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How to use your
Tatva Practice Book
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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Exercise-1: Basic Objective preparation content,
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TABLE OF CONTENTS
COORDINATION COMPOUNDS
Theory ................................................................................................................................................ 8
Solved Examples ............................................................................................................................... 28
CHEMICAL KINETICS
Theory ................................................................................................................................................ 63
SURFACE CHEMISTRY
COORDINATION COMPOUNDS
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.
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’
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.
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.
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
SCAN CODE
Coordination Compounds
COORDINATION COMPOUNDS 16
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
(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
x
Approach of Ligands in Octahedral Complex
SCAN CODE
Coordination Compounds
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
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
SCAN CODE
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 0.4t above weighted average energy of the
two groups (the Bari centre) and the eg orbitals are 0.6t 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
SCAN CODE
Coordination Compounds
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 :
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.
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Coordination Compounds
COORDINATION COMPOUNDS 20
This isomer gives a white percipitate of BaSO4 with BaCl2 solution. 10.1.6 Coordination Position Isomerism
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
COORDINATION COMPOUNDS 21
Example: Example:
Draw the geometrical isomers of [PtCl2(NH3)2] Draw the geometrical isomers of [PtClBr(Py) (NH3)]
Sol. Sol.
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Coordination Compounds
COORDINATION COMPOUNDS 22
Example: Sol.
Draw the geometrical isomers of [CrCl2(NH3)4]+
Sol.
7. [M(AA)2b2]
Example:
Draw the geometrical isomers of [CoCl2(en)2]+
Sol.
Example:
Draw the geometrical isomers of [RhCl3(py)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.
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
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
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
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
(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.
Write IUPAC name of the complex [Cr(H2O)5Cl]Cl2. Sol. Tetraamminedichloridoplatinum (IV) chloride.
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
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 - 24
(ii)
Example - 27
Example - 28
Example - 30
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
Example - 36
Example - 37
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
Example - 46
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.
Example - 49
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.
(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
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
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
(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
(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)
(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
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
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)
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.
(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
(d)
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
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
7. Among the following, the coloured compound is (2008) 14. The calculated spin magnetic of Cr NH3 6 and
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
Note:
Find Answer Key and Detailed Solutions at the end of this book
COORDINATION COMPOUNDS
CHEMICAL KINETICS
THEORY
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Chemical Kinetics
CHEMICAL KINETICS 65
NOTE 3.2 Order of a Reaction
aA + bB cC + dD aA + bB cC + dD
dt
Above equation is known as differential rate equation, k is a mol L1 1
Second order reaction 2
s (mol L1 ) 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
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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
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]
t In [R]0 = – k × 0 + I
In [R]0 = I
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CHEMICAL KINETICS 67
Substituting the value of I in equation (1) The first order rate equation (3) can also be written in the form
1 [R]0
or k ln ......... (3)
t [R]
At time t2
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]
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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CHEMICAL KINETICS 68
For the first order reaction, 4.5 Practical Analysis of First Order Reactions
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
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CHEMICAL KINETICS 69
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 AB+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
ax 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
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CHEMICAL KINETICS 70
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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CHEMICAL KINETICS 71
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.
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CHEMICAL KINETICS 72
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
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
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CHEMICAL KINETICS 73
The factor e Ea / RT corresponds to the fraction of molecules that
have kinetic energy greater than Ea.
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
k Ae Ea / RT
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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
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CHEMICAL KINETICS 75
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
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
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]n1
[ 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
SCAN CODE
Chemical Kinetics
CHEMICAL KINETICS 76
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 1.3 104
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
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 ?
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
n=0
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
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
For the reaction N2(g) + 3H2(g) 2NH3(g), how are the = 0.5 × 10–2 mol L–1 s–1
Rate = k [A]n
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. 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
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)
[R]0 = –k × 0 + I
[R]0 = I
= 2.303 × 2 × 10–4
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,
[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
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 ax Sol. t1/2 = 5730 year
2.303 a
log 0.693 0.693
t 3/ 4
k a 3a / 4 log 4 k t 1.209 104 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] 1.2 104 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
5 104 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]
5 104
CHEMICAL KINETICS 85
t = 1790 min.
[A]
log 0 0.4768 1.5232 Example-42
[A]
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
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
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]
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’
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)
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 ax
(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 ax 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
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
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
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
(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 L1s 1 to 2.4 mol L1s 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 L1 and it is 2.75 mol L1 after 30
and activation energy respectively)
minutes. The rate of formation of NO 2 is : (2019)
Choose the correct option: (2019)
(a) 1.667 102 mol L1 min 1
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) 106 s 1 (b) 2 10 4 s 1 without. The change in activation energy upon adding
enzyme is: (2020)
(c) 104 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
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]
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 2.40 102 mol L1 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). (2.47 103 )
by log k 20.35
[Use: ln 2 = 0.69, ln 10 = 2.3, ln 3 = 1.1] T
(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
(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).
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
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
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 :
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) 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)
(c) (d)
–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
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)
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
(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, 13.86 103 mol L1s 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, 3.46 103 mol L1s 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
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
Note:
Find Answer Key and Detailed Solutions at the end of this book
CHEMICAL KINETICS
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 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 E 0Red, cathode Eox, anode
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 Bb
cell
Electrical work done in one second is equal to electrical
potential multiplied by total charge passed.
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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, Ecell 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 ECl /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
2SO 24 aq S2 O82 aq 2e o
E SO 2
/S O 2
1.96 V
4 2 8
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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 1019 C 6.02 10 23 mol1 1.6021 1019
‘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
wE (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
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
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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/ Zn2 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
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/ Mg2 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
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 Eocell In Eocell 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.
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
0.059 103 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
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
-n FE = -n FE - -n FE
3
0
3 1
0
1 2
0
2
X = Zn , Y =Ni
o
o
o c
m HCl H Cl
0.01148 S cm 1 1000 cm3 L1
= 229.6 S cm2 mol–1
om NaCl oNa Cl
o
0.05 mol L1
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
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/ Zn2 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/ Fe2 = – 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 4 105 S / cm 1000
40S cm2 mol1
(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 1.19 105
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 L1
changes with concentration of solute. How is such
7.5 103 mol L1
change explained ?
165.87 1 cm 2 mol1 . (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
103 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)
EQ E
w= ×I×t
W 96500
F
F = 96500 C 10×7200
n×0.25=
E = equivalent weight of Ag (108 g) 96500
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)
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
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
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
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 ?
The potential for the cell EMF of the cell is 1.023 V. What is the value of x ?
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
EMg 2 2.34 V, ESn 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) 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) S m mol–1 (b) S2 m2 mol–2 respectively. To calculate oHOAc , the additional value
(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
(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
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 106 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
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:
(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 :
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 110 3 M Cu 2 0.250M 2Ag s Cd s +Hg 2SO 4s + H 2 O l CdSO 4 . H 2 Os +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 104 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 ____ 102 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
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
The EMF for the cell reaction, when 0.1M Cu2+ and 0.1 (c) ohm cm2 (g equivalent)
(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 ?
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
(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
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,
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
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 mol1 ,
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
Note:
Find Answer Key and Detailed Solutions at the end of this book
ELECTROCHEMISTRY
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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2.5.2 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.
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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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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)
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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
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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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Platinised
4 NH 3 (g) 5 O 2 (g)
asbestos (catalyst)
4 NO (g) 6 H 2 O (g)
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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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
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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.
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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
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.
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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
The gold sol, thus prepared, has a purple colour and is called
purple of cassius.
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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
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
1. Gelatin 0.005-0.01
3. Haemoglobin 0.03-0.07
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.
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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.
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
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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.
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
(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.
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
(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
(A) Cheese (p) dispersion of liquid in ...... 104 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
3. Rate of physisorption increases with (a) enthalpy is positive (b) entropy decreases
(a) decrease in temperature (c) entropy increases (d) free energy increases
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–
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
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
(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
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
Note:
Find Answer Key and Detailed Solutions at the end of this book
SURFACE CHEMISTRY
Answer Key
CHAPTER -17 COORDINATION COMPOUNDS
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS
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
EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS
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
EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS
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
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS
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
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
EXERCISE - 4 :
PREVIOUS YEAR JEE ADVANCED QUESTIONS
DIRECTION TO USE -
Scan the QR code and check detailed solutions.
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS
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
EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS
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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