 0.2 0.1 6.0 × 105
dt 3 0.2 0.1 0.2 1.2 × 10–4
X are mixed with one mole of Y to make 1.0 L of solution. At 4 0.3 0.1 0.1 6.0 × 10–5
50 s, 0.5 mole of Y is left in the reaction mixture. The correct
statement(s) about the reaction is(are) (Use : ln 2 : 0.693)
The rate of the reaction for [A] = 0.15 mol dm–3, [B] =0.25
(2021)
mol dm–3 and [C] = 0.15 mol dm–3 is found to be Y× 10–5 mol
(a) The rate constant, k, of the reaction is 13.86 × 10-4 s-1. dm–3s–1. The value of Y is _________ (2019)
(b) Half-life of X is 50 s. 33. The decomposition reaction
d[X] 2N2O5(g)  Δ
(c) At 50 s,   13.86  103 mol L1s 1 .  2N2O4(g) + O2(g) is started in a
dt closed cylinder under isothermal isochoric conditionat an
initial pressure of 1 atm. After Y × 103 s, the pressure inside
d[Y] the cylinder is found to be 1.45 atm. If the rate constant of
(d) At 100 s,   3.46  103 mol L1s 1 .
dt the reaction is 5 × 10–4 s–1, assuming ideal gas behavior, the
value of Y is _____. Truncate after 2 decimals. (2019)
Numerical Value Type Questions
238
28. A hydrogenation reaction is carried out at 500 K. If the same 34. 92 U is known to undergo radioactive decay to form
reaction is carried out in the presence of a catalyst at the 206
same rate, the temperature required is 400 K. Calculate the 82 Pb by emitting alpha and beta particles. A rock initially
activation energy of the reaction if the catalyst lowers the
–1
contained 68 × 10–6 g of 238 92 U . If the number of alpha
activation barrier by 20 kJ mol . (2000)
particles that it would emit during itsradioactive decay of
–1 –1
29. The rate of first order reaction is 0.04 mol L s at 10 min 238
92 U to 206 18
82 Pb in three half-lives is Z × 10 , then what is
–1 –1
and 0.03 mol L s at 20 min after initiation. Find the half-
the value of Z ? (2020)
life of the reaction. (2001)
30. An organic compound undergoes first order decomposition.
The time taken for its decomposition to
1/8 and 1/10 of its initial concentration are t1/8 and t1/10
[t1/8 ]
respectively. What is the value of [t ] × 10 ?
1/10

(log10 2 = 0.3) (2013)


CHEMICAL KINETICS 117

Paragraph Type Questions 37. A nuclear explosion has taken place leading to increase in
14 14
Use the following passage, to solve Q. 35 to Q. 37 concentration of C in nearby areas. C concentration is
Cl in nearby areas and C2 in areas far away. If the age of the
Passage
fossil is determined to be T1 and T2 at the places respectively
Carbon-14 is used to determine the age of organic material. The
then
procedure is based on the formation of 14 C by neutron capture in
(a) the age of fossil will increase at the place where explosion
the upper atmosphere.
1 C1
14
7 N+ 0 n1 14
6 C+ 1 p
1
has taken place and T1–T2 = ln C
 2
14
C is absorbed by living organisms during photosynthesis. The
(b) the age of fossil will decrease at the place where explosion
14
C content is constant in living organism once the plant or
1 C1
animal dies, the uptake of carbon dioxide by it ceases and the has taken place and T1  T2 = ln C
14  2
level of C in the dead being, falls due to the decay which C-14
underoges (c) the age of fossil will be determined to be the same
14
6 C 14
7 N+β
-
T1 C1
(d) T  C
14 2 2
The half-life period of C is 5770 yr .
Subjective Type Questions
The decay constant (λ) can be calculated by using the following
64 +
38. Cu (half-life = 12.8 h) decays by  emission (38%), 
formula λ= 0.693 emission (19%) and electron capture (43%). Write the decay
t1 products and calculate partial half-lives for each of the decay
2
processes. (2002)
The comparison of the β - activity of the dead matter with that of 39. For the given reaction,
the carbon still in circulation enables measurement of the period A + B  Products
of the isolation of the material from the living cycle. The method
Following data are given
however, ceases to be accurate over periods longer than
30,000 yr . The proportion of 14 C to 12 C in living matter is Initial conc. Initial conc. Initial rate
–1 –1
(m/L) (m/L) (mL s )
1 : 1012 . (2006)
[A]0 [B]0
35. Which of the following option is correct ?
14 0.1 0.1 0.05
(a) In living organisms, circulation of C from atmosphere
is high so the carbon content is constant in organism 0.2 0.1 0.1
(b) Carbon dating can be used to find out the age of earth 0.1 0.2 0.05
crust and rocks (a) Write the rate equation.
(c) Radioactive absorption due to cosmic radiation is equal (b) Calculate the rate constant. (2004)
to the rate of radioactive decay, hence the carbons
content remains constant in living organisms 40. 2X (g)  3Y (g) + 2Z (g)
(d) Carbon dating cannot be used to determine Time (in min) 0 100 200
14 Partial pressure of X
concentration of C in dead beings.
36. What should be the age of fossil for meaningful (in mm of Hg) 800 400 200
determination of its age ? Assuming ideal gas condition. Calculate
(a) 6 yr (a) Order of reaction
(b) 6000 yr (b) Rate constant
(c) 60,000 yr (c) Time taken for 75% completion of reaction
(d) Total pressure when px = 700 mm (2005)
(d) It can be used to calculate any age
CHEMICAL KINETICS 118

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ELECTROCHEMISTRY
Chapter 19 120

ELECTROCHEMISTRY

1. ELECTROCHEMISTRY
Electrochemistry is the study of production of electricity from
energy released during spontaneous chemical (redox) reactions
and the use of electrical energy to bring about non-spontaneous
chemical (redox) transformations.

2. ELECTROCHEMICAL CELLS
It is a device for converting chemical energy into electrical energy
and vice versa.
2.1 Types
(a) Galvanic Cells/Voltaic Cells: Converts chemical energy into
electrical energy.
Galvanic Cell
(b) Electrolytic Cells:
Converts electrical energy into chemical energy. Zn(s) + CuSO4 (aq.)  ZnSO4 (aq.)+ Cu(s)
 The oxidation half cell is known as Anode and the
reduction half cell is known as Cathode.
 Electrons flow from anode to cathode in the external
circuit.
 Current flow from cathode to anode in external circuit
and from anode to cathode in internal circuit(salt bridge)
 Anode is assigned negative polarity and cathode is
assigned positive polarity.
 In Daniell Cell, Zn acts as the anode and Cu acts as the
cathode.
 This cell converts chemical energy to electrical energy
and has an electric potential of 1.1V.

NOTE
Flow diagram for electrochemical cell
Remember the pneumonic-LOAN
2.1.1 Galvanic Cell/Voltaic Cells L- left
 Two half cells, in which metal rods are dipped into its solution O-oxidation
 Both rods are called electrodes connected with each other A-anode
by wire. N-negative polarity
 Solutions are connected with each other by salt bridge 2.1.2 Electrolytic Cell
(U- shaped tube)
 If an external opposite potential is applied in the Daniell
 In one half cell oxidation takes place and in other reduction cell which is more than 1.1 V, electrons start to flow from
takes place Cu to Zn.
 Then Zn ions would deposit on the Zn electrode and
Cu electrode dissolves.

SCAN CODE
Electrochemistry
ELECTROCHEMISTRY 121
 This is an electrolytic cell where electrical energy carries 2.3.2 Characteristics of Electrode Potential
non-spontaneous chemical reactions. (a) Both oxidation and reduction potentials are equal in
magnitude but opposite in sign.
EOx = - ERed.
(b) It is not an extensive thermodynamic property, so values of
E are not additive.
2.3.3 Standard Electrode Potential (EO)
Potential of an electrode when the concentration of the ions in
the solution is 1 mol/L (partial pressure for gases is 1 atm) and at
any temperature (if nothing is given assume 298K) is called
standard electrode potential

NOTE
If nothing is mentioned about the type of electrode potential
then it is assumed to be reduction electrode potential. By
Electrolytic Cell getting the value of standard electrode potential we can predict
2.2 Salt Bridge ease of oxidation/ reduction of various elements/ions.
 The two half cells are connected by an inverted ‘U’ E.g. E0Red E0Ox
shaped tube called as salt-bridge. A2+ + 2e–  A 2.5 V –2.5 V
 It contains strong electrolytes e.g. KCl, KNO3 or NH4NO3 B2+ + 2e–  B –1.0 V 1.0 V
in colloidal solution of agar-agar which allows only
C2+ + 2e–  C 1.5 V –1.5 V
movement of salt ions.
Highest tendency to get reduced: A2+ as it has highest E0 value
 Electrolyte to be used in salt bridges should be such
that the mobility of its cations is equal to mobility of its Tendency to get reduced : A2+ > C2+ > B2+
anions. Strength as an oxidizing agent : A2+ > C2+ > B2+
2.2.1 Functions of Salt Bridge Tendency to get oxidized : B>C>A
 It completes the circuit of the cell. Strength as a reducing agent. : B > C > A
 It maintains the electrical neutrality of the solution. 2.4 Electrochemical Series
 It prevents liquid junction potential. Series that describe arrangement of elements/ions, in order of
2.3 Electrode Potential increasing electrode potential value.
 The potential difference which facilitates the flow of
electrons between two phases is called electrode
potential.
 The electrode potential will be named as oxidation or
reduction potential depending upon whether oxidation or
reduction has taken place.
 Higher is the value of electrode potential, higher is the
tendency of reaction to take place.
2.3.1 Types of Electrode Potential
(a) Oxidation electrode potential (Eox)

A  A n   ne  ; E Ox Standard Electrode Potentials at 298 K


(b) Reduction electrode potential (ERed.)

A n   ne   A ; E Re d.

SCAN CODE
Electrochemistry
ELECTROCHEMISTRY 122
2.5 Cell Potential or EMF of a Cell  Electrode representation:
The difference between the electrode potentials of two half cells M(s) | Mn+(aq.) or Mn+(aq.) | M(s)
is called cell potential. It is known as electromotive force (EMF) (b) Gas Electrodes
of the cell if no current is drawn from the cell.
 In gas electrodes H2, Cl2 etc are used with their respective
Ecell = ERed, cathode - ERed, anode ions. For example Standard hydrogen electrode (SHE)
Ecell = ERed, cathode + Eox, anode  The metal should be inert so that it does not react with the
2.5.1 Standard EMF of a Cell acid.

E 0cell  E0Red, cathode  ERed, anode


E 0cell  E 0Red, cathode  Eox, anode

2.6 Cell Diagram or Representation of a Cell


 The following conventions or notations are applied for
writing the cell diagram in accordance with IUPAC
recommendations. The Daniell cell is represented as follows:
Zn(s) | Zn2+ (C1) || Cu2+ (C2) | Cu (s)
 Anode half cell is written on the left hand side while cathode
half cell is written on right hand side.
 A single vertical line separates the metal from aqueous
Standard Hydrogen Electrode
solution of its own ions.
Anode: H2(g)  2H+(aq.) + 2e–
Zn  s  | Zn 2   aq  ; Cu 2   aq  | Cu  s 
Anodic chamber Cathodic chamber Cathode: 2H+(aq.) + 2e– H2(g)
 The molar concentration (C) is placed in brackets after the  The hydrogen electrode is also used as the standard to
formula of the corresponding ion. measure other electrode potentials. Its own potential is set
to 0 V as a reference.
 The value of e.m.f. of the cell is written on the extreme
right of the cell. For example,  When it is used as a reference the concentration of dil. HCl
is taken as 1 M and the electrode is called “Standard
o
Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu Ecell = +1.1V Hydrogen Electrode (SHE)”.
 If an inert electrode like platinum is involved in the  Electrode representation :
construction of the cell, it may be written along with the Pt,H2(g) |H+(aq.) or Pt,H+(aq.)| H2(g)
working electrode in bracket, say for example, when a zinc (c) Metal-Insoluble salt electrode
anode is connected to a hydrogen electrode.
 Pure silver wire in a solution of KCl saturated with solid
Zn  s  | Zn 2   C1  || H   C 2  | H 2 |  Pt  s  silver chloride be identified in the following reaction:
 AgCl  s   e 
Anode : Ag  s   Cl  aq  
2.7 Electrodes
Point (terminal) where electrons enter or leaves a circuit.  Ag  s   Cl  aq.
Cathode : AgCl  s   e 
2.7.1 Types of Electrodes
 Electrode representation :
(a) Metal-Metal Ion Electrodes
Ag(s)|AgCl(s)|Cl-(aq.) or Cl- (aq.)|AgCl(s)|Ag(s)
 A metal rod/plate is dipped in an electrolyte solution
(d) Calomel electrode
containing metal ions. There is a potential difference between
these two phases and this electrode can act as a cathode or  Mercury is used with two other phases, one is a
anode both. calomel paste (Hg2Cl2) and electrolyte containing Cl–
ions.
Anode: M(s) Mn+(aq.) + ne–
Cathode: Mn+(aq.) + ne– M(s)

SCAN CODE
Electrochemistry
ELECTROCHEMISTRY 123
 If we want to obtain maximum work from a galvanic cell then
charge has to be passed reversibly
 The reversible work done by a galvanic cell is equal to
decrease in its Gibbs energy
G = –nFECELL
Where G change in gibbs free energy
n is number of moles of electrons involve in per mole of
chemical reaction
F is Faraday constant which is equal to 96500 C
ECELL is reduction potential of a cell
 If we take standard value of cell potential in the above
equation we will obtain a standard value of G as well.
G° = –n F EoCELL
 Gibbs free energy also related to equilibrium constant
At equilibrium,
G = 0
G° = - 2.303 RT log K
Calomel electrode
2.9 Nernst Equation
Anode :
The electrode potential at any concentration measured with
2Hg(l) + 2Cl–(aq) Hg2Cl2(s) + 2e– respect to standard electrodes can be represented by the Nernst
Cathode : equation.
Hg2Cl2(s) + 2e– 2Hg(l) + 2Cl–(aq) As we know
 This electrode is also used to measure potential of other G  G o  RT n Q ...(1)
electrodes.Its standard form is also called Standard Calomel
Also
Electrode (SCE).
G  nFE
 For saturated Calomel electrode, standard reduction potential
= 0.244 V at 25°C and G o  nFE o
 Electrode representation : Putting both value in eq. (1)
Pt(s)|Hg(l)|Hg2Cl2(s)|Cl-(aq)  nFE   nFE o  RT n Q
or Cl–(aq) | Hg2Cl2(s) | Hg(l) | Pt(s) Put the values of constants.
(e) Redox Electrode F = 96500 C
 In these electrodes, two different oxidation states of the T = 25°C or 298 K
same metal are used in the same half cell. R = 8.314 JK–1mol–1
 For example, Fe2+ and Fe3+ are dissolved in the same container 0.0591
and an inert electrode of platinum is used for the electron E  Eo  log Q
n
transfer. Following reactions can take place:
Where Q is reaction Quotient
Anode: Fe2+(aq.) Fe3+(aq.) + e–
For a general electrochemical cell reaction of the type.
Cathode: Fe3+(aq.) + e– Fe2+(aq.) 
aA  bB 
ne
cC  dD
 Electrode representation:
Nernst equation can be given as
Pt|Fe3+(aq.), Fe2+(aq.) or Fe2+(aq.),Fe3+(aq.)|Pt
RT  C  D 
c d
2.8 Electrochemical Cell and Gibbs Free Energy E cell  E o
 ln
nF  A a  Bb
cell
 Electrical work done in one second is equal to electrical
potential multiplied by total charge passed.

SCAN CODE
Electrochemistry
ELECTROCHEMISTRY 124

 C  D (b) pH of solution :
c d
2.303
E cell  E ocell  RT log Consider a reaction in cathode half cell
 A   B
a b
nF
Substituting the values of R and F we get Cathode : 2H   2e  H 2  g 

C  D , at 298 K
c d

E cell  E cell
o

0.0591
log E RP  E RP 
0.0591
log
P
 A  B R 
a b
n n
2.9.1 Representation of Nernst Equation for Different Half 0.0591 pH 2
Cell  0 log 2
2  H  
(a) Metal-Metal Ion electrodes :
(If pH2 = 1 atm)
M n   aq   ne  M  s 
0.0591 2

0.0591 1 E RP   log  H  
E Mn  / M  E 0
 log 2
Mn  / M
n  M n   ERP = 0.0591 log [H+]
(b) Gas Electrodes (SHE) : –ERP = –0.0591 log(H+)
 1/ 2H 2
H   aq   e   ERP = –0.0591 pHCathode
2.9.3 Use of G in Relating EMF values of half cell reaction
 pH 2 
1/ 2
0.0591
E H / H  E 0
H / H2
 log  When we have two half cell reactions such that on adding
2
1  H   them we obtain another half cell reaction then their emf values
(c) Metal-Insoluble salt electrode : cannot be added directly.
 Ag  s   Cl   aq 
AgCl  s   e   But in any case thermodynamic functions like ΔG can be
added and emf values can be related through them.
0.0591  Consider the following three half cell reactions.
E Cl / AgCl/ Ag  E 0Cl / AgCl/ Ag  log  Cl  
1
Fe2+ + 2e–  Fe ; E1
(d) Calomel Electrode :
Fe3+ + 3e–  Fe ; E2
 2Hg(l) + 2Cl–(aq)
Hg2Cl2(s) + 2e– 
Fe3+ + e–  Fe2+ ; E3
0.0591 2
 We can easily observe that the third reaction can be obtained
Eel  Eel0  log Cl 
2 by subtracting the first reaction from the second.
Electrode(el) = Cl–(aq) | Hg2Cl2(s) | Hg(l) | Pt(s)  But the same relation does not apply on the emf values.
(e) Redox Electrode : That is, E3 – E1.
 Fe 2   aq 
Fe3  aq   e    But the ΔG values can be related according to the
reactions. That is,
0.0591  Fe 2  
E Fe3 / Fe2  E 0
 log G3 = G2 – G1
Fe3 / Fe 2
1  Fe 3 
– n3FE3 = – n2FE2 + n1FE1
2.9.2 Application of Nernst Equation – E3 = – 3E2 + 2E1
(a) Equilibrium Constant from Nernst Equation : E3 = 3E2 – 2E1
0.0591
E  E0  log Q NOTE
n
At equilibrium cell potential is zero We should always remember that emf values are additive only
when two half cell reactions are added to give a complete
0.0591 balanced cell reaction. In any other case we will be using ΔG
0 = E0 – logK eq
n values to obtain relations between emf values.
n
log K eq  0
E Cell
0.059

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2.10 Concentration Cells 3. ELECTROLYSIS
 If two electrodes of the same metal are dipped separately
into two solutions of the same electrolyte having different Electric current is passed through a solution to bring chemical
concentrations and the solutions are connected through a change.
salt bridge, such cells are known as concentration cells. 3.1. Cases of Electrolysis
For example (a) Electrolysis of molten sodium chloride
Pt, H2 (1atm)| H+(c1) || H+ (c2) | H2 (1atm),Pt
Cu(s) | Cu+2 (c1) || Cu2+(c2) | Cu(s) 2NaCl (l )  2Na+ (l ) + 2Cl– (l )

In concentration cell, Ecell  0 The reactions occurring at the two electrodes may be shown
as follows :
These are of two types: At anode :
2.10.1 Electrode concentration cells
2Cl–(l)  Cl2 (g) + 2e– E Cl –
/ Cl
 1.36 V
Two similar electrodes at different gas pressure dipped in same At cathode :
solution of electrolyte. Pt, H2(g)(p1)|HCl (1M) |H2(g) (p2), Pt
2Na+(l) + 2e–  2Na(s) E Na  / Na  2.71V
0.0591 p
E cell  log 1  Overall reaction :
2 p2
2Na+ (l ) + 2 Cl– (l ) 
Electrolysis
 2Na (s ) + Cl2 (g)
2.10.2 Electrolyte concentration cell
or 2NaCl (l ) 
Electrolysis
 2Na (s) + Cl2 (g)
These types of cells consist of identical electrodes dipped in
the solutions of the same electrolytes but with varying concen- At cathode At anode
trations. The EMF of concentration cell at 298 K is given by (b) Electrolysis of aq. sodium chloride
Zn | Zn2+ (c1) || Zn2+ (c2) | Zn At anode:

Ecell  0
0.0591 c
log 1 2Cl  aq.  Cl2  g   2e  ECl  /Cl  1.36V
2
n c2  
2H 2 O     O 2  g   4H  aq.  4e

E H 2 O / O2  1.23V
0.0591 c
E cell  log 2 ,  Cl- ion discharge at anode although electrode potential value
n1 c1
where c2 > c1 for spontaneous reaction is smaller than water
2.11 Preferential Discharge of Ions:  This is due to extra potential required to initiate a reaction at
When there are more than one cation or anion, the process of a required rate in case of OH- called as over-voltage.
discharge becomes competitive in nature. Discharge of any ion  Formation of O2 from H2O is kinetically very slow (i.e. low
requires energy and in case of several ions being present, the rate). Thus, OH– ions will remain in the solution.
discharge of that ion will take place first which requires less At cathode:
energy.
Na   aq   e  Na  s  E oNa  / Na  2.71V

2H 2 O  l   2e  H 2  g   2OH   aq. E oH2O / H2  0.83 V


 H2 will be liberated at cathode because the reduction potential
of water is higher than sodium ion.
(c) Electrolysis of sulphuric acid
At anode:
2H 2O  l   O 2  g   4H   aq   4e  E oH2 O / O2  1.23V

2SO 24   aq   S2 O82   aq   2e  o
E SO 2
/S O 2 
 1.96 V
4 2 8

For dilute solution first is preferred and in conc. solution second


is preferred.

Tendency of cation and anion to discharge

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ELECTROCHEMISTRY 126
At cathode: QE  1 1  w Q
w     
F  F 96500  E F
2H 2 O  l   2e  H 2  g   2OH  aq.
 
E o
H 2 O/ H 2  0.83V
No. of gram equivalents = No. of Faradays of electricity
4. FARADAY’S LAW OF ELECTROLYSIS 1 gm eq. any substance = 1 F of electricity

(a) 1st Law: The amount of any substance that is deposited or 5. ELECTROLYTIC CONDUCTANCE
liberated at an electrode is directly proportional to the
quantity of electricity passing through the electrolyte Here we deal with conductance of electricity (charge) through
electrolytic solutions.
W  Q
W = ZQ (Q = Current  time) 5.1 Conductance
W= Z It  It is defined as the ease with which the electric current flows
Z-electrochemical equivalent of the substance. through a conductor.
Z = Mass deposited when 1 C of charge is passed into the
 It is reciprocal of resistance (R)
solution.
 The amount of electricity (or charge) required for oxidation 1
G
or reduction depends on the stoichiometry of the electrode R
reaction. SI unit is Siemen (S). 1 S = 1 ohm–1 (mho)
 One mole of the electron is required for the reduction of one 5.1.1 Measurement of conductance
mole of silver ions 1 
As we know,    The value of  could be known, if we
Ag (aq) + e  Ag(s)
+ –
R A
Charge on one mole of electron = measure l, A and R. The value of the resistance of the solution R
between two parallel electrodes is determined by using
N A  1.6021  1019 C  6.02  10 23 mol1  1.6021  1019
‘Wheatstones’ bridge method
C = 96487 C mol–1
This quantity of electricity is called Faraday and is
represented by the symbol F
1 F  96500 C
 If we take one mole of magnesium ion, it requires 2 Faraday
charge ( 2 mole electrons)
 It can be concluded that “1 gm eq. of a substance is deposited
by passing 1 Faraday of electricity”
(b) 2nd Law: The amount of different substances liberated by
the same quantity of electricity passing through the
electrolytic solution are proportional to their chemical It consists of two fixed resistance R3 and R4, a variable resistance
equivalent weights. R1 and the conductivity cell having the unknown resistance R2.
The bridge is balanced when no current passes through the
For two substances A and B in two different electrolytic
detector. Under these conditions,
cells ;
R1 R 3 RR
w A EA  or R2  1 4
 R2 R4 R3
w B EB
5.2 Conductivity 
From first and second law:
 Electric resistance of electrolytic solution is directly
w  Q (1st Law) proportional to its length () and inversely proporational to
wE (2 nd Law) its area of cross section (A).
 
R or R  
A A

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Where  is resistivity or specific resistance. S cm 1

 Conductivity is the reciprocal of resistivity (). equivalent cm 3
1 1   or Ohm 1 cm 2 equivalent 1 or S cm 2 equivalent 1
    G
 R A A
5.5 Variation of Conductivity and Molar Conductivity with
Now if  = 1 cm and A = 1 cm2, then k = G.. Dilution
 Hence, conductivity of an electrolytic solution may be  Conductivity decreases with decrease in concentration, this
defined as the conductance of a solution of 1 cm length with is because the number of ions per unit volume that carry the
area of cross-section equal to 1 cm2. current in the solution decreases on dilution.
Conductivity (k) = conductance(G)×(cell constant(G*))
 Molar conductivity   m    V  increases with decrease
  in concentration. This is because the total volume V of
 = cell constant and is denoted by G* 
A  solution containing one mole of electrolyte also increases

5.3 Molar Conductivity (m)  It has been found that the decrease in  on dilution of a
solution is more than compensated by increase in its
Conducting power of all the ions produced by dissolving one
volume.
mole of an electrolyte placed between two large electrodes at
one centimeter apart. Mathematically,  Graphic representation of the variation of  m vs C

Molar conductivity   m     V

Where V is volume in mL
Let the molarity of the solution ‘C’
We can say that C moles of electrolyte are present in 1 litre of
solution
1000
V
C
Putting the value of volume in above equation Molar conductivity versus c½ for acetic acid (weak
where V = Volume containing 1 mole of electrolyte in 1 mL of electrolyte) and potassium chloride (strong
solution. electrolyte) in aqueous solutions
5.6 Limiting Molar Conductivity (om)
1000
m     The value of molar conductivity when the concentration
C
5.4 Equivalent Conductivity(eq-) approaches zero is known as limiting molar conductivity
It is the conducting power of one equivalent electrolyte placed or molar conductivity at infinite dilution.
between two large electrodes one centimeter apart.  It is possible to determine the molar conductivity at infinite
Mathematically, dilution   m  in case of strong electrolyte by extrapolation
o

 eq    V
of curve of  m Vs c.
  1000
 eq   The mathematical relationship between  m and  m
N
Where, V is the volume of solution in cm3 containing 1 equivalent for strong electrolyte was developed by Debye, Huckel
of electrolyte and N is normality of solution. and Onsager. In simplified form, the equation can be given
Units : as  m   m0  b c1/ 2
  1000
 eq   where  0m is the molar conductivity at infinite dilution and b
N
is a constant which depends on the nature of the solvent
and temperature.

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 On the contrary, the value of molar conductivity of weak 6.1 Primary Batteries
electrolyte at infinite dilution cannot be determined by  Primary cells are those which can be used as long as the
extrapolation of the curve as the curve becomes almost active materials are present. Once they get consumed, the
parallel to the y-axis when concentration approaches zero. cell will stop functioning and cannot be reused.
 Conductance of a weak electrolyte at infinite dilution can be  Example: Dry cell or Leclanche cell and Mercury cell.
calculated by using Kohlrausch’s law.
6.1.1 Dry Cell
5.7 Kohlrausch’s Law
Anode : Zn container
 The molar conductance at infinite dilution for any electrolyte Cathode : Carbon (graphite) rod surrounded by powdered MnO2
is the sum of contribution of its constituent ions, i.e., anions and carbon.
and cations.
 In general, if an electrolyte on dissociation gives v+ cations
and v– anions then its limiting molar conductivity is given
by

 om  v   o  v   o

Here,  o and  o are the limiting molar conductivities of


cations and anions respectively.
5.7.1 Application of Kohlrausch’s Law
(a) Calculation of molar conductivities of weak electrolyte at
infinite dilution :
For example, molar conductivity of acetic acid at infinite dilution Dry cell
can be obtained from the knowledge of molar conductivities at
Electrolyte : NH4Cl and ZnCl2
infinite dilution of strong electrolyte like HCl, CH3COONa and
Anode : Zn Zn2+ + 2e–
NaCl as illustrated below.
Cathode : MnO2 + NH 4 e– MnO (OH) + NH3
 om  CH 3  COOH   CH
o
  Ho 
3  COO
The standard potential of this cell is 1.5 V and it falls as the cell
  oCH  COO   oNa     Ho    Cl
o
–   
  Na    Cl 
o o
gets discharged continuously and once used it cannot be
 3 
recharged.
i.e.  m  CH3  COOH    om  CH3  COONa    om  HCl    om  NaCl 
o

6.1.2 Mercury Cells


(b) Determination of Degree of Dissociation of Weak These are used in small equipment like watches, hearing aids.
Electrolytes :
Anode : Zn – Hg Amalgam
 cm
Degree of dissociation     o Cathode : Paste of HgO and carbon
m
Electrolyte : Paste of KOH and ZnO
(c) Determination of Dissociation Constant (K) of Weak
Electrolytes :
c 2  cm
K also  
1   0m
c   cm /  0m  c   cm 
2 2

 K 
1   cm /  0m  0m   0m   cm 

6.BATTERIES
When Galvanic cells are connected in series to obtain a higher
voltage the arrangement is called Battery.
Mercury cell

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Anode : Zn (Hg) + 2OH– ZnO (s) + H2O + 2e–
Cathode : HgO (s) + H2O + 2e– Hg (l) + 2OH–
Overall Reaction : Zn (Hg) + HgO (s) ZnO (s) + Hg (l)
The cell potential is approximately 1.35V and remains
constant during its life.
6.2 Secondary Batteries
Secondary cells are those which can be recharged again and
again for multiple uses. e.g. lead storage battery and Ni – Cd
battery.
Fuel cell
6.2.1 Lead Storage Battery
Anode : 2H2 (g) + 4OH (aq)

4H2O (l) + 4e–
Anode : Lead (Pb)
Cathode : Grid of lead packed with lead oxide (PbO2) Cathode : O2 (g) + 2H2O (l) + 4e– 4OH– (aq)
Electrolyte : 38% solution of H2SO4 Overall Reaction:
Anode: Pb(s) + SO42–(aq) PbSO4(s) + 2e– 2H2(g) + O2 (g) 2H2O (l)
Cathode:
PbO2(s) + 4H+(aq) + SO42–(aq) + 2e– PbSO4(s) + 2H2O(l)
8. CORROSION
Overall Reaction:  It involves a redox reaction and formation of an
Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O(l) electrochemical cell on the surface of iron or any other
To recharge the cell, it is connected with a cell of higher metal.
potential and this cell behaves as an electrolytic cell and  At one location, oxidation of iron takes place (anode) and at
the reactions are reversed. Pb(s) and PbO2(s) are another location, reduction of oxygen to form water takes
regenerated at the respective electrodes.These cells deliver place (cathode).
an almost consistent voltage.  First Fe gets oxidised to Fe2+ and then in the presence of
Recharging Reaction : oxygen from air it forms Fe3+ ion which then react with water
2PbSO4(s) + 2H2O(l) Pb(s) +PbO2(s) + 2H2SO4(aq) to form rust which is reprented by Fe2O3. xH2O
7. FUEL CELL Anode : 2Fe (s)  2 Fe2+ + 4e– Eº = - 0.44 V
Cathode : O2 (g) + 4H+ + 4e–  2H2O (l) Eº = 1.23 V
 One of the most successful fuel cells uses the reaction of
hydrogen with oxygen to form water Overall Reaction :
 In this cell, hydrogen and oxygen are bubbled through 2Fe (s) + O2 (g) + 4H+  2Fe2+(aq.) + 2H2O(l) ; Eºcell = 1.67V
porous carbon electrodes into concentrated aqueous sodium
hydroxide solution. Catalysts like finely divided platinum or
palladium metal are incorporated into the electrodes for
increasing the rate of electrode reactions
 It is designed to convert the energy of combustion of fuels
like hydrogen, methane, methanol, etc. directly into electrical
energy.
Corrosion of iron in atmosphere
 Rusting of iron can be avoided by painting it or by coating
it with some other metals like Zinc. The latter process is
known as Galvanisation.
 As the tendency of Zn to get oxidised is more than iron it
gets oxidised in preference and iron is protected. This method
of protecting one metal by the other is also called Cathodic
Protection.

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SUMMARY
 Electrochemical Cells  Electrochemical cell and Gibbs free energy
It is device for converting chemical energy into electrical G = –nFECELL
energy and vice versa
 Nernst Equation
 Types
C  D , at 298 K
c d
(i) Galvanic Cells/Voltaic Cells: 0.0591
E cell  E o
 log
 A  B
cell a b
n
Converts chemical energy into electrical energy
(ii) Electrolytic Cells:  Application of Nernst Equation
Converts electrical energy into chemical energy. (a) Equilibrium Constant from Nernst Equation
 Electrode Potential E  E0 
0.0591
log Q
The tendency of an element, when it is placed in contact n
with its own ions to either lose or gain electrons and in turn At equilibrium, cell potential is zero
becomes positively or negatively charged. n
log K eq  E 0Cell
 Electrochemical Series 0.059
The half cell potential values are standard values and are (b) pH of solution :
represented as the standard reduction potential values as Consider a reaction in cathode half cell
shown in the table at the end which is also called
Cathode : 2H   2e  H 2  g 
Electrochemical Series.
E RP  0.0591 pHCathode
 Cell potential or EMF of a cell
The difference between the electrode potentials of two half  Faraday Law of Electrolysis
cells is called cell potential. 1st Law:
ECell = ERed, cathode – ERed, anode W Q
 Cell Diagram or representation of a cell W = ZQ
2nd Law:
Zn  s  | Zn 2   aq  ; Cu 2   aq  | Cu  s 
Anodic chamber Cathodic chamber w A EA

w B EB
Zn(s) | Zn2+ (C1) || Cu2+ (C2) | Cu (s)
 Concentration Cells  Conductance(G)
H2 | H+(c1) || H+ (c2) | H2 1
G
Cu | Cu+2 (c1) || Cu2+(c2) | Cu R

In concentration cell, Ecell  0  Conductivity   


 Types of Electrodes 1 1  
(a) Metal-Metal Ion electrodes     G
 R A A
(b) Gas Electrodes
Now if  = 1 cm and A = 1 cm2, then  = G..
(c) Metal-Insoluble salt electrode
(d) Calomel Electrode

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Molar Conductivity  m   Batteries


Primary Batteries
  1000
m  Primary cells are those which can be used as long as the
C
active materials are present. Once they get consumed, the
Equivalent Conductivity    cell will stop functioning and cannot be reused.
 eq  Example: Dry Cell or Leclanche cell and Mercury cell.
  1000
 eq  Secondary Batteries
N
Secondary cells are those which can be recharged again and
 Kohlrausch’s Law again for multiple uses. e.g. lead storage battery and
It states that the limiting molar conductivity of an electrolyte Ni – Cd battery
can be represented as the sum of the individual contributions  Fuel Cell
of the anion and cation of the electrolyte.
It is designed to convert the energy of combustion of fuels
 Application of Kohlrausch’s law like hydrogen, methane, methanol, etc. directly into electrical
(i) Calculation of molar conductivities of weak electrolyte energy.
at infinite dilution  Corrosion
(ii) Determination of Degree of Dissociation of Weak It involves a redox reaction and formation of an
Electrolytes electrochemical cell on the surface of iron or any other metal.
(iii) Determination of Dissociation Constant (K) of Weak Rusting of iron can be avoided by painting it or by coating it
Electrolyte with some other metals like Zinc. This process is known as
Galvanisation.

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SOLVED EXAMPLES
Example - 1 as cathode. If zinc coating is broken, zinc undergoes
corrosion, protecting iron from rusting. No attack occurs
A cell is prepared by dipping copper rod in 1 M copper
on iron till all the zinc is corroded.
sulphate solution and zinc rod in 1 M zinc sulphate solution
and connected through a salt bridge. The standard (b)
reduction potentials of copper and zinc are 0.34 V and – 0.76 (i) At anode Cu  Cu2+ + 2e–
V respectively. At cathode [Ag+ + e–  Ag] × 2
(i) What will be the cell reaction?
(ii) What will be the standard electromotive force (EMF) of Cu + 2 Ag+ Cu2+ + 2Ag
the cell ?
(iii) Which electrode will be positive ?
Cell representation
(iv) How will the cell be represented ?
Cu | Cu2+ (conc.) || Ag+ (conc.) | Ag
Sol. (i) The cell reaction can be
Zn  Cu 2  
 Zn 2   Cu 0.059  Cu 2 
(ii) E cell  E o
cell  log 2
n  Ag  
or Cu  Zn 2  
 Cu 2  Zn
The EMF comes out to be positive for the 1st reaction. 0.059  0.01 
Hence, the cell reaction is 0 = (0.80 – 0.34)  log  2 
2  x 
Zn  Cu 2  
 Zn 2  Cu  0.01 
15.59  log  2 
(ii) E
o
cell E o
cathode E o
anode E o
Cu 2  / Cu
E o
Zn / Zn 2
 x 
= 0.34 - (- 0.76) = 1.10 V x = 1.597 × 10 –9 M
(iii) reduction takes place on copper electrode. Hence it is [Ag+] = 1.597 × 10–9M
positive
Example - 3
(iv) Zn | Zn2+ (1 M) || Cu2+ (1 M) | Cu
Calculate the standard free energy change and maximum
Example - 2
work obtainable for the reaction occurring in the cell : (Daniell
(a) Account for the following cell).
(i) Alkaline medium inhibits the rusting of iron Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
(ii) Iron does not rust even if the zinc coating is broken in
[Given E oZn 2 / Zn  0.76 V, E oCu 2 /Cu
a galvanized iron pipe.
(b) Cu2+ + 2e–  Cu ; Eo = + 0.34 V = + 0.34 V, F = 96, 500 C mol-1 ]
Ag+ + e–  Ag; Eo = + 0.80 V Also calculate the equilibrium constant for the reaction.
(i) Construct a galvanic cell using the above data.
Sol. (i) Ecell  ECu2 /Cu  EZn/ Zn2  0.34  (0.76)
o o o
(ii) For what concentration of Ag+ ions will the emf of the
cell be zero at 25oC, if the concentration of Cu2+ is 0.01 = 1.10 V
M? [log 3.919 = 0.593]
The reaction taking place in the Daniell cell is
Sol. (a)
 Cu(s) + Zn2+(aq)
Zn(s) + Cu2+(aq) 
(i) The alkalinity of the solution prevents the availability
of H+ ions. For this reaction, n = 2
(ii) Zinc is more electropositive than iron. Therefore, zinc Go = – nFE ocell
coating acts anode and the exposed iron portions act
= – 2 × 96500 C mol–1 × 1.10 V
ELECTROCHEMISTRY
133
= – 212300 CV mol–1 = 3.17 – 0.0295 × 7 = 3.17 – 0.21
= – 212300 J mol (1 CV = 1 J)
–1
Ecell = 2.96 V
= – 212.300 kJ mol –1
(c) (i) Mg | Mg2+ (0.1 M) || Ag+ (0.0001M) | Ag
Thus, the maximum work that can be obtained from the Daniel (ii) Yes, as the cell potential is positive.
cell = 212.3 kJ.
Example - 5
(ii) Go = – RT ln Kc = – 2.303 RT log Kc
–212300 = – 2.303 × 8.314 × 298 × log Kc A zinc rod is dipped in 0.1 M solution of ZnSO4. The salt is
95% dissociated at this dilution at 298 K. Calculate the
electrode potential  E Zn 2 / Zn  0.76 V  .
212300
or log K c   37.2074 o
2.303  8.314  298
Kc = Antilog 37.2074 = 1.6 ×1037 Sol. The electrode reaction written as reduction reaction is
Zn2+ + 2e–  Zn (n = 2)
Example - 4 Applying Nernst equation, we get

The following chemical reaction is occurring in an 0.0591 1


E Zn 2 / Zn  E oZn 2 / Zn  log
electrochemical cell. 2  Zn 2  

Mg(s) + 2 Ag+ (0.0001 M) 


 Mg2+ (0.10M) + 2Ag(s) As 0.1 M ZnSO4 solution is 95% dissociated, this means
that in the solution,
The E electrode values are
o

Mg2+ / Mg = – 2.36 V 95
 Zn 2     0.1M  0.095 M
100
Ag+ / Ag = 0.81 V
0.0591 1
For this cell calculate/write  E Zn 2 / Zn  0.76  log
2 0.095
(a) (i) Eo value for the electrode 2Ag+/2Ag.
= – 0.76 – 0.02955 (log 1000 – log 95)
(ii) Standard cell potential E ocell .
= – 0.76 – 0.02955 (3 – 1.9777)
(b) Cell potential (E)cell
= – 0.76 – 0.03021
(c) (i) Symbolic representation of the above cell.
= – 0.79021 V
(ii) Will the above cell reaction be spontaneous ?
Example - 6
Sol. (a) (i) E o
Ag  / Ag
 0.81V
Calculate the potential (emf) of the cell
(ii) E ocell  E cathode
o
 E anode
o Cd | Cd2+ (0.10 M) || H+ (0.20 M) | Pt, H2 (0.5 atm)
(Given Eo for Cd2+ / Cd = – 0.403 V, R = 8.14 JK–1 mol–1,
 EoAg / Ag  EoMg/ Mg2  0.81   2.36
F = 96,500 C mol–1).
E o
 3.17 V
cell
Sol. The cell reaction is
(b) At anode : Mg 
 Mg + 2e 2+ –
Cd + 2H+ (0.20 M)  Cd2+ (0.10 M) + H2 (0.5 atm)
A cathode : Ag+ + e– 
 Ag ]×2
E ocell  E oH  /1/ 2H  E Cd
o
2
/ Cd
 0 –(– 0.403) = 0.403 V
2
Mg + 2Ag+ 
 Mg2+ + 2Ag
Applying Nernst equation to the cell reaction,
0.059  Mg  2
Cd   PH2 2
Ecell = E ocell  log  2 E cell  E cell
o

2.303 RT
log 
n  Ag   nF  H  
2

0.059 0.1 2.303  8.314  298 0.1 0.5


 3.17  log  0.403  log
104   0.2 
2
2 2  96,500 2

= 3.17 – 0.0295 log 107 = 0.403 – 0.003 = 0.400 V


ELECTROCHEMISTRY
134
Example - 7 0.0591  Zn 2 
 0.36  log  2 
Represent the cell in which the following reaction takes place 2  Cd 
Mg(s) + 2Ag+ (0.0001 M)  Mg2+ (0.130 M) + 2 Ag(s)
0.0591  0.1 
 0.36  log   = 0.33V
Calculate its E(cell) if E
o
 cell  = 3.17 V.. 2  0.01 

Sol. The cell can be written as Mg | Mg2+ (0.130 M) || Ag+ (0.0001 Example - 9
M) | Ag (a) Depict the galvanic cell in which the following reaction
RT  Mg  2
2.303RT  Mg  2 takes place :
E  cell   Eocell  In   Eocell  log 
nF  2
 Ag  2F  Ag   Zn(s) + 2Ag+ (aq) 
 Zn2+(aq) + 2Ag(s)
0.059 V 0.130 Also indicate that in this cell
 3.17 V  log
 0.0001
2
2 (i) which electrode is negatively charged.
= 3.17 V – 0.21 V = 2.96 V (ii) what are the carrier of the current in the cell.

Example - 8 (iii) what is the individual reaction at each electrode.


(b) Write the Nernst equation and determine the e.m.f. of
(a) Explain why electrolysis of aqueous solution of NaCl
the following cell at 298 K:
gives H2 at cathode and Cl2 at anode. Write overall
reaction. Mg (s) | Mg2+ (0.001 M) || Cu2+ (0.0001 M) | Cu (s)

E
o o
o
= -2.71 V; E Ho 2 O / H 2 = - 0.83 V, (Given : E Mg 2 /Mg  2.375 V, E Cu 2 /Cu  0.34 V )
Na + / Na

E oCl
2 /2Cl
- = +1.36 V;E oH+ +O
2 / H2O
= 1.23 V  Sol. (a) Zn | Zn2+ (conc.) || Ag+ (conc) | Ag
(i) Zn electrode is negatively charged.
(b) Calculate the EMF of the cell of Zn / Zn (0.1 M) || Cd2+ 2+
(ii) Current carriers of cell are
(0.01 M) / Cd at 298 K,
- electrons in external wire
Given E o 2+ o
= -0.76 V and E Cd = -0.40V  - Zn2+ ions in anodic half cell.
 Zn / Zn 2+
/Cd 
- Ag+ ions in cathodic half cell.
Sol. (a) Because of higher reduction potential of water, water is
reduced in preference to sodium at therefore instead of - Ions of salt bridge, i.e., K+ and Cl–.
deposition of sodium metal, hydrogen is discharged at
 Zn 2  2e 
(iii) At anode Zn 
cathode.
H 2 O    2e  
 H 2 g   2OH  At cathode 2Ag   e  
 2Ag

2Cl  
 Cl2 g   Mg 2   2e 
(b) Mg 

H 2 O    2Cl 
 H 2 g   Cl 2 g   2OH  Cu 2   2e  
 Cu
At anode Cl2 gas is liberated because of overpotential of
oxygen. Mg  Cu 2  
 Cu  Mg 2 
Zn  Zn 2   2e  
 Half cell reactions
(b) Cd 2   2e  
 Cd  Nernst equation

0.059  Mg 2  
Zn + Cd2+  Zn2+ + Cd} cell reaction E cell  E o
 log
cell
n  Cu 2  

E ocell = E cathode
o
 E anode
o
= – 0.40 – (–0.76) = 0.36 V  Mg  

E cell  E o
Cu 2  / Cu
E o
Mg / Mg 2  
0.059
2
log
Cu 2  
0.0591
E=E o
cell  log Q
n
ELECTROCHEMISTRY
135
0.059 103 Ag2S(s) + 2e– 
 2Ag(s) + S2– is –0.71V
 0.34   2.375   log 4
2 10 and for Al3+ + 3e– 
 2Al(s) is – 1.66 V
= 0.34 + 2.375 – 0.0295 log 10
Sol. (a) E ocell  E co  E ao  0.403   0.763  0.360 V
Ecell = 2.6855 V
 nE o cell   2  0.360 
Example - 10 As log Kc =   
 0.059   0.059 
Calculate the equilibrium constant of the reaction
 0.720 
   12.20
Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s) E ocell  0.46 V  0.059 
Kc = antilog (12.20) = 1.585 × 1012
0.059
Sol. E
o
cell  log K c  0.46 V (b) M = Z I t
2
x
0.46  2 0.369   0.75  25  60
or log K c   15.6  K = Antilog 15.6 2  96500
0.059 c
(x = molar mass of copper) x = 63.5 g/mol
Kc = 3.92 × 1015
(c) E ocell for reaction of tarnished silver ware with aluminium
Example - 11
pan is (– 0.71 V) + 1.66 V i.e., + 0.95 V
Calculate the equilibrium constant, Kc for the reaction.
Tarnished silver ware, therefore, can be cleaned by
3Sn4+ + 2Cr 3Sn2+ + 2Cr3+
placing it in an aluminium pan as E ocell is positive.
Given Eo = 0.885 V.
Example - 13
0.059
Sol. E
o
cell  log K c , n  6 Two half cell reactions of an electrochemical cell are given
n
below :
0.059 MnO-4 aq  + 8H + aq  + 5e-  Mn 2+ aq  + 4H 2 O   ,
0.885  log K c
6
E o = 1.51V
6  0.885
log K c  Sn2+ (aq)  Sn4+ (aq) + 2e–, Eo = + 0.15 V
0.059
Construct the redox equation from the two half cell reactions
Kc = Antilog 90 = 1 × 1090 and predict if this reaction favours formation of reactants or
product shown in the quation
Sol. At cathode :
Example - 12
MnO 4  aq   8H   5e   Mn 2   aq   4H 2 O   ]  2
(a) Calculate the equilibrium constant for the reaction
Cd2+(aq) + Zn(s) 
 Zn2+(aq) + Cd(s) E o  1.51V
o
If E Cd 2 /Cd  0.403V  Sn 4   aq   2e  ]  5 Eo = + 0.15 V
At anode: Sn2+ 
Overall reaction :
E oZn 2 / Zn  0.763V
2MnO 4  aq   5Sn 2   aq   16H   aq  
 2Mn 2   aq 
(b) When a current of 0.75A is passed through a CuSO4
solution for 25 min, 0.369 g of copper is deposited at the + 5Sn4+(aq) + 8H2O   
cathode. Calculate the atomic mass of copper. o
ESn 4
/ Sn 2
  ESn
o
2
/ Sn 4
 0.15V
(c) Tarnished silver contains Ag2S. Can this tarnish be
removed by placing tarnished silver ware in an aluminium E ocell  E ocathode  E oanode  E oMnO / Mn 2  E Sn
o
4
/ Sn 2
4

pan containing an inert electrolytic solution such as = 1.51 – (– 0.15)


NaCl. The standard electrode potential for half reaction:
ELECTROCHEMISTRY
136
E ocell  1.66 V 2  4 Al + O2, Δ r G = + 966 kJ mol–1
Al2O3 
3 3
As E ocell is +ve therefore the reaction will take place in forward
direction, i.e., favours the formation of products. The potential difference needed for electrolytic reduction
of Al2O3 at 500ºC is at least
Example - 14
(a) 4.5 V (b) 3.0 V
Can nickel spatula be used to stir a copper sulphate solution? (c) 2.5 V (d) 5.0 V
Support your answer with a reason
Ans. (c)
E oNi2+ / Ni = -0.25 V, E oCu 2+ /Cu = +0.34 V. Sol. The ionic reaction are :
4 3+ 4
Sol. E ocell  E ocathode  E anode
o Al + 4e -  Al
3 3
E ocell  E Cu
o
2
/ Cu
 E oNi2 / Ni  0.34 V   0.25   0.59 V 2O2-  O2 + 4e-

As E ocell is +ve, G = – ve, because G = – nEo F, i.e, reaction Thus, no.of electrons transferred = 4 = n

will take place. Therefore, we cannot stir a copper sulphate G = -nFE = - 4×96500 ×E
solution with nickel spatula.
or 966×103 = - 4×96500× E
Example - 15 3
966×10
Given,  E=- = -2.5 V
4×96500
E oFe3+ / Fe = -0.336 V, E oFe 2+ /Fe = -0.439 V Example - 17

The value of standard electrode potential for the charge, The standard reduction potentials for Zn2+/Zn, Ni2+/Ni and
Fe3+ (aq) + e–  Fe2+(aq) will be Fe2+/Fe are – 0.76, –0.23 and – 0.44 V respectively. The

(a) –0.072 V (b) 0.385 V reaction X + Y+2 


 X+2 + Y will be spontaneous when
(c) 0.770 V (d) –0.270 V (a) X = Ni, Y = Fe (b) X = Ni, Y = Zn
Ans. (c) (c) X = Fe, Y = Zn (d) X = Zn, Y = Ni
Ans. (d)
Sol. Fe3+ +3e-  Fe ; E10 = -0.036 V
Sol. The element with high negative value of standard reduction
Fe 2+ +2e-  Fe ; E 2 = -0.439 V
0
potential are good reducing agents and can be easily
Required equation is oxidised .
Fe3+ + e-  Fe2+ ; E30 = ? Thus X should have high negative value of standard

Applying G = - nFE 0 potentinal than Y so that it will be oxidised to X 2+ by


reducing Y 2+ to Y
G 30 =G10 - G 02

 -n FE  =  -n FE  -  -n FE 
3
0
3 1
0
1 2
0
2
X = Zn , Y =Ni

E 30 = 3E10 - 2E 02 = 3 ×  -0.036  -2×  -0.439  Alternatively, for a spontaneous reaction E 0 must be


positive
E30 = -0.108+ 0.878 = 0.77 V
E 0 =E 0 reducedspecies -E 0 oxidised species
Example - 16
The Gibbs energy for the decomposition of Al2O3 at 500ºC = -0.23-  -0.76 
is as follows:
 E 0 = + 0.53V
ELECTROCHEMISTRY
137
Example - 18 Example-20
Explain Kohlrausch’s law of independent migration of ions. Give the relationship between equivalent and molar
Mention one application of Kohlrausch’s law. conductance ?
Sol. Kohlrausch’s law of independent migration of ions: The molar 1000 1000
conductivity of an electrolyte at infinite dilution is the sum Sol.  m    and  eq   
Molarity Normality
of the individual contributions of the anion and cation of
the electrolyte.  m Normality
  = n-factor
 eq Molarity
 0  v   0  v   0
Example - 21
where,  0 and  0 are the limiting molar conductivities of
the cation and anion respectively and v+ and v– are the The electrical resistance of a column of 0.05 mol L–1 NaOH
number of cations and anions formed from a formula unit solution of diameter 1 cm and length 50 cm is 5.55 × 103 ohm.
of the electrolyte. For example, one formula unit of Calculate its resistivity, conductivity and molar conductivity.
Al2(SO4)3 gives two Al3+ ions and three sulphate ions. Sol. A = r2 = 3.14 × 0.52 cm2 = 0.785 cm2 = 0.785 × 10–4 m2,
Therefore, l = 50 cm = 0.5 m
 om  Al2 (SO4  3  2 oAl3  3 SO
o
 RA 5.55  103   0.785
2
R or    

4
A 50 cm
Application : It can be used to determine molar conductivity = 87.135 cm
of weak electrolytes at infinite dilution :
1 1  1 1
Consider acetic acid as the example of a weak electrolyte. Conductivity =      S cm  0.01148 S cm
  87.135 
 om  CH3 COONa    oCH COO   oNa    1000
Molar conductivity,  m 
3

 o
 o
 o c
m  HCl  H Cl
0.01148 S cm 1  1000 cm3 L1
 = 229.6 S cm2 mol–1
 om  NaCl   oNa    Cl
o
 0.05 mol L1
From (i) + (ii) – (iii) we get Example - 22
 oCH COO   oNa    oH    oCl   oNa    oCl (a) State the relationship amongst cell constant of cell,
3

resistance of the solution in the cell and conductivity of the


  oCH COO   oH    oCH3 COOH
3 solution. How is molar conductivity of a solute related to
conductivity of its solution ?
Example - 19
(b) A voltaic cell is set up at 25oC with the following half-cells:
The conductivity of 0.0011028 mol L–1 acetic acid is
Al | Al3+ (0.001 M) and Ni | Ni2+ (0.50 M)
4.95 × 10 S cm . Calculate its dissociation constant if 
–5 –1 o
m
Calculate the cell voltage
for acetic acid is 390.5 S cm2 mol–1.
 E o +2 = -0.25 V, E o 3+ = -1.66 V 
 4.95  10 Scm 5
1000cm 1 3  Ni |Ni Al |Al 
Sol.  m   
c 0.0011028 mol L1 L 1  l 
Sol. (a)    
R A
= 44.88 S cm2 mol–1
where,   Conductivity
 m 44.88 Scm 2 mol 1
   0.115 1
 om 390.5 Scm 2 mol1 = Cell constant
A
0.0011028 mol L1   0.115
2
c 2 R = Resistance
K 
1    1  0.115 m 
  1000
= 1.65 × 10–5 mol L–1 M
where,  m = Molar conductivity
ELECTROCHEMISTRY
138
 = Conductivity Kc = Antilog 1.3536
M = Molarity of Solution Kc = 22.57
(b) At anode : Example - 24
Al  s  
 Al3  aq   3e ]  2
(a) Define the term molar conductivity. How is it related to
 Ni  s ]  3
At cathode : Ni2+ (aq) + 2e  conductivity of the related solution?
(b) One half-cell in a voltaic cell is constructed from a silver
2Al (s) + 3Ni (aq) 
2+  2Al (aq) + Ni(s)3+ wire dipped in silver nitrate solution of unknown
concentration. Its other half-cell consists of zinc
electrode dipping in 1.0 M solution of Zn(NO3)2. A voltage
2
0.0591  Al3  of 1.48 V is measured for this cell. Use this information to
E cell  E o
cell log  3 calculate the concentration of silver nitrate solution used.
n  Ni 2  
(EoZn 2 / Zn  0.76 V, E oAg2 /Ag  0.80 V)
Here, n = 6, [Al3+] = 0.001 M = 1 × 10–3 M, [Ni2+] = 0.5M
E ocell  1.41V Sol. (a) Molar conductivity   m  : It may be defined as the
conductivity of one molar electrolytic solution placed
103   1.41  0.0591 log 106
2
0.0591
E ocell  1.41V  log between two electrodes one centimetre apart and have
 0.5 
3
6 6 0.125
enough area of cross section to hold entire volume.
0.0591 0.0591 
 1.41  log 10 6  8   1.41   log106  log 23  m 
6 6 C
0.0591 0.0591
 1.41   6 log10  3log 2   1.41   6  3  0.3010  where,  = Conductivity
6 6
C = Concentration of solution in mol L–1
0.0591 0.3012
 1.41   5.097   1.41 
6 6  Zn 2   aq   2e 
(b) At anode : Zn  s  
= 1.41 + 0.0502 = 1.4602V
At cathode : Ag+(aq) + e– 
 Ag(s)] × 2
Ecell = 1.46 V
Zn(s) + 2Ag+ (aq) 
 Zn + 2Ag(s)
2+

Example - 23
0.0591 [Zn 2  ]
Calculate the equilibrium constant for the reaction. E cell  E o cell  log 2
n  Ag  
 Fe 2+ aq + Cd s
Fe s  + Cd 2+ aq   Here, n = 2, [Zn2+] = 1 M
  
Eocell = EAg / Ag  EZn/ Zn2  0.80V   0.76V
o o
(Given :E o Cd 2+ |Cd = -0.40 V, E oFe2+ |Fe - 0.44 V).
Eocell = 1.56 V
 Fe2+ + Cd
Sol. Fe(s) + Cd2+(aq)  (aq) (s)
0.0591 1
o
1.48  1.56  log 2
E 2  Ag  
log Kc  n cell

0.059
0.0591 1
Here, n = 2 0.08   log 2
2  Ag  
E ocell  E cathode
o
 E oanode
 E o Cd 2 / Cd  E o Fe/ Fe2 = – 0.4 – (– 0.44) 1 0.16
log 2
  2.7072
 Ag 
 0.0591
E ocell  0.04 V
2
2  0.04 0.08 log1  log  Ag    2.7072
log K c  
0.059 0.059 0  2 log  Ag    2.7072
log K c  1.3536
ELECTROCHEMISTRY
139
log  Ag    1.3536  2.6464 Gocell = – 6 × 96500 × – 4.37 V = + 2530.230 kJ/mol
Since r Go is positive, reaction is non-spontaneous.
 Ag   Anti log  2.6464   4.43  10 M
 2
Au3+/Au half cell will be a reducing agent, Ca2+/Ca half cell
will be an oxidising agent.
 Ag    0.044 M
1000
(b)  m   
Example - 25 molarity
 = Specific conductance
The measured resistance of a conductance cell containing
7.5 × 10–3 M solution of KCl at 25oC was 1005 ohms. Calculate 4  105 S / cm 1000
  40S cm2 mol1
(a) specific conductance (b) molar conductance of the 0.001
solution. Cell constant = 1.25 cm–1.
m 40
   0.103
1  om 390.5
Sol. Specific conductance      cell constant
R
C 2 0.001  0.103 
2

1 Kc    1.19  105
  1.25 cm 1  0.001244  1 cm 1 1  1  0.103
1005 
Example - 28
  1000
Molar conductance   m   (a) Define molar conductivity of a substance and describe
Molarity
how weak and strong electrolytes’ molar conductivity
0.001244  1 cm 1  1000 cm 3 L1
 changes with concentration of solute. How is such
7.5  103 mol L1
change explained ?
 165.87  1 cm 2 mol1 . (b) A voltaic cell is set up at 25 oC with the following half cells:
Example - 26 Ag+ (0.001 M) | Ag and Cu2+ (0.10 M) | Cu
What would be the voltage of this cell ?
 m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2
(Eocell = 0.46 V)
mol–1 respectively. Calculate  0m for HAc.
Sol. Molar Conductivity  m  : It may be defined as the
Sol.  0m HAc    Ho   oAc   Ho  oCl  oAc   oNa   Clo   oNa
        conductance of a solution containing 1 mole of electrolyte
such that the entire solution is placed in between two
  om  HCl   om NaAc   om NaCl
electrodes one centimetre apart.
= (425.9 + 91.0 – 126.4) S cm2 mol–1
= 390.5 S cm2 mol–1.
Example - 27
(a) Calculate the standard free energy change for the fol-
lowing reaction at 25oC.
Au(s) + Ca2+ (aq, 1M) 
 Au3+ (aq, 1M) + Ca(s)
E oAu 3 / Au  1.50 V, E Ca
o
2
/Ca
 2.87 V
Predict whether the reaction will be spontaneous or not
 1000
at 25oC. Which of the above two half cells will act as an  m   v or m 
oxidizing agent and which one will be a reducing agent? M
Molar conductivity increases with decrease in concentration
(b) The conductivity of 0.001 M acetic acid is 4 × 10–5 S/cm.
or increase in dilution as number of ions as well as mobility
Calculate the dissociation constant of acetic acid, if  om of ions increased with dilution.
for acetic acid is 390. 5 S cm2/mol. For strong electrolytes, the number of ions do not increase
Sol. (a) E o
= (– 2.87 V) – (1.50 V) = – 4.37 V appreciably on dilution and only mobility or ions increases
cell
ELECTROCHEMISTRY
140
due to decrease in interionic attractions. Therefore, (b) Write the reactions taking place at the anode and cathode
 m increases a little as shown in graph by a straight line. in the above cell if inert electrodes are used.
(c) Give reactions taking place at the two electrodes if these
For weak electrolytes, the number of ions as well as mobility
are made up of Ag.
of ions increases on dilution which results in a very large
increase in molar conducvity especially near infinite dilutuion Sol. (a) According to Faraday’s first law, charge required to
as shown by curve in the figure. deposit 1.50 g.

At anode :  Cu2+(aq) + 2e 
Cu(s)  96500
Ag   1.50  1340.27 coulombs
108
At cathode : 2Ag+(aq) + 2e  
 2Ag(s)
1340.27
Time taken   893.5s
1.50
Cu s   2Ag   aq  
 Cu 2   aq   2Ag s 
(b) Inert electrodes

Here, Anode:  O 2 g   4H   aq   4e 
2H 2 O   
Cu 2  
E cell  E o

0.0591
log  Ag  s 
Cathode : Ag+ (aq) + e– 
cell 2
n  Ag  
(c) Ag electrodes
Here, E ocell  0.46 V, n  2
Anode : Ag(s) 
 Ag+ (aq) + e–
[Ag+] = 0.001M = 1 × 10–3 M, [Cu2+] = 0.1 M
Cathode : Ag+ (aq) + e– 
 Ag(s)
0.0591 0.1
E cell  0.46  log
103  Example - 31
2
2
(a) State advantages of H2-O2 fuel cell over ordinary cell.
0.0591 0.0591
E cell  0.46  log 105  0.46  × 5 log 10 (b) Silver is electrodeposited on a metallic vessel of total
2 2
Ecell = 0.46 – 0.0591 × 2.5 × 1 = 0.46 – 0.14775 = 0.31225V surface area 500 cm2 by passing a current of 0.5 amp for
two hours. Calculate the thickness of silver deposited.
Ecell = 0.312 V [Given: Density of silver = 10.5 g cm–3, Atomic mass of
silver = 108 amu, F = 96500 C mol–1]
Example - 29
Sol. (a) Advantages Fuels Cells:
The highest electrical conductivity of the following
1. It is a pollution-free device since no harmful products
aqueous solutions is of
are formed.
(a) 0.1 M difluoroacetic acid
2. This is very efficient cell. Its efficiency is about 75%
(b) 0.1 M fluoroacetic acid which is considerably higher than conventional cells.
(c) 0.1 M chloroacetic acid 3. These cells are light in weight as compared to electrical
(d) 0.1 M acetic acid generators to produce corresponding quantity of power.
Ans. (a) 4. It is a continuous source of energy if the supply of
Sol. Higher the acidity, higher will be the tendency to release gases is maintained.
protons and hence lighter will be the electrical conductivity. (b) Mass of silver deposited
Difluoroacetic acid will be strongest acid due to electron m = z I t.
withdrawing effect of two fluorine atoms so as it will show
108
maximum electrical conductivity.   0.5  2  3600
96500
Example - 30 m = 4.029 g
(a) Current of 1.50 A was passed through an electrolytic cell m m
d v
containing AgNO3 solution with inert electrodes. The v d
weight of Ag deposited was 1.50g. How long did the current 4.029
flow ? V  0.3837 cm 3
10.5
ELECTROCHEMISTRY
141
Let the thickness of silver deposited be x cm. E
or W = ×Q
 V =A× x F
V W×F W×F
 x or Q = or Q =
A E A
0.3837 n
x (A= Atomic weight, n = valency of ion)
500
 x = 7.67 × 10–4 cm. n × w×F 3× 5.12×103 ×96500
or Q = = = 5.49×107 C
Example - 32 A 27
Example - 34
When during electrolysis of a solution of AgNO3, 9650 C
of charge pass through the electroplating bath, the mass A current of 10.0 A flows for 2.00 h through an electrolytic
of silver deposited on the cathode will be cell containing a molten salt of metal X. This result in the
(a) 1.08 g (b) 10.8 g decomposition of 0.250 mol of metal X at the cathode. The
oxidation state of X in the molten salt is: (F = 96, 500 C)
(c) 21.6 g (d) 108g
(a) + 1 (b) + 2
Ans. (b)
(c) + 3 (d) + 4
Sol. Given Q = 9650 C
Ans. (c)
From Faraday’s First law
Sol. t = 2 ×60×60 = 7200
W = ZQ Since (Z = E/F)
EQ E
w= ×I×t
W 96500
F
F = 96500 C 10×7200
n×0.25=
E = equivalent weight of Ag (108 g) 96500

The mass of silver deposited on the n=3

108×9650 Example - 35
cathode = =10.8g
96500 How many electrons would be required to deposit 6.35 g of
Example - 33 copper at the cathode during the electrolysis of an aqueous
solution of copper sulphate? (Atomic mass of copper = 63.5
Aluminium oxide may be electrolysed at 1000ºC to furnish u, NA = Avogadro’s constant):
aluminium metal (At. Mass = 27 amu; 1 Faraday = 96,500
Coulombs). The cathode reaction is– NA NA
(a) (b)
2 5
Al3+ + 3e–  Alº
NA NA
To prepare 5.12 kg of aluminium metal by this method we (c) (d)
require 10 20
Ans. (b)
(a) 5.49 × 101 C of electricity
(b) 5.49 × 104 C of electricity  Cu  s 
Sol. Cu 2+  2e 
(c) 1.83 × 107 C of electricity
63.5 g 2mol
(d) 5.49 × 107 C of electricity
63.5 g copper require = 2 mol electron
Ans. (d)
= 2 NA electron
st
Sol. From Faraday’s 1 law,, 2N A
1g copper ion require 
W = Z× Q (W = weight, Z = electrochemical equivalent, 63.5

Q = quantity of electricity) 2N A N
6.35 g copper ion require   6.35  A
63.5 5
Now E = Z × F (E = Equivalent weight, F = faraday)
ELECTROCHEMISTRY
142
Example - 36 Example - 38
Three iron sheets have been coated separately with three
o

The standard electrode potentials E M + /M  four metals metals A, B and C whose standards reduction potentials are
given below.
A, B, C and D are – 1.2 V, 0.6 V, 0.85 V and –0.76 V,
respectively. The sequence of deposition of metals on Metal A B C iron
applying potential is:
E oValue – 0.46 V –0.66V –0.20V –0.44V
(a) A, C, B, D (b) B, D, C, A
Identify in which case rusting will take place faster when
(c) C, B, D, A (d) D, A, B, C
coating is damaged.
Ans. (c)
Sol. As iron (–0.44V) has lower standard reduction potential than
Sol. Larger the standard reduction potential that deposit first C (– 0.20V) only therefore when coating is broken, rusting
sequence is as C > B > D > A will take place faster.

Example - 37 Example - 39

Give reasons for the following: (a) Corrosion is essentially an electrochemical phenomenon.
Explain the reactions occurring during corrosion of iron
(i) Rusting of iron is quicker in saline water than inordinary
kept in an open atmosphere.
water.
(b) Calculate the equilibrium constant for the equilibrium
(ii) Resistance of a conductivity cell filled with 0.1 M KCl
reaction.
solution is 100 ohm.If the resistance of the same
cell when filled with 0.02 M KCl solution is 520 ohms,  Fe 2  aq  Cd s
Fe s   Cd 2   aq     
calculate the conductivity and molar conductivity of
0.02 M KCl solution. (Given : E oCd 2 /Cd  0.40 V, E oFe2 / Fe  0.44V)
(Conductivity of 0.1 M KCl solution is 1.29 Sm–1). Sol. (a) At anode : Oxidation of Fe atoms takes place
Sol. (i) It is because in saline water, there is more H ions. Greater
+
Fe 
 Fe2+ + 2e– E o Fe2 / Fe  0.44 V
the number of H+ ions, quicker the rusting.
1 At cathode : Reduction of oxygen in the presence of H+
(ii)    cell constant ions. The H+ ions are produced by either H2O or H2CO3
R
 cell constant =  R (formed by dissolution of CO2 in moisture)

= 1.29 Sm–1 × 100 ohm 2H   aq   2e   


 2H

= 129 m–1 = 1.29 cm–1 1


2H  O 2   H 2O
For second solution 2 g 
1 Net reaction at cathodic area
  cell constant
R 1
2H   aq   O 2  2e  
 H 2O
1 2
  1.29  2.48  103 S cm 1
520 E o H / O  1.23 V
2 / H2 O
1000 The overall reaction
m 
M
1
Fe s   2H   aq   O 2 g  
 Fe 2   aq   H 2 O  
2.48 103 1000 248 2
 
0.02 2 E o cell  1.67 V
 m  124 S cm 2 mol 1 The ferrous ions are further oxidised by atmospheric oxygen
to ferric ions which come out as rust in the form of hydrated
ferric oxide (Fe2O3 . xH2O).
ELECTROCHEMISTRY
143
 Fe2+ (aq) + Cd(s)
(b) Fe(s) + Cd2+(aq)  Example - 43
Write the chemical equations for all the steps involved in the
E o cell
log Kc = n rusting of iron, Give any one method to prevent rusting of iron.
0.059
Here, n = 2  Fe 2   aq   2e  , E oFe
Sol. Anode: Fe  s    2
/ Fe
 0.44 V

E o cell  E o cathode — E o anode  


Cathode : O 2 g   4H  aq   4e 
 2H 2 O,
 E o Cd2 / Cd  E o Fe2 / Fe  40   0.44  E oH  / O
2 / H2 O
 1.23V
Eocell = 0.04V Overall reaction
2  0.04 0.08 Fe(s) 
 Fe2+(aq) + 2e– ] × 2
log K c  
0.059 0.059 O2(g) + 4H+ + 4e– 
 2H2O
log Kc = 1.3536
Kc = Antilog 1.3536 2Fe + O2 + 4H+(aq) 
 2Fe2+ + 2 H2O E ocell  1.67V
Kc = 22.57
Example - 40 Further 4Fe2+(aq) + O2(g) + 4H2O(l) 
 2Fe2O3 + 8H+(aq)
Fe 2 O3  xH 2 O 
 Fe 2 O3 .xH 2 O
Which type of a metal can be used in cathodic protection of Hydrated ferric oxide (Rust)
iron against rusting ?
Galvanisation is used to prevent rusting of iron.
Sol. A metal which is more electropositive than iron such as Al,
Example - 44
Zn, Mg can be used in cathode protection of iron against
rusting. Consider the following reaction at 1100ºC
o
Example - 41 (I) 2C + O2 
 2CO, ΔG = – 460 kJ mol
–1

o
Chromium metal can be plated out from an acidic solution (II) 2Zn + O2  2ZnO, ΔG = – 360 kJ mol
–1

containing CrO3 according to the following equation: Based on these, determine whether zinc oxide can be
reduced by carbon or not
CrO3(aq) + 6H+(aq) + 6e– Cr(s) + 3H2O
Sol. Yes
Calculate (i) how many grams of chromium will be plated out
1
by 24,000 coulombs and (ii) how long will it take to plate out ZnO  s   Zn  s  + O 2 ,ΔG=360 kJ mol
2
1.5 g of chromium by using 12.5 amp current ? (At. mass of
Cr = 52). 1
C  s  + O2  g   CO  g  ,ΔG=-460kJ mol
Sol. (i) 6 × 96, 500 coulomb deposit Cr = 1 mole = 52 g 2
ZnO  s  +C  s   Zn  s  +CO  g  ,ΔG=-100 kJ mol
52  24000
24,000 coulomb deposit Cr  g  2.1554 g Because net ΔG is-ve.
6  965000
Example - 45
(ii) 52 g of Cr is deposited by electricity = 6 × 96500 C
During the process of electrolytic refining of copper, some
6  96500 metals present as impurity settle as ‘anode mud’. These
1.5 g require electricity   1.5 C  16071C are
52
(a) Fe and Ni (b) Ag and Au
Time for which the current is required to be passed (c) Pb and Zn (d) Sn and Ag
Ans. (b)
16071.9 Sol. In electrolytic refining, the impure metal is made to act as
  1336s.
12.5 A anode. A strip of the same metal in pure form is used as
cathode.
Example - 42 Copper is refned by using electrolytic method.
Impurities blister copper deposit as anode mud which
What is galvanisation ? contains antimany selenium, tellurium, silver, gold and
Sol. The process of coating zinc over iron is called galvanisation. platinum.
ELECTROCHEMISTRY 144

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS


Electrochemical Cells occurs in the galvanic cell :
1. The standard reduction electrode potential values of the (a) Ag | AgCl(s) | KCl(sol) || AgNO3(sol) | Ag
element A, B and C are + 0.68, –2.50, and –0.50 V respectively. (b) Pt | H2(g) | HCl(sol) || AgNO3 (sol) | Ag
The order of their reducing power is :
(c) Pt | H2(g) | HCl (sol) || AgCl(s) | Ag
(a) A > B > C (b) A > C > B
(d) Pt | H2 (g) | KCl (sol) || AgCl(s) | Ag
(c) C > B > A (d) B > C > A
Electrode Potentials, Electrochemical Series and Its
2. A metal having negative reduction potential when dipped
Applications
in the solution of its own ions, has a tendency :
7. Four successive members of the first row transition
(a) to pass into the solution elements listed below with atomic numbers. Which one of
(b) to be deposited from the solution o
them is expected to have the highest E M3 / M2 value ?
(c) to become electrically positive
(a) Cr (Z = 24) (b) Mn (Z = 25)
(d) to remain neutral
(c) Fe (Z = 26) (d) Co (Z = 27)
3. The EM3 / M2 values for Cr, Mn, Fe and Co are – 0.41, + 1.57, 8. Zn can not displace following ions from their aqueous
+ 0.77 and + 1.97 V respectively. For which one of these solution :
+ 2+
metals the change in oxidation state from +2 to +3 is easiest? (a) Ag (b) Cu
2+ +
(a) Co (b) Mn (c) Fe (d) Na
(c) Fe (d) Cr 9. Which of the following displacement does not occur :
3+ 2+
4. An aqueous solution containing 1 M each of Au , Cu , +
(a) Zn + 2H  Zn + H2 
2+
+ +
Ag , Li is being electrolysed by using inert electrodes. The
+ 2+
value of standard potentials are : (b) Fe + 2Ag  Fe + 2Ag 
2+ 2+
EAg  /Ag = 0.80 V, ECu 2 /Cu = 0.34 V and (c) Cu + Fe  Cu + 2Fe 
2+ 2+
EAu 3 /Au = 1.50 V, ELi  /Li = – 3.03 V (d) Zn + Pb  Zn + Pb 

with increasing voltage, the sequence of deposition of metals 10. The position of some metals in the electrochemical series in
on the cathode will be : decreasing electropositive character is given as
Mg > Al > Zn > Cu > Ag. What will happen if a copper
(a) Li, Cu, Ag, Au (b) Cu, Ag, Au
spoon is used to stir a solution of aluminium nitrate ?
(c) Au, Ag, Cu (d) Au, Ag, Cu, Li
(a) The spoon will get coated with aluminium
5. Which of the following has been universally accepted as a
(b) An alloy of copper and aluminium is formed
reference electrode at all temperatures and has been
assigned a value of zero volt ? (c) The solution becomes blue
(a) platinum electrode (b) copper electrode (d) There is no reaction
(c) graphite electrode (d) standard hydrogen 11. Standard reduction electrode potentials of three metals A,
electrode B and C are + 0.5V, –3.0V and –1.2V respectively. The
6. The reaction reducing power of these metals are

1 (a) B > C > A (b) A > B > C


H 2  g   AgCl  s   H   aq   Cl   aq   Ag  s 
2 (c) C > B > A (d) A > C > B
ELECTROCHEMISTRY 145
Emf of a Galvanic Cell and Its Measurement  Zn2+(g) + 2e–
(b) Zn (g) 
12. The standard electrode potentials (reduction) of 2+ –
(c) Zn (g) + 2e 
 Zn
3+ 2+ 4+ 2+
Pt/Fe , Fe and Pt/Sn , Sn are + 0.77 V and 0.15 V 2+ –
respectively at 25°C. The standard EMF of the reaction (d) Zn (aq.) + 2e 
 Zn (s)
4+ 2+
Sn + 2Fe   Sn2+ + 2Fe3+ is Relationship Between Cell Potential and Gibbs’
(a) – 0.62 V (b) – 0.92 V Energy Change
(c) + 0.31 V (d) + 0.85 V 18. The standard free energy change for the following reaction
is – 210 kJ. What is the standard cell potential ?
13. Strongest reducing agent is :
2H2O2 (aq) 
 2H2O(l) + O2(g)
(a) K (b) Mg
(a) + 0.752 (b) + 1.09
(c) Al (d) I
(c) + 0.420 (d) + 0.640
14. The oxidation potential of Zn, Cu, Ag, H2 and Ni are 0.76,
19. Calculate the standard free energy change for the reaction,
–0.34, – 0.80, 0, 0.55 volt respectively. Which of the following + +
2 Ag + 2H  H2 + 2 Ag
reaction will provide maximum voltage ? + –
E° for Ag + e  Ag is 0.80 V
2+ 2+
(a) Zn + Cu 
 Cu + Zn (a) + 154.4 kJ (b) + 308.8 kJ
+ 2+ (c) –154.4 kJ (d) –308.8 kJ
(b) Zn + 2Ag 
 2Ag + Zn
20. The standard EMF of Daniell cell is 1.10 volt. The maximum
(c) H2 + Cu
2+

 2H + Cu + electrical work obtained from the Daniell cell is
(a) 212.3 kJ (b) 175.4 kJ
2+
(d) H2 + Ni  2H+ + Ni

(c) 106.15 kJ (d) 53.07 kJ
15. E° for the half cell reactions are as, 21. What is the free energy change for the half reaction
+ –
2+ –
(a) Zn  Zn + 2e ; E° = + 0.76 V Li + e  Li?
2+ – –1
(b) Fe  Fe + 2e ; E° = + 0.41 V Given E Li 
/ Li
 3.0V, F = 96500 C mol and T = 298 K.
–1 –1
The E° for half cell reaction, (a) 289.5 kJ mol (b) –298.5 kJ mol
–1 –1 –1
2+ 2+ (c) 32.166 CV mol (d) –289500 CV mol
Fe + Zn 
 Zn + Fe is :
22. The emf of Daniell cell is 1.1 volt. If the value of Faraday is
(a) – 0.35 V (b) + 0.35 V 96500 coulombs per mole, the change in free energy in kJ is
(c) + 1.17 V (d) – 0.17 V (a) 212.30 (b) –212.30
16. The standard electrode potential for the reaction (c) 106.15 (d) –106.15
23. When two half-cells of electrode potential of E1 and E2 are
+ –
Ag (aq) + e 
 Ag(s) combined to form a cell of electrode potential E3, then (when
n1, n2 and n3 are no. of electrons exchanged in first, second
2+ –
Sn (aq) + 2e 
 Sn(s) and combined half-cells) :
at 25°C are 0.80 volt and – 0.14 volt, respectively. The emf of E1 n 1  E 2 n 2
the cell. (a) E3 = E2 – E1 (b) E3 =
n3
2+ +
Sn | Sn (1 M) | | Ag (1M) | Ag is E1 n 1  E 2 n 2
(c) E3 = n 32 (d) E3 = E1 + E2
(a) 0.66 volt (b) 0.80 volt
(c) 1.08 volt (d) 0.94 volt 24. If E is 1.69 V and E is 1.40 V, then EAu /Au3
Au /Au Au3 /Au

17. The equation representing the process by which standard (a) 0.19 V (b) 2.945 V
reduction potential of zinc can be defined is :
2+ –
(c) 1.255 V (d) None of these
(a) Zn (s) + 2e 
 Zn
ELECTROCHEMISTRY 146
25. The reduction potential of hydrogen half-cell will be (c) reduction takes place at the anode
negative if
(d) reduction takes place at the cathode
+
(a) p(H2) = 1 atm and [H ] = 2.0 M 31. For a cell given below :
(b) p(H2) = 1 atm and [H+] = 1.0 M Ag | Ag+ || Cu2+ | Cu
(c) p(H2) = 2 atm and [H+] = 1.0 M
Ag+ + e– 
 Ag; Eº = x
(d) p(H2) = 2 atm and [H+] = 2.0 M
Cu2+ + 2e– 
 Cu; Eº = y
26. Which of the following reaction is possible at anode ?
(a) F2 + 2e–  2F– Eº cell is
(a) x + 2y (b) 2x + y
 1 
(b) 2H  O 2  2e  H 2 O (c) y – x (d) y – 2x
2
o
32. Consider the following E values :
(c) 2Cr 3  7H 2 O 
 Cr2 O72   14H   6e 
(d) None of these E oFe3 / Fe2   0.77V

27. For the redox reaction o


ESn 2
/ Sn
 0.14 V
Zn(s) + Cu2+ (0.1 M)  Zn2+ (1 M) + Cu (s) Under standard conditions the potential for the reaction

taking place in a cell, E ocell is 1.10V. E ocell for the cell will Sn(s) + 2Fe3+ (aq)  2Fe2+ (aq) + Sn2+ (aq) is
(a) 1.68 V (b) 1.40 V
 RT 
be  2.303  0.0591 (c) 0.91 V (d) 0.63 V
 F 
33. Which of the following represents the potential of silver
(a) 2.14 V (b) 1.80 V wire dipped in to 0.1 M AgNO3 solution at 25°C ?

(c) 1.07 V (d) 0.82 V (a) E°red (b) (E°red + 0.059)


(c) (E°ox – 0.059) (d) (E°red – 0.059)
28. The cell, Zn  Zn2+ (1M) Cu2+ (1M)  Cu (Eºcell = 1.10V) +
was allowed to be completely discharged at 298 K. The 34. The reduction electrode potential E, of 0.1 M solution of M
ions (E°RP = – 2.36 V) is :
 [ Zn 2  ] 
relative concentration of Zn 2+
to Cu , i.e., 
2+ 
2  is (a) – 2.41 (b) + 2.41
 [Cu ] 
(c) – 4.82 (d) None
(a) 9.65 × 104 (b) antilog (24.08)

(c) 37.3 (d) 1037.3 H 2 (Pt) H 3 O  (aq) Ag 


0 o
35. Consider the cell Ag. The measured
29. Given E Cr 3 / Cr  0.72 V, E Fe 2  / Fe  0.42 V. 1atm pH  5.5 x M

The potential for the cell EMF of the cell is 1.023 V. What is the value of x ?

Cr Cr3+ (0.1M)  Fe2+ (0.01M)  Fe is


E0
Ag  , Ag = + 0.799 V [T = 25°C]
(a) – 0.26 V (b) 0.26 V
–2 –3
(c) – 0.339 V (d) 0.336 V (a) 2 × 10 M (b) 2 × 10 M
30. Which of the following statement is wrong about galvanic (c) 1.5 × 10 M
–3
(d) 1.5 × 10 M
–2

cell ?
(a) cathode is positively charged
(b) anode is negatively charged
ELECTROCHEMISTRY 147
36. The emf of the cell 42. Adding powdered Pb and Fe to a solution containing 1.0 M
2+ 2+
+ 2+ is each of Pb and Fe ions would result into the formation
Ti | Ti (0.0001 M) | | Cu (0.01 M)/Cu is 0.83 V
of
The emf of this cell will be increased by : (a) More of Pb and Fe ions
2+

2+ 2+
(a) Increase the concentration of Cu ions (b) More of Fe and Pb ions
+
(b) Decreasing the concentration of Ti (c) More of Fe and Pb
2+ 2+
(c) Increasing the concentration of both (d) More of Fe and Pb ions

(d) (a) and (b) both 43. If the pressure of hydrogen gas is increased from 1 atm. to
100 atm., keeping the hydrogen ion concentration constant
37. The EMF of the cell at 1 M, the voltage of the hydrogen half-cell is at 25°C will
2+ 2+
Mg | Mg (0.01 M)| |Sn (0.1M)| Sn at 298 K is (Given be
EMg 2  2.34 V, ESn 2  0.14 V ) (a) 0.059 V (b) –0.059 V
/ Mg / Sn
(c) 0.295 V (d) 0.118 V.
(a) 2.17 V (b) 2.23 V + +
44. The emf of the cell H2(1 atm) Pt | H (a = x) | | H (a = 1) |
(c) 2.51 V (d) 2.45 V H2(1 atm) Pt at 25°C is 0.59 V. The pH of the solution is
38. In a cell that utilises the reaction (a) 1 (b) 4
+ 2+ (c) 7 (d) 10
Zn (s) + 2H (aq)  Zn (aq) + H2(g)
45. Given the data at 25ºC,
addition of H2SO4 to cathode compartment will
Ag + I–  AgI + e–; Eo = 0.152 V
(a) lower the E and shift equilibrium to the left
Ag  Ag+ + e–; Eo = – 0.800 V
(b) lower the E and shift the equilibrium to the right
What is the value of log Ksp for AgI ?
(c) increase the E and shift the equilibrium to the right

(d) increase the E and shift the equilibrium to the left  RT 


 2.303  0.059V 
 F 
39. What will be the emf for the given cell ?
+ +
Pt | H2 (g, P1) | H (aq) || H2 (g, P2) | Pt|H (aq) (a) – 8.12 (b) + 8.612

RT P1 RT P1 (c) – 37.83 (d) –16.13


(a) F ln P (b) 2F ln P
2 2
Concentration Cell and Electrolytic Cell
RT P2 2+ 2+
46. Co | Co (C2) || Co (C1) | Co for this cell, G is negative if :
(c) 2F ln P (d) None of these
1
(a) C2 > C1 (b) C1 > C2
40. The potential of the cell containing two hydrogen electrodes
(c) C1 = C2 (d) unpredictable
as represented below
+ –6 + –4
Pt, H2(g) | H (10 M) | |H (10 M)| H2(g), Pt at 298 K is 47. For the following cell with hydrogen electrodes at two
different pressure p1 and p2
(a) –0.118 V (b) –0.0591 V
(c) 0.118 V (d) 0.0591 V Pt (H 2 ) | H  (aq) | Pt (H 2 )
p1 1M p2
41. The hydrogen electrode is dipped in a solution of pH = 3 at
emf is given by
25°C. The potential of the cell would be (the value of 2.303
RT p
RT/F is 0.059 V) (a) RT log e p1 (b) log e 1
(a) 0.177 V (b) 0.087 V F p2 2F p2
(c) –0.177 V (d) 0.059 V RT p RT p
(c) log e 2 (d) log e 2
F p1 2F p1
ELECTROCHEMISTRY 148
48. Which reaction occur at cathode during electrolysis of fused Faraday’s Laws of Electrolysis
lead bromide ?
55. The electric charge for electrode deposition of one gram
equivalent of a substance is :
 Pb2+ + 2e–
(a) Pb  (b) Br + e 

 Br

(a) one amp/sec (b) 96,500 C/sec


– – 2+ –
(c) Br 
 Br + e (d) Pb + 2e 
 Pb (c) one amp/hour (d) 96,500 C
49. On electrolysing a solution of dilute H2SO4 between platinum 56. 13.5 g of Al get deposited when electricity is passed through
electrodes, the gas evolved at the anode is the solution of AlCl3. The number of faradays used are :
(a) SO2 (b) SO3 (a) 0.50 (b) 1.00
(c) O2 (d) H2 (c) 1.50 (d) 2.00
50. Reaction that takes place at graphite anode in dry cell is 20
57. An ion is reduced to the element when it absorbs 6 × 10
2+ –
(a) Zn + 2e  Zn(s) electrons. The number of equivalents of the ion is :
2+ –
(b) Zn(s)  Zn + 2e (a) 0.10 (b) 0.01
2+ –
(c) Mn + 2e  Mn(s) (c) 0.001 (d) 0.0001
+ –
(d) Mn(s)  Mn + e + 1.5 V.
58. Electrolysis can be used to determine atomic masses. A
Electrolysis and Its Applications current of 0.550 A deposits 0.55 g of a certain metal in 100
51. By the electrolysis of aqueous solution of CuSO 4, the minutes. Calculate the atomic mass of the metal if n = 3 :
products obtained at both the electrodes are (a) 100 (b) 45.0
(a) O2 at anode and H2 at cathode (c) 48.25 (d) 144.75
(b) H2 at anode and Cu at cathode 59. An electrolysis of a oxytungsten complex ion using 1.10 A
for 40 min produces 0.838 g of tungsten. What is the charge
(c) O2 at anode and Cu at cathode
of tungsten in the material ? (Atomic weight : W = 184)
(d) H2S2O8 at anode and O2 at cathode (a) 6 (b) 2
52. During the electrolysis of fused NaCl, the reaction that (c) 4 (d) 1
occurs at the anode is :
60. A current of 9.65 ampere is passed through the aqueous
(a) Chloride ions are oxidized solution NaCl using suitable electrodes for 1000 s. The
amount of NaOH formed during electrolysis is
(b) Chloride ions are reduced
(a) 2.0 g (b) 4.0 g
(c) Sodium ions are oxidized
(c) 6.0 g (d) 8.0 g
(d) Sodium ions are reduced
61. How many electrons are delivered at the cathode during
53. In electroplating the article to be electroplated is made :
electrolysis by a current of 1A in 60 seconds ?
(a) cathode 20 23
(a) 3.74 × 10 (b) 6.0 × 10
(b) anode
21 20
(c) either cathode or anode (c) 7.48 × 10 (d) 6.0 × 10

(d) simply suspended in the electrolytic bath. 62. The moles of electrons required to deposit 1 gm equivalent
54. A spoon to be electroplated with gold should be : aluminium (at. wt. = 27) from a solution of aluminium chloride
will be
(a) cathode (b) anode
(a) 3 (b) 1
(c) electrolyte (d) none of these
(c) 4 (d) 2
ELECTROCHEMISTRY 149
63. Time required to deposit one millimole of aluminium metal (c) electrochemical equivalent
by the passage of 9.65 amperes through aqueous solution
(d) one gram
of aluminium ion is :
71. Number of electrons involved in the electrodeposition of
(a) 30 s (b) 10 s
63.5 g of Cu from a solution of CuSO4 is :
(c) 30,000 s (d) 10,000 s 23 23
(a) 6.022 × 10 (b) 3.011 × 10
64. How many coulomb of electricity are consumed when 100 23 22
(c) 12.044 × 10 (d) 6.022 × 10
mA current is passed through a solution of AgNO3 for 30
minute during an electrolysis experiment? 72. When molten lithium chloride (LiCl) is electrolyzed, lithium
metal is formed at the cathode. If current efficiency is 75%
(a) 108 (b) 18000
then how many grams of lithium are liberated when 1930 C
(c) 180 (d) 3000 of charge pass through the cell : (Atomic weight : Li = 7)

65. A current of 9.65 amp. flowing for 10 minute deposits 3.0 g (a) 0.105 (b) 0.120
of a metal. The equivalent wt. of the metal is : (c) 0.28 (d) 0.240
(a) 10 (b) 30 73. The ratio of weights of hydrogen and magnesium deposited
by the same amount of electricity from aqueous H2SO4 and
(c) 50 (d) 96.5
fused MgSO4 are :
66. 108 g fairly concentrate solution of AgNO3 is electrolyzed
(a) 1 : 8 (b) 1 : 12
using 0.1 F of electricity. The weight of resulting solution is:
(c) 1 : 16 (d) None of these
(a) 94 g (b) 11.6 g
74. The weight of silver (eq. wt. = 108) displaced by the quantity
(c) 96.4 g (d) None of current which displaced 5600 mL of hydrogen at STP is :
67. When the same electric current is passed through the (a) 54 g (b) 108 g
solution of different elecrolytes in series the amounts of
elements deposited on the electrodes are in the ratio of their: (c) 5.4 g (d) None of these

(a) atomic number (b) atomic masses Conductance and Conductivity


(c) specific gravities (d) equivalent masses 75. Which of the following solutions of NaCl will have the
highest specific conductance ?
68. A current of 2 ampere was passed through solutions of
CuSO4 and AgNO3 in series. 0.635 g of copper was deposited. (a) 0.001 N (b) 0.1 N
Then the weight of silver deposited will be : (c) 0.01 N (d) 1.0 N
(a) 0.59 g (b) 3.24 g 76. The specific conductance of a salt of 0.01 M concentration
–4 1
(c) 1.08 g (d) 2.16 g is 1.061 × 10 S cm molar conductance of the same solution
will be :
69. The weight ratio of Al and Ag deposited using the same
–4
quantity of current is : (a) 1.061 × 10 (b) 1.061
(a) 9 : 108 (b) 2 : 12 (c) 10.61 (d) 106.1
–1
(c) 108 : 9 (d) 3 : 8 77. If x is specific resistance (in S cm) of the electrolyte solution
2 –1
70. When one coulomb of charge is passed through an and y is the molarity of the solution, then m (in S cm mol )
electrolytic solution for one sec, the mass deposited on the is given by :
electrode is equal to :
1000x 100y
(a) equivalent weight (a) y (b)
x
(b) molecular weight
1000 xy
(c) xy (d)
1000
ELECTROCHEMISTRY 150
–1
78. The conductivity of 0.1 N NaOH solution is 0.022 S cm .
Electrolyte : KCl KNO3 HCl NaOAc NaCl
When equal volume of 0.1 N HCl solution is added, the 84. 2 -1
conductivity of resultant solution decreases to ^ (S cm mol ) : 149.9 145 426.2 91 126.5
–1 2
0.0055 S-cm . The equivalent conductivity in S cm
–1 Calculate HOAc using appropriate molar conductances
equivalent of NaCl solution is
of the electrolytes listed above at infinite dilution in H2O
(a) 0.0055 (b) 0.11
at 25ºC
(c) 110 (d) none (a) 217.5 (b) 390.7
79. Conductivity (Seimen’s S) is directly proportional to area (c) 552.7 (d) 517.2
of the vessel and the concentration of the solution in it
85. The molar conductivities oNaOAc , and oHCl at infinite
and is inversely proportional to the length of the vessel,
then constant of proportionality is expressed in dilution in water at 25ºC are 91.0 and 426.2S cm2/mol

(a) S m mol–1 (b) S2 m2 mol–2 respectively. To calculate oHOAc , the additional value

(c) S m2 mol–1 (d) S2 m2 mol required is


(a) oNaOH (b) oNaCl
80. Resistance of a conductivity cell filled with a solution of
o
an electrolyte of concentration 0.1 M is 100. The (c)  H 2O (d) oKCl
–1
conductivity of this solution is 1.29S m . Resistance of 86. The equivalent conductances of two strong electrolytes
the same cell when filled with 0.02 M of the same solution at infinite dilution in H2O (where ions move freely through
is 520. The molar conductivity of 0.02 M solution of a solution) at 25ºC are given below :
electrolyte will be
oCH 3COONa = 91.0 S cm2/equiv..
(a) 1.24 × 10–4S m2 mol–1 (b) 12.4 × 10–4S m2 mol–1
(c) 124 × 10–4S m2 mol–1 (d) 1240 × 10–4S m2 mol–1 oHCl = 426.2 S cm2/equiv..
81. Resistance of 0.2 M solution of an electrolyte is 50. The
What additional information/quantity one needs to
specific conductance of the solution is 1.3 S m–1. If
calculate º of an aqueous solution of acetic acid ?
resistance of the 0.4M solution of the same electrolyte is
260, its molar conductivity is (a) º of chloroacetic acid (ClCH2COOH)

(a) 6250 S m2 mol–1 (b) 6.25 × 10–4S m2 mol–1 (b) º of NaCl

(c) 625 × 10–4S m2 mol–1 (d) 62.5 S m2 mol–1 (c) º of CH3COOK


 o
(d) The limiting equivalent conductance of H ( H  ).
82. Resistance of 0.2M solution of an electrolyte is 50 . The
specific conductance of the solution is 1.4S m–1. The Batteries and Fuel Cells
resistance of 0.5M solution of the same electrolyte is 280 . 87. When a lead storage battery is discharged
The molar conductivity of 0.5 M solution of the electrolyte
(a) PbSO4 is formed (b) Pb is formed
in S m2 mol–1 is :
(c) SO2 is consumed (d) H2SO4 is formed
(a) 5  10  3 (b) 5  103
88. As lead storage battery is charged
2 4
(c) 5  10 (d) 5  10 (a) lead dioxide dissolves
(b) sulphuric acid is regenerated
Kohlrausch’s Law and Its Applications
(c) lead electrode becomes coated with lead sulphate
83. The molar conductance at infinite dilution of AgNO3, AgCl
and NaCl are 116.5, 121.6 and 110.3 respectively. The molar (d) the concentration of sulphuric acid decreases.
conductances of NaNO3 is :
(a) 111.4 (b) 105.2
(c) 130.6 (d) 150.2
ELECTROCHEMISTRY 151
89. A fuel cell is : 94. How much electric charge is required to oxidise 1 mole of
H2O to O2?
(a) The voltaic cells in which continuous supply of fuels are
send at anode to give oxidation 95. The equivalent conductivity of 0.1 N CH3COOH at 25°C is
80 and at infinite dilution 400. The degree of dissociation of
(b) The votalic cell in which fuels such as : CH4, H2, CO are CH3COOH is
used up at anode
96. At infinite dilution, the eq. conductances of CH3COONa,
2
(c) It involves the reactions of H2 – O2 fuel cell such as : HCl and CH3COOH are 91, 426 and 391 mho cm respectively

at 25°C, The eq. conductance of NaCl at infinite dilution will
Anode : 2H2 + 4OH 
 4H2O(l) + 4e be :

Cathode : O2 + 2H2O(l) + 4e 
 4OH 97. The limiting molar conductivities  0 for NaCl, KBr and

(d) All of the above KCl are 126, 152 and 150 S cm2 mol–1 respectively, The  0
for NaBr is
90. In a hydrogen-oxygen fuel cell, combustion of hydrogen –1 2 –1
occurs to 98. Molar conductance of 0.1 M acetic acid is 7 ohm cm mol .
If the molar conductance of acetic acid at infinite dilution is
(a) generate heat –1 2 –1
380.8 ohm cm mol , the value of dissociation constant
(b) create potential difference between the two electrodes will be
(c) produce high purity water
99. The specific conductivity of a saturated solution of AgCl is
(d) remove adsorbed oxygen from electrode surfaces.
–6 –1 –1  –1 2 –1
3.40 × 10 ohm cm at 25 °C. If  Ag = 62.3 ohm cm mol
Numerical Value Type Questions
 –1 2 –1
91. Three faradays of electricity was passed through an aqueous &  Cl = 67.7 ohm cm mol , the solubility of AgCl at 25°C
solution of iron (II) bromide. The mass of iron metal (at. is :
mass 56) deposited at the cathode is -
100. How many minutes will it take to plate out 0.50 g of Cr from
92. The specific conductance of a N/10 KCl at 25°C is 0.0112 a Cr2(SO4)3 solution using a current of 1.50 A ? (Atomic
–1 –1
ohm cm . The resistance of cell containing solution at the weight : Cr = 52.0)
same temperature was found to be 55 ohms. The cell constant
will be
93. Resistance of 0.1 M KCl solution in a conductance cell is
–1
300 ohm and conductivity is 0.013 Scm . The value of cell
constant is :
ELECTROCHEMISTRY 152

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS


1. The equivalent conductance of NaCl at concentration C 7. Identify the correct statement : (Online 2016 Set - 2)
and at infinite dilution are  C and   respectively. The (a) Iron corrodes in oxygen-free water.
correct relationship between  C and   is given is (b) Iron corrodes more rapidly in salt water because its
electrochemical potential is higher.
(where the constant B is positive) (2014)
(c) Corrosion of iron can be minimized by forming a contact
(a)  C     (B)C (b)  C     (B)C with another metal with a higher reduction potential.
(d) Corrosion of iron can be minimized by forming an
(c) C     (B) C (d)  C    (B) C impermeable barrier at its surface.
2. Two Faraday of electricity is passed through a solution of 8. Given,
CuSO4. The mass of copper deposited at the cathode is :
E oCl   1.36 V, E oCr 3 /Cr  0.74 V
(at. mass of Cu =63.5 amu) (2015) 2 /Cl

(a) 2g (b) l27g E oCr O2 /Cr3  1.33 V, E oMnO / Mn 2  1.51 V


2 7 4
(c) 0 g (d) 63.5 g
Among the following, the strongest reducing agent is
3. At 298 K, the standard reduction potentials are 1.51 V for
(2017)
MnO 4 |Mn2+, 1.36 V for Cl2| Cl, 1.07 V for Br2|Br–, and 0.54
V for I2|I. At pH = 3, permanganate is expected to oxidize : (a) Cr (b) Mn 2
 RT  (c) Cr 3 (d) Cl–
  0.059 V  (Online 2015 Set - 1)
 F  9. What is the standard reduction potential (E°) for
 
(a) Cl , Br and I  
(b) Br and I  Fe3+  Fe ?
(c) Cland Br (d) Ionly Given that (Online 2017 Set - 1)
4. Galvanization is applying a coating of : (2016)
Fe 2   2e   Fe; Eo  0.47 V
(a) Cr (b) Cu Fe2 /Fe

(c) Zn (d) Pb
Fe3  e   Fe 2  ; Eo  0.77 V
5. What will happen if a block of copper metal is dropped into Fe3 /Fe2 
a beaker containing a solution of 1M ZnSO4 ? (a) – 0.057 V (b) + 0.057 V
(Online 2016 Set - 1) (c) + 0.030 V (d) – 0.30 V
(a) The copper metal will dissolve and zinc metal will be 10. To find the standard potential of M3+/M electrode, the
deposited. following cell is constituted :
(b) The copper metal will dissolve with evolution of Pt/M/M3+ (0.001 mol L–1)/Ag+ (0.01 mol L–1)/Ag
hydrogen gas.
The emf of the cell is found to be 0.421 volt at 298 K. The
(c) The copper metal will dissolve with evolution of oxygen standard potential of half reaction M3+ + 3e–  M at 298 K
gas. will be : (Online 2017 Set - 2)
(d) No reaction will occur.
 o 
6. Oxidation of succinate ion produces ethylene and carbon  Given E Ag /Ag at 298 K = 0.80 Volt 
 
dioxide gases. On passing 0.2 Faraday electricity through
an aqueous solution of potassium succinate, the total (a) 0.38 Volt (b) 0.32 Volt
volume of gases (at both cathode and anode) at STP (1 atm (c) 1.28 Volt (d) 0.66 Volt
and 273 K) is : (Online 2016 Set - 2)
11. How long (apporoximate) should water be electrolysed by
(a) 2.24 L (b) 4.48 L passing through 100 amperes current so that the oxygen
(c) 6.72 L (d) 8.96 L released can completely burn 27.66 g of diborane ? (Atomic
weight of B = 10.8u) (2018)
(a) 3.2 hours (b) 1.6 hours
(c) 6.4 hours (d) 0.8 hours
ELECTROCHEMISTRY 153
12. When an electric current is passed through acidified water, 17. Given :
112 mL of hydrogen gas at N.T.P. was collected at the
cathode in 965 seconds. The current passed, in ampere, is: Co 3  e   Co 2  ; E 0  1.81V
(Online 2018 Set - 1)
Pb 4   2e  Pb 2  ; E 0  1.67V
(a) 1.0 (b) 0.5
(c) 0.1 (d) 2.0 Ce 4   e   Ce3 ; E 0  1.61V
13. When 9.65 ampere current was passed for 1.0 hour into Bi 3   3e   B i; E 0  0.2V
nitrobenzene in acidic medium, the amount of
p-aminophenol produced is : (Online 2018 Set - 3) Oxidizing power of the species will increase in the order

(a) 9.81 g (b) 10.9 g (2019-04-12/Shift-1)

(c) 98.1 g (d) 109.0 g (a) Ce4   Pb3  Bi3  Co3


14. The standard Gibbs energy for the given cell reaction in (b) Co3  Pb4  Ce4  Bi3
1
kJ mol at 298 K is:
(c) Bi3  Ce4  Pb4  Co3
Zn(s)  Cu 2  (aq)  Zn 2  (aq)  Cu(s), E 0  2 V at 298 K
(d) Co3  Ce4   Bi3  Pb 4 
[Faraday’s constant F = 96000 C mol1 ] 18. The anodic half-cell of lead-acid battery is recharged using
(2019-04-09/Shift-1) electricity of 0.05 Faraday. The amount of PbSO4
(a) -192 (b) 384 electrolyzed in g during the process is:
(c) -384 (d) 192 (Molar mass of PbSO4 = 303 g mol1 )
15. A solution of Ni  NO3 2 is electrolysed between platinum (2019-01-09/Shift-1)
electrodes using 0.1 Faraday electricity. How many mole of (a) 22.8 (b) 15.2
Ni will be deposited at the cathode? (c) 7.6 (d) 11.4
(2019-04-09/Shift-2) 19. If the standard electrode potential for a cell is 2 V at 300 K,
(a) 0.20 (b) 0.05 the equilibrium constant (K) for the reaction
(c). 0.10 (d) 0.15  Zn 2  (aq)  Cu(s)
Zn(s)  Cu 2  (aq) 
16. Which one of the following graphs between molar
At 300 K is approximately
conductivity (  m ) versus C is correct?
(2019-04-10/Shift-1)  R  8 JK 1
mol1 , F  96500 C mol1 
(2019-01-09/Shift-2)
(a) e80 (b) e 160

(c) e320 (d) e160


(a) (b) 20. Consider the following
Zn 2   2e   Zn(s); E 0  0.76 V

Ca 2   2e   Ca(s); E 0  2.87V

Mg 2   2e   Mg(s); E 0  2.36V

Ni 2   2e   Ni(s); E 0  0.25V
(c) (d) The reducing power of the metals increases in the order
(2019-01-10/Shift-1)
(a) Ca  Zn  Mg  Ni (b) Ni  Zn  Mg  Ca

(c) Zn  Mg  Ni  Ca (d) Ca  Mg  Zn  Ni
ELECTROCHEMISTRY 154
21. In the cell BaSO4, respectively, at a temperature T. Which of the
following is false ? (2020-09-30/Shift-1)
Pt(s) | H 2 (g,1bar) | HCl(aq) | AgCl | Ag(s) | Pt(s)
(a) C NaCl (T2 )  C NaCl (T1 ) for T2  T1
the cell potential is 0.92 V when a 106 molal HCl solution is
(b) CBaSO4 (T2 )  CBaSO4 (T1 ) for T2  T1
used. The standard electrode potential of (Ag / AgCl)
electrode is : (2019-01-10/Shift-2) (c) Ionic mobilities of ions from both salts increase with T.
(d) CNaCl << CBaSO4 at a given T
 2.303RT 
Given,  0.06V at 298K  26.
 F 
(a) 0.94 V (b) 0.76 V
(c) 0.40 V (d) 0.20 V
22. For the cell

Zn(s) | Zn 2  (aq) || M x  (aq) | M(s) , different half cells and


their standard electrode potentials are given below:
Mx+(aq)/M(s) Au3+(aq)/ Ag+(aq)/ Fe3+(aq)/ Fe2+(aq)/
Au(s) Ag(s) Fe2+(aq) Fe(s)
E oM x  / M /  V  1.40 0.80 0.77 –0.44

0
If E Zn 2  / Zn  0.76 V , which cathode will given a
maximum value of E 0cell per electron transferred?
(2019-01-11/Shift-1) Eo = + 0.34 V
Cu 2+ Cu
 3 2
(a) Ag / Ag (b) Fe / Fe
E o 2+ = -0.76 V
(c) Au 3 / Au (d) Fe2 / Fe Zn Zn

23. Given the equilibrium constant: Identify the incorrect statement form the options below for
K C of the reaction: the above cell: (2020-09-04/Shift-1)
(a) If Eext=1.1 V, no flow of e- or current occurs
 2
Cu(s)  2Ag (aq)  Cu (aq)  2Ag(s) is (b) If Eext> 1.1 V, Zn dissolves at Zn electrode and Cu deposits
15 0 at Cu electrode
10  10 calculate the E cell
of the reaction at 298 K
(c) If Eext> 1.1 V, e- flows from Cu to Zn
 RT  (d) If Eext< 1.1 V, Zn dissolves at anode and Cu deposits at
 2.303 F at 298K  0.059V  (2019-01-11/Shift-2)
cathode
 
(a) 0.04736 mV (b) 0.4736 mV 27. 250 mL of a waste solution obtained from the workshop of
a goldsmith contains 0.1 M AgNO3 and 0.1 M AuCl. The
(c) 0.4736 V (d) 0.04736 V
solution was electrolyzed at 2 V by passing a current of 1 A
24.  0m for NaCl, HCl and NaA are 126.4, 425.9 and 100.5 S for 15 minutes. The metal/metals electrodeposited will be:

cm2 mol1 , respectively. If the conductivity of 0.001 M HA  0 0 


 E Ag  /Ag  0.80 V, E Au  /Au  1.69 V 
is 5  10 5 S cm 1 , degree of dissociation of HA is :  

(2019-01-12/Shift-2) (2020-09-04/Shift-2)
(a) 0.50 (b) 0.25 (a) Silver and gold in proportion to their atomic weights
(c) 0.125 (d) 0.75 (b) Silver and gold in equal mass proportion
(c) only silver
25. Let C NaCl and CBaSO4 be the conductances (in S)
(d) only gold
measured for saturated aqueous solution of NaCl and
ELECTROCHEMISTRY 155
28. The variation of molar conductivity with concentration of 33. Compound A used as a strong oxidizing agent is amphoteric
an electrolyte (X) in aqueous solution is shown in the given in nature. It is the part of lead storage batteries. Compound
figure. A is: (2021-02-26/Shift-2)
(a) PbO2 (b) PbSO4
(c) Pb3O4 (d) PbO
Numerical Value Type Questions
34. The Gibbs energy change (in J) for the given reaction
at [Cu2+] = [Sn2+] = 1 M and 298 K is :

Cu(s)  Sn 2  (aq.)  Cu 2 (aq.)  Sn (s)


The electrolyte X is : (2020-09-05/Shift-2)  Eo  0.16V, E o 2  0.34V, 
(a) HCl (b) CH3COOH  S n 2 |Sn Cu |Cu 
 
(c) NaCl (d) KNO3  F  96500 C mol1 
 
29. For the Given Cell ; (2020-09-02/Shift-1)
35. For the disproportionation reaction
Cu  s  Cu 2   C1M  Cu 2   C2 M  Cu  s 
2Cu  (aq)  Cu(s)  Cu 2  (aq) , ln K (where K is the
Change in Gibbs energy  G  is negative, if : equilibrium constant) is ………… × 10–1.
(2020-09-06/Shift-2) (2020-09-02/Shift-2)
Given :
C1
(a) C2  2C1 (b) C2 
2 E0  0.16 V
Cu 2  /Cu 
(c) C1  2C2 (d) C1  C2 E0   0.52 V
o 2+ + Cu /Cu
30. Given that the standard potential; (E ) of Cu /Cu and Cu /
Cu are 0.34 V and 0.522 V respectively, the Eo of Cu2+/Cu+ is RT
 0.025)
: (2020-01-07/Shift-1) F
(a) +0.158 V (b) -0.158 V 36. The photoelectric current from Na (Work function, w0 =
(c) 0.182 V (d) -0.182 V 2.3 eV) is stopped by the output voltage of the cell Pt
(s) H2 (g, 1 Bar) HCl (aq. pH = 1) | AgCl (s) | Ag(s).
31. The equation that is incorrect is: (2020-01-07/Shift-2)
The pH of aq. HCl required to stop the photoelectric
(a)  0m NaBr   0m NaI  0m KBr  0m NaBr current from K (w0 = 2.25 eV), all other conditions
remaining the same, is ……….. × 10–2 (to the nearest
(b)  0m NaBr   0m NaCl   0m KBr   0m KCl integer). (2020-09-30/Shift-1)

(c)  0m KCl   0m NaCl   0m KBr   0m NaBr RT


Given, 2.303  0.06 V; Eo  0.22 V
F AgCl|Ag|Cl
(d)  0m H 2 O   0m HCl   0m NaOH   0m NaCl 37. An acidic solution of dichromate is electrolyzed for 8
32. Amongst the following, the form of water with lowest minutes using 2A current. As per the following equation
ionic conductance at 298 K is :
Cr2 O 72   14H   6e  
 2Cr 3  7H 2 O
(a) distilled water
(b) sea water The amount of Cr 3 obtained was 0.104 g. The
(c) saline water used for intra venous injection efficiency of the process (in %) is (Take : F = 96000 C,
(d) water from a well (2020-01-09/Shift-2) At. Mass of chromium = 52).
(2020-09-30/Shift-2)
ELECTROCHEMISTRY 156
38. An oxidation-reduction reaction in which 3 electrons are 43. Emf of the following cell at 298 K in V is x 102 .
transferred has a G 0 of 17.37 kJ mol–1 at 25ºC. The value
Zn | Zn 2   0.1M  || Ag   0.01M  | Ag
of E 0cell (in V) is …………… × 10 . –2

The value of x is _____. (Rounded off to the nearest integer)


(1 F = 96,500 C mol–1) (2020-09-05/Shift-1) o
Given: E Zn2 / Zn  0.76V;
39. Potassium chlorate is prepared by the electrolysis of KCl
in basic solution 2.303RT
 
E o Ag / Ag  0.80V;  0.059
6OH  Cl  ClO3  3H 2 O  6e  F

If only 60% of the current is utilized in the reaction, the time (2021-02-26/Shift-2)
(rounded to the nearest hour) required to produce 10g of 44. –3
A 5.0 m mol dm aqueous solution of KCl has a conductance
KClO3using a current of 2A is …………… of 0.55 mS when measured in a cell of cell constant
(Given : 1.3 cm–1. The molar conductivity of this solution is ____ m
F = 96,500 C mol-1; molar mass of KClO3 = 122g mol-1) Sm2 mol–1. (Round off to the Nearest integer).
(2020-09-06/Shift-1) (2021-03-16/Shift-2)
45. A KCl solution of conductivity 0.14 S m–1 shows a resistance
of 4.19  in a conductivity cell. If the same cell is filled
40. What will be the electrode potential for the given half cell
reaction at pH= 5? with HCl solution, the resistance drops to 1.03  . The
conductivity of the HCl solution is …… x 10–2 S m–1. (Round
2H 2 O  O 2  4H   4e  ; E  1.23V off to the Nearest integer).
(R=8.314 J mol–1K–1; temp.=298 K; oxygen under std. atm. (2021-03-17/Shift-2)
Pressure of 1bar.) (2020-01-08/Shift-1) 46. For the reaction
41. For an electrochemical cell
2Fe3  aq   2I   aq   2Fe2  aq   I2  s 
2 2
Sn  s  Sn  aq.,1M  Pb  aq.,1M  Pb  s  the magnitude of the standard molar free energy change,
2 (Round off to the nearest integer).
Sn 
the ratio  2    E oFe2 / Fe s  0.440V; E oFe3 / Fe s  0.036V 
 Pb   
 o 
when this cell attains equilibrium is ______. E
 I2 / 2I  0.539V; F  96500C 
Given (2021-03-18/Shift-1)
E 0
 0.14V; E 0 47. The molar conductivities at infinite dilution of barium
Sn 2 /Sn Pb2 / Pb
chloride, sulphuric acid and hydrochloric acid are 280, 860
2.303RT
 0.13V,  0.06V and 426 S cm2 mol–1 respectively. The molar conductivity
F at infinite dilution of barium sulphate is ….. S cm2 mol–1.
42. Copper reduces NO3– into NO and NO2 depending upon (Round off to the nearest integer).
the concentration of HNO3 in solution. (Assuming fixed (2021-03-18/Shift-2)
[Cu2+] and PNO  PNO ), the HNO3 concentration at which 48. Potassium chlorate is prepared by electrolysis of KCl in
2
basic solution as shown by following equation.
the thermodynamic tendency for reduction of NO3– into
NO and NO2 by copper is same is 10x M. The value of 2x is 6OH   Cl   ClO3  3H 2 O  6e 
….. (Rounded-off to the nearest integer)
A current of x A has to be passed for 10 h to produce
[Given, 10.0 g of potassium chlorate. The value of x is ____.
(Nearest integer)
E o Cu 2 / Cu  0.34V, E o NO  / NO  0.96V, E o NO  / NO
3 3 2
(Molar mass of KClO3 = 122.6 g mol–1, F = 96500 C)
(2021-07-20/Shift-2)
RT
 0.79V and at 298 K, (2.303) = 0.059]
F
(2021-02-25/Shift-2)
ELECTROCHEMISTRY 157
49. Assume a cell with the following reaction 55. Consider the following cell reaction:
9 9
 
Cu s   2Ag  110 3 M  Cu 2   0.250M   2Ag s  Cd s  +Hg 2SO 4s  + H 2 O l   CdSO 4 . H 2 Os  +2Hg  l
5 5
E ocell  2.97V The value of E 0cell is 4.315 V at 25oC. If H o  825.2 kJ
mol–1, the standard entropy change So in J K–1 is ____.
E cell for the above reaction is _____V..
(Nearest integer) [Given: Faraday constant
(Nearest integer)
= 96487 C mol–1] (2021-08-31/Shift-1)
[Given: log 2.5 = 0.3979, T = 298 K]
(2021-07-22/Shift-2) 56. If the conductivity of mercury at 0°C is 1.07  106 S m 1
50. Consider the cell at 25oC. and the resistance of a cell containing mercury is 0.243  ,

Zn | Zn 2   aq  , 1M  || Fe3  aq  , Fe2  aq  | Pt  s  then the cell constant of the cell is x  104 m 1 . The value
of x is ____. (Nearest integer) (2021-09-01/Shift-1)
The fraction of total iron present as Fe3+ ion at the cell
potential of 1.500 V is x × 10–2. 57. The magnitude of the change in oxidising power of the
The value of x is_____. (Nearest integer) MnO 4 / Mn 2  couple is x  104 V , If the H+ concentration
0 0
[Given: EFe3 / Fe2  0.77V, E Zn2 / Zn  0.76V is decreased from 1 M to 10 –4 M at 25°C. (Assume
(2021-07-25/Shift-1) concentration of MnO 4 and Mn2+ to be same on change in
51. The cell H+ concentration). The value of x is (rounded offf to the
Cu(s) | Cu2+(aq) (0.1 M) || Ag+ (aq) (0.01 M) | Ag(s) 2.303RT
nearest integer) [Given:  0.059 ]
the cell potential E = 0.3095 V F
For the cell (2021-02-24/Shift-2)
Cu(s) | Cu2+(aq) (0.01 M) || Ag+(aq) (0.001 M) | Ag(s) 58. Consider the following reaction
the cell potential = _____ x 10–2 V. (Round off the Nearest
integer). MnO 4  8H   5e   Mn 2  4H 2 O, E   1.51V
2.303 The quantity of electricity required in faraday to reduce
[Use:  0.059 ] (2021-07-27/Shift-2)
F five moles of MnO 4 is________.
52. The conductivity of a weak acid HA of concentration (2021-02-26/Shift-1)
0
0.00l mol L is 2.0 x 10 S cm . If  (HA) = 190 S cm
–1 –5 –1
m
2
59. Given below are two statements: (2021-08-26/Shift-1)
mol–1, the ionization constant (Ka) of HA is equal to Statement I : The limiting molar conductivity of KCl (strong
____ × 10–6. (Round off to the Nearest integer) electrolyte) is higher compared to that of CH3COOH (weak
(2021-07-27/Shift-1)
electrolyte).
53. For the galvanic cell,
Zn(s) + Cu2+(0.02 M)  Zn2+ (0.04 M) + Cu(s), Statement II : Molar conductivity decreases with decrease
in concentration of electrolyte.
E cell  ____ 102 V . (Nearest integer)
o o
In the light of the above statements, choose the most
[Use: E Cu / Cu 2  0.34V, E Zn / Zn2  0.76V,
appropriate answer from the options given below.
2.303RT (a) Statement I is true, but Statement II is false
 0.059V ] (2021-08-26/Shift-2)
F
(b) Statement I is false, but Statement II is true
54. The resistance of a conductivity cell with cell constant
1.14 cm–1, containing 0.001 M KCl at 298 K is 1500  . The (c) Both Statement I and Statement II are true
molar conductivity of 0.001 M KCl solution at 298 K in
(d) Both Statement I and Statement II are false
S cm2 mol–1 is ____. (Integer answer)
(2021-08-27/Shift-2)
ELECTROCHEMISTRY 158
Match the Following Choose the most appropriate answer from the options given
below: (2021-08-31/Shift-2)
Each question has two columns. Four options are (a) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii)
given representing matching of elements from (b) (a)-(iii), (b)-(i), (c)-(ii), (d)-(iv)
Column-I and Column-II. Only one of these four (c) (a)-(i), (b)-(iv), (c)-(iii), (d)-(ii)
options corresponds to a correct matching. For the (d) (a)-(ii), (b)-(i), (c)-(iii), (d)-(iv)
question, choose the option corresponding to the
correct matching.
60. Match List-I with List-II
List - I (parameter) List - II (unit)
(a) cell constant (i) S cm2 mol–1
(b) Molar conductivity (ii) Dimensionless
(c) Conductivity (iii) m–1
(d) Degree of dissociation (iv)  1m 1
ELECTROCHEMISTRY 159

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS


Objective Questions I [Only one correct option] (a) To allow the flow of cations from one solution to the
other
1. Which one of the following reaction occurs at the
cathode? (b) To allow the flow of anions from one solution to the
other
(a) 2OH–  H2O + O + 2e–
(c) To allow the electrons to flow from one solution to the
(b) Ag  Ag+ + e– other
(c) Fe2+  Fe3+ + e– (d) To maintain electrical neutrality of the two solutions.
(d) Cu2+ + 2e–  Cu 8. Eº of a cell aA + bB  cC + dD is
2. Reaction taking place at anode is
[a ] A [ b] B RT [C]c [ D]d
(a) ionisation (b) reduction (a) E + RT ln (b) E  ln
[c]C [d]D nF [A]a [B]b
(c) oxidation (d) hydrolysis
3. Which of the following reaction is possible at anode ? RT [C]C [D]D RT [a ]A [B]B
(c) E  ln (d) E  ln
(a) 2Cr3+ + 7H2O  Cr2 O 72 + 14H+ nF [A]A [B]B nF [ C] C [ d ] D

(b) F2  2F– 9. In the reaction :

(c) ½O2 + 2H+  H2O Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s)

(d) None of these the reduction half cell reaction is

4. The electrochemical cell stops working after some time (a) Cu + 2e–  Cu2+
because (b) Cu – 2e–  Cu2+
(a) Electrode potentials of both the electrodes become (c) Ag+ + e–  Ag
zero (d) Ag – e–  Ag+
(b) Electrode potentials of both the electrodes become 10. In the cell, Zn  Zn2+  Cu2+  Cu, the negative terminal
equal is
(c) One of the electrode is eaten away (a) Cu (b) Cu2+
(d) The reaction starts proceeding in opposite direction (c) Zn (d) Zn2+
5. Cell reaction for the cell 11. If a strip of copper metal is placed in a solution of ferrous
Zn | Zn2+ (1.0 M) || Cd2+ (1.0 M) | Cd is given by sulphate
(a) Cd  Cd2+ + 2e– (a) Copper will precipitate out
(b) Zn2+  Zn – 2e– (b) Iron will precipitate out
2+ 2+
(c) Cd + Zn  Zn + Cd (c) Copper and iron both will be dissolved
2+ 2+
(d) Zn + Cd  Zn + Cd. (d) No reaction will take place.
6. If the salt bridge is removed suddenly from a working 12. To a mixture containing pieces of zinc, copper and silver,
cell, the voltage 1 M H2SO4 was added. H2 gas was found to be evolved.
(a) increases Which of the metal/metals do you think has/have reacted ?
(b) decreases
o o
Given E Zn / Zn 2   0.76 V, E Cu 2  / Cu  0.34 V,
(c) drops to zero
(d) may increases or decrease depending upon cell
reaction. E oAg  / Ag  + 0.80 V..
7. Which one of the following is not a function of a salt
(a) All the metals (b) Only Zn
bridge ?
(c) Both Zn and Cu (d) Only Ag.
ELECTROCHEMISTRY 160
13. In a simple electrochemical cell, which is in standard state, (II) 2Hg2+ + 2e  Hg 22 ; Eº = 0.92 V
half cell reactions with their appropriate oxidation
potentials are (III) PbO2 + 4H+ + 2e   Pb2+ + 2H2O;
Pb (s) – 2e–  Pb2+ (aq) E0 = + 0.13 volt Eº = + 1.45 V
Based on the above, which one of the following
Ag (s) – e–  Ag+ (aq) E0 = – 0.80 volt
statements is correct ?
Which of the following reaction takes place ?
(a) Sn4+ is a stronger oxidising agent than Pb4+
(a) Pb2+ (aq) + 2 Ag (s)  2 Ag+ (aq) + Pb (s)
(b) Sn2+ is a stronger reducing agent than Hg22+
2+ +
(b) Pb (aq) + Ag (s)  Ag (aq) + Pb (s)
(c) Pb2+ is a stronger oxidising agent than Pb4+
+ 2+
(c) Ag (aq) + Pb (s)  Ag (s) + Pb (aq)
(d) Pb2+ is a stronger reducing agent than Sn2+
(d) 2 Ag (aq) + Pb (s)  2Ag (s) + Pb2+ (aq)
+
18. Electrode potentials (Eºred) of four elements, A, B, C, D are
14. The standard reduction potential values of the three
–1.36, –0.32, 0, –1.26V respectively. The decreasing
metallic cations X, Y and Z are 0.52, – 3.03 and – 1.18V
reactivity order of these elements is
respectively. The order of reducing power of the
corresponding metals is (a) A, D, B and C (b) C, B, D and A
(a) Y > Z > X (b) X > Y > Z (c) B, D, C and A (d) C, A, D and B

(c) Z > Y > X (d) Z > X > Y 19. An unknown metal M displaces nickel from nickel (II)
sulphate solution but does not displace manganese from
15. Electrode potential data are given below : manganese sulphate solution. Which order represents the
correct order of reducing power ?
Fe (aq
3
) e
 2
  Fe ( aq ) ; Eº = + 0.77V
(a) Mn > Ni > M (b) Ni > Mn > M
Al 3( aq

 3e 
 Al(s); Eº = – 1.66 V (c) Mn > M > Ni (d) M > Ni > Mn
)
20. The standard reduction potentials of four elements are
Br2 (aq) + 2e–  2Br–(aq); Eº = + 1.08 V given below. Which of the following will be the most
suitable reducing agent ?
Based on the data, the reducing power of Fe2+, Al and
I = – 3.04 V II = – 1.90V
Br– will increase in the order
III = 0 V IV = 1.90 V
(a) Br– < Fe2+ < Al (b) Fe2+ < Al < Br–
(a) III (b) II
– 2+ 2+ –
(c) Al < Br < Fe (d) Al < Fe < Br (c) I (d) IV
16. The standard reduction potentials at 298K for the 21. A gas X at 1 atm is bubbled through a solution containing
following half reactions are given against each a mixture of 1M Y– and 1 M Z – at 25ºC. If the reduction
Zn2+(aq) + 2e  Zn(s); – 0.762 V potential is Z > Y > X, then
(a) Y will oxidise X and not Z
Cr3+(aq) + 3e  Cr(s); – 0.740 V
(b) Y will oxidise X and not X
2H+(aq) + 2e  H2 (g); 0.00V
(c) Y will oxidise both X and Z
Fe3+(aq) + e  Fe2+(aq) ; 0.770 V (d) Y will reduce both X and Z
Which is the strongest reducing agent ? 22. Standard reduction electrode potentials of three metals A,
B and C are respectively – 0.5, – 3.0 V and – 1.2 V. The
(a) Zn(s) (b) Cs(s)
reducing powers these metals are
(c) H2 (g) (d) Fe3+(aq) (a) B > C > A (b) A > B > C
17. Standard potentials (Eº) for some half-reactions are given (c) C > B > A (d) A > C > B
below :
(I) Sn4+ + 2e   Sn2+ ; Eº = + 0.15 V
ELECTROCHEMISTRY 161
23. I2 and Br2 are added to a solution containing 1 M each (c) 2.173 cm–1 (d) 3.324 cm–1
of I– and Br– ions. Which of the following reaction will 30. The units of cell constant are
take place ? (Given : standard reduction potentials of I2 (a) –1 (b) –1 cm–1
and Br2 are 0.53 and 1.09 volts respectively)
(c) cm–1 (d)  cm.
(a) Iodine will reduce bromide ions
31. Conductance (unit Siemen’s S) is directly proportional to
(b) Bromine will reduce iodide ions area of the vessel and the concentration of the solution
(c) Iodide ions will reduce bromine in it and is inversely proportional to the length of the
(d) Bromide ions will reduce iodine. vessel, then the unit of constant of proportionality is
24. When the cell reaction attains a state of equilibrium, the (a) S m mol–1 (b) S m2mol–1
EMF of the cell is (c) S–2m2mol (d) S2m2 mol–2
(a) zero (b) positive 32. The unit of specific conductivity is
(c) negative (d) not definite.
(a) ohms cm–1 (b) ohms cm–2
25. The standard reduction potentials Eº for the half reactions
are as (c) ohms–1 cm (d) ohms–1 cm–1
Zn  Zn2+ + 2e– ; Eº = 0.76V 33. The cell constant of a given cell is 0.47 cm–1. The
Fe  Fe2+ + 2e– ; Eº = 0.41V resistance of a solution placed in this cell is measured
to be 31.6 ohm. The conductivity of the solution
The EMF for the cell reaction will be
(in Scm–1 where S has usual meaning) is
(a) – 0.3V (b) 0.35V
(c) 1.17V (d) –1.17V (a) 0.15 (b) 1.5
(c) 0.015 (d) 150
26. The standard reduction potential for Fe 2+ /Fe and
Sn2+/Sn electrodes are – 0.44 and – 0.14 volt respectively. 34. –1 m–1 is the unit of
For the cell reaction (a) Molar conductivity
Fe2+ + Sn  Fe + Sn2+ (b) Specific conductivity
(c) Equivalent conductivity
the standard emf will be
(d) Molar conductivity at inifinite dilution.
(a) + 0.30 V (b) – 0.58 V
35. The value of specific conductance is equal to the
(c) + 0.58 V (d) – 0.30 V conductance of the solution when
27. The emf of the cell (a) The cell constant is zero
2+ 3+ (b) The cell constant is one
Ni/Ni (1.0M)  Au (1.0M)/Au is [Eº for
2+ 3+ (c) The electrodes are made of copper
Ni /Ni = – 0.25V ; Eº for Au /Au = 1.5 V]
(a) + 1.25 V (b) +1.75V (d) The size of the vessel is very large

(c) – 1.25V (d) – 1.75 V 36. The unit of equivalent conductivity is


28. The standard EMF for the cell reaction, (a) ohm cm

Zn + Cu2+  Cu + Zn2+ is 1.1 volt at 25ºC. (b) ohm–1 cm+2 (g equivalent)–1

The EMF for the cell reaction, when 0.1M Cu2+ and 0.1 (c) ohm cm2 (g equivalent)

M Zn2+ solutions are used, at 25ºC is (d) S cm–2


(a) 1.10 V (b) 0.10 V 37. The conductance of 0.1 M HCl solution is greater than
that of 0.1 M NaCl. This is because
(c) –1.10 V (d) – 0.110 V
(a) HCl is more ionized than NaCl
29. The specific conductivity of N/10 KCl solution at 20ºC is
(b) HCl is an acid whereas NaCl solution is neutral
0.212 ohm–1 cm–1 and the resistance of the cell containing
this solution at 20ºC is 55 ohm. The cell constant is (c) H+ ions have greater mobility than Na+ ions

(a) 4.616 cm–1 (b) 11.66 cm–1 (d) Interionic forces in HCl are weaker than those in NaCl.
ELECTROCHEMISTRY 162
38. If 0.01 M solution of an electrolyte has a resistance of 40 45. Equivalent conductances of NaCl, HCl and CH3COONa at
ohms in a cell having a cell constant of 0.4 cm–1 then its infinite dilution are 126.45, 426.16 and 91 ohm–1 cm2
–1 2 –1
molar conductance in ohm cm mol will be
respectively. The equivalent conductance of CH3COOH
(a) 104 (b) 103 at infinite dilution would be
(c) 102 (d) 10–6 (a) 101.38 ohm–1cm2 (b) 253.62 ohm–1cm2
39. Specific conductance of 0.1 M sodium chloride solution
(c) 390.71 ohm–1cm2 (d) 678.90 ohm–1cm2
is 1.06 × 10–2 ohm–1 cm–1. Its molar conductance in
46. According to Kohlrausch law, the limiting value of molar
ohm–1 cm2 mol–1 is conductivity of an electrolyte, A2B is
(a) 1.06 × 102 (b) 1.06 × 103    
(a)  ( A  )   ( B ) (b)  ( A  )   ( B )
(c) 1.06 × 104 (d) 5.3 × 102
40. Which of the following is wrong about molar conductivity?  1   
(c) 2 ( A  )    (d) 2 ( A  )  ( B )
(a) The solution contains Avogadro’s number of 2 (B )
molecules of the electrolyte 47. The limiting conductivity of NaCl, KCl and KBr are 126.5,
2 –1
(b) It is the product of specific conductivity and volume 150.0 and 151.5 S cm eq , respectively. The limiting
– 2 –1
of solution in cc containing 1 mole of the electrolyte equivalent ionic conductance for Br is 78 Scm eq . The
+
limiting equivalent ionic conductance for Na ions would
(c) Its units are ohm–1 cm2 mol–1
be :
(d) Its value for 1 M NaCl solution is same as that of 1M
(a) 128 (b) 125
glucose solution.
(c) 49 (d) 50
41. The cell constant of a conductivity cell______.
48. The reference electrode is made by using
(a) Changes with change of concentration of electrolyte.
(b) Changes with change of concentration of electrolyte. (a) ZnCl2 (b) CuSO4
(c) Changes with temperature of electrolyte. (c) HgCl2 (d) Hg2Cl2
(d) Remains constant for a cell 49. The standard hydrogen electrode potential is zero, because
42. The increase in the molar conductivity of HCl with dilution (a) there is no potential difference between the electrode
is due to and the solution
(a) increase in the self ionisation of water (b) hydrogen ions acquire electrons from a platinum
(b) hydrolysis of HCl electrode
(c) decrease in the self ionisation of water (c) it has been measured accurately
(d) decrease in the interionic forces. (d) it has been defined that way
43. The increase in the value of molar conductivity of acetic 50. The number of coulombs required for the deposition of
acid with dilution is due to 107.870g of silver is
(a) decrease in interionic forces
(a) 96500 (b) 48250
(b) increase in degree of ionisation
(c) 193000 (d) 10000
(c) increase in self ionisation of water
(d) none of these 51. 96500 C of electricity liberates from CuSO4 solution
44. Molar ionic conductivities of a two-bivalent electrolytes (a) 63.5g of Cu (b) 31.75 g of Cu
x2+ and y2– are 57 and 73 respectively. The molar
(c) 96500 g of Cu (d) 100 g of Cu
conductivity of the solution formed by them will be
52. A 5 ampere current is passed through a solution of zinc
(a) 130 S cm2 mol–1 (b) 65 S cm2 mol–1 sulphate for 40 minutes. Find the amount of zinc deposited
(c) 260 S cm2 mol–1 (d) 187 S cm2 mol–1 at the cathode
(a) 40.65 g (b) 4.065 g
(c) 0.4065 g (d) 65.04 g
ELECTROCHEMISTRY 163

53. On passing a current of 1.0 ampere for 16 min and 5 sec (a) Oxidation of Cl ion
through one litre solution of CuCl2, all copper of the (b) Reduction of Na ion
+

solution was deposited at cathode. The strength of CuCl2 (c) Reduction of H2O
solution was (Molar mass of Cu = 63.5, Faraday constant
(d) Oxidation of H2O
= 96500 C mol–1).
62. Which one of the following reactions takes place at the
(a) 0.07 M (b) 0.2 N anode when an aqueous solution of CuSO4 is electrolysed
(c) 0.005M (d) 0.02N using copper electrodes?
2+ –
54. In a solution of CuSO4 how much time will be required (a) Cu  Cu + 2e
to precipitate 2 g copper by 0.5 ampere current ?
(b) SO 24   SO 2  O 2  2e 
(a) 12157.48 sec (b) 102 sec
(c) 510 sec (d) 642 sec (c) 2SO 24   2H 2 O  2H 2SO 4  O 2  4e 
55. What is the amount of chlorine evolved when 2 amperes
of current is passed for 30 minutes in an aqueous solution (d) 2H 2 O  O 2  4H   4e 
of NaCl ? 63. Which of the following material is not present in mercury
(a) 66 g (b) 1.32 g cell ?
(c) 33 g (d) 99 g (a) HgO (b) KOH
56. When 9.65 coulombs of electricity is passed through a (c) Zinc (d) HgCl2.
solution of silver nitrate (atomic mass of
64. Which cell has a constant voltage throughout its life ?
Ag = 108 g mol–1), the amount of silver deposited is
(a) Leclanche cell (b) Electrolytic cell
(a) 16.2 mg (b) 21.2 mg
(c) 10.8 mg (d) 6.4 mg (c) Mercury cell (d) Daniell cell

57. The charge required to deposit 9 g of Al from Al3+ solution 65. Which of the following material is not present in a dry
is (At. wt. of Al = 27.0) cell ?

(a) 3216.3 C (b) 96500 C (a) MnO2 (b) NH4Cl


(c) 9650 C (d) 32163 C (c) ZnCl2 (d) KCl
58. By passing 0.1 Faraday of electricity through fused sodium 66. Which of the following cell is a secondary cell ?
chloride, the amount of chlorine liberated is (atomic mass (a) Mercury cell (b) Ni cell
of chlorine = 35.45 u)
(c) Dry cell (d) Fuel cell.
(a) 35.45 g (b) 70.9 g
67. When a lead storage battery is discharging, it acts as
(c) 3.545 g (d) 17.77 g
59. The electrolysis of silver nitrate solution is carried out using (a) a primary cell (b) an electrolytic cell
silver electrodes. Which of the following reaction occurs at (c) a galvanic cell (d) a concentration cell
the anode? 68. The electroplating with chromium is undertaken because
+ – + –
(a) Ag  Ag + e (b) Ag + e  Ag (a) Electrolysis of chromium is easier
+ – – –
(c) 2H2O  4H + O2 + 4e (d) 4 OH  2H2 + O2 + 4e (b) Chromium can form alloys with other metals
60. During electrolysis of a concentrated aqueous solution of (c) Chromium gives protective and decorative coating to
NaCl, what is the product at cathode? the base metal
(a) Na (b) Cl2 (d) Of the high reactivity of metallic chromium
(c) O2 (d) H2 69. Prevention of corrosion of iron by Zn coating is called
61. During the electrolysis of aqueous sodium chloride, the (a) Galvanization (b) Cathodic protection
cathodic reaction is (c) Electrolysis (d) Photoelectrolysis
ELECTROCHEMISTRY 164
70. The e.m.f. of a Daniell cell at 298K is E1 (a) Pb + SO 24 + 2 Ag+ (aq)  2 Ag (s) + PbSO4
ZnSO4 CuSO4 (b) PbSO4 + 2 Ag+ (aq)  Pb + SO 24 + 2 Ag (s)
Zn (0.01M) (1.0M) Cu
(c) Pb + SO 24 + Ag (s)  Ag+ (aq) + PbSO4
When the concentration of ZnSO4 is 1.0 M and that of
CuSO4 is 0.01 M, the e.m.f. changed to E2. What is the (d) PbSO4 + Ag (s)  Ag+ (aq) + Pb + SO 24 .
relationship between E1 and E2 ? 74. The standard potentials at 25ºC for the following half
reactions are given against them
(a) E1 < E2 (b) E1 = E2
Zn2+ + 2e–  Zn, Eº = – 0.762 V
(c) E2 = 0 E1 (d) E1 > E2
Mg2+ + 2e–  Mg, Eº = – 2.37 V
71. For the cell reaction,
When zinc dust is added to a solution of magnesium
Cu 2  [C1 ( aq ) ]  Zn ( s )   Zn  C 2 (aq)  Cu (s)
2
chloride
of an electrochemical cell, the change in free energy, G (a) No reaction will take place
at a given temperature is a function of (b) Zinc chloride is formed
(c) Zinc dissolves in the solution
 C2 
(a) ln (C1) (b) ln  C  (d) Magnesium is precipitated.
 1 
75. The relationship between standard reduction potential of
(c) ln (C1+ C2) (d) ln (C2) a cell and equilibrium constant is shown by
72. Which graph correctly correlates Ecell as a function of o n 0.059
o
concentrations for the cell (a) E cell  log K C (b) E cell  log K C
0.059 n
+ 2+
Zn(s) + 2Ag (aq) 
 Zn (aq) + 2Ag(s), log K C
o
E°cell = 1.56 V (c) E ocell  0.059 n log K C (d) E cell 
n
[Zn 2 ] 76. Eº for the cell,
Y-axis : Ecell, X-axis : log10 [Ag  ]
Zn  Zn2+(aq)  Cu2+(aq)  Cu is 1.10 V at 25ºC. The
equilibrium constant for the cell reaction
Zn + Cu2+(aq)  Cu + Zn2+(aq)

is of the order of
(a) (b)
(a) 10–37 (b) 1037
(c) 10–17 (d) 1017
77. For a cell reaction involving a two-electron change, the
standard e.m.f. of the cell is found to be 0.295V at 25ºC.
The equilibrium constant of the reaction at 25ºC will be
(a) 1 × 10–10 (b) 29.5 × 10–2
(c) (d)
(c) 10 (d) 1 × 1010
78. For the redox reaction :
73. The reduction potential of the two half cell reactions Zn (s) + Cu2+ (0.1M)  Zn2+ (1M) + Cu (s)
(occuring in an electrochemical cell) are
taking place in a cell, Eocell is 1.10 volt. Ecell for the cell

PbSO4 + 2e  Pb + SO 24 (Eº = – 0.31 V)
RT
 
+ – will be  2.303  0.0591
Ag (aq) + e  Ag (s) (Eº = 0.80 V)  F 
The feasible reaction will be (a) 2.14 volt (b) 1.80 volt
(c) 1.07 volt (d) 0.82 volt
ELECTROCHEMISTRY 165
79. Molar conductivity of a solution is 1.26 × 102 –1 cm2 (a) + 1 (b) + 2
–1
mol . Its molarity is 0.01. Its specific conductivity will be (c) + 3 (d) + 4

(a) 1.26 × 10–5 (b) 1.26 × 10–3 86. The quantity of electricity needed to deposit 127.08 g of
copper is
(c) 1.26 × 10–4 (d) 0.0063
(a) 1 Faraday (b) 4 Coulombs
80. The resistance of 0.1 N solution of a salt is found to be
(c) 4 Faraday (d) 1 Ampere
2.5 × 103 ohm. The equivalent conductance of the solution
87. Silver is monovalent and has atomic mass of 108. Copper
in Scm2/eq is (cell constant = 1.15 cm–1)
is divalent and has an atomic mass of 63.6. The same
(a) 4.6 (b) 5.6 electric current is passed for the same length of time
(c) 6.6 (d) 7.6 through a silver coulometer and a copper coulometer. If
81.
–6
The ionization constant of a weak electrolyte is 25 × 10 while 27.0 g of silver is deposited, then the corresponding
the equivalent conductance of its 0.01 M solution is 19.6 S amount of copper deposited is
2 –1
cm eq . The equivalent conductance of the electrolyte at (a) 63.60 g (b) 31.80 g
2 –1
infinite dilution (in S cm eq ) will be (c) 15.90 g (d) 7.95 g
(a) 250 (b) 196 88. Which one of the following reactions occurs at the anode
(c) 392 (d) 384 when CuSO 4 solution is electrolysed using platinum
82. The equivalent conductance at infinite dilution of a weak electrodes?
2+ –
acid such as HF (a) Cu  Cu + 2e
(a) can be determined by extrapolation of measurements
on dilute solutions of HCl, HBr and HI (b) 2SO 24   2H 2 O  2H 2SO 4  O 2  4e 
+ –
(b) can be determined by measurement on very dilute HF (c) 2H2O  O2 + 4H + 4e
solutions (d) SO 24   SO 2  O 2  2e 
(c) can be determined from measurements on dilute
89. The passage of current liberates H2 at cathode and Cl2 at
solutions of NaF, NaCl and HCl
anode. The solution is
(d) is an undefined quantity
(a) Copper chloride in water
83. Which one of the following represents a standard
hydrogen electrode correctly ? (b) NaCl in water
(a) Pt, H2 (1 atm) | H+ (1 M), 298 K (c) Ferric chloride in water

(b) Pt, H2 (1 atm) | H+ (0.1 M), 298 K (d) AuCl3 in water.


90. Which of the following reaction occurs at the anode during
(c) Pt, H2 (0.1 atm) | H+ (1 M), 273 K
the charging of lead storage battery ?
(d) Pt, H2 (0.1 atm) | H+ (0.1 M), 273 K.
(a) Pb2+ + 2e–  Pb
84. 1.08 g of pure silver was converted into silver nitrate and
(b) Pb2+ + SO 24  PbSO4
its solution was taken in a beaker. It was electrolysed
using platinum cathode and silver anode. 0.01 Faraday of (c) Pb  Pb2+ + 2e–
electricity was passed using 0.15 volt above the oxidation (d) PbSO4 + 2H2O  PbO2 + 4H+ + SO 24 + 2e–
potential of silver. The silver content of the beaker after
91. As lead storage battery is charged
the above shall be
(a) lead dioxide dissolves
(a) 0 g (b) 0.108g
(b) sulphuric acid is regenerated
(c) 0.108 g (d) 1.08 g
(c) lead electrode becomes coated with lead sulphate
85. A current of 2.0 A passed for 5 hours through a molten
(d) the concentration of sulphuric acid decreases
metal salt deposits 22.2 g of metal (At wt. = 177). The
oxidation state of the metal in the metal salt is
ELECTROCHEMISTRY 166
92. For the cell :- 96. Which one of the following statements is incorrect
regarding an electrochemical cell ?
2Ag + Pt2+  2Ag+ + Pt Eº = 0.4 volt
(a) The electrode on which oxidation takes place is called
2Ag + F2  2Ag+ + 2F– Eº = 2.07 volt anode.
If the potential for the reaction Pt  Pt2+ + 2e– is (b) Anode is a negative pole
assigned zero. Then (c) The direction of current is same as that of flow of
electrons
(a) E  Ag / Ag    0.4V (b) E  Ag  / Ag  0.4V
(d) The flow of current is partly due to flow of electrons
(c) E  F  1.67 V (d) E  F  2.74 V and partly due to flow of ions.
2 / F 2 / F
97. A calomel electrode is represented as Hg, Hg2Cl2,KCl. If
93. The variation of  m of acetic acid with concentration is in such a half cell
correctly represented by
(a) reduction takes place then Cl– ion concentration
increases
(b) oxidation takes place then Cl– ion concentration
decreases
(a) (b)
(c) the electrode reaction may be represented as

 2Hg (l ) + 2Cl– (aq)


Hg2Cl2(s) + 2e– 
(d) the electrode reaction taking place is

 Hg 22 (aq) + 2Cl– (aq)


Hg2Cl2(s) 

(c) (d) 98. Given that

E oNi 2  / Ni  0.25 V, E oCu 2  / Cu  0.34 V,

Objective Questions II E oAg  / Ag  0.80 V, E oZn 2  / Zn  0.76 V


[One or more than one correct option] Which of the following reactions under standard
conditions will not take place in the specified
94. Which of the following changes will increase the emf of directions?
cell ? (a) Ni2+ (aq) + Cu (s)  Ni (s) + Cu2+ (aq)
Co(s) | CoCl2 (M1) HCl (M2) | H2(g) (p1)| Pt(s) (b) Cu (s) + 2Ag+ (aq)  Cu2+ (aq) + 2Ag (s)
(a) increase volume of CoCl2 solution from 500 ml to (c) Cu (s) + 2H+ (aq)  Cu2+ (aq) + H2 (g)
1000 ml (d) Zn (s) + 2H+ (aq)  Zn2+ (aq) + H2(g)
(b) increase M2 from 0.1 to 0.5 M 99. Faraday’s law of electrolysis are not related to the

(c) decrease pressure of H2(g) from 0.2 to 0.1 atm (a) atomic number of cation
(b) atomic number of anion
(d) increase mass of cobalt electrode
(c) equivalent weight of the cation as well as anion
95. During the working of the cell, with the passage of time
(d) speed of cation
(a) spontaniety of the cell reaction decreases, E cell
decreases 100. If 9 g of H2O is electrolysed completely with 50% current
efficiency
(b) Q decreases, Ecell increases
(a) 1F of electricity will be needed
(c) Wuseful increases
(b) 2F of electricity is needed
(d) At equilibrium Q = Kc, Ecell = 0 (c) 5.6 L of O2 at STP will be formed
(d) 11.2 L of O2 will be formed at STP.
ELECTROCHEMISTRY 167
101. At an anode in an electrolytic cell where electrolysis is (C) If Assertion is true but Reason is false.
taking place, which of the following processes must occur? (D) If Assertion is false but Reason is true.
(a) Oxidation 108. Assertion (A) : If standard reduction potential for the
(b) Loss of electrons by anions reaction

(c) Formation of cations by anode Ag+ + e–  Ag is 0.80 volts then for the reaction

(d) Electron density is higher 3 Ag+ + 3 e–  3 Ag Eº = 2.4V


102. On passing electricity through an aqueous solution of Reason (R) : If concentration is increased, reduction
copper sulphate using copper electrodes then electrode potential is increased.

(a) copper is deposited at cathode (a) A (b) B


(c) C (d) D
(b) copper is dissolved at anode
109. Assertion (A) : We cannot add the electrode potentials in
(c) O2 is liberated at anode
order to get the cell potential if number of moles of electrons
(d) the concentration of the solution does not change exchanged are not same.
103. Iron tanks are protected from rusting by connecting them Reason (R) : Because the potentials are non thermodynamic
with magnesium wire. Which of the following statements properties.
(s) is/are correct ? (a) A (b) B
(a) Mg acts as anode and iron acts as cathode (c) C (d) D
(b) Moist soil acts as electrolyte 110. Assertion (A) : Increasing the concentration increases the
value of conductance.
(c) Corrosion prevention is electrochemical phenomenon
Reason (R) : Increasing the concentration increases
(d) Corrosion prevention is spontaneous phenomenon
interionic forces of attraction.
Numerical Value Type Questions (a) A (b) B
104. Find the strength of current that will liberate 5.60 L of O2 at (c) C (d) D

NTP from acidulated water in 3 h. 111. Assertion (A) : The correct order of equivalent conductance
at infinite dilution is KCl > NaCl > LiCl
105. How many amperes must be passed through a Down’s cell Reason (R) : KCl is stronger electrolyte than NaCl which is
3
to produce Na-metal at a rate of 30 kg/hr (in 10 ) ? stronger than LiCl.
(a) A (b) B
106. If a 500 mL brine is electrolyzed with a current of strength
(c) C (d) D
0.5 A, how many seconds would it take for the pH of solution
112. Assertion (A) : The voltage of mercury cell remains
to rise to a value of 9 ? constant for longer period of time.
107. A constant current of 30 A is passed through an aqueous Reason (R) : It is because net cell reaction does not involve
solution of NaCl for a time of 1.0 h. How many grams of any ion.
NaOH are produced ? (a) A (b) B
Assertion Reason (c) C (d) D
(A) If both Assertion and Reason are correct and
Reason is the correct explanation of Assertion.
(B) If both Assertion and Reason are true but
Reason is not the correct explanation of
Assertion.
ELECTROCHEMISTRY 168
Match the Following 115. When Ecell is 1.1591 volts. It implies,

Each question has two columns. Four options are [Cu 2  ] [ Zn 2  ]


(a)  0.01 (b)  0.01
given representing matching of elements from [ Zn 2  ] [Cu 2  ]
Column-I and Column-II. Only one of these four
[ Zn 2 ] [ Zn 2  ]
options corresponds to a correct matching, for (c)  0.1 (d) 1
[Cu 2  ] [Cu 2  ]
each question.
113. Column - I Column - II 116. When E cell is 1.1591 and concentration ratio is,
(A) Electrolytic cell (p) G = – ve [ Zn 2 ]
 10  2 it implies,
(B) Galvanic cell (q) G = + ve [Cu 2  ]
(C) Faraday’s First Law (r) Salt bridge (a) T = 273 ºC (b) T = 298 ºC
(D) Faraday’s Second Law (s) W = Z × I × t (c) T = 298 K (d) T = 300 K
W1 W2 117. The G for the process will be –ve if,
(t) E  E
1 2
[Cu 2  ] [ Zn 2  ]
114. Column - I Column - II (a)  10 2 (b)  10 3
[ Zn 2  ] [Cu 2  ]
(A) Charge on one mole (p) 1 F
of electrons [ Zn 2  ] [ Zn 2  ]
(c) 2
 10 (d) 2
 105
(B) 108g of silver (q) 96500 C [Cu ] [Cu ]
deposited at electrode Use the following passage, to solve Q. 118 to
from Q. 120
(C) 22.4L of hydrogen (r) 2 F Passage
at STP collected from
Electrochemical series is a series of elements arranged in
(D) 8g of oxygen collected (s) 5.6 L at STP o
increasing order of their reduction potential. E H  / H 2  0.
from
The metals above H have –ve reduction potential, they
Paragraph Type Questions
are more reactive than hydrogen whereas metals below
Use the following passage, to solve Q. 115 to hydrogen are less reactive than H. Reduction potential of
Q. 117 metal depends upon

Passage (i) sublimation energy

For the reaction (ii) ionisation energy and

Zn(s) + Cu2+ (aq)  Cu(s) + Zn2+ (aq) (iii) hydration energy of ions.
118. Which of the following is best oxidising agent ?
[ Zn 2  ]
Reaction Quotient = , variation of E with Q is (a) Cu2+ (b) Na+
[Cu 2 ] cell
given by (c) Ag+ (d) Al3+
(where Q = concentration quotient) 119. Which of the following is weakest reducing agent among
alkali metals in aqueous ?
(a) Na (b) K
(c) Rb (d) Cs
120. Which of the following cannot evolve H2 from dil. acid ?
(a) Pt (b) Zn
(c) Mg (d) Pb

0A = 1.10 volts, hence


ELECTROCHEMISTRY 169

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS


Objective Questions I [Only one correct option]
5. Zn | Zn2+ (a = 0.1 M) || Fe2+ (a = 0.01 M) | Fe.
1. Saturated solution of KNO3 is used to make ‘salt-bridge’
The emf of the above cell is 0.2905V. Equilibrium constant
because (2001)
for the cell reaction is (2004)
(a) velocity of K+ is greater than that of NO3
(a) 100.32/0.059 (b) 100.32/0.0295
(b) velocity of NO3 is greater than that of K+ (c) 100.26/0.0295 (d) 100.32/0.295
(c) velocities of both K+ and NO3 are nearly the same 6. The half cell reactions for rusting of iron are :
(d) KNO3 is highly soluble in water Cathode:
2. The correct order of equivalent conductance at infinite 1
2H aq   2e   O 2  g   H 2 O  l  ; E 0  1.23V
dilution of LiCl, NaCl and KCl is (2001) 2
(a) LiCl > NaCl > KCl (b) KCl > NaCl > LiCl Anode : Fe s   Fe aq2   2e  ; E 0  0.44V
(c) NaCl > KCl > LiCl (d) LiCl > KCl > NaCl The Gº (in kJ) for the reaction is (2005)
3. Standard electrode potential data are useful for (a) – 76 (b) – 322
understanding the suitability of an oxidant in a redox
(c) – 122 (d) – 176
titration. Some half-cell reactions and their standard
potentials are given below : 7. Electrolysis of dilute aqueous NaCl solution was carried
out by passing 10 milli ampere current. The time required
MnO 4 (aq)  8H  (aq)  5e  
 to liberate 0.01 mol of H2 gas at the cathode is

Mn 2  (aq)  4H 2 O(l ), E o  1.51 V (1 Faraday = 96500 C mol–1) (2008)

Cr2 O 72  (aq)  14H  (aq)  6e  


 (a) 9.65 × 104sec (b) 19.3 × 104sec

(c) 28.95 × 104sec (d) 38.6 × 104sec


2Cr 3 (aq)  7H 2 O(l ), E o  1.38 V
8. Consider the following cell reaction,
Fe3+ (aq) + e–  2+
 Fe (aq) Eo = 1.77V 2Fe(s)  O 2 (g)  4H  (aq) 
 2Fe2 (aq)  2H 2 O(l ),
Cl2 (g) + 2e–  –
 2Cl (aq) Eo = 1.40 V E o  1.67 V
At [Fe2+] = 10–3 M, P(O2) = 0.1 atm and pH =3, the cell
Identify the incorrect statement regarding the quantitative potential at 25ºC is (2011)
estimation of aqueous Fe (NO3)2 (2002) (a) 1.47 V (b) 1.77 V

(a) MnO 4
can be used in aqueous HCl (c) 1.87 V (d) 1.57 V
9. For the following electrochemical cells at 298K,
(b) Cr2 O72  can be used in aqueous HCl
Pt(s) | H 2 (g, 1bar) | H  (1M) || M 4 (aq), M2 (aq) | Pt(s)
(c) MnO 4 can be used in aqueous H2SO4
[M 2  (aq)]
E cell  0.092V w hen  10 X .
(d) Cr2 O72  can be used in aqueous H2SO4 [M 4  (aq)]
4. In the electrolytic cell, flow of electrons is from (2003) 0 RT
Given : E M 4  / M 2   0.151V; 2.303  0.059V
(a) cathode to anode in solution F
The value of x is (2016)
(b) cathode to anode through external supply
(a) –2 (b) –1
(c) cathode to anode through internal supply
(c) 1 (d) 2
(d) anode to cathode through internal supply.
ELECTROCHEMISTRY 170
10. For the following cell, (2017) (b) Stops the diffusion of ions from one electrode to another

Zn(s) | ZnSO 4 (aq) || CuSO 4 (aq) | Cu(s) (c) in necessary for the occurrence of the cell reaction.
(d) ensures mixing of the two electrolytic solutions.
When the concentration of Zn 2 is 10 times the concentration
14. Some standard electrode potentials at 298 K are given
2
of Cu , the expression for G (in J mol–1) is below: (2021)
[F is Faraday constant; R is gas contant; T is temperature; Pb2+/Pb  –0.13 V Ni2+/Ni  –0.24 V
Eº (cell) = 1.1 V] Cd2+/Cd  –0.40 V Fe2+/Fe  –0.44 V
(a) 2.303 RT + 1.1F (b) 1.1 F To a solution containing 0.001 M of X2+ and 0.1 M of Y2+,
(c) 2.303 RT – 2.2F (d) – 2.2 F the metal rods X and Y are inserted (at 298 K) and con-
nected by a conducting wire. This resulted in dissolution
11. Molar conductivity ( m ) of aqueous solution of sodium
of X. The correct combination(s) of X and Y, respectively,
stearate, which behaves as a strong electrolyte is recorded
is (are)
at varying concentrations (c) of sodium stearate. Which
one of the following plots provides the correct (Given: Gas constant, R = 8.314 J K–1 mol–1, Faraday con-
representation of micelle formation in the solution? (critical stant, F = 96500 C mol–1)
micelle concentration (CMC) is marked with an arrow in
(a) Cd and Ni (b) Cd and Fe
the figures) (2019)
(c) Ni and Pb (d) Ni and Fe
Numerical Value Type Questions
15. Find the equilibrium constant for the reaction
(a) (b)
 Cu+ + In3+
Cu2+ + In2+ 
Given
Eo  0.15V, E o 2  0.4V,
Cu 2 /Cu  In /In 

Eo 3  0.42 V (2004)
In /In 
(c) (d)
16. We have taken a saturated solution of AgBr, Ksp is
12 × 10–14. If 10–7 M of AgNO3 are added to 1L of this
Objective Questions II solution, find conductivity (specific conductance) of this
[One or more than one correct option] solution in terms of 10–7 Sm–1 units. (2006)
o 3 2 1
12. For the reduction of NO3 ion in an aqueous solution Eº Given  (Ag  )  6  10 Sm mol ,

is + 0.96V. Values of Eº for some metal ions are given  o(Br  )  8  10 3 Sm 2 mol1 ,
below
V2+ (aq) + 2e– 
 V Eº = – 1.19V  o( NO  )  7  10 3 Sm 2 mol 1.
3

3+ –
Fe (aq) + 3e 
 Fe Eº = – 0.04 V 17. For the electrochemical cell, (2018)
3+ –
Au (aq) + 3e 
 Au Eº = + 1.40 V
Mg(s) | Mg 2 (aq, 1M) || Cu 2 (aq, 1M) | Cu(s)
Hg2+ (aq) + 2e– 
 Hg Eº = + 0.86V
the standard emf of the cell is 2.70 V at 300 K. When the

The pair (s) of metals that is (are) oxidized by NO in 3 concentration of Mg 2+ is changed to x M, the cell
aqueous solution is (are) (2009) potential changes to 2.67 V at 300 K. The value of x is
............. .
(a) V and Hg (b) Hg and Fe
(c) Fe and Au (d) Fe and V F
(given, = 11500 K V–1, where F is the Faraday constant
13. In a galvanic cell, the salt bridge (2014) R
and R is the gas constant, ln (10) = 2.30)
(a) does not participate chemically in the cell reaction.
ELECTROCHEMISTRY 171
18. Consider an electrochemical cell : (2018) 21. 2Ag+ + C6H12O6 + H2O  2Ag (s) + C6H12O7 + 2H+
A(s) | A n  (aq, 2M) || B2n  (aq, 1M) | B(s). Find ln K of this reaction
(a) 66.13 (b) 58.38
The value of H o for the cell reaction is twice of G o at
(c) 28.30 (d) 46.29
300K. If the emf of the cell is zero,the So (in JK–1mol–1)
22. When ammonia is added to the solution, pH is raised to
of the cell reaction per mole of B formed at 300 K is .............
11. Which half-cell reaction is affected by pH and by how
(Given : ln(2) = 0.7, R (universal gas constant) much ? (2006)
= 8.3 J K–1 mol–1. H, S and G are enthalpy, entropy and (a) Eoxi will increases by a factor of 0.65 from E ooxi
Gibbs energy, respectively.)
(b) Eoxi will decrease by a factor of 0.65 from E ooxi
19. At 298 K, the limiting molar conductivity of a weak
monobasic acid is 4 × 102 S cm2 mol–1. At 298 K, for an (c) Ered will increase by a factor of 0.65 from E ored
aqueous solution of the acid the degree of dissociation
is  and the molar conductivity is y × 10 2 S cm2 (d) Ered will decrease by a factor of 0.65 from E ored
mol–1. At 298 K, upon 20 times dilution with water, the
23. Ammonia is always added in this reaction. Which of the
molar conductivity of the solution becomes 3y × 102 S
following must be incorrect ? (2006)
cm2 mol–1.
The value of  is _______. (round off up to two decimal (a) NH3 combines with Ag+ to form a complex
digits) (2021) (b) Ag(NH3)+2 is a stronger oxidising reagent than Ag+
20. At 298 K, the limiting molar conductivity of a weak (c) In absence of NH3 silver salt of gluconic acid is formed
monobasic acid is 4 × 102 S cm2 mol–1. At 298 K, for an
aqueous solution of the acid the degree of dissociation (d) NH3 has affected the standard reduction potential of
is  and the molar conductivity is y×102 S cm2 mol–1. At glucose/gluconic acid electrode
298 K, upon 20 times dilution with water, the molar Use the following passage, to solve Q. 24 to Q. 26
conductivity of the solution becomes
Passage
3y × 102 S cm2 mol–1.
Chemical reactions involve interaction of atoms and
The value of y is _______. (round off up to two decimal
molecules. A large number of atoms/molecules
digits) (2021)
(approximately 6.023 × 1023) are present in a few grams of
Paragraph Type Questions
any chemical compound varying with their atomic/
Use the following passage, to solve Q. 21 to Q. 23 molecular masses. To handle such large numbers
Passage conveniently, the mole concept was introduced. This
concept has implications in diverse areas such as
Tollen’s reagent is used for the detection of aldehydes. analytical chemistry, biochemistry, electrochemistry and
When a solution of AgNO3 is added to glucose with radiochemistry. The following example illustrates a typical
NH4OH, then gluconic acid is formed. case, involving chemical/electrochemical reaction, which
Ag+ + e–  Ag; E ored = 0.80 V requires a clear understanding of the mole concept.
C6H12O6 + H2O  C6 H12 O 7 + 2H+ + 2e–; A 4.0 M aqueous solution of NaCl is prepared and 500
gluconic acid
mL of this solution is electrolysed. This leads to the
E ooxidation = – 0.05 V evolution of chlorine gas at one of the electrodes (atomic
Ag( NH 3 ) 2  e   Ag (s) + 2NH3; E ored = 0.337V mass : Na = 23, Hg = 200; 1 Faraday = 96500 coulombs)
RT F 24. The total number of moles of chlorine gas evolved is
[Use 2.303 × = 0.0592 and = 38.92 at 298 K]
F RT (2007)
(2006) (a) 0.5 (b) 1.0
(c) 2.0 (d) 3.0
ELECTROCHEMISTRY 172
25. If the cathode is a Hg electrode, the maximum weight Use the following passage, to solve Q. 29 to Q. 30
(in g) of amalgam formed from this solution is (2007)
Passage
(a) 200 (b) 225
The concentration of potassium ions inside a biological
(c) 400 (d) 446 cell is at least twenty times higher than the outside. The
26. The total charge (coulombs) required for complete resulting potential difference across the cell is important
electrolysis is (2007) in several processes such as transmission of nerve
impulses and maintaining the ion balance. A simple model
(a) 24125 (b) 48250 for such a concentration cell involving a metal M is :
(c) 96500 (d) 193000
M(s) | M  (aq; 0.05 molar) || M  (aq; 1 molar) M (s)
Use the following passage, to solve Q. 27 to Q. 28 For the above electrolytic cell the magnitude of the cell
Passage potential |Ecell | = 70 mV.
Redox reaction play a pivotal role in chemistry and biology. 29. For the above cell (2010)
The values of standard redox potential (Eº) of two half-
(a) E cell  0; G  0 (b) E cell  0; G  0
cell reactions decide which way the reaction is expected
to proceed. A simple example is a Daniell cell in which (c) E cell  0; Gº  0 (d) E cell  0; Gº  0
zinc goes into solution and copper gets deposited. Given
below are a set of half-cell reactions (acidic medium) along 30. If the 0.05 molar solution of M+ is replaced by a 0.0025
with their Eº (V with respect to normal hydrogen electrode) molar M+ solution, then the magnitude of the cell potential
values.
would be. (2010)
I2 + 2e–– Eº = 0.54 (a) 35 mV (b) 70 mV
– –
Cl2 + 2e  2Cl Eº = 1.36 (c) 140 mV (d) 700 mV
3+ – 2+
Mn + e  Mn Eº = 1.50 Use the following passage, to solve Q. 31 to Q. 32
3+ – 2+
Fe + e  Fe Eº = 0.77 Passage
+ –
O2 + 4H + 4e  2H2O Eº = 1.23 The electrochemical cell shown below is a concentration
27. Among the following, identify the correct statement. cell. M|M2+ (saturated solution of a sparingly soluble salt,
(2007) MX2) | |M2+ (0.001 mol dm–3)|M.
(a) chloride ion is oxidised by O2 The emf of the cell depends on the difference in
concentration of M2+ ions at the two electrodes. The emf
(b) Fe2+ is oxidised by iodine
of the cell at 298 is 0.059 V.
(c) iodide ion is oxidised by chlorine
31. The solubility product (Ksp ; mol3 dm–9) of MX2 at 298
(d) Mn2+ is oxidised by chlorine based on the information available the given concentration
28. While Fe3+ is stable, Mn3+ is not stable in acid solution cell is (take 2.303 × R × 298/F = 0.059 V) (2012)
because (2007) (a) 1 × 10–15 (b) 4 × 10–15
2+ 3+
(a) O2 oxidises Mn to Mn (c) 1 × 10–12 (d) 4 × 10–12
(b) O2 oxidises both Mn2+ to Mn3+ and Fe2+ to Fe3+ 32. The value of G (kJ mol–1) for the given cell is (take 1F
(c) Fe3+ oxidises H2O to O2 = 96500 C mol–1) (2012)
(d) Mn3+ oxidises H2O to O2 (a) – 5.7 (b) 5.7
(c) 11.4 (d) – 11.4
ELECTROCHEMISTRY 173
Subjective Type Questions 35. (a) Calculate G or of the following reaction :
33. The standard potential of the following cell is 0.23 V at Ag  (aq)  Cl  (aq)   AgCl (s)
15ºC and 0.21 V at 35ºC. Given
Pt | H2(g) | HCl (aq) | AgCl (s) | Ag (s) G of (AgCl) – 109 kJ/mol
(i) Write the cell reaction. G of (Cl)  – 129 kJ/mol
o 
G (Ag ) 77 kJ/mol
(ii) Calculate Hº and Sº for the cell reaction by f

assuming that these quantitites remain unchanged Represent the above reaction in form of a cell.
in the range 15ºC to 35ºC. Calculate Eº of the cell. Find log10 Ksp of AgCl.
(b) 6.539 × 10–2 g of metallic Zn (M = 65.39) was added
(iii) Calculate the solubility of AgCl in water at 25ºC. to 100 mL of saturated solution of AgCl. Calculate
Given : The standard reduction potential of the
(Ag+ (aq)/Ag (s) is 0.80 V at 25ºC. (2001) [Zn 2  ]
log10 . Given that
[Ag  ]2
34. (a) Will pH value of water be same at temperature 25ºC
and 4ºC. Justify in not more than 2 or 3 sentences. Ag+ + e– 
 Ag Eº = 0.80V

(b) Two students use same stock solution of ZnSO4 and Zn2+ + 2e–   Zn Eº = – 76V
a solution of CuSO4. The emf of one cell is 0.03V Also find how many moles of Ag will be formed ?
higher than the other. The conc of CuSO4 in the cell (2005)
with higher emf value is 0.5 M. Find out the conc
of CuSO4 in the other cell. Given : 2.303 RT/F = 0.06V.
(2003)
ELECTROCHEMISTRY 174

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SURFACE CHEMISTRY
Chapter 20 176

SURFACE CHEMISTRY

1. INTRODUCTION Absorption

Surface Chemistry is that branch of chemistry which deals 2.1 Feature of Adsortion
with the study of the phenomena occurring at the surface or
2.1.1 Adsorbate and Adsorbent
interface, i.e., at the boundary separating two bulk phases.
The substance which gets adsorbed on any surface is called
The two bulk phases can be pure compounds or solutions.
The interface is represented by putting a hyphen or a slash adsorbate for example, if a gas gets adsorbed on to the
between the two bulk phases involved, e.g., solid-liquid or surface of a solid, then the gas is termed as the adsorbate.
solid/liquid. No interface exists between gases as they are The substance on the surface of which adsorption takes
completely miscible. Important phenomena occur at the place is called adsorbent.
interface, e.g., dissolution, crystallisation, corrosion, Adsorbent may be a solid or a liquid. Metal powders,
heterogeneous catalysis, electrode processes, etc. powdered charcoal, animal charcoal silica powder etc. are
commonly used as adsorbents.
2. ADSORPTION AND ABSORPTION
The phenomenon of attracting and retaining the molecules
of a substance on the surface of a liquid or solid resulting in
to higher concentration of the molecules on the surface is
called adsorption. Adsorption of gases at metal surface is
called occlusion

2.1.2 Desorption
The removal of the adsorbed substance from a surface is
called desorption. This can be done by heating or reducing
the pressure of the system.
2.1.3 Sorption
The phenomenon in which adsorption and absorption occur
simultaneously is called sorption. Dyes are absorbed as well
When the molecules of a substance are uniformly distributed absorbed in cotton fibre. Adsorption is instantaneous i.e. a
throughout the body of a solid or liquid, this phenomenon is fast process while absorption is a slow process.
called absorption.

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2.2 Difference between Adsorption and Absorption


Main points of difference between adsorption and absorption are given below:

Difference between Adsorption and Absorption


Adsorption Absorption
1. It is a surface phenomenon. 1. It concerns with the whole mass of the absorbent.
2. In it, the substance is only retained 2. It implies that a substance is uniformly distributed, through
on the surface and does not go into the body of the solid or liquid.
the bulk or interior of the solid or liquid.
3. In it the concentration of the adsorbed molecules is 3. In it the concentration is low.
always greater at the free phase.
4. It is rapid in the begining and slows 4. It occurs at the uniform rate that is slow rate.
down to attain equilibrium
Examples Examples
(i) Water vapours are adsorbed by CaCl2. (i) Water vapours are absorbed by anhydrous silica gel.
(ii) NH3 is adsorbed by charcoal. (ii) NH3 is absorbed in water forming NH4OH.

2.3 Mechanism of adsorption  Adsorption is invariably accompanied by evolution of heat,


Only the surface atoms of an adsorbent play an active role in i.e. it is an exothermic process. In other words, H of adsorption
adsorption. These atoms possess unbalanced forces of various is always negative.
 When a gas is adsorbed, the freedom of movement of its
types such as, Vander Waal’s forces and chemical bond forces molecules becomes restricted. On account of it, decrease in the
(free valencies). entropy of the gas after adsorption, i.e.S is negative.
Thus, due to residual or unbalanced inward forces of Adsorption is spontaneous process, so for the process G is
negative. According to Gibbs equation.
attraction or free valancies at the surface, liquids and solids have
G = H – TS
the property to attract and retain the molecules of a gas or a
H must necessarily be negative and. H|S|. The process
dissolved substance on to their surface. is exothermic because it involves forces of attraction between
adsorbate and adsorbent. As the process of adsorption
proceeds further H become less and less after certain time
period. When H becomes equal TS,G = 0 and system
attains equilibrium. At equilibrium, Rate of adsorption = Rate of
desorption
2.5 Types of adsorption
Molecules at the surface experiencing a net inward force Adsorption can be classified into two categories as described
of attraction in case of below:
(a) liquid (b) solid (c) metal with free valencies 2.5.1 Physical adsorption
If the forces of attraction existing between adsorbate and
2.4 Thermodynamic of adsorption
adsorbent are Vander Waal’s forces, the adsorption is called
 Adsorption refers to the existence of a higher concentration physical adsorption. This type of adsorption is also known
of any particular component at the surface of a liquid or a solid as physisorption or Vander Waal’s adsorption. It can be easily
phase. reversed by heating or decreasing the pressure.

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2.5.2 Chemical adsorption ads orp ti on. T his t yp e o f adsorption is also called as
If the forces of attraction existing between adsorbate chemisorption or Langmuir adsor pti on. T hi s type of
particles and adsorbent are almost of the same strength as adsorption cannot be easily reversed.
c he mi ca l bo nd s, t he a ds o r p ti on i s c a ll e d che mi ca l
Comparison between Physisorption and Chemisorption
Physisorption Chemisorption
(Vander Waal’s adsorption) (Langmuir adsorption)
1. Low heat of adsorption usually in range 1. High heat of adsorption in the range of
of 20-40 kJ/mol 80-240 kJ/mol.
2. Force of attraction are Vander Waal’s forces. 2. Forces of attraction are Chemical bond forces.
3. It is reversible. 3. It is irreversible.
4. It usually takes place at low 4. It takes place at high temperature. It increases with
temperature and decreases with the increase of temperature.
increasing temperature.
5. It forms multimolecular layers. 5. It forms monomolecular layers.
6. It does not require any activation 6. It requires high activation energy.
energy.
7. High pressure is favourable. Decrease 7. High pressure is favourable. Decrease
of pressure causes desorption. of pressure does not cause desorption
8. It is not very specific. 8. It is highly specific.

NOTE 2.6.1 Nature of the adsorbate (gas) and adsorbent (solid)


 Porous and finely powdered solid e.g. charcoal, fullers
Due to formation of multilayers physical adsorption decreases
earth, adsorb more as compared to the hard non-porous
after some times. Chemisorption and physisorption both are materials. Due to this property powdered charcoal is used
exothermic. in gas masks used in coal mines.
 Gases with high critical temperature are adsorbed at
higher extent as compared to gases with lower critical
2.6 Factors which affect the extent of adsorption on
temperatures.
solid surface
The following are the factors which affect the adsorption of gases
on solid surface:
Volumes of gases at N.T.P., adsorbed by 1g of charcoal at 288 K
Gas H2 N2 CO CH4 CO2 HCl NH3 SO2
Volume adsorbed (mL) 4.7 8.0 9.3 16.2 48 72 181 380
Critical temp (K) 33 126 134 190 304 324 406 430
Critical temperature increases 
Ease of liquefaction increases 
Adsorption increases 

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2.6.2 Surface area of the solid adsorbent 2.7.1 Freundlich adsorption isotherm
The extent of adsorption depends directly upon the surface area Freundlich adsorption isotherm is obeyed by the adsorptions
of the adsorbent, i.e. larger the surface area of the adsorbent, where the adsorbate forms a monomolecular layer on the surface
greater is the extent of adsorption.
of the adsorbent.
2.6.3 Effect of pressure on the adsorbate gas
1
 An increase in the pressure of the adsorbate gas increases x x 1
 kP n or log  log k  log P
the extent of adsorption. m m n
 At low temperature, the extent of adsorption increases rapidly where, x is the weight of the gas adsorbed by m gm of the
with pressure. adsorbent at a pressure P, thus x/m represents the amount of gas
 At low pressure, the extent of adsorption is found to be adsorbed by the adsorbent per gm (unit mass), k and n are
directly proportional to the pressure. constant at a particular temperature and for a particular adsorbent
 At high pressure (closer to the saturation vapour pressure and adsorbate (gas), n is always greater than one, indicating that
of the gas), the adsorption tends to achieve a limiting value. the amount of the gas adsorbed does not increase as rapidly as
the pressure.
 At low pressure, the extent of adsorption varies linearly with

pressure

x 1
 P1 ;  1
m n
 At high pressure, it becomes independent of pressure
x 1
 P0 ;  0
m n

x
Variation of adsorption of N2 on charcoal with pressure at  At moderate pressure depends upon pressure raised to
different constant temperatures m
1
2.6.4 Effect of temperature powers .
n
1
As adsorption is accompanied by evolution of heat, so according x
 Pn
to the Le-Chatelier’s principle, the magnitude of adsorption m
should decrease with rise in temperature.
NOTE
The amount of heat when one mole of the gas is adsorbed on
the adsorbent is called the heat of adsorption.
2.7 Adsorption Isotherms
A mathematical equation which describes the relationship
between pressure (p) of the gaseous adsorbate and the extent of Freundlich isotherm
adsorption at any fixed temperature is called adsorption isotherms. 2.8 Adsorption Isobar
Thus, if x g of an adsorbate is adsorbed on m g of the adsorbent, A graph drawn between the amount of the gas adsorbed per
then gram of the adsorbent (x/m) and temperature ‘T’ at a constant
equilibrium pressure of adsorbate gas is known as adsorption
x
Extent of adsorption  isobar.
m

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2.10 Factors affecting adsorption from solution


The adsorption from solutions by solid adsorbents is found to
depend upon the following factors :
  Nature of the adsorbate and the adsorbent.
 The adsorption decreases with temperature.
 Greater the surface area of the adsorbent greater is the
adsorption.
The physical adsorption isobar shows a decrease in x/m
 Concentration of the solute in the solution.
throughout with rise in temperature, the chemisorption isobar
shows an initial increase with temperature and then the expected 2.11 Positive and Negative Adsorption
decrease. The initial increase is because of the fact that the heat In case of adsorption by solids from the solutions, mostly the
supplied acts as activation energy required in chemisorption (like solute is adsorbed on the surface of the solid adsorbent so that
chemical reactions). concentration of solute on the surface of the adsrobent is greater
than in the bulk. However in some cases. the solvent from the
2.9 Adsorption from Solutions solution may be adsorbed by the adsorbent so that the
Solid surfaces can also adsorb solutes from solutions. A few concentration of the solution increases as compared to initial
concentration.
examples are :
When the concentration of the adsorbate is more on the surface
 When litmus solution is shaken with charcoal, it becomes of the adsorbent than in the bulk, it is called positive adsorption.
colourless because the dye of the litmus solution is adsorbed If the concentration of the adsorbate increases in the bulk after
adsorption, it is called negative adsorption.
by charcol.
Blood solution + Conc. KCl solution  Positive adsorption
 When the colourless Mg(OH)2 is precipitated in the presence
Blood solution + dilute KCl solution  Negative adsorption
of magneson reagent (a blue coloured dye). it acquires blue
2.12 Applications of Adsorption
colour because the dye is adsorbed on the solid precipitate.
The phenomenon of adsorption finds a number of applications.
 The extent of adsorption from solution depends upon the
Important applications are given as follows:
concentration of the solute in the solution, and can be
 Production of high vacuum
expressed by the Freundlich isotherm. The Freundlich
 In Gas masks
adsorption isotherm for the adsorption from solution is,
x  For desiccation or dehumidification
= kc1/ n where, x is the mass of the solute adsorbed, m is
m  Removal of colouring matter from solution
the mass of the solid adsorbent, c is the equilibrium
 Separation of inert gases
concentration of the solute in the solution, n is a constant
 Softening of hard water
having value greater than one. k is the proportionality
 De-ionisation of water
constant, (The value of k depends upon the nature of solid,
 In curing diseases
its particle size, temperature, and the nature of solute and
solvent etc.)  Cleaning agents
 Froth flotation process
The plot of x/m against c is similar to that Freundlich adsorption
isotherm. The above equations may be written in the following  In adsorption indicators

x 1  Chromatographic analysis
form, log  log k  log c where c, is the equilibrium
m n  In dyeing
concentration of the solute in the solution.

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 Heterogeneous catalysis : Mostly heterogeneous catalytic  Combination between nitrogen and hydrogen to form
reactions proceed through the adsorption of gaseous reactants ammonia in the presence of finely divided iron in Haber’s
on solid catalyst. For example, process.

(a) Finely powdered nickel is used for the hydrogenation of N 2 (g)  3H 2 (g) 
Fe(s)
 2NH3 (g)
oils.
 Oxidation of ammonia into nitric oxide in the presence of
(b) Finely divided vanadium pentaoxide (V2O5) is used in the platinum gauze as a catalyst in Ostwald’s process.
contact process for the manufacture of sulphuric acid.
(c) Pt, Pd are used in many industrial processes as catalyst. 4NH3 (g)  5O2 (g) 
Pt(s)
 4NO(g)  6H2 (g)

(d) Manufacture of ammonia using iron as a catalyst. 3.1.3 Positive catalysis


When the rate of the reaction is accelerated by the foreign
3. CATALYSIS
substance, it is said to be a positive catalyst and phenomenon as
Catalyst is a substance which speeds up and speeds down a positive catalysis. Some examples of positive catalysis are given
chemical reaction without itself being used up at the end of the below:
reaction and the phenomenon is known as catalysis.
3.1 Types of catalysis  Decomposition of H 2 O 2 in presence of colloidal platinum.

Catalytic reactions can be broadly divided into the following


2H 2 O2  l  
Pt
 2H 2 O  l   O2  g 
types:
3.1.1 Homogeneous catalysis 3.1.4 Negative catalysis
When the reactants and the catalyst are in the same phase (i.e.
There are certain, substance which, when added to the reaction
solid, liquid or gas). The catalysis is said to be homogeneous.
mixture, retard the reaction rate instead of increasing it. These
The following are some of the examples of homogeneous
are called negative catalyst or inhibitors and the phenomenon is
catalysis.
known as negative catalysis. Some examples are as follows:
 Oxidation of sulphur dioxide into sulphur trioxide with oxygen
in the presence of oxides of nitrogen as the catalyst in the  The oxidation of chloroform by air is retarded if some alcohol
lead chamber process. is added to it.

2SO2 (g)  O2 (g) 


NO(g)
 2SO3 (g) 2CHCl3 (l)  O2 (g) 
Alcohol(l)
 2COCl2 (g)  2HCl(g)
The reactants, products and catalyst all are in gaseous state
3.1.5 Auto-catalysis
i.e. same phase.
 Hydrolysis of methyl acetate is catalysed by H+ ions furnished In certain reactions, one of the product acts as a catalyst. In the
by hydrochloric acid. initial stages the reaction is slow but as soon as the products
 
CH 3 COOCH 3     H 2 O    
HCl 
 CH 3 COOH  CH 3 OH come into existence the reaction rate increases. This type of
3.1.2 Heterogeneous catalysis phenomenon is known as auto-catalysis. Some examples are as
The catalytic process in which the reactants and the catalyst are follows:
in different phases is known as heterogeneous catalysis. Some  The rate of oxidation of oxalic acid by acidified potassium
of the examples of heterogeneous catalysis are: permanganate increases as the reaction progresses. This
 Oxidation of sulphur dioxide into sulphur trioxide in the acceleration is due to the presence of Mn2+ ions which are
formed during reaction. Thus Mn2+ ions act as auto-catalyst.
presence of platinum metal or vanadium pentaoxide as
catalyst in the contact process for the manufacture of 5H 2 C2 O4  2KMnO4  3H 2SO 4 

sulphuric acid. The reactants are in gaseous state while the
catalyst is in solid state. 2 MnSO 4  K 2SO 4  10CO 2  8H 2 O

SO2 (g)  O2 (g) 


Pt(s)
 2SO3 (g)

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 When nitric acid is poured on copper, the reaction is very  Catalytic promoters : Substances which themselves are not
slow in the beginning, gradually the reaction becomes faster catalysts, but when mixed in small quantities with the
due to the formation of nitrous acid during the reaction catalysts increase their efficiency are called as promoters or
which acts as an auto-catalyst. activators.
3.1.6 Induced catalysis  Catalytic poisons : Substances which destroy the activity
of the catalyst by their presence are known as catalytic
When one reaction influences the rate of other reaction, which poisons.
does not occur under ordinary conditions, the phenomenon is
 Change of temperature alters the rate of catalytic
known as induced catalysis. Some examples are as follows: reaction as it does for the same reaction in absence of
 The reduction of mercuric chloride (HgCl2) with oxalic acid catalyst : By increasing the temperature, there is an
is very slow, but potassium permanganate is reduced readily increase in the catalytic power of a catalyst but after a
with oxalic acid. If, however, oxalic acid is added to a mixture certain temperature its power begins to decrease. A
catalyst has thus, a particular temperature at which its
of potassium permanganate and HgCl2 both are reduced
catalytic activity is maximum. This temperature is termed
simultaneously. The reduction of potassium permanganate,
as optimum temperature.
thus, induces the reduction of mercuric chloride.
3.3 Theories of Catalysis
3.1.7 Acid-base catalysis
3.3.1 Collision Theory of Homogeneous Catalysis
According to the Arrhenius and Ostwald H+ or OH– ions act as
catalysts. According to the collision theory, a reaction occurs on account
 For example, Hydrolysis of an ester, of effective collisions between the reacting molecules. For
effective collision, it is necessary that the molecules must
CH3COOC2H5 (l) + H2O (l)
possess a minimum amount of energy known as activation energy
H  or

OH 
 CH3COOH (l) + C2H5OH (l) (Ea).
After the collision molecules form an activated complex which
 Inversion of cane sugar,
dissociate to yield the product molecules. The catalyst provides
H+
C12 H 22 O11 (l) +H 2 O  C6 H12 O6  l  + C6 H12 O6  l  a new pathway involving lower amount of activation energy.
Sugar Fructose Glucose

3.2 Characteristics of catalysis


The following are the characteristics which are common to most
of catalytic reactions:
 A catalyst remains unchanged in mass and chemical
composition at the end of the reaction.
 The catalyst can not initiate the reaction: The function of
the catalyst is to alter the speed of the reaction rather than
to start it.
 The catalyst is generally specific in nature: A substance,
which acts as a catalyst for a particular reaction, fails to
catalyse the other reaction , different catalysts for the same 3.3.2 Adsorption theory of Heterogeneous Catalysis
reactant may give different products.
Heterogeneous catalytic reactions generally proceed via
 The catalyst can not change the position of equilibrium:
adsorption of reactants on the surface of the catalyst.
The catalyst catalyse both forward and backward reactions
to the same extent in a reversible reaction and thus have no Mechanism of such surface reactions may be explained in terms
effect on the equilibrium constant. of diffusion theory of catalysis. This theory postulates the
following sequence for gaseous reactions on a solid surface.

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Step: (i) Diffusion of the reactants to the surface. 3.4.2 Selectivity


Step: (ii) Adsorption of the reactant molecules onto the surface. Selectivity is the ability of catalysts to direct a reaction to yield
Step: (iii) Actual chemical reaction on the surface. particular products (excluding other).
Step: (iv) Desorption of the products from the surface. (i) CO  g   3H 2  g  
Ni
 CH 4  g   H 2 O  g 
Step: (v) Diffusion of the products away from the surface.
(ii) CO  g   2H 2  g  
Cu / ZnO  Cr2 O3
CH 3 OH  g 
In generally, Step (iii) determines the rate of reaction. However
step (ii) and (iv) may be rate determining.
(iii) CO  g   H 2  g  
Cu
 HCHO  g 

3.5 Zeolites (shape selective catalysis)


Zeolites are alumino–silicates of the general formula, M n
[AlO2]x.(SiO2)y .mH2O, where, M may be simple cation like Na  ,
 K  or Ca 2  , n is the charge on the simple cation, m is the number of
molecules of water of crystallization. They have honey comb like
structure called  cage. The reactions catalyzed by zeolites depend
upon the shape and size of the reactant and product molecules.
3.3.3 Advantages of modern adsorption theory
That is why these types of reactions are called shape selective-
This theory can explain the following :
catalysis. Zeolites are being very widely used as catalysts in
 Small quantity of the catalyst is sufficient because the petrochemical industries for cracking of hydrocarbons and
catalyst is regenerated again and again. isomerization. An important zeolite catalyst used in the petroleum
industry is ZSM–5 (Zeolite Sieve of Molecular Porosity 5). It
 The catalyst takes part in the reaction but is produced back converts alcohols directly into gasoline (petrol) by first
unchanged in mass and chemical composition at the end of dehydrating them so that a mixture of hydrocarbons is formed.
the reaction. ZS M  5
A lco h ols  Dehyd
ratio
 n H yd ro carb o n s
 Catalytic poisons, if present, are preferentially adsorbed on
the catalyst surface, thereby hindering the adsorption of Hydrated zeolites are used as ‘ion-exchangers’ in softening of
the reactant molecules. Hence, they slow down the activity hard water.
of the catalyst.
This theory, however, cannot explain satisfactorily the action of
catalytic promoters.

3.4 Important Features of Solid Catalysis

3.4.1 Activity
Activity is the ability of catalysts to accelerate chemical reactions.
The degree of acceleration can be as high as 10 10 times in certain
reactions. For example reaction between H2 and O2 to form H2O in
presence of platinum as catalyst takes place with explosive
violence.
In absence of catalyst, H2 and O2 can be stored indefinitely
without any reaction.

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3.6 Catalysis used in Industries


Some Industrial Catalytic Processes

Process Reactions with catalyst and other conditions

Finely divided iron (catalyst)


Haber’s process for the manufacture N 2 (g)  3 H 2 (g) 
Molydenum (Pr omoter)
 2 NH 3 (g)
200 bar pressure
of ammonia 723 773 K temp.

Platinised
4 NH 3 (g)  5 O 2 (g) 
asbestos (catalyst)
4 NO (g)  6 H 2 O (g)

Ostwald’s process for the 573K


2 NO (g)  O 2 (g)   2 NO 2 (g)
manufacture of nitric acid
4 NO 2 (g)  2 H 2 O (l )  O 2 (g)  4 HNO3 (l )

 2 SO3 (g)


Platinised asbestos
2 SO 2 (g)  O 2 (g) 
or V2O5 (catalyst)
Contact process for the manufacture 673  723K  H O (l )
2 
SO 3 (g)  H 2 SO 4 (l )      H 2 S 2 O 7 (l )     2H 2 SO 4 (aq)
of sulphuric acid
Oleum

Bosch’s process for the manufacture


Fe O (Catalyst)
CO  H 2  H 2 O(g) 
2 3
 CO 2 (g)  2 H 2 (g)
of hydrogen    Cr2O3 (promoter)
Water gas 673873K

Deacon’s process for the CuCl


4 HCl (g)  O2 (g) 
773K
2  2H O (l )  2 Cl (g)
2 2
manufacture of chlorine
Finely divided Ni
Hydrogenatino of vegetable oils Oil (l )  H 2 (g) 
423 473 K
 Vanaspati ghee (s)
High pressure

4. ENZYMES
Enzymes are complex nitrogenous substances secreted by low Thus, the enzyme catalysed reactions take place in two
forms of vegetables & organisms. Enzymes are actually protein steps as follows :
molecules of higher molecular mass. (ranging from 15,000 –
1,000,000 g/mol) Enzymes form colloidal solutions in water and Step 1. Formation of enzyme-substrate complex.
are very effective catalysts. E  S  ES
 (Fast and Reversible)
They catalyse numerous reactions, especially those connected Enzyme Substrate Enzyme 
with natural processes. Numerous reactions occur in the bodies Substrate complex
of animals and plants to maintain the life process. These reactions Step 2. Dissociation of enzyme-substrate complex to form the
products.
are catalysed by enzymes. The enzymes are thus, termed as bio-
chemical catalysts and the phenomenon is known as bio-chemical ES 
   EP  

catalysis Enzyme Enzyme  Pr oduct
for example:Nitrogenase is an enzyme present in bacteria on Substrate complex association
the root nodules of leguminous plants such as peas and beans,
E  P  Slow and Rate 
catalyses the conversion of atmospheric N2 to NH3.
 
 determining 
4.1 Mechanism of enzyme catalysis Enzyme Product
 Re generated 
The rate of formation of product depends upon the
concentration of ES.

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5. COLLOIDAL STATE 5.2 Suspension

The colloidal state depends on the particle size. It is regarded as The size of particles is large and, thus it can be seen by naked
intermediate state between true solution and suspension. eye and do not pass through filter paper. It is a heterogeneous
system.The size of different solutions are sometimes expressed in
5.1True solution
other units also as given below :
In true solutions the size of the particles of solute is very small
Size Range in Different Solutions
and thus, these can not be detected by any optical means and
freely diffuse through membranes. It is a homogenous system. True solutions Colloids Suspensions Relation

<10–9m 10–9m to > 10–7 m 10–7m


< 1nm 1 nm –1000 nm > 1000 nm 1 nm = 10–9m
< 10 Å 10 Å – 10000 Å > 10000 Å 1 Å = 10–10m
<1000 pm 1000 pm – > 105 pm 1 pm = 10–12m
105 pm

Particle size in different type of solution

Characteristics of True Solutions, Colloidal Solutions and Suspensions

S.No Property True Solutions Colloidal Solutions Suspensions

1. Nature Homogeneous Heterogeneous Heterogeneous


2. Particle size Less than 10–9 m or Between 10–9 to 10–6m More than 10–6m or
(diameters) 1 nm (i.e., < 10 Å) or 1 nm to 1000 nm 1000 nm (i.e., > 10000Å)
3. Filterability Pass through ordinary Pass through ordinary Do not pass through filter
filter paper as well filter paper but not paper and animal
as animal membrane. through animal membrane.
membrane.
4. Settling Do not settle. Do not settle. Settle on standing.
5. Visibility Particles are Scattering of light by Particles are visible to
invisible. the particles is observed naked eye or under a microscope
under ultra-microscope.
6. Diffusion Diffuse quickly. Diffuse slowly. Do not diffuse.
7. Appearance Clear and Transluscent. Opaque.
transparent

5.3 Dispersed phase and Dispersion Medium 5.4 Classification of Colloids


5.3.1 Dispersed phase 5.4.1 Classification based on the physical state of the dispersed
It is the component present in small proportion and is just like a phase and dispersion medium
solute in a solution. For example in the colloidal solution of silver Depending upon the physical state of dispersed phase and
in water (silver acts as a dispersed phase) dispersion medium whether these are solids, liquids or gases,
5.3.2 Dispersion medium eight types of colloidal systems are possible.
It is generally the component present in excess and is just like a
solvent in a solution. For example, in the colloidal solution of
silver in water. Water acts as a dispersion medium.

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Different types of Colloidal Systems

Sr. Dispersed Dispersion Colloidal System Examples


No phase

1. Liquid Gas Aerosol of liquids Fogs, clouds, mists, fine insecticide sprays
2. Solid Gas Aerosol of solids Smoke, volcanic dust, haze Foam or froth Soap lather.
3. Gas Liquid Foam or froth Lemonade froth, foam, whipped cream, soda water
4. Liquid Liquid Emulsions Milk, emulsified oils, medicines
5. Solid Liquid Sols Most paints, starch in water, proteins, gold sol, arsenic
sulphide sol, ink
6. Gas Solid Solid foam Pumice stone, styrene rubber, foam rubber
7. Liquid Solid Gels Cheese, butter, boot polish, jelly, curd
8. Solid Solid Solid sols Ruby glass, some gem stones and alloys
(coloured glass)

5.4.2 Classification based on Nature of interaction between dispersed Lyophobic colloids (water hating): The colloidal solutions in which
phase and dispersion medium there is no affinity between particles of the dispersed phase and
the dispersion medium are called lyophobic colloids.
Lyophilic colloids (water loving): The colloidal solutions in
which the particles of the dispersed phase have a great
affinity for the dispersion medium, are called lyophilic
colloids.

Distinction between Lyophilic and Lyophobic Sols

Sr. Property Lyophilic (suspensiod) Lyophobic Sols (Emulsoid)


No
1. Surface tension Lower than that of the medium Same as that of the medium
2. Viscosity Much higher than that of the Same as that of the medium
medium
3. Reversibility Reversible Irreversible
4. Stability More stable Less stable
5. Visibility Particles can’t be detected even Particles can be detected under
under ultramicroscope ultramicroscope.
6. Migration Particles may migrate in either Particles migrate either towards
direction or do not migrate in an cathode or anode in an electric
electric field because do not carry field because they carry charge.
any charge.
7. Action of Addition of smaller quantity of Coagulation takes place
electrolyte electrolyte has little effect
8. Hydration Extensive hydration takes place No hydration
Examples Gum, gelatin, starch, proteins, Metals like Ag and Au, hydroxides like Al(OH3),
rubber etc. Fe(OH)3, metal sulphides
like As2S3 etc.

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5.4.3 Classification based on types of particles of dispersed These macromolecules forming the dispersed phase are
phase generally polymers having very high molecular masses.
Naturally occurring macromolecules are starch, cellulose,
Depending upon the type of the particles of the dispersed phase,
proteins, enzymes, gelatin etc. Artificial macromolecules are
the colloids are classified as follows: synthetic polymers such as nylon, polythene, plastics,
Multimolecular colloids : When on dissolution, atoms or smaller polystyrene etc. Their solutions are quite stable and resemble
molecules of substances (having diameter less than 1nm) with true solution in many respects. They have usually
lyophobic character. The molecules are flexible and can take
aggregate together to form particles of colloidal dimensions,the
any shape.
particles thus formed are called multimolecular colloids.
Associated colloids : These are the substances which dissolved
In these sols the dispersed phase consists of aggregates of atoms in a medium behave as normal electrolytes at low concentration
or molecules with molecular size less than 1 nm. For example, sols but behave, as colloidal particles at higher concentration due to
of gold atoms and sulphur (S8) molecules. In these colloids, the the formation of aggregated particles. The aggregates particles
particles are held together by Vander Waal’s forces. They have thus formed are called micelles.
usually lyophilic character. Their molecules contain both lyophilic and lyophobic groups.
The colloidal behaviour of such substances is due to the
Macromolecular colloids : These are the substances having big
formation of aggregates or clusters in solutions. Such aggregated
size molecules (called macromolecules) which on dissolution form
particles are called micelles.
size in the colloidal range. Such substances are called
macromolecular colloids.
Difference between different Types of Colloids

Multimolecular colloids Macromolecular colloids Associated colloids

1. They are formed by the They are molecules of large They are formed by
aggregation of a large number size, e.g., polymers like rubber, aggergation of a large
of atoms or molecules which nylon, starch, proteins, etc. no. of ions in concen-
generally have diameters less trated solution e.g., soap
than 1 nm, e.g., sols of gold, sol.
sulphur, etc.
2. Their molecular masses are They have high molecular Their molecular masses
not very high masses. are generally high.
3. Their atoms or molecules are Due to long chain, the van der Higher is the concen-
held together by weak van der Waals forces holding them are tration, greater are the
Waals forces. comparatively stronger. van der Waals forces.

5.5 Micelles  For example sodium stearate (C17H35 COONa) is a typical


example of such type of molecules.
Micelles are the clusters or aggregated particles formed by
 When sodium stearate is dissolved in water, it gives Na+
association of colloid in solution. The common examples of micelles
and C17H35COO– ions.
are soaps and detergents. The formation of micelles takes place
above a particular temperature called Kraft temperature (T k) and
C 17 H 35 COONa  C 17 H 35 COO   Na 
above a particular concentration called critical micelle concentration Sodium stearate Stearate ion
(CMC). They are capable of forming ions. Micelles may contain as The stearate ions associate to form ionic micelles of colloidal
many as 100 molecules or more. size.
 It has long hydrocarbon part of C17H35 radical. Which is
lyophobic and COO– part which is lyophilic.

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When oil droplet comes in contact with soap solution, the stearate ions arrange themselves around it in such a way that hydrophobic
parts of the stearate ions are in the oil (or grease) and the hydrophilc part projects out of the grease droplet like the bristles. As
hydrophilic part is polar, these polar groups can interact with the water molecules present around the oil droplet. As a result, the oil
droplet is pulled away from the surface of the cloth into water to form ionic micelle which is then washed away with the excess of water.

(a) Grease or oil on surface of cloth (b) Stearate ions arranged around the oil droplet
(c) Ionic micelle formed surrounded by sheath of negative charge.

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In fact, the stearate ions of soap molecules help in making a stable By hydrolysis : Many salt solutions are rapidly hydrolysed
emulsion of oil with water which is washed away with the excess of by boiling dilute solutions of their salts. For example, ferric
water. It may be noted that a sheath of negative charge is formed hydroxide and aluminium hydroxide sols are obtained by
around the oil globule. boiling solutions of the corresponding chlorides.
Similarly, in case of detergents, e.g., sodium lauryl sulphate, viz, FeCl3  3H 2 O  Fe(OH)3  3HCl
CH3(CH2)11 OSO3 Na+, the polar group is OSO3 along with Colloidial Sol

the long hydrocarbon chain. It is an example of an anionic Similarly silicic acid sol is obtained by the hydrolysis of
detergent as anions associate together to form an ionic micelle, sodium silicate.
similar to that of soap. A well known example of a cationic detergent
forming an associated colloid is that of cetyl trimethyl , By double decomposition : A sol of arsenic sulphide is
CH3(CH2)15(CH3)3N+Br–. obtained by passing hydrogen sulphide through a cold
5.6 General Methods of preparation of Colloids solution of arsenious oxide in water.

Lyophilic and lyophobic colloidal solutions (or sols) are generally As 2 O3 +3H 2S  As 2S3 +3H 2 O
prepared by different types of methods. Some of the common
methods are as follows: Mechanical dispersion : In this method, the substance is
5.6.1 Preparation of Lyophilic colloids first ground to coarse particles. It is then mixed with the
dispersion medium to get a suspension. The suspension is
 The lyophilic colloids have strong affinity between particles then grinded in colloidal mill. It consists of two metallic discs
of dispersed phase and dispersion medium.These colloidal nearly touching each other and rotating in opposite
solutions are readily formed by simply mixing the dispersed directions at a very high speed about 7000 revolution per
phase and dispersion medium under ordinary conditions. minute. The space between the discs of the mill is so adjusted
 For example, the substance like gelatin, gum, starch, egg, that coarse suspension is subjected to great shearing force
albumin etc. pass readily into water to give colloidal solution. giving rise to particles of colloidal size. Colloidal solutions
They are reversible in nature because these can be of black ink, paints, varnishes, dyes etc. are obtained by this
precipitated and directly converted into colloidal state. method.

5.6.2 Preparation of Lyophobic colloids By electrical dispersion or Bredig’s arc method : This
By oxidation : A colloidal solution of sulphur can be obtained method is used to prepare sols of platinum, silver, copper or
by bubbling oxygen (or any other oxidising agent like gold.
HNO3 ,Br etc.) through a solution of hydrogen sulphide in The metal whose sol is to be prepared is made as two
water. electrodes which are immersed in dispersion medium such
as water etc. The dispersion medium is kept cooled by ice.
2H 2S  O2 ( or any other oxidising agent)  2H 2 O  2S
An electric arc is struck between the electrodes. The
By reduction : A number of metals such as silver, gold and tremendous heat generates by this method and give colloidal
platinum, have been obtained in colloidal state by treating solution. The colloidal solution prepared is stabilised by
the aqueous solution of their salts, with a suitable reducing adding a small amount of KOH to it.
agent such as formaldehyde, phenyl hydrazine, hydrogen
peroxide, stannous chloride etc.
2AuCl3  3SnCl 2  3SnCl4  2Au
GoldSol

2AuCl3  3HCHO  3H 2 O  2Au  3HCOOH  6HCl


GoldSol

The gold sol, thus prepared, has a purple colour and is called
purple of cassius.

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NOTE The distilled water is changed frequently to avoid accumulation


of the crystalloids otherwise they may start diffusing back into
 This method is not suitable when the dispersion medium
is an organic liquid as consider occurs. the bag. Dialysis can be used for removing HCl from the ferric
hydroxide sol.
 This method comprises both dispersion and condensation.
By Peptization : The process of converting a freshly 5.7.2 Electrodialysis
prepared precipitate into colloidal form by the addition of The ordinary process of dialysis is slow. To increase the pace of
suitable electrolyte is called peptization. The electrolyte is purification, the dialysis is carried out by applying electric field.
used for this purpose is called peptizing agent or stabilizing This process is called electrodialysis. Kidneys in the human
agent. Cause of peptisation is the adsorption of the ions of
body act as dialysers to purify blood which is colloidal in nature.
the electrolyte by the particles of the precipitate.

Important peptizing agents are sugar, gum, gelatin and


electrolytes. Freshly prepared ferric hydroxide can be converted
into colloidal state by shaking it with water containing Fe3+ or OH–
ions, viz. FeCl3 or NH 4 OH respectively..
3
Fe(OH)3  FeCl3   Fe  OH 3 Fe   3Cl –
Pr ecipitat electrolyte Colloidal sol

5.7 Purification of colloidal solution


Electrodialysis
The colloidal solutions prepared by the above methods usually
5.7.3 Ultra – filtration
contain impurities especially electrolytes which can destabilize
the sols. These impurities must be eliminated to make the colloidal Sol particles directly pass through ordinary filter paper because
solutions stable. The following methods are commonly used for their pores are larger (more than 1 or 1000 m) than the size of
the purification of colloidal solutions: sol particles (less than 200 m). If the pores of the ordinary filter
paper are made smaller by soaking the filter paper in a solution of
5.7.1 Dialysis
gelatin or colloidion and subsequently hardened by soaking in
The process of separating the particles of colloid from those of formaldehyde, the treated filter paper may retain colloidal particles
crystalloid, by means of diffusion through a suitable membrane and allow the true solution particles to escape. Such filter paper is
is called dialysis. known as ultra - filter and the process of separating colloids by using
It’s principle is based upon the fact that colloidal particles can ultra – filters is known as ultra – filtration.
not pass through a parchment or cellophane membrane while the 5.7.4 Ultra – centrifugation
ions of the electrolyte can pass through it.
The sol particles are prevented from setting out under the action
of gravity by kinetic impacts of the molecules of the medium.
The setting force can be enhanced by using high speed
centrifugal machines having 15,000 or more revolutions per
minute. Such machines are known as ultra–centrifuges.

Dialysis
The colloidal solution is taken in a bag (parchment paper).The
bag is suspended in fresh water. The impurities slowly diffused
out of the bag leaving behind pure colloidal solution .

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5.8 Properties of colloidal solutions Sedimentation : The colloidal particles settle down under the
The main characteristic properties of colloidal solutions are as influence of gravity at a very slow rate. This phenomenon is
follows: used for determining the molecular mass of the macromolecules.
5.8.1 Physical properties 5.8.4 Optical properties
Heterogeneous nature : Colloidal sols are heterogeneous in Tyndall effect: When light passes through a sol, its path becomes
nature. They consists of two phases; the Dispersed Phase and visible because of scattering of light by particles. It is called
the Dispersion Medium. Tyndall effect. This phenomenon was studied for the first time
Stable nature : The colloidal solutions are quite stable. Their by Tyndall. The illuminated path of the beam is called Tyndall
particles are in a state of motion and do not settle down at the cone. In a true solution, there are no particles of sufficiently large
bottom of the container. diameter to scatter light and hence no Tyndall effect is observed.
Filterability : Colloidal particles are readily passed through the The Tyndall effect has also been observed by an instrument
ordinary filter papers. However they can be retained by special called ultra – microscope.
filters known as ultrafilters (parchment paper).
5.8.2 Colligative properties
 Due to formation of associated molecules, observed values
of colligative properties like relative decrease in vapour
pressure, elevation in boiling point, depression in freezing
point, osmotic pressure are smaller than expected.
 For a given colloidal sol the number of particles will be very
small as compared to the true solution.
5.8.3 Mechanical properties
Brownian movement:The colloidal particles are moving at
random in a zig – zag motion. This type of motion is called
Brownian movement.

Tyndall effect
5.8.5 Origin of the charge on colloidal particles
The origin of the charge on the sol particles in most cases is due
to the preferential adsorption of either positive or negative ions
on their surface. The sol particles acquire electrical charge in any
one or more of the following ways.
Due to the dissociation of the surface molecules:
Some colloidal particles develop electrical charge due to the
dissociation / ionisation of the surface molecules. The charge on
the colloidal particles is balanced by the oppositely charged ions
Brownian movement of colloidal particles
in the sol. For example, an aqueous solution of soap (sodium
The reason of brownian motion is that the molecules of the
palmitate) which dissociates into ions as,
dispersion medium are constantly colloiding with the particles of
the dispersed phase. C15 H 31COON  C15 H 31COO   Na  .
Sodium palmitate
Diffusion : The sol particles diffuse from higher concentration to
lower concentration region. However, due to bigger size, they
diffuse at a lesser speed.

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The cations (Na +) pass into the solution while the anions

(C15 H31COO ) have a tendency to form aggregates due to weak


attractive forces present in the hydrocarbon chains.
Due to frictional electrification : It is believed that the frictional
electrification due to the rubbing of the dispersed phase particles
with that of dispersion medium results in some charge on the
colloidal particles. The dispersion medium must also get some
charge, because of the friction. Since it does not carry any charge, Process of Electrophoresis
the theory does not seem to be correct.
Electrical double layer theory :The electrical properties of
Due to selective adsorption of ions : The particles constituting the colloids can also be explained by electrical double layer theory.
dispersed phase adsorb only those ions preferentially which are According to this theory a double layer of ions appear at the
surface of solid. The ion preferentially adsorbed is held in fixed
common with their own lattice ions. For example, when a small
part and imparts charge to colloidal particles. The second part
quantity of silver nitrate (AgNO3) solution is added to a large consists of a diffused mobile layer of ions. This second layer
quantity of potassium iodide (KI) solution, the colloidal particles consists of both the type of charges. The net charge on the
 second layer is exactly equal to that on the fixed part. The existence
of silver iodide adsorb I from the solution to become negatively
of opposite sign on fixed and diffuse parts of double layer leads
charged, (at this stage KI is in excess, and I  being common to to appearance of a difference of potential, known as zeta potential
AgI) or electrokinetic potential.

AgI  I 
 (AgI)I 
(C olloidal (in excess (C olloidal particle
particle) in the becom es positively
m edium ) charged)
But, when a small quantity of potassium iodide (KI) solution is
added to a large quantity of silver nitrate solution (AgNO3) ; the
colloidal silver iodide particles adsorb Ag+ from the solution to
become positively charged, (at this stage AgNO3 is in excess
Formation of electrical double layer
and Ag+ is common to AgI),
A gI  Ag   (A gI)Ag 
 Electro-osmosis : In it the movement of the dispersed particles
(C olloidal
particle)
( ex cess in
the m edium )
(C olloidal p article
b ecom es po sitively
is prevented from moving by semipermeable membrane. Electro-
ch arged) osmosis is a phenomenon in which dispersion medium is allowed
5.8.6 Electrical properties to move under the influence of an electrical field, whereas colloidal
Colloidal particles carry an electric charge and the dispersion particles are not allowed to move. The existence of electro-
medium has an opposite and equal charge, the system as a whole osmosis has suggested that when liquid is forced through a
being electrically neutral. The presence of equal and similar porous material or a capillary tube, a potential difference is setup
charges on colloidal particles is largely responsible in giving between the two sides called as streaming potential.
stability to the system because the mutual forces of repulsion
between similarly charged particles prevent them from coalescing 5.9 Stability of sols
and coagulating when they come closer to one another.
Sols are thermodynamically unstable and the dispersed phase
Electrophoresis: The phenomenon of movement of colloidal (colloidal particles) tend to separate out on long standing due to
particles under an applied electric field is called Vander Waal’s attractive forces. However sols tend to exhibit
electrophoresis. If the particles accumulate near the negative some stability due to
electrode, the charge on the particles is positive. On the other
hand, if the sol particles accumulate near the positive Stronger repulsive forces between the similarly charged
electrode, the charge on the particles is negative. particles : All colloidal particles in any sol possess similar charge.
Therefore, due to the electrostatic repulsion these are not able to
come closer and form aggregates. Thus stronger repulsive forces
between the similarly charged particles in a sol promote its
stability.

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Particle-solvent interactions :Due to strong particle-solvent Coagulating power of an electrolyte is directly proportional to
(dispersion medium) interactions, the colloidal particles get the valency of the active ions (ions causing coagulation).
strongly solvated. Due to solvation, the effective distance
between the colloidal particles increases, and therefore, the Vander For example to coagulate negative sol of As2S3 , the coagulation
Waal’s force of attraction decreases. As a result, the particles are power of different cations has been found to decrease in the
not able to form aggregates. Lyophilic sols are mainly stabilized
by solvation effects due to strong interactions between the sol order as, Al3   Mg 2   Na 
particles and the dispersion medium.
Similarly, to coagulate a positive sol such as Fe(OH) 3, the
5.10 Coagulation or Flocculation or Precipitation coagulating power of different anions has been found to
The phenomenon of the precipitation of a colloidal solution by decrease in the order :
the addition of the excess of an electrolyte is called coagulation
or flocculation. [Fe(CN) 6 ]4   PO 34  SO 24   Cl

By electrophoresis : In electrophoresis the colloidal particles  Coagulation or flocculation value : The minimum
move towards oppositely charged electrode. When these come concentration of an electrolyte which is required to cause
in contact with the electrode for long these are discharged and the coagulation or flocculation of a sol is known as
precipitated. flocculation value or the number of millimoles of an electrolyte
By mixing two oppositely charged sols : When oppositely required to bring about the coagulation of one litre of a
charged sols are mixed in almost equal proportions, their charges colloidal solution is called its flocculation value.
are neutralised. Both sols may be partially or completely
Thus , a more efficient flocculating agent shall have lower
precipitated as the mixing of ferric hydroxide (+ve sal) and
flocculating value. Coagulating value or flocculating value
arsenious sulphide (–ve sal) brings them in precipitated form. 1
 .
This type of coagulation is called mutual coagulation or material coagulating pow er
coagulation.  Coagulation of lyophilic sols : There are two factors which
By boiling : When a sol is boiled, the adsorbed layer is disturbed are responsible for the stability of lyophilic sols. These
due to increased collisions with the molecules of dispersion factors are the charge and solvation of the colloidal particles.
medium. This reduces the charge on the particles and ultimately When these two factors are removed, a lyophilic sol can be
they settle down to form a precipitate. coagulated. This is done by adding electrolyte and by adding
suitable solvent. When solvent such as alcohol and acetone
By persistent dialysis : On prolonged dialysis, the traces of are added to hydrophilic sols the dehydration of dispersed
the electrolyte present in the sol are removed almost completely phase occurs. Under this condition a small quantity of
and the colloids become unstable. electrolyte can bring about coagulation.
By addition of electrolytes : The particles of the dispersed phase
5.11 Protection of colloids and Gold number
i.e., colloids bear some charge. When an electrolyte is added to
sol, the colloidal particles take up ions carrying opposite charge Lyophilic sols are more stable than lyophobic sols. Lyophobic
from the electrolyte. As a result, their charge gets neutralised sols can be easily coagulated by the addition of small quantity of
and this causes the uncharged, particles to come closer and to an electrolyte. When a lyophilic sol is added to any lyophobic
get coagulated or precipitated. sol, it becomes less sensitive towards electrolytes. Thus, lyophilic
5.10.1 Hardy schulze rule colloids can prevent the coagulation of any lyophobic sol.

The coagulation capacity of different electrolytes is different. The phenomenon of preventing the coagulation of a lyophobic
sol due to the addition of some lyophilic colloid is called sol
It depends upon the valency of the active ion are called
protection or protection of colloids. The protecting power of
flocculating ion, which is the ion carrying charge opposite to
different protective (lyophilic) colloids is different. The efficiency
the charge on the colloidal particles. Greater the valency of the
of any protective colloid is expressed in terms of gold number.
active ion or flocculating ion, greater will be its coagulating
power.

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5.11.1 Gold number  In rubber and tanning industry (coagulation and mutual
coagulation) : Several industrial processes such as rubber
Zsigmondy introduced a term called gold number to describe the
plating, chrome tanning, dyeing, lubrication etc are of
protective power of different colloids. This is defined as, weight
of the dried protective agent in milligrams, which when added to colloidal nature.
10 ml of a standard gold sol (0.0053 to 0.0058%) is just sufficient In rubber plating, the negatively charged particles of rubber
to prevent a colour change from red to blue on the addition of 1 (latex) are made to deposit on the wires or handle of various
ml of 10 % sodium chloride solution, is equal to the gold number tools by means of electrophoresis. The article on which
rubber is to be deposited is made anode.
of that protective colloid.
In tanning the positively charged colloidal particles of hides
and leather are coagulated by impregnating them in
negatively charged tanning materials (present in the barks
of trees). Among the tanning agent chromium salts are most
commonly used for the coagulation of the hide material and
the process is called chrome tanning.
 Artificial rains : It is possible to cause artificial rain by
throwing the electrified sand or silver iodide from an
aeroplane and thus coagulating the mist hanging in air.
 Smoke precipitation (Coagulation) : Smoke is a negative
Protection of colloids sol consisting of carbon particles dispersed in air. Thus,
these particles are removed by passing through a chamber
Thus, smaller is the gold number, higher is the protective action
provided with highly positively charged metallic knob.
of the protective agent.
1
Protective power 
Gold number

Gold Numbers of Some Hydrophillc Substances


Sr. Hydrophilic Gold
No. substance number

1. Gelatin 0.005-0.01

2. Sodium caseinate 0.01

3. Haemoglobin 0.03-0.07

4. Gum arabic 0.15-0.25 Cottrell Smoke Precipitator

5. Sodium oleate 0.4 – 1.0  Formation of deltas (Coagulation) : River water consists of
negatively charged clay particles of colloidal dimension.
6. Gum tragacanth 2 When the river falls into the sea, the clay particles are
7. Patato starch 25 coagulated by the positive Na  , K  , Mg 2  ions etc. present
in sea water and new lands called deltas are formed.
5.12 Application of colloids  Clotting of blood : Blood consists of negatively charged
 Purification of water by alum (coagulation) : Alum which colloidal particles (albuminoid substance). The colloidal
yield Al3+ ions, is added to water to coagulate the negatively nature of blood explains why bleeding stops by applying a
charged clay particles. ferric chloride solution to the wound. Actually ferric chloride
solution causes coagulation of blood to form a clot which
stops further bleeding.

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 Colloidal medicine : Argyrol and protargyrol are colloidal 6.2 Preparation of Emulsions
solution of silver and are used as eye lotions. Colloidal sulphur Emulsions are generally prepared by vigorously agitating a
is used as disinfectant. Colloidal gold, calcium and iron are mixture of the relevant oil and water by using either a high speed
used as tonics. mixer or by using ultrasonic vibrators. The emulsions obtained
 Photographic plates : These are thin glass plates coated by simple mechanical stirring are unstable.
with gelatin containing a fine suspension of silver bromide. The two components (oil and water) tend to separate out. To
The particles of silver bromide are colloidal in nature. obtain a stable emulsion, a suitable stabilizing substance is
generally added. The stabilizing substance is called emulsifier or
6. EMULSIONS
emulsifying agent. The emulsifier is added along with the oil and
Emulsions are the colloidal solutions in which both the dispersed water in the beginning.
phase and the dispersion medium are liquids. A good example of an
6.3 Properties of emulsion
emulsion is milk in which fat globules are dispersed in water. The
size of the emulsified globules is generally of the order of 10–6m.  Emulsions show all the characteristic properties of colloidal
Emulsion resemble lyophobic sols in some properties. solution such as Brownian movement, Tyndall effect,
electrophoresis etc.
6.1 Types of Emulsion
 These are coagulated by the addition of electrolytes
Depending upon the nature of the dispersed phase, the emulsions containing polyvalent metal ions indicating the negative
are classified as: charge on the globules.
6.1.1 Oil-in-water emulsions (O/W)  The size of the dispersed particles in emulsions in larger
The emulsion in which oil is present as the dispersed phase and than those in the sols. It ranges from 1000 Å to 10,000 Å.
water as the dispersion medium (continuous phase) is called an However, the size is smaller than the particles in suspensions.
oil-in-water emulsion. Milk is an example of the oil-in-water type of  Emulsions can be converted into two separate liquids by
emulsion. In milk liquid fat globules are dispersed in water. Other heating, centrifuging, freezing etc. This process is also
examples are, vanishing cream etc. known as demulsification.
6.1.2 Water-in-oil emulsion (W/O) 6.5 Applications of emulsions
The emulsion in which water forms the dispersed phase, and the  Concentration of ores in metallurgy
oil acts as the dispersion medium is called a water-in-oil emulsion.  In medicine (Emulsion water-in-oil type)
These emulsion are also termed oil emulsions. Butter and cold
cream are typical examples of this types of emulsions. Other  Cleansing action of soaps.
examples is cod liver oil etc.  Milk, which is an important constituent of our diet is an
emulsion of fat in water.
 Digestion of fats in intestine is through emulsification.

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SUMMARY
 Surface Chemistry is that branch of chemistry which  The colloidal state depends on the particle size. It is
deals with the study of the phenomena occurring at the regarded as an intermediate state between true solution
surface or interface. and suspension.

 The accumulation of molecular species at the  Classification of Colloids:


surface rather than in the bulk of a solid or - Lyophilic colloids (water loving) : “The colloidal
liquid is termed adsorption. solutions in which the particles of the dispersed phase
 The substance which gets adsorbed on any surface is have a great affinity for the dispersion medium, are called
called adsorbate lyophilic colloids.”
 The substance on the surface of which adsorption takes - Lyophobic colloids (water hating) : “The colloidal
place is called adsorbent. solutions in which there is no affinity between particles
of the dispersed phase and the dispersion medium are
 Factors which affect the extent of adsorption n solid called lyophobic colloids.”
surface
 Micelles are the clusters or aggregated particles
- Nature of the adsorbate (gas) and adsorbent formed by association of colloids in solution.
(solid)
 The origin of the charge on the sol particles in most
-Effect of pressure on the adsorbate gas : cases is due to the preferential adsorption of either
-Effect of temperature positive or negative ions on their surface.

 Freundlich adsorption isotherm  The phenomenon of the precipitation of a colloidal


solution by the addition of the excess of an electrolyte
1
x x 1 is called coagulation or flocculation.
 kP n or log  log k  log P 3.
m m n
 Hardy schulze rule: Coagulating power of an electrolyte
 Substances, which accelerate the rate of a chemical is directly proportional to the valency of the active ions
reaction and themselves remain chemically and (ions causing coagulation).
quantitatively unchanged after the reaction.
The minimum concentration of an electrolyte which is
- Homogeneous catalyst required to cause the coagulation or flocculation of a
- Heterogeneous catalyst sol is known as flocculation value.
 Zeolite: They are microporous aluminosilicates with  Gold Number: Weight of the dried protective agent in
a three dimensional network of silicates in which some milligrams,which when added to 10 ml of a standard
silicon atoms are replaced by aluminium atoms giving gold sol (0.0053 to 0.0058%) is just sufficient to prevent
Al–O–Si framework. a colour change from red to blue on the addition of 1
ml of 10 % sodium chloride solution, is equal to the gold
 Enzymes are complex nitrogenous organic compounds
number of that protective colloid.
produced by living animals and vegetables .
 Emulsions are the colloidal solutions in which both
the dispersed phase and the dispersion medium are
liquids.

SCAN CODE
Surface Chemistry
SURFACE CHEMISTRY 197

SOLVED EXAMPLES
Example - 1 At high pressure
(a) Adsorption of a gas on the surface of solid is generally x x x
 P o or  KP o i.e., K
accompanied by a decrease in entropy. Still it is a m m m
spontaneous process. Explain. In the intermediate range of pressure
(b) How does an increase in temperature affect both physical
x
as well as chemical adsorption ?  P1/ n
m
Sol. (a) According to the equation
ΔG = ΔH - TΔS x
or  KP1/ n (n > 1)
m
for a process to be spontaneous G should be negative.
G is negative because reaction is highly exothermic (b) Catalyst : Finely divided iron.
i.e., H is negative. Promoter: Molybdenum.
(b) On increasing temperature desorption occurs in physical
Example – 3
adsorption. Chemical adsorpation increases first and
then decreases with increase in temperature. Explain factors affecting adsorption.

Example – 2 Sol. Adsorption is generally affected by following factors:


(i) Temperature : Adsorption is an exothermic process.
Consider the adsorption isotherms given below and
Hence, according to Le chaterlier’s principle, the rate of
interpret the variation in the extent of adsorption (x/m) when
adsorption decreases with the increase in temperature and
(a) (i) temperature increases at constant pressure vice versa. Thus, adsorption is inversely proportional to
(ii) pressure increases at constant temperature. temperature at a constant pressure. In the graphs plotted,
(b) Name the catalyst and the promoter used in Haber’s showing the relationship between the rate of adsorption
process for manufacture of ammonia. and the temperature at a constant pressure, the physical
adsorption is favoured at low and chemical adsorption at
relatively high temperature.

x
Sol. (a) (i) Extent of adsorption   decreases with increase
m
in temperature at constant pressure as adsorption is an
exothermic process. (ii) Pressure : The curve shows the effect of temperature
(ii) Extent of adsorption increases with increase in on the rate of the adsorption at constant pressure, is called
pressure at constant temperature. At low value of adsorption isobar. In case of gases, adsorption increases
pressure. with increase in the pressure of the gas. However, increase
is not uniform. At low pressure the adsorption increases
x x linearly while at moderate pressure it increases exponentially.
 P or  KP
m m At high pressure complete surface area of adsorbent is
SURFACE CHEMISTRY 198

covered and hence adsorption becomes independent of Example – 4


pressure. How do size of particles of adsorbent, pressure of gas and
prevailing temperature influence the extent of adsorption of
a gas on a solid ?
Sol. The influence is in the following ways :
(i) Smaller the size of the particles of the adsorbent, greater
is the surface area and greater is the adsorption.
(ii) At constant temperature, adsorption first increases with
increase of pressure and then attains equilibrium at a
high pressure.
(iii) In physical adsorption, it decreases with increase of
(iii) Nature of adsorbent : The gases which are easily
temperature but in chemisorption, first it increases and
liquified and highly soluble in water are easily adsorbed.
then decreases.
NH3, HCl, Cl2, SO2, etc are adsorbed readily. These gases
have greater Van der Waal’s forces of attraction and hence Example – 5
get easily adsorbed. As molecular weight increases, 1 g of charcoal adsorbs 100 mL 0.5 M CH3COOH to form a
adsorption increases. e.g. SO2 is adsorbed more than CO2 monolayer, and thereby the molarity of CH3COOH reduces
at the same temperature. to 0.49. Calculate the surface area of the charcoal adsorbed
(iv) Nature of Adsorbent : Adsorption also depends on the by each molecule of acetic acid.
nature of adsorbent. The adsorbent with more free valencies (Surface area of charcoal = 3.0 × 102 m2/g.)
and unbalanced forces adsorb to greater extent. e.g. the
Sol. Number of moles of acetic acid which we present in 100 mL
transition metals. The same gas can be adsorbed to different
before adding charcoal = 0.05
extents on different adsorbents e.g. H2 is adsorbed by
Number of moles of acetic acid in 100 mL after adding
different metals in the following order. Pd > Pt > Ni > Fe
charcoal = 0.049
(v) Surface area of adsorbent : Since, adsorption is the
Number of moles of acetic acid adsorbed on the surface of
surface phenomenon, the rate of adsorption is directly
charcoal = (005 – 0.049) = 0.001
proportional to the surface area of the adosrbent. Thus,
greater the total surface area of the adsorbent, greater is So, number of molecules of acetic acid adsorbed on the
the adsorption. Therefore, finely divided particles of the surface of charcoal
adsorbent show greater adsorption due to their large surface = 0.001 × 6.02 × 1023 = 6.02 × 1020
area.  Surface area of charcoal = 3.01 × 102 m2
(vi) Concentration of adsorbate : The extent of adsorption Hence, area occupied by one molecule of acetic acid on the
depends upon the concentration of the adsorbate, used in surface of charcoal
a solution. The rate of adsorption increases with the
increase in concentration of solution of the adsorbate, but 3.01  10 2
  5  10  19 m 2 ,
upto certain limit. After the equilibrium is achieved, further 6.02  10 20
increase in the concentration has no effect on the rate of
adsorption. So, area = 5 × 10–19 m2.
SURFACE CHEMISTRY 199

Example – 6 Example – 8
Which has a higher enthalpy of adsorption, physisorption Indicate a chemical reaction involving a homogeneous
or chemisorption ? catalyst.
Sol. Chemisorption
Sol. 2SO 2  g   O 2  g   2SO3  g 
 
NO g

Example – 7
Example – 9
Distinguish between Homogeneous and Heterogeneous
catalysis. Give an example of a shape selective catalyst.
Sol. Sol. Zeolites are shape selective catalysts. A zeolite called ZSM-
Homogenous Heterogeneous 5 converts alcohol to gasoline.
Catalysis Catalysis
1. The catalyst and the 1. The catalyst and the Example – 10
reactant form a single reactant are in differnt What is meant by ‘shape selective’ catalysis?
phase. phases. Sol. Shape selective catalysis is a chemical reaction in which
2. The catalyst dissolves 2. The catalyst does not the rate depends on the pore size of the catalyst and also
into the gas phase or dissolve in the reacting on the shape and size of the reactant and product molecules.
solution (a reacting mixture. Zeolite acts as a shape selective catalyst. For example, ZSM-
mixture. 5 (Zeolite sieve of molecular porosity 5) is used as a shape
3. The reaction occurs in 3. The reaction does not selective catalyst to produce gasoline of high octane
the liquid phase or gas occur in gas or liquid number from methanol.
phase. phase but occurs on the Example – 11
surface of solid catalyst.
Give the mechanism of enzyme catalysis.
4. The catalyst is often 4. The catalyst adsorbs the
involved in the reactant molecules to Sol. An enzyme molecule has one or more active sites at which
chemical reaction. form a chemical bond a specific substrate (reactant) molecule fits. In other words
the active site acts like a lock into which fits only a specific
between catalyst and the
key (substrate or reactant). This concept of lock and key
reactant molecules. was developed by German chemist Emil Fischer in 1894.
5. The catalyst cannot be 5. The catalyst can be Now it is known that the structure of active site is flexible
easily separated from easily separated from and hence it can accomodate more than one type of
the products of reaction products. substrate. The active site returns to its original state after
reactions. the products are released.
6. The rate of the reaction 6. The rate of reaction
does not depend on is proportional to the
thesurface area of surface area of catalyst.
catalyst.
7. The homogeneously 7. The heterogeneously
catalyzed reactions catalyzed reactions
are often little faster are often slower than
than those which are those which are
The binding of substrate (reactant) at the active site
heterogeneously homogenously
of the enzyme catalyst produces enzyme – substrate
catalyzed. catalyzed.
complex which then decomposes to give the product
of reaction and the enzyme is recovered.
 ES
E + S   E+P
where, E and S are enzyme and substrate respectively.
ES is an enzyme-substrate complex and P is the product.
SURFACE CHEMISTRY 200
Example – 12 (ii) Macromolecular Colloids
Certain substances form larger molecules having the
What are the physical states of dispersed phase and
dimension of colloidal particles. Such molecules are
dispersion medium of froth ? called macromolecules. Macromolecules have very high
Sol. Dispersed phase : Gas molecular masses. Most lyophilic sols are
Dispersion medium : Liquid macromolecular colloids.
Example :
Example – 13 gelatin, starch, nucleic acids.
Write two differences between sols and emulsions. Example – 17
Sol. (i) Sols are dispersion of solids in liquids while emulsions Discuss Hardy – Schulze rule.
are dispersion of liquids in liquids.
(ii) Sols are quite stable whereas emulsions are less stable. Sol. The precipitation action of ions of an electrolyte depends
on the sign of charge and the valency of the ion. The effects
Example – 14
of these factors on the coagulation of colloidal particles
In what way is a sol different from a gel ? were stated by H. Schulze and Sir William Bate Hardy which
Sol. Colloidal system in which solid is dispersed in liquid is is known as Schulze – Hardy rule. Which is given as:
called sol and that in which liquid is dispersed in solid is (i) The ions of opposite sign to those present on the
surface of the particles cause the precipitation of the
called gel.
particles. For example, positively charged ions of an
Example – 15 electrolyte will cause the precipitation of negatively
Write two differences between multimolecular colloids and charged ions, negatively charged ions will effect the
macromolecular colloids. precipitation of positive particles.
Sol. (i) Multimolecular colloids are formed by aggregation of (ii) The precipitation power of an electrolyte increases very
small molecules (diameter < 1 nm) while rapidly with an increase in the valence of anion or cation.
macromolecular colloids are formed by macromolecules Thus, the precipitating power of ions decreases in the
(polymers) and consist of single molecules. order Al3+ > Mg2+ > Na+ and PO 34  SO 24   Cl  .
(ii) Multimolecular colloids are generally lyophobic whereas Example – 18
macromolecular colloids are generally lyophilic.
Define ultrafiltration.
Example – 16
Sol. In this process, colloidal solutions are purified by carrying
Classify colloids on the basis of number of molecules or
atoms. out filtration through special types of graded filters called
Sol. On the basis of number of molecules or atoms colloidal ultra-filters. Filter paper allows the passage of electrolyte
systems are classified as: but does not allow the passage of colloidal particles.
(i) Multimolecular Colloids : Example – 19
(a) Colloidal particles are bigger than molecule of true
What is an emulsion?
solutions and smaller than the particles of suspensions.
(b) When a substance is dispersed in a suitable dispersion Sol. Emulsion is a colloidal solution in which both the dispersed
medium, a larger number of atoms or molecules phase and dispersion medium are liquids e.g. milk, cod liver
aggregate to form a particle of colloidal size. oil, etc.
Example :
Au sol, Ag sol and Sulphur sol. Gold sol consists of
particles which are formed by aggregation of many gold
atoms.
SURFACE CHEMISTRY 201
Example – 20
Distinguish between true solution, colloidal solution and
suspension.
Sol.

S.No. True solution Colloidal dispersion Suspension


1. It is Homogeneous. It is heterogenous It is heterogenous.
2. The particles are ions or molecules. The particles are either single The particles are aggregates of
macromolecules or aggregates molecules or atoms.
of molecules or atoms.
3. The particle size range between The particles size lies between The particle size is larger than
1 nm to 103 nm. 103 nm.
4. The particles do not settle. The particles do not settle. Particles do not pass through
parchment.
5. The particles readily pass through The particles pass slowly through The particles do not pass through
parchment. parchment. parchment.
6. The particles are invisible even The particles are invisible in The particles are visible under
under powerful microscope. microscope. microscope or sometimes with named
eye.
7. The particles do not scatter light. The particles scatter light. It does not show the scattering of
light.
8. It does not show electrophoresis, It shows the properties like It does show the properties
Brownian movement etc. Brownian movement electrophoresis, Brownian movement,
Electrophoresis etc. etc.

Example – 21 Lyophobic sols : In this type of sols the particles of


Comment on the statement that “Colloid is not a substance dispersed phase have little or no affinity for the
but state of a substance.” dispersion medium, e.g., gold sol, Fe (OH)3 sol, As2S3
Sol. The given statement is true. This is because the same sol., etc. Therefore lyophobic colloid can be easily
substance may exist as a colloid under certain conditions coagulated.
and as a crystalloid under certain other conditons. For
Example – 23
example, NaCl in water behaves as a crystalloid while in
benzene, it behaves as a colloid. Similarly, dilute soap Give an example of an associated colloid.
solution behaves like a crystalloid while concentrated Sol. Soaps and detergents are associated colloids.
solution behaves as a colloid (called associated colloid). It
is the size of the particles which matters, i.e., the state in Example – 24
which the substance exists. If the size of the particles lies What is Kraft temperature ?
in the range 1 nm to 1000 nm, it is in the colloidal state.
Sol. Kraft temperature is the minimum temperature above
Example – 22 which the formulation of micelles takes place.
What are lyophilic and lyophobic sols ? Give one example Example – 25
of each type. Which one of these two types of sols is easily
Why is a colloidal sol stable ?
coagulated and why?
Sol. Lyophilic sols : Lyophilic sols are those sols in which Sol. All the particles in a colloidal sol carry the same charge
the particles of dispersed phase have great affinity for and hence keep on repelling each other and cannot
the dispersion medium, e.g., sols of gum, gelatine, aggregate together to form bigger particles.
starch, etc.
SURFACE CHEMISTRY 202

Example – 26 Sol. (a) It is due to greater force of attraction between dispersed


What happens in the following activities and why? phase and dispersion medium in lyophilic colloid than
(i) An electrolyte is added to a hydrated ferric oxide sol in lyophobic colloid.
(b) Fe(OH)3 sol is positively charged which is coagulated
water.
by negatively charged Cl– present in Sodium Chloride
(ii) A beam of light is passed through a colloidal solution.
solution.
(iii) An electric current is passed through a colloidal (c) Sky appears blue in colour due to scattering of light by
solution. colloidal particles. This is known as Tyndall effect.
Sol. (i) The positively charged colloidal particles of Fe(OH)3 Example – 29
get coagulated by the negatively charged ions provided
What causes Brownian movement in a colloidal solution?
by electrolyte.
(ii) The path of light becomes visible due to scattering of Sol. This is due to the unequal bombardment of colloidal particles
light by colloidal particles (Tyndall effect). by the molecules of dispersion medium.
(iii) Electrophoresis takes place in which colloidal particles Example – 30
move towards the oppositely charged electrode where Write a note on electrical properties of colloids.
they lose their charge and get coagulated.
Sol. (i) Electrical properties of colloidal dispersions are due to
Example – 27 existence of electrical charge on colloidal particles.
Write a note on optical properties of colloids (Tyndall effect). (ii) All particles in a given dispersion carry same charge
either + ve or – ve.
Sol. It was investigated by British physicist John Tyndall.
(iii) The repulsion between the particles carying the same
Colloidal system consist of discrete particles of dimensions
charge keeps them separated.
comparable to the wavelength of the Ultraviolet and visible
Due to the same charge, the particles do not come close
radiations So, whenever a beam of light is passed through
together to form large particles that will precipitate out.
a colloidal system, the colloidal particles scatter the light in
thus stability of colloids is associated with an electrical
all directions.
charge present on the particles.
Now if the particle is viewed through a microscope, against
a dark background, it becomes visible as a speck of light. Example – 31
This Scattering of light by the colloidal particles is known What are the various reasons for the origin of electrical
as Tyndall effect. Tyndall effect is more prominent when charge on colloidal particles ?
the wavlength of the incident light and the dimensions of
Sol. The various reasons for the origin of electrical charge on
the scattering particles are of the same order. That is why
the colloidal particles are as follows :
light is not scattered by true solutions. If the colloidal
(i) Frictional electrification caused by the mutual rubbing
particles are assumed to be small, and do not absorb
of the colloidal particles with molecules of the dispersion
light, it may be observed that
medium.
(i) The intensity of the scattered light is greater in the
(ii) Electron capture by particles from air and during electro-
direction parallel to the incident beam and smallest in
dispersion in Bredig’s method.
the direction perpendicular to the incident beam.
(ii) The intensity of the scattered light decreases and hence (iii) Preferential adsorption of ions from solutions.
the tyndall beam assumes a blue colour imparting the Example – 32
complementary yellow colour to the transmitted light.
What is the ‘coagulation’ process.
Example – 28
Sol. The process of settling of colloidal particles is called
Explain the following observations : coagulation.
(a) Lyophilic colloid is more stable than lyophobic colloid.
(b) Coagulation takes place when sodium chloride solution
is added to a colloidal solution of ferric hydroxide.
(c) Sky appears blue in colour.
SURFACE CHEMISTRY 203
Example – 33 Sol. (a) As ferric hydroxide, Fe (OH)3 is a positively charged sol,
Why is ferric chloride preferred over potassium chloride so it gets coagulated by chloride ions Cl–, released by
in case of a cut leading to bleeding ? NaCl solution.
(b) Cottrell’s smoke precipitator, neutralises the charge on
Sol. Fe3+ ion has greater coagulating power than K+ ion as
it has higher charge. unburnt carbon particles, coming out of chimney and
they get precipitated and settle down at the floor of the
Example – 34
chamber.
Mention two ways by which lyophilic colloids can be (c) As physical adsorption, involves only weak van der
coagulated. waal’s force of interaction, so many layers of adsorbate
Sol. This can be done by get attached, while chemisorption involves chemical
(i) adding an electrolyte bond formation between adsorbate and adsorbents, so
(ii) adding a suitable solvent. monolayer is formed.
Example – 35
Explain the following observations:
(a) Ferric hydroxide sol gets coagulated on addition of (a) Adsorption of a gas on the surface of solid is
generally accompanied by a decrease in entropy. Still it
sodium chloride solution. is a spontaneous process. Explain.
(b) Cottrell’s smoke precipitator is fitted at the mouth
of the chimney used in factories.
(c) Physical adsorption is multillayered, while
chemisorption is monolayered.
SURFACE CHEMISTRY 204

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS


Adsorption (c) Is irreversible in nature
1. Adsorption is phenomenon in which a substance (d) Increases with increase of temperature
(a) Goes into the body of the other substance 9. Which one of the following characteristics is not correct for
(b) Remains close the other substance physical adsorption ?
(c) Accumulates on the surface of the other substance (a) Adsorption on solids is reversible
(d) None of these (b) Adsorption increases with increase in temperature
2. In adsorption of oxalic acid on activated charcoal, the (c) Adsorption is spontaneous
activated charcoal is known as
(d) Both enthalpy and entropy of adsorption are negative
(a) Adsorbent (b) Adsorbate
10. Physical adsorption is essentially quite appreciable
(c) Adsorber (d) Absorber
(a) At room temperature
3. Which one of the following statement is not correct
(b) At higher temperature
(a) The extent of adsorption depends on the nature of the
adsorbent and adsorbate (c) At lower temperature
(b) The extent of adsorption depends on the pressure of (d) None of these
the gas 11. Which of the following is not a characteristic of
(c) The extent of adsorption depends on the temperature chemisorption
(d) The extent of adsorption has no upper limit (a) H is of the order of 400 kJ
4. Sorption is the term used when (b) Adsorption is irreversible
(a) Adsorption takes place (c) Adsorption may be multimolecular layer
(b) Absorption takes place (d) Adsorption is specific
(c) Both (a) and (b) 12. Chemisorption
(d) Desorption takes place (a) Involves the weak attractive interactions between
5. For adsorption, the thermodynamic requirement is that adsorbent and adsorbate
(a) H must be negative (b) Is irreversible in nature
(b) S must be negative (c) Decreases with increase of temperature
(c) G must be negative (d) Involves multilayer formation of adsorbent on
adsorbate
(d) H, S and G must be negative
13. Adsorption is always
6. If the adsorbate is held on a surface by weak Vander Waal’s (a) Endothermic (b) Exothermic
forces, the adsorption process is called
(c) Either (a) or (b) (d) None of these
(a) Physical adsorption
14. Physical Adsorption is
(b) Chemical adsorption
(a) Exothermic process hence increase in temperature
(c) Heat of adsorption decreases adsorption in cases where Vander Waal’s
(d) Enthalpy of adsorption forces exist between adsorbate and adsorbent.
7. Adsorption is multilayered in the case of (b) An endothermic process hence increase in temperature
increases adsorption
(a) Physical adsorption (b) Chemisorption
(c) An exothermic process hence increase in temperature
(c) Both (d) None of both increases adsorption
8. Physical adsorption (d) None of these
(a) Involves the weak attractive interaction between the
adsorbent and adsorbate
(b) Involves the chemical interactions between the
adsorbent and adsorbate
SURFACE CHEMISTRY 205

15. There is desorption of physical adsorption when 22. According to Freundlich adsorption isotherm which of the
(a) Temperature is increased following is correct ?
(b) Temperature is decreased
x
(c) Pressure is increased (a)  p0
m
(d) Concentration is increased
16. Which of the following statements is incorrect regarding x
(b)  p1
physisorption ? m
(a) It occurs because of van der Waals’ forces
x
(b) More easily liquefiable gases are adsorbed readily (c)  p1/ n
m
(c) Under high pressure it results into multi-molecular layer
(d) All of the above are correct for different range of
on adsorbent surface
pressure
(d) Enthalpy of adsorption (Hadsorption) is slow and positive Catalysis
17. Chemisorption 23. Which one is false in the following statements?
(a) Increases with temperature (a) A catalyst is specific in its action
(b) Decreases with temperature (b) A very small amount of the catalyst alters the rate of a
(c) Remains unaffected by change of temperature reaction
(d) first increases then decreases with temperature (c) The number of free valencies on the surface of the
18. When the temperature is lowered and pressure is raised, the catalyst increases on subdivision
adsorption of a gas on a solid (d) Ni is used as catalyst in the manufacture of ammonia
(a) Decreases 24. A catalyst is a substance which
(b) Increases (a) Alters the equilibrium in a reaction
(c) Remains unaffected (b) Is always in the same phase as the reactants
(d) Decreases first then increases (c) Participates in the reaction and provides easier pathway
19. Which one of the following is an example of adsorption? for the same
(a) ammonia in contact with water (d) Does not participate in the reaction but speeds it up
(b) anhydrous CaCl2 with water 25. In a homogeneous catalysis

(c) silica gel in contact with water vapours (a) The catalyst and the reactants should be gases
(b) The catalyst and the reactants should form a single phase
(d) all of these
(c) Catalyst and the reactants are all solids
20. Which one is Freundlich’s equation?
(d) The catalyst and the reactants are all liquids
x 1 x 26. A catalyst
(a)  log k  log P (b)  exp (kP )
m n m (a) Increases the free energy change in the reaction
x x 1 (b) Decreases the free energy change in the reaction
(c)  kP 2 (d) log  log k  log C
m m n (c) Does not increase or decrease the free energy change
in the reaction
21. In Langmuir’s model of adsorption of a gas on a solid surface
(d) Can either increase or decrease the free energy change
(a) the rate of dissociation of adsorbed molecules from the depending on what catalyst we use
surface does not depend on the surface covered
27. Addition of catalyst in a system
(b) the adsorption at a single site on the surface may involve (a) Increases equilibrium concentrations
multiple molecules at the same time
(b) No effect on equilibrium concentrations
(c) the mass of gas striking a given area of surface is
(c) Decreases equilibrium concentrations
proportional to the pressure of the gas
(d) Increases rate of forward reaction and decreases rate of
(d) the mass of gas striking a given area of surface is backward reaction
independent of the pressure of the gas
SURFACE CHEMISTRY 206
28. Enzymes are 36. Fog is an example of colloidal system
(a) Micro-organisms (a) Liquid dispersed in gas
(b) Proteins
(b) Gas dispersed in gas
(c) Inorganic compounds
(c) Solid dispersed in gas
(d) Moulds
29. Enzymes are (d) Gas dispersed in liquid
(a) Substances made by chemists to activate washing 37. The difference between a lyophilic and lyophobic colloid
powder is in their
(b) Very active vegetable catalysts (a) Particle size
(c) catalysts found in organisms (b) Behaviour towards dispersion medium
(d) synthetic catalysts (c) Filtrability
30. In the human body, enzyme that catalyses the reaction of (d) None of these
CO2 with H2O is
38. Colloidal solutions of metals like gold, silver and platinum
(a) Invertase (b) Urease are generally prepared by using
(c) Nitrogenase (d) Carbonic anhydrase
(a) Peptization (b) Bredig’s arc method
31. Which of the following statements about a catalyst is true
(c) Exchange of solvent (d) Oxidation method
(a) It lowers the energy of activation
(b) The catalyst altered during the reaction is regenerated 39. Dialysis is the process of separation of
(c) It does not alter the equilibrium (a) Suspended particles from colloids
(d) All of these (b) Suspended particles from crystalloids
32. Following are the terms about activity and selectivity (c) Colloidal particles from crystalloids
I : Activity is the ability of catalysts to accelerate chemical (d) Colloidal particles from gel
reactions and selectivity is the ability of catalysts to
direct reaction to yield particular products 40. Colloidal solution cannot be obtained from two such
II : Activity is the ability of catalysts to direct reaction to substances which are
yield particular products and selectivity is the ability of (a) Insoluble in each other
catalysts to accelerate chemical reactions.
(b) In same physical state
Select correct term :
(a) I (b) II (c) n different physical state
(c) I and II both (d) None of these (d) None of the above
Colloidal Solutions and Emulsions 41. Difference between colloids and crystalloids is of
33. In shaving cream, the dispersion medium is (a) Particle composition (b) Particle size
(a) Liquid (b) Gas (c) Concentration (d) Ionic character
(c) Solid (d) None of the above 42. The shape of colloidal particles is
34. Smoke is an example of (a) Sphere like (b) Rod like
(a) Gas dispersed in liquid (c) Disc like (d) All the above
(b) Gas dispersed in solid 43. Which characteristic is true in respect of colloidal solutions
(c) Solid dispersed in gas
(a) They always have two phases
(d) Solid dispersed in solid
(b) They are only in liquid state
35. When dispersion medium is water, the colloidal system is
called (c) They can’t be electrolysed
(a) Sol (b) Aerosol (d) They are only hydrophilic
(c) Organosol (d) Aquasol
SURFACE CHEMISTRY 207

44. The disperse phase in colloidal iron (III) hydroxide and 51. Which of the following statement is wrong for lyophobic
colloidal gold is positively and negatively charged, sol?
respectively. Which of the following statement is not (a) Dispersed phase is generally in organic material
correct? (b) Can be easily coagulated by small addition of electrolyte
(a) Coagulation in both sols can be brought about by (c) Dispersed phase particles are poorly hydrated and colloid
electrophoresis is stabilised due to charge on the colloidal particles
(d) Reversible in nature that is after coagulation can be
(b) Mixing the sols has no effect easily set into colloidal form
(c) Sodium sulphate solution causes coagulation in both 52. When a freshly precipitated substance is converted into a
sols colloidal solution with the help of a third substance, the
process is known as
(d) Magnesium chloride solution coagulates, the gold sol
more readily than the iron (III) hydroxide sol (a) Coagulation (b) Peptization
(c) Electrodispersion (d) Dialysis
45. When dispersed phase is liquid and dispersion medium is
gas, then the colloidal system is called 53. Which one of the sols acts as protective colloid
(a) Smoke (b) Clouds (a) As2S3 (b) Gelatin
(c) Emulsion (d) Jellies (c) Au (d) Fe(OH)3
46. Butter is a colloid. It is formed when 54. The coagulating power of electrolytes having ions Na+, Al3+
(a) Fat is dispersed in solid casein and Ba2+ for arsenic sulphide sol increases in the order
(b) Fat globules are dispersed in water (a) Al3+ < Ba2+ < Na+ (b) Na+ < Ba2+ < Al3+
(c) Water is dispersed in fat
(c) Ba2+ < Na2+ < Al3+ (d) Al3+ < Na+ < Ba2+
(d) Casein is suspended in H2O
47. When sugar is added to a colloidal solution it brings about 55. Gold numbers of protective colloids A, B, C and D are 0.50,
0.01, 0.10 and 0.005, respectively. The correct order of their
(a) Ionization (b) Coagulation
protective powers is
(c) Peptization (d) None of the above
(a) D < A < C < B (b) C < B < D < A
48. A cleared solution is again converted into colloidal solution.
The process is called (c) A < C < B < D (d) B < D < A < C
(a) Peptisation (b) Electrolytic addition 56. Milk is a colloid in which
(c) Electrophoresis (d) None of these (a) A liquid is dispersed in liquid
49. A colloidal system in which gas bubbles are dispersed in a (b) A solid is dispersed in liquid
liquid is known as
(c) A gas is dispersed in liquid
(a) Foam (b) Sol
(d) Some suger is dispersed in water
(c) Aerosol (d) Emulsion
57. Milk is
50. Following are various types of colloids. In electric field.
(a) Dispersed fats in oil
X (Colloids) Y (Classification) (b) Dispersed fats in water
I Rain cloud - A sol (c) Dispersed water in fats
II Milk of magnesia - B aerosol (d) Dispersed water in oil
III Soap suds - C emulsion Numerical Value Type Questions
IV Butter - D foam
58. The mass adsorbed per gram of adsorbed O2 having
Correct matching is pressure 10 atm at 400 K, if placed in contact with solid
I II III IV surface is 2 g in one litre vessel. The pressure of O2 after
(a) A B C D adsorption becomes 2 atm. Assume no change in
(b) A C B D temperature and R = 0.08 L-atm. K–1 mol–1.
(c) B A D C
(d) B A C D
SURFACE CHEMISTRY 208

59. When 9.0 ml of arsenius sulphide sol and 1.0 ml of 62. How many of the given are multimolecular colloids?
1.0×10–4 M BaCl2 are mixed, turbidity due to precipitation Nylon, Gold sol, Sulphur sol, Dacron, Starch.
just appears after 2 hours the coagulating value is
63. How many of the following are colloids?
60. How many of the following are correctly matched?
Chlorophyll, smoke, urea solution, milk
(I) Lyophilic colloids -reversible sols
x
(II) Associated colloides – micelles 64. When a graph is plotted between log and log p, it is a
m
(III) Tyndall effect – scattering of light by colloidal
straight line with an angle 45° and intercept 0.3010 on
particle y-axis. If initial pressure is 0.3 atm, what will be the amount
(IV) Electrophoresis – movement of dispersion medium of gas adsorbed per gm of adsorbent?
under the influence of electric field 65. The volume of a colloidal particle, VC as compared to the
61. How many of the following are aerosols of liquids? volume of a solute particle in a true solution VS , could be
Fog, Clouds, Smoke, Dust
SURFACE CHEMISTRY 209

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS


Objective Questions I [Only one correct option] 6. Adsorption of a gas on a surface follows Freundlich

1. 3 g of activated charcoal was added to 50 mL of acetic acid x


adsorption isotherm. Plot of log versus log p gives a
solution (0.06N) in a flask. After an hour it was filtered and m
the strength of the filtrate was found to be 0.042 N. The straight line with slope equal to 0.5, then :
amount of acetic acid adsorbed (per gram of charcoal) is :
x
(2015) ( is the mass of the gas adsorbed per gram of adsorbent)
m
(a) 42 mg (b) 54 mg
(2017)
(c) 18 mg (d) 36 mg
(a) Adsorption is independent of pressure.
2. Which one of the following is an incorrect statement for
physisorption? (2015) (b) Adsorption is proportional to the pressure.
(a) It is a reversible process
(c) Adsorption is proportional to the square root of pressure.
(b) It requires less heat of adsorption
(c) It requires activation energy (d) Adsorption is proportional to the square of pressure.

(d) It takes place at low temperature 7. Among the following, correct statement is: (2017)
3. For a linear plot of log (x/m) versus log p in a Freundlich (a) Brownian movement is more pronounced for smaller
adorption isotherm, which of the following statement is particles than for bigger–particles.
correct? (k and n are constants) (2016) (b) Sols of metal sulphides are lyophilic.
(a) 1/n appears as the intercept (c) Hardy Schulze law states that bigger the size of the
(b) Only 1/n appears as the slope. ions, the greater is its coagulating power.
(c) log (1/n) appears as the intercept (d) One would expect charcoal to adsorb Cl2 more than
hydrogen sulphide.
(d) both k and 1/n appear in the slope term.
8. Which of the following statements about colloids is False ?
4. A particular adsorption process has the following
characteristics : (i) It arises due to van der Waals forces (Online 2018 Set-1)
and (ii) it is reversible. Identify the correct statement that (a) Freezing point of colloidal solution is lower than true
describes the above adsorption process: (2016) solution at same concentration of a solute.
(a) Enthalpy of adsorption is greater than 100 kJ mol–1. (b) Colloidal particles can pass through ordinary filter
(b) Energy of activation is low. paper.
(c) Adsorption is monolayer. (c) When silver nitrate solution is added to potassium iodide
solution, a negatively charged colloidal solution is
(d) Adsorption increases with increase in temperature.
formed.
5. Gold numbers of some colloids are : Gelatin : 0.005 – 0.01,
(d) When excess of electrolyte is added to colloidal solution,
Gum Arabic : 0.15 – 0.25; Oleate : 0.04 – 1.0; Starch: 15 – 25.
colloidal particle will be precipitated.
Which among these is a better protective colloid ?
9. If x gram of gas is adsorbed by m gram of adsorbent at
(2016)
(a) Gelatin (b) Gum Arabic x
pressure P, the plot of log versus log P is linear. The
(c) Oleate (d) Starch m
slope of the plot is : (Online 2018 Set-2)
(n and k are constants and n > 1)
(a) 2k (b) log k

1
(c) n (d)
n
SURFACE CHEMISTRY 210

10. Which one of the following is not a property of physical 15. For coagulation of arsenious sulphide sol, which one of
adsorption ? (Online 2018 Set-3) the following salt solution will be most effective? (2019)
(a) Higher the pressure, more the adsorption (a) BaCl2 (b) AlCl3
(b) Lower the temperature, more the adsorption (c) NaCl (d) Na3PO4
(c) Greater the surface area, more the adsorption 16. Haemoglobin and gold sold are examples of: (2019)
(d) Unilayer adsorption occurs (a) positively and negatively charged sols, respectively
11. The aerosol is a kind of colloid in which: (2019) (b) positively charged sols
(a) solid is dispersed in gas (c) negatively charged sols
(b) gas is dispersed in solid (d) negatively and positively charged sols, respectively
(c) liquid is dispersed in water 17. Given
(d) gas is dispersed in liquid Gas: H2 CH4 CO2 SO2
12. A gas undergoes physical adsorption on a surface and Critical: 33 190 304 630
follows the given Freundlich adsorption isotherm equation Temp/K
x On the basis of data given, predict which of the following
 kp 0.5 gases shows least adsorption on a definite amount of
m
charcoal (2019)
Adsorption of the gas increases with: (2019)
(a) SO2 (b) CH4
(a) Increase in p and decrease in T
(c) CO2 (d) H2
(b) Increase in p and increase in T
18. Among the following, the false statement is: (2019)
(c) Decrease in p and increase in T
(a) It is possible to cause artificial rain by throwing
(d) Decrease in p and decrease in T electrified sand carrying charge opposite to the one on
13. The correct option among the following is: (2019) clouds from an aeroplane.
(a) Colloidal particles in lyophobic sols can be precipitated (b) Tyndall effect can be used to distinguish between a
by electrophoresis. colloidal solution and a true solution.
(b) Brownian motion in colloidal solution is faster the (c) Lyophilic sol can be coagulated by adding an electrolyte.
viscosity of the solution is very high. (d) Latex is a colloidal solution of rubber particles which
(c) Colloidal medicines are more effective because they are positively charged.
have small surface area. 19. Amongst the following statements regarding adsorption,
(d) Addition of alum to water makes it unfit for drinking. those that are valid are : (2020)
14. Among the following, the INCORRECT statement about (A)  becomes less negative as adsorption proceeds.
colloids is : (2019) (B) On a given adsorbent, ammonia is adsorbed more than
(a) The range of diameters of colloidal particles is between nitrogen gas.
1 and 1000 nm (C) On adsorption, the residual force acting along the surface
(b) The osmotic pressure of a colloidal solution is of higher of the adsorbent increases.
order than the true solution at the same concentration (D)With increase in temperature, the equilibrium
(c) They can scatter light concentration of adsorbate increases.
(d) They are larger than small molecules and have high (a) (B) and (C) (b) (C) and (D)
molar mass (c) (A) and (B) (d) (D) and (A)
SURFACE CHEMISTRY 211

20. Tyndall effect is observed when : (2020) 25. Most suitable salt which can be used for efficient
(a) The diameter of dispersed particles is much smaller clotting of blood will be (2021-02-24//Shift -2)
than the wavelength of light used. (a) FeSO4 (b) NaHCO3
(b) The diameter of dispersed particles is much larger (c) Mg(HCO3)2 (d) FeCl3
than the wavelength of light used.
26. In Freundlich adsorption isotherm at moderate pressure,
(c) The refractive index of dispersed phase is greater
than that of the dispersion medium. x
the extent of adsorption   is directly proportional to
(d) The diameter of dispersed particles is similar to the m
wavelength of light used. Px. The value of x is (2021-02-25//Shift -1)
21. A sample of red ink (a colloidal suspension) is prepared by
mixing eosin dye, egg white,HCHO and water. The (a) 1 (b) Zero
component which ensures stability of the ink sample is
(2020) 1
(c)  (d)
n
(a) HCHO (b) Water
(c) Eosin dye (d) Egg white 27. Which one of the following statements is FALSE for
hydrophilic sols? (2021-02-25//Shift -2)
22. Kraft temperature is the temperature: (2020)
(a) Their viscosity is of the order of that of H2O
(a) Above which the aqueous solution of detergents
(b) They do not require electrolytes for stability
starts boiling
(b) Below which the formation of micelles takes place (c) These sols are reversible in nature

(c) Above which the formation of micelles takes place (d) The sols cannot be easily coagulated
(d) Below which the aqueous solution of detergents 28. The nature of charge on resulting colloidal particles when
starts freezing FeCl3 is added to excess of hot water is
23. As per Hardy-Schulze formulation, the flocculation values (2021-02-26//Shift -2)
of the following for ferrichydroxide sol are in the order:
(a) Positive
(2020)
(b) Sometimes positive and sometimes negative
(a) AlCl8>K3[Fe(CN)6]>K2CrO4>KBr=KNO3
(c) Neutral
(b) K3[Fe(CN)6]<K2CrO4<AlCl3<KBr<KNO3
(d) Negative
(c) K3[Fe(CN)6] < K2CrO4< KBr = KNO3 = AlCl3
29. The INCORRECT statements below regarding
(d) K3[Fe(CN)6] > AlCl3> K2CrO4> KBr > KNO3
colloidal solutions is: (2021-03-16//Shift -2)
24. In Freundlich adsorption isotherm, slope of AB line is:
(a) A colloidal solution shows colligative properties.
(2021-02-24//Shift -1)
(b) An ordinary filter paper can stop the flow of colloidal
particles.
(c) The flocculating power of Al 3+ is more than that
of Na+
(d) A colloidal solution shows Brownian motion of
colloidal particles.

(a) log n with (n > 1) (b) n with (n, 0.1 to 0.5)

1 1 1
(c) log with(n  1) (d) with(  0 to 1)
n n n
SURFACE CHEMISTRY 212

30. With respect to drug-enzyme interaction, identify the 34. When silver nitrate solution is added to potassium
wrong statement. (2021-03-17/Shift - 1) iodide solution then the sol produced is:
(a) Competitive inhibitor binds to the enzyme’s active (2021-07-22/Shift - 2)
site (a) AgI/I -
(b) AgI/Ag+
(b) Allosteric inhibitor competes with the enzyme’s
(c) KI / NO3 (d) AgNO3 / NO 3
active site
(c) Allosteric inhibitor changes the enzyme’s active 35. Sodium stearate CH 3 (CH 2 )16 COO  Na  is an anionic
site
surfactant which forms micelles. Choose the correct
(d) Non-Competitive inhibitor binds to the allosteric statement for it from the following:
site
(2021-07-25/Shift - 1)
31. The charges on the colloidal CdS sol and TiO2 sol are,
respectively: (2021-03-18/Shift - 2) (a) It forms spherical micelles with CH3 (CH 2 )16  group

(a) negative and negative pointing towards the centre of sphere.

(b) positive and negative (b) It forms non-spherical micelles with - COO– group
pointing outwards on the surface.
(c) positive and positive
(c) It forms spherical micelles with CH3(CH2)16 - group
(d) negative and positive pointing outwards on the surface of sphere
32. The conditions given below are in the context of (d) It forms non-spherical micelles with CH 3(CH 2)16-
observing Tyndall effect in colloidal solutions: group pointing towards the centre.
(2021-07-20/Shift - 1) 36. Which one of the following is correct for the
(A) The diameter of the colloidal particles is adsorption of a gas at a given temperature on a solid
comparable to the wavelength of light used. surface? (2021-08-26/Shift - 1)
(B) The diameter of the colloidal particles is much (a) H  0, S  0 (b) H  0, S  0
smaller than the wavelength of light used.
(c) H  0, S  0 (d) H  0, S  0
(C) The diameter of the colloidal particles is much
larger than the wavelength of light used. 37. The sol given below with negatively charged colloidal
(D) The refractive indices of the dispersed phase and particles is: (2021-08-26/Shift - 2)
the dispersion medium are comparable. (a) FeCl3 added to hot water
(E) The dispersed phase has a very different (b) KI added to AgNO3 solution
refractive index from the dispersion medium. (c) AgNO3 added to KI solution
Choose the most appropriate conditions from the (d) Al2O3.xH2O in water
options given below:
38. Tyndall effect is more effectively shown by:
(a) (A) and (E) only (b) (C) and (D) only
(2021-08-27/Shift - 1)
(c) (A) and (D) only (d) (B) and (E) only
(a) true solution (b) lyophilic colloid
33. Which one of the following statements is not true
(c) lyophobic colloid (d) suspension
about enzymes? (2021-07-20/Shift - 2)
39. Lyophilic sols are more stable than lyophobic sols
(a) Enzymes are non-specific for a reaction and
because (2021-08-27/Shift - 2)
substrate.
(a) there is a strong electrostatic repulsion between
(b) Almost all enzymes are proteins.
the negatively charged colloidal particles.
(c) Enzymes work as catalysts by lowering the
(b) the colloidal particles have positive charge.
activation energy of a biochemical reaction.
(c) the colloidal particles have no charge.
(d) The action of enzymes is temperature and
pH specific (d) the colloidal particles are solvated.
SURFACE CHEMISTRY 213

40. Select the graph that correctly describes the Assertion Reason
adsorption isotherms at two temperatures T 1 and T 2
(A) If both Assertion and Reason are correct and
(T 1 > T 2) for a gas: (x – mass of the gas adsorbed;
m – mass of adsorbent; P – pressure) Reason is the correct explanation of Assertion.
(2021-08-31/Shift - 1) (B) If both Assertion and Reason are true but
Reason is not the correct explanation of
Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
(a)
43. Assertion (A) : SO2(g) is adsorbed to a large extent than
H2(g) on activated charcoal.
Reason (R) : SO 2(g) has a higher critical temperature
than H2(g). (2021-07-27/Shift - 2)
(a) A (b) B
(c) C (d) D
Match the Following
(b)
Each question has two columns. Four options are
given representing matching of elements from
Column-I and Column-II. Only one of these four
options corresponds to a correct matching. For
each question, choose the option corresponding
to the correct matching

(c)
44. The correct match between Column I and Column II is
(2019)
Column I Column II
(A) Allosteric effect (p) Molecule binding to the
active site of enzyme
(B) Competitive (q) Molecule crucial for
(d) inhibitor communication in the body
(C) Receptor (r) Molecule binding to a site
other than the active site of
41. A colloidal system consisting of a gas dispersed in a enzyme
solid is called a/an: (2021-03-17/Shift - 1)
(D) Poison (s) Molecule binding to the
(a) aerosol (b) gel
enzyme covalently
(c) foam (d) solid sol (a) (A)  (r); (B)  (p); (C)  (q); (D)  (s)
42. For the coagulation of a negative sol, the species (b) (A)  (p); (B)  (r); (C)  (q); (D)  (s)
below, that has the highest flocculating power is:
(c) (A)  (r); (B)  (p); (C)  (s); (D)  (q)
(2021-03-17/Shift - 2)
+ 2+
(d) (A)  (p); (B)  (r); (C)  (s); (D)  (p)
(a) Na (b) Ba

(c) PO34 (d) SO 24 


SURFACE CHEMISTRY 214
45. Match the following: (2020) 48. Match Column I with Column II (2021-09-01/Shift - 2)
(A) Foam (p) smoke Column - I Column - II
(B) Gel (q) cell fluid
(Colloid Preparation (Chemical Reaction)
(C) Aerosol (r) jellies
(D) Emulsion (s) rubber Method)
(t) froth (A) Hydrolysis (p) 2AuCl3 + 3HCHO +
(u) milk 3H2O2Au(sol) + 3HCOOH
+6HCl
(a) (A)  (t); (B)  (r); (C)  (p); (D)  (u)
(B) Reduction (q) As2O3 + 3H2S  As2S3 (sol) +
(b) (A)  (q); (B)  (r); (C)  (t); (D)  (s) 3H2O
(c) (A)  (s); (B)  (q); (C)  (p); (D)  (t) (C) Oxidation (r) SO2 + 2H2S  3S(sol) + 2H2O
(d) (A)  (s); (B)  (q); (C)  (t); (D)  (u) (D) Double (s) FeCl2+3H2O  Fe(OH)3
46. Match Column -I with Column-II : (2021-03-18/Shift - 1) (sol) + 3HCl
Column - I (Process) Column-II (Catalyst) (a) (A)-(p), (B)-(r), (C)-(q), (D)-(s)
(b) (A)-(s), (B)-(p), (C)-(r), (D)-(q)
(A) Deacon’s process (p) ZSM-5
(c) (A)-(s), (B)-(q), (C)-(r), (D)-(p)
(B) Contact process (q) CuCl2 (d) (A)-(p), (B)-(q), (C)-(s), (D)-(r)
(C) Cracking of (r) Particles ‘Ni’ Numerical Value Type Question
hydrocarbons 49. The mass of gas adsorbed, x, per unit mass of adsorbate, m,
(D) Hydrogenation of (s) V2O5 was measured at various pressures, p. A graph between
Vegetables oils x
log and log p gives a straight linewith slope equal to 2
Choose the most appropriate answer from the options m
given below :
x
(a) (A)  (s), (B)  (q), (C)  (p), (D)  (r) and the intercept equal to 0.4771. The value of at a
m
(b) (A)  (r), (B)  (p), (C)  (s), (D)  (q) pressure of 4 atm is: (Given log3 = 0.47771) (2020)
(c) (A)  (q), (B)  (s), (C)  (p), (D)  (r)
50. For Freundlich adsorption isotherm, a plot of log (x/ m)(y -
(d) (A)  (p), (B)  (r), (C)  (q), (D)  (s)
axis) and log p (x - axis) gives a straight line.
47. Match Column I with Column II (2021-07-25/Shift - 2) The intercept and slope for the line is 0.4771 and 2,
Column- I Column- II respectively. The mass of gas, adsorbed per gram of
(Example of colloids) (Classification) adsorbent if the initial pressure is 0.04 atm, is

(A) Cheese (p) dispersion of liquid in ...... 104 g.  log 3  0.4771 (2020)
liquid
51. The flocculation value of HCl for As2S3 sol is 30 mmolL–1. If
(B) Pumice stone (q) dispersion of liquid in gas H2SO4 is used for the flocculation of arsenic sulphide, the
(C) Hair cream (r) dispersion of gas in solid amount, in grams, of H2SO4 in 250 mL required for the above
(D) Cloud (s) disperion of liquid in solid purpose is ____. (2020)

Choose the most appropriate answer from the options 52. 3.12 g of oxygen is adsorbed on 1.2 g of platinum
given below: metal. The volume of oxygen adsorbed per gram of
the adsorbent at 1 atm and 300 K in L is ______.
(a) (A)  (s), (B)  (r), (C)  (q), (D)  (p)
(2021-02-26/Shift - 1)
(b) (A)  (s), (B)  (p), (C)  (r), (D)  (q)
(c) (A)  (r), (B)  (s), (C)  (p), (D)  (q) 53. 100 ml of 0.0018% (w/v) solution of Cl - ion was the
(d) (A)  (s), (B)  (r), (C)  (p), (D)  (q) minimum concentration of Cl- required to precipitate a
sol in one hr. The coagulating value of Cl - ion is
________. Round off your answer up to one decimal
place. (2021-07-20/Shift - 2)
SURFACE CHEMISTRY 215

54. CO 2 gas adsorbs on charcoal following Freundlich 55. CH 4 is adsorbed on 1 g charcoal at 0°C following the
adsorption isotherm. For a given amount of charcoal, Freundlich adsorption isotherm. 10.0 mL of CH 4 is
the mass of CO2 adsorbed becomes 64 times when the adsorbed at 100 mm of Hg, whereas 15.0 mL is
pressure CO 2 is doubled. The value of n in the adsorbed at 200 mm of Hg. The volume of CH 4
Freundlich isotherm equation is __________ × 10–2 . adsorbed at 300 mm of Hg is 10xmL. The value of x is
(Round off to the Nearest Integer) (2021-07-27/Shift - 1) _______ × 10–2 .(Nearest integer) (31-08-2021//Shift -2)
[Use log102 = 0.3010, log103 = 0.4771]
SURFACE CHEMISTRY 216

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS


Objective Questions I [Only one correct option] 8. Coagulation or demulsification can be done by some of the
methods given below
1. Following are the events taking place to explain adsorption
theory I: By addition of substance which would destory the
emulsifier
I : Desorption
II: By addition of an electrolyte which would destroy
II : Diffusion of the reactants along the surface
the charge
III : Adsorption of the reactants
III: By heating, freezing and centrifuging
IV : Formation of the activated surface complex
Select correct methods
These events are taking place in the following order
(a) I, II (b) I, II, III
(a) I, II, III, IV (b) III, II, IV, I
(c) II only (d) III only
(c) III, IV, I, II (d) IV, III, II, I
9. As2S3 sol has a negative charge. Capacity to precipitate it
2. There are certain properties related to physical adsorption
is highest in
I : Reversible
(a) AlCl3 (b) Na3PO4
II : Formation of unimolecular layer
(c) CaCl2 (d) K2SO4
III : Low heat of adsorption
10. Maximum coagulation power is in
IV : Occurs at low temperature and decreases with increasing
temperature (a) Na+ (b) Ba2+
Which of the above properties are for physical adsorption? (c) Al3+ (d) Sn4+
(a) I, II, III (b) I, III, IV 11. Adsorption of gases on solid surface is generally
(c) II, III, IV (d) I, III exothermic because

3. Rate of physisorption increases with (a) enthalpy is positive (b) entropy decreases

(a) decrease in temperature (c) entropy increases (d) free energy increases

(b) increases in temperature 12. In neutralisation of KI by AgNO3 positive charge is due to


absorption of
(c) decrease in pressure
(a) Ag+ ions (b) Ag
(d) decrease in surface area (c) I– ions (d) Both (b) and (c)
4. In Freundlich adsorption isotherm, adsorption is 13. Shape-selective catalysis is a reaction catalysed by:-
proportional to pressure P as
(a) Zeolites (b) Enzymes
(a) P0 (b) P
n
(c) Platinum (d) Zeigler-Natta catalyst
(c) P (d) P1/n
14. The adsorption of a gas on a solid surface varies with
5. Colloidal solution is not purified by pressure of the gas in which of the following manner
(a) Dialysis (b) Electrodialysis
(a) Fast , slow, independent of the pressure
(c) Electrophoresis (d) Ultrafiltration
(b) Slow , fast, independent of the pressure
6. Sky looks blue due to
(c) Independent of the pressure , fast, slow
(a) Dispersion effect (b) Reflection
(c) Transmission (d) Scattering (d) Independent of the pressure, slow, fast
7. Colloidal particles carrying charge is best shown by
(a) Brownian movement (b) Tyndall effect
(c) Electrophoresis (d) Dialysis
SURFACE CHEMISTRY 217

15. In the following isotherm 20. Among the following, the surfactant that will form micelles
in aqueous solution at the lowest molar concentration at
A B ambient conditions is
x
m (a) CH3(CH2)15N+ (CH3)3 Br–

O (b) CH3(CH2)11 OSO3 Na 


Pressure P

(c) CH3(CH2)6COO– Na+


x
(a)  p when point A is reached (d) CH3(CH2)11N+(CH3)3Br–
m
21. Cleansing action of soap occurs because
(b) Desorption may start along AB
(a) Oil and grease can be absorbed into the hydrophobic
x centres of soap micelles and washed away
(c)  p1/ n along OA
m (b) Oil and grease can be absorbed into the hydrophilic
centres of soap micelles and washed away
(d) All of these
(c) Oil and grease can be absorbed into both hydrophilic
16. The colloidal solutions of gold prepared by different and hydrophobic centres but not washed away
methods have different colors due to:
(d) Cleansing action is not related to micelles
(a) difference in the size of colloidal particles
22. Enzymes are
(b) the fact that gold exhibits variable valancy (a) Micro-organisms
(c) Different concentration of gold (b) Protein
(d) Presence of different types of foreign particles. (c) Inorganic compounds
x (d) Moulds
17. Graph between log and log P is a straight line inclined at
m
23. Which of the following statements is incorrect?
an angle   45 0 . When pressure is 0.5 atm and log k =
(a) Enzymes are in colloidal state
0.699, the amount of solute adsorbed per g of adsorbent
(b) Enzymes are catalysts
will be
(c) Enzymes can catalyse any reaction
(a) 1 g/g adsorbent (b) 1.5 g/g adsorbent
(d) Urease is an enzyme
(c) 2.5 g/g adsorbent (d) 0.25 g/g adsorbent
24. Enzymes are known to increase the rate of reaction by
18. For the adsorption of a gas on a solid, the plot of
log (x/m) versus log P is linear with slope equal to (a) 102 times (b) 10–2 times
(a) k (b) log k (c) 105 times (d) 1012 times
(c) n (d) 1/n 25. The ability of the catalyst to direct the reaction to yield
particular product is called
19. For the adsorption of solution on a solid surface,
(a) Reactivity (b) Selectivity
x
 kC 1 / n . (c) Activity (d) Fugacity
m
26. Blood may be purified by
Adsorption isotherm of log  x  and log C was found of
the type m  (a) Dialysis (b) Electro - osmosis
(c) Coagulation (d) Filtration
27. The simplest way to check whether a system is colloidal, is
x (a) Tyndall effect (b) Electro dialysis
log
m (c) Brownian movement (d) Finding out particle size
log k
28. The colloidal particles can pass through

log C
(a) Filter paper as well as animal membrane
(b) Animal membrane but not through filter paper
This is when
(c) Filter paper but not through animal membrane
(a) C = 0 (b) C = 1 M
(d) Semipermeable membrane
(c) C = constant (d) C = 2 M
SURFACE CHEMISTRY 218
29. Ultramicroscope is used for observing
(a) Light reflection (b) Light absorption
(c) Light scattering (d) Light polarisation
30. Colloidal paints are used to paint metallic portions of cars. (c) (d)
This application is based on
(a) Coagulation (b) Electro-osmosis
(c) Peptization (d) Electrophoresis
Objective Questions II
31. Ferric hydroxide sol is positively charged colloid. The
coagulating power of NO 3 ,SO 24  and PO34 ions would be
[One or more than one correct option]
in the order 37. Which of the following is/are correct about Freunlich’s
adsorption isotherm for gases and solutions?
(a) NO 3  SO 42   PO34 (b) SO 24   NO 3  PO34
x
(a)  KC1/ n
(c) PO34  SO 24   NO 3 (d) NO 3  SO 24   PO34 m
32. Peptising agent is
x 1  bP
(a) Always an electrolyte (b) 
m a
(b) Always a non - electrolyte
(c) Electrolyte or non - electrolyte x
(d) A lyophilic colloid (c) log    log K  n log P
m
33. Which of the following is most effective in coagulating a
ferric hydroxide sol x 1
(a) KCl (b) KNO3 (d) log    log K  log C
m n
(c) K2SO4 (d) K3[Fe(CN)6]
38. Select the correct statements among following.
34. Energy of activation of forward and backward reaction are
equal in cases (numerical values) where (a) Foam is a colloidal solution of gas in liquid
(b) Aerosol is a colloidal solution of liquid in gas
(a) H  0
(c) Gel is a colloidal solution of solid in liquid
(b) No catalyst present (d) Emulsion is a colloidal solution of liquid in liquid
(c) S  0 39. Select the correct statements among following.
(d) Stoichiometry is the mechanism (a) At 83 K, N2 is physisorbed on the surface of iron
35. Addition of catalyst in a system (b) At 773 K and above N2 is che isorbed on the iron surface
(a) Increases equilibrium concentrations (c) Activation energy is +ve in case of physiosorption and
zero in case of chemisorption
(b) No effect on equilibrium concentrations
(d) Activation energy is zero in case of physiosorption
(c) Decreases equilibrium concentrations and +ve in case of chemisorption
(d) Increases rate of forward reaction and decreases rate of 40. Which of the following are correct about the catalyst?
backward reaction (a) They participate in the reaction but recovered at last
36. Oxidation of oxalic acid by acidified KMnO4 is an example (b) It does not affect G
of autocatalysis. Which of the following graph represents
the variation of rate of this reaction with time? (c) It does not affect H
(d) It alters the mechanism of reaction
41. Which of the following is/are not affected by the catalyst?
(a) Heat of reaction
(a) (b) (b) Equilibrium constant
(c) Amount of product
(d) Rate constant of the reaction
SURFACE CHEMISTRY 219
42. Which of the following act as negative catalyst? 48. Assertion(A) : A reaction cannot become fast by itself
(a) Ethanol in oxidation of chloroform unless a catalyst is added in the reaction mixture.
(b) Tetra ethyl lead used as antiknocking agent Reason(R) : Catalyst may increase or decrease the rate of a
reaction.
(c) Glycerol in the decomposition
(a) A (b) B
(d) Fe in the formation of ammonia by Haber process
(c) C (d) D
43. Select the correct statements about enzymes.
49. Assertion (A) : Positive catalysts increase the rate of
(a) Enzymes are biological catalysts found in organisms chemical reaction.
(b) All enzymes are proteins Reason (R) : Catalysts increase the rate of reaction by
(c) Enzymes can catalyse any reaction lowering the activation energy of the reaction.
(d) Enzymes activity is optimum at 27oC (a) A (b) B
44. Which of the following statments are true? (c) C (d) D
(a) Flocculation value is inversely proportional to 50. Assertion (A) : Micelles are formed by surfactant molecules
coagulating power above the critical micelle concentration (CMC).
(b) Colloidal silica is protective colloid Reason (R) : The conductivity of a solution having
(c) Alum is used for cleaning muddy water surfactant molecules decrease sharply at the CMC.
(d) Gelatin is added in ice cream, it acts as emulsifier (a) A (b) B
45. Select the correct statements for Brownian movement: (c) C (d) D
(a) It becomes more intense with increase in temperature 51. Assertion(A) : For coagulation of positively charged sols,
(b) It increases with increase in particle size [Fe(CN)6]4– ion has higher coagulating power than that of
(c) It is due to collision of molecules of dispersion medium PO 34 , SO 24  , Cl–.
with the colloidal particles
Reason(R) : Because according to Hardy Schulze rule,
(d) It increases the stability of colloidal solution
higher is the valency of ions for the oppositely charged sol
Assertion Reason particles, better will be the precipitation.
(A) If both Assertion and Reason are correct and (a) A (b) B
Reason is the correct explanation of Assertion. (c) C (d) D
Match the Following
(B) If both Assertion and Reason are true but
Reason is not the correct explanation of Each question has two columns. Four options are
given representing matching of elements from
Assertion. Column-I and Column-II. Only one of these four
(C) If Assertion is true but Reason is false. options corresponds to a correct matching, For
each question.
(D) If Assertion is false but Reason is true.
52. Mathc the column - I to Column - II
46. Assertion (A): For adsorption G, H, S all have -ve
values. Column–I Column–II

Reason (R) : Adsorption is a exothermic process in which (A) Chemisorption (p) Exothermic
randomness decreases due to force of attraction between (B) Physical adsorption (q) Endothermic
adsorbent and adsorbate. (C) Desorption (r) Removal of adsorbed material
(a) A (b) B (D)Activation of (s) Highly specific in nature
(c) C (d) D adsorbent
47. Assertion (A): The extent of adsorption of CO2 is much
more higher than of H2.
Reason(R): CO2(g) has higher critical temperature and more
van der Waals’ force of attraction as compare to H2(g).
(a) A (b) B
(c) C (d) D
SURFACE CHEMISTRY 220

53. Mathc the column - I to Column - II The coagulation values of different electrolytes are different.
Column-I Column-II This behaviour can be easily understood by Hardy-Schulze rule
(A) BaSO4 (p) Inhibitor for decomposition which states.
of H2O2 “The greater is the valency of the effective ion greater is its
(B) Acetamide (q) Catalyst precipitating power.”
(C) Zeolite (r) Remove hardness of water 57. Which one has the highest coagulation power?
(D) Nickel (s) Poison for Pd in Lindlar’s (a) K+ (b) Ca2+
catalyst (c) Al3+ (d) Sn4+
54. Mathc the column - I to Column - II 58. The ability of an ion to bring coagulation of a given colloid
depends upon:
Column–I Column–II
(A) Liquid dispersed in (p) Foam (a) the sign of its charge
gas (b) magnitude of its charge
(B) Gas dispersed in (q) Emulsion (c) both magnitude and sign
liquid (d) none of these
(C) Liquid dispersed in (r) Aerosol
solid 59. The coagulation of colloidal particles of the sol can be
(D) Liquid dispersed in (s) Gel caused by:
liquid (a) heating
55. Mathc the column - I to Column - II (b) adding electrolyte
Column–I Column–II (c) adding oppositely charged sol
(A) Milk (p) Aerosol (d) all of these
60. As2S3 sol is negatively charged, capacity to precipitate it is
(B) Dust (q) Emulsion
highest in:
(C) Cheese (r) Gel
(a) K2SO4 (b) Na3PO4
(D) Froth (s) Foam
(c) AlCl3 (d) CaCl3
56. Mathc the column - I to Column - II
Use the following passage, to solve Q. 61 to Q. 62
Column–I Column–II
Passage
(A) Peptization (p) Preparation of sols
Emulsions are normally prepared by shaking the two components
(B) Ultra centrifugation (q) Purification of sols together vigorously although some kind to emulsifying agent
(C) Electrodialysis (r) Preparation of metal sols usually has to added to stabilize the product. This emulsifying
agent may be a soap or other surfactant (surface active) species
(D) Bredig’s are method (s) Movement of ion across or a lyophilic sol that forms a protective film around the dispersed
the membrane in presence phase.
of electric field Emulsions broadly classified into two types:
Paragraph Type Question (i) Oil in water emulstions (O/W): Oil acts as dispersed phase
and water acts as dispersion medium.
Use the following passage, to solve Q. 57 to Q. 60
(ii) Water in oil emulsions (W/O): Water acts as dispersed phase
Passage and oil acts as dispersion medium. Dye test, dilution test may be
Coagulation is the process by which the dispersed phase of a employed for identification of emulsions.
colloid is made to aggregate and thereby separate from the 61. Read two statements.
continuous phase.The minimum concentration of an electrolyte
(1) Milk is an example of oil in water (O/W) type emulsion
in milli-moles per litre of the electrolyte solution which is required
to cause the coagulation of colloidal sol is called coagulation (2) Cold cream is an example of water in oil (W/O) type
value. emulsions
Therefore higher is the coagulating power of effective ion, smaller Which of the following option is correct?
will be the coagulation value of the electrolyte.
(a) Only statement 1 is correct
1 (b) Only statement 2 is correct
Coagulation value 
coagulating power (c) Both are correct
(d) None of these
SURFACE CHEMISTRY 221

62. Select correct statement. x


64. Adsorption isotherm of log   and log P was found of
(a) Water in oil emulsions are more viscous than the m
aqueous emulsions the type:
(b) Electrical conductance of aqueous emulsions is less
than that of oil emulsions
(c) Deemulsification can be done by soap or detergent
(d) An emulsion can be diluted with H2O then it is oil in
water (O/W) type
Use the following passage, to solve Q. 63 to Q. 65
Passage
A graph between x/m and the pressure P of the gas at a constant
temperature is called adsorption isotherm. Where x is the no. of
This is true when:
moles of the adsorbate and m is the mass of the adsorbent.
Adsorption isotherms of different shapes have been (a) P = 0 (b) P = 1
experimentally observed. According to Fruendlich adsorption
1 1
isotherm. (c) =1 (d) 
n n
x/m = kP1/n
where k and n are constant parameters depending upon the nature x
65. Graph between log   and log P is a straight line at
of the solid and gas. m
63. In the given isotherm select the incorrect statement: angle 45o with intercept OA as shown.

x x
(a)  P1/n along OA Hence,   at a pressure of 2 atm is:
m m

x (a) 2 (b) 4
(b)  P 0 when point B is reached
m (c) 8 (d) 1

x
(c) does not increase as rapidly with pressure along
m
BC due to less surface area available for adsorption
(d) nature of isotherm is different for two gases for same
adsorbent
SURFACE CHEMISTRY 222

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS


Objective Questions I 6. Choose the correct reason(s) for the stability of the
Lyophobic colloidal particles. (2012)
[Only one correct option]
1. Rate of physisorption increases with (2003) (a) Preferential adsorption of ions on their surface from the
solution
(a) decrease in temperature
(b) Preferential adsorption of solvent on their surface from
(b) increase in temperature
the solution.
(c) decrease in pressure
(c) Attraction between different particles having opposite
(d) decrease in surface area
charges on their surface.
2. Lyophilic sols are (2005)
(d) Potential difference between the fixed layer and the
(a) irreversible sols diffused layer of opposite charges around the colloidal
(b) prepared from inorganic compounds particles.

(c) coagulated by adding electrolytes 7. When O2 is adsorbed on a metallic surface, electron transfer
occurs from the metal to O2. The true statement(s) regarding
(d) self-stabilishing
this adsorption is (are) (2015)
3. Among the following, the surfactant that will form micelles
(a) O2 is physisorbed
in aqueous solution at the lowest molar concentration at
ambient conditions, is (2008) (b) Heat is released

(a) CH 3 (CH 2 )15 N  (CH 3 )3 Br  (c) Occupancy of *2 of O2 is increased

(b) CH 3 (CH 2 )11 OSO 3 Na 


(d) Bond length of O2 is increased
(c) CH 3 (CH 2 )6 COO  Na  8. The correct statement(s) about surface properties is(are)

(d) CH 3 (CH 2 )11 N  (CH 3 )3 Br  (2017)

4. Among the electrolytes Na2SO4, CaCl2, Al2(SO4)3 and NH4Cl, (a) Adsorption is accompanied by decrease in enthalpy
the most effective coagulating agent for Sb2S3 is and decrease in entropy of the system
(2009)
(b) The critical temperatures of ethane and nitrogen are 563
(a) Na2SO4 (b) CaCl2 K and 126 K, respectively. The adsorption of ethane
(c) Al2(SO4)3 (d) NH4Cl will be more than that of nitrogen on same amount of
Objective Questions II activated charcoal at a given temperature

[One or more than one correct option] (c) Cloud is an emulsion type of colloid in which liquid is
dispersed phase and gas is dispersion medium
5. The correct statement(s) pertaining to the adsorption of a
gas on a solid surface is(are) (2011) (d) Brownian motion of colloidal particles does not
(a) Adsorption is always exothermic. depend on the size of the particles but depends on
viscosity of the solution
(b) Physisorption may transform into chemisorption at high
temperature
(c) Physisorption increases with increasing temperature but
chemisorption decreases with increasing temperature
(d) Chemisorption is more exothermic than physisorption
however it is very slow due to higher energy of
activation.
SURFACE CHEMISTRY 223

9. The correction statement(s) related to colloids is(are) Assertion Reason


(2021) (A) If both Assertion and Reason are correct and
(a) The process of precipitating colloidal sol by an reason is the correct explanation of Assertion.
electrolyte is called peptization. (B) If both Assertion and Reason are true but
(b) Colloidal solution freezes at higher temeprature than reason is not the correct explanation of
the true solution at the same concentration. Assertion.
(c) Surfactants from micelle above critical micelle (C) If Assertion is true but Reason is false.
concentration (CMC). CMC depends on temperature.
(D) If Assertion is false but Reason is true.
(d) Micelles are macromolecular colloids. 10. Assertion (A): Micelles are formed by surfactant molecules
above the critical micelle concentration(CMC).
Reason (R) : The conductivity of a solution having
surfactant molecules decreases sharply at the CMC.
(2007)
(a) A (b) B
(c) C (d) D
SURFACE CHEMISTRY 224

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ANSWER KEY 225

Answer Key
CHAPTER -17 COORDINATION COMPOUNDS

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

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1. (d) 2. (d) 3. (b) 4. (b) 5. (c) 1. (d) 2. (a) 3. (d) 4. (b) 5. (a)
6. (c) 7. (a) 8. (d) 9. (b) 10. (c) 6. (d) 7. (a) 8. (c) 9. (d) 10. (a)
11. (d) 12. (b) 13. (c) 14. (d) 15. (a) 11. (a) 12. (b) 13. (c) 14. (c) 15. (c)
16. (c) 17. (d) 18. (d) 19. (d) 20. (c) 16. (a) 17. (c) 18. (b) 19. (d) 20. (d)
21. (c) 22. (c) 23. (d) 24. (c) 25. (b) 21. (a) 22. (d) 23. (a) 24. (a) 25. (d)
26. (c) 27. (d) 28. (b) 29. (c) 30. (b) 26. (b) 27. (a) 28. (d) 29. (a) 30. (d)
31. (d) 32. (d) 33. (b) 34. (b) 35. (d)
31. (b) 32. (d) 33. (a) 34. (c) 35. (c)
36. (d) 37. (d) 38. (c) 39. (a) 40. (a)
36. (c) 37. (c) 38. (a) 39. (d) 40. (d)
41. (c) 42. (d) 43. (c) 44. (b) 45. (d)
41. (c) 42. (a) 43. (c) 44. (a) 45. (d) 46. (b) 47. (a) 48. (c) 49. (a) 50. (a)
46. (c) 47. (d) 48. (a) 49. (d) 50. (a) 51. (a) 52. (b) 53. (a) 54. (b) 55. (d)
51. (d) 52. (b) 53. (d) 54. (c) 55. (d) 56. (b) 57. (c) 58. (c) 59. (a) 60. (b)
56. (a) 57. (c) 58. (b) 59. (a) 60. (d) 61. (d) 62. (d) 63. (c) 64. (b) 65. (b)
61. (a) 62. (b) 63. (a) 64. (b) 65. (c) 66. (a) 67. (d) 68. (a) 69. (a) 70. (b)
66. (b) 67. (d) 68. (b) 69. (d) 70. (c) 71. (a) 72. (6.00) 73. (0.00) 74. (20.00) 75. (1.00)
71. (d) 72. (d) 73. (d) 74. (b) 75. (d) 76. (0.00) 77. (3.00) 78. (2.00) 79. (4.00) 80. (3.00)
76. (c) 77. (d) 78. (d) 79. (b) 80. (c) 81. (2.00) 82. (2.00) 83. (1.00) 84. (0.00) 85. (6.00)
81. (c) 82. (d) 83. (b) 84. (d) 85. (b) 86. (2.00) 87. (5.00) 88. (2.00) 89. (2.00) 90. (2.00)
86. (c) 87. (a) 88. (c) 89. (a) 90. (a)
91. (a) 92. (b) 93. (d) 94. (d) 95. (a)
96. (c) 97. (b) 98. (d) 99. (b) 100. (a)
ANSWER KEY 226

CHAPTER -17 COORDINATION COMPOUNDS

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

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


6. (d) 7. (d) 8. (b) 9. (b) 10. (d) 5. (a) 6. (a) 7. (c) 8. (b)
11. (a) 12. (b) 13. (c) 14. (a) 15. (d) 9. (c) 10. (a) 11. (d) 12. (c)
16. (a) 17. (a) 18. (d) 19. (d) 20. (c) 13. (b) 14. (a) 15. (c,d) 16. (b,d)
21. (d) 22. (b) 23. (c) 24. (a) 25. (b) 17. (b,c) 18. (a,b,c) 19. (a,b,d) 20. (8.00)
26. (a) 27. (a) 21. (8.00) 22. (6.00) 23. (6.00) 24. (a)
28. (a,b,c) 29. (a,b,d) 30. (a,b,d) 25. (b)
31. (a,d) 32. (a,b,d) 33. (6.00) 26. (A - p,q,s; B - p,r,s; C - q,s; D - q,s)
34. (6.00) 35. (36.00) 36. (2.00) 27. (c) 28. (a) 29. (c) 30. (a)
37. (c) 38. (a) 39. (b) 40. (d) 41. (b)
42. (A - s; B - t; C - q; D - p)
43. (A - p; B - q; C - s; D - r)
44. (A - q,r; B - q,s,t; C - q,s; D - p,r,s)
45. (A - q,r; B - p,s; C - p,s; D - p,s)
46. (d) 47. (d) 48. (d) 49. (a) 50. (b)
ANSWER KEY 227

CHAPTER -18 CHEMICAL KINETICS


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

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1. (c) 2. (b) 3. (b) 4. (d) 5. (b) 1. (c) 2. (a) 3. (d) 4. (a) 5. (b)
6. (a) 7. (d) 8. (c) 9. (b) 10. (c) 6. (a) 7. (d) 8. (c) 9. (c) 10. (d)
11. (b) 12. (d) 13. (b) 14. (d) 15. (a) 11. (c) 12. (b) 13. (a) 14. (b) 15. (d)
16. (b) 17. (d) 18. (b) 19. (c) 20. (c) 16. (d) 17. (b) 18. (d) 19. (a) 20. (a)
21. (d) 22. (d) 23. (a) 24. (b) 25. (d) 21. (b) 22. (a) 23. (d) 24. (b) 25. (c)
26. (d) 27. (a) 28. (b) 29. (c) 30. (a) 26. (a) 27. (c) 28. (b) 29. (c) 30. (c)
31. (c) 32. (b) 33. (c) 34. (b) 35. (c) 31. (b) 32. (b) 33. (a) 34. (d) 35. (d)
36. (d) 37. (a) 38. (c) 39. (d) 40. (a) 36. (c) 37. (c)
41. (c) 42. (b) 43. (b) 44. (a) 45. (a)
38. (100.00) 39. (23.03)
46. (a) 47. (a) 48. (b) 49. (c) 50. (c)
40. (3.98) 41. (26.00)
51. (c) 52. (a) 53. (d) 54. (b) 55. (a)
42. (81.00) 43. (526.00)
56. (b) 57. (b) 58. (c) 59. (d) 60. (a)
44. (52.00) 45. (50.00)
61. (b) 62. (d) 63. (d) 64. (c) 65. (b)
46. (14.00) 47. (10.00)
66. (b) 67. (a) 68. (b) 69. (d)
48. (108.00) 49. (2.02)
70. (0.0031)
50. (27.00) 51. (3.00)
71. ( 3.3 × 10–4)
52. (10.00) 53. (106.00)
72. (5 × 10–3)
54. (1.34) 55. (60.00)
73. (5.4 × 10–3)
56. (84297.47) 57. (7.00)
74. (3 × 10–12)
58. (4.00) 59. (658.00)
75. (9.1 × 10–2)
60. (1.00) 61. (4.00)
76. (34.06)
62. (16.00) 63. (2.00)
77. (3.46 × 10–3 )
64. (45.00) 65. (47.00)
78. (2.7 × 10–4 )
79. (99.9)
80. (4.68)
ANSWER KEY 228

CHAPTER -18 CHEMICAL KINETICS

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

DIRECTION TO USE - DIRECTION TO USE -


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

1. (c) 2. (c) 3. (b) 4. (d) 5. (a) 1. (d) 2. (b) 3. (a) 4. (c) 5. (c)
6. (b) 7. (d) 8. (d) 9. (b) 10. (a) 6. (c) 7. (d) 8. (d) 9. (c) 10. (b)
11. (b) 12. (d) 13. (d) 14. (d) 15. (c) 11. (d) 12. (a) 13. (d) 14. (b) 15. (d)
16. (b) 17. (a) 18. (d) 19. (c) 20. (d) 16. (b) 17. (a) 18. (d) 19. (a) 20. (d)
21. (c) 22. (a) 23. (d) 24. (d) 25. (d)
21. (b) 22. (a) 23. (b, c, d) 24. (a, b)
26. (b) 27. (d) 28. (c) 29. (a) 30. (b)
25. (a, d) 26. (a,b,d)
31. (c) 32. (b) 33. (b) 34. (d) 35. (a)
36. (a) 37. (a) 38. (b) 39. (c) 40. (d) 27. (b,c,d) 28. (100)
41. (b) 42. (c) 43. (d) 44. (a) 45. (b) 29. (25.00) 30. (9.00)
46. (c) 47. (c) 48. (c) 49. (d) 50. (d) 31. (–8500.00) 32. (6.75)
51. (b) 52. (b) 53. (b) 54. (a) 55. (d) 33. (2.30) 34. (1.20)
56. (d) 57. (d) 58. (a) 59. (a) 60. (a) 35. (c) 36. (b) 37. (b)
61. (b) 62. (d) 63. (b) 64. (a) 65. (c)
66. (a,d) 67. (a,b)
68. (a,b,c) 69. (a, c)
70. (a, b, c) 71. (a, b)
72. (a, b, c) 73. (b, c)
74. (a, b) 75. (a, b, c)
76. (8.00) 77. (4.00)
78. (3.00)
79. (c) 80. (b) 81. (a) 82. (b) 83. (a)
84. (A-r; B-s; C-q; D-p)
85. (d) 86. (b) 87. (c) 88. (c) 89. (d)
90. (b)
ANSWER KEY 229

CHAPTER -19 ELECTROCHEMISTRY

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

DIRECTION TO USE - DIRECTION TO USE -


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

1. (d) 2. (a) 3. (d) 4. (c) 5. (d) 1. (c) 2. (d) 3. (b) 4. (c) 5. (d)
6. (c) 7. (d) 8. (d) 9. (c) 10. (d) 6. (d) 7. (d) 8. (a) 9. (a) 10. (d)
11. (a) 12. (a) 13. (a) 14. (b) 15. (b) 11. (a) 12. (a) 13. (a) 14. (c) 15. (b)
16. (d) 17. (d) 18. (d) 19. (a) 20. (a) 16. (b) 17. (c) 18. (c) 19. (d) 20. (b)
21. (a) 22. (d) 23. (b) 24. (d) 25. (c) 21. (d) 22. (c) 23. (c) 24. (c) 25. (d)
26. (c) 27. (c) 28. (d) 29. (b) 30. (c) 26. (b) 27. (a) 28. (b) 29. (a) 30. (a)
31. (c) 32. (c) 33. (d) 34. (a) 35. (a) 31. (a) 32. (a) 33. (a) 34. (96500.00)
36. (d) 37. (b) 38. (c) 39. (b) 40. (c) 35. (144.00) 36. (58.00)
41. (c) 42. (a) 43. (b) 44. (d) 45. (d) 37. (60.00) 38. (6.00)
46. (d) 47. (b) 48. (d) 49. (c) 50. (b) 39. (11.00) 40. (1.52)
51. (c) 52. (a) 53. (a) 54. (a) 55. (d) 41. (2.15) 42. (4.00)
56. (c) 57. (c) 58. (c) 59. (a) 60. (b)
43. (147.00) 44. (14.00)
61. (a) 62. (b) 63. (a) 64. (c) 65. (c)
45. (56.00) 46. (45.00)
66. (c) 67. (d) 68. (d) 69. (a) 70. (c)
47. (28.00) 48. (1.00)
71. (c) 72. (a) 73. (d) 74. (a) 75. (d)
49. (3.00) 50. (24.00)
76. (c) 77. (c) 78. (c) 79. (c) 80. (c)
51. (43) 52. (12.00)
81. (b) 82. (d) 83. (b) 84. (b) 85. (b)
86. (b) 87. (a) 88. (b) 89. (d) 90. (b) 53. (109.00) 54. (760.00)
91. (84 g) 92. (0.616 cm ) –1 55. (25.00) 56. (26.00)
93. (3.90 cm–1) 94. (193000 .00) 57. (3776.00) 58. (25.00)
95. (0.20) 96. (126.00) 59. (d) 60. (a)
97. (128 S cm mol )
2 –1

98. (3.442 × 10–5 mol dm–3) 99. (2.6 × 10–5 M)


100. (30.928 min)
ANSWER KEY 230

CHAPTER -19 ELECTROCHEMISTRY

EXERCISE - 3 :
ADVANCED OBJECTIVE QUESTIONS

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

1. (d) 2. (c) 3. (a) 4. (b) 69. (a) 70. (d) 71. (b) 72. (b)
5. (d) 6. (c) 7. (c) 8. (d) 73. (a) 74. (a) 75. (b) 76. (b)
9. (c) 10. (c) 11. (d) 12. (b) 77. (b) 78. (c) 79. (b) 80. (a)
13. (b) 14. (a) 15. (a) 16. (a) 81. (c) 82. (c) 83. (a) 84. (a)
17. (b) 18. (a) 19. (c) 20. (c) 85. (c) 86. (c) 87. (d) 88. (c)
21. (a) 22. (a) 23. (c) 24. (a) 89. (b) 90. (d) 91. (b) 92. (c)
25. (b) 26. (d) 27. (d) 28. (a) 93. (c) 94. (a,b,c) 95. (a,d) 96. (c)
29. (b) 30. (c) 31. (b) 32. (d) 97. (a,b,c) 98. (a,c) 99. (a,b,d) 100. (b,c)
33. (c) 34. (b) 35. (b) 36. (b) 101. (a,b) 102. (a,b,d) 103. (a,b,c,d) 104. (9.00)
37. (c) 38. (b) 39. (a) 40. (d) 105. (35.00) 106. (1.00)
41. (d) 42. (d) 43. (b) 44. (a) 107. (44.76) 108. (d)
45. (c) 46. (c) 47. (d) 48. (d) 109. (a) 110. (d) 111. (d) 112. (a)
49. (d) 50. (a) 51. (b) 52. (b) 113. (A  q; B  p,r; C  s; D  t)
53. (c) 54. (a) 55. (b) 56. (c) 114. (A  p, q; B  p,q; C  r; D  p,q,s)
57. (b) 58. (c) 59. (a) 60. (d)
115. (d) 116. (c) 117. (a,b,c,d) 118. (c)
61.(c) 62. (a) 63. (d) 64. (c) 119. (a) 120. (a)
65. (d) 66. (b) 67. (b) 68. (c)
ANSWER KEY 231

CHAPTER -19 ELECTROCHEMISTRY

EXERCISE - 4 :
PREVIOUS YEAR JEE ADVANCED QUESTIONS

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

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


6. (b) 7. (b) 8. (d) 9. (d) 10. (c)
11. (a) 12. (a,b,d) 13. (a,c) 14. (a,c)
15. (1010) 16. (55.00)
17. (10.00)18. (–11.62)
19. (0.22) 20. (0.86) 21. (b) 22. (a) 23. (d)
24. (b) 25. (d) 26. (d) 27. (c) 28. (d)
29. (d) 30. (c) 31. (b) 32. (d)
ANSWER KEY 232

CHAPTER -20 SURFACE CHEMISTRY

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

DIRECTION TO USE - DIRECTION TO USE -


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

1. (c) 2. (a) 3. (d) 4. (c) 5. (c) 1. (c) 2. (c) 3. (b) 4. (b) 5. (a)
6. (a) 7. (a) 8. (a) 9. (b) 10. (c) 6. (c) 7. (b) 8. (a) 9. (d) 10. (d)
11. (c) 12. (b) 13. (b) 14. (a) 15. (a) 11. (a) 12. (a) 13. (a) 14. (b) 15. (c)
16. (d) 17. (d) 18. (b) 19. (c) 20. (d) 16. (a) 17. (a) 18. (d) 19. (c) 20. (d)
21. (c) 22. (d) 23. (d) 24. (c) 25. (b) 21. (d) 22. (c) 23. (c) 24. (d) 25. (d)
26. (c) 27. (b) 28. (b) 29. (c) 30. (d)
26. (d) 27. (a) 28. (a) 29. (b) 30. (b)
31. (d) 32. (a) 33. (a) 34. (c) 35. (d)
31. (d) 32. (a) 33. (a) 34. (a) 35. (a)
36. (a) 37. (b) 38. (b) 39. (c) 40. (d)
36. (c) 37. (c) 38. (c) 39. (d) 40. (d)
41. (b) 42. (d) 43. (a) 44. (b) 45. (b)
41. (d) 42. (b) 43. (a) 44. (a) 45. (a)
46. (c) 47. (d) 48. (d) 49. (a) 50. (c)
46. (c) 47. (d) 48. (b)
51. (d) 52. (b) 53. (b) 54. (b) 55. (c)
49. (48.00) 50. (48.00)
56. (a)
51. (0.3675) 52. (2.00)
57. (b) 58. (4.00)
53. (0.5) 54. (17.00)
59. (10.00) 60. (3.00)
55. (128.00)
61. (2.00) 62. (2.00)
63. (2.00) 64. (0.60)
65. (1000.00)
ANSWER KEY 233

CHAPTER -20 SURFACE CHEMISTRY

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

DIRECTION TO USE - DIRECTION TO USE -


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

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


6. (d) 7. (c) 8. (b) 9. (a) 10. (d) 4. (c) 5. (a,b,d) 6. (a,d)
11. (b) 12. (a) 13. (a) 14. (a) 15. (d) 7. (b,c,d) 8. (a,b) 9. (b, c)
16. (a) 17. (c) 18. (d) 19. (b) 20. (a) 10. (b)
21. (a) 22. (b) 23. (c) 24. (d) 25. (b)
26. (a) 27. (a) 28. (c) 29. (c) 30. (d)
31. (c) 32. (a) 33. (d) 34. (a) 35. (b)
36. (c) 37. (a,c,d)
38. (a,b,d) 39. (a,b,d)
40. (a,b,c,d) 41. (a,b,c)
42. (a,b,c) 43. (a,b,d)
44. (a,c,d) 45. (a,c,d)
46. (a) 47. (a)
48. (d) 49. (a)
50. (a) 51. (a)
52. (A – p, s; B – p; C – q, r; D – q)
53. (A – s; B – p; C – q, r; D – q)
54. (A – r; B – p; C – s; D – q)
55. (A – q; B – p; C – r; D – s)
56. (A – p; B – q; C – q, s; D – p, r)
57. (d) 58. (c) 59. (d) 60. (c) 61. (c)
62. (d) 63. (b) 64. (b) 65. (b)
MASTER INDEX
VOLUME 1:
Solutions
Solid State
General Organic Chemistry (Revision) & Isomerism
Alkyl and Aryl Halides
Alcohols, Phenols and Ethers

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

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

VOLUME 4:
Coordination Compounds
Chemical Kinetics
Electrochemistry
Surface Chemistry
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