Chemistry Notes

I – The Solid State
Questions (From Textbook)

1.1. Define the term amorphous? Give a few examples of amorphous solids.
Ans. Amorphous solids have short-range order with irregular shapes of constituent particles.
They have isotropic nature and melt over a range of temperatures. They do not have a
definite enthalpy of fusion.
Examples of amorphous solids are glass, rubber, plastic, etc.
1.2. What make a glass different from a solid such as quartz? Under what conditions could
quartz be converted to glass?
Ans. Glass is an amorphous solid in which the constituent particles (SiO 4 tetrahedra) have
only a short range order. Quartz is a crystalline form of silica in which SiO 4 units are
arranged in such a way that they have long ranged order. Quartz can be converted into
glass by melting it and cooling it rapidly.
1.3. Classify each of the following solids are ionic, metallic, molecular, network (covalent) or
amorphous.
1. Tetra phosphorous decoxide (P4O10) 2. Ammonium phosphate (NH4)3PO4
3. SiC 4. I2 5. P4 6. Plastic 7.Graphite 8. Brass 9.Rb 10.LiBr 11.Si
Ans. The different solids are classified below:
Ionic solids: Ammonium phosphate ((NH4)3PO4),LiBr
Metallic solids : Brass, Rb
Molecular solids : Tetraphosphorous decaoxide (P4O10), Iodine (I2), P4
Network (covalent) solids: Graphite, SiC,Si
Amorphous solid : Plastics
1.4. (i) What is meant by the term ‘co-ordination number’?
(ii) What is the co-ordination number of atoms
(a) In a cubic close-packed structure
(b) In a body-centered cubic structure
Ans. (i) Coordination number is the number of nearest neighbors with which a given atom is
in contact. In an ionic crystal, the coordination number of an ion refers to the number
of oppositely charged ions that surround that ion.
(ii) The coordination number of atoms in a
(a) cubic close-packed structure is 12.
(b) body-centred cubic structure is 8.
1.5. How can you determine the atomic mass of an unknown metal if you know its density
and the dimension of its unit cell? Explain
Ans.
1.6. ‘Stability of a crystal is reflected in the magnitude of its melting point’. Comment.
Collect melting points of solid water, ethyl alcohol, diethyl ether and methane from a
data book. What can you say about the intermolecular forces between these
molecules?
Ans. (i) Stability of a crystal is directly proportional to the magnitude of its melting points.
Higher is the magnitude of forces holding the constituent particles together, higher will
be the melting point and higher will be the stability. Thus ionic crystals (NaCl, KNO 3,
etc.) have very high melting points and stable crystal lattices. On other hand, molecular
solids (naphthalene, iodine etc.) have low melting points and low stability.
(ii) The melting point of different substances are :
(a) Water = 273 K
(b) Ethyl alcohol =155.7K
(c) Diethyl ether = 156.8 K
(d) Methane = 90.5 K
Solid water and ethyl alcohol have higher melting points due to presence of inter-
molecular hydrogen bonds. Since the extent of hydrogen bonding in solid water is
greater than the extent of hydrogen bonding in ethyl alcohol, the melting point of solid
water is higher than the melting point of ethyl alcohol. Polar diethyl ether involves
dipole-dipole interactions. Non polar methane involves weak van der Waals forces
(London dispersion forces) which are weaker than dipole-dipole interactions. Hence,
the melting point of methane is much lower than the melting point of diethyl ether.
1.7. How will you distinguish between the following pairs of terms:
(i) Hexagonal close-packing and cubic close-packing?
(ii) Crystal lattice and unit cell?
(iii) Tetrahedral void and octahedral void?
Ans. In hexagonal close packing (hcp), the spheres of the third layer are vertically above the
spheres of the first layer. It means tetrahedral voids of the second layer are covered by
the spheres of the third layer. The AB AB AB..... type.
In cubic close packing (ccp), the spheres of third layer cover the octahedral voids of
second layer. But the spheres of the fourth layers are aligned with those of the first
layer. The pattern is ABC ABC...... type.
(ii) Crystal lattice is the three dimensional arrangement of identical point in the space
which represent how the constituent particles (atoms, ions, molecules) are arranged in
a crystal.
Unit cell is the smallest portion of a crystal lattice which, when repeated in different
directions, generates the entire lattice.
(iii) Tetrahedral voids are surrounded by four spheres which lie at the vertices of a
regular tetrahedron. There are 2 tetrahedral voids per atom in a crystal. Octahedral
voids are surrounded by six spheres and formed by a combination of two triangular
voids of the first and second layer. There is one octahedral void per atom in a crystal.
1.8. How many lattice points are there in one unit cell of each of the following lattice?
(i) Face-centered cubic
(ii) Face-centered tetragonal
(iii) Body-centered
Ans. (i) Face-centered cubic
Face centered lattice have atoms at corners which is shared by eight atoms and at the
centered of face of cube which is shared by two faces.
An atom at corner contributes one eight to the unit cell and atom at face center
contribute one half.
Total number of lattice points per unit cell: 8×81+6×21=1+3=4
(ii) Face-centered tetragonal

centered of face of cube which is shared by two faces.
An atom at corner contributes one eight to the unit cell and atom at face center
contribute one half.
(iii) Body centered

centered of cube which is shared by one cube.
An atom at corner contributes one eight to the unit cell and atom at center of cube
contribute by one.
1.9. Explain
(i) The basis of similarities and differences between metallic and ionic crystals
(ii) Ionic solids are hard and brittle
Ans. Similarities
(a) Ionic and metallic crystals both have electrostatic force of attraction. In ionic
crystals, this force is between oppositely charged ions whereas, in metals, this force is
in between the valence electrons and the kernels.
(b) In both cases, the bond is non - directional
Differences
(a) In ionic crystals, ions are not free to move. So, they don't conduct electricity in solid-
state. They are conductors only in molten state or aqueous solution. In metals, valence
electrons can move. Hence, they can conduct electricity in solid-state.
(b) Ionic bonds are strong whereas metallic bonds may be weak or strong.
(ii) Ionic crystals are hard because there are strong electrostatic forces of attraction
among the oppositely charged ions. They are brittle because the ionic bond is non-
directional.
1.10. Calculate the efficiency of packing in case of a metal crystal for
(i) simple cubic
(ii) body-centered cubic
(iii) face-centered cubic (with assumptions that atoms are touching each other)
Ans. Solution:
(i) The efficiency of packing in case of simple cubic unit cell is given below:
A simple cubic unit cell contains one atom per unit cell.
Also, a=2r, where a is the edge length and r is the radius of atom.
Total volume of unit cell =a3.
(ii) The efficiency of packing in case of body-centred cubic unit cell is given below:
A body-centred cubic unit cell contains two atoms per unit cell.
Also, √3a=4r, where a is the edge length and r is the radius of atom.
Total volume of unit cell =a3.
(iii) The efficiency of packing in case of face-centered cubic unit cell (with the
assumptions that atoms are touching each other) is given below:
A face-centered cubic unit cell contains four atoms per unit cell.
Also, a=2√2r, where a is the edge length and r is the radius of atom.
Total volume of unit cell =a3
1.11. Silver crystallises in fcc lattice. If edge length of the cell is 4.07 x 10e-8 cm and density is
10.5 g cm-3, calculate the atomic mass of silver.
Ans. Solution:
1.12. A cubic solid is made of two elements P and Q. Atoms of Q are at the corners of the
cube and P at the body-centre. What is the formula of the compound? What are the co-
ordination numbers of P and Q?
Ans. P atoms are present at the 8 corners and contribution of every corner is one-eighth.
Therefore, total P atom is 1. Q is present inside the cube so number of Q atom is 1. The
formula is PQ. Q atom is surrounded by 8 P atoms and vice versa. So the coordination
number is 8.
1.13. Niobium crystallises in body-centered cubic structure. If density is 8.55 g cm-3, calculate
atomic radius of niobium using its atomic mass 93 u.
Ans. Solution:
1.14. If the radius of the octahedral void is r and radius of the atoms in close-packing is R,
derive relation between r and R
Ans.
1.15. Copper crystallises into a fcc lattice with edge length 3.61 x 10e-8 cm. Show that the
calculated density is in agreement with its measured value of 8.92 g cm-3.
Ans.
1.16. Analysis shows that nickel oxide has the formula Ni 0.98 O1.00. What fractions of nickel
exist as Ni2+ and Ni3+ ions
Ans. The ratio of Ni and O atoms in pure nickel oxide (NiO) = 1 : 1 Let x be the number of Ni
(II) atoms replaced by Ni (III) atoms in the oxide.
∴ Number of Ni (III) atoms present = (0.98 - x)
Since, the oxide is neutral in nature,
Total charge on Ni atoms = Charge on oxygen atoms
3(0.98 - x) + 2x = 2
2.94 - 3x + 2x = 2
x = 2.94 - 2 = 0.94
hence, Number of Ni (III) atoms present = 0.98-.94=0.04
Hence, the fraction of Ni+2 and Ni+3 is 0.94 and 0.04 respectively.
1.17. What is a semiconductor? Describe the two main types of semiconductors and contrast
their conduction mechanism.
Ans. Semiconductors are substances with conductance in the intermediate range of 10 −6 to
104 ohm−1m−1.
(i) n-type semiconductor: In this semiconductors, increase in conductivity is due to
negatively charged electrons. For example, Si or Ge (group 14 elements) doped with P
or As (group 15 elements containing 5 valence electrons).
Out of five valence electrons of group 15 elements, 4 valence electrons form covalent
bonds with four neighboring Si or Ge atoms and the remaining fifth electron becomes
de-localized and increases the conductivity of doped Si or Ge.
(ii) p-type semiconductor. In this semiconductors, increase in conductivity is due to
positively charged holes. For example, Si or Ge (group 14 elements) doped with B, Al or
Ga (group 13 elements containing 3 valence electrons). In presence of electric field,
electrons move toward the positively charged plate through electron holes. However, it
appears as if the electron holes are positively-charged and are moving towards the
negatively-charged plate.
1.18. Non-stoichiometric cuprous oxide, Cu2O can be prepared in laboratory. In this oxide,
copper to oxygen ratio is slightly less than 2:1. Can you account for the fact that this
substance is a p-type semiconductor?
Ans. Non-stoichiometric cuprous oxide, Cu2O can be prepared in laboratory. In this oxide,
copper to oxygen ratio is slightly less than 2:1. This substance is a p-type
semiconductor. Slight difference in ratio factor corresponds to absence of Cu(I) ions
from their lattice site leaving behind holes which helps in electrical conductivity.
1.19. Ferric oxide crystallises in a hexagonal close-packed array of oxide ions with two out of
every three octahedral holes occupied by ferric ions. Derive the formula of the ferric
oxide.
Ans.
1.20. Classify each of the following as being either a p-type or a n-type semiconductor
(i) Ge doped with In (ii) Si doped with B
Ans. 1. Ge is group 14 element and In is group 13 element. Hence an electron deficient hole
is created and therefore, it is p–type.
2. B is group 13 elements and Si is group 14 elements, there will be a free electron.
Hence, it is n-type
1.21. Gold (atomic radius = 0.144 nm) crystallised in a face-centered unit cell. What is the
length of a side of the cell?
Ans. For fcc unit cell, a=2√2r.
Here, a is the edge length and r is the atomic radius (0.144 nm).
a=2√2×0.144=0.407 nm
Hence, the length of a side of a cell is 0.407 nm.
1.22. In terms of band theory, what is the difference
(i) between a conductor and an insulator
(ii) between a conductor and a semiconductor
Ans. The differences are given below:
(i) Conductor and insulator
In conductor, the valence band is partially filled and it overlaps with a high energy
unoccupied conduction band.
Electrons can easily flow under an applied electric field.
In case of insulator, the valence band is fully-filled and there is large energy gap
between the valence band and the conduction band.
(ii) Conductor and semiconductor
In conductor, the valence band is partially filled and it overlaps with a high energy
unoccupied conduction band.
Electrons can easily flow under an applied electric field.
In semiconductor, the valence band is filled and there is a small gap between the
valence band and the next higher conduction band.
Some electrons can jump from the valence band to the conduction band and conduct
electricity
1.23. Explain the following terms with suitable example:

(i) Schottky defect (ii) Frenkel defect (iii) Interstitials and (iv) F-centres
Ans. (i) Schottky defect: Schottky defect is basically a vacancy defect shown by ionic
solids. In this defect, an equal number of cations and anions are missing to maintain
electrical neutrality. It decreases the density of a substance. Significant number of
Schottky defects is present in ionic solids. For example, in NaCl, there are approximately
106 Schottky pairs per cm3 at room temperature. Ionic substances containing similar-
sized cations and anions show this type of defect. For example: NaCl, KCl, CsCl, AgBr,
etc.
(ii) Frenkel defect: Ionic solids containing large differences in the sizes of ions show
this type of defect. When the smaller ion (usually cation) is dislocated from its normal
site to an interstitial site, Frenkel defect is created. It creates a vacancy defect as well as
an interstitial defect. Frenkel defect is also known as dislocation defect. Ionic solids
such as AgCl, AgBr, AgI, and ZnS show this type of defect.
(iii) Interstitials: Interstitial defect is shown by non-ionic solids. This type of defect is
created when some constituent particles (atoms or molecules) occupy an interstitial
site of the crystal. The density of a substance increases because of this defect.
(iv) F-centres: When the anionic sites of a crystal are occupied by unpaired electrons,
the ionic sites are called F-centres. These unpaired electrons impart colour to the
crystals. For example, when crystals of NaCl are heated in an atmosphere of sodium
vapour, the sodium atoms are deposited on the surface of the crystal. The Cl ions
diffuse from the crystal to its surface and combine with Na atoms, forming NaCl. During
this process, the Na atoms on the surface of the crystal lose electrons. These released
electrons diffuse into the crystal and occupy the vacant anionic sites, creating F-centres.
1.24. Aluminium cystallises in a cubic close-packed structure. Its metallic radius is 125 pm.
(i) What is the length of the side of the unit cell?
(ii) How many unit cells are there in 1.00 cm3 of auminium?
Ans.
1.25. If NaCl is doped with 10-3 mol % of SrCl2, what is the concentration of cation vacancies?
Ans.
1.26. Explain the following with suitable examples.

(i) Ferromagnetism (ii) Paramagnetism (iii) Ferrimagnetism (iv) Antiferromagnetism
(v)12-16 and 13-15 group compounds.
Ans. (i) Ferromagnetism
Certain substances exhibit very strong magnetic property. They can be permanently
magnetised. They contain large number of unpaired electrons and the magnetic
moment associated with it are equal in magnitude and aligned in the same direction.
Examples: Iron, cobalt, nickel, gadolinium, CrO2 etc.
(ii) Paramagnetism
When unpaired electrons revolve in the orbitals, a net magnetic field is associated with
the substance containing these unpaired electrons.
Due to presence of unpaired electrons, certain substances experiences pull in magnetic
field. The number of unpaired electrons determine the extent of paramagnetism.
Examples : Oxygen, Cu2+, Fe3+ and Cr3+
(iii) Ferrimagnetism
Unequal magnitude of magnetic moment associated with unpaired electrons are
aligned in the same directions, the net magnetic moment is not zero.
Example: Ferrite Fe2O3
(iv) Antiferromagnetism
Equal magnitude of magnetic moment associated with unpaired electrons are aligned in
opposite directions, the net magnetic moment is zero.
Example: MnO, Mn2O3 and MnO2
Question (From Question Bank)

One Mark Question
1. What is anisotropy?
Ans. Anisotropic:
-Anisotropic refers to the properties of a material that is dependent on the direction.
-Another condition that can fit the anisotropic definition is the presence of different
properties in different directions.
-A different chemical bonding in all directions is also a condition for anisotropy.
2. Between glass and copper, which one is isotropic in nature?
Ans. Glass is isotropic because of its amorphous nature. Copper is anisotropic.
3. Arrange these solids in their increasing order of inter molecular attractions: ice,I2, solid
ammonia
Ans. Ice > Solid ammonia >
Ice has strong hydrogen-bonding, using oxygen. Solid ammonia has weaker hydrogen-
bonding, using nitrogen. Iodine has no hydrogen bonding. In its solid form, it only has
London forces as forces of attraction.
4. Ionic solids conduct electricity in molten state but not in solid state. Give reason
Ans. The conductivity of ionic Solids:
The particles in ionic solids are fixed in their positions and have very little freedom for
movement. Hence, ionic solids are characterized by poor conduction in solid states.
In a molten state, the compounds dissociate into ions that can move freely. Hence, in
molten state ionic solids can freely conduct electricity.
5. Is diamond a network or a metallic solid?
Ans. Diamond, an allotrope of carbon, consists of a three – dimensional network of carbon
atoms attached to each other. Since carbon atoms have properties for catenation, they
form covalent bonds with each other in a 3 – D frame network. Therefore diamond is
termed as a network covalent solid.
6. What type of crystalline solid is AlN?
Ans. AlN is a covalently bonded network solid crystallized into a wurtzite structure.
7. Which type of crystalline solids have very high melting point?
Ans. Atoms are bonded to each other by strong covalent bond have very high melting point.
Example: Diamond.
8. Define coordination number
Ans. The Coordination number of an atom in a given molecule or a crystal refers to the total
number of atoms, ions, or molecules bonded to the atom in question. ‘Ligancy’ is
another term used to refer to the coordination number of an atom.
(The atoms, ions, or molecules that are bonded to the central atom (or molecule/ion)
are called ligands. The ligancy of molecules is calculated differently when compared to
calculating the coordination number of a central atom in a crystal.)
9. How many 3 dimensional crystal lattices are possible?
Ans. Crystal lattice:
The atoms or particles in crystal formations are arranged in a regular pattern. A crystal
lattice is a three-dimensional representation of such an atom arrangement. Thus, a
lattice is a set of points arranged in a specific sequence that describes the arrangement
of particles in a crystalline solid. According to a French scientist, there are fourteen
different three-dimensional lattices that can be created. They have six basic shapes.
Therefore, there are 14 three-dimensional lattices.
10. What is the coordination number of a particle in hcp?

Ans. Coordination number:
The number of particles that surround a single particle in a crystal lattice is known as
the coordination of that particle of the lattice. It also helps to measure the hardness of
the crystal
HCP:
HCP is a Hexagonal closed pack structure which is an example of 3-dimensional
packing. There are six spheres in one plane, 3 spheres above, and three spheres below
the plane making it 12. Thus, each sphere is surrounded by 12 spheres which makes the
coordination number of each particle 12.
11. How many octahedral voids are in ccp unit cell?
Ans. A cubic closed packing (CCP) unit cell comprises atoms placed at all the corners and at
the centre of all the faces of the cube. The atom present at the centre of the face is
shared between two adjacent unit cells and only half of each atom belongs to an
individual cell. It is also referred to as face-centred cubic (FCC).
The total number of octahedral void(s) present in a cubic close packed structure is four.
Besides the body centre, there is one octahedral void at the centre of each of the
twelve edges. It is surrounded by six atoms, where four atoms belong to the same unit
cell (i.e. two on the corners and two on face centres) and two belonging to two
adjacent unit cells. As, we can see that each edge of the cube is shared between four
adjacent unit cells, so is the octahedral void located on it.
Only one-fourth of each void belongs to a particular unit cell. Thus, in a cubic close
packed structure, the octahedral void at the body centre of the cube will be one.
Twelve octahedral voids are located at each edge and are shared by four-unit cells;
thus, the number of octahedral voids will be 12×1/4=3.
So, the total number of octahedral voids in cubic closed packed is four.
We know, in CCP structure each unit cell has four atoms. Thus, the number of
octahedral voids will be 4/4=1.
Thus, the total number of octahedral void(s) per atom present in a cubic close packed
structure is one.
Note: Possibly you may get confused with the tetrahedral voids but remember
tetrahedral voids are formed between the two layers, when the atom of the second
layer rests on the hollow part of the first layer whereas octahedral void is formed when
two triangle voids of second and first join. CCP has two tetrahedral voids.
12. What is an end centred unit cell?
Ans.
If one constituent particle lies at the centre of any two opposite faces besides the
particles lying at the corners, it is known as End-Centred Unit Cell.
It is also known as base-centred unit cell. In each end centered unit cell, there are 8
atoms at the eight corners of the cube, one atom each is present at the centre of any
two opposite faces. The coordination number of end centerd cell is 4.
13. What is the formula of the compound if the unit cell of it contains atoms A, B and C and
occupy the lattice points as shown?
Ans.
14. Nickel crystallizes as FCC. How many unit cells are required to accommodate one mole
of nickel atoms?
Ans. No Solution Found
15. Define packing efficiency.
Ans. Packing Efficiency is the percentage of total space in a unit cell that is filled by the
constituent particles, such as atoms, ions, or molecules, packed within the lattice. It is
the total amount of space occupied by these particles in three-dimensional space.
Simply, it can be understood as the specified percentage of the total volume of a solid
which is occupied by spherical atoms. The formula for packing efficiency is,
Packing Efficiency = Total Volume of Sphere/Total Volume of Cube×100
Packing Efficiency can be evaluated through three different structures of geometry

which are:
 Cubic Close Packing (CCP) and Hexagonal Close Packing (HCP).
 Body-Centred Cubic Structures (BCC)
 Simple Lattice Structures of Cubic
16. Write the relationship between density and edge length of a unit cell.
Ans.
17. What type of defect is exhibited by the solid solution of CdCl2 and AgCl?
Ans. Impurity defect is produced when Agcl is doped with Cdcl2
AgCl
18. What are F-centres?

Ans. In ionic compounds having non stoichiometric defects, when an anion is missing from
the crystal lattice and electron is trapped at the position of missing anion, it is known as
F-centre (Farbenzenter centre). F-centre imparts colour to the crystal.
19. What is the colour imparted to/by KCl due to anionic vacancies?
Ans. Violet or Lilac
20. ZnO turns yellow on heating. Name the type of defect created?
Ans.
21. What are non stoichiometric defects?

Ans. Non-stoichiometric defect:
Non-stoichiometric compounds are those compounds in which proportion of cation and
anion is not similar and defects of these compounds are known as non-stoichiometric
defects. In this defect a large number of positive and negative charges are present. As
we know, crystals remain neutral so, if a spare amount of negative charge is present
then it will be maintained by extra positive charge presence. Because of this positive
and negative charge, solid crystal structure shapes will become improper, and solid
become imperfect. This defect can be happened due to 2 reasons:
In a lattice, substances have a cation whose proportion is more than in an anion. Hence,
known as a metal excess defect.
In a lattice, substances have a cation whose proportion is lesser than in an anion. And
hence known as the metal deficiency defect.
22. A sample of nickel oxide has the formula Ni0.98O. Name the type of non stoichiometric
defect it exhibits.
Ans. Crystal possess metal deficiency defect.
23. What are intrinsic semiconductors?
Ans. Semiconductors that are chemically pure, in other words, free from impurities are
termed as intrinsic semiconductors. The number of holes and electrons is therefore
determined by the properties of the material itself instead of the impurities. In intrinsic
semiconductors, the number of excited electrons is equal to the number of holes; n = p.
They are also termed as undoped semiconductors or i-type semiconductors. Silicon and
germanium are examples of i-type semiconductors. These elements belong to the IVth
Group of the periodic table and their atomic numbers are 14 and 32 respectively.
24. How does electrical conductivity of an electrolyte vary with temperature?
Ans. In electrolytic conductors, the ions are charge carriers and with increase in
temperature, ionization increases and hence, conductivity increases.
25. What are Ionic Solids?
Ans. Ionic Solids:
An ionic bond is defined as the attractive electrostatic force that is present between
two oppositely charged ions. The formation of an ionic bond occurs when excess
electrons from an anion are transferred to a cation in order to attain their nearest inert
gas configuration. Strong electrostatic forces act on ionic compounds, they are tightly
packed with each other to form a crystal lattice. Generally, these crystal lattices are
very hard to break.
Questions (From Question Bank)

Two Marks Questions
Distinguish crystalline and amorphous solids with respect to: i) melting point ii) heat of
1.
fusion
2. What type of attractive force exists between constituent particles in: i) solid CO2 ii) SiO2
3. Write the differences between metallic and ionic crystalline solids
4. Write the differences between metallic and molecular crystalline solids

5. Name two types of 2 dimensional close packing arrangement.
6. Name the two parameters that characterise a unit cell.
7. Define unit cell and crystal lattice.
How many possible variations are in a cubic crystal system? Which one of these has 4
8.
particles / unit cell?
What portion of the atom (or particle) belongs to a unit cell if it is located i) in the body
9.
of the unit cell ii) at the centre of an edge of the unit cell?
10. How many lattice points in unit cell of i) FCC ii) end centred
Ans.
11. Write one similarity and one difference between hcp and ccp
12. Calculate the number of atoms in face centred cubic unit cell.
13. Calculate the number of atoms in body centred cubic unit cell.
In a compound, atoms A form ccp, atoms of B occupy all the tetrahedral voids and atom
14.
C occupy all the octahedral voids. What is the formula of the compound?
A metal oxide crystallises in hcp arrangement for its oxide ions. 2/3rds of octahedral
15.
voids are occupied by metal ions. What is the formula of the metal oxide?
Aluminium crystallizes in ccp structure. Its metallic radius is 125 pm. Calculate the
16.
length of the face diagonal of the unit cell.
A metal crystallizes in bcc structure. Edge length of the unit cell is 300 pm. How many
17.
unit cells are in 5 cm3 of the metal?
18. What are point defects and line defects?
19. Distinguish between Frenkel and Schottky defects.
20. Explain metal excess defect due to anionic vacancy.
21. Explain metal deficiency defect using ZnO as an example.
Electrical conductivity of a semiconductor (i) increases with temperature (ii) increases

22.
on doping with a suitable material. Give reasons.
23. Write the differences between n-type and p-type semiconductors.
What type of semiconductor is obtained when: i) silicon is doped with phosphorus ii)
24.
silicon is doped with boron?
25. Mention the factors responsible for the magnetic moment of an electron.
26. Write the differences between ferrimagnetic and ferromagnetic substances

Three Marks Questions
Based on intermolecular forces, name the three types of molecular solids. Mention the
1.
forces of attraction in them.
On the basis of intermolecular forces solids can be classified as follows:
Molecular Solids
Solid composed of molecules as constituent particles. These solids can further be
categorized into following types:
(i) Non polar Molecular Solids:

They are composed of either atom.
H2, Cl2 and I2.are some of the typical example.
In non-polar Molecular solids the comprised atoms or molecules are held together by
weak dispersion forces or London forces.
They are soft and non-conductors of electricity.
They have low melting points and usually exist in liquid or gaseous state at room
temperature and pressure.
Ans. (ii) Polar Molecular Solids:

The molecules like HCl, SO2, are formed by polar covalent bonds.
In polar Molecular solids the comprised atoms or molecules are held together by
stronger dipole-dipole interactions.
They are soft and non-conductors of electricity.
The melting points of these solids are higher than those of non-polar molecular solids
and usually exist in liquid or gaseous state at room temperature and pressure.
Molecules like SO2 and solid NH3 are some examples of such solids.
(iii) Hydrogen Bonded Molecular Solids:

Hydrogen Bonded Molecular Solids contain polar covalent bonds between H and F, O
or N atoms.
Strong hydrogen bonding binds molecules of such solids like H2O (ice).
They are non-conductors of electricity and are volatile liquids or soft solids under
room temperature and pressure.
Differentiate covalent and polar molecular solids based on i) constituent particles ii)
2.
bonding iii) melting point
Ans. (Exact answer not found)
Match the type of packing in column-I to column-II:
Column – I Column – II
i) Square close packing in 3 dimensions a) The first layer and the fourth layer are
identical
3.
ii) Hexagonal close packing in 3 b) All layers are identical
dimensions
iii) Cubic close packing in 3 dimensions c) The first layer and the third layer are
identical
Ans. i-b, ii-c, iii-a
What type of unit cells are A and B? How many particles per unit cell in B?
4.
A – Primitive Cubic Cell Unit

From the diagram we can see that 8 atoms are arranged in all the corners of the cube,
therefore, the contribution per unit cell will be 1 atom,
∵8x1/8=1 atom or molecule
Ans. B – Body Centered Unit Cell

From the diagram we can see that 8 atoms are arranged in all the corners of the cube
and there is 1 atom in the centre of the unit cell. Therefore, the contribution per unit
cell will be –
= 1 atom (primitive) + 1 atom (body centred)
=2
5. Calculate the packing efficiency in cubic close packing (ccp) structure .
Ans.
6. Calculate the packing efficiency in bcc structure.
Ans.
7. Calculate the packing efficiency in simple cubic lattice.

Ans.
An element crystalises in fcc and has edge length 0.56 nm. Calculate the density of the
8.
element. Molar mass of the element is 40 gmol-1.
An element X has a density of 6.23 g cm-3. If the edge length of the unit cell is 4´ 10-8
9.
cm, identify the type of cubic unit cell. Given : molar mass of the element = 60 gmol-1.
Ans.
A metal crystallizes in bcc unit cell. The atomic mass of the metal is 55.8 g mol-1,
10.
density = 7.9 g cm-3. Calculate the edge length of the unit cell?
Ans. (No solution found)
What type i) of defect is introduced when molten NaCl is crystallised with SrCl2? ii) of
11. vacancy is produced? How many moles of these vacancies are created if the crystal
obtained has 10-3 mole of Sr+2 ions?
Ans.
Account for the following: i) Silicon doped with Al is p type semiconductor ii) Frenkel
12. defect does not change the density of ionic crystals iii) non-polar molecular solids have
very low melting and boiling points.
Ans. (Answer not found)
13. Differentiate metals, insulators and semiconductors in terms of band theory.
Ans. Metals: In metals, the conduction band is either somewhat filled, or the valence band is
partly empty. Some electrons act as free electrons as they move to higher energy levels
by obtaining energy beyond the Fermi level in the conduction band. There is no
restricted-energy gap in the metals. Since there is no forbidden gap, the electron
numbers available for the conduction increase the material's conductivity. Metals work
as a conductor because of the motion of the free electrons when a minute amount of
electric current is implemented. Silver, Aluminium, etc., are good conductors.
Insulators: In insulators, the valence band is occupied while the conduction band is
blank. This ends in a large energy gap. Since the energy passage between the
conduction band and the valence band is higher, there is no shift of electrons from the
valence band to the conduction band. Mica, ebonite, glass, etc., are examples of
insulators.
Semiconductor: In a semiconductor, the valence band is loaded with electrons while
the conduction band is blank. The energy gap separating the bands is smaller. For
electrons to escape from the valence band to the conduction band, the temperature of
the room must be reserved. If the temperature is zero Kelvin, there is no motion of
electrons from the valence band to the conduction band.
There is a small gap between conduction and valence band in metals. The conduction
band is completely occupied. On applying a small electric field, metals can carry
current. However, there is a large gap between conduction and valence band. The
conduction band is empty. When an electric field is applied on insulators, electrons find
it challenging to reach the conduction band. Therefore, no current flows in insulators.
Arrangement of magnetic domains are as given:
14.
What type of magnetic property is in (i) and (ii)? Which one of this becomes
paramagnetic on heating?
Ans. (No answer found)

Five Marks Questions
a) A cubic solid has elements P and Q. Atoms of Q at the corners and atom P at the
body centre.
i) what is the formula of the solid?
1. ii) What is the coordination number of P & Q?
b) A compound forms hcp structure. What is the total number of voids in 0.4 mol of it?
How many of these are tetrahedral voids? Given NA = 6.022 ´ 1023.
Ans. a:
P atoms are present at the 8 corners and contribution of every corner is one-eighth.
Therefore, total P atom is 1. Q is present inside the cube so number of Q atom is 1. The
formula is PQ. Q atom is surrounded by 8 P atoms and vice versa. So the coordination
number is 8.
b:
(a) octahedral voids = 2.41 × 10²³
(b) tetrahedral voids = 4.82 × 10²³
(c) total voids = 7.23 × 10²³
Explanation:
In the close packing of spheres, certain hollows left vacant, these holes in the crystal s is
called interstitial voids.
There are two types of voids : octahedral voids and tetrahedral voids. Therefore, the
total number of voids is equal to sum of octahedral voids and tetrahedral voids.
Number of octahedral voids is equal to number of atoms (lattice points) present in the
crystal.
Number of tetrahedral voids is equal to twice of number of number of atoms.
We have given 0.4 moles of compound.

We know that number of atoms in 1 mole = 6.023×10²³ atoms
Then number of atoms in 0.4 moles = 0.4×6.023×10²³
= 2.41 × 10²³ atoms
(a) Number of octahedral voids = Number of atoms in 0.4mol of compound
Number of octahedral voids = 2.41 × 10²³
(b) Number of tetrahedral voids = 2× Number of atoms in 0.4mol crystal
= 2× 2.41 × 10²³
= 4.82 × 10²³
(c) Total number of voids = octahedral voids + tetrahedral voids
Total voids = 2.41 × 10²³ + 4.82 × 10²³
Total voids = 7.23 × 10²³ Voids.
With respect to Frenkel and Schottky defects:
i) In which type of crystalline solids are these found?
2.
ii) When is Frenkel defect possible?
iii) What type of defect does these show? i) ZnS ii) NaCl iii) AgBr
i) AgBr has both schottky and frenkel defects. In general, silver haldies show both
schottky and frenkel defects. In schottky defect, equal number of cations and anions
are missing from crystal lattice.
ii) Frenkel defect is also known as interstitial defect. In this defect, a cation (or an anion)
is dislocated from its normal site to interstitial site. Interstitial site is the place between
the lattice sites. This defect is observed in solids when the difference in ionic radii of
two participating ions is large. This defect is observed in AgCl and ZnS solids. Density is
not affected due to this defect.
Ans.
As shown in the figure, the cation has left its own lattice site vacant and it has moved to
a new place between the cations and anions.
iii) ZnS shows Frenkel Defect. AgBr shows Frenkel Defect and Schottky Defect. NaCl
exhibits Schottky defect.
a) In FeO solid, some Fe2+ ions are missing, but the charge is balanced by the presence
of Fe3+ ions.
i) If Fe2+ ions missing are 15, how many Fe3+ ions balance the charge?
ii) What type of defect does this lead to?
3. iii) If for 100 O-2 ions the number of Fe2+ and Fe3+ are 85 and 10 respectively,
what is the composition of the non-stoichiometric FeO solid formed?
b) i) How many types of primitive unit cells are known?

ii) Name any one crystal system for which only primitive unit cells are possible.
Ans. (Answer not found)
Unit II – Solutions
2.1 Define the term solution. How many types of solutions are formed? Write briefly about
each type with an example.
Ans. A solution is a homogeneous mixtures of two or more than two substances on
molecular level.The constitutent of the mixture present in a smaller amount is called
the SOLUTE & the one present in larger amount is called the SOLVENT.For eg. Small
amount of sugar(solute) dissolved in water(solvent).
SOLUTE + SOLVENT = SOLUTION
Solution type Solute Solvent Example

Gas in Gas Gas Gas Air
Gas in Liquid Gas Liquid Soda water
Gas in Solid Gas Solid H2 in Pt
Liquid in gas Liquid Gas Water vapor in the air
Liquid in Liquid Liquid Liquid Alcoholic beverages.
Liquid in Solid Liquid Solid Water into ice
Solid in Gas Solid Gas Camphor in air
Solid in Liquid Solid Liquid Salt in water
Solid in Solid Solid Solid Metal alloys, Bronze
Nine kinds of solution are possible.

(i) Gas in gas. When one gas is mixed with another gas, it is called solution of gas in gas.
Example: Air is a mixture of nitrogen and oxygen.
(ii) Liquid in gas. When liquid is mixed with large amount of gas, it is called liquid in gas
solution. Example: Moisture (water in air).
(iii) Solid in gas. When small amount of solid particles are dispersed in gas, it is called
solution of solid in gas. Example: Smoke.
(iv) Gas in liquid. When gas is dissolved in liquid, it is called gas in liquid solution.
Examples: CO2 gas dissolved in water, oxygen dissolved in water.
(v) Liquid in liquid. When a liquid is miscible with another liquid, it forms solution of
liquid in liquid. Examples. Ethanol dissolved in water, methanol dissolved in water.
(vi) Solid in liquid. When solid is dissolved in water, the solution is called solid in liquid.
Examples: Cane sugar dissolved in water, sodium chloride dissolved in water.
(vii) Gas in solid. When gas is present, the solution is called gas in solid. Example: H2 gas
in palladium.
(viii) Liquid in solid. When liquid is present in solid, the homogeneous mixture is called
solution of liquid in solid. Example: Amalgam of mercury with sodium.
(ix) Solid in solid. When solid is dissolved in another solid, the homogeneous mixture is
called solution of solid in solid. Examples: Alloys are solid in solid solution, copper
dissolved in gold.
2.2 Give an example of a solid solution in which the solute is a gas.
Ans. In case a solid solution is formed between two substances (one having very large
particles and the other having very small particles), an interstitial solid solution will be
formed. For example, a solution of hydrogen in palladium is a solid solution in which
the solute is a gas.
2.3 Define the following terms:
(i) Mole fraction (ii) Molality (iii) Molarity (iv) Mass percentage.
Ans. a) Mole Fraction - it is defined as the ratio of number of moles of one component to the
total number of moles of solute & solvent present in the solution.
Mole fraction = number of moles of the component / total number of moles of all
components
It is denoted by x.
Take it as binary solution, the number of the moles of solute will be nA and the number
of moles of solvent will be nB, then the mole fraction of the solute in the solution is
given as:
In the same manner, the mole fraction of the solvent in the solution is given as:
b) Molality- it is the number of moles of the solute dissolved per 1000g of the solvent.
It is denoted by m
Molality = mole of solute / mass of solvent in kg
Unit for molality are moles/kg
c) Molarity- it is the number of moles of the solute dissolved per litre of the solution.
It is represented by M.
Molarity = moles of solute / volume of solute in litres
Unit for molarity is moles/litre
d) Mass Percentage- the mass percentage of a component in a given solution is the

mass of the component per 100g of the solution.
Mass percentage of the component = (mass of the component in the solution/total
mass of the solution) x100
2.4 Concentrated nitric acid used in laboratory work is 68% nitric acid by mass in aqueous
solution. What should be the molarity of such a sample of the acid if the density of the
solution is 1.504 g mL–1?
Ans.
2.5 A solution of glucose in water is labelled as 10% w/w, what would be the molality and
mole fraction of each component in the solution? If the density of solution is 1.2 g mL–
1, then what shall be the molarity of the solution?
Ans. 10% w/w solution of glucose in water means that 10 g of glucose in present in 100 g of
the solution i.e., 10 g of glucose is present in (100 - 10) g = 90 g of water.
Molar mass of glucose (C6H12O6) = 6 × 12 + 12 × 1 + 6 × 16 = 180 g mol - 1
Then, number of moles of glucose = 10 / 180 mol
= 0.056 mol
∴ Molality of solution = 0.056 mol / 0.09kg = 0.62 m
Number of moles of water = 90g / 18g mol-1 = 5 mol
Mole fraction of glucose (xg) = 0.056 / ( 0.056+5) = 0.011
And, mole fraction of water xw = 1 - xg
= 1 - 0.011 = 0.989
If the density of the solution is 1.2 g mL - 1, then the volume of the 100 g solution can be
given as:
= 100g / 1.2g mL-1
= 83.33 mL
=83.33 x 10-3 L
∴ Molarity of the solution = 0.056 mol / 83.33 x 10-3 L
= 0.67 M
2.6 How many mL of 0.1 M HCl are required to react completely with 1 g mixture of
Na2CO3 and NaHCO3 containing equimolar amounts of both?
Ans. let the amount of Na2CO3 be x
& that of NaHCO3 be 1-x
Now moles of Na2CO3 = x / 106
& moles of NaHCO3 = 1-x / 84
Now according to question , number of moles of Na2Co3 = number of moles of NaHCO3
Therefore x / 106 = 1-x / 84
84x = 106-106x
84x +106x = 106
190x = 106
Or
x = 106 / 190 = 0.558
Therefore moles of Na2Co3 = 0.558 / 106 = 0.00526
&
moles of NaHCO3 = 1 - 0.558 / 84 = 0.0053
Now Hcl reacts with Na2Co3 & NaHCO3 as follows:
Na2Co3 + 2Hcl 2Nacl + H2o + CO2
NaHCO3 + Hcl Nacl + H2o + CO2
From the above reactions, 1 mol of Na2Co3 will react with 2 mol of Hcl
Therefore 0.00526 mol of Na2Co3 will react with 2 x 0.00526 mol of Hcl & similarly
0.00526 mol of NaHCO3 will react with 0.00526 mol of Hcl
Total moles of Hcl required to react with mixture of of NaHCO3 & Na2Co3
= 2 X 0.00526 + 0.00526 =0.01578 mol
Also according to question 0.1 mol of 0.1 M Hcl is present in 1000 ml
Or
0.01578 mol of 0.1 M Hcl is present in (1000/0.1) x 0.01578 = 157.8 ml
Hence, 158 mL of 0.1 M of HCl is required to react completely with 1 g mixture of
Na2CO3 and NaHCO3, containing equimolar amounts of both.
2.7 A solution is obtained by mixing 300 g of 25% solution and 400 g of 40% solution by
mass. Calculate the mass percentage of the resulting solution.
Ans. Mass of solute in I solution =25/100×300g=75g
Mass of solute in II solution =40/100×400=160g
After mixing both solutions,
Total mass of solute = (75 + 160) g = 235 g
Total mass of solution = (300 + 400) g = 700 g
Mass % of solute in final solution =(235g)/(700g)×100=33.57%
Mass % solvent in final solution =100−33.57=66.43%
2.8 An antifreeze solution is prepared from 222.6 g of ethylene glycol (C2H6O2) and 200 g
of water. Calculate the molality of the solution. If the density of the solution is 1.072 g
mL–1, then what shall be the molarity of the solution?
Ans.
2.9 A sample of drinking water was found to be severely contaminated with chloroform
(CHCl3) supposed to be a carcinogen. The level of contamination was 15 ppm (by
mass):
(i) express this in percent by mass
(ii) determine the molality of chloroform in the water sample.
Ans.
2.10 What role does the molecular interaction play in a solution of alcohol and water?
Ans. In pure alcohol and water, the molecules are held tightly by a strong hydrogen bonding.
The interaction between the molecules of alcohol and water is weaker than
alcohol−alcohol and water−water interactions. As a result, when alcohol and water are
mixed, the intermolecular interactions become weaker and the molecules can easily
escape. This increases the vapour pressure of the solution, which in turn lowers the
boiling point of the resulting solution.
2.11 Why do gases always tend to be less soluble in liquids as the temperature is raised?
Ans. The solubility of a gas in a liquid at a particular temperature is directly proportional to
the pressure of the gas in equilibrium with the liquid at that temperature. The
dissolution of a gas in a liquid is an exothermic process, that is, it is accompanied by the
evolution of heat. Thus,
Gas + Solvent ⇌ Solution + Heat
Applying Le Chatelier's principle, the increase of temperature would shift the
equilibrium in the backward direction, that is, solubility would decrease. Therefore,
gases always tend to be less soluble in liquids as the temperature is raised.
2.12 State Henry’s law and mention some important applications.
Ans. Henry's Law
Henry's law states that the partial pressure of a gas in the vapour phase is proportional
to a mole fraction of the gas in the solution.
Applications:
Henry's law in respiration: The main application of Henry's law in respiratory
physiology is that gases will dissolve in the alveoli and bloodstream during gas
exchange.
The amount of oxygen that dissolves in the bloodstream is directly proportional
to the partial pressure of oxygen in the alveoli air.
Henry's law in carbonated soft drinks: (a) The carbonated drink is almost pure
carbon dioxide at a pressure slightly higher than the atmospheric pressure.
When the bottle is opened some of the gas escapes giving a specific pop, this is
due to the lower pressure above the liquid and carbon dioxide comes out as bubbles.
To avoid bends (due to blockage of capillaries) and the toxic effects of high
concentrations of nitrogen in the blood, the tanks used by scuba divers are filled with
air diluted with helium (11.7% helium, 56.2% nitrogen and 32.1% oxygen).
Therefore, Henry's law states the relationship between partial pressure and the
concentration of gases.
2.13 The partial pressure of ethane over a solution containing 6.56 × 10–3 g of ethane is 1
bar. If the solution contains 5.00 × 10–2 g of ethane, then what shall be the partial
pressure of the gas?
Ans.
2.14 What is meant by positive and negative deviations from Raoult's law and how is the
sign of ∆mixH related to positive and negative deviations from Raoult's law?
Ans. According to Raoult’s law, the partial vapour pressure of each volatile component in
any solution is directly proportional to its mole fraction. The solutions which obey
Raoult’s law over the entire range of concentration are known as ideal solutions. The
solutions that do not obey Raoult’s law (non-ideal solutions) have vapour pressures
either higher or lower than that predicted by Raoult’s law. If the vapour pressure is
higher, then the solution is said to exhibit positive deviation, and if it is lower, then the
solution is said to exhibit negative deviation from Raoult’s law.
Vapour pressure of a two-component solution showing positive deviation from Raoult’s
law
Vapour pressure of a two-component solution showing negative deviation from

Raoult’s law
In the case of an ideal solution, the enthalpy of the mixing of the pure components for
forming the solution is zero.
ΔsolH = 0
In the case of solutions showing positive deviations, absorption of heat takes place.
∴ΔsolH = Positive
In the case of solutions showing negative deviations, evolution of heat takes place.
∴ΔsolH = Negative
2.15 An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar at the
normal boiling point of the solvent. What is the molar mass of the solute?
Ans. Here,
Vapour pressure of the solution at normal boiling point (p1) = 1.004 bar (Given)
Vapour pressure of pure water at normal boiling point (p10) = 1.013 bar
Mass of solute, (w2) = 2 g
Mass of solvent (water), (w1) = 100 - 2 = 98 g
Molar mass of solvent (water), (M1) = 18 g mol - 1
According to Raoult's law,
(p10 - p1) / p10 = (w2 x M1 ) / (M2 x w1 )
(1.013 - 1.004) / 1.013 = (2 x 18) / (M2 x 98 )
0.009 / 1.013 = (2 x 18) / (M2 x 98 )
M2 = (2 x 18 x 1.013) / (0.009 x 98)
M2 = 41.35 g mol - 1
Hence, the molar mass of the solute is 41.35 g mol - 1.
2.16 Heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two
liquid components are 105.2 kPa and 46.8 kPa respectively. What will be the vapour
pressure of a mixture of 26.0 g of heptane and 35 g of octane?
Ans. Number of moles of octane (nA)=Mass/Molar mass=35g/114 g mol−1
=0.307 mol
[Molar mass of octane
C8H18=(12×8)+(1×18)=114 g mol−1]
Number of moles of heptane
(nB)=26g/100 g mol−1=0.26 mol
[Molar mass of heptane
C7H16=(12×7)+16=100 g mol−1]
Mole fraction of octane
(xA)=nAnA+nB=(0.307 mol)/(0.307+0.26) mol=0.542
Mole fraction of Heptane
(xB)=nBnA+nB=(0.26 mol)/(0.307+0.26) mol=0.458
Vapour pressure of pure heptane (p∘B)=105.2 kPa
Vapour pressure of pure octane (p∘A)=46.8 kPa
In the mixture of 26.0 g heptane and 35.0 g octane
(i) Vapour pressure of heptane (pB)=p∘BxB
=(105.2 kPa×0.458)
=48.18 kPa
(ii) Vapour pressure of octane
(pA)=p∘AxA=(46.8 kPa×0.542)
=25.36 kPa
(iii) Total vapour pressure of the mixture (p) =pA+pB
= 25.36 + 48.18 = 73.54 kPa
2.17 The vapour pressure of water is 12.3 kPa at 300 K. Calculate vapour pressure of 1 molal
solution of a non-volatile solute in it.
Ans. 1 molal solution means 1 mol of the solute is present in 1000 g of the solvent (water).
Molar mass of water = 18 g mol - 1
∴ Number of moles present in 1000 g of water = 1000/18
= 55.56 mol
Therefore, mole fraction of the solute in the solution is
x2 = 1 / (1+55.56) = 0.0177.
It is given that,
Vapour pressure of water, p10 = 12.3 kPa
Applying the relation, (P10 - P1) / P10 = X2
⇒ (12.3 - p1) / 12.3 =0.0177
⇒ 12.3 - P1 = 0.2177
⇒ p1 = 12.0823
= 12.08 kPa (approximately)
Hence, the vapour pressure of the solution is 12.08 kPa.
2.18 Calculate the mass of a non-volatile solute (molar mass 40 g mol–1) which should be
dissolved in 114 g octane to reduce its vapour pressure to 80%.
Ans. Let the vapour pressure of pure octane be p10.
Then, the vapour pressure of the octane after dissolving the non-volatile solute is
80/100 p10 = 0.8 p10.
Molar mass of solute, M2 = 40 g mol - 1
Mass of octane, w1 = 114 g
Molar mass of octane, (C8H18), M1 = 8 × 12 + 18 × 1 = 114 g mol - 1
Applying the relation,
(p10 - p1) / p10 = (w2 x M1 ) / (M2 x w1 )
⇒ (p10 - 0.8 p10) / p10 = (w2 x 114 ) / (40 x 114 )
⇒ 0.2 p10 / p10 = w2 / 40
⇒ 0.2 = w2 / 40
⇒ w2 = 8 g
Hence, the required mass of the solute is 8 g.
2.19 A solution containing 30 g of non-volatile solute exactly in 90 g of water has a vapour
pressure of 2.8 kPa at 298 K. Further, 18 g of water is then added to the solution and
the new vapour pressure becomes 2.9 kPa at 298 K. Calculate:
(i) molar mass of the solute (ii) vapour pressure of water at 298 K.
Ans. Let, the molar mass of the solute be M g mol - 1
Now, the no. of moles of solvent (water),n1 = 90g / 18g mol-1
And, the no. of moles of solute,n2 = 30g / M mol-1 = 30 / M mol
p1 = 2.8 kPa
Applying the relation:
(p10 - p1) / p10 = n2 / (n1 + n2)
⇒ (p10 - 2.8) / p10 = (30/M) / {5 + (30/M)}
⇒ 1 - (2.8/p10) = (30/M) / {(5M+30)/M}
⇒ 1 - (2.8/p10) = 30 / (5M + 30)
⇒ 2.8/p10 = 1 - 30 / (5M + 30)
⇒ 2.8/p10 = (5M + 30 - 30) / (5M + 30)
⇒ 2.8/p10 = 5M / (5M+30)
⇒ p10 / 2.8 = (5M+30) / 5M ----------------(1)
After the addition of 18 g of water:
n1 = (90+18g) / 18 = 6 mol
and the new vapour pressure is p1 = 2.9 kPa (Given)
Again, applying the relation:
(p10 - p1) / p10 = n2 / (n1 + n2)
⇒ (p10 - 2.9) / p10 = (30/M) / {6 + (30/M)}
⇒ 1 - (2.9/p10) = (30/M) / {(6M+30)/M}
⇒ 1 - (2.9/p10) = 30 / (6M + 30)
⇒ 2.9/p10 = 1 - 30 / (6M + 30)
⇒ 2.9/p10 = (6M + 30 - 30) / (6M + 30)
⇒ 2.9/p10 = 6M / (6M+30)
⇒ p10 / 2.9 = (6M+30) / 6M ----------------(2)
Dividing equation (1) by (2),we get:
2.9 / 2.8 = {(5M+30) / 5M} / {(6M+30) / 6M}
⇒ 2.9 x (6M+30 / 6) = (5M+30 / 5) x 2.8
⇒ 2.9 x (6M +30) x 5 = (5M+30) x 2.8 x 6
⇒ 87M + 435 = 84M + 504
⇒ 3M = 69
⇒ M = 23u
Therefore, the molar mass of the solute is 23 g mol - 1.
(ii) Putting the value of 'M' in equation (i), we get:

⇒ p10 / 2.8 = (5M+30) / 5M
⇒ p10 / 2.8 = (5x23+30) / 5x23
⇒ p10 = (145 x 2.8) / 115
⇒ p10 = 3.53
Hence, the vapour pressure of water at 298 K is 3.53 kPa.
2.20 A 5% solution (by mass) of cane sugar in water has freezing point of 271K. Calculate the
freezing point of 5% glucose in water if freezing point of pure water is 273.15 K.
Ans. In case of cane sugar:
ΔTf = (273.15 - 271) K = 2.15 K
Molar mass of sugar (C12H22O11) = 12 × 12 + 22 × 1 + 11 × 16 = 342 g mol - 1
5% solution (by mass) of cane sugar in water means 5 g of cane sugar is present in (100
- 5)g = 95 g of water.
Now, number of moles of cane sugar =5/342 mol
= 0.0146 mol
Therefore, molality of the solution,m =0.0146mol / 0.095kg
= 0.1537 kg mol - 1
Now applying the relation,
ΔTf = Kf × m
⇒ Kf = ΔTf / m
⇒ 2.15K / 0.1537 kg mol-1
= 13.99 K kg mol-1
Molar of glucose (C6H12O6) = 6 × 12 + 12 × 1 + 6 × 16 = 180 g mol - 1
5% glucose in water means 5 g of glucose is present in (100 - 5) g = 95 g of water.
∴ Number of moles of glucose = 5/180 mol
= 0.0278 mol
Therefore, molality of the solution, m =0.0278 mol / 0.095 kg
= 0.2926 mol kg - 1
Applying the relation,
ΔTf = Kf × m
= 13.99 K kg mol - 1 × 0.2926 mol kg - 1
= 4.09 K (approximately)
Hence, the freezing point of 5% glucose solution is (273.15 - 4.09) K= 269.06 K.
2.21 Two elements A and B form compounds having formula AB2 and AB4. When dissolved
in 20 g of benzene (C6H6), 1 g of AB2 lowers the freezing point by 2.3 K whereas 1.0 g
of AB4 lowers it by 1.3 K. The molar depression constant for benzene is 5.1 K kg mol–1.
Calculate atomic masses of A and B.
Ans. As We know that:
MB = (Kf x wB x 1000) / (wA X ΔTf)
Now ΔTf = 2.3 , wB = 1.0 , wA = 20, KF = 5.1 (given)
PUTTING THE VALUES IN THE EQUATION
MB = (5.1 x 1 x 1000) / (20 x 2.3) = 110.87 g/mol
Therefore MAB2 = 110.9
For AB4 compound
ΔTf = 1.3 , wb = 1 ,wa = 20
MB = (5.1 X 1 X 1000) / (20 X 1.3) = 196 g/mol
Therefore MAB = 196
Let x be the atomic mass of A & y be the atomic mass of B,
THEN MAB2 = x + 2y = 110.9 ----------------------------------(1)
And MAB = x + 4y = 196 ----------------------------------(2)
Subtracting 2 from 1 ,we get
2y = 196-110.9
y = 85.1 / 2
y = 42.6
Putting the value of y in 1 we get
x = 110.9 - 2 x 42.6
x = 25.7
Therefore atomic mass of A = 25.7 u Atomic mass of B = 42.6 u.
2.22 At 300 K, 36 g of glucose present in a litre of its solution has an osmotic pressure of
4.98 bar. If the osmotic pressure of the solution is 1.52 bars at the same temperature,
what would be its concentration?
Ans.
2.23 Suggest the most important type of intermolecular attractive interaction in

the following pairs.
(i) n-hexane and n-octane (ii) I2 and CCl4 (iii) NaClO4 and water (iv) methanol and
acetone (v) acetonitrile (CH3CN) and acetone (C3H6O).
Ans. (i)London’s forces
(ii)London’s forces
(iii)Ion-dipole interactions
(iv)Intermolecular hydrogen bonding
(v)Dipole-dipole interactions
2.24 Based on solute-solvent interactions, arrange the following in order of increasing
solubility in n-octane and explain. Cyclohexane, KCl, CH3OH, CH3CN.
Ans. Hint:Like dissolves like, i.e., polar substance dissolves in polar solvent and non-polar
solute dissolves in non-polar solvent
(i)Cyclohexane and n-octane both are non-polar. So, they mix completely in all
proportions.
(ii)KCl is an ionic compound, but n-octane is non-polar. So, KCl does not dissolve in n-
octane.
(iii)CH3OH and CH3CN both are polar but CH3CN is less polar than CH3OH. As the
solvent is non-polar, CH3CN will dissolve more than CH3OH in n-octane.
Order of solubility is KCl < CH3OH < CH3CN < cyclohexane.

2.25 Amongst the following compounds, identify which are insoluble, partially
soluble and highly soluble in water?
(i) phenol (ii) toluene (iii) formic acid (iv) ethylene glycol (v) chloroform (vi) pentanol.
Ans. (i) Phenol (C6H5OH) has the polar group -OH and non-polar group -C6H5. Thus, phenol is
partially soluble in water.
(ii) Toluene (C6H5-CH3) has no polar groups. Thus, toluene is insoluble in water.
(iii) Formic acid (HCOOH) has the polar group -OH and can form H-bond with water.
Thus, formic acid is highly soluble in water.
(iv) Ethylene glycol has polar -OH group and can form H-bond. Thus, it is
highly soluble in water.
(v) Chloroform is insoluble in water.
(vi) Pentanol (C5H11OH) has polar -OH group, but it also contains a very bulky non-polar
-C5H11 group. Thus, pentanol is partially soluble in water.
2.26 If the density of some lake water is 1.25g mL–1 and contains 92 g of Na+ ions per kg of
water, calculate the molarity of Na+ ions in the lake.
Ans. Step 1:
Mass of sodium ions = 92 g
Molar mass of sodium ions = 23 g/mol
Number of moles of sodium ions = 92g/23gmol−1=4
Mass of water = 1 kg
Volume = mass/density=1000g/1.25gmL−1=0.8L
Step 2:
As we know, molarity = Numberofmoles/volumeofsolution
Molarity of Na+ ions (m) =Number of moles Na+ ions/Volume of solution in litres
∴Molarity=4mol/0.8L=5molL−1 or 5M
2.27 If the solubility product of CuS is 6 × 10–16, calculate the maximum molarity of CuS in
aqueous solution.
Ans.
2.28 Calculate the mass percentage of aspirin (C9H8O4) in acetonitrile (CH3CN) when 6.5 g
of C9H8O4 is dissolved in 450 g of CH3CN.
Ans.
2.29 Nalorphene (C19H21NO3), similar to morphine, is used to combat withdrawal

symptoms in narcotic users. Dose of nalorphene generally given is 1.5 mg. Calculate the
mass of 1.5 × 10–3 m aqueous solution required for the above dose.
Ans.
2.30 Calculate the amount of benzoic acid (C6H5COOH) required for preparing 250 mL of
0.15 M solution in methanol.
Ans. We know Molarity = moles of the solute / volume of solution
Putting the given values in above equation,we get
0.15 = (mole of benzoic acid / 250) x 1000
Or
moles of benzoic acid = (0.15 x 250) / 1000
= 0.0375 mol of benzoic acid
Also molecular mass of benzoic acid (C6H5COOH)
= 7 × 12 + 6 × 1 + 2 × 16
= 122 g/mol
Therefore amount of benzoic acid = 0.0375 x 122 = 4.575 g
2.31 The depression in freezing point of water observed for the same amount of acetic acid,
trichloroacetic acid and trifluoroacetic acid increases in the order given above. Explain
briefly.
Ans. The depression in freezing point of a solute in water depends upon the number of
particles or ions in its aqueous solution or its degree of dissociation (α). Three acids are
arranged in the order of their increasing acidic strengths as follows:
CH3COOH<CCl3COOH<CF3COOH
Fluorine is more electronegative than chlorine. So, trifluoracetic acid is stronger than
trichloroacetic acid which in turn stronger than acetic acid. The order of depression in
freezing point is also the same. Since fluorine has strongest electron withdrawing
inductive effect (-I) effect hence it is the strongest acid.
When strong electron withdrawing groups are attached to the alpha carbon atom of
acetic acid the value of degree of dissociation increases and the acid strength also
increases. Consequently this increase in acidic strength increases the value of vant Hoff
factor (i) and thus there occurs depression in freezing point.
2.32 Calculate the depression in the freezing point of water when 10 g of CH3CH2CHClCOOH
is added to 250 g of water. Ka = 1.4 × 10–3, Kf = 1.86 K kg mol–1.
Ans. Molar mass of CH3CH2CHClCOOH
15 + 14 + 13 + 35.5 + 12 + 16 + 16 + 1
= 122.5 g/mol
∴ Moles of CH3CH2CHClCOOH = 10g / 122.5 g/mol
= 0.0816 mol
Therefore molality of the solution
= (0.0816 x 1000) / 250
= 0.3265 mol kg-1
Now if a is the degree of dissociation of CH3CH2CHClCOOH,
So, Ka = (Cα x Cα) / (C (1-α))

Ka = Cα2 / (1-α)
Since α is very small with respect to 1, 1 - α = 1
Ka = Cα2
α = √Kα / C
Putting the values ,We get
α = √1.4 x 10-3 / 0.3265
= 0.0655
Now at equilibrium,the van’t hoff factor i = 1-α +α +α/1
= 1 + 0.0655
= 1.0655
Hence, the depression in the freezing point of water is given as:
Therefore ΔTf = i Kf m v
= 1.065 v x 1.86 x 0.3265
= 0.647°
2.33 19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in the freezing point
of water observed is 1.00 C. Calculate the van’t Hoff factor and dissociation constant of
fluoroacetic acid.
Ans. Molecular mass of CH2FCOOH
14 + 19 + 12 + 16 + 16 + 1 = 78 g/mol
Now, Moles of CH2FCOOH = 19.5 / 78
= 0.25
Taking the volume of the solution as 500 mL, we have the concentration:
C = (0.25 / 500) X 1000
Therefore Molality = 0.50m
So now putting the value in the formula :
ΔTf = Kf x m
=1.86 x 0.50 = 0.93K
Van’t hoff factor = observed freezing point depression / calculated freezing point
depression
= 1 / 0.93 = 1.0753
Let α be the degree of dissociation of CH2FCOOH
Now total number of moles = m(1-a) + ma +ma = m(1+a)

Or
i = α(1+α) / α = 1 +α = 1.0753
Therefore α = 1.0753- 1
= 0.0753
Now the Value of Ka is given as:
Ka = [CH2FCOO-][H+] / CH2FCOOH
= (Cα x Cα) / (C (1-α))
= Cα2 / (1-α)
Ka = 0.5 X (0.0753)2 / (1-0.0753)
= 0.5 X 0.00567 / 0.09247
= 0.00307 (approx.)
= 3.07 X 10-3
2.34 Vapour pressure of water at 293 K is 17.535 mm Hg. Calculate the vapour pressure of
water at 293 K when 25 g of glucose is dissolved in 450 g of water.
Ans. Vapour pressure of water, p1° = 17.535 mm of Hg
Mass of glucose, w2 = 25 g
Mass of water, w1 = 450 g
We know that,
Molar mass of glucose (C6H12O6),
M2 = 6 × 12 + 12 × 1 + 6 × 16 = 180 g mol - 1
Molar mass of water, M1 = 18 g mol - 1
Then, number of moles of glucose, n1 = 25/180 = 0.139 mol
And, number of moles of water, n2 =450/18 = 25 mol
Now, we know that,
(p1° - p°) / p1° = n1 / n2 + n1
⇒ 17.535 - p° / 17.535 = 0.139 / (0.139+25)
⇒ 17.535 - p1 = 0.097
⇒ p1 = 17.44 mm of Hg
Hence, the vapour pressure of water is 17.44 mm of Hg
2.35 Henry’s law constant for the molality of methane in benzene at 298 K is 4.27 × 105 mm
Hg. Calculate the solubility of methane in benzene at 298 K under 760 mm Hg.
Ans.
2.36 100 g of liquid A (molar mass 140 g mol–1) was dissolved in 1000 g of liquid B (molar
mass 180 g mol–1). The vapour pressure of pure liquid B was found to be 500 torr.
Calculate the vapour pressure of pure liquid A and its vapour pressure in the solution if
the total vapour pressure of the solution is 475 Torr.
Ans. Number of Moles of Liquid A, nA = 100 / 140 = 0.714
Number of Moles of Liquid B, nB = 1000 / 180 = 5.556
Then Mole fraction of A = nA / nA + nB = 0.714 / 0.714 + 5.556
= 0.114
Now Mole of fraction of B = 1 - 0.114 = 0.886
Now ptotal = pA + pB
Or ptotal = p°AXA + p°BxB
OR
475 = p°A X 0.114 + 500 X 0.886
OR
p°A = 280.7 torr
Therefore vapour pressure of pure A = 280.7 torr
Vapour pressure of A in solution = 280.7 x 0.114
= 32 torr
Now
pA = p°AXA
Or
p°A = pA / XA
⇒ 32 / 0.114
= 280.7 torr
Hence, the vapour pressure of pure liquid A is 280.7 torr.
2.37 Vapour pressures of pure acetone and chloroform at 328 K are 741.8 mm Hg and 632.8
mm Hg respectively. Assuming that they form ideal solution over the entire range of
composition, plot ptotal, pchloroform, and pacetone as a function of xacetone. The
experimental data observed for different compositions of mixture is:
Plot this data also on the same graph paper. Indicate whether it has positive
deviation or negative deviation from the ideal solution.
Ans.
It can be observed from the graph that the plot for the ptotalof the solution curves
downwards. Therefore, the solution shows negative deviation from the ideal behaviour.
2.38 Benzene and toluene form ideal solution over the entire range of composition. The
vapour pressure of pure benzene and toluene at 300 K are 50.71 mm Hg and 32.06 mm
Hg respectively. Calculate the mole fraction of benzene in vapour phase if 80 g of
benzene is mixed with 100 g of toluene.
Ans. Molar mass of benzene(C6H6) = 6 X 12 + 6 X 1 = 78 g/mol
Molar mass of toluene = 7 x 12 + 8 x 1 = 92 g/mol
Now no of moles in 80g of benezen = 80 / 78 = 1.026 mol
No of moles in 100g of toluene = 100 / 92 = 1.087 mol
∴Mole fraction of benzene xb = 1.026 / 1.026 + 1.087 = 0.486
And Mole fraction of toluene,xt = 1 - 0.486 = 0.514
We have given that
Vapor pressure of pure benzene pb° = 50.71 mm Hg
And, vapour pressure of pure toluene, pt° = 32.06 mm Hg
Therefore partial Vapor pressure of benzene, pb = pb X xb
= 50.71 x 0.486
= 24.65 mm Hg
And partial Vapor pressure of toluene, pt = pt X xt
Pt = p°t X xt = 32.06 x 0.514
= 16.48
Total vapour pressure = 24.65 + 16.48 = 41.13 mm Hg
Mole fraction of benzene in vapour phase = 24.65 / 41.13 = 0.60
2.39 The air is a mixture of a number of gases. The major components are oxygen and
nitrogen with approximate proportion of 20% is to 79% by volume at 298 K. The water
is in equilibrium with air at a pressure of 10 atm. At 298 K if the Henry’s law constants
for oxygen and nitrogen at 298 K are 3.30 × 107 mm and 6.51 × 107 mm respectively,
calculate the composition of these gases in water.
Ans. Percentage of oxygen (O2) in air = 20 %
Percentage of nitrogen (N2) in air = 79%
Also, it is given that water is in equilibrium with air at a total pressure of 10 atm, that is,
(10 × 760) mm Hg = 7600 mm Hg
Therefore, Partial pressure of oxygen, po2 = 20/100 *7600
=1520 mm Hg
Partial pressure of nitrogen,pN2 = 79/100 *7600
= 6004 mmHg
Now, according to Henry's law:
p = KH.x
For oxygen:
po2 = KH. xO2
⇒xO2 = po2 / KH
= 1520 / 3.30 X 107
= 4.61 10-5
For nitrogen:
pN2 = KH.xN2
⇒xN2 = pN2 / KH
= 6004 / 6.51 x 107
= 9.22 x 10-5
Hence, the mole fractions of oxygen and nitrogen in water are 4.61 ×10 - 5 and 9.22 × 10
-5
respectively.
2.40 Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 litre of water such
that its osmotic pressure is 0.75 atm at 27° C.
Ans. We know that
π = i n/V RT
⇒π = i w/MV iRT
⇒ w = πMV / iRT .......................(1)
Now we have given below values:
π = 0.75 atm
V = 2.5L
i = 2.47
T = (27+273) K = 300K
Here,
R = 0.0821L atm k-1 mol-1
M = 1x40 + 2x35.5
= 111 g/mol
Now putting the value in equation 1:
w = 0.75x111x2.5 / 2.47x0.0821x300
=3.42g
Hence, the required amount of CaCl2 is 3.42 g.
2.41 Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4 in
2 litre of water at 25° C, assuming that it is completely dissociated.
Ans. If K2SO4 is completely dissociated then these ions are produced
Then K2SO4 = 2K+ + SO42-
So total number of ions produced = 3
Therefore I =3
Now molecular mass of K2SO4 = 2 x 39 + 1 x 32 + 4 x 16 = 174 g/mol
Now π = I Crt
= I WB X RT / MB X V
= 3 X 25 X 10-3 X 0.082 X 298 / 174 X 2
= 5.27 X 10-3 atm.
Unit - II - Solutions
One mark questions:
1. What is a binary solution?
Ans.
2. Give an example for a solution of a solid in a gas.
Ans.
3. 5 g of glucose is dissolved in 95g of water. What is the mass percentage of glucose?
Ans.
4. Write the expression to calculate volume percentage of solute.
Ans.
5. In a binary solution, mole fraction of a component is 0.85. What is the mole
fraction of the other component?
Ans.
6. What is the mass of sodium hydroxide present in 500mL of 1M NaOH solution? (Molar
mass of NaOH is 40 gmol-1).
Ans.
7. Name a concentration term which is independent of temperature.
Ans.
8. How does the solubility of a solid solute in a liquid vary with increase in temperature if
the dissolution process is endothermic?
Ans.
9. Write the mathematical expression for Henry's law.
Ans.
10. KH values for the gases argon and methane in water at 298K are 40.3 /k bar and 0.413 /
k bar respectively. Which gas is more soluble at this temperature?
Ans.
11. Cylinders used by Scuba divers is diluted with helium gas. Why?
Ans.
12. State Raoult’s law.
Ans.
13. Vapour pressures of chloroform and dichloromethane are 200mm of Hg and 415mm of
Hg at 298K respectively. Which one is more volatile?
Ans.
14. What are ideal solutions?
Ans.
15. Give an example for a non ideal solution showing negative deviation from Raoult’s law.
Ans.
16. Based on inter molecular interactions, give the reason for a solution of A and B to show
positive deviation from Raoult’s law.
Ans.
17. Arrange the following aqueous solutions in decreasing order of their relative lowering
of vapour pressure:
i) 0.1M sucrose ii) 0.1 M NaCl iii) 0.05 M glucose iv) 0.1 M acetic acid
Ans.
18. Molal elevation constant for water is 0.52 Kkg mol-1. What is the elevation in boiling
point produced for one molal aqueous solution of a solute for which i=1?
Ans.
19. Write the SI unit for Ebullioscopic constant.
Ans.
20. Write the relationship between Kb and enthalpy of vapourisation of the solvent.
Ans.
21. Which of the following aqueous solutions should have higher boiling point?
0.01M NaCl
or 0.01M Na2SO4 (assume both undergo almost complete ionisation)
Ans.
22. Sea water freezes at a temperature lower than that of pure water. Why?
Ans.
23. Ethylene glycol is added as antifreeze to petrol in cold countries. Why?
Ans.
24. Which solution would exhibit lower osmotic pressure? Aqueous solution of urea or
aqueous solution of common salt, both of same concentration.
Ans.
25. Give a definition for van't Hoff factor 'i'.
Ans.
26. Write the modified equation to calculate ∆Tb for i ¹ 1.
Ans.
Two mark questions:
1 Differentiate molarity and molality of a solution. Which one of these varies with
temperature?
Ans.
2 Concentration of urea in an aqueous solution is 45% by mass. Calculate the mass of
urea in 100g of water.
Ans.
3 10mL of ethanol is mixed with 250 mL of water. Calculate the volume percent of
ethanol.
Ans.
4 20g of glucose is present in 500mL of its solution. Calculate the mass by volume
percentage of glucose.
Ans.
5 20g of HCl is present in 2dm3 of its solution. Calculate the molarity of HCl solution.
Given molar mass of HCl =36.5g/ mol
Ans.
6 30g of urea is dissolved in 500g of water. Calculate the molality of this solution. Given
molar mass of urea =60 g/mol.
Ans.
7 One kg of a sample of hard water contains 3mg of calcium carbonate. Express the
concentration of calcium carbonate in ppm.
Ans.
8 State Henry's law. Aquatic species are more comfortable towards respiration in
cold water than in warm water. Why?
Ans.
9 Draw the graph of partial pressure of a gas in vapour phase versus mole fraction of the
gas in solution. What is the slope of a line equal to?
Ans.
10. Mention any two factors affecting solubility of a gas in a liquid.
Ans.
11. Draw the graph for, the plot of vapour pressure versus mole fraction of an ideal
solution.
Ans.
12. Write any two differences between ideal and non ideal solutions.
Ans.
13. What are azeotropes? What type of solutions form minimum boiling azeotropes?
Ans.
14. What are colligative properties? Molal cryoscopic constant of acetic acid is 3.9 Kkgmol-
1. What does this mean?
Ans.
15. 3 moles of a non-volatile solute is dissolved in 15 mol of a solvent. Calculate the relative
lowering of vapour pressure.
Ans.
16. Vapour pressure of pure benzene at some temperature is 0.95 bar. Calculate the
vapour pressure of 1 molal solution of a non-volatile solute (i=1) in it. Given molar mass
of benzene = 78 gmol-1.
Ans.
17. Vapour pressure of water at 295 K is 18.5 mm of Hg. Calculate the vapour pressure of
the solution containing 25 g urea dissolved in 400 g of water at the same temperature.
Given molar mass of urea = 60 g mol-1.
Ans.
18. How does boiling point and freezing point of a solvent vary when a non volatile solute is
added to it?
Ans.
19. What is the effect on the i) vapour pressure ii) boiling point of a solvent, when a non-
volatile solute is dissolved in it?
Ans.
20. The molal depression constant of water is 1.86 K/m. Calculate the depression in
freezing point of 0.1 molal aqueous urea solution.
Ans.
21. Molal elevation constant for benzene is 2.52K/m. A solution of benzene containing a
solute (i=1) boils at 0.126°C higher than benzene. Calculate the molality of the solution.
Ans.
22. i) Define osmotic pressure. ii) What are isotonic solutions?
Ans.
23. Molecular mass of polymers or proteins are more often determined by measuring
osmotic pressure rather than by any other colligative property. Give two reasons.
Ans.
24. What is the observation made when blood cells are placed in saturated salt solution?
What are such solutions called?
Ans.
25. What does the value of Van’t-Hoff factor indicate? What is the value i for a solute that
dissociates in a solvent?
Ans.
26. The value of i for acetic acid is i) > 1 in water ii) < 1 in benzene. What inference can be
drawn regarding acetic acid in these solvents?
Ans.
27. Normal molar mass of a solute is 246 g mol-1 and molar mass of the same in a solvent
is 346 gmol-1. What is the value of i? Comment on the state of the solute in the
solvent.
Ans.
28. Explain the desalination of sea water using reverse osmosis technique.
Ans.
29. Name the phenomenon involved: i) a piece of raw mango in salt solution shrinks.
ii) when pressure greater than osmotic pressure is applied on the solution side
Ans.
Three mark questions:
1 3 moles of sodium chloride is dissolved in 250 moles of water. What is the mole
fraction of NaCl and water in the solution?
2 Give reasons:
i) solubility of a gas in a solvent is always exothermic
ii) there is volume expansion when ethanol is added to water
iii) elevation in boiling point is observed when sea water is boiled at 1 bar pressure
Ans. i). (Exact answer not found)
ii). (May be the question is wrong. Answer says the volume decreases)
iii). (Exact answer not found)
3 Give reasons:
i) Liquids A and B on mixing produce a warmer solution
ii) Freezing point depression of 0.1 M aqueous NaCl is nearly twice that of 0.1 M
aqueous sucrose solution
iii) Blood cells when placed in water swells.
Ans. i). On mixing A and B, the solution becomes warm. This means heat released in
formation of new bonds between A and B molecules is more than the heat absorbed
for the breaking of molecules of A and B.Therefore, the vapour pressure of the solution
is reduced and thus the mixture shows negative deviation from Roult's law.
ii). NaCl is an electrolyte and it dissociates completely whereas glucose being a non-
electrolyte does not dissociate. Hence, the number of particles in 0.1 M NaCl solution is
nearly double for NaCI solution than that for glucose solution of same molarity.
Therefore depression in freezing point being a colligative property ¡s nearly twice for
NaCl solution than that for glucose solution of same molarity.
iii). A red blood cell that is placed in a hypotonic solution, i.e. a solution with a lower
concentration, the cell will swell as a result of more water moving into the cell than out.
This may lead to potential hemolysis (bursting) of the cell. Pure water is a hypotonic
solution compared to red blood cells, hence if placed in it the cell will swell.
4 Give reasons:
i) there is no osmosis when 0.1 M urea solution is separated from 0.1 M sucrose
solution by a semi-permeable membrane.
ii) molar mass of an electrolyte in a polar solvent determined by any colligative
property is less than its theoretical molar mass.
iii) 95% aq. ethanol by volume cannot be concentrated by fractional distillation
Ans. i). (Exact answer not found)
ii). (Incomplete answer) Due to association or dissociation of solute molecules there is a
change in number of particles. Since colligative properties depend on number of
particles there is a change in molecular mass.
iii). (Exact answer not found)
5 The vapour pressure of pure water at 50°C is 12260Pa. 18.2g of solute was dissolved in
100g of water at the same temperature. The lowering of vapour pressure produced is
660Pa. Calculate the molar mass of the solute. [A: 60.85 gmol-1]
Ans. (Ambiguous question)
6 The vapour pressure of pure water at 298K is 3.3kPa. Calculate the relative lowering of
vapour pressure of an aqueous solution containing 20g of glucose dissolved in 90g of
water at the same temperature. (Molar mass of glucose = 180gmol-1, molar mass of
water = 18 gmol-1). [A : 0.02173 ]
Ans.
7 At 100° C, benzene and toluene have vapour pressure of 1375 torr and 558 torr,
respectively. Assuming these two form an ideal binary solution, calculate the mole
fraction of benzene in vapour phase at 1 atm and 100° C. [A : 0.247]
Ans.
8 The vapour pressure of pure benzene at a certain temperature is 200mm of Hg. At the
same temperature, the vapour pressure of solution containing 2g of a non volatile, non
electrolytic solute in 78g of benzene is 195mm of Hg. Calculate the molar mass of the
solute. [A : 80 g mol-1]
Ans.
9 12.6g of a non electrolyte is dissolved in 75g of water. The freezing point of this
solution is 271.9K. If molar depression constant is 1.86 Kkgmol-1, calculate the molar
mass of the solute. (Freezing point of pure water = 273.15 K) [A: 250 g mol-1]
Ans.
10. Using the graph answer the following:

i) What type of non-ideal solution shows such a behaviour?
ii) What can you infer about the molecular interactions before & after mixing A and B?
iii) What type of azeotrope will the mixture of A and B form?

11. The boiling point of benzene is 353.23K. When 1.8g of a non volatile solute was
dissolved in 90g of benzene, the boiling point is raised to 354.11K. Calculate the molar
mass of solute. (Kb = 2.52 K kg mol-1) [A : 57.2 g mol-1]
Ans.
12. 20 g of an organic acid is dissolved in 500 g of water. The depression in freezing point of
water was by 1°. Calculate the Van't Hoff factor and degree of dissociation of the acid.
(Molar mass of acid = 79 gmol-1, Kf =1.86 K kgmol-1). [A: i = 1.06 ; 0.06]
13. Acetic acid exists in benzene solution in the dimeric form. In an actual experiment the
Van’t Hoff factor was found to be 0.52. Calculate the degree of association of acetic
acid. [A : 0.96]
Ans.
14. Calculate the boiling point of the solution which has 15 g of MgSO4 dissolved in 550 g
of water. Assume i = 2 for the solute. Boiling point of pure water = 373.15 K. (Molar
mass of MgSO4 = 120 g mol-1, Kb = 0.52 K kgmol-1 ) [A : 373.38 K]
Ans. (Similar problem, but values are different)
15. Calculate the osmotic pressure of 5% (m/V) solution of urea at 300K. (The value of R is
0.0821 L atm K-1, Molar mass of urea = 60 g mol-1). [A : 20.5 atm]
Ans. Explanation:
The osmotic pressure is given by the formula:
p=i×C×R×T
Where,
i = Van’t-Hoff factor = 1 (for non-electrolyte solution)
C = Concentration of solute
R = Gas constant = 0.082 L.atm/mol.K
T = Temperature
5% of urea = 5 g of urea in 100 ml of solution
Mole = (Given weight)/(Molecular weight)
On substituting the values, we get,
Moles = 5/60 = 0.083 mol
Now, the concentration of urea is given by the formula:
Molarity = (Moles of urea)/(Volume of solution) × 1000
Molarity = 0.083/100 × 1000
Molarity = 0.83 M
Now, the osmotic pressure is:
p = 1 × 0.83 × 0.082 × 300
∴ p = 20.418 atm
16. A 1.46% solution of a compound has an osmotic pressure of 783 mm of Hg at 300K.
Calculate the molar mass of the compound. R = 62.36 L mm Hg K-1 mol-1. [A : 348.8 g
mol-1]
Ans.
17. Normal saline is 0.9% mass/volume sodium chloride solution. Calculate the osmotic
pressure of normal saline at 300 K. Given molar mass of NaCl=58.5 gmol-1, R=0.083
Lbar mol-1 K-1. [A : 3.8 bar]
Ans.
Unit III - Electrochemistry
3.1 Arrange the following metals in the order in which they displace each other from the
solution of their salts.
Al, Cu, Fe, Mg and Zn.
Ans. A metal having stronger reducing power displaces another metal having weaker
reducing power from its salt solution.
The increasing order of reducing power is Cu<Fe<Zn<Al<Mg.
Thus, Mg can displace Al from its salt solution but Al cannot displace Mg.
The order in which the metals displace each other from their salt solutions is
Mg>Al>Zn>Fe>Cu.
3.2 Given the standard electrode potentials,
K+/K = –2.93V, Ag+/Ag = 0.80V,
Hg2+/Hg = 0.79V
Mg2+/Mg = –2.37 V, Cr3+/Cr = – 0.74V
Arrange these metals in their increasing order of reducing power.
Ans. The lower the reduction potential, the higher is the reducing power. The given standard
electrode potentials increase in the order of
K+/ K < Mg2+ / Mg < Cr3+ / Cr < Hg2+ / Hg < Ag+ / Ag.
Hence, the reducing power of the given metals increases in the following order:
Ag < Hg < Cr < Mg < K
3.3 Depict the galvanic cell in which the reaction
Zn(s)+2Ag+(aq) →Zn2+(aq)+2Ag(s) takes place. Further show:
(i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell.
(iii) Individual reaction at each electrode.
Ans. The galvanic cell in which the given reaction takes place is depicted as:
(i) Zn electrode (anode) is negatively charged.
(ii) Ions are carriers of current in the cell and in the external circuit, current will flow
from silver to zinc.
(iii) The reaction taking place at the anode is given by,

Zn(s) → Zn2+(aq) + 2e-
The reaction taking place at the cathode is given by,
Ag+(aq) + e- → Ag(s)
3.4 Calculate the standard cell potentials of galvanic cell in which the following
reactions take place:
(i) 2Cr(s) + 3Cd2+(aq) → 2Cr3+(aq) + 3Cd
(ii) Fe2+(aq) + Ag+(aq) → Fe3+(aq) + Ag(s)
Calculate the ∆rG⊖ and equilibrium constant of the reactions.
Ans. (i) Eø Cr3+ / Cr = - 0.74 V
Eø Cd2+ / Cd = - 0.40 V
The galvanic cell of the given reaction is depicted as:
Now, the standard cell potential is
Eø = EøR - EøL
= -0.40 - (-0.74)
= + 0.34 V
ΔrGø = -nFEøcell
In the given equation,
n=6
F = 96487 C mol - 1
Eøcell = +0.34 V
Then, ΔrGø = - 6 × 96487 C mol - 1 × 0.34 V
= - 196833.48 CV mol - 1
= - 196833.48 J mol - 1
= - 196.83 kJ mol - 1
Again,
ΔrGø = - RT ln K
= 34.496
K = antilog (34.496)
= 3.13 × 1034
(ii) Eø Fe3+ / Fe2+ = 0.77 V
Eø Ag+ / Ag = 0.80 V
The galvanic cell of the given reaction is depicted as:
Now, the standard cell potential is
Eø = EøR - EøL
= 0.80 - 0.77
= 0.03 L
Here, n = 1.
Then, ΔrGø = -nFEøcell
= - 1 × 96487 C mol - 1 × 0.03 V
= - 2894.61 J mol - 1
= - 2.89 kJ mol - 1
Again, ΔrGø = - 2.303 RT ln K
= 0.5073
K = antilog (0.5073)
= 3.2 (approximately)
3.5 Write the Nernst equation and emf of the following cells at 298 K:
(i) Mg(s)|Mg2+(0.001M)||Cu2+(0.0001 M)|Cu(s)
(ii) Fe(s)|Fe2+(0.001M)||H+(1M)|H2(g)(1bar)| Pt(s)
(iii) Sn(s)|Sn2+(0.050 M)||H+(0.020 M)|H2(g) (1 bar)|Pt(s)
(iv) Pt(s)|Br–(0.010 M)|Br2(l )||H+(0.030 M)| H2(g) (1 bar)|Pt(s).
Ans. (i) For the given reaction, the Nernst equation can be given as:
= 2.7 - 0.02955 = 2.67 V (approximately)
(ii) For the given reaction, the Nernst equation can be given as:
= 0.52865 V = 0.53 V (approximately)
(iii) For the given reaction, the Nernst equation can be given as:
= 0.14 - 0.0295 × log125
= 0.14 - 0.062
= 0.078 V
= 0.08 V (approximately)
(iv) For the given reaction, the Nernst equation can be given as:
3.6 In the button cells widely used in watches and other devices the following
reaction takes place:
Zn(s) + Ag2O(s) + H2O(l) → Zn2+(aq) + 2Ag(s) + 2OH–(aq)
Determine ∆r G⊖ and E⊖ for the reaction.
Ans.
Eø = 1.104 V
We know that,
ΔrGø = -nFEø
= - 2 × 96487 × 1.04
= - 213043.296 J
= - 213.04 kJ
3.7 Define conductivity and molar conductivity for the solution of an electrolyte.
Discuss their variation with concentration.
Ans. Conductivity of a solution is defined as the conductance of a solution of 1 cm in length
and area of cross-section 1 sq. cm. The inverse of resistivity is called conductivity or
specific conductance. It is represented by the symbol k. If p is resistivity, then we can
write:
k=1/p
The conductivity of a solution at any given concentration is the conductance (G) of one
unit volume of solution kept between two platinum electrodes with the unit area of
cross-section and at a distance of unit length.
i.e.,
(Since a = 1, l = 1)
Conductivity always decreases with a decrease in concentration, both for weak and
strong electrolytes. This is because the number of ions per unit volume that carry the
current in a solution decreases with a decrease in concentration.
Molar conductivity:
Molar conductivity of a solution at a given concentration is the conductance of volume

V of a solution containing 1 mole of the electrolyte kept between two electrodes with
the area of cross-section A and distance of unit length.
Now, l = 1 and A = V (volume containing 1 mole of the electrolyte).
Am = kV
Molar conductivity increases with a decrease in concentration. This is because the total
volume V of the solution containing one mole of the electrolyte increases on dilution.
The variation of Am with for strong and weak electrolytes is shown in the following
plot:
3.8 The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm–1. Calculate its molar
conductivity.
Ans.
3.9 The resistance of a conductivity cell containing 0.001M KCl solution at 298
K is 1500 Ω. What is the cell constant if conductivity of 0.001M KCl solution
at 298 K is 0.146 × 10–3 S cm–1.
Ans. Given, k = 0.0248 S cm - 1
c = 0.20 M
Molar conductivity, Am = (k x 1000) / c
= 0.0248 x1000 / 0.20
124 Scm2 mol - 1

3.10
Ans.
3.11
Ans.
3.12 How much charge is required for the following reductions:

(i) 1 mol of Al3+ to Al?
(ii) 1 mol of Cu2+ to Cu?
(iii) 1 mol of MnO4 – to Mn2+?
Ans. (i) Al3+ + 3e- → Al
Required charge = 3 F
= 3 × 96487 C = 289461 C
(ii) Cu2+ + 2e- → Cu
Required charge = 2 F
= 2 × 96487 C
= 192974 C
(iii) MnO4- → Mn2+
i.e.,
Mn7+ +5e- → Mn2+

Required charge
=5F
= 5 × 96487 C
= 482435 C
3.13 How much electricity in terms of Faraday is required to produce
(i) 20.0 g of Ca from molten CaCl2?
(ii) 40.0 g of Al from molten Al2O3?
Ans. Molar mass of calcium & Aluminium are 40 g mol−1 & 27 g mol−1 respectively
3.14 How much electricity is required in coulomb for the oxidation of

(i) 1 mol of H2O to O2?
(ii) 1 mol of FeO to Fe2O3?
Ans.
3.15 A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5

amperes for 20 minutes. What mass of Ni is deposited at the cathode?
Ans. Given,
Current = 5A
Time = 20 × 60 = 1200 s
Charge = current × time
= 5 × 1200
= 6000 C
According to the reaction,
Nickel deposited by 2 × 96487 C = 58.71 g

Therefore, nickel deposited by 6000 C = (58.71 X 6000) / (2 X 96487) g
= 1.825 g
Hence, 1.825 g of nickel will be deposited at the cathode.
3.16 Three electrolytic cells A,B,C containing solutions of ZnSO4, AgNO3 and CuSO4,
respectively are connected in series. A steady current of 1.5 amperes was passed
through them until 1.45 g of silver deposited at the cathode of cell B. How long did the
current flow? What mass of copper and zinc were deposited?
Ans.
3.17 Using the standard electrode potentials given in Table 3.1, predict if the
reaction between the following is feasible:
(i) Fe3+(aq) and I–(aq)
(ii) Ag+ (aq) and Cu(s)
(iii) Fe3+ (aq) and Br– (aq)
(iv) Ag(s) and Fe
3+ (aq)
(v) Br2 (aq) and Fe2+ (aq).
Ans.
Since Eº for the overall reaction is positive, the reaction between Fe 3+(aq) and I - (aq) is
feasible.
Since Eº for the overall reaction is positive, the reaction between Ag +(aq) and Cu(s) is
feasible.
Since Eº for the overall reaction is negative, the reaction between Fe 3+(aq) and Br - (aq) is
not feasible.
Since Eº for the overall reaction is negative, the reaction between Ag (s) and Fe3+(aq) is not
feasible.
Since for the overall reaction is positive, the reaction between Br 2(aq) and Fe2+(aq) is
feasible.
3.18 Predict the products of electrolysis in each of the following:
(i) An aqueous solution of AgNO3 with silver electrodes.
(ii) An aqueous solution of AgNO3 with platinum electrodes.
(iii) A dilute solution of H2SO4 with platinum electrodes.
(iv) An aqueous solution of CuCl2 with platinum electrodes.
Ans. (i) At cathode: The following reduction reactions compete to take place at the cathode.
The reaction with a higher value of Eº takes place at the cathode. Therefore, deposition
of silver will take place at the cathode.
At anode:
The Ag anode is attacked by NO3- ions. Therefore, the silver electrode at the anode
dissolves in the solution to form Ag+.
(ii) At cathode:
The following reduction reactions compete to take place at the cathode.
At anode:
Since Pt electrodes are inert, the anode is not attacked by NO 3- ions. Therefore, OH - or
NO3- ions can be oxidized at the anode. But OH - ions having a lower discharge potential
and get preference and decompose to liberate O2.
OH- → OH + e-
4OH- → 2H2O +O2
(iii) At the cathode, the following reduction reaction occurs to produce H 2 gas.
H+ (aq) + e- → ½ H2(g)
At the anode, the following processes are possible.
For dilute sulphuric acid, reaction (i) is preferred to produce O 2 gas. But for
concentrated sulphuric acid, reaction (ii) occurs.
(iv) At cathode:
The following reduction reactions compete to take place at the cathode.
of copper will take place at the cathode.
At anode:
The following oxidation reactions are possible at the anode.
At the anode, the reaction with a lower value of Eº is preferred. But due to the over-
potential of oxygen, Cl - gets oxidized at the anode to produce Cl2 gas.

One Mark Questions
1. When can a Galvanic cell become an electrolytic cell?
Ans.
2. What is limiting molar conductivity?
Ans.
Why does the molar conductivity increase on decreasing the concentration of the
3.
weak electrolyte?
Ans.
4.
Ans.
5.
Ans.
When 1F of charge is passed through 1M HCl, volume of hydrogen liberated was 11.35L
6. at STP. What is the volume of hydrogen liberated when same quantity of electricity is
passed through 1M H2SO4. [11.35 L]
Ans.
7. Differentiate between reactive and inert electrodes.
Ans.
8. What is the role of platinum in SHE?
Ans.
9. What is the value assigned to the electrode potential of SHE at 300K?
Ans.
A galvanic cell is constructed using SHE and silver electrode . [Ag+] = 1M and EoAg+/Ag
10.
= +0.8V. What is the cell potential? [0.8V]
Ans.
11.
Ans.
12. Mention an observation made when an iron rod is dipped into 0.1M CuSO4 solution?
Ans.
13.
Ans.
Ans.
What is the electrode potential of a Daniell cell when the concentrations of copper
14.
and zinc ions are 1M each.
Ans.
15.
Ans.
16. Write the relationship between Eocell and equilibrium constant.
Ans.
17. What is the major difference between a primary battery and a secondary battery?
Ans.
18. Name one metal which can be used as sacrificial electrode to prevent rusting of iron.
Ans.

Two Marks Questions
1. Differentiate between strong and weak electrolytes.
Ans.
2. Define conductivity of a solution. Write its SI unit.
Ans.
How does (i) conductivity (ii) molar conductivity of an electrolyte change with
3.
dilution?
Ans.
The cell constant of a given cell is 0.47 cm-1. The resistance of a solution taken in the
4. cell was found to be 31.6W. Calculate the conductivity of the solution. [A : 0.0148S cm-
1]
Ans.
The conductivity of 0.025 M solution of methanoic acid is 1.1525 S cm-1. Calculate
5. its molar conductivity.
[A:46100 S cm2 mol–1]
Ans.
6. State (i) Faraday’s II law of electrolysis (ii) Kohlrausch law
Ans.
A solution of Ni(NO3)2 is electrolysed between Pt electrodes using current of 5 amps
7. for 20 mins. What mass of nickel is deposited at the cathode? (Molar mass of Ni=58.7 g
mol-1. 1F = 96487 C) [1.82g]
Ans.
96487C of charge is passed through both CuSO4 solution and AgNO3 solution. The
mass of copper deposited is 32g. What would be the mass of silver deposited?
8.
(Molar mass of copper = 64gmol-1 and silver =108g mol-1) (1F=96487C)
[108g]
Ans.
In electrolysis, lower the electrode potential, higher is the tendency for oxidation
reaction to occur. When aqueous NaCl is electrolysed, following two reactions are
possible. Which of these two is preferred and why?
9.
Ans.
A total of 49750C of charge was required to reduce 9.5g of M+3 ion to metal. Calculate
10.
the molar mass of the metal. 1F = 96500C. [A:55.28]
Ans.
11.
Ans.
Write the anodic reaction occurring during the electrolysis of dilute H2SO4. What would
12.
be the product if higher concentration of sulphuric acid is electrolysed?
Ans.
What are the conditions under which a hydrogen electrode is considered a standard
13.
hydrogen electrode?
Ans.
14. Draw a neat labeled diagram of SHE and write its symbolic representation.
Ans.
15. Given . Identify a stronger redox couple. Give

reason.
Ans.
16.
Ans.
The reduction potential of Mg+2 and Al+3 are -2.37 and -1.66 volts respectively.
17. Constructing a Galvanic cell using these electrodes, give the cell representation, and
write the Nernst equation .
Ans.
18. At which electrode will oxidation occur in a (i) Galvanic cell (ii) electrolytic cell
Ans.
19. Copper does not dissolve in HCl but dissolves in HNO3. Explain.
Ans.
20. EMF of a galvanic cell is 1.05V and 193000 Coulomb of charge is passed. Calculate the
reversible work done by the cell. [A: 202650J]
Ans.
Write the overall cell reaction occurring in a mercury-cell. Its cell potential remains a
21.
constant value of approximately 1.35V during its life. Why?
Ans.
22. Write the reactions occurring during discharging of lead storage battery.
Ans.
What are the advantages of fuel cell over other conventional power plants in producing
23.
energy?
Ans.
i) Chemically “what is rust”? ii) Write anodic reaction occurring during the rusting of
24.
iron
Ans.
25. Give two methods for the prevention of corrosion.
Ans.

Three Marks Questions
What do we mean by cell constant in conductivity measurements. If the resistance of a
1. conductivity cell filled with 0.02 M KCl solution is 520 Ω, calculate its cell constant, given
κ = 0.248 Sm-1. [A: 128.96 m-1]
Ans. (Exact solution not found. Similar problem found, but cell constant is given and K is to
be calculated)
Molar conductivity of 0.05M acetic acid solution at 298K is 7.36 Sm2mol-1. Calculate
2.
the degree of dissociation of acetic acid and also Ka. Sm2mol-1.
Ans. (Exact solution not found)
Predict the products of electrolysis for the following
i) aqueous solution of NaCl with graphite electrodes
3.
ii) aqueous solution of CuSO4 with platinum electrodes
iii) aqueous solution of AgNO3 with silver electrodes
Ans. i) and ii) not found
iii) At cathode: The following reduction reactions compete to take place at the cathode.
At anode:
The Ag anode is attacked by NO 3- ions. Therefore, the silver electrode at the anode
dissolves in the solution to form Ag+.
4. Electrolysis of aqueous sodium chloride solution was carried out by passing 5 A current
for 3 hours. Calculate the volume of hydrogen liberated at STP, at the cathode. [1F =
96500C, molar volume of hydrogen at STP = 22,400 cm3]. [A: 2089 cm3]
In the electrolysis of copper sulphate solution using current of 5.3A, the mass of
cathode increased by 4.6g. Calculate the time taken in min for the electrolysis (molar
5.
mass of copper = 64gmol-1, 1F = 96500C)
[A: 43.6 mins]
Given is the plot of Λm Vs C½ for a electrolyte ‘X’. What type of electrolyte is X? What
does the intercept refer to? What is its value?
6.

Name the following:
i) The difference between the electrode potentials of two electrodes when no current is
7. drawn through the cell
ii) the quantity length/area of the electrode in a conductivity cell
iii) Mn+/M
Ans. i. EMF
ii. (No solution found)
iii. (No solution found)
8.
9.
10.
11.

12.
Ans.
13.
14.

Five Marks Questions
1.
Ans. a). A standard dry cell comprises a zinc anode, usually in the form of a cylindrical pot,
with a carbon cathode in the form of a central rod. The electrolyte is ammonium
chloride in the form of a paste next to the zinc anode. The remaining space between
the electrolyte and carbon cathode is taken up by a second paste consisting of
ammonium chloride and manganese dioxide, the latter acting as a depolarizer. In some
designs, the ammonium chloride is replaced by zinc chloride.
b). (No solution found)

a) What are fuel cells? Write the schematic diagram of H2-O2 fuel cell and give the
2. electrode reactions.
b) How is molar conductivity related to conductivity?
Ans. a).
The diagram of H2−O2 fuel cell is shown below:
The reaction occurs at cathode of the cell is given below:

The Reducing process at cathode: Oxygen gas water molecules are reduced to
Hydroxide ions:
O2(g)+2H2O(l)+4e−→4OH−(aq).
Fuel cells are galvanic cells in which the energy of combustion of fuels is directly
converted into the electrical energy. This Fuel Cell is also known as H2−O2 cell. In this
cell the commonly used fuels are methanol, hydrogen etc.
The cell reactions in H2−O2 cell takes place at both the electrodes that are at cathodes
and anodes. At Cathodes the reduction process takes place while on an Anode the
Oxidation process takes place. The reaction at the both the terminals is explained
below:
At Anode: The reaction (Oxidation) which takes place at anode is given below:
2H2(g)+4OH−(aq)→4H2O(l)+4e−2H2(g)+4OH−(aq)→4H2O(l)+4e−
In this reaction Hydrogen Gas and hydroxide ions are oxidized to form water. The
valency of all the components are taken care of.
At cathode: Reduction process takes place –
O2(g)+2H2O(l)+4e−→4OH−(aq)
In this reaction Oxygen gas and Water molecules are reduced to Hydroxide ions. The
valency of all the elements have been taken care of and fulfilled.
b).
Molar conductivity of an electrolytic solution can be defined as the conductance of
volume V of an electrolytic solution containing one mole of electrolyte and kept
between two electrodes between two electrodes with an area of cross-section A and
distance of unit length.
Molar conductivity is denoted by symbol Λm and it is given by the formula-

Λm=Kc
Here, c = concentration in moles per volume
K=Specific Conductivity/Conductivity
Λm = Molar Conductivity
Now, in the above formula K is the specific conductivity/ conductivity which can be
defined as the conductivity of an electrolyte solution at any given concentration of unit
volume of solution kept between two platinum electrodes with a unity area of cross-
section and at a unit distance.
3.
Ans. a).
The galvanic cell in which the given reaction takes place is depicted as:
Zn(s)∣Zn2+(aq)∣∣Ag+(aq)∣Ag(s)
(i) The negatively charged electrode is the zinc electrode. It acts as an anode.
(ii) In the external circuit, the current will flow from silver to zinc.
(iii) Oxidation at anode: Zn(s)→Zn2+(aq)+2e−
Reduction at cathode: Ag+(aq)+e−→Ag(s)
4.
5.
Ans. a).
b). Factors Affecting Products of Electrolysis are as follows
i. Products of electrolysis depend on the material or nature being electrolyzed, i.e. the
nature and concentration of electrolyte govern the process of electrolysis. The process
is faster for a strong electrolyte, whereas it is slower for a weaker electrolyte. Thus an
extra potential said as over-potential is necessary where the extra amount depicts the
rate of reaction involved.
ii. It also depends on the nature of electrodes. That is, in the case of the inert electrode,
it doesn’t participate in the reaction, whereas if the electrode used is reactive in nature,
then it takes part in the reaction.
iii. Presence of various oxidizing and reducing agents present in the electrolytic cell
manipulate electrolysis products.
iv. It depends upon standard electrode potentials of the different oxidizing and reducing
species present in the electrolytic cell.
v. In the case of multiple reactions, it depends on the standard electrode potential of

various reactions taking the place of which the reduction reaction, which has the
highest value of standard electrode potential, occurs at the cathode. And similarly, the
oxidation reaction, which has the lowest value of standard electrode potential, takes
place at the anode.
6.
a).
The reaction taking place in Daniel cell are
Zinc electrode: Zn(s) → Zn2+(aq) + 2e–
Copper electrode: Cu2+(aq) + 2e– → Cu(s)
———————————————————————————————
Net reaction: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
———————————————————————————————
→ When Emf < 1.1V

Ans.
Electrons flow from Zn rod to Cu rod and hence current flows from Cu to Zn electrode.
Zinc dissolves at anode and copper deposits at cathode.
→ When Emf = 1.1V
The reaction stops altogether and there is no flow of electrons or current in the circuit.
There is no chemical reactions at the electrode.
→ When Emf > 1.1V
When the current flows in opposite direction and the reaction proceeds in the opposite
direction. Electrons flow from Cu to Zn and current flows from Zn to Cu.

Unit IV - Chemical Kinetics
From the rate expression for the following reactions, determine their
order of reaction and the dimensions of the rate constants.
(i) 3NO(g) → N2O (g) Rate = k[NO]2
4.1
(ii) H2O2 (aq) + 3I– (aq) + 2H+ → 2H2O (l) + 3I− Rate = k[H2O2][I-]
(iii) CH3CHO (g) → CH4 (g) + CO(g) Rate = k [CH3CHO]3/2
(iv) C2H5Cl (g) → C2H4 (g) + HCl (g) Rate = k [C2H5Cl]
Ans. (i) Given rate = k [NO]2
Therefore, order of the reaction = 2
Dimension of k = Rate / [NO]2
= mol L-1 s-1 / (mol L-1)2
= mol L-1 s-1 / mol2 L-2
= L mol-1 s-1
(ii) Given rate = k [H2O2][I - ]
Therefore, order of the reaction = 2
Dimension of k = Rate / [H2O2][I - ]
= mol L-1 s-1 / (mol L-1) (mol L-1)
= L mol-1 s-1
(iii) Given rate =k [CH3CHO]3/2
Therefore, order of reaction = 3/2
Dimension of k = Rate / [CH3CHO]3/2
= mol L-1 s-1 / (mol L-1)3/2
= mol L-1 s-1 / mol3/2 L-3/2
= L½ mol-½ s-1
(iv) Given rate = k [C2H5Cl]
Therefore,order of the reaction = 1
Dimension of k = Rate / [C2H5Cl]
= mol L-1 s-1 / mol L-1
= s-1
For the reaction:
2A + B → A2B
4.2 the rate = k[A][B]2 with k = 2.0 × 10–6 mol–2 L2 s–1. Calculate the initial
rate of the reaction when [A] = 0.1 mol L–1, [B] = 0.2 mol L–1. Calculate
the rate of reaction after [A] is reduced to 0.06 mol L–1.
The reaction is 2A+B→A2B.
The rate law expression is as follows:

Rate =k[A][B]2
The rate constant k=2.0×10−6mol−2L2s−1.
When [A]=0.1molL−1,[B]=0.2 molL−1,
Ans. The initial rate of the reaction is,

Rate=2.0×10−6×(0.1)×(0.2)2=8.0×10−9molL−1s−1
After [A] is reduced to 0.06 molL−1, the rate of reaction is as follows:
Rate =2.0×10−6×0.06×(0.18)2=3.89×10−9molL−1s−1
[Note: A reacted =0.1−0.06=0.04

B reacted =0.02
[B]=0.2−0.02=0.18molL−1]
The decomposition of NH3 on platinum surface is zero order reaction. What are the
4.3
rates of production of N2 and H2 if k = 2.5 × 10–4 mol–1 L s–1?
Ans.
The decomposition of dimethyl ether leads to the formation of CH4, H2 and CO and the
reaction rate is given by
Rate = k [CH3OCH3]3/2
The rate of reaction is followed by increase in pressure in a closed vessel, so the rate
4.4 can also be expressed in terms of the partial pressure of dimethyl ether, i.e.,
If the pressure is measured in bar and time in minutes, then what are the units of rate
and rate constants?
Ans.
4.5 Mention the factors that affect the rate of a chemical reaction.
Ans. There are a number of factors which influence the rate of a reaction. Some of the
important factors are:
1) Concentration of the reacting species.

2) Temperature of the system
3) Nature of the reactants and products.
4) Presence of a catalyst.
5) Surface area.
6) Exposure to radiation.
1) Concentration of the Reactants
a) The rate of a chemical reaction keeps on decreasing with time. The concentration of
the reactants is maximum at the start of the reaction and, therefore, the rate of change
of concentration is also maximum.
b) As the concentration of the reactants decreases, it brings about the corresponding

decrease in the rate of the reaction. This means that the rate of a reaction is directly
proportional to the concentration of the reactants.
For example : The rate of burning of wood depends upon the concentration of oxygen.
A piece of wood burns slowly in air (containing about 20 % oxygen) but burns rapidly in
pure Oxygen (i.e. 100% oxygen ) because the concentration of oxygen in air is less.
2) Temperature of the System
An increase in the temperature increases the rate of almost all chemical reactions. A
decrease in temperature decreases the rate. The reaction rate for most of the chemical
reactions becomes almost double, for every 10°C rise in temperature.
3) Nature of reactants and the products
Rates of reactions are influenced by the nature of reactants and products. A chemical
reaction involves the breaking of old bonds and formation of new bonds. The reactivity
of a substance can be related to the ease with which the specific bonds are broken or
formed and the number of such bonds involved.
For example: the oxidation of nitric oxide to nitrogen dioxide takes place fairly rapidly
while oxidation of carbon monoxide to carbon dioxide takes place slowly.
2NO2 + O2 ——–> 2 NO2 (Fast)
2CO + O2 ——–> 2 CO2 (slow)
The reacting species appear to be very similar to each other, still they differ in reaction
rates.
4) Presence of catalyst
A catalyst is a substance which influences the rate of a reaction without undergoing any
chemical change itself.
Many reactions are made to proceed at an increased rate by the presence of certain
catalysts.
For example: A mixture of H2 and O2 does not react at room temperature. However, in
the presence of a catalyst such as finely divided platinum, the reaction becomes quite
vigorous.
5) Surface area
The larger the surface area of the reactants, the faster is rate of reaction. If one of the
reactants is a solid, then the rate of the reaction depends upon the state of sub-division
of the solid. Finely divided solids react faster than massive substances.
For example: a log of wood burns slowly but if it is cut into small wooden chips, the
burning takes place rapidly. The total surface area of the smaller particles is greater
than that of large particles and this permits more molecules of the reactants to come in
contact and form products.
6) Exposure to radiation
The rate of a chemical reaction is considerably increased by the use of certain

radiations. The photons of these radiations having frequencies (ν) possess sufficient
energies (E = hv) to break certain bonds in reactants.
For example: Reaction of hydrogen and chlorine takes place very slowly in the absence
of light. However, in the presence of light, the reaction takes place very rapidly.
A reaction is second order with respect to a reactant. How is the rate of reaction
4.6
affected if the concentration of the reactant is (i) doubled (ii) reduced to half ?
Ans.
What is the effect of temperature on the rate constant of a reaction? How can this
4.7
effect of temperature on rate constant be represented quantitatively?
Ans. The rate constant is nearly doubled with a rise in temperature by 10° for a chemical
reaction.
The temperature effect on the rate constant can be represented quantitatively by

Arrhenius equation,
K = Ae -Ea / RT
where, kis the rate constant,

A is the Arrhenius factor or the frequency factor,
R is the gas constant,
T is the temperature, and
Ea is the energy of activation for the reaction

In a pseudo first order reaction in water, the following results were
obtained:
4.8
Calculate the average rate of reaction between the time interval 30 to 60 seconds.
(i) Average rate of reaction between the time interval, 30 to 60 seconds, = d[ester] / dt
= (0.31-0.17) / (60-30)
= 0.14 / 30
= 4.67 × 10 - 3mol L - 1s - 1
(ii) For a pseudo first order reaction,
k = 2.303/ t log [R]º / [R]
For t= 30 s, k1 = 2.303/ 30 log 0.55 / 0.31
Ans. = 1.911 × 10 - 2s - 1
For t = 60 s, k2 = 2.303/ 60 log 0.55 / 0.17
= 1.957 × 10 - 2s - 1
For t= 90 s, k3 = 2.303/ 90 log 0.55 / 0.085
= 2.075 × 10 - 2s - 1
Then, average rate constant, k = k1 + k2+ k3 / 3
= 1.911 × 10 - 2 + 1.957 × 10 - 2 + 2.075 × 10 - 2 / 3
= 1.981 x 10-2 s - 1
A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
4.9
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when the concentrations of both A and B are doubled?
Ans.
In a reaction between A and B, the initial rate of reaction (r0) was measured for
different initial concentrations of A and B as given below:
4.10
What is the order of the reaction with respect to A and B?

Ans. Let the order of the reaction with respect to A be xand with respect to B be y.
Therefore,
= 1.496
= 1.5 (approximately)
Hence, the order of the reaction with respect to A is 1.5 and with respect to B is zero.
The following results have been obtained during the kinetic studies of the reaction:
2A + B → C + D
4.11
Determine the rate law and the rate constant for the reaction.
Ans.
The reaction between A and B is first order with respect to A and zero order
with respect to B. Fill in the blanks in the following table:
4.12
Ans. The given reaction is of the first order with respect to A and of zero order with respect
to B.
Therefore, the rate of the reaction is given by,
Rate = k [A]1[B]0
⇒ Rate = k [A]
From experiment I, we obtain

2.0 x 10-2mol L-1min-1= k (0.1 mol L-1)
⇒ k = 0.2 min-1
From experiment II, we obtain
4.0 x 10-2mol L-1min-1= 0.2 min-1[A]
⇒ [A] = 0.2 mol L-1
From experiment III, we obtain
Rate = 0.2 min-1 x 0.4 mol L-1
= 0.08 mol L-1min-1
From experiment IV, we obtain
2.0 x 10-2mol L-1min-1= 0.2 min-1[A]
⇒ [A] = 0.1 mol L-1

Calculate the half-life of a first order reaction from their rate constants given
4.13
below: (i) 200 s–1 (ii) 2 min–1 (iii) 4 years–1
(i) Half life, t½ = 0.693 / k
= 0.693 / 200 s-1
= 3.47 ×10 -3 s (approximately)
(ii) Half life, t½ = 0.693 / k
Ans. = 0.693 / 2 min-1
= 0.35 min (approximately)
(iii) Half life,t½ = 0.693 / k
= 0.693 / 4 years-1
= 0.173 years (approximately)

The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact
4.14 containing wood had only 80% of the 14C found in a living tree. Estimate the age of the
sample.
Ans. Here,
K = 0.693 / t½
= 0.693 / 5730 years-1
It is known that,
= 1845 years (approximately)
Hence, the age of the sample is 1845 years.
The experimental data for decomposition of N2O5

[2N2O5 → 4NO2 + O2]
in gas phase at 318K are given below:
4.15
(i) Plot [N2O5] against t.
(ii) Find the half-life period for the reaction.
(iii) Draw a graph between log[N2O5] and t.
(iv) What is the rate law ?
(v) Calculate the rate constant.
(vi) Calculate the half-life period from k and compare it with (ii).
Ans. (i)
(ii) Time corresponding to the concentration, 1630x10 2 / 2 mol L-1 = 81.5 mol L-1 is the
half life. From the graph, the half life is obtained as 1450 s.
(iii)
t/s 102 × [N2O5] mol L-1 Log [N2O5]

0 1.63 -1.79
400 1.36 -1.87
800 1.14 -1.94
120
0.93 -2.03
0
160
0.78 -2.11
0
200
0.64 -2.19
0
240
0.53 -2.28
0
280
0.43 -2.37
0
320
0.35 -2.46
0
(iv) The given reaction is of the first order as the plot, log[N 2O5] v/s t, is a straight line.
Therefore, the rate law of the reaction is
Rate = k [N2O5]
(v) From the plot, log[N2O5]
v/s t, we obtain
Slope = -2.46 -(1.79) / 3200-0
= -0.67 / 3200
Again, slope of the line of the plot log[N2O5] v/s t is given by
- k / 2.303
.Therefore, we obtain,
- k / 2.303 = - 0.67 / 3200
⇒ k = 4.82 x 10-4 s-1
(vi) half life is given by,
t½ = 0.693 / k
= 0.639 / 4.82x10-4 s
=1.438 x 103 s
Or we can say
1438 S
Which is very near to what we obtain from graph.

The rate constant for a first order reaction is 60 s–1. How much time will it take to
4.16
reduce the initial concentration of the reactant to its 1/16 th value?
Ans. It is known that,
Hence, the required time is 4.6 × 10−2 s.
During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1µg
4.17 of 90Sr was absorbed in the bones of a newly born baby instead of calcium, how much
of it will remain after 10 years and 60 years if it is not lost metabolically.
Ans.
Therefore, 0.7814 μg of 90Sr will remain after 10 years.
Again,
Therefore, 0.2278 μg of 90Sr will remain after 60 Years

For a first order reaction, show that time required for 99% completion is twice the time
4.18
required for the completion of 90% of reaction.
Ans. For a first order reaction, the time required for 99% completion is
t1 = 2.303/k Log 100/100-99

= 2.303/k Log 100
= 2x 2.303/k
For a first order reaction, the time required for 90% completion is
t2 = 2.303/k Log 100/100-90
= 2.303/k Log 10
= 2.303/k
Therefore, t1 = 2t2
Hence, the time required for 99% completion of a first order reaction is twice the time
required for the completion of 90% of the reaction.
4.19 A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
Ans.
For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following
data are obtained.
4.20
Calculate the rate constant.

Ans. The decomposition of azoisopropane to hexane and nitrogen at 543 K is represented by
the following equation.
After time, t, total pressure, Pt = (Pº - p) + p + p
⇒ Pt = (Pº + p)
⇒ p = Pt - Pº
therefore, Pº - p = Pº - Pt - Pº
= 2 Pº - Pt
For a first order reaction,
k = 2.303/t Log Pº / Pº - p
= 2.303/t Log Pº / 2 Pº - Pt
When t = 360 s, k = 2.303 / 360s log 35.0 / 2x35.0 - 54.0
= 2.175 × 10 - 3 s - 1
When t = 720 s, k = 2.303 / 720s log 35.0 / 2x35.0 - 63.0
= 2.235 × 10 - 3 s - 1
Hence, the average value of rate constant is
k = (2.175 × 10 - 3 + 2.235 × 10 - 3 ) / 2 s - 1
= 2.21 × 10 - 3 s - 1
The following data were obtained during the first order thermal decomposition of
SO2Cl2 at a constant volume.
4.21
Calculate the rate of the reaction when total pressure is 0.65 atm.
Ans.
The rate constant for the decomposition of N2O5 at various temperatures is given
below:
4.22
Draw a graph between ln k and 1/T and calculate the values of A and Ea. Predict the
rate constant at 30° and 50°C.
Ans. From the given data, we obtain
T/°C 0 20 40 60 80
T/K 273 293 313 333 353
1/T / k-1 3.66×10 - 3 3.41×10 - 3 3.19×10 - 3 3.0×10 - 3 2.83 ×10 - 3
105 X K /S-1 0.0787 1.70 25.7 178 2140
In k -7.147 -4.075 -1.359 -0.577 3.063
Slope of the line,

In k= - 2.8
Therefore, k = 6.08x10-2s-1
Again when T = 50 + 273K = 323K,
1/T = 3.1 x 10-3 K
In k = - 0.5
Therefore, k = 0.607 s-1

The rate constant for the decomposition of hydrocarbons is 2.418 × 10–5s–1 at 546 K. If
4.23 the energy of activation is 179.9 kJ/mol, what will be the value of pre-exponential
factor.
k= 2.418 × 10-5 s-1
T= 546 K
Ea= 179.9 kJ mol - 1 = 179.9 × 103J mol - 1
According to the Arrhenius equation,
Ans.
= (0.3835 - 5) + 17.2082
= 12.5917
Therefore, A = antilog (12.5917)
= 3.9 × 1012 s - 1(approximately)

Consider a certain reaction A → Products with k = 2.0 × 10 –2s–1. Calculate the
4.24
concentration of A remaining after 100 s if the initial concentration of A is 1.0 mol L–1.
Ans.
Sucrose decomposes in acid solution into glucose and fructose according to the first
4.25 order rate law, with t1/2 = 3.00 hours. What fraction of sample of sucrose remains after
8 hours ?
Ans. For a first order reaction,
k = 2.303/t Log [R]º / [R]
It is given that, t1/2 = 3.00 hours
Therefore, k = 0.693 / t1/2
= 0.693 / 3 h-1
= 0.231 h - 1
Then, 0.231 h - 1 = 2.303 / 8h Log [R]º / [R]

Hence, the fraction of sample of sucrose that remains after 8 hours is 0.158.
The decomposition of hydrocarbon follows the equation
4.26 k = (4.5 × 1011s–1) e-28000K/T
Calculate Ea.
The given equation is
k = (4.5 x 1011 s-1) e-28000 K/T (i)
Arrhenius equation is given by,
k= Ae -Ea/RT (ii)
From equation (i) and (ii), we obtain

Ans.
Ea / RT = 28000K / T
⇒ Ea = R x 28000K
= 8.314 J K - 1mol - 1× 28000 K
= 232792 J mol - 1
= 232.792 kJ mol - 1
The rate constant for the first order decomposition of H2O2 is given by the
following equation:
4.27 log k = 14.34 – 1.25 × 104K/T
Calculate Ea for this reaction and at what temperature will its half-period be 256
minutes?
Ans. Arrhenius equation is given by,
k= Ae -Ea/RT
⇒In k = In A - Ea/RT
⇒In k = Log A - Ea/RT

⇒ Log k = Log A - Ea/2.303RT (i)
The given equation is
Log k = 14.34 - 1.25 104 K/T (ii)
From equation (i) and (ii), we obtain
Ea/2.303RT = 1.25 104 K/T
⇒ Ea =1.25 × 104K × 2.303 × R
= 1.25 × 104K × 2.303 × 8.314 J K - 1mol - 1
= 239339.3 J mol - 1 (approximately)
= 239.34 kJ mol - 1
Also, when t1/2= 256 minutes,
k = 0.693 / t1/2
= 0.693 / 256
= 2.707 × 10 - 3 min - 1
= 4.51 × 10 - 5s - 1
It is also given that, log k= 14.34 - 1.25 × 104K/T
= 668.95 K
= 669 K (approximately)
The decomposition of A into product has value of k as 4.5 × 103 s–1 at 10°C and energy
4.28
of activation 60 kJ mol–1. At what temperature would k be 1.5 × 104s–1?
Ans. From Arrhenius equation, we obtain
log k2/k1 = Ea / 2.303 R (T2 - T1) / T1T2
Also, k1 = 4.5 × 103 s - 1
T1 = 273 + 10 = 283 K
k2 = 1.5 × 104 s - 1
Ea = 60 kJ mol - 1 = 6.0 × 104 J mol - 1
Then,
= 297 K = 24°C
Hence, k would be 1.5 × 104 s - 1 at 24°C.

The time required for 10% completion of a first order reaction at 298K is equal to that
4.29 required for its 25% completion at 308K. If the value of A is 4 × 1010s–1. Calculate k at
318K and Ea.
Ans. For a first order reaction,
t = 2.303 / k log a / a - x
At 298 K,
t = 2.303 / k log 100 / 90
= 0.1054 / k
At 308 K,
t' = 2.303 / k' log 100 / 75
= 2.2877 / k'
According to the question,

t = t'
⇒ 0.1054 / k = 2.2877 / k'
⇒ k' / k = 2.7296
From Arrhenius equation,we obtain
To calculate k at 318 K,
It is given that, A = 4 x 1010 s-1, T = 318K
Again, from Arrhenius equation, we obtain
Therefore, k = Antilog (-1.9855)
= 1.034 x 10-2 s -1
The rate of a reaction quadruples when the temperature changes from 293 K to 313 K.
4.30 Calculate the energy of activation of the reaction assuming that it does not change with
temperature.
Ans. From Arrhenius equation, we obtain
Hence, the required energy of activation is 52.86 kJ mol - 1.
One mark questions
1. Differentiate between average and instantaneous rate of a reaction.
Ans.
2. Express the rate of the reaction in terms of different reactants and products for:
Ans.
3. Define order of a reaction.
Ans.
4. What is an elementary reaction?
Ans.
5. Define molecularity of reaction.
Ans.
6. What is the slowest step in a complex reaction also called?
Ans.
7. For what type of reactions is molecularity and order the same?
Ans.
8. What is the order of the reaction for which the rate law is; Rate
Ans.
Unit of rate constant of a reaction is same as the unit of rate of reaction. What is the
9.
order of the reaction?
Ans.
Mention any one condition under which a second order reaction of rate law: rate =
10.
k[A]1[B]1 can be made a pseudo first order reaction.
Ans.
For a reaction, the graph of rate of the reaction against molar concentration of the
reactant is as shown. What is the order of the reaction?
11.
Ans.
Rate law of a reaction is : rate = k [NO] 2 [O2]. By how many times does the rate of the
12.
reaction increase if the volume of the reaction vessel is halved?
Ans.
By how many times does the t½ of zero order reaction increase if the initial
13.
concentration of the reactant is doubled.
Ans.
t½ of a reaction is 10 minutes, for a first order reaction. What percent of the reactant
14.
remains unreacted at the end of 50 minutes? [A:3.125%]
Ans.
15. If t½ for a first order reaction is 25 s, what is the time required for 10 g of a reactant to
get reduced to 1.25 g? [A: 75 s]
Ans.
Oxygen is available in air, yet fuels do not burn spontaneously at room temperature.
16.
Why?
Ans.
17.
Ans.
18. What is the relationship between the rate constant and activation energy of a reaction?
Ans.
19. Differentiate between activation energy and threshold energy of a reaction.
Ans.
For many reactions, it is found that a large number of colliding molecules have energy
20. more than threshold value, yet the rate of the reaction is slow. What might be the
reason?
Ans.
21. What is collision frequency?
Ans.

Two mark questions
1. Mention the factors which affect the rate of a reaction.
Ans.
In a reaction 2A → products, the concentration of A decreases from 0.5 to 0.4 mol L-1
2.
in 10 minutes. Calculate the rate of reaction during this interval. [A: 5 ´ 10-3 Mmin-1]
Ans.
Identify the order of the reaction from the unit of rate constants.
3.
i) L mol-1 s-1 ii) M-2 min-1
Ans.
Write the order of the reaction and unit of the rate constant for the reaction:
4.
CH3CHO (g) → CH4 (g) + CO (g). Rate = k [CH3CHO]3/2
Ans.
2A→ P; is second order reaction. How is the rate of the reaction affected if the
5.
concentration of A is (a) doubled (b) reduced to half?
Ans.
6. Define half-life period of a reaction. Give an expression for t½ for a zero order reaction.
Ans.
Show that half-life period for a zero order reaction R → P, is directly proportional to
7.
initial concentration of the reactant.
Ans.
Show that the half-life period of a first order reaction R → P is independent of initial
8.
concentration of the reactant.
Ans.
9.
Ans.
Time required to decompose SO2Cl2 to half of its initial amount in 55 minutes. If the
10.
decomposition is a first order reaction, calculate the rate constant of the reaction.
Ans.
What happens to half life time of a first order reaction when temperature is increased?
11.
Give reason.
Ans.
Draw a graph of concentration of R versus time for a zero order reaction → P. What is
12.
the intercept of the line equal to?
Ans.
The decomposition of a hydrocarbon follows the equation: k = 4.5 ´ 1011 e-28000/T.
13.
Calculate Ea. Given R = 8.314 J K-1 mol-1. [A: 232.79 kJ]
Ans.
The activation energy for a reaction at the temperature T was found to be 2.303RT J
14.
mol-1. Calculate the ratio of the rate constant to Arrhenius factor. [A: 1.25 ´ 10-2]
Ans.
Draw the plot of the distribution curves showing the temperature dependence on the
rate of the reaction at two temperatures t and (t+10). Mark Ea and shade the relevant
15.
regions to show that fraction of molecules having energy greater than Ea doubles when
temperature is increased by 10°.
Ans.
In the graph, what is the intercept and slope of the line equal to?
16.
Ans.
17.
Ans.

Three mark questions
A reaction is first order in X and second order in Y:
i) Write the differential rate law of the reaction.
1.
ii) How is the rate affected on increasing the concentration of Y three times?
iii) Write the SI unit for the rate constant.
Ans.
For a general reaction A→B, plot of concentration of A vs. time is given. Answer the
following questions:
i) What is the order of the reaction?
2. ii) What is the slope of the line equal to?
iii) What is the unit of the rate constant?
Ans.
3. Derive an integrated rate equation for the rate constant of a zero order reaction.
4. Derive an integrated rate equation for the rate constant of a first order reaction.
Ans.
The initial concentration of N2O5 in the following first order reaction
5. was 1.24 ´ 10-2 M at 318 K. The concentration of N2O5

after 60 minutes was 0.2 ´ 10-2 M. Calculate the rate constant of the reaction at 318K.
[A: k = 0.304]
Ans.
6. A first order reaction takes 40 minutes for 30% completion. Calculate the rate constant.
Ans.
The rate constant of a first order reaction is 3 ´ 10-3 s-1. Calculate the concentration of
7.
the reactant after 30 minutes if the initial concentration is 0.5 M. [A: 0.00228 M]
A first order reaction takes 69.3 minutes for 50% completion. How much time will be
8.
needed for 80% completion? [A:160.9 min]
Ans.
The rate constant of a first order reactions 3 ´ 10-4 s-1. What percentage of the
9.
reactant will decompose in one hour? [A:66%]
Show that the time required for 99% completion of a first order reaction is twice the
10.
time required for completion of 90% of the reaction.
For a first order reaction, the time required for 99% completionis
t1 = 2.303/k Log 100/100-99
= 2.303/k Log 100
= 2x 2.303/k
For a first order reaction, the time required for 90% completion is
Ans.
t2 = 2.303/k Log 100/100-90
= 2.303/k Log 10
= 2.303/k
Therefore, t1 = 2t2
Hence, the time required for 99% completion of a first order reaction is twice the time
required for the completion of 90% of the reaction.
The rate constant of a first order reaction is 60 s-1. How much time will it take for the
11. reaction to reduce the initial concentration of the reactant to 1/16th of its initial value?
[A: 4.62 ´ 10-2 s]
It is known that,
Ans.
Hence, the required time is 4.6 × 10−2 s.

The first order rate constant for the decomposition of ethyl iodide at 600K is 1.6 ´ 10-5
12. s-1. Its activation energy is 209 kJ/mol. Calculate the rate constant of the reaction at
700K. [A: 6.353 ´ 10-3 s-1]
Ans.
What is the effect of catalyst on a reaction with respect to its
i) energy of activation
13.
ii) ΔG of the reaction
iii) time required for 50% of the reaction to be completed?
(i). Catalysts provide a new reaction pathway in which a lower Activation energy is
offered. A catalyst increases the rate of a reaction by lowering the activation energy so
that more reactant molecules collide with enough energy to surmount the smaller
energy barrier.
(ii). Effect of catalyst on Gibbs free energy : There is no effect of the catalyst on gibbs
Ans. free energy
Explanation :
as ΔG=ΔH−TΔS
Since on adding catalyst, enthalpy, entropy and temperature remain same therefore
there is no effect on gibbs free energy.
(iii). (No solution found)

Five mark questions
a) The rate constants of a reaction at 500K and 700K are 0.02 s-1 and 0.07 s-1
respectively. Calculate the energy of activation of the reaction.
1.
[A:18.23 kJ mol-1]
b) What is pseudo first order reaction? Give an example.
Ans. (a). (Different answers in different websites)
(b) Those reactions which are not of 1st order but approximated or appear to be of 1st
order due to higher concentration of the reactant/s than other reactants are known as
pseudo-first-order reactions. The order of a chemical reaction can be defined as the
sum of the power of concentration of reactants in the rate law expression is called the
order of that chemical reaction. Reactions can be a first-order reaction, second-order
reaction, pseudo-first-order reaction, etc. depending on the concentration of the
reactants.
Pseudo-first-order reaction can be well explained by the following examples –
1. Hydration of Alkyl halide

CH3I + H2O CH3OH + H+ + I-
Rate of reaction = k [CH3I] [ H2O]
As methyl iodide is also used in aqueous solution form so the concentration of
water is far higher than methyl iodide.
[CH3I] <<< [ H2O]
So, the concentration of water doesn’t change much and can be approximated
as no change or constant.
Now we can write – Rate of reaction = k’ [CH3I]
Where k’ = k [H2O]
Thus, the reaction appears to be first-order, but it is actually of second-order
that’s why it is known as a pseudo-first-order reaction.
2. Hydrolysis of Cane Sugar

C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Water Glucose Fructose
Rate of reaction = k [C12H22O11] [H2O]
But [H2O] >>> [C12H22O11]
So, the concentration of water can be approximated as constant as its
concentration doesn’t change a lot during the reaction.
Now the rate of reaction can be written as –
r = k’ [C12H22O11]
where k’ = k [H2O]
thus, hydrolysis of cane sugar is a pseudo-first-order reaction.
3. Hydrolysis of ester
Reaction – CH3COOC2H5 + H2O CH3COOH + C2H5OH

Ethyl ethanoate Water Ethanoic acid Ethanol
Rate of reaction = k [CH3COOC2H5] [H2O]
But [H2O] >>> [CH3COOC2H5]
So, we can say the concentration of water remains almost constant during the
reaction.
So, we can write –
Rate of reaction = k’ [CH3COOC2H5]
K’ = k [H2O]
Thus, hydrolysis of the ester is a pseudo-first-order reaction.
a) The graph of log k vs. 1/T for a reaction is linear with intercept of 10 and slope of -5.1
´ 103. Calculate the frequency factor and Ea of the reaction. R = 8.314 JK-1mol-1 [A:
2. Frequency factor : 1010, Ea = 97.65 kJ]
b) A reaction is 50% complete in 2 hours and 75% complete in 4 hours. What is the
order of the reaction? Explain.
(a). (No solution found)
(b). The reaction goes to 50% completion in first 2 hours. If the initial concentration is
A, it becomes A/2 in 2 hours. Then, in the next 2 hours, it comes A/4 from A/2. This
Ans.
means it again reduced by half in 2 hours. This means the half-life of the reaction is 2
hours which is constant. Half-life is constant in the first order reaction. Hence, the order
of the reaction is 1.
3.
Ans. (Unsatisfactory answer)

a) Explain collision theory of reaction rate.
4. b) Draw a graph of potential energy vs. reaction co-ordinate to show the effect of
catalyst on the activation energy.
Ans. (a).
Collision theory states that the rate of a chemical reaction is proportional to the
number of collisions between reactant molecules. The more often reactant molecules
collides, the more often they react with one another, and the faster the reaction rate.
In reality, only a small fraction of the collisions are effective collisions. Effective
collisions are those that result in a chemical reaction.
In order to produce an effective collision, reactant particles must possess some

minimum amount of energy. This energy, used to initiate the reaction, is called the
activation energy. For every sample of reactant particles there will be some that
possess this amount of energy.
The larger the sample, the greater the number of effective collisions, and the faster the
rate of reaction. The number of particles possessing enough energy is dependent on
the temperature of the reactants. If reactant particles do not possess the required
activation energy when they collide, they bounce off each other without reacting.
Some chemical reactions also require that the reactant particles be in a particular
orientation to produce an effective collision. Unless the reactant particles possess this
orientation when they collide, the collision will not be an effective one. The reaction of
ozone with nitrogen monoxide is an example of how orientation can be important.
To summarize, the requirements for an effective collision (for a chemical reaction to
occur):
1. The reactants must collide with each other.
2. The molecules must have sufficient energy to initiate the reaction (called activation
energy).
3. The molecules must have the proper orientation.
(b).
a) Hydrogen peroxide (H2O2 (aq)) decomposes to H2O (l) and O2 (g) in a reaction that
is of first order in H2O2 and has a rate constant k = 1.06 ´ 10-3 min. How long will it
5.
take for 15% of a sample of H2O2 to decompose? [A: t15% =153.4 min]
b) Mention two criteria for effective collision.
Ans. (a).
(b).
Collision: Two objects coming towards each other with some momentum and then
coming in contact with each other is known as a Collision.
Explanation:
According to the collision theory, the molecules must collide with enough energy,
known as the activation energy, to prevent the chemical bonds from breaking, in order
for a chemical reaction to occur.
Additionally, the molecules must collide in the proper orientation.
If these two requirements are satisfied, a collision is referred to be a successful
collision or an effective collision. The frequency of the effective collisions is equal to the
rate of a chemical reaction.
Criteria for effective collision.
(i) The frequency of collision.
(ii) The effective fraction of collisions.
a) Distinguish between molecularity and order of a reaction.
b) The activation energy for the reaction 2HI (g) → H2(g)+I2 (g) is 209.5 kJ/mol at 581 K.
6.
Calculate the fraction of molecules having energy equal to or greater than activation
energy (R = 8.314 Jk-1 mol-1) [A: 1.471 ´ 10-19]
Ans. (a)
Order of reaction Molecularity of reaction
Order is defined as the sum of the Molecularity is defined as the number of
powers of the concentration of reactants reacting molecules taking part in the
taking part in a chemical reaction. rate-determining step.
Order of reaction can only be Molecularity is a theoretical quantity,
determined experimentally and can not which can be determined through
be calculated. reaction mechanisms.
Molecularity of reaction is always in a
Order of reaction can be a whole
whole number or integer, it can never be
number, zero, integer, or fraction.
fraction or zero.
The value of molecularity is always 3 or
The value of the order in any reaction
less because more than three molecules
can be 0, 1 and 2. Order of reaction
usually don’t come close during a
beyond 2 is not possible.
chemical reaction.
We use order to know the number of We use molecularity in the chemical
molecules of the reactant whose reaction to know how many molecules
concentration changes during a given affect the rate of a given chemical
chemical reaction. equation.
The Molecularity of the reaction can
Order of reaction can be based on
only be based on a balanced chemical
unbalanced chemical reactions.
equation.
(b).
In the given case:
Ea = 209.5 kJ mol - 1 = 209500 J mol - 1
T = 581 K
R = 8.314 JK - 1 mol - 1
Now, the fraction of molecules of reactants having energy equal to or greater than
activation energy is given as
In a pseudo first order hydrolysis of ester in water the following results are obtained.
7.
i) Calculate the average rate of reaction between the time interval 30 to 60 seconds.
ii) Calculate the pseudo first order rate constant for the hydrolysis of ester. [A: (i) 4.67 ´
10-3 mol L-1 s-1 (ii) 1.91 ´ 10-2 s-1 ]
Ans. (i) Average rate of reaction between the time interval, 30 to 60 seconds, = d[ester] / dt
= (0.31-0.17) / (60-30)
= 0.14 / 30
= 4.67 × 10 - 3mol L - 1s - 1
(ii) For a pseudo first order reaction,
k = 2.303/ t log [R]º / [R]
For t= 30 s, k1 = 2.303/ 30 log 0.55 / 0.31
= 1.911 × 10 - 2s - 1
For t = 60 s, k2 = 2.303/ 60 log 0.55 / 0.17
= 1.957 × 10 - 2s - 1
For t= 90 s, k3 = 2.303/ 90 log 0.55 / 0.085
= 2.075 × 10 - 2s - 1
Then, average rate constant, k = k1 + k2+ k3 / 3
= 1.911 × 10 - 2 + 1.957 × 10 - 2 + 2.075 × 10 - 2 / 3
= 1.981 x 10-2 s - 1
8.
(a).
Ans.
(b). (No solution found)

a) Sucrose decomposes in an acid solution, following first order kinetics. Half-life for the
9. reaction is 3 hrs. Calculate the fraction of sucrose that remains after 8 hrs. [A: 0.1576]
b) What is the effect of temperature on the (i) rate constant and (ii) t1/2 of a reaction.
(a).
For a first order reaction,
k = 2.303/t Log [R]º / [R]
It is given that, t1/2 = 3.00 hours
Therefore, k = 0.693 / t1/2
= 0.693 / 3 h-1
= 0.231 h - 1
Then, 0.231 h - 1 = 2.303 / 8h Log [R]º / [R]

Ans.
Hence, the fraction of sample of sucrose that remains after 8 hours is 0.158.
(b). (No solution found)

Following data was obtained for the reaction : A + B → P
10.
i) What is the order of the reaction with respect to A and B?

ii) Write the rate law.
iii) What is the rate constant.
iv) What is the half-life of the reaction

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I – The Solid State

Questions (From Textbook)

(ii) Face-centered tetragonal

(iii) Body centered

1.23. Explain the following terms with suitable example:

1.26. Explain the following with suitable examples.

Question (From Question Bank)

10. What is the coordination number of a particle in hcp?

Packing Efficiency = Total Volume of Sphere/Total Volume of Cube×100

Packing Efficiency can be evaluated through three different structures of geometry

18. What are F-centres?

21. What are non stoichiometric defects?

Questions (From Question Bank)

3. Write the differences between metallic and ionic crystalline solids

4. Write the differences between metallic and molecular crystalline solids

6. Name the two parameters that characterise a unit cell.

7. Define unit cell and crystal lattice.

18. What are point defects and line defects?

19. Distinguish between Frenkel and Schottky defects.

20. Explain metal excess defect due to anionic vacancy.

21. Explain metal deficiency defect using ZnO as an example.

Electrical conductivity of a semiconductor (i) increases with temperature (ii) increases

26. Write the differences between ferrimagnetic and ferromagnetic substances

Question (From Question Bank)

(i) Non polar Molecular Solids:

Ans. (ii) Polar Molecular Solids:

(iii) Hydrogen Bonded Molecular Solids:

A – Primitive Cubic Cell Unit

Ans. B – Body Centered Unit Cell

6. Calculate the packing efficiency in bcc structure.

7. Calculate the packing efficiency in simple cubic lattice.

Questions (From Question Bank)

We have given 0.4 moles of compound.

b) i) How many types of primitive unit cells are known?

SOLUTE + SOLVENT = SOLUTION

Solution type Solute Solvent Example

Nine kinds of solution are possible.

d) Mass Percentage- the mass percentage of a component in a given solution is the

Na2Co3 + 2Hcl 2Nacl + H2o + CO2

NaHCO3 + Hcl Nacl + H2o + CO2

Vapour pressure of a two-component solution showing negative deviation from

(ii) Putting the value of 'M' in equation (i), we get:

2.23 Suggest the most important type of intermolecular attractive interaction in

Order of solubility is KCl < CH3OH < CH3CN < cyclohexane.

2.29 Nalorphene (C19H21NO3), similar to morphine, is used to combat withdrawal

So, Ka = (Cα x Cα) / (C (1-α))

Let α be the degree of dissociation of CH2FCOOH

Now total number of moles = m(1-a) + ma +ma = m(1+a)

10. Using the graph answer the following:

Ans. (No solution found)

(i) Zn electrode (anode) is negatively charged.

(iii) The reaction taking place at the anode is given by,

The galvanic cell of the given reaction is depicted as:

Now, the standard cell potential is

In the given equation,

Then, ΔrGø = - 6 × 96487 C mol - 1 × 0.34 V

The galvanic cell of the given reaction is depicted as:

Now, the standard cell potential is

Then, ΔrGø = -nFEøcell

= - 1 × 96487 C mol - 1 × 0.03 V

Again, ΔrGø = - 2.303 RT ln K

= 0.52865 V = 0.53 V (approximately)

= 0.14 - 0.0295 × log125